CN102260364A - Acrylate resin and preparation method thereof - Google Patents
Acrylate resin and preparation method thereof Download PDFInfo
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- CN102260364A CN102260364A CN2011100393948A CN201110039394A CN102260364A CN 102260364 A CN102260364 A CN 102260364A CN 2011100393948 A CN2011100393948 A CN 2011100393948A CN 201110039394 A CN201110039394 A CN 201110039394A CN 102260364 A CN102260364 A CN 102260364A
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Abstract
The invention relates to acrylate resin which comprises the following components by weight percent: 8-17% of alkoxy ethanol, 10-20% of (methyl) crylic acid, 5-15% of methacrylate, 20-50% of acrylate, 0-5% of styrene, 12-25% of (methyl) hydroxyl acrylate-caprolactone compound, 0-1% of alkyl hydrosulfide and 1-10% of mixed hydrocarbon solution. The invention provides acrylate resin which is a coating ingredient with large hardness, good elasticity and good solvent resistance. The acrylate resin has the advantages of simple preparation method, common raw material and low cost, and is suitable for industrial production in large scale.
Description
One, technical field
The invention belongs to macromolecular material and preparation field thereof, relate to a kind of acrylate resin and preparation method thereof.
Two, background technology
Along with developing rapidly of coating technology, coating in the application in fields such as industry, life more and more widely, and is also more and more harsher in the requirement aspect the environmental protection to coating.At present, the coating that is used for metal material surface on the market has characteristics such as strong adhesion, glossiness be good, but generally have hardness little, lack flexibility and defective such as poor solvent resistance, thereby greatly influence the quality of coating.Therefore, the coating that develop that a kind of hardness is big, good springiness and solvent resistance is good and form compound and be the industry active demand.
Three, summary of the invention
Technical problem to be solved by this invention provides that a kind of hardness is big, good springiness and the good coating composition acrylate resin of solvent resistance, and this acrylate resin preparation method is simple, raw material is common, cost is lower, be fit to large-scale industrial production.
For realizing technical problem to be solved by this invention, the technical scheme of employing is: a kind of acrylate resin, by weight percentage, by constituting following the composition:
The present invention is that also described alkoxyethanol is at least a in methyl cellosolve, ethoxy ethanol, propoxy-ethanol, the n-butoxy ethanol.
The present invention is that also described methacrylic ester is that methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, carbonatoms are at least a in the ester class methacrylic compound of 5-10.Wherein carbonatoms is that the ester class methacrylic compound of 5-10 is methacrylic acid pentyl ester, N-Hexyl methacrylate, methacrylic heptyl heptylate, Octyl methacrylate, nonyl methacrylate, decyl-octyl methacrylate.
The present invention is that also described acrylate is that methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, carbonatoms are at least a in the ester class acrylic compound of 5-10.Wherein carbonatoms is that the ester class acrylic compound of 5-10 is vinylformic acid pentyl ester, Ethyl acrylate, vinylformic acid heptyl ester, Octyl acrylate, vinylformic acid ester in the ninth of the ten Heavenly Stems, decyl acrylate.
The present invention is that also described (methyl) crylic acid hydroxy ester-caprolactone compound is that (methyl) crylic acid hydroxy ester of 42～70%, 30～55% 6-caprolactone, 0～2% tertiary butylated hydroquinone and 0～2% tosic acid mix by weight percentage, and described (methyl) crylic acid hydroxy ester is at least a in (methyl) vinylformic acid hydroxy methyl, (methyl) Hydroxyethyl Acrylate, (methyl) vinylformic acid hydroxy propyl ester, (methyl) vinylformic acid hydroxyl butyl ester.
The present invention is that also described alkyl sulfhydryl is that n-dodecyl mercaptan is or/and carbon atom is the alkyl sulfhydryl of 1-11.
The present invention is that also described hydrocarbon mixture solution is 60～80% the tertiary butyl-superoxide and the mixing solutions of 2-ethylhexanoate.
A kind of preparation method of acrylate resin, its preparation process is:
A, take by weighing (methyl) vinylformic acid, methacrylic ester, acrylate, vinylbenzene and (methyl) crylic acid hydroxy ester-caprolactone compound by predetermined formulation and make reactant A;
B, the alkyl sulfhydryl that takes by weighing formula ratio join in the reactant A, make mixture B;
C, take by weighing the alkoxyethanol of formula ratio, drop into and be equipped with in the reactor of rare gas element conduit, agitator, refrigerating unit and heating unit, be heated to 100～150 ℃, with 4 hours dropping mixture B;
D, with the hydrocarbon mixture solution that dripped formula ratio in 5 hours, drip the back and under 100～150 ℃ of conditions, stirred 1～3 hour, make acrylate resin.
The present invention is that also the preparation process of described (methyl) crylic acid hydroxy ester-caprolactone compound is:
A, (methyl) crylic acid hydroxy ester and the 6-caprolactone that take by weighing formula ratio fully stir, and mix;
B, in the mixture in a step, add the tertiary butylated hydroquinone and the tosic acid of formula ratio, make reactant C;
C, reactant C was heated to 120～150 ℃ with 3 hours makes (methyl) crylic acid hydroxy ester-caprolactone compound.
Beneficial effect of the present invention is:
1, acrylate resin polymerization technique of the present invention is simple, stirring reaction under lesser temps and condition of normal pressure, energy-saving safe.
2, acrylate resin of the present invention is as the important component of water-dilutable acrylate resin coating, and this paint coatings hardness is big, and pencil hardness is greater than 2H.
3, acrylate resin of the present invention is as the important component of water-dilutable acrylate resin coating, this paint coatings good springiness.
4, this acrylate resin and water-dilutable acrylate resin coating solvent resistance are good, and anti-methylethylketone is greater than 120 times, and 1 grade of water logging in 48 hours test is had good protective action to being coated with the surface.
5, this water-dilutable acrylate resin coating is of many uses, is applicable to the application of members such as heat-resisting ground, metal, glass, timber, plastics, cardboard, pottery.
Four, embodiment
For better understanding the present invention, those skilled in the art can implement technical solution of the present invention, the present invention are done further specifying below in conjunction with embodiment.
Embodiment 1:
A kind of acrylate resin, its prescription consists of: methyl cellosolve 12 grams, (methyl) vinylformic acid 14 grams, methyl methacrylate 10 grams, ethyl propenoate 33 grams, vinylbenzene 2 grams, (methyl) crylic acid hydroxy ester-caprolactone compound 17 grams, n-dodecyl mercaptan 0.2 gram, hydrocarbon mixture solution 5 grams.
Wherein, the composition and the prescription of (methyl) crylic acid hydroxy ester-caprolactone compound are: (methyl) vinylformic acid hydroxy methyl 57.5 grams, 6-caprolactone 42 grams, tertiary butylated hydroquinone 0.2 gram, tosic acid 0.3 gram.
Wherein, hydrocarbon mixture solution is 60% the tertiary butyl-superoxide and the mixing solutions of 2-ethylhexanoate.
The preparation method of this acrylate resin:
A, (methyl) vinylformic acid that takes by weighing above-mentioned formula ratio, methyl methacrylate, ethyl propenoate, vinylbenzene and (methyl) crylic acid hydroxy ester-caprolactone compound evenly make reactant A;
B, the n-dodecyl mercaptan that takes by weighing formula ratio join in the reactant A, make mixture B;
C, take by weighing the methyl cellosolve of formula ratio, drop into and be equipped with in the reactor of rare gas element conduit, agitator, refrigerating unit and heating unit, be heated to 120 ℃, with 4 hours dropping mixture B;
D, with the hydrocarbon mixture solution that dripped formula ratio in 5 hours, drip the back and under 120 ℃ of conditions, stirred 2 hours, make acrylate resin.
Wherein, the preparation process of (methyl) crylic acid hydroxy ester-caprolactone compound is:
A, (methyl) the vinylformic acid hydroxy methyl and the 6-caprolactone that take by weighing formula ratio fully stir, and mix;
Add the tertiary butylated hydroquinone and the tosic acid of formula ratio in b, the mixture that makes in a step, make reactant C;
C, reactant C was heated to 130 ℃ with 3 hours makes (methyl) crylic acid hydroxy ester-caprolactone compound.
Embodiment 2:
A kind of acrylate resin, its prescription consists of: n-butoxy ethanol 12 grams, (methyl) vinylformic acid 14 grams, Jia Jibingxisuanyizhi 5 grams, methacrylic heptyl heptylate 5 grams, methyl acrylate 10 grams, butyl acrylate 23 grams, vinylbenzene 2 grams, (methyl) crylic acid hydroxy ester-caprolactone compound 17 grams, n-dodecyl mercaptan 0.2 gram, hydrocarbon mixture solution 5 grams.
Wherein, the composition and the prescription of (methyl) crylic acid hydroxy ester-caprolactone compound are: (methyl) vinylformic acid hydroxy methyl 20 grams, (methyl) Hydroxyethyl Acrylate 20 grams, (methyl) vinylformic acid hydroxy propyl ester 17.5 grams, 6-caprolactone 42 grams, tertiary butylated hydroquinone 0.2 gram, tosic acid 0.3 gram.
Wherein, hydrocarbon mixture solution is 60% the tertiary butyl-superoxide and the mixing solutions of 2-ethylhexanoate.
The preparation method of this acrylate resin:
A, take by weighing (methyl) vinylformic acid, Jia Jibingxisuanyizhi, methacrylic heptyl heptylate, methyl acrylate, butyl acrylate, vinylbenzene and (methyl) crylic acid hydroxy ester-caprolactone compound by predetermined formulation and make reactant A;
B, the n-dodecyl mercaptan that takes by weighing formula ratio join in the reactant A, make mixture B;
C, take by weighing the n-butoxy ethanol of formula ratio, drop into and be equipped with in the reactor of rare gas element conduit, agitator, refrigerating unit and heating unit, be heated to 125 ℃, with 4 hours dropping mixture B;
D, with the hydrocarbon mixture solution that dripped formula ratio in 5 hours, drip the back and under 125 ℃ of conditions, stirred 2.5 hours, make acrylate resin.
Wherein, the preparation process of (methyl) crylic acid hydroxy ester-caprolactone compound is:
A, (methyl) vinylformic acid hydroxy methyl, (methyl) Hydroxyethyl Acrylate, (methyl) vinylformic acid hydroxy propyl ester and the 6-caprolactone that take by weighing formula ratio fully stir, and mix;
B, in the mixture in a step, add the tertiary butylated hydroquinone and the tosic acid of formula ratio, make reactant C;
C, reactant C was heated to 135 ℃ with 3 hours makes (methyl) crylic acid hydroxy ester-caprolactone compound.
Embodiment 3:
A kind of acrylate resin, its prescription consists of: n-butoxy ethanol 15 grams, (methyl) vinylformic acid 16 grams, methyl methacrylate 12 grams, methyl acrylate 20, ethyl propenoate 16 grams, vinylbenzene 3 grams, (methyl) crylic acid hydroxy ester-caprolactone compound 20 grams, n-dodecyl mercaptan 0.25 gram, hydrocarbon mixture solution 7 grams.
Wherein, the composition and the prescription of (methyl) crylic acid hydroxy ester-caprolactone compound are: (methyl) vinylformic acid hydroxy methyl 50 grams, (methyl) Hydroxyethyl Acrylate 20 grams, 6-caprolactone 30 grams.
Wherein, hydrocarbon mixture solution is 60% the tertiary butyl-superoxide and the mixing solutions of 2-ethylhexanoate.
The preparation method of this acrylate resin:
A, take by weighing (methyl) vinylformic acid, methyl methacrylate, methyl acrylate, ethyl propenoate, vinylbenzene and (methyl) crylic acid hydroxy ester-caprolactone compound by predetermined formulation and make reactant A;
B, the n-dodecyl mercaptan that takes by weighing formula ratio join in the reactant A, make mixture B;
C, take by weighing the n-butoxy ethanol of formula ratio, drop into and be equipped with in the reactor of rare gas element conduit, agitator, refrigerating unit and heating unit, be heated to 140 ℃, with 4 hours dropping mixture B;
D, with the hydrocarbon mixture solution that dripped formula ratio in 5 hours, drip the back and under 140 ℃ of conditions, stirred 1 hour, make acrylate resin.
Wherein, the preparation process of (methyl) crylic acid hydroxy ester-caprolactone compound is:
A, (methyl) vinylformic acid hydroxy methyl, (methyl) Hydroxyethyl Acrylate and the 6-caprolactone that take by weighing formula ratio fully stir, and mix;
B, mixture was heated to 150 ℃ with 3 hours makes (methyl) crylic acid hydroxy ester-caprolactone compound.
Embodiment 4:
A kind of acrylate resin, its prescription consists of: methyl cellosolve 10 grams, ethoxy ethanol 5 grams, (methyl) vinylformic acid 16 grams, Jia Jibingxisuanyizhi 8 grams, methacrylic acid pentyl ester 4 grams, propyl acrylate 20 grams, butyl acrylate 16 grams, vinylbenzene 3 grams, (methyl) crylic acid hydroxy ester-caprolactone compound 20 grams, carbon atom is alkyl sulfhydryl 0.25 gram of 1-11, hydrocarbon mixture solution 7 grams.
Wherein, the composition and the prescription of (methyl) crylic acid hydroxy ester-caprolactone compound are: (methyl) vinylformic acid hydroxy methyl 70 grams, 6-caprolactone 30 grams.
Wherein, hydrocarbon mixture solution is 60% the tertiary butyl-superoxide and the mixing solutions of 2-ethylhexanoate.
The preparation method of this acrylate resin:
A, take by weighing (methyl) vinylformic acid, Jia Jibingxisuanyizhi, methacrylic acid pentyl ester, propyl acrylate, butyl acrylate, vinylbenzene and (methyl) crylic acid hydroxy ester-caprolactone compound by predetermined formulation and make reactant A;
B, the carbon atom that takes by weighing formula ratio are that the alkyl sulfhydryl of 1-11 joins in the reactant A, make mixture B;
C, take by weighing the methyl cellosolve of formula ratio, drop into and be equipped with in the reactor of rare gas element conduit, agitator, refrigerating unit and heating unit, be heated to 100 ℃, with 4 hours dropping mixture B;
D, with the hydrocarbon mixture solution that dripped formula ratio in 5 hours, drip the back and under 100 ℃ of conditions, stirred 3 hours, make acrylate resin.
Wherein, the preparation process of (methyl) crylic acid hydroxy ester-caprolactone compound is:
A, (methyl) the vinylformic acid hydroxy methyl and the 6-caprolactone that take by weighing formula ratio fully stir, and mix;
B, mixture was heated to 150 ℃ with 3 hours makes (methyl) crylic acid hydroxy ester-caprolactone compound.
Embodiment 5:
A kind of acrylate resin, its prescription consists of: methyl cellosolve 8 grams, (methyl) vinylformic acid 15 grams, N-Hexyl methacrylate 15 grams, butyl acrylate 35 grams, vinylbenzene 3 grams, (methyl) crylic acid hydroxy ester-caprolactone compound 20 grams, n-dodecyl mercaptan 0.5 gram, hydrocarbon mixture solution 3.5 grams.
Wherein, the composition and the prescription of (methyl) crylic acid hydroxy ester-caprolactone compound are: (methyl) vinylformic acid hydroxy methyl 44 grams, 6-caprolactone 55 grams, tertiary butylated hydroquinone 0.5 gram, tosic acid 0.5 gram.
Wherein, hydrocarbon mixture solution is 60% the tertiary butyl-superoxide and the mixing solutions of 2-ethylhexanoate.
The preparation method of this acrylate resin:
A, take by weighing (methyl) vinylformic acid, N-Hexyl methacrylate, butyl acrylate, vinylbenzene and (methyl) crylic acid hydroxy ester-caprolactone compound by predetermined formulation and make reactant A;
B, the n-dodecyl mercaptan that takes by weighing formula ratio join in the reactant A, make mixture B;
C, take by weighing the methyl cellosolve of formula ratio, drop into and be equipped with in the reactor of rare gas element conduit, agitator, refrigerating unit and heating unit, be heated to 130 ℃, with 4 hours dropping mixture B;
D, with the hydrocarbon mixture solution that dripped formula ratio in 5 hours, drip the back and under 130 ℃ of conditions, stirred 3 hours, make acrylate resin.
Wherein, the preparation process of (methyl) crylic acid hydroxy ester-caprolactone compound is:
A, (methyl) the vinylformic acid hydroxy methyl and the 6-caprolactone that take by weighing formula ratio fully stir, and mix;
B, in the mixture in a step, add the tertiary butylated hydroquinone and the tosic acid of formula ratio, make reactant C;
C, reactant C was heated to 140 ℃ with 3 hours makes (methyl) crylic acid hydroxy ester-caprolactone compound.
Embodiment 6:
A kind of acrylate resin, its prescription consists of: ethoxy ethanol 8 grams, (methyl) vinylformic acid 15 grams, propyl methacrylate 15 grams, butyl acrylate 35 grams, vinylbenzene 3 grams, (methyl) crylic acid hydroxy ester-caprolactone compound 20 grams, carbon atom is alkyl sulfhydryl 0.5 gram of 1-11, hydrocarbon mixture solution 3.5 grams.
Wherein, the composition and the prescription of (methyl) crylic acid hydroxy ester-caprolactone compound are: (methyl) vinylformic acid hydroxy propyl ester 44 grams, 6-caprolactone 55 grams, tertiary butylated hydroquinone 0.5 gram, tosic acid 0.5 gram.
Wherein, hydrocarbon mixture solution is 60% the tertiary butyl-superoxide and the mixing solutions of 2-ethylhexanoate.
The preparation method of this acrylate resin:
A, take by weighing (methyl) vinylformic acid, propyl methacrylate, butyl acrylate, vinylbenzene and (methyl) crylic acid hydroxy ester-caprolactone compound by predetermined formulation and make reactant A;
B, the carbon atom that takes by weighing formula ratio are that the alkyl sulfhydryl of 1-11 joins in the reactant A, make mixture B;
C, take by weighing the ethoxy ethanol of formula ratio, drop into and be equipped with in the reactor of rare gas element conduit, agitator, refrigerating unit and heating unit, be heated to 120 ℃, with 4 hours dropping mixture B;
D, with the hydrocarbon mixture solution that dripped formula ratio in 5 hours, drip the back and under 120 ℃ of conditions, stirred 2 hours, make acrylate resin.
Wherein, the preparation process of (methyl) crylic acid hydroxy ester-caprolactone compound is:
A, (methyl) the vinylformic acid hydroxy propyl ester and the 6-caprolactone that take by weighing formula ratio fully stir, and mix;
B, in the mixture in a step, add the tertiary butylated hydroquinone and the tosic acid of formula ratio, make reactant C;
C, reactant C was heated to 125 ℃ with 3 hours makes (methyl) crylic acid hydroxy ester-caprolactone compound.
Embodiment 7:
A kind of acrylate resin, its prescription consists of: methyl cellosolve 10 grams, n-butoxy ethanol 7 grams, (methyl) vinylformic acid 10 grams, N-Hexyl methacrylate 5 grams, butyl acrylate 27 grams, vinylbenzene 5 grams, (methyl) crylic acid hydroxy ester-caprolactone compound 25 grams, n-dodecyl mercaptan 0.5 gram, carbon atom are alkyl sulfhydryl 0.5 gram of 1-11, hydrocarbon mixture solution 10 grams.
Wherein, the composition and the prescription of (methyl) crylic acid hydroxy ester-caprolactone compound are: (methyl) vinylformic acid hydroxy methyl 20 grams, (methyl) Hydroxyethyl Acrylate 22 grams, 6-caprolactone 54 grams, tertiary butylated hydroquinone 2 grams, tosic acid 2 grams.
Wherein, hydrocarbon mixture solution is 60% the tertiary butyl-superoxide and the mixing solutions of 2-ethylhexanoate.
The preparation method of this acrylate resin:
A, take by weighing (methyl) vinylformic acid, N-Hexyl methacrylate, butyl acrylate, vinylbenzene and (methyl) crylic acid hydroxy ester-caprolactone compound by predetermined formulation and make reactant A;
B, the n-dodecyl mercaptan that takes by weighing formula ratio and carbon atom are that the alkyl sulfhydryl of 1-11 joins in the reactant A, make mixture B;
C, the methyl cellosolve that takes by weighing formula ratio and n-butoxy ethanol dropped into and are equipped with in the reactor of rare gas element conduit, agitator, refrigerating unit and heating unit, are heated to 140 ℃, with 4 hours dropping mixture B;
D, with the hydrocarbon mixture solution that dripped formula ratio in 5 hours, drip the back and under 140 ℃ of conditions, stirred 1.5 hours, make acrylate resin.
Wherein, the preparation process of (methyl) crylic acid hydroxy ester-caprolactone compound is:
A, (methyl) vinylformic acid hydroxy methyl, (methyl) Hydroxyethyl Acrylate and the 6-caprolactone that take by weighing formula ratio fully stir, and mix;
B, in the mixture in a step, add the tertiary butylated hydroquinone and the tosic acid of formula ratio, make reactant C;
C, reactant C was heated to 140 ℃ with 3 hours makes (methyl) crylic acid hydroxy ester-caprolactone compound.
Embodiment 8:
A kind of acrylate resin, its prescription consists of: propoxy-ethanol 17 grams, (methyl) vinylformic acid 10 grams, Jia Jibingxisuanyizhi 5 grams, butyl acrylate 27 grams, vinylbenzene 5 grams, (methyl) crylic acid hydroxy ester-caprolactone compound 25 grams, n-dodecyl mercaptan 1 gram, hydrocarbon mixture solution 10 grams.
Wherein, the composition and the prescription of (methyl) crylic acid hydroxy ester-caprolactone compound are: (methyl) vinylformic acid hydroxy methyl 57.5 grams, 6-caprolactone 42 grams, tertiary butylated hydroquinone 0.2 gram, tosic acid 0.3 gram.
Wherein, hydrocarbon mixture solution is 60% the tertiary butyl-superoxide and the mixing solutions of 2-ethylhexanoate.
The preparation method of this acrylate resin:
A, take by weighing (methyl) vinylformic acid, Jia Jibingxisuanyizhi, butyl acrylate, vinylbenzene and (methyl) crylic acid hydroxy ester-caprolactone compound by predetermined formulation and make reactant A;
B, the n-dodecyl mercaptan that takes by weighing formula ratio join in the reactant A, make mixture B;
C, take by weighing the propoxy-ethanol of formula ratio, drop into and be equipped with in the reactor of rare gas element conduit, agitator, refrigerating unit and heating unit, be heated to 135 ℃, with 4 hours dropping mixture B;
D, with the hydrocarbon mixture solution that dripped formula ratio in 5 hours, drip the back and under 135 ℃ of conditions, stirred 2.5 hours, make acrylate resin.
Wherein, the preparation process of (methyl) crylic acid hydroxy ester-caprolactone compound is:
A, (methyl) the vinylformic acid hydroxy methyl and the 6-caprolactone that take by weighing formula ratio fully stir, and mix;
B, in the mixture in a step, add the tertiary butylated hydroquinone and the tosic acid of formula ratio, make reactant C;
C, reactant C was heated to 128 ℃ with 3 hours makes (methyl) crylic acid hydroxy ester-caprolactone compound.
Embodiment 9:
A kind of acrylate resin, its prescription consists of: methyl cellosolve 10 grams, (methyl) vinylformic acid 20 grams, methyl methacrylate 7 grams, methyl acrylate 50 grams, (methyl) crylic acid hydroxy ester-caprolactone compound 12 grams, hydrocarbon mixture solution 1 gram.
Wherein, the composition and the prescription of (methyl) crylic acid hydroxy ester-caprolactone compound are: (methyl) vinylformic acid hydroxy methyl 44 grams, 6-caprolactone 55 grams, tertiary butylated hydroquinone 0.5 gram, tosic acid 0.5 gram.
Wherein, hydrocarbon mixture solution is 60% the tertiary butyl-superoxide and the mixing solutions of 2-ethylhexanoate.
The preparation method of this acrylate resin:
A, take by weighing (methyl) vinylformic acid, methyl methacrylate, methyl acrylate and (methyl) crylic acid hydroxy ester-caprolactone compound by predetermined formulation and make reactant A;
B, take by weighing the methyl cellosolve of formula ratio, drop into and be equipped with in the reactor of rare gas element conduit, agitator, refrigerating unit and heating unit, be heated to 150 ℃, with 4 hours dropwise reaction thing A;
C, with the hydrocarbon mixture solution that dripped formula ratio in 5 hours, drip the back and under 150 ℃ of conditions, stirred 1 hour, make acrylate resin.
Wherein, the preparation process of (methyl) crylic acid hydroxy ester-caprolactone compound is:
A, (methyl) the vinylformic acid hydroxy methyl and the 6-caprolactone that take by weighing formula ratio fully stir, and mix;
B, in the mixture in a step, add the tertiary butylated hydroquinone and the tosic acid of formula ratio, make reactant C;
C, reactant C was heated to 100 ℃ with 3 hours makes (methyl) crylic acid hydroxy ester-caprolactone compound.
Embodiment 10:
A kind of acrylate resin, its prescription consists of: methyl cellosolve 12 grams, (methyl) vinylformic acid 15 grams, Octyl methacrylate 12 grams, butyl acrylate 20 grams, vinylbenzene 5 grams, (methyl) crylic acid hydroxy ester-caprolactone compound 25 grams, n-dodecyl mercaptan 1 gram, hydrocarbon mixture solution 10 grams.
Wherein, the composition and the prescription of (methyl) crylic acid hydroxy ester-caprolactone compound are: (methyl) vinylformic acid hydroxy propyl ester 57.5 grams, 6-caprolactone 42 grams, tertiary butylated hydroquinone 0.2 gram, tosic acid 0.3 gram.
Wherein, hydrocarbon mixture solution is 60% the tertiary butyl-superoxide and the mixing solutions of 2-ethylhexanoate.
The preparation method of this acrylate resin:
A, take by weighing (methyl) vinylformic acid, Octyl methacrylate, butyl acrylate, vinylbenzene and (methyl) crylic acid hydroxy ester-caprolactone compound by predetermined formulation and make reactant A;
B, the n-dodecyl mercaptan that takes by weighing formula ratio join in the reactant A, make mixture B;
C, take by weighing the methyl cellosolve of formula ratio, drop into and be equipped with in the reactor of rare gas element conduit, agitator, refrigerating unit and heating unit, be heated to 135 ℃, with 4 hours dropping mixture B;
D, with the hydrocarbon mixture solution that dripped formula ratio in 5 hours, drip the back and under 135 ℃ of conditions, stirred 2 hours, make acrylate resin.
Wherein, the preparation process of (methyl) crylic acid hydroxy ester-caprolactone compound is:
A, (methyl) the vinylformic acid hydroxy propyl ester and the 6-caprolactone that take by weighing formula ratio fully stir, and mix;
B, in the mixture in a step, add the tertiary butylated hydroquinone and the tosic acid of formula ratio, make reactant C;
C, reactant C was heated to 140 ℃ with 3 hours makes (methyl) crylic acid hydroxy ester-caprolactone compound.
Embodiment 11:
A kind of acrylate resin, its prescription consists of: n-butoxy ethanol 400 grams, (methyl) vinylformic acid 430 grams, methyl methacrylate 330 grams, methyl acrylate 1000 grams, vinylbenzene 90 grams, (methyl) crylic acid hydroxy ester-caprolactone compound 550 grams, n-dodecyl mercaptan 6 grams, hydrocarbon mixture solution 170 grams.
Wherein, the composition and the prescription of (methyl) crylic acid hydroxy ester-caprolactone compound are: (methyl) vinylformic acid hydroxy methyl 320 grams, 6-caprolactone 235 grams, tertiary butylated hydroquinone 0.5 gram, tosic acid 1.1 grams.
Wherein, hydrocarbon mixture solution is 60% the tertiary butyl-superoxide and the mixing solutions of 2-ethylhexanoate.
The preparation method of this acrylate resin:
A, take by weighing (methyl) vinylformic acid, methyl methacrylate, methyl acrylate, vinylbenzene and (methyl) crylic acid hydroxy ester-caprolactone compound by predetermined formulation and make reactant A;
B, the n-dodecyl mercaptan that takes by weighing formula ratio join in the reactant A, make mixture B;
C, take by weighing the n-butoxy ethanol of formula ratio, drop into and be equipped with in the reactor of rare gas element conduit, agitator, refrigerating unit and heating unit, be heated to 130 ℃, with 4 hours dropping mixture B;
D, with the hydrocarbon mixture solution that dripped formula ratio in 5 hours, drip the back and under 130 ℃ of conditions, stirred 2 hours, make acrylate resin.
Wherein, the preparation process of (methyl) crylic acid hydroxy ester-caprolactone compound is:
A, (methyl) the vinylformic acid hydroxy methyl and the 6-caprolactone that take by weighing formula ratio fully stir, and mix;
B, in the mixture in a step, add the tertiary butylated hydroquinone and the tosic acid of formula ratio, make reactant C;
C, reactant C was heated to 135 ℃ with 3 hours makes (methyl) crylic acid hydroxy ester-caprolactone compound.
Embodiment 12:
A kind of acrylate resin, its prescription consists of: ethoxy ethanol 150 grams, n-butoxy ethanol 250 grams, (methyl) vinylformic acid 430 grams, methyl methacrylate 100 grams, propyl methacrylate 100 grams, methacrylic heptyl heptylate 130 grams, butyl acrylate 1000 grams, vinylbenzene 90 grams, (methyl) crylic acid hydroxy ester-caprolactone compound 550 grams, n-dodecyl mercaptan 6 grams, hydrocarbon mixture solution 170 grams.
Wherein, the composition and the prescription of (methyl) crylic acid hydroxy ester-caprolactone compound are: (methyl) vinylformic acid hydroxy methyl 150 grams, (methyl) Hydroxyethyl Acrylate 170 grams, 6-caprolactone 235 grams, tertiary butylated hydroquinone 0.5 gram, tosic acid 1.1 grams.
Wherein, hydrocarbon mixture solution is 60% the tertiary butyl-superoxide and the mixing solutions of 2-ethylhexanoate.
The preparation method of this acrylate resin:
A, take by weighing (methyl) vinylformic acid, methyl methacrylate, propyl methacrylate, methacrylic heptyl heptylate, butyl acrylate, vinylbenzene and (methyl) crylic acid hydroxy ester-caprolactone compound by predetermined formulation and make reactant A;
B, the n-dodecyl mercaptan that takes by weighing formula ratio join in the reactant A, make mixture B;
C, the ethoxy ethanol that takes by weighing formula ratio, n-butoxy ethanol dropped into and are equipped with in the reactor of rare gas element conduit, agitator, refrigerating unit and heating unit, are heated to 130 ℃, with 4 hours dropping mixture B;
D, with the hydrocarbon mixture solution that dripped formula ratio in 5 hours, drip the back and under 130 ℃ of conditions, stirred 2.5 hours, make acrylate resin.
Wherein, the preparation process of (methyl) crylic acid hydroxy ester-caprolactone compound is:
A, (methyl) vinylformic acid hydroxy methyl, (methyl) Hydroxyethyl Acrylate and the 6-caprolactone that take by weighing formula ratio fully stir, and mix;
B, in the mixture in a step, add the tertiary butylated hydroquinone and the tosic acid of formula ratio, make reactant C;
C, reactant C was heated to 130 ℃ with 3 hours makes (methyl) crylic acid hydroxy ester-caprolactone compound.
Embodiment 13:
A kind of acrylate resin, its prescription consists of: n-butoxy ethanol 450 grams, (methyl) vinylformic acid 480 grams, propyl methacrylate 350 grams, propyl acrylate 1200 grams, vinylbenzene 100 grams, (methyl) crylic acid hydroxy ester-caprolactone compound 590 grams, n-dodecyl mercaptan 8 grams, hydrocarbon mixture solution 180 grams.
Wherein, the composition and the prescription of (methyl) crylic acid hydroxy ester-caprolactone compound are: (methyl) vinylformic acid hydroxy methyl 350 grams, 6-caprolactone 260 grams, tertiary butylated hydroquinone 0.7 gram, tosic acid 1.5 grams.
Wherein, hydrocarbon mixture solution is 60% the tertiary butyl-superoxide and the mixing solutions of 2-ethylhexanoate.
The preparation method of this acrylate resin:
A, take by weighing (methyl) vinylformic acid, propyl methacrylate, propyl acrylate, vinylbenzene and (methyl) crylic acid hydroxy ester-caprolactone compound by predetermined formulation and make reactant A;
B, the n-dodecyl mercaptan that takes by weighing formula ratio join in the reactant A, make mixture B;
C, take by weighing the n-butoxy ethanol of formula ratio, drop into and be equipped with in the reactor of rare gas element conduit, agitator, refrigerating unit and heating unit, be heated to 138 ℃, with 4 hours dropping mixture B;
D, with the hydrocarbon mixture solution that dripped formula ratio in 5 hours, drip the back and under 138 ℃ of conditions, stirred 2 hours, make acrylate resin.
Wherein, the preparation process of (methyl) crylic acid hydroxy ester-caprolactone compound is:
A, (methyl) the vinylformic acid hydroxy methyl and the 6-caprolactone that take by weighing formula ratio fully stir, and mix;
B, in the mixture in a step, add the tertiary butylated hydroquinone and the tosic acid of formula ratio, make reactant C;
C, reactant C was heated to 145 ℃ with 3 hours makes (methyl) crylic acid hydroxy ester-caprolactone compound.
Embodiment 14:
A kind of acrylate resin, its prescription consists of: methyl cellosolve 150 grams, propoxy-ethanol 100 grams, n-butoxy ethanol 200 grams, (methyl) vinylformic acid 480 grams, propyl methacrylate 150 grams, methacrylic acid pentyl ester 100 grams, N-Hexyl methacrylate 100 grams, ethyl propenoate 500 grams, propyl acrylate 300 grams, butyl acrylate 400 grams, vinylbenzene 100 grams, (methyl) crylic acid hydroxy ester-caprolactone compound 590 grams, n-dodecyl mercaptan 8 grams, hydrocarbon mixture solution 180 grams.
Wherein, the composition and the prescription of (methyl) crylic acid hydroxy ester-caprolactone compound are: (methyl) vinylformic acid hydroxy methyl 100 grams, (methyl) Hydroxyethyl Acrylate 100 grams, (methyl) vinylformic acid hydroxy propyl ester 150 grams, 6-caprolactone 260 grams, tertiary butylated hydroquinone 0.7 gram, tosic acid 1.5 grams.
Wherein, hydrocarbon mixture solution is 60% the tertiary butyl-superoxide and the mixing solutions of 2-ethylhexanoate.
The preparation method of this acrylate resin:
A, take by weighing (methyl) vinylformic acid, propyl methacrylate, methacrylic acid pentyl ester, N-Hexyl methacrylate, ethyl propenoate, propyl acrylate, butyl acrylate, vinylbenzene and (methyl) crylic acid hydroxy ester-caprolactone compound by predetermined formulation and make reactant A;
B, the n-dodecyl mercaptan that takes by weighing formula ratio join in the reactant A, make mixture B;
C, the methyl cellosolve that takes by weighing formula ratio, propoxy-ethanol, n-butoxy ethanol dropped into and are equipped with in the reactor of rare gas element conduit, agitator, refrigerating unit and heating unit, are heated to 125 ℃, with 4 hours dropping mixture B;
D, with the hydrocarbon mixture solution that dripped formula ratio in 5 hours, drip the back and under 125 ℃ of conditions, stirred 2.5 hours, make acrylate resin.
Wherein, the preparation process of (methyl) crylic acid hydroxy ester-caprolactone compound is:
A, (methyl) vinylformic acid hydroxy methyl, (methyl) Hydroxyethyl Acrylate, (methyl) vinylformic acid hydroxy propyl ester and the 6-caprolactone that take by weighing formula ratio fully stir, and mix;
B, in the mixture in a step, add the tertiary butylated hydroquinone and the tosic acid of formula ratio, make reactant C;
C, reactant C was heated to 135 ℃ with 3 hours makes (methyl) crylic acid hydroxy ester-caprolactone compound.
Claims (9)
1. an acrylate resin is characterized in that, by weight percentage, and by constituting following the composition:
2. a kind of acrylate resin according to claim 1 is characterized in that, described alkoxyethanol is at least a in methyl cellosolve, ethoxy ethanol, propoxy-ethanol, the n-butoxy ethanol.
3. a kind of acrylate resin according to claim 1, it is characterized in that described methacrylic ester is that methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, carbonatoms are at least a in the ester class methacrylic compound of 5-10.
4. a kind of acrylate resin according to claim 1 is characterized in that, described acrylate is that methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, carbonatoms are at least a in the ester class acrylic compound of 5-10.
5. a kind of acrylate resin according to claim 1, it is characterized in that, described (methyl) crylic acid hydroxy ester-caprolactone compound is that (methyl) crylic acid hydroxy ester of 42～70%, 30～55% 6-caprolactone, 0～2% tertiary butylated hydroquinone and 0～2% tosic acid mix by weight percentage, and described (methyl) crylic acid hydroxy ester is at least a in (methyl) vinylformic acid hydroxy methyl, (methyl) Hydroxyethyl Acrylate, (methyl) vinylformic acid hydroxy propyl ester.
6. a kind of acrylate resin according to claim 1 is characterized in that, described alkyl sulfhydryl is that n-dodecyl mercaptan is or/and carbon atom is the alkyl sulfhydryl of 1-11.
7. a kind of acrylate resin according to claim 1 is characterized in that, described hydrocarbon mixture solution is 60～80% the tertiary butyl-superoxide and the mixing solutions of 2-ethylhexanoate.
8. according to the preparation method of each described a kind of acrylate resin in the claim 1 to 7, it is characterized in that preparation process is:
A, take by weighing (methyl) vinylformic acid, methacrylic ester, acrylate, vinylbenzene and (methyl) crylic acid hydroxy ester-caprolactone compound by predetermined formulation and make reactant A;
B, the alkyl sulfhydryl that takes by weighing formula ratio join in the reactant A, make mixture B;
C, take by weighing the alkoxyethanol of formula ratio, drop into and be equipped with in the reactor of rare gas element conduit, agitator, refrigerating unit and heating unit, be heated to 100～150 ℃, with 4 hours dropping mixture B;
D, with the hydrocarbon mixture solution that dripped formula ratio in 5 hours, drip the back and under 100～150 ℃ of conditions, stirred 1～3 hour, make acrylate resin.
9. the preparation method of a kind of acrylate resin according to claim 8 is characterized in that, the preparation process of described (methyl) crylic acid hydroxy ester-caprolactone compound is:
A, (methyl) crylic acid hydroxy ester and the 6-caprolactone that take by weighing formula ratio fully stir, and mix;
B, in the mixture in a step, add the tertiary butylated hydroquinone and the tosic acid of formula ratio, make reactant C;
C, reactant C was heated to 120～150 ℃ with 3 hours makes (methyl) crylic acid hydroxy ester-caprolactone compound.
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| CN2011100393948A CN102260364A (en) | 2011-02-17 | 2011-02-17 | Acrylate resin and preparation method thereof |
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| CN2011100393948A CN102260364A (en) | 2011-02-17 | 2011-02-17 | Acrylate resin and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110804124A (en) * | 2019-11-06 | 2020-02-18 | 广昌立骅科技股份有限公司 | High-hardness and high-toughness acrylic resin and preparation method thereof |
| CN112457443A (en) * | 2020-11-25 | 2021-03-09 | 武汉双虎涂料有限公司 | Acrylic resin for automobile varnish and preparation method thereof |
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| US6130286A (en) * | 1998-12-18 | 2000-10-10 | Ppg Industries Ohio, Inc. | Fast drying clear coat composition with low volatile organic content |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110804124A (en) * | 2019-11-06 | 2020-02-18 | 广昌立骅科技股份有限公司 | High-hardness and high-toughness acrylic resin and preparation method thereof |
| CN112457443A (en) * | 2020-11-25 | 2021-03-09 | 武汉双虎涂料有限公司 | Acrylic resin for automobile varnish and preparation method thereof |
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