CN1200740A - Compositions of polytetramethylene ether glycols and polyoxy alkylene polyether polyols having low degree of unsaturation - Google Patents
Compositions of polytetramethylene ether glycols and polyoxy alkylene polyether polyols having low degree of unsaturation Download PDFInfo
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- CN1200740A CN1200740A CN 97191228 CN97191228A CN1200740A CN 1200740 A CN1200740 A CN 1200740A CN 97191228 CN97191228 CN 97191228 CN 97191228 A CN97191228 A CN 97191228A CN 1200740 A CN1200740 A CN 1200740A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4866—Polyethers having a low unsaturation value
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/58—Ethylene oxide or propylene oxide copolymers, e.g. pluronics
Abstract
Thus, there is provided according to the present invention polyol compositions comprising(A) a polytetramethylene ether glycol, and(B) a trifunctional active hydrogen compound-initiated polyoxyalkylene polyether polyol having a degree of unsaturation of not greater than 0.04 milliequivalents per gram of said polyether polyol.
Description
The present invention relates to the polytetramethylene polyether glycol and have the blend that low-unsaturation-degree is the polyoxyalkylene polyether polyol below 0.04 or 0.04 and the casting elastomerics for preparing by its, spandex (spandex) fiber, and thermoplastic polyurethane.
Polyurethane elastomer often uses one or more polytetramethylene ether diols, and (PTMEG ' s) reacts as polyol component and one or more polyisocyanates such as MDI, because they have for to the desired high mechanical characteristics of application-specific elastomerics.PTMEG ' s is often used in the Application Areas that wherein needs high tensile, low compression deformation, high resilience and/or high elastic coefficient.Yet the formation acquired and undesirable side reaction product in synthetic that is difficult for owing to its parent material is difficult to and obtains expensively PTMEG ' s.
Therefore, be desirable to provide and can be used in the polyol composition that the high-quality polyurethane elastomer of preparation can reduce needed PTMEG consumption simultaneously.
Therefore, polyol composition according to the present invention comprises: (A) polytetramethylene ether diol and (B) to have degree of unsaturation be to be not more than polyoxyalkylene polyether polyol 0.04 milliequivalent/gram polyether polyol, that caused by difunctional and/or trifunctional active dydrogen compounds.
Can prepare polyurethane elastomer by single stage method or prepolymer technology according to polyol composition of the present invention.Need the good over-all properties such as tensile strength, compressive set, rebound resilience and/or the Young's modulus that use purified PTMEG to obtain before going out based on the elastomer display of polyol composition of the present invention.Other performance, blend composition that also usually can the application of the invention as elongation and rebound resilience is improved.
Therefore, in one embodiment of the invention, providing a kind of comprises above-mentioned at least PTMEG and has polyhydric alcohol composition and the organic multiple isocyanate that degree of unsaturation is the polyoxyalkylene polyether polyol below 0.04 or 0.04 and react the prepolymer that obtains by allowing.This prepolymer can be isocyanate-terminated by add substoichiometric polyol composition in isocyanic ester, or hydroxy-end capped by the polyol composition that adds molar excess in isocyanic ester.
In another embodiment of the invention, provide a kind of by allow organic two or polyisocyanates and polyol composition by NCO: the OH equivalence ratio is the elastomerics that at least 1.5: 1 reaction makes, this reaction is chosen wantonly in the presence of hydroxyl and/or amine-functionalized chainextender and is carried out, and wherein polyol composition is by PTMEG at least with to have degree of unsaturation be that polyoxyalkylene polyether polyol below 0.04 or 0.04 is formed.Polyol composition of the present invention is to form urea alkane elastomerics to be introduced in urea alkane elastomerics with main many alkoxide components (being single stage method) of reaction mixture or it and to form and be first drawn into (being prepolymer process) in the prepolymer in the reaction before.
It is 500-5000 that the PTMEG ' s that is used for the invention process has number-average molecular weight usually, preferred 800-3000, the more preferably scope of 1000-2600.The technology of preparation PTMEG is known in the prior art, as in US patent 4,294,997 and 4,213, described in 000, it is for referencial use that their disclosure is introduced into this paper.The example of useful PTMEG ' s comprises POLYTHF 650, POLYTHF 1000, POLYTHF 2000 and POLYTHF 2900.
Usually PTMEG ' s is the open loop chain extending reaction synthetic by monomer tetrahydrofuran (THF) (THF).In a well-known method, ring-opening reaction is come catalysis by fluosulfonic acid, subsequently, carries out the hydrolysis of sulphonate and the water extraction of acid, neutralizes then and drying.In many cases, PTMEG at room temperature is a solid, because its high-crystallinity.In this case, people wish to use room temperature liquid PTMEG, THF can with alkylene oxide (also being known as cyclic ethers or monoepoxide) copolymerization, as in US patent 4,211,854, advised like that, be hereby incorporated by.This analog copolymer has A-B-A and mixes the embedding structure, and wherein block A is the random copolymers of tetrahydrofuran (THF) and alkylene oxide, and B block is made up of the polyoxygenated tetramethylene.
Can have no particular limits with the cyclic ethers of tetrahydrofuran (THF) copolymerization, if they be can ring-opening polymerization cyclic ethers, and comprise that 3-annulus ether for example, 4-annulus ether, cyclic ethers such as tetrahydrofuran derivatives and cyclic ethers is as 1,3-diox ， trioxane etc.The example of cyclic ethers comprises oxyethane, 1, and the 2-butylene oxide ring, 1,2-epoxy hexane, 1,2-tertiary butyl oxyethane, cyclohexene oxide, 1, the 2-octylene oxide, cyclohexyl ring oxidative ethane, Styrene oxide 98min., phenylglycidyl ether, allyl glycidyl ether, 1,2-oxidation decene, 1,2-oxidation laurylene, Epicholorohydrin, epibromohydrin, epiiodohydrin, the oxidation perfluoro propylene, cyclopentene oxide, 1,2-oxidation amylene, propylene oxide, oxidation iso-butylene, oxidation trimethylene ethene, oxidation tetramethylene ethene, Styrene oxide 98min., 1,1-oxidation diphenylethlene, epichlorhydrin, Epicholorohydrin, epibromohydrin, epiiodohydrin, 1,1,1-three fluoro-2-propylene oxides, 1,1,1-three fluoro-2-methyl-2-propylene oxides, 1,1,1-three chloro-2-methyl-3-bromo-2-propylene oxidation, 1,1,1-three bromo-2-butylene oxide compounds, 1,1,1-three fluoro-2-butylene oxide compounds, 1,1,1-three chloro-2-butylene oxide compounds, trimethylene oxide, 3-methyl trimethylene oxide, 3,3-dimethyl trimethylene oxide, 3,3-diethyl trimethylene oxide, 3, two (chloromethyl) trimethylene oxide of 3-, 3, two (brooethyl) trimethylene oxide of 3-, 3, two (iodomethyl) trimethylene oxide of 3-, 3, two (methyl fluoride) trimethylene oxide of 3-, 2-methyltetrahydrofuran, the 3-methyltetrahydrofuran, 2-methyl-3-chloromethyl tetrahydrofuran (THF), 3-ethyltetrahydrofuran, 3-sec.-propyl tetrahydrofuran (THF), 2-isobutyl-tetrahydrofuran (THF), 7-oxabicyclo (2,2,1) heptane etc.
If present, the content of the cyclic ethers of copolymerization in PTMEG can be in the scope of 5-95wt%, but, when the copolymerization polyether glycol that obtains to contain the oxidation tetramethylene during as main ingredient (this component is effective as the soft chain segment among polyurethane elastomer such as the spandex (spandex)), with the block A of THF copolymerization in the amount of cyclic ethers be generally 30-70wt%.In this case, people are chosen in and allow cyclic ethers and THF random copolymerization in the whole mixture, and the consumption of cyclic ethers accounts for the 5-60wt% of multipolymer.
In addition, in the building-up reactions of PTMEG, the initial THF of part can be replaced as starting raw material by the PTMEG oligopolymer.And in the polyether glycol building-up reactions of copolymerization, the oligopolymer of the PTMEG that is synthesized or the oligopolymer of polyether glycol also can be used as part material and add and react.In this case, oligopolymer has the molecular weight that is lower than the polymkeric substance that will be synthesized usually.More particularly, when the composite number average molecular weight is polymkeric substance more than 1000 or 1000, people can use has the oligopolymer of number-average molecular weight in the 100-800 scope, when being polymkeric substance more than 3000 or 3000 when the composite number average molecular weight, can use to have the oligopolymer of number-average molecular weight in the 100-2000 scope.Also can use from the polyether glycol of the PTMEG that is synthesized or copolymerization by fractionation extraction or the isolated oligopolymer of vacuum distilling.This oligopolymer can join in the initial monomers with the amount of 10wt% at the most.
The polymerization degree reduces along with the rising of temperature of reaction and simultaneously owing to the polyreaction productive rate, therefore, polymeric reaction temperature is preferably between-10 ℃-120 ℃, more preferably between 30 ℃-80 ℃.If temperature surpasses 120 ℃, productive rate will descend.Reacting the needed time is generally 0.5-20 hour, although it changes according to catalyst consumption and temperature of reaction.This reaction can carried out in employed any system such as jar type or the tower container usually.Also can be undertaken by batch system or continuous system.
Employed catalyzer is known in preparation PTMEG, and it comprises any cationic catalyst such as strong-acid cation-exchange resin, oleum, and boron trifluoride.
Of the present invention how pure blend comprises the polyoxyalkylene polyether polyol that difunctional's active dydrogen compounds causes.The polyoxyalkylene polyether polyol that employed in the embodiment of this invention difunctional's active dydrogen compounds causes should have the number-average molecular weight that is suitable for specific area, be generally 400-7000, preferred 1000-6500, more preferably 1500-3500 and most preferably 2000-3000.
The hydroxyl value that is used for polyoxyalkylene polyether polyol of the present invention is consistent with the described number-average molecular weight of following formula:
OH=(f) 56,100/ equivalents
For most applications, the scope of the suitable hydroxyl value of polyoxyalkylene polyether polyol is 15-250, and that the most frequently used is 25-120.
Be used for degree of unsaturation that polyoxyalkylene polyether polyol of the present invention has and be 0.04 many alcohol of millinormal KOH/ gram or still less, below preferred 0.03 or 0.03, more preferably below 0.02 or 0.02.
The structure of polyoxyalkylene polyether polyol comprised difunctional and/or trifunctional active dydrogen compounds initiator (this compound contain at least two can with the hydrogen atom of reactions of alkylene oxide) nuclear.Particularly, the reaction of atomic on the initiator compounds should be able to fully be opened the oxirane ring on the oxyethane.Initiator compounds has low relatively molecular weight, is generally below 400, more preferably below 150.
The example that is used to implement initiator compounds of the present invention includes, but not limited to ethylene glycol, propylene glycol, Diethylene Glycol, dipropylene glycol, 2,3-butyleneglycol, 1,3 butylene glycol, 1,5-pentanediol, 1,6-hexylene glycol, glycerine, TriMethylolPropane(TMP) etc.The another kind of reactive behavior hydrogen compound that can be used is alkylamine and has the alkylene polyamine class such as the methylamine of at least two active hydrogen atoms, ethylamine, propyl group amine, butylamine, hexyl amine, ethylene diamine, diethylenediamine, 1,6-hexane diamines, and ammonia, thanomin, diethanolamine, trolamine, Yi Bingchunan, diisopropanolamine (DIPA), tri-isopropanolamine etc.Be necessary selecting catalyst and adjust reaction conditions to make and primary amine hydrogen and secondary amine hydrogen open loop oxyalkylene make monoamine difunctional and diamines trifunctional.On the contrary, be necessary to select only to help the catalyzer of primary amine hydrogen and adjust reaction conditions so that diamines difunctional and triamine trifunctional.Also can use cyclammonium such as piperazine, 2-methylpiperazine and 2,5-lupetazin.Acid amides has been formed an other class of this reactive behavior hydrogen compound, as ethanamide, and succinic diamide, and benzsulfamide.An other class of this reactive behavior hydrogen compound is a dicarboxylic acid, as hexanodioic acid etc.Initiator also can be to contain those of different functional groups with active hydrogen atom, as oxyacetic acid, and thanomin etc.
In a preferred embodiment, be used for polyoxyalkylene polyether polyol of the present invention and comprise the hydrophobic block that at least one makes from the mixture of propylene oxide or propylene oxide and other cyclic ethers.These other cyclic ethers or be hydrophobic type with respect to the polyoxyethylene group, perhaps if the words of hydrophilic then it mixes with propylene oxide with the relative quantities that can not make many alcohol and lost efficacy in final use.Hydrophobic block is made up of the propylene oxide group of the equal block of propylene oxide group or random distribution and the block of other oxyalkylene group.Mix when using as the surrogate of propylene oxide or with propylene oxide, also can use oxybutylene, it demonstrates hydrophobic performance and obtains having the how pure of low-unsaturation-degree simultaneously.
Polyethers of the present invention also can directly or indirectly carry out the inside block that addition reaction forms the propylene oxide group with quantitative propylene oxide by suitable initiator compounds, and subsequently, directly or indirectly one or more other oxide compounds of addition prepare.
The polyoxyalkylene polyether polyol can only contain oxyethane, if especially molecular weight is less than 600.Yet it preferably contains the oxypropylene group of 50-100wt%, and the oxypropylene group of preferred 70-96wt% is based on the weight of the whole cyclic ether groups that added.
In a preferred embodiment of the invention, propylene oxide be added into and by the active hydrogen atom position directly and initiator compounds react the inside block that forms the polyoxytrimethylene base.The structure of this midbody compound can be represented according to following formula: R[(C
3H
6O)
W]
ZWherein R is the nuclear of initiator; W is illustrated in the integer of oxypropylene group number in the block, make the weight of oxypropylene group be 50-less than 100wt%, (or 100wt% is if wish that preparation is only based on many alcohol of oxypropylene group and initiator) is based on the weight of the whole oxyalkylenes that added; With the Z number (preferred 2 or 3) of reaction active site on the initiator molecule of oxypropylene group of having represented on it keyed jointing.
Polyether polyol also comprises the inside block of an above oxypropylene group.Inner block is meant that the oxypropylene group block structurally should be between the different blocks of the nuclear of initiator compounds and one or more inhomogeneous oxyalkylene groups.Within the scope of the present invention, between initiator nuclear and oxypropylene group block, insert the block of different oxyalkylene groups, if especially different oxyalkylene groups also is hydrophobic.Yet in a preferred embodiment, the inside block of oxypropylene group is directly connected on the nuclear of initiator compounds by its reactive hydrogens position.
It is end capped with the reactive hydrogens of isocyanic ester being used for polyoxyalkylene polyether polyol of the present invention.Reactive hydrogens can be uncle or secondary hydroxyl, or the form of uncle or secondary amine.In elastomeric preparation, often wish to introduce the isocyanate reaction active group that has more reactive behavior than secondary hydroxyl.Primary hydroxyl can be introduced on the polyether polyol by the polyether polyol and the reacting ethylene oxide of growing.Therefore, in a preferred embodiment of the invention, the polyoxytrimethylene polyether polyol is end capped with the end block of oxyethylene group.Additionally, in another embodiment, polyether polyol of the present invention can come end capped with the mixture of primary and secondary terminal hydroxy group, when using the mixture of oxyethane and for example propylene oxide in the preparation in end group.The primary and secondary amido can pass through as US patent No.3, and the reduction amination method described in 654,370 is introduced on the polyether polymer, is hereby incorporated by.
When using, the weight of the end block of oxyethylene group is at least 4-30wt%, and preferred 10-25wt% is based on the weight that adds to all compounds in the initiator.
The method of polymerization polyether polyol of the present invention without limits, it can pass through negatively charged ion, positively charged ion or coordination mechanism carry out.
The method of anionoid polymerization is normally known in the prior art.Typically, in the presence of basic catalyst such as alkoxide or alkali metal hydroxide, with initiator molecule and reactions of alkylene oxide.This reaction can be in super-atmospheric pressure and aprotonic solvent such as dimethyl sulfoxide (DMSO) or tetrahydrofuran (THF), or carries out in body.
Be used to prepare the polyoxyalkylene polyether polyol catalyzer type also without limits, as long as catalyzer is can produce have the sort of type that degree of unsaturation is the polyoxyalkylene polyether polyol below 0.04 or 0.04 under the desirable number-average molecular weight.Appropriate catalyst comprises alkali metal compound, alkaline earth metal compound, ammonium and as at US patent NO.3, the DMC catalysts described in 829,505 is hereby incorporated by and the oxyhydroxide and the alcoxylates of lithium and rubidium.Other useful catalysts comprises the oxide compound of barium or strontium, oxyhydroxide, the oxyhydroxide of hydration and single hydroxide salt.
Suitable alkali metal compound comprises that those contain sodium, potassium, lithium, the compound of rubidium and caesium.These compounds can be basic metal, oxide compound, oxyhydroxide, carbonate, organic acid salt, alcoxylates, supercarbonate, natural mineral matter, silicate, the form of hydrate etc. and its mixture.Suitable alkaline earth metal compound and its mixture comprise that those comprise calcium, strontium, magnesium, beryllium, copper, zinc, titanium zirconium, lead, arsenic, antimony, bismuth, molybdenum, tungsten, manganese, iron, nickel, cobalt, the compound of barium.Suitable ammonium compound includes, but not limited to those and comprises ammonium such as ammonia, those compounds of aminocompound, and such as urea, alkyl urea, Dyhard RU 100, melamine, guanidine, aminoguanidine; Amine, aliphatic amine for example, aromatic amine; Organic ammonium salt, for example, volatile salt, quaternary ammonium hydroxide, pure aluminium silicate and their mixture.Ammoniate can mix with aforementioned alkaline salt-forming compound.Other typical negatively charged ion comprises the halide-ions of fluorine, chlorine, bromine and iodine and so on, or nitrate radical, benzoate anion, acetate moiety, sulfonate radical and analogue.
In basic metal, caesium is most preferred.Lithium, sodium, potassium than high equivalent weight often Chang Buneng reduce the degree of unsaturation of polyoxyalkylene polyether polyol effectively.In a preferred embodiment, the polyoxyalkylene polyether polyol prepares with containing the caesium catalyzer.The example that contains the caesium catalyzer comprises Cs2O, cesium acetate, and cesium carbonate has C
1-C
8The alkyl Cs2O and the cesium hydroxide of low-grade alkane alcohol.These catalyzer can reduce the degree of unsaturation of the many alcohol of high equivalent weight with a large amount of oxypropylene group effectively.Different with DMC catalysts, it also can reduce the degree of unsaturation of polyoxyalkylene polyether polyol effectively, and caesium is catalyst based needn't be removed from reaction vessel before ethylene oxide group is added to polyether polyol.Therefore, the preparation with polyoxytrimethylene polyether polyol of oxyethane end group can be carried out in entire reaction by enough catalyzer based on caesium.
Degree of unsaturation can by polyether polyol and mercuric acetate and methyl alcohol reacts release acetoxyl group mercury methoxylation compound in methanol solution and acetate is determined.Make mercuric acetate change into bromine with the Sodium Bromide processing any residual mercuric acetate.Subsequently, with the potassium hydroxide titration of the acetate in the solution, degree of unsaturation with the mole number of titrating acetate calculate.More particularly, weigh 30g polyether polyol sample in the sample flask, subsequently 50ml SILVER REAGENT mercuric acetate is added in sample flask and the blank flask.Sample is stirred till content is dissolved.Sample and blank flask were left standstill 30 minutes, once in a while jolting in addition.Subsequently, join the 8-10g Sodium Bromide in each flask and stirred 2 minutes, afterwards, the 1ml phenolphthalein indicator joined in each flask and be titrated to pink terminal point with the 1.0N potassium hydroxide methanol solution of standard.Calculating degree of unsaturation also represents with milligramequivalent/gram:
Only proofread and correct, be worth equivalent/gram with 56.1 except that this in the case when the acid number of sample carries out acid number greater than 0.04 the time.
Reaction conditions is set at those employed conditions in preparation polyoxyalkylene polyether polyol.The general about 5wt% of 0.005-that uses with respect to polyether polymer, preferably 0.005-2.0wt% and the most preferably catalyzer of 0.005-0.5wt%.
Any catalyzer that remains in the polyether polymer prepared in accordance with the present invention can adsorb by any known method of describing in the prior art as by acid treatment, water washing, or ion-exchange neutralizes.Be used for and technology in acid example comprise solid and liquid organic acid, as 2 ethyl hexanoic acid and acetate.For ion-exchange, can use phosphoric acid or sulfuric acid.Extraction or adsorption method use activated clay or synthetic magnesium silicate.Wish to remove metallic cation and make it content and be reduced to and be less than 500ppm, preferably be lower than 100ppm, most preferably from 0.1-5ppm.
For other processing condition, the temperature of polyether polymer polyreaction is usually 80 ℃-160 ℃ scope, preferred 95 ℃-115 ℃.This reaction can be at tower reactor, tubular reactor, or the autoclave pressure discontinuous is carried out.In batch technology, this reaction is to carry out in encloses container joining under the pressure of regulating in the reactor by rare gas element buffering with oxyalkylene.Usually, be scope by adding working pressure that oxyalkylene produced at 10-50psi.The pressure that surpasses 100psi that is produced can increase the danger of uncontrolled reaction.Oxyalkylene joins in the reaction vessel with gas or liquid.The content of stirring reaction container is with the good distribution of maintenance catalyzer and the uniform rate of reaction of whole materials tempestuously.The process of polyreaction can be added till each oxyalkylene controlled up to addition needed amount by continuous measurement.When needing the oxyalkylene block of random or statistical distribution in polyether polymer, oxyalkylene is metered in the reaction vessel as mixture.Under temperature of reaction, continue to stir with the content in the reaction vessel, till pressure is reduced to low value.Then, final reaction product is cooled off,, and isolated if need be neutralized.
Polyol composition of the present invention also comprises other how alcohol except that PTMTG and above-mentioned polyether polyol.For example, comprise that other functionality is promptly greater than 3 how alcohol.These type of many alcohol can prepare by above method, only are to use the initiator such as the tetramethylolmethane of higher functionality, minashi sugar alcohol, and sucrose etc., and amine, as ethylene diamine, tolylene diamine etc.Many alcohol of higher functionality can be by the physical blendings of the many alcohol of finished product, or with reactions of alkylene oxide before with the mixture of above-mentioned two functionality initiators in comprise the high functionality initiator and be introduced into.Therefore, the mixture of initiator compounds can be used to make the functionality of initiator to adjust to total value intermediary certain value.If wishing to prepare, people only have lightly crosslinked elastomerics, then a high proportion of functionality is 2 initiator, added a small amount of three or high functionality initiator initiator compounds more therein, be mixed together and obtain having average functionality near 2 and at the most 2.3 initiator.On the other hand, when needs are highly cross-linked, with higher proportion three or more the high functionality initiator compounds mix with two functionality initiator compounds.
Many alcohol of other type also are included in the polyol composition of the present invention.For example, polyester polyol be can add and the elastomeric specific mechanical property such as the modulus of tensile strength and urea alkane polymkeric substance improved.Yet for some flexible application, preferably only use polyether polyol, because they are more stable than polyester polyol hydrolysis, simultaneously because its lower viscosity and processing characteristics is good.When the needs high hydrophobicity, other alcohols that can be used except that polyoxyalkylene polyether polyol of the present invention is hydroxy-end capped hydrocarbon, and is how pure as polyhutadiene.Also can use Viscotrol C and other natural oils.In addition, polycaprolactone can be used to increase elastomeric tensile strength.Other polyether polyol also can be added into, and preferably these polyether polyols have low degree of unsaturation to optimize mechanical performance of products.
Other composition in the polyether composition except that PTMEG and polyoxyalkylene polyether polyol, comprises also how pure other is, chainextender or solidifying agent, catalyzer, filler, pigment, UV stablizer etc.
The said components of polyol composition can enough standard techniques be mixed, and preferably by PTMEG: the weight ratio of polyether polyol is 20: 80-95: 5, though also be fine greater than 95: 5 ratio.Be solid as fruit component (A) or (B), they should liquefy before mixing, preferably by fusion.Preferably, polyol composition of the present invention should form uniform blend and not have observable being separated.Be necessary to adjust component (A) (B) or both relative molecular weights obtain uniform blend.
According to elastomeric purposes, the average actual functionality of blend should be 1.5-3.0, preferred 1.95-2.6 and be low to moderate 1.95-2.1.In these embodiments, can use functionality to exceed the how pure of these scopes, as long as average functionality drops within this scope.Is in the embodiment preferred at one to specific purposes, and the functionality of blend should remain on below 3.0 or 3.0 to avoid losing too many elongation and the desired feature that has concerning specific flexible application.
In hope high rigidity is arranged, in the application of high tensile and low elongation, require the actual average functionality of blend to surpass 3.0.Concerning most elastomerics was used, the mean number average molecular weight of polyol composition of the present invention was the scope of 500-5000, the preferably scope of 900-4500 and the more preferably scope of 900-3000.
The single component elastomerics can solidify by airborne moisture.Bi-component elastomer can come together to solidify with chainextender and the compound that contains isocyanate-reactive hydrogen.These chainextenders can be included in the polyol composition.Can use single stage method or prepolymer technology to prepare elastomerics.If the use prepolymer technology in the preparation of prepolymer, does not have chainextender usually in polyol composition.Then, with prepolymer and any remaining polyol composition (at this moment, this polyol composition contains chainextender) reaction.In single stage method, during beginning polyisocyanates and the polyol composition that comprises chainextender are reacted.
Chainextender can and typically, be used in the preparation of polyurethane elastomer.Term " chainextender " is used in reference to the compound than low equivalent, is usually less than about 250 equivalents, preferably is lower than 100 equivalents, has the active hydrogen atom of a plurality of isocyanate reactions.Chainextender comprises water, hydrazine, primary and secondary aliphatic series or aromatic diamine, alkamine, amino acid, alcohol acid, ethylene glycol, or its mixture.The preferred example of alcohol chainextender comprises water, ethylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,10-decane glycol, o ,-m ,-p-dihydroxyl hexanaphthene, Diethylene Glycol, 1,6-hexane diol, glycerine, TriMethylolPropane(TMP), 1,2,4-, 1,3,5-trihydroxy-hexanaphthene and two (2-hydroxyethyl) hydroxyl quinone.The preferred example of amine chainextender comprises 1.3-diamines hexanaphthene, piperazine, ethylene diamine, trimethylene diamine and its mixture.
The example of secondary aromatic diamine comprises N, the aromatic diamine that N '-dialkyl group replaces, and it can be unsubstituted or be replaced by alkyl on aryl, on the N-alkyl, have 1-20, preferred 1-4 carbon atom, N, N '-diethyl-, N, N '-di-sec-amyl, N, N '-two Sec-Hexyl, N, N '-di-secondary decyl, and N, N '-dicyclohexyl-p-and m-phenylenediamine, N, N '-dimethyl-, N, N '-diethyl-, N, N '-di-isopropyl-, N, N '-two sec-butyl and N, N '-dicyclohexyl-4,4 '-diaminodiphenyl-methane and N, N '-di-secondary butyl biphenyl amine.
The amount of employed chainextender changes according to needed elastomeric physical properties.The chainextender of higher proportion and isocyanic ester make elastomerics have a large amount of hard segments, thereby make elastomerics have bigger toughness and heat distortion temperature.The isocyanic ester of a spot of chainextender produces more flexible elastomerics.Usually, for the isocyanate-reactive components of per 100 parts of polyether polymers and PTMEG and any other higher molecular weight, can use about 2-70, the chainextender of preferably about 10-40 part.
Catalyzer can be used for promoting comprising the reaction of the compound and the polyisocyanates of hydroxyl.The example of suitable compound is a curing catalysts, and it can shorten the time of being clamminess, and promotes initial strength, prevents to shrink.Suitable curing catalysts includes organic metal catalyst, preferred organotin catalysts, yet, might use metal such as lead, titanium, copper, mercury, cobalt, nickel, iron, alum, antimony, manganese.Suitable organo-metallic catalyst is given an example tin as metal at this, is expressed from the next: R
nSn[X-R
1-Y]
2, wherein R is C
1-C
8Alkyl or aryl, R
1Be arbitrariness C
1-C
4That alkyl replaces or grafted C
0-C
18Methylene group, Y are hydrogen or hydroxyl, preferred hydrogen, and X is methylene radical-S-,-SR
2COO-,-SOOC-,-O
3S-, or-OOC-, wherein R
2Be C
1-C
4Alkyl, n are 0 or 2, as long as when X is methylene radical, and R
1Be C
0Special example is tin acetate (II), stannous octoate (II), thylhexoic acid tin (II) and month silicic acid tin (II); Have 1-32 carbon atom, organic carboxyl acid dialkyl group (1-8C) pink salt (IV) of preferred 1-20 carbon atom is as the oxalic acid tin ethide, dibutyltin diacetate, dibutyltin diacetate, dibutyl tin dilaurate, toxilic acid dibutyl tin, oxalic acid dihexyl tin and oxalic acid dioctyl tin.The list that other suitable organic catalyst is organotin alcoxylates and mineral compound or many alkyl (C
1-C
8) pink salt (IV) is as the trichlorine butyl tin, dimethyl-, and diethyl-, and dibutyl-, and dioctyl-and the oxide compound of phenylbenzene-Xi, dibutoxy dibutyl tin, two (2-ethylhexyl) tin-oxide and dichloro dibutyl tins.Yet, preferably have the tin catalyst of water-proof tin-sulfide linkage, as dialkyl group (C
1-C
20) the tin dithiol, comprise dimethyl-, dibutyl-, and the dithiol of dioctyl-Xi.
Tertiary amine also can promote urea alkane to connect the formation of base, and comprises triethylamine, 3-methoxy-propyl dimethyl amine, triethylenediamine, tributylamine, dimethyl benzyl amine, the N-methyl-, the N-ethyl-, with N-cyclohexyl morpholine, N, N, N ', N ' ,-tetramethylethylened, N, N, N ', N ',-tetramethyl butane diamine or N, N, N ', N ' ,-tetramethyl-hexane diamines, N, N, N '-trimethyl isopropyl trimethylene diamine, pentamethyl-diethylenediamine, tetramethyl-diamino ethyl ether, two (dimethylaminopropyl) urea, lupetazin, 1-methyl-4-dimethyl aminoethyl piperazine, 1,2 dimethylimidazole, 1-azabicyclo [3.3.0] octane and preferred 1,4-diazabicyclo [2.2.2] octane, and triacontanol amine compound, as trolamine, tri-isopropanolamine, the N-methyl-and N-ethyldiethanolamine and dimethylethanolamine.
In order to prevent to carry bubble secretly in seal gum or the elastomerics, after each component mixes, batch mixtures is under reduced pressure outgased.In degas method, blended is formed urethane under vacuum, be heated to comparatively high temps to reflect or to volatilize remaining moisture with component.By being heated to comparatively high temps, residual water and isocyanate reaction discharge carbonic acid gas, and it can be removed from mixture by decompression.
Additionally, or except that degassing step, urethane forms to dilute with the component useable solvents and reduces the viscosity that forms urethane usefulness mixture.This solvent should be not have reactive behavior and comprise tetrahydrofuran (THF), acetone, dimethyl formamide, N,N-DIMETHYLACETAMIDE, common methyl-2-pyrrolidone, methyl ethyl ketone etc.Urethane forms the extrudable property that reduces to help urethane with component viscosity.Yet for the seal gum purposes, the consumption of solvent should hang down as much as possible to avoid destroying its cohesiveness to basic unit.Other solvent comprises dimethylbenzene, ethyl acetate, toluene and cellosolve acetate ester.
Softening agent also can be included in and be used for softening elastomerics in A or the B component and lower its temperature limit of brittleness.The example of softening agent comprises bialkyl ortho phthalate, phthalic acid dibutyl benzyl ester, lindol, hexanodioic acid dialkyl and tricresyl phosphate octyl group ester.
Desolventize with softening agent outside, amount (based on weight polyurethane) that also can 0-75wt% adds other composition such as adhesive accelerant, filler, and pigment, as clay, silica, forge the system silica, carbon black, talcum, phthalocyanine blue or green, titanium dioxide, manganous carbonate, lime carbonate, the UV-absorption agent, antioxidant, and HALS.Other filler comprises the dissolved gel, plasticells, the lime carbonate of classification and coating, urea solid, the reaction product of hydrogenant Viscotrol C and amine, and fiber.
Polyurethane elastomer of the present invention can prepare by prepolymer technology or single stage method.Elastomerics of the present invention can pass through the reaction injection molding(RIM) technology, or prepares in the casting method, wherein forms urethane and is mixed together with each composition, is poured into pressure treatment in the heating mould then.Other technology comprises that hand commonly used mixes technology and low pressure or high pressure and collides hybrid technology, afterwards, will form urethane and inject mould with composition.
In one trip technique, will constitute the PTMEG of the present invention and the polyoxyalkylene polyether polyol of polyol composition (being also referred to as the B component), catalyzer and other isocyanate reaction active ingredient are reacted with organic isocyanate (A component) simultaneously.In case there is the B component to be mixed together, the reaction of urea alkane will begin; These components are prepared the casting elastomerics by impouring or injection mould, or component extrusion molding or spinning are prepared thermoplastic polyurethane or spandex (spandex) fiber.
In prepolymer technology, all or part of PTMEG and to have degree of unsaturation be polyoxyalkylene polyether polyol below 0.04 or 0.04, how pure with other any isocyanate reaction activity in polyol composition, and, react with the excessive organic isocyanate of stoichiometry and to form isocyanate-terminated prepolymer usually without any chainextender.The content that these prepolymers have free NCO usually is 0.5-30wt% and uses for many elastomericss that the content with free NCO is 1-15wt%.Subsequently, isocyanate-terminated prepolymer is formed polyurethane elastomer as A component and any remaining B component reaction.In some cases, whole B components are the end capped prepolymer forms of active hydrogen.In other cases, have only part polyol composition and stoichiometric excessive organic isocyanate to react and form isocyanate-terminated prepolymer, subsequently, with the residuum reaction of this prepolymer and polyol composition, as bi-component elastomer.Usually with isocyanate-terminated prepolymer and the reaction of the active functional group of isocyanate reaction (equivalence ratio by NCO: OH was at least 1.5: 1) in polyol composition.
Additionally, can prepare the end capped prepolymer of active hydrogen, if with all or part of PTMEG with have a polyoxyalkylene polyether polyol that the end group degree of unsaturation is 0.04 or 0.04 following end group, how pure with other any isocyanate reaction activity in polyol composition, usually without any chainextender, react with the organic isocyanate of stoichiometric shortage and to form the end capped prepolymer of active hydrogen.Subsequently, prepolymer is formed polyurethane elastomer as B component and A component reaction.
In one embodiment of the invention, use blend of the present invention to prepare spandex (spandex) fiber.Know that by definition spandex (spandex) is to comprise hard segment/soft chain segment, the urea-alkyl containing polymkeric substance of forming by the chain segment polyurethane of 85wt% (or polyureas) at least.Term " segmentization " is meant that territory, soft hard area alternately exists in polymer architecture.
Typically, use one of four kinds of different methods to prepare spandex (spandex): to melt extrude reaction spinning, solution dry spinning, and solution wet spinning.All method all relates to the different practical uses of similar basically chemical process.Usually, segmented copolymer be by vulcabond and polyol composition of the present invention with about 1: 2 molar ratio reaction, subsequently, use near normal low molecular weight diols of stoichiometry or diamines the prepolymer chain extension is prepared.If chain extension carries out in solvent, so resulting solution can become fiber with wet method or dry-spinning.Prepolymer can be extruded beginning polyreaction in moisture or water-free diamines is bathed and form fiber and react spinning or prepolymer is melt extruded with diol chain extender and with the form of resulting segmented copolymer with fiber in body.Melt-spinning is to be similar to the polyolefinic mode that melt extrudes and to carry out with a kind of.Typical reaction spinning is carried out after polyol composition and di-isocyanate reaction formation prepolymer.Subsequently, prepolymer is extruded in diamines is bathed, wherein the formation of monofilament and prepolymer is simultaneous, as at US patent No.4, in 002,711 described in detail like that.In another embodiment of the invention, provide a kind of thermoplastic polyurethane (TPU) elastomerics by blend preparation of the present invention.TPU is by comprising PTMEG and having polyol composition that the polyoxyalkylene polyether polyol of low-unsaturation-degree forms and organic diisocyanate reacts and forms the linear polymer structure and prepare.When other have than 2 big high functionalities many alcohol when mixing with glycol, these should use with minimum.The functionality that is preferred for preparing the initiator of polyoxyalkylene polyether polyol is 2, does not use to have functionality and be higher or lower than 2 initiator, so that the polymer chain of preparation is linear.Also use aforesaid identical chainextender, preferred chainextender is difunctional's glycol.
Reacting available single stage method or prepolymer technology carries out.In single stage method, pigment component is joined in the reaction zone of forcing machine, be heated under the temperature of effective polymerization reaction take place, extrude on travelling belt, and granulation.Prepolymer technology is similarly, and just prepolymer and chainextender are the materials that joins in the reaction zone of forcing machine.The type of employed forcing machine for example, can be used twin screw or single screw extruder without limits.
The following examples further are used for describing the present invention.Raw material
The propylene glycol adducts that many pure A are a kind of propylene oxide and oxyethane, polyoxyethylene cardinal extremity base and inside block with 20wt% with polyoxytrimethylene base, molecular weight is about 3000, and degree of unsaturation is 0.069, uses KOH as the polymerisation catalysts preparation.
Many pure B are propylene oxide-ethylene oxide adducts of a kind of propylene glycol, and it is about 3000 to have the polyoxyethylene cardinal extremity base of 20wt% and a molecular weight, use cesium hydroxide as the polymerisation catalysts preparation, and degree of unsaturation is 0.025.
Many pure C are propylene oxide-ethylene oxide adducts of a kind of propylene glycol, and it is about 2500 to have the polyoxyethylene cardinal extremity base of 20wt% and a molecular weight, use cesium hydroxide as the polymerisation catalysts preparation, and degree of unsaturation is 0.016.
Many pure D are propylene oxide-ethylene oxide adducts of a kind of propylene glycol, polyoxyethylene cardinal extremity base and molecular weight with 20wt% are 1250, use cesium hydroxide to be prepared into the adducts that degree of unsaturation is the many alcohol of 0.008 millinormal KOH/ gram as polymerisation catalysts.
PTMEG is prepared into the polytetramethylene ether diol of specifying molecular weight from tetrahydrofuran (THF).
Embodiment 1-15
In these embodiments, with use PTMEG and have degree of unsaturation greater than the prepared elastomeric compressive set of casting of the blend of 0.04 polyether polyol be that the compressive set that the blend of the polyether polyol 0.04 or 0.04 below prepares compares by using PTMEG and having degree of unsaturation.
The blend of the polyether polyol of type described in diphenylmethanediisocyanate and the following table 1 and consumption is reacted free NCO content to 6%.With prepolymer and 1, the plate of 1/4-inch is reacted and casts in the agent of 4-chain expansion of succinic acid in mould subsequently.Every block of plate is carried out thermofixation and analyze subsequently.Test modulus according to ASTM D790, come test tensile strength and elongation according to ASTM D412, testing Graves according to ASTM 624 tears, use a mouthful mould C, test resilience per-cent according to ASTM 2632-79, with under 25% deflection, come test compression deformation according to ASTM D395.
Below two tables (2 and 3) described from the retention value of the compressive set of 0-30wt% and the how pure resulting plate of the low unsaturated polyether PTMEG blend.Table 2 has been described by same procedure, according to embodiment 1, and the elastomeric physicals of casting of also using the blend of the how pure B of PTMEG/ to make.Table 3 has been described identical method, only is to use the blend of the how pure C of PTHF2500/.Table 4 has been described by same procedure, the elastomeric physicals of casting that the blend of the how pure C of use PTHF1000/ makes.
Table 1 embodiment PTMEG 2000 modulus 100% tensile elongation % tears rebound resilience compressive set Durometer A hardness embodiment 1 80,/20 1,050 2,449 410 441 58 26 88
The how pure A embodiment 2 70,/30 990 2,162 427 454 56 29 87 of 80,/20 869 2,443 599 440 55 49 76 routine A is implemented in many pure B contrasts
The how pure A of 70,/30 850 1,894 505 366 52 73 78 routine B is implemented in many pure B contrasts
Table 2
Comparative example C embodiment 3 embodiment 4 embodiment 5 embodiment 6 modulus 10,0/0 9,5/5 90,/10 80,/20 70/30100% 1,059 1,034 985 904 857300% 1,812 1,613 1,675 1,360 1224 stretching 2,767 2,465 2,822 1,848 1501 elongation % 468 556 513 494 450 tear (GRAVES) 502 509 458 460 375 Durometer A hardness 81 83 80 80 82 resilience % 58 61 26 60 49 compressive deformations 25% 21 14 9.1 20.2 28.2 table 3
Comparative example D embodiment 7 embodiment 8 embodiment 9 embodiment 10 modulus 10,0/0 9,5/5 90,/10 80,/20 70/30100% 1,059 1,000 953 943 827300% 1,812 1,678 1,601 1,532 1367 stretching 2,767 2,450 2,461 2,318 2035 elongation % 468 481 517 507 517 tear (GRAVES) 502 489 459 449 392 Durometer A hardness 81 80 79 81 79 resilience % 58 60 60 58 61 compressive deformations 25% 21 14.9 20.2 19.5 33 table 4
Comparative example E embodiment 11 embodiment 12 embodiment 13 embodiment 14 embodiment 15 modulus 10,0/0 90,/10 80,/20 70,/30 60,/40 50/50100% 1,281 1,117 1,098 984 888 726200% 1,872 1,646 1,562 1,421 1,249 978 stretching 2,650 2734 * 2,748 2,753 2,324 2238 elongation % 278 333 * 351 386 392 513 tear (GRAVES) 414 359 347 345 325 337 Durometer A hardness 92 89 90 90 88 90 resilience % 52 52 49 46 41 44 compressive deformations 25% 22 24 25 24 38 47
The result of table 1 shows: use the potassium hydroxide catalyst of standard to make compressive set bring up to 49 significantly with common polyether polyol PTMEG blend that make, that have higher degree of unsaturation, wherein in the more serious raising of 70/30 weight ratio lower compression deformation.On the contrary, the compressive set of PTMEG/ with polyether polyol of low-unsaturation-degree keeps very low compression set values and even still keeps this lower compression set values when the amount of the polyether polyol of low-unsaturation-degree is increased to 30wt%.Compressive set under 25% deflection can not deflect away from ± 15, when with under same free NCO content by only using polytetramethylene ether diol to be equal to elastomerics relatively the time as polyvalent alcohol and polyhydric alcohol composition manufacturing.This can be at other physicals such as Xiao A hardness, and tensile strength, modulus and tear strength do not have to realize under the significantly reduced situation.
Table is 2-4 result separately show, can be used and mixes with PTMEG with the casting elastomerics of the polyether polyol preparation with low-unsaturation-degree, but can not sacrifice the elastomerics compressive set.Generally use the polyol composition according to the present invention to improve elongation, some sample has also illustrated the rebound resilience of having improved.And other physicals such as modulus, tensile strength and tear strength do not reduce, and fully remain unchanged under the blend ratio of wide range.
Embodiment 16
Many alcohol are prepared to the assorted shape adducts of oxyethane (10%)/propylene oxide of glycerine, have the oxyethane end group of 5wt%, and molecular weight about 2854 and hydroxyl value are 57.0, and the use cesium hydroxide prepares as polymerisation catalysts, and degree of unsaturation is 0.012.These many alcohol can be under various levels be used to prepare urea alkane elastomerics with the PTMEG blend of 2000 molecular weight.
Embodiment 17
With weight 200 gram have that hydroxyl value is 57.0, molecular weight is that 300 glycerine causes polyoxyalkylene polyether polyol and 5 gram antioxidants and 600 and restrains that to have molecular weight be that 2000 polytetramethylene ether diol mixes.Mixture is stirred 2 hours under 60 ℃ in the nitrogen protection container, subsequently, be cooled to 40 ℃.(MDI) and subsequently resulting mixture is heated to 90 ℃ by the 175 gram methylene-biss (4-phenyl isocyanate) of interpolation in many alcohol mixtures under vacuum and keeps preparing in 3.5 hours end capped prepolymer.Resulting prepolymer is cooled to 50 ℃, and spandex fibre is to form by adopting reaction spining technology commonly used that prepolymer is extruded in the solvent of the quadrol that contains 2.5wt% is bathed.The 840 dawn spandex fibre of (932 dtex) has following physicals:
The second circulation unload forces (unload power) under 100% elongation: 0.016 gram/spy (tex)
The second circulation set: 28%
Fracture toughness: 0.51 gram/spy
The present invention is described in detail preferred embodiment, it should be understood, however, that within the spirit and scope of the present invention to make various changes and modifications.
Claims (10)
1, a kind of polyol composition, it comprises:
(A) polytetramethylene ether diol and
(B) having degree of unsaturation is to be not more than polyoxyalkylene polyether polyol 0.04 milliequivalent/gram polyether polyol, that caused by difunctional and/or trifunctional active dydrogen compounds.
2, according to the polyol composition of claim 1, wherein at least 33% hydroxyl is end capped with primary hydroxyl on many alcohol (B).
3, according to the polyol composition of claim 1, wherein many alcohol are end capped with the oxyalkylene group that obtains from oxyethane of the 4-30wt% amount that accounts for all oxyalkylene group weight.
4, according to the polyol composition of claim 2, wherein the number-average molecular weight of polyol composition is 500-5000.
5, according to the polyol composition of claim 1, the weight ratios of wherein being somebody's turn to do many alcohol and this polyether polyol are the scopes at 99: 1 to 20: 80.
6, according to the polyol composition of claim 1, wherein polyether polyol is with the glycol that contains the caesium Preparation of Catalyst.
7, according to the polyol composition of claim 1, wherein two pure and mild polyether polyols form uniform mixture.
8, a kind of prepolymer, it is a polyisocyanates and reaction product according to the polyol composition of claim 1.
9, a kind of elastomerics, it is the reaction product that comprises following mixture of ingredients:
(A) polyisocyanates,
(B) according to the polyol composition of claim 1 and
(C) preferably, active hydrogen chainextender.
10, a kind of spandex fibre, it is the reaction product of drawing together following mixture of ingredients:
(A) polyisocyanates,
(B) according to the polyol composition of claim 1 and
(C) preferably, active hydrogen chainextender.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/678,001 US6040413A (en) | 1996-07-10 | 1996-07-10 | Composition of polytetramethylene ether glycols and polyoxy alkylene polyether polyols having a low degree of unsaturation |
| US08/678,001 | 1996-07-10 | ||
| US08/678,028 US5998574A (en) | 1996-07-10 | 1996-07-10 | Compositions of polytetramethylene ether glycols and polyoxy alkylene polyether polyols having a low degree of unsaturation |
| US08/678,028 | 1996-07-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1200740A true CN1200740A (en) | 1998-12-02 |
Family
ID=27101930
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97191228 Pending CN1200740A (en) | 1996-07-10 | 1997-07-03 | Compositions of polytetramethylene ether glycols and polyoxy alkylene polyether polyols having low degree of unsaturation |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0850258A1 (en) |
| CN (1) | CN1200740A (en) |
| AU (1) | AU3540997A (en) |
| WO (1) | WO1998001492A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103755948A (en) * | 2014-01-17 | 2014-04-30 | 金骄特种新材料（集团）有限公司 | Bio-based polyalkylene glycol and preparation method thereof |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19826398A1 (en) † | 1998-06-12 | 1999-12-16 | Basf Ag | Process for the production of polyurethane elastomers |
| AU763608B2 (en) * | 1999-03-17 | 2003-07-31 | Asahi Glass Company Limited | Polyurethane / polyurethane-urea resin and process for producing the same |
| US6294638B1 (en) * | 1999-10-08 | 2001-09-25 | Bayer Corporation | Soft, transparent and processable thermoplastic polyurethane |
| JPWO2003074582A1 (en) * | 2002-03-07 | 2005-06-30 | 旭硝子株式会社 | Thermosetting polyurethane elastomer composition, polyurethane elastomer and method for producing the same |
| US6903179B2 (en) | 2002-05-30 | 2005-06-07 | Bayer Materialscience Llc | Polyurethane/ureas useful for the production of spandex and a process for their production |
| US6906163B2 (en) * | 2002-05-30 | 2005-06-14 | Bayer Materialscience Llc | Prepolymer catalysts suitable for preparing spandex fibers |
| DE102005011784A1 (en) * | 2005-03-11 | 2006-09-14 | Basf Ag | Prepolymers and cellular polyisocyanate polyaddition products prepared therefrom |
| CN112608447B (en) * | 2020-12-15 | 2022-09-09 | 无锡吉兴汽车部件有限公司 | High-air-permeability semi-rigid polyurethane foam and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4985491A (en) * | 1989-10-05 | 1991-01-15 | Olin Corporation | Polyurethane sealants made using high molecular weight polyols prepared with double metal cyanide catalysts |
| US5437822A (en) * | 1992-01-29 | 1995-08-01 | Asahi Glass Company Ltd. | Method for producing a skin-formed polyurethane foam molded product |
| US5340902A (en) * | 1993-06-04 | 1994-08-23 | Olin Corporation | Spandex fibers made using low unsaturation polyols |
-
1997
- 1997-07-03 EP EP97931765A patent/EP0850258A1/en not_active Withdrawn
- 1997-07-03 AU AU35409/97A patent/AU3540997A/en not_active Abandoned
- 1997-07-03 CN CN 97191228 patent/CN1200740A/en active Pending
- 1997-07-03 WO PCT/EP1997/003522 patent/WO1998001492A1/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103755948A (en) * | 2014-01-17 | 2014-04-30 | 金骄特种新材料（集团）有限公司 | Bio-based polyalkylene glycol and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| AU3540997A (en) | 1998-02-02 |
| WO1998001492A1 (en) | 1998-01-15 |
| EP0850258A1 (en) | 1998-07-01 |
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