A thermoplastic polyurethane elastomer material

Abstract

The invention discloses a thermoplastic polyurethane elastomer material. The thermoplastic polyurethane elastomer material comprises diisocyanate, macromolecular diol, modified castor oil-based diol, diol chain extender, and di-secondary amine chain extender. The modified castor oil-based diol is preferably thiol-modified, and the di-secondary amine chain extender is preferably polyaspartic acid ester. The obtained thermoplastic polyurethane elastomer material has high transparency, good hydrolysis resistance and excellent processing performance. The tensile strength of a 2mm injection molded test piece is ≥40MPa, the transmittance is ≥91%, and the haze is ≤0.5. After being immersed in deionized water at 80°C for 1 week, 4 weeks and 8 weeks, the tensile strength retention rate reaches 90%, 65% and 30% respectively. The thermoplastic polyurethane elastomer material can be used to prepare extruded films and pipe products with high requirements for transparency and hydrolysis resistance, and is particularly suitable for underwater environments.

Description

Technical Field

[0001] The invention relates to the field of thermoplastic polyurethane elastomers, and in particular to a highly transparent hydrolysis-resistant thermoplastic polyurethane elastomer material and a preparation method and application thereof. Background Art

[0002] Compared with other engineering plastics, thermoplastic polyurethane elastomers have excellent strength, wear resistance and biocompatibility, and their performance can be adjusted within a wide range as needed, with many processing methods and a wide range of applications. Among them, transparent thermoplastic polyurethane materials have more important practical value in production and life than non-transparent ones, but usually, on the basis of ensuring the transparency of the material, its physical properties and hydrolysis resistance will decrease to a certain extent, which seriously limits the use of transparent thermoplastic polyurethane materials.

[0003] The methods currently widely adopted to improve the transparency of thermoplastic polyurethane elastomers are mainly the following:

[0004] (1) From the perspective of raw material structure: Chinese patent CN201510565896.2 uses a mixture of IPDI and HDI and a mixture of BDO and diethylene glycol to improve the transparency of the material. The hard segment crystallization is weakened by the presence of isomers of IPDI and a mixed chain extender, thereby improving the transparency of the material. However, this method only starts from the hard segment, and the improvement in transparency is limited. In addition, the physical properties and hydrolysis resistance of the TPU product obtained are poor;

[0005] (2) From the perspective of blending modification: Chinese patent CN98110958.6 improves the transparency of the material by blending polyurethane with polymethyl methacrylate and epoxy resin. The blending modification method can improve the transparency of the material to a certain extent, but this method is relatively complicated and requires additional blending processes. In addition, the degree of mixing of several materials will have a significant impact on the final material performance.

[0006] Therefore, the preparation of a highly transparent, hydrolysis-resistant thermoplastic polyurethane material with high strength and good processing performance has become an urgent problem to be solved in the industry. Summary of the invention

[0007] The present invention aims to solve the problem of poor hydrolysis resistance and strength of polyester-type thermoplastic polyurethane elastomer in the prior art while ensuring that the material has high transparency, and to provide a highly transparent and hydrolysis-resistant thermoplastic polyurethane elastomer material.

[0008] Another object of the present invention is to provide a method for preparing the thermoplastic polyurethane elastomer material.

[0009] The present invention uses two raw materials, namely, modified castor oil diol containing S element and long aliphatic chain segment and polyaspartic acid ester containing long aliphatic chain segment with large steric hindrance, to introduce a large number of aliphatic / alicyclic groups with large steric hindrance and strong hydrophobicity into the TPU molecular chain, and hinders the invasion of water molecules through its own hydrophobicity and steric hindrance, plays a role in protecting the easily hydrolyzed groups, and reduces the ester group concentration, thereby achieving the purpose of improving the hydrolysis resistance of the material. At the same time, the introduction of sulfur element in the modified castor oil-based diol improves the transparency of the material.

[0010] To achieve the above object, the present invention provides the following technical solutions:

[0011] A thermoplastic polyurethane elastomer material, based on the total weight of the thermoplastic polyurethane elastomer, comprises the following components:

[0012] Diisocyanate 20-50wt%, preferably 20-45wt%;

[0013] 5-70 wt% of macromolecular diol, preferably 10-50 wt%;

[0014] Castor oil-based glycol 5-50wt%, preferably 10-50wt%;

[0015] 1 to 20 wt % of diol chain extender, preferably 3 to 10 wt %;

[0016] The di-secondary amine chain extender is 1-20 wt%, preferably 3-10 wt%.

[0017] In a specific embodiment, the diisocyanate is selected from aromatic and / or aliphatic diisocyanates; preferably, the aromatic diisocyanate is selected from toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate (NDI), p-phenylene diisocyanate (PPDI), xylylene diisocyanate (XDI) and one or more thereof; the aliphatic diisocyanate is selected from hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (HDI). 12 MDI), 1,4-cyclohexyl dimethylene diisocyanate (CHDI) or more thereof.

[0018] In a specific embodiment, the macromolecular diol is selected from one or more of polyether macromolecular diols or polyester macromolecular diols; preferably, the polyether macromolecular diol is selected from one or more of polytetramethylene glycol, polyethylene glycol, polypropylene glycol and polyethylene glycol-propylene glycol diol, and the polyester macromolecular diol is selected from one or more of polyethylene adipate glycol ester diol, polybutylene adipate glycol ester diol, polyhexane adipate glycol ester diol, polycaprolactone diol and polycarbonate diol; preferably, the number average molecular weight of the macromolecular diol is 500-4000 g / mol, preferably 500-1000 g / mol.

[0019] In a specific embodiment, the modified castor oil-based diol is selected from the modified castor oil-based diol obtained by the modified alkyd polycondensation; preferably, the modified castor oil-based diol obtained by the alkyd polycondensation is a diol obtained by the alkyd polycondensation of modified castor oil alcohol and dibasic acid, or modified castor oil acid and diol, or castor oil alcohol or modified castor oil alcohol and castor oil acid or modified castor oil acid. The above-mentioned modified castor oil alcohol and modified castor oil acid are selected from mercaptan modification, wherein the mercaptan structure used is: HS-R, wherein R is selected from a linear alkyl group consisting of 2-18 carbon atoms, a cycloalkyl group, preferably a cycloalkyl group consisting of 6-12 carbon atoms.

[0020] The above-mentioned mercaptan can be selected from 1-ethanethiol, 1-hexylthiol, 1-heptylthiol, 1-octylthiol, 1-nonylthiol, 1-decylthiol, 1-undecylthiol, 1-dodecylthiol, cyclohexylthiol, and 4-pentylcyclohexylthiol.

[0021] The cycloalkyl group in the thiol structure has a large steric hindrance, and the symmetrical non-polar group can significantly affect the orderly arrangement of the polar groups in the soft segment, hinder the crystallization of the soft segment, and improve the transparency of the material.

[0022] The long aliphatic chain or cycloalkyl group in the modified castor oil diol can play a good steric hindrance role, and it itself has strong hydrophobicity, which can significantly prevent water molecules from penetrating into the interior of the material.

[0023] In a specific embodiment, the diol chain extender is selected from one or more of ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,5-pentanediol, isoprene glycol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, diethylene glycol, and hydroquinone dihydroxyethyl ether; more preferably, the diols are selected from one or more of 1,2-propylene glycol, 1,4-butanediol, 1,5-pentanediol, isoprene glycol, 2-methyl-2,4-pentanediol, and 3-methyl-1,5-pentanediol.

[0024] In a specific embodiment, the di-secondary amine chain extender is selected from polyaspartic acid ester, and the molecular structure is:

[0025]

[0026] Wherein, R1 is an alkyl chain consisting of 2-8 carbon atoms, preferably an alkyl chain consisting of 4-6 carbon atoms, and R2 is a straight chain alkyl or cycloalkyl consisting of 2-18 carbon atoms, preferably a cycloalkyl. The urea bond generated by the reaction of amino groups and isocyanate groups in polyaspartic acid ester can significantly enhance the physical properties of the material, and the presence of aliphatic side chains with large steric hindrance further improves the hydrolysis resistance of the material.

[0027] The optimal length of the R1 group of the above-mentioned preferred polyaspartic acid ester is 4-6 carbons. If it is too long, it will easily lead to a decrease in the overall reaction activity, while if it is too short, it will not have the effect of disrupting the regularity of the hard segment; the R2 group is preferably a cyclic structure, and it is introduced into the polyurethane main chain to increase the steric hindrance of the main chain, hinder the invasion of water molecules, and achieve the purpose of improving the hydrolysis resistance.

[0028] In a specific embodiment, the isocyanate index (molar ratio of -NCO to -OH) of the thermoplastic polyurethane elastomer material is 0.8 to 1.2, preferably 0.95 to 1.05.

[0029] In a specific embodiment, the raw materials for preparing the thermoplastic polyurethane elastomer material also include a catalyst and a mixing aid, the mixing aid includes a light stabilizer, an antioxidant, and a hydrolysis stabilizer. The amount of the catalyst and the mixing aid added is based on the total mass of the diisocyanate, the macromolecular diol, the castor oil-based diol, the diol chain extender, and the disecondary amine chain extender. The amount of the catalyst added is 1-200ppm, and the amount of the mixing aid added is 2-5wt%.

[0030] In a specific embodiment, the steps include:

[0031] (1) forming a thermoplastic polyurethane elastomer by extruding a diisocyanate, a macromolecular diol, a castor oil-based diol, a diol chain extender, a disecondary amine chain extender, an optional catalyst and a mixing aid; preferably, the extruder temperature is set to between 80° C. and 240° C.;

[0032] (2) Cooling the thermoplastic polyurethane elastomer, crushing it, and granulating it.

[0033] In step (1) of the present invention, the components are reacted in an extruder by a one-step polymerization process.

[0034] In a specific embodiment, the prepared thermoplastic polyurethane elastomer material is tested according to ASTM D412 standard, and the tensile strength of a 2 mm injection molded specimen is ≥40 MPa, the transmittance of a 2 mm injection molded specimen is ≥91%, the haze is ≤0.5, and the 2 mm injection molded specimen is immersed in 80°C deionized water for 1 week, and the tensile strength retention rate is ≥90%, the tensile strength retention rate is ≥65% after immersion for 4 weeks, and the tensile strength retention rate is ≥30% after immersion for 8 weeks.

[0035] In a specific embodiment, the thermoplastic polyurethane elastomer can be used to prepare underwater extrusion-grade films and tubular products with high requirements for strength and transparency, preferably clothing, shoes, underwater cables, water pipes and diving equipment.

[0036] Compared with the prior art, the present invention has the following beneficial effects:

[0037] 1) The present invention uses modified castor oil-based diol and adds a polyaspartic acid ester di-secondary amine chain extender to prepare TPU materials, and utilizes a large number of large sterically hindered fatty side chains in polyaspartic acid ester and modified castor oil diol to cooperate with sulfur element to reduce the degree of crystallization of materials in hard segments and soft segments and improve transparency. At the same time, due to the large number of hydrophobic and large sterically hindered aliphatic / alicyclic chain segments in polyaspartic acid and modified castor oil diol materials, the hydrolysis resistance of the material is further improved, which can meet the requirements of water-related materials for this performance and has high commercial application value.

[0038] 2) The TPU material prepared by the present invention has excellent processing performance, stable extrusion during processing, fewer crystal points, and can be recycled and reused. The transparency and hydrolysis resistance of the recycled material are still relatively good.

[0039] 3) The thermoplastic polyurethane elastomer prepared by the present invention can be used in a specific embodiment to prepare extrusion-grade film and pipe products with high requirements on transparency, hydrolysis resistance and physical strength, such as clothing, footwear, underwater cables, water pipes and diving equipment, etc., under the premise of ensuring high transparency. DETAILED DESCRIPTION

[0040] In order to better understand the technical solution of the present invention, the following examples will further illustrate the method provided by the present invention, but the present invention is not limited to the listed examples, and should also include any other known changes within the scope of the claims of the present invention.

[0041] The present invention is further described below by more specific examples, but the scope of the present invention is not limited in any way.

[0042] The raw materials used in the following examples or comparative examples are all universal standard products, without any special supply company requirements.

[0043] The catalyst and mixing aids described in the following examples and comparative examples are added based on the total mass of diisocyanate, macromolecular diol, castor oil-based diol, diol chain extender, and disecondary amine chain extender.

[0044] In the specific implementation manner, "parts" are all "parts by mass".

[0045] In the following examples and comparative examples, the preparation method of polyaspartic acid ester is known to those skilled in the art, and is mainly prepared by using maleic acid glycol ester and primary amine for Michael addition reaction, and the reaction process steps are as follows:

[0046] (1) Add the amine component and the catalyst group into a four-necked flask equipped with a stirrer and a thermometer, start the stirrer, and introduce nitrogen;

[0047] (2) slowly adding maleic acid glycol ester dropwise while maintaining the temperature at about 40° C. and completing the addition within 2 hours;

[0048] (3) heating to 90-100° C. and reacting for 12-16 hours;

[0049] (4) Determine the amine value and terminate the reaction after the test is qualified.

[0050] In the following examples and comparative examples, polycastor oil adipate diol is mainly prepared by alkyd polycondensation reaction, and the reaction process steps are as follows:

[0051] At room temperature, diol and diacid are added into a 20L reactor in a molar ratio of 1.6, and 0.5% of tetrabutyl titanate is added into the reactor. A nitrogen atmosphere is filled for protection. The mixture is gradually heated to 210-240°C while stirring. The reaction is stirred at this temperature for 10-14h. The mixture is removed from excess unreacted diol and generated water under a vacuum of 400 mPa until the acid value of the mixture is less than 1 mgKOH / g. The obtained polymer diol is collected for later use.

[0052] Example 1

[0053] A thermoplastic polyurethane elastomer comprising the following components:

[0054] 31.98 parts of diphenylmethane diisocyanate;

[0055] 50.00 parts of polybutylene adipate diol;

[0056] 10.00 parts of polyricinoleyl adipate diol;

[0057] 1,4-Butanediol 5.09 parts;

[0058] 2.94 parts of polyaspartic acid;

[0059] Dibutyltin dilaurate 100ppm;

[0060] 1.5 parts of antioxidant 1010;

[0061] Antioxidant 626 1 part;

[0062] 0.5 part of hydrolysis-resistant agent carbodiimide;

[0063] Wherein, the number average molecular weight of polybutylene adipate diol and polyricinoleyl adipate diol is 1000 g / mol;

[0064] The preparation method of polyricinoleyl adipate diol is as follows: at room temperature, ricinoleyl alcohol and adipic acid are added into a reactor with a capacity of 20 L in a molar ratio of 1.6, and 0.5% of tetrabutyl titanate is added to the total mass fraction of the raw materials, and a nitrogen atmosphere is filled for protection. The mixture is gradually heated to 220° C. while stirring, and stirred for reaction at this temperature for 11 hours. The excess unreacted ricinoleyl alcohol and the generated water are removed from the mixture under a vacuum of 400 mPa until the acid value of the mixture is tested to be less than 1 mgKOH / g, and the obtained polyricinoleyl adipate diol is collected for later use.

[0065] Among them, the isocyanate index of thermoplastic polyurethane elastomer is 1;

[0066] Wherein, the above-mentioned polyaspartic acid ester structure is

[0067]

[0068] Among them, R1 is R2 is

[0069] Wherein, the preparation method of thermoplastic polyurethane material is as follows:

[0070] (1) adding each component into a heated extruder, wherein the temperature of each temperature zone of the extruder is set to 140-220° C., and reacting in the heated extruder by a one-step polymerization method to form a thermoplastic polyurethane elastomer;

[0071] (2) Cooling the thermoplastic polyurethane elastomer, crushing and granulating.

[0072] Example 2

[0073] A thermoplastic polyurethane elastomer comprising the following components:

[0074] 31.02 parts of diphenylmethane diisocyanate;

[0075] 40.00 parts of polybutylene adipate diol;

[0076] 20.00 parts of polyadipic acid-modified castor oil ester diol;

[0077] 1,4-Butanediol 4.61 parts;

[0078] Polyaspartic acid 4.37 parts;

[0079] Dibutyltin dilaurate 100ppm;

[0080] 1.5 parts of antioxidant 1010;

[0081] Antioxidant 626 1 part;

[0082] 0.5 part of hydrolysis-resistant agent carbodiimide;

[0083] Among them, polyadipic acid-modified castor oil ester diol is obtained by polycondensation of adipic acid and modified castor oil diol through alkyd acid. The structure of modified castor oil diol is shown below:

[0084]

[0085] Among them, the number average molecular weight of polybutylene adipate diol and polyadipic acid-modified castor oil alcohol ester diol is 1000 g / mol;

[0086] Among them, the preparation method of modified ricinoleyl alcohol is as follows: under argon protection conditions, ricinoleyl alcohol and 1-undecanethiol are added in a three-necked flask at room temperature in a molar ratio of 1, and THF is added to fully dissolve under stirring conditions, a photoinitiator (benzoin dimethyl ether) is added, and the reaction is carried out under ultraviolet light for 30 minutes, and the solvent THF is distilled off under reduced pressure, and the product is stored in a light-proof container for later use.

[0087] Among them, the preparation method of polyadipic acid modified castor oil alcohol ester diol is as follows: at room temperature, modified castor oil alcohol and adipic acid are added into a reactor with a capacity of 20L in a molar ratio of 1.6, and tetrabutyl titanate with a total mass fraction of 0.5% of the raw materials is added, and a nitrogen atmosphere is filled for protection. The mixture is gradually heated to 230°C while stirring, and stirred for reaction at this temperature for 11 hours. The mixture is removed from excess unreacted modified castor oil alcohol and generated moisture under a vacuum of 400 mPa until the acid value of the mixture is tested to be less than 1 mgKOH / g, and the obtained polyadipic acid modified castor oil alcohol ester diol is collected for later use.

[0088] Among them, the isocyanate index of thermoplastic polyurethane elastomer is 1;

[0089] Wherein, the above-mentioned polyaspartic acid ester structure is

[0090]

[0091] Among them, R1 is R2 is

[0092] The preparation method of the thermoplastic polyurethane is the same as that in Example 1.

[0093] Example 3

[0094] A thermoplastic polyurethane elastomer comprising the following components:

[0095] 30.52 parts of diphenylmethane diisocyanate;

[0096] 30.00 parts of polybutylene adipate diol;

[0097] 30.00 parts of polyadipic acid-modified castor oil ester diol;

[0098] 1,4-Butanediol 4.18 parts;

[0099] Polyaspartic acid 5.30 parts;

[0100] Dibutyltin dilaurate 100ppm;

[0101] 1.5 parts of antioxidant 1010;

[0102] Antioxidant 626 1 part;

[0103] 0.5 part of hydrolysis-resistant agent carbodiimide;

[0104] Among them, polyadipic acid-modified castor oil ester diol is obtained by polycondensation of adipic acid and modified castor oil diol through alkyd acid. The structure of modified castor oil diol is shown below:

[0105]

[0106] Among them, the number average molecular weight of polybutylene adipate diol and polyadipic acid-modified castor oil alcohol ester diol is 1000 g / mol;

[0107] Among them, the preparation method of modified ricinoleyl alcohol is as follows: under argon protection conditions, ricinoleyl alcohol and cyclohexanethiol are added in a three-necked flask at room temperature in a molar ratio of 1, and THF is added to fully dissolve under stirring conditions, a photoinitiator (benzoin dimethyl ether) is added, and the reaction is carried out under ultraviolet light for 40 minutes, and the solvent THF is evaporated by reduced pressure distillation, and the product is stored in a light-proof container for later use.

[0108] Among them, the preparation method of polyadipic acid modified castor oil alcohol ester diol is as follows: at room temperature, modified castor oil alcohol and adipic acid are added into a reactor with a capacity of 20L in a molar ratio of 1.6, and tetrabutyl titanate with a total mass fraction of 0.5% of the raw materials is added, and a nitrogen atmosphere is filled for protection. The mixture is gradually heated to 235°C while stirring, and stirred for reaction at this temperature for 12 hours. The mixture is removed from excess unreacted modified castor oil alcohol and generated moisture under a vacuum of 400 mPa until the acid value of the mixture is tested to be less than 1 mgKOH / g, and the obtained polyadipic acid modified castor oil alcohol ester diol is collected for later use.

[0109] Among them, the isocyanate index of thermoplastic polyurethane elastomer is 1;

[0110] Wherein, the above-mentioned polyaspartic acid ester structure is

[0111]

[0112] Among them, R1 is R2 is

[0113] The preparation method of the thermoplastic polyurethane is the same as that in Example 1.

[0114] Example 4

[0115] A thermoplastic polyurethane elastomer comprising the following components:

[0116] 28.62 parts of diphenylmethane diisocyanate;

[0117] 20.00 parts of polybutylene adipate diol;

[0118] 40.00 parts of polyadipic acid-modified castor oil ester diol;

[0119] 3.26 parts of 1,4-butanediol;

[0120] Polyaspartic acid 8.12 parts;

[0121] Dibutyltin dilaurate 100ppm;

[0122] 1.5 parts of antioxidant 1010;

[0123] Antioxidant 626 1 part;

[0124] 0.5 part of hydrolysis-resistant agent carbodiimide;

[0125] Among them, the number average molecular weight of polybutylene adipate diol and polyadipic acid-modified castor oil alcohol ester diol is 1000 g / mol;

[0126] Among them, the isocyanate index of thermoplastic polyurethane elastomer is 1;

[0127] Wherein, the preparation method of modified ricinoleyl alcohol is the same as that of Example 3;

[0128] Among them, polyadipic acid-modified castor oil ester diol is obtained by polycondensation of adipic acid and modified castor oil diol through alkyd acid. The structure of modified castor oil diol is shown below:

[0129]

[0130] Wherein, the above-mentioned polyaspartic acid ester structure is

[0131]

[0132] Among them, R1 is R2 is

[0133] The preparation method of the thermoplastic polyurethane is the same as that in Example 1.

[0134] Example 5

[0135] A thermoplastic polyurethane elastomer comprising the following components:

[0136] 27.76 parts of diphenylmethane diisocyanate;

[0137] 10.00 parts of polybutylene adipate diol;

[0138] 50.00 parts of polyadipic acid-modified castor oil ester diol;

[0139] 2.75 parts of 1,4-butanediol;

[0140] Polyaspartic acid 9.49 parts;

[0141] Dibutyltin dilaurate 100ppm;

[0142] 1.5 parts of antioxidant 1010;

[0143] Antioxidant 626 1 part;

[0144] 0.5 part of hydrolysis-resistant agent carbodiimide;

[0145] Wherein, the number average molecular weight of polybutylene adipate diol and polyricinoleyl adipate diol is 1000 g / mol;

[0146] Among them, the isocyanate index of thermoplastic polyurethane elastomer is 0.99;

[0147] Wherein, the preparation method of modified ricinoleyl alcohol is the same as that of Example 3;

[0148] Among them, polyadipic acid-modified castor oil ester diol is obtained by polycondensation of adipic acid and modified castor oil diol through alkyd acid. The structure of modified castor oil diol is shown below:

[0149]

[0150] Wherein, the above-mentioned polyaspartic acid ester structure is

[0151]

[0152] Among them, R1 is R2 is

[0153] The preparation method of the thermoplastic polyurethane is the same as that in Example 1.

[0154] Example 6

[0155] A thermoplastic polyurethane elastomer comprising the following components:

[0156] 27.46 parts of diphenylmethane diisocyanate;

[0157] 10.00 parts of polybutylene adipate diol;

[0158] 50.00 parts of polyricinoleyl adipate glycol;

[0159] 2.55 parts of 1,4-butanediol;

[0160] Polyaspartic acid 9.99 parts;

[0161] Dibutyltin dilaurate 100ppm;

[0162] 1.5 parts of antioxidant 1010;

[0163] Antioxidant 626 1 part;

[0164] 0.5 part of hydrolysis-resistant agent carbodiimide;

[0165] Wherein, the number average molecular weight of polybutylene adipate diol and polyricinoleyl adipate diol is 1000 g / mol;

[0166] Wherein, the preparation method of modified ricinoleyl alcohol is the same as that of Example 3;

[0167] Among them, polyadipic acid-modified castor oil ester diol is obtained by polycondensation of adipic acid and modified castor oil diol through alkyd acid. The structure of modified castor oil diol is shown below:

[0168]

[0169] Among them, the isocyanate index of thermoplastic polyurethane elastomer is 1;

[0170] Wherein, the above-mentioned polyaspartic acid ester structure is

[0171]

[0172] Among them, R1 is R2 is

[0173]

[0174] The preparation method of the thermoplastic polyurethane is the same as that in Example 1.

[0175] Comparative Example 1

[0176] A thermoplastic polyurethane elastomer comprising the following components:

[0177] 33.39 parts of diphenylmethane diisocyanate;

[0178] 10.00 parts of polybutylene adipate diol;

[0179] 50.00 parts of polyricinoleyl adipate glycol;

[0180] 1,4-Butanediol 6.61 parts;

[0181] Dibutyltin dilaurate 100ppm;

[0182] 1.5 parts of antioxidant 1010;

[0183] Antioxidant 626 1 part;

[0184] 0.5 parts of anti-hydrolysis agent carbodiimide.

[0185] Wherein, the number average molecular weight of polybutylene adipate diol and polyricinoleyl adipate diol is 1000 g / mol;

[0186] Among them, the isocyanate index of thermoplastic polyurethane elastomer is 1;

[0187] The preparation method of the thermoplastic polyurethane is the same as that in Example 1.

[0188] Comparative Example 2

[0189] A thermoplastic polyurethane elastomer comprising the following components:

[0190] 33.39 parts of diphenylmethane diisocyanate;

[0191] 60.00 parts of polybutylene adipate diol;

[0192] 2.75 parts of 1,4-butanediol;

[0193] Polyaspartic acid 9.49 parts;

[0194] Dibutyltin dilaurate 100ppm;

[0195] 1.5 parts of antioxidant 1010;

[0196] Antioxidant 626 1 part;

[0197] 0.5 part of hydrolysis-resistant agent carbodiimide;

[0198] Wherein, the number average molecular weight of polybutylene adipate diol and polyricinoleyl adipate diol is 1000 g / mol;

[0199] Among them, the isocyanate index of thermoplastic polyurethane elastomer is 1;

[0200] Wherein, the above-mentioned polyaspartic acid ester structure is

[0201]

[0202] Among them, R1 is R2 is

[0203]

[0204] The preparation method of the thermoplastic polyurethane is the same as that in Example 1.

[0205] The products obtained in the above embodiments and comparative examples were subjected to performance tests, wherein the transmittance and haze test samples were all 2 mm injection molded test pieces, and the tensile strength test was conducted according to the ASTM D412 standard on the 2 mm injection molded test pieces; the hydrolysis resistance test conditions were as follows: the 2 mm injection molded test pieces were immersed in 80° C. deionized water for 1 week, 4 weeks and 8 weeks, dried in an oven at 80° C. for 8 hours, and placed in a standard laboratory environment for 8 hours, and then the tensile strength retention rate was tested according to the ASTM D412 standard. The test results are shown in Table 1 below:

[0206] Table 1 Performance test results of the embodiments and comparative examples

[0207]

[0208] The thermoplastic polyurethane elastomer prepared by the present invention can be used to prepare extrusion-grade film and pipe products with high requirements for transparency and hydrolysis resistance, such as clothing, footwear, underwater cables, water pipes and diving equipment, due to its excellent transparency and hydrolysis resistance, but is not limited thereto.

[0209] Although the content of the present invention has been described in detail through the above preferred embodiments, it should be appreciated that the above description should not be considered as limiting the present invention. Those skilled in the art will appreciate that, under the guidance of this specification, some modifications or adjustments may be made to the present invention. These modifications or adjustments should also be within the scope defined by the claims of the present invention.

Claims

1. A thermoplastic polyurethane elastomer material, comprising the following components based on the total weight of the thermoplastic polyurethane elastomer: The castor oil-based diol is selected from a diol obtained by polycondensation of modified castor oil alcohol and a dibasic acid, or modified castor oil acid and a diol, or castor oil alcohol and a modified castor oil acid, or modified castor oil alcohol and a castor oil acid, or modified castor oil alcohol and a modified castor oil acid, wherein the modified castor oil alcohol and / or the modified castor oil acid are selected from mercaptan-modified, wherein the mercaptan structure used is: HS-R, wherein, R is selected from a straight chain alkyl group or a cycloalkyl group consisting of 2 to 18 carbon atoms; The di-secondary amine chain extender is selected from polyaspartic acid ester, and the structural formula is: Wherein, R1 is an alkyl chain consisting of 2 to 8 carbon atoms, and R2 is a straight chain alkyl or cycloalkyl consisting of 2 to 18 carbon atoms; The number average molecular weight of the macromolecular diol is 500 to 4000 g / mol.

2. The thermoplastic polyurethane elastomer material according to claim 1, characterized in that: The diisocyanate is selected from aromatic and / or aliphatic diisocyanates.

3. The thermoplastic polyurethane elastomer material according to claim 2, characterized in that: The aromatic diisocyanate is selected from one or more of toluene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, and xylylene diisocyanate; the aliphatic diisocyanate is selected from one or more of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, and 1,4-cyclohexyldimethylene diisocyanate.

4. The thermoplastic polyurethane elastomer material according to claim 1, characterized in that: The macromolecular diol is selected from one or more of polyether macromolecular diols or polyester macromolecular diols.

5. The thermoplastic polyurethane elastomer material according to claim 4, characterized in that: The polyether macromolecular diol is selected from one or more of polytetramethylene glycol, polyethylene glycol, polypropylene glycol and polyethylene glycol-propylene glycol diol, and the polyester macromolecular diol is selected from one or more of polyethylene adipate diol, polybutylene adipate diol, polyhexane adipate diol, polycaprolactone diol and polycarbonate diol.

6. The thermoplastic polyurethane elastomer material according to claim 4, characterized in that: The number average molecular weight of the macromolecular diol is 500 to 1000 g / mol.

7. The thermoplastic polyurethane elastomer material according to claim 1, characterized in that: The R is selected from a cycloalkyl group consisting of 6 to 12 carbon atoms.

8. The thermoplastic polyurethane elastomer material according to claim 1, characterized in that: The diol chain extender is selected from one or more of ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,5-pentanediol, isoprene glycol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, diethylene glycol, and hydroquinone dihydroxyethyl ether.

9. The thermoplastic polyurethane elastomer material according to claim 1, characterized in that: Based on the total weight of the thermoplastic polyurethane elastomer, it comprises the following components: Diisocyanate 20-45wt%; Macromolecular diol 10-50wt%; Castor oil-based glycol 10-50 wt%; 3-10 wt% of diol chain extender; 3-10 wt% of di-secondary amine chain extender.

10. The thermoplastic polyurethane elastomer material according to claim 1, characterized in that: The R1 is an alkyl chain consisting of 4 to 6 carbon atoms.

11. The thermoplastic polyurethane elastomer material according to claim 1, characterized in that: The isocyanate index is 0.8 to 1.

2.

12. The thermoplastic polyurethane elastomer material according to claim 1, characterized in that: The isocyanate index is 0.95 to 1.

05.

13. The thermoplastic polyurethane elastomer material according to claim 1, characterized in that: The thermoplastic polyurethane elastomer material also includes a catalyst. The catalyst addition amount is 1-200ppm based on the total mass of diisocyanate, macromolecular diol, castor oil-based diol, diol chain extender and disecondary amine chain extender.

14. The thermoplastic polyurethane elastomer material according to claim 1, characterized in that: The thermoplastic polyurethane elastomer material also includes mixing aids, which include light stabilizers, antioxidants, and hydrolysis stabilizers. The amount of mixing aids added is 2-5wt% based on the total mass of diisocyanate, macromolecular diol, castor oil-based diol, diol chain extender, and disecondary amine chain extender.

15. The thermoplastic polyurethane elastomer material according to any one of claims 1 to 14, characterized in that: The preparation method of the thermoplastic polyurethane elastomer comprises the following steps: (1) forming a thermoplastic polyurethane elastomer by extruding a diisocyanate, a macromolecular diol, a castor oil-based diol, a diol chain extender, a disecondary amine chain extender, an optional catalyst and a mixing aid; wherein the temperature of the extruder is set at 80-240° C.; (2) Cooling the thermoplastic polyurethane elastomer, crushing it, and granulating it.

Images