A novel three-component blended polyurethane thermoplastic elastomer and its preparation method

Abstract

The present invention provides a novel three-component blended polyurethane thermoplastic elastomer and a preparation method thereof, belonging to the technical field of polyurethane thermoplastic elastomer. The novel three-component blended polyurethane thermoplastic elastomer of the present invention is mixed with 20 to 60 parts of polysiloxane-polyurethane, 40 to 80 parts of polyether-polyurethane and 5 to 35 parts of a graft polymer having a polysiloxane-polyurethane and a polyether-polyurethane structure, wherein the hard segment content in the polysiloxane-polyurethane and the polyether-polyurethane is independently 20 to 50wt%, and the isocyanate index is independently 0.98 to 1.02. The novel three-component blended polyurethane thermoplastic elastomer prepared by the present invention has the weather resistance, water resistance, temperature resistance and flexibility of polysiloxane, as well as the excellent properties of high strength, high modulus and the like of polyurethane, and has excellent comprehensive performance.

Description

Technical Field

[0001] The invention relates to the field of polyurethane thermoplastic elastomers, in particular to a novel three-component blended polyurethane thermoplastic elastomer and a preparation method thereof. Background Art

[0002] Polyurethane thermoplastic elastomer is a block polymer generated by the reaction of isocyanate compounds and hydroxyl compounds. It consists of two parts, a hard segment and a soft segment. The properties of the elastomer can be controlled by adjusting the molecular structure and ratio of the soft segment and the hard segment. Polysiloxane is a typical flexible segment and can be used as a soft segment component of polyurethane elastomer to improve certain properties of traditional polyurethane, such as hydrophobicity, weather resistance, and low temperature resistance. Therefore, polysiloxane-modified polyurethane thermoplastic elastomer has always been a research hotspot.

[0003] Currently, there are two methods to introduce polysiloxane into polyurethane. One is to use polysiloxane alone as a soft segment. We named the polyurethane prepared in this way polysiloxane-polyurethane. The other is to mix polysiloxane with traditional terminal hydroxyl polyether as a soft segment. We named the polyurethane prepared in this way polysiloxane-modified polyurethane.

[0004] Patent CN108285519A uses hydroxyl polysiloxane as a soft segment, isocyanate and dihydroxy compounds as hard segments, and prepares polysiloxane-polyurethane, and the tensile strength of the elastomer can reach 18MPa. However, due to the high content of the hard segment of 40%, the elongation at break of polysiloxane-polyurethane is only 197%, which is much lower than the conventional polyurethane with polyether as a soft segment. Patent CN109575233B uses a mixture of polysiloxane and polyether diol as a soft segment, isocyanate and dihydroxy compounds as hard segments, and prepares polysiloxane-modified polyurethane by a two-step method. The mechanical properties of the obtained material are between polysiloxane-polyurethane and polyether-polyurethane. It overcomes the defects of low strength of polysiloxane-polyurethane and poor weather resistance and hydrophobicity of polyether-polyurethane to a certain extent, but compared with traditional polyether-polyurethane, its strength is still insufficient. The tensile strength of some formulas in which the content of polysiloxane in the mixed soft segment is only 10-20% is higher than 20MPa. Due to the low content of polysiloxane, the modified polyurethane is difficult to reflect the characteristics of silicone, which deviates from the original intention of silicone-modified polyurethane. Cooper et al. used polydimethylsiloxane and polybutylene glycol as mixed soft segments with diphenylmethane diisocyanate and 1,4-butanediol to prepare polysiloxane-modified polyurethane, whose glass transition temperature is around -105℃. Compared with the glass transition temperature of polydimethylsiloxane at around -123℃, the low-temperature performance of the silicone-modified polyurethane needs to be improved. (Reference: HernandezR, Weksler J, Macromolecules 2007, 40, 15, 5441–5449).

[0005] Therefore, it is of great significance to develop a new three-component blended polyurethane thermoplastic elastomer and improve the mechanical properties, high and low temperature resistance and hydrophobicity of the polyurethane thermoplastic elastomer. Summary of the invention

[0006] The purpose of the present invention is to provide a novel three-component blended polyurethane thermoplastic elastomer and a preparation method thereof, so as to solve the technical problem of poor comprehensive performance of polyurethane thermoplastic elastomer in the prior art.

[0007] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0008] The invention provides a novel three-component blended polyurethane thermoplastic elastomer, which is prepared by mixing 20 to 60 parts of polysiloxane-polyurethane, 40 to 80 parts of polyether-polyurethane and 5 to 35 parts of a graft polymer having a polysiloxane-polyurethane and polyether-polyurethane structure, wherein the hard segment content in the polysiloxane-polyurethane and the polyether-polyurethane is independently 20 to 50 wt%, and the isocyanate index is independently 0.98 to 1.02.

[0009] Preferably, the polysiloxane-polyurethane has the general formula (I):

[0010]

[0011] The polyether-polyurethane has the general formula shown in formula (II):

[0012]

[0013] Wherein, a, b, c, d, e, and f are independently selected from integers greater than 1 and less than or equal to 100; M is independently selected from one of (CH2)2, (CH2)3, (CH2)4, and (CH2)6; -J- is independently selected from

[0014]

[0015] One of; R is independently selected from one of (CH2)3, (CH2)3O(CH2)2 and (CH2)4.

[0016] Preferably, the graft polymer having polysiloxane-polyurethane and polyether-polyurethane structure has the general formula shown in formula (III):

[0017]

[0018] Wherein, g is selected from an integer greater than 1 and less than or equal to 100; h and i are independently selected from integers greater than 1 and less than or equal to 4; Z is independently a polysiloxane-polyurethane chain segment; T is a polyether-polyurethane chain segment; -J- is selected from One of them.

[0019] The present invention provides a method for preparing a novel three-component blended polyurethane thermoplastic elastomer, comprising the following steps:

[0020] (1) mixing a diisocyanate compound and a hydroxyl-terminated polysiloxane to react to obtain a prepolymer; mixing a mixture of a diol compound, a double-bond diol compound, a catalyst and a solvent with the prepolymer to react to obtain a polymer III-1;

[0021] (2) mixing polymer III-1, compound N and benzoin dimethyl ether to react to obtain polymer III-2;

[0022] (3) mixing a diisocyanate compound and a hydroxyl-terminated polyether to react to obtain an isocyanate-terminated prepolymer; mixing a mixture of a diol compound, a catalyst, and a solvent with the isocyanate-terminated prepolymer to react to obtain a polymer III-3;

[0023] (4) mixing polymer III-2 and polymer III-3 to react, thereby obtaining a graft polymer having a polysiloxane-polyurethane and polyether-polyurethane structure;

[0024] (5) A novel three-component blended polyurethane thermoplastic elastomer is obtained by mixing polysiloxane-polyurethane, polyether-polyurethane and a grafted polymer having a polysiloxane-polyurethane and polyether-polyurethane structure and then drying the mixture.

[0025] Preferably, in steps (1) and (3), the solvent independently comprises one or more of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, toluene, tetrahydrofuran, xylene, butanone and 1,4-dioxane.

[0026] Preferably, in the steps (1) and (3), the diisocyanate compound independently comprises one or more of toluene diisocyanate, diphenylmethane diisocyanate, tetramethylxylene diisocyanate, hexamethylene diisocyanate and p-phenylene diisocyanate; in the steps (1) and (3), the diol compound independently comprises one or more of 1,4-butanediol, ethylene glycol, 1,6-hexanediol and 1,3-propylene glycol.

[0027] Preferably, the hydroxyl-terminated polysiloxane is selected from one of the general formulas (IV), (V) and (VI):

[0028]

[0029] Wherein, a is independently selected from integers greater than 1 and less than or equal to 100;

[0030] The hydroxyl-terminated polyether has the general formula shown in formula (VII):

[0031]

[0032] Wherein, d is an integer greater than 1 and less than or equal to 100;

[0033] The double bond-containing diol compound has the general formula shown in formula (VIII):

[0034]

[0035] Wherein, h is independently selected from integers greater than 1 and less than or equal to 4;

[0036] The compound N has the general formula shown in formula (IX):

[0037]

[0038] Here, i is an integer greater than 1 and less than or equal to 4.

[0039] Preferably, in steps (1) and (3), the catalyst independently comprises stannous isooctanoate and / or dibutyltin dilaurate, wherein the amount of the catalyst used is 0.4 to 4% of the mass of the diisocyanate compound.

[0040] Preferably, in the step (1), the mass ratio of the diisocyanate compound, the terminal hydroxyl polysiloxane, the diol compound, the double bond-containing diol compound and the solvent is 1-6: 5-10: 0.2-1.6: 0.1-0.8: 60-120; the mass ratio of the terminal hydroxyl polysiloxane, the compound N and benzoin dimethyl ether is 5-10: 0.1-1.2: 0.3-0.6; in the step (3), the mass ratio of the diisocyanate compound, the terminal hydroxyl polyether, the diol compound and the solvent is 5-30: 15-45: 1-9: 100-350; in the step (4), the mass ratio of the polymer III-2 and the polymer III-3 is 1: 1.5-4.0.

[0041] Preferably, in the steps (1) and (3), the reaction temperature is independently 70-90°C, and the reaction time is independently 1-4h; in the step (2), the reaction is carried out under ultraviolet light, and the reaction time is 15-30min; in the step (4), the reaction temperature is 70-90°C, and the reaction time is 30-42h.

[0042] Beneficial effects of the present invention:

[0043] (1) The present invention introduces a method for preparing a polymer blend to obtain a novel three-component blended polyurethane thermoplastic elastomer.

[0044] (2) The present invention adopts solution blending, and the preparation of a novel three-component blended polyurethane thermoplastic elastomer can be completed at room temperature, without the need for complex heating equipment, which is different from the melt blending method in the prior art. The present invention uses a graft polymer having a polysiloxane-polyurethane and polyether-polyurethane structure as a compatibilizer, which has a certain volume-increasing effect, and the obtained elastomer has a thermodynamically stable structure, avoiding the defects of melt blending.

[0045] (3) The novel three-component blended polyurethane thermoplastic elastomer provided by the present invention has the weather resistance, water resistance, temperature resistance and flexibility of polysiloxane, as well as the excellent properties of high strength, high modulus and the like of polyurethane, and has excellent comprehensive performance. DETAILED DESCRIPTION

[0046] Terminology Note:

[0047] Polysiloxane-polyurethane: A polyurethane prepared using hydroxyl polysiloxane alone as a soft segment.

[0048] Polyether-polyurethane: Polyurethane prepared using hydroxy polyether alone as the soft segment.

[0049] Isocyanate index: the molar ratio of NCO groups to hydroxyl groups in a system.

[0050] Hard segment content: refers to the mass percentage of isocyanate compounds and chain extenders in the material.

[0051] The invention provides a novel three-component blended polyurethane thermoplastic elastomer, which is prepared by mixing 20 to 60 parts of polysiloxane-polyurethane, 40 to 80 parts of polyether-polyurethane and 5 to 35 parts of a graft polymer having a polysiloxane-polyurethane and polyether-polyurethane structure, wherein the hard segment content in the polysiloxane-polyurethane and the polyether-polyurethane is independently 20 to 50 wt%, and the isocyanate index is independently 0.98 to 1.02.

[0052] In the present invention, the mass fraction of the polysiloxane-polyurethane is preferably 25 to 55 parts, and more preferably 30 to 50 parts; the mass fraction of the polyether-polyurethane is preferably 45 to 75 parts, and more preferably 50 to 70 parts; the mass fraction of the graft polymer having polysiloxane-polyurethane and polyether-polyurethane structures is preferably 8 to 30 parts, and more preferably 15 to 25 parts; the hard segment content in the polysiloxane-polyurethane and polyether-polyurethane is independently preferably 25 to 45wt%, and more preferably 27 to 43wt%, and more preferably 30 to 40wt%; the isocyanate index is independently 0.98 to 1.02, and preferably 0.99 to 1.01.

[0053] In the present invention, the polysiloxane-polyurethane has the general formula (I):

[0054]

[0055] The polyether-polyurethane has the general formula shown in formula (II):

[0056]

[0057] Wherein, a, b, c, d, e, and f are independently selected from integers greater than 1 and less than or equal to 100, a and d are independently preferably integers of 15 to 65, and b, c, e, and f are independently preferably integers of 40 to 70; M is independently selected from one of (CH2)2, (CH2)3, (CH2)4, and (CH2)6, preferably one of (CH2)2, (CH2)3, and (CH2)4; -J- is independently selected from one of

[0058] One of, preferably selected from

[0059] One of; R is independently selected from one of (CH2)3, (CH2)3O(CH2)2 and (CH2)4, preferably selected from (CH2)3 or (CH2)3O(CH2)2.

[0060] Preferably, the graft polymer having polysiloxane-polyurethane and polyether-polyurethane structure has the general formula shown in formula (III):

[0061]

[0062] Wherein, g is selected from an integer greater than 1 and less than or equal to 100, preferably an integer of 40 to 70; h and i are independently selected from integers greater than 1 and less than or equal to 4, preferably an integer of 2 to 3; Z is independently a polysiloxane-polyurethane chain segment; T is a polyether-polyurethane chain segment; -J- is selected from

[0063] One of, preferably selected from One of them.

[0064] The present invention provides a method for preparing a novel three-component blended polyurethane thermoplastic elastomer, comprising the following steps:

[0065] (1) mixing a diisocyanate compound and a hydroxyl-terminated polysiloxane to react to obtain a prepolymer; mixing a mixture of a diol compound, a double-bond diol compound, a catalyst and a solvent with the prepolymer to react to obtain a polymer III-1;

[0066] (2) mixing polymer III-1, compound N and benzoin dimethyl ether to react to obtain polymer III-2;

[0067] (3) mixing a diisocyanate compound and a hydroxyl-terminated polyether to react to obtain an isocyanate-terminated prepolymer; mixing a mixture of a diol compound, a catalyst, and a solvent with the isocyanate-terminated prepolymer to react to obtain a polymer III-3;

[0068] (4) mixing polymer III-2 and polymer III-3 to react, thereby obtaining a graft polymer having a polysiloxane-polyurethane and polyether-polyurethane structure;

[0069] (5) A novel three-component blended polyurethane thermoplastic elastomer is obtained by mixing polysiloxane-polyurethane, polyether-polyurethane and a grafted polymer having a polysiloxane-polyurethane and polyether-polyurethane structure and then drying the mixture.

[0070] In the present invention, in the steps (1) and (3), the solvent independently comprises one or more of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, toluene, tetrahydrofuran, xylene, butanone and 1,4-dioxane, and is preferably independently a mixed solvent of toluene and N,N-dimethylformamide, a mixed solvent of tetrahydrofuran and N,N-dimethylformamide, a mixed solvent of butanone and N,N-dimethylformamide, or a mixed solvent of tetrahydrofuran and dimethyl sulfoxide.

[0071] In the present invention, in the steps (1) and (3), the diisocyanate compound independently comprises one or more of toluene diisocyanate, diphenylmethane diisocyanate, tetramethylxylene diisocyanate, hexamethylene diisocyanate and p-phenylene diisocyanate, preferably one or more of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and p-phenylene diisocyanate, and more preferably one or more of toluene diisocyanate, diphenylmethane diisocyanate and p-phenylene diisocyanate; in the steps (1) and (3), the diol compound independently comprises one or more of 1,4-butanediol, ethylene glycol, 1,6-hexanediol and 1,3-propylene glycol, preferably one or more of 1,4-butanediol, ethylene glycol and 1,3-propylene glycol, and more preferably 1,4-butanediol and / or ethylene glycol.

[0072] In the present invention, the hydroxyl-terminated polysiloxane is selected from one of the general formulas represented by formula (IV), (V) and (VI):

[0073]

[0074] Wherein, a is independently selected from integers greater than 1 and less than or equal to 100, and is preferably independently an integer of 15 to 65, and more preferably 20 to 60;

[0075] The hydroxyl-terminated polyether has the general formula shown in formula (VII):

[0076]

[0077] Wherein, d is an integer greater than 1 and less than or equal to 100, preferably an integer from 15 to 65, and more preferably from 20 to 60;

[0078] The double bond-containing diol compound has the general formula shown in formula (VIII):

[0079]

[0080] Wherein, h is independently selected from integers greater than 1 and less than or equal to 4, and is preferably independently an integer of 2 or 3;

[0081] The compound N has the general formula shown in formula (IX):

[0082]

[0083] Here, i is an integer greater than 1 and less than or equal to 4, and is preferably an integer of 2 or 3.

[0084] In the present invention, in the steps (1) and (3), the catalyst independently comprises stannous isooctanoate and / or dibutyltin dilaurate, wherein the amount of the catalyst is 0.4 to 4% by mass of the diisocyanate compound, preferably 0.5 to 3.5%, and more preferably 0.8 to 3.0%.

[0085] In the present invention, in the step (1), the mass ratio of the diisocyanate compound, the terminal hydroxyl polysiloxane, the diol compound, the double bond-containing diol compound and the solvent is 1-6: 5-10: 0.2-1.6: 0.1-0.8: 60-120, preferably 1.5-5.5: 5.5-9.5: 0.3-1.5: 0.2-0.7: 65-115, and more preferably 2-5: 6-9: 0.4-1.4: 0.3-0.6: 70-110.

[0086] In the present invention, the mass ratio of the terminal hydroxyl polysiloxane, compound N and benzoin dimethyl ether is 5-10: 0.1-1.2: 0.3-0.6, preferably 5.5-9.5: 0.2-1.1: 0.4-0.5, and more preferably 6-9: 0.3-1.0: 0.4.

[0087] In the present invention, in the step (3), the mass ratio of the diisocyanate compound, the terminal hydroxyl polyether, the diol compound and the solvent is 5-30:15-45:1-9:100-350, preferably 8-27:20-40:1.5-8.5:110-340, and more preferably 10-25:22-47:2-8:120-330; in the step (4), the mass ratio of the polymer III-2 and the polymer III-3 is 1:1.5-4.0, preferably 1:1.8-3.7, and more preferably 1:2.0-3.5.

[0088] In the present invention, in the steps (1) and (3), the reaction temperature is independently 70 to 90°C, preferably 75 to 85°C, and more preferably 80°C; the reaction time is independently 1 to 4h, preferably 1.5 to 3.5h, and more preferably 2 to 3h.

[0089] In the present invention, in the step (2), the reaction is carried out under ultraviolet light, and the reaction time is 15 to 30 minutes, preferably 15 to 20 minutes, and more preferably 15 minutes; in the step (4), the reaction temperature is 70 to 90°C, preferably 75 to 85°C, and more preferably 80°C; the reaction time is 30 to 42 hours, preferably 32 to 40 hours, and more preferably 34 to 38 hours.

[0090] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0091] Example 1

[0092] 1.180 g of toluene diisocyanate was added to a reactor equipped with a reflux condenser, a T-type three-way piston, a constant pressure dropping funnel, and a mechanical stirrer. When the temperature rose to 70°C, 10.000 g of the compound of formula (IV) was added dropwise to the reactor through a constant pressure dropping funnel, wherein the relative molecular mass of the compound of formula (IV) was 3000 g / mol, and the reaction was carried out at 70°C for 3 hours to obtain a prepolymer. 0.330 g of 1,4-butanediol, 0.110 g of 1,4-butenediol, and 0.040 g of stannous isooctanoate were dissolved in 90 g of a solvent, wherein the solvent was a mixed solvent obtained by mixing toluene and N,N-dimethylformamide in a mass ratio of 4:1, and then added dropwise to the prepolymer through a constant pressure dropping funnel, and reacted at 70°C for 3 hours to obtain a polymer III-1.

[0093] The polymer III-1 obtained in the previous step, 0.100 g of mercaptoethanol and 0.300 g of benzoin dimethyl ether were mixed, and stirred for reaction for 15 minutes under ultraviolet light to obtain polymer III-2.

[0094] 5.830 g of toluene diisocyanate was added to a reactor equipped with a reflux condenser, a T-type three-way piston, a constant pressure dropping funnel, and a mechanical stirrer. When the temperature rose to 70°C, 22.870 g of the compound of formula (VII) was added dropwise into the reactor through a constant pressure dropping funnel, wherein the relative molecular mass of the compound of formula (VII) was 2000 g / mol, and the mixture was reacted at 70°C for 2 h to obtain an isocyanate-terminated prepolymer; 1.000 g of 1,4-butanediol and 0.100 g of stannous isooctanoate were dissolved in 120 g of a solvent, wherein the solvent was a mixed solvent obtained by mixing toluene and N,N-dimethylformamide in a mass ratio of 4:1, and then the mixture was added dropwise into the isocyanate-terminated prepolymer through a constant pressure dropping funnel, and the mixture was reacted at 70°C for 3 h to obtain a polymer III-3.

[0095] Polymer III-2 and polymer III-3 were mixed in a mass ratio of 1:2.5, and the reaction was continued at 70° C. for 36 hours to obtain a graft polymer (III) having a polysiloxane-polyurethane and polyether-polyurethane structure.

[0096] 40 parts of a polysiloxane-polyurethane compound of formula (I) with a hard segment content of 21 wt% (wherein the isocyanate index is 0.98), 60 parts of a polyether-polyurethane compound of formula (II) with a hard segment content of 23 wt% (wherein the isocyanate index is 1.02), and 8 parts of a graft polymer of formula (III) having a polysiloxane-polyurethane and polyether-polyurethane structure are uniformly mixed, and the obtained blend solution is put into a mold after removing the solvent, and then dried in a vacuum drying oven to obtain a novel three-component blended polyurethane thermoplastic elastomer, wherein M in the polysiloxane-polyurethane compound of formula (I) is (CH2)2, -J- is R is (CH2)3O(CH2)2, M in the polyether-polyurethane compound of formula (II) is (CH2)4, and -J- is

[0097] Performance test results:

[0098] The mechanical properties of the new three-component blended polyurethane thermoplastic elastomer were tested, and the tensile strength was 15MPa and the elongation at break was 590%. At the same time, the elastomer was immersed in water at room temperature for 30 days, and its water absorption rate was only 0.5%.

[0099] Example 2

[0100] 3.820 g of diphenylmethane diisocyanate was added to a reactor equipped with a reflux condenser, a T-type three-way piston, a constant pressure dropping funnel, and a mechanical stirrer. When the temperature rose to 70°C, 10.000 g of the compound of formula (IV) was added dropwise to the reactor through a constant pressure dropping funnel, wherein the relative molecular mass of the compound of formula (IV) was 2000 g / mol, and the reaction was carried out at 70°C for 3 hours to obtain a prepolymer. 0.680 g of 1,4-butanediol, 0.220 g of 1,4-butenediol, and 0.050 g of stannous isooctanoate were dissolved in 100 g of a solvent, wherein the solvent was a mixed solvent obtained by mixing toluene and N,N-dimethylformamide in a mass ratio of 4:1, and then added dropwise to the prepolymer through a constant pressure dropping funnel, and reacted at 70°C for 3 hours to obtain a polymer III-1.

[0101] The polymer III-1 obtained in the previous step, 0.670 g of mercaptoethanol and 0.600 g of benzoin dimethyl ether were mixed, and stirred for reaction for 15 minutes under ultraviolet light to obtain polymer III-2.

[0102] 15.620 g of diphenylmethane diisocyanate was added to a reactor equipped with a reflux condenser, a T-type three-way piston, a constant pressure dropping funnel, and a mechanical stirrer. When the temperature rose to 70°C, 40.800 g of the compound of formula (VII) was added dropwise to the reactor through a constant pressure dropping funnel, wherein the relative molecular mass of the compound of formula (VII) was 2000 g / mol, and the reaction was carried out at 70°C for 2 hours to obtain an isocyanate-terminated prepolymer; 3.630 g of 1,4-butanediol and 0.150 g of stannous isooctanoate were dissolved in 240 g of a solvent, wherein the solvent was a mixed solvent obtained by mixing toluene and N,N-dimethylformamide in a mass ratio of 4:1, and then added dropwise to the isocyanate-terminated prepolymer through a constant pressure dropping funnel, and reacted at 70°C for 3 hours to obtain a polymer III-3.

[0103] Polymer III-2 and polymer III-3 were mixed in a mass ratio of 1:4, and the reaction was continued at 70° C. for 36 hours to obtain a graft polymer (III) having a polysiloxane-polyurethane and polyether-polyurethane structure.

[0104] 60 parts of a polysiloxane-polyurethane compound of formula (I) with a hard segment content of 33 wt% (wherein the isocyanate index is 0.99), 40 parts of a polyether-polyurethane compound of formula (II) with a hard segment content of 35 wt% (wherein the isocyanate index is 1.02), and 15 parts of a graft polymer of formula (III) having a polysiloxane-polyurethane and polyether-polyurethane structure are uniformly mixed, and the obtained blend solution is put into a mold after removing the solvent, and then dried in a vacuum drying oven to obtain a novel three-component blended polyurethane thermoplastic elastomer, wherein M in the polysiloxane-polyurethane compound of formula (I) is (CH2)6, -J- is R is (CH2)4, M in the polyether-polyurethane compound of formula (II) is (CH2)3, -J- is

[0105] Performance test results:

[0106] The mechanical properties of the new three-component blended polyurethane thermoplastic elastomer were tested, and the tensile strength was 22.36MPa and the elongation at break was 921%. The weather resistance of the elastomer was investigated. After being exposed to sunlight at room temperature for 30 days, the mechanical properties did not change much, the tensile strength remained at 21.30MPa, and the strength retention rate reached 95.3%. At the same time, the elastomer was immersed in room temperature water for 30 days, and its water absorption rate was only 0.7%.

[0107] Example 3

[0108] 5.125 g of diphenylmethane diisocyanate was added to a reactor equipped with a reflux condenser, a T-type three-way piston, a constant pressure dropping funnel, and a mechanical stirrer. When the temperature rose to 70°C, 10.000 g of the compound of formula (V) was added dropwise to the reactor through a constant pressure dropping funnel, wherein the relative molecular mass of the compound of formula (V) was 2000 g / mol, and the reaction was carried out at 70°C for 3 hours to obtain a prepolymer. 0.790 g of ethylene glycol, 0.280 g of 1,6-hexenediol, and 0.060 g of stannous isooctanoate were dissolved in 100 g of a solvent, wherein the solvent was a mixed solvent obtained by mixing tetrahydrofuran and N,N-dimethylformamide in a mass ratio of 4:1, and then added dropwise to the prepolymer through a constant pressure dropping funnel, and reacted at 70°C for 4 hours to obtain a polymer III-1.

[0109] The polymer III-1 obtained in the previous step, 0.700 g of mercaptobutanol and 0.600 g of benzoin dimethyl ether were mixed, and stirred for reaction for 15 minutes under ultraviolet light to obtain polymer III-2.

[0110] 18.320 g of diphenylmethane diisocyanate was added to a reactor equipped with a reflux condenser, a T-type three-way piston, a constant pressure dropping funnel, and a mechanical stirrer. When the temperature rose to 70°C, 34.870 g of the compound of formula (VII) was added dropwise to the reactor through a constant pressure dropping funnel, wherein the relative molecular mass of the compound of formula (VII) was 2000 g / mol, and the reaction was carried out at 70°C for 2 hours to obtain an isocyanate-terminated prepolymer; 4.720 g of 1,4-butanediol and 0.150 g of stannous isooctanoate were dissolved in 230 g of a solvent, wherein the solvent was a mixed solvent obtained by mixing tetrahydrofuran and N,N-dimethylformamide in a mass ratio of 4:1, and then added dropwise to the isocyanate-terminated prepolymer through a constant pressure dropping funnel, and reacted at 70°C for 3 hours to obtain a polymer III-3.

[0111] Polymer III-2 and polymer III-3 were mixed in a mass ratio of 1:4, and the reaction was continued at 70° C. for 36 hours to obtain a graft polymer (III) having a polysiloxane-polyurethane and polyether-polyurethane structure (wherein g is 60).

[0112] 30 parts of a polysiloxane-polyurethane compound of formula (I) with a hard segment content of 35 wt% (wherein the isocyanate index is 1.01), 70 parts of a polyether-polyurethane compound of formula (II) with a hard segment content of 33 wt% (wherein the isocyanate index is 1.01), and 25 parts of a graft polymer of formula (III) having a polysiloxane-polyurethane and polyether-polyurethane structure are uniformly mixed, and the obtained blend solution is put into a mold after removing the solvent, and then dried in a vacuum drying oven to obtain a novel three-component blended polyurethane thermoplastic elastomer, wherein M in the polysiloxane-polyurethane compound of formula (I) is (CH2)4, -J- is R is (CH2)3, M in the polyether-polyurethane compound of formula (II) is (CH2)3, -J- is

[0113] Performance test results:

[0114] The mechanical properties of the new three-component blended polyurethane thermoplastic elastomer were tested, and the tensile strength was 30MPa and the elongation at break was 836%. At the same time, the elastomer retained the good hydrophobicity of polysiloxane, and the water contact angle was 110.2°.

[0115] Example 4

[0116] 4.200 g of p-phenylene diisocyanate was added to a reactor equipped with a reflux condenser, a T-type three-way piston, a constant pressure dropping funnel, and a mechanical stirrer. When the temperature rose to 70°C, 10.000 g of the compound of formula (VI) was added dropwise to the reactor through a constant pressure dropping funnel, wherein the relative molecular mass of the compound of formula (VI) was 2000 g / mol, and the reaction was carried out at 70°C for 3 hours to obtain a prepolymer. 0.930 g of ethylene glycol, 0.580 g of 1,6-hexenediol, and 0.060 g of stannous isooctanoate were dissolved in 100 g of a solvent, wherein the solvent was a mixed solvent obtained by mixing tetrahydrofuran and N,N-dimethylformamide in a mass ratio of 4:1, and then added dropwise to the prepolymer through a constant pressure dropping funnel, and reacted at 70°C for 3 hours to obtain a polymer III-1.

[0117] The polymer III-1 obtained in the previous step, 0.700 g of mercaptobutanol and 0.600 g of benzoin dimethyl ether were mixed, and stirred for reaction for 15 minutes under ultraviolet light to obtain polymer III-2.

[0118] 18.320 g of diphenylmethane diisocyanate was added to a reactor equipped with a reflux condenser, a T-type three-way piston, a constant pressure dropping funnel, and a mechanical stirrer. When the temperature rose to 70°C, 34.870 g of the compound of formula (VII) was added dropwise into the reactor through a constant pressure dropping funnel, wherein the relative molecular mass of the compound of formula (VII) was 2000 g / mol, and the reaction was carried out at 70°C for 2 hours to obtain an isocyanate-terminated prepolymer; 4.720 g of 1,4-butanediol and 0.150 g of stannous isooctanoate were dissolved in 300 g of a solvent, wherein the solvent was a mixed solvent obtained by mixing tetrahydrofuran and N,N-dimethylformamide in a mass ratio of 4:1, and then added dropwise to the isocyanate-terminated prepolymer through a constant pressure dropping funnel, and reacted at 70°C for 3 hours to obtain a polymer III-3.

[0119] Polymer III-2 and polymer III-3 were mixed in a mass ratio of 1:3.5, and the reaction was continued at 70° C. for 36 hours to obtain a graft polymer (III) having a polysiloxane-polyurethane and polyether-polyurethane structure.

[0120] 40 parts of a polysiloxane-polyurethane compound of formula (I) with a hard segment content of 33 wt% (wherein the isocyanate index is 0.98), 60 parts of a polyether-polyurethane compound of formula (II) with a hard segment content of 31 wt% (wherein the isocyanate index is 1.01), and 17 parts of a graft polymer of formula (III) having a polysiloxane-polyurethane and polyether-polyurethane structure are uniformly mixed, and the obtained blend solution is put into a mold after removing the solvent, and then dried in a vacuum drying oven to obtain a novel three-component blended polyurethane thermoplastic elastomer, wherein M in the polysiloxane-polyurethane compound of formula (I) is (CH2)2, -J- is R is (CH2)3O(CH2)2, M in the polyether-polyurethane compound of formula (II) is (CH2)4, and -J- is

[0121] Performance test results:

[0122] The mechanical properties of the new three-component blended polyurethane thermoplastic elastomer were tested, and the tensile strength was 25MPa and the elongation at break was 875%. The weather resistance of the elastomer was investigated. After being exposed to sunlight at room temperature for 30 days, the mechanical properties did not change much, and the tensile strength retention rate was 95.5%.

[0123] Example 5

[0124] 5.125 g of diphenylmethane diisocyanate was added to a reactor equipped with a reflux condenser, a T-type three-way piston, a constant pressure dropping funnel, and a mechanical stirrer. When the temperature rose to 70°C, 10.000 g of the compound of formula (V) was added dropwise to the reactor through a constant pressure dropping funnel, wherein the relative molecular mass of the compound of formula (V) was 2000 g / mol, and the reaction was carried out at 70°C for 3 hours to obtain a prepolymer. 1.500 g of 1,6-hexanediol, 0.340 g of 1,6-octenediol, and 0.050 g of stannous isooctanoate were dissolved in 100 g of a solvent, wherein the solvent was a mixed solvent obtained by mixing tetrahydrofuran and N,N-dimethylformamide in a mass ratio of 4:1, and then added dropwise to the prepolymer through a constant pressure dropping funnel, and reacted at 70°C for 3 hours to obtain a polymer III-1.

[0125] The polymer III-1 obtained in the previous step, 1.100 g of mercaptohexanol and 0.600 g of benzoin dimethyl ether were mixed, and stirred for reaction for 15 minutes under ultraviolet light to obtain polymer III-2.

[0126] 17.800 g of diphenylmethane diisocyanate was added to a reactor equipped with a reflux condenser, a T-type three-way piston, a constant pressure dropping funnel, and a mechanical stirrer. When the temperature rose to 70°C, 34.870 g of the compound of formula (VII) was added dropwise to the reactor through a constant pressure dropping funnel, wherein the relative molecular mass of the compound of formula (VII) was 2000 g / mol, and the reaction was carried out at 70°C for 2 hours to obtain an isocyanate-terminated prepolymer; 4.700 g of 1,4-butanediol and 0.450 g of stannous isooctanoate were dissolved in 230 g of a solvent, wherein the solvent was a mixed solvent obtained by mixing tetrahydrofuran and N,N-dimethylformamide in a mass ratio of 4:1, and then added dropwise to the isocyanate-terminated prepolymer through a constant pressure dropping funnel, and reacted at 70°C for 3 hours to obtain a polymer III-3.

[0127] Polymer III-2 and polymer III-3 were mixed in a mass ratio of 1:3.5, and the reaction was continued at 70° C. for 42 hours to obtain a graft polymer (III) having a polysiloxane-polyurethane and polyether-polyurethane structure.

[0128] 50 parts of a polysiloxane-polyurethane compound of formula (I) with a hard segment content of 32 wt% (wherein the isocyanate index is 0.99), 50 parts of a polyether-polyurethane compound of formula (II) with a hard segment content of 33 wt% (wherein the isocyanate index is 1.01), and 15 parts of a graft polymer of formula (III) having a polysiloxane-polyurethane and polyether-polyurethane structure are uniformly mixed, and the obtained blend solution is put into a mold after removing the solvent, and then dried in a vacuum drying oven to obtain a novel three-component blended polyurethane thermoplastic elastomer, wherein M in the polysiloxane-polyurethane compound of formula (I) is (CH2)6, -J- is R is (CH2)3, M in the polyether-polyurethane compound of formula (II) is (CH2)6, -J- is

[0129] Performance test results:

[0130] The mechanical properties of the new three-component blended polyurethane thermoplastic elastomer were tested. The tensile strength of the elastomer was 19.09 MPa and the elongation at break was 897%. At the same time, when the elastomer was immersed in water at room temperature for 30 days, its water absorption rate was only 0.8%. At the same time, the elastomer retained the good hydrophobicity of polysiloxane, and the water contact angle was 108°.

[0131] Example 6

[0132] 3.870 g of diphenylmethane diisocyanate was added to a reactor equipped with a reflux condenser, a T-type three-way piston, a constant pressure dropping funnel, and a mechanical stirrer. When the temperature rose to 70°C, 10.000 g of the compound of formula (IV) was added dropwise to the reactor through a constant pressure dropping funnel, wherein the relative molecular mass of the compound of formula (IV) was 2000 g / mol, and the reaction was carried out at 70°C for 3 hours to obtain a prepolymer. 0.960 g of 1,3-propylene glycol, 0.210 g of 1,4-butenediol, and 0.060 g of stannous isooctanoate were dissolved in 100 g of a solvent, wherein the solvent was a mixed solvent obtained by mixing tetrahydrofuran and N,N-dimethylacetamide in a mass ratio of 4:1, and then added dropwise to the prepolymer through a constant pressure dropping funnel, and reacted at 70°C for 3 hours to obtain a polymer III-1.

[0133] The polymer III-1 obtained in the previous step, 0.790 g of 3-mercaptopropanol and 0.600 g of benzoin dimethyl ether were mixed, and stirred for reaction under ultraviolet light for 15 minutes to obtain polymer III-2.

[0134] 18.320 g of diphenylmethane diisocyanate was added to a reactor equipped with a reflux condenser, a T-type three-way piston, a constant pressure dropping funnel, and a mechanical stirrer. When the temperature rose to 70°C, 34.870 g of the compound of formula (VII) was added dropwise to the reactor through a constant pressure dropping funnel, wherein the relative molecular mass of the compound of formula (VII) was 2000 g / mol, and the reaction was carried out at 70°C for 2 hours to obtain an isocyanate-terminated prepolymer; 4.720 g of 1,4-butanediol and 0.150 g of stannous isooctanoate were dissolved in 300 g of a solvent, wherein the solvent was a mixed solvent obtained by mixing tetrahydrofuran and N,N-dimethylacetamide in a mass ratio of 4:1, and then added dropwise to the isocyanate-terminated prepolymer through a constant pressure dropping funnel, and reacted at 70°C for 3 hours to obtain a polymer III-3.

[0135] Polymer III-2 and polymer III-3 were mixed in a mass ratio of 1:3.9, and the reaction was continued at 70° C. for 30 hours to obtain a graft polymer (III) having a polysiloxane-polyurethane and polyether-polyurethane structure.

[0136] 40 parts of a polysiloxane-polyurethane compound of formula (I) with a hard segment content of 39 wt% (wherein the isocyanate index is 0.99), 60 parts of a polyether-polyurethane compound of formula (II) with a hard segment content of 37 wt% (wherein the isocyanate index is 1.01), and 20 parts of a graft polymer of formula (III) having a polysiloxane-polyurethane and polyether-polyurethane structure are uniformly mixed, and the obtained blend solution is put into a mold after removing the solvent, and then dried in a vacuum drying oven to obtain a novel three-component blended polyurethane thermoplastic elastomer, wherein M in the polysiloxane-polyurethane compound of formula (I) is (CH2)3, -J- is R is (CH2)3, M in the polyether-polyurethane compound of formula (II) is (CH2)6, -J- is

[0137] Performance test results:

[0138] The mechanical properties of the new three-component blended polyurethane thermoplastic elastomer were tested, and the tensile strength was 38MPa and the elongation at break was 664%. At the same time, when the elastomer was immersed in water at room temperature for 30 days, its water absorption rate was only 1.1%.

[0139] Example 7

[0140] 3.870 g of diphenylmethane diisocyanate was added to a reactor equipped with a reflux condenser, a T-type three-way piston, a constant pressure dropping funnel, and a mechanical stirrer. When the temperature rose to 70°C, 10.000 g of the compound of formula (IV) was added dropwise to the reactor through a constant pressure dropping funnel, wherein the relative molecular mass of the compound of formula (IV) was 2000 g / mol, and the reaction was carried out at 70°C for 3 hours to obtain a prepolymer. 0.960 g of 1,3-propylene glycol, 0.210 g of 1,4-butenediol, and 0.060 g of stannous isooctanoate were dissolved in 100 g of a solvent, wherein the solvent was a mixed solvent obtained by mixing tetrahydrofuran and N,N-dimethylacetamide in a mass ratio of 4:1, and then added dropwise to the prepolymer through a constant pressure dropping funnel, and reacted at 70°C for 3 hours to obtain a polymer III-1.

[0141] The polymer III-1 obtained in the previous step, 0.670 g of mercaptoethanol and 0.600 g of benzoin dimethyl ether were mixed, and stirred for reaction for 30 minutes under ultraviolet light to obtain polymer III-2.

[0142] 18.320 g of diphenylmethane diisocyanate was added to a reactor equipped with a reflux condenser, a T-type three-way piston, a constant pressure dropping funnel, and a mechanical stirrer. When the temperature rose to 70°C, 34.870 g of the compound of formula (VII) was added dropwise to the reactor through a constant pressure dropping funnel, wherein the relative molecular mass of the compound of formula (VII) was 2000 g / mol, and the reaction was carried out at 70°C for 2 hours to obtain an isocyanate-terminated prepolymer; 4.720 g of 1,4-butanediol and 0.150 g of stannous isooctanoate were dissolved in 300 g of a solvent, wherein the solvent was a mixed solvent obtained by mixing tetrahydrofuran and N,N-dimethylacetamide in a mass ratio of 4:1, and then added dropwise to the isocyanate-terminated prepolymer through a constant pressure dropping funnel, and reacted at 70°C for 3 hours to obtain a polymer III-3.

[0143] Polymer III-2 and polymer III-3 were mixed in a mass ratio of 1:3.9, and the reaction was continued at 70° C. for 30 hours to obtain a graft polymer (III) having a polysiloxane-polyurethane and polyether-polyurethane structure.

[0144] 40 parts of a polysiloxane-polyurethane compound of formula (I) with a hard segment content of 39 wt% (wherein the isocyanate index is 0.99), 60 parts of a polyether-polyurethane compound of formula (II) with a hard segment content of 39 wt% (wherein the isocyanate index is 1.01), and 20 parts of a graft polymer of formula (III) having a polysiloxane-polyurethane and polyether-polyurethane structure are uniformly mixed, and the obtained blend solution is put into a mold after removing the solvent, and then dried in a vacuum drying oven to obtain a novel three-component blended polyurethane thermoplastic elastomer, wherein M in the polysiloxane-polyurethane compound of formula (I) is (CH2)6, -J- is R is (CH2)3, M in the polyether-polyurethane compound of formula (II) is (CH2)3, -J- is

[0145] Performance test results:

[0146] The mechanical properties of the new three-component blended polyurethane thermoplastic elastomer were tested, and the tensile strength was 42MPa and the elongation at break was 550%. At the same time, when the elastomer was immersed in water at room temperature for 30 days, its water absorption rate was only 1.1%.

[0147] Example 8

[0148] 3.130 g of diphenylmethane diisocyanate was added to a reactor equipped with a reflux condenser, a T-type three-way piston, a constant pressure dropping funnel, and a mechanical stirrer. When the temperature rose to 70°C, 5.000 g of the compound of formula (IV) was added dropwise to the reactor through a constant pressure dropping funnel, wherein the relative molecular mass of the compound of formula (IV) was 4000 g / mol, and the reaction was carried out at 70°C for 3 hours to obtain a prepolymer. 0.800 g of 1,4-butanediol, 0.220 g of 1,4-butenediol, and 0.0350 g of stannous isooctanoate were dissolved in 75 g of a solvent, wherein the solvent was a mixed solvent obtained by mixing tetrahydrofuran and dimethyl sulfoxide in a mass ratio of 4:1, and then added dropwise to the prepolymer through a constant pressure dropping funnel, and reacted at 70°C for 3 hours to obtain a polymer III-1.

[0149] The polymer III-1 obtained in the previous step, 0.190 g of mercaptoethanol and 0.300 g of benzoin dimethyl ether were mixed, and stirred for reaction for 25 minutes under ultraviolet light to obtain polymer III-2.

[0150] 14.040 g of diphenylmethane diisocyanate was added to a reactor equipped with a reflux condenser, a T-type three-way piston, a constant pressure dropping funnel, and a mechanical stirrer. When the temperature rose to 70°C, 15.720 g of the compound of formula (VII) was added dropwise to the reactor through a constant pressure dropping funnel, wherein the relative molecular mass of the compound of formula (VII) was 2000 g / mol, and the reaction was carried out at 70°C for 2 hours to obtain an isocyanate-terminated prepolymer; 4.220 g of 1,4-butanediol and 0.075 g of stannous isooctanoate were dissolved in 175 g of a solvent, wherein the solvent was a mixed solvent obtained by mixing tetrahydrofuran and dimethyl sulfoxide in a mass ratio of 4:1, and then added dropwise to the isocyanate-terminated prepolymer through a constant pressure dropping funnel, and reacted at 70°C for 3 hours to obtain a polymer III-3.

[0151] Polymer III-2 and polymer III-3 were mixed in a mass ratio of 1:3, and the reaction was continued at 70° C. for 40 hours to obtain a graft polymer (III) having a polysiloxane-polyurethane and polyether-polyurethane structure.

[0152] 40 parts of a polysiloxane-polyurethane compound of formula (I) with a hard segment content of 47 wt% (wherein the isocyanate index is 0.99), 60 parts of a polyether-polyurethane compound of formula (II) with a hard segment content of 50 wt% (wherein the isocyanate index is 1.01), and 35 parts of a graft polymer of formula (III) having a polysiloxane-polyurethane and polyether-polyurethane structure are uniformly mixed, and the obtained blend solution is put into a mold after the solvent is removed, and then dried in a vacuum drying oven to obtain a novel three-component blended polyurethane thermoplastic elastomer, wherein M in the polysiloxane-polyurethane compound of formula (I) is (CH2)2, -J- is R is (CH2)4, M in the polyether-polyurethane compound of formula (II) is (CH2)2, -J- is

[0153] Performance test results:

[0154] The mechanical properties of the new three-component blended polyurethane thermoplastic elastomer were tested, and the tensile strength was 48MPa and the elongation at break was 370%. The elastomer was immersed in water at room temperature for 30 days, and its water absorption rate was only 0.9%. At the same time, the elastomer was tested by DSC, and its glass transition temperature was -123℃; the TGA test showed that the 5% thermal weight loss temperature of the elastomer was 300℃, so the elastomer has good high and low temperature resistance.

[0155] Comparative Example 1

[0156] The performance test was carried out using the polysiloxane-polyurethane formula (I) compound with a hard segment content of 33 wt% used in Example 2. The test results showed that the tensile strength of the elastomer was 11.57 MPa, the elongation at break was 335%, and the mechanical properties were poor.

[0157] Comparative Example 2

[0158] The performance test was carried out using the polyether-polyurethane compound of formula (II) with a hard segment content of 33wt% used in Example 3. The test results were as follows: the tensile strength was 20.21MPa and the elongation at break was 576%. However, the polyether-polyurethane elastomer was hydrophilic, with a water contact angle of only 69.4°. At the same time, the elastomer was immersed in room temperature water for 30 days, and its water absorption was 4.69%.

[0159] Comparative Example 3

[0160] A preparation method for a polysiloxane-polyurethane / polyether-polyurethane blend elastomer, wherein the blend elastomer comprises a polysiloxane-polyurethane compound of formula (I) and a polyether-polyurethane compound of formula (II), wherein the polysiloxane-polyurethane compound of formula (I) is the polysiloxane-polyurethane compound of formula (I) with a hard segment content of 33 wt% used in Example 2, and the polyether-polyurethane compound of formula (II) is the polyether-polyurethane compound of formula (II) with a hard segment content of 33 wt% used in Example 3, and the two compounds are uniformly mixed in a mass ratio of (I): (II) = 40:60 to obtain a blend solution; the solvent in the blend solution is removed, the mixture is formed in a mold, and the mixture is thoroughly dried in a vacuum drying oven to obtain a polysiloxane-polyurethane / polyether-polyurethane blend elastomer.

[0161] Performance test results:

[0162] The mechanical properties of the elastomer were tested, and the tensile strength was 13MPa and the elongation at break was 439%.

[0163] In Comparative Example 3, two polyurethanes were directly blended in a solvent, and obvious macroscopic phase separation occurred, resulting in poor performance of the blend.

[0164] Comparative Example 4

[0165] A preparation method of a polysiloxane-polyether-polyurethane elastomer, the preparation steps are as follows:

[0166] A mixed solvent of toluene and N,N-dimethylformamide was prepared in a mass ratio of 4:1. 15.320 g of toluene diisocyanate was added to a reactor equipped with a reflux condenser, a T-type three-way piston, a constant pressure dropping funnel, and a mechanical stirrer. When the temperature rose to 70°C, 20.000 g of a compound of formula IV (a is 15) with a relative molecular mass of 2000 g / mol was added dropwise to the reactor through a constant pressure dropping funnel, and reacted at 70°C for 2 hours; after the system was stabilized, 20.000 g of a compound of formula VII (d is 20) with a relative molecular mass of 2000 g / mol was continued to be added dropwise to the reactor to obtain an isocyanate-terminated prepolymer; 3.640 g of 1,4-butanediol and 0.200 g of stannous isooctanoate were dissolved in 100 g of a mixed solvent, and added dropwise to the reaction solution through a constant pressure dropping funnel, and reacted at 70°C for 3 hours to obtain a polysiloxane-polyether-polyurethane elastomer containing a mixed soft segment.

[0167] The mechanical properties of the elastomer were tested, and the tensile strength was 20.00 MPa and the elongation at break was 270%. At the same time, the elastomer was immersed in water at room temperature for 30 days, and its water absorption rate was 1.69%.

[0168] Comparative Example 4 adopts the method of preparing elastomer by traditional mixed soft segments. Although the mechanical properties are improved compared with those of polysiloxane-polyurethane, the improvement is limited and the water absorption rate is relatively high.

[0169] Comparative Example 5

[0170] A preparation method for a polysiloxane-polyurethane / polyether-polyurethane blend elastomer, wherein the blend comprises a polysiloxane-polyurethane compound of formula (I), a polyether-polyurethane compound of formula (II) and a polyether-grafted polysiloxane compatibilizer. In the preparation process, the polysiloxane-polyurethane compound of formula (I) is the polysiloxane-polyurethane compound of formula (I) with a hard segment content of 33 wt % used in Example 2, and the polyether-polyurethane compound of formula (II) is the polyether-polyurethane compound of formula (II) with a hard segment content of 33 wt % used in Example 3. The preparation steps are as follows:

[0171] (1) Preparation of polyether grafted polysiloxane compatibilizer

[0172] The polyether grafted polysiloxane compatibilizer was prepared according to Example 6 of patent CN114805730A.

[0173] (2) The compound of formula I, the compound of formula II and the polyether grafted polysiloxane compatibilizer are uniformly mixed in a mass ratio of 40:60:15 to obtain a blend solution.

[0174] (3) removing the solvent from the blend solution, forming the blend solution in a mold, and thoroughly drying the blend solution in a vacuum drying oven to obtain a blended elastomer.

[0175] The mechanical properties of the elastomer were tested, and the tensile strength was 11 MPa and the elongation at break was 390%.

[0176] In Comparative Example 5, two polyurethanes were directly blended in a solvent, and obvious macroscopic phase separation occurred, resulting in poor performance of the blend.

[0177] It can be seen from the above embodiments that the present invention provides a novel three-component blended polyurethane thermoplastic elastomer and a preparation method thereof. The novel three-component blended polyurethane thermoplastic elastomer of the present invention is mixed with 20 to 60 parts of polysiloxane-polyurethane, 40 to 80 parts of polyether-polyurethane and 5 to 35 parts of a graft polymer having a polysiloxane-polyurethane and a polyether-polyurethane structure, wherein the hard segment content in the polysiloxane-polyurethane and the polyether-polyurethane is independently 20 to 50 wt %, and the isocyanate index is independently 0.98 to 1.02. The present invention firstly obtains a graft polymer having a polysiloxane-polyurethane and a polyether-polyurethane structure as a compatibilizer, which has a certain volume-increasing effect, so that the obtained elastomer has the weather resistance, water resistance, temperature resistance and flexibility of polysiloxane, as well as the excellent properties of high strength, high modulus and the like of polyurethane, and has excellent comprehensive performance.

[0178] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A three-component blended polyurethane thermoplastic elastomer, characterized in that: The three-component blended polyurethane thermoplastic elastomer is prepared by mixing 20 to 60 parts of polysiloxane-polyurethane, 40 to 80 parts of polyether-polyurethane and 5 to 35 parts of a graft polymer having a polysiloxane-polyurethane and polyether-polyurethane structure, wherein the hard segment content in the polysiloxane-polyurethane and the polyether-polyurethane is independently 20 to 50 wt%, and the isocyanate index is independently 0.98 to 1.02; The graft polymer having polysiloxane-polyurethane and polyether-polyurethane structures has the general formula shown in formula (III): Wherein, g is selected from an integer greater than 1 and less than or equal to 100; h and i are independently selected from integers greater than 1 and less than or equal to 4; Z is independently a polysiloxane-polyurethane chain segment; T is a polyether-polyurethane chain segment; -J- is selected from One of them.

2. The three-component blended polyurethane thermoplastic elastomer according to claim 1, characterized in that: The polysiloxane-polyurethane has the general formula (I): The polyether-polyurethane has the general formula shown in formula (II): Wherein, a, b, c, d, e, and f are independently selected from integers greater than 1 and less than or equal to 100; M is independently selected from one of (CH2)2, (CH2)3, (CH2)4, and (CH2)6; -J- is independently selected from One of; R is independently selected from one of (CH2)3, (CH2)3O(CH2)2 and (CH2)4.

3. The method for preparing the three-component blended polyurethane thermoplastic elastomer according to claim 1 or 2, characterized in that: The following steps are involved: (1) mixing a diisocyanate compound and a hydroxyl-terminated polysiloxane to react to obtain a prepolymer; mixing a mixture of a diol compound, a double-bond diol compound, a catalyst and a solvent with the prepolymer to react to obtain a polymer III-1; (2) mixing polymer III-1, compound N and benzoin dimethyl ether to react to obtain polymer III-2; (3) mixing a diisocyanate compound and a hydroxyl-terminated polyether to react to obtain an isocyanate-terminated prepolymer; mixing a mixture of a diol compound, a catalyst, and a solvent with the isocyanate-terminated prepolymer to react to obtain a polymer III-3; (4) mixing polymer III-2 and polymer III-3 to react, thereby obtaining a graft polymer having a polysiloxane-polyurethane and polyether-polyurethane structure; (5) mixing polysiloxane-polyurethane, polyether-polyurethane and a graft polymer having a polysiloxane-polyurethane and polyether-polyurethane structure and drying the mixture to obtain a three-component blended polyurethane thermoplastic elastomer; The double bond-containing diol compound has the general formula shown in formula (VIII): Wherein, h is independently selected from integers greater than 1 and less than or equal to 4; The compound N has the general formula shown in formula (IX): Here, i is an integer greater than 1 and less than or equal to 4.

4. The preparation method according to claim 3, characterized in that: In the steps (1) and (3), the solvent independently comprises one or more of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, toluene, tetrahydrofuran, xylene, butanone and 1,4-dioxane.

5. The preparation method according to claim 4, characterized in that: In the steps (1) and (3), the diisocyanate compound independently comprises one or more of toluene diisocyanate, diphenylmethane diisocyanate, tetramethylxylene diisocyanate, hexamethylene diisocyanate and p-phenylene diisocyanate; in the steps (1) and (3), the diol compound independently comprises one or more of 1,4-butanediol, ethylene glycol, 1,6-hexanediol and 1,3-propylene glycol.

6. The preparation method according to claim 4 or 5, characterized in that: The hydroxyl-terminated polysiloxane is selected from one of the general formulas shown in formula (IV), (V) and (VI): Wherein, a is independently selected from integers greater than 1 and less than or equal to 100; The hydroxyl-terminated polyether has the general formula shown in formula (VII): Wherein, d is an integer greater than 1 and less than or equal to 100.

7. The preparation method according to claim 6, characterized in that: In the steps (1) and (3), the catalyst independently comprises stannous isooctanoate and / or dibutyltin dilaurate, wherein the amount of the catalyst used is 0.4 to 4% of the mass of the diisocyanate compound.

8. The preparation method according to claim 3 or 4 or 5 or 7, characterized in that: In the step (1), the mass ratio of the diisocyanate compound, the hydroxyl-terminated polysiloxane, the diol compound, the double-bond diol compound and the solvent is 1-6: 5-10: 0.2-1.6: 0.1-0.8: 60-120; the mass ratio of the hydroxyl-terminated polysiloxane, the compound N and benzoin dimethyl ether is 5-10: 0.1~1.2:0.3~0.6; in the step (3), the mass ratio of the diisocyanate compound, the terminal hydroxyl polyether, the diol compound and the solvent is 5~30:15~45:1~9:100~350; in the step (4), the mass ratio of the polymer III-2 and the polymer III-3 is 1:1.5~4.

0.

9. The preparation method according to claim 3, characterized in that: In the steps (1) and (3), the reaction temperature is independently 70-90° C., and the reaction time is independently 1-4 h. In the step (2), the reaction is carried out under ultraviolet light, and the reaction time is 15-30 min. In the step (4), the reaction temperature is 70-90° C., and the reaction time is 30-42 h.

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