Polymer, preparation method thereof and curable composition

Abstract

The invention provides a polymer, a preparation method thereof and a curable composition, the polymer comprises a repeating unit shown as a formula a1, a repeating unit shown as a formula a2, a repeating unit shown as a formula 1, a repeating unit shown as a formula 1, a repeating unit shown as a formula a3, a repeating unit shown as a formula 2, a repeating unit shown as a formula a4, a repeating unit shown as a formula 3, a repeating unit shown as a formula a5 and a repeating unit shown as a formula a6, according to the present invention, the requirement of the low carbon-carbon double bond equivalent of the polymer is achieved, and the polymers are cross-linked through the carbon-carbon double bonds, such that the good cross-linking can be achieved through the plurality of the carbon-carbon double bonds in the polymers under the condition of the small use amount of the polymer so as to improve the curing performance of the solution containing the polymer;

Description

Technical Field

[0001] The present application relates to the field of optoelectronic technology, and in particular to a polymer, a preparation method thereof, and a curable composition. Background Art

[0002] Color filters can be used in color display devices to present a colorful picture, thereby achieving color display. The curable composition used to make the color filter generally includes: pigments, polymers, photoinitiators, solvents and other additives. Under light or heating conditions, the polymers are cross-linked, so that the curable composition changes from a liquid state to a solid state to achieve curing. As the thickness of the color filter gradually decreases, while ensuring that the amount of pigment remains unchanged to ensure color performance, the amount of other substances such as polymers gradually decreases, which leads to a decrease in the curing performance of the curable composition, and ultimately leads to a decrease in the performance of the color filter.

[0003] Based on this, how to improve the curing performance of the curable composition has become an urgent problem to be solved. Summary of the invention

[0004] The present application provides a polymer, a preparation method thereof and a curable composition, which are used to improve the curing performance of the curable composition.

[0005] In a first aspect, an embodiment of the present application provides a polymer, which may include repeating units represented by formula a1, formula a2, formula a3, formula a4, formula a5 and formula a6:

[0006]

[0007] wherein each R0 is independently selected from H or methyl;

[0008] R1 is selected from any one of a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C7-C30 aralkyl group;

[0009] R2, R3, and R4 are each independently selected from the group consisting of a single bond, a substituted or unsubstituted C1-C30 alkylene group, a substituted or unsubstituted C1-C30 alkyleneoxy group, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C6-C30 aryleneoxy group, and a substituted or unsubstituted C7-C30 aralkylene group;

[0010] R5, R6, and R7 are each independently selected from: a single bond, a substituted or unsubstituted C1-C30 alkylene group, and a substituted or unsubstituted C1-C30 ester group;

[0011] R8 is selected from: any one of a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aromatic group, a substituted or unsubstituted C6-C30 aryloxy group, and a substituted or unsubstituted C1-C30 ester group;

[0012] The substituents in the substituted C1-C30 alkyl, substituted C6-C30 aryl, substituted C7-C30 aralkyl, substituted C1-C30 alkylene, substituted C1-C30 alkyleneoxy, substituted C6-C30 arylene, substituted C6-C30 aryleneoxy, substituted C7-C30 aralkylene, substituted C1-C30 esterene, substituted C1-C30 alkoxy, substituted C6-C30 aromatic group, substituted C6-C30 aryloxy, substituted C1-C30 ester group are each independently selected from the group consisting of halogen, C1-C10 alkyl or C6-C30 aromatic group;

[0013] a, b, c, d, e, and f are the molar percentages of the corresponding repeating units in the total repeating units, a is greater than 0 and not greater than 70%, b is greater than 0 and not greater than 60%, c is 0-80%, d is 2%-70%, e is 0-80%, f is 0-70%, and a+b+c+d+e+f=100%.

[0014] It should be understood that the repeating unit shown in formula a1 can be called the first repeating unit, the repeating unit shown in formula a2 can be called the second repeating unit, the repeating unit shown in formula a3 can be called the third repeating unit, the repeating unit shown in formula a4 can be called the fourth repeating unit, the repeating unit shown in formula a5 can be called the fifth repeating unit, and the repeating unit shown in formula a6 can be called the sixth repeating unit. The polymer is a copolymer, and its molecular structure is formed by linking different repeating units. The arrangement of each repeating unit can be designed according to actual conditions and is not limited here. As long as the polymer includes the above-mentioned repeating units, it belongs to the protection scope of the embodiments of the present application.

[0015] In this way, the side groups of the polymer contain at least two carbon-carbon double bonds, achieving the requirement of low carbon-carbon double bond equivalent of the polymer. Since the polymers are cross-linked through carbon-carbon double bonds, even if the amount of the polymer is small, the multiple carbon-carbon double bonds in each polymer can still achieve good cross-linking, thereby improving the curing performance of the solution containing the polymer.

[0016] Furthermore, when the polymer is used to make a photoresist, the uncrosslinked polymer can be washed away by the developer during development because the carboxyl group in the second repeating unit is acidic, while the crosslinked polymer will not be washed away by the developer even if it contains a carboxyl group, thereby achieving patterning. The acid value of the polymer in the embodiment of the present application can reach 10 mg-KOH / g to 150 mg-KOH / g, which can promote the uncrosslinked polymer to be washed away by the developer, thereby improving the effect of patterning.

[0017] Exemplarily, R1 is selected from: C1-C5 alkyl, phenyl or C7-C10 aralkyl, wherein the C1-C5 alkyl as R1 can be any of linear, branched or cyclic, such as but not limited to: methyl, ethyl, propyl, isopropyl, pentyl, cyclopentyl, etc.; the C7-C10 aralkyl as R1 can be selected from but not limited to: benzyl, phenethyl, naphthylmethyl, methylbenzyl, etc. The group selection of R1 can be selected according to actual conditions.

[0018] R2, R3, and R4 are each independently selected from: a single bond or a C1-C5 alkylene group, wherein when R2 and R3 are each independently selected from a single bond, it means that the carboxyl group is directly connected to the main chain, and the ester group in the side chain of the third repeating unit is directly connected to the main chain; when R2 and R3 are each independently selected from a non-single bond, it means that the carboxyl group is connected to the main chain through other groups, and the ester group in the side chain of the third repeating unit is connected to the main chain through other groups. The C1-C5 alkylene group of R2, R3, and R4 can be, but is not limited to, selected from the C1-C5 alkyl group listed in R1 above that becomes a divalent alkylene group, such as methylene, ethylene, propylene, isopropylene, butylene, pentylene, etc. The group selection of R2, R3, and R4 can be selected according to actual conditions.

[0019] When R5, R6, and R7 are independently selected from substituted or unsubstituted C1-C30 ester groups, and C in C=O is connected to C in a carbon-carbon double bond by a single bond, the side chains of the fourth repeating unit and the fifth repeating unit include (meth)acrylate groups. Since (meth)acrylate groups have high activity when the polymer is cross-linked, they have a promoting effect on the cross-linking reaction. Therefore, when the side group end of the polymer contains (meth)acrylate groups, the cross-linking property of the polymer can be further improved, thereby further improving the curing performance of the solution containing the polymer. Exemplarily, according to the different side group structures of each repeating unit, the equivalent weight of (meth)acrylic acid in the polymer can reach 150 g / mol to 2000 g / mol, so that the polymer has better curing performance. Wherein R5, R6, and R7 are each independently selected from: C1-C10 ester groups, such as but not limited to: methylene ester groups, ethylene ester groups, propylene ester groups, isopropylene ester groups, pentyl ester groups, heptyl ester groups, hexyl ester groups, decyl ester groups, etc. The group selection of R5, R6, and R7 can be selected according to actual conditions. It should be understood that the equivalent weight of (meth) acrylic acid can be understood as: the mass of the resin corresponding to each 1 mol of unsaturated group (i.e., (meth) acrylic acid), in g / mol; therefore, the lower the equivalent weight of (meth) acrylic acid, the higher the content of (meth) acrylic acid contained in the polymer, and the better the curing performance of the polymer.

[0020] Based on this, the polymer can be selected from the following general structure:

[0021]

[0022] Wherein, R5', R6', and R7' are each independently selected from: C1-C5 alkylene.

[0023] R8 is not limited to a specific group, and R8 can be designed according to actual conditions and is not limited here.

[0024] That is to say, the polymer can be: a polymer consisting of the first repeating unit, the second repeating unit and the fourth repeating unit, or a polymer consisting of the first repeating unit, the second repeating unit, the third repeating unit and the fourth repeating unit, or a polymer consisting of the first repeating unit, the second repeating unit, the third repeating unit, the fourth repeating unit and the fifth repeating unit, or a polymer consisting of the first repeating unit, the second repeating unit, the third repeating unit, the fourth repeating unit and the sixth repeating unit, or a polymer consisting of the first repeating unit, the second repeating unit, the third repeating unit, the fourth repeating unit, the fifth repeating unit and the sixth repeating unit, and so on. Which specific repeating units the specific polymer includes can be designed according to actual needs, but it only needs to include the first repeating unit, the second repeating unit and the fourth repeating unit.

[0025] Exemplarily, the molar percentage a of the first repeating unit can be optimized to 10%-70%, and further optimized to 10%-40%. Because this ester group can promote the curing of the polymer, when the polymer contains an appropriate proportion of ester groups, the curing performance of the polymer can be further improved. The molar percentage b of the second repeating unit can be optimized to 10%-50%, and further optimized to 10%-35%. Because the presence of carboxyl groups can achieve patterning, the polymer contains an appropriate proportion of carboxyl groups, which can improve the patterning effect of the polymer. The molar percentage c of the third repeating unit can be optimized to 0-80%, and further optimized to 0-10%. In this way, the amount of the fourth repeating unit and the fifth repeating unit generated can be controlled, so that the polymer has an appropriate proportion of carbon-carbon double bonds to improve the curing performance of the polymer. The molar percentage d of the fourth repeating unit can be optimized to 10%-70%, and further optimized to 20%-60%. Because the carbon-carbon double bonds can achieve polymer cross-linking, the polymer contains an appropriate proportion of carbon-carbon double bonds, which can improve the cross-linking and curing performance of the polymer. The molar percentage e of the fifth repeating unit can be optimized to 0-80%, and further optimized to 0-30%, so that the amount of carbon-carbon double bonds in the polymer can be increased, and the cross-linking and curing performance of the polymer can be further improved. The molar percentage f of the sixth repeating unit can be 0, and the sixth repeating unit is not included in the polymer. When the value of f is greater than 0, it means that the polymer contains the sixth repeating unit, and the molar percentage f of the sixth repeating unit can be designed according to actual conditions, and is not limited here, so as to meet the needs of the polymer in different application scenarios and improve the flexibility of the design. In addition, d: (a + b + c + e + f) can be set to 0.25-1.50, so that the molar percentage of the four repeating units in the polymer can be further adjusted to further improve the curing performance and patterning treatment effect of the polymer.

[0026] Based on this, the weight average molecular weight of the polymer can be 3000 g / mol to 30000 g / mol, and the polymer dispersion index can reach above 1.6, so that the polymer can be liquid before solidification and easy to store, and can also make the polymer better dispersed in the solvent, thereby improving the uniformity of the solution containing the polymer.

[0027] In a second aspect, an embodiment of the present application further provides a method for preparing a polymer, which can be used to prepare the polymer described in the first aspect and any embodiment of the first aspect, and the preparation method may include: grafting a precursor with a substance containing an isocyanate group to obtain a polymer; the precursor includes repeating units shown in formula a1, formula a2, formula a3' and formula a6, and the hydroxyl groups in at least part of the repeating units shown in formula a3' react with the isocyanate groups to introduce the carbon-carbon double bonds in the substance into the side chains of at least part of the repeating units shown in formula a3', so that at least part of the repeating units shown in formula a3' are converted into repeating units shown in formula a4, or at least part of the repeating units shown in formula a3' are converted into repeating units shown in formula a4 and repeating units shown in formula a5; the remaining repeating units shown in formula a3' are converted into repeating units shown in formula a3;

[0028] Wherein, the substance containing an isocyanate group is a compound represented by formula b1, or the substance containing an isocyanate group is a compound represented by formula b1 and a compound represented by formula b2:

[0029]

[0030] The repeating unit represented by a3' is And c'=c+d+e.

[0031] If the repeating unit represented by formula a3' that participates in the grafting reaction among all the repeating units represented by formula a3' is recorded as the repeating unit to be reacted, then when the grafting reaction is carried out, the -NCO in the substance containing the isocyanate group reacts with the -OH in the repeating unit to be reacted, so that the C in -NCO is connected to the O in -OH, and at the same time, the C=C in the substance containing the isocyanate group is introduced into the side chain of the repeating unit to be reacted, thereby converting the repeating unit to be reacted into the fourth repeating unit or into the fourth repeating unit and the fifth repeating unit, so that a polymer can be prepared based on the precursor, and the side group of the prepared polymer contains at least two carbon-carbon double bonds, thereby achieving the requirement of low carbon-carbon double bond equivalent of the polymer. Since the polymers are cross-linked through carbon-carbon double bonds, even if the amount of the polymer is small, the multiple carbon-carbon double bonds in the polymers can still achieve good cross-linking, thereby improving the curing performance of the solution containing the polymer.

[0032] Based on this, when the substance containing an isocyanate group is a compound represented by formula b1 and a compound represented by formula b2, the synthesis route of the polymer is as follows:

[0033]

[0034] Where c' = c + e + d;

[0035] When the substance containing an isocyanate group is a compound represented by formula b1, the synthesis route of the polymer is as follows:

[0036]

[0037] Among them, c'=c+d.

[0038] Of course, the arrangement order of the repeating units is not limited to the arrangement shown in the above synthesis route, and can also be other arrangements, such as but not limited to arranging the sixth repeating unit with a molar percentage of f at the end, which is not limited here.

[0039] Thus, in the above-mentioned synthetic route, the residues other than the isocyanate group in the substance can be introduced into the repeating unit to be reacted through a one-step grafting reaction, so that the side chain of the polymer carries the residues other than the isocyanate group in the substance, and the residue has multiple carbon-carbon double bonds, so that the polymer has multiple carbon-carbon double bonds in the measurement, which can not only improve the curing performance of the polymer, but also improve the preparation efficiency of the polymer and simplify the preparation process.

[0040] Exemplarily, the precursor can be obtained commercially or homemade, wherein the preparation method of the precursor can specifically include: free radical polymerization of four monomers having a (meth) acrylic acid structure to obtain the precursor, and the specific free radical polymerization reaction route is as follows:

[0041]

[0042] Thus, the precursor can be obtained through the above synthesis method.

[0043] It should be understood that since the principle of solving the problem of the polymer prepared in the preparation method is similar to the principle of solving the problem of the aforementioned polymer, the implementation and technical effects of the preparation method can refer to the implementation and technical effects of the aforementioned polymer, and the repeated parts will not be repeated.

[0044] In a third aspect, the present application also provides a curable composition, which includes a solvent and a polymer as described in the first aspect and any one of the embodiments of the first aspect, and the polymer can be dispersed in the solvent. In this way, when the side group of the polymer contains at least two carbon-carbon double bonds, even if the amount of the polymer is small, the carbon-carbon double bonds in each polymer can still be fully cross-linked, thereby improving the curing effect of the curable composition.

[0045] The concentration of the polymer in the curable composition can be 1wt%-40wt%, can be optimized to 5wt%-30wt%, and can be further optimized to 10wt%-25wt%. In this way, even when the amount of polymer used is small, a good curing effect can still be achieved.

[0046] For example, in addition to the solvent and the polymer, other components may be added to the curable composition according to the application scenario of the curable composition. For example, when the curable composition needs to have a color function, the curable composition may also include a pigment, a dispersant, etc.

[0047] It should be understood that since the principle of solving the problem by the curable composition is similar to the principle of solving the problem by the aforementioned polymer, the implementation and technical effects of the curable composition can refer to the implementation and technical effects of the aforementioned polymer, and the repeated parts will not be repeated. DETAILED DESCRIPTION

[0048] In order to make the objectives, technical solutions and advantages of the present application clearer, the present application will be described in further detail below.

[0050] In order to facilitate understanding of the technical solution provided by the embodiments of the present application, its application scenario is first described below.

[0051] Polymer materials with photosensitive functions are commonly used in the fields of inks, displays, image sensors, etc. Taking the color filter in the display as an example, the production process of the color filter can generally include: depositing a curable composition on a substrate, the curable composition includes: pigments, polymers, photoinitiators, solvents and other additives, under heating or light conditions, the curable composition is cured, and the curable composition is transformed from a liquid to a solid to form a film layer, and then the formed film layer is patterned to obtain a color filter with a specific pattern. Among them, the side group of the polymer generally includes a carbon-carbon double bond. When the curable composition is cured, the carbon-carbon double bond opens and cross-links, so that the curable composition is transformed from a liquid to a solid.

[0052] As the thickness of the color filter continues to decrease, while keeping the total proportion of pigments with color properties unchanged, the proportion of other components decreases accordingly. However, when the amount of polymer used continues to decrease, the curing effect of the curable composition may be affected, making it difficult for the curable composition to be fully cured.

[0053] In order to improve the curing performance of the curable composition, an embodiment of the present application provides a polymer, which may include repeating units represented by formula a1, formula a2, formula a3, formula a4, formula a5 and formula a6:

[0054]

[0055]

[0056] Among them, the repeating unit shown in formula a1 can be called the first repeating unit, the repeating unit shown in formula a2 can be called the second repeating unit, the repeating unit shown in formula a3 can be called the third repeating unit, the repeating unit shown in formula a4 can be called the fourth repeating unit, the repeating unit shown in formula a5 can be called the fifth repeating unit, and the repeating unit shown in formula a6 can be called the sixth repeating unit.

[0057] In this way, the side groups of the polymer contain at least two carbon-carbon double bonds, achieving the requirement of low carbon-carbon double bond equivalent of the polymer. Since the polymers are cross-linked through carbon-carbon double bonds, even if the amount of the polymer is small, the multiple carbon-carbon double bonds in each polymer can still achieve good cross-linking, thereby improving the curing performance of the solution containing the polymer.

[0058] Furthermore, when the polymer is used to make a photoresist, the uncrosslinked polymer can be washed away by the developer during development because the carboxyl group in the second repeating unit is acidic, while the crosslinked polymer will not be washed away by the developer even if it contains a carboxyl group, thereby achieving patterning. The acid value of the polymer in the embodiment of the present application can reach 10 mg-KOH / g to 150 mg-KOH / g, which can promote the uncrosslinked polymer to be washed away by the developer, thereby improving the effect of patterning.

[0059] Exemplarily, each R0 is independently selected from H or methyl.

[0060] R1 is selected from any one of substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C7-C30 aralkyl; further, R1 is selected from C1-C5 alkyl, phenyl, or C7-C10 aralkyl, wherein the C1-C5 alkyl as R1 can be any one of linear, branched, or cyclic, such as but not limited to: methyl, ethyl, propyl, isopropyl, pentyl, cyclopentyl, etc.; the C7-C10 aralkyl as R1 can be selected from, but not limited to: benzyl, phenethyl, naphthylmethyl, methylbenzyl, etc. The group selection of R1 can be selected according to actual conditions.

[0061] R2, R3, and R4 are each independently selected from: a single bond, a substituted or unsubstituted C1-C30 alkylene group, a substituted or unsubstituted C1-C30 alkyleneoxy group, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C6-C30 aryleneoxy group, and a substituted or unsubstituted C7-C30 arylalkylene group; further, R2, R3, and R4 are each independently selected from: a single bond or a C1-C5 alkylene group, wherein when R2 and R3 are each independently selected from a single bond, it means that the carboxyl group is directly connected to the main chain, and the ester group in the side chain of the third repeating unit is directly connected to the main chain; when R2 and R3 are each independently selected from a non-single bond, it means that the carboxyl group is connected to the main chain through other groups, and the ester group in the side chain of the third repeating unit is connected to the main chain through other groups. The C1-C5 alkylene group of R2, R3 and R4 can be selected from, but not limited to, the C1-C5 alkyl group listed in R1 above that is converted into a divalent alkylene group, such as methylene, ethylene, propylene, isopropylene, pentylene, etc. The group selection of R2, R3 and R4 can be selected according to actual conditions.

[0062] R5, R6, and R7 are each independently selected from: any one of a single bond, a substituted or unsubstituted C1-C30 alkylene group, and a substituted or unsubstituted C1-C30 ester group; further, when R5, R6, and R7 are each independently selected from a substituted or unsubstituted C1-C30 ester group, the side chains of the fourth repeating unit and the fifth repeating unit include (meth)acrylate groups. Because (meth)acrylate groups have high activity when the polymer is cross-linked, they have a promoting effect on the cross-linking reaction. Therefore, when the side group end of the polymer contains (meth)acrylate groups, the cross-linking property of the polymer can be further improved, thereby further improving the curing performance of the solution containing the polymer. Exemplarily, according to the different side group structures of each repeating unit, the equivalent weight of (meth)acrylic acid in the polymer can reach 150g / mol to 2000g / mol, so that the polymer has better curing performance. Wherein R5, R6, and R7 are each independently selected from: C1-C10 ester groups, such as but not limited to: methylene ester groups, ethylene ester groups, propylene ester groups, isopropylene ester groups, pentyl ester groups, heptyl ester groups, hexyl ester groups, decyl ester groups, etc. The group selection of R5, R6, and R7 can be selected according to actual conditions.

[0063] R8 is not limited to a specific group, and R8 can be designed according to actual conditions and is not limited here.

[0064] The molar percentage a of the first repeating unit can be optimized to 10%-70%, and further optimized to 10%-40%. Since the ester group can promote the curing of the polymer, when the polymer contains an appropriate proportion of ester groups, the curing performance of the polymer can be further improved. The molar percentage b of the second repeating unit can be optimized to 10%-50%, and further optimized to 10%-35%. Since the presence of the carboxyl group can achieve patterning, the polymer contains an appropriate proportion of carboxyl groups, which can improve the patterning effect of the polymer. The molar percentage c of the third repeating unit can be optimized to 0-80%, and further optimized to 0-10%. In this way, the amount of the fourth repeating unit and the fifth repeating unit generated can be controlled, so that the polymer has an appropriate proportion of carbon-carbon double bonds to improve the curing performance of the polymer. The molar percentage d of the fourth repeating unit can be optimized to 10%-70%, and further optimized to 20%-60%. Since the carbon-carbon double bond can achieve polymer cross-linking, the polymer contains an appropriate proportion of carbon-carbon double bonds, which can improve the cross-linking curing performance of the polymer. The molar percentage e of the fifth repeating unit can be optimized to 0-80%, and further optimized to 0-30%, so that the amount of carbon-carbon double bonds in the polymer can be increased, and the cross-linking and curing performance of the polymer can be further improved. The molar percentage f of the sixth repeating unit can be 0, and the sixth repeating unit is not included in the polymer. When the value of f is greater than 0, it means that the polymer contains the sixth repeating unit, and the molar percentage f of the sixth repeating unit can be designed according to actual conditions, and is not limited here, so as to meet the needs of the polymer in different application scenarios and improve the flexibility of the design. In addition, d: (a + b + c + e + f) can be set to 0.25-1.50, so that the molar percentage of the four repeating units in the polymer can be further adjusted to further improve the curing performance and patterning treatment effect of the polymer.

[0065] Exemplarily, the weight average molecular weight of the polymer can be 3000 g / mol to 30000 g / mol, and the polymer dispersion index can be above 1.6, which can make the polymer liquid before solidification and easy to store, and can also make the polymer better dispersed in the solvent, thereby improving the uniformity of the solution containing the polymer.

[0066] The present application also provides a method for preparing a polymer, which may include:

[0067] The precursor is subjected to a grafting reaction with a substance containing an isocyanate group to obtain a polymer;

[0068] The precursor includes repeating units represented by formula a1, formula a2, formula a3' and formula a6, and the hydroxyl groups in at least part of the repeating units represented by formula a3' react with the isocyanate groups to introduce the carbon-carbon double bonds in the substance into the side chains of at least part of the repeating units represented by formula a3', so that at least part of the repeating units represented by formula a3' are converted into repeating units represented by formula a4, or at least part of the repeating units represented by formula a3' are converted into repeating units represented by formula a4 and repeating units represented by formula a5; the remaining repeating units represented by formula a3' are converted into repeating units represented by formula a3; the substance containing the isocyanate group is the compound represented by formula b1, or the compound represented by formula b1 and the compound represented by formula b2 containing the isocyanate group:

[0069]

[0070] The repeating unit represented by a3' is And c'=c+d+e.

[0071] Thus, in the above-mentioned synthetic route, the residues other than the isocyanate group in the substance can be introduced into the repeating unit to be reacted through a one-step grafting reaction, so that the side chain of the polymer carries the residues other than the isocyanate group in the substance, and the residue has multiple carbon-carbon double bonds, so that the polymer has multiple carbon-carbon double bonds in the measurement, which can not only improve the curing performance of the polymer, but also improve the preparation efficiency of the polymer and simplify the preparation process.

[0072] The polymer is described below with reference to specific examples.

[0073] Example 1: The structural formula of polymer 1 is as follows:

[0074]

[0075] The synthetic route of polymer 1 is as follows:

[0076]

[0077] Among them, ABVN is azobisisoheptanenitrile.

[0078] The specific synthesis steps may include:

[0079] (1) Free radical polymerization reaction: Install a reflux condenser, a nitrogen inlet tube, a constant pressure dropping funnel and other devices on a three-necked flask, and add a suitable stirrer in the flask. Add 5.613g of initiator ABVN and 25g of mixed solvent a to the three-necked flask, the mixed solvent a including propylene glycol methyl ether acetate (PGMEA) and cyclohexane in a mass ratio of 2:1; introduce nitrogen to replace the air in the three-necked flask, and the replacement time is about 15min; then add 7.965g of benzyl methacrylate (BzMA), 2.918g of methacrylic acid (MAA), 19.117g of hydroxyethyl methacrylate (HEMA) and 45g of mixed solvent a to the constant pressure dropping funnel to form a monomer mixture, introduce nitrogen to replace the air in the constant pressure dropping funnel, and the replacement time is about 15min. Raise the temperature, set the reaction temperature to 70℃, and gradually add the above-mentioned monomer mixture to the three-necked flask, and control the addition to be complete within 2h. The reaction solution was stirred and reacted for 6 hours under a nitrogen atmosphere. The reaction temperature was raised to 100° C. and the reaction was continued for 1.5 hours to consume the remaining initiator, and then cooled to room temperature to obtain the precursor.

[0080] (2) Grafting reaction: Add 222.7 mg of catalyst dibutyltin dilaurate (DBTDL), 77.8 mg of stabilizer 2,6-di-tert-butyl-4-methylphenol (BHT), and 58.396 g of mixed solvent a to the reaction solution, raise the temperature to 80°C, and drop 42.170 g of monomer 1,1-bis(acryloyloxymethyl)ethyl isocyanate (BEI) and 40.000 g of mixed solvent a to the reaction solution, and control the addition to be complete within 0.5 h. Continue to react at 80°C for 1.5 h, and then cool to room temperature. The reaction solution is diluted with dichloromethane solvent, precipitated and purified in petroleum ether, and filtered to obtain a white powder solid, which is dried in a vacuum oven for 24 h to obtain polymer 1. The polymer 1 had an acid value of 27 mg-KOH / g, a weight average molecular weight Mw of 9400 g / mol, a polymer dispersion index PDI of 1.65, and a methacrylic acid equivalent of 258 g / mol.

[0081] Of course, when the amount of initiator added during the free radical polymerization reaction is adjusted, the degree of free radical polymerization can be changed, thereby changing the properties of the polymer. For example, when the amount of initiator added is reduced from 5.613 g to 2.245 g, and other reaction conditions remain unchanged, the acid value of the polymer is 30 mg-KOH / g, the weight average molecular weight Mw of the polymer is 17000 g / mol, the polymer dispersion index PDI is 1.83, and the equivalent weight of methacrylic acid is 284 g / mol.

[0082] Example 2: The structural formula of polymer 2 is as follows:

[0083]

[0084] The synthetic route of polymer 2 is as follows:

[0085]

[0086] The specific synthesis steps may include:

[0087] (1) Free radical polymerization reaction: The reaction process in this Example 2 is basically similar to the reaction process in the above Example 1, except that: the amount of initiator added is 6.340 g, the amount of BzMA added is 5.111 g, the amount of MAA added is 3.296 g, and the amount of HEMA added is 21.593 g; the specific reaction process can refer to the process of free radical polymerization reaction in the above Example 1, which will not be described in detail here.

[0088] (2) Grafting reaction: The reaction process in this Example 2 is basically similar to the reaction process in the above Example 1, except that: the amount of DBTDL added is 251.5 mg, the amount of BHT added is 87.7 mg, and the amount of BEI added is 47.631 g; the specific reaction process can refer to the process of free radical polymerization in the above Example 1, which will not be described in detail here. The acid value of the obtained polymer 2 is 21 mg-KOH / g, the weight average molecular weight Mw is 9200 g / mol, the polymer dispersion index PDI is 1.69, and the equivalent weight of methacrylic acid is 281 g / mol.

[0089] Example 3: The structural formula of polymer 3 is as follows:

[0090]

[0091] The synthetic route of polymer 3 is as follows:

[0092]

[0093] The specific synthesis steps may include:

[0094] (1) Free radical polymerization reaction: The reaction process in this embodiment 3 is basically similar to the principle of the reaction process in the above embodiment 1. The specific reaction process can be referred to the free radical polymerization process in the above embodiment 1, which will not be described in detail here.

[0095] (2) Grafting reaction: The reaction process in this Example 3 is basically similar to the principle of the reaction process in the above Example 1, except that two different compounds containing isocyanate groups are added, and the side groups of the obtained polymer contain residues of the two compounds other than isocyanate groups. The specific reaction process can be found in the free radical polymerization process in the above Example 1, which will not be described in detail here.

[0096] Obviously, those skilled in the art can make various changes and modifications to the embodiments of the present application without departing from the spirit and scope of the embodiments of the present application. Thus, if these modifications and variations of the embodiments of the present application fall within the scope of the claims of the present application and their equivalents, the present application is also intended to include these modifications and variations.

Claims

1. A polymer, characterized in that include: Repeating units represented by formula a1, formula a2, formula a3, formula a4, formula a5 and formula a6: Wherein, each of the R0 is independently selected from H or methyl; R1 is selected from any one of a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C7-C30 aralkyl group; R2, R3, and R4 are each independently selected from the group consisting of a single bond, a substituted or unsubstituted C1-C30 alkylene group, a substituted or unsubstituted C1-C30 alkyleneoxy group, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C6-C30 aryleneoxy group, and a substituted or unsubstituted C7-C30 aralkylene group; R5, R6, and R7 are each independently selected from: a single bond, a substituted or unsubstituted C1-C30 alkylene group, and a substituted or unsubstituted C1-C30 ester group; R8 is selected from: any one of a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aromatic group, and a substituted or unsubstituted C6-C30 aryloxy group; The substituents in the substituted C1-C30 alkyl, substituted C6-C30 aryl, substituted C7-C30 aralkyl, substituted C1-C30 alkylene, substituted C1-C30 alkyleneoxy, substituted C6-C30 arylene, substituted C6-C30 aryleneoxy, substituted C7-C30 aralkylene, substituted C2-C30 esterene, substituted C1-C30 alkoxy, substituted C6-C30 aromatic group, substituted C6-C30 aryloxy, substituted C1-C30 ester group are each independently selected from the group consisting of halogen, C1-C10 alkyl or C6-C30 aromatic group; a, b, c, d, e, and f are the molar percentages of the corresponding repeating units in the total repeating units, a is greater than 0 and not greater than 70%, b is greater than 0 and not greater than 60%, c is 0-80%, d is 2%-70%, e is 0-80%, f is 0-70%, and a+b+c+d+e+f=100%.

2. The polymer according to claim 1, characterized in that The R1 is selected from: C1-C5 alkyl, phenyl or C7-C10 aralkyl.

3. The polymer according to claim 1 or 2, characterized in that The R2, the R3, and the R4 are each independently selected from: a single bond or a C1-C5 alkylene group.

4. The polymer according to any one of claims 1 to 3, characterized in that The R5, the R6, and the R7 are each independently selected from: C1 to C10 ester groups.

5. The polymer according to claim 4, characterized in that The equivalent weight of (meth)acrylic acid in the polymer is 150 g / mol to 2000 g / mol.

6. The polymer according to any one of claims 1 to 5, characterized in that a is 10%-70%.

7. The polymer according to any one of claims 1 to 6, characterized in that b is 10%-50%.

8. The polymer according to any one of claims 1 to 7, characterized in that d is 10%-70%.

9. The polymer according to any one of claims 1 to 8, characterized in that d:(a+b+c+e+f)=0.25-1.

50.

10. The polymer according to any one of claims 1 to 9, characterized in that The polymer is selected from the following general formula: Wherein, R5', R6', and R7' are each independently selected from: C1-C5 alkylene.

11. The polymer according to any one of claims 1 to 10, characterized in that The weight average molecular weight of the polymer is 3000 g / mol to 30000 g / mol.

12. The polymer according to any one of claims 1 to 10, characterized in that The acid value of the polymer is 10 to 150 mg-KOH / g.

13. A method for preparing a polymer according to any one of claims 1 to 12, characterized in that: include: The precursor is subjected to a grafting reaction with a substance containing an isocyanate group to obtain the polymer; the precursor includes repeating units represented by formula a1, formula a2, formula a3' and formula a6, the hydroxyl groups in at least part of the repeating units represented by formula a3' react with the isocyanate groups, and the carbon-carbon double bonds in the substance are introduced into the side chains of at least part of the repeating units represented by formula a3', so that at least part of the repeating units represented by formula a3' are converted into repeating units represented by formula a4, or at least part of the repeating units represented by formula a3' are converted into repeating units represented by formula a4 and repeating units represented by formula a5; the remaining repeating units represented by formula a3' are converted into repeating units represented by formula a3; Wherein, the substance containing an isocyanate group is a compound represented by formula b1, or the substance containing an isocyanate group is a compound represented by formula b1 and a compound represented by formula b2: The repeating unit represented by a3' is: And c'=c+d+e.

14. A curable composition, characterized in that include: A solvent, and the polymer according to any one of claims 1 to 12, wherein the polymer is dispersed in the solvent.

15. The curable composition according to claim 14, characterized in that The concentration of the polymer in the curable composition is 1 wt% to 40 wt%.

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