Polymer as well as preparation method and application thereof

Abstract

The invention relates to a polymer preparation method, which comprises: S1, carrying out an esterification reaction on diamine, dihydric alcohol and dibasic acid to obtain carboxyl-terminated polyesteramide; s2, adding an epoxy organic silicon monomer into the carboxyl-terminated polyesteramide obtained in the step S1, and carrying out an addition reaction to obtain a hydroxyl-terminated intermediate monomer; and S3, adding an isocyanate monomer into the hydroxyl-terminated intermediate monomer obtained in the step S2, and carrying out a polymerization reaction to obtain the polymer, wherein in the step S1, the ratio of the molar weight of the diamine to the molar weight of the binary acid is (0.2-0.5): 1; the ratio of the total molar weight of the dihydric alcohol and the diamine to the molar weight of the binary acid is 1: (1.1-1.3). The preparation method has the advantages of simple process, high crystallization rate, good fluidity, and certain wear resistance and flexibility.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to a polymer, its preparation method, and its applications. Background Technology

[0002] Ultra-high line speed 3D printing represents a significant leap in printing efficiency compared to traditional 3D printing technologies, propelling the technology from "prototype manufacturing" to a new stage of "mass production." Achieving ultra-high line speeds relies on the collaborative innovation of hardware structure, intelligent algorithms, and specialized materials. Because traditional materials struggle to withstand extremely rapid heating and extrusion processes, manufacturers have developed dedicated high-speed printing filaments with superior flowability, abrasion resistance, toughness, and crystallization rate.

[0003] In the prior art, patent CN111808259B discloses a 3D printing silicone rubber, its preparation method, and its application. This involves reacting amino- or hydroxyl-terminated polydimethylsiloxane, diisocyanate, aminopyrazole compounds, and a crosslinking agent in a specific molar ratio to prepare a prepolymer, which is then cured by heating, effectively improving the mechanical strength of the printed product. CN112679691B discloses an organosilicon-modified polyamide-imide for cookware coatings and its preparation method. This method achieves organosilicon-modified polyamide-imide through chemical bonding, improving the poor compatibility between PAI and organosilicon. However, both methods require a large amount of solvent during the reaction process, which needs to be removed at the end, making the process complex. On the other hand, CN116715950A discloses a 3D printing elastomer material and its preparation method that accelerates the crystallization rate. This method increases the crystallization rate by adding a crystallization aid to the 3D printing elastomer material. However, this scheme is based on physical blending, which can lead to poor material compatibility and aid migration problems during later use.

[0004] Therefore, there is an urgent need to develop a polymer suitable for ultra-high linear speed 3D printing, which has a simple synthesis process and equipment, high crystallization rate, good flowability, and certain wear resistance and flexibility. Summary of the Invention

[0005] To address the aforementioned problems, this invention provides a method for preparing a polymer. The preparation method is simple, has a high crystallization rate, good flowability, and certain wear resistance and flexibility.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: This invention provides a method for preparing a polymer, comprising the following steps: S1: Diamine, diol and diacid undergo esterification to obtain carboxyl-terminated polyesteramide; S2: Add an epoxy organosilicon monomer to the carboxyl-terminated polyesteramide obtained in step S1 to carry out an addition reaction to obtain a hydroxyl-terminated intermediate monomer. S3: Add isocyanate monomer to the hydroxyl-terminated intermediate monomer obtained in step S2 to carry out a polymerization reaction to obtain the polymer; In step S1, the molar ratio of the diamine to the dicarboxylic acid is (0.2~0.5):1. The ratio of the total molar amount of the diol and the diamine to the molar amount of the dicarboxylic acid is 1:(1.1~1.3).

[0007] Preferably, in step S1, the diamine is selected from C 6-14 The aliphatic linear diamine; preferably one or more of hexamethylenediamine, decanediamine, dodecanediamine, and tetradecanediamine.

[0008] Preferably, the dicarboxylic acid is selected from one or more of terephthalic acid, isophthalic acid, succinic acid, adipic acid, and sebacic acid.

[0009] Preferably, the diol is selected from one or more of ethylene glycol, butanediol, 2-methyl-1,3-propanediol, hexanediol, and 1,4-cyclohexanediethanol.

[0010] Preferably, in step S1, the esterification reaction is carried out in the presence of catalyst A.

[0011] Preferably, the catalyst A is selected from one or more of tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate, p-toluenesulfonic acid, zinc acetate, and tetraisopropyl titanate, and is preferably tetrabutyl titanate and / or zinc acetate.

[0012] Preferably, the esterification reaction is carried out at a temperature of 230~240℃.

[0013] Preferably, the esterification reaction is carried out at a stirring rate of 60-100 r / min.

[0014] Preferably, the esterification reaction ends with a hydroxyl value of less than 5 mg KOH / g.

[0015] Preferably, in step S2, the epoxy organosilicon monomer is selected from single-terminated epoxy polysiloxanes with the following structural formula: ; Wherein, n is 5 to 20, and the number average molecular weight of the epoxy organosilicon monomer is 500 to 2000.

[0016] Preferably, the ratio of the total molar amount of the diol, the diamine, and twice the molar amount of the epoxy organosilicon monomer to the molar amount of the diacid is 1:1.

[0017] Preferably, in step S2, the temperature of the addition reaction is 110~120℃.

[0018] Preferably, the addition reaction is carried out at a stirring rate of 60-100 r / min.

[0019] Preferably, the addition reaction ends with an acid value of less than 5 mg KOH / g.

[0020] Preferably, in step S3, the isocyanate monomer is selected from one or more of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate, and is more preferably diphenylmethane diisocyanate.

[0021] Preferably, the molar ratio of the NCO group in the isocyanate monomer to the OH group in the hydroxyl-terminated intermediate monomer is (1.0-1.02):1.

[0022] Preferably, in step S3, the polymerization reaction is carried out in the presence of catalyst B.

[0023] Preferably, the catalyst B is selected from one or more of dibutyltin dilaurate, stannous octoate, and stannous chloride, and is preferably dibutyltin dilaurate.

[0024] Preferably, the polymerization reaction is carried out at a temperature of 80~100℃.

[0025] Preferably, the polymerization reaction takes 0.5 to 4 hours.

[0026] The present invention also provides a polymer, which is prepared by any of the preparation methods described above.

[0027] The present invention also provides a polymer prepared by any of the above methods or the application of the above polymer in 3D printing filaments.

[0028] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. The preparation method of this invention adopts a stepwise feeding approach. By precisely controlling the material ratio at each reaction stage, the accurate design of the product's molecular structure and the reliability of its performance are ensured. Diamine, diol, and diacid are added to a reaction vessel to synthesize carboxyl-terminated polyesteramide. The ratio of the total molar amount of the diol and diamine to the molar amount of the diacid is strictly controlled to be 1:(1.1~1.3), and the amount of diamine added is limited to 20-50% of the molar amount of the diacid. This lays the foundation for constructing a prepolymer with suitable chain length and sufficient carboxyl reaction sites, directly affecting the crystallization properties and subsequent modification effects of the material.

[0029] 2. In the key step of introducing organosilicon segments, the molar ratio of the diol, the diamine, and twice the molar amount of the epoxy organosilicon monomer to the molar amount of the diacid was precisely calculated and added by controlling the ratio to 1:1. This ratio control ensures that the organosilicon can be uniformly and quantitatively grafted onto the polymer backbone through chemical bonds, thereby effectively regulating the final polymer's flowability, abrasion resistance, and high-temperature resistance.

[0030] 3. The final performance of this invention depends on a precise chain extension reaction guided by the hydroxyl value. By measuring the hydroxyl value of the hydroxyl-terminated intermediate monomer and strictly adding isocyanate monomers within the range of NCO:OH molar ratio (1.0-1.02):1, the precise ratio within this range is the key to obtaining a polymer with high hydrogen bond density, which directly determines the final strength, toughness, and rapid crystallization ability of the material.

[0031] 4. This invention employs a one-step reactor synthesis method, completing all steps within the same reactor. This avoids the use of large amounts of solvent and cumbersome solvent removal processes found in existing technologies, thus reducing energy consumption and environmental impact. The entire preparation process also sets clear control indicators for reaction endpoints, such as a hydroxyl value of less than 5 mg KOH / g at the completion of the first-stage esterification reaction and an acid value of less than 5 mg KOH / g at the completion of the second-stage addition reaction. These precise quantitative indicators and strict material ratio control make it suitable for industrial production. Detailed Implementation

[0032] To make the technical solution and beneficial effects of the present invention more apparent and understandable, a detailed description is provided below by listing specific embodiments. Unless otherwise defined, the technical and scientific terms used herein have the same meanings as those in the technical field to which this application pertains.

[0033] This invention provides a method for preparing a polymer, comprising the following steps: S1: Diamine, diol and diacid undergo esterification to obtain carboxyl-terminated polyesteramide; S2: Add an epoxy organosilicon monomer to the carboxyl-terminated polyesteramide obtained in step S1 to carry out an addition reaction to obtain a hydroxyl-terminated intermediate monomer. S3: Add isocyanate monomer to the hydroxyl-terminated intermediate monomer obtained in step S2 to carry out a polymerization reaction to obtain the polymer; In step S1, the molar ratio of the diamine to the dicarboxylic acid is (0.2~0.5):1. The ratio of the total molar amount of the diol and the diamine to the molar amount of the dicarboxylic acid is 1:(1.1~1.3).

[0034] In some embodiments, in step S1, the diamine is selected from C 6-14 Aliphatic linear diamines.

[0035] In some embodiments, in step S1, the diamine is selected from one or more of bis(diamine), decanediamine, dodecanediamine, and tetradecanediamine.

[0036] In some embodiments, in step S1, the diamine is selected from self-diamine and / or decanediamine.

[0037] In some embodiments, in step S1, the diamine is selected as self-diamine.

[0038] In some embodiments, in step S1, the diamine is selected from sebacic acid.

[0039] In some embodiments, the dicarboxylic acid is selected from one or more of terephthalic acid, isophthalic acid, succinic acid, adipic acid, and sebacic acid.

[0040] In some embodiments, the dicarboxylic acid is selected from one or more of terephthalic acid, isophthalic acid, and adipic acid.

[0041] In some embodiments, the dicarboxylic acid is selected from a mixed solution of terephthalic acid, isophthalic acid, and adipic acid.

[0042] In some embodiments, the molar ratio of terephthalic acid, isophthalic acid and adipic acid in the mixed solution is (1~5):(1~5):(1~5).

[0043] In some embodiments, the molar ratio of terephthalic acid, isophthalic acid and adipic acid in the mixed solution is (2~5):1:(2~4).

[0044] In some embodiments, the molar ratio of terephthalic acid, isophthalic acid and adipic acid in the mixed solution is (2.5~5):1:(2~4).

[0045] In some embodiments, the diol is selected from one or more of ethylene glycol, butanediol, 2-methyl-1,3-propanediol, hexanediol, and 1,4-cyclohexanediethanol.

[0046] In some embodiments, the diol is selected from one or more of butanediol, hexanediol, and 1,4-cyclohexanediethanol.

[0047] In some embodiments, the diol is selected from a mixed solution of butanediol, hexanediol, and 1,4-cyclohexanediethanol.

[0048] In some embodiments, the molar ratio of butanediol, hexanediol and 1,4-cyclohexanediethanol in the mixed solution is (1~10):(0~10):(1~12).

[0049] In some embodiments, in step S1, the esterification reaction is carried out in the presence of catalyst A.

[0050] In some embodiments, the catalyst A is selected from one or more of tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate, p-toluenesulfonic acid, zinc acetate, and tetraisopropyl titanate.

[0051] In some embodiments, catalyst A is selected from one or more of tetrapropyl titanate, tetrabutyl titanate, zinc acetate, and tetraisopropyl titanate.

[0052] In some embodiments, catalyst A is selected from tetrapropyl titanate and / or zinc acetate.

[0053] In some embodiments, catalyst A is selected from tetrapropyl titanate and zinc acetate.

[0054] In some embodiments, catalyst A is selected from tetrabutyl titanate and / or zinc acetate.

[0055] In some embodiments, catalyst A is selected from tetrabutyl titanate and zinc acetate.

[0056] In some embodiments, in step S1, the amount of catalyst A is 50 to 500 ppm of the total amount of feed into the reaction system.

[0057] In some embodiments, in step S1, the amount of catalyst A is 100-300 ppm of the total amount of feed into the reaction system.

[0058] In some embodiments, in step S1, the amount of catalyst A is 100-150 ppm of the total amount of feed into the reaction system.

[0059] In some embodiments, the esterification reaction is carried out under nitrogen protection.

[0060] In some embodiments, the heating rate of the esterification reaction is 1~2 °C / min.

[0061] In some embodiments, the esterification reaction is carried out at a temperature of 230-240°C.

[0062] In some embodiments, the esterification reaction is carried out at a stirring rate of 60 to 100 r / min.

[0063] In some embodiments, the esterification reaction is defined as ending with a hydroxyl value of less than 5 mg KOH / g.

[0064] In some embodiments, in step S2, the epoxy organosilicon monomer is selected from single-terminated epoxy polysiloxanes with the structural formula: ; Wherein, n is 5~20, for example, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, etc.; the number average molecular weight of the epoxy organosilicon monomer is 500~2000, for example, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, etc.

[0065] In some implementations, n is 7 to 15.

[0066] In some implementations, n is 9 to 12.

[0067] In some embodiments, the number-average molecular weight of the epoxy silicone monomer is 700 to 1500.

[0068] In some embodiments, the number-average molecular weight of the epoxy silicone monomer is 900-1200.

[0069] In some embodiments, the total molar amount of the diol, the diamine, and twice the molar amount of the epoxy organosilicon monomer is in a 1:1 ratio to the molar amount of the diacid.

[0070] In some embodiments, the temperature of the addition reaction in step S2 is 110~120°C.

[0071] In some embodiments, the addition reaction is carried out under nitrogen protection.

[0072] In some embodiments, the addition reaction is carried out at a stirring rate of 60 to 100 r / min.

[0073] In some embodiments, the addition reaction is defined as ending with an acid value of less than 5 mg KOH / g.

[0074] In some embodiments, after step S2, the method further includes: performing a hydroxyl value test on the hydroxyl-terminated intermediate monomer.

[0075] In some embodiments, in step S3, the isocyanate monomer is selected from one or more of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.

[0076] In some embodiments, in step S3, the isocyanate monomer is selected from diphenylmethane diisocyanate.

[0077] In some embodiments, the molar ratio of the NCO group in the isocyanate monomer to the OH group in the hydroxyl-terminated intermediate monomer is (1.0-1.02):1.

[0078] In some embodiments, in step S3, the polymerization reaction is carried out in the presence of catalyst B.

[0079] In some embodiments, the catalyst B is selected from one or more of dibutyltin dilaurate, stannous octoate, and stannous chloride.

[0080] In some embodiments, the catalyst B is selected from dibutyltin dilaurate.

[0081] In some embodiments, in step S3, the amount of catalyst B is 50 to 500 ppm of the total feed amount of the reaction system.

[0082] In some embodiments, in step S3, the amount of catalyst B is 200-400 ppm of the total feed amount of the reaction system.

[0083] In some embodiments, in step S3, the amount of catalyst B is 250-350 ppm of the total feed amount of the reaction system.

[0084] In some embodiments, the polymerization reaction is carried out under nitrogen protection.

[0085] In some embodiments, the polymerization reaction is carried out at a temperature of 80-100°C, for example, 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, 86°C, 87°C, 88°C, 89°C, 90°C, 91°C, 92°C, 93°C, 94°C, 95°C, 96°C, 97°C, 98°C, 99°C, 100°C, etc.

[0086] In some embodiments, the polymerization reaction takes 0.5 to 4 hours.

[0087] In some embodiments, the polymerization reaction takes 0.5 to 2 hours.

[0088] The present invention also provides a polymer, which is prepared by any of the preparation methods described above.

[0089] The present invention also provides a polymer prepared by any of the above methods or the application of the above polymer in 3D printing filaments.

[0090] In some embodiments, the 3D printing filament is an ultra-high line speed 3D printing filament.

[0091] Where specific experimental steps or conditions are not specified in the embodiments, they can be performed according to the conventional experimental steps or conditions described in the literature in this field. All materials used are commercially available conventional products, including but not limited to the materials used in the embodiments of this invention.

[0092] The methods for determining AV (acid value) and OHV (hydroxyl value) in this invention are as follows: AV (Acid Value): GB / T 12008.5-2010 Plastics Polyether Polyols Part 5 - Determination of Acid Value; OHV (hydroxyl value): GB / T 12008.3-2009 Plastics Polyether Polyols Part 3 - Determination of Hydroxyl Value.

[0093] In this invention, the single-ended epoxy polysiloxane is selected from Anhui Aiyota Silicon Oil Co., Ltd., with the model number IOTA 105-4 (single-ended type) and a number-average molecular weight of 1000.

[0094] The method of the present invention will be described below through specific embodiments. It should be understood that these embodiments are used to illustrate the basic principles, main features and advantages of the present invention, and the present invention is not limited to the scope of the following embodiments. The implementation conditions used in the embodiments can be further adjusted according to specific requirements, and the implementation conditions not specified are usually the conditions in conventional experiments.

[0095] Example 1 In a 2L reactor under nitrogen protection, 73.22g hexamethylenediamine, 209.37g terephthalic acid, 83.75g isophthalic acid, 147.34g adipic acid, 199.92g 1,4-cyclohexanediethanol, 11.36g butanediol, 14.89g hexanediol, 0.1g tetrabutyl titanate, and 0.1g zinc acetate were added to the reactor. The reaction was carried out at atmospheric pressure with a stirring rate of 100r and a heating rate of 1℃ / min, reaching a maximum temperature of 230℃. The esterification reaction ended when the hydroxyl value of the sample in the reactor was less than 5 mg KOH / g. The temperature was lowered to 110℃, and 560.13g of single-ended epoxy polysiloxane was added to the reactor. The temperature was maintained at 120℃, the stirring rate was 100r, and the reaction was maintained for 1 hour. The acid value was tested, and the addition reaction ended when the acid value was less than 5 mg KOH / g, yielding an intermediate monomer. 800g of the above intermediate monomer was taken, and under nitrogen protection, the temperature was lowered to 80℃. The hydroxyl value of the intermediate monomer was tested to be 60.42 mg KOH / g. According to the NCO:OH molar ratio of 1.01:1, 108.886g of diphenylmethane diisocyanate and 2.72g of dibutyltin dilaurate were added. The reaction was maintained at 90℃ for 2 hours, and the final target polymer was obtained.

[0096] Example 2 In a 2L reactor under nitrogen protection, 131.86g hexamethylenediamine, 198.42g terephthalic acid, 39.68g isophthalic acid, 139.64g adipic acid, 86.12g 1,4-cyclohexanediethanol, 10.76g butanediol, 0.1g tetrapropyl titanate, and 0.15g zinc acetate were added to the reactor. The reaction was carried out at atmospheric pressure with a stirring rate of 100 rpm and a heating rate of 1℃ / min, reaching a maximum temperature of 235℃. The esterification reaction ended when the hydroxyl value of the sample in the reactor was less than 5 mg KOH / g. The temperature was then lowered to 110℃, and 693.51g of single-terminated epoxy polysiloxane was added to the reactor. The temperature was maintained at 120℃ with a stirring rate of 100 rpm for 1 hour. The acid value was measured, and the addition reaction ended when the acid value was less than 5 mg KOH / g, yielding the intermediate monomer. Take 800g of the above intermediate monomer, protect with nitrogen, cool to 80℃, and test the hydroxyl value of the intermediate monomer to be 65.73 mg KOH / g. According to the NCO:OH molar ratio of 1.02, add 119.629g of diphenylmethane diisocyanate and 2.75g of dibutyltin dilaurate. Maintain the reaction at 90℃ for 2h, and the final target polymer can be obtained by removing it from the reactor.

[0097] Example 3 In a 2L reactor under nitrogen protection, 91.03g hexamethylenediamine, 260.26g terephthalic acid, 104.10g isophthalic acid, 183.15g adipic acid, 266.58g 1,4-cyclohexanediethanol, 28.24g butanediol, 18.51g hexanediol, 0.1g tetrabutyl titanate, and 0.1g zinc acetate were added to the reactor. The reaction was carried out at atmospheric pressure with a stirring rate of 100r and a heating rate of 1℃ / min, reaching a maximum temperature of 230℃. The esterification reaction ended when the hydroxyl value of the sample in the reactor was less than 5 mg KOH / g. The temperature was lowered to 110℃, and 348.13g of single-ended epoxy polysiloxane was added to the reactor. The temperature was maintained at 120℃, the stirring rate was 100r, and the reaction was maintained for 1 hour. The acid value was tested, and the addition reaction ended when the acid value was less than 5 mg KOH / g, yielding an intermediate monomer. 800g of the above intermediate monomer was taken, and under nitrogen protection, the temperature was lowered to 80℃. The hydroxyl value of the intermediate monomer was tested to be 52.15 mg KOH / g. According to the NCO:OH molar ratio of 1.01, 93.983g of diphenylmethane diisocyanate and 2.68g of dibutyltin dilaurate were added. The reaction was maintained at 90℃ for 2 hours, and the final target polymer was obtained.

[0098] Example 4 In a 2L reactor under nitrogen protection, 65.07g hexamethylenediamine, 186.04g terephthalic acid, 74.42g isophthalic acid, 130.92g adipic acid, 161.49g 1,4-cyclohexanediethanol, 10.09g butanediol, 13.23g hexanediol, 0.15g tetrabutyl titanate, and 0.1g zinc acetate were added to the reactor. The reaction was carried out at atmospheric pressure with a stirring rate of 100r and a heating rate of 1℃ / min, reaching a maximum temperature of 230℃. The esterification reaction was considered complete when the hydroxyl value of the sample in the reactor was less than 5 mg KOH / g. The temperature was lowered to 110℃, and 658.73g of single-ended epoxy polysiloxane was added to the reactor. The temperature was maintained at 120℃, the stirring rate was 100r, and the reaction was maintained for 1.5h. The acid value was tested, and the addition reaction ended when the acid value was less than 5 mg KOH / g, yielding an intermediate monomer. 800g of the above intermediate monomer was taken, and under nitrogen protection, the temperature was lowered to 80℃. The hydroxyl value of the intermediate monomer was tested to be 68.54 mg KOH / g. According to the NCO:OH molar ratio of 1.01, 123.52g of diphenylmethane diisocyanate and 2.77g of dibutyltin dilaurate were added. The reaction was maintained at 90℃ for 2h, and the final target polymer was obtained.

[0099] Example 5 In a 2L reactor under nitrogen protection, 73.23g hexamethylenediamine, 209.37g terephthalic acid, 83.75g isophthalic acid, 147.34g adipic acid, 199.92g 1,4-cyclohexanediethanol, 11.36g butanediol, 14.89g hexanediol, 0.1g tetrabutyl titanate, and 0.1g zinc acetate were added to the reactor. The reaction was carried out at atmospheric pressure with a stirring rate of 100r and a heating rate of 1℃ / min, reaching a maximum temperature of 230℃. The esterification reaction ended when the hydroxyl value of the sample in the reactor was less than 5 mg KOH / g. The temperature was lowered to 110℃, and 560.13g of single-ended epoxy polysiloxane was added to the reactor. The temperature was maintained at 120℃, the stirring rate was 100r, and the reaction was maintained for 1 hour. The acid value was tested, and the addition reaction ended when the acid value was less than 5 mg KOH / g, yielding an intermediate monomer. 800g of the above intermediate monomer was taken, and under nitrogen protection, the temperature was lowered to 80℃. The hydroxyl value of the intermediate monomer was tested to be 61.45 mg KOH / g. According to the NCO:OH molar ratio of 1.005, 110.194g of diphenylmethane diisocyanate and 2.73g of dibutyltin dilaurate were added. The reaction was maintained at 90℃ for 2 hours, and the final target polymer was obtained.

[0100] Example 6 In a 2L reactor under nitrogen protection, 73.23g hexamethylenediamine, 209.37g terephthalic acid, 83.75g isophthalic acid, 147.34g adipic acid, 199.92g 1,4-cyclohexanediethanol, 11.36g butanediol, 14.89g hexanediol, 0.1g tetrabutyl titanate, and 0.1g zinc acetate were added to the reactor. The reaction was carried out at atmospheric pressure with a stirring rate of 100r and a heating rate of 1℃ / min, reaching a maximum temperature of 230℃. The esterification reaction ended when the hydroxyl value of the sample in the reactor was less than 5 mg KOH / g. The temperature was lowered to 110℃, and 560.13g of single-ended epoxy polysiloxane was added to the reactor. The temperature was maintained at 120℃, the stirring rate was 100r, and the reaction was maintained for 1 hour. The acid value was tested, and the addition reaction ended when the acid value was less than 5 mg KOH / g, yielding an intermediate monomer. 800g of the above intermediate monomer was taken, and under nitrogen protection, the temperature was lowered to 80℃. The hydroxyl value of the intermediate monomer was tested to be 58.99 mg KOH / g. According to the NCO:OH molar ratio of 1.015, 106.836g of diphenylmethane diisocyanate and 2.72g of dibutyltin dilaurate were added. The reaction was maintained at 90℃ for 2 hours, and the final target polymer was obtained.

[0101] Example 7 In a 2L reactor under nitrogen protection, 105.71g of decanediamine, 203.83g of terephthalic acid, 81.53g of isophthalic acid, 143.44g of adipic acid, 194.63g of 1,4-cyclohexanediethanol, 11.06g of butanediol, 14.50g of hexanediol, 0.1g of tetrabutyl titanate, and 0.1g of zinc acetate were added to the reactor. The reaction was carried out at atmospheric pressure with a stirring rate of 100r and a heating rate of 1℃ / min, reaching a maximum temperature of 230℃. The esterification reaction was considered complete when the hydroxyl value of the sample in the reactor was less than 5 mg KOH / g. The temperature was lowered to 110℃, and 545.30g of single-ended epoxy polysiloxane was added to the reactor. The temperature was maintained at 120℃, the stirring rate was 100r, and the reaction was maintained for 1 hour. The acid value was tested, and the addition reaction ended when the acid value was less than 5 mg KOH / g, yielding an intermediate monomer. 800g of the above intermediate monomer was taken, and under nitrogen protection, the temperature was lowered to 80℃. The hydroxyl value of the intermediate monomer was tested to be 60.65 mg KOH / g. According to the NCO:OH molar ratio of 1.01, 109.301g of diphenylmethane diisocyanate and 2.73g of dibutyltin dilaurate were added. The reaction was maintained at 90℃ for 2 hours, and the final target polymer was obtained.

[0102] Comparative Example 1 In a 2L reactor under nitrogen protection, 62.34g hexamethylenediamine, 234.53g terephthalic acid, 46.91g isophthalic acid, 165.05g adipic acid, 223.95g 1,4-cyclohexanediethanol, 12.72g butanediol, 16.68g hexanediol, 0.1g tetrabutyl titanate, and 0.1g zinc acetate were added to the reactor. The reaction was carried out at atmospheric pressure with a stirring rate of 100r and a heating rate of 1℃ / min, reaching a maximum temperature of 230℃. The esterification reaction ended when the hydroxyl value of the sample in the reactor was less than 5 mg KOH / g. The temperature was lowered to 110℃, and 537.81g of single-ended epoxy polysiloxane was added to the reactor. The temperature was maintained at 120℃, the stirring rate was 100r, and the reaction was maintained for 1 hour. The acid value was tested, and the addition reaction ended when the acid value was less than 5 mg KOH / g, yielding an intermediate monomer. 800g of the above intermediate monomer was taken, and under nitrogen protection, the temperature was lowered to 80℃. The hydroxyl value of the intermediate monomer was tested to be 58.34 mg KOH / g. According to the NCO:OH molar ratio of 1.01, 105.138g of diphenylmethane diisocyanate and 2.71g of dibutyltin dilaurate were added. The reaction was maintained at 90℃ for 2 hours, and the final target polymer was obtained.

[0103] Comparative Example 2 In a 2L reactor under nitrogen protection, 154.55g hexamethylenediamine, 346.57g terephthalic acid, 43.32g isophthalic acid, 38.11g adipic acid, 94.01g 1,4-cyclohexanediethanol, 11.75g ​​butanediol, 0.1g tetrabutyl titanate, and 0.1g zinc acetate were added to the reactor. The reaction was carried out at atmospheric pressure with a stirring rate of 100 rpm and a heating rate of 1℃ / min, reaching a maximum temperature of 230℃. The esterification reaction ended when the hydroxyl value of the sample in the reactor was less than 5 mg KOH / g. The temperature was then lowered to 110℃, and 611.68g of single-terminated epoxy polysiloxane was added to the reactor. The temperature was maintained at 120℃ with a stirring rate of 100 rpm for 1 hour. The acid value was measured, and the addition reaction ended when the acid value was less than 5 mg KOH / g, yielding the intermediate monomer. Take 800g of the above intermediate monomer, protect with nitrogen, cool to 80℃, and test the hydroxyl value of the intermediate monomer to be 63.04 mg KOH / g. According to the NCO:OH molar ratio of 1.01, add 113.608g of diphenylmethane diisocyanate and 2.74g of dibutyltin dilaurate. Maintain the reaction at 90℃ for 2h, and the final target polymer can be obtained by removing it from the reactor.

[0104] Comparative Example 3 In a 2L reactor under nitrogen protection, 93.46g hexamethylenediamine, 296.90g terephthalic acid, 59.38g isophthalic acid, 208.94g adipic acid, 309.27g 1,4-cyclohexanediethanol, 42.24g hexanediol, 0.1g tetrabutyl titanate, and 0.1g zinc acetate were added to the reactor. The reaction was carried out at atmospheric pressure with a stirring rate of 100 rpm and a heating rate of 1℃ / min, reaching a maximum temperature of 230℃. The esterification reaction ended when the hydroxyl value of the sample in the reactor was less than 5 mg KOH / g. The temperature was then lowered to 110℃, and 289.81g of single-terminated epoxy polysiloxane was added to the reactor. The temperature was maintained at 120℃ with a stirring rate of 100 rpm for 1 hour. The acid value was measured, and the addition reaction ended when the acid value was less than 5 mg KOH / g, yielding the intermediate monomer. Take 800g of the above intermediate monomer, protect it with nitrogen, cool it to 80℃, and test the hydroxyl value of the intermediate monomer to be 48.37mg KOH / g. According to the NCO:OH molar ratio of 1.01, add 87.17g of diphenylmethane diisocyanate and 2.66g of dibutyltin dilaurate. Maintain the reaction at 90℃ for 2h, and the final target polymer can be obtained by removing it from the reactor.

[0105] Comparative Example 4 In a 2L reactor under nitrogen protection, 57.54g of hexamethylenediamine, 182.80g of terephthalic acid, 36.56g of isophthalic acid, 128.64g of adipic acid, 134.88g of 1,4-cyclohexanediethanol, 26.01g of hexanediol, 0.1g of tetrabutyl titanate, and 0.1g of zinc acetate were added to the reactor. The reaction was carried out at atmospheric pressure with a stirring rate of 100 rpm and a heating rate of 1℃ / min, reaching a maximum temperature of 230℃. The esterification reaction ended when the hydroxyl value of the sample in the reactor was less than 5 mg KOH / g. The temperature was then lowered to 110℃, and 733.57g of single-terminated epoxy polysiloxane was added to the reactor. The temperature was maintained at 120℃ with a stirring rate of 100 rpm for 1 hour. The acid value was measured, and the addition reaction ended when the acid value was less than 5 mg KOH / g, yielding the intermediate monomer. Take 800g of the above intermediate monomer, protect with nitrogen, cool to 80℃, and test the hydroxyl value of the intermediate monomer to be 72.49mg KOH / g. According to the NCO:OH molar ratio of 1.01:1, add 130.638g of diphenylmethane diisocyanate and 2.79g of dibutyltin dilaurate. Maintain the reaction at 90℃ for 2h, and the final target polymer can be obtained by removing it from the reactor.

[0106] Comparative Example 5 In a 2L reactor under nitrogen protection, 73.23g hexamethylenediamine, 209.37g terephthalic acid, 83.75g isophthalic acid, 147.34g adipic acid, 199.92g 1,4-cyclohexanediethanol, 11.36g butanediol, 14.89g hexanediol, 0.1g tetrabutyl titanate, and 0.1g zinc acetate were added to the reactor. The reaction was carried out at atmospheric pressure with a stirring rate of 100r and a heating rate of 1℃ / min, reaching a maximum temperature of 230℃. The esterification reaction ended when the hydroxyl value of the sample in the reactor was less than 5 mg KOH / g. The temperature was lowered to 110℃, and 560.13g of single-ended epoxy polysiloxane was added to the reactor. The temperature was maintained at 120℃, the stirring rate was 100r, and the reaction was maintained for 1 hour. The acid value was tested, and the addition reaction ended when the acid value was less than 5 mg KOH / g, yielding an intermediate monomer. 800g of the above intermediate monomer was taken, and under nitrogen protection, the temperature was lowered to 80℃. The hydroxyl value of the intermediate monomer was tested to be 61.82mg KOH / g. According to the NCO:OH molar ratio of 0.99:1, 109.203g of diphenylmethane diisocyanate and 2.72g of dibutyltin dilaurate were added. The reaction was maintained at 90℃ for 2 hours, and the final target polymer was obtained.

[0107] Comparative Example 6 In a 2L reactor under nitrogen protection, 73.23g hexamethylenediamine, 209.37g terephthalic acid, 83.75g isophthalic acid, 147.34g adipic acid, 199.92g 1,4-cyclohexanediethanol, 11.36g butanediol, 14.89g hexanediol, 0.1g tetrabutyl titanate, and 0.1g zinc acetate were added to the reactor. The reaction was carried out at atmospheric pressure with a stirring rate of 100r and a heating rate of 1℃ / min, reaching a maximum temperature of 230℃. The esterification reaction ended when the hydroxyl value of the sample in the reactor was less than 5 mg KOH / g. The temperature was lowered to 110℃, and 560.13g of single-ended epoxy polysiloxane was added to the reactor. The temperature was maintained at 120℃, the stirring rate was 100r, and the reaction was maintained for 1 hour. The acid value was tested, and the addition reaction ended when the acid value was less than 5 mg KOH / g, yielding an intermediate monomer. 800g of the above intermediate monomer was taken, and under nitrogen protection, the temperature was lowered to 80℃. The hydroxyl value of the intermediate monomer was tested to be 61.82mg KOH / g. According to the NCO:OH molar ratio of 1.03:1, 114.075g of diphenylmethane diisocyanate and 2.74g of dibutyltin dilaurate were added. The reaction was maintained at 90℃ for 2 hours, and the final target polymer was obtained.

[0108] Experimental Example 1 The target polymers prepared in Examples 1-7 and Comparative Examples 1-6 of this invention were subjected to the following tests: 1. Crystallization rate: The test method is specified in GB / T 19466.2-2004 Differential Scanning Calorimetry (DSC) for Plastics; the crystallization peak temperature (Tc) range indicates the temperature range in which the crystallization process occurs; the crystallization peak area (ΔHc) indicates the amount of heat released or absorbed during the crystallization process; the shape and width of the crystallization peak reflect the degree and rate of crystallization. 2. Coefficient of friction: Tested according to EN 13893 standard, using a 500*1000mm sample and a dynamic friction coefficient tester to measure the corresponding coefficient of friction; 3. Abrasion resistance: Tested according to standard ASTM D5963; abrasion resistance is expressed as an abrasion index with volume loss in cubic millimeters, and the smaller the volume loss value, the better the abrasion resistance; 4. Mass Flow Rate (MFR): The test method is as specified in GB / T 3682.1-2018 Mass Flow Rate (MFR) for Plastics, and is determined at 230℃ and a load of 2.16 kg. The higher the MFR value, the better the melt flow. 5. Tensile properties (flexibility): The test method is specified in GB / T 1040.1-2018 Test for tensile properties of plastics.

[0109] The test results are shown in Table 1.

[0110] Table 1 Test Results

[0111] The data from Examples 1-7 are generally superior to those from Comparative Examples 1-6. For example, the increased crystallization peak area (ΔHc) indicates an increase in the heat released or absorbed during crystallization, thus enhancing the crystallization rate. The polymer prepared by the method of this invention simultaneously possesses a high crystallization rate, good flowability, and certain wear resistance and flexibility.

[0112] It should be understood that the above embodiments are exemplary and are not intended to encompass all possible implementations included in the claims. Various modifications and changes can be made to the above embodiments without departing from the scope of this disclosure. Similarly, the various technical features of the above embodiments can be arbitrarily combined to form other embodiments of the present invention that may not be explicitly described. Therefore, the above embodiments only illustrate several implementations of the present invention and do not limit the scope of protection of this patent.

Claims

1. A method for the preparation of a polymer, characterized in that, The method comprises the following steps: S1: esterification reaction of dihydric amine, dihydric alcohol and dihydric acid to obtain carboxyl-terminated polyester amide; S2: addition reaction of epoxy organosilicon monomer to the carboxyl-terminated polyester amide obtained in step S1 to obtain hydroxyl-terminated intermediate monomer; S3: polymerization reaction of isocyanate monomer to the hydroxyl-terminated intermediate monomer obtained in step S2 to obtain the polymer; In step S1, the molar ratio of the dihydric amine to the dihydric acid is (0.2-0.5):1; The total molar amount of the dihydric alcohol and the dihydric amine to the molar amount of the dihydric acid is 1:(1.1-1.3).

2. The production method according to claim 1, characterized by, In step S1, the diamine is selected from C 6-14 aliphatic linear diamines; preferably one or more of hexamethylenediamine, decanediamine, dodecanediamine, tetradecanediamine; Preferably, the dihydric acid is selected from one or more of terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid; Preferably, the dihydric alcohol is selected from one or more of ethylene glycol, butanediol, 2-methyl-1,3-propanediol, hexanediol, 1,4-cyclohexane dimethanol.

3. The preparation method according to claim 1, characterized in that, In step S1, the esterification reaction is carried out in the presence of catalyst A; Preferably, the catalyst A is selected from one or more of tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate, p-toluene sulfonic acid, zinc acetate, tetraisopropyl titanate, preferably tetrabutyl titanate and / or zinc acetate; Preferably, the temperature of the esterification reaction is 230-240°C; Preferably, the esterification reaction is carried out at a stirring rate of 60-100 r / min; Preferably, the esterification reaction is terminated when the hydroxyl value is less than 5 mg KOH / g.

4. The method of claim 1, wherein, In step S2, the epoxy silicone monomer is selected from mono-epoxy polysiloxane having the structure ; Preferably, the molar amount of the dihydric alcohol, the molar amount of the dihydric amine and 2 times the molar amount of the epoxy organosilicon monomer to the molar amount of the dihydric acid is 1:

1. In step S2, the temperature of the addition reaction is 110-120°C; 5. The preparation method according to claim 1, characterized in that, Preferably, the addition reaction is carried out at a stirring rate of 60-100 r / min; Preferably, the addition reaction is terminated when the acid value is less than 5 mg KOH / g. In step S3, the isocyanate monomer is selected from one or more of toluene diisocyanate, diphenyl methane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, preferably diphenyl methane diisocyanate; 6. The method of claim 1, wherein, Preferably, the molar ratio of NCO groups in the isocyanate monomer to OH groups in the hydroxyl-terminated intermediate monomer is (1.0-1.02):

1. In step S3, the polymerization reaction is carried out in the presence of catalyst B; 7. The preparation method according to claim 1, characterized in that, Preferably, the catalyst B is selected from one or more of dibutyl tin dilaurate, stannous octoate, stannous chloride, preferably dibutyl tin dilaurate. In step S3, the temperature of the polymerization reaction is 80-100°C; 8. The method of claim 1, wherein, Preferably, the reaction time of the polymerization reaction is 0.5-4 hours. The polymer is prepared by the preparation method of any one of claims 1-8.

9. A polymer characterized in that, ​ 10. Use of a polymer produced according to the process of any one of claims 1 to 8 or of a polymer according to claim 9 in a 3D printing filament.

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