CN101351515A - Reactive (meth)acrylate monomer compositions and preparation and use thereof - Google Patents

Reactive (meth)acrylate monomer compositions and preparation and use thereof Download PDF

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CN101351515A
CN101351515A CNA2006800502798A CN200680050279A CN101351515A CN 101351515 A CN101351515 A CN 101351515A CN A2006800502798 A CNA2006800502798 A CN A2006800502798A CN 200680050279 A CN200680050279 A CN 200680050279A CN 101351515 A CN101351515 A CN 101351515A
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oil
acid
methyl
beta
hydrogen
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J·E·怀特
J·D·厄尔斯
P·S·马丁
M·B·麦金托什
R·M·韦迈尔
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Dow Global Technologies LLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C235/08—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/28—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and unsaturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • C09D167/07—Unsaturated polyesters having carbon-to-carbon unsaturation having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • C09J167/07—Unsaturated polyesters having carbon-to-carbon unsaturation having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/006—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by oxidation

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  • Life Sciences & Earth Sciences (AREA)
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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Paints Or Removers (AREA)

Abstract

The present invention relates to new meth (acrylate) compositions, their preparation and their use in ultraviolet light curable applications such as coatings, inks and adhesives.

Description

Reactive (methyl) acrylate monomer compositions and preparation and application
Technical field
The application requires the U.S. Provisional Application No.60/756 of proposition on January 4th, 2006,147 rights and interests.
The present invention relates generally to novel chemically-reactive (methyl) acrylate monomer compositions and the method that is used to prepare said composition.The present invention relates more particularly to derived from renewable raw material resources, as the reactive monomer compositions of unsaturated seed oil or vegetables oil.The present invention also relates more particularly to contain at least one the reactive monomer compositions in amide moieties, ester moiety or the triglyceride level part.The present invention also relates to this reactive monomer compositions at preparation coating, particularly hardenable coatings, especially the application in ultraviolet ray (UV) hardenable coatings.This reactive monomer compositions also can be used for preparing binder composition or sealant composition.
Background technology
Traditional acrylate resin or composition such as Epocryl are when being used for showing many shortcomings when the UV hardenable coatings is used.Gained UV-solidified coating tends to fragility rather than flexible, and to most of (if not all) required application, the ground that applies is lacked enough bonding.Those skilled in the art can understand Impact Test (as detailed below) provides adhesion of coatings and flexible to show.More particularly, after the Impact Test coating not leafing shown minimum acceptable bonding at least.If the experiment after coating or the film Impact Test demonstrates seldom (preferred nothing) visible crack, those skilled in the art are considered as having at least this coating or film minimum acceptable flexible.In addition, traditional acrylate resin, especially Epocryl, have surpass 4,000 centipoises (cps) (4.0 pascals. second (Pa.s)) undiluted viscosity.In order for example to use this resin in the UV-hardenable coatings, must add thinner as three (propylene glycol) diacrylate to reduce coating composition viscosity to being no more than 4,000 centipoises (4.0Pa.s) and preferably being no more than room temperature (the being generally 25 ℃) dope viscosity of the application of 2500 centipoises (2.5Pa.s).
Use reactive monomer or reactive monomer compositions, especially in the UV curable compositions, use this monomer or monomer composition, even for example comprise in total coating weight at the most during the solid of 40 weight % (40wt%) (particulate additive such as pigment) when the UV curable compositions, need the reactive monomer that can use with (or preferred do not have) thinner seldom.Also need said composition to obtain, improved UV-solidified coating at least one in shock resistance, hardness and scratch-resistant with respect to the UV-solidified coating that uses the preparation of traditional acrylate resin such as epoxy acrylate.Other are required (but optional), and characteristics comprise when solidified, obtain flexible coating or film, preferably with respect to the film of being made by present available reactive monomer improved coating composition at least one in moistureproofness and stain resistance.
United States Patent (USP) (USP) 3,713,864 disclose ink composite comprises epoxy soybean oil acrylate or derivatives thereof, traditional colorant (for example your precious (red), diarylide yellow of pigment such as lithol, active emerald green (Green Shade), phthalocyanine blue, barba hispanica and carbon black (channel process or oven process) and radiosensitizer (for example methyl phenyl ketone or benzophenone).USP 3,713,864 also disclose the method for printing with this composition for ink, comprise this composition for ink is exposed to the ground that the polymeric component that is enough to composition for ink is polymerized to a certain amount of actinic radiation of not offset state (non-offsetting) and obtains the printing of this method preparation.
USP 3,713, and 864 walk to the preparation that the 3rd hurdle the 7th row discloses epoxy soybean oil or epoxy linseed oil acrylate on the 2nd hurdle the 54th.Preparation is from using traditional epoxidizing agent such as peracetic acid or hydrogen peroxide epoxidised soybean oil or linseed oil.The propylene acidylate (Acrylation) of epoxidised oil is by for example, epoxidised oil and vinylformic acid 100 degrees centigrade (℃) temperature under in the presence of stopper such as thiodiphenylamine, react and take place.USP 3,713, and 864 also disclose the reaction of dihydroxyphenyl propane-epichlorohydrin epoxy and acrylic or methacrylic acid.
USP 4,243, and 818 on the 5th hurdle, 8-12 be about to " hydroformylation " be defined as by unsaturated compound and produce aldehyde by in the presence of catalyzer, reacting with hydrogen and carbon monoxide.Preferred unsaturated compound (capable by the 5th hurdle 36-38) is an oleyl alcohol, but inferior oleyl alcohol (linoleylalcohol) or linolenyl alcohol also can be used as unsaturated compound.On the 9th hurdle, 52-58 is capable, and ' 818 disclose and use acyl halide such as acrylate chloride alcohol is converted into its corresponding unsaturated ester (for example acrylate or methacrylic ester).
USP 4,128, and 600 disclose IPN double cured resin composition.Curable resin composition contains radiosensitive reactive diluent, saturated polyvalent alcohol and isocyanic ester.Said composition is exposed to the curing that influences reactive diluent in the radiation.Follow-up thermofixation forms urethane bonds.According to the 3rd hurdle, row 38-44, reactive diluent can be polyfunctional alcohol's complete substituted polyacrylic ester or polymethacrylate.On the 5th hurdle, 10-13 is capable, and ' 600 spell out reactive diluent must not contain hydroxyl, amine, carboxyl, primary and secondary acid amides or isocyanate functional group.The polyfunctional alcohol comprises nonyl, decyl, undecyl, dodecyl, tridecyl and the myristyl alcohol of (by the 5th hurdle, 43-46 is capable) common and isomeric form.On the 18th hurdle, 43-45 is capable, and ' 600 have defined pencil hardness test, and it is as the demonstration of " cold coating scratch-resistant, wherein 9H be that the hardest and 6B is the softest ".
USP 4,626, and 582 have discussed the methyl substituted fatty compounds of acryloxy, and it is by general formula CH 3-(CH 2) m-((Y)-C-(Z))-(CH 2) n-X represents that wherein m and n are integer, and n is greater than 3, and m and n sum are 7 to 19; Y is hydrogen, methylol or acryloxy methyl group; One among X and the Z is the acryloyl-oxy ylmethyl, and another is selected from (a)-CN, (b)-and C (O)-NR 1R 2, (c)-C (O)-OR 3, or (d)-CH 2-NR 4R 5, R wherein 1, R 2, R 3Be more rudimentary alkyl independently, condition is R 1And R 2Can form together and have 4,5 or 6 aliphatic carbons, or the divalence hydrocarbon of 3,4 or 5 aliphatic carbon atoms and heteroatoms or group; R 4Be more rudimentary acyl group; And R 5Be hydrogen or more rudimentary alkyl; Condition is when X is the acryloyl-oxy ylmethyl, and Y is a hydrogen.By the 2nd hurdle, 9-14 is as can be known capable, and this compound can be used for the preparation of hardenable coatings.The 4th hurdle, 16-31 is capable to have proposed to relate to the disclosing of radiation curing of this coating.
USP 5,312,889 in that the 1st hurdle 23-28 is capable discloses " hydroxy fatty acid in natural fat and the oil and derivative thereof; or can be specially adapted to product useful on the manufacturing process by the hydroxy fatty acid or the amino lipid acid of reactive fatty acids (for example; oleic acid; linolic acid) preparation, especially polymkeric substance and plastics ".According to the 2nd hurdle, 52-57 is capable, " the lipid acid residue that contains amino-group ... use known chemical process by unsaturated fatty acid ester for example by to two key addition hydrohalogens such as Hydrogen bromide, obtains with ammonia nucleophilic substitution halogenide then ".
As the 1st hurdle, 12-21 is capable described, USP 6,174,948 relate to and contain vinyl ether or vinyl ester, or derived from half-and/or the new type latex or the emulsion compositions of the acrylate of the long-chain vinyl monomer of non--siccative oil, its manufacture method, with said composition at coating, the application in tackiness agent and the ink (it does not have volatile organic constituents (VOC) substantially), and the characteristic enhanced is used and use properties.By the 5th hurdle, 5-9 is capable, and the example of half-siccative oil comprises Thistle oil, sunflower oil, soybean oil and tobacco-seed oil, and the example of non-drying oil comprises that Oleum Gossypii semen, Oleum Cocois, rape seed oil, Viscotrol C and Leix restrain lazyness and rein in oil.On the 16th hurdle, 36-43 is capable, and ' 948 disclose vinyl ester replacement or non-replacement, 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 that preferred parent material comprises lipid acid.The non-limiting representation example of these parent materials comprises oleic vinyl ester, vinylformic acid oil base ester, methacrylic acid oil base ester, oil base acrylamide, oil base Methacrylamide and vinyl oleyl ether.' 948 embodiment 1 react to obtain methacrylic acid oil base ester methacrylic chloride and oleyl alcohol in the presence of triethylamine.' 948 embodiment 2 repeat embodiment 1, but replace methacrylic chloride with acrylate chloride.' 948 embodiment 8 use the oil base acrylate of embodiment 2 in the UV-curable formulations.
USP 6,245, and 829 have discussed the list that comprises the compound that contains the beta-hydroxy alkylamide group-or the radiation-curable compositions of many-divalent carboxylic acid ester, carboxylicesters derived from alpha wherein, β-ethylenic unsaturated carboxylic acid.According to the 2nd hurdle, 47-50 is capable, and said composition can be by making beta-hydroxy alkylamide and unsaturated carboxyl acyl chloride (carboxylic acid chloride), acid anhydrides or ester prepared in reaction.The 3rd hurdle, 42-48 is capable to be noticed, after curing, coating by said composition preparation has many required character, as good thermostability and and the good weathering resistance of good chemical property (solvent resistance, acid resistance, alkali resistance and moisture resistivity), good optical character and outward appearance, good mechanical character (as hardness, flexible, bonding, wear resistance, intensity and weather resistance).
Summary of the invention
Used in the whole text as this specification sheets, appear at this section, the definition of the elsewhere of subsequent paragraph or specification sheets all has the meaning that gives it when defining for the first time.Therefore, " alkyl " means and has 1 to 60 carbon atom (C 1To C 60) list-or multivalence, straight or branched, saturated aliphatic hydrocarbon part.
" alkenyl " means and contains at least one two key and have 2 to 60 carbon atom (C 2To C 60) list-or multivalence, straight or branched, unsaturated part.
" (methyl) acrylate " is for comprising acrylic acid ester (acid alkyl ester resin); wherein acrylate chloride is as the ester (alkyl methacrylate resin) of acylating agent and methacrylic acid, and wherein methacrylic chloride is as acylating agent; α, collective's term of beta-unsaturated acyl thing.
" lipid acid " means and is mainly the aliphatic acid that has greater than 8 carbon.
" fatty acid ester " means and is mainly the aliphatic ester that has greater than 8 carbon.
When narrating scope in this article, as in 2 to 10 scope, two end values of scope (for example 2 and 10) include in scope, unless specified otherwise is in it is not included in.
A first aspect of the present invention relates to and comprises that the acid amides of being represented by general formula I gathers-α the reactive monomer compositions of beta-unsaturated acyl thing:
Figure A20068005027900121
General formula I
R wherein 1Be multivalence alkenyl part; R 2Be hydrogen or monovalent alkyl part; R 3For not existing or multivalence alkenyl part; R 4Be multivalence alkenyl part; R 5Be H, monovalent alkyl part or the part represented by general formula I I:
Figure A20068005027900122
General formula I I
R wherein 4As above definition, R 7, R 8And R 9Be hydrogen or monovalent alkyl part independently; R 6For having the part of general formula III:
Figure A20068005027900123
General formula III
R wherein 7, R 8And R 9As above definition independently; M, n and o are 0 or 1 independently, however condition be, m, n and o sum are the positive integer (for example 1) greater than 0.
A second aspect of the present invention relates to the method for the reactive monomer for preparing first aspect.This method comprises the step of following order:
A. make alkanolamine and the compound reaction with at least one reactive hydroxyl groups or part, this compound is selected from polyunsaturated vegetable oil (modification or unmodified), lipid acid or fatty acid ester, compound is converted into the acid amides polyvalent alcohol; With
B. make acid amides polyvalent alcohol and α, beta-unsaturated acyl agent reaction gathers-α the beta-unsaturated acyl thing the acid amides polyvalent alcohol is converted into acid amides.
A third aspect of the present invention relates to the poly--α that comprises by the representative of one of following general formula, the reactive monomer compositions of beta-unsaturated acyl thing:
General formula I V
Or
Figure A20068005027900132
General formula V
R wherein 1Definition as described above; R 10Part for following general formula:
Figure A20068005027900133
R wherein 7, R 8And R 9Definition as described above; R 11Be hydrogen or hydrocarbyl portion; N and p are 0 or the positive integer in the 1-20 scope; A, b, c, d, e, f, g, h, i, j, k and l are 0 or 1 independently, however condition be in a, b, c, d, e, f, g, h and i sum or j, k and the l sum at least one for greater than 0 positive integer (for example 1); With X be:
R 10---O---or R 12---O---or
Figure A20068005027900134
R wherein 10As above definition, R 12And R 13Be hydrogen or hydrocarbyl portion independently.
A fourth aspect of the present invention relates to the reactivity for preparing the third aspect poly--α, the method for beta-unsaturated acyl thing.This method comprises the step of following order:
(a) in the presence of acid catalyst, make epoxy-functionalized vegetables oil, epoxidised lipid acid or epoxidised fatty acid ester and water, carboxylic acid or alcohol reaction to form polyvalent alcohol; With
(b) make the polyvalent alcohol and the α of step (a), beta-unsaturated acyl agent reaction comprises poly--α, the reactive monomer compositions of beta-unsaturated acyl thing with formation.
A fifth aspect of the present invention relates to preparation feedback α, the method for beta-unsaturated acyl thing monomer composition, and this method comprises the step of following order:
(a) with at least a lipid acid of polyol initiator polymerization or fatty acid ester (this lipid acid or fatty acid ester contain at least one reactive hydroxyl part) to form hydroxyl-functionalized aliphatic polyester;
(b) make the polyester and the α of step (a), the beta-unsaturated acyl agent is reacted to form reactive α, the beta-unsaturated acyl thing.
A sixth aspect of the present invention relates to the reactive α according to the method preparation of the 5th aspect, beta-unsaturated acyl thing.
A seventh aspect of the present invention relates to the reactive monomer compositions that comprises a first aspect of the present invention or the of the present invention the 3rd or the UV-curable compositions of the reactive acylate of the 6th aspect.
A eighth aspect of the present invention relates to UV-curable ink, binder composition or the coating composition of the UV-curable compositions that comprises the 7th aspect.
A ninth aspect of the present invention relates to UV-solidified ink, binder composition or the coating composition by the corresponding preparation of compositions of eight aspect.
The reactive monomer compositions of first aspect comprise or comprise by the acid amides of general formula I representative poly--α, the beta-unsaturated acyl thing:
Figure A20068005027900141
General formula I
R wherein 1Be multivalence alkenyl part; R 2Be hydrogen or monovalent alkyl part; R 3For not existing or multivalence alkenyl part; R 4Be multivalence alkenyl part; R 5Be H, monovalent alkyl part or the part represented by general formula I I:
General formula I I
R wherein 4As above definition, R 7, R 8And R 9Be hydrogen or monovalent alkyl part independently; R 6For having the part of general formula III:
Figure A20068005027900152
General formula III
R wherein 7, R 8And R 9As above definition independently; M, n and o are 0 or 1 independently, yet condition is that m, n and o sum are the positive integer (for example 1,2 or 3) greater than 0.
In the preferred implementation of acid amides, R 1Divalent alkyl or alkenyl part for 1-20 carbon; R 2For hydrogen or contain the moieties of 1 to 20 carbon; R 3For not existing or methylene radical; R 4Be ethylidene or propylidene; R 5Be the part of hydrogen, methyl or general formula I I representative, wherein R 4Be ethylidene, R 7Be hydrogen or methyl, R 8And R 9Be hydrogen; And R 6Be the part of general formula III representative, wherein R 7Be hydrogen or methyl and R 8And R 9Be hydrogen.
The object lesson of the acid amides of suitable (methyl) acrylate-replacement comprises methyl 11-hydroxyl undecylate acid amides acrylate, 12-hydroxyl stearylamide acrylate, methyl 12-hydroxyl stearylamide acrylate and Viscotrol C acid amides acrylate.
Acid amides gathers-α, and the preparation of beta-unsaturated acyl thing comprises the step a. and the b. of at least two orders.Step a. comprises makes alkanolamine and the compound reaction with at least one reactive hydroxyl part, and this compound is selected from polyunsaturated vegetable oil (modification or non-modification), lipid acid or fatty acid ester, compound is converted into the acid amides polyvalent alcohol.Step b. comprises makes acid amides polyvalent alcohol and α, and beta-unsaturated acyl agent reaction gathers-α the beta-unsaturated acyl thing the acid amides polyvalent alcohol is converted into acid amides.
In step a., alkanolamine and compound exist than the mol ratio of compound in 4: 1 to 1: 1 scopes with alkanolamine.Preferred 3: 1 to 1: 1 of this scope, more preferably 2: 1 to 1: 2, also more preferably 2: 1 to 1.5: 1.
Step a. is thermo-negative reaction, requires the reacting by heating thing at least 60 ℃, preferably at least 80 ℃, and more preferably at least 100 ℃ temperature also.This temperature preferably is no more than 150 ℃, more preferably no more than 130 ℃ with also more preferably no more than 120 ℃.
Step a. preferably includes reactant is used non--reactive solvents.Solvent is to be enough to placing the amount of solution to use solid reactant under above-mentioned assigned temperature.Solvent is preferably selected from toluene, chloroform or ether, most preferably toluene.
Step a. preferably includes and uses catalyzer such as potassium hydroxide.The more preferably solution of the potassium hydroxide of 30 weight % in methyl alcohol.Though use methyl alcohol to choose wantonly, it also is preferred, because it helps catalyst dissolution.Other available catalyzer comprise sodium hydroxide and sodium methylate.Catalyzer preferably uses with 0 weight part (pbw) to the amount in 5 weight parts/100 weight part diethanolamine scopes.
The recovery of the acid amides polyvalent alcohol of producing in step a. takes place by standard step (as describing in detail among the embodiment that provides below).This step comprises, with salt brine solution (as the sodium chloride aqueous solution of 2 weight %, this weight percentage is in total solution weight) washing, uses anhydrous magnesium sulfate drying and rotary evaporation to remove toluene.
In step b., acid amides polyvalent alcohol and α, the beta-unsaturated acyl agent with the mol ratio be the acid amides polyvalent alcohol than α, the amount of beta-unsaturated acyl agent in 1: 1 to 0.2: 1 scope exists.Preferred 0.75: 1 to 0.2: 1 of this scope, more preferably 0.5: 1 to 0.2: 1 and also more preferably 0.4: 1 to 0.2: 1.
A. is similar with step, and step b. preferably includes reactant is used non--reactive solvents.The specified solvent of step a. also is fit to step b..
Step b. is thermopositive reaction, need the cooling reactant to be no more than 30 degrees centigrade (℃) temperature, preferably be no more than 20 ℃, also more preferably no more than 10 ℃.Preferably at least 0 ℃ and more preferably at least 5 ℃ of temperature.Be lower than under 0 ℃ the temperature (for example-5 ℃), reactant tends to solidify, thus further processing of influence.
The acid amides of producing in step b. gathers-α, and the recovery of beta-unsaturated acyl thing is by taking place as the standard step that describes in detail among the embodiment (especially embodiment 2) that provides below.
When using the compound of non-Viscotrol C or castor oil derivative; acid amides gathers-α; the preparation of beta-unsaturated acyl thing preferably is contained in the precursor step before the step a; this precursor step comprises the reduction hydroformylation to the small part parent material, and wherein parent material is selected from polyunsaturated vegetable oil, lipid acid or fatty acid ester.
USP 4,243, and 818 (they openly incorporate this paper into as a reference) disclosed hydroformylation.When using, the precursor step before step a. comprise be enough to functionalized or with greater than 0% the hydroformylation of unsaturated reaction to maximum 100% the parent material.Hydroformylation preferably is enough to and the unsaturated reaction of (〉=) 20 per-cents (%) at least, more preferably 〉=50% unsaturated, most preferably 〉=80% unsaturated.
Other documents (it openly incorporates this paper into as a reference to greatest extent with allowed by law) that hydroformylation is discussed comprise USP 4,423,162 (especially embodiment 34), USP4; 723,047, Canadian patent application (CA) 2,162; 083, WO 2004/096744, USP4,496,487, USP 4; 216; 344, USP 4,304, and 945 and USP 4; 229,562.
USP 4,423,162 disclose, and especially on the 3rd hurdle, the 50th walks to the 4th hurdle, and the 36th row those disclosed is that directive significance is arranged especially to practice reduction hydroformylation.In this part, the hydroxy ester monomer parent material that preparation is made by the unsaturated carboxylic acid or the ester of hydrogenation acylations.Can obtain suitable unsaturated acid by triglyceride level being decomposed into its each component fatty acids.USP 4,423, and 162 sources of indicating lipid acid comprise fatty oil such as animal grease and most of plant origin, particularly soybean, sesame, Sunflower Receptacle, Yatall MA and other analogous materials, but the starting fatty acid of preferable methyl ester-formin.
USP 4,423, and 162 introducings that disclose methylol groups can use cobalt or rhodium catalyst easily to finish by hydroformylation process, then by catalysis process or chemical reduction hydrogenation formyl radical group to obtain methylol groups.Meanwhile, USP 4,423, and 162 also relate to (being incorporated herein by reference) at USP 4,216,343, and USP 4,216,344, and USP 4,304,945, and USP4, the step of describing in detail in 229,562.
Preferred α, the beta-unsaturated acyl agent comprises acyl halide.Especially preferred α, the beta-unsaturated acyl agent comprises acrylate chloride (when preparation contains the composition of acrylate) or methacrylic chloride (when preparation contains the composition of methacrylic ester).The mixture or the adulterant of acrylate part and methacrylic acid ester moiety if desired can use the mixture of acrylate chloride and methacrylic chloride.
When in step a. with the compound deriving of alkanolamine reaction during from polyunsaturated vegetable oil, compound is preferably hydroxyl-functionalized vegetables oil, polyunsaturated vegetable oil and is selected from Thistle oil, sunflower oil, soybean oil, linseed oil, peanut oil, sweet oil, tobacco-seed oil, Oleum Gossypii semen, Oleum Cocois, rape seed oil, Tower rape oil, Semen Maydis oil, and gram lazyness in Leix is reined in oil (lesquerella oil) or these oily modification modification arbitrarily.These oily modifications comprise the reduction hydroformylation.
When in step a. with the compound deriving of alkanolamine reaction during from lipid acid, compound is preferably hydroxyl-functionalized acid, this acid is selected from oleic acid, linolic acid or linolenic acid.
When in step a. with the compound deriving of alkanolamine reaction during from fatty acid ester, compound is preferably hydroxyl-functionalized ester, more preferably hydroxyl-functionalized fatty acid methyl ester, especially hydroxyl-functionalized fatty acid methyl ester, wherein this methyl ester is selected from Witconol 2301,10 hendecenoic acid methyl esters, 9-decylenic acid methyl esters, Linolenic acid methylester or methyl linoleate.
Preferred parent material comprises methylol fatty acid, methylol fatty acid ester, Viscotrol C and castor oil derivative.Especially preferred parent material comprises those that are selected from hydroxymethylstearat, methylol methyl stearate, ricinoleate acid or monoricinolein.
Preferred alkanolamine comprises thanomin, 1, at least one in 2-Propanolamine or the diethanolamine.
The reactive monomer compositions of the third aspect comprises the poly--α by the expression of one of following general formula, the beta-unsaturated acyl thing:
Figure A20068005027900181
General formula I V
Or
Figure A20068005027900191
General formula V
R wherein 1Definition as described above; R 10Be the part shown in the following general formula:
Figure A20068005027900192
R wherein 7, R 8And R 9Definition as described above; R 11Be hydrogen or hydrocarbyl portion; N and p are 0 or the positive integer in the 1-20 scope; A, b, c, d, e, f, g, h, i, j, k and l are 0 or 1 independently, however condition be in a, b, c, d, e, f, g, h and i sum or j, k and the l sum at least one for greater than 0 positive integer (for example 1,2,3,4 or 5); With X be:
R 10---O---or R 12---O---or
Figure A20068005027900193
R wherein 10As above definition, R 12And R 13Be hydrogen or hydrocarbyl portion independently.
Poly--the α of the third aspect, beta-unsaturated acyl thing are preferably by step that comprises following order (a) and the preparation of method (b).Step (a) is included in acid catalyst and exists and to make at least a first reactant that is selected from epoxy-functionalized vegetables oil, epoxidised lipid acid or epoxidised fatty acid ester and at least a second reactant reaction of water, carboxylic acid or alcohol that is selected from the formation polyvalent alcohol down.The step (b) of order comprises polyvalent alcohol and the α that makes step (a), and beta-unsaturated acyl agent reaction comprises poly--α, the reactive monomer compositions of beta-unsaturated acyl thing with formation.α, the beta-unsaturated acyl agent is preferably selected from above those disclosed.
The suitable preferred epoxy-functionalized vegetables oil that is used as first reactant comprises ringdove elecampane oil (vernonia oil), epoxy soybean oil or epoxy linseed oil.
The suitable preferred epoxidised lipid acid that is used as first reactant comprises epoxidised undecylenic acid and epoxidised oleic acid.
The suitable preferred epoxidised fatty acid ester that is used as first reactant comprises epoxidised Witconol 2301, epoxidised 10 hendecenoic acid methyl esters and epoxidised 9-decylenic acid methyl esters.
The suitable preferred carboxylic acid that is used as second reactant comprises acetate and formic acid.
The suitable preferred alcohol that is used as second reactant comprises methyl alcohol, ethanol, propyl alcohol and butanols.
Preferred acid catalyst comprises ion exchange material, preferred cationic exchange resin such as DOWEX TMZeo-karb MSC-1 (The Dow Chemical Company) and mineral acid (for example sulfuric acid).
Step (a) is opened the oxirane ring structure in first reactant (for example epoxy-functionalized or epoxidised vegetables oil) effectively, and produces polyvalent alcohol.Step (a) comprises the combination of stirring down and preferably heating first reactant, second reactant and acid catalyst at inert atmosphere (for example nitrogen) down.
Step (a) is thermo-negative reaction, needs the reacting by heating thing at least 25 ℃, preferably at least 50 ℃, and more preferably at least 65 ℃ design temperature also.This temperature preferably is no more than 150 ℃, more preferably no more than 120 ℃ with also more preferably no more than 100 ℃.
Can use other rare gas elementes such as helium, or the mixture of rare gas element is as the substitute of nitrogen.
The recovery of open loop first reactant of producing in step (a) is by carrying out as the standard step that describes in detail among the embodiment (especially embodiment 6) that provides below.Vacuum filtration with nitrogen purging provides quite gratifying result earlier before vacuum filtration.
The step (b) of order comprises polyvalent alcohol and the α that makes step (a), and beta-unsaturated acyl agent reaction comprises poly--α, the reactive monomer compositions of beta-unsaturated acyl thing with formation.The most of step b. that repeats above detailed description of step (b) is except the acid amides polyvalent alcohol that replaces with the polyvalent alcohol of producing in the step (a) producing among the step a..Explain step (b) and reclaim poly--α, the details of beta-unsaturated acyl thing of following embodiment 7.
The method of a fifth aspect of the present invention produces the described reactive α in the 6th aspect, beta-unsaturated acyl thing monomer composition.This method comprises the step (a) of following order and (b).Step (a) comprises with at least a first reactant (this first reactant is lipid acid or fatty acid ester) that contains at least one reactive hydroxyl part of polyol initiator polymerization, to form hydroxyl-functionalized aliphatic polyester.The step (b) of order comprises hydroxyl-functionalized aliphatic polyester and the α that makes step (a), and the beta-unsaturated acyl agent is reacted to form reactive α, the beta-unsaturated acyl thing.This α, the beta-unsaturated acyl agent is preferably selected from above-mentioned those disclosed.
With polyol initiator polymerization first reactant is 168 ℃ to 230 ℃ in temperature range preferably, more preferably takes place in 190 ℃ to 200 ℃ scopes.Polymerization preferably (also claims in the presence of the rare gas element medium) to take place under layer of inert to minimize so that color is formed.
The reaction that takes place in step (b) preferably takes place in 0 ℃ to 30 ℃ temperature range under rare gas element (for example nitrogen) atmosphere, more preferably in 5 ℃ to 20 ℃ scopes and most preferably 5 ℃ to 10 ℃.When using rotary evaporation to remove solvent (for example toluene) as a part that reclaims product, the temperature in the restriction rotary evaporation process be 60 ℃ of maximums, obtains gratifying result.
First reactant can be by the preparation of partial hydrogenation formylation at least, as above definition, condition be the formylated minimum level of the partial hydrogenation of the 5th aspect be exist in preceding first reactant of hydroformylation undersaturated 80%.
Be suitably in the preferred lipid acid that is used as first reactant in the method for the 5th aspect and comprise 12-(methylol) stearic acid, (methylol) stearic acid glycol and (hydroxymethyl) stearic acid triol.
Be suitably in the preferred fatty acid ester that is used as first reactant in the method for the 5th aspect and comprise 12-(methylol) stearate, (methylol) stearate glycol and (hydroxymethyl) stearate triol.
The preferred polyhydric alcohols initiator comprises glycerol, glycerol ethoxylate, polyoxyethylene glycol and polypropylene glycol.
Above-mentioned disclosed acid amides gathers-α; beta-unsaturated acyl thing and α; beta-unsaturated acyl thing monomer composition has the curable compositions as UV-, as the practical purposes of the UV-curable components of UV-curable ink composition, UV-curable adhesive composition and UV-curable coating composition.These compositions, be exposed to be enough to influence composition solidified UV-condition of cure after, respectively at the solidified ink, obtain commercial required result in solidified tackiness agent and the solidified coating.
Composition of the present invention can comprise that one or more tradition join the non--reactive component in the UV-curable coating composition.These non--reactive component include but not limited to pigment, filler, stablizer and solvent.
In the ink of preparation, can use any traditional tinting material well known in the art or pigment based on reactive monomer of the present invention.For example, multiple pigment dyestuff and mineral dye can be widely used as tinting material, but preferred non-toxic anticorrosion pigment.The example of this pigment comprises phosphoric acid salt-type anti-corrosion paint, for example zinc phosphate, calcium phosphate, aluminum phosphate, titanium phosphate, phosphoric acid silicon and just-and phosphoric acid salt of merging; Molybdate-type anti-corrosion paint such as zinc molybdate, calcium molybdate, zinc molybdate calcium, zinc molybdate potassium, phospho-molybdic acid zinc potassium and phospho-molybdic acid calcium potassium; And borate-type anti-corrosion paint such as lime borate, zinc borate, barium borate, barium metaborate and calcium metaborate.The tinting material of appropriate amount or selection of pigment depend on reactive monomer of the present invention, and whether given terminal applies requires or help the painted of pigment or tinting material.To radiation-curable ink, in the gross weight of this ink, pigment load obtains gratifying result up to 40 weight %.To needing the terminal applies of colorless product, can omit pigment or tinting material.
Analytical procedure
Be used for H 1NMR, 13CNMR, the analytical procedure of FTIR is based on standard method, is described in " polymkeric substance spectrum (Spectroscopy of Polymers) " as ACS specialty book of reference (the ACS Professional Reference Book) title of JackL.Koening.Other testing method used herein as detailed below.
By titration records hydroxyl per-cent according to ASTM testing method D4274.
Coat-thickness
Use Fisher Multiscope Thickness measuring instrument to measure the thickness that is deposited on the non magnetic coating on the ferro-magnetic ground.Fisher Multiscope comprises probe, after probe being placed facing to coating and activated this Multiscope, operates by magnetic induction density and to show coat-thickness.Bao Dao coat-thickness value is represented the mean value of 15 coating thickness measurements herein.
The two frictions of methyl ethyl ketone (MEK)-ASTM method D 5402
Become the rounded end of hemispheric iron hammer or the point end on the surface of the plate that applies, to move back and forth to lose efficacy with being coated with 8 layers of 2 pounds of (4.4 kilograms (kg)) end that has absorbed the gauze of MEK up to coating.In this test, only use the weight of iron hammer and guide the sharp end that is coated with gauze to cross the required power of power of coating.The boards supporting substrates of coating inefficacy under coating takes place when exposing.Using acid copper sulfate to expose with coating with the checking ground lost efficacy.Repeat this test twice, determine the arithmetical av of this test and report that this value is " the two friction of coating MEK inefficacy numerical value ".
Film hardness-ASTM method the D 3363 of pencil test
The plate that applies is placed on the firm horizontal plane.Allow the operator hold to have the pencil of known hardness effectively to coating or film angle at 45 and pencil is pushed away operator's health with the stroke of 1/4 inch (6.5 millimeters).Pencil (6B) with refined lead begins this test, and with gradually more the pencil of antimonial lead (to 9H) continue test, make pencil incision or dig this film of cutter or coating until this stroke.Report the coating pencil hardness by the plumbous hardness of pencil at once in the pencil incision or before digging this coating of cutter.
The test of nail cut
In this subjective testing, the operator makes him cross coatingsurface by the nail of (or she) with suitable pressure, checks the visible damage on surface then, as damaging.
Organic coating is to the resistance-ASTM method D 2794 of quick deformation (impact) influence
(4 pounds (lbs) (8.8 (kg)) falls on the impression meter from certain distance, makes that ground or the plate under solidified film and solidified film or the coating is out of shape together with standard weights.The impression meter can invade and estimate direct ballistic opposing to apply with the solidified film is staggered relatively, or facing to ground or plate surface (reverse side of the face that cured coating is adhered to) to apply the power of extruding and to estimate resistance to reverse impact.Increase the distance that weight falls gradually, until reaching the distance that coating lost efficacy.As seen solidified film or coating lost efficacy by the crack gradually, more obvious when it is observed by magnifying glass, especially after deformation to after solidified film or the coatings applications acid copper sulfate.
Embodiment
Following embodiment explains but does not limit the present invention.All umbers and percentage ratio by weight, unless otherwise specified.All temperature in ℃.Embodiments of the invention (Ex) indicate with Arabic numerals, and comparative example (Comp Ex) indicates with capitalization.Unless explanation separately herein, " room temperature " and " envrionment temperature " is generally 25 ℃.
Embodiment
Embodiment 1-prepares the acid amides triol by diethanolamine and 11-hydroxyl methyl undecylenate
Use the above-mentioned this paper that incorporates into as reference step (especially USP 4,496,487 the 4th hurdles, 9-19 is capable), with 10 hendecenoic acid methyl esters (available from Aldrich) reduction hydroformylation with preparation 11-hydroxyl methyl undecylenate.
With 158.4 gram (g) (0.7322 mole) 11-hydroxyl methyl undecylenates, 154.8 gram (1.472 moles) diethanolamine; 2.6 potassium hydroxide solution (in methyl alcohol) and 140 milliliters of (ml) toluene of gram (0.39 mole) 85 weight % are put into 500 milliliters of round-bottomed flasks that magnetic stirring bar and water-cooled reflux condenser are housed.Flask is placed in the sand-bath in the electric mantle.Use is connected to the temperature regulator control sand-bath temperature that immerses the thermopair in the sand-bath.Use sand-bath, stir down heating flask contents to 60 ℃, by stirring, the solid ingredient of flask contents is dissolved in the toluene to obtain colorless cleared solution.
Carry out fourier-transform infrared (FTIR) analysis at the taking-up solution example with to sample before, keep solution temperature and continue to stir 24 hours at 60 ℃.The ester that analysis demonstrates trace absorbs (as 1729cm -1The small peak at place is shown).
Before flask contents was cooled to room temperature, the diethanolamine and the holding temperature that add other 10.2 grams (0.1 mole) continued for 60 ℃ to stir 18 hours.Rotary evaporation flask contents 2 hours to be removing the methyl alcohol that produces in the container contents reaction process under 35 ℃ and 4 inches of mercury (Hg) (15 kPas (kPa)) vacuum, thereby obtains solid reaction product.
In flask, added 350 milliliters 2 weight % sodium-chlor (NaCl) aqueous solution and stirred flask content (solid reaction product and the NaCl aqueous solution) 3 hours.By thick sintered glass B vacuum filtration flask contents.With the solids content in 100 milliliters the 2%NaCl aqueous solution rinsing funnel, repeat then solids content and 350 milliliters of fresh 2%NaCl aqueous solution were stirred 3 hours.Repeat at first to use 2 100 milliliters fresh 2%NaCl aqueous solution aliquots containig rinsings, use the rinsing of 2 100 ml deionized water aliquots containigs then by the solids content in B filtration and the rinsing funnel.
With solids content in stink cupboard air-dry 3 days.This exsiccant solids content weight is 180.7 grams.This exsiccant solids content and 500 milliliters of toluene are put into mixing vessel and it was mixed 2 hours.By the content of thick this mixing vessel of sintered glass B vacuum filtration, use 2 the 200 milliliters solids content in the toluene aliquots containig rinsing funnel then, it is overnight to follow air-dry solids content.Rotary evaporation exsiccant solids content demonstrates constant weight until content with the form of white powder.This constant weight, 158.9 grams, 75% of representation theory output.
To the FTIR of white powder, hydrogen nuclear magnetic resonance ( 1H NMR) wave spectrum and carbon-13NMR ( 13C NMR) the acid amides triol structure of Spectrum Analysis support shown in following general formula VI.
Figure A20068005027900241
The acid amides triol of general formula VI. experiment
The propylene acidylate of the acid amides triol of embodiment 2-embodiment 1
With (0.144 mole of 41.6 gram; 0.431 hydroxyl (OH) equivalent) acid amides three pure and mild 200 milliliters of toluene of embodiment 1 are put into the 1-that mechanical stirring and reflux exchanger (water-ethylene glycol mixture is cooled to-5 ℃) are housed and are risen round-bottomed flask.Use ice bath that flask contents is cooled to 7 ℃, in flask, add 46.82 gram (0.517 mole) acrylate chloride and other 50 milliliters toluene then.Dropwise added 58.62 in the clockwise flask through 15 minutes and restrain (0.453 mole) N, the N-diisopropylethylamine is kept ice bath simultaneously at 7 ℃.In flask, add second 50 milliliters of toluene aliquots containig, remove ice bath and stirred flask content 24 hours then.
Use separating funnel, with 200 milliliters 2%NaCl solution washing toluene layers once, use 200 milliliters 3% sodium bicarbonate (NaHCO again 3) aqueous solution aliquots containig washed twice.With sodium sulfate (Na 2SO 4) dry washed toluene layer, then should washing and exsiccant toluene layer by the vacuum filtration of intermediate sintered glass B.Add the 4-methoxyphenol (in 5 ml methanol (MeOH)) of 0.1 gram to filtrate, then 40 ℃ and 9mm Hg (1.2kPa) down rotation evaporated filtrate 5.5 hours to obtain not having the residue of toluene.Add 200 milliliters of anhydrous methanols to residue under stirring, use No. 1 filter paper from filtrate, to isolate solid then.The rotation evaporated filtrate is to remove methyl alcohol and to obtain clarifying liquid final product under 40 ℃ and 9mmHg.This final product weighs 66.07 grams, its be equivalent to theoretical yield 74.0% and have record according to American Society for Testing and Materials (ASTM) step D4287 as the I.C.I. cone-and-plate-rheometer 25 ℃ viscosity of 110 centipoises (0.11Pa.s) down.The FTIR of final product and 1H NMR analyzes the acid amides acylate structure of supporting shown in following general formula VII.
Figure A20068005027900251
The acid amides triacrylate of general formula VII. experiment
Embodiment 3-uses the acid amides triacrylate of embodiment 2 to prepare the UV cured coating
In vial, stir 50/50 adulterant (IRGACURE of the acid amides triacrylate, 0.24 gram benzophenone and the 1-hydroxyl cyclohexyl-phenyl ketone that make 8.727 gram embodiment 2 TM500, available from Aldrich), 0.2 gram methyl diethylamide, two polysiloxane (BYK TM307, available from BYK Chemie, Japan Ltd.) and four non-silicone defoamer (BYK TMA-555,, Japan Ltd.) in conjunction with being the coating solution of the prescription of 120 centipoises (0.12Pa.s) to obtain 25 ℃ of following viscosity available from BYK Chemie.
Use (No.) BYK-Gardner scraper plate No. 32, on aluminium sheet, draw or the coating solution coating of deposition formulation by the clamping plate holding position.Coat-thickness is 2 to 3 mils (0.05 millimeter (mm) is to 0.08 millimeters).By the plate that applies is delivered to mercury lamp (H-ball-type lamp, UV ProcessSupply Inc., parts number HS6808A4C-410) solidified coating that gets off, this mercury lamp are placed on 3.5 inches (in.) (7.6 centimetres (cm)) in plate top of coating, and speed is 10 feet per minute clocks (fpm) (5.08 * 10 -2Meter per second (m/s)).The mercury lamp radiation temperature be 101 ° of Fahrenheit degrees (°F) (38.3 ℃).
Temperature programming rate determination cured coating second-order transition temperature (T by 10 ℃/minute of differential scanning calorimeter (DSC) uses g).Those skilled in the art assert the T of material gThe point that the sudden change of material hot-fluid takes place when being rubbery state for material on the DSC figure by glassy transition.Estimate pencil hardness according to ASTM D3363 as mentioned above.Coating Tg and pencil hardness are respectively 29 ℃ and HB.
Embodiment 3 shows that acid amides acylate representative of the present invention obtains having the commercial acceptable work viscosity UV curable coating composition that is less than or equal to 4,000 centipoises (4.0Pa.s).In case deposition and solidify, coating have commercial required T greater than 25 ℃ gThe pencil hardness of HB fully satisfies the requirement of multiple application, especially needs is surpassed the timber coating of the hardness (preferred 2B or higher) of 6B.Whether those skilled in the art can easily determine the hardness of its specific end-use HB enough.
Embodiment 4-is by the fusion of the acid amides triacrylate of epoxy acrylate and embodiment 2 Thing prepares the UV cured coating
Under several variations, repeat embodiment 3.First variation, reduce amount to 5.168 gram of acid amides triacrylate, (25 ℃ of following viscosity are 19 to the bisphenol A epoxy acrylate of adding 7.517 gram experiments, 000 centipoise (19Pa.s), density is 1.11 to 1.15 gram/cubic centimetres (g/cc), the epoxy acrylic ester content is that 3.6 millis rub/restrain, in advance available from The Dow ChemicalCompany, commodity are called XZ 92554.00) and the bottle that will contain epoxy acrylate and acid amides triacrylate be placed on the wobbler (Eberbach Corporation manufacturing), under the heating lamp (this lamp is placed on the position of leaving bottle 6 inches (15.2cm)), and bottle is exposed to following 15 minutes of about 50 ℃ temperature to obtain clarification, uniform mixture.Stir to add identical IRGACURE among 0.35 gram and the embodiment 3 then TM, 0.30 gram methyl diethylamide, two BYK TMA-555 and a BYK TM307 to obtain the coating composition that viscosity is the prescription of 900 centipoises (0.9Pa.s).In following table 1, sum up T gWith the pencil hardness data.Think and mention that with above-mentioned the suitable bisphenol A epoxy acrylate material of the material that no longer can buy is SARTOMER TM(Sartomer Company, 25 ℃ of following viscosity are 18,900 centipoises (18.9Pa.s) to CN104.
Comparative Examples A-mixing based on epoxy acrylate and three (propylene glycol) diacrylate Compound prepares the UV cured coating
Under several variations, repeat embodiment 4.At first, the amount to 22.6 of increase bisphenol A epoxy acrylate restrains and replaces with 15.067 gram three (propylene glycol) diacrylates (Aldrich ChemicalCompany) the acid amides triacrylate of embodiment 2.The second, be increased in the time to 20 minute on the wobbler.The 3rd, increase IRGACURE TM500 and the amount of methyl diethylamide, restrain to 1.02 grams and 0.87 respectively, double BYK TM307 and BYK TM555 amount.In following table 1, sum up T gWith the pencil hardness data.
The character of table 1.UV cured coating
Embodiment/comparative example Solidification rate (fpm) Solidification rate (m/s) The test of nail cut Pencil hardness The two frictions of methylethylketone
4 5 25.4×10 -3 By 2H ＞200
A 5 25.4×10 -3 By 2B ＞200
4 25 127×10 -3 By 2B ＞200
A 25 127×10 -3 Failure 2B ＞200
4 30 152.4×10 -3 By 2B ＞200
A 30 152.4×10 -3 Failure 2B ＞200
4 35 177.8×10 -3 Failure 2B ＞200
A 35 177.8×10 -3 Failure 2B ＞200
Data presentation in the table 1 acid amides acylate of the present invention, illustrated as the acid amides acylate of embodiment 2, as the gratifying thinner of the epoxy acrylate in the UV curable formulations.At low solidification rate as 5 feet per minute clocks (25.4 * 10 -3M/s) under, with respect to traditional acrylate thinner (being three (propylene glycol) diacrylate in this case), the acid amides acylate provides the pencil hardness of increase.At 25 feet per minute clocks (127 * 10 -3M/s) or 30 feet per minute clocks (152.4 * 10 -3M/s) under the solidification rate faster, with respect to identical conventional acrylic ester thinner, the acid amides acylate also provides improved scratch-resistant.If scratch-resistant importance is very little or inessential,, can use (the 35 feet per minute clocks (177.8 * 10 that have higher solidification rate as in ink is used -3M/s) or bigger) composition of the present invention.
Embodiment 5-preparation is based on the curable China ink of UV of the acid amides triacrylate of embodiment 2 Water composition
Prepare pigment concentrate 5 times by the combination that makes 4 kinds of materials by three-roll rolling machine (three roll mill).Material and amount (in concentrate weight) are as follows: the blue pigments of 37.15 weight % (Phthalo Blue 249-3054, Sun Chemical), 37.15 the acid amides triacrylate of the embodiment 2 of weight %, the improved polyester acrylate (FLEXCURE of 15.7 weight % TMD30, Ashland) and the Viscoat 295 of 10.0 weight % (SARTOMER SR TM-351, Sartomer Company).
Prepare the coating ink by the following component of manual mixing in wide-necked bottle: 32.1 weight parts (weight part) pigment concentrate; 45.5 the polyester acrylate (SARTOMERCN of weight part patent TM2273, Sartomer Company); 10.3 same Viscoat 295 in weight part and the pigment concentrate; 0.5 parts by weight of acrylic acid polymer flow control additive (RESIFLOW TMLG-99, Estron Chemical Co.); With 9.2 weight part phosphine oxides, α hydroxyketone and benzophenone derivates (SARCURE SR TM1135, Sartomer Company).
Use is equipped with the ceramic printing rubber roll of 550 laser plate-makings and is had volume is 4.19 cubic centimetres of/square metre (cm 3/ m 2) the hand-held spreader (hand proofer) of Pamarco of screen cloth be coated in ink on the wide variety of substrates and form coating layer.Ground is 80 pounds of (176kg) Centura Gloss, paper tinsel, the former printing material of paper (available from Leneta commodity 5DX by name) and polyester film.
Use the step of this hand-held spreader as follows: (a) raw material to be printed to be placed on smooth clean flat surfaces; (b) position of adjusting printing rubber roll locks it on this position to required setting and with little wing screw; (c) about 1/2 (2.5 milliliters) ink to be coated or coating are dropped on the top of the folder between the rubber rollers of the printing rubber roll and the second contact raw material; (d) rotate roller by hand " to go up printing ink " for this anilox roll fully; (e) arrest spreader, use level and smooth, balanced, medium fast stroke, only use the enough pressure of rotating roller under the situation of not slippage so that rubber rollers rests on the raw material and with it drags to the operator.
By making coating layer come solidified ink by the Hanovia UV-6 delivery unit that 300 watts of H bulbs are housed with linear velocity 200 feet per minute clocks (1.01m/s).On the solidified coating layer, estimate ink and show that ink is very glossy, and have strong blueness, the recognizable muddiness of no naked eyes.
It is curable that the polyester acrylate that comparative example B-can buy based on commerce prepares UV Composition for ink
Repeat embodiment 6, but when preparation pigment concentrate, with polyester acrylate (the SARTOMER CN of patent TM2270, Sartomer Company) replaces the acid amides triacrylate of embodiment 2.On the solidified coating layer, estimate ink and show as if with respect to the solidified coating layer of embodiment 5, the solidified ink of comparative example B is compared more not dense and opaquer with embodiment 5 solidified inks.
Embodiment 6-prepares the epoxy soybean oil of open loop
With 250 gram epoxy soybean oil (ESO) (FLEXOL TMPlasticizer, EPO, 7.0 weight % epoxide oxygen, about 1.09 moles of epoxide, available from The Dow ChemicalCompany) and 250 gram (7.8 moles) methyl alcohol (MeOH) adding 1-liters, be equipped with in the three neck round-bottomed flasks of mechanical stirrer and heating jacket.In a neck condenser is housed, there is the nitrogen/vacuum inlet condenser top.The thermocouple probe that links to each other with electronic temperature controller is housed in second neck.Clog the 3rd neck.
In with 300 rev/mins of (rpm) stirred flask of stir speed (S.S.) content (ESO and MeOH), emptying flask and recharge three times to remove air from flask and to replace with nitrogen atmosphere with nitrogen.The heating flask contents is to 65 ℃ of set point temperatures under the lasting stirring of same speed.In heat-processed, flask contents becomes clarifying light yellow homogeneous solution at about 50 ℃.
After flask contents reaches set point temperatures, in flask, add 38.1 grams in advance with MeOH washing and air-dry ion-exchange resin bead (DOWEX TMMSC-1, The DowChemical Company).In set point temperatures, increase stirring velocity to 500rpm keeping reactor content, continue under this speed, to stir 18 hours.Stop to stir and, clarifying uniform pale yellow solution and ion-exchange resin bead, be cooled to room temperature (common 25 ℃) flask contents.The vacuum filtration flask contents is with separation solution (filtrate) and ion-exchange resin bead.Use Rotary Evaporators to bathe in 60 ℃ of down operation temperature of design temperature under nitrogen purging, (through about 1 hour time span) is decompressed to pressure vacuum distilling filtrate in 10 to 15 mmhg (mm Hg) (1.3 to 2kPa) scope simultaneously gradually.After under the pressure of design temperature and reduction by 1 hour, increase design temperature to 70 ℃ and kept this temperature 2 hours under purging in vacuum a little, close vacuum and heating then, make vacuum-distillatory filtrate be cooled to room temperature and constant pressure.
By using the oh group of ASTM testing method D4274 titrimetry vacuum-distillatory filtrate (clarifying light golden yellow oil).This method is based on after making filtrate aliquots containig and known excessive phthalic anhydride, with 1.0 equivalents (N) sodium hydroxide (NaOH) back titration.This oily oh group content is 5.16 weight %.
The propylene acidylate of the ESO of the open loop of embodiment 7-embodiment 6
Under several variations, repeat the ESO of embodiment 2 with the open loop of acidylate embodiment 6.At first, the ESO of the open loop of use 60 gram (0.1819 hydroxyl (OH) equivalent) embodiment 6 rather than acid amides triol and 200 milliliters of toluene of embodiment 1, the amount to 24.7 that reduces acrylate chloride restrains (0.2183 mole).Also reduce N, the amount to 24.7 of N-diisopropylethylamine gram (0.191 mole), but increase joining day to 50 minute, keep ice bath simultaneously in 6 ℃ to 9 ℃ scopes.In addition, after adding second 50 milliliters of toluene aliquots containig, remove ice bath, and churning time was reduced to 22 hours from 24 hours.
Reclaim final product, it is as the clarified liq among the embodiment 2.This liquid viscosity is 1550 centipoises (1.55Pa.s); There is the acylate structure in the FTIR analysis revealed liquid.Embodiment 7 obtains containing the ESO of the open loop of acylate, and it has the suitable low work viscosity less than 4,000 centipoises (4.0Pa.s).Those skilled in the art need make work viscosity minimize as far as possible, especially ink are used.
Embodiment 8-uses the product of embodiment 7 to prepare the UV cured coating
Under several variations, repeat embodiment 3.At first, use embodiment 7 products rather than embodiment 2 products of 18.38 grams, and increase IRGACURE TM500 amount to 0.50 gram.In addition, reduce BYK TMAmount to 3 droplet.The coating solution viscosity of prescription is 1525 centipoises (1.52Pa.s).
Use the coating solution of prescription as in Example 2, but use phosphatic steel plate rather than aluminium sheet, Enhanced Radiation Reduced Blast temperature to 110 (43 ℃) and reduce solidification rate to 5 feet per minute clock (2.54m/s).Cured coating character is summarized as follows table 2.
Embodiment 9-prepares UV by the adulterant of the product of epoxy acrylate and embodiment 7 Cured coating
Under several variations, repeat embodiment 4.At first, use product rather than the acid amides triacrylate of embodiment 3 and amount to 18.42 gram of increase epoxy acrylate of 27.63 gram embodiment 7.Also increase IRGACURE TM500 amount to 1.24 gram, amount to 1.06 gram of methyl diethylamide, BYK TM307 amount to 4 droplet, BYK TMThe amount to 6 of A-555 droplet.In addition, as embodiment 8 rather than the coating solution of using prescription according to ground and the condition of embodiment 4.Cured coating character is summarized as follows table 2.
Comparative example C
Repeat Comparative Examples A, but the amount that changes epoxy acrylate and diacrylate reduces IRGACURE to all being 15.92 grams TM500 amount to 0.86 gram, methyl diethylamide to 0.73 gram.In addition, change BYK respectively TM307 and BYK TMThe amount to 3 of A-555 droplet and 6.Must make and add diacrylate to obtain the required work viscosity that is less than or equal to 4,000 centipoises (4.0Pa.s), because epoxy acrylate has the undiluted viscosity (under 25 ℃) of 19,000 centipoises (19Pa.s).In addition, described in embodiment 8 rather than Comparative Examples A, use and solidified coating.Cured coating character is summarized as follows table 2.Reported that unit is in-lb (in-lbs)/kg-m (kg-m) according to the shock resistance value of the ASTM method D2794 mensuration of above explanation.
Table 2
Embodiment/comparative example Viscosity under 25 ℃ (cps/Pa.s) Coat-thickness (mil/mm) Shock resistance-directly (in-lbs/kg-m) Shock resistance-reverse side (in-lbs./kg-m) Pencil hardness The two frictions of methylethylketone
8 1525/1.52 2.44/0.062 48/2.7 2/0.11 ＜4B 175
9 4000/4.0 2.60/0.066 72/4.0 10/0.56 HB ＞200
C 700/0.7 2.20/0.56 40/2.2 ＜2/＜0.11 2H ＞200
Data in the table 2 show; when as reactive diluent (in embodiment 9); with respect to traditional acrylate thinner (three (propylene glycol) diacrylate or TPGDA) (in comparative example C), the ESO of the open loop that contains acylate of embodiment 7 provides improved shock resistance.Though for embodiment 9 and comparative example C, reactive diluent is approaching more identical than the ratio of bisphenol A epoxy acrylate, amount (with respect to the bisphenol A epoxy acrylate) comparison of reactive diluent among the embodiment 9 (embodiment 7) is than big slightly in the Embodiment C, to reduce composition viscosity to 4,000 centipoise (4.0Pa.s).The amount of the reactive diluent of embodiment 7 makes composition viscosity further reduce with respect to the further increase of bisphenol A epoxy acrylate.Data in the table 2 also show with respect to embodiment 8; even without bisphenol A epoxy acrylate, also provide the shock resistance of traditional coating (in comparative example C) of the prescription that equals to contain bisphenol A epoxy acrylate at least based on the cured coating of the ESO that contains acylate, open loop of this embodiment 7.Because it is with respect to the required low viscosity of bisphenol A epoxy acrylate, the use of also can under the condition that does not have TPGDA or some other reactive diluent, filling a prescription of the composition of embodiment 8.
Embodiment 10-prepares the acid amides triol based on the 12-hydroxymethylstearat
Take by weighing 200 gram 12-hydroxymethylstearat (PARACIN TM1, CasChem ofRutherford Chemicals) and 276.0 gram diethanolamine, put into 2000 milliliters that heating jacket, thermopair, mechanical stirrer and sparger (sparger) are housed, 3-neck flask.Heating flask and its content are to 120 ℃ of design temperatures.Keep flask contents under this temperature, while mixed content thing also makes the subsurface nitrogen purge of its process 30 minutes.Continue to mix, but subsurface purification is changed into the headspace purification and keeps these conditions overnight.
Flask contents is cooled to room temperature (common 25 ℃), in flask, adds 1000 milliliters of chloroforms then to change content into chloroformic solution.With 700 gram deionized water wash these solution 4 times, restrain sal epsom (MgSO4) drying solution with 75 then.As described in example 1 above by rotary evaporation separated product from solution.Product is a solid, at room temperature weighs 216.7 grams, is equivalent to 88.6% of theoretical yield.Assay products as described in example 1 above, it is consistent on acid amides triol structure.
The propylene acidylate of the acid amides triol of embodiment 11-embodiment 10
Take by weighing 400 gram diethyl ether, the acid amides three pure and mild 72.0 gram acrylate chlorides of 95.0 gram embodiment 10 are put into 2000 milliliters of 3-neck flasks that immerse ice bath and feed hopper, thermopair, mechanical stirrer and nitrogen headspace purification pipe are housed.Start mechanical stirrer stirred flask content.Take by weighing 96.9 gram N, the N-diisopropylethylamine adds feed hopper and dropwise it was added in the content that stirs through 100 minutes.
Remove ice bath, in flask, add 250 gram diethyl ether to form mixture and to stir the mixture overnight at ambient temperature.In flask, added 150 gram diethyl ether and 1000 ml deionized water and continuously stirring 60 minutes then.
Flask contents is transferred to separating funnel so that its phase-splitting is water layer and liquid organic layer, abandons water layer then.With the 5 weight %NaCl solution washing liquid organic layers 2 times of 170 grams, with the 170 5 weight %H that restrain 2SO 4Solution washing twice is at last with the 170 5 weight %NaHCO that restrain 3Solution washing twice is then with 25 gram MgSO 4Dry.In washing and dried organic liquid, add 0.12 gram 4-methoxyphenol, then by rotary evaporation separation of liquid products (as described in example 10 above).Product liquid weighs 97.8 grams, and 73.3% of representation theory output, viscosity are 250 centipoises (0.25Pa.s).Product 1H NMR and FTIR analyze the existence that has confirmed acid amides triacrylate structure.
The preparation of embodiment 12-Viscotrol C acid amides triol
Under several variations, repeat embodiment 10 with preparation Viscotrol C acid amides triol.At first, replace the 12-hydroxymethylstearat with 200.1 gram Viscotrol C.Secondly, at every turn with 400 gram 5 weight %NaCl solution washings and minimizing MgSO 4Amount to 20 gram.The product that reclaims weighs 195.5 grams, 78.0% of representation theory output.Product 1H NMR and FTIR analyze with Viscotrol C acid amides triol structure on consistent.
The propylene acidylate of the Viscotrol C acid amides triol of embodiment 13-embodiment 12
Under several variations, repeat embodiment 11.At first take by weighing 200 gram diethyl ether, the product of 47.5 gram embodiment 12 and 36.9 gram acrylate chlorides are put into 1000 milliliters, and in the 3-neck flask, wherein the position of this flask is identical with 2000 ml flasks of embodiment 11 with outfit.Reduce N, amount to 50.5 gram of N-diisopropylethylamine and amount to 139 gram of minimizing diethyl ether.
Different with the amount and the mixing time of diethyl ether concrete among the embodiment 11 and deionized water, add 96 gram diethyl ether and 500 grams, 3 weight %NaHCO 3The aqueous solution and reduce mixing time to 30 minute.
Abandon after the water layer, change the product recycling step.At first in organic layer, add 210 gram diethyl ether to form the organic layer of dilution, then with 150 grams, 5 weight %NaHCO 3The organic layer that solution washing should dilute 3 times is next with 10 gram MgSO 4Dry.The amount of the 4-methoxyphenol that adds before the rotary evaporation separated product is reduced by half.Product weighs 51.1 grams, and 75.8% of representation theory output, viscosity are 193 centipoises (0.19Pa.s).Product 1H NMR and FTIR analyze with Viscotrol C acid amides acylate structure on consistent.
Embodiment 14-prepares the acid amides triol by diethanolamine and 12-methylol methyl stearate
Use the step of listing among the USP 4,496,487 (it is open with the allowed by law this paper that incorporates into to greatest extent), contain the product of 12-methylol methyl stearate by the preparation of reduction hydroformylation Witconol 2301.Product of distillation to be to remove volatiles, obtains having the reactant (in reactant weight) of the 12-methylol methyl stearate content of 94 weight %.
Change ground repetition embodiment 10 by making some, prepare the acid amides triol based on 12-methylol methyl stearate.Modifier is with the sparger of the dean stark trap replacement embodiment 10 that has condenser and nitrogen headspace purification pipe.Take by weighing above preparation 400.0 the gram 94 weight % contain 12-methylol methyl stearate reactant and 511.7 the gram diethanolamine put into flask.Be added in 10 ml methanol (MeOH) solution of 0.93 gram potassium hydroxide (KOH), heat flask contents then to 110 ℃ of design temperatures and maintain stirred overnight under this temperature.
Use is with respect to embodiment 10 improved method for product recovery.At first replace chloroform with toluene.Change washing step with 2 weight %NaHCO with 1600 grams 3Solution washing 3 times, and with 80 the gram rather than 75 the gram MgSO 4Dry.
Under reduced pressure reclaim the liquid that product obtains heavy 450 grams, 92.0% of representation theory output down for 60 ℃ by rotary evaporation at design temperature.Product 1H NMR analyzes consistent on acid amides triol structure with FTIR.
The propylene acidylate of the acid amides triol of embodiment 15-embodiment 14
Under changing, some repeat embodiment 11.At first take by weighing 704 gram diethyl ether, the acid amides triol of 180.1 gram embodiment 14 and 139.2 gram acrylate chlorides are put into 2000 milliliters of 3-neck flasks of the device of embodiment 11.Increase N, amount to 174.1 gram of N-diisopropylethylamine and adding as described in example 11 above, but through time of 220 minutes.
Remove ice bath and under envrionment temperature (common 25 ℃), stir the mixture overnightly, but before stirred overnight, do not add any diethyl ether.After the stirred overnight, in flask contents, add the 260 gram diethyl ether and 400 grams, the 2 weight %NaCl aqueous solution.
Improve the recycling step of embodiment 11, the back keeps water layer and organic layer being separated.5 weight %NaHCO with 400 grams 3Organic layer after the solution washing organic layer also will wash for 4 times is placed on one side.Stir adding 400 gram deionized waters and 116 gram diethyl ether in the water layer that keeps down, stop then stirring and it being separated in separating funnel being water layer and ether layer.
5 weight %NaHCO with 400 grams 3Solution washing ether layer is placed the ether layer after the washing overnight, and then restrains NaHCO with 400 3Solution washing 3 times.Ether layer after the washing and the organic layer that is placed on before after the washing are on one side combined, and restrain MgSO with 30 4Dry bonded layer.To exsiccant organic/the ether layer is in conjunction with adding 0.32 gram 4-methoxyphenol, and as described in example 11 above by rotary evaporation recovering liquid product.Product viscosity is 250 centipoises (0.25Pa.s) and passes through 1H NMR and FTIR analyze, with consistent on the acid amides triacrylate structure.
Embodiment 16-prepares the acid amides polyvalent alcohol by the ESO of open loop
Under some changes, repeat the method for embodiment 10, prepare the acid amides polyvalent alcohol based on the ESO of open loop.At first take by weighing the epoxy soybean oil (preparation as described in example 6 above) and the 200.3 gram diethanolamine of 232.6 gram open loops, put into the device of embodiment 10.Reduce design temperature to 110 that flask and content thereof be heated to ℃.
After flask contents is cooled to room temperature, add 600 milliliters of toluene rather than 1000 milliliters of chloroforms, to change content into toluene solution.Change washing and drying step,, next, restrain MgSO with 160 then with 1,000 3 weight %NaCl solution washings that restrain 2 times at first with 1000 gram deionized water wash 2 times 4Dry.(under decompression and 60C, as described in example 1 above) from solvent (toluene), isolate product by rotary evaporation.Separated products weighs 209.7 grams, by 1H NMR and FTIR analyze, and have the structure consistent with the acid amides polyvalent alcohol.
The propylene acidylate of the acid amides polyvalent alcohol of embodiment 17-embodiment 16
The improved method that the device of use embodiment 13 and this place are described is come the acid amides polyvalent alcohol of acidylate embodiment 16.Replace the product of embodiment 12 with the acid amides polyvalent alcohol of embodiment 16, and reduce amount to 36.1 gram of acrylate chloride.Reduce N, amount to 47.9 gram of N-diisopropylethylamine, and it is dropwise added through 110 minutes time.
After shifting out ice bath, under agitation add 150 gram diethyl ether, and continue stirred overnight at ambient temperature, and then add 150 gram diethyl ether and 500 ml deionized water, continue simultaneously to stir 45 minutes.
After abandoning water layer, use improved step to reclaim the acid amides polyvalent alcohol of acidylate.At first, with the 5 weight %NaCl solution washing organic layers 2 times of 110 grams, then with the 110 5 weight % sulfuric acid (H that restrain 2SO 4) solution washing 2 times and with the 5 weight %NaHCO3 solution washings 2 times of 110 grams, restrain MgSO with 15 then 4Dry organic layer.The 4-methoxyphenol that adds 0.07 gram, and by decompression and rotary evaporation separated product at ambient temperature is to obtain 46 gram products (theoretical yield 69.8%).Product viscosity is 650 centipoises (0.65Pa.s), by 1HNMR and FTIR analyze, and be consistent with the acid amides polyol structure of acidylate.
Embodiment 18-is by the polyester manufacture acylate derived from 12-methylol methyl stearate
In 2 liters of glass reaction flasks, the glycerol that adds 1050.3 gram (3.15 moles) soybean (soy) monomers and 328.9 gram (0.53 mole) ethoxylations is as initiator.Sealed flask also makes its degassing with nitrogen purging under 20 holder (2.67kPa) vacuum, heat flask contents simultaneously to 50 ℃ of design temperatures.The of short duration vacuum of breaking adds 0.78 gram (565ppm) stannous octoate in flask.Again be evacuated to 20 holders (2.67kPa), remove or disconnect nitrogen purging and heat flask and content to 195 ℃ of design temperatures, keep flask and content thereof under this condition 4 hours, in dry ice trap, collect methyl alcohol (MeOH) by product.Alternatively, also can use vacuum, nitrogen purging or both arbitrary combination are removed to influence MeOH.After 4 hours, remove vacuum and make that reactor flask and content thereof are cooled to room temperature under nitrogen overnight.Add 0.77 gram (558 parts per million by weight flask contents (ppm)) stannous octoate and connect nitrogen sparge tube to reactor flask.Under slow nitrogen purging heating flask and content thereof to 195 ℃ of design temperatures 4 hours to finish reaction.
Use same apparatus and improved embodiment 17 methods among use and the embodiment 17, use the polyester synthesizing polyester acylate that in the last period, prepares.This improved method at first takes by weighing 700 milliliters of toluene, and (OH equivalent 398.6 (OH equivalent=1701 are divided by hydroxyl per-cent, and wherein hydroxyl per-cent is by determining according to ASTM testing method D4274 titration) and 54.5 gram acrylate chlorides are put into flask to 200 gram polyester.Increase N, amount to 68.1 gram of N-diisopropylethylamine, but reduce joining day to 100 minute.
As described in embodiment 17, removing ice bath, do not add other compositions before overnight but stir the mixture at ambient temperature.Before carrying out separation, add the 3 weight %NaCl aqueous solution of 400 grams to flask.After using separating funnel to separate, abandon water layer as described in example 17 above and with the 400 3 weight %NaHCO that restrain 3Solution washing organic (toluene) layer 3 times, with 400 gram deionized water wash once, then with 119.4 gram Na 2SO 4Dry organic layer.The 4-methoxyphenol that in washing and exsiccant organic layer, adds 0.29 gram, then as described in example 17 above (but temperature is 40 ℃) by rotary evaporation from the toluene separated product.This isolating product is a liquid, weighs 188.8 grams, represents product output to be 83.1% of theory.Product viscosity is 550 centipoises (0.55Pa.s), according to 1H NMR and FTIR analyze, and have the structure consistent with the polyester acylate.
Embodiment 19-is by 12-methylol methyl stearate preparation list-acylate
Use with embodiment 18 in identical device and improved embodiment 18 methods prepare list-acylate by 12-methylol methyl stearate.At first take by weighing 700 milliliters of toluene, 200 gram 12-methylol methyl stearates (the reduction hydroformylation by Witconol 2301 prepares as mentioned above) and 66.1 gram acrylate chlorides are put into flask.Increase N, amount to 82.8 gram of N-diisopropylethylamine, but reduce its time to 85 that dropwise adds by feed hopper minute.
Reclaim product as described in example 18 above, but increase amount to 127.6 gram of Na2SO4 and amount to 0.11 gram of minimizing 4-methoxyphenol.The product that reclaims weighs 231.5 grams, and 99.3% of representation theory output, viscosity are 12.5 centipoises (0.012Pa.s).The FTIR analysis revealed structure of product is consistent with list-acylate.
Embodiment 20-is by 11-hydroxyl methyl undecylenate preparation list-acylate
Use the device identical, but the step of embodiment 19 has been done several improvement, prepare list-acylate by 11-hydroxyl methyl undecylenate with embodiment 19.This improved method at first takes by weighing 600 milliliters of toluene, and 200 gram 11-hydroxyl methyl undecylenates and 100.4 gram acrylate chlorides are put into flask.Increase N, amount to 125.5 gram of N-diisopropylethylamine and by feed hopper with its time to 140 that dropwise adds minute.
Reclaim product as described in example 19 above, but reduce Na 2SO 4Amount to 103.3 gram, increase amount to 0.12 gram of 4-methoxyphenol.Reclaim product as described in example 19 above.Products therefrom weighs 244.5 grams, and 99.0% of representation theory output, viscosity are 10 centipoises (0.02Pa.s).0.12 gram 4-methoxyphenol is added toluene solution, and under reduced pressure rotation evaporates the separated from solvent product under 40 ℃.Reclaim 244.5 gram products, and viscosity is 10 centipoises.The FTIR analytical table of product reveals the structure consistent with list-acylate structure.
Novel acylate material of the present invention, especially those of embodiment 11,13,15 and 17-20 have very low in the viscosity of 10 centipoises (0.01Pa.s) to 650 centipoises (0.65Pa.s) scope.This low viscosity causes improved processibility in the curable application of multiple arbitrarily UV-(as ink and coating).Therefore think that these materials are hydrophobic, make them water-fast, and be flexible with respect to the proprietary concentrate that can buy now.Therefore, think that also these novel acylate materials are applicable to processibility and the performance of improving existing oligopolymer such as bisphenol A epoxy acrylate.In addition, some in the novel acylate material can be used as the substitute of one or more oligopolymer effectively.
Other acylate materials are also expected similar result, particularly the acid amides acylate material of basis open preparation herein.
Claims (according to the modification of the 19th of treaty)
1, preparation feedback α, the method for beta-unsaturated acyl thing monomer composition, this method comprises the step of following order:
(a) with at least a lipid acid of polyol initiator polymerization or fatty acid ester, this lipid acid or fatty acid ester contain at least one reactive hydroxyl part, to form hydroxyl-functionalized aliphatic polyester;
(b) make the polyester and the α of step (a), the beta-unsaturated acyl agent is reacted to form reactive α, the beta-unsaturated acyl thing.
2, method according to claim 1, wherein polyol initiator is selected from glycerol, glycerol ethoxylate, polyoxyethylene glycol or polypropylene glycol.
3, method according to claim 1 and 2; wherein lipid acid or fatty acid ester are at step (a) fore portion hydroformylation, and condition is that this partial hydrogenation formylation hydroformylation thing has be present in this lipid acid or the fatty acid ester undersaturated at least 80% before the partial hydrogenation formylation.
4, according to each described method in the claim 1 to 3, wherein lipid acid is 12-(methylol) stearic acid.
5, according to each described method in the claim 1 to 3, wherein fatty acid ester is 12-(methylol) methyl stearate.
6, according to each described method in the claim 1 to 5, α wherein, the beta-unsaturated acyl agent be ethyl propenoate, methyl methacrylate be selected from acrylate chloride or the acyl halide of methacrylic chloride at least a.
7, reactive α, the beta-unsaturated acyl thing, it is by each described method preparation in the claim 1 to 6.
8, UV-curable compositions, it comprises the described reactive α of claim 7, beta-unsaturated acyl thing.
9, UV-curable ink, binder composition or coating composition, it comprises the described UV-curable compositions of claim 8.
10, UV-solidified ink, binder composition or coating, it is by the described preparation of compositions of corresponding claim 9.

Claims (32)

1, reactive monomer compositions comprises that the acid amides of general formula I representative gathers-α the beta-unsaturated acyl thing:
Figure A2006800502790002C1
General formula I
R wherein 1Be multivalence alkenyl part; R 2Be hydrogen or monovalent alkyl part; R 3Do not exist or for multivalence alkenyl part; R 4Be multivalence alkenyl part; R 5Part for H, monovalent alkyl part or general formula I I representative:
General formula I I
R wherein 4As above definition, R 7, R 8And R 9Be hydrogen or monovalent alkyl part independently; R 6For having the part of general formula III:
Figure A2006800502790002C3
General formula III
R wherein 7, R 8And R 9Be as above definition independently; M, n and o are 0 or 1 independently, are the positive integer greater than 0 yet condition is m, n and o sum.
2, composition according to claim 1, wherein R 1Divalent alkyl or alkenyl part for 1-20 carbon; R 2For hydrogen or contain the moieties of 1 to 20 carbon; R 3Do not exist or for methylene radical; R 4Be ethylidene or propylidene; R 5Be the part of hydrogen, methyl or general formula I I representative, wherein R 4Be ethylidene, R 7Be hydrogen or methyl, R 8And R 9Be hydrogen; And R 6Be the part of general formula III representative, wherein R 7Be hydrogen or methyl, R 8And R 9Be hydrogen.
3, preparation is according to the method for claim 1 or the described reactive monomer compositions of claim 2, and this method comprises:
A. make alkanolamine and compound reaction with at least one reactive hydroxyl groups or part, this compound is selected from hydroxyl-functionalized vegetables oil, the hydroxyl-functionalized lipid acid or hydroxyl-functionalized fatty acid ester of modification or non-modification, compound is converted into the acid amides polyvalent alcohol; With
B. make acid amides polyvalent alcohol and α, beta-unsaturated acyl agent reaction gathers-α the beta-unsaturated acyl thing the acid amides polyvalent alcohol is converted into acid amides.
4, method according to claim 3 comprises that further the parent material that is selected from polyunsaturated vegetable oil, lipid acid or fatty acid ester by partial reduction hydroformylation at least prepares the precursor step of compound.
5, method according to claim 4, wherein parent material is at least a hydroxyl-functionalized vegetables oil, and wherein vegetables oil is to be selected from the lazy unsaturated oil of oil or these oily modification modification of reining in of Thistle oil, sunflower oil, soybean oil, linseed oil, peanut oil, sweet oil, tobacco-seed oil, Oleum Gossypii semen, Oleum Cocois, rape seed oil, Tower rape oil, Semen Maydis oil or Leix gram.
6, method according to claim 4, wherein parent material is hydroxyl-functionalized fatty acid methyl ester.
7, method according to claim 6, wherein the methyl ester of the fatty acid methyl ester of hydroxyl-functionalized is at least a methyl ester that is selected from Witconol 2301,10 hendecenoic acid methyl esters, 9-decylenic acid methyl esters, Linolenic acid methylester or methyl linoleate.
8, method according to claim 3, wherein parent material is be selected from ricinoleate acid or monoricinolein at least a.
9, method according to claim 3, wherein compound is hydroxymethylstearat or methylol methyl stearate.
10, according to each described method in the claim 3 to 9, α wherein, the beta-unsaturated acyl agent be ethyl propenoate, methyl methacrylate be selected from acrylate chloride or the acyl halide of methacrylic chloride at least a.
11, according to each described method in the claim 3 to 10, wherein alkanolamine is a thanomin, 1, at least a in 2-Propanolamine or the diethanolamine.
12, a kind of reactive monomer compositions is selected from the poly--α by the one of the following representative, the beta-unsaturated acyl thing:
General formula I V
Or
Figure A2006800502790004C2
General formula V
R wherein 1Definition as described above; R 10Be the part shown in the following general formula:
Figure A2006800502790005C1
R wherein 7, R 8And R 9Definition as described above; R 11Be hydrogen or hydrocarbyl portion; N and p are 0 or the positive integer in the 1-20 scope; A, b, c, d, e, f, g, h, i, j, k and l are 0 or 1 independently, yet condition is that at least one is the positive integer greater than 0 in a, b, c, d, e, f, g, h and i sum or j, k and 1 sum; With X be:
R 10---O---or R 12---O---or
Figure A2006800502790005C2
R wherein 10As above definition, R 12And R 13Be hydrogen or hydrocarbyl portion independently.
13, composition according to claim 12, wherein R 1Moieties for hydrogen or 1-20 carbon; R 7Be hydrogen or methyl; R 8And R 9Be hydrogen; R 11Be hydrogen or methyl; R 12And R 13Be methyl.
14, preparation comprises the step of following order according to claim 12 or the described method for compositions of claim 13:
Epoxy-functionalized vegetables oil, epoxidised lipid acid or epoxidised fatty acid ester are reacted to form polyvalent alcohol with water, carboxylic acid or alcohol in the presence of an acidic catalyst; With
B. make polyvalent alcohol and a of step a., beta-unsaturated acyl agent reaction comprises poly--α, the reactive monomer compositions of beta-unsaturated acyl thing with formation.
15, method according to claim 14 wherein epoxy-functionalized vegetables oil be selected from ringdove elecampane oil, epoxy soybean oil or epoxy linseed oil.
16, according to claim 14 or the described method of claim 15, wherein carboxylic acid is acetate or formic acid.
17, according to claim 14 or the described method of claim 15, wherein alcohol is methyl alcohol.
18, according to each described method in the claim 14 to 17, wherein an acidic catalyst is Zeo-karb or mineral acid.
19, according to each described method in the claim 14 to 18, α wherein, the beta-unsaturated acyl agent be ethyl propenoate, methyl methacrylate be selected from acrylate chloride or the acyl halide of methacrylic chloride at least a.
20, radiation curable composition, said composition comprise at least a being selected from according to claim 1, the monomer and the radiation curing promotor of each described reactive monomer compositions in 2,12 or 13.
21, radiation curable composition according to claim 20 further comprises the radiation adjustable curing material that is selected from radiation-curable acrylate monomer, radiation-curable methacrylate monomer, radiation-curable oligopolymer or radiation-curable reactive diluent.
22,, further comprise at least a pigment and randomly, one or more non--reactive additive according to claim 20 or the described radiation curable composition of claim 21.
23, radiation-curable coating comprises according to each described radiation curable composition in the claim 20 to 22.
24, radiation-curable ink comprises according to each described radiation curable composition in the claim 20 to 22.
25, radiation-curable adhesive composition comprises according to each described radiation curable composition in the claim 20 to 22.
26, preparation feedback α, the method for beta-unsaturated acyl thing monomer composition, this method comprises the step of following order:
(a) with at least a lipid acid of polyol initiator polymerization or fatty acid ester, this lipid acid or fatty acid ester contain at least one reactive hydroxyl part, to form hydroxyl-functionalized aliphatic polyester;
(b) make the polyester and the α of step (a), the beta-unsaturated acyl agent is reacted to form reactive α, the beta-unsaturated acyl thing.
27, method according to claim 26, wherein polyol initiator is selected from glycerol, glycerol ethoxylate, polyoxyethylene glycol or polypropylene glycol.
28, according to claim 26 or 27 described methods; wherein lipid acid or fatty acid ester are at step (a) fore portion hydroformylation, and condition is that this partial hydrogenation formylation hydroformylation thing has be present in this lipid acid or the fatty acid ester undersaturated at least 80% before the partial hydrogenation formylation.
29, according to each described method in the claim 26 to 28, wherein lipid acid is 12-(methylol) stearic acid.
30, according to each described method in the claim 26 to 28, wherein fatty acid ester is 12-(methylol) methyl stearate.
31, according to each described method in the claim 26 to 30, α wherein, the beta-unsaturated acyl agent be ethyl propenoate, methyl methacrylate be selected from acrylate chloride or the acyl halide of methacrylic chloride at least a.
32, reactive α, the beta-unsaturated acyl thing, it prepares by each described method in the claim 26 to 31.
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CN107129714B (en) * 2017-04-13 2019-06-07 河北科技大学 A kind of preparation method of soybean oil acrylate type UV-cured resin
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CN109776347B (en) * 2019-02-18 2021-03-26 华南农业大学 Thermosetting vegetable oil-based acrylate derivative and preparation method and application thereof

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