CN101641324A - Hydroxyl-terminated or carboxylic acid- terminated reactive monomer compositions, their preparation and their use - Google Patents

Hydroxyl-terminated or carboxylic acid- terminated reactive monomer compositions, their preparation and their use Download PDF

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CN101641324A
CN101641324A CN200780052083A CN200780052083A CN101641324A CN 101641324 A CN101641324 A CN 101641324A CN 200780052083 A CN200780052083 A CN 200780052083A CN 200780052083 A CN200780052083 A CN 200780052083A CN 101641324 A CN101641324 A CN 101641324A
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monomer
acid
hydroxy
formula
end capped
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法比奥·阿吉雷瓦尔加斯
吉姆·D·厄尔斯
泽农·莱森科
莫里斯·J·马克斯
杰里·E·怀特
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Dow Global Technologies LLC
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Abstract

The present invention relates to new reactive monomer compositions that have a plurality of reactive, functional moieties, such as one or both of a hydroxyl moiety or a carboxylic acid moiety. The present invention also further relates to use of such reactive monomer compositions as a component of curable coating compositions, especially curable powder coating compositions.

Description

Hydroxy-end capped or carboxylic acid-terminated reactive monomer compositions, Its Preparation Method And Use
The application requires the rights and interests of U.S. Provisional Application of submitting on January 12nd, 2,007 60/880,332 and the U.S. Provisional Application of submitting on March 29th, 2,007 60/920,599.
Relate generally to of the present invention has a plurality of reactive functional moieties, for example the novel chemically-reactive monomer composition of the one or both in hydroxylic moiety or the carboxylic moiety.The invention particularly relates to (adjacent) the reactive part that has at least one end and 1 reactive monomer compositions of (arranging) reactive part to 3 inside of as many as randomly away from monomer is terminal with the monomer end.This reactive monomer compositions can comprise account for the reactive monomer compositions gross weight at least 70wt% have the reactive monomer of at least one end reactivity part and at least one internal-response part and have at least one end reactivity part and do not have the mixture of the reactive monomer of internal-response part based on the maximum 30wt% of reactive monomer compositions gross weight.The invention still further relates to this reactive monomer compositions of preparation, particularly prepare by reproducible starting material resource for example unsaturated seed oil or vegetables oil (perhaps naturally occurring oil or the oil that obtains by the plant of improvement of genes) the employed method of deutero-reactive monomer compositions.The invention further relates to this reactive monomer compositions as the component in the curable coating composition, the purposes of the component in the particularly curable powder paint compositions.
United States Patent (USP) (USP) 5,744,531 and PCT apply for corresponding text WO 97/49772 (for people such as Kerr total) a kind of anionic electrodeposition coating combination disclosed, it contain at least a particular type the beta-hydroxy alkylamide solidifying agent and can with the crosslinked electrodepositable polymkeric substance of this solidifying agent.This solidifying agent comprises and a) contains 8-60 carbon atom (C 8-C 60), b) be derived from and replace or unsubstituted aliphatic series, alicyclic or aromatic hydrocarbyl, and c) be bonded to the organic group on n the beta-hydroxy alkylamide (n is the integer of 1-4).People such as Kerr instructed have or the situation of catalyst-free under, the lower alkyl ester (for example methyl esters) and β-hydroxyalkyl amine reaction of the mixture by making carboxylicesters, preparation beta-hydroxy alkylamide solidifying agent.Electrodepositable polymkeric substance can be sour functional polymkeric substance, for example the reaction product or the adducts of siccative oil or semi-drying oil fatty acid ester and dicarboxylic acid or acid anhydrides.The sour functional polymkeric substance that exemplifies comprises sour functional acrylate copolymer, poly styrene polymer, polyester polymers, epoxy polymer or its combination.The example of beta-hydroxy alkylamide solidifying agent comprises: N, N-(2-hydroxyethyl) dodecane acid amides; N, N-(2-hydroxyethyl) coconut oleoyl amine; N, N-(2-hydroxyethyl) 12-hydroxyl stearylamide; N, N-(2-hydroxyethyl) stearylamide; Two [N, N-two (2-hydroxyethyl)] 2-[CH 3CH (CH) 15] succinic diamide; Two [N, N-two (2-hydroxyethyl)] 2-[CH 3(CH 16)]-succinic diamide; Two [N, N-two (2-hydroxyethyl)] 2-[CH 3(CH) 13] succinic diamide; [(CH 2) 18(COOH) 2] two [N, N ,-two (2-hydroxyethyls)] acid amides; Two [N, N ,-two (2-hydroxyethyls)] eicosane acid amides; Two [N, N ,-two (2-hydroxyethyl) amide dimers; [(CH) 8(CH 2) 24(CH 3) 2(COOH) 2] two [N, N ,-two (2-hydroxyethyls)] acid amides of dimeracid.
USP 5,216, and 090 (people such as Merritt) instructed a kind of powder thermosetting compositions, but it comprises the polyester that contains the carboxylic acid group or contains the material of vinylformic acid, lipid acid hydroxyalkylamide groups and the reaction mixture of beta-hydroxy alkylamide solidifying agent.
USP 4,101,606 (people such as Cenci) discussed contain one or more carboxyl or anhydride functional group the beta-hydroxy alkylamide polymkeric substance as the polymkeric substance solidifying agent.The beta-hydroxy alkylamide polymkeric substance that exemplifies comprises two [N, N-two (beta-hydroxyethyl)] maleimide, two [N, N-two (β-hydroxypropyl)] fumaramide, two [N, N-two (beta-hydroxyethyl)] citraconoyl amine, two [N, N-two (β-hydroxypropyl)] maleimide and two [N, N-two (beta-hydroxyethyl)] mesaconoyl amine.
The claimed beta-hydroxy alkylamide that has at least two beta-hydroxy alkylamide bases by polyester and each molecule of coextrusion carboxy blocking of European patent (EP) 0 698 645 people such as () Hoppe; and/or the mixture of difunctionality and polyfunctional beta-hydroxy alkylamide, prepare the method for the coating powder of heat-setting not ring-containing oxide.
WO 94/03545 (people such as Stanssens) has discussed the powder paint compositions with hydroxyalkyl amide linking agent.This linking agent comprises at least two kinds of combination of compounds that contain the beta-hydroxy alkylamide base, and wherein each compound has different beta-hydroxy alkylamide functionality.A kind of beta-hydroxy alkylamide functionality of compound is at least 3, and the beta-hydroxy alkylamide functionality of another kind of compound is not more than 3.
EP 0 471 409 people such as () Schippers relates to a kind of powder paint compositions, and it comprises the polymkeric substance with one or more free carboxylic acid group and contains the compound of one or more beta-hydroxy alkylamide base.
Constantly need to improve at coating formulation or Composition Aspects.Required improvement is one or more environment acceptabilitys, for example low-down toxicity and preferably do not have toxicity, cost, the selection of renewable resources, and physicals (for example, the flexibility of coating, toughness, binding property, hardness, wet fastness or chemical resistant properties).
USP 5,312,889 people such as () Frische disclose " hydroxy fatty acid in natural fat and oil and derivative thereof; perhaps can be particularly suitable for preparing industry useful product, particularly polymkeric substance and plastics by hydroxy fatty acid or the amino lipid acid that reactive fatty acids (for example oleic acid, linolic acid) is produced " in that the 1st hurdle 23-28 is capable.Capable according to the 2nd hurdle 52-57, " use known chemical process, for example by hydrogen halide, for example Hydrogen bromide adds on two keys, uses halogenide nucleophilic substitution ammonia subsequently, obtains to contain amino fatty acid residue by unsaturated fatty acids ... ".
Capable described as the 1st hurdle 12-21, USP 6,174,948 (people such as Thames) relate to novel latex or emulsion compositions, it contains vinyl ether, vinyl ester or acrylate by semi-drying oil and/or non-drying oil deutero-long-chain olefinic type monomers, its preparation method and the purposes of this composition in coating, tackiness agent and ink, described coating, tackiness agent and ink do not have volatile organic constituents (VOC) basically and have the improved feature of using with performance characteristics.Capable according to the 5th hurdle 5-9, the example that exemplifies of semi-drying oil comprises Thistle oil, sunflower oil, soybean oil and tobacco-seed oil, and the example that exemplifies of non-drying oil comprises Oleum Gossypii semen, cocounut oil, Toenol 1140, Viscotrol C and lesquerella oil.In the 16th hurdle 36-43 was capable, the `948 patent instructed preferred starting material to comprise replacement or unsubstituted vinyl ester, the vinyl ether of Fatty Alcohol(C12-C14 and C12-C18) and the acrylate and the acrylamide of Fatty Alcohol(C12-C14 and C12-C18) or aliphatic amide of lipid acid.The representative example of this starting material comprises oleic vinyl acetate, vinylformic acid oil base ester, methacrylic acid oil base ester, oil base acrylamide, oil base Methacrylamide and vinyl oleyl ether ad lib.The embodiment 1 of `948 discloses in the presence of triethylamine, makes the reaction of methacrylic chloride and oleyl alcohol, obtains methacrylic acid oil base ester.The embodiment 2 of `948 repeats embodiment 1, but substitutes methacrylic chloride with acrylate chloride.The embodiment 8 of `948 uses the vinylformic acid oil base ester of embodiment 2 in the curable formulation of UV.
USP 6,245, and 829 (people such as Meij) have discussed radiation curable compositions, and it comprises the unit price that contains the beta-hydroxy alkylamide base or multivalent carboxylate's compound, and wherein carboxylicesters is derived from α, β-ethylenic unsaturated carboxylic acid.Capable according to the 2nd hurdle 47-50, can prepare this component by making beta-hydroxy alkylamide and unsaturated carboxylic acid acyl chlorides, acid anhydrides or ester reaction.The 3rd hurdle 42-48 is capable thinks, after solidifying, coating by this preparation of compositions has many required performances, for example good chemical property (anti-solvent, acid, alkali and moisture), good optical performance and outward appearance, favorable mechanical performance (for example hardness, flexible, binding property, wear resistance, intensity and weather resistance), good thermostability and good weathering resistance.
As employed in the middle of this specification sheets, at this paragraph, paragraph subsequently or the definition of listing in the specification sheets other places have the implication that at first defines under them, and therefore, " alkyl " is meant (C that mainly has 1-60 carbon atom 1-C 60) unit price, the saturated or undersaturated hydrocarbon part of straight or branched." alkylene " is meant main 1-60 carbon atom (C 1-C 60) multivalence, the saturated or undersaturated hydrocarbon part of straight or branched.
" lipid acid " is meant the aliphatic acid that mainly has greater than 8 carbon.
" fatty acid ester " is meant the aliphatic ester that mainly has greater than 8 carbon.
When this paper described scope, for example in the scope of 2-10, then two of this scope end points (for example 2 and 10) were included in this scope, unless specially get rid of in addition.
A first aspect of the present invention is the hydroxy-end capped monomer shown in the formula I.
Formula I
In formula I, R 1Be the alkylene part, R 2Be hydrogen or hydrocarbon part, R 3There is not or the alkylene part R 4Be the alkylene part, R 8Be the part that hydrogen (H), hydrocarbyl portion or formula II represent:
-R 4-OH
Formula II
R wherein 4As defined above; M, n and o are 0 or 1 independently, and condition is that m, n and o sum are greater than 0.
A second aspect of the present invention comprises hydroxy-end capped monomer composition, and the hydroxy-end capped monomer that said composition comprises first aspect and wherein m, n shown in an amount of formula I and o sum are 0 the second hydroxy-end capped monomeric mixture.
A third aspect of the present invention is curable composition, said composition comprises the hydroxy-end capped monomer of first aspect or the hydroxy-end capped monomer composition of second aspect, carboxylic acid-terminated monomer, randomly be different from the hydroxyalkyl amide of hydroxy-end capped monomer composition of the hydroxy-end capped monomer of first aspect or second aspect and the one or both in the polyfunctional Resins, epoxy.
A fourth aspect of the present invention comprises reactive monomer compositions, and said composition comprises the acid amides carboxylic acid shown in the formula III:
Figure G2007800520837D00042
Formula III
R wherein 1Be the alkylene part, R 2Be hydrogen or hydrocarbyl portion, R 3There is not or the alkylene part R 4Be the alkylene part, R 5Be H or hydrocarbyl portion, or the part represented of formula IV:
-R 4-O-R 6
Formula IV
R wherein 4As defined above, and R 6Be the part of formula V:
Figure G2007800520837D00051
Formula V
R wherein 7Be the alkylene part, and m, n and o be 0 or 1 independently, condition is that m, n and o sum are greater than 0.
A fifth aspect of the present invention comprises curable resin combination, this curable resin combination comprises the reactive monomer compositions of fourth aspect, polyfunctional Resins, epoxy and randomly have the monomer (this monomer is the monomer that is different from reactive monomer compositions) of end carboxylic moiety and the one or both in the curing catalysts.
A sixth aspect of the present invention is the method that preparation has the reactive monomer of end carboxylic moiety, and this method comprises makes carboxylic acid anhydride and the reaction of at least a following substances:
A. the open loop epoxidized oil represented of formula VI:
Figure G2007800520837D00052
Formula VI
B. epoxidised fatty acid ester of open loop or the epoxidised lipid acid of open loop represented of formula VII:
Figure G2007800520837D00053
Formula VII
R wherein 2Be hydrogen or hydrocarbyl portion, R 9Be hydrogen or hydrocarbyl portion, n and p be 0 or scope be the positive integer of 1-20, a, b, c, d, e, f, g, h, i, j, k and l are 0 or 1 independently, condition is that a, b, c, d, e, f, g, h and i sum or j, k and l sum are greater than 0; With X be:
R 10-O-or
Figure G2007800520837D00061
R wherein 10Be hydrogen, hydroxy alkylene part or hydrocarbyl portion independently, and R 11Be hydrogen or hydrocarbyl portion independently; Perhaps
C. the alcoholysis reaction product between Viscotrol C and the polyvalent alcohol.
An aspect that relates to the 6th aspect comprises the reactive monomer by the method preparation of the 6th aspect.
A seventh aspect of the present invention is a kind of curable compositions, it comprises the reactive monomer by the method preparation of the 6th aspect, polyfunctional epoxy resin and randomly have the monomer (described monomer is different from the reactive monomer of the method preparation by the 6th aspect) of end carboxylic moiety and the one or both in the curing catalysts.
A eighth aspect of the present invention is a coating composition, this coating composition comprises any one curable compositions in the 3rd, the 5th or the 7th aspect of the present invention, perhaps the reactive monomer compositions of fourth aspect or the reactive monomer by the 6th aspect preparation.Discovery can be used for various application based on the powder coating of this composition, coating comprising building aluminium, family expenses or the office coating of furniture and the employed hardware of this furniture, building products such as soffit (soffits), beam (fascia), wooden partition (siding), door and window frame, and the coating of plumbing fixtures (plumbing fixtures), the coating of electronics such as transformer or generator, the coating of machine tool or shelf (pallet rack), household electrical appliance such as washing machine, drying machine, water heater, the coating of wet pad water cooler and stove, the coating of automotive component, parts below hood component and inner mounting and flange particularly, and the surfacer/shatter-resistant that serves as priming paint (antichip) coating and the universal metal apparatus such as the box of purolator and vehicle body, toy, stamping parts, frame, the coating of family physical activities device and exercise device.
As mentioned above, available formula I represents the hydroxy-end capped monomer of first aspect.
Figure G2007800520837D00071
Formula I
In formula I, R 1Be the alkylene part, R 2Be hydrogen or hydrocarbyl portion, R 3There is not or the alkylene part R 4Be the alkylene part, R 8Be the part that hydrogen (H), hydrocarbyl portion or formula II represent:
-R 4-OH
Formula II
R wherein 4As defined above; M, n and o are 0 or 1 independently, and condition is that m, n and o sum are greater than 0.
This hydroxy-end capped monomeric example that exemplifies comprises N, N-(2-hydroxyethyl) 12-hydroxyl stearylamide, N, N-(2-hydroxyethyl) 12-methylol stearylamide, N, N-(2-hydroxyethyl) 9,12-methylol stearylamide, N, N-(2-hydroxyethyl) 9,12,15-methylol stearylamide and 11-hydroxyl undecanoic amide.
Hydroxy-end capped monomer composition is the mixture of at least two kinds of different monomers representing of following formula I in the second aspect.A kind of monomeric m, n and o sum are greater than 0, and another monomeric m, n and o sum equal 0.It is N that m, n and o sum equal 0 the monomeric example that exemplifies, N-(2-hydroxyethyl) stearylamide.Hydroxy-end capped monomer composition preferably contains more than or equal to 70wt%, more preferably greater than or equal 75wt%, and also more preferably greater than or equal m, the n of 90wt% and o sum greater than 0 monomer, in each case, be benchmark with the composition gross weight.
The curable compositions of the third aspect comprises monomer or the monomer composition of second aspect and the carboxylic acid-terminated monomeric mixture of first aspect.This curable compositions randomly comprises one or both in two kinds of additional component.A kind of extra component is an oxyamide, and it is different from any component in the monomer composition of the monomer of first aspect or second aspect.If exist, then the amount of this oxyamide is 5wt%-95wt%, preferred 25wt%-75wt%, and more preferably 25wt%-50wt%, in each case, (equivalent COOH) is a benchmark with the carboxylic acid that exists in the carboxylic acid-terminated monomer.Second kind of extra component is polyfunctional Resins, epoxy.If exist, then the amount of polyfunctional Resins, epoxy is 5wt%-95wt%, preferred 25wt%-75wt%, and more preferably 25wt%-50wt%, in each case, (equivalent COOH) is a benchmark with the carboxylic acid that exists in the carboxylic acid-terminated monomer.Carboxylic acid-terminated monomer serves as the main curable components in the curable compositions.
Suitable carboxylic acid-terminated monomer comprises by making the hydroxy-end capped monomer and the anhydrides of first and second aspects of the present invention, for example maleic anhydride, succinyl oxide, Tetra hydro Phthalic anhydride, cis-1,2,3,6-Tetra Hydro Phthalic Anhydride, 1,2,4, those that 5-benzene tertacarbonic acid dianhydride and trimellitic acid anhydride reactant obtain.Preferred carboxylic acid-terminated monomer comprises based on succinyl oxide, cis-1,2,3,6-Tetra Hydro Phthalic Anhydride, Tetra hydro Phthalic anhydride and 1,2,4, those of 5-benzene tertacarbonic acid dianhydride.Most preferred carboxylic acid-terminated monomer is based on Tetra hydro Phthalic anhydride and 1,2,4, the monomer of the combination of 5-benzene tertacarbonic acid dianhydride.
When the additional component of oxyamide is selected from N, N, N`, N`-four (2-hydroxyethyl) Cyclohexamide, N, N, N`, N`-four (2-hydroxyethyl) adipamide and N, N, N` during N`-four (2-hydroxyethyl) succinic diamide, obtains satisfied result.Oxyamide is preferably selected from N, N, N`, N`-four (2-hydroxyethyl) adipamide and N, N, N`, N`-four (2-hydroxyethyl) succinic diamide, N most preferably, N, N`, N`-four (2-hydroxyethyl) adipamide.
Resins, epoxy is preferably selected from the multifunctional bis-phenol glycidyl ether that epoxy equivalent (weight) is 150-4000.Resins, epoxy more preferably is selected from the multifunctional bis-phenol glycidyl ether that epoxy equivalent (weight) is 150-2600, and most preferably epoxy equivalent (weight) is the multifunctional bis-phenol glycidyl ether of 150-1000.
The reactive monomer compositions of fourth aspect comprises the acid amides carboxylic acid that formula III is represented:
Figure G2007800520837D00081
Formula III
R wherein 1Be the alkylene part, R 2Be hydrogen or hydrocarbyl portion, R 3There is not or the alkylene part R 4Be the alkylene part, R 5Be the part that H, hydrocarbyl portion or formula IV represent:
-R 4-O-R 6
Formula IV
R wherein 4As defined above, and R 6Be the part of formula V:
Figure G2007800520837D00082
Formula V
R wherein 7It is the alkylene part; M, n and o are 0 or 1 independently, and condition is that m, n and o sum are greater than 0.
Drop on the acid amides carboxylic acid that exemplifies in the structure that formula III represents comprise above-described those.
This acid amides carboxylic acid when and polyfunctional epoxy resin and randomly be different from described acid amides carboxylic acid and have the monomer of end carboxylic moiety and any one or both in the curing catalysts in conjunction with the time, constitute the curable resin composition of the 5th aspect.
It is 80wt%-120wt% that the curable resin composition that only comprises acid amides carboxylic acid and polyfunctional epoxy resin has scope, preferred 90wt%-110wt%, the more preferably polyfunctional epoxy resin content of 95wt%-105wt%, in each case, (COOH) equivalent is a benchmark with the carboxylic acid that exists in the carboxylic acid-terminated monomer.Polyfunctional epoxy resin can be above-described any in those.
When curable resin composition comprises when being different from the acid amides carboxylic acid and having the monomer of end carboxylic moiety, this monomeric amount is 5wt%-95wt%, preferred 25wt%-75wt%, more preferably 25wt%-50wt%, in each case, the equivalent with the epoxy moieties that exists in the curable compositions is a benchmark.
The monomer that exemplifies comprises carboxylic acid-terminated polyester.This monomer is preferably selected from URALAC TMP5271 and URALAC TM5998.
When curable resin composition comprised curing catalysts, the amount of curing catalysts was 0.1wt%-5.0wt%, preferred 0.1wt%-2.0wt%, and more preferably 0.1wt%-1.0wt% in each case, is a benchmark with the weight of curable compositions.
The curing catalysts that exemplifies comprises tetrahydroglyoxaline.Preferred solidifying agent catalyzer is 2-phenyl-2-tetrahydroglyoxaline.
The preparation of the reactive monomer with end reactivity part of the 6th aspect comprises makes carboxylic acid anhydride and the reaction of at least a following substances:
A. the open loop epoxidized oil represented of formula VI:
Formula VI
B. open loop epoxidized fatty acid ester or the open loop epoxidized fatty acid represented of formula VII:
Figure G2007800520837D00102
Formula VII
R wherein 2Be hydrogen or hydrocarbyl portion, R 9Be hydrogen or hydrocarbyl portion, n and p be 0 or scope be the positive integer of 1-20, a, b, c, d, e, f, g, h, i, j, k and l are 0 or 1 independently, condition be a, b, c, d, e, f, g, h and i sum or j, k and l sum greater than 0 and X be:
R 10-O-or
Figure G2007800520837D00103
R wherein 10Be hydrogen, hydroxy alkylene part or hydrocarbyl portion independently, and R 11Be hydrogen or hydrocarbyl portion independently; Or
C. the alcoholysis reaction product between Viscotrol C and the polyvalent alcohol.
Suitable carboxylic acid anhydride comprises maleic anhydride, succinyl oxide, Tetra hydro Phthalic anhydride, cis-1,2,3,6-Tetra Hydro Phthalic Anhydride, 1,2,4,5-benzene tertacarbonic acid dianhydride and trimellitic acid 1,2-anhydride, preferred especially Tetra hydro Phthalic anhydride.
The open loop epoxy base oil that formula VI represents comprises open loop epoxidised soybean oil and the epoxidised Toenol 1140 of open loop.When the open loop epoxidized oil is the epoxidised soybean oil of open loop, obtain particularly preferred reactive monomer.
The epoxidised fatty acid ester of the open loop that formula VII represents comprises the epoxidised Witconol 2301 of open loop, the epoxidised Linolenic acid methylester of open loop, the epoxidised methyl linoleate of open loop, the epoxidised ethyl linoleate of open loop and the epoxidised methyl undecylenate of open loop.When the epoxidised fatty acid ester of open loop is the epoxidised Witconol 2301 of open loop, obtain particularly preferred reactive monomer.
The epoxidised lipid acid of the open loop that formula VII represents comprises the epoxidised oleic acid of open loop, the epoxidised linolic acid of open loop, the epoxidised linolenic acid of open loop, the epoxidised undecylenic acid of open loop (undecylenic acid) and the epoxidised 10 hendecenoic acid of open loop (10-undecenoate acid).When the epoxidised lipid acid of open loop is the epoxidised oleic acid of open loop, obtain particularly preferred reactive monomer.
The polyvalent alcohol that is suitable for using in preparation alcoholysis reaction product comprises dibasic alcohol, propylene glycol, ethylene glycol and glycol ether.
U.S. Patent Application Publication (USPAP) 2002/0035282A1 discloses alcoholysis reaction, is incorporated herein its relevant teachings.Usually, this instruction comprises with glycol ether alcoholysis soybean oil.
USP 3,291, and 764 have described the preparation of open loop epoxidized oil, are incorporated herein its relevant teachings.Usually, this instruction comprises and makes the epoxidised soybean oil open loop.
When the method for the 6th aspect was used any open loop epoxidized oil, open loop epoxidized fatty acid ester or open loop epoxidized fatty acid, processing condition comprised 100 ℃-140 ℃ temperature, and normal atmosphere and scope are 2 hours-6 hours reaction times.
A seventh aspect of the present invention is a curable compositions, it comprises the reactive monomer of the 6th aspect, polyfunctional Resins, epoxy and randomly is different from the reactive monomer of the 6th aspect and has the monomer of end carboxylic moiety and any one or both in the curing catalysts.
When curable compositions only comprises the reactive monomer of the 6th aspect and polyfunctional epoxy resin, the amount scope of polyfunctional epoxy resin is 80wt%-120wt%, preferred 90wt%-110wt%, more preferably 95wt%-105wt%, in each case, (equivalent COOH) is a benchmark with the carboxylic acid that exists in the carboxylic acid-terminated monomer.Polyfunctional epoxy resin can be above-described any in those.
Contain the monomeric curable compositions that is different from the 6th aspect and comprise that amount ranges is 5wt%-95wt%, preferred 25wt%-75wt%, more preferably this monomer of 25wt%-50wt% in each case, is a benchmark with the equivalent of the epoxy moieties that exists in the curable compositions.
The monomer that exemplifies comprises carboxylic acid-terminated polyester.Particularly preferred monomer comprises URALAC TMP5271 and URALAC TM5998.
When curable resin composition comprised curing catalysts, the amount of curing catalysts was 0.1wt%-5.0wt%, preferred 0.1wt%-2.0wt%, and more preferably 0.1wt%-1.0wt% in each case, is a benchmark with the weight of curable compositions.
The curing catalysts that exemplifies comprises tetrahydroglyoxaline.Preferred curing catalysts comprises 2-phenyl-2-tetrahydroglyoxaline.
USP 4,243,818 (Rogier) capable definition of the 5th hurdle 8-12 " hydroformylation " in the presence of catalyzer, by with hydrogen and reaction of carbon monoxide, produce aldehyde by unsaturated compound, at this by with reference to its instruction of introducing.Capable according to the 5th hurdle 36-38, preferred unsaturated compound is an oleyl alcohol, but inferior oleyl alcohol or linolenyl alcohol also can be used as unsaturated compound.In the 9th hurdle 52-58 was capable, `818 had instructed use carboxylic acid halides such as acrylate chloride that alcohol is changed into its corresponding unsaturated ester (for example, acrylate or methacrylic ester).If use, then the degree of hydroformylation is enough in functionalized or the start material material greater than 0% degree of unsaturation until this degree of unsaturation of 100%.Hydroformylation preferably is enough to be reflected at the degree of unsaturation of (〉=) at least 20% that exists in the starting material, degree of unsaturation more preferably 〉=50%, and degree of unsaturation most preferably 〉=80%.
USP 3,787, and 459 (Frankel) disclose by hydroformylation, make the polyunsaturated vegetable oil material change into the method for formyl radical (aldehyde) product.The vegetables oil material that exemplifies comprises soybean oil, Toenol 1140 and Flos Carthami oil and their derivative.
Other reference that hydroformylation is discussed comprise USP 4,423,162 people such as () Peerman (particularly Ex 34), USP 4; 723,047 (people such as Bahrmann), Canadian patent application (CA) 2,162; 083, WO 2004/096744 (people such as Lysenko), USP 4,496,487 (people such as Peerman), USP 4; 216,344 (Rogier), USP 4,304; 945 (Rogier) and USP 4; 229,562 (Rogier), it is taught in this at utmost to introduce the present invention.
The exemplifying of those methods that the instruction of people such as Peerman in `162, particularly those that occur in the 4th hurdle the 36th row at the 3rd hurdle the 50th row especially seek to implement to reduce hydroformylation.In this part, unsaturated carboxylic acid or ester by the hydrogenation hydroformylation prepare hydroxyl ester monomer starting material.Can obtain suitable unsaturated acid by triglyceride level cracking (splitting) is become its corresponding fatty acid component.People such as Peerman point out that in `162 fatty acid source comprises fatty oil, for example butter and most of plant resources, especially soybean, sesame, Sunflower Receptacle, Yatall MA and other similar substances, but the starting fatty acid of preferred methyl ester form.
People such as Peerman instruct in `162, by hydroformylation technology, use cobalt or rhodium catalyst, and then, the hydrogenation formyl radical obtains methylol by catalysis process or by chemical reduction, thereby easily realizes the introducing of methylol.In carrying out this step, people such as Peerman also mention in `162 at USP 4,216,343 (Rogier), USP 4,216,344 (Rogier), USP 4,304,945 (Rogier) and USP 4, the method that describes in detail among 229,562 (Rogier) is introduced by reference at this.
Seed oil comprise saturated and unsaturated fatty acids the two, fatty acid ester, perhaps the two mixture of lipid acid and fatty acid ester.Typical seed oil comprise greater than about 10wt% arrive less than monounsaturated fatty acids, fatty acid ester or the lipid acid of about 80wt% and fatty acid ester the two, greater than about 1wt% to less than two unsaturated fatty acidss, fatty acid ester or the lipid acid of about 45wt% and fatty acid ester the two, with greater than about 1wt% to less than about 45wt% three unsaturated fatty acidss, fatty acid ester or lipid acid and fatty acid ester the two, in each case, the gross weight with seed oil is a benchmark.
The non-limiting example of the suitable unsaturated fatty acids that can be obtained by the seed oil raw material comprises 3-hexenoic acid (hydrosorbic acid), trans-the 2-heptenoic acid, the 2-octylenic acid, the 2-nonenoic acid, cis and trans-4-decylenic acid, 9-decylenic acid (decylenic acid), 10-undecylenic acid (undecylenic acid), trans-3-dodecenoic acid (lauroleic acid), tridecylenic acid, cis-9-tetradecenoic acid (Oleomyristic acid), pentadecylenic acid, cis-palmitoleic acid (cis-9-Zoomeric acid), trans-palmitoleic acid (trans-the 9-Zoomeric acid), the 9-heptadecenoic acid, cis-petroselinic acid (petroselinum olefin(e) acid (petroselinic)), tarelaidic acid (anti-petroselinum olefin(e) acid (petroselaidic)), cis-9-octadecenic acid (oleic acid), trans-9-octadecenic acid (elaidic acid), cis-11-octadecenic acid, anti-form-1 1-octadecenic acid (octadecenoic acid), cis-5-eicosenoic acid, gadoleic acid (refreshing oleic acid (godoleic)), cis-11-eicosenoic acid (cetoleic acid), cis-13-docosenoic acid (erucic acid), anti-form-1 3-docosenoic acid (brassidic acid), cis-15-nervonic acid (zoomaric acid), cis-17-ximenic acid (ximenic acid) and cis-21-lumequeic acid (30 (carbon)-21-olefin(e) acid (lumequeic)), and 2,4-Sorbic Acid (Sorbic Acid), cis-9-cis-12-octadecadienoic acid (linolic acid), cis-9-cis-12-cis-15-punicic acid (linolenic acid), eleostearic acid, 12-hydroxyl-cis-9-octadecenic acid (ricinolic acid), cis-5-eicosenoic acid, cis-5,13-two dodecadienoic acids, 12,13-epoxy group(ing)-cis-9-octadecenic acid (vernolic acid) and 14-hydroxyl-cis-11-eicosenoic acid (lesquerolic).Most preferred unsaturated fatty acids is an oleic acid.
In seed oil, the pure fragment in the fatty acid ester is a glycerine, a kind of trivalent alcohol.Usually, carry out transesterify, obtain employed fatty acid ester in preparation aldehyde of the present invention or alcohol composition by making seed oil and low-grade alkane alcohol.Transesterify produces the mixture of the saturated and unsaturated fatty acid ester of corresponding low-grade alkane alcohol.Because triglyceride level may be difficult to processing and separate, so the transesterify of seed oil and low-grade alkane alcohol obtains being more suitable for chemical conversion and isolating mixture.Typically, lower alcohol has about 15 carbon atoms of 1-.Carbon atom in pure fragment can be arranged with straight chain or branched structure, and can be replaced by various substituting groups, this substituting group discloses before for example above relevant those with the lipid acid fragment, and condition is that these substituting groups do not hinder and handle and the application in downstream.Preferably, alcohol is the C of straight chain or branching 1-8Alkanol, more preferably C 1-4Alkanol.Even more preferably low-grade alkane alcohol is selected from methyl alcohol, ethanol and Virahol.Most preferably low-grade alkane alcohol is a methyl alcohol.
Can use any known ester exchange method suitably, as long as obtain the ester product of low-grade alkane alcohol.Prior art discloses the transesterify (for example methyl alcohol is separated, ethanolysis) of seed oil fully; For example with reference to WO2001/012581, DE 19908978 and BR 953081.Typically, in these methods, low-grade alkane alcohol contacts under the temperature between about 30 ℃-Yue 100 ℃ with basic metal (preferred sodium), preparation corresponding metal alkoxide.Then, seed oil is joined in this alkoxide mixt, and under about 30 ℃-Yue 100 ℃ temperature heating gained reaction mixture, up to carrying out transesterify.Can pass through methods known in the art,, from reaction mixture, separate thick transesterify component comprising for example being separated, extracting and/or distilling.Also can use column chromatography, for example have the column chromatography of silica gel, separate crude product and by product and/or decolouring.The modification of aforesaid method is disclosed in the literature.
If wish the mixture of lipid acid rather than fatty acid ester as raw material of the present invention, the selected seed oil of hydrolyzable then obtains the mixture of corresponding lipid acid.The method that seed oil is hydrolyzed into their fatty acid component also is well-known in the art.
Although lipid acid or fatty acid ester are mentioned in being described in herein in the replacement scheme, this description does not plan to get rid of the possibility of using and obtaining the mixture of lipid acid and fatty acid ester.Preferably, on the degree of practice, composition mainly comprises acid or mainly comprises ester; But, also can consider its mixture as described.
Preferred starting material comprises methylol fatty acid, methylol fatty acid ester, Viscotrol C and castor oil derivative.Particularly preferred starting material comprises and is selected from stearic acid hydroxyl methyl esters, methylol methyl stearate, ricinolic acid and the ricinoleate ester those.
Preferred alkanolamine comprises at least a thanomin, 1,2-Propanolamine or diethanolamine.
Be suitable for comprising ringdove elecampane oil (vernonia oil), epoxidised soybean oil or epoxy linseed oil as the preferred epoxy-functional vegetables oil of first reactant.
Be suitable for comprising epoxidation undecylenic acid and epoxyoleic acid as the preferred epoxidized fatty acid of first reactant.
Be suitable for comprising epoxyoleic acid methyl esters, epoxidation 10 hendecenoic acid methyl esters and epoxidation 9-decylenic acid methyl esters as the preferred epoxidized fatty acid ester of first reactant.
Be suitable for comprising acetate and formic acid as the preferred carboxylic acid of second reactant.
Be suitable for comprising methyl alcohol, ethanol, propyl alcohol and butanols as the preferred alcohol of second reactant.
Preferred acid catalyst comprises the ion-exchange object of reference, preferred cationic exchange resin, for example DOWEX TMZeo-karb MSC-1 (The Dow Chemical Company) and mineral acid (for example, sulfuric acid).
Composition of the present invention can comprise one or more non-reactive component that are routinely added in the coating composition.This non-reactive component comprises pigment, filler, stablizer and solvent ad lib.
Analytical procedure
The employed analytical procedure of FTIR is based on standard method, and for example the title of Jack L.Koening is the standard method described in the professional book of reference of American Chemical Society (ACS) of " Spectroscopy of Polymers (polymkeric substance spectroscopy) ".Other test methods as used herein are as described below.
Second-order transition temperature (Tg)
Use 10 ℃/minute programmed heating speed, measure the second-order transition temperature (Tg) of solidified coating by dsc (DSC).
Coat-thickness
Use Fisher Multiscope Thickness measuring instrument, be determined at the thickness of sedimentary non magnetic coating on the ferromagnetic substrate.Fisher Multiscope comprises probe and by the magneticinduction operation, to be presented at probe is being pasted the coating placement and activating Multiscope coat-thickness afterwards.Ji Lu coat-thickness value is represented the mean value of 15 coating thickness measurements herein.
% hydroxyl (being also referred to as hydroxyl value) is measured (ASTM D 4274)
After adding the known excessive Tetra hydro Phthalic anhydride in pyridine, use 1.0N sodium hydroxide (NaOH) aqueous solution, be dissolved in sample in the pyridine by the potentiometric titration measurement.
%COOH measures
Use 0.1N sodium hydroxide (NaOH) aqueous solution as titrating solution and dibromothymolsulfonphthalein as indicator, measure the carboxyl percentage ratio (%COOH) of polymers soln (in acetone) by the manual titration.
Film hardness-ASTM method D 3363 by the pencil test measurement
The panel of coating is placed on the firm horizontal surface.Make the operator firmly hold the known pencil of hardness and pasting coating or film, and promote the stroke (stroke) that pencil leaves operator's health 1/4 inch (6.5mm) with 45 ° angle.Adopt the softest pencil (6B) to begin this test, and pencil (until 9H) the continuation test of adopting hardness to increase gradually, make pencil incision or cutter dig this film or coating up to the trip.Write down the pencil hardness of coating according to plumbous hardness in the pencil before incision or cutter dig the pencil of coating just in time.
Twice wiping of methylethylketone (MEK)-ASTM method D 5402
Make the rounded ends of 2 pounds of (4.4kg) rounded hammers that covered by 8 layers of gauze that in MEK, soak or tup process back and forth on the panel surface of coating, up to breakdown of coating.In this test, only utilize the weight of hammer and the tup of guiding gauze covering to pass through the required power of coating.Breakdown of coating appears when exposing the panel substrate of coating below.Use the exposure and the breakdown of coating of acid copper sulfate check substrate.Carry out this test twice repeatedly, measuring the arithmetical av of this test and writing down this mean value is " twice wiping destruction of coating MEK value (Coating MEK DoubleRub Failure Number) ".
1/8 inch taper shaft rod bending test (ASTM method D 522-93a)
Use Gardner Lab, the testing installation of Inc. supply is measured and is fixed to flexible (resistance to cracking) that thickness is not more than the organic coating on the sheet metal substrate of 1/32 inch (0.8mm).This testing installation is by slick metal taper mandrel rod (mandrel) (length is that 8 inches (20.3cm), end diameter are that 1/8 inch (3.2mm) and outside diameter are 1.5 inches (38.1mm)), the panel bending arm of rotation and panel holder are formed, and all are installed on the metal base.The sheet metal substrate of coating clipped in the device and the substrate of coating is bent to about 135 ° from vertical direction.Near the crackle of metal substrate bending of check coating if there is crackle, then measured from the crack length of the small end of taper mandrel rod.Writing down measured crack length is " destruction range ".
Wedge shape bending (wedge bend) test
When panel is 0.0089 inch (0.23 millimeter (mm)) not during stanniferous steel disc, estimate the deformation effect of the panel of coating.Crooked this coated sheet in the mandrel rod of 1/16 inch (1.6mm), use Garner " Coverall " Impact Tester (Impact Test machine) then, with the load shock of 40 ft-lbs (5.5 kg-ms (kg-m)) should bending sheet material, obtain 0T bending (180 °).By: a) the knee and with the knee near use pressure sensitive adhesive tape; B) remove adhesive tape in mode evenly and fast; C) containing 0.03mol copper sulfate (CuSO 4) 1N hydrochloric acid (HCl) solution in dipping this bent sheet 1 minute; D) with this bent sheet of water rinse and blot the sheet material of (blot drying) rinsing; And e) after at least 12 hours, observes near be full of cracks and the binding property loss of the bent sheet 0T bending, thereby estimate the binding property loss of coating.If there is loss, then begin and loss place that can see of adhesive tape therein stops in the 0T knee, measure binding property loss distance.
Dsc
Dsc (DSC) test use be furnished with the TA Instrument DSC2920 of refrigeration system and in-60 ℃ to 275 ℃ temperature range with 10 ℃/minute rate of heating heating.
With respect to temperature survey viscosity
Use I.C.I cone-plate formula rheometer, locate, estimate the viscosity of monomer and coating formulation 25 ℃ of 6 temperature, 100 ℃, 125 ℃, 150 ℃, 175 ℃ and 200 ℃.
Gelation time reactivity measurement (the method PCI#6 that Powder Coatings Institute recommends)
With 0.2g powder formulation place the circulation (stroke) that is heated to 150 ℃ or 204 ℃ solidify hot plate (Tetrahedron of San Diego, CA) on.Use stopwatch to measure the mobile melt and be changed to thermosetting resin (the immovable solid that is called hard in other cases) required time.
Cross-hatching binding property (ASTM D 3359-90, test method B)
Use the pocket knife of 11 blades, cutting sedimentary solidified coating on panel produces three and draws the lattice zone.Firmly the masking tape bar is pressed onto on each stroke lattice part, takes off masking tape then apace and use the lens examination coating, removed how many coatings (if any) to measure masking tape.When the cut edge looks smooth fully and do not remove any coating in stroke square of lattice part, give precoat " qualified " grade.Near at least a portion coating is not present in the cutting contact or when drawing the inside of lattice part or all not being present in the two, give precoat " failure " grade.
Organic coating resists fast, and distortion (impact) effect-ASTM method D 2794 (directly impacts with reverse (reverse) impact)
Go up at impression meter (indenter) and to fall standard weight (4 pounds (lbs) (8.8kg)) in a distance, described impression meter makes cured film and the substrate below cured film or coating or the two distortion of panel.The impression meter can or paste cured film and is placing, and to invade and to estimate anti-direct impact by force, the substrate or the panel surface that perhaps can be combined with solidified coating on it are placed, and to apply squeeze, estimate anti-reverse impact.Usually, increase the weight drop, the distance when reaching coating appearance destruction.Cured film or coating be usually because of be full of cracks destroys, and when observing by amplifier, described be full of cracks is more visual obviously, particularly on cured film after acid copper sulfate solution is applied to distortion or the coating after.
Gloss (ASTM D523)
Use Gardner Micro Tri Gloss Meter, the spectrum gloss measurement is located to carry out for 20 °, 60 ° and 85 ° in each comfortable dried up plane, measures and be recorded in these angle everywheres then, the mean value of gloss measurement.
Anti-zoned property (ASTM D7027-05)
Use is at Surface﹠amp; Described in Coatings Technology 201 (2006) 2970-2976 and be furnished with the delineation tip the cut testing tool, use delineation speed, the cut length of 100mm/s and the applied load that increases gradually to 70N from 1 newton (N), on coated sample, apply cut controlled, that use device measuring.At Epson Perfection TMOn the 4990Photo scanner, under the resolving power of 3200dpi (pixel/inch) (1260 pixels/centimetre (cm)), scanning cut image, measure the destruction of epoxy coat with the form of applied load point, at first visually penetrate coating on the panel and the metal decking surface below the contact at this POL place delineation tip.
Following embodiment sets forth, but does not limit the present invention.All parts and percentage ratio are benchmark with weight, except as otherwise noted.All temperature are ℃.Embodiments of the invention (Ex) are represented with Arabic numerals, and Comparative Examples (Comp Ex) is represented with capitalization.Unless this paper has explanation in addition, " room temperature " and " envrionment temperature " normally 25 ℃.
Raw material:
A. Viscotrol C (Aldrich, catalog number (Cat.No.) 25,985-3).
B.12-hydroxymethylstearat (PARACIN TM, CasChem of Rutherford Chemicals), purify by recrystallization, obtain 57 ℃ DSC crystalline melting point.
C.12-methylol methyl stearate, reduction hydroformylation (HF) product of the methyl esters of sunflower oil.
D. mixtures of methyl esters, the reduction HF product of the methyl esters of soybean oil.
E.11-hydroxyl undecanoic acid methyl esters-by reduction hydroformylation soybean oil methyl esters, then methyl alcohol is separated this methyl esters (according to USP 4,496, the method described in 487), then the product that obtains by distillation purifying.It contains the 11-hydroxyl undecanoic acid methyl esters that accounts for product gross weight 94wt% gas-chromatography (GC) analysis revealed.
F. diethanolamine (DEA) (Aldrich, catalog number (Cat.No.) 39,817-9).
G. solid epoxy (D.E.R. TM663U and D.E.R. TM661, The Dow ChemicalCompany).
H. the glycerolysis product (FLEXRICIN of Viscotrol C TM13, CasChem of RutherfordChemicals).
I. dimethyl silicone polymer surface properties-correcting agent (BYK TM310, BYK Chemie USA).
J. ethylene glycol monobutyl ether (DOWANOL TMEB, The Dow Chemical Company).
K. pimelinketone (Aldrich, catalog number (Cat.No.) 39,824-1).
L. polyester (the URALAC of carboxylic-acid functional TM5271, DSM, titrating hydrogen equivalent is 720).
M. by hexanodioic acid and DEA deutero-hydroxyalkyl amide (PRIMID TMXL-552, EMS-PRIMID, it was reported hydroxyl value be 620-700 milligram potassium hydroxide/gram (mg KOH/g).
N. the epoxidised soybean oil of binary alcoholization ( Referring toEx 34 is about the preparation of the epoxidised soybean oil of binary alcoholization).
Ex 1-prepares hydroxyalkyl amide by diethanolamine and 12-methyl hydroxystearate
In being furnished with the 500ml round-bottomed flask of magnetic stirring bar and water-cooled reflux condenser, place 100.5 grams (g) (0.32mol) 12-methyl hydroxystearate, 139.4g (1.325mol) diethanolamine and 0.13g (0.002mol) 85wt% potassium hydroxide (in methyl alcohol) solution.Flask is placed in the electrically heated cover.The thermostat that use links to each other with thermopair in being immersed in flask contents, the temperature of control flask contents.Under agitation, heating flask contents to 110 ℃, thus flask contents becomes the solution of clear, colorless.
Continuing to keep 110 ℃ temperature overnight (about 14 hours) under the stirring, take out solution example afterwards and sample is carried out Fourier transform infrared (FTIR) spectroscopic analysis.There is the absorption of the ester of trace in analysis revealed, as at 1729cm -1The small peak at place shows.
Make flask contents be cooled to 65 ℃ temperature, add 400 milliliters of (ml) chloroform (CHCl then 3), obtain the CHCl of flask contents 3Solution.With 250g 5wt% sodium-chlor (NaCl) solution washing CHCl 3Solution 4 times, and from the NaCl aqueous solution separation of C HCl 3Solution obtains washed CHCl 3Solution.
Adopt anhydrous magnesium sulfate, washed CHCl in the dry flask contents 3Solution is removed residual water, then by filtering, separates the dry CHCl that crosses 3Solution and anhydrous magnesium sulfate.
Under the vacuum tightness of 60 ℃ temperature and 4.5 millimeters (mm) mercury (Hg) post (600 handkerchiefs (Pa)), to the drying and the isolating CHCl of flask contents 3Solution is rotated evaporation 4 hours, removes CHCl from flask contents 3, stay 1069.6g (87% theoretical yield) thus and be the waxy solid reaction product down in room temperature (common 25 ℃).
The FTIR analysis revealed of this wax, wax is the oxyamide with structure shown in the following formula VIII, is also referred to as the acid amides polyvalent alcohol.
Figure G2007800520837D00191
Formula VIII. acid amides polyvalent alcohol
Ex 2-uses the hydroxyalkyl amide of Ex1 to prepare coating composition
Miniature ball mill pulverizer (Bel-Art Products) is placed on the dry ice box interior 2 hours, operated this ball mill then 1 minute, merge hydroxyalkyl amide and the 20g polyester resin of carboxylation (URALAC of 3.56g Ex1 TMP 5271, are available commercially from DSM) and produce fine not sintered powder.With the 6.5g powder dissolution at 80: 20 (volumes: ethylene glycol monobutyl ether (DOWANOL volume) TMEB, The DowChemical Company) and in the mixture of pimelinketone, obtains coating solution or composition.
Use numbering (No.) 28 BYK-Gardner spreader (draw down bar) of filming, two Wuxis, free of contamination tin free steel sheet (inch (30.5cm) * 0.03,4 inches (10.2cm) * 12 inch (0.76mm)) goes up the coating of blade coating (draw) or deposition coating solution.Similarly, use the No.48BYK-Gardner spreader of filming, the coating of Spreed coated paint solution on the cold-rolled steel sheet of two hair sides (ground).
It is 204 ℃ of following time periods of 10 minutes in the forced air convection baking oven of the heating of operation that the panel of coating is placed on set point temperatures, and the hydroxyalkyl amide of merging and polyester resin of carboxylation are cured.The Fisherscope film thickness gauge shows that the mean thickness of the coating on free of contamination tin free steel sheet is 0.35 mil (0.89x10 -5Rice (m)).The mean thickness of the coating on cold-rolled steel sheet is 0.459 mil (1.16x10 -5M).
The ASTM D3363 pencil hardness of the coating on the cold-reduced sheet is H.
According to four measurements, the wedge shape crooked test of coating does not show not destruction on tin free steel sheet.
Cold-reduced sheet coating on cold-reduced sheet has physicals as described below:
Pencil hardness (ASTM D 3363)=H
Taper mandrel rod bending (ASTM D 522-93a)=do not destroy
Cross-hatching bounding force (ASTM D 3359)=qualified
Direct impact strength (ASTM D 2784)=greater than (＞) 160 in-lbs (metric system equivalence values of 1.84 kg-ms)
Indirect stroke intensity (ASTM D 2784)=greater than (＞) 160 in-lbs (metric system equivalence values of 1.84 kg-ms)
Comp Ex A-prepares powder paint compositions by Resins, epoxy and carboxylic acid-terminated vibrin
Repeating Ex 2, and operated ball mill 1 minute, prepare free-pouring powder, is that 10g is also with 10g Resins, epoxy (D.E.R. but reduce the polyester resin of carboxylation amount TM663U, The Dow ChemicalCompany) replaces the hydroxyalkyl amide of Ex1.Under 150 ℃, the gelation time of powder is 7.1 minutes (min.), is 1.25 minutes under 204 ℃, and Tg is 80 ℃.
With the free-pouring powder of 7.3g, 0.0365g 2-phenyl-2-tetrahydroglyoxaline, 17.03g 80: 20DOWANOL TMEB: the dimethyl silicone polymer surface properties-correcting agent (BYK of cyclohexanone mixture and 3 polyester modifications TM310, BYK Chemie USA) be incorporated in the vial, and this bottle is placed on the wobbler, promote the dissolving of solid ingredient.The same panel that is coated with Ex2.The same panel to coating with Ex2 is tested, and has concluded test-results in following table 1 and 2.
Comp?Ex?B
Repeat Comp ExA, but the consumption of increase polyester resin of carboxylation is 20g and uses 2.21g oxyamide (PRIMID TMXL-552, EMS-Primid, hydroxyl value is a 620-700 milligram potassium hydroxide/gram (mgKOH/g)) the displaced loop epoxy resins.The gelation time of this powder blend under 204 ℃ is 2.3 minutes, and Tg is 15 ℃ (secondary peaks) and 61 ℃ (main peak).
Ex 3-prepares the acid amides polyvalent alcohol by DEA and Viscotrol C
In being furnished with 2 liters of round-bottomed flasks of mechanical stirring and reflux exchanger, place 200.07g Viscotrol C and 276.03g (2.62mol) diethanolamine (DEA).This flask is placed in the electrically heated cover, and described electrically heated cover is by having the thermostat control of the thermopair in the flask contents of being immersed in.Under agitation, the set point temperatures of heating flask contents to 120 ℃, and under continuing to stir, keep this temperature overnight (about 14 hours).The FTIR analysis revealed of flask contents is at 1733cm -1The place has the absorption of trace ester.
By increasing CHCl 3Addition to 1 kilogram (kg), changing wash water solution is the aliquots containig of 400g 2wt%NaCl solution, and to change the rotary evaporation condition be 5 hours time length and 2.3mm Hg (306.6Pa), improves product and reclaims.The rotation evaporated filtrate is 5 hours under 60 ℃ and 2.3mm Hg, removes CHCl 3Final product at room temperature is that liquid and %OH are 12.56.FTIR and 1The ricinolic acid acid amides triol structure that H NMR provides below analyzing and supporting.
Acid amides polyvalent alcohol (ricinolic acid acid amides triol)
Figure G2007800520837D00211
The anhydride esterifying of the ricinolic acid acid amides triol of Ex 4-Ex 3
In the same 500ml round-bottomed flask that is equipped with, place the acid amides polyvalent alcohol of 232.7g (1.717OH equivalent) Ex.3 with Ex3, and the set point temperatures of heating flask contents to 90 ℃, afterwards, stir the limit with 18.73g pyromellitic acid anhydride (PMDA or 1 in the following continuation of the stirring velocity of 400 rev/mins (rpm), 2,4,5-benzene tertacarbonic acid dianhydride; 0.172 equivalent) join in the flask.After the interpolation of finishing PMDA, continuing under the stirring, add 228.89g Tetra hydro Phthalic anhydride (1.545 equivalent) in flask, and rising set point temperatures to 135 ℃, with keep content under this temperature about 3 hours or up to carboxyl by titration determination (COOH) content reaches stable or consistent level.
On aluminium foil, topple over flask contents, then aluminium foil and content thereof are placed in the refrigerator (15 ℃), the sclerosis content, this content is ground into bulk also to be placed on this bulk material in the bottle, bottle and content thereof are turned back in the refrigerator, when further use or test, need.
Compare with 16.1% theoretical %COOH, the %COOH of flask contents or resin is 15.4%.The FTIR analysis revealed of flask contents is at 1852cm -1The place has the acid anhydrides carbonyl absorption of residual quantity.The viscosity of resin under 150 ℃ is 600 centipoises (0.6Pa.s), and is 150 centipoises (0.15Pa.s) under 200 ℃.The Tg of this resin also is 6 ℃.
Ex?5
Use device identical and 1 minute pulverizing time, but the time in the dry ice box reduces to 45 minutes, the ground mixt of the resin for preparing among Resins, epoxy that preparation 15.76g (0.0204 equivalent) is identical with Comp Ex B and the 6.0gEx 4 with Ex 2.Use gas blower, warm this ground mixt obtains fine free-pouring powder to room temperature, and its Tg is that 12 ℃ and the gelation time under 204 ℃ are 1.7 minutes.
This powder of 1g is placed in the aluminium dish, this aluminium dish is placed in the forced air convection baking oven of operating under 204 ℃ the set point temperatures 11 minutes, carry out the crosslinked of resin or solidify, transparent crosslinking polymerization resin is provided.The dsc analysis of cured resin shows that a Tg is 63 ℃.The dsc analysis second time of identical cured resin shows that the 2nd Tg is 73 ℃.The 2nd Tg is higher than a Tg, most likely extra curing or crosslinked result.
Ex?6
Use the apparatus and method identical with Ex5, the Resins, epoxy that 19.7g (0.0254 equivalent) and Ex 5 is identical, the resin and the 0.54g 2-phenyl-2-tetrahydroglyoxaline of 7.5g (0.0255 equivalent) Ex 4 preparations change into fine, free-pouring powder.The gelation time of this powder under 204 ℃ is that 1.0 minutes and Tg are 12 ℃.After solidify the same with Ex5, analyze for a DSAC, the Tg of transparent crosslinking polymerization resin is 79 ℃, and for the second time of identical crosslinking polymerization resin be 78 ℃ the dsc analysis.Those skilled in the art understand dsc measurement to have+/-3 ℃ experimental error.
Ex?7
Use the method for Comp Ex A, the test plate (panel) of preparation coating, but the powder of employing Ex 6, rather than the powder of Comp Ex A do not add 2-phenyl-2-tetrahydroglyoxaline, and (curing) time under 204 ℃ is 11 minutes rather than 10 minutes.The test-results of coat-thickness and coating performance sees Table 1.
Ex?8
Repeat Ex 4, but be changed to acid amides polyvalent alcohol with maleic anhydride (MAH) rather than PMDA esterification Ex3.Change and comprise that the addition that reduces the acid amides polyvalent alcohol is to 227.14g (1.673OH equivalent), reduce stirring velocity to 350rpm, before adding 164.02g MAH, heating flask contents to 50 ℃ after adding MAH, increases flask contents temperature to 100 ℃, at 100 ℃ after following 3 hours, topple over flask contents in the flask in bottle rather than use among the Ex 4 step that content is poured on the aluminium foil, freezing, be ground into bulk and be stored in the refrigerator subsequently.
Compare with 19.3% theoretical %COOH, the %COOH of flask contents or resin is 18.8%.The FTIR analysis revealed of flask contents is at 1849cm -1The place has the acid anhydrides carbonyl absorption of residual quantity.
The viscosity (cone-plate formula rheometer) of resin under 150 ℃ be 440 centipoises (cps) (1.1 handkerchiefs. second (Pa.s)) and Tg be-19 ℃.
Ex?9
Repeating Ex 7, is the resin of 1.86g (0.0073 equivalent) Ex 8 but change the bottle content, 5.67g (0.0073 equivalent) and the employed identical Resins, epoxy of Comp Ex A, 80: 20 DOWANOL described in the 17.57g Comp Ex A TMEB: the dimethyl silicone polymer surface properties-correcting agent of the polyester modification described in cyclohexanone mixture and the 3 Comp ExA.Coating performance Referring toTable 1 and 2.
Ex?10
Be furnished with mechanical stirring, merging the resin of 5.66g (0.0229 equivalent) Ex 8 in the 100ml round-bottomed flask of fill the nitrogen device (nitrogen pad), condenser and thermostat, (17.67g 0.229 equivalent) and Ex 9 employed identical Resins, epoxy and 60ml dry toluenes.Heating flask contents to 100 ℃ also maintains following 3 hours time period of this temperature, " B-rank " product that obtains diluting.B-rank product to this dilution under 60 ℃ and 4.5mm Hg (600Pa) is rotated evaporation 4 hours, removes toluene, and to obtain %COOH be 2.99 undiluted basically B-rank product.This %COOH explanation following result: 32.2%COOH that in resin or B-rank product, exists and Resins, epoxy reaction.B-rank product has the cone-plate viscosity of 4500cps (4.5Pa.s).First dsc analysis of B-rank product shows that Tg is 23 ℃, and then heat release 5J/g and beginning temperature and peak temperature are respectively 153 ℃ and 178 ℃.It is 69 ℃ that the dsc analysis second time of identical B-rank products (by the product of the dsc analysis first time) demonstrates Tg.The same with Ex5, the curing of additional quantity or crosslinked is represented in the increase of Tg most probably.
Ex?11
Repeat Ex 9, but substitute resin and the Resins, epoxy of Ex 8 with the B-rank product of 9g (0.0078 equivalent) Ex 10.The content that changes bottle is the resin of 1.86g (0.0073 equivalent) Ex 8,5.67g (0.0073 equivalent) and the employed identical Resins, epoxy of Comp Ex A, 80: 20 DOWANOL described in the 17.57gComp Ex A TMEB: the dimethyl silicone polymer surface properties-correcting agent of the polyester modification described in cyclohexanone mixture and the 3 Comp ExA.Coating performance Referring toTable 1 and 2.
Ex?12
Repeat Ex 8, but several variations are arranged.The first, the consumption that reduces the acid amides polyvalent alcohol is 25g (a 0.1846OH equivalent).The second, substitute all MAH with 18.59g (0.1846 COOH equivalent) succinyl oxide.The 3rd, change flask and be of a size of 50ml.The 4th, after rising flask contents temperature to 100 ℃, add the 0.14g glyoxal ethyline in flask.The 5th, keep the flask contents temperature and descended about 2.75 hours at 100 ℃, up to the same with Ex 4, %COOH reaches maintenance level.The %COOH of product is 20.36, and the viscosity under 150 ℃ (cone-plate formula rheometer) is 50 centipoises (0.05Pa.s).
Ex?13
Repeat Ex 9, but several variations are arranged.The first, the product of usefulness 1.86g (0.0084COOH equivalent) Ex 12 substitutes the product of Ex 8.The second, the consumption that increases Resins, epoxy is 6.5g (0.0084 epoxy equivalent (weight)) and 80: 20DOWANOL TMEB: the consumption of cyclohexanone mixture is 19.5g.Coating performance is referring to table 1 and 2.
Ex?14
Repeat Ex 4, but several variations are arranged, with the hydroxyalkyl amide of esterification Ex 1.The first, change flask and be of a size of the acid amides polyvalent alcohol that 50ml and flask contents become 25.8g (0.194OH equivalent) Ex 14,25.86g (0.175 equivalent) Tetra hydro Phthalic anhydride, 2.12g (0.0194 equivalent) PMDA.With theoretical %COOH is 16.23% to compare, and the %COOH of flask contents or resin is 15.84%.The viscosity (cone-plate formula rheometer) of resin under 150 ℃ is that 1000cps (1.0Pa.s) and Tg are 6 ℃.
Ex?15
Repeat Ex 5, preparation contains the pulverized powder of the resin of Ex 14, but has following variation.First, in the dry ice box, placed pulverizer 0.5 hour rather than 45 minutes, the pulverizing time was increased to 2 minutes from 1 minute, and to change pulverized material be 15.0g (0.0194 equivalent) Resins, epoxy identical with Ex 5, the pulverized powder of (5.51g 0.0194 equivalent) Ex 17 and 0.41g 2-phenyl-2-tetrahydroglyoxaline (URALAC TM5271, DSM).The gelation time of this powder under 204 ℃ is 0.8 minute.
Use the method identical, this powder of 1.03g is changed into transparent crosslinking polymerization resin with Ex5.The dsc analysis of cured resin shows that Tg is 83 ℃.The dsc analysis second time of same cured resin shows that Tg is 83 ℃.
Ex?16
Repeat Ex 7, but substitute the resin of Ex4 with the resin of Ex14.The solidified coating performance is referring to table 1 and 2.
Ex?17
Repeat Ex 1, prepare the acid amides polyvalent alcohol by DEA and methyl stearic acid 12-hydroxyl methyl esters, but following variation is arranged.Flask is become 2 liters of round-bottomed flasks, and flask contents becomes the methanol solution of 400g (1.217mol) methyl stearic acid 12-hydroxyl methyl esters (the reduction hydroformylation products that the methyl esters of use sunflower oil obtains as base mateiral), 511g (4.86mol) DEA and 0.915g (0.014mol) 85%KOH.Be cooled to 50 ℃ rather than with 65 ℃ of Ex14 before, FTIR analyzes and the product recovery shows at 1729cm -1The place exists the ester of trace to absorb.Referring to above-described instruction, particularly USP 4,496, and about the method for reduction hydroformylation, these two pieces of patents are incorporated herein by reference preceding for 487 people such as () Peerman and USP 4,423,162 people such as () Peerman.
For product is reclaimed, substitute employed 400ml CHCl in Ex 1 with 780g toluene 3, and the change wash fluid is 560g 3wt% sodium bicarbonate (NaHCO 3) aqueous solution.In addition, increase rotary evaporation time to 6 hour, vacuum tightness is 1.5mm Hg (200Pa.s).Be that 450.3g (theoretical yield 92.1%) and %OH are 12.092 at room temperature for the product weight of liquid.FTIR and 1H NMR analyzes the acid amides polyvalent alcohol that support has structure shown below.
Figure G2007800520837D00251
Ex?18
Repeat Ex 1, use the acid amides polyvalent alcohol product of Ex17, the preparation esterification products, but have following variation.The first, the change flask contents is acid amides polyvalent alcohol product and 17.89g (0.1777COOH equivalent) succinyl oxide of 25g (0.1777OH equivalent) Ex 17.The second, heating flask contents to 100 ℃ is added the 0.14g glyoxal ethyline, keeps flask contents then under 100 ℃, up to %COOH stable (about 3 hours).Compare with 18.59% theoretical %COOH, the %COOH of this resin is 18.44%, and the viscosity under 150 ℃ (cone-plate formula rheometer) is 70cps (0.07Pa.s).
Ex?19
In vial, use the method for Comp Ex A, merge the resin of 1.85g (0.00758COOH equivalent) Ex 18, the Resins, epoxy that 5.86g (0.00758 epoxy equivalent (weight)) and Ex 5 are identical, 80: 20 DOWANOL described in the 18gComp Ex A TMEB: cyclohexanone mixture and 3 polysiloxane surface-modifying agents identical, the test plate (panel) that the same preparation is coated with among same and the Comp Ex A with CompExA.Coating performance is referring to table 1 and 2.
Ex?20
Repeat Ex 3, prepare the acid amides polyvalent alcohol by the soybean oil methyl esters of DEA and reduction hydroformylation, but have following variation.It is the same with above Ex 14, Referring toInstruction cited above, particularly USP4, about the method for reduction hydroformylation, these two pieces of patents are incorporated herein by reference preceding for 496,487 people such as () Peerman and USP 4,423,162 people such as () Peerman.At first, use 3 liters of round-bottomed flasks rather than 2 liters of round-bottomed flasks, and change soybean oil methyl esters and 514.33g (4.89mol) DEA that flask contents is a 400g reduction hydroformylation.The second, changing temperature is 110 ℃.After the same heating under agitation with Ex3, FTIR analyzes flask contents and shows at 1735cm -1There is the absorption of trace ester in the place.
For product is reclaimed, to use the method for Ex17, but increase the toluene addition to 1500ml, the washing lotion amount is the aliquots containig of 1000g.At room temperature for the %OH of semisolid product be 11.59.FTIR and 1H NMR analysis revealed product are the acid amides polyol structure.
Ex?21
Repeat Ex 4, the acid amides polyvalent alcohol of esterification Ex20, but have following variation.The first, in round-bottomed flask, place the acid amides polyvalent alcohol of 252.16g (1.842OH equivalent) Ex 20 rather than the acid amides polyvalent alcohol of Ex 3.The second, before adding PMDA, heating flask contents to 70 ℃, and the consumption that changes PMDA is 20.09g (0.184 equivalent).The 3rd, the consumption that increases Tetra hydro Phthalic anhydride is 245.55g (1.658 equivalent).The %COOH of this product is 15.78%, and by contrast, theoretical %COOH is 16.02%, and the cone-plate viscosity under 150 ℃ is 1100cps (1.1Pa.s), and Tg is 12 ℃.
Ex?22
Repeat Ex 6, based on the product of Ex21, preparation powder coating formulation, but have following variation.At first, change the material of handling with pulverizer and be the identical Resins, epoxy of 7.63g (0.00987 equivalent) and Ex 6, the product of 2.94g (0.00988 equivalent) Ex 24, the 2-phenyl-2-tetrahydroglyoxaline identical with 0.21g and Ex 6.The second, increasing the pulverizing time is 2 minutes, and fine free-pouring powder is provided.The dsc analysis of powder shows to have the fusion heat absorption under 60 ℃, and then heat release 66J/g and beginning temperature and peak temperature are respectively 91 ℃ and 153 ℃.The gelation time of this powder under 204 ℃ is that 0.78 minute and Tg are 12 ℃.With Ex 5 the same curing after, the Tg of transparent crosslinking polymerization resin is 84 ℃.
Ex?23
Repeat Ex 7, use the powder of Ex22, the panel of preparation coating.Coating performance is referring to table 1 and 2.
Ex?24
Repeat Ex 21, use maleic anhydride (MAH), rather than PMDA and Tetra hydro Phthalic anhydride, the acid amides polyvalent alcohol of esterification Ex 20, but have following variation.The first, use the acid amides polyvalent alcohol of 226.68g (1.640OH equivalent) Ex 20 and heat flask contents to 60 ℃, rather than 70 ℃, add 161.74g MAH afterwards in flask.The second, after the interpolation of MAH, heating flask contents to 90 ℃, rather than among the Ex 24 135 ℃.Product is that %COOH is 18.38% liquid, and by contrast, theoretical %COOH is 19.10%.Cone-plate viscosity under 125 ℃ is that 125cps (1.45Pa.s) and Tg are-28 ℃.The FTIR assay products shows at 1849cm -1The place has the acid anhydrides carbonyl absorption of residual quantity.
Ex?25
In vial, place the product of 1.93g (0.00783 COOH equivalent) Ex 21, the Resins, epoxy that 6.06g (0.99784 epoxy equivalent (weight)) and Ex 5 are identical, 0.303g 2-phenyl-2-tetrahydroglyoxaline, 80: 20 DOWANOL described in the 14.13g Comp Ex A TMEB: cyclohexanone mixture and 3 polysiloxane surface-modifying agents identical with CompEx A, and the same with Comp Ex A, shaking flasks content, dissolved solids.Equally with Ex7 prepare the test plate (panel) of coating and in following table 1 and 2, write down the result.
Ex?26
Repeat Ex 17, prepare the acid amides polyvalent alcohol by DEA and 11-hydroxyl undecanoic acid methyl esters, but have following variation.The first, changing flask is that 1 liter of round-bottomed flask and flask contents are 200g (0.9246mol) 11-hydroxyl undecanoic acid methyl esters, 388g (3.6903mol) DEA, the 85%KOH solution that 0.62g (0.009mol) is identical with Ex20.The second, under agitation, heating flask contents to 80 ℃ obtains transparent colourless solution and continues under this temperature stirring 20 hours.Before cooling, the FTIR analysis revealed of this solution is at 1729cm -1There is the absorption of trace ester in the place.The 3rd, cool off this solution to room temperature (common 23 ℃), under 60 ℃ and 4mm Hg (533.3Pa), rotary evaporation flask contents 3 hours is removed methyl alcohol then.
The content that the merging flask contents and 400ml 2wt% sodium-chlor (NaCl) aqueous solution and stirring merge 3 hours.The content that merges by the vacuum filtration of coarse glass-fritted B, and with the solid part in the content of extra 400ml 2wt%NaCl aqueous solution rinsing merging.The solid part of rinsing and the fresh 2wt%NaCl solution of 500ml are 3 hours in the mixing flask contents, then by the vacuum filtration of coarse glass-fritted B.Cross filterable solid with the 800ml rinsed with deionized water, sky was done this solid 3 days in stink cupboard then.Mixed this solid and 650ml toluene 3 hours, then by passing through coarse glass-fritted B vacuum filtration, separate solid and toluene.With the solid that the toluene rinsing of two parts of independent five equilibriums separated, under 70 ℃, the isolating solid of rotary evaporation is to constant weight then.The solid of rotary evaporation or final product are that weight is the white solid (theoretical yield 88%) of 231.8g.FTIR and 1H NMR analyze and support acid amides polyvalent alcohol (trivalent alcohol) structure as follows:
Figure G2007800520837D00271
Ex?27
Repeat the method for Comp Ex A, but increasing the pulverizing time is 2 minutes, change the polyester of the carboxylic-acid functional among 15g (0.0208 equivalent (COOH equivalent)) the Comp Ex A and the acid amides polyvalent alcohol of 1.96g (0.0194 equivalent) Ex 26 into fine free-pouring powder, its gelation time under 204 ℃ is 1 minute 46 seconds.The dsc analysis powder shows that then heat release 8.35J/g and beginning temperature and peak temperature are respectively 180 ℃ and 230 ℃ 69 ℃ and 79 ℃ of following fusion heat absorptions.The same with Comp Ex A, solidified the 1.4g powder 11 minutes down at 204 ℃, obtain transparent cure polymer, in DSC scanning, its Tg is 56 ℃, in the second time or multiple scanning, its Tg is 65 ℃.
Ex?28
Repeat Ex 14, the acid amides polyvalent alcohol of esterification Ex 26, but have following variation.First, in the 50ml round-bottomed flask, place the acid amides polyvalent alcohol of 17.53g (0.1733 OH equivalent) Ex 26, (21.97g 0.1444 equivalent) cis-1,2,3,6-Tetra Hydro Phthalic Anhydride, and 3.15g (0.0289 equivalent) PMDA and heat flask contents to 120 ℃ add the 0.14g glyoxal ethyline afterwards in this flask.Continue down to stir at 120 ℃, 17.2%, by contrast, theoretical %COOH is 18.2% up to the %COOH that equally measures according to Ex17 stable (about 2 hours).Topple over flask contents (being liquid down) in bottle in envrionment temperature (common 23 ℃).This liquid, being also referred to as the cone-plate viscosity of polyfunctional acid under 150 ℃ is 650cps (0.65Pa.s).
Ex?29
Repeat the method for Ex 25, but wobbler is placed under the heating lamp, by the polyfunctional acid of 2.2g (0.0077 COOH equivalent) Ex28, the Resins, epoxy that 5.97g (0.0077 epoxy equivalent (weight)) and Ex 25 are identical, 18.64g and 80: 20 identical DOWANOL described in the Comp Ex A TMEB: the merging thing after the shaking of cyclohexanone mixture and 3 polysiloxane surface-modifying agents identical, the test plate (panel) of preparation coating with Comp Ex A.Summarized coating performance in the following table 1.
Ex?30
Repeat Ex 28, but have following variation, comprising substituting Tetra Hydro Phthalic Anhydride, the acid amides polyvalent alcohol of esterification Ex 26 with Tetra hydro Phthalic anhydride.First, the change flask contents is the acid amides polyvalent alcohol of 22g (0.2175OH equivalent) Ex 26, (28.99g 0.196 equivalent) Tetra hydro Phthalic anhydride and 2.37g (0.0217 equivalent) PMDA, and under agitation be heated to 135 ℃, but do not add glyoxal ethyline, up to stablizing (about 3 hours) to %COOH by titration determination, obtain %COOH and be 17.87% liquid, by contrast, theoretical %COOH be 18.34 and the cone-plate viscosity under 150 ℃ be 2000cps (2Pa.s).
Ex?31
Repeat Ex 22, prepare the powder coating formulation by the acid amides polyvalent alcohol of the esterification of Ex30, but have following variation.In pulverizer, place the identical Resins, epoxy of 15g (0.0194 epoxy equivalent (weight)) and Ex 29, the esterification liquid of (4.89g 0.0194COOH equivalent) Ex 30, with 0.1g 2-phenyl-2-tetrahydroglyoxaline, pulverizer was placed in the dry ice box 2 hours, then the content of pulverizer was pulverized 2 minutes.Be warming under the envrionment temperature with air-blaster after, the content of pulverizing forms fine free-pouring powder, and its gelation time under 400 ℃ is that 43 seconds and Tg are 13 ℃.The dsc analysis powder shows that also then heat release 45J/g, and beginning and peak value are respectively 110 ℃ and 168 ℃ 60 ℃ of following fusion heat absorptions.Solidify the 1.34g powder and obtain transparent polymer, wherein the Tg of DSC scanning for the first time is 91 ℃, is 89 ℃ and the repetition or the second time scan Tg.
Ex?32
Use the equipment identical, the glycerolysis product (FLEXRICIN of placement 25g Viscotrol C in the 50ml round-bottomed flask with Ex 30 TM13, CasChem, the OH equivalent that is calculated is 165.3g, about 0.1515 OH equivalent), 15.25g (0.1515 COOH equivalent) succinyl oxide and 0.14g glyoxal ethyline quinoline, heating flask contents to 100 ℃, and under continuing to stir, kept this temperature 2 hours.The mark picture that the FTIR analysis revealed does not have hydroxyl to absorb.In bottle, place flask contents (liquid acid anhydrides esterification products or polyfunctional acid).The %COOH of content is 18.4%, and theoretical by contrast %COOH is 20.0%, and the cone-plate viscosity under 150 ℃ is 30cps (0.03Pa.s).
Ex?33
Repeat the method for Ex 25, by the polyfunctional acid of 2.16g (0.0088 COOH equivalent) Ex 32, the Resins, epoxy that 4.79g (0.0088 epoxy equivalent (weight)) and Ex 25 are identical, 16.2g and 80: 20 identical DOWANOL described in the Comp Ex A TMEB: the merging thing among the mixture of pimelinketone and the 3 Comp Ex A after the shaking of identical polysiloxane surface-modifying agent, the test plate (panel) of preparation coating.Summarized coating performance in the following table 1.Use the #22 spreader of filming to come deposited coatings, and will the times of coating panels be reduced to 10 minutes down at 204 ℃.After solidifying, the thickness of coating is 0.346 mil (8.79x10 -6M), the Tg of DSC scanning for the second time is 48 ℃, and wedge shape flexural failure is that the destruction value of 0mm and twice wiping of MEK is 25.
Ex?34
The epoxidised soybean oil of preparation binary alcoholization as described below.At first, in the 500ml three neck round-bottomed flasks of being furnished with magnetic stirrer, place 222g (3.58mol) ethylene glycol and 4.7g sodium methylate (the 25wt% methanol solution is based on the gross weight of sodium methylate and methyl alcohol).With flask with and content be placed on the heating jacket.The cervical fixation of flask have Thermowatch (a kind of temperature regulating device) thermometer, have the Dean Stark water trap of condenser and nitrogen inlet and the dropping funnel of 50g (0.053mol) epoxidised soybean oil (ESO) be housed.Open nitrogen gas stream by nitrogen inlet and open the current of condenser, heat the set point temperatures of flask contents to 150 ℃ then, in 20 minutes time period, dropwise add ESO afterwards.Under agitation continue heating 1 hour, from heating jacket, take out flask and content thereof then, and make its cool to room temperature (common 25 ℃), use in the acetate afterwards and content (just in time begins to become acidity up to content, this is by the indication of pH test paper), then, use wiped film evaporator (WFE), reclaim the binary alcoholization ESO of purifying.The WFE operational condition comprises: jacket temperature=90 ℃; Finger-type chiller temperature=33.5 ℃; Pressure=2.2 torrs (293.3 handkerchiefs (Pa)), stirring velocity=530rpm and interpolation speed=6ml/min (ml/min).
Use the apparatus and method of Ex 33, the ESO of esterification binary alcoholization.In the 50ml round-bottomed flask, place the ESO of 22.91g (0.2147 equivalent) binary alcoholization, 28.62g (0.1932 equivalent) Tetra hydro Phthalic anhydride and 2.34g PMDA, and the same flask contents of handling with Ex30.FTIR analyzes flask contents and shows do not have hydroxyl to absorb, so show the hydroxylic moiety complete reaction.The %COOH of flask contents is 16.44%, and by contrast, theoretical %COOH is 16.41%.The cone-plate viscosity of flask contents (a kind of liquid) under 150 ℃ is 150 centipoises (0.15Pa.s).
Ex?35
Use the method for device and the change Ex 31 of Ex 31, the time that increases in the dry ice box is 14 hours, and the reduction pulverizing time is 1 minute, the Resins, epoxy that 12g (0.0155 epoxy equivalent (weight)) and Ex 34 is identical, 4.25g (0.0194COOH equivalent) derives from liquid and the 0.08g 2-phenyl-2-tetrahydroglyoxaline of Ex 34 and change into fines, the gelation time of described fines under 400 ℃ is 0.72 minute.This powder of dsc analysis demonstrates Tg and locates and absorb heat 60 ℃ of fusions at 13 ℃ and 30 ℃, and then heat release 58J/g, and beginning temperature and peak temperature are respectively 101 ℃ and 167 ℃.Powder curing becomes transparent polymkeric substance, the Tg of its DSC be 70 ℃ and for the second time the Tg of DSC be 76 ℃.
Ex?36
Use the device of Ex 33, with 80: 20 DOWANOL of powder, 17.03g of 7.3g Ex 35 TMEB: the mixture of pimelinketone is transformed into the coating solution that shook with 3 polysiloxane surface-modifying agents identical with Comp Ex A.Use the #46 spreader of filming, coating cold-rolled steel sheet and use the #26 spreader of filming, coating tin free steel sheet.The thickness of solidified cold-rolled steel sheet coating is 0.62 mil (1.57x10 -5M), the crooked grade of 1/8 inch mandrel rod: occur destroying at 8mm place, the bonding grade of cross-hatching is not for destroying, and shock resistance grade (directly/reverse) is 140/ less than 10, in in-lb.The coat-thickness of tin free steel sheet is 0.389 mil (9.88x10 -6M) and wedge shape flexural failure grade be 94mm.
The performance of solidified coating on table 1. cold-rolled steel sheet
The embodiment numbering Catalyst content (phw) Coat-thickness (mils) 1/8 inch mandrel rod bending The cross-hatching binding property Shock resistance (directly/oppositely) unit: lbs Pencil hardness Twice wiping of methylethylketone
??A ??0.50 ??0.371 Do not destroy Do not destroy ??＞160/??＞160 ??2H ??＜25
??2 ??0 ??0.459 Do not destroy Do not destroy ??＞160/??＞160 ??H ??25
??7 ??1.99 ??0.672 Do not destroy Do not destroy ??＞160/??＞160 ??HB ??50
??9 ??0 ??0.368 Do not destroy Do not destroy ??＞160/??＞160 ??3H ??25
??11 ??0 ??0.866 Do not destroy Do not destroy ??＞160/??140 Do not measure ??50
??13 ??0 ??0.416 Do not destroy Do not destroy ??＞160/??＞160 ??4H ??25
??16 ??2.00 ??0.604 Do not destroy Do not destroy ??＞160/??＞160 ??2H ??25
??19 ??0 ??0.460 Do not measure Do not measure ??＞160/??＞160 ??3H ??50
??23 ??2.00 ??0.765 Do not destroy Do not destroy ??＞160/??＞160 ??3H ??75
??25 ??0.38 ??0.941 11mm destroys 5% destroys ??120/80 ??HB ??25
??29 ??0 ??0.377 Do not destroy Do not destroy ??＞160/??＞160 ??2H ??25
Remarks: phw=umber/100 weight parts
The coating that listed data sheet Benq applies in the solvent of the present composition in the table 1 demonstrates good in extraordinary flexible, toughness, binding property and hardness, and has improved solvent resistance with respect to Comp Ex A.
The performance of solidified coating on table 2 tin free steel sheet
The embodiment numbering Catalyst content (phw) Coat-thickness, mil/ μ m Wedge bend test, mm destroys
??A ??0.50 ??0.392/9.96 ??0
??2 ??0 ??0.350/8.89 ??0
??7 ??1.99 ??0.452/11.48 ??0
??9 ??0 ??0.333/8.46 ??67
??11 ??0 ??0.866/22 ??62
??13 ??0 ??0.303/7.7 ??0
??16 ??2.00 ??0.399/10.13 ??0
??19 ??0 ??0.392/9.96 ??17
??23 ??2.00 ??0.475/12.06 ??0
??25 ??0.38 ??0.524/13.31 ??31
??33 ??0 ??0.346/8.79 ??0
Listed digital proof in the table 2, the coating that applies based on the solvent of several typical composition of the present invention (for example, Ex 2, Ex 7, Ex 13, Ex 16, Ex 23 and Ex 33) in wedge bend test, do not destroy, this is the indication of good binding property, flexible and toughness.Although Ex 9, Ex 11, Ex19 and Ex 25 are than the value height of the wedge bend test of expectation, they can be used for not relating in the application of the degree of crook that runs in the wedge shape crooked test.
Table 3. is based on the performance of the powder formulation of the polyester of carboxylic-acid functional and hydroxyalkyl amide
The embodiment numbering Catalyst content (phw) Gelation time under 204 ℃ (min) The second-order transition temperature of solidified formulation 1(℃)
??A ??0 ??1.25 ??80
??5 ??0 ??1.7 ??73
??6 ??2.0 ??1.0 ??79
??15 ??2.0 ??0.83 ??83
??22 ??2.0 ??0.78 ??84
??31 ??0.5 ??0.72 ??89
Remarks 1: at 204 ℃ of formulations that solidify 11 minutes down.
The digital proof of listing in the table 3 has the Tg that is similar to Comp Ex A based on the solidified coating of the acid-functionalized composition of the present invention, and wherein said Comp Ex A is based on carboxylic acid-terminated polyester.Just because of this, the acid-functionalized composition of the present invention provides the acceptable replacement scheme of carboxylic acid-terminated polyester.Because acid-functionalized composition of the present invention has short gelation time, promptly have the higher reactivity and the sign of curing speed more fast with respect to carboxylic acid-terminated polyester, therefore, composition of the present invention can be better than the carboxylic acid-terminated polyester of routine.
Table 1,2 and 3 data further prove, provide and fossil oil deutero-material such as the carboxylic acid-terminated suitable performance of polyester based on the present composition of renewable resources (as seed oil).Therefore, use composition of the present invention to provide to reduce cost and rely on chance based on the raw material of fossil oil.
The viscosity of table 4. carboxylic acid derivative
The embodiment numbering Viscosity under 150 ℃, cps
??A&B(URALAC TM?5271) ??＞4000
??4 ??600
??8 ??440
??10 ??4500
??12 ??50
??14 ??1000
??18 ??70
??21 ??1100
??24 ??125
??28 ??650
??30 ??2000
??32 ??30
??34 ??150
The data of listing in the table 4 show that composition of the present invention has the much lower viscosity of the polyester more carboxylic acid-terminated than routine (Comp Ex A and B).This means to have processed edge, for example improved mixing and substrate soak into (wet out) performance.
Ex 37-prepares the hybrid-powder coating composition
Employed flask among the above Ex 8 and residue content (after taking-up is used for the material of Ex 9 and Ex 10) thereof be placed in the baking oven of operating under 60 ℃ the set point temperatures 2 hours time period.From baking oven, take out flask and content is poured on the high glass pallet (45 centimetres (cm) length * 30cm wide * 5cm is dark).Make content cool to room temperature (common 25 ℃), place it in temperature then and be in the dry ice container of-109.3 (78.5 ℃) 1 hour, solidify content.
Take out the hardened content from the glass pallet, the content that will solidify is ground into fritter, and 16.4 weight parts (pbw) fritter is placed on super mixer (Prism Pilot TM, Thermo ElectronCorporation) in.Add 54.21pbw and the employed identical Resins, epoxy of Comp Ex A, the reaction product (EPI-CURE of 0.14pbw Resins, epoxy and imidazoles TMP101, Hexioin SpecialtyChemicals, Inc.) as first catalyzer, 0.21pbw triphenylphosphine (Rhodia Inc.) is as second catalyzer, 27.4pbw TiO 2 pigment (Ti-
Figure G2007800520837D00331
R-706, E.I.du Pont de Nemours﹠amp; Company), 1.32pbw ethyl propenoate/2-EHA multipolymer and silicon-dioxide (
Figure G2007800520837D00332
POWDER IIIResin Modifier, Cytec Surface Specialties Inc.) blend is as flow ability modifying agent, with 0.49pbw bitter almond oil camphor (Sigma Aldrich) as air release agent, add the mixing tank content of 20 weight part dry ice/100 weight parts except that dry ice.The operation mixing tank is 15 seconds under the speed of 200 rev/mins (rpm), makes the content degassing of mixture, and under the step that outgases in 15 seconds and in the middle of following afterwards, the mixer speed that raises gradually obtains thin efflorescence mixture to 2300rpm.
Use is furnished with the twin screw compounding forcing machine (PRISM of three heating zone, chill roll and belt wobbler and slicing machine TMTSE 24PC, Thermo Electron Corporation), fine atomizing mixture is changed into extrudate.Heating zone and their set point temperatures separately are: feeding zone=20 ℃; Intermediate zone=70 ℃; And heating zone=90 ℃.The screw diameter of forcing machine is that 24mm and screw speed are 400rpm.
Pulverize the hardened extrudate and become fritter or thin slice, and fritter or thin slice are fed into HosokawaMIKRO PUL TMIn the ACM-2L pulverizer (Micron Powder Systems), obtain mean particle size and be 46 microns (μ m) and be 51.4 seconds pulverized powder 204 ℃ average gelation time.
On pulverized powder electrostatic spraying to two kind of the different metal substrate with five equilibrium, obtain the substrate of two sprayings.The substrate of a spraying is placed 130 ℃ following 20 minutes of solidification value, the substrate of another or second spraying is placed 180 ℃ following 20 minutes of solidification value.After solidifying, the coat-thickness of the substrate of first spraying is 2.25 mil (5.7x10 -5Rice (m)), bonding percentage ratio (percentadhesion) (ASTM D3359) is that 5B and the ASTM D523 gloss number under 20 ° are 26.8, is being 76.1 under 60 ° and is being 80.3 under 85 °.Similarly, the coat-thickness of the substrate of second spraying is 3.19 mil (8.1x10 -5Rice (m)), bonding percentage ratio (ASTM D3359) is that 5B and the ASTM D523 gloss number under 20 ° are 7.1, is being 42 under 60 ° and is being 63.9 under 85 °.Solidified spraying substrate all has the coating of band delustring outward appearance, and according to ASTM D522 (taper mandrel rod), obtains destroying grade.Second solidified spraying substrate has slightly yellowish coating.Directly two solidified sprayings of Impact Test substrate provides ASTM D 2794 grades of 20 in-lbs.Twice wiping of MEK test provides for first substrate, and the destruction of twice wiping of coating is worth less than 10, and for second substrate, less than 100.The pencil hardness of these two coatings is 3H.
Ex 38-41 and Comp Ex C
Use the formulation shown in the following table 5, Ex 38 and 40 uses the castor oil derivative of Ex4, and Ex 39 and Ex 41 use the soybean oil derivative of Ex 21, and Comp Ex C does not use any derivative, repeats Ex 37.All embodiment all contain an amount of Resins, epoxy (DER 663U, The DowChemical Company).Comp Ex C and Ex 38 and 39 comprise the saturated polyester resin of carboxylation (URALAC that is used for epoxy resin cure in right amount TM5998, DSM Coating Resins Europe B.B.).Each contains the identical titania powder of 28.1wt% and Ex 37 Ex 38-41 and Comp Ex C, the flow ability modifying agent that 1.0wt% and Ex 37 are identical, the air release agent that 0.4wt% and Ex 37 are identical and 0.18wt%2-phenyl-2-tetrahydroglyoxaline (
Figure G2007800520837D00341
B 31, Degussa Corporation).Wt% value in these wt% values and the following table 5 is a benchmark with the coating composition gross weight all.Condition of cure comprises 200 ℃ temperature and 20 minutes time.Table 5 has also been summarized the physical property test result of solidified coating.
Table 5
Ex ID/ component or test ??Comp?Ex?C ??Ex?38 ??Ex?39 ??Ex?40 ??Ex?41
Castor oil derivative Do not have ??11.9 Do not have ??18.36 Do not have
Soybean oil derivative Do not have Do not have ??12.0 Do not have ??18.66
Resins, epoxy ??36.2 ??46.6 ??46.3 ??51.95 ??51.64
Vibrin ??34.2 ??11.9 ??12.0 Do not have Do not have
Physicals
Gelation time (sec) ??63.5 ??49.3 ??26.3 ??48 ??18.4
20 ° of gloss ??83.4 ??43.1 ??15.9 ??15.6 ??1.9
60 ° of gloss ??96.9 ??91.1 ??66.3 ??65.1 ??10.8
Thickness (mil/x10 -5m) ??2.02/5.1 ??2.02/5.1 ??2.02/5.1 ??2.15/5.5 ??2.77/7.0
Impact directly/oppositely (in-lb) ??120/120 ??140/140 ??140/160 ??120/120 ??140/60
Twice wiping value of MEK ??85 ??85 ??61 ??200 ??50
Pencil hardness ??3H ??3H ??3H ??2H ??2H
Scratch test load (N) ??53 ??49 ??52 ??66 ??57
The data that table 5 is listed show, with respect to the anti-zoned property that the carboxylic acid polyester of routine provides, the anti-zoned property (Ex 40 and 41 is with respect to Comp Ex C) of using the seed oil acid derivative to be improved.These data also show uses the seed oil derivative to substitute part (Ex 38 and 39) or whole (Ex 40 and 41) conventional carboxylic acid polyester, and the two all descends will to cause gelation time and gloss.

Claims (14)

1. the hydroxy-end capped monomer shown in the formula I:
Figure A2007800520830002C1
Formula I
R wherein 1Be the alkylene part, R 2Be hydrogen or hydrocarbyl portion, R 3There is not or the alkylene part R 4Be the alkylene part, R 8Be the part shown in H, hydrocarbyl portion or the formula II:
-R 4-OH
Formula II
R wherein 4As defined above, m, n and o are 0 or 1 independently, and condition is that m, n and o sum are greater than 0.
2. hydroxy-end capped monomer composition, it comprises the hydroxy-end capped monomer of claim 1, and mixes the second hydroxy-end capped monomer that wherein m, the n shown in an amount of formula I and o sum equal 0.
3. the hydroxy-end capped monomer composition of claim 2, wherein the hydroxy-end capped monomeric consumption of claim 1 is more than or equal to the 70wt% of composition gross weight.
4. the hydroxy-end capped monomer composition of claim 2, wherein the hydroxy-end capped monomeric consumption of claim 1 is more than or equal to the 75wt% of composition gross weight.
5. curable compositions, said composition comprise hydroxy-end capped monomer, the carboxylic acid-terminated monomer of claim 1 and randomly comprise polyfunctional epoxy resin or be different from claim 1 described hydroxy-end capped monomeric hydroxyalkyl amide or polyfunctional epoxy resin and be different from the described hydroxy-end capped monomeric hydroxyalkyl amide of claim 1.
6. curable compositions, said composition comprise the described hydroxy-end capped monomer composition of claim 2, carboxylic acid-terminated monomer and randomly comprise polyfunctional epoxy resin or be different from the hydroxy-end capped monomeric hydroxyalkyl amide or the polyfunctional epoxy resin of claim 2 and be different from the hydroxy-end capped monomeric hydroxyalkyl amide of claim 2.
7. reactive monomer compositions, it comprises the acid amides carboxylic acid shown in the formula III:
Figure A2007800520830003C1
Formula III
R wherein 1Be the alkylene part, R 2Be hydrogen or hydrocarbyl portion, R 3Do not exist or the alkylene part; R 4Be the alkylene part, R 5Be the part shown in H, hydrocarbyl portion or the formula IV:
-R 4-O-R 6
Formula IV
R wherein 4As defined above, and R 6Be the part of formula V:
Figure A2007800520830003C2
Formula V
R wherein 7Be the alkylene part, m, n and o are 0 or 1 independently, and condition is that m, n and o sum are greater than 0.
8. curable resin combination, it comprises the reactive monomer compositions of claim 7, polyfunctional Resins, epoxy, randomly comprise monomer or curing catalysts or monomer with end carboxylic moiety and curing catalysts with end carboxylic moiety, wherein said monomer with end carboxylic moiety is the monomer that is different from reactive monomer compositions.
9. preparation has the method for the reactive monomer of end carboxylic moiety, and this method comprises makes carboxylic acid anhydride and the reaction of at least a following substances:
A. the epoxidised oil of representing with formula VI of open loop:
Figure A2007800520830004C1
Formula VI
B. epoxidised fatty acid ester of open loop or the epoxidised lipid acid of representing with formula VII of open loop:
Figure A2007800520830004C2
Formula VII
R wherein 2Be hydrogen or hydrocarbyl portion, R 9Be hydrogen or hydrocarbyl portion, n and p be 0 or scope be the positive integer of 1-20; A, b, c, d, e, f, g, h, i, j, k and l are 0 or 1 independently, condition be a, b, c, d, e, f, g, h and i sum or j, k and l sum greater than 0 and X be:
R10-O-or
R wherein 10Be hydrogen, hydroxy alkylene part or hydrocarbyl portion independently, and R 11Be hydrogen or hydrocarbyl portion independently; Or
C. the alcoholysis reaction product between Viscotrol C and the polyvalent alcohol.
10. the method for claim 9, wherein polyvalent alcohol is selected from dibasic alcohol, propylene glycol, ethylene glycol and glycol ether.
11. pass through the reactive monomer of the method preparation of claim 9.
12. curable compositions, it comprises the reactive monomer of claim 11, polyfunctional Resins, epoxy, have the monomer of end carboxylic moiety and any one or both in the curing catalysts with optional, wherein said monomer with end carboxylic moiety is different from the reactive monomer of claim 12.
13. a coating composition, it comprises claim 5,6 or 8 each curable compositions.
14. a coating composition, it comprises the reactive monomer compositions of claim 7 or the reactive monomer of claim 11.
CN200780052083A 2007-01-12 2007-12-11 Hydroxyl-terminated or carboxylic acid- terminated reactive monomer compositions, their preparation and their use Pending CN101641324A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104211931A (en) * 2014-08-12 2014-12-17 江西科技师范大学 Pure plant oil based UV curable prepolymer

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104211931A (en) * 2014-08-12 2014-12-17 江西科技师范大学 Pure plant oil based UV curable prepolymer
CN104211931B (en) * 2014-08-12 2016-05-11 江西科技师范大学 A kind of pure plant oil based polyenoid class UV-curable prepolymer

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