Polymer compound and preparation method thereof

Abstract

The present application discloses a polymer compound and a preparation method thereof, and relates to the technical field of polymer materials. The structural formula of the polymer compound is shown as follows: A1-A2-A3-A2'-A1', wherein the A1 group and the A1' group are selected from a group having at least two ester groups, A2 and A2' are selected from a group having a polyether group and a diphenylmethane group, and A3 is selected from a group having at least two amide groups and at least two aryloxy groups. The polymer compound provided by the present application has high bonding strength, high light transmittance and excellent resistance to ultraviolet aging.

Description

Technical Field

[0001] The present application relates to the technical field of polymer materials, and in particular to a polymer compound and a preparation method thereof. Background Art

[0002] Thermoplastic polymer compounds flow and wet the surface of the substrate when heated; after cooling and solidification, they provide good bonding strength due to the cohesive effect of the polymer. Polymer compounds have the advantages of fast bonding speed, strong bonding ability, and high solid content, and are widely used in electronic equipment, automobile manufacturing, aerospace and other fields.

[0003] Polymer compounds with thermoplastic polyurethane as the main component have the advantages of high bonding strength, wide application of substrates, and good low-temperature toughness due to their rich polar carbamate groups, and have attracted widespread attention. However, due to their single chemical structure, traditional polymer compounds are difficult to meet high-demand application scenarios in terms of performance when used in fields such as bonding. For example, polyester polyurethane polymer compounds have strong crystallinity and high cohesive strength, but poor flexibility and poor moisture and heat resistance. Polyether polyurethane polymer compounds are the opposite. In addition, various additives are usually required to obtain polyurethane polymer compounds with excellent performance and strong practicality. For example, tackifying resin: improves the interfacial adhesion between polymer compounds and substrates; thermoplastic resin: improves the cohesion of polymer compounds; anti-ultraviolet agent: prevents polyurethane polymer compounds from failing and causing appearance problems due to ultraviolet aging during use. The addition of various additives seriously affects the transparency of polyurethane polymer compounds and limits their application in the pre-coating film industry. Summary of the invention

[0004] In view of this, the present application provides a polymer compound and a preparation method thereof.

[0005] The embodiments of the present application are implemented as follows. In a first aspect, the embodiments of the present application provide a polymer compound, the structural formula of the polymer compound is as shown below:

[0006] ;

[0007] Wherein, n is an integer selected from 10-20;

[0008] R1 is selected from ;

[0009] R2 is selected from .

[0010] In a second aspect, the present invention also provides a method for preparing a polymer compound, comprising the following steps:

[0011] Providing polypropylene glycol and diphenylmethane diisocyanate, mixing and reacting, and obtaining a first intermediate product, wherein the first intermediate product has a polyether group and a diphenylmethane group; wherein the molar ratio of the polypropylene glycol to the diphenylmethane diisocyanate is (0.1-0.5): (0.2-1); the structural formula of the first intermediate product is shown as follows:

[0012] ;

[0013] n is an integer selected from 10-20;

[0014] Providing 4-amino-4'-hydroxybenzophenone and N,N-methylenebisacrylamide, mixing and reacting to obtain a second intermediate product, the structural formula of the second intermediate product is shown as follows:

[0015] ;

[0016] Hydroxyethyldiethylenetriamine and methyl acrylate are provided, mixed, and reacted to obtain a third intermediate product, the structural formula of the third intermediate product is shown as follows: ;

[0017] The first intermediate product, the second intermediate product and the third intermediate product are mixed and reacted to obtain a polymer compound.

[0018] Optionally, in some embodiments of the present application, the mixing of the polypropylene glycol and the diphenylmethane diisocyanate further comprises adding a first solvent; the first solvent is selected from one or more of tetrahydrofuran, dioxane, acetone, acetonitrile, N,N-dimethylformamide, and dimethyl sulfoxide; the molar concentration of the polypropylene glycol in the first solvent is 0.1 mol / L to 0.5 mol / L; the molar concentration of the diphenylmethane diisocyanate in the first solvent is 0.2 mol / L to 1 mol / L; and / or

[0019] The reaction temperature of the polypropylene glycol and the diphenylmethane diisocyanate is 30° C. to 80° C., and the reaction time is 1 h to 8 h.

[0020] Optionally, in some embodiments of the present application, the mixing of the 4-amino-4'-hydroxybenzophenone and the N,N-methylenebisacrylamide comprises: providing a 4-amino-4'-hydroxybenzophenone dispersion and an N,N-methylenebisacrylamide dispersion, wherein the 4-amino-4'-hydroxybenzophenone dispersion comprises 4-amino-4'-hydroxybenzophenone and a second solvent, and the N,N-methylenebisacrylamide dispersion comprises N,N-methylenebisacrylamide and a third solvent; mixing the 4-amino-4'-hydroxybenzophenone dispersion and the N,N-methylenebisacrylamide dispersion;

[0021] Wherein, the second solvent and the third solvent are selected from dioxane; in the 4-amino-4'-hydroxybenzophenone dispersion, the molar concentration of the 4-amino-4'-hydroxybenzophenone is 0.2 mol / L to 1 mol / L; in the N,N-methylenebisacrylamide dispersion, the molar concentration of the N,N-methylenebisacrylamide is 0.2 mol / L to 1 mol / L; and / or

[0022] The molar ratio of the 4-amino-4'-hydroxybenzophenone to the N,N-methylenebisacrylamide is (0.2-1): (0.1-0.5); and / or

[0023] The reaction temperature of the 4-amino-4'-hydroxybenzophenone and the N,N-methylenebisacrylamide is 30°C to 80°C, and the reaction time is 8h to 20h.

[0024] Optionally, in some embodiments of the present application, the mixing of the hydroxyethyldiethylenetriamine and the methyl acrylate further comprises adding a fourth solvent; the fourth solvent is selected from one or more of methanol, ethanol, propylene glycol, butanol, trimethoxymethanol, tetrahydrofuran, acetone, acetonitrile, N,N-dimethylformamide, and dimethyl sulfoxide; the molar concentration of the hydroxyethyldiethylenetriamine in the fourth solvent is 0.1 mol / L to 0.5 mol / L; the molar concentration of the methyl acrylate in the fourth solvent is 0.4 mol / L to 2 mol / L; and / or

[0025] The molar ratio of the hydroxyethyldiethylenetriamine to the methyl acrylate is (0.1-0.5): (0.4-2); and / or

[0026] The reaction temperature of the hydroxyethyldiethylenetriamine and the methyl acrylate is 20° C. to 40° C., and the reaction time is 8 h to 20 h.

[0027] Optionally, in some embodiments of the present application, the mixing reaction of the first intermediate product, the second intermediate product and the third intermediate product includes: mixing the first intermediate product and the second intermediate product to perform a first reaction; adding the third intermediate product to perform a second reaction.

[0028] Optionally, in some embodiments of the present application, the molar ratio of the first intermediate product, the second intermediate product and the third intermediate product is (2-3): (1-2): (0.4-1); and / or

[0029] The temperature of the first reaction is 50°C to 100°C; the reaction time is 5h to 10h; and / or

[0030] The temperature of the second reaction is 50° C. to 100° C.; the reaction time is 1 h to 5 h.

[0031] Optionally, in some embodiments of the present application, the structural formula of the polymer compound is as shown below:

[0032] ;

[0033] Wherein, n is an integer selected from 10-20; R1 is selected from ; R2 is selected from .

[0034] The polymer compound provided by the present application uses polyether polyol as the soft segment of the polymer compound to ensure its transparency and flexibility; synthesizes functional diphenols with anti-ultraviolet groups and bisamide groups as chain extenders, and utilizes the strong hydrogen bonding effect of the bisamide groups and the π-π stacking effect between benzene rings to improve its cohesive strength; and connects branched molecules with multiple polar ester groups to the ends of the polyurethane chains to improve its interfacial adhesion. The polymer compound provided by the present application has high bonding strength, high light transmittance and excellent anti-ultraviolet aging ability, and has great application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For those skilled in the art, other drawings can be obtained based on these drawings without paying any creative work.

[0036] Figure 1 It is a flow chart of a method for preparing a polymer compound provided in an embodiment of the present application. DETAILED DESCRIPTION

[0037] The technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without making creative work belong to the scope of protection of the present application. In addition, it should be understood that the specific implementation methods described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0038] In this application, unless otherwise stated, directional words such as "upper" and "lower" generally refer to the upper and lower parts of the device in actual use or working state, specifically the drawing direction in the accompanying drawings; while "inner" and "outer" refer to the outline of the device. In addition, in the description of this application, the term "including" means "including but not limited to". The terms first, second, third, etc. are used only as labels and do not impose numerical requirements or establish an order.

[0039] In this application, "and / or" describes the association relationship of associated objects, indicating that there may be three relationships. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone. A and B can be singular or plural.

[0040] In this application, "at least one" means one or more, and "plurality" means two or more. "One or several", "at least one of the following" or similar expressions refer to any combination of these items, including any combination of single or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0041] Various embodiments of the present application may be presented in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity, and should not be understood as a rigid limitation on the scope of the present application; therefore, the range description should be considered to have specifically disclosed all possible sub-ranges and single numerical values ​​within the range. For example, the range description from 1 to 6 should be considered to have specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5 and 6, which apply regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any cited number (fractional or integer) within the indicated range.

[0042] In this application, "connected with a single key" " indicates a joining site or a fusion site. For example,

[0043] In express The site where R1 is connected to -OONH-.

[0044] The structural formula and molecular weight of some chemical reagents used in this application are described as follows:

[0045] Polypropylene glycol: , n = 10 ~ 20, number average molecular weight = 1000;

[0046] Diphenylmethane diisocyanate: , molecular weight = 250.26;

[0047] 4-Amino-4'-hydroxybenzophenone: , molecular weight = 213.23;

[0048] N,N-Methylenebisacrylamide: , molecular weight = 154.17;

[0049] Hydroxyethyldiethylenetriamine: , molecular weight = 147.22;

[0050] Methyl acrylate: , molecular weight = 86.09.

[0051] The technical solution of this application is as follows:

[0052] In a first aspect, an embodiment of the present application provides a polymer compound, the structural formula of the polymer compound is shown as follows: A1-A2-A3-A2'-A1', wherein the A1 group and the A1' group are selected from groups having at least two ester groups, the A2 and the A2' are selected from groups having a polyether group and a diphenylmethane group, and the A3 is selected from a group having at least two amide groups and at least two aromatic oxygen groups.

[0053] It should be noted that, in this application, an ester group refers to a structure The polyether group refers to a group with a structure of " ". Diphenylmethane refers to a group with the structure " ". Amide group refers to a group with the structure " " group.

[0054] The polymer compound provided by the present application uses polyether polyol as the soft segment of the polymer compound to ensure its transparency and flexibility; synthesizes functional diphenols with anti-ultraviolet groups and bisamide groups as chain extenders, and utilizes the strong hydrogen bonding effect of the bisamide groups and the π-π stacking effect between benzene rings to improve its cohesive strength; and connects branched molecules with multiple polar ester groups to the ends of the polyurethane chains to improve its interfacial adhesion. The polymer compound provided by the present application has high bonding strength, high light transmittance and excellent anti-ultraviolet aging ability, and has great application prospects.

[0055] In some embodiments, the A1 group and the A1' group are the same.

[0056] In some embodiments, the A2 group and the A2' group are the same.

[0057] In some embodiments, the A3 group has a symmetrical structure.

[0058] It can be understood that when the A1 group is the same as the A1' group, the A2 group is the same as the A2' group, and the A3 group has a symmetrical structure, the polymer compound has a symmetrical structure, is more stable in properties, and is more convenient to synthesize and prepare.

[0059] In some embodiments, the structural formula of the A1 group and the A1' group is as shown below:

[0060] .

[0061] In some embodiments, the structural formula of the A2 group and the A2' group is as shown below:

[0062] .

[0063] In some embodiments, the structural formula of the A3 group is as follows:

[0064] .

[0065] In some embodiments, the structural formula of the polymer compound is as shown below:

[0066] ;

[0067] Wherein, n is an integer selected from 10-20;

[0068] R1 is selected from ;

[0069] R2 is selected from .

[0070] Second, see Figure 1 The present invention provides a method for preparing a polymer compound, comprising the following steps:

[0071] S11, providing polypropylene glycol and diphenylmethane diisocyanate, mixing and reacting them to obtain a first intermediate product, wherein the first intermediate product has a polyether group and a diphenylmethane group;

[0072] S12, providing 4-amino-4'-hydroxybenzophenone and N,N-methylenebisacrylamide, mixing and reacting to obtain a second intermediate product, wherein the second intermediate product has at least two amide groups and two aromatic hydroxyl groups;

[0073] S13, providing hydroxyethyldiethylenetriamine and methyl acrylate, mixing and reacting to obtain a third intermediate product, wherein the third intermediate product has at least two ester groups;

[0074] S14, mixing the first intermediate product, the second intermediate product and the third intermediate product, and reacting them to obtain a polymer compound.

[0075] The preparation method of the polymer compound provided in the present application has simple and readily available raw materials and is easy to operate, and a polymer compound with high bonding strength, high light transmittance and excellent resistance to ultraviolet aging is prepared.

[0076] In the S11:

[0077] In some embodiments, the mixing of the polypropylene glycol and the diphenylmethane diisocyanate further comprises adding a first solvent.

[0078] In some embodiments, the first solvent is selected from one or more of tetrahydrofuran, dioxane, acetone, acetonitrile, N,N-dimethylformamide (DMF), and dimethyl sulfoxide (DMSO).

[0079] In some embodiments, the molar concentration of the polypropylene glycol in the first solvent is 0.1 mol / L to 0.5 mol / L, for example, 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L, or a range between any two values, etc. Within the molar concentration range, the polypropylene glycol is facilitated to be uniformly dissolved and dispersed.

[0080] In some embodiments, the molar concentration of the diphenylmethane diisocyanate in the first solvent is 0.2 mol / L to 1 mol / L, for example, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L, 0.6 mol / L, 0.7 mol / L, 0.8 mol / L, 0.9 mol / L, 1 mol / L or a range between any two values, etc. Within the molar concentration range, the diphenylmethane diisocyanate is facilitated to be uniformly dissolved and dispersed.

[0081] In some embodiments, the molar ratio of the polypropylene glycol to the diphenylmethane diisocyanate is (0.1-0.5): (0.2-1), for example, 0.1:0.2, 0.2:0.5, 0.3:0.7, 0.4:0.9 or any range between two values. Within the molar ratio range, it is beneficial for the diphenylmethane diisocyanate to fully react with the -H at the end of the polypropylene glycol through the cyanate group.

[0082] In some embodiments, the reaction temperature of the polypropylene glycol and the diphenylmethane diisocyanate is 30°C to 80°C, for example, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, or a range between any two values, etc.; the reaction time is 1h to 8h, for example, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, or a range between any two values, etc. Thus, under the reaction conditions, it is beneficial for the polypropylene glycol and the diphenylmethane diisocyanate to react efficiently to generate the first intermediate product.

[0083] In some embodiments, the structural formula of the first intermediate product is shown below:

[0084] ; n is an integer selected from 10-20.

[0085] In some embodiments, the synthesis route of the polypropylene glycol and the diphenylmethane diisocyanate to generate the first intermediate product is shown in the following formula:

[0086] .

[0087] It should be noted that, as shown in the first intermediate product synthesis route, 1 mol of polypropylene glycol and 2 mol of diphenylmethane diisocyanate react and combine to form 1 mol of the first intermediate product. In order to improve the reaction efficiency, an excessive amount of diphenylmethane diisocyanate can be added in an appropriate amount, but there will still be only 2 mol of diphenylmethane diisocyanate combined with 1 mol of polypropylene glycol. Therefore, after the first intermediate product is formed, the excess diphenylmethane diisocyanate needs to be removed. The following related reactions are similar. When the molar ratio of the raw materials combined is fixed, if an excessive amount of reaction raw materials is added, after each reaction, measures should be taken to remove the excess uncombined raw materials.

[0088] In S12:

[0089] In some embodiments, the mixing of the 4-amino-4'-hydroxybenzophenone and the N,N-methylenebisacrylamide comprises: providing a 4-amino-4'-hydroxybenzophenone dispersion and an N,N-methylenebisacrylamide dispersion, wherein the 4-amino-4'-hydroxybenzophenone dispersion comprises 4-amino-4'-hydroxybenzophenone and a second solvent, and the N,N-methylenebisacrylamide dispersion comprises N,N-methylenebisacrylamide and a third solvent; and mixing the 4-amino-4'-hydroxybenzophenone dispersion and the N,N-methylenebisacrylamide dispersion.

[0090] In some embodiments, the second solvent and the third solvent are selected from dioxane.

[0091] In some embodiments, in the 4-amino-4'-hydroxybenzophenone dispersion, the molar concentration of the 4-amino-4'-hydroxybenzophenone is 0.2 mol / L to 1 mol / L, for example, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L, 0.6 mol / L, 0.7 mol / L, 0.8 mol / L, 0.9 mol / L, 1 mol / L or a range between any two values, etc. Within the molar concentration range, the 4-amino-4'-hydroxybenzophenone is facilitated to be uniformly dissolved and dispersed.

[0092] In some embodiments, in the N,N-methylenebisacrylamide dispersion, the molar concentration of the N,N-methylenebisacrylamide is 0.2 mol / L to 1 mol / L, for example, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L, 0.6 mol / L, 0.7 mol / L, 0.8 mol / L, 0.9 mol / L, 1 mol / L or a range between any two values, etc. Within the molar concentration range, the uniform dissolution and dispersion of the N,N-methylenebisacrylamide is facilitated.

[0093] In some embodiments, the molar ratio of the 4-amino-4'-hydroxybenzophenone to the N,N-methylenebisacrylamide is (0.2-1):(0.1-0.5), for example, 0.2:0.1, 0.5:0.2, 0.7:0.3, 0.9:0.4, or any range between two values. Within the molar ratio range, the N,N-methylenebisacrylamide is conducive to the reaction with the 4-amino-4'-hydroxybenzophenone.

[0094] In some embodiments, the temperature of the reaction of the 4-amino-4'-hydroxybenzophenone and the N,N-methylenebisacrylamide is 30°C to 80°C, for example, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, or a range between any two values, etc.; the reaction time is 8h to 20h, for example, 8h, 10h, 12h, 15h, 18h, 20h, or a range between any two values, etc. Thus, under the reaction conditions, it is conducive to the efficient reaction of the 4-amino-4'-hydroxybenzophenone and the N,N-methylenebisacrylamide to generate the second intermediate product.

[0095] In some embodiments, the structural formula of the second intermediate product is as shown below:

[0096] .

[0097] In some embodiments, the synthesis route of the reaction of the 4-amino-4'-hydroxybenzophenone and the N,N-methylenebisacrylamide to generate the second intermediate product is shown in the following formula:

[0098] .

[0099] In S13:

[0100] In some embodiments, the mixing of the hydroxyethyldiethylenetriamine and the methyl acrylate further comprises adding a fourth solvent.

[0101] In some embodiments, the fourth solvent is selected from one or more of methanol, ethanol, propylene glycol, butanol, trimethoxymethanol, tetrahydrofuran, acetone, acetonitrile, N,N-dimethylformamide (DMF), and dimethyl sulfoxide (DMSO).

[0102] In some embodiments, the molar concentration of the hydroxyethyldiethylenetriamine in the fourth solvent is 0.1 mol / L to 0.5 mol / L, for example, 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L or a range between any two values, etc. Within the molar concentration range, the hydroxyethyldiethylenetriamine is facilitated to be uniformly dissolved and dispersed.

[0103] In some embodiments, the molar concentration of the methyl acrylate in the fourth solvent is 0.4 mol / L to 2 mol / L, for example, 0.4 mol / L, 0.5 mol / L, 0.8 mol / L, 1 mol / L, 1.2 mol / L, 1.5 mol / L, 1.8 mol / L or a range between any two values, etc. Within the molar concentration range, the methyl acrylate is facilitated to be uniformly dissolved and dispersed.

[0104] In some embodiments, the molar ratio of the hydroxyethyldiethylenetriamine to the methyl acrylate is (0.1-0.5):(0.4-2), for example, 0.1:0.4, 0.2:0.9, 0.3:1.4, 0.4:1.9 or any range between two values. Within the molar ratio range, it is beneficial for the methyl acrylate to fully react with the amino group in the hydroxyethyldiethylenetriamine.

[0105] In some embodiments, the reaction temperature of the hydroxyethyldiethylenetriamine and the methyl acrylate is 20°C to 40°C, for example, 20°C, 22°C, 25°C, 28°C, 30°C, 32°C, 35°C, 38°C, 40°C, or any range between two values, etc.; the reaction time is 8h to 20h, for example, 8h, 10h, 12h, 15h, 18h, 20h, or any range between two values, etc. Thus, under the reaction conditions, the hydroxyethyldiethylenetriamine and the methyl acrylate are conducive to the efficient reaction to generate the third intermediate product.

[0106] In some embodiments, the third intermediate product has a structural formula as shown below:

[0107] .

[0108] In some embodiments, the synthesis route of the reaction of the hydroxyethyldiethylenetriamine and the methyl acrylate to generate the third intermediate product is shown in the following formula:

[0109] .

[0110] In said S14:

[0111] In some embodiments, the mixing reaction of the first intermediate product, the second intermediate product and the third intermediate product includes: mixing the first intermediate product and the second intermediate product to perform a first reaction; adding the third intermediate product to perform a second reaction.

[0112] In some embodiments, the molar ratio of the first intermediate product, the second intermediate product and the third intermediate product is (2-3): (1-2): (0.4-1), for example, 2:1.5:1, 2:1.6:0.8, 2:1.7:0.6, 2:1.8:0.4 or a range between any two values. Within the molar ratio range, the first intermediate product, the second intermediate product and the third intermediate product are conducive to reacting.

[0113] In some embodiments, the temperature of the first reaction is 50°C to 100°C, for example, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, or any range between two values, etc.; the reaction time is 5h to 10h, for example, 5h, 6h, 7h, 8h, 9h, or any range between two values, etc. Thus, under the reaction conditions, the first intermediate product and the second intermediate product are conducive to efficient reaction.

[0114] In some embodiments, the temperature of the second reaction is 50°C to 100°C, for example, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, or any range between two values, etc.; the reaction time is 1h to 5h, for example, 1h, 2h, 3h, 4h, 5h, or any range between two values, etc. Thus, under the reaction conditions, it is conducive to the efficient reaction of the third intermediate product to generate a polymer compound.

[0115] In some embodiments, the structural formula of the polymer compound is as shown below:

[0116] ;

[0117] Wherein, n is an integer selected from 10-20;

[0118] R1 is selected from ;

[0119] R2 is selected from .

[0120] The present application is described in detail below through specific embodiments. The following embodiments are only partial embodiments of the present application and are not limitations of the present application.

[0121] Embodiment 1: This embodiment provides a polymer compound, and its preparation method comprises the following steps:

[0122] Step 1: Weigh 0.02 mol of polypropylene glycol and 100 g of anhydrous tetrahydrofuran into a 250 mL three-necked flask, stir and mix evenly, add 0.04 mol of diphenylmethane diisocyanate, pass nitrogen gas for protection, react at 60° C. for 4 h, and remove tetrahydrofuran in the system by rotary evaporation at 50° C. to obtain a first intermediate product;

[0123] Step 2: Weigh 0.02 mol of 4-amino-4'-hydroxybenzophenone and 50 g of dioxane into a 250 mL three-necked flask, heat to 60° C., stir until 4-amino-4'-hydroxybenzophenone is completely dissolved, then dissolve 0.01 mol of N,N-methylenebisacrylamide in 20 g of dioxane, gradually drop N,N-methylenebisacrylamide / dioxane dispersion into 4-amino-4'-hydroxybenzophenone / dioxane dispersion under nitrogen protection, react at 60° C. for 12 h, and remove residual dioxane by rotary evaporation at 60° C. to obtain a second intermediate product;

[0124] Step 3: Weigh 0.02 mol of hydroxyethyldiethylenetriamine, 0.08 mol of methyl acrylate, and 50 g of methanol into a 100 mL three-necked flask, introduce nitrogen gas for protection, react at 25° C. for 12 h, and remove residual methanol by rotary evaporation at 40° C. to obtain a third intermediate product;

[0125] Step 4: Add 100 g of dioxane to 0.02 mol of the first intermediate product obtained in step 1, heat to 80°C, stir until the product is completely dissolved, add 0.015 mol of the second intermediate product obtained in step 2, add 2 drops of dibutyltin dilaurate (catalyst), react at 80°C for 8 hours in a nitrogen atmosphere, then add 0.01 mol of the third intermediate product obtained in step 3, continue to react for 2 hours, pour out the product, and dry it in a vacuum oven at 80°C for 3 hours to obtain a polymer compound.

[0126] Example 2: This example is basically the same as Example 1, except that the amounts of the intermediate products in step 4 are: 0.02 mol of the first intermediate product, 0.016 mol of the second intermediate product, and 0.008 mol of the third intermediate product.

[0127] Example 3: This example is basically the same as Example 1, except that the amounts of the intermediate products in step 4 are: 0.02 mol of the first intermediate product, 0.017 mol of the second intermediate product, and 0.006 mol of the third intermediate product.

[0128] Example 4: This example is basically the same as Example 1, except that the amounts of the intermediate products in step 4 are: 0.02 mol of the first intermediate product, 0.018 mol of the second intermediate product, and 0.004 mol of the third intermediate product.

[0129] In addition, the polymer compound provided by the present invention can also be applied to other use scenarios, such as when the bonding substrate cannot withstand the hot melting temperature of the polymer compound; the polymer compound of the present invention can also be formulated into a solvent-based polymer composition for pre-coating bonding. The present application is specifically described below through specific examples, and the following examples are only some examples of the present application and are not intended to limit the present application.

[0130] Embodiment 5: This embodiment provides a solvent-based adhesive, and its preparation method comprises the following steps:

[0131] Step 1: Weigh 0.02 mol of polypropylene glycol and 100 g of anhydrous tetrahydrofuran into a 250 mL three-necked flask, stir and mix evenly, add 0.04 mol of diphenylmethane diisocyanate, pass nitrogen gas for protection, react at 60° C. for 4 h, and remove tetrahydrofuran in the system by rotary evaporation at 50° C. to obtain a first intermediate product;

[0132] Step 2: Weigh 0.02 mol of 4-amino-4'-hydroxybenzophenone and 50 g of dioxane into a 250 mL three-necked flask, heat to 60° C., stir until 4-amino-4'-hydroxybenzophenone is completely dissolved, then dissolve 0.01 mol of N,N-methylenebisacrylamide in 20 g of dioxane, gradually drop N,N-methylenebisacrylamide / dioxane dispersion into 4-amino-4'-hydroxybenzophenone / dioxane dispersion under nitrogen protection, react at 60° C. for 12 h, and remove residual dioxane by rotary evaporation at 60° C. to obtain a second intermediate product;

[0133] Step 3: Weigh 0.02 mol of hydroxyethyldiethylenetriamine, 0.08 mol of methyl acrylate, and 50 g of methanol into a 100 mL three-necked flask, introduce nitrogen gas for protection, react at 25° C. for 12 h, and remove residual methanol by rotary evaporation at 40° C. to obtain a third intermediate product;

[0134] Step 4: Add 100 g of dioxane to 0.02 mol of the first intermediate product obtained in step 1, heat to 80°C, stir until the product is completely dissolved, add 0.017 mol of the second intermediate product obtained in step 2, add 2 drops of dibutyltin dilaurate (catalyst), react at 80°C for 8 hours in a nitrogen atmosphere, then add 0.006 mol of the third intermediate product obtained in step 3, continue to react for 2 hours, add about 300 g of dioxane, stir to mix evenly, pour out the reaction solution, and obtain a solvent-based adhesive with a solid content of 10 wt%.

[0135] Example 6: This example is basically the same as Example 5, except that in step 4, about 150 g of dioxane is added, stirred and mixed evenly, and the reaction liquid is poured out to obtain a solvent-based adhesive with a solid content of 15 wt%.

[0136] Example 7: This example is basically the same as Example 5, except that in step 4, about 80 g of dioxane is added, stirred and mixed evenly, and the reaction liquid is poured out to obtain a solvent-based adhesive with a solid content of 20 wt%.

[0137] Example 8: This example is basically the same as Example 5, except that in step 4, about 40 g of dioxane is added, stirred and mixed evenly, and the reaction liquid is poured out to obtain a solvent-based adhesive with a solid content of 20 wt%.

[0138] Comparative Example: This comparative example 1 provides a hot-melt polymer compound, which is a commercially available polyurethane polymer special adhesive strip (purchased from Jianliang Adhesive Products Factory, Shunde District, Foshan City).

[0139] This comparative example 2 provides a solvent-based polymer composition, which is a commercially available single-component moisture-curing polyurethane adhesive (purchased from Hengshui Shuohan Road and Bridge Maintenance Engineering Co., Ltd.).

[0140] The polymer compounds of Examples 1 to 4 and the hot-melt polymer compound of Comparative Example 1 were tested for bonding strength (T-peel strength, shear strength). The polymer compounds of the same mass were melted at 150°C, pressed with two substrates, cooled to room temperature and solidified, and then tested. The test results are shown in Table 1.

[0141] The solvent-based polymer compositions of Examples 5 to 8 and the solvent-based polymer composition of Comparative Example 2 were tested for bonding strength (T-peel strength, shear strength). The same volume of solvent-based polymer compositions were selected, compacted with two substrates, heated and dried at 50° C. to solidify the solvent, and then tested. See Table 1 for the test results.

[0142] The T-peel strength test was carried out in accordance with the standard GB / T 2791-1995, and the substrate used in the test was PVC artificial leather. The shear strength test was carried out in accordance with the standard GB / T 7124-2008, and the substrate used was hard PVC board.

[0143] The UV aging experiment was carried out in a UV aging box, using a UVA lamp with a wavelength of 315-400nm as the light source, the aging temperature was 90℃, and the aging time was 24h;

[0144] .

[0145] As shown in Table 1, the hot-melt polymer compounds provided in Examples 1 to 4 and the solvent-based polymer compositions provided in Examples 5 to 8 have significantly higher T-peel strength and shear strength than the comparative example, whether in normal state or after UV aging. Before UV aging, the polymer compound of Example 4 has higher bonding strength, and after UV aging, the polymer compound of Example 3 has better bonding strength. When applied to the field of pre-coating bonding, the polymer compound provided in this application has higher bonding strength and excellent resistance to UV aging.

[0146] The technical solutions provided by the embodiments of the present application are introduced in detail above. Specific examples are used herein to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the method of the present application and its core idea. At the same time, for technical personnel in this field, according to the idea of ​​the present application, there will be changes in the specific implementation methods and application scope. In summary, the content of this specification should not be understood as a limitation on the present application.

Claims

1. A polymer compound, characterized in that The structural formula of the polymer compound is shown below: ； Wherein, n is an integer selected from 10-20; R1 is selected from ; R2 is selected from .

2. A method for preparing a polymer compound, characterized in that: The steps include: Providing polypropylene glycol and diphenylmethane diisocyanate, mixing and reacting, and obtaining a first intermediate product, wherein the first intermediate product has a polyether group and a diphenylmethane group; wherein the molar ratio of the polypropylene glycol to the diphenylmethane diisocyanate is (0.1-0.5): (0.2-1); the structural formula of the first intermediate product is shown as follows: ； n is an integer selected from 10-20; Providing 4-amino-4'-hydroxybenzophenone and N,N-methylenebisacrylamide, mixing and reacting to obtain a second intermediate product, the structural formula of the second intermediate product is shown as follows: ； Hydroxyethyldiethylenetriamine and methyl acrylate are provided, mixed, and reacted to obtain a third intermediate product, the structural formula of the third intermediate product is shown as follows: ; The first intermediate product, the second intermediate product and the third intermediate product are mixed and reacted to obtain a polymer compound.

3. The preparation method according to claim 2, characterized in that: The mixing of the polypropylene glycol and the diphenylmethane diisocyanate further comprises adding a first solvent; the first solvent is selected from one or more of tetrahydrofuran, dioxane, acetone, acetonitrile, N,N-dimethylformamide, and dimethyl sulfoxide; the molar concentration of the polypropylene glycol in the first solvent is 0.1 mol / L to 0.5 mol / L; the molar concentration of the diphenylmethane diisocyanate in the first solvent is 0.2 mol / L to 1 mol / L; and / or The reaction temperature of the polypropylene glycol and the diphenylmethane diisocyanate is 30° C. to 80° C., and the reaction time is 1 h to 8 h.

4. The preparation method according to claim 2, characterized in that: The mixing of the 4-amino-4'-hydroxybenzophenone and the N,N-methylenebisacrylamide comprises: providing a 4-amino-4'-hydroxybenzophenone dispersion and an N,N-methylenebisacrylamide dispersion, wherein the 4-amino-4'-hydroxybenzophenone dispersion comprises 4-amino-4'-hydroxybenzophenone and a second solvent, and the N,N-methylenebisacrylamide dispersion comprises N,N-methylenebisacrylamide and a third solvent; mixing the 4-amino-4'-hydroxybenzophenone dispersion and the N,N-methylenebisacrylamide dispersion; Wherein, the second solvent and the third solvent are selected from dioxane; in the 4-amino-4'-hydroxybenzophenone dispersion, the molar concentration of the 4-amino-4'-hydroxybenzophenone is 0.2 mol / L to 1 mol / L; in the N,N-methylenebisacrylamide dispersion, the molar concentration of the N,N-methylenebisacrylamide is 0.2 mol / L to 1 mol / L; and / or The molar ratio of the 4-amino-4'-hydroxybenzophenone to the N,N-methylenebisacrylamide is (0.2-1): (0.1-0.5); and / or The reaction temperature of the 4-amino-4'-hydroxybenzophenone and the N,N-methylenebisacrylamide is 30°C to 80°C, and the reaction time is 8h to 20h.

5. The preparation method according to claim 2, characterized in that: The mixing of the hydroxyethyldiethylenetriamine and the methyl acrylate further comprises adding a fourth solvent; the fourth solvent is selected from one or more of methanol, ethanol, propylene glycol, butanol, trimethoxymethanol, tetrahydrofuran, acetone, acetonitrile, N,N-dimethylformamide, and dimethyl sulfoxide; the molar concentration of the hydroxyethyldiethylenetriamine in the fourth solvent is 0.1 mol / L to 0.5 mol / L; the molar concentration of the methyl acrylate in the fourth solvent is 0.4 mol / L to 2 mol / L; and / or The molar ratio of the hydroxyethyldiethylenetriamine to the methyl acrylate is (0.1-0.5): (0.4-2); and / or The reaction temperature of the hydroxyethyldiethylenetriamine and the methyl acrylate is 20° C. to 40° C., and the reaction time is 8 h to 20 h.

6. The preparation method according to claim 2, characterized in that: The mixing reaction of the first intermediate product, the second intermediate product and the third intermediate product includes: mixing the first intermediate product and the second intermediate product to perform a first reaction; adding the third intermediate product to perform a second reaction.

7. The preparation method according to claim 6, characterized in that: The molar ratio of the first intermediate product, the second intermediate product and the third intermediate product is (2-3): (1-2): (0.4-1); and / or The temperature of the first reaction is 50°C to 100°C; the reaction time is 5h to 10h; and / or The temperature of the second reaction is 50° C. to 100° C.; the reaction time is 1 h to 5 h.

8. The preparation method according to claim 2, characterized in that: The structural formula of the polymer compound is shown below: ； Wherein, n is an integer selected from 10-20; R1 is selected from ; R2 is selected from .

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