Raw material composition for preparing thermoplastic polyurethane and thermoplastic polyurethane elastomer

Abstract

The invention provides a raw material composition for preparing thermoplastic polyurethane and a preparation method of a thermoplastic polyurethane elastomer, the raw material composition of the thermoplastic polyurethane comprises polymer polyol, a chain extender and diisocyanate, the polymer polyol comprises a structure shown in a formula 1: # imgabs0 #, R is fluoroalkyl, R is alkyl, and R is alkyl. X is an integer greater than or equal to 1. The fluorine-containing structure shown in the formula 1 is introduced into the polymer polyol, so that the thermoplastic polyurethane elastomer with higher heat resistance can be prepared, the problem of compatibility between the polymer polyol and other raw materials such as a chain extender and polyol can be solved, and the preparation process is further simplified.

Description

Technical Field

[0001] The invention relates to the field of thermoplastic polyurethane elastomers, in particular to a raw material composition for preparing thermoplastic polyurethane and a thermoplastic polyurethane elastomer. Background Art

[0002] Thermoplastic polyurethane elastomer (TPU) is a polymer synthetic material with excellent comprehensive performance. It has excellent mechanical properties such as high strength, high elasticity, high wear resistance and high flexibility, and has excellent chemical properties such as oil resistance, solvent resistance and chemical resistance. Therefore, it is widely used in automotive wiring harnesses, automation cables, automotive steering shaft sleeves, cylinder pistons and other parts. With the development of industry, in order to ensure that the products have safer and more reliable performance, the market has put forward higher requirements on the heat resistance of thermoplastic polyurethane elastomers.

[0003] At present, the methods for improving the heat resistance of thermoplastic polyurethane elastomers can be summarized into the following two categories: one is to introduce molecules containing aromatic ring structures into macromolecular polyols and / or diisocyanates and / or chain extenders by chemical methods; the other is to add polyimide powder with high polarity as filler through physical blending modification. For example: Patent CN104017167A uses 1,5-naphthalene diisocyanate containing an aromatic ring structure to react with polyester polyols and chain extenders, and then blends epoxy resin with polyurethane prepolymers to prepare a polyurethane thermoplastic elastomer containing naphthalene aromatic rings with excellent heat resistance; Patent CN103923291A uses diol hydroquinone dihydroxyethyl ether and resorcinol bis(2-hydroxyethyl) ether containing aromatic ring structures as chain extenders, and macromolecular polyols and p-phenylene diisocyanate to prepare a thermoplastic polyurethane elastomer with good heat resistance; Patent CN105062039A uses organic polymer polyimide powder with excellent temperature resistance as a filler, and blends it with a thermoplastic polyurethane elastomer to prepare a heat-resistant polyurethane polyimide composite material.

[0004] However, the existing technology for improving the heat resistance of thermoplastic polyurethane elastomers has defects such as many preparation steps and poor compatibility of raw material components to a certain extent, and the durability of existing thermoplastic polyurethane elastomers when used in high temperature environments is poor. Summary of the invention

[0005] In view of the above problems, the present invention provides a raw material composition for preparing thermoplastic polyurethane. By introducing a fluorine-containing molecular structure into a polymer polyol, the composition can not only prepare a thermoplastic polyurethane elastomer with higher heat resistance and longer service life, but also solve the compatibility problem of the polymer polyol with other raw materials such as a chain extender and a polyol, thereby simplifying the preparation process.

[0006] The present invention also provides a thermoplastic polyurethane elastomer, which is prepared from raw materials including the raw material composition. Therefore, the thermoplastic polyurethane elastomer has better durability when used in a high temperature environment.

[0007] The present invention also provides a method for preparing a thermoplastic polyurethane elastomer. Since the method includes the step of using the raw material composition, the method can prepare a thermoplastic polyurethane elastomer with higher heat resistance and longer service life, and the process is simple.

[0008] In a first aspect, the present invention provides a raw material composition of thermoplastic polyurethane, comprising: a polymer polyol, a chain extender and a diisocyanate, wherein the polymer polyol comprises a structure shown in Formula 1:

[0009] Wherein, R is a fluoroalkyl group, and x is an integer greater than or equal to 1.

[0010] Optionally, at least one terminal group of the polymer polyol is a hydroxyl group;

[0011] And / or, R is a C4-C10 perfluoroalkane, preferably a hexafluoroethane, an octafluoropropane or a decafluorobutane.

[0012] Optionally, the polymer polyol includes one or more of polyester polyol, polyether polyol, polycaprolactone polyol and polycarbonate polyol.

[0013] Optionally, the polyether polyol has a structure as described in Formula 2:

[0014] Wherein, n is an integer greater than or equal to 1;

[0015] And / or, the polyester polyol has the structure described in Formula 3:

[0016] Wherein, m is an integer greater than or equal to 1;

[0017] And / or, the polycaprolactone polyol has the structure described in Formula 4:

[0018] Wherein, f is an integer greater than or equal to 1; and / or, the polycarbonate polyol has the structure described in Formula 5:

[0019] wherein g is an integer greater than or equal to 1. Optionally, the average functionality of the polymer polyol is 1.8 to 3.0, preferably 2.0;

[0020] and / or, the number average molecular weight of the polymer polyol is 500 to 5000 g / mol, preferably 800 to 3000 g / mol. Optionally, the chain extender comprises a saturated diol;

[0021] Preferably, the molecular formula of the saturated diol is HO-C a H 2a -OH, wherein a is a natural number of 1 to 10. Optionally, at least one end group of the chain extender is a structure shown in Formula 6 or Formula 7:

[0022] Wherein, Z is a fluoroalkyl group;

[0023]

[0024] Optionally, the chain extender includes one or more compounds of any one of the following formulas 8 to 11:

[0025]

[0026]

[0027] Optionally, the raw material composition comprises, by weight:

[0028] 30-70 parts of polymer polyol;

[0029] 4 to 21 parts of a chain extender;

[0030] 6 to 57 parts of diisocyanate;

[0031] 0.3 to 2.0 parts of additives;

[0032] Preferably, the diisocyanate is selected from one or more of aromatic diisocyanate, aliphatic diisocyanate and alicyclic diisocyanate, more preferably aromatic diisocyanate and / or aliphatic diisocyanate;

[0033] Preferably, the auxiliary agent includes an antioxidant auxiliary agent and / or a processing release auxiliary agent;

[0034] Preferably, the ratio of the equivalent weight of the diisocyanate to the total equivalent weight of the hydroxyl groups in the polymer polyol and the chain extender is 0.80 to 1.40, more preferably 0.90 to 1.20.

[0035] In a second aspect, the present invention provides a thermoplastic polyurethane elastomer prepared from raw materials including the raw material composition described in the first aspect.

[0036] In a third aspect, the present invention provides a method for preparing a thermoplastic polyurethane elastomer, comprising the following steps: reacting and molding a material comprising the raw material composition described in the first aspect.

[0037] The raw material composition of thermoplastic polyurethane provided by the present invention can be used to prepare thermoplastic polyurethane elastomer, and because the composition introduces a unique fluorine-containing molecular structure into the raw material polymer polyol, it can not only improve the heat resistance of the thermoplastic polyurethane elastomer and extend its service life, but also solve the compatibility problem of polymer polyol with other raw materials such as chain extenders and polyols, thereby simplifying the preparation process. DETAILED DESCRIPTION

[0038] In order to enable those skilled in the art to better understand the scheme of the present invention, the present invention is further described in detail below. The specific implementation methods listed below are only for describing the principles and features of the present invention. The examples are only used to explain the present invention and are not intended to limit the scope of the present invention. Based on the embodiments of the present invention, all other implementation methods obtained by ordinary technicians in the field without creative work are within the scope of protection of the present invention.

[0039] In this application, the term "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. The character " / " generally indicates that the associated objects are in an "or" relationship.

[0040] In this application, the term "at least one" means one or more, and "plurality" means two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single items 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, c can be single or multiple, respectively.

[0041] In this application, references to "one embodiment", "an example", or "an example" mean that a particular feature, structure, or characteristic described in conjunction with the embodiment, embodiment, or example is included in at least one embodiment of the present invention. Therefore, the phrases "one embodiment", "an embodiment", "an example", or "an example" appearing in various places throughout the specification do not necessarily refer to the same embodiment or example. In addition, particular features, structures, or characteristics may be combined in one or more embodiments or examples in any appropriate combination and / or sub-combination.

[0042] Thermoplastic polyurethane elastomer (TPU) is a multi-block polymer containing soft segments and hard segments. The molecular structure of the combination of soft and hard segments gives the thermoplastic polyurethane elastomer elasticity, high mechanical strength and other properties; and the carbamate, ester group and the like in the specific molecule have polar groups that can form aggregated hard segments, which is an important factor affecting the heat resistance of thermoplastic polyurethane elastomer. The present invention finds that by introducing fluorine-containing structure molecules into polymer polyols by chemical methods, by introducing high bond energy CF bonds, the intermolecular forces of the aggregated hard segments are significantly improved at the same time, thereby improving the heat resistance of thermoplastic polyurethane elastomers, and the specific structure of the fluorine-containing structure molecules and their relative positions in the polymer polyols can further affect the compatibility between the polymer polyols and other raw materials. In detail, the present invention provides the following technical solutions:

[0043] In a first aspect, the present invention provides a raw material composition for preparing thermoplastic polyurethane, comprising: a polymer polyol, a chain extender and a diisocyanate, wherein the polymer polyol comprises a structure shown in Formula 1:

[0044] Wherein, R is a fluoroalkyl group, and x is an integer greater than or equal to 1.

[0045] In the present invention, by introducing the structure shown in Formula 1 into the polymer polyol, not only the heat resistance of the thermoplastic polyurethane elastomer can be improved, but also the compatibility problem between the polymer polyol and other raw materials such as the chain extender and the polyol can be solved, thereby simplifying the preparation process. The main reasons include: the molecular structure of the branched fluoroalkyl group in the structure shown in Formula 1, the electron nuclear radius of the fluorine element is small, and the chemical bonds with large chemical bond energy (such as CF) can be formed with the surrounding elements. These chemical bonds make the thermoplastic polyurethane elastomer very stable when heated, providing support for maintaining the mechanical strength of the material; secondly, in Formula Compared with introducing fluoroalkyl groups into the main chain, the introduction of fluoroalkyl groups into the side chain of the structure shown in 1 can further improve the polarity of the polymer polyol molecular chain and solve the problem of poor compatibility with other raw materials, which is helpful to prepare a thermoplastic polyurethane elastomer product with good phase separation and good mechanical strength. At the same time, due to the better flexibility of the fluoroalkyl groups introduced into the side chain, the rebound effect of the thermoplastic polyurethane elastomer can be further enhanced when subjected to external stress. Therefore, the thermoplastic polyurethane elastomer prepared from the above raw material composition based on the above factors has the advantages of high heat resistance, high mechanical strength, good rebound resilience, etc.

[0046] In some embodiments, x is any value of 2-1000, 5-900, 10-800, 20-700, 30-600, 40-500, 50-400, 60-300, 70-200, 80-100, etc.

[0047] In an optional embodiment, at least one terminal group of the polymer polyol is a hydroxyl group. The hydroxyl group (-OH) of the polymer polyol can undergo an addition reaction with the isocyanate group (-NCO) of the diisocyanate to generate a urethane bond. This reaction is the basis for the formation of thermoplastic polyurethane elastomers, and the hydroxyl group at the terminal group of the polymer polyol makes the above reaction easier to proceed, which helps to form long-chain polymers, that is, increase the molecular weight of the thermoplastic polyurethane elastomer, and thus give the thermoplastic polyurethane excellent heat resistance and mechanical strength.

[0048] In an optional embodiment, the R is a hexafluoroethane group, an octafluoropropane group or a decafluorobutane group. Wherein, R is a perfluoroalkyl group, which can further improve the heat resistance of the thermoplastic polyurethane elastomer.

[0049] In an alternative embodiment, the polymer polyol includes one or more of polyester polyol, polyether polyol, polycaprolactone polyol and polycarbonate polyol.

[0050] As for the specific selection of polymer polyols, it can be determined according to the application of the thermoplastic polyurethane elastomer and the required performance characteristics. Among them, the thermoplastic polyurethane elastomer prepared from polyester polyols usually has excellent wear resistance, good tolerance to grease, solvents and some chemicals, and is suitable for application scenarios requiring high wear resistance and mechanical strength; the thermoplastic polyurethane elastomer prepared from polyether polyols usually has better low-temperature flexibility and elasticity, good hydrolysis stability, and is suitable for use in humid environments; polycaprolactone polyols have good biocompatibility and are suitable for medical and biological applications; polycarbonate polyols have excellent heat resistance and chemical resistance, and the prepared thermoplastic polyurethane elastomers are suitable for use in harsh environments.

[0051] In an optional embodiment, the polyether polyol has a structure as described in Formula 2:

[0052] Wherein, n is an integer greater than or equal to 1;

[0053] And / or, the polyester polyol has the structure described in Formula 3:

[0054] Wherein, m is an integer greater than or equal to 1;

[0055] And / or, the polycaprolactone polyol has the structure described in Formula 4:

[0056] Wherein, f is an integer greater than or equal to 1;

[0057] And / or, the polycarbonate polyol has the structure described in Formula 5:

[0058] Here, g is an integer greater than or equal to 1.

[0059] In some embodiments, n is any value in the range of 2-1000, 5-900, 10-800, 20-700, 30-600, 40-500, 50-400, 60-300, 70-200, 80-100, etc.; m is any value in the range of 2-1000, 5-900, 10-800, 20-700, 30-600, 40-500, 50-400, 60-300, 70-200, 80-100, etc. any value; f is any value among 2-1000, 5-900, 10-800, 20-700, 30-600, 40-500, 50-400, 60-300, 70-200, 80-100, etc.; g is any value among 2-1000, 5-900, 10-800, 20-700, 30-600, 40-500, 50-400, 60-300, 70-200, 80-100, etc.

[0060] The polymer polyols described above can be purchased directly or prepared according to conventional methods, for example, by catalytic ring-opening and ring-closing reactions. In some embodiments, the polymer polyols are prepared by a method comprising the following process:

[0061] First, fluorine-containing glycidyl ether is synthesized: fluorine-containing alcohol (taking octafluoropentanol OFP as an example) and epichlorohydrin (ECH) are used as raw materials, and reacted under alkaline conditions to obtain octafluoropentanol glycidyl ether (OFP-GE), and the reaction formula is shown in Formula I; in this step, different series of fluorine-containing glycidyl ethers are synthesized by adjusting the chain length and type of fluorine-containing alcohol (hexafluorobutanol, octafluoropentanol, decafluorohexanol, etc.);

[0062]

[0063] Synthesizing a branched fluorine-containing polymer polyol: using OFP-GE and different types of polymer polyols (any one of aliphatic polyester polyol PBA, polyether polyol PTMG, polycaprolactone polyol PCL, and polycarbonate polyol PCDL, specifically taking polyether polyol as an example) to carry out a ring-opening reaction under the catalyst of BF3·Et2O, and the reaction formula is shown in Formula II. In this step, polymer polyols with different molecular weights and different fluorine contents are obtained by adjusting the ratio of different starting materials;

[0064]

[0065] In an alternative embodiment, the average functionality of the polymer polyol is 1.8 to 3.0, preferably 2.0.

[0066] The average functionality of the polymer polyol is the average number of hydroxyl groups in the polymer polyol molecular chain. The specific value of the average functionality of the polymer polyol can be determined according to the application scenario and performance requirements of the thermoplastic polyurethane elastomer. For example, when the average functionality of the polymer polyol is any integer greater than or equal to 1.8 and less than or equal to 2, it is helpful to form a thermoplastic polyurethane elastomer with excellent flexibility and elasticity. When the average functionality of the polymer polyol is any integer greater than or equal to 2 and less than or equal to 3, it is helpful to form a thermoplastic polyurethane elastomer with higher mechanical strength and hardness.

[0067] A polymer polyol with a higher number average molecular weight generally results in a longer polymer chain, which helps to improve the elasticity, flexibility and thermal stability of the thermoplastic polyurethane elastomer. A polymer polyol with a lower number average molecular weight generally improves the fluidity of the material, making it easier to process and form. In order to make the thermoplastic polyurethane elastomer have higher elasticity, flexibility, thermal stability and easy processability, in an optional embodiment, the number average molecular weight of the polymer polyol is 500 to 5000 g / mol, more preferably 800 to 3000 g / mol.

[0068] In an alternative embodiment, the chain extender includes a saturated diol, wherein the saturated diol has a straight chain or a simple molecular structure, which helps to form a linear polymer chain and reduce cross-linking, thereby improving the mechanical properties of the thermoplastic polyurethane elastomer.

[0069] In one embodiment, the molecular formula of the saturated diol is HO-C a H 2a -OH, wherein a is a natural number of 1 to 10. The saturated diol described above contributes to further improving the mechanical properties of the thermoplastic polyurethane elastomer.

[0070] In an optional embodiment, at least one end group of the chain extender is a structure shown in Formula 6 or Formula 7:

[0071] Wherein, Z is a fluoroalkyl group;

[0072]

[0073] Among them, the above-mentioned embodiment can introduce more CF, C-Si, Si-O, FH bonds with larger chemical bond energy into the molecular structure of the thermoplastic polyurethane elastomer by introducing the structure shown in Formula 6 or Formula 7 into the end group of the chain extender, thereby further improving the heat resistance of the thermoplastic polyurethane elastomer.

[0074] In an optional embodiment, one end group of the chain extender has a structure shown in Formula 6, and one end group has a structure shown in Formula 7.

[0075] The chain extender as described above can be purchased directly or prepared according to conventional methods, for example, using small molecule diols (ethylene glycol, butanediol) as ring-opening initiators.

[0076] In an alternative embodiment, the chain extender includes one or more compounds of any one of the following Formulae 8 to 11.

[0077] In the implementation described above, by introducing fluorine- and silicon-containing structural compounds into the chain extender, due to the molecular structure with similar chemical bond energy, its compatibility with polymer polyols can be improved, which is convenient for operation, and more fluorine and silicon bonds can be introduced, thereby improving the heat resistance of the material.

[0078]

[0079] Generally speaking, polymer polyols mainly form soft segments of thermoplastic polyurethane elastomers, affecting their flexibility and elasticity. Chain extenders react with diisocyanates to form hard segments, affecting the hardness and strength of thermoplastic polyurethane elastomers. The present invention introduces the structure shown in Formula 1 into polymer polyols, which can further impart improved heat resistance to thermoplastic polyurethane elastomers. However, in order to further balance the relationship between the flexibility, elasticity, strength and heat resistance of thermoplastic polyurethane elastomers, in an optional embodiment, the raw material composition includes 30%-70% of polymer polyols.

[0080] In one specific embodiment, the raw material composition comprises, by weight:

[0081] 30-70 parts of polymer polyol;

[0082] 4 to 21 parts of a chain extender;

[0083] 6 to 57 parts of diisocyanate;

[0084] 0.3-2.0 parts of additives.

[0085] The present invention does not limit the specific types of the auxiliary agent and diisocyanate. In some implementations, the auxiliary agent includes an antioxidant and / or a processing release agent; the diisocyanate is selected from one or more of aromatic diisocyanates, aliphatic diisocyanates and alicyclic diisocyanates, and is more preferably aromatic diisocyanates and / or aliphatic diisocyanates.

[0086] In an optional embodiment, the ratio of the (molar) equivalent of the diisocyanate to the total (molar) equivalent of the hydroxyl groups in the polymer polyol and the chain extender is 0.80 to 1.40, more preferably 0.90 to 1.20. The diisocyanate, polymer polyol and chain extender as described above can react to form a thermoplastic polyurethane elastomer with high elasticity and flexibility and high heat resistance.

[0087] In some embodiments, the raw material composition also includes a catalyst, wherein the added amount of the catalyst is 1-500ppm based on the total mass of the raw material composition; the catalyst includes a first catalyst that promotes the reaction or a second catalyst that inhibits the reaction, the first catalyst is selected from organic acid salts, inorganic acid salts and organometallic derivatives of tin, bismuth, cobalt, zinc, nickel, molybdenum, zirconium, copper, aluminum, and iron, preferably an organotin catalyst, more preferably one or more of stannous octoate, dibutyl tin dilaurate, and dibutyl tin dioctoate; the second catalyst is selected from a protonic acid containing free active H+, preferably one or more of phosphoric acid, dilute sulfuric acid, and sulfonic acid.

[0088] In a second aspect, the present invention provides a thermoplastic polyurethane elastomer prepared from raw materials including the raw material composition described in the first aspect.

[0089] In a third aspect, the present invention provides a method for preparing a thermoplastic polyurethane elastomer, comprising the following steps: reacting materials comprising the raw material composition described in the first aspect to obtain the thermoplastic polyurethane elastomer.

[0090] In some embodiments, the specific molding process of the thermoplastic polyurethane elastomer as described above can be conventional manual casting molding or machine casting molding. In some embodiments, manual casting molding is used. The preparation method of the thermoplastic polyurethane elastomer includes the following steps:

[0091] 1) mixing a polymer polyol, a chain extender, an optional auxiliary agent, and an optional catalyst at 50-110° C. to obtain a first mixed material;

[0092] 2) adding isocyanate to the mixed material at 20-40° C., stirring and heating until the temperature reaches 90-150° C., and stopping stirring to obtain a gel-like second mixed material;

[0093] 3) The second mixed material is poured into a mold, and is ripened, crushed, and injection molded to obtain the product.

[0094] Exemplarily, the aging temperature is 90 to 130° C., and the aging time is 4 to 20 hours.

[0095] Exemplarily, the above-mentioned heating time is 10 to 240 seconds, preferably 30 to 120 seconds.

[0096] Exemplarily, the temperature is raised to 110-130° C., and stirring is stopped to obtain the gel.

[0097] In some embodiments, a twin-screw reaction extruder is used for molding, and the preparation method of the thermoplastic polyurethane elastomer includes the following steps: a polymer polyol, a chain extender, an optional auxiliary agent, and an optional catalyst are mixed to obtain a mixed material, and the uniformly mixed liquid is injected into a twin-screw reaction extruder for extrusion molding.

[0098] It can be understood that the thermoplastic polyurethane elastomer prepared by the above-mentioned method for preparing the thermoplastic polyurethane elastomer is also within the protection scope of the present invention.

[0099] In some embodiments, the thermoplastic polyurethane elastomer prepared above is annealed in an oven and then tested for its resilience. The thermal decomposition temperature reaches 320° C.-400° C. through TGA test, and the high temperature compression rebound is in the range of 25%-50%.

[0100] Exemplarily, the annealing treatment is performed at a temperature of 70°C to 130°C for a time of 4h to 24h; after the annealing treatment, the process also includes: placing the sample in a standard constant temperature and humidity laboratory (23°C, 50% humidity) for 6h to 30h, and then cutting test specimens of different shapes.

[0101] In order to further understand the present invention, the technical solution of the present invention will be clearly and completely described below in conjunction with specific embodiments. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0102] Unless otherwise specified, the reagents involved in the embodiments of the present invention are all commercially available products and can be purchased through commercial channels. Among them, some raw materials are shown in Table 1;

[0103] The preparation method of polymer polyol comprises the following steps:

[0104] First, synthesize fluorinated glycidyl ether: use fluorinated alcohol and epichlorohydrin (ECH) as raw materials, react under alkaline (pH 8-14) N2 conditions to obtain octafluoropentanol glycidyl ether (OFP-GE); by adjusting the chain length and type of fluorinated alcohol (hexafluorobutanol, octafluoropentanol, decafluorohexanol, etc.), different series of fluorinated glycidyl ethers can be synthesized;

[0105] Synthesize branched fluorine-containing polymer polyols: use OFP-GE and different types of polymer polyols (any one of aliphatic polyester polyol PBA, polyether polyol PTMG, polycaprolactone polyol PCL, polycarbonate polyol PCDL) to carry out ring-opening reaction under the catalysis of catalyst BF3·Et2O, and obtain branched fluorine-containing alkyl polymer polyols with different molecular weights and different fluorine contents by adjusting different proportions of starting materials.

[0106] The analysis methods involved in the embodiments of the invention are as follows: heat resistance test is based on GB / T2951, Shore hardness test is based on ASTM D2240, tensile test is based on ASTM D412, rebound performance is based on ASTM D395, and wear resistance is based on ASTMD624.

[0107] The analytical instruments involved in the embodiments of the invention are shown in Table 2:

[0108] Table 1:

[0109]

[0110]

[0111] Table 2:

[0112] Instrument Name model factory Injection molding machine JPH80 Guangdong Hongli Machinery Co., Ltd. DSC DSC822 METTLER TOLEDO, Switzerland Hardness Tester LX-A, LX-D Shanghai Liuling Instrument Factory Tensile testing machine MY-9000-S Mingyu Electronic Technology Co., Ltd. Cutting Machine GT-7016-AR High-speed Railway Testing Instrument Co., Ltd. Abrasion Tester GT-7012-D High-speed Railway Testing Instrument Co., Ltd. Vicat Thermal Deformation Tester CEAST HV6A INSTRON Benchtop Drill Press ZHX-13 Hangzhou West Lake Drilling Co., Ltd. Hot air oven DHG-9246 Shanghai Jinghong Experimental Equipment Company

[0113] Example 1

[0114] This example provides a raw material composition of thermoplastic polyurethane, including: 600g polymer polyol, 86.4g chain extender, 313.6g diisocyanate, 5g antioxidant, and 5g demoulding aid, wherein the molecular structure of the polymer polyol is:

[0115] Wherein, x=1, m=7; the weight average molecular weight of the polymer polyol is 2000 g / mol, the average functionality is 2, the chain extender is 1,4-butanediol, and the diisocyanate is diphenylmethane diisocyanate (MDI).

[0116] Example 2

[0117] This example provides a raw material composition of thermoplastic polyurethane, including: 600g polymer polyol, 124g chain extender, 276g diisocyanate, 5g antioxidant, and 5g demoulding aid, wherein the molecular structure of the polymer polyol is:

[0118] Wherein, x=1, n=19, the weight average molecular weight of the polymer polyol is 1800 g / mol, the average functionality is 2, the chain extender is hexanediol, and the diisocyanate is hexamethylene diisocyanate (HDI).

[0119] Example 3

[0120] This example provides a raw material composition of thermoplastic polyurethane, including: 600g polymer polyol, 93g chain extender, 307g diisocyanate, 5g antioxidant, and 5g demoulding aid, wherein the molecular structure of the polymer polyol is:

[0121] Wherein, x=1, f=21, the weight average molecular weight of the polymer polyol is 3000 g / mol, the average functionality is 2, the chain extender is 1,4-butanediol, and the diisocyanate is diphenylmethane diisocyanate (MDI).

[0122] Example 4

[0123] This example provides a raw material composition of thermoplastic polyurethane, including: 600g polymer polyol, 86.4g chain extender, 313.6g diisocyanate, 5g antioxidant, and 5g demoulding aid, wherein the molecular structure of the polymer polyol is:

[0124] Wherein, x=1, g=14, the weight average molecular weight of the polymer polyol is 2000 g / mol, the average functionality is 2, the chain extender is 1,4-butanediol, and the diisocyanate is diphenylmethane diisocyanate (MDI).

[0125] Example 5

[0126] This example provides a raw material composition of thermoplastic polyurethane, which is different from Example 2 only in that the molecular structure of the polymer polyol is the same as that of Example 2, x=3, and the weight average molecular weight of the polymer polyol is 3000 g / mol.

[0127] Example 6

[0128] The raw material composition of a thermoplastic polyurethane provided in this example is different from that in Example 4 only in that in the molecular structure formula of the polymer polyol, x=2, and the weight average molecular weight of the polymer polyol is 2500 g / mol.

[0129] Example 7

[0130] This example provides a raw material composition of thermoplastic polyurethane, including: 600g polymer polyol, 235g chain extender, 203g diisocyanate, 5g antioxidant, and 5g release aid, wherein the molecular structures of diisocyanate, antioxidant, release aid, and polymer polyol are consistent with those in Example 2, and the molecular structure of the chain extender is shown in Formula 8.

[0131] Example 8

[0132] This example provides a raw material composition of thermoplastic polyurethane, including: 600g polymer polyol, 250g chain extender, 188g diisocyanate, 5g antioxidant, and 5g release aid, wherein the molecular structures of diisocyanate, antioxidant, release aid, and polymer polyol are consistent with those in Example 1, and the molecular structure of the chain extender is shown in Formula 9.

[0133] Example 9

[0134] This example provides a raw material composition of thermoplastic polyurethane, including: 600g polymer polyol, 199.8g chain extender, 200.2g diisocyanate, 5g antioxidant, and 5g release aid, wherein the molecular structures of diisocyanate, antioxidant, release aid, and polymer polyol are consistent with those in Example 4, and the molecular structure of the chain extender is shown in Formula 10.

[0135] Example 10

[0136] This example provides a raw material composition of thermoplastic polyurethane, including: 600g polymer polyol, 212g chain extender, 186g diisocyanate, 5g antioxidant, and 5g release aid, wherein the molecular structures of diisocyanate, antioxidant, release aid, and polymer polyol are consistent with those in Example 4, and the molecular structure of the chain extender is shown in Formula 11.

[0137] Comparative Example 1

[0138] The raw material composition of a thermoplastic polyurethane provided in this example is different from that in Example 1 only in that the polymer polyol is polybutylene adipate with a molecular weight of 2000 g / mol.

[0139] Comparative Example 2

[0140] The raw material composition of a thermoplastic polyurethane provided in this example is different from that in Example 2 only in that the polymer polyol is polytetramethylene glycol with a molecular weight of 1800 g / mol.

[0141] Comparative Example 3

[0142] The raw material composition of a thermoplastic polyurethane provided in this example is different from that in Example 4 only in that the polymer polyol contains a fluorine structure polymer polyol as the main chain, the molecular structure is as follows: 12, and the molecular weight is 2000 g / mol.

[0143]

[0144] Comparative Example 4

[0145] The raw material composition of a thermoplastic polyurethane provided in this example is different from that in Example 4 only in that the polymer polyol contains an aromatic ring structure in the main chain, the molecular structure is as shown in Formula 13, and the molecular weight is 2000 g / mol.

[0146]

[0147] Test example

[0148] Thermoplastic polyurethane elastomer is prepared by using the raw material composition of the thermoplastic polyurethane, and the preparation process includes:

[0149] At room temperature, polymer polyol, chain extender, antioxidant, demoulding aid and stannous octoate catalyst are stirred and mixed at 70°C (the catalyst accounts for 30ppm of the raw materials other than the catalyst), and then diisocyanate is added so that the ratio of the equivalent of diisocyanate to the total equivalent of hydroxyl groups in the polymer polyol and the chain extender is 0.995, and stirred at a speed of 500rpm until the temperature rises to above 110°C, and stirring is stopped. After gelling, it is quickly poured into a mold, and ripened at 100°C for 12h, and then broken, and different shapes of test pieces are injection molded. The test pieces obtained by injection molding are placed in a 100°C oven for annealing for 12h, and then taken out and placed in a standard constant temperature and humidity laboratory (23°C, 50% humidity) for 24h to obtain thermoplastic polyurethane elastomer test pieces. Different shapes of strips are cut from each test piece for test evaluation. The test results are shown in Table 3.

[0150] Experimental phenomenon: Due to the incompatibility problem in Comparative Example 3, the components did not react. Specifically, when the polymer polyol was added to the chain extender, it was observed that the polyol completely precipitated at the bottom in the form of oil droplets and could not be well mixed with the chain extender. This phenomenon did not exist in other embodiments or comparative examples, and they all dissolved well with each other.

[0151] Table 3:

[0152]

[0153] As shown in Table 3, the thermoplastic polyurethane elastomer product prepared by the composition of the embodiment has higher heat resistance (heat-resistant decomposition temperature, heat-resistant strength retention rate, etc.) than the comparative example, especially the heat resistance of the embodiments 7-10 in which the polymer polyol and the chain extender are both introduced with fluorine-containing and silicon-containing structures is more excellent, and the heat resistance of the thermoplastic polyurethane elastomer product prepared by the composition of the comparative example is increased by 5-30%. Secondly, the thermoplastic polyurethane elastomer product prepared by the composition of the embodiment maintains the same mechanical properties, appearance transparency and processing properties as the comparative example product, therefore, it is suitable for industrial products such as cables, pipes, mechanical seals, etc. with high heat resistance requirements.

[0154] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A raw material composition for preparing thermoplastic polyurethane, characterized in that: It includes a polymer polyol, a chain extender and a diisocyanate, wherein the polymer polyol includes a structure shown in Formula 1: Wherein, R is a fluoroalkyl group, and x is an integer greater than or equal to 1.

2. The raw material composition according to claim 1, characterized in that At least one terminal group of the polymer polyol is a hydroxyl group; And / or, R is a C4-C10 perfluoroalkane, preferably a hexafluoroethane, an octafluoropropane or a decafluorobutane.

3. The raw material composition according to claim 2, characterized in that The polymer polyol includes one or more of polyester polyol, polyether polyol, polycaprolactone polyol and polycarbonate polyol; Preferably, the polyether polyol has a structure as described in Formula 2: Wherein, n is an integer greater than or equal to 1; And / or, the polyester polyol has the structure described in Formula 3: Wherein, m is an integer greater than or equal to 1; And / or, the polycaprolactone polyol has the structure described in Formula 4: Wherein, f is an integer greater than or equal to 1; And / or, the polycarbonate polyol has the structure described in Formula 5: Here, g is an integer greater than or equal to 1.

4. The raw material composition according to any one of claims 1 to 3, characterized in that: The average functionality of the polymer polyol is 1.8 to 3.0, preferably 2.0; And / or, the number average molecular weight of the polymer polyol is 500 to 5000 g / mol, preferably 800 to 3000 g / mol.

5. The raw material composition according to any one of claims 1 to 3, characterized in that: The chain extender includes a saturated diol; Preferably, the molecular formula of the saturated diol is HO-C a H 2a -OH, wherein a is an integer of 1 to 10.

6. The raw material composition according to any one of claims 1 to 3, characterized in that: At least one end group of the chain extender is a structure shown in Formula 6 or Formula 7: Wherein, Z is a fluoroalkyl group; 7. The raw material composition according to claim 6, characterized in that The chain extender includes one or more compounds in any one of the following formulas 8 to 11:

8. The raw material composition according to any one of claims 1 to 7, characterized in that: The raw material composition comprises, by mass: 30-70 parts of polymer polyol; 4 to 21 parts of a chain extender; 6 to 57 parts of diisocyanate; 0.3 to 2.0 parts of additives; Preferably, the diisocyanate is selected from one or more of aromatic diisocyanate, aliphatic diisocyanate and alicyclic diisocyanate, more preferably aromatic diisocyanate and / or aliphatic diisocyanate; Preferably, the auxiliary agent includes an antioxidant auxiliary agent and / or a processing release auxiliary agent; Preferably, the ratio of the equivalent weight of the diisocyanate to the total equivalent weight of the hydroxyl groups in the polymer polyol and the chain extender is 0.80 to 1.40, more preferably 0.90 to 1.

20.

9. A thermoplastic polyurethane elastomer, characterized in that: The method is prepared from raw materials comprising the raw material composition described in any one of claims 1 to 8.

10. A method for preparing a thermoplastic polyurethane elastomer, characterized in that: The following steps are involved: The material comprising the raw material composition according to any one of claims 1 to 8 is reacted to obtain the thermoplastic polyurethane elastomer.

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