CN115926059A - Modified copolymerized acrylic resin and preparation method thereof, paint and film product - Google Patents
Modified copolymerized acrylic resin and preparation method thereof, paint and film product Download PDFInfo
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- CN115926059A CN115926059A CN202211435221.2A CN202211435221A CN115926059A CN 115926059 A CN115926059 A CN 115926059A CN 202211435221 A CN202211435221 A CN 202211435221A CN 115926059 A CN115926059 A CN 115926059A
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Abstract
The invention provides a modified copolymerized acrylic resin and a preparation method thereof, a coating and a film product, wherein the modified copolymerized acrylic resin is prepared from the following raw materials: the modified polymer, a comonomer, a hydroxyl functional monomer, an initiator and a first solvent; the comonomer comprises an acrylic monomer; wherein, the preparation raw materials of the modified polymer comprise: polyamide, aliphatic dihydric alcohol, aliphatic polyhydric alcohol A, maleic anhydride, dibasic acid and a second solvent; one molecule of the aliphatic polyhydric alcohol A contains three or more hydroxyl groups; the polyamide is prepared from the following raw materials: the solvent comprises alicyclic diamine, cyclic anhydride, functional assistant and third solvent, wherein the cyclic anhydride contains at least one structure of naphthenic base and aromatic base. When the modified copolymerized acrylic resin is applied to preparing a coating, the hardness of the coating after film forming can be improved, and the wear resistance is further improved.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a modified copolymerized acrylic resin, a preparation method thereof, a coating and a coating product.
Background
With the development of economy, automobiles enter thousands of households, the automobile industry also becomes the pillar industry of national economy, the status is more and more important, and the automobile coating industry also develops rapidly.
The automobile is taken as an important outdoor vehicle, and inevitably cleaned in the using process, and a paint film of the automobile is inevitably subjected to friction cleaning in the cleaning process, however, after repeated cleaning of the paint film formed by the traditional automobile coating, tiny scratches often appear, the aesthetic degree of the automobile is reduced, and more importantly, the existence of the scratches causes the reduction of the protective performance of the paint film on automobile parts, and the service life of the automobile is influenced.
Therefore, the conventional techniques still need to be improved.
Disclosure of Invention
Based on the modified copolymerized acrylic resin, the invention provides a modified copolymerized acrylic resin, a preparation method thereof, a coating and a coating product, and aims to improve the wear resistance of the coating after film formation.
The technical scheme of the invention is as follows.
The invention provides a modified copolymerized acrylic resin, which is prepared from the following raw materials: the modified polymer, a comonomer, a hydroxyl functional monomer, an initiator and a first solvent; the comonomer comprises an acrylic monomer;
wherein, the preparation raw materials of the modified polymer comprise: polyamide, aliphatic dihydric alcohol, aliphatic polyhydric alcohol A, maleic anhydride, dibasic acid and a second solvent; one molecule of the aliphatic polyhydric alcohol A contains three or more hydroxyl groups;
the polyamide is prepared from the following raw materials: the solvent comprises alicyclic diamine, cyclic anhydride, functional assistant and third solvent, wherein the cyclic anhydride contains at least one structure of naphthenic base and aromatic base.
The raw materials of the modified copolymerized acrylic resin comprise specific substances, wherein alicyclic diamine and cyclic anhydride are used as preparation raw materials to prepare polyamide, amide bond is introduced to improve the wear resistance of the resin, and the polyamide is further used as a raw material to perform polycondensation with aliphatic diol, aliphatic polyol A, maleic anhydride and dibasic acid; the modified polymer, the comonomer and the hydroxyl functional monomer are further polymerized under the action of an initiator, a propylene polymer chain segment is introduced on the modified polymer, and meanwhile, a hydroxyl functional group is introduced through the hydroxyl functional monomer to provide a crosslinking site and improve the crosslinking degree of the resin after curing.
In some of the embodiments, the modified copolymerized acrylic resin satisfies at least one of the following conditions (1) to (2):
(1) The modified copolymerized acrylic resin is prepared from the following raw materials: 31% -42% of the modified polymer, 13% -18.5% of the comonomer, 19% -27% of the hydroxyl functional monomer, 0.5% -1.5% of the initiator and 14% -39% of the first solvent;
the hardness of the resin after film forming is further improved by further adjusting the proportion of the preparation raw materials.
(2) The modified copolymerized acrylic resin is a multi-branched polymer.
In some of these embodiments, the comonomers include a first comonomer and a second comonomer, the first comonomer being represented by formula (1):
R 1 selected from C1-15 alkane;
optionally, the first comonomer comprises at least one of acrylic acid and methacrylic acid;
the second comonomer comprises at least one of a compound shown in a formula (2) and an aromatic group-containing vinyl monomer:
wherein R is 3 R is any one selected from the group consisting of a C1-15 chain alkyl group and a C3-15 cycloalkyl group 2 Selected from a C1-5 chain alkyl group;
optionally, the compound of formula (2) comprises at least one of methyl acrylate, n-butyl acrylate, isobutyl acrylate, isobornyl acrylate, isooctyl acrylate, dodecyl acrylate, methyl methacrylate, n-butyl methacrylate, isobutyl acrylate, isobornyl methacrylate, isooctyl methacrylate, and dodecyl methacrylate;
alternatively, the aromatic group-containing vinyl monomer comprises styrene.
In some embodiments, the mass ratio of the first comonomer is 0.5-1% and the mass ratio of the second comonomer is 12.5-17.5% based on the total mass of the raw materials for preparing the modified copolymerized acrylic resin.
In some of the embodiments, the modified polymer satisfies at least one of the following conditions (3) to (4):
(3) Based on the total mass of the raw materials for preparing the modified copolymerized acrylic resin, the mass ratio of the polyamide is 17-22%, the mass ratio of the aliphatic dihydric alcohol is 1-6%, the mass ratio of the aliphatic polyhydric alcohol A is 5.5-9.5%, the mass ratio of the dibasic acid is 5.5-12%, the mass ratio of the maleic anhydride is 0.2-0.5%, and the mass ratio of the second solvent is 2-3%;
(4) The modified polymer is a branched copolymer.
In some embodiments, the weight ratio of the alicyclic diamine is 2% to 7.5%, the weight ratio of the cyclic anhydride is 5.3% to 14.5%, the weight ratio of the functional additive is 0.01% to 0.1%, and the weight ratio of the third solvent is 2% to 7%, based on the total weight of the raw materials for preparing the modified copolymerized acrylic resin.
In some embodiments, the hydroxy functional monomer is of formula (3):
wherein R is 4 Selected from the group consisting of alkanyl having 1 to 5 carbon atoms, R 5 Selected from a C1-5 chain alkyl group;
optionally, the hydroxyl functional monomer comprises at least one of hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, hydroxybutyl acrylate and hydroxybutyl methacrylate.
In some of these embodiments, the initiator comprises a peroxy compound initiator;
the first solvent includes at least one of an aromatic hydrocarbon solvent and an alcohol ether solvent.
In some of the embodiments, the raw material for preparing the modified polymer satisfies at least one of the following conditions (5) to (7):
(5) The aliphatic diol comprises at least one of 2, 2-dimethyl-1, 3-propanediol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol and 2-ethyl-2-butyl-1, 3-propanediol;
optionally, the aliphatic diol comprises at least one of 2, 2-dimethyl-1, 3-propanediol and 1, 6-hexanediol;
(6) The aliphatic polyol A comprises at least one of trimethylolpropane and pentaerythritol;
(7) The dibasic acid comprises at least one of aromatic dibasic acid and aliphatic dibasic acid;
optionally, the dibasic acid comprises at least one of isophthalic acid, adipic acid, 1, 4-cyclohexanedicarboxylic acid.
In some of the examples, the raw materials for preparing the polyamide satisfy at least one of the following conditions (8) to (10):
(8) The number of the ring atoms of the alicyclic diamine is 4-6;
alternatively, the cycloaliphatic diamine comprises at least one of 1, 2-cyclobutanediamine, 1, 3-cyclobutanediamine, 1, 2-cyclopentanediamine, 1, 3-cyclopentanediamine, 1, 2-cyclohexanediamine, 1, 3-cyclohexanediamine, 1, 4-cyclohexanediamine, and isophoronediamine;
(9) The cyclic anhydride comprises at least one of phthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride;
(10) The functional assistant comprises an antioxidant.
In some embodiments, the solid content of the modified copolymerized acrylic resin is 60wt% to 80wt%, the hydroxyl value is 185mgKOH/g to 240mgKOH/g, and the weight-average molecular weight is 6000 to 18000.
In another aspect of the present invention, there is provided a method for preparing the modified copolymerized acrylic resin, comprising the steps of:
mixing the cyclic anhydride, the auxiliary agent and part of the third solvent to prepare a first mixed solution;
mixing the alicyclic diamine with the remaining part of the third solvent to prepare a second mixed solution;
dripping the second mixed solution into the first mixed solution to carry out ring-opening addition polymerization reaction to prepare the polyamide;
mixing the polyamide, the aliphatic dihydric alcohol, the aliphatic polyhydric alcohol A, the maleic anhydride and the dibasic acid to perform polycondensation reaction, and adding the second solvent to perform azeotropic dehydration to prepare the modified polymer;
mixing the modified polymer and a first part of the first solvent to prepare a third mixed solution;
mixing the comonomer, the hydroxyl functional monomer and a second part of the first solvent to prepare a fourth mixed solution;
mixing a part of the initiator with a third part of the first solvent to prepare a fifth mixed solution;
mixing the rest part of the initiator with the fourth part of the first solvent to prepare a sixth mixed solution;
and dripping the fourth mixed solution and the fifth mixed solution into the third mixed solution for polymerization reaction, then adding the sixth mixed solution for curing treatment, and finally adding the rest of the first solvent for dilution to prepare the modified copolymerized acrylic resin.
In the preparation method, alicyclic diamine and cyclic anhydride are used as preparation raw materials to prepare polyamide through ring-opening addition polymerization reaction, amide bond is introduced to improve the wear resistance of resin, and the polyamide is further used as a raw material to perform polycondensation with aliphatic diol, aliphatic polyol A, maleic anhydride and dibasic acid, so that on one hand, the aliphatic diol and the aliphatic polyol A can be esterified and modified with carboxylic acid on the polyamide, on the other hand, the aliphatic diol and the aliphatic polyol A are subjected to polar polycondensation with the maleic anhydride and the dibasic acid to introduce polyester segment modification, and one molecule of the aliphatic polyol A contains three or more hydroxyl groups, thus the branching degree of the modified polymer can be improved, and the wear resistance of the resin can be improved; the modified polymer, the comonomer and the hydroxyl functional monomer are further polymerized under the action of an initiator, a propylene polymer chain segment is introduced on the modified polymer, and meanwhile, the hydroxyl functional monomer enters a hydroxyl functional group to provide a crosslinking site and improve the crosslinking degree of the resin.
In some of the embodiments, the ring-opening addition polymerization reaction satisfies at least one of the following conditions (11) to (12);
(11) The temperature of the ring-opening addition polymerization is 50-80 ℃;
(12) In the process of preparing the polyamide, when the acid value of a reaction system is 230-280 mg KOH/g, the ring-opening addition polymerization is stopped;
the polycondensation reaction satisfies at least one of the following conditions (13) to (14);
(13) The temperature of the polycondensation reaction is 160 +/-2-230 +/-2 ℃;
(14) In the process of preparing the modified polymer, when the acid value of a reaction system is 7-9 mg KOH/g, stopping the polycondensation reaction;
the polymerization reaction satisfies at least one of the following conditions (15) to (16);
(15) The temperature of the polymerization reaction is 130-150 ℃, and the time is 3.5-6 h;
(16) The curing treatment temperature is 130-150 ℃ and the curing treatment time is 0.5-1.5 h.
In still another aspect of the present application, there is provided a coating material containing the modified copolymerized acrylic resin as described above.
The coating comprises the modified copolymerized acrylic resin, and the acrylic resin has high hardness and can improve the wear resistance of a coating film formed by the coating.
In yet another aspect of the present application, there is provided a coated film article comprising a coating film formed from the coating material as described above.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The term "acrylic monomer" refers to the monomers used to make acrylic resins, primarily acrylic acid and its homologs, and acrylates and its homologs.
The term "aliphatic" is also called open chain compound, and carbon atoms in a molecule are connected in a chain shape and is classified into saturated aliphatic compounds and unsaturated aliphatic compounds.
The term "alicyclic" includes carbocyclic rings of 3 or more than 3 carbon atoms connected in a molecule.
In the present invention, the term "alkyl" refers to a group formed by an alkane losing one hydrogen, for example, methane losing one hydrogen to form a methyl group; the term "alkyl" refers to a group formed by alkane in which carbon atoms are all connected by a carbon-carbon single bond and are not cyclic, and the other valences are all combined with hydrogen, and one hydrogen is lost, and includes straight-chain alkyl and branched-chain alkyl; the term "cycloalkyl" refers to a group formed when at least 3 or more carbon atoms are connected and a cyclic cycloalkane loses one hydrogen.
In the present invention, the "alkyl group having 1 to 15 carbon atoms" may have any integer of 1 to 15 carbon atoms, including 1,2, 3, 4, 5, 6, 7, 8, 9 or 10, 12, 13, 14 or 15, and means a group formed by a paraffin containing 1 to 15 carbon atoms after losing one hydrogen, and specific examples thereof include a group formed by a paraffin containing 1 to 15 carbon atoms after losing one hydrogen, a C1 alkane, a C2 alkane, a C3 alkane, a C4 alkane, a C5 alkane, a C6 alkane, a C7 alkane, a C8 alkane, a C9 alkane or a C10 alkane, a C11 alkane, a C12 alkane, a C13 alkane or a C14 alkane, non-limiting examples of "C1-15 alkanes" include methane, ethane, n-propane, iso-propane, n-butane, iso-butane, 2-ethylbutane, 3-dimethylbutane, n-pentane, iso-pentane, neopentane, 1-methylpentane, 3-methylpentane, 2-ethylpentane, 4-methyl-2-pentane, n-hexane, 1-methylhexane, 2-ethylhexane, 2-butylhexane, n-heptane, 1-methylheptane, 2-dimethylheptane, 2-ethylheptane, n-octane, n-nonane, n-decane, dodecane.
Similarly, non-limiting examples of "an alkyl group having 1 to 5 carbon atoms" include the above-mentioned groups formed by losing one hydrogen from a C1 to 5 alkane.
Similarly, non-limiting examples of "any one of cycloalkyl groups having 3 to 15 carbon atoms" include the above-mentioned groups formed by losing one hydrogen of a C3-15 cycloalkane.
In summary, the wear resistance of the paint film formed by the conventional automobile paint is limited, and the traditional preparation process focuses on designing a high-elasticity coating to improve the wear resistance.
However, the skilled person in the present application has found that: although the high-elasticity coating can be elastically deformed when being subjected to scratch stress, and the coating can be recovered after the scratch stress disappears, the traditional high-elasticity coating has slightly low hardness, and can cause the whole resin structure to be damaged when being subjected to an external force higher than the elastic deformation stress, and meanwhile, the lower hardness of the coating can cause other problems, such as unqualified pencil hardness and the like, so that the improvement on the wear resistance is very limited.
Therefore, technicians of the application break through the limitation of the prior art, creatively and directly start from improving the hardness of the coating, and obtain the modified copolymerized acrylic resin in the application after a large number of creative experiments.
One embodiment of the present invention provides a modified copolymerized acrylic resin, which is prepared from the following raw materials: the modified polymer, a comonomer, a hydroxyl functional monomer, an initiator and a first solvent; the comonomer comprises an acrylic monomer;
wherein, the preparation raw materials of the modified polymer comprise: polyamide, aliphatic dihydric alcohol, aliphatic polyol A, maleic anhydride, dibasic acid and a second solvent; one molecule of aliphatic polyol A contains three or more hydroxyl groups;
the preparation raw materials of the polyamide comprise: the solvent comprises alicyclic diamine, cyclic anhydride, functional assistant and a third solvent, wherein the cyclic anhydride contains at least one structure of naphthenic base and aromatic base.
The raw materials of the modified copolymerized acrylic resin comprise specific substances, wherein alicyclic diamine and cyclic anhydride are used as preparation raw materials to prepare polyamide, amide bond is introduced to improve the wear resistance of the resin, and the polyamide is further used as a raw material to perform polycondensation with aliphatic diol, aliphatic polyol A, maleic anhydride and dibasic acid; the modified polymer, the comonomer and the hydroxyl functional monomer are further polymerized under the action of an initiator, a propylene polymer chain segment is introduced on the modified polymer, and meanwhile, a hydroxyl functional group is introduced through the hydroxyl functional monomer to provide a crosslinking site and improve the crosslinking degree of the resin after curing.
In some embodiments, the modified copolymerized acrylic resin is prepared from the following raw materials: 31 to 42 percent of modified polymer, 13 to 18.5 percent of comonomer, 19 to 27 percent of hydroxyl functional monomer, 0.5 to 1.5 percent of initiator and 14 to 39 percent of first solvent.
The hardness of the resin after film forming is further improved by further adjusting the proportion of the preparation raw materials.
It should be noted that when a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values of the range as well as each value between such minimum and maximum values.
For example, "31% to 42%" includes but is not limited to: 31%, 31.46%, 32%, 32.5%, 33%, 33.5%, 34%, 34.5%, 35%, 35.5%, 36%, 36.1%, 36.2%, 36.3%, 36.4%, 36.5%, 36.6%, 36.64%, 36.65%, 36.7%, 36.8%, 36.9%, 37%, 37.1%, 37.2%, 37.3%, 37.4%, 37.5%, 37.6%, 37.7%, 37.8%, 37.9%, 38%, 38.1%, 38.2%, 38.3%, 38.4%, 38.5% 38.6%, 38.7%, 38.8%, 38.9%, 39%, 39.1%, 39.16%, 39.2%, 39.3%, 39.4%, 39.5%, 39.6%, 39.7%, 39.8%, 39.9%, 40%, 40.1%, 40.2%, 40.3%, 40.4%, 40.5%, 40.6%, 40.7%, 40.8%, 40.9%, 41%, 41.1%, 41.2%, 41.3%, 41.4%, 41.5%, 41.6%, 41.7%, 41.8%, 41.9% and 42%, or any two of the values.
For example, "13% to 18.5%" includes but is not limited to: 13%, 13.1%, 13.2%, 13.3%, 13.35%, 13.37%, 13.4%, 13.5%, 13.6%, 13.7%, 13.8%, 13.9%, 14%, 14.1%, 14.2%, 14.3%, 14.4%, 14.5%, 14.6%, 14.7%, 14.8%, 14.9%, 15%, 15.1%, 15.2%, 15.3%, 15.4%, 15.48%, 15.5%, 15.57%, 15.6%, 15.7%, 15.8%, 15.9%, 16%, 16.1%, 16.2%, 16.3%, 16.4%, 16.5%, 16.6%, 16.7%, 16.8%, 16.9%, 17%, 17.1%, 17.11%, 17.2%, 17.3%, 17.4%, 17.5%, 17.6%, 17.7%, 17.78%, 17.8%, 17.9%, 18.1%, 18.2%, 18.3%, 18.4%, 18.5%; or any two of the values.
For example, "19% to 27%" includes but is not limited to: 19%, 19.2%, 19.29%, 20%, 20.05%, 20.07%, 20.5%, 21%, 22%, 22.47%, 23%, 24%, 25%, 26.59%, 25.64%, 26%, 27%, or a range of any two values.
For example, "0.5% to 1.5%" includes but is not limited to: 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 0.98%, 1%, 1.1%, 1.14%, 1.2%, 1.3%, 1.4%, 1.42%, 1.5%, or a range of any two values.
For example, "14% to 39%" includes but is not limited to: 14%, 14.1%, 14.2%, 14.3%, 14.4%, 14.5%, 14.6%, 14.7%, 14.8%, 14.9%, 15%, 15.1%, 15.2%, 15.3%, 15.4%, 15.48%, 15.5%, 15.57%, 15.6%, 15.7%, 15.8%, 15.9%, 16%, 16.1%, 16.2%, 16.3%, 16.4%, 16.5%, 16.6%, 16.7%, 16.8%, 16.9%, 17%, 17.1%, 17.11%, 17.2%, 17.3%, 17.4%, 17.5%, 17.6%, 17.7%, 17.78%, 17.8%, 17.9%, 18%, 18.1%, 18.2%, 18.3%, 18.4%, 18.5%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 36%, 35%, or any two of the values may make up the range.
In some of the examples, the modified copolymerized acrylic resin is a multi-branched polymer. Specifically, 2 or more branches are included.
In some embodiments, the comonomers include a first comonomer and a second comonomer, the first comonomer being represented by formula (1):
R 1 selected from paraffin hydrocarbons having 1 to 15 carbon atoms.
Optionally, the first comonomer comprises at least one of acrylic acid and methacrylic acid;
the second comonomer comprises at least one of a compound shown in a formula (2) and an aromatic group-containing vinyl monomer:
wherein R is 3 R is any one selected from the group consisting of a C1-15 chain alkyl group and a C3-15 cycloalkyl group 2 Is selected from a C1-5 chain alkyl group.
In some embodiments, the compound of formula (2) comprises at least one of methyl acrylate, n-butyl acrylate, isobutyl acrylate, isobornyl acrylate, isooctyl acrylate, dodecyl acrylate, methyl methacrylate, n-butyl methacrylate, isobutyl acrylate, isobornyl methacrylate, isooctyl methacrylate, and dodecyl methacrylate.
In some of these embodiments, the compound of formula (2) comprises at least one of isooctyl acrylate (2-EHA), dodecyl acrylate (SLA), isooctyl methacrylate (2-EHMA), and dodecyl methacrylate (SLMA).
Alternatively, the aromatic group-containing vinyl monomer comprises styrene.
In some embodiments, the mass ratio of the first comonomer is 0.5-1% and the mass ratio of the second comonomer is 12.5-17.5% based on the total mass of the raw materials for preparing the modified copolymerized acrylic resin.
The performance of the resin is further improved by regulating and controlling the type and quality of the comonomer.
"0.5% to 1%" includes but is not limited to: 0.5%, 0.59%, 0.6%, 0.69%, 0.7%, 0.74%, 0.79%, 0.8%, 0.9%, 0.98%, 1%, or a range of any two values.
"12.5% to 17.5%" includes but is not limited to: 12.5%, 12.78%, 13%, 13.32%, 14%, 14.1%, 14.2%, 14.3%, 14.4%, 14.5%, 14.6%, 14.68%, 14.7%, 14.8%, 14.88%, 14.9%, 15%, 15.1%, 15.2%, 15.28%, 15.3%, 15.4%, 15.48%, 15.5%, 15.57%, 15.6%, 15.7%, 15.8%, 15.9%, 16%, 16.1%, 16.2%, 16.3%, 16.4%, 16.5%, 16.6%, 16.7%, 16.8%, 16.9%, 16.99%, 17%, 17.1%, 17.2%, 17.3%, 17.31%, 17.4%, 17.5%, or a range of any two values.
In some of these embodiments, the hydroxy functional monomer is of formula (3):
wherein R is 4 Selected from the group consisting of C1-5 alkanyl radicals, R 5 Is selected from a C1-5 chain alkyl group.
In some of these embodiments, R 4 Selected from the group consisting of C1-4 alkanyl radicals, R 5 Is selected from a chain alkyl group with 1-2 carbon atoms.
Optionally, the hydroxyl functional monomer comprises at least one of hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, hydroxybutyl acrylate and hydroxybutyl methacrylate.
In some embodiments, the hydroxyl functional monomer comprises at least one of hydroxyethyl acrylate, hydroxypropyl acrylate (HPA), 2-hydroxyethyl methacrylate (HEMA), and 2-hydroxypropyl methacrylate.
In some of these embodiments, the initiator comprises a peroxy compound initiator.
In some of these embodiments, the peroxide initiator comprises at least one of di-tert-butyl hydroperoxide (DTBP) and a peroxy ester-based peroxide.
Specifically, the peroxide initiator includes one or more of di-tert-amyl hydroperoxide (DTAP) and Perbutylo.
In some of these embodiments, the first solvent comprises at least one of an aromatic hydrocarbon solvent and an alcohol ether solvent.
Specifically, the aromatic hydrocarbon solvent is one or more of toluene and xylene, and specifically, the aromatic hydrocarbon solvent is xylene; the alcohol ether solvent comprises propylene glycol methyl ether acetate.
In some embodiments, based on the total mass of the raw materials for preparing the modified copolymerized acrylic resin, the mass ratio of the polyamide is 17% to 22%, the mass ratio of the aliphatic diol is 1% to 6%, the mass ratio of the aliphatic polyol a is 5.5% to 9.5%, the mass ratio of the dibasic acid is 5.5% to 12%, the mass ratio of the maleic anhydride is 0.2% to 0.5%, and the mass ratio of the second solvent is 2% to 3%.
The performance of the modified polymer is further improved by further adjusting the proportion of each preparation raw material.
In some embodiments, based on the total mass of the raw materials for preparing the modified copolymerized acrylic resin, the mass ratio of the polyamide is 17% to 22%, the mass ratio of the aliphatic diol is 2% to 6%, the mass ratio of the aliphatic polyol A is 5.5% to 7.5%, the mass ratio of the dibasic acid is 5.5% to 8%, and the mass ratio of the maleic anhydride is 0.2% to 0.4%.
In some of these embodiments, the modifying polymer is a branched copolymer.
Specifically, the branched copolymer comprises one or more branches.
In some of these embodiments, the aliphatic diol comprises at least one of 2, 2-dimethyl-1, 3-propanediol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, and 2-ethyl-2-butyl-1, 3-propanediol.
Alternatively, the aliphatic diol comprises at least one of 2, 2-dimethyl-1, 3-propanediol and 1, 6-hexanediol.
In some of the embodiments, the aliphatic polyol a includes at least one of trimethylolpropane and pentaerythritol.
In some of these embodiments, the diacid includes at least one of an aromatic diacid, an alicyclic diacid, and an aliphatic diacid.
In some of these embodiments, the diacid includes at least one of an aliphatic diacid.
Optionally, the dibasic acid comprises at least one of isophthalic acid, adipic acid, and 1, 4-cyclohexanedicarboxylic acid.
Optionally, the dibasic acid is adipic acid.
In some of these embodiments, the second solvent comprises an aromatic hydrocarbon solvent.
Specifically, the aromatic hydrocarbon solvent is one or more of toluene and xylene, and specifically, the aromatic hydrocarbon solvent is xylene.
In some embodiments, the weight ratio of the alicyclic diamine is 2% to 7.5%, the weight ratio of the cyclic anhydride is 5.3% to 14.5%, the weight ratio of the functional additive is 0.01% to 0.1%, and the weight ratio of the third solvent is 2% to 7%, based on the total weight of the raw materials for preparing the modified copolymerized acrylic resin.
In some of the examples, the ratio of the alicyclic diamine to the cyclic acid anhydride is 2 to 7.1% by mass and 5.3 to 13.5% by mass, based on the total mass of the raw materials for producing the modified copolymerized acrylic resin.
In some of the examples, the alicyclic diamine has 4 to 6 ring atoms.
In some of these embodiments, the cycloaliphatic diamine is a saturated cycloaliphatic diamine.
Alternatively, the alicyclic diamine may include at least one of 1, 2-cyclobutanediamine, 1, 3-cyclobutanediamine, 1, 2-cyclopentanediamine, 1, 3-cyclopentanediamine, 1, 2-cyclohexanediamine, 1, 3-cyclohexanediamine, 1, 4-cyclohexanediamine, and isophoronediamine.
Optionally, the cycloaliphatic diamine comprises at least one of 1, 4-cyclohexanediamine, isophoronediamine (IPDA).
In some of these embodiments, the cyclic anhydride has the structure:
wherein Ar comprises any one of substituted or unsubstituted naphthenic base with 3-20 carbon atoms and substituted or unsubstituted aromatic base with 6-10 carbon atoms; r is 7 Each occurrence is independently selected from H or alkyl of 1 to 5 carbon atoms.
When the above groups are substituted, the substituent includes an alkyl group having 1 to 5 carbon atoms.
In some of these embodiments, the cyclic anhydride comprises at least one of phthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.
In some of these embodiments, the cyclic anhydride comprises hexahydrophthalic anhydride (HHPA), methylhexahydrophthalic anhydride (MeHHPA).
In some of these embodiments, the functional additive comprises an antioxidant. Specifically, the antioxidant is 2, 6-di-tert-butyl-4-methylphenol (BHT).
In some of these embodiments, the third solvent comprises an aromatic hydrocarbon solvent.
Specifically, the aromatic hydrocarbon solvent is one or more of toluene and xylene, and specifically, the aromatic hydrocarbon solvent is xylene.
As used herein, "at least one" or "one or more" may be a mixture of one, two, three, four and more species.
In some embodiments, the modified copolymerized acrylic resin has a solid content of 60wt% to 80wt%, a hydroxyl value of 185mgKOH/g to 240mgKOH/g, and a weight average molecular weight of 6000 to 18000.
An embodiment of the present invention also provides a method for preparing the modified copolymerized acrylic resin, including the following steps S10 to S90.
S10, mixing the cyclic anhydride, the auxiliary agent and part of the third solvent to prepare a first mixed solution.
And S20, mixing the alicyclic diamine and the rest part of the third solvent to prepare a second mixed solution.
And S30, dripping the second mixed solution into the first mixed solution to perform ring-opening addition polymerization reaction to prepare the polyamide.
It should be noted that, step S10 and step S20 have no specific sequence, and may be performed sequentially or simultaneously.
In some of these embodiments, the ring-opening addition polymerization temperature is from 50 ℃ to 80 ℃.
In some embodiments, the first mixture is heated to 50 ℃ to 80 ℃ before step S30.
In some of the examples, the ring-opening addition polymerization was stopped when the acid value of the reaction system was 230 to 280mg KOH/g in the production of the polyamide.
In some embodiments, the mass ratio of the portion of the third solvent added in step S10 is 50% to 90% based on the total mass of the third solvent.
S40, mixing polyamide, aliphatic dihydric alcohol, aliphatic polyhydric alcohol A, maleic anhydride and dibasic acid for polycondensation reaction, and adding a second solvent for azeotropic dehydration to prepare the modified polymer.
In some of these embodiments, the temperature of the polycondensation reaction is from 160. + -. 2 ℃ to 230. + -. 2 ℃.
In some of the examples, the polycondensation reaction was stopped when the acid value of the reaction system was 7mg KOH/g to 9mg KOH/g in the process of preparing the modified polymer.
In one particular example, the process of the polycondensation reaction comprises: heating the system to 160 +/-2 ℃ in 30min, heating to 230 +/-2 ℃ in 180min, carrying out heat preservation reaction for 60min, and then adding a second solvent for azeotropic dehydration until the acid value of the reaction system is 7-9 mg KOH/g.
It will be appreciated that there is still some polycondensation during the azeotropic dehydration.
It should be noted that, steps S10 to S30 and step S40 have no specific sequence, and may be performed sequentially or simultaneously.
And S50, mixing the modified polymer and the first part of the first solvent to prepare a third mixed solution.
And S60, mixing the comonomer, the hydroxyl functional monomer and the second part of the first solvent to prepare a fourth mixed solution.
And S70, mixing part of the initiator with the third part of the first solvent to prepare a fifth mixed solution.
And S80, mixing the rest of the initiator with the fourth part of the first solvent to prepare a sixth mixed solution.
And S90, dripping the fourth mixed solution and the fifth mixed solution into the third mixed solution for polymerization reaction, then adding the sixth mixed solution for curing treatment, and finally adding the rest first solvent for dilution to prepare the modified copolymerized acrylic resin.
In some embodiments, in step S90, the fourth mixed solution and the fifth mixed solution are simultaneously dropped into the third mixed solution in parallel to perform the polymerization reaction.
In some embodiments, the polymerization reaction is carried out at a temperature of 130 ℃ to 150 ℃ for 3.5h to 6h.
The time of the polymerization reaction including the time of the dropwise addition was measured as the time of the start of the dropwise addition.
Further, in step S90, the dropping time is 3-5 h during the polymerization reaction, and then the temperature is kept for 0.5-1 h.
In some embodiments, the third mixture is heated to 130 ℃ to 150 ℃ before step S90.
In some embodiments, the curing treatment is performed at a temperature of 130-150 ℃ for 0.5-1.5 h.
In some embodiments, the mass ratio of the first part of the first solvent, the second part of the first solvent, the third part of the first solvent, the fourth part of the first solvent and the rest part of the first solvent is (2-24): (3-4): (2-3): (0.01-2): (1-4).
In some embodiments, the mass ratio of the remaining portion of the initiator added in step S80 is 1% to 15% based on the total mass of the initiator.
In the preparation method, alicyclic diamine and cyclic anhydride are adopted as preparation raw materials to prepare polyamide through ring-opening addition polymerization reaction, amide bond is introduced to improve the wear resistance of resin, and further the polyamide is adopted as the raw material to be subjected to polycondensation with aliphatic diol, aliphatic polyol A, maleic anhydride and dibasic acid, on one hand, the aliphatic diol and the aliphatic polyol A can be esterified and modified with carboxylic acid on the polyamide, on the other hand, the aliphatic diol and the aliphatic polyol A are subjected to polar polycondensation with the maleic anhydride and the dibasic acid to introduce polyester segment modification, and one molecule of aliphatic polyol A contains three or more hydroxyl groups, so that the branching degree of the modified polymer can be improved, and the wear resistance of numerical values can be improved; the modified polymer, the comonomer and the hydroxyl functional monomer are further polymerized under the action of an initiator, a propylene polymer chain segment is introduced on the modified polymer, and meanwhile, the hydroxyl functional monomer enters a hydroxyl functional group to provide a crosslinking site and improve the crosslinking degree of the resin after curing.
Further, an embodiment of the present invention provides a coating material containing the modified copolymerized acrylic resin.
The coating comprises the modified copolymerized acrylic resin, and the acrylic resin has high hardness and can improve the wear resistance of a coating film formed by the coating.
In some embodiments, the coating further comprises an auxiliary agent.
It is understood that the above-mentioned auxiliaries can be selected according to the actual application of the coating, and for example, the auxiliaries belonging to the aspect of improving the surface activity of the coating are dispersants, wetting agents, emulsifiers, demulsifiers, antifoaming agents, foaming agent antistatic agents, etc.; the auxiliary agents with catalytic action include initiator, drier, curing agent, coupling agent, polymerization inhibitor, photoinitiator, anti-skinning agent, antioxidant, anti-microbial agent, mildew preventive and the like; belongs to functional additives such as metal powder, graphite powder, carbon fiber and the like which need to be added into the conductive coating, and materials such as titanium, aluminum, chromium and the like which can absorb and dissipate gamma rays and the like adopted by the radiation-proof coating.
In some of these embodiments, the coating is a clear coat coating.
An embodiment of the present invention further provides a coated article containing a coating film formed from the above-described coating material.
The wear resistance of the coating is high, and the service life of the coating product can be prolonged.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The technical solutions according to the present invention are exemplified herein, but the present invention is not limited to the following examples.
Example 1
(1) Preparation of the polyamide:
putting hexahydrophthalic anhydride HHPA (13.11%), antioxidant BHT (0.01%) and xylene (2.96%) in a four-neck round-bottom flask, heating to 80 ℃, then dropwise adding 1, 3-cyclic butanediamine (3.66%) into the four-neck round-bottom flask at a constant speed within 15min, keeping the temperature at 80 ℃ for reaction, stopping heating, and cooling to obtain polyamide for later use, wherein the acid value to be detected is 280-290 mgKOH/g.
(2) Preparation of modified Polymer:
taking the prepared polyamide (19.74%), 2-dimethyl-1, 3-propylene glycol NPG (1.48%), 1, 6-hexanediol 1,6-HD (3.35%), trimethylolpropane TMP (7.61%), adipic acid AD (6.21%) and maleic anhydride MAH (0.35%) in a four-neck flask, heating for 30min to 160 +/-2 ℃, uniformly heating for 180min to 230 +/-2 ℃, then keeping the temperature at 230 +/-2 ℃ for 60min, switching a water separator, adding a reflux solvent toluene (2.54%), keeping the temperature at 230 +/-2 ℃ until the acid value is 7-9 mgKOH/g, stopping heating, wherein the total reflux dehydration amount is about 4.63%; cooling to obtain the modified polymer for later use.
(3) Preparation of modified copolymerized acrylic resin:
putting the modified polymer (36.65%) prepared above, propylene glycol monomethyl ether acetate PMA (5.89%) and 100# aromatic hydrocarbon solvent (7.28%) into a four-neck flask, and heating to 150 ℃; putting hydroxyethyl acrylate HEA (20.05%), isooctyl acrylate 2-EHA (5.97%), styrene St (11.34%), acrylic acid AAc (0.69%), 100# aromatic solvent (2.00%), propylene glycol monomethyl ether acetate PMA (2.00%) in a beaker I; putting hydrogen peroxide di-tert-amyl DTAP (1.04%), a 100# aromatic solvent (2.00%) and propylene glycol monomethyl ether acetate PMA (1.00%) in a beaker II; dropwise adding the systems in the beaker II and the beaker I into a four-neck flask system in parallel for 3h, and after dropwise adding is finished, keeping the temperature at 150 ℃ for reaction for 30min;
putting 0.1 percent of hydrogen peroxide di-tert-amyl DTAP (DTAP), 1.00 percent of 100# aromatic hydrocarbon solvent and 1.00 percent of propylene glycol monomethyl ether acetate PMA (1.00 percent) into a beaker III, adding the mixture into a four-neck flask system within 10min, keeping the temperature at 150 ℃ for 60min, adding 2.00 percent of 100# aromatic hydrocarbon solvent to dilute the mixture to the solid content (70 +/-2 percent), and filtering and discharging the mixture through 200-mesh filter cloth to obtain the modified copolymerized acrylic resin (solid content: 70 percent).
Wherein, the proportion of each raw material (percentage in brackets) is calculated by taking the total mass of the preparation raw materials of the modified copolymerized acrylic resin as a reference, namely: the total mass of the modified polymer, the comonomer, the hydroxyl functional monomer, the initiator and the first solvent is calculated by taking the reference. The concrete raw materials and the proportion thereof are shown in the table 1,
(4) The acid value of the prepared modified copolymerized acrylic resin is tested by referring to GB/T2895-2008, and the weight average molecular weight is tested by adopting a gel permeation chromatography method. The results are reported in Table 1.
Example 2
(1) Preparation of the polyamide:
putting methylhexahydrophthalic anhydride MeHHPA (10.94%), antioxidant BHT (0.01%) and xylene (2.59%) in a four-neck round-bottom flask, heating to 80 ℃, dropwise adding 1, 4-cyclohexanediamine (3.71%) into the four-neck round-bottom flask at a constant speed within 15min, keeping the temperature at 80 ℃ for reaction, stopping heating, and cooling to obtain polyamide for later use, wherein the acid value to be detected is 280-290 mgKOH/g.
(2) Preparation of modified Polymer:
taking the prepared polyamide (17.25%), 3-methyl-1, 5-pentanediol MPD (1.28%), 1, 6-hexanediol 1,6-HD (2.56%), pentaerythritol PETS (5.9%), 1, 4-cyclohexanedicarboxylic acid CHDA (5.6%) and maleic anhydride MAH (0.27%) in a four-neck flask, heating for 30min to 160 +/-2 ℃, uniformly heating for 180min to 230 +/-2 ℃, then keeping the temperature at 230 +/-2 ℃ for 60min, switching a water separator, adding a reflux solvent xylene (2.13%), keeping the temperature at 230 +/-2 ℃ until the acid value is 7-9 mgKOH/g, stopping heating, wherein the total reflux dehydration amount accounts for about 3.53%; cooling to obtain the modified polymer for later use.
(3) Preparation of modified copolymerized acrylic resin:
putting the modified polymer (31.46%), propylene glycol monomethyl ether acetate (PMA) (5.9%) and 100# aromatic solvent (17.99%) into a four-neck flask, and heating to 150 ℃; putting hydroxypropyl acrylate HPA (19.29%), dodecyl acrylate SLA (4.11%), styrene St (8.67%), methacrylic acid MAAc (0.59%), 100# aromatic solvent (2.00%), propylene glycol monomethyl ether acetate PMA (2.00%) in a beaker I; placing Perbutylo (0.88%), 100# aromatic solvent (2.00%), propylene glycol monomethyl ether acetate PMA (1.00%) in beaker II; dropwise adding the systems in the beaker II and the beaker I into a four-neck flask system in parallel for 3h, and after dropwise adding is finished, keeping the temperature at 150 ℃ for reaction for 30min;
putting Perbutyllo (0.1%), 100# aromatic solvent (1.00%), propylene glycol monomethyl ether acetate PMA (1.00%) in a beaker III, adding the Perbutyllo into a four-neck flask system within 10min, keeping the temperature at 150 ℃ for 60min, adding 100# aromatic solvent (2.00%) to dilute to solid content (60 +/-2%), filtering with 200-mesh filter cloth, and discharging to obtain the modified copolymerized acrylic resin (solid content: 60%).
Step (4) is the same as step (4) of example 1.
Example 3
(1) Preparation of the polyamide:
putting hexahydrophthalic anhydride HHPA (12.8%), antioxidant BHT (0.01%) and xylene (3.51%) in a four-neck round-bottom flask, heating to 80 ℃, dropwise adding isophoronediamine IPDA (7.07%) into the four-neck round-bottom flask at a constant speed within 15min, keeping the temperature at 80 ℃ for reaction, stopping heating until the acid value is 280-290 mgKOH/g, and cooling to obtain polyamide for later use.
(2) Preparation of modified Polymer:
taking the prepared polyamide (23.39%), 2-ethyl-2-butyl-1, 3-propylene glycol BEPG (2.22%), 1, 6-hexanediol 1,6-HD (3.27%), trimethylolpropane TMP (7.43%), isophthalic acid IPA (6.9%) and maleic anhydride MAH (0.34%) in a four-neck flask, heating for 30min to 160 +/-2 ℃, uniformly heating for 180min to 230 +/-2 ℃, then keeping the temperature at 230 +/-2 ℃ for 60min, switching a water separator, adding a reflux solvent xylene (2.76%), keeping the temperature at 230 +/-2 ℃ until the acid value is 7-9 mgKOH/g, stopping heating, and then keeping the total reflux dehydration amount to be 4.51%; cooling to obtain the modified polymer for later use.
(3) Preparation of modified copolymerized acrylic resin:
putting the modified polymer (41.8%) and propylene glycol monomethyl ether acetate PMA (2.47%) in a four-neck flask, and heating to 150 ℃; putting hydroxyethyl methacrylate HEMA (25.64%), isooctyl methacrylate 2-EHMA (5.92%), styrene St (11.07%), acrylic acid AAc (0.79%), 100# aromatic solvent (2.00%) and propylene glycol monomethyl ether acetate PMA (2.00%) in a beaker I; putting hydrogen peroxide di-tert-butyl DTBP (1.2%), 100# aromatic solvent (1.60%) and propylene glycol monomethyl ether acetate PMA (1.40%) in a beaker II; dropwise adding the systems in the beaker II and the beaker I into a four-neck flask system in parallel for 3h, and after dropwise adding is finished, keeping the temperature at 150 ℃ for reaction for 30min;
putting hydrogen peroxide di-tert-butyl DTBP (0.1%) and propylene glycol monomethyl ether acetate PMA (2.00%) in a beaker III, adding the hydrogen peroxide di-tert-butyl DTBP and the propylene glycol monomethyl ether acetate PMA into a four-neck flask system within 10min, keeping the temperature at 150 ℃ for 60min, adding the propylene glycol monomethyl ether acetate PMA (2.00%) to dilute the mixture to a solid content (80 +/-2%), and filtering and discharging through 200-mesh filter cloth to obtain the modified copolymerized acrylic resin (solid content: 80%).
Step (4) is the same as step (4) of example 1.
Example 4
(1) Preparation of the polyamide:
putting hexahydrophthalic anhydride HHPA (14.01%), antioxidant BHT (0.01%) and xylene (3.16%) in a four-neck round-bottom flask, heating to 80 ℃, dropwise adding 1, 3-cyclic butanediamine (3.91%) into the four-neck round-bottom flask at a constant speed within 15min, keeping the temperature at 80 ℃ for reaction, stopping heating, and cooling to obtain polyamide for later use, wherein the acid value to be detected is 280-290 mgKOH/g.
(2) Preparation of modified Polymer:
taking the prepared polyamide (21.09%), 2-dimethyl-1, 3-propylene glycol NPG (1.58%), 1, 6-hexanediol 1,6-HD (3.58%), trimethylolpropane TMP (8.13%), adipic acid AD (6.64%) and maleic anhydride MAH (0.37%) in a four-neck flask, heating for 30min to 160 +/-2 ℃, uniformly heating for 180min to 230 +/-2 ℃, then keeping the temperature at 230 +/-2 ℃ for 60min, switching a water separator, adding a reflux solvent toluene (2.71%), keeping the temperature at 230 +/-2 ℃ until the acid value is 7-9 mgKOH/g, stopping heating, and then keeping the total reflux dehydration amount to be 4.94%; cooling to obtain the modified polymer for later use.
(3) Preparation of modified copolymerized acrylic resin:
placing the modified polymer (39.16%), propylene glycol monomethyl ether acetate (PMA) (5.86%) and 100# aromatic solvent (1.92%) in a four-neck flask, and heating to 150 ℃; putting hydroxyethyl methacrylate HEMA (26.59%), dodecyl acrylate SLA (10.6%), isooctyl methacrylate 2-EHMA (2.72%), acrylic acid AAc (0.74%), 100# aromatic solvent (2.00%) and propylene glycol monomethyl ether acetate PMA (2.00%) in a beaker I; putting hydrogen peroxide di-tert-amyl DTAP (1.32%), a 100# aromatic solvent (2.00%) and propylene glycol monomethyl ether acetate PMA (1.00%) in a beaker II; dropwise adding the systems in the beaker II and the beaker I into a four-neck flask system in parallel for 3h, and after dropwise adding is finished, keeping the temperature at 150 ℃ for reaction for 30min;
putting hydrogen peroxide di-tert-amyl DTAP (0.10%), 100# aromatic hydrocarbon solvent (1.00%) and propylene glycol monomethyl ether acetate PMA (1.00%) in a beaker III, adding the beaker III into a four-neck flask system within 10min, keeping the temperature at 150 ℃ for 60min, adding 100# aromatic hydrocarbon solvent (2.00%) to dilute to solid content (75 +/-2%), filtering through 200-mesh filter cloth, and discharging to obtain the modified copolymerized acrylic resin (solid content: 75%).
Step (4) is the same as step (4) of example 1.
Example 5
(1) Preparation of the polyamide:
putting hexahydrophthalic anhydride HHPA (5.7%), methylhexahydrophthalic anhydride MeHHPA (6.22%), antioxidant BHT (0.01%) and dimethylbenzene (3.04%) in a four-neck round-bottom flask, heating to 80 ℃, dropwise adding 1, 4-cyclohexanediamine (2.11%) and isophoronediamine IPDA (3.15%) into the four-neck round-bottom flask at constant speed within 15min, keeping the temperature at 80 ℃ for reaction, stopping heating, cooling to obtain polyamide for later use, wherein the acid value is 280-290 mgKOH/g, and the acid value is to be measured.
(2) Preparation of modified Polymer:
taking the prepared polyamide (20.23%), 2-ethyl-2-butyl-1, 3-propylene glycol BEPG (1.98%), 1, 6-hexanediol 1,6-HD (2.92%), trimethylolpropane TMP (6.62%), isophthalic acid IPA (6.15%) and maleic anhydride MAH (0.3%) in a four-neck flask, heating for 30min to 160 +/-2 ℃, uniformly heating for 180min to 230 +/-2 ℃, then keeping the temperature at 230 +/-2 ℃ for 60min, switching a water separator, adding a reflux solvent xylene (2.46%), keeping the temperature at 230 +/-2 ℃ until the acid value is 7-9 mgKOH/g, stopping heating, and then keeping the total reflux dehydration amount to be 4.02%; cooling to obtain the modified polymer for later use.
(3) Preparation of modified copolymerized acrylic resin:
putting the modified polymer (36.64%) prepared above, propylene glycol monomethyl ether acetate PMA (5.89%) and 100# aromatic hydrocarbon solvent (7.28%) into a four-neck flask, and heating to 150 ℃; taking hydroxyethyl methacrylate HEMA (10.47%), hydroxypropyl methacrylate HPMA (11.6%), isooctyl acrylate 2-EHA (5.42%), styrene St (4.93%), dodecyl methacrylate SLMA (4.93%), AAc (0.69%), 100# aromatic solvent (2.00%), propylene glycol monomethyl ether acetate PMA (2.00%) and Perbutylo (1.04%), 100# aromatic solvent (2.00%) and propylene glycol monomethyl ether acetate PMA (1.00%) to be placed in a beaker I; dropwise adding the systems in the beaker II and the beaker I into a four-neck flask system in parallel for 3h, and after dropwise adding is finished, keeping the temperature at 150 ℃ for reaction for 30min;
putting Perbutyllo (0.1%), 100# aromatic solvent (1.00%) and propylene glycol monomethyl ether acetate PMA (1.00%) in a beaker III, adding the Perbutyllo into a four-neck flask system within 10min, keeping the temperature at 150 ℃ for 60min, adding 100# aromatic solvent (2.00%) to dilute to solid content (70 +/-2%), filtering with 200-mesh filter cloth, and discharging to obtain the modified copolymerized acrylic resin (solid content: 70%).
Step (4) is the same as step (4) of example 1.
Example 6
(1) Preparation of the polyamide:
putting hexahydrophthalic anhydride HHPA (5.81%), methylhexahydrophthalic anhydride MeHHPA (6.34%), antioxidant BHT (0.01%) and dimethylbenzene (3.09%) in a four-neck round-bottom flask, heating to 80 ℃, dropwise adding 1, 4-cyclohexanediamine (2.15%) and isophoronediamine IPDA (3.21%) into the four-neck round-bottom flask at a constant speed within 15min, keeping the temperature at 80 ℃ for reaction, stopping heating, cooling to obtain polyamide for later use, wherein the acid value is 280-290 mgKOH/g, and the acid value is to be measured.
(2) Preparation of modified Polymer:
taking the prepared polyamide (20.61%), 2-ethyl-2-butyl-1, 3-propanediol BEPG (2.01%), 1, 6-hexanediol (1, 6-HD) (2.97%), trimethylolpropane TMP (6.74%), adipic acid AD (2.56%), isophthalic acid IPA (3.13%) and maleic anhydride MAH (0.31%) in a four-neck flask, heating for 30min to 160 +/-2 ℃, uniformly heating for 180min to 230 +/-2 ℃, then keeping the temperature at 230 +/-2 ℃ for 60min, switching a water separator, adding a reflux solvent xylene (2.41%), keeping the temperature at 230 +/-2 ℃ until the acid value is 7-9 mgKOH/g, stopping heating, wherein the total reflux dehydration amount is about 4.09%; cooling to obtain the modified polymer for later use.
(3) Preparation of modified copolymerized acrylic resin:
placing the modified polymer (36.65%) prepared above, propylene glycol monomethyl ether acetate PMA (5.89%) and 100# aromatic solvent (7.28%) in a four-neck flask, and heating to 150 ℃; putting hydroxyethyl methacrylate HEMA (10.66%), hydroxypropyl methacrylate HPMA (11.81%), isooctyl acrylate 2-EHA (4.84%), styrene St (5.02%), dodecyl methacrylate SLMA (5.02%), acrylic acid AAc (0.69%), 100# aromatic solvent (2.00%) and propylene glycol monomethyl ether acetate PMA (2.00%) in a beaker I; placing hydrogen peroxide di-tert-butyl DTBP (0.54%), hydrogen peroxide di-tert-amyl DTAP (0.5%), 100# aromatic solvent (2.00%), propylene glycol methyl ether acetate PMA (1.00%) in a beaker II, dropwise adding a monomer and an initiator into the system at constant speed for 3h in parallel, and after dropwise adding is finished, keeping the temperature at 150 ℃ for 30min;
putting hydrogen peroxide di-tert-butyl DTBP (0.1%), 100# aromatic hydrocarbon solvent (1.00%) and propylene glycol monomethyl ether acetate PMA (1.00%) in a beaker III, adding the beaker III into a four-neck flask system within 10min, preserving heat for 60min at 150 ℃, adding 100# aromatic hydrocarbon solvent (2.00%) to dilute the mixture to solid content (70 +/-2%), and filtering and discharging through 200-mesh filter cloth to obtain the modified copolymerized acrylic resin (solid content: 70%).
Step (4) is the same as step (4) of example 1.
Comparative examples 1 to 2
Comparative examples 1 to 2 are substantially the same as example 1 except that: the parameters in table 1 are specifically listed in table 1. Other steps and conditions were the same as in example 1.
Comparative example 3
(1) Preparation of modified Polymer:
taking hexahydrophthalic anhydride HHPA (11.9%), 2-ethyl-2-butyl-1, 3-propanediol BEPG (5.13%), 1, 6-hexanediol 1,6-HD (5.3%), trimethylolpropane TMP (6.88%), adipic acid AD (2.62%), isophthalic acid IPA (3.19%) and maleic anhydride MAH (0.31%) in a four-neck flask, heating for 30min to 160 +/-2 ℃, uniformly heating for 180min to 230 +/-2 ℃, then keeping the temperature at 230 +/-2 ℃ for 60min, switching a water separator, adding reflux solvent xylene (5.5%), keeping the temperature at 230 +/-2 ℃ until the acid value is 7-9 mgKOH/g, stopping heating, and then keeping the total reflux dehydration amount to be 4.18%; cooling to obtain the polyester prepolymer for later use.
(2) Preparation of modified copolymerized acrylic resin:
placing the modified polymer (36.65%) prepared above, propylene glycol monomethyl ether acetate PMA (5.88%) and 100# aromatic solvent (7.28%) in a four-neck flask, and heating to 150 ℃; putting hydroxyethyl methacrylate HEMA (10.89%), hydroxypropyl methacrylate HPMA (12.06%), isooctyl acrylate 2-EHA (4.15%), styrene St (5.13%), dodecyl methacrylate SLMA (5.13%), acrylic acid AAc (0.69%), 100# aromatic solvent (2.00%) and propylene glycol monomethyl ether acetate PMA (2.00%) in a beaker I; putting hydrogen peroxide di-tert-amyl DTAP (1.04%), a 100# aromatic hydrocarbon solvent (2.00%) and propylene glycol monomethyl ether acetate PMA (1.00%) in a beaker II, dropwise adding a monomer and an initiator into the system at constant speed for 3 hours in parallel, and preserving heat for 30min at 150 ℃ after dropwise adding;
putting hydrogen peroxide di-tert-amyl DTAP (0.1%), 100# aromatic hydrocarbon solvent (1.00%) and propylene glycol monomethyl ether acetate PMA (1.00%) in a beaker III, adding the beaker III into a four-neck flask system within 10min, preserving heat for 60min at 150 ℃, adding 100# aromatic hydrocarbon solvent (2.00%) to dilute to solid content (70 +/-2%), filtering through 200-mesh filter cloth, and discharging to obtain the modified copolymerized acrylic resin (solid content: 70%).
The composition formulations of examples 1 to 6 and comparative examples 1 to 3 are shown in Table 1.
TABLE 1
Example 7: preparation of the varnish
Paints were prepared by charging according to the formulation table shown in Table 2, the modified copolymerized acrylic resins obtained in examples 1 to 6 and comparative examples 1 to 2 were formulated into corresponding varnish paints A1 to A6 and B1 to 2, the modified copolymerized acrylic resin in comparative example 3 was formulated into a comparative paint B3, and the Mitsubishi positive modified acrylic resin CZ-2620 was formulated into a comparative paint B4, to perform the evaluation of the paint performance parameters. Wherein the coating has fixed NCO: OH = 1.1. The method comprises the following specific steps:
the coatings were applied to a coating and tested using a SDL ATLAS M238BB Model CM-5 Moire tester according to the following protocol:
1. experimental equipment and model: SDL ATLAS M238BB Model CM-5 rubbing color fastness instrument;
2. sand paper for experiments: siC back adhesive sand paper with granularity of 2400 circles and diameter of 30 mm;
3. experimental procedure and result evaluation:
3.1 marking a scratch test position and a position for measuring the glossiness at the position 3 on the test plate, wherein the position for measuring the glossiness evenly divides the scratch test position into 4 equal parts;
3.2 gloss measurement of the location of the mark where the gloss was measured with a gloss meter, recording the 20 ° gloss (initial G20);
3.3 setting the wiping times to be 15 times;
3.4, the sand paper is pasted on the instrument, and the sand paper is not allowed to be pasted and has the abnormity of deflection, corrugation and the like;
3.5 placing the sample plate on an operation table, wherein the test surface faces upwards, fixing the test plate by two hands, and not allowing the sample plate to shake or move any more in the test process;
4.6 starting the test, measuring the glossiness of the position marked with the glossiness by using a glossiness instrument after the test is finished, and recording the 20-degree gloss (G20 after scratching);
3.7A total of three experiments were averaged, and if one of the three results deviated from the average by more than 10%, the result was removed and retested. If there are 2 results that deviate by 10% from the mean, the plate test must be repeated.
4. Other requirements are as follows:
4.1 Prior to testing, the panels were subjected to temperature (23. + -. 2 ℃ C.) and relative humidity (50. + -. 5%) for at least 24 hours.
4.2 the experimental conditions were temperature (23. + -. 2). Degree.C., relative humidity (50. + -. 5)%.
4.3 observe and record whether the experiment process has abnormal phenomena.
4.4 the surface of the test panel does not allow for particles, scratches, etc. that affect the measurement.
The specific components are shown in Table 2, and the test results are shown in Table 3.
TABLE 2
TABLE 3
| Initial G20 (mean) | After scratching G20 (mean) | Light loss ratio | |
| A1 | 88.1 | 81.9 | 7.04％ |
| A 2 | 89.4 | 78.1 | 12.64％ |
| A 3 | 88.7 | 79.5 | 10.37％ |
| A 4 | 89.5 | 83.5 | 6.70％ |
| A 5 | 88.2 | 80.5 | 8.73％ |
| A 6 | 88.6 | 80.1 | 9.59％ |
| B1 | 84.2 | 62.5 | 25.77％ |
| B2 | 85.3 | 57.2 | 32.94％ |
| B3 | 87.5 | 55.3 | 36.80％ |
| B4 | 87.8 | 72.5 | 17.43％ |
Wherein the loss of gloss = (initial G20-post-scratching G20)/initial G20X 100%
Analysis of the data in Table 1 shows that compared with the coatings prepared by comparative examples 1-2, the amide-free modified resin comparative example 3 and the Mitsubishi positive modified acrylic resin CZ-2620, the resins prepared by the examples 1-6 of the technical scheme of the application can obviously improve the scratch resistance of the coating.
Meanwhile, various indexes such as appearance, acid resistance, alkali resistance, weather resistance and the like of the coating are detected, and the performance requirements can be met.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above examples only show some embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (15)
1. The modified copolymerized acrylic resin is characterized in that the modified copolymerized acrylic resin is prepared from the following raw materials: the modified polymer, a comonomer, a hydroxyl functional monomer, an initiator and a first solvent; the comonomer comprises an acrylic monomer;
wherein, the preparation raw materials of the modified polymer comprise: polyamide, aliphatic dihydric alcohol, aliphatic polyol A, maleic anhydride, dibasic acid and a second solvent; one molecule of the aliphatic polyhydric alcohol A contains three or more hydroxyl groups;
the preparation raw materials of the polyamide comprise: the solvent comprises alicyclic diamine, cyclic anhydride, a functional assistant and a third solvent, wherein the cyclic anhydride contains at least one structure of naphthenic base and aromatic base.
2. The modified copolymerized acrylic resin of claim 1, wherein the modified copolymerized acrylic resin satisfies at least one of the following conditions (1) to (2):
(1) The modified copolymerized acrylic resin is prepared from the following raw materials: 31% -42% of the modified polymer, 13% -18.5% of the comonomer, 19% -27% of the hydroxyl functional monomer, 0.5% -1.5% of the initiator and 14% -39% of the first solvent;
(2) The modified copolymerized acrylic resin is a multi-branched polymer.
3. The modified copolymerized acrylic resin of any one of claims 1-2, wherein the comonomers comprise a first comonomer and a second comonomer, the first comonomer being represented by formula (1):
R 1 selected from C1-15 alkane;
optionally, the first comonomer comprises at least one of acrylic acid and methacrylic acid;
the second comonomer comprises at least one of a compound shown in a formula (2) and an aromatic group-containing vinyl monomer:
wherein R is 3 R is any one selected from the group consisting of a C1-15 chain alkyl group and a C3-15 cycloalkyl group 2 Selected from a C1-5 chain alkyl group;
optionally, the compound represented by formula (2) comprises at least one of methyl acrylate, n-butyl acrylate, isobutyl acrylate, isobornyl acrylate, isooctyl acrylate, dodecyl acrylate, methyl methacrylate, n-butyl methacrylate, isobutyl acrylate, isobornyl methacrylate, isooctyl methacrylate, and dodecyl methacrylate;
alternatively, the aromatic group-containing vinyl monomer comprises styrene.
4. The modified copolymerized acrylic resin of claim 3, wherein the first comonomer is present in an amount of 0.5 to 1% by mass and the second comonomer is present in an amount of 12.5 to 17.5% by mass, based on the total mass of raw materials for preparing the modified copolymerized acrylic resin.
5. The modified copolymerized acrylic resin of any one of claims 1 to 2, wherein the modified polymer satisfies at least one of the following conditions (3) to (4):
(3) Based on the total mass of the raw materials for preparing the modified copolymerized acrylic resin, the mass ratio of the polyamide is 17-22%, the mass ratio of the aliphatic dihydric alcohol is 1-6%, the mass ratio of the aliphatic polyhydric alcohol A is 5.5-9.5%, the mass ratio of the dibasic acid is 5.5-12%, the mass ratio of the maleic anhydride is 0.2-0.5%, and the mass ratio of the second solvent is 2-3%;
(4) The modified polymer is a branched copolymer.
6. The modified copolymerized acrylic resin according to any one of claims 1 to 2, wherein the alicyclic diamine is 2 to 7.5% by mass, the cyclic acid anhydride is 5.3 to 14.5% by mass, the functional assistant is 0.01 to 0.1% by mass, and the third solvent is 2 to 7% by mass, based on the total mass of raw materials for producing the modified copolymerized acrylic resin.
7. The modified copolymerized acrylic resin of any one of claims 1-2, wherein the hydroxyl functional monomer is represented by formula (3):
wherein R is 4 Selected from the group consisting of alkanyl having 1 to 5 carbon atoms, R 5 Selected from a C1-5 chain alkyl group;
optionally, the hydroxyl functional monomer comprises at least one of hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, hydroxybutyl acrylate and hydroxybutyl methacrylate.
8. The modified copolymerized acrylic resin of any one of claims 1 to 2, wherein the initiator comprises a peroxy compound initiator;
the first solvent includes at least one of an aromatic hydrocarbon solvent and an alcohol ether solvent.
9. The modified copolymerized acrylic resin of any one of claims 1 to 2, wherein the modified polymer is prepared from a raw material satisfying at least one of the following conditions (5) to (7):
(5) The aliphatic diol comprises at least one of 2, 2-dimethyl-1, 3-propanediol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol and 2-ethyl-2-butyl-1, 3-propanediol;
optionally, the aliphatic diol comprises at least one of 2, 2-dimethyl-1, 3-propanediol and 1, 6-hexanediol;
(6) The aliphatic polyol A comprises at least one of trimethylolpropane and pentaerythritol;
(7) The dibasic acid comprises at least one of aromatic dibasic acid and aliphatic dibasic acid;
optionally, the dibasic acid comprises at least one of isophthalic acid, adipic acid, 1, 4-cyclohexanedicarboxylic acid.
10. The modified copolymerized acrylic resin of any one of claims 1 to 2, wherein the raw materials for producing the polyamide satisfy at least one of the following conditions (8) to (10):
(8) The number of the ring atoms of the alicyclic diamine is 4-6;
alternatively, the cycloaliphatic diamine comprises at least one of 1, 2-cyclobutanediamine, 1, 3-cyclobutanediamine, 1, 2-cyclopentanediamine, 1, 3-cyclopentanediamine, 1, 2-cyclohexanediamine, 1, 3-cyclohexanediamine, 1, 4-cyclohexanediamine, and isophoronediamine;
(9) The cyclic anhydride comprises at least one of phthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride;
(10) The functional assistant comprises an antioxidant.
11. The modified copolymerized acrylic resin of any one of claims 1-2, wherein the modified copolymerized acrylic resin has a solid content of 60wt% to 80wt%, a hydroxyl value of 185mgKOH/g to 240mgKOH/g, and a weight-average molecular weight of 6000 to 18000.
12. A method for preparing a modified copolymerized acrylic resin according to any one of claims 1 to 11, comprising the steps of:
mixing the cyclic acid anhydride, the auxiliary agent and part of the third solvent to prepare a first mixed solution;
mixing the alicyclic diamine and the rest of the third solvent to prepare a second mixed solution;
dripping the second mixed solution into the first mixed solution to carry out ring-opening addition polymerization reaction to prepare the polyamide;
mixing the polyamide, the aliphatic dihydric alcohol, the aliphatic polyhydric alcohol A, the maleic anhydride and the dibasic acid to perform polycondensation reaction, and adding the second solvent to perform azeotropic dehydration to prepare the modified polymer;
mixing the modified polymer and a first part of the first solvent to prepare a third mixed solution;
mixing the comonomer, the hydroxyl functional monomer and a second part of the first solvent to prepare a fourth mixed solution;
mixing a part of the initiator with a third part of the first solvent to prepare a fifth mixed solution;
mixing the rest part of the initiator and the fourth part of the first solvent to prepare a sixth mixed solution;
and dripping the fourth mixed solution and the fifth mixed solution into the third mixed solution for polymerization reaction, then adding the sixth mixed solution for curing treatment, and finally adding the rest of the first solvent for dilution to prepare the modified copolymerized acrylic resin.
13. The method for producing a modified copolymerized acrylic resin according to claim 12, wherein the ring-opening addition polymerization reaction satisfies at least one of the following conditions (11) to (12);
(11) The temperature of the ring-opening addition polymerization is 50-80 ℃;
(12) In the process of preparing the polyamide, when the acid value of a reaction system is 230-280 mg KOH/g, the ring-opening addition polymerization is stopped;
the polycondensation reaction satisfies at least one of the following conditions (13) to (14);
(13) The temperature of the polycondensation reaction is 160 +/-2-230 +/-2 ℃;
(14) In the process of preparing the modified polymer, when the acid value of a reaction system is 7-9 mg KOH/g, stopping the polycondensation reaction;
the polymerization reaction satisfies at least one of the following conditions (15) to (16);
(15) The temperature of the polymerization reaction is 130-150 ℃, and the time is 3.5-6 h;
(16) The curing treatment temperature is 130-150 ℃ and the curing treatment time is 0.5-1.5 h.
14. A coating material characterized by containing the modified copolymerized acrylic resin of any one of 1 to 11.
15. A coated article comprising a coating film formed from the coating material according to claim 14.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117946350A (en) * | 2024-03-27 | 2024-04-30 | 安徽三旺化学有限公司 | Normal-temperature-cured aqueous acrylic resin emulsion |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117946350A (en) * | 2024-03-27 | 2024-04-30 | 安徽三旺化学有限公司 | Normal-temperature-cured aqueous acrylic resin emulsion |
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