CN1946684A

CN1946684A - Sulfur-containing compositions and processes for making same

Info

Publication number: CN1946684A
Application number: CN200580012290.0A
Authority: CN
Inventors: M·D·雷夫韦克; D·M·哈森伯格; C·W·布朗; M·S·马特森; J·D·拜尔斯; D·M·索拉斯; M·S·汉金森; S·J·赫伦; L·L·卡斯滕斯; B·邢
Original assignee: Agrium Co; Chevron Phillips Chemical Co LLC
Current assignee: Agrium Co; Chevron Phillips Chemical Co LLC
Priority date: 2004-02-17
Filing date: 2005-02-17
Publication date: 2007-04-11
Anticipated expiration: 2025-02-17
Also published as: ES2356165T3; CN1946684B

Abstract

Thiol ester compositions, methods of making the thiol ester compositions, and methods of using the thiol ester compositions are provided. In some embodiments, the thiol ester compositions include thiol esters, hydroxy thiol esters and cross-linked thiol esters. The thiol ester composition can be used to produce cross-linked thiol esters, sulfonic acid-containing esters, sulfonate containing esters and thiocrylates containing esters. The thiol ester composition can be used to produce polythiourethanes. The polythiourethanes can be used in fertilizers and fertilizer coatings.

Description

Sulfur-containing compositions and manufacture method thereof

The cross reference of related application

[0001] the application requires to comprise the U.S. serial 60/545 of submission on February 17th, 2004,260, the U.S. serial of submitting on April 13rd, 2,004 60/561,614, the U.S. serial of submitting on April 13rd, 2,004 60/561, the U.S. serial 60/561 that on April 13rd, 685 and 2004 submitted to, 855 rights and interests at four interior temporary patent applications are incorporated this paper into as a reference at this with its full content.

Background of invention

Invention field

[0002] the present invention relates to sulfur-bearing alcohol ester composition, it generally is to react with the material that can form thiol group by the unsaturated ester composition to prepare.The invention still further relates to this preparation method who contains composition of mercaptans and contain the purposes of composition of mercaptans with this.

Association area is described

[0003] chemical industry is devoted to the product with in liberal supply, cheap more raw material production such as polymkeric substance, fertilizer, fuel.Because fossil oil is exhausted at leisure in time, people are seeking the alternate resources substitute that acts as a fuel always.In addition, chemical industry is all the time at the raw material of producing product and environment for use close friend hardy, with minimizing potential hazard and the risk relevant with safety and environmental problem.

Summary of the invention

[0004] the present invention has advantageously provided the method that contains composition of mercaptans and make said composition.Except these compositions and make these method for compositions, also provide the product that comprises these compositions.

[0005] as a kind of embodiment of the present invention, advantageously provided a kind of thiol ester composition.In this embodiment, this thiol ester composition comprises that each thiol ester molecule contains the thiol ester molecule of average at least 1.5 ester groups.Each thiol ester molecule also contains on average at least 1.5 thiol groups in this type of thiol ester molecule.This type of thiol ester molecule also has episulfide and the thiol group mol ratio below 1.5.

[0006] in some respects, the thiol ester molecule has the episulfide and the thiol group mol ratio of scope from 0 to 1.0.In some respects, each thiol ester molecule contains 1.5 to 9 thiol groups of average out in the thiol ester molecule.In some embodiments, the thiol ester molecule has carbon-to-carbon double bond and the thiol group mol ratio below 1.5.

[0007] contained mercaptan sulfur (thiol sulfur) or mercaptan sulfur (mercaptan sulfur) content of thiol ester molecule also can change.For example, in some embodiments, the thiol ester molecule contains the above mercaptan sulfur of average 5wt.%.In other embodiments, the thiol ester molecule contains average 8 to 10wt.% mercaptan sulfur.In some embodiments, the thiol ester molecule contains the following sulphur of average 30 moles of %, and this sulphur exists with the episulfide form.Alternatively, the thiol ester molecule contains average 2 moles of % sulphur following, that exist with the episulfide form.

[0008] in some embodiments, the thiol ester molecule is made by unsaturated ester, this unsaturated ester contain average 25wt.% following, comprise 3 side chains that adjoin by methylene radical carbon-to-carbon double bond at interval.In yet another aspect, 40% above sulfur-bearing of whole side chains of being contained of thiol ester molecule.

[0009] except that the thiol ester composition,, advantageously provided a kind of manufacture method of thiol ester composition as another embodiment of the present invention.For the production thiol ester composition, hydrogen sulfide is contacted with the unsaturated ester composition.The unsaturated ester composition comprises the unsaturated ester of average at least 1.5 ester groups of each unsaturated ester molecule.Each unsaturated ester molecule of unsaturated ester also contains on average at least 1.5 carbon-to-carbon double bonds.Hydrogen sulfide and unsaturated ester react, and produce or form thiol ester composition.It is thiol ester molecule below 1.5 that this thiol ester composition advantageously comprises episulfide and thiol group mol ratio.

[0010] in embodiments of the invention, relevant with the unsaturated ester reactions steps with hydrogen sulfide process variable can be adjusted variation.On the one hand, the reactions steps of hydrogen sulfide and unsaturated ester is to take place under the situation that solvent exists.On the other hand, the reactions steps of hydrogen sulfide and unsaturated ester takes place under solvent-free substantially situation.In some embodiment, the reactions steps of hydrogen sulfide and unsaturated ester is catalytic by heterogeneous catalyst.Alternatively, the reaction of hydrogen sulfide and unsaturated ester is caused by radical initiator or ultraviolet light irradiation.The temperature of reaction of hydrogen sulfide and unsaturated ester can be adjusted variation.In some embodiment, the reaction of hydrogen sulfide and unsaturated ester is to take place under the temperature more than-20 ℃.As another example, this process is the successive process, and the reaction of hydrogen sulfide and unsaturated ester lack solvent, temperature and cause and carry out more than-20 ℃ by ultraviolet radiation.In embodiments of the invention, the process variable of other type and combination thereof also can change, as those skilled in the art will recognize.

[0011], advantageously provided the another kind of manufacture method of thiol ester composition as another embodiment of the present invention.In this method embodiment, hydrogen sulfide contacts with the unsaturated ester composition.This unsaturated ester composition comprises that each unsaturated ester molecule contains average at least 1.5 ester groups and each unsaturated ester molecule contains the on average unsaturated ester of at least 1.5 carbon-to-carbon double bonds.Hydrogen sulfide and unsaturated ester react under solvent-free substantially condition then, form thiol ester composition.This thiol ester composition comprises the thiol ester molecule.It is thiol ester molecule below 1.5 that thiol ester composition advantageously comprises episulfide and thiol group mol ratio.

[0012] in embodiments of the invention, relevant with the unsaturated ester reactions steps with hydrogen sulfide process variable can be adjusted variation.On the one hand, the reactions steps of hydrogen sulfide and unsaturated ester is to take place under the situation that has solvent to exist.On the other hand, the reactions steps of hydrogen sulfide and unsaturated ester takes place under solvent-free substantially situation.In some embodiment, the reactions steps of hydrogen sulfide and unsaturated ester is catalytic by heterogeneous catalyst.Alternatively, the reaction of hydrogen sulfide and unsaturated ester is caused by radical initiator or ultraviolet light irradiation.The temperature of reaction of hydrogen sulfide and unsaturated ester can be adjusted variation.In some embodiment, the reaction of hydrogen sulfide and unsaturated ester is to take place under the temperature more than-20 ℃.

[0013] in embodiments of the invention, the unsaturated ester composition comprises the oil of natural origin, as described here.In some embodiment, the unsaturated ester composition comprises soya-bean oil.The unsaturated ester composition of other type is also described herein.

[0014] the thiol ester molecule that forms with this method production has multiple advantage.For example, in some embodiment, the thiol ester molecule has the hydrogen sulfide/carbon-to-carbon double bond mol ratio more than 2.As another example, in other embodiments, the thiol ester molecule has the above mercaptan sulfur of average 5wt.%.Aspect some, 40% above sulfur-bearing of the whole side chains of thiol ester molecule.

[0015], advantageously provided the another kind of making method of thiol ester composition as another embodiment of the present invention.In this embodiment, polyhydric alcohol composition contacts with the thiol carboxylic acid composition and reacts, and generates thiol ester composition.This thiol ester composition comprises that each thiol ester molecule contains the thiol ester molecule of average at least 1.5 ester groups and average at least 1.5 thiol groups of each thiol ester molecule.

[0016] except that the thiol ester composition,, advantageously provided other composition as embodiment of the present invention.For example, as another embodiment of the present invention, provide the hydroxyl thiol ester composition.This hydroxyl thiol ester composition comprises that each hydroxyl thiol ester molecule contains the hydroxyl thiol ester molecule of average at least 1.5 ester groups and average at least 1.5 the Alpha-hydroxy thiol groups of each hydroxyl thiol ester molecule.

[0017] as described here, the Alpha-hydroxy thiol group contains alcohol or oh group and thiol group in same group.In embodiments of the invention, the Alpha-hydroxy thiol group alcohol and the thiol group that can be separated from each other replaces.In these embodiments, the Alpha-hydroxy group of the equal amts alcohol and the thiol group that can be used for being separated from each other.For example, in some embodiment, hydroxyl thiol ester molecule contains on average at least 1.5 Alpha-hydroxy thiol groups.In the embodiment that contains the alcohol that is separated from each other and thiol group, hydroxyl thiol ester molecule will contain on average at least 1.5 alcohol groups and average at least 1.5 thiol groups.

[0018] aspect some, each hydroxyl thiol ester molecule contains 1.5 to 9 Alpha-hydroxy thiol groups of average out in the hydroxyl thiol ester molecule.In some embodiment, the thiol ester molecule has carbon-to-carbon double bond and the thiol group mol ratio below 1.5.

[0019] in some embodiment, the thiol ester molecule is made by unsaturated ester, and these unsaturated ester have the side chain that average 25wt.% is following, contain 3 methylene radical that adjoin carbon-to-carbon double bond at interval.On the other hand, 40% above sulfur-bearing of whole side chains of being contained of Alpha-hydroxy thiol ester molecule.

[0020] mercaptan sulfur content that contains in the hydroxyl thiol ester molecule also can change.For example: in some embodiment, hydroxyl thiol ester molecule has the above mercaptan sulfur of average 5wt.%.In other embodiments, hydroxyl thiol ester molecule has average 8 to 10wt.% mercaptan sulfur.

[0021] in some embodiment, hydroxyl thiol ester molecule has epoxide group and the Alpha-hydroxy thiol group mol ratio below 2.In others, said composition does not contain epoxide group substantially.

[0022] beyond the hydroxyl-removal thiol ester composition,, advantageously provided the making method or the process of hydroxyl thiol ester composition as embodiment of the present invention.In one embodiment, provide a kind of preparation method of hydroxyl thiol ester composition, comprised making hydrogen sulfide and the contacted step of epoxidation unsaturated ester composition.This epoxidation unsaturated ester composition comprises that each epoxidation unsaturated ester molecule contains the epoxidation unsaturated ester of average at least 1.5 ester groups and average at least 1.5 epoxide groups of each epoxidation unsaturated ester molecule.Then hydrogen sulfide therewith the epoxidation unsaturated ester react, form the hydroxyl thiol ester composition.

[0023] in embodiments of the invention, epoxidation unsaturated ester composition comprises the oil of epoxidised natural origin, as described here.In some embodiment, epoxidation unsaturated ester composition comprises epoxidized soybean oil.The epoxidation unsaturated ester composition of other type also is described at this.

[0024] in some embodiment, hydrogen sulfide in the epoxidation unsaturated ester and epoxide group mol ratio are more than 1.

[0025] on the one hand, hydrogen sulfide therewith the reactions steps of epoxidation unsaturated ester be under the situation that has catalyzer to exist, to take place.

[0026], advantageously provided the another kind of making method of hydroxyl thiol ester composition as another embodiment of the present invention.In this method embodiment, polyhydric alcohol composition and hydroxyl thiol carboxylic acid composition are in contact with one another and react, and generate the hydroxyl thiol ester composition.In this embodiment, the hydroxyl thiol ester composition comprises that each hydroxyl thiol ester molecule contains the hydroxyl thiol ester molecule of average at least 1.5 ester groups and average at least 1.5 the Alpha-hydroxy thiol groups of each hydroxyl thiol ester molecule.

[0027], advantageously provided a kind of crosslinked thiol ester composition as another embodiment of the present invention.This crosslinked thiol ester composition comprises and contains at least two monomeric thiol ester oligopolymer of thiol ester, these thiol ester monomers quilt-S _QThe poly-sulfide linkage of-structure is connected, and wherein the Q value is greater than 1.In some embodiment, the thiol ester oligopolymer contains at least three thiol ester monomers that are connected with poly-sulfide linkage.On the other hand, the thiol ester oligopolymer contains 3 to 20 thiol ester monomers that connect with poly-sulfide linkage.

[0028] on the one hand, crosslinked thiol ester composition had both comprised that the thiol ester monomer also comprised the thiol ester oligopolymer.In some embodiment, thiol ester monomer and thiol ester oligopolymer have total mercaptan sulphur content of 0.5 to 8wt.%, perhaps alternatively, are 8 to 15wt.%.Thiol ester monomer that combines and thiol ester oligopolymer can have the molecular-weight average more than 2000; Perhaps alternatively, in 2000 to 20000 scope.

[0029] as another embodiment of the present invention, advantageously provided a kind of crosslinked thiol ester composition, its making method comprises and this thiol ester composition contacted with a kind of oxygenant and this thiol ester and this oxygenant are reacted and forms the step of thiol ester oligopolymer.In this embodiment, the thiol ester oligopolymer contains at least two thiol ester monomers, between monomer with-S _QThe poly-sulfide linkage of-structure is connected, and wherein the Q value is greater than 1.

[0030], advantageously provided a kind of making method of crosslinked thiol ester composition as another embodiment of the present invention.In this method, thiol ester composition contacts and reacts with oxygenant, forms the thiol ester oligopolymer, and these oligopolymer contain at least two thiol ester monomers, between monomer with-S _QThe poly-sulfide linkage of-structure is connected, and wherein the Q value is greater than 1.In some embodiment, oxygenant is elementary sulfur, oxygen or hydrogen peroxide.On the one hand, oxygenant is an elementary sulfur.

[0031] on the one hand, thiol ester is the hydroxyl thiol ester.In others, the elementary sulfur in the thiol ester molecule and the weight ratio of mercaptan sulfur are 0.5 to 32.

[0032] reactions steps of thiol ester and oxygenant can carried out in 25 ℃ to 150 ℃ temperature range.The production process of crosslinked thiol ester composition also can comprise the step of removing remaining hydrogen sulfide from the crosslinked thiol ester composition of being produced.On the other hand, the reaction of thiol ester and element sulphur is by catalytic.In some embodiment, catalyzer is an amine.

[0033] another target of the present invention provides novel fertilizer.

[0034] another target of the present invention provides a kind of novel method of producing fertilizer.

[0035] therefore, an aspect the present invention relates to the release and release control fertilizer that attrition resistant polythiourethane and/or epoxy polymer encapsulate therein.

[0036] another aspect therein, the present invention relates to release and release control fertilizer, it comprises the particulate state plant nutrient substance that is surrounded by coating, this coating is the reaction product that comprises the mixture of following component: (i) first kind of composition, be selected from isocyanic ester and/or Resins, epoxy, (ii) first kind of composition that contains active hydrogen is selected from thiol ester composition; The hydroxyl thiol ester composition; Crosslinked thiol ester composition and composition thereof.

[0037] another aspect therein, the present invention relates to release and release control fertilizer, it comprises the particulate state plant nutrient substance that is surrounded by coating, and this coating is the reaction product that comprises the mixture of following component: (i) isocyanic ester and/or Resins, epoxy and (ii) sulfur-bearing vegetables oil.

[0038] another aspect therein, the present invention relates to release and release control fertilizer, it comprises the particulate state plant nutrient substance that is surrounded by coating, and this coating is the reaction product that comprises the mixture of following component: (i) isocyanic ester and/or Resins, epoxy and (ii) sulfur-bearing soya-bean oil.

[0039] another aspect therein the present invention relates to release and release control fertilizer, and it comprises by one deck at least and contains the particulate state plant nutrient substance that the coating of polythiourethane and/or epoxy polymer surrounds.

[0040] another aspect therein, the present invention relates to release and release control fertilizer, it comprises the particulate state plant nutrient substance that is surrounded by one deck coating at least, described coating comprises the reaction product of the mixture that comprises isocyanic ester, wax and active hydrogen-contg compound, and described active hydrogen-contg compound comprises the sulfur-bearing vegetables oil.

[0041] another aspect therein, the present invention relates to the release and release control fertilizer particulate production method of a kind of attrition resistant polythiourethane and/or epoxy polymer encapsulation, it is that sulfocompound is mixed in urethane ester polymer and/or the epoxy polymer, form reaction mixture and carry out, sulfocompound such as thiol ester composition, hydroxyl thiol ester composition, crosslinked thiol ester composition, one or more in described other sulfur-based compound and composition thereof after this.

[0042] preferably, for producing the release and release control fertilizer of this polythiourethane encapsulation, sulfocompound (for example: one or more in thiol ester composition, hydroxyl thiol ester composition, the crosslinked thiol ester composition) be used as one of isocyanic ester-reactive behavior composition (separately or contain compound bearing active hydrogen with other use).Preferably, sulfocompound comprises the sulfur-bearing vegetables oil.In a kind of embodiment preferred, the sulfur-bearing vegetables oil comprises a kind of mercaptan vegetables oil (mercaptanized vegetable oil (MVO)), and more preferably, so the place describes in detail more, even more preferably, be by in vegetables oil, adding the MVO that hydrogen sulfide is produced.In another embodiment preferred, the sulfur-bearing vegetables oil comprises sulfydryl-hydroxyl vegetables oil (mercapto-hydroxyvegetable oil (MHVO)), more preferably, so the place describes in detail more, even more preferably, be by in epoxidized vegetable oil, adding the MHVO that hydrogen sulfide is produced.In another embodiment preferred, the sulfur-bearing vegetables oil comprises sulfur-crosslinked mercaptan vegetables oil (crosslinked mercaptanized vegetable oil (CMVO)), more preferably, so the place describes in detail more, even more preferably, be by in mercaptan vegetables oil (MVO), adding the CMVO that elementary sulfur is produced.

[0043] preferably, be to produce the release and release control fertilizer of epoxy polymer encapsulation, sulfocompound (for example: one or more in thiol ester composition, hydroxyl thiol ester composition, the crosslinked thiol ester composition) be used as one of isocyanic ester-reactive behavior composition (separately or contain compound bearing active hydrogen with other use).Preferably, sulfocompound comprises sulfur-bearing vegetables oil (for example: MVO and/or MHVO and/or CMVO), can be used as one of Resins, epoxy-reactive behavior composition and uses.

[0044] in a kind of preferred embodiment of method, the release and release control fertilizer of polythiourethane encapsulation is to adopt following steps to produce:

(i) isocyanic ester-reactive behavior composition that will comprise sulfur-bearing vegetables oil (being preferably one or more among MVO described herein, MHVO and the CMVO) is applied to fertiliser granulates, form coating fertiliser granulates and

(ii) isocyanic ester is applied to the fertiliser granulates of coating, forms fertilizer.

Step (i) and (ii) can randomly repeat repeatedly (for example: 2 to 10 times) continuously is with the polythiourethane coating of the encapsulation fertiliser granulates of making expectation thickness.It is about by weight 1.5 to 20% that the release and release control fertilizer of producing with this method preferably contains, more preferably about by weight 2 to 15%, most preferably about by weight 2.5 to 10% polythiourethane coating, and this is based on the coated fertilizer total weight.

[0045] in another embodiment, the release and release control fertilizer of polythiourethane encapsulation is to adopt following steps to produce:

(i) isocyanate component is applied to fertiliser granulates, form coating fertiliser granulates and

The compound bearing active hydrogen that contains that (ii) will comprise sulfur-bearing vegetables oil (preferably, one or more among MVO described herein, MHVO and the CMVO) is applied to the coated fertilizer particle, forms fertilizer.

Equally, with step (i) with (ii) randomly repeat repeatedly (for example: 2 to 10 times) continuously to make the polythiourethane coating of encapsulation fertiliser granulates of expectation thickness.The release and release control fertilizer of producing with this method preferably contains by weight from about 1.5 to 20%, and more preferably from about 2 to 15%, most preferably from about 2.5 to 10% polythiourethane coating, this is based on the coated fertilizer total weight.

[0046] in further embodiment, the release and release control fertilizer of polythiourethane encapsulation is to adopt following steps to produce:

(i) with isocyanic ester with comprise that (preferably, one or more among MVO described herein, MHVO and the CMVO prepolymer of) active hydrogen-contg compound is applied to fertiliser granulates to the sulfur-bearing vegetables oil, forms the fertiliser granulates of coating, to make fertilizer;

(ii) this prepolymer is changed into polythiourethane, make fertilizer.

Prepolymer used in the step (i) can comprise the sulfur-bearing vegetables oil (preferably by making (a), MVO described herein, among MHVO and the CMVO one or more) active hydrogen-contg compound and (b) isocyanic ester contact, produce prepolymer and produce with continuous or batch-wise mode, its amount makes in the component (b) that the contained ratio that (does not promptly react) the active hydrogen part freely is about 0.8: 1 to about 2.0: 1 in contained (promptly do not react) freely isocyanate groups and the component (a), preferably, about 0.9: 1 to about 1.5: 1, more preferably, about 0.95: 1 to about 1.3: 1.

[0047] therefore, in one embodiment, used prepolymer contains excessive isocyanate groups in the step (i).In this case, step conversion (ii) comprises further interpolation active hydrogen-contg compound, this active hydrogen-contg compound can with step (i) in used identical or different.In another embodiment, used prepolymer contains excessive active hydrogen group in the step (i).In this case, step conversion (ii) comprises further interpolation isocyanic ester, and this isocyanic ester can be identical or different with used isocyanic ester in the step (i).Preferably, step (ii) comprises active hydrogen-contg compound or the isocyanic ester (as the situation that may occur) that adds capacity, with nearly all isocyanic ester freely or reactive with active hydrogen group on the balanced prepolymer.

[0048] the embodiment care should be used to that relates to prepolymer is operated, because co-reactant is in a single day admixed together, reaction promptly begins to form polythiourethane; Simultaneously the viscosity of mixture increases, and this may reduce component and be easy to smearing property on fertiliser granulates.But, the increase of this viscosity can be by before being applied to fertiliser granulates, the mixing time of co-reactant and temperature limited controlled.

[0049] in further preferred embodiment, organic additive can: (1) is added into (pre-mixing) in one or more co-reactants; And/or (2) were applied to fertiliser granulates (precoating) earlier before co-reactant; And/or (3) are applied to the fertiliser granulates (skin) of polythiourethane coating as final step.The limiting examples of suitable organic additive can be selected from: wax, vaseline, pitch, lipid acid, soap, fatty acid ester, higher alcohols, silicone and composition thereof.

[0050] in addition, can contain linking agent in the coating prescription, polyether polyols with reduced unsaturation production field technician often can use.Suitable crosslinking agent can be selected from: polyethylene (amine initiatedpolyethylene) that low molecular weight diols, amine cause and polypropylene glycol, glycerine, sorbyl alcohol, neopentyl glycol, alkyl diamine, aryl diamine and composition thereof.

[0051] in addition, the catalyzer that is generally used for polyurethane production may be used to present method, to improve the curing speed of polythiourethane coating.Appropriate catalyst can be selected from tertiary amine, organo-tin compound and composition thereof.

[0052] randomly, other additive that is used to improve the mobile of coated fertilizer and/or be easy to smearing property also can be used for present method.These additives comprise conventional flowing agent (flow agent) and the spreading agent (spread agent) that uses of polyurethane production those skilled in the art.

[0053] in a kind of embodiment preferred, the production process of the release and release control fertilizer of epoxy polymer encapsulation comprises following each step:

(i) will comprise the sulfur-bearing vegetables oil (preferably, one or more among MVO described herein, MHVO and the CMVO) epoxy reaction activeconstituents is applied to fertiliser granulates, with the fertiliser granulates that forms coating and

(ii) the Resins, epoxy composition is applied to the fertiliser granulates of coating, to make fertilizer.

Step (i) and (ii) can randomly repeat repeatedly (for example: 2 to 10 times) continuously is with the epoxy polymer coating of the encapsulation fertiliser granulates of making expectation thickness.The release and release control fertilizer of producing with this method preferably contains by weight from about 1.5 to 20%, more preferably by weight from about 2 to 15%, most preferably by weight from about 2.5 to 10% epoxy polymer coating, this is based on the total weight of coated fertilizer.

[0054] for the epoxy polymer of being made by the mercaptan vegetables oil, it is highly preferred having found to use tertiary amine catalyst.This amine catalyst forms the hydrocarbon sulphur negatively charged ion of mercaptan vegetables oil.The mercaptan vegetables oil of this hydrocarbon sulphur anionic form has reactive behavior for Resins, epoxy just, and as Wicks, Z.W. etc. are at " Organic Coatings:Science and Technology ", Vol.1, John Wiley ﹠amp; Sons, 1992, described in p.179.

[0055] the invention still further relates to the encapsulation Ru 2006101161 of producing with these methods (encapsulatedfertilizer compositon).

[0056] useful preferred sulfur-bearing vegetables oil is those that discuss more in detail herein in the present invention relates to the each side of fertilizer materials.A kind of particularly preferred sulfur-bearing vegetables oil is Polymercaptan 358, can obtain from Chevron Phillips Chemical company, and it is the reaction product of soya-bean oil and hydrogen sulfide.

[0057] wondrous and beyond thought discovery is, when the sulfur-bearing vegetables oil is used as the isocyanate reaction activeconstituents, when being used to form the fertilizer of polythiourethane encapsulation, can produce improved controlled release (for example slowly-releasing) fertilizer.Moreover, wondrous and beyond thought discovery is when the sulfur-bearing vegetables oil is used as epoxy material-reactive behavior composition, when being used to form the fertilizer of epoxy polymer encapsulation, can produce improved controlled release (for example slowly-releasing) fertilizer.Use such sulfur-bearing vegetables oil to have many benefits, comprising: the fertilizer that obtains, its wear resistance improve (promptly produce and/or treating processes in, have the weather resistance of improvement); The sulfur-bearing vegetables oil derives from natural renewable resource material; Compare with containing the more conventional polyvalent alcohol of multipolarity oxygen functional group, because sulphur content improves the hydrophobicity of sulfur-bearing vegetables oil; And might with lower coating weight (for example: with United States Patent (USP) 5,538,531[Hudson] and 6,358,296[Markusch] described in data compare), obtain the fertilizer release rate profile figure predesignate, thereby significantly reduce the production cost of final fertilizer.

Brief Description Of Drawings

[0058] in order to understand will become clearly aspect of characteristics of the present invention, advantage, target and other in more detail, for the present invention who makes summary hereinbefore, it is described more specifically can be with reference to the embodiment that is illustrated in the accompanying drawings, and accompanying drawing forms an integral part of this specification sheets.But, it should be noted that accompanying drawing has just illustrated specific embodiments of the present invention, because it also can allow other equal effectively embodiment, so should be by as limiting the scope of the present invention.

[0059] Fig. 1 comprises two figure, has contrasted soya-bean oil, and is as shown above and the sulfur-bearing alcohol ester of producing with soya-bean oil according to a kind of embodiment of the present invention as shown below, nucleus magnetic resonance (NMR) figure.

[0060] Fig. 2 comprises two figure, has contrasted epoxidized soybean oil, and is as shown above and the sulfur-bearing alcohol ester of producing with epoxidized soybean oil according to a kind of embodiment of the present invention as shown below, nucleus magnetic resonance (NMR) figure.

[0061] Fig. 3 is gas-chromatography (GC)/mass spectrum (MS) figure of sulfur-bearing alcohol ester, and this sulfur-bearing alcohol ester is handled with soya-bean oil production and through methanolysis according to a kind of embodiment of the present invention.

[0062] Fig. 4 is gas-chromatography (GC)/mass spectrum (MS) figure through the epoxidized soybean oil of methanolysis processing.

[0063] Fig. 5 is gas-chromatography (GC)/mass spectrum (MS) figure of the ester of hydroxyl mercaptan, and the ester of this hydroxyl mercaptan is handled with epoxidized soybean oil production and through methanolysis according to a kind of embodiment of the present invention.

[0064] Fig. 6 A-6F is the physical data table according to numerous polythiourethane compositions of embodiment of the present invention preparation.

[0065] Fig. 7 illustrates according to a kind of embodiment of the present invention, the water release performance of the CRF material that produces in fertilizer embodiment 1-3 (water release performance).

[0066] Fig. 8 illustrates according to a kind of embodiment of the present invention, the water release performance of the CRF material that produces in fertilizer embodiment 4-6.

[0067] Fig. 9 illustrates according to a kind of embodiment of the present invention, the water release performance of the CRF material that produces in fertilizer embodiment 7-10.

[0068] Figure 10 illustrates according to a kind of embodiment of the present invention, the water release performance of the CRF material that produces in fertilizer embodiment 11-14.

[0069] Figure 11 illustrates according to a kind of embodiment of the present invention, the water release performance of the CRF material that produces in fertilizer embodiment 15-17.

Detailed Description Of The Invention

[0070] in the following description, all numerals of herein announcing no matter whether have word " pact " or " being similar to " to be used in conjunction with it, all represent approximation. They can with 1%, 2%, 5%, sometimes be 10 to 20% changes in amplitude. When disclosing a lower limit R_LWith a upper limit R_UDigital scope the time, anyly fall into numeral in this scope all by specifically open. Particularly the following numeral in this scope is by specifically open: R=R_L+k*(R _U-R _L), wherein k is that one 1% to 100%, increment are 1% variable, namely k be 1%, 2%, 3%, 4%, 5% ..., 50%, 51%, 52% ..., 95%, 96%, 97%, 98%, 99% or 100%. And any digital scope that limits by two R numerals as defined above is also by specifically open.

[0071] in this manual, " natural " refers to take from by any mode the material of naturally occurring fruit, nut, vegetables, plant and animal. Such as an example, natural origin oil refers to extract, and randomly purifying is originated from the oil of naturally occurring fruit, nut, vegetables, plant and animal. In addition, unsaturated natural origin oil refers to extract, and randomly purifying is oily from the unsaturated source of naturally occurring fruit, nut, vegetables, plant and animal.

[0072] in this manual, " natural origin raw material " refers to by the material that " natural " material is extracted, chemical breakdown or chemical process obtain. A limiting examples comprises the various natural origin oil that can extract from naturally occurring fruit, nut, vegetables, plant and animal. Such as another limiting examples, glycerine and carboxylic acid or carboxylate, saturated or unsaturated, can be by carrying out chemical process and produce and separate extracting triglycerides from naturally occurring fruit, nut, vegetables, plant and animal.

[0073] in this manual, " synthetic " refer to generation from the chemical building unit (chemical building block), but not directly come from the material of natural origin. For example, synthetic unsaturated ester oil can be that acrylic acid or propionic acid reaction produce by synthetic ethylene glycol and synthetic carboxylic acid. The synthetic material of other type will be apparent to those skilled in the art, and be considered within category of the present invention.

[0074] no matter to natural and synthetic how defining, material described herein can produce from natural and combination synthetic material, i.e. " semisynthetic ". Such as a limiting examples, the unsaturated ester oil described in this specification can derive from or produce the combination from synthetic and natural source raw material. For example: unsaturated ester oil can produce with the elaidin reaction that separates from natural origin oil by synthetic ethylene glycol. Alternatively, unsaturated ester oil can be by separating from the glycerine of natural origin oil and synthetic carboxylic acid, i.e. acrylic acid reaction produces. Alternatively, unsaturated ester oil can produce with the elaidin reaction that separates from natural origin oil by glycerine.

[0075] in this manual, " thiol ester composition (thiol ester composition) " refers to comprise the ester composition of " thiol ester molecule ". Contain at least one thiol group and at least one ester group in this thiol ester molecule.

[0076] in this manual, " hydroxyl thiol ester composition " refers to comprise the ester composition of " hydroxyl thiol ester molecule ". Contain at least one thiol group, at least one ester group and at least one hydroxyl or alcohol groups in this hydroxyl thiol ester molecule. Alternatively, alcohol groups and thiol group can be bonded in the same group, and it is called as " Alpha-hydroxy thiol group ".

[0077] in this manual, " contain the sulphonic acid ester composition " and refer to comprise the composition that contains the sulphonic acid ester molecule. Contain and contain at least one sulfonic acid group and at least one ester group in the sulphonic acid ester molecule.

[0078] in this manual, " ester composition that contains sulphonic acid ester " refers to comprise the ester composition of the ester molecule that contains sulphonic acid ester. Contain and contain at least one sulfonate ester group and at least one ester group in the ester molecule of sulphonic acid ester.

[0079] in this manual, " beta-unsaturated esters composition " refers to comprise the ester composition of beta-unsaturated esters molecule. Contain at least one ester group and at least one carbon-to-carbon double bond in the beta-unsaturated esters molecule.

[0080] in this manual, " epoxidation beta-unsaturated esters composition " refers to the ester composition by the oxidation of beta-unsaturated esters composition initial ring is produced.

[0081] in this manual, " polythiourethane " refers to contain the carbamate composition of lower array structure more than:

The existence of sulfo-aethylis carbamas group can be measured with method known to those skilled in the art (for example infra-red sepectrometry, Raman spectroscopy and/or nuclear magnetic resonance method).

Thiol ester composition

[0082] the present invention has advantageously provided thiol ester composition, as a kind of embodiment of the present invention. This thiol ester composition comprises that each thiol ester molecule contains the thiol ester molecule of average at least 1.5 ester groups and average at least 1.5 thiol groups. This thiol ester composition also has episulfide and the thiol group mol ratio below 1.5, as described here.

[0083] in general, thiol ester composition comprises the molecule that contains at least one ester group and at least one thiol group. Thiol ester composition of the present invention can produce from any beta-unsaturated esters, as described here. Because each beta-unsaturated esters molecule can contain a plurality of carbon-to-carbon double bonds in the raw material beta-unsaturated esters, so reactivity and the statistical probability of carbon-to-carbon double bond have determined, generation each thiol ester molecule in the thiol ester composition of beta-unsaturated esters composition does not have identical thiol group number, unreacted carbon-to-carbon double bond number, episulfide number, the two keys of carbon-carbon and thiol group mol ratio, episulfide and thiol group mol ratio and other number of functional groups and mol ratio, as disclosed as the raw material beta-unsaturated esters herein. In addition, the raw material beta-unsaturated esters also can comprise the mixture of each beta-unsaturated esters that contains different carbon-to-carbon double bond numbers and/or ester group number. Therefore, many will the discussion according to the average ratio of each thiol ester molecule in the group average of each thiol ester molecule in the thiol ester composition or the thiol ester composition arranged in these character. In other embodiments, the mercaptan sulfur content in the desired control thiol ester. Because be difficult to guarantee that each carbon-to-carbon double bond in hydrogen sulfide and the beta-unsaturated esters reacts, Duo or few thiol group so some molecule of thiol ester may contain than other molecule. Therefore, the percentage by weight of thiol group is described to the mean value of all thiol ester molecules in the thiol ester composition.

[0084] thiol ester can derive from any beta-unsaturated esters described herein.

[0085] thiol ester composition can be described to comprise one or more separation or discrete thiol ester molecule and/or the functional group of thiol ester composition. These independently functional group can comprise: the ester group number (or average) of each thiol ester molecule, the thiol group number (or average) of each thiol ester molecule, unreacted carbon-to-carbon double bond number (or average) on each thiol ester molecule, the average mercaptan sulfur content of thiol ester composition, the percentage (or average percentage) of the sulfide linkage percentage (or average percentage) of each thiol ester molecule and each thiol ester molecule pressed on ring sulfide group. In addition, thiol ester composition can be described with the combination of independent a kind of ratio or ratio, the ratio, episulfide that comprises two keys and thiol group and the ratio of thiol group and similar ratio. As the factor of each separation, these functional groups of composition of mercaptans will be discussed respectively.

[0086] minimally, in some embodiment, thiol ester comprises the thiol ester molecule that contains at least one ester group and a thiol group on each thiol ester molecule. Owing to thiol ester comes from beta-unsaturated esters preparation, so this thiol ester can contain the ester group with beta-unsaturated esters equal number described herein. In one embodiment, each thiol ester molecule contains on average at least 1.5 ester groups in the thiol ester molecule. Alternatively, each thiol ester molecule contains on average at least 2 ester groups in the thiol ester molecule; Alternatively, average at least 2.5 ester groups of each thiol ester molecule; Perhaps alternatively, average at least 3 ester groups of each thiol ester molecule. In other embodiments, each thiol ester molecule contains average 1.5 to 8 ester groups in the thiol ester; Alternatively, each thiol ester molecule contains average 2 to 7 ester groups; Alternatively, each thiol ester molecule contains average 2.5 to 5 ester groups; Perhaps alternatively, each thiol ester molecule contains average 3 to 4 ester groups. Still in other embodiments, each thiol ester molecule comprises average 3 ester groups in the thiol ester, perhaps alternatively, and average 4 ester groups of each beta-unsaturated esters molecule.

[0087] minimally, each thiol ester molecule comprises average at least one thiol group in the thiol ester. In one embodiment, each thiol ester molecule contains on average at least 1.5 thiol groups in the thiol ester molecule; Alternatively, mercaptan contains on average at least 2 thiol groups in each thiol ester molecule; Alternatively, average at least 2.5 thiol groups of each thiol ester molecule; Perhaps alternatively, average at least 3 thiol groups of each thiol ester molecule. In other embodiments, each thiol ester molecule contains average 1.5 to 9 thiol groups in the thiol ester molecule; Alternatively, average 3 to 8 thiol groups of each thiol ester molecule; Alternatively, mercaptan contains average 2 to 4 thiol groups in each thiol ester molecule; Perhaps alternatively, average 4 to 8 thiol groups of each thiol ester molecule.

[0088] in other embodiments, thiol ester can be described with the average mercaptan sulfur content that exists in the thiol ester. In one embodiment, each thiol ester molecule contains the average at least mercaptan sulfur of 5wt.% in the thiol ester molecule; Alternatively, the average at least mercaptan sulfur of 10wt.% of each thiol ester molecule; Perhaps alternatively, each thiol ester molecule on average contains the above mercaptan sulfur of 15wt.%. In one embodiment, each thiol ester molecule contains average 5 to 25wt.% mercaptan sulfur in the thiol ester molecule; Alternatively, average 5 to 20wt.% the mercaptan sulfur of each thiol ester molecule; Alternatively, the mercaptan sulfur of average 6 to 15 wt.% of each thiol ester molecule; Perhaps alternatively, average 8 to 10wt.% the mercaptan sulfur of each thiol ester molecule.

[0089] in general, the position of thiol group is not particular importance in the thiol ester, and will decide by producing the used method of thiol ester. By contacting with beta-unsaturated esters to produce in the embodiment of thiol ester, the position of thiol group will be decided by the position of carbon-to-carbon double bond. When carbon-to-carbon double bond is interior carbon-to-carbon double bond, this method of producing thiol ester will produce secondary thiol group (secondary thiol group). But, when double bond position during in terminal position, then might select reaction condition, produce the thiol ester that contains uncle's thiol group (primary thiol group) or secondary thiol group.

[0090] method of some production thiol ester composition may produce the sulfur-bearing functional group except thiol group extraly. For example, in some thiol ester production method, the thiol group of introducing can with same beta-unsaturated esters in carbon-to-carbon double bond react and form sulfide linkage. When reaction be with second beta-unsaturated esters in two keys take place, will form monosulfidic bond. But, in some situation, second carbon-to-carbon double bond is arranged in same beta-unsaturated esters molecule. When second carbon-to-carbon double bond in thiol group and the same beta-unsaturated esters molecule reacted, sulfide linkage had just formed. In some situation, carbon-to-carbon double bond can be in second ester group of beta-unsaturated esters molecule. Yet in other situation, carbon-to-carbon double bond can be in the identical ester group of beta-unsaturated esters molecule.

[0091] when the carbon-to-carbon double bond in second ester group of thiol group and same beta-unsaturated esters molecule reacts, episulfide will contain two ester groups in circulus. When the carbon-to-carbon double bond in thiol group and the same ester group reacts, episulfide will not be contained in the ester group in the circulus. In this manual, the episulfide of this second type namely is the episulfide (cyclic sulfide) of indication. In this manual, this episulfide of first type namely is the simple sulfide (simple sulfide) of indication. In the episulfide situation, sulfide linkage produces the episulfide degree of functionality in the single ester group of thiol ester. Application purpose is called episulfide with this key for this reason. Such sulfide group that can produce is episulfide. The episulfide ring that can form comprises tetrahydrochysene sulfo-pyrans (tetrahydrothiopyran) ring, Thietane (thiophane) ring, thiphene ring (thiophane ring).

[0092] in some embodiment, the average content of the sulphur that exists with the episulfide form in the desired control thiol ester. In one embodiment, the sulphur average content that exists with the episulfide form in the thiol ester molecule consists of below 30 % by mole. The average content of the sulphur that exists with the episulfide form in the thiol ester alternatively, consists of below 20 % by mole; Alternatively, below 10 % by mole; Alternatively, below 5 % by mole; Perhaps alternatively, below 2 % by mole. In other embodiments, the mol ratio of desired control episulfide and thiol group. In other embodiments, expectation has the mol ratio of episulfide and thiol group. In one embodiment, the molar average ratio of episulfide group and thiol group is below 1.5 in each thiol ester. Alternatively, the molar average ratio of episulfide group and thiol group is below 1 in each thiol ester; Alternatively, below 0.5; Alternatively, below 0.25; Perhaps alternatively, 0.1. In some embodiment, the ratio ranges of episulfide group and thiol group is 0 to 1 in each thiol ester; Perhaps alternatively, the molar average of episulfide group and thiol group is between 0.05 and 1 than scope in each thiol ester.

[0093] in some situation, may be desirably in has carbon-to-carbon double bond to exist in the thiol ester composition, and in other embodiments, may expect that the quantity of carbon-to-carbon double bond minimizes in the thiol ester composition. The molar average that has available carbon-to-carbon double bond and mercaptan sulfur of carbon-to-carbon double bond is recently described in the thiol ester. In one embodiment, the remaining carbon-to-carbon double bond that does not react and the mean ratio of mercaptan sulfur are that each is below the thiol ester molecule 1 .5 in the thiol ester composition. Alternatively, the mean ratio of carbon-to-carbon double bond and mercaptan sulfur is that each is below the thiol ester molecule 1 .2; Alternatively, each is below the thiol ester molecule 1 .0; Alternatively, each thiol ester molecule is below 0.75; Alternatively, each thiol ester molecule is below 0.5; Alternatively, each thiol ester molecule is below 0.2; Perhaps alternatively, each thiol ester molecule is below 0.1.

[0094] in specific embodiment, thiol ester produces from the beta-unsaturated esters composition. Because the raw material beta-unsaturated esters is by specifically forming, it contains definite ester group number, so each thiol ester molecule of thiol ester composition product will contain the ester group number roughly the same with the raw material beta-unsaturated esters. Described herein other independently thiol ester characteristic can be used to further describe thiol ester composition.

[0095] in some embodiment, the thiol ester molecule produces that average 25wt.% is following, the beta-unsaturated esters of the side chain of the carbon-to-carbon double bond that contains 3 methylene intervals of adjoining from having, as described here. In some embodiment, but contain the sulfur-bearing more than 40% of whole side chains of the natural origin of mercaptan. In some embodiment, but the sulfur-bearing more than 60% of the whole side chains of thiol ester molecule. In other embodiments, but the sulfur-bearing more than 50%, 70% or 80% of the whole side chains of thiol ester molecule.

[0096] in one embodiment, thiol ester is the natural origin oil that contains mercaptan, as described here. When thiol ester is natural origin when oil that contains mercaptan, can describe based on " each thiol ester molecule " or " each triglycerides " in this functional group that contains in the natural origin oil of mercaptan. The natural origin oil that contains mercaptan can have and the essentially identical characteristic of thiol ester composition, such as mol ratio and other independently descriptive factor described herein.

[0097] contain in the natural origin oil of mercaptan, thiol group average is about more than 1.5 in each triglycerides. In some embodiment, the thiol group average of each triglycerides can be about 1.5 to about 9.

[0098] thiol ester composition also can be described to a kind of product, and it is made hydrogen sulfide and the contacted method of beta-unsaturated esters composition by comprising, and can be further limited by method described herein. Also molecular weight or the mean molecule quantity of available side chain are described to contain the natural origin oil of mercaptan.

The hydroxyl thiol ester composition

[0099] in embodiments of the invention, thiol ester composition also can contain hydroxyl or alcohol groups. When thiol ester composition contained oh group, thiol ester composition namely referred to the hydroxyl thiol ester composition herein. The quantity of alcohol groups or number can be independent of the quantity of other functional group in this hydroxyl thiol ester composition (being thiol group, ester group, sulfide, episulfide) in the hydroxyl thiol ester composition. In addition, ratio between the percentage by weight of mercaptan sulfur and each functional group (be the mol ratio of mol ratio, epoxide group and the Alpha-hydroxy thiol group of mol ratio, epoxide group and the thiol group of episulfide and thiol group, and the mol ratio of other disclosed number of functional groups and they and thiol group) be to be used to describe the independence of hydroxyl thiol ester composition or discrete factor. The hydroxyl thiol ester composition can with the separate functional group of hydroxyl thiol ester composition described herein or between them arbitrary combination of ratio describe.

[00100] in one embodiment, the hydroxyl thiol ester composition is to produce by hydrogen sulfide and epoxidation beta-unsaturated esters composition described herein are reacted. Because the epoxidation beta-unsaturated esters can contain a plurality of epoxide groups, so reactivity and the statistical probability of epoxide group have determined, and all hydroxyl thiol ester molecules all will have and the same number of oh group of epoxidation beta-unsaturated esters composition in the non-hydroxyl thiol ester composition, thiol group, the Alpha-hydroxy thiol group, sulfide, episulfide, episulfide and thiol group mol ratio, epoxide group and thiol group mol ratio, epoxide group and Alpha-hydroxy thiol group mol ratio, mercaptan sulfur percentage by weight and other disclosed number of functional groups and mol ratio thereof. Therefore in these characteristics, many all will be with the average in each hydroxyl thiol ester molecule or on average recently discuss. In other embodiments, the mercaptan sulfur content in the desired control hydroxyl thiol ester. Because be difficult to guarantee that each epoxide group reacts in hydrogen sulfide and the epoxidation beta-unsaturated esters, so some hydroxyl thiol ester molecule may contain than the some more or less thiol group of other molecule in the hydroxyl thiol ester composition. Therefore, the percentage by weight of thiol group can be described as the average weight percentage on whole hydroxyl thiol ester molecules.

[00101] as a kind of embodiment of the present invention, the hydroxyl thiol ester composition comprises that each hydroxyl thiol ester molecule contains the hydroxyl thiol ester molecule of average at least 1 ester group and average at least 1 Alpha-hydroxy thiol group. As a kind of embodiment of the present invention, the hydroxyl thiol ester composition comprises that each hydroxyl thiol ester molecule contains the hydroxyl thiol ester molecule of average at least 1.5 ester groups and average at least 1.5 Alpha-hydroxy thiol groups.

[00102] minimally, in some embodiment, the hydroxyl thiol ester comprises at least one ester group, at least one thiol group and at least one oh group. Because the hydroxyl thiol ester is to be prepared from by the epoxidation beta-unsaturated esters, so the hydroxyl thiol ester can contain and the same number of ester group of epoxidation beta-unsaturated esters. In one embodiment, each hydroxyl thiol ester molecule contains on average at least 1.5 ester groups in the hydroxyl thiol ester molecule. Alternatively, average at least 2 ester groups of each hydroxyl thiol ester molecule in the hydroxyl thiol ester molecule; Alternatively, average at least 2.5 ester groups of each hydroxyl thiol ester molecule; Perhaps alternatively, average at least 3 ester groups of each hydroxyl thiol ester molecule. In other embodiments, each hydroxyl thiol ester molecule contains average 1.5 to 8 ester groups in the hydroxyl thiol ester molecule; Alternatively, average 2 to 7 ester groups of each hydroxyl thiol ester molecule; Alternatively, average 2.5 to 5 ester groups of each hydroxyl thiol ester molecule; Perhaps alternatively, average 3 to 4 ester groups of each hydroxyl thiol ester molecule. Still in other embodiments, each hydroxyl thiol ester molecule comprises average 3 ester groups in the Alpha-hydroxy thiol ester, perhaps alternatively, and average 4 ester groups of each hydroxyl thiol ester molecule.

[00103] in some embodiment, oh group and thiol group are bonded in the same group, and this produces the Alpha-hydroxy thiol group. In other embodiments, thiol group and hydroxyl or alcohol groups be not in same group. When this happens, produce the hydroxyl thiol ester composition, alcohol groups is independent of thiol group and is added into. For example, such as another embodiment of the present invention, the hydroxyl thiol ester composition advantageously comprises hydroxyl thiol ester molecule. Each hydroxyl thiol ester molecule contains on average at least 1.5 ester groups, on average at least 1.5 thiol groups and average at least 1.5 alcohol groups in this hydroxyl thiol ester molecule.

[00104] minimally, in some embodiment, each hydroxyl thiol ester molecule comprises at least 1 thiol group in the hydroxyl thiol ester. In one embodiment, each hydroxyl thiol ester molecule contains on average at least 1.5 thiol groups in the hydroxyl thiol ester molecule; Alternatively, average at least 2 thiol groups of each hydroxyl thiol ester molecule; Alternatively, average at least 2.5 thiol groups of each hydroxyl thiol ester molecule; Perhaps alternatively, average at least 3 thiol groups of each hydroxyl thiol ester molecule. In other embodiments, each hydroxyl thiol ester molecule contains average 1.5 to 9 thiol groups in the hydroxyl thiol ester molecule; Alternatively, average 3 to 8 thiol groups of each hydroxyl thiol ester molecule; Alternatively, average 2 to 4 thiol groups of each hydroxyl thiol ester molecule; Perhaps alternatively, average 4 to 8 thiol groups of each hydroxyl thiol ester molecule.

[00105] minimally, in some embodiment, each hydroxyl thiol ester molecule comprises on average at least 1 hydroxyl or alcohol groups in the hydroxyl thiol ester composition. In some embodiment, each hydroxyl thiol ester molecule comprises on average at least 1.5 oh groups in the hydroxyl thiol ester composition; Alternatively, average at least 2 oh groups of each hydroxyl thiol ester molecule; Alternatively, average at least 2.5 oh groups of each hydroxyl thiol ester molecule; Perhaps alternatively, average at least 3 oh groups of each thiol ester molecule. In other embodiments, each hydroxyl thiol ester molecule comprises average 1.5 to 9 oh groups in the thiol ester composition; Alternatively, average 3 to 8 oh groups of each hydroxyl thiol ester molecule; Alternatively, average 2 to 4 oh groups of each hydroxyl thiol ester molecule; Perhaps alternatively, average 4 to 8 oh groups of each hydroxyl thiol ester molecule.

[00106] still in other embodiments, the number of oh group is recently to explain with the molar average of oh group and thiol group. Minimally, in some embodiment, oh group and thiol group mol ratio are at least 0.25. In some embodiment, oh group and thiol group mol ratio are at least 0.5; Alternatively, at least 0.75; Alternatively, at least 1.0; Alternatively, at least 1.25; Perhaps alternatively, at least 1.5. In other embodiments, oh group and thiol group molar ratio range are from 0.25 to 2.0; Alternatively, from 0.5 to 1.5; Perhaps alternatively, from 0.75 to 1.25.

[00107] produce in the embodiment of epoxidation beta-unsaturated esters at the hydroxyl thiol ester, the hydroxyl thiol ester can be described to contain ester group and Alpha-hydroxy thiol group. The number of the number of ester group and Alpha-hydroxy thiol group is factor independently, and therefore the hydroxyl thiol ester can be described to have arbitrary combination of ester group described herein and Alpha-hydroxy thiol group. Minimally, each hydroxyl thiol ester molecule comprises on average at least 1 Alpha-hydroxy thiol group in the hydroxyl thiol ester. In some embodiment, each hydroxyl thiol ester molecule comprises on average at least 1.5 Alpha-hydroxy thiol groups in the hydroxyl thiol ester composition; Alternatively, average at least 2 the every hydroxyl thiol ester of Alpha-hydroxy thiolic acid group molecules; Alternatively, average at least 2.5 Alpha-hydroxy thiol groups of each hydroxyl thiol ester molecule; Perhaps alternatively, average at least 3 Alpha-hydroxy thiol groups of each hydroxyl thiol ester molecule. In other embodiments, each hydroxyl thiol ester molecule comprises average 1.5 to 9 Alpha-hydroxy thiol groups in the hydroxyl thiol ester composition; Alternatively, average 3 to 8 the Alpha-hydroxy thiol groups of each hydroxyl thiol ester molecule; Alternatively, average 2 to 4 the Alpha-hydroxy thiol groups of each hydroxyl thiol ester molecule; Perhaps alternatively, average 4 to 8 the Alpha-hydroxy thiol groups of each hydroxyl thiol ester molecule.

[00108] the hydroxyl thiol ester can derive from by contact the epoxidised ester production of beta-unsaturated esters (being the epoxidation beta-unsaturated esters), as described here. In some situation, may expect to contain epoxide group in the hydroxyl thiol ester composition. And in other embodiments, may expect that the epoxide group number in the hydroxyl thiol ester composition minimizes. Therefore the existence of remaining epoxide group can be another independently functional group that is used to describe the hydroxyl thiol ester.

[00109] existence of epoxide group can be described as average, epoxide group and thiol group mol ratio, epoxide group and Alpha-hydroxy thiol group mol ratio or its any combination of epoxide group in each hydroxyl thiol ester independently in the hydroxyl thiol ester. In some embodiment, each hydroxyl thiol ester molecule comprises average epoxide group below 2 in the hydroxyl thiol ester molecule, and namely the mol ratio of the epoxide group of this hydroxyl thiol ester molecule and α-hydroxy thiol group is below 2. Alternatively, each hydroxyl thiol ester molecule comprises average epoxide group below 1.5 in the hydroxyl thiol ester; Alternatively, the average epoxide group below 1 of each hydroxyl thiol ester molecule; Alternatively, the average epoxide group below 0.75 of each hydroxyl thiol ester molecule; Perhaps alternatively, the average epoxide group below 0.5 of each hydroxyl thiol ester molecule. In other embodiments, epoxide group and thiol group mol ratio average out to are below 1.5. Alternatively, epoxide group and thiol group mol ratio average out to are below 1; Alternatively, average out to is below 0.75; Alternatively, average out to is below 0.5; Alternatively, average out to is below 0.25; Perhaps alternatively, average out to is below 0.1. Still in other embodiments, epoxide group and Alpha-hydroxy thiol group mol ratio average out to are below 1.5. Alternatively, epoxide group and Alpha-hydroxy thiol group mol ratio average out to are below 1; Alternatively, average out to is below 0.75; Alternatively, average out to is below 0.5; Alternatively, average out to is below 0.25; Perhaps alternatively, average out to is below 0.1.

[00110] in some embodiment, the hydroxyl thiol ester composition does not contain epoxide group substantially.

[00111] in other embodiments, the hydroxyl thiol ester can be described with the mercaptan sulfur average content in the hydroxyl thiol ester. In one embodiment, each hydroxyl thiol ester molecule contains the average at least mercaptan sulfur of 2.5wt.% in the hydroxyl thiol ester molecule; Alternatively, the average at least mercaptan sulfur of 5wt.% of each hydroxyl thiol ester molecule; Alternatively, the average at least mercaptan sulfur of 10wt.% of each hydroxyl thiol ester molecule; Perhaps alternatively, the average at least mercaptan sulfur of 15wt.% of each hydroxyl thiol ester molecule. In one embodiment, each hydroxyl thiol ester molecule contains average 5 to 25wt.% mercaptan sulfur in the hydroxyl thiol ester molecule; Alternatively, average 5 to 20wt.% the mercaptan sulfur of each hydroxyl thiol ester molecule; Alternatively, average 6 to 15wt.% the mercaptan sulfur of each hydroxyl thiol ester molecule; Perhaps alternatively, average 8 to 10wt.% the mercaptan sulfur of each hydroxyl thiol ester molecule.

[00112] in some embodiment, all have at least 20% to comprise the Alpha-hydroxy thiol group in the side chain. In some embodiment, all have at least 20% to comprise the Alpha-hydroxy thiol group in the side chain. In some embodiment, all have at least 60% to comprise the Alpha-hydroxy thiol group in the side chain; Alternatively, all have at least 70% to comprise the Alpha-hydroxy thiol group in the side chain. Still in other embodiments, all have at least 80% to comprise α-hydroxy thiol group in the side chain.

[00113] aspect some, 20% above sulfur-bearing of the whole side chains of hydroxyl thiol ester molecule. Aspect some, 40% above sulfur-bearing of the whole side chains of hydroxyl thiol ester molecule. Aspect some, 60% above sulfur-bearing of the whole side chains of hydroxyl thiol ester molecule; Alternatively, 70% above sulfur-bearing of whole side chains; Perhaps alternatively, 80% above sulfur-bearing of whole side chains.

[00114] in specific embodiment, produce from epoxidation beta-unsaturated esters composition for the synthesis of the epoxidation beta-unsaturated esters of hydroxyl thiol ester, comprise epoxidation natural origin oil. Because natural origin oil has the specific composition relevant with the ester group number that exists, so the hydroxyl thiol ester will have the ester group with the oily roughly the same number of raw material natural origin. Described herein other independently characteristic also can be used to further describe the hydroxyl thiol ester.

[00115] in other embodiments, the epoxidation beta-unsaturated esters for the production of the hydroxyl thiol ester produces from synthetic (or semisynthetic) unsaturated ester oil. Because synthetic ester oil may have the specific composition relevant with the ester group number that exists, so the hydroxyl thiol ester will have the ester group with the roughly the same number of synthetic ester oil. No matter comprise natural origin or synthetic oil in the beta-unsaturated esters, other autonomous behavior of beta-unsaturated esters all can be used to further describe the hydroxyl thiol ester composition.

[00116] the hydroxyl thiol ester composition also can be described to a kind of product, and it is made hydrogen sulfide and the contacted method of epoxidation beta-unsaturated esters composition by comprising, and can be further limited by method described herein. The natural origin oil of the hydroxyl mercaptan also mean molecule quantity of available mean molecule quantity or its side chain is described.

Crosslinked thiol ester composition

[00117] on the one hand, the present invention relates to crosslinked thiol ester composition. Generally speaking, crosslinked thiol ester molecule is the oligomer of thiol ester, by poly-sulfide linkage-S_X-, thiol ester is joined together, and wherein X is an integer more than 1. Because crosslinked thiol ester is described to the oligomer of thiol ester, so thiol ester can be described to produce the monomer of crosslinked thiol ester.

[00118] on the one hand, crosslinked thiol ester composition comprises the thiol ester oligomer, and it contains at least two and passes through-S_QThe thiol ester monomer that the poly-sulfide linkage of-structure is connected, Q is an integer more than 1 herein. On the one hand, this poly-sulfide linkage can be poly-sulfide linkage-S_Q-, wherein Q is 2,3,4 or its mixing. In other embodiments, Q can be 2; Alternatively, 3; Or alternatively, 4.

[00119] on the one hand, crosslinked thiol ester composition comprises the thiol ester oligomer, and it contains at least 3 thiol ester monomers that are connected by poly-sulfide linkage; Alternatively, 5 thiol ester monomers that are connected by poly-sulfide linkage; Alternatively, 7 thiol ester monomers that are connected by poly-sulfide linkage; Perhaps alternatively, 10 thiol ester monomers that are connected by poly-sulfide linkage. Still in other embodiments, crosslinked thiol ester composition comprises the thiol ester oligomer, and it contains from 3 to 20 thiol ester monomers that are connected by poly-sulfide linkage; Alternatively, from 5 to 15 thiol ester monomers that are connected by poly-sulfide linkage; Perhaps alternatively, from 7 to 12 thiol ester monomers that are connected by poly-sulfide linkage.

[00120] on the one hand, crosslinked thiol ester composition comprises thiol ester monomer and thiol ester oligomer. In some embodiment, crosslinked thiol ester composition contains combined thiol ester monomer and thiol ester oligomer, and its mean molecule quantity is more than 2,000. In other embodiments, crosslinked thiol ester composition contains combined thiol ester monomer and thiol ester oligomer, and its mean molecule quantity is more than 5,000; Perhaps alternatively, more than 10,000. Still in other embodiments, crosslinked thiol ester composition contains combined thiol ester monomer and thiol ester oligomer, its average molecular weight range from 2,000 to 20,000; Alternatively, from 3,000 to 15,000; Or alternatively, from 7,500 to 12,500.

[00121] on the one hand, thiol ester monomer and thiol ester oligomer have the total mercaptan sulfur content more than 0.5. In other embodiments, thiol ester monomer and thiol ester oligomer have the total mercaptan sulfur content more than 1; Alternatively, more than 2; Alternatively, more than 4. Still in other embodiments, thiol ester monomer and thiol ester oligomer have total mercaptan sulfur content of from 0.5 to 8; Alternatively, from 4 to 8; Perhaps alternatively, from 0.5 to 4.

[00122] on the one hand, thiol ester monomer and thiol ester oligomer have the total sulfur content more than 8. In some embodiment, thiol ester monomer and thiol ester oligomer have the total sulfur content more than 10; Alternatively, more than 12. Still in other embodiments, thiol ester monomer and thiol ester oligomer have the total sulfur content of scope from 8 to 15wt.%; Alternatively, from 9 to 14; Perhaps alternatively, from 10 to 13.

[00123] crosslinked thiol ester composition also can be described to a kind of product, and it is made thiol ester and the contacted method of oxidant by comprising, and can be further limited by method described herein.

The sulfur compound ester composition

[00124] the present invention has advantageously comprised the sulfur compound ester composition, as embodiment of the present invention. Generally speaking, the sulfur compound ester composition can be described to be included in the molecule that contains at least one ester group and at least one sulfide group in every a part. Sulfur compound ester used among the present invention can contact to produce with containing mercaptan compound by making beta-unsaturated esters or epoxidation beta-unsaturated esters, as described here.

[00125] except sulfide group and ester group, the sulfur compound ester can also be described as comprising other functional group and ratio described herein. Each other functional group, ratio, sulfide group number and ester group number are separate factors, this so that arbitrary combination of sulfur compound ester sulfur compound ester independent factor can be enough described herein described. The non-limiting list of sulfur compound independent factor comprises the ester group average of each sulfur compound ester molecule, the sulfide group number of each sulfur compound ester molecule, the X part average of each sulfur compound ester molecule, the Y part average of each sulfur compound ester molecule, Z part average and the similar factor of each sulfur compound ester molecule.

[00126] each beta-unsaturated esters molecule can contain a plurality of carbon-to-carbon double bonds in the raw material beta-unsaturated esters. But, reactivity and the statistical probability of carbon-to-carbon double bond have determined that generation each sulfur compound ester molecule in the sulfur-bearing alcohol ester composition of beta-unsaturated esters composition will not have quantity and the mol ratio of disclosed functional group in identical sulfide group number, unreacted carbon-to-carbon double key number, the two keys of carbon-carbon and sulfide group mol ratio, episulfide and thiol group mol ratio and other literary composition. In addition, the raw material beta-unsaturated esters also can comprise the mixture of the various beta-unsaturated esters with different number carbon-to-carbon double bonds and/or ester group. In these characteristics, the average ratio of each sulfur-bearing alcohol ester molecule in many group averages that are discussed as herein each sulfur compound ester molecule in the sulfur compound ester composition or the sulfur compound ester composition is arranged.

[00127] relating to generation in the embodiment of the sulfur compound ester of epoxidation beta-unsaturated esters, each beta-unsaturated esters molecule of raw material epoxidation beta-unsaturated esters can contain a plurality of epoxide groups. Reactivity and the statistical probability of each epoxide group have determined that generation each sulfur compound ester molecule in the sulfur compound ester composition of beta-unsaturated esters composition will can not have disclosed number of functional groups and mol ratio in identical sulfide group number, unreacted epoxide group number, epoxide group and sulfide group mol ratio and other literary composition. In addition, raw material epoxidation beta-unsaturated esters also can comprise the mixture of the various epoxidation beta-unsaturated esters with different number epoxide groups and/or ester group. Therefore, in these characteristics, the average ratio of each sulfur-bearing alcohol ester molecule in many group averages that are described to each sulfur compound ester molecule in the sulfur compound ester composition or the sulfur compound ester composition is arranged.

[00128] minimally, in some embodiment, each sulfur compound ester molecule comprises at least 1 ester group in the sulfur compound ester. In some embodiment, each sulfur compound ester molecule contains on average at least 1.5 ester groups in the sulfur compound ester. Alternatively, each sulfur compound ester molecule contains on average at least 2 ester groups in the sulfur compound ester molecule; Alternatively, average at least 2.5 ester groups of each sulfur compound ester molecule; Perhaps alternatively, average at least 3 ester groups of each sulfur compound ester molecule. In other embodiments, each sulfur compound ester molecule contains average 1.5 to 9 ester groups in the sulfur compound ester molecule; Alternatively, average 1.5 to 8 ester groups of each sulfur compound ester molecule; Alternatively, average 2 to 8 ester groups of each sulfur compound ester molecule; Alternatively, average 2 to 7 ester groups of each sulfur compound ester molecule; Alternatively, average 2.5 to 5 ester groups of each sulfur compound ester molecule; Alternatively, average 3 to 5 ester groups of each sulfur compound ester molecule; Perhaps alternatively, average 3 to 4 ester groups of each sulfur compound ester molecule. Still in other embodiments, each sulfur compound ester molecule comprises average about 3 ester groups in the hydroxyl mercaptan ester; Perhaps alternatively, average about 4 ester groups of each sulfur compound ester molecule.

[00129] minimally, in some embodiment, sulfur compound ester molecule composition comprises that each sulfur compound ester molecule contains the sulfur compound ester molecule of at least 1 sulfide group. In some embodiment, each sulfur compound ester molecule contains on average at least 1.5 sulfide groups in the sulfur compound ester molecule. In other embodiments, each sulfur compound ester molecule contains on average at least 2 sulfide groups in the sulfur compound ester molecule; Alternatively, average at least 2.5 sulfide groups of each sulfur compound ester molecule; Perhaps alternatively, average at least 3 sulfide groups of each sulfur compound ester molecule. In other side, each sulfur compound ester molecule contains average 1.5 to 9 sulfide groups in the sulfur compound ester molecule. Alternatively, each sulfur compound ester molecule contains average 3 to 8 sulfide groups in the sulfur compound ester molecule; Alternatively, average 2 to 4 sulfide groups of each sulfur compound ester molecule; Perhaps alternatively, average 4 to 8 sulfide groups of each sulfur compound ester molecule.

[00130] another independently aspect, the sulfur compound ester composition comprises the molecule that contains following X part:

In this X part-structure, Q is hydrogen or oh group; R ¹And R ²Be independently selected from hydrogen, C ₁To C ₂₀Organic group (organyl group) and C ₁To C ₂₀Hydrocarbyl group; R ³Be C ₁To C ₂₀Organic group or C ₁To C ₂₀Hydrocarbyl group; The chemical valence that does not mark in the X part is represented the remainder of this sulfur compound ester molecule.Q, R ¹, R ²And R ³Be integral part independently in the X part, they allow X partly to have more Q, R described herein ¹, R ²And R ³Any combination of integral part.In some specific embodiment, R ¹And R ²Be hydrogen, R ³Be the C that is selected from group described herein ₁To C ₂₀Organic group.

[00131] in specific embodiment, each sulfur compound ester molecule contains on average at least 1.5 X parts in the sulfur compound ester molecule.In other embodiments, each sulfur compound ester molecule contains on average at least 2 X parts in the sulfur compound ester molecule; Alternatively, average at least 2.5 X parts of each sulfur compound ester molecule; Perhaps alternatively, average at least 3 X parts of each sulfur compound ester molecule.In others, each sulfur compound ester molecule contains average 1.5 to 9 X parts in the sulfur compound ester molecule.Alternatively, each sulfur compound ester molecule contains average 3 to 8 X parts in the sulfur compound ester molecule; Alternatively, average 2 to 4 the X parts of each sulfur compound ester molecule; Perhaps alternatively, average 4 to 8 the X parts of each sulfur compound ester molecule.

[00132] in a particular aspects, the sulfur compound ester composition comprises the molecule that contains following Y part:

In this Y part-structure, R ¹And R ²Be independently selected from hydrogen and C ₁To C ₂₀Hydrocarbyl group; R ³Be C ₁To C ₂₀Organic group or C ₁To C ₂₀Hydrocarbyl group; The chemical valence that does not mark in the Y part is represented the remainder of this sulfur compound ester molecule.R ¹, R ²And R ³Be integral part independently in the Y part, they allow Y partly to have more R described herein ¹, R ²And R ³Any combination of embodiment.In some embodiment, R ¹And R ²Be hydrogen, R ³Be the C that is selected from group described herein ₁To C ₂₀Organic group.

[00133] in specific embodiment, each sulfur compound ester molecule contains on average at least 1.5 Y parts in the sulfur compound ester molecule.In other embodiments, each sulfur compound ester molecule contains on average at least 2 Y parts in the sulfur compound ester molecule; Alternatively, average at least 2.5 Y parts of each sulfur compound ester molecule; Perhaps alternatively, average at least 3 Y parts of each sulfur compound ester molecule.In others, each sulfur compound ester molecule contains average 1.5 to 9 Y parts in the sulfur compound ester molecule.Alternatively, each sulfur compound ester molecule contains average 3 to 8 Y parts in the sulfur compound ester molecule; Alternatively, average 2 to 4 the Y parts of each sulfur compound ester molecule; Perhaps alternatively, average 4 to 8 the Y parts of each sulfur compound ester molecule.

[00134] in another particular aspects, the sulfur compound ester composition comprises the molecule that contains following Z part:

In this Z part-structure, R ¹And R ²Be independently selected from hydrogen and C ₁To C ₂₀Hydrocarbyl group; R ³Be C ₁To C ₂₀Organic group or C ₁To C ₂₀Hydrocarbyl group; The chemical valence that does not mark in the Z part is represented the remainder of this sulfur compound ester molecule.R ¹, R ²And R ³Be integral part independently in the Z part, they allow Z partly to have more R described herein ¹, R ²And R ³Any combination of integral part.In some embodiment, R ¹And R ²Be hydrogen, R ³Be the C that is selected from group described herein ₁To C ₂₀Organic group.

[00135] in specific embodiment, each sulfur compound ester molecule contains on average at least 1.5 Z parts in the sulfur compound ester molecule.In other embodiments, each sulfur compound ester molecule contains on average at least 2 Z parts in the sulfur compound ester molecule; Alternatively, average at least 2.5 Z parts of each sulfur compound ester molecule; Perhaps alternatively, average at least 3 Z parts of each sulfur compound ester molecule.In others, each sulfur compound ester molecule contains average 1.5 to 9 Z parts in the sulfur compound ester molecule.Alternatively, each sulfur compound ester molecule contains average 3 to 8 Z parts in the sulfur compound ester molecule; Alternatively, average 2 to 4 the Z parts of each sulfur compound ester molecule; Perhaps alternatively, average 4 to 8 the Z parts of each sulfur compound ester molecule.

[00136] in some embodiment, R ³Comprise at least a functional group.On the one hand, this functional group is selected from oh group, hydroxy-acid group, carboxylate group, amine groups, sulfide group and secondary thiol group.Aspect some, R ³Comprise at least two kinds of functional groups.Aspect some, these two kinds of functional groups are selected from oh group, hydroxy-acid group, carboxylate group, amine groups, sulfide group, secondary thiol group and composition thereof.

[00137], advantageously provided the sulfur compound ester composition that comprises the sulfur compound ester molecule as another embodiment of the present invention.In this embodiment, each sulfur compound ester molecule contains on average on average at least 1 X part of at least 1 ester group and each sulfur compound ester molecule in the sulfur compound ester molecule.X partly has structure as described here.In addition, ester group mean number and X part mean number are separate factors.Therefore, the sulfur compound ester molecule can have arbitrary combination of ester group mean number described herein and X part mean number in the sulfur compound ester composition.

[00138], advantageously provided the sulfur compound ester composition that comprises the sulfur compound ester molecule as another embodiment of the present invention.In this embodiment, each sulfur compound ester molecule contains on average on average at least 1 Y part of at least 1 ester group and each sulfur compound ester molecule in the sulfur compound ester molecule.Y partly has structure as described here.In addition, ester group mean number and Y part mean number are separate factors.Therefore, the sulfur compound molecule can have arbitrary combination of ester group mean number described herein and Y part mean number in the sulfur compound ester composition.

[00139], advantageously provided the sulfur compound ester composition that comprises the sulfur compound ester molecule as another embodiment of the present invention.In this embodiment, each sulfur compound ester molecule contains on average on average at least 1 Z part of at least 1 ester group and each sulfur compound ester molecule in the sulfur compound ester molecule.Z partly has structure as described here.In addition, ester group mean number and Z part mean number are separate factors.Therefore, the sulfur compound molecule in the sulfur compound ester composition can have arbitrary combination of ester group mean number described herein and Z part mean number.

[00140] the sulfur compound ester composition also can be described to a kind of product, and it is made unsaturated ester and the contacted method of mercaptan by comprising, and can be further limited by method described herein.In other embodiments, the sulfur compound ester composition also can be described to a kind of product, and it is made epoxidation unsaturated ester and the contacted method of mercaptan by comprising, and can be further limited by method described herein.

The ester composition of sulfo-acrylate (thioacrylate ester composition)

[00141], advantageously provided the ester composition of sulfo-acrylate as a kind of embodiment of the present invention.In the description of the ester composition of sulfo-acrylate, term " acrylate (acrylate) " and " sulfo-acrylate (thioacrylate) " can be used to describe the unit of the ester (thioacrylate ester) of sulfo-acrylate.Although the sulfo-acrylate group can be by the member as esters of acrylic acid, the ester composition purpose of description of this sulfo-acrylate that comprises for this place, term acrylate (acrylate) be meant contain below the group of general structure:

Term sulfo-acrylate (thioacrylate) is meant the group that contains following general structure:

In the general structure of this sulfo-acrylate (thioacrylate), unspecified chemical valence can further specify in the text on the carbon-to-carbon double bond of acrylate and sulfo-acrylate (thioacrylate).

[00142] generally speaking, the ester composition of sulfo-acrylate can be described to, comprise various sulfo-acrylate molecules, the any acrylate in these molecules on being present in sulfo-acrylate molecule or the ester group of sulfo-acrylate, also contain at least one ester group and at least one sulfo-acrylate group.At this hereinafter, the ester group (one or more) except that the ester group of any acrylate or sulfo-acrylate is called as " replenishing ester group (supplementary ester group) " in the sulfo-acrylate molecule.The ester composition of sulfo-acrylate described herein can by with acrylate composition with contain the ester composition of mercaptan and/or the contacted method of ester composition of hydroxyl mercaptan is made, both are all described herein.

[00143] except that sulfo-acrylate group and additional ester group, it is to comprise other functional group and mol ratio described herein that the ester composition of sulfo-acrylate can be further described.The sulfo-acrylate group that exists in the sulfo-acrylate molecule, replenish each independent factor that mol ratio between ester group, other functional group and the functional group has been represented the ester molecule of sulfo-acrylate, these factors allow to use arbitrary combination of described herein they to describe the ester composition of sulfo-acrylate.The non-limiting list of the independent factor of the ester of sulfo-acrylate comprises: acrylate group mean number, X on the sulfo-acrylate group number of the additional ester group mean number of additional ester group number, each sulfo-acrylate molecule, sulfo-acrylate group number, each sulfo-acrylate molecule, acrylate group number, each sulfo-acrylate molecule ¹X on part number, each sulfo-acrylate molecule ¹Part mean number, Y ¹Y on part number, each sulfo-acrylate molecule ¹Part mean number, Z ¹Z on part number, each sulfo-acrylate molecule ¹Part mean number and similar factor.

[00144] raw material thiol ester composition and/or hydroxyl thiol ester composition can comprise the mixture of various molecules, and these molecules contain ester group, thiol group, oh group and other group and the mol ratio described herein of average quantity.In addition, the reactivity and the statistical probability of each thiol group and hydroxy thiol group have determined in sulfur-bearing alcohol ester composition and/or the hydroxyl thiol ester composition, and each the sulfo-acrylate molecule in the ester composition of the sulfo-acrylate of being produced may not have functional group, part and the mol ratio of disclosed quantity in ester group, sulfo-acrylate group, acrylate group and other literary composition of similar number.Therefore, in the ester composition of sulfo-acrylate, the various characteristics of sulfo-acrylate molecule, having many is to describe with the group mean number on each sulfo-acrylate molecule in the ester composition of sulfo-acrylate or with the mean ratio on each sulfo-acrylate molecule in the ester composition of sulfo-acrylate.

[00145] minimally, in some embodiment, each sulfo-acrylate molecule comprises at least 1 additional ester group in the ester composition of sulfo-acrylate.In some embodiment, each sulfo-acrylate molecule contains on average at least 1.5 additional ester groups in the ester of sulfo-acrylate.Alternatively, each sulfo-acrylate molecule contains on average at least 2 additional ester groups in the sulfo-acrylate molecule; Alternatively, average at least 2.5 additional ester groups of each sulfo-acrylate molecule; Perhaps alternatively, average at least 3 additional ester groups of each sulfo-acrylate molecule.In other embodiments, each sulfo-acrylate molecule contains average 1.5 to 9 additional ester groups in the ester of sulfo-acrylate; Alternatively, average 1.5 to 8 the additional ester groups of each sulfo-acrylate molecule; Alternatively, average 2 to 8 the additional ester groups of each sulfo-acrylate molecule; Alternatively, average 2 to 7 the additional ester groups of each sulfo-acrylate molecule; Alternatively, average 2.5 to 5 the additional ester groups of each sulfo-acrylate molecule; Alternatively, average 3 to 5 the additional ester groups of each sulfo-acrylate molecule; Perhaps alternatively, average 3 to 4 the additional ester groups of each sulfo-acrylate molecule.Still in other embodiments, each sulfo-acrylate molecule comprises average about 3 additional ester groups in the sulfo-acrylate; Perhaps alternatively, average about 4 the additional ester groups of each sulfo-acrylate molecule.

[00146] minimally, in some embodiment, the ester of sulfo-acrylate comprises at least 1 sulfo-acrylate group.In some embodiment of the present invention, each sulfo-acrylate molecule contains on average at least 1.5 sulfo-acrylate groups in the sulfo-acrylate molecule.In other embodiments, each sulfo-acrylate molecule contains on average at least 2 sulfo-acrylate groups in the sulfo-acrylate molecule; Alternatively, average at least 2.5 sulfo-acrylate groups of each sulfo-acrylate molecule; Perhaps alternatively, average at least 3 sulfo-acrylate groups of each sulfo-acrylate molecule.In one aspect, each sulfo-acrylate molecule contains average 1.5 to 9 sulfo-acrylate groups in the sulfo-acrylate molecule; Alternatively, average 3 to 8 the sulfo-acrylate groups of each sulfo-acrylate molecule; Alternatively, average 2 to 4 the sulfo-acrylate groups of each sulfo-acrylate molecule; Perhaps alternatively, average 4 to 8 the sulfo-acrylate groups of each sulfo-acrylate molecule.

[00147] of the present invention aspect some, sulfo-acrylate molecule further comprises acrylate group.In some embodiment, each sulfo-acrylate molecule contains at least 1 acrylate group in the sulfo-acrylate molecule.In other embodiments, each sulfo-acrylate molecule contains on average at least 1.5 acrylate groups in the sulfo-acrylate molecule; Alternatively, average at least 2 acrylate groups of each sulfo-acrylate molecule; Alternatively, average at least 2.5 acrylate groups of each sulfo-acrylate molecule; Perhaps alternatively, average at least 3 acrylate groups of each sulfo-acrylate molecule.In one aspect, each sulfo-acrylate molecule contains average 1.5 to 9 acrylate groups in the sulfo-acrylate molecule; Alternatively, average 3 to 8 acrylate groups of each sulfo-acrylate molecule; Alternatively, average 2 to 4 acrylate groups of each sulfo-acrylate molecule; Perhaps alternatively, average 4 to 8 acrylate groups of each sulfo-acrylate molecule.

[00148] as another embodiment of the present invention, the sulfo-acrylate composition comprises that each sulfo-acrylate molecule contains on average on average at least 1 X of at least 1 additional ester group and each sulfo-acrylate molecule ¹The sulfo-acrylate molecule of part, X ¹Part contains following structure:

At this X ¹In the part-structure, R ^T1And R ^T2Be independently selected from hydrogen, C ₁To C ₂₀Organic group and C ₁To C ₂₀Hydrocarbyl group; Q ^T1Be to be independently selected from hydrogen and acrylate group; And the sulfo-acrylate group that the TA representative has following structure:

X ¹Unspecified chemical valence is represented the remainder of this sulfo-acrylate molecule in the part.Contain X at sulfo-acrylate molecule ¹In the embodiment of part, replenish the X that is present on ester group mean number and each sulfo-acrylate molecule in the sulfo-acrylate molecule on each sulfo-acrylate ¹Part mean number is separate factor.

[00149] in further embodiment, each sulfo-acrylate molecule contains on average at least 1.5 X in the sulfo-acrylate molecule ¹Part.In other embodiments, each sulfo-acrylate molecule contains on average at least 2 X in the sulfo-acrylate molecule ¹Part; Alternatively, average at least 2.5 X of each sulfo-acrylate molecule ¹Part; Perhaps alternatively, average at least 3 X of each sulfo-acrylate molecule ¹Part.In one aspect, each sulfo-acrylate molecule contains average 1.5 to 9 X in the sulfo-acrylate molecule ¹Part; Alternatively, average 3 to 8 X of each sulfo-acrylate molecule ¹Part; Alternatively, average 2 to 4 X of each sulfo-acrylate molecule ¹Part; Perhaps alternatively, average 4 to 8 X of each sulfo-acrylate molecule ¹Part.

[00150] in some embodiment, the ester of sulfo-acrylate (thioacrylate ester) contains the sulfo-acrylate group with following structure:

Generally speaking, in the structure of sulfo-acrylate group, R ⁴, R ⁵And R ⁶Be independently selected from hydrogen, C ₁To C ₂₀Organic group and C ₁To C ₂₀Hydrocarbyl group.In further embodiment, R ⁴, R ⁵And R ⁶Be selected from hydrogen, C ₁To C ₁₀Organic group and C ₁To C ₁₀Hydrocarbyl group; Perhaps alternatively, be selected from C ₁To C ₅Organic group and C ₁To C ₅Hydrocarbyl group.In certain embodiments, R ⁴, R ⁵And R ⁶Be independently selected from hydrogen and methyl.In some specific embodiment, R ⁵And R ⁶Be hydrogen, and R ⁴Be to be selected from hydrogen, methyl or their mixture; Alternatively, R ⁵And R ⁶Be hydrogen, and R ⁴It is methyl; Perhaps alternatively, R ⁴, R ⁵And R ⁶All be hydrogen.

[00151] in some embodiment, the ester of sulfo-acrylate (thioacrylate ester) contains the acrylate group with following structure:

Generally speaking, in the structure of acrylate group, R ⁷, R ⁸And R ⁹Be independently selected from hydrogen, C ₁To C ₂₀Organic group and C ₁To C ₂₀Hydrocarbyl group.In further embodiment, R ⁷, R ⁸And R ⁹Be selected from hydrogen, C ₁To C ₁₀Organic group and C ₁To C ₁₀Hydrocarbyl group; Perhaps alternatively, be selected from C ₁To C ₅Organic group and C ₁To C ₅Hydrocarbyl group.In certain embodiments, R ⁷, R ⁸And R ⁹Be independently selected from hydrogen and methyl.In some specific embodiment, R ⁸And R ⁹Be hydrogen, and R ⁷Be to be selected from hydrogen, methyl or their mixture; Alternatively, R ⁸And R ⁹Be hydrogen, and R ⁷It is methyl; Perhaps alternatively, R ⁷, R ⁸And R ⁹All be hydrogen.

[00152] as another embodiment of the present invention, advantageously provided the sulfo-acrylate composition, it comprises sulfo-acrylate molecule.In this embodiment, sulfo-acrylate molecule contains on average average at least 1 Y of at least 1 additional ester group and each sulfo-acrylate molecule of each sulfo-acrylate molecule ¹Part, Y ¹Part has following structure:

At this Y ¹In the part-structure, R ^T1And R ^T2Be independently selected from hydrogen, C ₁To C ₂₀Organic group and C ₁To C ₂₀Hydrocarbyl group; And the sulfo-acrylate group that the TA representative has following structure:

Y ¹Unspecified chemical valence is represented the remainder of this sulfo-acrylate molecule in the part.Contain Y relating to ¹In the embodiment of sulfo-acrylate molecule of part, the additional ester group mean number of each sulfo-acrylate and each sulfo-acrylate molecule be present in Y in the sulfo-acrylate molecule ¹Part mean number is separate factor.

[00153] in further embodiment, each sulfo-acrylate molecule contains on average at least 1.5 Y in the sulfo-acrylate molecule ¹Part.In other embodiments, each sulfo-acrylate molecule contains on average at least 2 Y in the sulfo-acrylate molecule ¹Part; Alternatively, average at least 2.5 Y of each sulfo-acrylate molecule ¹Part; Perhaps alternatively, average at least 3 Y of each sulfo-acrylate molecule ¹Part.In one aspect, each sulfo-acrylate molecule contains average 1.5 to 9 Y in the sulfo-acrylate molecule ¹Part; Alternatively, average 3 to 8 Y of each sulfo-acrylate molecule ¹Part; Alternatively, average 2 to 4 Y of each sulfo-acrylate molecule ¹Part; Perhaps alternatively, average 4 to 8 Y of each sulfo-acrylate molecule ¹Part.

[00154] as another embodiment of the present invention, advantageously provided the sulfo-acrylate composition, it comprises sulfo-acrylate molecule.In this embodiment, each sulfo-acrylate molecule contains on average on average at least 1 Z of at least 1 additional ester group and each sulfo-acrylate molecule in the sulfo-acrylate molecule ¹Part, Z ¹Part has following structure:

At this Z ¹In the part-structure, R ^T1And R ^T2Be independently selected from hydrogen, C ₁To C ₂₀Organic group and C ₁To C ₂₀Hydrocarbyl group; Q ^T1Be independently selected from hydrogen and acrylate group; The sulfo-acrylate group that the TA representative has following structure:

And A represents the acrylate group with following structure:

Z ¹Unspecified chemical valence is represented the remainder of this sulfo-acrylate molecule in the part.Contain Z at sulfo-acrylate molecule ¹In the embodiment of part, the additional ester group mean number of each sulfo-acrylate and each sulfo-acrylate molecule be present in Z in the sulfo-acrylate molecule ¹Part mean number is separate factor.

[00155] in further embodiment, each sulfo-acrylate molecule contains on average at least 1.5 Z in the sulfo-acrylate molecule ¹Part.In other embodiments, each sulfo-acrylate molecule contains on average at least 2 Z in the sulfo-acrylate molecule ¹Part; Alternatively, average at least 2.5 Z of each sulfo-acrylate molecule ¹Part; Perhaps alternatively, average at least 3 Z of each sulfo-acrylate molecule ¹Part.In one aspect, each sulfo-acrylate molecule contains average 1.5 to 9 Z in the sulfo-acrylate molecule ¹Part; Alternatively, average 3 to 8 Z of each sulfo-acrylate molecule ¹Part; Alternatively, average 2 to 4 Z of each sulfo-acrylate molecule ¹Part; Perhaps alternatively, average 4 to 8 Z of each sulfo-acrylate molecule ¹Part.

[00156] as another embodiment of the present invention, advantageously provided the sulfo-acrylate composition, it comprises sulfo-acrylate molecule.In this embodiment, each sulfo-acrylate molecule contains on average on average at least 1 X of at least 1 additional ester group and each sulfo-acrylate molecule in the sulfo-acrylate molecule ¹Part.X ¹Part has structure as described here.In addition, the additional ester group mean number and the X of each sulfo-acrylate molecule ¹Part mean number is separate factor.

[00157] as another embodiment of the present invention, advantageously provided the sulfo-acrylate composition, it comprises sulfo-acrylate molecule.In this embodiment, each sulfo-acrylate molecule contains on average on average at least 1 Y of at least 1 additional ester group and each sulfo-acrylate molecule in the sulfo-acrylate molecule ¹Part.Y ¹Part has structure as described here.In addition, the additional ester group mean number and the Y of each sulfo-acrylate molecule ¹Part mean number is separate factor.

[00158] as another embodiment of the present invention, advantageously provided the ester composition of sulfo-acrylate, it comprises sulfo-acrylate molecule.In this embodiment, each sulfo-acrylate molecule contains on average on average at least 1 Z of at least 1 additional ester group and each sulfo-acrylate molecule in the sulfo-acrylate molecule ¹Part.Z ¹Part has structure as described here.In addition, the additional ester group mean number and the Z of each sulfo-acrylate molecule ¹Part mean number is separate factor.

[00159] in some embodiment, sulfo-acrylate molecule is provided, it comprises an additional ester group and the following sulfo-acrylate group of structure:

In the structure of this sulfo-acrylate group, R ⁴, R ⁵And R ⁶Be independently selected from hydrogen, C ₁To C ₂₀Organic group and C ₁To C ₂₀Hydrocarbyl group.Replenish ester group and the separate integral part of sulfo-acrylate group representative in the sulfo-acrylate molecule.Sulfo-acrylate molecule can have the arbitrary combination of these integral parts described herein.In addition, each R in the sulfo-acrylate structural ⁴, R ⁵And R ⁶Group is all represented independently integral part.Sulfo-acrylate structural described herein can have R ⁴, R ⁵And R ⁶The arbitrary combination of group.

[00160] in some embodiment, comprises the sulfo-acrylate molecule that replenishes ester group and sulfo-acrylate group and contain at least 1 additional ester group.In other embodiments, sulfo-acrylate molecule contains at least 2 additional ester groups; Perhaps alternatively, at least 3 additional ester groups.In other embodiments, comprise the sulfo-acrylate molecule that replenishes ester group and sulfo-acrylate group and contain 2 to 9 additional ester groups; Alternatively, 2 to 8 additional ester groups; Alternatively, 2 to 7 additional ester groups; Alternatively, 3 to 5 additional ester groups; Perhaps alternatively, 3 to 4 additional ester groups.Still in other embodiments, the sulfo-acrylate comprises 3 additional ester groups, perhaps alternatively, comprises 4 additional ester groups.

[00161] in further embodiment, comprises the sulfo-acrylate molecule that replenishes ester group and sulfo-acrylate group and can further comprise at least 1 sulfo-acrylate group; Alternatively, at least 2 sulfo-acrylate groups; Perhaps alternatively, at least 3 sulfo-acrylate groups.In other embodiments, sulfo-acrylate molecule comprises 2 to 9 sulfo-acrylate groups; Alternatively, 3 to 8 sulfo-acrylate groups; Alternatively, 2 to 4 sulfo-acrylate groups; Perhaps alternatively, 4 to 8 sulfo-acrylate groups.

[00162] in other embodiments, comprise the acrylate group that the sulfo-acrylate molecule that replenishes ester group and sulfo-acrylate group can further comprise following structure:

In the structure of this acrylate group, R ⁷, R ⁸And R ⁹Be independently selected from hydrogen, C ₁To C ₂₀Organic group and C ₁To C ₂₀Hydrocarbyl group.In some embodiment, sulfo-acrylate molecule comprises at least 2 acrylate groups; Perhaps alternatively, at least 3 acrylate groups.In other embodiments, sulfo-acrylate molecule comprises 2 to 9 acrylate groups; Alternatively, 3 to 8 acrylate groups; Alternatively, 2 to 4 acrylate groups; Perhaps alternatively, 4 to 8 acrylate groups.

[00163] in some embodiment, sulfo-acrylate molecule comprises at least one additional ester group and at least one Y ¹Part, Y ¹Part-structure is as follows:

At this Y ¹In the part-structure, R ^T1And R ^T2Be independently selected from hydrogen, C ₁To C ₂₀Organic group and C ₁To C ₂₀Hydrocarbyl group; And TA represents the sulfo-acrylate group of following structure:

Y ¹Unspecified chemical valence is represented the remainder of this sulfo-acrylate molecule in the part.Additional ester group and Y in the sulfo-acrylate molecule ¹Part is represented separate integral part.Sulfo-acrylate molecule can have the arbitrary combination of these integral parts described herein.Replenishing other embodiment of ester group number describes herein.Contain R ⁴, R ⁵And R ⁶Other embodiment of the sulfo-acrylate structural of group is described herein.

[00164] comprises additional ester group and Y ¹The sulfo-acrylate molecule of part can comprise additional ester group number and any Y described herein ¹Portion's fractional arbitrary combination.Comprise and replenish ester group and Y ¹Ester group number in the sulfo-acrylate molecule of part is described herein.In further embodiment, comprise and replenish ester group and Y ¹The sulfo-acrylate molecule of part can comprise at least 1 Y ¹Part; Alternatively, at least 2 Y ¹Part; Perhaps alternatively, at least 3 Y ¹Part.In other embodiments, comprise additional ester group and Y ¹The sulfo-acrylate molecule of part can comprise 2 to 9 Y ¹Part; Alternatively, 3 to 8 Y ¹Part; Alternatively, 2 to 4 Y ¹Part; Perhaps alternatively, 4 to 8 Y ¹Part.

[00165] ester of sulfo-acrylate also can be described to a kind of product, and it is by comprising the ester composition and the contacted method of acrylate composition that contain mercaptan to be made, and can be further limited by method described herein.In other embodiments, the ester composition of sulfo-acrylate also can be described to a kind of product, it is by comprising the ester composition and the contacted method of acrylate composition of hydroxyl mercaptan to be made, and can be further limited by method described herein.

Contain sulphonate

[00166] the present invention has advantageously provided and has contained sulphonate, as a kind of embodiment of the present invention.Generally speaking, among the present invention contain sulphonate comprise contain at least one ester group and at least one sulfonic acid group contain the sulphonate molecule.Described herein contain sulphonate and can produce, as described here by thiol ester and oxygenant are contacted.Can contain a plurality of thiol groups because be used to produce the raw material that contains sulphonate, contain the sulphonate molecule and will not have the sulfonic acid group of similar number so the reactivity of thiol group and statistical probability have determined to contain in the sulphonate each.In addition, the raw material thiol ester also can comprise the mixture of each the thiol ester molecule with different number thiol groups and/or ester group.Therefore, containing many groups in the sulphonate is to contain the group mean number of sulphonate molecule or mean ratio that each contains the sulphonate molecule is described herein to contain in the sulphonate each.

[00167] containing sulfonic acid group number contained in the sulphonate and ester group number is separate factor, and its permission use arbitrary combination that contains the sulphonate independent factor described herein is described this and contained sulphonate.The non-limiting list that contains the sulphonate independent factor comprises the ester group number, each contains sulphonate molecule ester group mean number, sulfonic acid group number, each contains sulphonate molecule sulfonic acid group mean number, X ²The part number, each contains sulphonate molecule X ²Part mean number, ester molecule, Y ²The part number, each contains sulphonate molecule Y ²Part mean number, ester molecule, Z ²The part number, each contains sulphonate molecule Z ²Part mean number and similar factor.

[00168] minimally contains sulphonate and comprises that each contains at least 1 ester group of sulphonate molecule.In some embodiment, contain sulphonate and contain each and contain on average at least 1.5 ester groups of sulphonate molecule.Alternatively, containing sulphonate contains each and contains on average at least 2 ester groups of sulphonate molecule; Alternatively, each contains on average at least 2.5 ester groups of sulphonate molecule; Perhaps alternatively, each contains on average at least 3 ester groups of sulphonate molecule.In other embodiments, containing sulphonate contains each and contains average 1.5 to 9 ester groups of sulphonate molecule; Alternatively, each contains average 1.5 to 8 ester groups of sulphonate molecule; Alternatively, each contains average 2 to 8 ester groups of sulphonate molecule; Alternatively, each contains average 2 to 7 ester groups of sulphonate molecule; Alternatively, each contains average 2.5 to 5 ester groups of sulphonate molecule; Alternatively, each contains average 3 to 5 ester groups of sulphonate molecule; Perhaps alternatively, each contains average 3 to 4 ester groups of sulphonate molecule.Still in other embodiments, containing sulphonate comprises each and contains average 3 ester groups of sulphonate molecule; Perhaps alternatively, each contains average 4 ester groups of sulphonate molecule.

[00169] minimally contains the sulphonate molecule and comprises each and contain on average at least 1 sulfonic acid group of sulphonate molecule.In some embodiment, sulphonate contains each and contains on average at least 1.5 sulfonic acid groups of sulphonate molecule; Alternatively, each contains the sulphonate molecule and contains on average at least 2 sulfonic acid groups; Alternatively, each contains on average at least 2.5 sulfonic acid groups of sulphonate molecule; Perhaps alternatively, each contains on average at least 3 sulfonic acid groups of sulphonate molecule.In other embodiments, containing sulphonate contains each and contains average 1.5 to 9 sulfonic acid groups of sulphonate molecule; Alternatively, each contains average 3 to 8 sulfonic acid groups of sulphonate molecule; Alternatively, each contains average 2 to 4 sulfonic acid groups of sulphonate molecule; Perhaps alternatively, each contains average 4 to 8 sulfonic acid groups of sulphonate molecule.

[00170] on the other hand, contain sulphonate and further comprise oh group.In some embodiment, contain sulphonate and comprise each and contain average at least one oh group of sulphonate molecule.

[00171] in some embodiment of the present invention, sulphonate does not contain thiol group substantially.

[00172] another independent aspect, contain sulphonate and comprise and each contain the sulphonate molecule on average at least 1 ester group and each contain average at least one X of sulphonate molecule ²Part, wherein X ²Part has following structure:

At this X ²In the part-structure, Q ^S1Be hydrogen or oh group; R ^S1And R ^S2Be independently selected from hydrogen, C ₁To C ₂₀Organic group and C ₁To C ₂₀Hydrocarbyl group; X ²On behalf of this, unspecified chemical valence contain the remainder of sulphonate molecule in the part.Q ^S1, R ^S1And R ^S2Be X ²Independent integral part in the part, it allows X ²Part has more Q described herein ^S1, R ^S1And R ^S2The arbitrary combination of integral part.In some specific embodiment, R ^S1And R ^S2Be hydrogen.

[00173] in specific embodiment, contains sulphonate and contain each and contain on average at least 1.5 X of sulphonate molecule ²Part.In other embodiments, containing sulphonate contains each and contains on average at least 2 X of sulphonate molecule ²Part; Alternatively, each contains on average at least 2.5 X of sulphonate molecule ²Part; Perhaps alternatively, each contains on average at least 3 X of sulphonate molecule ²Part.In others, contain sulphonate and contain each and contain average 1.5 to 9 X of sulphonate molecule ²Part.Alternatively, containing sulphonate contains each and contains average 3 to 8 X of sulphonate molecule ²Part; Alternatively, each contains average 2 to 4 X of sulphonate molecule ²Part; Perhaps alternatively, each contains average 4 to 8 X of sulphonate molecule ²Part.

[00174] another independent aspect, contain sulphonate and comprise and each contain the sulphonate molecule on average at least 1 ester group and each contain average at least one Y of sulphonate molecule ²Part, wherein Y ²Part has following structure:

At this Y ²In the part-structure, R ^S1And R ^S2Be independently selected from hydrogen, C ₁To C ₂₀Organic group and C ₁To C ₂₀Hydrocarbyl group, and Y ²On behalf of this, unspecified chemical valence contain the remainder of sulphonate molecule in the part.R ^S1And R ^S2Be Y ²Independent integral part in the part, it allows Y ²Part has more R described herein ^S1And R ^S2The arbitrary combination of integral part.In some specific embodiment, R ^S1And R ^S2Be hydrogen.

[00175] in specific embodiment, contains sulphonate and contain each and contain on average at least 1.5 Y of sulphonate molecule ²Part.In other embodiments, containing sulphonate contains each and contains on average at least 2 Y of sulphonate molecule ²Part; Alternatively, each contains on average at least 2.5 Y of sulphonate molecule ²Part; Perhaps alternatively, each contains on average at least 3 Y of sulphonate molecule ²Part.In others, contain sulphonate and contain each and contain average 1.5 to 9 Y of sulphonate molecule ²Part.Alternatively, containing sulphonate contains each and contains average 3 to 8 Y of sulphonate molecule ²Part; Alternatively, each contains average 2 to 4 Y of sulphonate molecule ²Part; Perhaps alternatively, each contains average 4 to 8 Y of sulphonate molecule ²Part.

[00176] another independent aspect, contain sulphonate and comprise and each contain the sulphonate molecule on average at least 1 ester group and each contain average at least one Z of sulphonate molecule ²Part, wherein Z ²Part has following structure:

At this Z ²In the part-structure, R ^S1And R ^S2Be independently selected from hydrogen, C ₁To C ₂₀Organic group and C ₁To C ₂₀Hydrocarbyl group, and Z ²On behalf of this, unspecified chemical valence contain the remainder of sulphonate molecule in the part.R ^S1And R ^S2Be Z ²Independent integral part in the part, it allows Z ²Part has more R described herein ^S1And R ^S2The arbitrary combination of integral part.In some specific embodiment, R ^S1And R ^S2Be hydrogen.

[00177] in specific embodiment, contains sulphonate and contain each and contain on average at least 1.5 Z of sulphonate molecule ²Part.In other embodiments, containing sulphonate contains each and contains on average at least 2 Z of sulphonate molecule ²Part; Alternatively, each contains on average at least 2.5 Z of sulphonate molecule ²Part; Perhaps alternatively, each contains on average at least 3 Z of sulphonate molecule ²Part.In others, contain sulphonate and contain each and contain average 1.5 to 9 Z of sulphonate molecule ²Part.Alternatively, containing sulphonate contains each and contains average 3 to 8 Z of sulphonate molecule ²Part; Alternatively, each contains average 2 to 4 Z of sulphonate molecule ²Part; Perhaps alternatively, each contains average 4 to 8 Z of sulphonate molecule ²Part.

[00178] as another embodiment of the present invention, advantageously provided and contained sulphonate, it comprises and contains the sulphonate molecule.In this embodiment, containing the sulphonate molecule contains each and contains on average at least 1 ester group and contain each and contain on average at least 1 X of sulphonate molecule of sulphonate molecule ²Part.X ²Part has structure as described here.In addition, ester group mean number and X ²Part mean number is separate factor, and its sulphonate molecule that contains that allows to contain in the sulphonate has ester group mean number and X described herein ²The arbitrary combination of part mean number.

[00179] as another embodiment of the present invention, advantageously provided and contained sulphonate, it comprises and contains the sulphonate molecule.In this embodiment, containing sulphonate contains each and contains on average at least 1 ester group and contain each and contain on average at least 1 Y of sulphonate molecule of sulphonate molecule ²Part.Y ²Part has structure as described here.In addition, ester group mean number and Y ²Part mean number is separate factor, and its sulphonate molecule that contains that allows to contain in the sulphonate has ester group mean number and Y described herein ²The arbitrary combination of part mean number.

[00180] as another embodiment of the present invention, advantageously provided and contained sulphonate, it comprises and contains the sulphonate molecule.In this embodiment, containing sulphonate contains each and contains on average at least 1 ester group and contain each and contain on average at least 1 Z of sulphonate molecule of sulphonate molecule ²Part.Z ²Part has structure as described here.In addition, ester group mean number and Z ²Part mean number is separate factor, and its sulphonate molecule that contains that allows to contain in the sulphonate has ester group mean number and Z described herein ²The arbitrary combination of part mean number.

[00181] in some embodiment, provide to contain sulphonate, it comprises at least 1 ester group and at least 1 sulfonic acid group.Ester group number and sulfonic acid group number are separate factors, and it allows to contain the sulphonate molecule and contains the ester group described herein and the arbitrary number of sulfonic acid group.

[00182] in some embodiment, contains the sulphonate molecule and comprise at least 2 ester groups.Alternatively, in some embodiment, contain the sulphonate molecule and comprise at least 3 ester groups.In one aspect, containing the sulphonate molecule comprises each and contains 2 to 9 ester groups of sulphonate molecule.In one aspect, containing the sulphonate molecule comprises each and contains 2 to 8 ester groups of sulphonate molecule; Alternatively, 2 to 7 ester groups; Alternatively, each contains 3 to 5 ester groups of sulphonate molecule; Perhaps alternatively, 3 to 4 ester groups.Still in other embodiments, contain the sulphonate molecule and comprise 3 ester groups; Perhaps alternatively, comprise 4 ester groups.

[00183] in further embodiment, contains the sulphonate molecule and comprise at least 1 ester group and at least 1 sulfonic acid.In other embodiments, contain the sulphonate molecule and comprise at least 2 sulfonic acid groups; Perhaps alternatively, at least 3 sulfonic acid groups.In other embodiments, contain the sulphonate molecule and comprise 2 to 9 sulfonic acid groups; Alternatively, 3 to 8 sulfonic acid groups; Alternatively, 2 to 4 sulfonic acid groups; Perhaps alternatively, 4 to 8 sulfonic acid groups.

[00184] in some embodiment, contains the sulphonate molecule and comprise at least 1 ester group and at least 1 X ²Part.Comprise ester group and X ²The containing the sulphonate molecule and can contain ester group number and arbitrary number X as described here of part ²Arbitrary combination of part.Comprising ester group and X ²Containing in the sulphonate molecule of part, illustrate before its ester group number.In further embodiment, comprise ester group and X ²The containing the sulphonate molecule and can contain at least one 1 X of part ²Part; Alternatively, at least 2 X ²Part; Perhaps alternatively, at least 3 X ²Part.In other embodiments, comprise ester group and X ²The sulphonate molecule that contains of part contains 2 to 9 X ²Part; Alternatively, 3 to 8 X ²Part; Alternatively, 2 to 4 X ²Part; Perhaps alternatively, 4 to 8 X ²Part.

[00185] in some embodiment, contains the sulphonate molecule and comprise at least 1 ester group and at least 1 Y ²Part.Comprise ester group and Y ²The containing the sulphonate molecule and can comprise ester group number and arbitrary number Y as described here of part ²Arbitrary combination of part.Comprising ester group and Y ²Containing in the sulphonate molecule of part, illustrate before its ester group number.In further embodiment, comprise ester group and Y ²The containing the sulphonate molecule and can contain at least one 1 Y of part ²Part; Alternatively, at least 2 Y ²Part; Perhaps alternatively, at least 3 Y ²Part.In other embodiments, comprise ester group and Y ²The sulphonate molecule that contains of part contains 2 to 9 Y ²Part; Alternatively, 3 to 8 Y ²Part; Alternatively, 2 to 4 Y ²Part; Perhaps alternatively, 4 to 8 Y ²Part.

[00186] in some embodiment, contains the sulphonate molecule and comprise at least 1 ester group and at least 1 Z ²Part.Comprise ester group and Z ²The containing the sulphonate molecule and can contain ester group number and arbitrary number Z as described here of part ²Arbitrary combination of part.Comprising ester group and Z ²Containing in the sulphonate molecule of part, illustrate before its ester group number.In further embodiment, comprise ester group and Z ²The containing the sulphonate molecule and can contain at least one 1 Z of part ²Part; Alternatively, at least 2 Z ²Part; Perhaps alternatively, at least 3 Z ²Part.In other embodiments, comprise ester group and Z ²The sulphonate molecule that contains of part contains 2 to 9 Z ²Part; Alternatively, 3 to 8 Z ²Part; Alternatively, 2 to 4 Z ²Part; Perhaps alternatively, 4 to 8 Z ²Part.

[00187] contain sulphonate and also can be described to a kind of product, it is by comprising thiol ester described herein and the contacted method of oxygenant to be made.

Contain the sulfonate ester composition

[00188] minimally in some embodiments, contains the sulfonate ester and contains each and contain average at least one ester group of sulfonate ester molecule and each contains at least one sulphonate of sulfonate ester molecule.Generally speaking, containing the sulfonate ester can react and produce by making sulphonate and the alkali of containing described herein.The group number that contains in the sulfonate ester because containing sulphonate, raw material can comprise the mixture that contains the sulphonate molecule, so can contain the group mean number of sulfonate ester molecule or mean ratio that each contains the sulfonate ester molecule is discussed with containing in the sulfonate ester composition each with different ester group numbers and different sulfonic acid group numbers.

[00189] the ester group number, each contains the ester group mean number, sulfonate groups number of sulfonate ester molecule, the sulfonate groups mean number that each contains the sulfonate ester molecule is the separate factor that contains the sulfonate ester, is X ³Part number, X ³Part mean number, Y ³Part number, Y ³Part mean number, Z ³Part number, Z ³Part mean number, X ⁴Part number, X ⁴Part mean number, Y ⁴Part number, Y ⁴Part mean number, Z ⁴Part number and Z ⁴Part mean number.Produce self-contained sulphonate because contain the sulfonate ester, so each that contains that the sulfonate ester can have any number contains the ester group number or the ester group mean number of sulfonate ester molecule, as described at containing sulphonate.Contain the sulfonate groups, the X that exist in the sulfonate ester ³Partly, Y ³Partly, Z ³Partly, X ⁴Partly, Y ⁴Part and Z ⁴The quantity and the identity of part will further specify in this article.

[00190] minimally in some embodiment, contains the sulfonate ester and contains each and contain the sulfonate ester molecule on average at least 1 ester group and each contain at least 1 sulfonate groups of sulfonate ester molecule.Possible each addressed before containing sulfonate ester molecule ester group mean number.In some embodiment, contain the sulfonate ester and contain each and contain on average at least 1.5 sulfonate groups of sulfonate ester molecule; Alternatively, each contains the sulfonate ester molecule and contains on average at least 2 sulfonate groups; Alternatively, each contains on average at least 2.5 sulfonate groups of sulfonate ester molecule; Perhaps alternatively, each contains on average at least 3 sulfonate groups of sulfonate ester molecule.In other embodiments, containing the sulfonate ester contains each and contains average 1.5 to 9 sulfonate groups of sulfonate ester molecule; Alternatively, each contains average 3 to 8 sulfonate groups of sulfonate ester molecule; Alternatively, each contains average 2 to 4 sulfonate groups of sulfonate ester molecule; Perhaps alternatively, each contains average 4 to 8 sulfonate groups of sulfonate ester molecule.

[00191] on the other hand, contain the sulfonate ester and further comprise oh group.In some embodiment, contain the sulfonate ester and comprise each and contain average at least one oh group of sulfonate ester molecule.

[00192] another independent aspect, contain the sulfonate ester composition and comprise and each contain the sulfonate ester molecule on average at least 1 ester group and each contain on average at least 1 X of sulfonate ester molecule ³Part, wherein X ³Part has following structure:

At this X ³In the part-structure, Q ^S1Be hydrogen or oh group; R ^S1And R ^S2Be independently selected from hydrogen, C ₁To C ₂₀Organic group and C ₁To C ₂₀Hydrocarbyl group; It is the atoms metal of n that M represents oxidation value; The scope of y is between 1 to oxidation value n; And X ³On behalf of this, unspecified chemical valence contain the remainder of sulfonate ester molecule in the part.Q ^S1, R ^S1, R ^S2, M, n and y be X ³Independent integral part in the part, it allows X ³Part has more Q described herein ^S1, R ^S1, R ^S2, M, n and y integral part arbitrary combination.In some specific embodiment, R ^S1And R ^S2Be hydrogen.In other embodiments, n is 1 to 3 integer.In one aspect, atoms metal is selected from sodium, potassium, calcium, magnesium, barium and composition thereof.In others, atoms metal is a sodium.Still in others, atoms metal is calcium or magnesium.Still in others, atoms metal is a barium.

[00193] in specific embodiment, contains the sulfonate ester and contain each and contain on average at least 1.5 X of sulfonate ester molecule ³Part.In other embodiments, containing the sulfonate ester contains each and contains on average at least 2 X of sulfonate ester molecule ³Part; Alternatively, each contains on average at least 2.5 X of sulfonate ester molecule ³Part; Perhaps alternatively, each contains on average at least 3 X of sulfonate ester molecule ³Part.In others, contain the sulfonate ester and contain each and contain average 1.5 to 9 X of sulfonate ester molecule ³Part.Alternatively, containing the sulfonate ester contains each and contains average 3 to 8 X of sulfonate ester molecule ³Part; Alternatively, each contains average 2 to 4 X of sulfonate ester molecule ³Part; Perhaps alternatively, each contains average 4 to 8 X of sulfonate ester molecule ³Part.

[00194] another independent aspect, contain the sulfonate ester composition and comprise and each contain the sulfonate ester molecule on average at least 1 ester group and each contain on average at least 1 Y of sulfonate ester molecule ³Part, wherein Y ³Part has following structure:

At this Y ³In the part-structure, R ^S1And R ^S2Be independently selected from hydrogen, C ₁To C ₂₀Organic group and C ₁To C ₂₀Hydrocarbyl group; It is the atoms metal of n that M represents oxidation value; The scope of y is between 1 to oxidation value n; And Y ³On behalf of this, unspecified chemical valence contain the remainder of sulfonate ester molecule in the part.R ^S1, R ^S2, M, n and y be Y ³Individual elements in the part, it allows Y ³Part has more R described herein ^S1, R ^S2, M, n and y key element arbitrary combination.In some specific embodiment, R ^S1And R ^S2Be hydrogen.In other embodiments, n is 1 to 3 integer.In one aspect, atoms metal is selected from sodium, potassium, calcium, magnesium, barium and composition thereof.In others, atoms metal is a sodium.Still in others, atoms metal is calcium or magnesium.Still in others, atoms metal is a barium.

[00195] in specific embodiment, contains the sulfonate ester and contain each and contain on average at least 1.5 Y of sulfonate ester molecule ³Part.In other embodiments, containing the sulfonate ester contains each and contains on average at least 2 Y of sulfonate ester molecule ³Part; Alternatively, each contains on average at least 2.5 Y of sulfonate ester molecule ³Part; Perhaps alternatively, each contains on average at least 3 Y of sulfonate ester molecule ³Part.In others, contain the sulfonate ester and contain each and contain average 1.5 to 9 Y of sulfonate ester molecule ³Part.Alternatively, containing the sulfonate ester contains each and contains average 3 to 8 Y of sulfonate ester molecule ³Part; Alternatively, each contains average 2 to 4 Y of sulfonate ester molecule ³Part; Perhaps alternatively, each contains average 4 to 8 Y of sulfonate ester molecule ³Part.

[00196] another independent aspect, contain the sulfonate ester composition and comprise and each contain the sulfonate ester molecule on average at least 1 ester group and each contain on average at least 1 Z of sulfonate ester molecule ³Part, wherein Z ³Part has following structure:

At this Z ³In the part-structure, R ^S1And R ^S2Be independently selected from hydrogen, C ₁To C ₂₀Organic group and C ₁To C ₂₀Hydrocarbyl group; It is the atoms metal of n that M represents oxidation value; The scope of y is between 1 to oxidation value n; And Z ³On behalf of this, unspecified chemical valence contain the remainder of sulfonate ester molecule in the part.R ^S1, R ^S2, M, n and y be Z ³Independent factor in the part, it allows Z ³Part has more R described herein ^S1, R ^S2, M, n and y factor arbitrary combination.In some specific embodiment, R ^S1And R ^S2Be hydrogen.In other embodiments, n is 1 to 3 integer.In one aspect, atoms metal is to be selected from sodium, potassium, calcium, magnesium, barium and composition thereof.In others, atoms metal is a sodium.Still in others, atoms metal is calcium or magnesium.Still in others, atoms metal is a barium.

[00197] in specific embodiment, contains the sulfonate ester and contain each and contain on average at least 1.5 Z of sulfonate ester molecule ³Part.In other embodiments, containing the sulfonate ester contains each and contains on average at least 2 Z of sulfonate ester molecule ³Part; Alternatively, each contains on average at least 2.5 Z of sulfonate ester molecule ³Part; Perhaps alternatively, each contains on average at least 3 Z of sulfonate ester molecule ³Part.In others, contain the sulfonate ester and contain each and contain average 1.5 to 9 Z of sulfonate ester molecule ³Part.Alternatively, containing the sulfonate ester contains each and contains average 3 to 8 Z of sulfonate ester molecule ³Part; Alternatively, each contains average 2 to 4 Z of sulfonate ester molecule ³Part; Perhaps alternatively, each contains average 4 to 8 Z of sulfonate ester molecule ³Part.

[00198] another independent aspect, contain the sulfonate ester composition and comprise and each contain the sulfonate ester molecule on average at least 1 ester group and each contain on average at least 1 X of sulfonate ester molecule ⁴Part, X here ⁴Part has following structure:

At this X ⁴In the part-structure, Q ^S1Be hydrogen or oh group; R ^S1And R ^S2Be independently selected from hydrogen, C ₁To C ₂₀Organic group and C ₁To C ₂₀Hydrocarbyl group; R ^S3, R ^S4And R ^S5Be independently selected from hydrogen, C ₁To C ₂₀Organic group and C ₁To C ₂₀Hydrocarbyl group; And X ⁴On behalf of this, unspecified chemical valence contain the remainder of sulfonate ester molecule in the part.Q ^S1, R ^S1, R ^S2, R ^S3, R ^S4And R ^S5Be X ⁴Independent integral part in the part, it allows X ⁴Part has more Q described herein ^S1, R ^S1, R ^S2, R ^S3, R ^S4And R ^S5The arbitrary combination of integral part.Aspect some, structure NR ^S3R ^S4R ^S5Representative is selected from the compound of trialkylamine, dialkylamine and monoalkylamine.In some embodiment, NR ^S3R ^S4R ^S5Represent trolamine.In some specific embodiment, R ^S1And R ^S2Be hydrogen.

[00199] in specific embodiment, contains the sulfonate ester and contain each and contain on average at least 1.5 X of sulfonate ester molecule ⁴Part.In other embodiments, containing the sulfonate ester contains each and contains on average at least 2 X of sulfonate ester molecule ⁴Part; Alternatively, each contains on average at least 2.5 X of sulfonate ester molecule ⁴Part; Perhaps alternatively, each contains on average at least 3 X of sulfonate ester molecule ⁴Part.In others, contain the sulfonate ester and contain each and contain average 1.5 to 9 X of sulfonate ester molecule ⁴Part.Alternatively, containing the sulfonate ester contains each and contains average 3 to 8 X of sulfonate ester molecule ⁴Part; Alternatively, each contains average 2 to 4 X of sulfonate ester molecule ⁴Part; Perhaps alternatively, each contains average 4 to 8 X of sulfonate ester molecule ⁴Part.

[00200] another independent aspect, contain the sulfonate ester composition and comprise and each contain the sulfonate ester molecule on average at least 1 ester group and each contain on average at least 1 Y of sulfonate ester molecule ⁴Part, Y here ⁴Part has following structure:

At this Y ⁴In the part-structure, R ^S1And R ^S2Be independently selected from hydrogen, C ₁To C ₂₀Organic group and C ₁To C ₂₀Hydrocarbyl group; R ^S3, R ^S4And R ^S5Be independently selected from hydrogen, C ₁To C ₂₀Organic group and C ₁To C ₂₀Hydrocarbyl group; And Y ⁴On behalf of this, unspecified chemical valence contain the remainder of sulfonate ester molecule in the part.R ^S1, R ^S2, R ^S3, R ^S4And R ^S5Be Y ⁴Independent integral part in the part, and so Y ⁴Part can have more as described here R ^S1, R ^S2, R ^S3, R ^S4And R ^S5The arbitrary combination of embodiment.Aspect some, structure NR ^S3R ^S4R ^S5Representative is selected from the compound of trialkylamine, dialkylamine and monoalkylamine.In some embodiment, NR ^S3R ^S4R ^S5Represent trolamine.In some specific embodiment, R ^S1And R ^S2Be hydrogen.

[00201] in specific embodiment, contains the sulfonate ester and contain each and contain on average at least 1.5 Y of sulfonate ester molecule ⁴Part.In other embodiments, containing the sulfonate ester contains each and contains on average at least 2 Y of sulfonate ester molecule ⁴Part; Alternatively, each contains on average at least 2.5 Y of sulfonate ester molecule ⁴Part; Perhaps alternatively, each contains on average at least 3 Y of sulfonate ester molecule ⁴Part.In others, contain the sulfonate ester and contain each and contain average 1.5 to 9 Y of sulfonate ester molecule ⁴Part.Alternatively, containing the sulfonate ester contains each and contains average 3 to 8 Y of sulfonate ester molecule ⁴Part; Alternatively, each contains average 2 to 4 Y of sulfonate ester molecule ⁴Part; Perhaps alternatively, each contains average 4 to 8 Y of sulfonate ester molecule ⁴Part.

[00202] another independent aspect, contain the sulfonate ester composition and comprise and each contain the sulfonate ester molecule on average at least 1 ester group and each contain on average at least 1 Z of sulfonate ester molecule ⁴Part, Z here ⁴Part has following structure:

At this Z ⁴In the part-structure, R ^S1And R ^S2Be independently selected from hydrogen, C ₁To C ₂₀Organic group and C ₁To C ₂₀Hydrocarbyl group; R ^S3, R ^S4And R ^S5Be independently selected from hydrogen, C ₁To C ₂₀Organic group and C ₁To C ₂₀Hydrocarbyl group; And Z ⁴On behalf of this, unspecified chemical valence contain the remainder of sulfonate ester molecule in the part.R ^S1, R ^S2, R ^S3, R ^S4And R ^S5Be Z ⁴Independent integral part in the part, it allows Z ⁴Part has more as described here R ^S1, R ^S2, R ^S3, R ^S4And R ^S5The arbitrary combination of embodiment.Aspect some, structure NR ^S3R ^S4R ^S5Representative is selected from the compound of trialkylamine, dialkylamine and monoalkylamine.In some embodiment, NR ^S3R ^S4R ^S5Represent trolamine.In some specific embodiment, R ^S1And R ^S2Be hydrogen.

[00203] in specific embodiment, contains the sulfonate ester and contain each and contain on average at least 1.5 Z of sulfonate ester molecule ⁴Part.In other embodiments, containing the sulfonate ester contains each and contains on average at least 2 Z of sulfonate ester molecule ⁴Part; Alternatively, each contains on average at least 2.5 Z of sulfonate ester molecule ⁴Part; Perhaps alternatively, each contains on average at least 3 Z of sulfonate ester molecule ⁴Part.In others, contain the sulfonate ester and contain each and contain average 1.5 to 9 Z of sulfonate ester molecule ⁴Part.Alternatively, containing the sulfonate ester contains each and contains average 3 to 8 Z of sulfonate ester molecule ⁴Part; Alternatively, each contains average 2 to 4 Z of sulfonate ester molecule ⁴Part; Perhaps alternatively, each contains average 4 to 8 Z of sulfonate ester molecule ⁴Part.

[00204] in some embodiment, provide to contain the sulfonate ester molecule, it comprises at least 1 ester group and at least 1 sulfonate groups.Ester group number and sulfonate groups number are separate factors, and contain ester group as described here and sulfonate groups that the sulfonate ester molecule can contain any number.

[00205] in some embodiment, contains the sulfonate ester molecule and comprise at least 2 ester groups.Alternatively, in some embodiment, contain the sulfonate ester molecule and comprise at least 3 ester groups.On the one hand, contain the sulfonate ester molecule and comprise 2 to 9 ester groups.On the one hand, contain the sulfonate ester molecule and comprise 2 to 8 ester groups; Alternatively, 2 to 7 ester groups; Alternatively, 3 to 5 ester groups; Perhaps alternatively, 3 to 4 ester groups.Still in other embodiments, contain the sulfonate ester molecule and comprise 3 ester groups; Perhaps alternatively, comprise 4 ester groups.

[00206] in further embodiment, contains the sulfonate ester molecule and comprise at least 1 sulfonate groups.In other embodiments, contain the sulfonate ester molecule and comprise at least 2 sulfonate groups; Perhaps alternatively, at least 3 sulfonate groups.In other embodiments, contain the sulfonate ester molecule and comprise 2 to 9 sulfonate groups; Alternatively, 3 to 8 sulfonate groups; Alternatively, 2 to 4 sulfonate groups; Perhaps alternatively, 4 to 8 sulfonate groups.

[00207] in some embodiment, contains the sulfonate ester molecule and comprise at least 1 ester group and at least 1 X ³Part.In some embodiment, comprise ester group and X ³The containing the sulfonate ester molecule and can comprise ester group number and arbitrary X as described here of part ³The arbitrary combination of portion's fractional.Comprising ester group and X ³Containing in the sulfonate ester molecule of part, illustrate before its ester group number.In further embodiment, comprise ester group and X ³The sulfonate ester molecule that contains of part can at least 2 X ³Part; Perhaps alternatively, at least 3 X ³Part.In other embodiments, comprise ester group and X ³The sulfonate ester molecule that contains of part comprises 2 to 9 X ³Part; Alternatively, 3 to 8 X ³Part; Alternatively, 2 to 4 X ³Part; Perhaps alternatively, 4 to 8 X ³Part.

[00208] in some embodiment, contains the sulfonate ester molecule and comprise at least 1 ester group and at least 1 Y ³Part.In some embodiment, comprise ester group and Y ³The containing the sulfonate ester molecule and can comprise ester group number and arbitrary Y as described here of part ³The arbitrary combination of portion's fractional.Comprising ester group and Y ³Containing in the sulfonate ester molecule of part, illustrate before its ester group number.In further embodiment, comprise ester group and Y ³The sulfonate ester molecule that contains of part can at least 2 Y ³Part; Perhaps alternatively, at least 3 Y ³Part.In other embodiments, comprise ester group and Y ³The sulfonate ester molecule that contains of part comprises 2 to 9 Y ³Part; Alternatively, 3 to 8 Y ³Part; Alternatively, 2 to 4 Y ³Part; Perhaps alternatively, 4 to 8 Y ³Part.

[00209] in some embodiment, contains the sulfonate ester molecule and comprise at least 1 ester group and at least 1 Z ³Part.In some embodiment, comprise ester group and Z ³The containing the sulfonate ester molecule and can comprise ester group number and arbitrary Z as described here of part ³The arbitrary combination of portion's fractional.Comprising ester group and Z ³Containing in the sulfonate ester molecule of part, illustrate before its ester group number.In further embodiment, comprise ester group and Z ³The sulfonate ester molecule that contains of part can at least 2 Z ³Part; Perhaps alternatively, at least 3 Z ³Part.In other embodiments, comprise ester group and Z ³The sulfonate ester molecule that contains of part comprises 2 to 9 Z ³Part; Alternatively, 3 to 8 Z ³Part; Alternatively, 2 to 4 Z ³Part; Perhaps alternatively, 4 to 8 Z ³Part.

[00210] in some embodiment, contains the sulfonate ester molecule and comprise at least 1 ester group and at least 1 X ⁴Part.In some embodiment, comprise ester group and X ⁴The containing the sulfonate ester molecule and can comprise ester group number and arbitrary X as described here of part ⁴The arbitrary combination of portion's fractional.Comprising ester group and X ⁴Containing in the sulfonate ester molecule of part, illustrate before its ester group number.In further embodiment, comprise ester group and X ⁴The sulfonate ester molecule that contains of part can at least 2 X ⁴Part; Perhaps alternatively, at least 3 X ⁴Part.In other embodiments, comprise ester group and X ⁴The sulfonate ester molecule that contains of part comprises 2 to 9 X ⁴Part; Alternatively, 3 to 8 X ⁴Part; Alternatively, 2 to 4 X ⁴Part; Perhaps alternatively, 4 to 8 X ⁴Part.

[00211] in some embodiment, contains the sulfonate ester molecule and comprise at least 1 ester group and at least 1 Y ⁴Part.In some embodiment, comprise ester group and Y ⁴The containing the sulfonate ester molecule and can comprise ester group number and arbitrary Y as described here of part ⁴The arbitrary combination of portion's fractional.Comprising ester group and Y ⁴Containing in the sulfonate ester molecule of part, illustrate before its ester group number.In further embodiment, comprise ester group and Y ⁴The sulfonate ester molecule that contains of part can at least 2 Y ⁴Part; Perhaps alternatively, at least 3 Y ⁴Part.In other embodiments, comprise ester group and Y ⁴The sulfonate ester molecule that contains of part comprises 2 to 9 Y ⁴Part; Alternatively, 3 to 8 Y ⁴Part; Alternatively, 2 to 4 Y ⁴Part; Perhaps alternatively, 4 to 8 Y ⁴Part.

[00212] in some embodiment, contains the sulfonate ester molecule and comprise at least 1 ester group and at least 1 Z ⁴Part.In some embodiment, comprise ester group and Z ⁴The containing the sulfonate ester molecule and can comprise ester group number and arbitrary Z as described here of part ⁴The arbitrary combination of portion's fractional.Comprising ester group and Z ⁴Containing in the sulfonate ester molecule of part, illustrate before its ester group number.In further embodiment, comprise ester group and Z ⁴The sulfonate ester molecule that contains of part can at least 2 Z ⁴Part; Perhaps alternatively, at least 3 Z ⁴Part.In other embodiments, comprise ester group and Z ⁴The sulfonate ester molecule that contains of part comprises 2 to 9 Z ⁴Part; Alternatively, 3 to 8 Z ⁴Part; Alternatively, 2 to 4 Z ⁴Part; Perhaps alternatively, 4 to 8 Z ⁴Part.

[00213] contain sulfonate ester oil composition and also can be described to a kind of product, it is to contain sulphonate and the contacted method of alkali is made by comprising with described herein, and can be further limited by method described herein.

The preparation method of thiol ester composition

[00214] the present invention has advantageously provided the production method of thiol ester composition, as embodiment of the present invention.As a kind of embodiment, the present invention advantageously comprises the production method of thiol ester composition, this method contacts with the unsaturated ester composition that contains unsaturated ester by making hydrogen sulfide, and hydrogen sulfide and unsaturated ester are reacted to form or to produce thiol ester composition and carry out.As another embodiment of the present invention, advantageously provided the production method of thiol ester composition.In this embodiment, this method comprises that the composition that will contain polyvalent alcohol contacts with the composition of sulfur-bearing polyol carboxylic acid composition, and polyvalent alcohol and sulfur-bearing polyol carboxylic acid composition are reacted to form thiol ester composition.

[00215] in some embodiments that comprise the production thiol ester composition of the present invention, the unsaturated ester composition is a natural origin oil.In one aspect, the unsaturated ester composition is soya-bean oil or is Viscotrol C alternatively.The unsaturated ester composition of other adequate types is illustrated herein, and can be used in the production method of thiol ester composition.

Derive from the thiol ester of unsaturated ester

[00216] as a kind of embodiment of the present invention, thiol ester described herein can be made by following method, this method comprises hydrogen sulfide is contacted with the unsaturated ester composition, and hydrogen sulfide and this unsaturated ester composition are reacted to generate thiol ester composition.In one embodiment, the unsaturated ester composition comprises the unsaturated ester that contains average at least 1.5 ester groups of each unsaturated ester molecule and average at least 1.5 carbon-carbon double bonds.In this embodiment, thiol ester composition comprises that the mol ratio of episulfide and thiol group is the thiol ester molecule below 1.5.

[00217] production method of thiol ester composition can be applied to any unsaturated ester described herein, and is used to produce any thiol ester described herein.The production method of thiol ester composition also can comprise any additional process steps or processing condition described herein.

[00218] aspect some, the reaction between hydrogen sulfide and the unsaturated ester is to take place under the condition that has solvent to exist.In others, the reaction between unsaturated ester and the hydrogen sulfide takes place under solvent-free substantially condition.When solvent existed, solvent can be selected from aliphatic hydrocrbon, ether, aromatic compound, alcohol or their composition.In further embodiment, solvent can be aliphatic hydrocrbon, ether or aromatic compound.Generally speaking, solvent is no matter its chemical species comprises from 1 to 20 carbon atom; Perhaps alternatively, 3 to 10 carbon atoms.When solvent comprised aliphatic solvents, this aliphatic solvents was butane, Trimethylmethane, pentane, hexane, heptane, octane or their any mixture.When solvent comprised aromatic solvent, this aromatic solvent was benzene,toluene,xylene, ethylbenzene or its any mixture.When solvent comprised alcohol, this alcohol was methyl alcohol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, 2-methyl-2-propyl alcohol or its mixture.When solvent comprised ether, this ether was diethyl ether, dipropyl ether, tetrahydrofuran (THF) or its mixture.The solvent that other type is suitable is conspicuous for the person of ordinary skill of the art, and will be considered within the scope of the invention.

[00219] when solvent was used to reaction between unsaturated ester and the hydrogen sulfide, quantity of solvent can be any consumption that reaction is had promoter action.In some embodiment, the quality of solvent is below 30 times of unsaturated ester quality.In other embodiments, the quality of solvent is below 20 times of unsaturated ester quality; Alternatively, below 15 of the unsaturated ester quality times; Alternatively, below 10 of the unsaturated ester quality times; Perhaps alternatively, below 5 of the unsaturated ester quality times.In other embodiments, the quality of solvent is 2 to 20 times of unsaturated ester quality; Alternatively, 3 of the unsaturated ester quality to 15 times; Alternatively, 4 of the unsaturated ester quality to 15 times; Perhaps alternatively, 5 of the unsaturated ester quality to 10 times.

[00220] mol ratio of hydrogen sulfide that uses in the thiol ester composition production process and unsaturated ester carbon-carbon double bond molar equivalent can be the required any mol ratio of thiol ester of producing expectation.Unsaturated ester carbon-carbon double bond molar equivalent can calculate with following equation:

\frac{UESMass}{UESGMW} \times UESC = C

In this equation, UES GMW is the mean molal quantity of unsaturated ester, and UES Mass is the quality of raw material unsaturated ester, and UES C=C is two key mean numbers of each unsaturated ester molecule.In some embodiment, the hydrogen sulfide of thiol ester molecule and unsaturated ester carbon-carbon double bond mol ratio are more than 2.In other embodiments, hydrogen sulfide and unsaturated ester carbon-carbon double bond mol ratio are more than 5; Alternatively, more than 10; Alternatively, more than 15; Perhaps alternatively, more than 20.In other embodiments, hydrogen sulfide and unsaturated ester carbon-carbon double bond mol ratio can be 2 to 500; Alternatively, 5 to 200; Alternatively, 10 to 100; Perhaps alternatively, 100 to 200.

[00221] aspect some, the reaction between unsaturated ester and the hydrogen sulfide is by catalytic.In some embodiment, the reaction between unsaturated ester and the hydrogen sulfide can be by heterogeneous catalyst or homogeneous catalyst catalysis.In other embodiments, the reaction between unsaturated ester and the hydrogen sulfide is caused by radical initiator or ultraviolet ray (UV) radiation.The catalysis that other the is suitable and method of initiation will become apparent to those skilled in the art that and will be considered within the scope of the invention.

[00222] heterogeneous catalyst is selected from acid clay (as Filtrol -24, can buy from Englehard), acid zeolite is (as LZY-84, can buy from UOP), cobalt/molybdenum oxide supported catalyst is (as TK-554, can buy from Haldor-Topsoe) and nickel/molybdenum load oxide catalyst (as TK-573, can buy from Haldor-Topsoe).Homogeneous catalyst is methylsulfonic acid or toluenesulphonic acids.Heterogeneous and the homogeneous catalyst of other adequate types will become apparent to those skilled in the art that and will be considered within the scope of the invention.

[00223] radical initiator can be any radical initiator that can form free radical under heat or light photolysis.Generally speaking, radical initiator be selected from contain-the N=N-group or-total classification compound of O-O-group.The radical initiator of concrete kind comprises diazonium compound, dialkyl peroxide, hydrogen peroxide and peroxyester.Concrete initiator comprises nitrogen benzide, 2,2 '-azo two (2-methyl propionitrile), 4,4 '-azo two (4-cyanovaleric acid), 1,1 '-azo two (cyclohexane nitrile), 2,2 '-azo two (2-methylpropane), 2,2 '-azo two (2-methyl-prop amidine), dihydrochloride, methyl propionitrile, azodicarboamide, tert-butyl hydroperoxide, ditertiary butyl peroxide, peroxybenzoic acid monooctyl ester (octylperbenzoate).In some embodiment, the reaction that free radical caused be temperature of reaction in ± 50 ℃, transformation period of radical initiator is to carry out under 1 hour the condition.In other embodiments, the reaction that free radical caused be temperature of reaction in ± 25 ℃, transformation period of radical initiator is to carry out under 1 hour the condition; Alternatively, temperature of reaction in ± 20 ℃, transformation period of radical initiator is under 1 hour the condition; Alternatively, temperature of reaction in ± 15 ℃, transformation period of radical initiator is under 1 hour the condition; Alternatively, temperature of reaction in ± 10 ℃, transformation period of radical initiator is under 1 hour the condition.In the reaction of catalytic unsaturated ester of radical initiator and hydrogen sulfide is that light can be any light that can produce free radical in the embodiment that causes of the photolysis by light.In some embodiment, ultraviolet irradiation only.

[00224] on the other hand, the reaction between unsaturated ester and the hydrogen sulfide is caused by ultraviolet irradiation.In these embodiments, ultraviolet irradiation can be to cause any ultraviolet irradiation that reacts between unsaturated ester and the hydrogen sulfide.In some embodiment, ultraviolet irradiation produces by medium pressure mercury lamp.Although ultraviolet irradiation is described to light source, the light source of other adequate types will become apparent to those skilled in the art that and will be considered within the scope of the invention.

[00225] reaction of unsaturated ester and hydrogen sulfide can take place in batch-type reactor or flow reactor.The example of flow reactor comprises continuously stirring formula reactor, fixed bed type reactor and similar reactor.The example of batch-type reactor comprises ultraviolet batch-type reactor.Can be used for other type batch-type of embodiment of the present invention and flow reactor will become apparent to those skilled in the art that and will be considered within the scope of the invention.

[00226] when using flow reactor, weight hourly space velocity is that 0.1 to 5 raw material unsaturated ester can be used to produce the thiol ester of expectation.Alternatively, the weight hourly space velocity scope of raw material unsaturated ester is between 0.1 to 5; Alternatively, from 0.1 to 2.Alternatively, the weight hourly space velocity of raw material unsaturated ester is 0.1; Alternatively, the weight hourly space velocity of raw material unsaturated ester is 0.25; Perhaps alternatively, the weight hourly space velocity of raw material unsaturated ester is 2.

[00227] the reaction required time of unsaturated ester and hydrogen sulfide can be to form the needed any time of described thiol ester.Generally speaking, the reaction required time of unsaturated ester and hydrogen sulfide is at least 5 minutes.In some embodiment, the reaction required time scope of unsaturated ester and hydrogen sulfide is from 5 minutes to 72 hours; Alternatively, from 10 minutes to 48 hours; Perhaps alternatively, from 15 minutes to 36 hours.

[00228] in some embodiment, the production process of thiol ester is removed this step with excessive or residual hydrogen sulfide after further being included in hydrogen sulfide and unsaturated ester composition react.In some embodiment, thiol ester is through the vacuum removing residue.In some embodiment, thiol ester is through the vacuum removing residue in the temperature range between 25 ℃ to 250 ℃; Perhaps alternatively, between 50 ℃ to 200 ℃.In other embodiments, thiol ester sprays to remove hydrogen sulfide with rare gas element.In some embodiment, thiol ester is to spray to remove hydrogen sulfide with rare gas element in the temperature range between 25 ℃ to 250 ℃; Perhaps alternatively, between 50 ℃ to 200 ℃.Aspect some, rare gas element is a nitrogen.Generally speaking, comprise hydrogen sulfide below the 0.1wt.% through the thiol ester of removing or sprayed.In other embodiments, comprise sulphur below the 0.05wt.% through the thiol ester of removing or sprayed; Alternatively, the following hydrogen sulfide of 0.025wt.%; Perhaps alternatively, the following hydrogen sulfide of 0.01wt.%.

[00229] reaction between unsaturated ester and the hydrogen sulfide can be carried out can forming under any temperature of thiol ester.In some embodiment, unsaturated ester and hydrogen sulfide can react under the temperature more than-20 ℃.In other embodiments, unsaturated ester and hydrogen sulfide can react under the temperature more than 0 ℃; Alternatively, more than 20 ℃; Alternatively, more than 50 ℃; Alternatively, more than 80 ℃; Perhaps alternatively, more than 100 ℃.Still in other embodiments, unsaturated ester and hydrogen sulfide can react under-20 ℃ to 200 ℃ temperature; Alternatively, from 120 ℃ to 240 ℃; Alternatively, from 170 ℃ to 210 ℃; Alternatively, from 185 ℃ to 195 ℃; Alternatively, from 20 ℃ to 200 ℃; Alternatively, from 20 ℃ to 170 ℃; Perhaps alternatively, from 80 ℃ to 140 ℃.

[00230] reaction between unsaturated ester and the hydrogen sulfide can make hydrogen sulfide partly keep carrying out under liquid any pressure.In some embodiment, the reaction between unsaturated ester and the hydrogen sulfide can be carried out under the condition of 100psig to 2000psig in pressure range.In other embodiments, the reaction between unsaturated ester and the hydrogen sulfide can be carried out under 150 to 1000psig condition in pressure range; Perhaps alternatively, from 200 to 600psig.

[00231] thiol ester of low episulfide content can be produced with disclosed method.On the one hand, the production method of thiol ester can form or produce the mol ratio of episulfide and thiol group at the thiol ester below 1.5.The mol ratio of other episulfide and thiol group is disclosed at this.

[00232] except that low episulfide content, the also available disclosed method production of thiol ester of low carbon-carbon double bond and thiol group mol ratio.On the one hand, method described herein can be produced carbon-carbon double bond and thiol group mol ratio at the thiol ester below 1.5.The mol ratio of other carbon-carbon double bond and thiol group is disclosed at this.

[00233] aspect some, method production described herein contains the thiol ester molecule of the above mercaptan sulfur of average 5wt.%.Other mercaptan sulfur content is disclosed at this.In others, the production method of thiol ester can form the thiol ester of the total side chain 40% above sulfur-bearing of thiol ester.Other sulfur-bearing per-cent of the total side chain of thiol ester is disclosed at this.

[00234] in some embodiment, the production method of thiol ester composition comprises to be made unsaturated ester contact with hydrogen sulfide and unsaturated ester and hydrogen sulfide is reacted to form thiol ester.Thiol ester comprises that the ratio of episulfide and thiol group is at the thiol ester molecule below 1.5.

Derive from the thiol ester of polyvalent alcohol and sulfur-bearing polyol carboxylic acid derivative

[00235], advantageously provided the production method of another kind of thiol ester composition as another embodiment of the present invention.In this embodiment, this production method comprises following each step: the composition that contains polyvalent alcohol is contacted with the composition that comprises sulfur-bearing polyol carboxylic acid and/or sulfur-bearing polyol carboxylic acid derivative; And polyvalent alcohol and sulfur-bearing polyol carboxylic acid and/or sulfur-bearing polyol carboxylic acid derivative are reacted with the production thiol ester composition.This method can be applied to any polyvalent alcohol described herein, sulfur-bearing polyol carboxylic acid or sulfur-bearing polyol carboxylic acid derivative.The production method of thiol ester composition also can comprise any extra processing step or processing condition described herein.In addition, the production method of thiol ester composition can form any thiol ester described herein.

[00236] in some embodiment, thiol ester composition comprises that each thiol ester molecule has the thiol ester molecule of average at least 1.5 ester groups and average at least 1.5 thiol groups.

[00237] (for example: the contacted mode mercaptan carboxylate methyl ester), the polyvalent alcohol that is used to produce thiol ester can be any polyvalent alcohol or the polyol blends that can produce described sulfur-bearing alcohol ester by making polyvalent alcohol and mercaptan carboxylic acid and/or mercaptan carboxylic acid equivalent.

[00238] on the one hand, the polyvalent alcohol that is used to produce thiol ester can comprise from 2 to 20 carbon atoms.In other embodiments, polyvalent alcohol can comprise from 2 to 10 carbon atoms; Alternatively, from 2 to 7 carbon atoms; Alternatively, from 2 to 5 carbon atoms.In further embodiment, polyvalent alcohol can be the mixture that contains the polyvalent alcohol of average from 2 to 20 carbon atoms; Alternatively, average from 2 to 10 carbon atoms; Alternatively, average from 2 to 7 carbon atoms; Alternatively, average from 2 to 5 carbon atoms.

[00239] on the other hand, the polyvalent alcohol that is used to produce thiol ester can contain the oh group of producing the required any number of thiol ester as described here.In certain embodiments, polyvalent alcohol contains 2 oh groups; Alternatively, 3 oh groups; Alternatively, 4 oh groups; Alternatively, 5 oh groups; Perhaps alternatively, 6 oh groups.In other embodiments, polyvalent alcohol comprises at least 2 oh groups; Alternatively, at least 3 oh groups; Alternatively, at least 4 oh groups; Perhaps alternatively, at least 5 oh groups; At least 6 oh groups.Still in other embodiments, polyvalent alcohol comprises from 2 to 8 oh groups; Alternatively, from 2 to 4 oh groups; Perhaps alternatively, from 4 to 8 oh groups.

[00240] further, the polyvalent alcohol that is used to produce thiol ester is a polyol blends.In one embodiment, polyol blends contains on average at least 1.5 oh groups of each polyvalent alcohol molecule.In other embodiments, polyol blends contains on average at least 2 oh groups of each polyvalent alcohol molecule; Alternatively, average at least 2.5 oh groups of each polyvalent alcohol molecule; Alternatively, average at least 3.0 oh groups of each polyvalent alcohol molecule; Perhaps alternatively, average at least 4 oh groups of each polyvalent alcohol molecule.Still in other embodiments, polyol blends contains average 1.5 to 8 oh groups of each polyvalent alcohol molecule; Alternatively, average 2 to 6 oh groups of each polyvalent alcohol molecule; Alternatively, average 2.5 to 5 oh groups of each polyvalent alcohol molecule; Alternatively, average 3 to 4 oh groups of each polyvalent alcohol molecule; Alternatively, average 2.5 to 3.5 oh groups of each polyvalent alcohol molecule; Perhaps alternatively, average 2.5 to 4.5 oh groups of each polyvalent alcohol molecule.

[00241] still on the other hand, be used to produce the polyvalent alcohol of thiol ester or polyol blends and have molecular weight or molecular-weight average below 500.In other embodiments, polyvalent alcohol or polyol blends have molecular weight or the molecular-weight average below 300; Alternatively, below 200; Alternatively, below 150; Perhaps alternatively, below 100.

[00242] by making polyvalent alcohol and mercaptan carboxylic acid and/or the contacted mode of mercaptan carboxylic acid equivalent, the mercaptan carboxylic acid and/or the mercaptan carboxylic acid equivalent that are used to produce thiol ester can be the mixtures that can produce any mercaptan mixture of carboxylic acids, the mercaptan carboxylic acid equivalent that comprise the mercaptan carboxylic acid of described sulfur-bearing alcohol ester or comprise the mercaptan carboxylic acid equivalent.When referring to feature mercaptan carboxylic acid equivalent or mercaptan carboxylic acid equivalent, character for example carbonatoms, average carbon atom number, molecular weight or molecular-weight average, thiol group number and average sulfur alcohol groups are counted, the reader is to be understood that these character will be applied to join polyvalent alcohol to form the part mercaptan carboxylic acid equivalent of thiol ester.

[00243] on the one hand, mercaptan carboxylic acid and/or the mercaptan carboxylic acid equivalent that is used to produce thiol ester comprises 2 to 28 carbon atoms.In one embodiment, mercaptan carboxylic acid and/or mercaptan carboxylic acid equivalent comprise 4 to 26 carbon atoms; Alternatively, 8 to 24 carbon atoms; Alternatively, 12 to 24 carbon atoms; Perhaps alternatively, 14 to 20 carbon atoms.In other embodiments, comprise the mixture of mercaptan carboxylic acid and/or comprise that the mixture of mercaptan carboxylic acid equivalent contains each carboxylic acid and/or average 2 to 28 carbon atoms of carboxylic acid equivalent; Alternatively, each carboxylic acid and/or carboxylic acid equivalent, 4 to 26 carbon atoms; Alternatively, each carboxylic acid and/or carboxylic acid equivalent, 8 to 24 carbon atoms; Alternatively, each carboxylic acid and/or carboxylic acid equivalent, 12 to 24 carbon atoms; Perhaps alternatively, each carboxylic acid and/or carboxylic acid equivalent, 14 to 20 carbon atoms.

[00244] on the other hand, mercaptan carboxylic acid and/or the mercaptan carboxylic acid equivalent that is used to produce thiol ester contains at least 1 thiol group; Alternatively, 2 thiol groups.In some embodiment, comprise the mixture of mercaptan carboxylic acid and/or comprise that the mixture of mercaptan carboxylic acid equivalent contains each carboxylic acid and/or average 0.5 to 3 thiol group of carboxylic acid equivalent; Alternatively, average 1 to 2 thiol group of each carboxylic acid and/or carboxylic acid equivalent.

[00245] on the other hand, be used to produce the mercaptan carboxylic acid of thiol ester and/or mercaptan carboxylic acid equivalent and have molecular weight more than 100; Alternatively, more than 180; Alternatively, more than 240; Perhaps alternatively, more than 260.In other embodiments, mercaptan carboxylic acid and/or mercaptan carboxylic acid equivalent have 100 to 500 molecular weight; Alternatively, 120 to 420; Alternatively, 180 to 420; Alternatively, 240 to 420; Perhaps alternatively, 260 to 360.In some embodiment, comprise the mixture of mercaptan carboxylic acid and/or comprise that the mixture of mercaptan carboxylic acid equivalent has each carboxylic acid and/or the molecular-weight average of carboxylic acid equivalent more than 100; Alternatively, each carboxylic acid and/or carboxylic acid equivalent are more than 180; Alternatively, each carboxylic acid and/or carboxylic acid equivalent are more than 240; Alternatively, each carboxylic acid and/or carboxylic acid equivalent are more than 260.Still in other embodiments, comprise the mixture of mercaptan carboxylic acid and/or comprise that the mixture of mercaptan carboxylic acid equivalent has the molecular-weight average of each carboxylic acid and/or carboxylic acid equivalent from 100 to 500; Alternatively, each carboxylic acid and/or carboxylic acid equivalent from 120 to 420; Alternatively, each carboxylic acid and/or carboxylic acid equivalent from 180 to 420; Alternatively, each carboxylic acid and/or carboxylic acid equivalent from 240 to 420; Perhaps alternatively, each carboxylic acid and/or carboxylic acid equivalent from 260 to 360.

[00246] aspect some, instead under the situation that has solvent to exist, taking place between polyvalent alcohol and sulfur-bearing polyol carboxylic acid and/or the sulfur-bearing polyol carboxylic acid derivative.In others, the reaction between polyvalent alcohol and sulfur-bearing polyol carboxylic acid and/or the sulfur-bearing polyol carboxylic acid derivative takes place under solvent-free substantially situation.In the reaction between polyvalent alcohol and sulfur-bearing polyol carboxylic acid and/or the sulfur-bearing polyol carboxylic acid derivative be take place under the situation that is having solvent to exist aspect, solvent is selected from aliphatic hydrocrbon, ether, aromatic compound or its arbitrary combination.Generally speaking, solvent is no matter its chemical species can comprise from 1 to 20 carbon atom; Perhaps alternatively, from 3 to 10 carbon atoms.When solvent comprised aliphatic hydrocrbon, this aliphatic hydrocrbon was butane, Trimethylmethane, pentane, hexane, heptane, octane or its arbitrary mixture.When solvent comprised aromatic compound, this aromatic compound was benzene,toluene,xylene, ethylbenzene or its arbitrary mixture.When solvent comprised ether, this ether was diethyl ether, dipropyl ether, tetrahydrofuran (THF) or its arbitrary mixture.

[00247] when solvent was used to reaction between polyvalent alcohol and sulfur-bearing polyol carboxylic acid and/or the sulfur-bearing polyol carboxylic acid derivative, quantity of solvent can be any consumption that reaction is had promoter action.In some embodiment, the quality of solvent is sulfur-bearing polyol carboxylic acid and/or below 30 times of sulfur-bearing polyol carboxylic acid derivative quality.In other embodiments, the quality of solvent is below 20 times of unsaturated ester oil quality; Alternatively, sulfur-bearing polyol carboxylic acid and/or below 15 times of sulfur-bearing polyol carboxylic acid derivative quality; Alternatively, sulfur-bearing polyol carboxylic acid and/or below 10 times of sulfur-bearing polyol carboxylic acid derivative quality; Perhaps alternatively, sulfur-bearing polyol carboxylic acid and/or below 5 times of sulfur-bearing polyol carboxylic acid derivative quality.In other embodiments, the quality of solvent is sulfur-bearing polyol carboxylic acid and/or sulfur-bearing polyol carboxylic acid derivative quality 2 to 20 times; Alternatively, 3 to 15 times of sulfur-bearing polyol carboxylic acid and/or sulfur-bearing polyol carboxylic acid derivative quality; Perhaps alternatively, 5 to 10 times of sulfur-bearing polyol carboxylic acid and/or sulfur-bearing polyol carboxylic acid derivative quality.

The hydroxy-acid group equivalent of sulfur-bearing polyol carboxylic acid that [00248] in the production process of thiol ester composition, uses and/or sulfur-bearing polyol carboxylic acid derivative and the normal mol ratio of hydroxyl groups group (hereinafter referred to as " hydroxy-acid group and polyvalent alcohol oh group mol ratio) can be to produce the hydroxy-acid group of the thiol ester composition of expecting and any mol ratio of polyvalent alcohol oh group.In some embodiment, the mol ratio of hydroxy-acid group and polyvalent alcohol oh group is more than 0.4.In other embodiments, the mol ratio of hydroxy-acid group and polyvalent alcohol oh group is more than 0.6; Alternatively, more than 0.8; Alternatively, more than 1; Perhaps alternatively, more than 1.1.In other embodiments, the molar ratio range of hydroxy-acid group and polyvalent alcohol oh group can be from 0.4 to 1.3; Alternatively, from 0.6 to 1.2; Perhaps alternatively, from 0.8 to 1.1.

[00249] aspect some, the reaction between polyvalent alcohol and sulfur-bearing polyol carboxylic acid and/or the sulfur-bearing polyol carboxylic acid derivative is by catalytic.In some embodiment, catalyzer is a mineral acid, as sulfuric acid or phosphoric acid.In other embodiments, catalyzer is an organic acid.For example in embodiments, organic acid is methylsulfonic acid or toluenesulphonic acids.The catalyzer of other adequate types will become apparent to those skilled in the art that and will be considered within the scope of the invention.

[00250] reaction of polyvalent alcohol and sulfur-bearing polyol carboxylic acid and/or sulfur-bearing polyol carboxylic acid derivative can take place in batch-type reactor or flow reactor, as described here.Reaction between polyvalent alcohol and sulfur-bearing polyol carboxylic acid and/or the sulfur-bearing polyol carboxylic acid derivative can be carried out can forming under any temperature of thiol ester.In some embodiment, polyvalent alcohol and sulfur-bearing polyol carboxylic acid and/or sulfur-bearing polyol carboxylic acid derivative can react in temperature more than 20 ℃.In other embodiments, polyvalent alcohol and sulfur-bearing polyol carboxylic acid and/or sulfur-bearing polyol carboxylic acid derivative can react in temperature more than 50 ℃; Alternatively, more than 75 ℃; Perhaps alternatively, more than 100 ℃.Still in other embodiments, polyvalent alcohol and sulfur-bearing polyol carboxylic acid and/or sulfur-bearing polyol carboxylic acid derivative can react in 20 ℃ to 250 ℃ temperature range; Alternatively, from 50 ℃ to 200 ℃; Alternatively, from 75 ℃ to 175 ℃; Perhaps alternatively, from 100 ℃ to 150 ℃.

[00251] the reaction required time of polyvalent alcohol and sulfur-bearing polyol carboxylic acid and/or sulfur-bearing polyol carboxylic acid derivative can be to form the described required any time of thiolic acid ester oil.Generally speaking, the reaction times of polyvalent alcohol and sulfur-bearing polyol carboxylic acid and/or sulfur-bearing polyol carboxylic acid derivative is at least 5 minutes.In some embodiment, the reaction times is at least 30 minutes; Alternatively, at least 1 hour; Perhaps alternatively, at least 2 hours.Still in other embodiments, reaction time range is from 5 minutes to 72 hours; Alternatively, from 30 minutes to 48 hours; Alternatively, from 1 hour to 36 hours; Perhaps alternatively, from 2 hours to 24 hours.

[00252] when using flow reactor, weight hourly space velocity can be used to produce the thiol ester of expectation for from 0.1 to 5 raw polyol weight unsaturated ester.Alternatively, the weight hourly space velocity scope of raw polyol is between 0.1 to 5; Alternatively, from 0.1 to 2.Alternatively, the weight hourly space velocity of raw polyol ester is 0.1; Alternatively, the weight hourly space velocity of raw polyol is 0.25; Perhaps alternatively, the weight hourly space velocity of raw polyol is 2.

[00253] reaction between polyvalent alcohol and sulfur-bearing polyol carboxylic acid and/or the sulfur-bearing polyol carboxylic acid derivative can be carried out under any reaction pressure that makes polyvalent alcohol and sulfur-bearing polyol carboxylic acid and/or sulfur-bearing polyol carboxylic acid derivative maintenance liquid state.In some embodiment, the reaction between polyvalent alcohol and sulfur-bearing polyol carboxylic acid and/or the sulfur-bearing polyol carboxylic acid derivative can be carried out under the condition of 0psia to 2000psia in pressure range.In other embodiments, the reaction pressure scope is from 0psia to 1000psia; Alternatively, from 0 to 500psia; Perhaps alternatively, from 0 to 300psia.

[00254] in some embodiment, after the method for producing thiol ester by polyvalent alcohol and sulfur-bearing polyol carboxylic acid and/or sulfur-bearing polyol carboxylic acid derivatives reaction can comprise further that polyvalent alcohol and sulfur-bearing polyol carboxylic acid and/or sulfur-bearing polyol carboxylic acid derivative are finished reaction, excessive or residual polyvalent alcohol, sulfur-bearing polyol carboxylic acid and/or sulfur-bearing polyol carboxylic acid derivative are removed this step.In some embodiment, thiol ester is through the vacuum removing residue.In some embodiment, thiol ester is through the vacuum removing residue in the temperature range between 25 ℃ to 250 ℃; Perhaps alternatively, between 50 ℃ to 200 ℃.In other embodiments, thiol ester is to spray with rare gas element, to remove excessive polyvalent alcohol, sulfur-bearing polyol carboxylic acid and/or sulfur-bearing polyol carboxylic acid derivative.In some embodiment, thiol ester is to spray with rare gas element in the temperature range between 25 ℃ to 250 ℃; Perhaps alternatively, between 50 ℃ to 200 ℃.Aspect some, rare gas element is a nitrogen.Generally speaking, comprise polyvalent alcohol excessive below 5, sulfur-bearing polyol carboxylic acid or sulfur-bearing polyol carboxylic acid derivative through the thiol ester of removing or sprayed.In other embodiments, comprise polyvalent alcohol excessive below the 2wt.%, sulfur-bearing polyol carboxylic acid and/or sulfur-bearing polyol carboxylic acid derivative through the thiol ester of removing or sprayed; Alternatively, following excessive polyvalent alcohol, sulfur-bearing polyol carboxylic acid and/or the sulfur-bearing polyol carboxylic acid derivative of 1wt.%; Perhaps alternatively, following excessive polyvalent alcohol, sulfur-bearing polyol carboxylic acid and/or the sulfur-bearing polyol carboxylic acid derivative of 0.5wt.%.

The preparation method of hydroxyl thiol ester composition

[00255] the present invention has advantageously provided the production method of hydroxyl thiol ester, as embodiment of the present invention.As a kind of embodiment, the present invention includes a kind of production method of hydroxyl thiol ester.This method comprises makes hydrogen sulfide contact with epoxidation unsaturated ester composition, and hydrogen sulfide and this epoxidation unsaturated ester are reacted, and forms the step of hydroxyl thiol ester.As another embodiment of the present invention, provide the another kind of production method of hydroxyl thiol ester.In this embodiment, this method comprises that the composition of the carboxylic acid derivative that makes composition that contains polyvalent alcohol and the carboxylic acid that comprises hydroxyl mercaptan or hydroxyl mercaptan contacts, and the carboxylic acid of polyvalent alcohol and this hydroxyl mercaptan or the carboxylic acid derivative of hydroxyl mercaptan are reacted to form the step of hydroxyl thiol ester.

Derive from the hydroxyl thiol ester of hydrogen sulfide and epoxidation unsaturated ester composition

[00256] as a kind of embodiment of the present invention, the hydroxyl thiol ester composition can be made by a kind of method, this method comprises hydrogen sulfide is contacted with epoxidation unsaturated ester composition, and hydrogen sulfide and this epoxidation unsaturated ester are reacted to produce the step of hydroxyl thiol ester composition.

[00257] in some embodiment, epoxidation unsaturated ester composition comprises that each epoxidation unsaturated ester molecule contains the epoxidation unsaturated ester of average at least 1 ester group and average at least 1 epoxide group.

[00258] production of hydroxyl thiol ester composition or preparation method can be applied to any epoxidation unsaturated ester described herein, and are used to produce any hydroxyl thiol ester described herein.The production method of hydroxyl thiol ester also can comprise any as described here extra processing step or processing condition.In addition, the production method of hydroxyl thiol ester can form any hydroxyl thiol ester described herein.

[00259] in some embodiment, epoxidation unsaturated ester composition is an epoxidation natural origin oil.In some embodiment, epoxidation unsaturated ester composition is a soya-bean oil.The epoxidation unsaturated ester composition of other adequate types comprises natural origin oil described herein, will become apparent to those skilled in the art that and will be included in the scope of the present invention.

[00260] aspect some, the hydroxyl thiol ester is by hydrogen sulfide being contacted under the reaction conditions and under the situation that optional catalyst exists with epoxidation natural origin oil, forming the hydroxyl thiol ester and prepare.In some embodiment, catalyzer can be heterogeneous catalyst or homogeneous catalyst.The appropriate catalyst example illustrates at this.Other type appropriate catalyst will become apparent to those skilled in the art that and will be considered within the scope of the invention.

[00261] aspect some, the reaction of epoxidation unsaturated ester is to take place under the condition that has solvent to exist.In others, the reaction between epoxidation unsaturated ester and the hydrogen sulfide takes place under solvent-free substantially condition.Comprise exist solvent aspect, solvent is selected from aliphatic hydrocrbon, ether, aromatic compound or their composition.Generally speaking, solvent is no matter its chemical species comprises from 1 to 20 carbon atom; Perhaps alternatively, from 3 to 10 carbon atoms.When solvent comprised aliphatic hydrocrbon, this aliphatic hydrocrbon was butane, Trimethylmethane, pentane, hexane, heptane, octane or its arbitrary mixture.When solvent comprised aromatic compound, this aromatic compound was benzene,toluene,xylene, ethylbenzene or its arbitrary mixture.When solvent comprised ether, this ether was diethyl ether, dipropyl ether, tetrahydrofuran (THF) or its arbitrary mixture.Other suitable solvent will become apparent to those skilled in the art that and will be considered within the scope of the invention.

[00262] when solvent was used to reaction between hydrogen sulfide and the epoxidation unsaturated ester, quantity of solvent can be any consumption that reaction is had promoter action.In some embodiment, the quality of solvent is below 30 times of epoxidation unsaturated ester quality.In other embodiments, the quality of solvent is below 20 times of epoxidation unsaturated ester quality; Alternatively, below 15 of epoxidation unsaturated ester quality times; Alternatively, below 10 of epoxidation unsaturated ester quality times; Perhaps alternatively, epoxidation unsaturated ester quality below 5 times.In other embodiments, the quality of solvent is 2 to 20 times of epoxidation unsaturated ester quality; Alternatively, 3 of epoxidation unsaturated ester quality to 15 times; Alternatively, 4 of epoxidation unsaturated ester quality to 15 times; Perhaps alternatively, 5 to 10 of epoxidation unsaturated ester quality times.

[00263] ratio (after this being called " mol ratio of hydrogen sulfide and epoxide group ") of epoxide group molar equivalent can be to produce the hydrogen sulfide of hydroxyl thiol ester of expectation and any mol ratio of epoxide group in the hydrogen sulfide that uses in hydroxyl thiol ester production process and the epoxidation unsaturated ester.The molar equivalent of epoxidation unsaturated ester epoxidation group can calculate with following equation:

\frac{EUESMass}{EUESGMW} \times EUESEpoxide

In this equation, EUES GMW is the mean molal quantity of epoxidation unsaturated ester, and EUES Mass is the quality of epoxidation unsaturated ester, and EUES Epoxide is the epoxide group mean number of each epoxidation unsaturated ester molecule.In some embodiment, the mol ratio of hydrogen sulfide and epoxide group is more than 0.2.In other embodiments, the mol ratio of hydrogen sulfide and epoxide group is more than 0.5; Alternatively, more than 1; Perhaps alternatively, more than 2.In other embodiments, the molar ratio range of hydrogen sulfide and epoxide group is from 0.2 to 5; Alternatively, from 0.5 to 4; Perhaps alternatively, from 0.75 to 3.In some embodiment, the mol ratio of hydrogen sulfide and epoxide group is more than 2.In other embodiments, the mol ratio of hydrogen sulfide and epoxide group is more than 5; Alternatively, more than 10; Alternatively, more than 15; Perhaps alternatively, more than 20.In other embodiments, the mol ratio of hydrogen sulfide and epoxide group can be from 0.2 to 500; Alternatively, from 0.5 to 400; Alternatively, from 1 to 300; Alternatively, from 2 to 250; Alternatively, from 5 to 200; Perhaps alternatively, from 10 to 100.

[00264] reaction of epoxidation unsaturated ester and hydrogen sulfide can take place in batch-type reactor or flow reactor.The batch-type of adequate types and flow reactor are as described here.The batch-type of other type and flow reactor will become apparent to those skilled in the art that and will be considered within the scope of the invention.

[00265] epoxidation unsaturated ester and hydrogen sulfide reaction required time can be to form the described needed any time of hydroxyl thiol ester.Generally speaking, the reaction required time of epoxidation unsaturated ester and hydrogen sulfide is at least 15 minutes.In some embodiment, the reaction required time scope of unsaturated ester and hydrogen sulfide is from 15 minutes to 72 hours; Alternatively, from 30 minutes to 48 hours; Alternatively, from 45 minutes to 36 hours.

[00266] in some embodiment, the hydroxyl thiol ester composition comprises the hydroxyl thiol ester molecule that contains the above mercaptan sulfur of average 2.5wt.%.In some embodiment, the hydroxyl thiol ester composition comprises the hydroxyl thiol ester molecule that contains the above mercaptan sulfur of average 5wt.%.Alternatively, in some embodiment, hydroxyl thiol ester molecule contains average 8 to 10wt.% mercaptan sulfur.

[00267] in others, the production method of hydroxyl thiol ester composition comprises produces such hydroxyl thiol ester molecule, the average sulfide group that contains more than 40% in the whole side chains of its sulfur compound ester.Other embodiment that the hydroxyl thiol ester comprises the whole side chain per-cents of sulfur compound ester as described here.

[00268] in embodiments, the production method of hydroxyl thiol ester is removed this step of residual hydrogen sulfide after further being included in hydrogen sulfide and epoxidation unsaturated ester composition react.In some embodiment, the hydroxyl thiol ester is through the vacuum removing residue.In some embodiment, the hydroxyl thiol ester is through the vacuum removing residue in the temperature range between 25 ℃ to 250 ℃; Perhaps alternatively, between 50 ℃ to 200 ℃.In other embodiments, the hydroxyl thiol ester sprays to remove hydrogen sulfide with rare gas element.In some embodiment, the hydroxyl thiol ester is to spray to remove hydrogen sulfide with rare gas element in the temperature range between 25 ℃ to 250 ℃; Perhaps alternatively, between 50 ℃ to 200 ℃.Aspect some, rare gas element is a nitrogen.Generally speaking, comprise hydrogen sulfide below the 0.1wt.% through the hydroxyl thiol ester of removing or sprayed.In other embodiments, comprise hydrogen sulfide below the 0.05wt.% through the hydroxyl thiol ester of removing or sprayed; Alternatively, the following hydrogen sulfide of 0.025wt.%; Perhaps alternatively, the following hydrogen sulfide of 0.01wt.%.

[00269] reaction between hydrogen sulfide and the epoxidation unsaturated ester can be carried out can forming under any temperature of hydroxyl thiol ester.In some embodiment, epoxidation unsaturated ester and hydrogen sulfide can react under the temperature of reaction more than-20 ℃.In other embodiments, temperature of reaction is more than 0 ℃; Alternatively, more than 20 ℃; Alternatively, more than 50 ℃; Perhaps alternatively, more than 80 ℃.Still in other embodiments, range of reaction temperature is from-20 ℃ to 200 ℃; Alternatively, from 20 ℃ to 170 ℃; Perhaps alternatively, from 80 ℃ to 140 ℃.

[00270] reaction between epoxidation unsaturated ester and the hydrogen sulfide can be carried out under any reaction pressure of the essential part maintenance liquid state that makes hydrogen sulfide.In some embodiment, the reaction pressure scope is from 100psig to 2000psig.In other embodiments, the reaction pressure scope is to 1000psig from 150; Perhaps alternatively, from 200 to 600psig.

[00271] on the other hand, the production method of hydroxyl thiol ester can be produced epoxide group and thiol group mol ratio at the hydroxyl thiol ester below 3.3.On the other hand, the production method of hydroxyl thiol ester can be produced epoxide group and thiol group mol ratio at the hydroxyl thiol ester below 2.The epoxide group of other hydroxyl thiol ester and thiol group mol ratio are as described here.Alternatively, the epoxide group of hydroxyl thiol ester and thiol group mol ratio can be below 1.5; Alternatively, below 1.0; Alternatively, below 0.5; Alternatively, below 0.25; Perhaps alternatively, below 0.1.In other embodiments, the hydroxyl thiol ester can not contain epoxide group substantially.

[00272] on the other hand, the production method of hydroxyl thiol ester can be produced the hydroxyl thiol ester that at least 20% side chain comprises the Alpha-hydroxy thiol group.Other hydroxyl thiol ester embodiment that contains the per-cent of the side chain that comprises the Alpha-hydroxy thiol group in the hydroxyl thiol ester is described at this.

Hydroxyl thiol ester from the carboxylic acid derivative of polyvalent alcohol and hydroxyl mercaptan

As another embodiment of the invention, advantageously provided the production method of another kind of hydroxyl thiol ester.In this embodiment, this production method comprises following each step: the composition that makes composition that contains polyvalent alcohol and the carboxylic acid that comprises hydroxyl mercaptan and/or contain the carboxylic acid derivative of mercaptan contacts; And the carboxylic acid of polyvalent alcohol and hydroxyl mercaptan and/or the carboxylic acid derivative of hydroxyl mercaptan are reacted, to form the hydroxyl thiol ester composition.This method can be applied to carboxylic acid or any carboxylic acid derivative that contains mercaptan of any polyvalent alcohol described herein, any hydroxyl mercaptan.The production method of hydroxyl thiol ester composition also can comprise any extra processing step or processing condition described herein.In addition, the production method of hydroxyl thiol ester composition can form any thiol ester described herein.

[00273] in some embodiment, the hydroxyl thiol ester composition comprises the hydroxyl thiol ester molecule of average at least 1 ester group of each hydroxyl thiol ester molecule and average at least 1 the Alpha-hydroxy thiol group of each hydroxyl thiol ester molecule.

[00274] (for example: the hydroxy thiol carboxylate methyl ester) contact, the polyvalent alcohol that is used to produce the hydroxyl thiol ester can be any polyvalent alcohol or polyol blends that produces described sulfur-bearing alcohol ester by making polyvalent alcohol and hydroxy thiol carboxylic acid and/or hydroxy thiol carboxylic acid equivalent.

[00275] on the one hand, the polyvalent alcohol that is used to produce the hydroxyl thiol ester can comprise from 2 to 20 carbon atoms.In other embodiments, polyvalent alcohol comprises from 2 to 10 carbon atoms; Alternatively, 2 to 7 carbon atoms; Alternatively, 2 to 5 carbon atoms.In further embodiment, polyvalent alcohol can be the mixture that contains the polyvalent alcohol of average 2 to 20 carbon atoms; Alternatively, average 2 to 10 carbon atoms; Alternatively, average 2 to 7 carbon atoms; Alternatively, average 2 to 5 carbon atoms.

[00276] on the other hand, the polyvalent alcohol that is used to produce the hydroxyl thiol ester can contain the oh group of producing the required any number of hydroxyl thiol ester as described here.In certain embodiments, polyvalent alcohol contains 2 oh groups; Alternatively, 3 oh groups; Alternatively, 4 oh groups; Alternatively, 5 oh groups; Perhaps alternatively, 6 oh groups.In other embodiments, polyvalent alcohol comprises at least 2 oh groups; Alternatively, at least 3 oh groups; Alternatively, at least 4 oh groups; Perhaps alternatively, at least 5 oh groups; At least 6 oh groups.Still in other embodiments, polyvalent alcohol comprises 2 to 8 oh groups; Alternatively, 2 to 4 oh groups; Perhaps alternatively, 4 to 8 oh groups.

[00277] further, the polyvalent alcohol that is used to produce the hydroxyl thiol ester is a polyol blends.In one embodiment, polyol blends contains on average at least 1.5 oh groups of each polyvalent alcohol molecule.In other embodiments, polyol blends contains on average at least 2 oh groups of each polyvalent alcohol molecule; Alternatively, average at least 2.5 oh groups of each polyvalent alcohol molecule; Alternatively, average at least 3.0 oh groups of each polyvalent alcohol molecule; Perhaps alternatively, average at least 4 oh groups of each polyvalent alcohol molecule.Still in other embodiments, polyol blends contains average 1.5 to 8 oh groups of each polyvalent alcohol molecule; Alternatively, average 2 to 6 oh groups of each polyvalent alcohol molecule; Alternatively, average 2.5 to 5 oh groups of each polyvalent alcohol molecule; Alternatively, average 3 to 4 oh groups of each polyvalent alcohol molecule; Alternatively, average 2.5 to 3.5 oh groups of each polyvalent alcohol molecule; Perhaps alternatively, average 2.5 to 4.5 oh groups of each polyvalent alcohol molecule.

[00278] still on the other hand, be used to produce the polyvalent alcohol of hydroxyl thiol ester or polyol blends and have molecular weight or molecular-weight average below 500.In other embodiments, polyvalent alcohol or polyol blends have molecular weight or the molecular-weight average below 300; Alternatively, below 200; Alternatively, below 150; Perhaps alternatively, below 100.

[00279] by polyvalent alcohol and hydroxy thiol carboxylic acid and/or hydroxy thiol carboxylic acid equivalent are contacted, the hydroxy thiol carboxylic acid and/or the hydroxy thiol carboxylic acid equivalent that are used to produce the hydroxyl thiol ester can be the mixtures that can produce any hydroxy thiol mixture of carboxylic acids that comprises the hydroxy thiol carboxylic acid of described hydroxyl mercaptan ester, any hydroxy thiol carboxylic acid equivalent or comprise the hydroxy thiol carboxylic acid equivalent.When referring to feature hydroxy thiol carboxylic acid equivalent or hydroxy thiol carboxylic acid equivalent, when character such as carbonatoms, average carbon atom number, molecular weight or molecular-weight average, thiol group number and thiol group mean number, the reader is to be understood that these character will be applied to add the part mercaptan carboxylic acid equivalent that forms thiol ester in the polyvalent alcohol.

[00280] on the one hand, hydroxy thiol carboxylic acid and/or the hydroxy thiol carboxylic acid equivalent that is used to produce thiol ester comprises from 2 to 28 carbon atoms.In one embodiment, hydroxy thiol carboxylic acid and/or hydroxy thiol carboxylic acid equivalent comprise from 4 to 26 carbon atoms; Alternatively, from 8 to 24 carbon atoms; Alternatively, from 12 to 24 carbon atoms; Perhaps alternatively, from 14 to 20 carbon atoms.In other embodiments, the mixture that comprises the mixture of hydroxy thiol carboxylic acid and/or comprise the hydroxy thiol carboxylic acid equivalent contains each carboxylic acid and/or average 2 to 28 carbon atoms of carboxylic acid equivalent; Alternatively, 4 to 26 carbon atoms of each carboxylic acid and/or carboxylic acid equivalent; Alternatively, 8 to 24 carbon atoms of each carboxylic acid and/or carboxylic acid equivalent; Alternatively, 12 to 24 carbon atoms of each carboxylic acid and/or carboxylic acid equivalent; Perhaps alternatively, 14 to 20 carbon atoms of each carboxylic acid and/or carboxylic acid equivalent.

[00281] on the other hand, hydroxy thiol carboxylic acid and/or the hydroxy thiol carboxylic acid equivalent that is used to produce thiol ester contains at least 1 thiol group; Alternatively, at least 2 thiol groups.In some embodiment, the mixture that comprises the mixture of hydroxy thiol carboxylic acid and/or comprise the hydroxy thiol carboxylic acid equivalent contains each carboxylic acid and/or average 0.5 to 3 thiol group of carboxylic acid equivalent; Alternatively, average 1 to 2 thiol group of each carboxylic acid and/or carboxylic acid equivalent.

[00282] on the other hand, hydroxy thiol carboxylic acid and/or the hydroxy thiol carboxylic acid equivalent that is used to produce thiol ester contains at least 1 oh group; Alternatively, at least 2 oh groups.In some embodiment, the mixture that comprises the mixture of hydroxy thiol carboxylic acid and/or comprise the hydroxy thiol carboxylic acid equivalent contains each carboxylic acid and/or average 0.5 to 3 oh group of carboxylic acid equivalent; Alternatively, average 1 to 2 oh group of each carboxylic acid and/or carboxylic acid equivalent.

[00283] on the other hand, be used to produce the hydroxy thiol carboxylic acid of hydroxyl thiol ester and/or hydroxy thiol carboxylic acid equivalent molecular weight more than 100 is arranged; Alternatively, more than 180; Alternatively, more than 240; Perhaps alternatively, more than 260.In other embodiments, hydroxy thiol carboxylic acid and/or hydroxy thiol carboxylic acid equivalent have from 100 to 500 molecular weight; Alternatively, from 120 to 420; Alternatively, from 180 to 420; Alternatively, from 240 to 420; Perhaps alternatively, from 260 to 360.In some embodiment, the mixture that comprises the mixture of hydroxy thiol carboxylic acid and/or comprise the hydroxy thiol carboxylic acid equivalent has each carboxylic acid and/or the molecular-weight average of carboxylic acid equivalent more than 100; Alternatively, each carboxylic acid and/or carboxylic acid equivalent are more than 180; Alternatively, each carboxylic acid and/or carboxylic acid equivalent are more than 240; Perhaps alternatively, each carboxylic acid and/or carboxylic acid equivalent are more than 260.Still in other embodiments, comprise the mixture of hydroxy thiol carboxylic acid and/or comprise the molecular-weight average that the mixture of hydroxy thiol carboxylic acid equivalent has each carboxylic acid and/or carboxylic acid equivalent from 100 to 500; Alternatively, each carboxylic acid and/or carboxylic acid equivalent from 120 to 420; Alternatively, each carboxylic acid and/or carboxylic acid equivalent from 180 to 420; Alternatively, each carboxylic acid and/or carboxylic acid equivalent from 240 to 420; Perhaps alternatively, each carboxylic acid and/or carboxylic acid equivalent from 260 to 360.

[00284] aspect some, the reaction between the carboxylic acid of polyvalent alcohol and hydroxyl mercaptan and/or the carboxylic acid derivative of hydroxyl mercaptan is to take place under the situation that has solvent to exist.In others, the reaction between the carboxylic acid of polyvalent alcohol and hydroxyl mercaptan and/or the carboxylic acid derivative of hydroxyl mercaptan takes place under solvent-free substantially situation.In the reaction between the carboxylic acid derivative of the carboxylic acid of polyvalent alcohol and hydroxyl mercaptan and/or hydroxyl mercaptan be take place under the situation that is having solvent to exist aspect, solvent is to be selected from aliphatic hydrocrbon, ether, aromatic compound or its arbitrary combination.Generally speaking, solvent is no matter its chemical species comprises from 1 to 20 carbon atom; Alternatively, from 3 to 10 carbon atoms.When solvent comprised aliphatic hydrocrbon, this aliphatic hydrocrbon was butane, Trimethylmethane, pentane, hexane, heptane, octane or its arbitrary mixture.When solvent comprised aromatic compound, this aromatic compound was benzene,toluene,xylene, ethylbenzene or its arbitrary mixture.When solvent comprised ether, this ether was diethyl ether, dipropyl ether, tetrahydrofuran (THF) or its arbitrary mixture.

[00285] when solvent was used to reaction between the carboxylic acid derivative of the carboxylic acid of polyvalent alcohol and hydroxyl mercaptan and/or hydroxyl mercaptan, quantity of solvent can be any consumption that reaction is had promoter action.In some embodiment, the quality of solvent is the carboxylic acid of hydroxyl mercaptan and/or below 30 times of carboxylic acid derivatives amount of hydroxyl mercaptan.In other embodiments, the quality of solvent is below 20 times of hydroxyl thiol ester quality; Alternatively, the carboxylic acid derivatives amount of the carboxylic acid of hydroxyl mercaptan and/or hydroxyl mercaptan below 15 times; Alternatively, the carboxylic acid derivatives amount of the carboxylic acid of hydroxyl mercaptan and/or hydroxyl mercaptan below 10 times; Perhaps alternatively, the carboxylic acid derivatives amount of the carboxylic acid of hydroxyl mercaptan and/or hydroxyl mercaptan below 5 times.In other embodiments, the quality of solvent is 2 to 20 times of carboxylic acid derivatives amount of the carboxylic acid of hydroxyl mercaptan and/or hydroxyl mercaptan; Alternatively, 3 to 15 of the carboxylic acid derivatives amount of the carboxylic acid of hydroxyl mercaptan and/or hydroxyl mercaptan times; Perhaps alternatively, 5 to 10 of the carboxylic acid derivatives amount of the carboxylic acid of hydroxyl mercaptan and/or hydroxyl mercaptan times.

The carboxylic acid derivative of the hydroxyl mercaptan that [00286] uses in the production process of hydroxyl thiol ester and/or the carboxylic acid derivative hydroxy-acid group equivalent of hydroxyl mercaptan and the normal mol ratio of polyvalent alcohol oh group (after this being called " mol ratio of hydroxy-acid group and polyvalent alcohol oh group ") can be to produce the hydroxy-acid group of the hydroxyl thiol ester of expecting and any mol ratio of polyvalent alcohol oh group.In some embodiment, the mol ratio of hydroxy-acid group and polyvalent alcohol oh group is more than 0.4.In other embodiments, the mol ratio of hydroxy-acid group and polyvalent alcohol oh group is more than 0.6; Alternatively, more than 0.8; Alternatively, more than 1; Perhaps alternatively, more than 1.1.In other embodiments, the molar ratio range of hydroxy-acid group and polyvalent alcohol oh group can be from 0.4 to 1.3; Alternatively, from 0.6 to 1.2; Perhaps alternatively, from 0.8 to 1.1.

[00287] aspect some, the reaction between the carboxylic acid of polyvalent alcohol and hydroxyl mercaptan and/or the carboxylic acid derivative of hydroxyl mercaptan is by catalytic.In some embodiment, catalyzer is a mineral acid, as sulfuric acid or phosphoric acid.In other embodiments, catalyzer is an organic acid.For example in embodiments, organic acid is methylsulfonic acid or toluenesulphonic acids.The catalyzer of other adequate types will become apparent to those skilled in the art that and will be considered within the scope of the invention.

[00288] reaction of the carboxylic acid derivative of the carboxylic acid of polyvalent alcohol and hydroxyl mercaptan and/or hydroxyl mercaptan can take place in batch-type reactor or flow reactor, as described here.Reaction between the carboxylic acid derivative of the carboxylic acid of polyvalent alcohol and hydroxyl mercaptan and/or hydroxyl mercaptan can be carried out can forming under any temperature of hydroxyl thiol ester.In some embodiment, the carboxylic acid of polyvalent alcohol and hydroxyl mercaptan and/or the carboxylic acid derivative of hydroxyl mercaptan can react in temperature more than 20 ℃.In other embodiments, the carboxylic acid derivative of the carboxylic acid of polyvalent alcohol and hydroxyl mercaptan and/or hydroxyl mercaptan can react in temperature more than 50 ℃; Alternatively, more than 75 ℃; Perhaps alternatively, more than 100 ℃.Still in other embodiments, the carboxylic acid derivative of the carboxylic acid of polyvalent alcohol and hydroxyl mercaptan and/or hydroxyl mercaptan can react in 20 ℃ to 250 ℃ temperature range; Alternatively, from 50 ℃ to 200 ℃; Alternatively, from 75 ℃ to 175 ℃; Perhaps alternatively, from 100 ℃ to 150 ℃.

[00289] the reaction required time of the carboxylic acid derivative of the carboxylic acid of polyvalent alcohol and hydroxyl mercaptan and/or hydroxyl mercaptan can be to form the described required any time of hydroxyl thiol ester composition.Generally speaking, the reaction times is at least 5 minutes.In some embodiment, the reaction times is at least 30 minutes; Alternatively, at least 1 hour; Perhaps alternatively, at least 2 hours.Still in other embodiments, reaction time range is from 5 minutes to 72 hours; Alternatively, from 30 minutes to 48 hours; Alternatively, from 1 hour to 36 hours; Perhaps alternatively, from 2 hours to 24 hours.

[00290] reaction between the carboxylic acid derivative of the carboxylic acid of polyvalent alcohol and hydroxyl mercaptan and/or hydroxyl mercaptan can be carried out under the carboxylic acid derivative of carboxylic acid that makes polyvalent alcohol and hydroxyl mercaptan and/or hydroxyl mercaptan keeps liquid any reaction pressure.In some embodiment, the pressure range of reaction is from 0psia to 2000psia.In other embodiments, the pressure range of reaction is from 0psia to 1000psia; Alternatively, from 0psia to 500psia; Perhaps alternatively, from 0psia to 300psia.

[00291] in some embodiment, the carboxylic acid by polyvalent alcohol and hydroxyl mercaptan and/or the carboxylic acid derivative of hydroxyl mercaptan react after carboxylic acid derivative that the method for producing the hydroxyl thiol ester can further be included in the carboxylic acid of polyvalent alcohol and hydroxyl mercaptan or hydroxyl mercaptan finishes reaction, and the carboxylic acid of excessive or residual polyvalent alcohol, hydroxyl mercaptan and/or the carboxylic acid derivative of hydroxyl mercaptan are removed this step.In some embodiment, the hydroxyl thiol ester is through the vacuum removing residue.In some embodiment, the hydroxyl thiol ester is through the vacuum removing residue in the temperature range between 25 ℃ to 250 ℃; Perhaps alternatively, between 50 ℃ to 200 ℃.In other embodiments, the hydroxyl thiol ester is to spray with the carboxylic acid derivative of the carboxylic acid of removing excessive polyvalent alcohol, hydroxyl mercaptan and/or hydroxyl mercaptan with rare gas element.In some embodiment, the hydroxyl thiol ester is to spray with rare gas element in the temperature range between 25 ℃ to 250 ℃; Perhaps alternatively, between 50 ℃ to 200 ℃.Aspect some, rare gas element is a nitrogen.Generally speaking, comprise the carboxylic acid of polyvalent alcohol excessive below 5, hydroxyl mercaptan or the carboxylic acid derivative of hydroxyl mercaptan through the hydroxyl thiolic acid ester oil of removing or sprayed.In other embodiments, comprise the carboxylic acid of polyvalent alcohol excessive below the 2wt.%, hydroxyl mercaptan and/or the carboxylic acid derivative of hydroxyl mercaptan through the hydroxyl thiolic acid ester oil of removing or sprayed; Following excessive polyvalent alcohol, the carboxylic acid of hydroxyl mercaptan and/or the carboxylic acid derivative of hydroxyl mercaptan of 1wt.%; Perhaps alternatively, following excessive polyvalent alcohol, the carboxylic acid of hydroxyl mercaptan and/or the carboxylic acid derivative of hydroxyl mercaptan of 0.5wt.%.

The preparation method of the ester of sulfo-acrylate (thioacrylate ester)

[00292], advantageously provided the preparation method of the ester composition that contains the sulfo-acrylate as another embodiment of the present invention.The production method that contains the ester of sulfo-acrylate comprises, thiol ester is contacted with acrylate, and at least one thiol group is converted into the sulfo-acrylate group.This method can be applied to any thiol ester described herein, and is used to produce the ester of any sulfo-acrylate described herein.The production method of the ester of sulfo-acrylate also can comprise any other processing step or processing condition described herein.

[00293] acrylic compound can be to react with thiol group, forms any acrylic compound of sulfo-acrylate group.In some embodiment, acrylic compound can be a vinylformic acid halogenide.In other embodiments, acrylic compound can be a vinylformic acid.Still in other embodiments, acrylic compound can be an acrylic anhydride.

[00294] in some embodiment of the present invention, acrylate composition has following structure:

In the structure of acrylate composition, Y is selected from hydrogen, halogen and OR ⁴And R ⁷, R ⁸And R ⁹Be independently selected from hydrogen, C ₁To C ₂₀Organic group and C ₁To C ₂₀Hydrocarbyl group.In further embodiment, R ⁷, R ⁸And R ⁹Be selected from hydrogen, C ₁To C ₁₀Organic group and C ₁To C ₁₀Hydrocarbyl group; Perhaps alternatively, be selected from C ₁To C ₅Organic group and C ₁To C ₅Hydrocarbyl group.In certain embodiments, R ⁷, R ⁸And R ⁹Be independently selected from hydrogen and methyl group.In some specific embodiment, R ⁸And R ⁹Be hydrogen, and R ⁷Be selected from hydrogen, methyl group or their mixture; Alternatively, R ⁸And R ⁹Be hydrogen, and R ⁷It is methyl group; Perhaps alternatively, R ⁷, R ⁸And R ⁹All be hydrogen.In some embodiment, R ⁴Be independently selected from C ₁To C ₂₀Organic group and C ₁To C ₂₀Hydrocarbyl group; Alternatively, be selected from C ₁To C ₁₀Organic group and C ₁To C ₁₀Hydrocarbyl group; Perhaps alternatively, be selected from C ₁To C ₅Organic group and C ₁To C ₅Hydrocarbyl group.

[00295] in other embodiments, acrylic compound can be an acrylic anhydride, has following structure:

In the structure of this acrylic anhydride, Y is selected from hydrogen, halogen and OR ⁴And R ⁷, R ⁸And R ⁹Be independently selected from hydrogen, C ₁To C ₂₀Organic group and C ₁To C ₂₀Hydrocarbyl group.In further embodiment, R ⁷, R ⁸And R ⁹Be selected from hydrogen, C ₁To C ₁₀Organic group and C ₁To C ₁₀Hydrocarbyl group; Perhaps alternatively, be selected from C ₁To C ₅Organic group and C ₁To C ₅Hydrocarbyl group.In certain embodiments, R ⁷, R ⁸And R ⁹Be independently selected from hydrogen and methyl group.In some specific embodiment, R ⁸And R ⁹Be hydrogen, and R ⁷Be selected from hydrogen, methyl group or their mixture; Alternatively, R ⁸And R ⁹Be hydrogen, and R ⁷It is methyl group; Perhaps alternatively, R ⁷, R ⁸And R ⁹Can be hydrogen.In some embodiment, R ⁴Be independently selected from C ₁To C ₂₀Organic group and C ₁To C ₂₀Hydrocarbyl group; Alternatively, be selected from C ₁To C ₁₀Organic group and C ₁To C ₁₀Hydrocarbyl group; Perhaps alternatively, be selected from C ₁To C ₅Organic group and C ₁To C ₅Hydrocarbyl group.

[00296] in some embodiment of the present invention, the Y in the acrylate composition can be a halogenide.For example: halogenide can be chlorine, bromine and iodine.Acrylate composition can comprise acryloyl chloride, methyl acryloyl chloride and composition thereof.The acrylic anhydride compound can comprise acrylic anhydride, methacrylic anhydride or its mixture.

[00297] aspect some, thiol group is to take place under the situation that is having solvent to exist to the conversion of sulfo-acrylate group.In others, thiol group takes place under solvent-free substantially situation to the conversion of sulfo-acrylate group.To aspect the conversion of sulfo-acrylate group having solvent to exist to take place under the situation, solvent can be aliphatic hydrocrbon, ether, aromatic compound at thiol group.Generally speaking, solvent is no matter its chemical species comprises from 1 to 20 carbon atom; Alternatively, 3 to 10 carbon atoms.When solvent comprised aliphatic hydrocrbon, this aliphatic hydrocrbon was butane, Trimethylmethane, pentane, hexane, heptane, octane or its arbitrary mixture.When solvent comprised aromatic compound, this aromatic compound was benzene,toluene,xylene, ethylbenzene or its arbitrary mixture.When solvent comprised ether, this ether was diethyl ether, dipropyl ether, tetrahydrofuran (THF) or its arbitrary mixture.

[00298] when solvent was used to thiol group to the conversion of sulfo-acrylate group, quantity of solvent can be any consumption that reaction is had promoter action.In some embodiment, the quality of solvent is below 30 times of thiol ester quality.In other embodiments, the quality of solvent is below 20 times of thiol ester quality; Alternatively, below 15 of the thiol ester quality times; Alternatively, below 10 of the thiol ester quality times; Perhaps alternatively, below 5 of the thiol ester quality times.In other embodiments, the quality of solvent is 2 to 20 times of thiol ester quality; Alternatively, 3 of the thiol ester quality to 15 times; Alternatively, 4 of the thiol ester quality to 15 times; Perhaps alternatively, 5 of the thiol ester quality to 10 times.

[00299] aspect some, thiol group is to take place under the condition that is having catalyzer to exist to the conversion of sulfo-acrylate group.In some embodiment, catalyzer is a homogeneous.In some embodiment, catalyzer is an organic amine.Suitable organic amine example comprises triethylamine, tripropyl amine, Tributylamine and pyridine.In other embodiments, catalyzer is a heterogenetic.The appropriate catalyst example comprises Amberlyst A-21 and Amberlyst A-26.Other appropriate catalyst will become apparent to those skilled in the art that and will be considered within the scope of the invention.

[00300] thiol group can carry out under any invert point that thiol group can be converted into the sulfo-acrylate group to the conversion of sulfo-acrylate group.In some embodiment, invert point is more than-20 ℃.In other embodiments, invert point is more than 0 ℃; Alternatively, more than 20 ℃; Alternatively, more than 50 ℃; Alternatively, more than 80 ℃; Perhaps alternatively, more than 100 ℃.Still in other embodiments, the invert point scope is-20 ℃ to 250 ℃; Alternatively, 20 ℃ to 200 ℃; Perhaps alternatively, 50 ℃ to 150 ℃.

[00301] thiol group can be to form the described required any time of sulfo-acrylate ester that contains to the required transformation time of sulfo-acrylate group conversion.Generally speaking, transformation time is at least 5 minutes.In some embodiment, transformation time is at least 15 minutes; Alternatively, at least 30 minutes; Alternatively, at least 45 minutes; Perhaps alternatively, at least 1 hour.Still in other embodiments, the transformation time scope is from 15 minutes to 12 hours; Alternatively, from 30 minutes to 6 hours; Perhaps alternatively, from 45 minutes to 3 hours.

[00302] thiol group transforms and can carry out under any reaction pressure that makes thiol ester and acrylic compound maintenance liquid state to the sulfo-acrylate group.In some embodiment, the pressure range of conversion is from 0psia to 2000psia.In other embodiments, the pressure range of conversion is from 0psia to 1000psia; Perhaps alternatively, from 0psia to 500psia.

The production method of crosslinked thiol ester

[00303], advantageously provided the production method of crosslinked thiol ester composition as a kind of embodiment of the present invention.Minimally, in some embodiment, the production method of crosslinked thiol ester composition comprises makes thiol ester composition contact with oxygenant, and thiol ester composition and oxygenant are reacted, form the thiol ester oligopolymer, this oligopolymer contains at least two thiol ester monomers that connected by poly-sulfide linkage, and this poly-sulfide linkage has-S _Q-structure, Q is the integer more than 1 herein.Disclosed method can be applicable to any thiol ester described herein, to produce any as described here crosslinked thiol ester composition.The production method of crosslinked thiol ester composition also can comprise any as described here other processing step and processing condition.

[00304] on the one hand, oxygenant can be elementary sulfur, oxygen or hydrogen peroxide.In some embodiment, oxygenant can be an elementary sulfur.In other embodiments, oxygenant can be an oxygen.In the embodiment of some peroxygen oxidising agent, oxygenant is an air.In further embodiment, oxygenant is a hydrogen peroxide.

[00305] when using elementary sulfur as oxygenant, the elementary sulfur consumption that is used to form crosslinked thiol ester composition is determined as the function of mercaptan sulfur content in the thiol ester composition.On the one hand, the weight ratio of elementary sulfur and mercaptan sulfur is at least 0.5 in the thiol ester composition.In some embodiment, the weight ratio of elementary sulfur and mercaptan sulfur is at least 5 in the thiol ester composition; Alternatively, at least 10; Alternatively, at least 15; Perhaps alternatively, at least 20.In other embodiments, the weight ratio scope of elementary sulfur and mercaptan sulfur is from 0.5 to 32 in the thiol ester composition; Alternatively, scope is from 1 to 24; Alternatively, scope is from 2 to 16; Perhaps alternatively, scope is from 3 to 10.

[00306] in one aspect, the reaction of thiol ester and elementary sulfur is to take place under the condition that has catalyzer to exist.Catalyzer can be any catalyzer that catalysis is formed at least two poly-sulfide linkages between the thiol ester monomer.In some embodiment, catalyzer is an amine.In further embodiment, catalyzer is a tertiary amine.

[00307] formation of crosslinked thiol ester can take place in batch-type reactor or flow reactor, as described here.The formation of crosslinked thiol ester can be carried out can forming under any temperature of thiol ester.In some embodiment, the formation of crosslinked thiol ester can take place under the temperature more than 25 ℃.In other embodiments, the formation of crosslinked thiol ester can take place under the temperature more than 50 ℃; Alternatively, more than 70 ℃; Perhaps alternatively, more than 80 ℃.Still in other embodiments, the formation of crosslinked thiol ester can take place in 25 ℃ to 150 ℃ temperature range; Alternatively, from 50 ℃ to 150 ℃; Alternatively, from 70 ℃ to 120 ℃; Perhaps alternatively, from 80 ℃ to 110 ℃.

[00308] forming the required time of crosslinked thiol ester can be the required any time of crosslinked thiol ester that forms expectation.Generally speaking, forming the required time of crosslinked thiol ester is at least 15 minutes.In some embodiment, forming the required time of crosslinked thiol ester is at least 30 minutes; Alternatively, at least 1 hour; Perhaps alternatively, at least 2 hours.Still in other embodiments, forming the required time range of crosslinked thiol ester is from 15 minutes to 72 hours; Alternatively, from 30 minutes to 48 hours; Alternatively, from 1 hour to 36 hours; Perhaps alternatively, from 2 hours to 24 hours.

[00309] in some embodiment, the production method of crosslinked thiol ester can further comprise removes residual this step of hydrogen sulfide.In some embodiment, crosslinked thiol ester is through the vacuum removing residue.In some embodiment, crosslinked thiol ester is through the vacuum removing residue in the temperature range between 25 ℃ to 250 ℃; Alternatively, between 50 ℃ to 200 ℃; Perhaps alternatively, between 75 ℃ to 150 ℃.In some embodiment, crosslinked thiolic acid ester oil is to spray to remove residual hydrogen sulfide with rare gas element.In other embodiments, crosslinked thiol ester is to spray with rare gas element in the temperature range between 25 ℃ to 250 ℃; Alternatively, between 50 ℃ to 200 ℃; Perhaps alternatively, between 75 ℃ to 150 ℃.Still in other embodiments, carry out vacuum and remove, spray crosslinked thiol ester with rare gas element simultaneously.Still in other embodiments, carry out vacuum and remove, simultaneously with spraying crosslinked thiol ester in the temperature range of rare gas element between 25 ℃ to 250 ℃; Alternatively, between 50 ℃ to 200 ℃; Perhaps alternatively, between 75 ℃ to 150 ℃.In some embodiment, rare gas element is a nitrogen.

[00310] generally speaking, comprise hydrogen sulfide below the 0.1wt.% through the crosslinked thiol ester of removing or sprayed.In other embodiments, comprise hydrogen sulfide below the 0.05wt.% through the crosslinked thiolic acid ester oil of removing or sprayed; Alternatively, the following hydrogen sulfide of 0.025wt.%; Perhaps alternatively, the following hydrogen sulfide of 0.01wt.%.

The preparation method of sulfur compound ester composition

[00311] the present invention has advantageously provided the preparation method of sulfur compound ester, as embodiment of the present invention.Generally speaking, the sulfur compound ester can prepare with two kinds of methods.As a kind of embodiment of the present invention, the first method that is used to produce the sulfur compound ester comprises makes unsaturated ester contact with mercaptan, and unsaturated ester and mercaptan are reacted, to form the sulfur compound ester.As another embodiment of the present invention, the second method that is used to produce the sulfur compound ester comprises makes the epoxidation unsaturated ester contact with mercaptan sulfide, and both are reacted, to form the sulfur compound ester.The others of two kinds of production methods of sulfur compound ester are as described below.

Sulfur compound ester from unsaturated ester

[00312] sulfur compound ester described herein and sulfur compound ester composition can make mercaptan contact with unsaturated ester and both are reacted by comprising, produce with the method that forms the sulfur compound ester.This method can be applied to any unsaturated ester and mercaptan described herein.The production method of sulfur compound ester also can comprise any other production craft step or processing condition described herein.In addition, the production method of sulfur compound ester can form any sulfur compound ester described herein.

[00313] aspect some, the reaction between mercaptan and the unsaturated ester is to take place under the situation that has solvent to exist.In others, the reaction between mercaptan and the unsaturated ester takes place under solvent-free substantially situation.When reaction occurs in the following time of situation that solvent exists, solvent is to be selected from aliphatic hydrocrbon, ether, aromatic compound, alcohol or its arbitrary combination.Generally speaking, solvent is no matter its chemical species can comprise from 1 to 20 carbon atom; Alternatively, 3 to 10 carbon atoms.When solvent comprised aliphatic hydrocrbon, this aliphatic hydrocrbon was butane, Trimethylmethane, pentane, hexane, heptane, octane or its arbitrary mixture.When solvent comprised aromatic compound, this aromatic compound was benzene,toluene,xylene, ethylbenzene or its arbitrary mixture.When solvent comprised alcohol, this alcohol was methyl alcohol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, 2-methyl-2-propyl alcohol or its arbitrary mixture.When solvent comprised ether, this ether was diethyl ether, dipropyl ether, tetrahydrofuran (THF) or its arbitrary mixture.

[00314] when solvent was used to reaction between mercaptan and the unsaturated ester, the consumption of this solvent can be any consumption that reaction is had promoter action, as the skilled personnel can understand.In some embodiment, the quality of solvent is below 30 times of unsaturated ester quality.In other embodiments, the quality of solvent is below 20 times of unsaturated ester quality; Alternatively, below 15 of the unsaturated ester quality times; Alternatively, below 10 of the unsaturated ester quality times; Perhaps alternatively, below 5 of the unsaturated ester quality times.In other embodiments, the quality of solvent is 2 to 20 times of unsaturated ester quality; Alternatively, 3 of the unsaturated ester quality to 15 times; Alternatively, 4 of the unsaturated ester quality to 15 times; Perhaps alternatively, 5 of the unsaturated ester quality to 10 times.

[00315] mol ratio (after this being called " mol ratio of mercaptan and carbon-carbon double bond ") of mercaptan that uses in sulfur-bearing alcohol ester production process and unsaturated ester carbon-carbon double bond molar equivalent can be to produce the mercaptan of the sulfur-bearing alcohol ester of expecting and any mol ratio of carbon-carbon double bond.Unsaturated ester carbon-carbon double bond molar equivalent can calculate with following equation:

\frac{UESMass}{UESGMW} \times UESC = C

In this equation, UES GMW is the mean molal quantity of unsaturated ester, and UES Mass is the quality of unsaturated ester, and UES C=C is each unsaturated ester molecule pair key mean numbers.In some embodiment, mercaptan and carbon-carbon double bond mol ratio are more than 0.25.In other embodiments, mercaptan and carbon-carbon double bond mol ratio are more than 0.5; Alternatively, more than 0.75; Alternatively, more than 1; Alternatively, more than 1.25; Perhaps alternatively, more than 1.5.In other embodiments, mercaptan and carbon-carbon double bond mol ratio can be 0.25 to 2; Alternatively, 0.5 to 1.5; Perhaps alternatively, 0.75 to 1.25.

[00316] aspect some, the reaction between mercaptan and the unsaturated ester is by catalytic.The reaction of mercaptan and unsaturated ester can be by heterogeneous catalyst or homogeneous catalyst catalysis, as described here.Aspect some, the reaction between mercaptan and the unsaturated ester is caused by radical initiator or ultraviolet irradiation, as described here.

[00317] when using heterogeneous catalyst, this heterogeneous an acidic catalyst is selected from acid clay, zeolite, cobalt/molybdenum oxide supported catalyst or nickel/molybdenum load oxide catalyst.The appropriate catalyst example is described at this.

[00318] radical initiator can be any radical initiator that can form free radical under heat or light photolysis.Generally speaking, radical initiator be selected from contain-the N=N-group or-the total classification of compound of O-O-group.The radical initiator of concrete kind comprises diazonium compound, dialkyl peroxide, hydrogen peroxide and peroxyester.Concrete initiator comprises nitrogen benzide, 2,2 '-azo two (2-methyl propionitrile), 4,4 '-azo two (4-cyanovaleric acid), 1,1 '-azo two (cyclohexane nitrile), 2,2 '-azo two (2-methylpropane), 2,2 '-azo two (2-methyl-prop amidine), dihydrochloride, methyl propionitrile, azodicarboamide, tert-butyl hydroperoxide, ditertiary butyl peroxide, peroxybenzoic acid monooctyl ester.In some embodiment, the mercaptan that free radical caused and the reaction of unsaturated ester are to carry out under ± 50 ℃ of conditions with interior, 1 hour transformation period of radical initiator in temperature of reaction.In other embodiments, temperature of reaction is within ± 25 ℃, 1 hour transformation period of radical initiator; Alternatively, temperature of reaction within ± 20 ℃, 1 hour transformation period of radical initiator; Alternatively, temperature of reaction within ± 15 ℃, 1 hour transformation period of radical initiator; Perhaps alternatively, temperature of reaction within ± 10 ℃, 1 hour transformation period of radical initiator.At the mercaptan of free radical initiation and the reaction of unsaturated ester is that light can be any light that can produce free radical in the embodiment that is caused by the light photolysis.In some embodiment, ultraviolet irradiation only.The light that can produce free radical in other source will be conspicuous for a person skilled in the art, and will be considered within the scope of the invention.

[00319] on the other hand, the reaction of mercaptan and unsaturated ester is caused by ultraviolet irradiation.In these embodiments, ultraviolet irradiation can be any ultraviolet irradiation that can cause mercaptan and unsaturated ester reaction.In some embodiment, ultraviolet irradiation produces by medium pressure mercury lamp.

[00320] reaction of mercaptan and unsaturated ester can take place in batch-type reactor or flow reactor.Any batch-type or flow reactor described herein all can be used in this reaction.Other suitable reactor will be conspicuous for a person skilled in the art, and will be considered within the scope of the invention.

[00321] reaction times of mercaptan and unsaturated ester can be to form the sulfur compound needed any time of ester.Generally speaking, the reaction times is at least 5 minutes.In some embodiment, reaction time range is from 5 minutes to 72 hours; Alternatively, from 10 minutes to 48 hours; Perhaps alternatively, from 15 minutes to 36 hours.

[00322] in some embodiment, the production process of sulfur compound ester is removed any this step of residual mercaptan after further being included in mercaptan and unsaturated ester reaction.In some embodiment, the sulfur compound ester is removed to remove residual mercaptan through vacuum.In some embodiment, the sulfur compound ester is through the vacuum removing residue in the temperature range between 25 ℃ to 250 ℃; Perhaps alternatively, between 50 ℃ to 200 ℃.In other embodiments, the sulfur compound ester sprays to remove residual mercaptan with rare gas element.In some embodiment, the sulfur compound ester is to spray with rare gas element in the temperature range between 25 ℃ to 250 ℃; Perhaps alternatively, between 50 ℃ to 200 ℃.Aspect some, rare gas element is a nitrogen.Generally speaking, comprise mercaptan below the 5wt.% through the sulfur compound ester of removing or sprayed.In other embodiments, comprise mercaptan below the 2wt.% through the sulfur compound ester of removing or sprayed; Alternatively, the following mercaptan of 1wt.%; Perhaps alternatively, the following mercaptan of 0.5wt.%.

[00323] reaction between mercaptan and the unsaturated ester can be carried out forming under any temperature of sulfur compound ester.In some embodiment, mercaptan and unsaturated ester can react under the temperature more than-20 ℃.In other embodiments, temperature of reaction is more than 0 ℃; Alternatively, more than 20 ℃; Alternatively, more than 50 ℃; Alternatively, more than 80 ℃; Perhaps alternatively, more than 100 ℃.Still in other embodiments, mercaptan and unsaturated ester can react under-20 ℃ to 250 ℃ temperature; Alternatively, from 20 ℃ to 200 ℃; Perhaps alternatively, from 80 ℃ to 160 ℃.

[00324] reaction between mercaptan and the unsaturated ester can be carried out under any pressure that makes mercaptan and unsaturated ester maintenance liquid state.In some embodiment, the reaction of mercaptan and unsaturated ester can be carried out under the condition of 0psig to 2000psig in the reaction pressure scope.In other embodiments, the reaction pressure scope is from 0psig to 1000psig; Alternatively, from 0psig to 500psig; Perhaps alternatively, from 0psig to 200psig.

[00325] uses disclosed method, can produce the sulfur compound ester of low carbon-carbon double bond and sulfide group mol ratio.On the one hand, the production method of sulfur compound ester can form carbon-carbon double bond and thiol group mol ratio at the sulfur compound ester below 1.5.The mol ratio of other carbon-carbon double bond and sulfur compound group is disclosed at this.

[00326] in others, the method for producing the sulfur compound ester comprises produces the average sulfur compound ester molecule of 40wt.% at least of sulfur compound ester side chain.The sulfur compound ester comprises that other embodiment of sulfur compound ester side chain per-cent is described at this.

Sulfur compound ester from the epoxidation unsaturated ester

[00327], advantageously provided the another kind of method of producing a class sulfur compound ester, comprising hydroxyl sulfide ester (hydroxy sulfide-containing ester) as another embodiment of the present invention.In this embodiment, hydroxyl sulfide ester and hydroxyl sulfide ester composition can be by comprising the method production of following each step: mercaptan is contacted with the epoxidation unsaturated ester, and both are reacted to produce or to form hydroxyl sulfide ester.This method can be applicable to any mercaptan described herein and/or any epoxidation unsaturated ester.The production method of hydroxyl sulfide ester also can comprise any as described here other processing step or processing condition.In addition, the production method of hydroxyl sulfide ester can form any as described here hydroxyl sulfide ester.

[00328] aspect some, the reaction between mercaptan and the unsaturated ester is to take place under the situation that has solvent to exist.In others, the reaction between mercaptan and the unsaturated ester takes place under solvent-free substantially situation.When reaction occurs in the following time of situation that solvent exists, solvent is selected from aliphatic hydrocrbon, ether, aromatic compound or its arbitrary combination.Generally speaking, solvent is no matter its chemical species can comprise from 1 to 20 carbon atom; Alternatively, 3 to 10 carbon atoms.When solvent comprised aliphatic hydrocrbon, this aliphatic hydrocrbon was butane, Trimethylmethane, pentane, hexane, heptane, octane or its arbitrary mixture.When solvent comprised aromatic compound, this aromatic compound was benzene,toluene,xylene, ethylbenzene or its arbitrary mixture.When solvent comprised ether, this ether was diethyl ether, dipropyl ether, tetrahydrofuran (THF) or its arbitrary mixture.

[00329] when solvent was used to reaction between mercaptan and the epoxidation unsaturated ester, the consumption of this solvent can be any consumption that reaction is had promoter action, as the skilled personnel can understand.In some embodiment, the quality of solvent is below 30 times of epoxidation unsaturated ester quality.In other embodiments, the quality of solvent is below 20 times of epoxidation unsaturated ester quality; Alternatively, below 15 of epoxidation unsaturated ester quality times; Alternatively, below 10 of epoxidation unsaturated ester quality times; Perhaps alternatively, epoxidation unsaturated ester quality below 5 times.In other embodiments, the quality of solvent is 2 to 20 times of epoxidation unsaturated ester quality; Alternatively, 3 of epoxidation unsaturated ester quality to 15 times; Alternatively, 4 of epoxidation unsaturated ester quality to 15 times; Perhaps alternatively, 5 to 10 of epoxidation unsaturated ester quality times.

[00330] mercaptan and the reaction of epoxidation unsaturated ester can be adopted the ratio (after this being called " mol ratio of mercaptan and epoxide group ") of epoxide group molar equivalent in any mercaptan that can produce Alpha-hydroxy thiol ester described herein and the epoxidation unsaturated ester and carry out.The epoxidation group molar equivalent of epoxidation unsaturated ester can calculate with following equation:

【00331】

\frac{EUESMass}{EUESGMW} \times EUESEpoxide

[00332] in this equation, EUES GMW is the mean molal quantity of epoxidation unsaturated ester, and EUESMass is the quality of epoxidation unsaturated ester, and EUES Epoxide is each epoxidation unsaturated ester molecule epoxide group mean number.In some embodiment, mercaptan and epoxide group mol ratio are more than 0.2.In other embodiments, mercaptan and epoxide group mol ratio are more than 0.5; Alternatively, more than 1; Perhaps alternatively, more than 2.In other embodiments, hydrogen sulfide and epoxide group mol ratio are 0.2 to 10; Alternatively, 0.5 to 8; Alternatively, 0.75 to 5; Perhaps alternatively, 1 to 3.

[00333] aspect some, the reaction of mercaptan and epoxidation unsaturated ester is to take place under the condition that has catalyzer to exist.Generally speaking, catalyzer is any catalyzer of the reaction of capable catalysis mercaptan and epoxidation unsaturated ester with the hydroxyl thiol ester of generation expectation.On the one hand, catalyzer is selected from homogeneous phase and heterogeneous catalyst.In others, catalyzer is selected from zeolite, heterogeneous catalyst, homogeneous catalyst and composition thereof.On the other hand, catalyzer is an amine.In others, catalyzer is selected from cyclic conjugated amine (cyclic conjugated amine), 1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene (1,8-diazabicyclo[5.4.0] undec-7-ene), 1,5-diazabicyclo [4.3.0] ninth of the ten Heavenly Stems-5-alkene (1,5-diazabicyclo[5.4.0] non-7-ene) and composition thereof.

[00334] aspect some, the reaction of mercaptan and epoxidation unsaturated ester is to take place under the condition that has catalyzer to exist.Generally speaking, catalyzer is any catalyzer of the reaction of capable catalysis mercaptan and epoxidation unsaturated ester with the hydroxyl thiol ester of generation expectation.In some embodiment, catalyzer is an organic bases.In some embodiment, catalyzer can be 1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene (1,8-diazabicyclo[5.4.0] undec-7-ene).Can (other what catalyzer be used?)

[00335] reaction of mercaptan and epoxidation unsaturated ester can take place in batch-type reactor or flow reactor.Any batch-type or flow reactor described herein all can be used in this reaction.Other suitable reactor will be conspicuous to those skilled in the art, and will be considered within the scope of the invention.

[00336] the reaction required time of mercaptan and epoxidation unsaturated ester can be to form described required any reaction times of hydroxyl sulfide ester.Generally speaking, the reaction times is at least 15 minutes.In some embodiment, reaction time range is from 15 minutes to 72 hours; Alternatively, from 30 minutes to 48 hours; Perhaps alternatively, from 45 minutes to 36 hours.

[00337] in some embodiment, the production process of hydroxyl sulfide ester is removed any this step of residual mercaptan after further being included in mercaptan and the reaction of epoxidation unsaturated ester.In some embodiment, hydroxyl sulfide ester is removed to remove residual mercaptan through vacuum.In some embodiment, hydroxyl sulfide ester is through the vacuum removing residue in the temperature range between 25 ℃ to 250 ℃; Perhaps alternatively, between 50 ℃ to 200 ℃.In other embodiments, hydroxyl sulfide ester sprays to remove mercaptan with rare gas element.In some embodiment, hydroxyl sulfide ester is to spray with rare gas element in the temperature range between 25 ℃ to 250 ℃; Perhaps alternatively, between 50 ℃ to 200 ℃.Aspect some, rare gas element is a nitrogen.Generally speaking, comprise mercaptan below the 5wt.% through the hydroxyl sulfide ester of removing or sprayed.In other embodiments, comprise mercaptan below the 2wt.% through the hydroxyl sulfide ester of removing or sprayed; Alternatively, the following mercaptan of 1wt.%; Perhaps alternatively, the following mercaptan of 0.5wt.%.

[00338] reaction between mercaptan and the epoxidation unsaturated ester can be carried out under any temperature of reaction that can form hydroxyl sulfide ester.In some embodiment, temperature of reaction is more than-20 ℃.In other embodiments, temperature of reaction is more than 0 ℃; Alternatively, more than 20 ℃; Alternatively, more than 50 ℃; Perhaps alternatively, more than 80 ℃.Still in other embodiments, range of reaction temperature is from-20 ℃ to 200 ℃; Alternatively, from 20 ℃ to 170 ℃; Perhaps alternatively, from 80 ℃ to 140 ℃.

[00339] reaction between mercaptan and the epoxidation unsaturated ester can be carried out under any pressure that makes mercaptan and epoxidation unsaturated ester maintenance liquid state.In some embodiment, the pressure range of reaction is from 0psig to 2000psig.In other embodiments, the pressure range of reaction is from 0psig to 1000psig; Alternatively, from 0psig to 500psig; Perhaps alternatively, from 0psig to 200psig.

[00340] on the other hand, the mol ratio of the production method of hydroxyl sulfide ester production epoxide group and sulfide group is the hydroxyl sulfide ester below 2.The epoxide group of other hydroxyl sulfide ester and the mol ratio of sulfide group are described at this.(next paragraph and first in this paragraph insert hydroxyl thiol ester part together.) alternatively, the epoxide group of hydroxyl sulfide ester and the mol ratio of thiol group can be below 1.5; Alternatively, below 1.0; Alternatively, below 0.5; Alternatively, below 0.25; Perhaps alternatively, below 0.1.In other embodiments, hydroxyl sulfide ester can not contain epoxide group substantially.

[00341] on the other hand, the production method of hydroxyl sulfide ester is produced such hydroxyl sulfide ester, and its side chain of at least 20% comprises the hydroxyl sulfide group.The embodiment of other hydroxyl sulfide ester---wherein hydroxyl sulfide ester comprises the per-cent of the side chain that contains the hydroxyl sulfide group---is described at this.In other embodiments, the production method of hydroxyl sulfide ester is produced such hydroxyl sulfide ester composition, wherein contained hydroxyl sulfide ester molecule, and average at least 20% side chain contains the Z part.In other embodiments, the production method of hydroxyl sulfide ester is produced such hydroxyl sulfide ester composition, wherein contained hydroxyl sulfide ester molecule, and all side chains on average at least 40% contains the Z part; Alternatively, all side chains on average at least 60% contain the Z part; Alternatively, all side chains on average at least 70% contain the Z part; Perhaps alternatively, all side chains on average at least 80% contain the Z part.(embodiment (and embodiment of X and Y part) of Z part is inserted sulfur compound ester composition part.)

[00342] contains sulphonate or contain the preparation method of sulfonate ester

[00343] as a kind of embodiment of the present invention, the present invention has advantageously provided preparation and has contained the method for sulphonate and the method that preparation contains the sulfonate ester.Generally speaking, the preparation method who contains sulphonate comprises makes thiol ester contact with oxygenant, and makes at least one thiol group oxidation in this thiol ester to produce the step of sulfonic acid group.The preparation method who contains the sulfonate ester comprises making and contains sulphonate and contact with alkali and form the step that contains the sulfonate ester.

The preparation method who contains sulphonate

[00344] in one embodiment, containing the sulphonate preparation method comprises and thiol ester is contacted with oxygenant and makes this thiol ester oxidation contain the step of sulphonate with generation.Generally speaking, oxygenant is oxidized to sulfonate groups with at least one thiol group of thiol ester.Production contains the sulphonate method for compositions and can be applicable to any thiol ester described herein, to prepare any sulphonate that contains described herein.In some embodiment, thiol ester comprises oh group.For example: thiol ester can be any hydroxyl thiol ester described herein.Oxygenant can be any oxygenant described herein.

[00345] aspect some, the oxidation of thiol ester is to take place under the situation that has solvent to exist.Aspect some, solvent is a water.

[00346] can be any oxygenant that thiol group can be oxidized to sulfonic acid group with the contacted oxygenant of thiol ester.In some embodiment, oxygenant is an oxygen.In some embodiment, oxygenant is a chlorine.In other embodiments, oxygenant is a methyl-sulphoxide.Still in other embodiments, oxygenant is the dialkyl sulfide of hydrogen halide and catalytic amount such as the binding substances of methyl-sulphoxide.Other suitable oxygenant will be conspicuous to those skilled in the art, and will be considered within the scope of the invention.

[00347] oxidation of thiol ester can be carried out thiol ester can being converted under any temperature that contains sulphonate.In some embodiment, thiol ester is oxidized under the temperature condition more than-20 ℃.In other embodiments, thiol ester is oxidized under the temperature condition more than 0 ℃; Alternatively, more than 20 ℃; Perhaps alternatively, more than 50 ℃.

[00348] the required time of thiol ester oxidation can be form expectation contain the required any time of sulphonate.Generally speaking, the required time of thiol ester oxidation is at least 15 minutes; Alternatively, at least 30 minutes; Alternatively, at least 45 minutes; Perhaps alternatively, at least 1 hour.In some embodiment, the required time range of thiol ester oxidation is from 15 minutes to 12 hours; Alternatively, from 30 minutes to 6 hours; Alternatively, from 45 minutes to 3 hours.

[00349] carries out under the oxidation of thiol ester can make thiol ester and oxygenant keep appropriate state any pressure of---being not always liquid---, contain sulphonate so that thiol ester is oxidized to.For example: when oxygenant was chlorine, chlorine was gasiform.In some embodiment, the oxidation of thiol ester can carried out in the pressure range of 0psig to 2000psig.In other embodiments, the oxidation of thiol ester can carried out in the pressure range of 0psig to 1000psig; Perhaps alternatively, 0psig to 500psig.

[00350] oxidation of thiol ester can be carried out in batch-type reactor or flow reactor, as described here.In addition, contain the sulphonate preparation method can comprise those skilled in the art cognitive other production stage.

The preparation method who contains the sulfonate ester

[00351] in one aspect of the invention, advantageously provided the preparation method who contains the sulfonate ester.In one embodiment, the preparation method who contains the sulfonate ester comprises making and contains sulphonate and contact with alkali and form the step that contains the sulfonate ester composition.The preparation method who contains the sulfonate ester can be applicable to any sulphonate that contains described herein, to prepare any sulfonate ester that contains described herein.Aspect some, the preparation method who contains the sulfonate ester also comprises the step that contains the sulphonate preparation method, as described here except the preparation process that contains the sulfonate ester.

[00352] aspect some, the formation that contains the sulfonate ester is to take place under the condition that has solvent to exist.Aspect some, solvent is a water.

[00353] aspect some, alkali can be metal hydroxides.In some embodiment, metal hydroxides is selected from sodium, potassium, barium, calcium, magnesium and composition thereof.In specific embodiment, metal hydroxides is a sodium hydroxide.In others, metal hydroxides is calcium hydroxide or magnesium hydroxide.Still in others, metal hydroxides is a hydrated barta.In others, alkali is organic amine.In some embodiment, amine has the NRs3Rs4Rs5 structure, and wherein Rs3, Rs4 and Rs5 are independently selected from hydrogen, C ₁To C ₁₀Organic group and C ₁To C ₁₀Hydrocarbyl group.In other embodiments, organic amine is trialkylamine, dialkylamine or monoalkylamine.In a specific embodiment, NRs3Rs4Rs5 represents trolamine.

[00354] formation that contains the sulfonate ester can be carried out under any temperature of reaction that the sulfonic acid group that contains sulphonate can be converted into sulfonate groups.In some embodiment, containing the sulfonate ester is to form under the temperature more than-20 ℃.In other embodiments, thiol ester is oxidized under the temperature more than 0 ℃; Alternatively, more than 20 ℃; Perhaps alternatively, more than 50 ℃.Still in other embodiments, thiol ester is oxidized in 0 ℃ to 250 ℃ temperature range; Alternatively, from 0 ℃ to 150 ℃; Perhaps alternatively, from 20 ℃ to 100 ℃.

[00355] containing the sulfonate ester, to form the required time can be that the sulfonic acid group that will contain sulphonate is converted into the required any time of sulfonate groups.Generally speaking, containing the sulfonate ester, to form the required time be at least 15 minutes; Alternatively, at least 30 minutes; Alternatively, at least 45 minutes; Perhaps alternatively, at least 1 hour.In some embodiment, containing the sulfonate ester, to form required time range be from 15 minutes to 12 hours; Alternatively, from 30 minutes to 6 hours; Alternatively, from 45 minutes to 3 hours.

[00356] formation that contains the sulfonate ester can contain sulphonate, alkali and optional solvent and keep carrying out under liquid any pressure making.In some embodiment, the formation that contains the sulfonate ester is to carry out in the pressure range of 0psig to 2000psig.In other embodiments, the formation that contains the sulfonate ester is to carry out in the pressure range of 0psig to 1000psig; Perhaps alternatively, 0psig to 500psig.

[00357] on the one hand, the preparation process that contains the sulfonate ester is carried out with batch mode.In others, the preparation process that contains the sulfonate ester is carried out in a continuous manner.

The release and release control fertilizer of polythiourethane and/or epoxy polymer encapsulation

[00358] therefore, at it on the one hand, the present invention relates to the release and release control fertilizer of polythiourethane and/or epoxy polymer encapsulation.Term " release and release control fertilizer (controlled release fertilizer material) " and " CRF material " can exchange use in this manual, and they are defined as has identical implication.Further, as used in this specification sheets, term " vegetables oil " is intended to have implication widely, and it comprises the fatty acid triglycercide source, as soya-bean oil, Semen Maydis oil, Canola oil, rapeseed oil and analogue.Most preferred vegetables oil used herein is a soya-bean oil.

[00359] generally speaking, fertilizer comprises the particulate state plant nutrient substance.The selection that is used for the particulate state plant nutrient substance of this CRF material is not limited especially, and in those skilled in the art's scope.

[00360] for example: used plant nutrient substance can be selected from disclosed those materials of Hudson.Preferably, such plant nutrient comprises water-soluble cpds, and more preferably, compound contains at least a nitrogen, phosphorus, potassium, sulphur, micro-nutrients or its ingredients of a mixture of being selected from.Preferred such plant nutrient comprises urea.The example of the plant nutrient that other is useful is at United States Patent (USP) 5,571,303[Bexton] and/or United States Patent (USP) 6,663,686[Geiger etc.] in instructed---for example ammonium sulfate, ammonium phosphate and composition thereof.The limiting examples of useful micro-nutrients can be selected from copper, zinc, boron, manganese, iron and composition thereof.

[00361] preferably, the coating (coating) of parcel plant nutrient substance, its content is about 0.1 to about 20% scope by weight, more preferably be about 2.0 to about 15% by weight, and most preferably be about 2.5 to about 10% by weight, this weight that is based on plant nutrient substance is calculated.

[00362] in a kind of embodiment preferred of the present invention, the sulfur-bearing vegetables oil is used to the reaction of isocyanate (for example the coating in expectation is under the situation of polythiourethane) as unique active hydrogen-contg compound or is used for reaction (promptly the coating in expectation is under the situation of epoxy polymer) with epoxy resin ingredient.Alternatively, might use the composition of sulfur-bearing vegetables oil and another kind of active hydrogen-contg compound-as polyvalent alcohol.

[00363] selection to polyvalent alcohol is not limited especially, and in the scope that those skilled in the art understood.Herein, polyvalent alcohol refers to the compound bearing active hydrogen that contains with isocyanate reaction.Polyvalent alcohol can be the polyvalent alcohol of single type or the mixture of different polyvalent alcohols.For example, polyvalent alcohol can be the hydroxyl-end capped skeleton of following compound: polyethers, polyester, polycarbonate, polydiene and polycaprolactone.Preferably, such polyvalent alcohol is selected from hydroxyl-dead-end polymerization hydrocarbon, fatty acid triglycercide, hydroxyl-end capped polyesters, methylol-end capped polyesters, methylol-end capped perfluoro-methyl (perfluoromethylene), polyalkylene ether glycols (polyalkyleneetherglycol), polyalkylene arylene ether glycol (polyalkylenearyleneether glycol) and polyalkylene ether triol (polyalkyleneether triol).Preferred polyvalent alcohol be selected from polyoxyethylene glycol, hexanodioic acid-polyglycol ester, poly-(butyleneglycol), poly-(propylene glycol) and hydroxyl-end-blocking polyhutadiene-referring to, for example British Patent No. 1,482,213.Most preferred such polyvalent alcohol is a polyether polyol.Preferably, the molecular weight ranges of such polyether polyol is from about 60 to about 20,000, more preferably from about 60 to about 10,000, and most preferably from about 60 to about 8,000.

[00364] as using, particularly preferred polyvalent alcohol kind is that those comprise about 2 polyvalent alcohols to about 12 hydroxylic moieties.Preferably, this class polyvalent alcohol is to have those of low equivalent (equivalent weitght) and high functionality.Preferred equivalent is 29-400.More preferably, equivalent is 29-200.Most preferably, equivalent is 29-150.The polyvalent alcohol functionality is meant the preferred functionality of elementary cell (or monomer) as used herein.Preferably, the polyvalent alcohol functionality is between about 2 to about 12, more preferably between about 3 to about 8, and most preferably between about 3 to 6.More preferably, such polyether polyol is made as initiator with amine.Most preferably, polyvalent alcohol comprises Huntsman Jeffol A480TM and another kind of polyvalent alcohol, is preferably the mixture of Viscotrol C.

[00365] in addition, as using, polyvalent alcohol can derive from fatty acid triglycercide source such as soybean, corn, rape and analogue (promptly in order to produce the oil of naturally occurring modification).Synthetic polyvalent alcohol example like this comprises rape alkali, can (Princeton Illinois) buys, and its functionality is more than 3 from Urethane Soy Systems company.The polyol blends that has to certainty ratio and molecular weight distribution can be used, for example, the mixture of the Huntsman Jeffol A480TM of different functionality and molecular weight or 800TM and ethylene glycol, Huntsman Jeffol A480TM or 800TM and oiliness polyvalent alcohol (oleo polyol), Huntsman Jeffol A480TM or 800TM and polyoxyethylene glycol, Huntsman Jeffol A480TM or 800TM and polypropylene glycol, Huntsman Jeffol A480TM or 800TM and polypropylene glycol (or polyoxyethylene glycol).

[00366] be applicable to that the isocyanic ester of producing coating is not limited especially, and it is chosen in the scope that those skilled in the art understand.Isocyanic ester can be the isocyanic ester of single kind or the mixture of different isocyanic ester.Generally speaking, the isocyanate compound of Shi Yonging can be represented with following general formula:

Q(NCO)i

Wherein i is 2 or above integer, and Q is the organic group of i valency.Q can be replace or unsubstituted hydrocarbyl group (as alkylidene group or arylene group).And Q can represent with following general formula:

Q1-Z-Q1

Wherein Q1 is alkylidene group or arylene group, Z is selected from-O-,-O-Q1-,-CO-,-S-,-S-Q1-S-and-SO2-.The isocyanate compound example that falls in this range of definition comprises hexamethylene diisocyanate, 1,8-two isocyanic acids-right-naphthalene (1,8-diisocyanato-p-naphthalene), two isocyanic acid methylbenzyl esters (xylyldiisocyanate), (OCNCH2CH2CH2OCH2O) 2,1-methyl-2,4-two cyclic isocyanate hexanes, phenylene vulcabond, tolylene diisocyanate (tolylene diisocyanate), chloro phenylene vulcabond (chlorophenylene diisocyanate), 4,4-diphenylmethanediisocyanate, naphthalene-1, the 5-vulcabond, triphenyl methane-4-4-4-triisocyanate and isopropyl benzene-α-4-vulcabond.

[00367] in another embodiment, Q also can represent the polyurethane-base of i valency.In this case, Q (NCO) i is the compound that is commonly referred to prepolymer in this area.Generally speaking, prepolymer can prepare by the reaction of the excessive isocyanate compound of stoichiometry (as discussing before this) with sulfur-bearing vegetables oil (being discussed before this) and/or polyvalent alcohol (being discussed before this).In the present embodiment, polymeric polyisocyanate can be for example according to respect to active hydrogen part in sulfur-bearing vegetables oil and/or the polyvalent alcohol, about 5% uses to the excessive ratio of about 200% stoichiometry.

[00368] be applicable to that the isocyanate compound of the inventive method also can be selected from the dipolymer and the trimer of isocyanic ester and vulcabond, and be selected from polymerization vulcabond with following general formula:

[Q”(NCO) _i] _j

Wherein i and j are that value is 2 or above integer, Q " be multifunctional organic group, and/or, as component extra in the reaction mixture, be compound with following general formula:

L(NCO) _i

Wherein i is that value is 1 or above integer, and L is simple function or multifunctional atom or group.Fall into isocyanate compound example in this range of definition and comprise two isocyanic acid ethyl phosphine esters (ethylphosphonic diisocyanate), two isocyanic acid phosphniline esters (phenylphosphonic diisocyanate), contain=compound of Si-NCO group, derive from sulphonamide (QSO ₂NCO), the isocyanate compound of cyanic acid and thiocyanic acid.

[00369] also can referring to, for example, English Patent the 1st, 453, No. 258.

[00370] limiting examples of suitable isocyanic ester comprises 1, the 6-hexamethylene diisocyanate, 1,4-butylidene vulcabond, the furfurylidene vulcabond, 2, the 4-toluene-2,4-diisocyanate, 2, the 6-toluene-2,4-diisocyanate, 2,4 '-diphenylmethanediisocyanate, 4,4 '-diphenylmethanediisocyanate, 4,4 '-diphenyl propane vulcabond, 4,4 '-phenylbenzene-3,3 '-dimethylmethane vulcabond, 1, the 5-naphthalene diisocyanate, 1-methyl-2,4-vulcabond-5-chlorobenzene (1-methyl-2,4-diisocyanate-5-chlorobenzene), 2,4-two isocyanic acids-s-triazine, 1-methyl-2,4-two cyclic isocyanate hexane (1-methyl-2,4-diisocyanato cyclohexane), right-phenylene vulcabond, between-phenylene vulcabond, 1, the 4-naphthalene diisocyanate, the dianisidine vulcabond, the ditolyl vulcabond, 1,4-xylylene vulcabond, 1,3-xylylene vulcabond, two-(4-isocyanic acid phenyl) methane, two-(3-methyl-4-isocyanic acid phenyl) methane, polymethylene polyphenyl base polymeric polyisocyanate and composition thereof.

[00371] particularly preferred one group of isocyanic ester is that those are described in Hudson and Markusch.

[00372] preferably, isocyanic ester contains per molecule about 1.5 to about 16 NCO groups.More preferably, isocyanic ester contains per molecule about 2 to about 16 NCO groups.Most preferably, isocyanic ester contains per molecule about 3 to about 16 NCO groups.

[00373] preferably, isocyanic ester contains about by weight 10 to about 50% NCO group.More preferably, isocyanic ester contains about by weight 12 to about 50% NCO group.Most preferably, isocyanic ester contains about by weight 15 to about 50% NCO group.

[00374] the sulfur-bearing vegetables oil that is used for this CRF material is selected from preferably that those illustrate in detail at this.

[00375] preferred sulfur-bearing vegetables oil is MVO, obtains from Chevron Phillips Chemical company, and commodity are called Polymercaptan 358.Polymercaptan 358 makes the free radical addition of two keys in the soya-bean oil by hydrogen sulfide.Typically, the mercaptan sulfur content of Polymercaptan 358 and equivalent are respectively 5 to 10% and 640 to 320.

[00376] as the part of isocyanate-reactive components, another preferred sulfur-bearing vegetables oil is MHVO, as sulfydryl-hydroxyl soya-bean oil.It is as described here, preferred that sulfydryl-hydroxyl soya-bean oil is by hydrogen sulfide the free radical addition of epoxidized soybean oil to be made.Typically, the functionality of sulfydryl and hydroxyl equates, and mercaptans content is about 8.3% mercaptan sulfur.The equivalent of this material is 192, comprises the functionality of sulfydryl and hydroxyl.

[00377] as the part of isocyanate-reactive components, also having another preferred sulfur-bearing vegetables oil is CMVO, as sulfur-crosslinked mercaptan soya-bean oil.Sulfur-crosslinked mercaptan soya-bean oil is made by addition element sulphur in mercaptan soya-bean oil.In this process, the part thiol group is consumed as the cross-linking part of sulphur.The typical sulfur-crosslinked mercaptan soya-bean oil that ChevronPhillips Chemical company produces comprises Runs#22,194,195,196 and 197, and its mercaptan sulfur content and equivalent are respectively about 8.0% to 1.4% and about 400 to about 2250.

[00378] in order to improve the cross-linking density of polythiourethane coating, other isocyanate reaction activeconstituents can use with the sulfur-bearing vegetables oil.Example, but, comprise the polyoxyethylene glycol of low molecular poly and polypropylene glycol, amine initiation and polyoxyethylene glycol and polypropylene glycol, glycerol, sorbyl alcohol, neopentyl glycol, quadrol and the tolylene diamine that polypropylene glycol, aromatic amine cause to linking agent those skilled in the art and nonrestrictive.The consumption of used linking agent and being chosen in the scope that those of ordinary skills understand, and determined by the coating rerum natura of expectation.

[00379] be used for the catalyzer of sulfur-bearing vegetables oil and isocyanate reaction, its use is conventional.Selection of catalysts is in the scope that those of ordinary skills understood.The appropriate catalyst example includes, but not limited to tertiary amine and organo-tin compound.Useful especially catalyzer is the polypropylene glycol that amine causes, because in its katalysis of performance, they also can be used as linking agent.

[00380] if expects that organic additive can randomly be joined in the material coated prescription of CRF, to improve the hydrophobicity and/or the useful life longevity of coating.Before organic additive was applied to fertiliser granulates, they be introduced in isocyanate reaction active ingredient or the polyisocyanate component.Suitable organic additive includes, but not limited to synthetic and natural wax, vaseline, pitch, lipid acid, soap, fatty acid ester, higher alcohols, silicone and its mixture.Useful especially organic additive is that the synthetic alpha-olefin wax made of Chevron Phillips Chemical company is (as C ₂₀₊Alpha-olefin wax).Another useful organic additive is a Microcrystalline Wax, as Calwax ^TM170, available from Calwax company.

[00381] preferably, the addition of organic additive or organic additive mixture can reach about 90% by coating weight, preferably by coating weight about 0.1% to about 90% scope, more preferably by coating weight about 1% to about 80% scope, most preferably by coating weight in about scope of 2% to 50%.

[00382] before they are applied to fertiliser granulates, also may in isocyanate reaction active ingredient or polyisocyanate component, add other additive.Possible additive comprises, for example, and other additive known to glidant, tensio-active agent, defoamer and those of ordinary skills.Any additive that helps to form the polythiourethane coating of encapsulation fertiliser granulates can be added in these two kinds of components one or both.

[00383] for the object of the invention, the suitable Resins, epoxy that uses with the mercaptan vegetables oil comprises, but be not limited to, the liquid bisphenol A diglycidyl ether, as Dow Plastics D.E.R.331 and 324 and Resolution Performance Products Epon Resin 282 and 8121 and composition thereof.Also can use epoxidized soybean oil, for example available from the Vikoflex7170 of AtoChem and with the mixture of other Resins, epoxy.

[00384] for the CRF material of the epoxy polymer encapsulation of being made by the sulfur-bearing vegetables oil, it is highly preferred having found to use tertiary amine catalyst.Its consumption is enough to provide for the slow release fertilizer product of producing encapsulation the speed of reaction of expectation.A limiting examples of suitable amine catalyst is the diazabicyclo undecylene, be also referred to as 1,8-diazabicyclo [5,4,0] 11 carbon-7-alkene [CAS# 6674-22-2] or " DBU ", its preferred use range is about 0.1% to 0.5% by coating weight.Other appropriate catalyst material will be conspicuous for those of ordinary skill in the art.

[00385] preferably, amine catalyst and sulfur-bearing vegetables oil premix, and side by side or in tandem this mixture is applied to fertiliser granulates with Resins, epoxy subsequently.

[00386] the preferred sulfur-bearing vegetables oil that is used to produce the CRF material of epoxy polymer coating is MHVO, as sulfydryl-hydroxyl soya-bean oil.A kind of this type of material is the sulfydryl-hydroxyl soya-bean oil that is called as MHSO 566-84, and ChevronPhillips Chemical company produces.This preferred material contains 8.33% mercaptan sulfur, and based on the functionality of mercaptan, its equivalent is 384.

[00387] if expects that organic additive can randomly be joined in the prescription, to improve the hydrophobicity and/or the useful life longevity of epoxy polymer coating.Before organic additive was applied to fertiliser granulates, they be introduced in epoxy reaction active ingredient or the sulfur-bearing vegetables oil component.Suitable organic additive includes, but not limited to synthetic and natural wax, vaseline, pitch, lipid acid, soap, fatty acid ester, higher alcohols, silicone and its mixture.Useful especially organic additive is the synthetic alpha-olefin wax that Chevron Phillips Chemical company makes.

[00388] preferably, the organic additive that uses with epoxy polymer or the addition of organic additive mixture can reach about 90% by coating weight, preferably by coating weight about 0.1% to about 90% scope, more preferably by coating weight about 1% to about 80% scope, most preferably by coating weight in about scope of 2% to 50%.

[00389] before they are applied to fertiliser granulates, also may in epoxy reaction active ingredient (sulfur-bearing vegetables oil) or epoxy resin ingredient, add other additive.Possible additive comprises, for example, and known other additive of glidant, tensio-active agent, defoamer and those of ordinary skills.Any additive that helps to form the epoxy polymer coating of encapsulation fertiliser granulates can join in these two kinds of components one or both.

[00390] according to embodiment preferred, this CRF material can by with the isocyanate reaction active ingredient at room temperature (20 ℃ to about 30 ℃ according to appointment) use with polyisocyanate component and produce.Preferably, fertiliser granulates is preheated in about 50 ℃ to 100 ℃ temperature range, more preferably, and about 60 ℃ to 80 ℃.

[00391] according to another embodiment preferred of the present invention, this CRF material can comprise amine catalyst by with the Resins, epoxy reactive components, and at room temperature (20 ℃ to about 30 ℃ according to appointment) are used with epoxy resin ingredient and produced.Preferably, fertiliser granulates is preheated in about 50 ℃ to 100 ℃ temperature range, more preferably, and about 60 ℃ to 80 ℃.

[00392] in the coating operating process, preferably makes the equipment that keeps the low shear of successive, low shock motion between the fertiliser granulates.Suitable mixing equipment example comprises that fluidized-bed, rotating cylinder, pan-type pelletizer and other can be the similar devices that fertiliser granulates provides the low shear campaign of successive.

[00393] preferably, the CRF material of polythiourethane encapsulation can be operated as follows and produce: the fertiliser granulates that some amount (i) is provided, (ii) stir fertiliser granulates, make it keep gentle mixing, (iii) in the fertiliser granulates that stirs, add and comprise that the isocyanate reaction active ingredient of sulfur-bearing vegetables oil (contains or do not contain one or more linking agents as indicated above, hydrophobic organic additive or other additive), (iv) the ratio according to NCO group and isocyanate reaction active function groups is about 0.8: 1 to about 2.0: 1, preferably about 0.9: 1 to about 1.5: 1 and most preferably about 0.95 to about 1.3: 1 quantity, in the fertiliser granulates that stirs, add isocyanic ester (containing or do not contain one or more hydrophobic organic additives or other additive as indicated above), (isocyanic ester and isocyanate reaction active ingredient are reacted, form solidified polythiourethane coating on the fertiliser granulates surface, (vi) with the fertiliser granulates behind the coating under continuous gentle the stirring, be cooled to about room temperature or a little more than room temperature.

[00394],, then can repeatedly repeat (for example from 2 to 10 times) step (ii) to (vi) to obtain the slow release fertilizer of expectation as needs multilayer coating layer.

[00395] according to CRF material of the present invention, the unnecessary isocyanate reaction active function groups that contains in the fertiliser granulates.

[00396] for obtaining predetermined fertilizer release rate profile, many factors are depended in the polythiourethane encapsulation of fertiliser granulates, comprise: (i) the correct metering of co-reactant and additive, (ii) precise dose control relatively, (iii) fertiliser granulates basic successive motion in the low shear environment of gentleness, (iv) select the catalyzer of suitable type and consumption, to guarantee before using each successive layers (multilayer is used in supposition), isocyanate reaction active ingredient and polyisocyanate component complete reaction, and/or (v) cool off the fertiliser granulates of coating, to avoid the finished product caking.

[00397], before adding isocyanic ester, the sulfur-bearing vegetables oil is applied to fertiliser granulates with hydrophobic organic additive (if any) as independently logistics (stream) according to a kind of embodiment preferred.Equally, preferably, if any, catalyzer and linking agent conduct independently logistics are added into fertiliser granulates.Its interpolation order is unimportant, and in the scope that those skilled in the art understood.

[00398] preferably, the CRF material of epoxy polymer encapsulation can be operated as follows and produce: the fertiliser granulates that some amount (i) is provided, (ii) stir fertiliser granulates to keep gentle mixing, (iii) in the fertiliser granulates that stirs, add the epoxy reaction active ingredient (containing or do not contain one or more hydrophobic organic additives or other additive as indicated above) that comprises the sulfur-bearing vegetables oil, (iv) the ratio according to the ethylene oxide group in the Resins, epoxy and epoxy reaction active function groups is about 0.8: 1 to about 2.0: 1, preferably about 0.9: 1 to about 1.5: 1, more preferably about 0.95 to about 1.3: 1 and most preferably about 0.95 to about 1.05: 1 quantity, in the fertiliser granulates that stirs, add epoxy resin ingredient (containing or do not contain one or more hydrophobic organic additives or other additive as indicated above), (Resins, epoxy and epoxy reaction active substance are reacted, thereby be formed on the lip-deep solidified epoxy polymer of fertiliser granulates coating, (vi) with the fertiliser granulates behind the coating under continuous gentle the stirring, be cooled to about room temperature or a little more than room temperature.

[00399],, then can repeatedly repeat (for example from 2 to 10 times) step (ii) to (vi) to obtain the slow release fertilizer of expectation as needs multilayer coating layer.

[00400] for obtaining predetermined fertilizer release rate profile, many factors are depended in the epoxy polymer encapsulation of fertiliser granulates, comprise: (i) the correct metering of co-reactant and additive, (ii) precise dose control relatively, (iii) fertiliser granulates basic successive motion in the low shear environment of gentleness, the catalyzer of (iv) selecting suitable type and consumption is guaranteeing (multilayer is used in supposition) epoxy reaction active ingredient and epoxy resin ingredient complete reaction before using each successive layers, and/or (v) cooling off, the fertiliser granulates of coating lumps to avoid the finished product.

[00401], before adding epoxy resin ingredient, the sulfur-bearing vegetables oil is applied to fertiliser granulates with hydrophobic organic additive (if any) as independently logistics (stream) according to a kind of embodiment preferred.Equally, preferably, if any, catalyzer and the conduct of other additive independently logistics are added in the fertiliser granulates.Its interpolation order is unimportant, and in the scope that those skilled in the art understood.

[00402] in a kind of further embodiment of the present invention, the binding substances of epoxy polymer layer and polythiourethane layer can be applied to fertiliser granulates, for the CRF material provides the composition polymer coating.Epoxy polymer coating and polythiourethane coating can be employed with any order.

Raw material

Unsaturated ester

[00403] can describe with many diverse ways as the raw material unsaturated ester of producing thiol ester composition described herein.A kind of method of describing the unsaturated ester raw material is by ester group number that constitutes each unsaturated ester oil molecule and carbon-carbon double bond number.Comprise at least one ester group and at least one carbon-carbon double bond as the proper raw material unsaturated ester bottom line of producing thiol ester composition described herein.But, be not subjected to this to require restriction, the ester group number and the carbon-carbon double bond number that constitute unsaturated ester are independent factors, and can change independently of each other.Therefore, unsaturated ester can have the ester group number described respectively at this and arbitrary combination of carbon-carbon double bond number.Suitable unsaturated ester also can contain other functional group as alcohol, aldehyde, ketone, epoxy, ether, aromatic group and combination thereof.As an example, unsaturated ester also can contain oh group.The unsaturated ester example of a hydroxyl group is a Viscotrol C.Other suitable unsaturated ester will be conspicuous for a person skilled in the art, and will be considered within the scope of the invention.

[00404] minimally, unsaturated ester comprise at least one ester group.In other embodiments, unsaturated ester comprises at least 2 ester groups.Alternatively, unsaturated ester comprises 3 ester groups.Alternatively, unsaturated ester comprises 4 ester groups.Alternatively, unsaturated ester comprises from 2 to 8 ester groups.Alternatively, unsaturated ester comprises from 2 to 7 ester groups.Alternatively, unsaturated ester comprises from 3 to 5 ester groups.As another optional scheme, unsaturated ester comprises from 3 to 4 ester groups.

[00405] in other embodiments, unsaturated ester comprises the mixture of various unsaturated ester.In these cases, the ester group mean number of each unsaturated ester molecule of the most handy formation unsaturated ester of ester group number composition is described.In some embodiment, unsaturated ester contains on average at least 1.5 ester groups of each unsaturated ester molecule; Alternatively, average at least 2 ester groups of each unsaturated ester molecule; Alternatively, average at least 2.5 ester groups of each unsaturated ester molecule; Perhaps alternatively, average at least 3 ester groups of each unsaturated ester molecule.In other embodiments, unsaturated ester contains on average from 1.5 to 8 ester groups of each unsaturated ester molecule; Alternatively, average from 2 to 7 ester groups of each unsaturated ester molecule; Alternatively, average from 2.5 to 5 ester groups of each unsaturated ester molecule; Alternatively, average from 3 to 4 ester groups of each unsaturated ester molecule.In another embodiment, unsaturated ester contains on average about 3 ester groups of each unsaturated ester molecule or alternatively, on average about 4 ester groups of each unsaturated ester molecule.

[00406] minimally, unsaturated ester comprise each at least one carbon-carbon double bond of unsaturated ester molecule.In one embodiment, unsaturated ester comprises at least 2 carbon-carbon double bonds; Alternatively, at least 3 carbon-carbon double bonds; Perhaps alternatively, at least 4 carbon-carbon double bonds.In other embodiments, unsaturated ester comprises from 2 to 9 carbon-carbon double bonds; Alternatively, from 2 to 4 carbon-carbon double bonds; Alternatively, from 3 to 8 carbon-carbon double bonds; Perhaps alternatively, from 4 to 8 carbon-carbon double bonds.

[00407] in some embodiment, unsaturated ester comprises the mixture of various unsaturated ester.In this regard, the most handy each the unsaturated ester oil molecule carbon-carbon double bond mean number of the carbon-carbon double bond number in the unsaturated ester mixture is described.In some embodiment, unsaturated ester contains on average at least 1.5 carbon-carbon double bonds of each unsaturated ester molecule; Alternatively, average at least 2 carbon-carbon double bonds of each unsaturated ester molecule; Alternatively, average at least 2.5 carbon-carbon double bonds of each unsaturated ester molecule; Perhaps alternatively, average at least 3 carbon-carbon double bonds of each unsaturated ester molecule.In other embodiments, unsaturated ester contains on average from 1.5 to 9 carbon-carbon double bonds of each unsaturated ester molecule; Alternatively, average from 3 to 8 carbon-carbon double bonds of each unsaturated ester molecule; Alternatively, average from 2 to 4 carbon-carbon double bonds of each unsaturated ester molecule; Perhaps alternatively, average from 4 to 8 carbon-carbon double bonds of each unsaturated ester molecule.

[00408] although ester group number (or mean number) and double key number (or mean number) are the independent factors of unsaturated ester,, still to mention some specific embodiments for illustrational purpose.In one embodiment, the unsaturated ester molecule contains on average average at least 1.5 carbon-carbon double bonds of at least 1.5 ester groups and each unsaturated ester molecule of each unsaturated ester molecule.Alternatively, the unsaturated ester molecule contains on average average at least 1.5 carbon-carbon double bonds of at least 3 ester groups and each unsaturated ester molecule of each unsaturated ester molecule.Alternatively, the unsaturated ester molecule contains on average average from 1.5 to 9 carbon-carbon double bonds of at least 3 ester groups and each unsaturated ester molecule of each unsaturated ester molecule.As the optional scheme of another kind, the unsaturated ester molecule contains on average average from 1.5 to 9 carbon-carbon double bonds of from 2 to 8 ester groups and each unsaturated ester oil of each unsaturated ester molecule.

[00409] the ester group number (or mean number) that exists in the unsaturated ester molecule and the carbon-carbon double bond number (or mean number), the carbon-carbon double bond situation of arranging that contains in the unsaturated ester molecule of 2 or a plurality of carbon-carbon double bonds also is the factor of considering.Contain in some embodiments of 2 or a plurality of carbon-carbon double bonds at the unsaturated ester molecule, carbon-carbon double bond can be a conjugated.In other embodiments, carbon-carbon double bond can be by only a carbon atom is separate.When two carbon-carbon double bonds were with dihydro carbon atoms separate, methylene group for example, these carbon-carbon double bonds can be called as methylene radical two keys at interval.Still in other embodiments, carbon-carbon double bond is isolating, and is separate by 2 or more carbon atoms as carbon-carbon double bond.In further embodiment, carbon-carbon double bond can be and the carbonyl conjugated.

[00410] aspect some, unsaturated ester can be described to the ester of polyvalent alcohol and unsaturated carboxylic acid.In this described, the unsaturated carboxylic acid part of unsaturated ester can be called as the side chain (or being called side chain simply) of polyvalent alcohol.In some embodiment, unsaturated ester comprises the side chain that contains the at interval two keys of methylene radical below 30%.In other embodiments, unsaturated ester comprises the side chain that contains the at interval two keys of methylene radical more than 30%.Still in other embodiments, unsaturated ester comprises and contains 3 side chains that adjoin methylene radical interval carbon-carbon double bond below 25%.In further embodiment, unsaturated ester comprises the linolenic acid side chain below 25%.In further embodiment, unsaturated ester comprises and contains 3 side chains that adjoin methylene radical interval carbon-carbon double bond more than 25%.In further embodiment, unsaturated ester comprises the linolenic acid side chain more than 25%.In other embodiments, unsaturated ester comprises at least 30% and contains 2 and adjoin methylene radical and at interval contain 3 below the side chain and 25% of carbon-carbon double bond and adjoin the methylene radical side chains of carbon-carbon double bond at interval.

[00411] other functional group also can appear in the unsaturated ester.The non-limiting list of functional group comprises oh group, ether group, aldehyde group, ketone groups, amine groups, hydroxy-acid group and other group and combination thereof.On the one hand, unsaturated ester can comprise oh group.In some embodiment, unsaturated ester contains on average at least 1.5 oh groups of each unsaturated ester molecule; Alternatively, average at least 2 oh groups of each unsaturated ester molecule; Alternatively, average at least 2.5 oh groups of each unsaturated ester molecule; Perhaps alternatively, average at least 3 oh groups of each unsaturated ester molecule.In other embodiments, unsaturated ester contains on average from 1.5 to 9 oh groups of each unsaturated ester molecule; Alternatively, average from 3 to 8 oh groups of each unsaturated ester molecule; Alternatively, average from 2 to 4 oh groups of each unsaturated ester molecule; Perhaps alternatively, average from 4 to 8 oh groups of each unsaturated ester molecule.In one embodiment, unsaturated ester comprises at least 2 oh groups; Alternatively, at least 3 oh groups; Perhaps alternatively, at least 4 oh groups.In other embodiments, unsaturated ester comprises from 2 to 9 oh groups; Alternatively, from 2 to 4 oh groups; Alternatively, from 3 to 8 oh groups; Perhaps alternatively, from 4 to 8 oh groups.

The source of unsaturated ester oil

[00412] the unsaturated ester oil as raw material of the present invention can be to have each the unsaturated ester grease group number described herein and any unsaturated ester oil of carbon-carbon double bond number.Unsaturated ester oil can come from natural origin, can synthetic be made by the natural origin raw material, can be made by the synthetic raw material, can be by mixture manufacturing or its combination of natural and synthetic materials.

The unsaturated oil of natural origin

[00413] in one embodiment, unsaturated ester oil is unsaturated natural origin oil.Unsaturated natural origin oil can derive from naturally occurring nut, vegetables, plant and animal-origin.In one embodiment, unsaturated ester oil derives from nut, vegetables, plant and the animal-origin through genetic modification.In one embodiment, unsaturated ester oil comprises the triglyceride level of the nut, vegetables, plant and the animal-origin that derive from through genetic modification.

[00414] on the one hand, unsaturated natural origin oil can be butter, sweet oil, peanut oil, Semen Ricini oil, sunflower oil, sesame oil, poppy seed oil, seed oil, plam oil, Prunus amygdalus oil, hazelnut oil, rapeseed oil, Canola oil, soybean oil, Semen Maydis oil, Thistle oil, Canola oil, Oleum Gossypii semen, false flax oil, Toenol 1140 or Walnut oil..In some embodiment, unsaturated natural origin oil can be soybean oil, Semen Maydis oil, Semen Ricini oil, Thistle oil, Canola oil, Oleum Gossypii semen, false flax oil, Toenol 1140 or Walnut oil..In further embodiment, unsaturated natural origin oil can be soybean oil; Alternatively, Semen Maydis oil; Alternatively, Semen Ricini oil; Perhaps alternatively, Canola oil.

[00415] unsaturated natural origin oil comprises triglyceride level, and triglyceride level can be described to the ester that formed by glycerine and unsaturated carboxylic acid.In this manual, the unsaturated carboxylic acid of triglyceride level part can be called as the side chain (perhaps more simply, being called side chain) of glycerine.In some embodiment, triglyceride level comprises the side chain that contains the at interval two keys of methylene radical below 30%.In other embodiments, triglyceride level comprises the side chain that contains the at interval two keys of methylene radical more than 30%.Still in other embodiments, triglyceride level comprises and contains 3 side chains that adjoin methylene radical interval carbon-carbon double bond below 25%.In further embodiment, triglyceride level comprises the linolenic acid side chain below 25%.In further embodiment, triglyceride level comprises and contains 3 side chains that adjoin methylene radical interval carbon-carbon double bond more than 25%.In further embodiment, triglyceride level comprises the linolenic acid side chain more than 25%.In other embodiments, triglyceride level comprises at least 30% and contains 2 and adjoin methylene radical and at interval contain 3 below the side chain and 25% of carbon-carbon double bond and adjoin the methylene radical side chains of carbon-carbon double bond at interval.

[00416] in another embodiment, unsaturated natural ester oil comprises " natural " triglyceride level that derives from unsaturated natural origin oil.In one embodiment, unsaturated ester oil is synthetic.In one embodiment, unsaturated ester oil had both comprised that synthetic also comprised natural raw material.In one embodiment, unsaturated ester oil comprises the synthetic triglyceride level.

The synthetic unsaturated ester

[00417] the synthetic unsaturated ester raw material that is used for each side of the present invention can adopt ester group preparation method well known by persons skilled in the art to produce.Term " ester group " meaning is the part that is formed by oh group and carboxylic acid or carboxylic acid derivative reaction.Typically, ester can prepare by alcohol and the reaction of transesterification, alcohol and the carboxylic acid anhydride of reaction, carboxylicesters and the alcohol of carboxylic acid or alcohol and carboxylic acid halide's reaction.Any in these methods all can be used to produce synthetic unsaturated ester oil, with as in a certain respect raw material among the present invention.That alcohol, unsaturated carboxylic acid, esters of unsaturated carboxylic acids, the unsaturated carboxylic acid anhydrides raw material that is used to prepare unsaturated ester oil can come from is natural, arbitrary combination in the source of synthetic, heredity or natural, heredity and synthetic source.

[00418], is used to produce the polyvalent alcohol of unsaturated ester and unsaturated carboxylic acid, single esters of unsaturated carboxylic acids or unsaturated carboxylic acid anhydrides and is independently key element as the raw material of each side of the present invention.That is to say that these key elements can independently change each other, so these key elements can be used with arbitrary combination, producing unsaturated ester, this unsaturated ester can be used as the raw material of the described composition of production the application or as the raw material of the described method of the application.

Unsaturated ester oil-the polyol component of synthetic

[00419] polyvalent alcohol that is used to produce unsaturated ester oil can be any polyvalent alcohol or polyol blends, and they can react under reaction conditions well known by persons skilled in the art with unsaturated carboxylic acid, unsaturated monocarboxylic ester, carboxylic acid anhydride or carboxylic acid halide.

[00420] carbonatoms in the polyvalent alcohol is not a particularly important.On the one hand, the polyvalent alcohol that is used to produce unsaturated ester can comprise from 2 to 20 carbon atoms.In other embodiments, polyvalent alcohol comprises from 2 to 10 carbon atoms; From 2 to 7 carbon atoms alternatively; From 2 to 5 carbon atoms alternatively.In further embodiment, polyvalent alcohol can be the mixture that contains the polyvalent alcohol of average 2 to 20 carbon atoms; Alternatively, average from 2 to 10 carbon atoms; Alternatively, average from 2 to 7 carbon atoms; Alternatively, average from 2 to 5 carbon atoms.

[00421] on the other hand, the polyvalent alcohol that is used to produce unsaturated ester can have and produces the required any oh group number of unsaturated ester as described here.In some embodiment, polyvalent alcohol contains 2 oh groups; Alternatively, 3 oh groups; Alternatively, 4 oh groups; Alternatively, 5 oh groups; Perhaps alternatively, 6 oh groups.In other embodiments, polyvalent alcohol comprises at least 2 oh groups; Alternatively, at least 3 oh groups; Alternatively, at least 4 oh groups; Perhaps alternatively, at least 5 oh groups; Alternatively, at least 6 oh groups.Still in other embodiments, polyvalent alcohol comprises from 2 to 8 oh groups; Alternatively, from 2 to 4 oh groups; Perhaps alternatively, from 4 to 8 oh groups.

[00422] aspect further, the polyvalent alcohol that is used to produce unsaturated ester is a polyol blends.In one embodiment, polyol blends contains on average at least 1.5 oh groups of each polyvalent alcohol molecule.In other embodiments, polyol blends contains on average at least 2 oh groups of each polyvalent alcohol molecule; Alternatively, average at least 2.5 oh groups of each polyvalent alcohol molecule; Alternatively, average at least 3 oh groups of each polyvalent alcohol molecule; Perhaps alternatively, average at least 4 oh groups of each polyvalent alcohol molecule.Still in other embodiments, polyol blends contains average 1.5 to 8 oh groups of each polyvalent alcohol molecule; Alternatively, average 2 to 6 oh groups of each polyvalent alcohol molecule; Alternatively, average 2.5 to 5 oh groups of each polyvalent alcohol molecule; Alternatively, average 3 to 4 oh groups of each polyvalent alcohol molecule; Alternatively, average 2.5 to 3.5 oh groups of each polyvalent alcohol molecule; Perhaps alternatively, average 2.5 to 4.5 oh groups of each polyvalent alcohol molecule.

[00423] still on the other hand, be used to produce the polyvalent alcohol of unsaturated thiol ester or polyol blends and have molecular weight or molecular-weight average below 500.In other embodiments, polyvalent alcohol or polyol blends have molecular weight or the molecular-weight average below 300; Alternatively, below 200; Alternatively, below 150; Perhaps alternatively, below 100.

[00424] in some embodiment, suitable polyvalent alcohol comprises 1,2-ethylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, dihydroxy methylpropane, neo-pentyl propane, 2-propyl group-2-ethyl-1, ammediol, 1,2-propylene glycol, 1,3 butylene glycol, Diethylene Glycol, triethylene glycol, polyoxyethylene glycol, dipropylene glycol, tripropylene glycol and polypropylene glycol; Cyclohexanedimethanol, 1,3-two  alkane-5,5-dimethanol; And 1,4-xylylene dimethanol and 1-phenyl-1,2-ethylene glycol, TriMethylolPropane(TMP), trimethylolethane, tri hydroxy methyl butane, glycerol, 1,2,5-hexanetriol, tetramethylolmethane, ditrimethylolpropane, contract two glycerol, two trimethylolethane, 1,3,5-trihydroxybenzene, 1,4-xylylene dimethanol and 1-phenyl-1 or its arbitrary combination.In further embodiment, polyvalent alcohol is glycerol, tetramethylolmethane or its mixture.In other embodiments, polyvalent alcohol is a glycerol, or alternatively, tetramethylolmethane.

Unsaturated ester oil-carboxylic acid of synthetic or carboxylic acid equivalent component

[00425] carboxyl acid component of unsaturated ester oil can be any carboxylic acid or the mixture of carboxylic acids of carbon-carbon double bonds.Because carboxyl acid component will combine with the polyvalent alcohol or the polyol blends that contain average 1.5 above oh groups or other any oh group number described herein, so carboxyl acid component can be any mixture that comprises unsaturated carboxylic acid, this carboxylic acid produces the unsaturated ester oil that satisfies ingredient requirement described herein.In some embodiment, carboxyl acid component can be arbitrary mixture of saturated carboxylic acid and unsaturated carboxylic acid, and this unsaturated carboxylic acid produces the unsaturated ester oil that satisfies ingredient requirement described herein.Therefore, be used to produce the carboxylic acid of synthetic unsaturated ester oil or each carboxylic acid equilibrating factor number that mixture of carboxylic acids can be described to have regulation.

[00426] independent factor of carboxylic acid comprises carbon atom mean number and each the carboxylic acid carbon-carbon double bond mean number in each carboxylic acid molecules hydroxy-acid group mean number, the carboxylic acid.Other independent factor comprises the position of two keys in the carbochain, and when having a plurality of pairs of keys, the relative position between two keys.

[00427] as the component of the carboxylic acid composition that is used to produce unsaturated ester oil, concrete carboxylic acid can contain 3 to 30 carbon atoms of each carboxylic acid molecules.In some embodiment, carboxylic acid is a straight chain.In some embodiment, carboxylic acid is a side chain.In some embodiment, carboxylic acid is the mixture of straight chain and branched carboxylic acids.In some embodiment, carboxylic acid also can comprise other functional group, comprises alcohol, aldehyde, ketone and epoxide and other functional group.

[00428] the suitable carboxylic acid that can be used as the unsaturated carboxylic acid composition component can have from about 3 to about 30 carbon atoms; Alternatively, 8 to 25 carbon atoms; Perhaps alternatively, from 12 to 20 carbon atoms.In other embodiments, the carboxylic acid of composition unsaturated carboxylic acid composition comprises average 2 to 30 carbon atoms; Alternatively, average 8 to 25 carbon atoms; Perhaps alternatively, average 12 to 20 carbon atoms.

[00429] carbon-carbon double bond can be positioned at any position of carbon carbochain total length.In one embodiment, two keys position endways.In another embodiment, carbon-carbon double bond can be in inner portion.Still in another embodiment, carboxylic acid or mixture of carboxylic acids can not only contain terminal but also contain inner carbon-carbon double bond.Two keys also can be described by indicating the replacement radix that links to each other with carbon-carbon double bond.In some embodiment, carbon-carbon double bond can be mono-substituted, disubstituted, trisubstituted, quaternary or have the unsaturated carboxylic acid mixture of single replacement, two replacement, three replacements and the arbitrary combination of four replacement carbon-carbon double bonds.

[00430] suitable unsaturated carboxylic acid comprises vinylformic acid (acrylic), agonandoic, agonandric, alchornoic, ambrettolic acid (ambrettolic), angelicic acid (angelic), pleurisy foot acid (asclepic), auricolic, oat oleic acid (avenoleic), axillarenic, anti-erucic acid (brassidic), decylenic acid (caproleic), anti-cetoleic acid (cetelaidic), cetoleic acid (cetoleic), civet acid (civetic), CLA, coriaric acid (coriolic), hat GOUYAHUA acid (coronaric), crepenynic acid (crepenynic), densipolic, two high linolic acids (dihomolinoleic), two high Japanese yew oleic acid (dihomotaxoleic), dimorphic flower oleic acid (dimorphecolic), elaidic acid (elaidic), Chinese ephedra acid (ephedrenic), erucic acid (erucic), gadelaidic acid (gadelaidic), gadoleic acid (gadoleic), cod acid (gaidic), gondolo, gondoic acid (gondoleic), gorlic acid (gorlic), helenynolic acid (helenynolic), hydrosorbic acid (hydrosorbic), isoricinoleic acid (isoricinoleic), keteleeria fortunei acid (keteleeronic), labellenic, lauronic acid (lauroleic), lesquerolic, anti-linolic acid (linelaidic), cis-dodecenoic acid (linderic), lumequeic acid (lumequic), malvalic acid (malvalic), beet acid (mangold ' s acid), palmitinic acid (margarolic), megatomic, mikusch ' sacid, mycolipenic acid (mycolipenic), anti-tetradecanoic acid (myristelaidic), Selacholeic acid (nervoic), obtusilic acid (obtusilic), oleic acid (oleic), Zoomeric acid (palmitelaidic), anti-petroselinic acid (petroselaidic), petroselinic acid (petroselinic), phlomic, physeteric acid (physeteric), phytenic acid (phytenoic), 17 alkene-10-alkynes-8-acid (pyrulic), ricinelaidic acid (ricinelaidic), anti-vaccinic acid (rumenic), shark oleic acid (selacholeic), Sorbic Acid (sorbic), stearolic acid (stearolic), Sterculinic acid (sterculic), sterculynic, stillingic acid (stillingic), strophanthus hispidus acid (strophanthus), tariric acid (tariric), Japanese yew oleic acid (taxoleic), wound hormone (traumatic), tsuduic acid (tsuduic), tsudzuic acid (tsuzuic), undecylenic acid (undecylenic), vaccinic acid (vaccenic), vernolic acid (vernolic), ximenic acid (ximenic), ximenynic acid (ximenynic), ximenynolic and combination thereof.In further embodiment, suitable unsaturated carboxylic acid comprises oleic acid, Zoomeric acid, ricinolic acid, linolenic acid and combination thereof.

[00431] in some embodiment, unsaturated ester can prepare by the monoesters of carboxylic acid described herein or mixture of carboxylic acids and polyhydric alcohol composition described herein are carried out transesterify.In some embodiment, monoesters is the methyl esters or the ethyl ester of carboxylic acid or mixture of carboxylic acids.In further embodiment, the monocarboxylate is a carboxylate methyl ester as described here.

The epoxidation unsaturated ester

[00432] on the one hand, the epoxidation unsaturated ester is used as the raw material of producing material described herein, and is used in the manufacture method of material described herein.Generally speaking, the epoxidation unsaturated ester can obtain by epoxidation any unsaturated ester described herein.Unsaturated ester oil can be from natural origin, synthetic and make, make, make or its combination from the mixture of natural and synthetic materials from the synthetic raw material from the natural origin raw material.

[00433] MIN, the epoxidation unsaturated ester comprises at least one epoxide group.In one embodiment, the epoxidation unsaturated ester comprises at least 2 epoxide groups; Alternatively, at least 3 epoxide groups; Perhaps alternatively, at least 4 epoxide groups.In other embodiments, the epoxidation unsaturated ester comprises 2 to 9 epoxide groups; Alternatively, 2 to 4 epoxide groups; Alternatively, 3 to 8 epoxide groups; Perhaps alternatively, 4 to 8 epoxide groups.

[00434] in some embodiment, unsaturated ester comprises the mixture of epoxidation unsaturated ester.In this respect, the epoxide group number in the epoxidation unsaturated ester preferably is described as each epoxidation unsaturated ester molecule epoxide group mean number.In some embodiment, the epoxidation unsaturated ester contains on average at least 1.5 epoxide groups of each epoxidation unsaturated ester molecule; Alternatively, average at least 2 epoxide groups of each epoxidation unsaturated ester molecule; Alternatively, average at least 2.5 epoxide groups of each epoxidation unsaturated ester molecule; Perhaps alternatively, average at least 3 epoxide groups of each epoxidation unsaturated ester molecule.In other embodiments, the epoxidation unsaturated ester contains average 1.5 to 9 epoxide groups of each epoxidation unsaturated ester molecule; Alternatively, average 3 to 8 epoxide groups of each epoxidation unsaturated ester molecule; Alternatively, average 2 to 4 epoxide groups of each epoxidation unsaturated ester molecule; Perhaps alternatively, 4 to 8 epoxide groups of each epoxidation unsaturated ester molecule.

[00435] on the one hand, the epoxidation unsaturated ester can be the unsaturated natural origin oil of epoxidation (an epoxidation natural origin oil).Unsaturated natural origin oil can be from naturally occurring nut, vegetables, plant and animal source.In one embodiment, unsaturated ester oil nut, vegetables, the plant and animal source of genetic modification of can hanging oneself.In one embodiment, unsaturated ester oil comprises the triglyceride level that nut, vegetables, the plant and animal of the genetic modification of hanging oneself are originated.

[00436] on the one hand, epoxidation natural origin oil can be butter, sweet oil, peanut oil, Semen Ricini oil, sunflower oil, sesame oil, poppy seed oil, seed oil, plam oil, Prunus amygdalus oil, hazelnut oil, rapeseed oil, Canola oil, soybean oil, Semen Maydis oil, Thistle oil, Canola oil, Oleum Gossypii semen, false flax oil, Toenol 1140 or Walnut oil..In some embodiment, epoxidation natural origin oil can be soybean oil, Semen Maydis oil, Semen Ricini oil, Thistle oil, Canola oil, Oleum Gossypii semen, false flax oil, Toenol 1140 or Walnut oil..In further embodiment, epoxidation natural origin oil can be soybean oil; Alternatively, Semen Maydis oil; Alternatively, Semen Ricini oil; Perhaps alternatively, Canola oil.

[00437] composition of mercaptans can comprise each triglyceride level average more than 0 to about 4 epoxide groups.Composition of mercaptans also can comprise each triglyceride level average more than 1.5 to about 9 epoxide groups.

Mercaptan

[00438] in some embodiment, unsaturated ester or epoxidation unsaturated ester contact with mercaptan.In these embodiments, mercaptan can be any mercaptan that comprises 1 to 20 carbon atom.Generally speaking, mercaptan can have following structure:

HS-R ³

Wherein, R ³Be C ₁To C ₂₀Organic group or C ₁To C ₂₀Hydrocarbyl group.In further embodiment, R ³Can be C ₂To C ₁₀Organic group or C ₂To C ₁₀Hydrocarbyl group.In some embodiment, composition of mercaptans comprises solvent.On the one hand, composition of mercaptans comprises at least a other functional group.

[00439] at least a other functional group can be selected from several different groups.For example: at least a other functional group is methyl esters or ethyl ester or its combination of alcohol groups, carboxylic acid alcohol groups, carboxylate group, amine groups, sulfide group, thiol group, hydroxy-acid group.The functional group of other type will be conspicuous to those skilled in the art, and will be considered within the scope of the invention.

[00440] in some embodiment, mercaptan is selected from 3-mercapto propyl group-Trimethoxy silane, the 2-mercaptopyridine, the 4-mercaptopyridine, the 2-mercaptopyrimidine, mercaptopyruvate, mercaptosuccinic acid, 2-sulfydryl nicotinic acid, 6-sulfydryl nicotinic acid, the 2-mercapto-phenol, the 4-mercapto-phenol, 3-sulfydryl-1, the 2-propylene glycol, 3-sulfydryl-1, the 2-propylene glycol, 3-sulfydryl-1-propanesulfonic acid, 1-sulfydryl-2-propyl alcohol, 3-sulfydryl-1-propyl alcohol, 2 mercaptopropionic acid, the 3-thiohydracrylic acid, 2-sulfydryl phenylcarbinol, 3-sulfydryl-2-butanols, 4-sulfydryl-1-butanols, mistabrom, 2 mercapto ethanol, 2-sulfydryl ether, 2-sulfydryl ethyl-sulfide, 16-sulfydryl palmitic acid, 6-sulfydryl-1-hexanol, 4 '-sulfydryl-monoacetylaniline, Thiovanic acid, the 2-Thiosalicylic acid, the 3-Thiosalicylic acid, the 4-Thiosalicylic acid, 2-mercaptothiazoline, 3-sulfydryl-1H-1,2, the 4-triazole, 11-sulfydryl undeeanoic acid, 11-sulfydryl-1-undecyl alcohol and combination thereof.

[00441] in some embodiment, mercaptan is selected from beta-mercaptoethanol, 2-mercapto-phenol, 3-mercapto-phenol, 4-mercapto-phenol, 1-sulfydryl-2-propyl alcohol, 1-sulfydryl-3-propyl alcohol, Thiovanic acid, 2 mercaptopropionic acid, 3-thiohydracrylic acid, 2-Thiosalicylic acid, 3-Thiosalicylic acid, 4-Thiosalicylic acid, 2-sulfydryl phenylcarbinol, 3-sulfydryl-2-butanols, 4-sulfydryl-1-butanols, 2-sulfydryl ether, 2-sulfydryl ethyl-sulfide, 6-sulfydryl hexanol, 3-Mercapto-1, mercaptosuccinic acid and composition thereof.In further embodiment, mercaptan is selected from beta-mercaptoethanol, 1-sulfydryl-2-propyl alcohol, 1-sulfydryl-3-propyl alcohol, 2-sulfydryl phenylcarbinol, 3-sulfydryl-2-butanols, 4-sulfydryl-1-butanols, 6-sulfydryl hexanol, 3-Mercapto-1 and composition thereof.In further embodiment, mercaptan be selected from 2-mercapto-phenol, 3-mercapto-phenol, 4-mercapto-phenol, and composition thereof.Still in further embodiment, mercaptan selected from mercapto acetate, 2 mercaptopropionic acid, 3-thiohydracrylic acid, 2-Thiosalicylic acid, 3-Thiosalicylic acid, 4-Thiosalicylic acid, mercaptosuccinic acid and composition thereof.

Isocyanic ester

[00442] in some embodiment, invention composition described herein and isocyanate compound react and generation polythiourethane composition.Isocyanic ester can be to react with thiol ester described herein, hydroxyl thiol ester and crosslinked thiol ester, forms any isocyanic ester of polythiourethane composition.Generally speaking, isocyanate compound contains at least two isocyanate groups.

[00443] on the one hand, isocyanic ester can be selected from 1, the 4-tetramethylene diisocyanate, 1, the 6-hexamethylene diisocyanate, 2,2,4-trimethylammonium-1, the 6-hexamethylene diisocyanate, 1,12-ten dimethylene diisocyanates, hexanaphthene-1,3-and-1, the 4-vulcabond, 1-isocyanato-3-isocyanato methylcyclopentane, 1-isocyanato-3-isocyanato methyl-3,5,5 ,-trimethyl-cyclohexane (isophorone diisocyanate or IPDI), two-(4-isocyanato cyclohexyl) methane, 1,3-and 1,4-pair-(isocyanato methyl)-hexanaphthene, two-(4-isocyanato cyclohexyl) methane, 2,4 '-two isocyanatos-dicyclohexyl methyl hydride, two-(4-isocyanato-3-methyl-cyclohexyl base) methane, α, α, α ', α '-tetramethyl--1,3-and/or-1,4-xylylene vulcabond, 1-isocyanato-1-methyl-4 (3)-isocyanato methylcyclohexane, 2,4-and/or 2,6-six hydrogen-tolylene diisocyanate, 1,3-and/or 1, the 4-phenylene vulcabond, 2,4-and/or 2, the 6-tolylene diisocyanate, 2,4-and/or 4,4 '-diphenylmethanediisocyanate and 1,5-two isocyanato naphthalenes and composition thereof.In some embodiment, isocyanate compound is selected from two-(4-isocyanato cyclohexyl) methane, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, α, α, α ', α '-tetramethyl--1,3-and/or-1,4-xylylene vulcabond, 2,4-and/or 2,6-tolylene diisocyanate and 2,4-and/or 4,4 '-diphenylmethanediisocyanate.In other embodiments, isocyanate compound is selected from isophorone diisocyanate, 2,4 toluene diisocyanate and 2,4-and 2, the mixture of 6-tolylene diisocyanate.Still in other embodiments, isocyanate compound can be 4,4 '-methylene-bis (phenyl) vulcabond (MDI), 4,4 '-methylene-bis (cyclohexyl) vulcabond (hydrogenation MDI), 2,4-tolylene diisocyanate (TDI), 1,6-two isocyanato hexane (HDI) and Luprinate ^TMM20S.

Embodiment

Mercaptan soya-bean oil

[00444] according to each step of method described herein, soya-bean oil is reacted with hydrogen sulfide existing under the condition of initiator, produce mercaptan soya-bean oil.Several embodiment follow the identical method of using.

[00445] soya-bean oil and hydrogen sulfide are existed among the embodiment that reacts under the condition of UV-light comprising, used following raw material: refining (food grade) soya-bean oil (Cargill); The non-refining soya-bean oil (ADM supplier) that do not come unstuck; Hydrogen sulfide (Tessenderlo Sourcing, gas products, purity＞99.9%); And tri-n-butylphosphite (Aldrich, 90%).

[00446] for the quantitative measurment mercaptan sulfur, adopt silver nitrate titration method that mercaptan sulfur is analyzed, with reference to ASTM D3227, and designed following change the silver salt incrustation of probe is minimized: sample is with the tetrahydrofuran (THF) dilution of known quality.Silver nitrate concentration is 0.01N, demarcates through potassiumiodide.

Embodiment 1

[00447] (referring to above-mentioned source, 500mL) pack in one 5 liters the stainless steel autoclave reactor, this reactor is furnished with and adorns the horizontal silica tube of pressing the UV lamp among 100 watts of Hanovia in one with soya-bean oil.With this system of nitrogen wash and at the normal pressure lower seal.With liquid hydrogen sulfide (1.96kg) reactor of packing into.Reactor pressure is 307psig.Too much heat is to eliminate by 18 ℃ of modes of moving the circulation bath down.Start the agitator of reactor.Ultraviolet lamp was opened 30 minutes.Discharge outlet by reactor head slowly reduces pressure reactor, puts to high pressure waste-gas burning pipeline (flare line).Use the nitrogen jet reaction product subsequently, waste gas is put to high pressure waste-gas burning pipeline.By the bleed valve of bottom, thick mercaptan soya-bean oil is discharged then.

[00448] the mercaptan soya-bean oil of reaction generation can be used nitrogen jet 4 hours under 100 ℃ of reduced pressure, to remove any residual hydrogen sulfide.

[00449] mercaptan sulfur is analyzed by three kinds of different tests.First test method that adopts is the ASTM D3227 that revises, and its mercaptan sulfur test result is 4.64%.Second kind of test method that is used to test mercaptan sulfur is SLP-1204, is a kind of test method of Chevron Phillips Chemical Company LLP exploitation.By using the SLP-1204 test, the mercaptan sulfur test result that reaction produces is 4.28%.At last, total sulfur is measured by the combustion analysis method, and its total sulfur test result is 4.27%.

Embodiment 2

[00450] vegetables oil (42kg) is packed in one 100 gallons the preservation container.This container is through nitrogen purge and return back to normal pressure.Hydrogen sulfide (174kg) packed into, and this preserves container.When container pressure typically remained on 380-400psig, vessel temp was controlled at 25-30 ℃.Reactant overturns from preserving container by stainless steel tubulose photochemical reactor continuously, joins a 7.5KW Hanovia medium pressure mercury lamp that is contained in the silica tube in this stainless steel tubulose photochemical reactor.In reaction process, the temperature of monitoring reaction device, pressure and composition.The mercaptan sulfur that reaction times is reached by expectation is formed decision.In case finish, unreacted hydrogen sulfide is discharged from system lentamente.When a nitrogen jet pipe, remaining hydrogen sulfide is eliminated under the condition of 100 ℃ and decompression.Reaction product enters the clean container drum from reactor bottom.When adopting the ASTM D3227 that revises, the measuring result of mercaptan sulfur is 11.0%, when adopting SLP-1204, is 8.74%, and when adopting combustion analysis (total sulfur), total sulfur is 11.21%.

Embodiment 3

[00451] with soya-bean oil (referring to above-mentioned source, 180mL) and tri-n-butylphosphite (1.8mL) pack in one 1.5 liters the stainless steel autoclave reactor, this reactor is furnished with and adorns the horizontal silica tube of pressing the UV lamp among 100 watts of Hanovia in one.With this system of nitrogen wash and at the normal pressure lower seal.With liquid hydrogen sulfide (1.96kg) reactor of packing into.Reactor pressure is 307psig.Start circulation bath and bath temperature and be set at 18 ℃.Start the agitator of reactor.Ultraviolet lamp was opened 30 minutes.Discharge outlet by reactor head slowly reduces pressure reactor, puts to high pressure waste-gas burning pipeline.Use the product in the nitrogen jet reactor subsequently, waste gas is put to high pressure waste-gas burning pipeline.By the bleed valve of bottom thick mercaptan soya-bean oil is discharged then.

[00452] the mercaptan soya-bean oil of reaction generation can be used nitrogen jet 4 hours under 100 ℃ of reduced pressure, to remove any residual hydrogen sulfide.When adopting the ASTM D3227 that revises, the measuring result of mercaptan sulfur is 13.0%, when adopting SLP-1204, is 9.82%, and when adopting combustion analysis, is 11.69%.

[00453] table 1 provides some characteristics of the mercaptan soya-bean oil that is produced among the embodiment 1-3.

Table 1 mercaptan soya-bean oil product performance

Embodiment	Mercaptan sulfur ^ (wt.％)	Episulfide and thiol group mol ratio	C=C and thiol group mol ratio
Embodiment	Mercaptan sulfur ^ (wt.％)	Episulfide and thiol group mol ratio	C=C and thiol group mol ratio	1 2 3	4.28 11.0 13.0	0.02 0.03 0.03	2.79 0.26 0.51

^Mercaptan sulfur content is to measure by the ASTM D3227 that revises

[00454] modified soya-bean oil and modified Toenol 1140 sample also can be substantially with reference to United States Patent (USP)s the 3rd, 991, and method is carried out methanolysis described in No. 089, is incorporated herein the document as a reference.1 gram mercaptan soya-bean oil is put into round-bottomed flask.With the methanol solution of sodium methylate (25%, 2.0mL) add in this mercaptan carburetion and stir about 1 hour at room temperature.Add toluene (10mL) and distilled water (5mL).With this mixture of hcl acidifying of 0.5N until obtaining the about 2-3 of pH.Each layer of gained is separated from each other and the superiors is placed on the sal epsom dry before filtration.The gained sample is analyzed with gas chromatography-mass spectrometry machine (GC-MS).

Embodiment 4

[00455] soya-bean oil and hydrogen sulfide react in one 1000 gallons reactor, and this reactor has presses 7500 watts of ultraviolet lamps of ultraviolet ray in six.The general method that is used for five kinds of mercaptan soya-bean oil production tests provides as follows.

[00456] soya-bean oil is packed in one 1000 gallons the stirring reactor.And then hydrogen sulfide packed in the reactor.After hydrogen sulfide is packed reactor into, turn on agitator and ultraviolet lamp, and when the reaction when carrying out temperature and pressure can be set.Continue reaction until the minimum mercaptan sulfur content that obtains 8wt.%.After question response is finished, excessive hydrogen sulfide is flashed off from reactor.For 2-5 number test, mercaptan soya-bean oil product will carry out extra hydrogen sulfide and remove step, is included in vacuum, and 50mmHg (only is used for carrying out 2-5 number test) under the 250  conditions and removes hydrogen sulfide from product.

[00457] table 2 provides the soya-bean oil and the hydrogen sulfide charging situation of five 1000 gal reactor tests.Table 2 also provides based on the carbon-carbon double bond of average 4.5 carbon-carbon double bonds of each soya-bean oil molecule and the roughly ratio of hydrogen sulfide.In addition, table 2 provides the temperature and pressure scope of reactor in soya-bean oil and the hydrogen sulfide reaction process.

Table 2-1000 gal reactor mercaptan soya-bean oil production test condition

Test number	Soya-bean oil (lbs)	Hydrogen sulfide (lbs)	C=C and H ₂The S mol ratio	Time (hour)	Temperature (℃)	Pressure (psig)
Test number	Soya-bean oil (lbs)	Hydrogen sulfide (lbs)	C=C and H ₂The S mol ratio	Time (hour)	Temperature (℃)	Pressure (psig)	1 2 3 4 5	2264 971 513 524 276	4526 6039 6500 6528 6648	12 38 78 77 148	35 10 ＜5.1 3 2	29-41 31-44 29-48 26-43 40-43	295-384 323-429 309-449 279-424 241-355

[00458] table 3 provides the detailed analysis of the mercaptan soya-bean oil of producing in five kind of 1000 gal reactor test.

Table 3-1000 gal reactor mercaptan soya-bean oil product performance

Test number	Mercaptan sulfur ^ (wt.％)	Episulfide and thiol group mol ratio	C=C and thiol group mol ratio	Contain thiol group side chain (%)
Test number	Mercaptan sulfur ^ (wt.％)	Episulfide and thiol group mol ratio	C=C and thiol group mol ratio	Contain thiol group side chain (%)	1 2 3 4 5	9.3 9.6 9.2 9.3 10.1	- 0.04 0.03 0.03 0.03	- 0.48 0.59 0.62 0.54	71.6 72.3 69.1 71.6 72.3

^Mercaptan sulfur content is measured by Raman spectroscopy

The mercaptan Semen Ricini oil

[00459] with reference to method steps described herein, Viscotrol C is reacted with hydrogen sulfide existing under the condition of initiator, produce the mercaptan Semen Ricini oil.Several embodiment follow the identical method of using.Make in the example that Semen Ricini oil and hydrogen sulfide reacts comprising, used following raw material: Viscotrol C (Aldrich); Hydrogen sulfide (Tessenderlo Sourcing, gas products, purity＞99.9%); And tri-n-butylphosphite (Aldrich, 90%).

Embodiment 1

[00460] Viscotrol C 140mL is packed in one 1.5 liters the stainless steel autoclave reactor, this reactor is furnished with and adorns the horizontal silica tube of pressing ultraviolet lamp among 100 watts of Hanovia in one.With this system of nitrogen wash and at the normal pressure lower seal.With liquid hydrogen sulfide (0.76kg) reactor of packing into.Reactor pressure is 419psig.Start the agitator of reactor and transfer to 800rpm.Opened ultraviolet lamp 2 hours.Temperature of reaction changes in 33.9 to 40.8 ℃ scope.The reactor resulting pressure is 448psig.Close ultraviolet lamp and reactor is slowly reduced pressure, put to high pressure waste-gas burning pipeline by the top discharge mouth.Use the nitrogen jet reactor product subsequently, waste gas straightens to high pressure waste-gas burning pipeline.By bottom drain valve, thick mercaptan soya-bean oil is discharged then.

Embodiment 2

[00461] Viscotrol C (140mL) and tri-n-butylphosphite (1.4mL) are packed in one 1.5 liters the stainless steel autoclave reactor, this reactor is furnished with and adorns the horizontal silica tube of pressing ultraviolet lamp among 100 watts of Hanovia in one.With this system of nitrogen wash and at the normal pressure lower seal.With liquid hydrogen sulfide (0.76kg) reactor of packing into.Reactor pressure is 418psig.Start the agitator of reactor and transfer to 800rpm.Opened ultraviolet lamp 4 hours.Temperature of reaction changes in from 33.2 to 40.9 ℃ scope.The reactor resulting pressure is 456psig.Close ultraviolet lamp and reactor is slowly reduced pressure, put to high pressure waste-gas burning pipeline by the top discharge mouth.Use the nitrogen jet reactor product subsequently, waste gas is put to high pressure waste-gas burning pipeline.By bottom drain valve thick mercaptan soya-bean oil is discharged then.

[00462] in table 4, provides the analytical characteristics of these two kinds of mercaptan castor oil products.

Table 4-mercaptan castor oil products characteristic

Embodiment	Mercaptan sulfur ^ (wt.％)	C=C and thiol group mol ratio	Contain thiol group side chain (%)
Embodiment	Mercaptan sulfur ^ (wt.％)	C=C and thiol group mol ratio	Contain thiol group side chain (%)	1 2	6.4 7.4	0.52 0.26	64.1 77.7

^Mercaptan sulfur content is measured by Raman spectroscopy

Sulfydryl hydroxyl soya-bean oil synthetic method

Embodiment 1 (CPC407-81D)

[00463] with epoxidized soybean oil (700g ,～0.7mol) and 1, (DBU, 4.7g's 8-diazabicyclo [5,4,0]-11 carbon-7-alkene 30.5mmol) pack in one 1 liter the Hastelloy C high pressure tank reactor, and this reactor pressure test reaches 630psig.By the dipping tube in the fluid space, with hydrogen sulfide (H ₂S, 132.0g 3.87mol) is pressed in the reactor content that is stirring.The reacting by heating mixture also remains on 85 ℃, stirs simultaneously, continues 8 hours, and reactor pressure is reduced to 219psig from maximum value 351psig during this period.Stop to stir, and (80-85 ℃) slowly discharges excessive hydrogen sulfide while hot, to low pressure exhaust gas burning pipeline.Use the vapour space 1 hour in the nitrogen purging reactor then, and (80-85 ℃) discharges reactor content while hot.Vacuum (＜5mmHg), under the 130-140 ℃ of condition, nitrogen jet reaction product 16 hours is removed remaining hydrogen sulfide.The mercaptan sulfur of the faint yellow viscous oil that produces (by the ASTM D3227 burette test of revising) content is 7.53wt.%, 2.5SH/ molecule or 2.35meq SH/g.Combustion analysis shows C 64.37%, H 10.20%, N＜0.15% and S 9.51%.

Embodiment 2 (CPC407-83)

[00464] with epoxidized soybean oil (600g ,～0.6mol) and 1, (DBU, 5.0g's 8-diazabicyclo-[5,4,0]-11 carbon-7-alkene 32.4mmol) pack in one 1 liter the Hastelloy C high pressure tank reactor, and this reactor pressure test reaches 630psig.Then by the dipping tube in the fluid space, with hydrogen sulfide (H ₂S, 204.0g 5.99mol) is pressed in the reactor content that is stirring.The reacting by heating mixture also remains on 97 ℃, stirs simultaneously, continues 14 hours, and reactor pressure is reduced to 229psig from maximum value 509psig during this period.Stop to stir, and (90-95 ℃) while hot, excessive hydrogen sulfide slowly discharged, to low pressure exhaust gas burning pipeline.With the vapour space in the nitrogen purging reactor 1 hour, and (80-85 ℃) discharged reactor content while hot.Vacuum (＜50mmHg), under the 130-140 ℃ of condition, nitrogen jet reaction product 16 hours is to remove remaining hydrogen sulfide.The mercaptan sulfur of the faint yellow viscous oil that produces (by the ASTM D3227 burette test of revising) content is 4.14wt.%, 1.4SH/ molecule or 1.29meq SH/g.Combustion analysis shows C 65.18%, H 10.17%, N＜0.15% and S 7.80%.

Embodiment 3 (CPC407-86)

[00465] with epoxidized soybean oil (600g ,～0.6mol) and 1, (DBU, 5.0g's 8-diazabicyclo-[5,4,0]-11 carbon-7-alkene 32.4mmol) pack in one 1 liter the Hastelloy C high pressure tank reactor, and this reactor pressure test reaches 630psig.By the dipping tube in the fluid space, with hydrogen sulfide (H ₂S, 204.0g 5.99mol) is pressed in the reactor content that is stirring.The reacting by heating mixture also remains on 85 ℃, stirs simultaneously, continues 10 hours, and reactor pressure is reduced to 489psig from maximum value 578psig during this period.Stop to stir, and (80-85 ℃) slowly discharges excessive hydrogen sulfide while hot, to low pressure exhaust gas burning pipeline.With the vapour space in the nitrogen purging reactor 1 hour, and (80-85 ℃) discharged reactor content while hot.Vacuum (＜50mmHg), under the 130-140 ℃ of condition, nitrogen jet reaction product 16 hours is to remove remaining hydrogen sulfide.The mercaptan sulfur of the faint yellow viscous oil that produces (by the ASTM D3227 burette test of revising) content is 8.28wt.%, 2.8SH/ molecule or 2.58meq SH/g.Combustion analysis shows C 65.24%, H 9.52%, N 0.18% and S 9.53%.

Embodiment 4 (CPC407-88)

[00466] with epoxidized soybean oil (600g ,～0.6mol) and 1, (DBU, 5.0g's 8-diazabicyclo-[5,4,0]-11 carbon-7-alkene 32.4mmol) pack in one 1 liter the Hastelloy C high pressure tank reactor, and this reactor pressure test reaches 630psig.By the dipping tube in the fluid space, with hydrogen sulfide (H ₂S, 204.0g 5.99mol) is pressed in the reactor content that is stirring.The reacting by heating mixture also remains on 85 ℃, stirs simultaneously, continues 12 hours, and reactor pressure is reduced to 498psig from maximum value 587psig during this period.Stop to stir, and (80-85 ℃) slowly discharges excessive hydrogen sulfide while hot, to low pressure exhaust gas burning pipeline.With the vapour space in the nitrogen purging reactor 1 hour, and (80-85 ℃) discharged reactor content while hot.Vacuum (＜50mmHg), under the 130-140 ℃ of condition, nitrogen jet reaction product 16 hours is to remove remaining hydrogen sulfide.The mercaptan sulfur of the faint yellow viscous oil that produces (by the ASTM D3227 burette test of revising) content is 8.24wt.%, 2.8SH/ molecule or 2.57meq SH/g.Combustion analysis shows C 63.39%, H 10.01%, N＜0.15% and S 8.76%.

Embodiment 5 (CPC407-93)

[00467] with epoxidized soybean oil (600g ,～0.6mol) and 1, (DBU, 5.0g's 8-diazabicyclo-[5,4,0]-11 carbon-7-alkene 32.4mmol) pack in one 1 liter the Hastelloy C high pressure tank reactor, and this reactor pressure test reaches 630psig.By the dipping tube in the fluid space, with hydrogen sulfide (H ₂S, 204.0g 5.99mol) is pressed in the reactor content that is stirring.The reacting by heating mixture also remains on 85 ℃, stirs simultaneously, continues 8 hours, and reactor pressure is reduced to 537psig from maximum value 606psig during this period.Stop to stir, and (80-85 ℃) slowly discharges excessive hydrogen sulfide while hot, to low pressure exhaust gas burning pipeline.With the vapour space in the nitrogen purging reactor 1 hour, and (80-85 ℃) discharged reactor content while hot.Vacuum (＜50mmHg), under the 130-140 ℃ of condition, nitrogen jet reaction product 16 hours is to remove remaining hydrogen sulfide.The mercaptan sulfur of the faint yellow viscous oil that produces (by the ASTM D3227 burette test of revising) content is 7.34wt.%, 2.5SH/ molecule or 2.29meq SH/g.Combustion analysis shows C 64.47%, H 10.18%, N＜0.15% and S 8.40%.

Embodiment 6 (CPC407-94)

[00468] with epoxidized soybean oil (600g ,～0.6mol) and 1, (DBU, 5.0g's 8-diazabicyclo-[5,4,0]-11 carbon-7-alkene 32.4mmol) pack in one 1 liter the Hastelloy C autoclave reactor, and this reactor pressure test reaches 630psig.By the dipping tube in the fluid space, with hydrogen sulfide (H ₂S, 204.0g 5.99mol) is pressed in the reactor content that is stirring.The reacting by heating mixture also remains on 85 ℃, stirs simultaneously, continues 6 hours, and reactor pressure is reduced to 556psig from maximum value 586psig during this period.Stop to stir, and (80-85 ℃) slowly discharges excessive hydrogen sulfide while hot, to low pressure exhaust gas burning pipeline.With the vapour space in the nitrogen purging reactor 1 hour, and (80-85 ℃) discharged reactor content while hot.Vacuum (＜50mmHg), under the 130-140 ℃ of condition, nitrogen jet reaction product 16 hours is to remove remaining hydrogen sulfide.The mercaptan sulfur of the faint yellow viscous oil that produces (by the ASTM D3227 burette test of revising) content is 5.93wt.%, 2.0SH/ molecule or 1.85meq SH/g.Combustion analysis shows C 65.26%, H 10.19%, N＜0.15% and S 8.43%.

Embodiment 7 (CPC407-95)

[00469] with epoxidized soybean oil (600g ,～0.6mol) and 1, (DBU, 5.0g's 8-diazabicyclo-[5,4,0]-11 carbon-7-alkene 32.4mmol) pack in one 1 liter the Hastelloy C autoclave reactor, and this reactor pressure test reaches 630psig.By the dipping tube in the fluid space, with hydrogen sulfide (H ₂S, 204.0g 5.99mol) is pressed in the reactor content that is stirring.The reacting by heating mixture also remains on 85 ℃, stirs simultaneously, continues 4 hours, and reactor pressure is reduced to 554psig from maximum value 595psig during this period.Stop to stir, and (80-85 ℃) slowly discharges excessive hydrogen sulfide while hot, to low pressure exhaust gas burning pipeline.With the vapour space in the nitrogen purging reactor 1 hour, and (80-85 ℃) discharged reactor content while hot.Vacuum (＜50mmHg), under the 130-140 ℃ of condition, nitrogen jet reaction product 16 hours is to remove remaining hydrogen sulfide.The mercaptan sulfur of the faint yellow viscous oil that produces (by the ASTM D3227 burette test of revising) content is 5.36wt.%, 1.8SH/ molecule or 1.67meq SH/g.Combustion analysis shows C 65.67%, H 10.17%, N0.34% and S 9.84%.

Embodiment 8 (CPC407-97)

[00470] with epoxidized soybean oil (600g ,～0.6mol) and 1, (DBU, 5.0g's 8-diazabicyclo-[5,4,0]-11 carbon-7-alkene 32.4mmol) pack in one 1 liter the Hastelloy C autoclave reactor, and this reactor pressure test reaches 630psig.By the dipping tube in the fluid space, with hydrogen sulfide (H ₂S, 204.0g 5.99mol) is pressed in the reactor content that is stirring.The reacting by heating mixture also remains on 85 ℃, stirs simultaneously, continues 4 hours, and reactor pressure is reduced to 519psig from maximum value 577psig during this period.Stop to stir, and (80-85 ℃) while hot, excessive hydrogen sulfide slowly discharged, to low pressure exhaust gas burning pipeline.With the vapour space in the nitrogen purging reactor 1 hour, and (80-85 ℃) discharged reactor content while hot.Vacuum (＜50mmHg), under the 130-140 ℃ of condition, nitrogen jet reaction product 16 hours is to remove remaining hydrogen sulfide.The mercaptan sulfur of the faint yellow viscous oil that produces (is used AgNO ₃Titration) content is 5.85wt.%, 2.0SH/ molecule or 1.82meq SH/g.Combustion analysis shows C 65.09%, H 10.15%, N 0.35% and S 10.63%.

Embodiment 9 (CPC407-98)

[00471] with epoxidized soybean oil (600g ,～0.6mol) and 1, (DBU, 5.0g's 8-diazabicyclo [5,4,0]-11 carbon-7-alkene 32.4mmol) pack in one 1 liter the Hastelloy C autoclave reactor, and this reactor pressure test reaches 630psig.By the dipping tube in the fluid space, with hydrogen sulfide (H ₂S, 204.0g 5.99mol) is pressed in the reactor content that is stirring.The reacting by heating mixture also remains on 85 ℃, stirs simultaneously, continues 2 hours, and reactor pressure is reduced to 508psig from maximum value 577psig during this period.Stop to stir, and (80-85 ℃) slowly discharges excessive hydrogen sulfide while hot, to low pressure exhaust gas burning pipeline.With the vapour space in the nitrogen purging reactor 1 hour, and (80-85 ℃) discharged reactor content while hot.Vacuum (＜5mmHg), under the 130-140 ℃ of condition, nitrogen jet reaction product 16 hours is to remove remaining hydrogen sulfide.The mercaptan sulfur of the faint yellow viscous oil that produces (by the ASTM D3227 burette test of revising) content is 5.07wt.%, 1.7SH/ molecule or 1.58meq SH/g.Combustion analysis shows C 63.96%, H 10.01%, N0.35% and S 11.22%.

[00472] table 5 provides the characteristic of the sulfydryl hydroxyl soya-bean oil sample of producing among the embodiment 1-10.

Table 5

Embodiment	Reaction times (hour)	Temperature of reaction (℃)	Mercaptan sulfur (wt.%) ¹	The SH/ molecule ²	Per molecule residual epoxide group ³	Epoxide: SH mol ratio
Embodiment	Reaction times (hour)	Temperature of reaction (℃)	Mercaptan sulfur (wt.%) ¹	The SH/ molecule ²	Per molecule residual epoxide group ³	Epoxide: SH mol ratio	1 2 3 4 5 6 7 8 9 10	0 8 14 10 12 8 6 4 4 2	N/A 85 97 85 85 85 85 85 85 85	N/A 7.53 4.14 8.28 8.24 7.34 5.93 5.36 5.85 5.07	0 2.5 1.4 2.8 2.8 2.5 2.0 1.8 2.0 1.7	4.3 1.8 2.9 1.5 1.5 1.8 2.3 2.5 2.3 2.6	- 0.72 2.07 0.54 0.54 0.72 1.15 1.40 1.15 1.529

¹Mercaptan sulfur is by ASTM D3227 method Silver Nitrate oxidimetry

²Measure by the wt.% mercaptan sulfur

³Determine by from the epoxide content of raw material, deducting the SH/ molecule

Embodiment 1L

[00473] other sulfydryl hydroxyl soya-bean oil is epoxidized soybean oil, hydrogen sulfide and the catalyzer that adopts different amounts, and adopts different temperature and reaction times to prepare.The general method that is used to produce sulfydryl hydroxyl soya-bean oil provides as follows.

[00474] epoxidized soybean oil and catalyzer are packed in one 1 liter the Hastelloy C autoclave reactor, this reactor pressure test reaches 1000psig.Dipping tube by in the fluid space is pressed into hydrogen sulfide in the reactor content that is stirring.The reacting by heating mixture also keeps temperature to stir simultaneously in for some time, continues 12 hours, and reactor pressure can descend usually between this reaction period.In reaction times end, stop to stir, and slowly discharge excessive hydrogen sulfide while hot, to low pressure exhaust gas burning pipeline.With the vapour space in the nitrogen purging reactor 1 hour, and discharge reactor content.Vacuum (＜50mmHg), under 100 ℃ of conditions, nitrogen jet reaction product 16 hours is to remove remaining hydrogen sulfide.Table 6 provides the reaction conditions of the several tests that are used for the production of sulfydryl hydroxyl soya-bean oil and the mercaptan sulfur content of the sulfydryl hydroxyl soya-bean oil produced.

The production test of table 6-sulfydryl hydroxyl soya-bean oil

Test	Epoxidized soybean oil (g)	Catalyzer (g)	H ₂S (g)	H ₂S: epoxide mol ratio	Temperature (℃)	Time (minute)	Mercaptan sulfur ^a (wt.％)
Test	Epoxidized soybean oil (g)	Catalyzer (g)	H ₂S (g)	H ₂S: epoxide mol ratio	Temperature (℃)	Time (minute)	Mercaptan sulfur ^a (wt.％)	556-41 ^ 556-53 ^ 556-47 ^ 407-81D ^ 407-86 ^ 556-79 ^ 556-80 ^	249.6 250.0 250.5 500.0 600.0 250.0 251.0	1.950 2.000 1.050 4.200 5.000 2.600 5.000	214.0 213.0 213.0 255.0 204.0 214.0 214.0	5.86 5.81 5.81 3.49 2.07 5.83 5.81	64 100 101 85 85 100 100	728 370 720 480 600 720 720	5.69 9.04 10.47 7.53 8.28 6.68 9.51

^Catalyzer is DBU

^Catalyzer is triethylamine (TEA)

^aMercaptan sulfur is to measure with the ASTM D3327 silver nitrate titration method of revising

[00475] test number 407-86 is carried out sodium methylate methanolysis method, and carry out GC-MS subsequently and analyze.GC-MS analysis revealed, product have about 0.14 the epoxide group and the mol ratio of thiol group.The methanolysis data also show, average 80.4% sulfydryl hydroxyl soya-bean oil product sulfur-bearing.

Low dimerization MSO (MERCAPTANIZED SOYBEAN OIL (mercaptan soya-bean oil))

Embodiment 1

[00476] with mercaptan soya-bean oil (900.1g; The 10.92wt.% mercaptan sulfur) packs in the three-necked flask with element sulfur particle (9.6g).Reaction mixture is heated to 120 ℃ to the sulphur dissolving, is cooled to 99 ℃ then.(4.8g) is added drop-wise in the reaction mixture with another funnel with Tributylamine.Reaction mixture mixed 2 hours at 90 ℃.Observe H ₂The progress of S.Under 110 ℃ of conditions of vacuum, with nitrogen jet reaction product (904.8g) 4 hours to remove remaining hydrogen sulfide.Final product is that mercaptan sulfur is the light yellow oil of 6.33wt.% (by the ASTMD3227 method of revising).The combustion analysis result of element is 70.19% C; 10.37% H; And 11.21%S.

Embodiment 2

[00477] with mercaptan soya-bean oil (900.0g; The 10.92wt.% mercaptan sulfur) packs in the three-necked flask with element sulfur particle (36.0g).Reaction mixture is heated to 120 ℃ to the sulphur dissolving, is cooled to 100 ℃ then.(4.8g) is added drop-wise in the reaction mixture with another funnel with Tributylamine.Reaction mixture mixed 36 hours at 90 ℃.Observe H ₂The progress of S.Under 90 ℃ of conditions of vacuum, with nitrogen jet reaction product (825.6g) 36 hours to remove remaining hydrogen sulfide.Then, under 110 ℃ of conditions of vacuum, with nitrogen jet reaction product 3 hours to remove remaining hydrogen sulfide.Final product is that mercaptan sulfur is the light yellow oil of 2.36wt.% (by the ASTM D3227 method of revising).The combustion analysis result of element is 68.90% C; 11.07% H; And 12.25% S.

Embodiment 3

[00478] with mercaptan soya-bean oil (900.1g; The 10.92wt.% mercaptan sulfur) packs in the three-necked flask with element sulfur particle (18.0g).Reaction mixture is heated to 125 ℃ to the sulphur dissolving, is cooled to 101 ℃ then.(4.8g) is added drop-wise in the reaction mixture with another funnel with Tributylamine.Reaction mixture mixed 2 hours at 90 ℃.Observe H ₂The progress of S.Under 110 ℃ of conditions of vacuum, reaction product (901.5g) with nitrogen jet 4 hours to remove remaining hydrogen sulfide.Final product is that mercaptan sulfur is the light yellow oil of 4.9wt.% (by the ASTMD3227 method of revising).The combustion analysis result of element is 69.58% C; 11.25% H; And 11.31%S.

Embodiment 4

[00479] with mercaptan soya-bean oil (900.2g; The 10.92wt.% mercaptan sulfur) packs in the three-necked flask with element sulfur particle (45.0g).Reaction mixture is heated to 125 ℃ to the sulphur dissolving, is cooled to 100 ℃ then.(4.8g) is added drop-wise in the reaction mixture with another funnel with Tributylamine.Reaction mixture mixed 2 hours at 90 ℃.Observe H ₂The progress of S.Under 110 ℃ of conditions of vacuum, reaction product (915.0g) with nitrogen jet 4 hours to remove remaining hydrogen sulfide.End product is that mercaptan sulfur is the light yellow oil of 1.41wt.% (by the ASTMD3227 method of revising).The combustion analysis result of element is 68.35% C; 10.98% H; And 13.28%S.

[00480] table 7 provides the viscosity of the low dimerization mercaptan soya-bean oil of producing among the embodiment 1-4 (crosslinked mercaptan soya-bean oil) under several differing tempss.

The viscosity of the low dimerization MSO of table 7-

Embodiment	25 ℃ of viscosity (cP)	50 ℃ of viscosity (cP)	75 ℃ of viscosity (cP)	100 ℃ of viscosity (cP)
Embodiment	25 ℃ of viscosity (cP)	50 ℃ of viscosity (cP)	75 ℃ of viscosity (cP)	100 ℃ of viscosity (cP)	1 2 3 4	610.5 3240 843 ＞10000	162.8 - 321.7 1502	52.14 200 68.8 398	29.60 106.3 38.5 213

By the Brookfield viscometer determining

[00481] by the different oligomer mixture of gpc analysis.The GPC data show have various oligopolymer to exist, and it comprises that nearly 20 triglyceride level unit connect together.

The preparation of polythiourethane polymkeric substance

Take by weighing mercaptan soya-bean oil (MSO), sulfydryl hydroxyl soya-bean oil (MHSO) or crosslinked mercaptan soya-bean oil (CMSO-hangs down dimerization MSO) (after this all referring to linking agent), put into a polyethylene beaker.The polymeric polyisocyanate that in linking agent, adds expectation.The catalyzer that in reaction mixture, adds expectation.Manually stir this three component reaction mixture with wooden Popsicle rod then.Subsequently whole pre-polymer mixtures are poured in the suitable mould, so that solidify.The mould example comprises the aluminium dish of diameter 50mm or diameter 70mm.Pass through technical scheme A, B or the C of expectation then, solidified sample.After finishing set time, under the room temperature sample is stored in 2 weeks in the reclosable plastic sandwich bag.And then take off sample from aluminium-making mould, and detect, or be sealed in the interlayer bag once more and store with ASTM D2240-02B, ASTM E1545-95A and/or E228-95 method.

Polythiourethane is formed

Table 8
Table 8				The R﹠T raw material	Vulcabond	Stoichiometry	Catalyzer
The MSO-trifunctional	Luprinate TM-gathers MDI	≈0.9	DABCO	The R﹠T raw material	Vulcabond	Stoichiometry	Catalyzer
The MSO-trifunctional	Luprinate TM-gathers MDI	≈0.9	DABCO	MSO-two functional groups	MDI	≈1	DBTDL
MSO-TBP handles	HMDI	≈1.25	JeffolA-480	MSO-two functional groups	MDI	≈1	DBTDL
MSO-TBP handles	HMDI	≈1.25	JeffolA-480	MHSO-three mercaptan	TDI
MHSO-two mercaptan	HDI			MHSO-three mercaptan	TDI
MHSO-two mercaptan	HDI			The CMSO-height is crosslinked
Crosslinked among the CMSO-				The CMSO-height is crosslinked
Crosslinked among the CMSO-				The CMSO-low cross-linking
Viscotrol C				The CMSO-low cross-linking

[00482], under the situation that has catalyzer to exist, make thiol ester composition and di-isocyanate reaction prepare numerous polythiourethane compositions with this type of polythiourethane method for compositions of preparation described herein.These compositions are different variable preparations of raw material, vulcabond, stoichiometry and catalyzer shown in the employing table 8.Adopt each variable combination, can produce the composition more than 1200 kinds.Each raw material can react with each stoichiometry with each vulcabond under each listed catalyst action, produces 1200+ kind composition.Stoichiometry is based on the equivalence ratio of active hydrogen (mercaptan and oh group) and vulcabond in the mercaptan ester composition (MSO, MHSO, CMSO, MCO).For example: use Jeffol  A-480 to make catalyzer, Viscotrol C and tolylene diisocyanate react with stoichiometric number 1.25.Another example uses the DABCO catalyzer, and thiol ester composition and methane diisocyanate (methane diisocyanate) react with stoichiometric number 0.9.

[00483] in addition, the polythiourethane that produces from above two kinds of polythiourethane parents prepares from mercaptan Viscotrol C (MCO).

[00484] in first kind of MCO polythiourethane embodiment, takes by weighing MCO and put into a polyethylene beaker.Mercaptan with 0.95 and isocyanic ester mol ratio add Luprinate in this MCO reagent.Based on each composition gross weight, 0.125 adds dibutyl tin laurate (DBTDL) in reaction mixture by weight percentage.Manually stir this three component reaction mixture with wooden Popsicle rod then.Subsequently whole pre-polymer mixtures are poured into and solidified, and be cured to solidify option b with in the mould.After finishing set time, can determine that this preparation process made the polythiourethane polymkeric substance.

[00485] in second kind of MCO polythiourethane embodiment, takes by weighing MCO and put into a polyethylene beaker.Mercaptan with 1.00 and isocyanic ester mol ratio add Luprinate M20S in this MCO reagent.Based on each composition gross weight, 0.125 adds dibutyl tin laurate (DBTDL) in reaction mixture by weight percentage.Manually stir this three component reaction mixture with wooden Popsicle rod then.Subsequently whole pre-polymer mixtures are poured in the curing mold and and solidified to solidify option b.After finishing set time, can determine that this preparation process made the polythiourethane polymkeric substance.

[00486] in the polythiourethane composition, used thiol ester composition raw material comprises MSO (mercaptan soya-bean oil), MHSO (sulfydryl hydroxyl soya-bean oil), CMSO (crosslinked mercaptan soya-bean oil), Viscotrol C and MCO (mercaptan Viscotrol C).The vulcabond that is used to produce these compositions comprises MDI (4,4 '-methylene-bis (phenyl) vulcabond), HMDI (4,4 '-methylene-bis (cyclohexyl) vulcabond, be also referred to as hydrogenation MDI), TDI (2, the 4-tolylene diisocyanate), HDI (1,6-two isocyanato hexanes are also referred to as hexamethylene diisocyanate) and Luprinate ^TMM20S (be the low dimerization form of MDI, and also can be described as polymeric MDI, produce) by BASF AG.Catalyst system therefor comprises DABCO (diazabicyclo octane-two-tertiary amine), DBTDL (dibutyl tin laurate-organo-metallic catalyst), Jeffol  A-480 (a kind of tertiary amine polyvalent alcohol, Huntsman Based Chemicals produces) and BDMA (Bian Ji dimethylamine).

[00487] for the polythiourethane composition of picked at random in the 1200+ kind composition, its various rerum naturas are determined, and the result is included in appended each table of accompanying drawing 7A-7F.Used curing scheme is as follows: solidified under the A=room temperature 1-8 hour, and 65 ℃ of solidify overnight then, 95 ℃ solidified 8 hours subsequently; B=65 ℃ of solidify overnight, 95 ℃ solidified 24 hours subsequently; And C=120 ℃ solidified 3 hours, and 95 ℃ solidified 24 hours subsequently.CTE 1 represents the thermal expansivity between the glass transition temperature and first invert point.CTE 2 represents the thermal expansivity between first invert point and second invert point.

Fertilizer embodiment

[00488] various embodiments of the present invention will be illustrated with reference to following examples, and this embodiment should not be used for restriction or explain the present invention.Those of ordinary skills will be easy to recognize that concrete reaction conditions and the method mentioned among the fertilizer embodiment can change, to produce same or analogous composition.Unless otherwise mentioned, all temperature all are degree centigrade, and the percentage composition of all the components all by weight.

[00489] in fertilizer embodiment, used following material:

A: fertiliser granulates-particulate state fertilizer grade urea, SGN250 is available from Agrium;

B1: mercaptan soya-bean oil (MVO embodiment discussed above)-Polymercaptan 358, available from Chevron Phillips Chemical Co.; 8.65% mercaptan sulfur; 370 equivalents; Viscosity 510.6cSt in the time of 21 ℃;

B2: a kind of sulfydryl-hydroxyl soya-bean oil of sulfydryl-hydroxyl soya-bean oil (MHVO the embodiment discussed above)-free radical addition of epoxidized soybean oil is produced by hydrogen sulfide; The functionality of sulfydryl and hydroxyl equates; 8.335% mercaptan sulfur; Equivalent 192 (functionality that comprises sulfydryl and hydroxyl simultaneously);

B3: sulfur-crosslinked mercaptan soya-bean oil (CMVO embodiment discussed above)-by in mercaptan soya-bean oil, adding a kind of sulfur-crosslinked mercaptan soya-bean oil that elementary sulfur is produced; Mercaptan sulfur content 6.33%; Equivalent 506;

B4: sulfur-crosslinked mercaptan soya-bean oil (CMVO embodiment discussed above)-by in mercaptan soya-bean oil, adding a kind of sulfur-crosslinked mercaptan soya-bean oil that elementary sulfur is produced; Mercaptan sulfur content 7.64%; Equivalent 419; C1: isocyanic ester #17-a kind of poly-MDI, available from Canadian BASF, equivalent 133;

C2: Resins, epoxy-5 minute Resins, epoxy, available from American I TW Devcon, Danvers, MA 01923, equivalent 198;

D1: organic additive-Gulftene C30-HA alhpa olefin wax, available from Chevron Phillips ChemicalCo., 65 ℃-80 ℃ of fusing points;

D2: organic additive-Calwax 170, a kind of Microcrystalline Wax is available from Calwax company;

E: linking agent-Jeffol A480, available from Huntsman Polyurethanes; Equivalent 120; Functionality 4.0; Viscosity 4000cPs in the time of 25 ℃;

F1: amine catalyst: Exp-9 is available from Huntsman Polyurethanes; And

F2: amine catalyst: 1,8-diazabicyclo [5,4,0] 11 carbon-7-alkene (DBU), CAS#6674-22-2.

Fertilizer embodiment 1-6

[00490] by prescription shown in the table 4, adopt following method to prepare a series of CRF materials.In each fertilizer embodiment, be 1000g by the fertiliser granulates of coating (A) amount.

[00491] employed stainless steel applies drum, 12 inches of diameters, and 6 inches are dark, have the back plate of sealing and have the header board of 8 inches central openings.Apply drum four equally spaced longitudinal baffles are housed, 1/2 inch of every agreement that contracts a film or TV play to an actor or actress is high.Apply drum and link to each other, set with the 18rpm barrel tumbler with a speed-changing driving device.

[00492] in this process,, make the internal temperature of drum and content thereof be maintained at about 70 ℃ by a speed change electric heat gun.Various coating compositions use independent automatic constant transfer pipet to add, and can once add 1/3 weight of every kind of coating composition.In other words, applied coating divides 3 layers-coating gross weight to report in table

4.In fertilizer embodiment

2,3 and 6, use after this 3-layer coating, also used the wax skin.When this end of processing,, will rouse and content is cooled to 40 ℃ by in drum, being blown into the room temperature air-flow.The taking-up content also leaves in the plastics bag.

[00493] coating vibrator test (paint shaker test) is used to assess the power operation tolerance of every kind of product among the fertilizer embodiment." simulation of coating vibrator " that be used for simulating the damage of controlled release coating tested and carried out by the following method at the coating vibrator.

[00494] at first 200 gram slow release fertilizers is put into the metal tin with cover of a diameter 6 ", dark 5.5 ".In jar, put into mechanical bolt and 8 ( inch) square-head nuts of 8 ( inch *  inch) trough of belt seam spiral shell heads then again.The metal tin that slow release fertilizer, nut and bolt will be housed is subsequently put in one paint regulator/vibrator (Red Devil, 1/4H.P. type) safely.With the frequency of per minute 730 circles, acutely jolting is 6 minutes in the coating vibrator for specimen.Operating time, is stopped when arriving the scheduled time automatically by an electronic timer (Gralab model 451) control.After the coating vibrator stops to shake, take out metal tin, and filter wherein content with one 3  purpose sieves, remove nuts and bolt.Slow release fertilizer is collected in the dish, and it is put back in the raw sample bag, prepare to carry out the rate of release analysis.

[00495] carried out simultaneous test, so that the simulate effect of coating vibrator is associated with damage in some commercial fertilizer agitators.The operating time of coating vibrator and bolts and nuts number are established a capital really and are based on this simultaneous test.These default test parameters that are used for this patent can be simulated the damage that commercial fertilizer agitator causes suitably.

[00496] measured subsequently before coating vibrator simulation test and the water release rate graphic representation of slow release fertilizer afterwards.In this analytic process,, proofread and correct and use TechniconAutoAnalyzer according to the instruction of Automated Determination of Urea and AmmoniacalNitrogen (University of Missouri, 1980) ^TMAdopt following steps:

1. accurately take by weighing 15 the gram (± 0.1mg) sample is gone in the pan.The record example weight.Shift sample to the 125mL erlenmeyer flask.

2. add the 75mL softening water and clog flask.

3. gentleness is shaken sample and water is submerged until whole particles.

4. allow sample at normal temperatures (typically, under the room temperature) place one section specified time.

5. gentle shaking flasks is also only poured solution in the one 100mL volumetric flask gently with mixing solutions.

6. add volumetric flask with softening water rinsing sample, and with rinse water.

7. be added to the capacity and the thorough mixing of volumetric flask.

8. test another time period if repeat this, begin repetition from step 2.

With Technicon AutoAnalyzer II online after, part solution (perhaps if desired, carrying out necessary dilution) can be transferred in the Technicon sample cup, be used for analyzing.

10. with per 1,000,000 N-NH ₃Umber record result's (directly reading) from the Shimadzu totalizing instrument.

[00497] the water release performance of the CRF material of producing among the fertilizer embodiment 1-3 in Fig. 8, represent-under each situation, the water release performance all use before the coating vibrator service test and afterwards two kinds of forms represent.The water release performance of the CRF material of producing among the fertilizer embodiment 4-6 represents in Fig. 9-under each situation, the water release performance all use before the coating vibrator service test and afterwards two kinds of forms represent.

[00498] result among Fig. 7 and 8 shows, the polythiourethane coating can be produced with mercaptan soya-bean oil, thereby produces the CRF material with expectation slow release characteristic.These results also illustrate, by the selection to organic additive (for example wax), can control its release performance.

Fertilizer embodiment 7-10

[00499] a series of CRF materials are produced and are tested, and use the prescription shown in the reported method and table 5 among the above-mentioned fertilizer embodiment 1-6.

[00500] the water release performance of the CRF material of producing among the fertilizer embodiment 7-10 in Fig. 9, represent-under each situation, the water release performance all use before the coating vibrator service test and afterwards two kinds of forms represent.

[00501] result among Fig. 9 shows, the polythiourethane coating can be produced with sulfur-crosslinked mercaptan soya-bean oil, thereby produces the CRF material with expectation slow release characteristic.These results also illustrate, add linking agent and can be used for reducing rate of release by coated fertilizer in the coating prescription.

Fertilizer embodiment 11-14

[00502] a series of CRF materials are produced and are tested, and use the prescription shown in the reported method and table 6 among the above-mentioned fertilizer embodiment 1-6.

[00503] the water release performance of the CRF material of producing among the fertilizer embodiment 11-14 in Figure 10, represent-under each situation, the water release performance all use before the coating vibrator service test and afterwards two kinds of forms represent.

[00504] result among Figure 10 shows, the polythiourethane coating can be used the production of sulfydryl-hydroxyl soya-bean oil, thereby produces the CRF material with expectation slow release characteristic.These results illustrate that also the polythiourethane coating can have the CRF material of expecting slow release characteristic thereby produce with the mixture production of mercaptan soya-bean oil and sulfydryl-hydroxyl soya-bean oil.

Fertilizer embodiment 15-17

[00505] a series of CRF materials are produced and are tested, and use the prescription shown in the reported method and table 7 among the above-mentioned fertilizer embodiment 1-6.

[00506] the water release performance of the CRF material of producing among the fertilizer embodiment 15-17 in Figure 11, represent-under each situation, the water release performance all use before the coating vibrator service test and afterwards two kinds of forms represent.

[00507] result among Figure 11 shows, the epoxy polymer coating can be used the production of sulfydryl-hydroxyl soya-bean oil, thereby produces the CRF material with expectation slow release characteristic.

[00508] although the present invention is described with reference to illustrative embodiment and embodiment, this specification sheets does not wish to be explained with certain restrictive, sense.Therefore, the various changes of illustrative embodiment and other embodiment of the present invention will be for will being conspicuous with reference to those skilled in the art of this specification sheets.So expected is that appended claims will cover any such change or embodiment.

[00509] all publications, patent and application for patent cited herein are all incorporated into this paper as a reference with its full content, and its incorporated extent as the full content of specifically and individually incorporating each single publication, patent or patent application into as a reference.

Analyze

Sulfur-bearing alcohol ester, hydroxyl mercaptan ester and contain the analysis of crosslinked mercaptan ester

[00510] special aspects of sulfur-bearing alcohol ester, hydroxyl mercaptan ester, crosslinked thiol ester, unsaturated ester and epoxidation unsaturated ester is to measure with special analytical technology.The mercaptan sulfur number is to adopt silver nitrate titration method, and method described in ASTM D3227 or Raman spectroscopy obtain.Carbon-carbon double bond and thiol group mol ratio, episulfide and thiol group mol ratio are by to sulfur-bearing alcohol ester or hydroxyl mercaptan ester side chain ¹³C NMR and/or GC analyze to determine.

The mercaptan sulfur content that Raman spectroscopy is measured

[00511] mercaptan sulfur content is by silver nitrate titration method, and ASTM D3227 and/or Raman spectroscopy are measured.Raman spectroscopy is by measuring the Raman spectrum of sulfur-bearing alcohol ester, hydroxyl mercaptan ester, crosslinked thiol ester, and this spectrum compared with the calibration standard that contains the known mercaptan compound of tool dose known amounts thiol group carries out.Generally speaking, the calibration standard mercaptan compound has the structure similar to analyzed sulfur-bearing alcohol ester.

[00512] mercaptans content of sulfur-bearing alcohol ester, hydroxyl mercaptan ester and crosslinked thiol ester is to compare to determine that by Raman spectrum and calibration standard with sulfur-bearing alcohol ester, hydroxyl mercaptan ester and crosslinked thiol ester this standard is diluted to known mercaptan sulfur content with mercaptan carburetion acid methyl esters with soya-bean oil and prepares.The mercaptan carburetion acid methyl esters of the different concentration known of mercaptan sulfur calibration standard product employing soya-bean oil dilution is formulated as standard substance.

[00513] Raman spectrum of calibration standard product and sulfur-bearing alcohol ester, hydroxyl mercaptan ester and crosslinked thiol ester is to use Kaiser Hololab 5000 Process Raman spectrometers to measure, and uses 785nm laser.The Raman spectrum of sulfur-bearing alcohol ester, hydroxyl mercaptan ester and crosslinked thiol ester sample and mercaptan sulfur calibration standard product is by gathering scanning in four times 10 seconds, and with Holoreact software it is handled and to obtain.Use (the center: 2575cm-1, SH peak of mercaptan then; Area: 2500-2650cm-1) with (center: 1745cm-1, C=O peak; Area: the ratio of peak area value 1700-1800cm-1), the peak area value of itself and calibration standard product is compared, and the mercaptan sulfur content of interior insertion sulfur-bearing alcohol ester, hydroxyl mercaptan ester and crosslinked thiol ester, calculate the mercaptan sulfur number of sulfur-bearing alcohol ester, hydroxyl mercaptan ester and crosslinked thiol ester.Through bimestrial measurement, use 5 samples of % mercaptan sulfur content scope as 3.1-10.6wt.%, the repeatability that demonstrates the mercaptan sulfur number of Raman spectroscopy measurement is the standard deviation of 0.05-0.1 and the %RSD of 0.6-1.5.

[00514] Raman spectroscopy of measuring sulfur-bearing alcohol ester, hydroxyl mercaptan ester and containing the mercaptan sulfur content of crosslinked mercaptan ester illustrates by the sulfur-bearing alcohol ester of making from soya-bean oil.But, those skilled in the art can change and use the mercaptan sulfur content that Raman spectroscopy is measured other sulfur-bearing alcohol ester, hydroxyl mercaptan ester described herein and contained crosslinked mercaptan ester.

By ¹³C NMR measures the mol ratio of C=C and thiol group and episulfide group and thiol group

[00515] mole of carbon-carbon double bond and thiol group when the mol ratio of episulfide group and thiol group be by ¹³C NMR determines.The sulfur-bearing alcohol ester ¹³C NMR spectrum is at Varian Mercury INOVA400NMR, Varian Mercury Plus 300 NMR or suitable with it spectrometer (75.5MHz ¹³C NMR) upward obtains.Episulfide carbon atom, thiol group HS-C carbon atom and the definite of carbon-carbon double bond carbon atom peak area have used shown in the following table ¹³C NMR zone.

Functional group	¹³C NMR zone	Carbonatoms/group
Functional group	¹³C NMR zone	Carbonatoms/group	Episulfide carbon atom HS-C carbon atom C=C carbon atom	49-49.5ppm 40-41.5ppm 120-140ppm	2 1 2

[00516] by with the episulfide carbon atom ¹³C NMR peak area is divided by 2 (illustrating that each episulfide group has 2 carbon atoms), and with numeral as a result divided by the HS-C carbon atom of thiol group ¹³C NMR peak area calculates the episulfide and the thiol group mol ratio of sulfur-bearing alcohol ester.By with the carbon-carbon double bond carbon atom ¹³The CNMR peak area is divided by 2 (illustrating that each carbon-carbon double bond has 2 carbon atoms), and with numeral as a result divided by the HS-C carbon atom of thiol group ¹³C NMR peak area calculates the carbon-carbon double bond and the thiol group mol ratio of sulfur-bearing alcohol ester.Soya-bean oil sample and the sulfur-bearing alcohol ester sample produced from soya-bean oil with disclosed method ¹³C NMR skew as shown in Figure 1.

[00517] each unsaturated ester molecule carbon-carbon double bond mean number can adopt similar methods, usefulness carbonyl group carbon atom or C-O ester group carbon atom ¹³C NMR peak area and carbon-carbon double bond ¹³C NMR peak area is measured.

[00518] is used to analyze unsaturated ester and sulfur-bearing alcohol ester that the NMR technology of the sulfur-bearing alcohol ester produced from unsaturated ester has been produced by soya-bean oil and from soya-bean oil ¹³C NMR illustrates.But, those skilled in the art can revise and use ¹³C NMR or ¹H NMR technology, the sulfur-bearing alcohol ester of analyzing unsaturated ester described herein and producing from unsaturated ester.

By ¹³C NMR or ¹H NMR measures the mol ratio of epoxide group and thiol group

[00519] mol ratio of epoxide group and thiol group is by using ¹H or ¹³C NMR determines.Hydroxyl mercaptan ester ¹H or ¹³C NMR spectrum is by Varian Mercury INOVA400 NMR, VarianMercury Plus 300 NMR or suitable with it spectrometer (300MHz ¹H NMR-75.5MHz ¹³CNMR) obtain.The definite of epoxide group and sulfide group peak area used shown in the following table ¹³C or ¹The H zone:

Functional group	¹H NMR zone	¹³C NMR zone	Carbonatoms/group	Number of hydrogen atoms/group
Functional group	¹H NMR zone	¹³C NMR zone	Carbonatoms/group	Number of hydrogen atoms/group	Epoxide group carbon atom HS-C carbon atom	2.75-3.2ppm 3.2-4ppm	53.6-56.6ppm 40-41.5ppm	2 1	2 1

[00520] by with the epoxide group carbon atom ¹H NMR peak area is divided by 2 (explanation has 2 hydrogen atoms to be connected on the carbon atom of epoxide group), and numeral is as a result calculated the epoxide group and the thiol group mol ratio of hydroxyl mercaptan ester divided by the HS-C carbon atom hydrogen 1CNMR peak area of thiol group.Similarly, the epoxide group of hydroxyl mercaptan ester and thiol group mol ratio can be used ¹³H NMR calculated by peak area.

[00521] the epoxide group mean number of each epoxidation unsaturated ester molecule can adopt similar methods, usefulness carbonyl group carbon atom or C-O ester group carbon atom ¹³C NMR peak area and epoxide group ¹³C NMR peak area is determined.Epoxidized soybean oil sample and the sulfur-bearing alcohol ester sample of producing from epoxidized soybean oil ¹H NMR as shown in Figure 2.

[00522] is used to analyze the epoxidation unsaturated ester and the NMR technology of the sulfur-bearing alcohol ester (hydroxyl mercaptan ester) produced from the epoxidation unsaturated ester adopted epoxidized soybean oil and the sulfur-bearing alcohol ester produced from epoxidized soybean oil ¹HNMR illustrates.But, those skilled in the art can revise and use ¹H NMR or ¹³C NMR technology, the sulfur-bearing alcohol ester of analyzing epoxidation unsaturated ester described herein and producing from the epoxidation unsaturated ester.

Analyze unsaturated ester, epoxidation unsaturated ester, sulfur-bearing alcohol ester and hydroxyl mercaptan ester by methanolysis

[00523] forms polyvalent alcohol and carboxylate methyl ester by the complex ester molecule being converted into it, measured and/or can measure the numerous characteristics of unsaturated ester, epoxidation unsaturated ester, sulfur-bearing alcohol ester and hydroxyl mercaptan ester.By gas-chromatography (GC) and/or gas chromatography/mass spectrometry (GC/MS), analyze the ester after transforming subsequently, to determine the composition of this complex ester side chain.Analyze by methanolysis and subsequently carboxylate methyl ester GC or GC/MS, by or can determined characteristic comprise molecular weight distribution (or molecular-weight average), each ester molecule epoxide group number (or mean number), episulfide and thiol group mol ratio, carbon-carbon double bond and thiol group mole when epoxide group and thiol group mol ratio and other character of percentage ratio, each ester molecule double key number (or mean number), the ester side chain of the side chain number that contains thiol group, thiol group sulphur.

[00524] according to the material that carries out the methanolysis method, two kinds of methanolysis methods is arranged, be applied to the unsaturated ester described in the experimental section, epoxidised ester, sulfur-bearing alcohol ester and hydroxyl mercaptan ester.

[00525] carries out methanolysis method to unsaturated ester and from the sulfur-bearing alcohol ester of unsaturated ester production based on hydrogenchloride.In the methanolic hydrogen chloride decomposition method, 50-100mg sulfur-bearing alcohol ester sample contacts with the HCl methanol solution of 3mL 3N and reacted 2 hours at 50 ℃.Solution is cooled and neutralizes with the sodium hydrogen carbonate solution that dilutes subsequently.The organic composition that goes out in the solution with the ether extracting is also analyzed with GC and/or GC/MS then.Other details of hydrogen chloride methanol solution (methanolic hydrogen chloride) methanolysis method can find in 0.5N that Supelco provides and 3N HCl methanol solution product description list.

[00526] carries out methanolysis method to the epoxidation unsaturated ester with from the hydroxyl mercaptan ester of epoxidation unsaturated ester production based on sodium methylate.The methanolysis method of sodium methylate is based on United States Patent (USP) 3,991,089 disclosed method.In the methanolysis method of sodium methylate, about 1g ester is put into the 50mL tubule that 5.0mL 25% methanol solution of sodium methylate and 10mL methyl alcohol are housed.Vibration is about 1 hour under this mixture room temperature, and solution becomes a phase during this period.Then mixture is poured in the 25mL distilled water.In this solution, add diethyl ether 25mL, and with this mixture of 0.5N HCl acidifying to pH about 5.From water layer, isolate organic layer with separating funnel.With distilled water (15mL) and salt brine solution (15mL) continuous washing organic layer, use dried over mgso then.Filtering separation sal epsom and remove solvent from organic solution by rotary evaporation.

[00527] will carry out GC and/or GC/MS subsequently through the methanolysis ester products of each methanolysis method analyzes.Two kinds of possible GC and/or GC/MS post and analysis condition provide as follows:

Table 8-methanol decomposition products-GC or GC/MS analysis condition 1

Analytical column HP-5 30m * 0.32mm id * 0.25 μ m film thickness GC post
		The GC analysis condition:
Injector temperature detection actuator temperature post helium gas flow between the whole furnace temperature terminal hour of initial furnace temperature initial time furnace temperature climbing speed	60 ℃ 5 minutes 8 ℃/minute 260 ℃ 20 minutes 250 ℃ 300 ℃ 1mL/ minute	The GC analysis condition:

Table 9-methanol decomposition products-GC or GC/MS analysis condition 2

Analytical column DB 30m * 0.25mm id * 0.25 μ m film thickness
		The GC analysis condition:
Between the whole furnace temperature terminal hour of initial furnace temperature initial time furnace temperature climbing speed	100 ℃ 10 minutes 5 ℃/minute 270 ℃ 10 minutes	The GC analysis condition:

Sampler temperature detection actuator temperature post helium gas flow

250 ℃ 300 ℃ 2mL/ minute

[00528] table 10 provides a kind of GC/MS record peak of soya-bean oil GC/MS record to demarcate situation, and this soya-bean oil has passed through the methanolysis method and carried out GC/MS with HP-5 30m * 0.32mm id * 0.25 μ m film thickness GC post and analyze.

The methanolysis test GC/MS data of table 10-soya-bean oil

The GC retention time	The demarcation of carboxylate methyl ester
The GC retention time	The demarcation of carboxylate methyl ester	21.58 23.66 23.74 23.96	Methyl palmitate 18 carbon monoenoic acid methyl esters (methyl (C18 monoene) oate) 18 carbon monoenoic acid methyl esters Methyl Stearates

[00529] Fig. 3 provides a kind of GC/MS record of mercaptan soya-bean oil, and this soya-bean oil has passed through the methanolysis method and carried out GC/MS with HP-5 30m * 0.32mm id * 0.25 μ m film thickness GC post and analyze.Table 11 provides the demarcation situation at its GC/MS record peak.

Table 11-is from the GC/MS data of the methanolysis of the sulfur-bearing alcohol ester of soya-bean oil preparation

The GC retention time	The demarcation of carboxylate methyl ester
The GC retention time	The demarcation of carboxylate methyl ester	21.58 23.66 23.74 23.96 26.46 26.59 26.66 26.80 27.31 27.44 29.04	Methyl palmitate 18 carbon monoenoic acid methyl esters 18 carbon monoenoic acid methyl esters Methyl Stearates, 18 carbon monoene list thiolic acid methyl esters (methyl (C18 monoene monomercaptan) oate) 18 carbon monoene list thiolic acid methyl esters, 18 carbon monoene list thiolic acid methyl esters, 18 carbon list thiolic acid methyl esters (methyl (C18 monomercaptan) oate) ten eight ring carbon sulfide acid methyl esters (methyl (C18 cyclic sulfide) oate) ten eight ring carbon sulfide acid methyl esters 18 carbon, two thiolic acid methyl esters (methyl (C18 dimercaptan) oate)

29.15 29.37 29.46 30.50

18 carbon, two thiolic acid methyl esters, 18 carbon monoene, two thiolic acid methyl esters (methyl (C18 monoene dimercaptan) oate), 18 carbon monoene, two thiolic acid methyl esters, 18 carbon bicyclic sulfides acid methyl esters (methyl (C18 di (cyclic sulfide)) oate)

29.37 or 29.46 peaks also can contain ten eight ring carbon sulfide list thiolic acid methyl esters isomer, as the part at these peaks.

[00530] Fig. 4 provides a kind of GC/MS record of epoxidized soybean oil, and this soya-bean oil has passed through the methanolysis method, and carries out GC/MS with HP-5 30m * 0.32mm id * 0.25 μ m film thickness GC post and analyze.Table 12 provides the demarcation situation at its GC/MS record peak.

The GC/MS data of table 12-epoxidized soybean oil methanolysis

The GC retention time	The demarcation of carboxylate methyl ester
The GC retention time	The demarcation of carboxylate methyl ester	16.09 17.68 18.94 19.94 20.14 21-21.5	Methyl palmitate Methyl Stearate 18 carbon monoepoxides acid methyl esters (methyl (C18 monoepoxide) oate) 18 carbon diepoxides acid methyl esters 18 carbon diepoxides acid methyl esters 18 carbon triepoxides acid methyl esters

【00531】

[00532] Fig. 5 provides the GC/MS record of a kind of epoxidized soybean oil that contacts with hydrogen sulfide (hydroxyl mercaptan ester), and this soya-bean oil has passed through the methanolysis method, and carries out GC/MS with HP-5 30m * 0.32mm id * 0.25 μ m film thickness GC post and analyze.Table 13 provides the demarcation situation at its GC/MS record peak.

Table 13-is from the GC/MS data of the methanolysis of the hydroxyl mercaptan ester of epoxidized soybean oil preparation

The GC retention time	The demarcation of carboxylate methyl ester
The GC retention time	The demarcation of carboxylate methyl ester	16.09 17.68 18.94 19.94 20.14	Methyl palmitate Methyl Stearate 18 carbon monoepoxides acid methyl esters 18 carbon diepoxides acid methyl esters 18 carbon diepoxides acid methyl esters

20.75 21-21.75 22.82 22.90 27-27.5

The unidentified 18 carbon sulfur-bearing mixtures of methyl esters of 18 carbon monohydroxy list thiolic acid methyl esters, 18 carbon triepoxides acid methyl esters 18 carbon dihydroxy two thiolic acid methyl esters, 18 carbon monoepoxide monohydroxy list thiolic acid methyl esters

[00533] methanolysis method and GC/MS method are with soya-bean oil, epoxidized soybean oil and derive from soya-bean oil and the mercaptan product that contains of epoxidized soybean oil illustrates.But, those skilled in the art can revise this method at an easy rate, in order to analyze as described here other unsaturated ester, epoxidation unsaturated ester and to derive from unsaturated ester and the sulfur-bearing alcohol ester product of epoxidation unsaturated ester.

The analysis of polythiourethane

[00534] adopt ASTM E1545-95A and E228-95 to analyze by sulfur-bearing alcohol ester, hydroxyl mercaptan ester and the polythiourethane that contains the production of crosslinked mercaptan ester, so that second-order transition temperature and thermal expansivity to be provided.The Shore hardness of polythiourethane adopts ASTM D2240-02A to determine.Polythiourethane is also according to having carried out subjective analysis as hardness, pliability, elasticity, rigidity, toughness, fragility and other property sort.

Use

[0100] except that the purposes that relates to fertilizer described herein, embodiment of the present invention also are useful in other multiple application facet.For example, embodiment of the present invention are being useful aspect the various polymer application, comprising but be not limited to, as polythiourethane, foam materials, tackiness agent, epoxy curing agent, coating and polyester resin with polyacrylic ester and polymethacrylate template, printing ink binder polymer, Synolac linking agent, based on the coating template of sulphur, polymkeric substance, mining and probing chemistry, special-purpose chain-transfer agent, rubber modifier and the similar aspect of hardening with radiation.Because raw material economics and being easy to get should believe that embodiment of the present invention will be useful in this type of application and other application facet.

[0101] the present invention is carried out explanation with reference to specific preferred embodiment.But, owing to the considerable change to above-mentioned embodiment will be conspicuous to one skilled in the art, so the present invention is not limited to this.

Table 4

	Embodiment
	Embodiment						Composition	#
1	#2	#3	#4	#5	#6		Composition	#
1	#2	#3	#4	#5	#6	B1(g)	14.16	11.04	8.19	13.38	13.38	11.91
D1(g)	-	-	1.35	1.5	-	B1(g)	14.16	11.04	8.19	13.38	13.38	11.91	-
D1(g)	-	-	1.35	1.5	-	D2(g)	-	-	-	-	1.5	1.35	-
E(g)	2.73	2.13	4.59	2.58	2.58	D2(g)	-	-	-	-	1.5	1.35	2.28
E(g)	2.73	2.13	4.59	2.58	2.58	F1(g)	0.15	0.09	-	0.15	0.15	0.12	2.28
C1(b)	9.96	7.74	9.87	9.39	9.39	F1(g)	0.15	0.09	-	0.15	0.15	0.12	8.34
C1(b)	9.96	7.74	9.87	9.39	9.39	Coating gross weight (g)	27.00	21.00	24.00	27.00	27.00	24.00	8.34
D1 skin (g)	-	6.00	3.00	-	-	Coating gross weight (g)	27.00	21.00	24.00	27.00	27.00	24.00	3.00
D1 skin (g)	-	6.00	3.00	-	-	Coating total content (%)	2.7	2.7	2.7	2.7	2.7	2.7	3.00

Table 5

	Embodiment
	Embodiment				Composition	#
7	#8	#9	#10		Composition	#
7	#8	#9	#10	B3(g)	15.12	12.45	-	-
B4(g)	-	-	11.01	B3(g)	15.12	12.45	-	-	11.01
B4(g)	-	-	11.01	D1(g)	6.00	6.00	6.00	-	11.01
E(g)	0	1.68	2.13	D1(g)	6.00	6.00	6.00	-	2.13
E(g)	0	1.68	2.13	F1(g)	0.09	0.06	0.12	0.12	2.13
C1(b)	5.79	6.81	7.74	F1(g)	0.09	0.06	0.12	0.12	7.74
C1(b)	5.79	6.81	7.74	Coating gross weight (g)	27.00	27.00	27.00	21.00	7.74
D1 skin (g)	-	-	-	Coating gross weight (g)	27.00	27.00	27.00	21.00	6.00
D1 skin (g)	-	-	-	Coating total content (%)	2.7	2.7	2.7	2.7	6.00

Table 6

	Embodiment
	Embodiment				Composition	#11	#12	#13	#14
B2(g)	9.33	13.86	11.34	6.09	Composition	#11	#12	#13	#14
B2(g)	9.33	13.86	11.34	6.09	B1(g)	-	-	-	3.18
D1(g)	1.35	1.35	6.00	6.00	B1(g)	-	-	-	3.18
D1(g)	1.35	1.35	6.00	6.00	E(g)	2.28	-	-	2.67
F1(g)	-	-	-	-	E(g)	2.28	-	-	2.67
F1(g)	-	-	-	-	C1(b)	11.04	11.79	9.66	9.06
Coating gross weight (g)	24.00	27.00	27.00	27.00	C1(b)	11.04	11.79	9.66	9.06
Coating gross weight (g)	24.00	27.00	27.00	27.00	D1 skin (g)	3.00	-	-	-
Coating total content (%)	2.7	2.7	2.7	2.7	D1 skin (g)	3.00	-	-	-

Table 7

	Embodiment
	Embodiment			Composition	#
15	#16	#17		Composition	#
15	#16	#17	B2(g)	14.37	13.89	14.37
D1(g)	4.95	4.8	B2(g)	14.37	13.89	14.37	-
D1(g)	4.95	4.8	D2(g)	-	-	1.95	-
F2(g)	0.12	0.12	D2(g)	-	-	1.95	0.12
F2(g)	0.12	0.12	C1(g)	-	0.90	-	0.12
C2(b)	7.56	7.29	C1(g)	-	0.90	-	7.56
C2(b)	7.56	7.29	Coating gross weight (g)	27.00	27.00	24.00	7.56
D1 skin (g)	-	-	Coating gross weight (g)	27.00	27.00	24.00	3.00
D1 skin (g)	-	-	Coating total content (%)	2.7	2.7	2.7	3.00

Claims

1. thiol ester composition, it comprises that each thiol ester molecule has the thiol ester molecules that average at least 1.5 ester groups, each thiol ester molecule have average at least 1.5 thiol groups and have 1.5 following episulfide and thiol group mol ratio.

2. the thiol ester composition described in the claim 1, wherein said thiol ester molecule has the episulfide and the thiol group mol ratio of scope from 0 to 1.0.

3. the thiol ester composition described in the claim 1, wherein said thiol ester molecule has 1.5 to 9 thiol groups of each thiol ester molecule average out to.

4. the thiol ester composition described in the claim 1, wherein said thiol ester molecule has carbon-carbon double bond and the thiol group mol ratio below 1.5.

5. the thiol ester composition described in the claim 1, wherein said thiol ester molecule have the above mercaptan sulfur of average 2wt.%.

6. the thiol ester composition described in the claim 1, wherein said thiol ester molecule has the mercaptan sulfur of average out to 8 to 10wt.%.

7. the thiol ester composition described in the claim 1, wherein said thiol ester molecule have the following total sulfur that exists with the episulfide form of average 30 moles of %.

8. the thiol ester composition described in the claim 1, wherein said thiol ester molecule have the following total sulfur that exists with the episulfide form of average 10 moles of %.

9. the thiol ester composition described in the claim 1,40% above sulfur-bearing of the whole side chains of wherein said thiol ester molecule.

10. the production method of a thiol ester composition may further comprise the steps:

A) hydrogen sulfide is contacted with the unsaturated ester composition, said composition comprises that each unsaturated ester molecule has average at least 1.5 ester groups and each unsaturated ester molecule has the on average unsaturated ester of at least 1.5 carbon-carbon double bonds; With

B) make the reaction of described hydrogen sulfide and described unsaturated ester, form thiol ester composition, said composition comprises the thiol ester molecule with 1.5 following episulfide and thiol group mol ratio.

11. the method described in the claim 10, wherein said unsaturated ester composition comprises natural origin oil.

12. the method described in the claim 10, wherein said unsaturated ester composition comprises soya-bean oil.

13. the method described in the claim 10 takes place under the situation that is reflected at the solvent existence of wherein said hydrogen sulfide and described unsaturated ester.

14. the method described in the claim 10, the reactions steps of wherein said hydrogen sulfide and described unsaturated ester takes place under solvent-free substantially situation.

15. the method described in the claim 10, wherein said thiol ester molecule have hydrogen sulfide and carbon-carbon double bond mol ratio more than 2.

16. the method described in the claim 10, the reactions steps of wherein said hydrogen sulfide and described unsaturated ester is by heterogeneous catalyst or homogeneous catalyst catalysis.

17. the method described in the claim 10, the reactions steps of wherein said hydrogen sulfide and described unsaturated ester is caused by radical initiator or UV irradiation.

18. the method described in the claim 10, wherein said thiol ester molecule have the above mercaptan sulfur of average 5wt.%.

19. the method described in the claim 10, being reflected under the temperature more than-20 ℃ of wherein said hydrogen sulfide and described unsaturated ester takes place.

20. the method described in the claim 10,40% above sulfur-bearing of the whole side chains of wherein said thiol ester molecule.

21. the method described in the claim 10, wherein said method are the successive processes, and the reaction of described hydrogen sulfide and described unsaturated ester is to carry out under solvent-free, temperature more than-20 ℃, and are caused by UV irradiation.

22. the production method of a thiol ester composition may further comprise the steps:

B) described hydrogen sulfide and described unsaturated ester are reacted under solvent-free substantially condition, form the thiol ester composition that comprises the thiol ester molecule.

23. the method described in the claim 22, wherein said unsaturated ester composition comprises natural origin oil.

24. the method described in the claim 22, wherein said unsaturated ester composition comprises soya-bean oil.

25. the method described in the claim 22, wherein said thiol ester molecule have episulfide and thiol group mol ratio below 1.5.

26. the method described in the claim 22, wherein said thiol ester molecule have hydrogen sulfide and carbon-carbon double bond mol ratio more than 1.

27. the method described in the claim 22, the reactions steps of wherein said hydrogen sulfide and described unsaturated ester is by heterogeneous catalyst or homogeneous catalyst catalysis.

28. the method described in the claim 22, the reaction of wherein said hydrogen sulfide and described unsaturated ester is caused by radical initiator or UV irradiation.

29. the method described in the claim 22, wherein said thiol ester molecule have the above mercaptan sulfur of average 5wt.%.

30. the method described in the claim 22, being reflected under the temperature more than-20 ℃ of wherein said hydrogen sulfide and described unsaturated ester takes place.

31. the method described in the claim 22,40% above sulfur-bearing of the whole side chains of wherein said thiol ester molecule.

32. the production method of a thiol ester composition may further comprise the steps:

A) polyhydric alcohol composition is contacted with the mercaptan carboxylic acid composition; With

B) make the reaction of described polyhydric alcohol composition and described mercaptan carboxylic acid composition, produce thiol ester composition, said composition comprises that each thiol ester molecule has average at least 1.5 ester groups and each thiol ester molecule has the on average thiol ester molecule of at least 1.5 thiol groups.

33. the hydroxyl thiol ester composition, it comprises that each hydroxyl thiol ester molecule has average at least 1 ester group and each hydroxyl thiol ester molecule has the on average hydroxyl thiol ester molecule of at least 1 Alpha-hydroxy thiol group.

34. the composition described in the claim 33, wherein said hydroxyl thiol ester molecule have average 1.5 to 9 the Alpha-hydroxy thiol groups of each hydroxyl thiol ester molecule.

35. the composition described in the claim 33, wherein said hydroxyl thiol ester molecule have the above mercaptan sulfur of average 2.5wt.%.

36. the composition described in the claim 33, wherein said hydroxyl thiol ester molecule has average 8 to 10wt.% mercaptan sulfur.

37. the composition described in the claim 33, wherein said hydroxyl thiol ester molecule have epoxide group and Alpha-hydroxy thiol group mol ratio below 2.

38. the composition described in the claim 33,40% above sulfur-bearing of the whole side chains of wherein said hydroxyl thiol ester molecule.

39. the composition described in the claim 33, wherein said composition does not have epoxide group substantially.

40. the hydroxyl thiol ester composition, it comprises that each hydroxyl thiol ester molecule has average at least 1 ester group, each hydroxyl thiol ester molecule and has the hydroxyl thiol ester molecule that average at least 1 thiol group and each hydroxyl thiol ester molecule have average at least 1 alcohol groups.

41. the composition described in the claim 40, wherein said hydroxyl thiol ester molecule have average 1.5 to 9 thiol groups of each hydroxyl thiol ester molecule.

42. the composition described in the claim 40, wherein said hydroxyl thiol ester molecule have average 1.5 to 9 alcohol groups of each hydroxyl thiol ester molecule.

43. the composition described in the claim 40, wherein said hydroxyl thiol ester molecule have the above mercaptan sulfur of average 2.5wt.%.

44. the composition described in the claim 40, wherein said hydroxyl thiol ester molecule has average 8 to 10wt.% mercaptan sulfur.

45. the composition described in the claim 40, wherein said hydroxyl thiol ester molecule has epoxide group and the thiol group mol ratio below 2.

46. the composition described in the claim 40,40% above sulfur-bearing of the whole side chains of wherein said hydroxyl thiol ester molecule.

47. the composition described in the claim 40, wherein said composition does not have epoxide group substantially.

48. the production method of a hydroxyl thiol ester composition may further comprise the steps:

A) hydrogen sulfide is contacted with epoxidation unsaturated ester composition, said composition comprises that each epoxidation unsaturated ester molecule has average at least 1 ester group and each epoxidation unsaturated ester molecule has the on average epoxidation unsaturated ester of at least 1 epoxide group; With

B) make the reaction of described hydrogen sulfide and described epoxidation unsaturated ester, form described hydroxyl thiol ester composition.

49. the method described in the claim 48, wherein said epoxidation unsaturated ester composition comprises epoxidation natural origin oil.

50. the method described in the claim 48, wherein said epoxidation unsaturated ester composition comprises epoxidized soybean oil.

51. the method described in the claim 48, the mol ratio of hydrogen sulfide and epoxide group is more than 1 in the wherein said epoxidation unsaturated ester.

52. the method described in the claim 48, the reaction of wherein said hydrogen sulfide and described epoxidation unsaturated ester are to carry out under the situation that has catalyzer to exist.

53. the method described in the claim 48, wherein said hydroxyl thiol ester composition comprise the hydroxyl thiol ester molecule with the above mercaptan sulfur of average 2.5wt.%.

54. the method described in the claim 48, wherein said hydroxyl thiol ester composition comprise the hydroxyl thiol ester molecule with average mercaptan sulfur of 8 to 10wt.%.

55. the method described in the claim 48, wherein said hydroxyl thiol ester composition comprise the hydroxyl thiol ester molecule of 40% above sulfur-bearing of the whole side chains of hydroxyl thiol ester molecule.

56. the production method of a hydroxyl thiol ester composition may further comprise the steps:

A) polyhydric alcohol composition is contacted with the hydroxy thiol carboxylic acid composition; With

B) make the reaction of described polyhydric alcohol composition and described hydroxy thiol carboxylic acid composition, produce described hydroxyl thiol ester composition, said composition comprises that each hydroxyl thiol ester molecule has average at least 1 ester group and each hydroxyl thiol ester molecule has the on average hydroxyl thiol ester molecule of at least 1 Alpha-hydroxy thiol group.

57. crosslinked thiol ester composition, it comprises having at least two monomeric thiol ester oligopolymer of thiol ester, and these at least two thiol ester monomers are by tool-S _QThe poly-sulfide linkage of-structure connects, and wherein Q is more than 1.

58. the crosslinked thiol ester composition described in the claim 57, wherein said thiol ester oligopolymer have at least three thiol ester monomers that connected by poly-sulfide linkage.

59. the crosslinked thiol ester composition described in the claim 57, wherein said thiol ester oligopolymer have 3 to 20 thiol ester monomers that connected by poly-sulfide linkage.

60. the crosslinked thiol ester composition described in the claim 57, wherein said crosslinked thiol ester composition comprises thiol ester monomer and thiol ester oligopolymer.

61. the crosslinked thiol ester composition described in the claim 60, wherein said thiol ester monomer and described thiol ester oligopolymer have total mercaptan sulphur content of 0.5 to 8wt.%.

62. the crosslinked thiol ester composition described in the claim 60, thiol ester monomer that wherein combines and thiol ester oligopolymer have the molecular-weight average more than 2000.

63. the crosslinked thiol ester composition described in the claim 60, wherein said thiol ester monomer and described thiol ester oligopolymer have 2000 to 20,000 molecular-weight average.

64. the crosslinked thiol ester composition described in the claim 60, wherein said thiol ester monomer and described thiol ester oligopolymer have 8 to 15wt.% total sulfur content.

65. crosslinked thiol ester composition, its method production by may further comprise the steps:

A) thiol ester composition is contacted with oxygenant; With

B) make described thiol ester and oxidant reaction, produce the thiol ester oligopolymer, this oligopolymer has at least two thiol ester monomers, between monomer by tool-S _QThe poly-sulfide linkage of-structure connects, and wherein Q is more than 1.

66. the production method of a crosslinked thiol ester composition comprises:

A) thiol ester composition is contacted with oxygenant; With

67. the method described in the claim 66, wherein said oxygenant are elementary sulfur, oxygen or hydrogen peroxide.

68. the method described in the claim 66, wherein said oxygenant is an elementary sulfur.

69. the method described in the claim 66, wherein said thiol ester are the hydroxyl thiol esters.

70. the method described in the claim 66, the elementary sulfur in the wherein said thiol ester molecule and the weight ratio of mercaptan sulfur are 0.5 to 32.

71. the method described in the claim 66, the reactions steps of wherein said thiol ester and described oxygenant is carried out in 25 ℃ to 150 ℃ temperature range.

72. the method described in the claim 66, wherein residual hydrogen sulfide is removed from the crosslinked thiol ester composition of being produced.

73. the method described in the claim 68, the reaction of wherein said thiol ester and elementary sulfur is by catalytic.

74. the method described in the claim 73, wherein said catalyzer is an amine.

75. a preparation method who is used to make the catalyst composition of olefin oligomerizationization, this catalyst composition comprises and contains chromium cpd, and described method comprises and reduces all from comprise the composition that contains chromium cpd or the water of part, sour proton or both.

76. the method described in the claim 75, the wherein said chromium cpd that contains contacts with the non-halide metal alkylide.

77. the method described in the claim 76, wherein said non-halide metal alkylide is a triethyl aluminum.

78. the method described in the claim 75, the wherein said chromium cpd that contains contacts with solvent phase, forms solution, and described solution is carried out component distillation.

79. the method described in the claim 78, wherein said solvent comprise aromatic compound, halogenated compound, paraffinic hydrocarbons or its combination.

80. the method described in the claim 78, wherein said solvent are the aromatic compounds that comprises benzene, toluene, ethylbenzene, xylol, o-Xylol, m-xylene, p-Xylol or its combination.

81. the method described in the claim 75, the wherein said chromium cpd that contains contacts with absorption agent to remove moisture.

82. the method described in the claim 81, wherein said absorption agent comprise 3 dust molecular sieves, 5 dust molecular sieves, aluminum oxide, silicon-dioxide or its combination.