Thermoplastic polyurethane elastomer with low processing temperature and high resilience

Abstract

The invention provides a thermoplastic polyurethane elastomer with low processing temperature and high resilience. A chain extender with a specific structure and dihydric alcohol react with diisocyanate to obtain a multi-hydrogen-bond structure, the rebound resilience of the thermoplastic polyurethane elastomer is enhanced due to the introduction of the multi-hydrogen-bond structure, and meanwhile, the thermoplastic polyurethane elastomer has a relatively low initial flow temperature and is easy to process. The bonding adaptability to elastic fabrics such as sports underwear and yoga clothes is high, and the comprehensive performance is excellent.

Description

Technical Field

[0001] The invention belongs to the field of polyurethane elastomers, and in particular relates to a low-processing-temperature high-rebound thermoplastic polyurethane elastomer. Background Art

[0002] With the promotion and development of thermoplastic polyurethane elastomers, in the field of seamless footwear and elastic clothing, there are high requirements for the resilience of the materials and a large demand.

[0003] CN 100344666 C discloses a chain extender 2,4-diamino-6-R-1,3,5-triazine for synthesizing polyurethane elastomer, wherein R is an alkyl group. A thermoplastic polyurethane elastomer is synthesized by using the chain extender, polyol and isocyanate. The thermoplastic polyurethane elastomer has the characteristics of low tensile hysteresis deformation and high resilience. However, the chain extender increases the initial flow temperature of the thermoplastic polyurethane elastomer, which affects subsequent processing and use.

[0004] CN 110903805 A discloses a polyurethane hot melt adhesive prepared by synthesizing a thermoplastic polyurethane elastomer with modified terminal hydroxyl hydrogenated polybutadiene polyol, diisocyanate and a small molecule chain extender, and then mixing it with SEBS / SEPS rubber powder. The hot melt adhesive has the advantages of low polarity, high resilience and low thermal activation temperature. However, the addition of SEBS / SEPS rubber powder makes the product non-degradable and its application is limited.

[0005] The existing technology has the problem of being unable to maintain high resilience performance at low processing temperatures, and is unable to achieve both high resilience and low processing temperature for thermoplastic polyurethane elastomers. Summary of the invention

[0006] One of the purposes of the present invention is to provide a high-resilience thermoplastic polyurethane elastomer, which has low processing temperature and high resilience, so that the thermoplastic polyurethane elastomer can have both high resilience and low processing temperature.

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

[0008] A thermoplastic polyurethane elastomer is prepared by comprising the following raw materials in parts by weight:

[0009] Polyol 60-80wt%, preferably 60-80wt%,

[0010] Isocyanate 19-39wt%, preferably 20-35wt%,

[0011] Small molecule diol 0-20wt%, preferably 0-10wt%,

[0012] 1-21wt% of small molecule diamine, preferably 2-20wt%;

[0013] Wherein, the small molecule diamine comprises the following structure:

[0014]

[0015] Wherein, R1 and R2 independently represent O, S, -NR 1 One of them, R 1 is a linear C1-C30 alkyl group or a branched C1-C30 alkyl group; R3 independently represents a linear C1-C 30 Alkyl, branched C1-C 30 Alkyl, C6-C 10 Aryl, -OR 2 One of them, R 2 is H, linear C1-C 30 Alkyl, branched C1-C 30 Alkyl; n is an integer of 1-3; R4 and R5 independently represent C1-C 30 Alkyl, preferably C1-C 15 alkyl.

[0016] The invention obtains a multiple hydrogen bond structure by using a chain extender with a specific structure and a diol to react with a diisocyanate. The introduction of the multiple hydrogen bond structure enhances the resilience of the thermoplastic polyurethane elastomer, and at the same time has a lower initial flow temperature, is easy to process, has high bonding adaptability to elastic fabrics such as sports bras and yoga clothes, and has excellent comprehensive performance.

[0017] In one embodiment of the present invention, the polyol is a polyester polyol, preferably one or more of polyethylene adipate diol, polypropylene adipate diol, polybutylene adipate diol, polyhexylene adipate diol, polyethylene adipate diol, polybutylene adipate hexylene adipate diol, and polycaprolactone diol, more preferably one or more of polybutylene adipate diol, polyethylene adipate diol, polybutylene adipate hexylene adipate diol, and polycaprolactone diol; preferably, the molecular weight of the polyol is 400-4500, preferably 500-2500.

[0018] In one embodiment of the present invention, the diisocyanate is an aromatic diisocyanate and / or an aliphatic diisocyanate, preferably one or more of diphenylmethane diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, isophorone diisocyanate, meta-xylylene diisocyanate, 1,5-naphthalene diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate, more preferably one or more of hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, diphenylmethane diisocyanate and isophorone diisocyanate.

[0019] In one embodiment of the present invention, the small molecule diol is a C2-C12 small molecule diol, preferably one or more of ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, methyl propanediol, diethylene glycol, 1,4-cyclohexanol, neopentyl glycol, 1,6-hexanediol, and 1,10-decanediol.

[0020] Another object of the present invention is to provide a method for preparing a thermoplastic polyurethane elastomer.

[0021] A method for preparing a thermoplastic polyurethane elastomer, the method for preparing the above-mentioned elastomer is a one-step method, comprising the following steps: uniformly mixing a polyol component with a diisocyanate component, a small molecule diol and a small molecule diamine, and preparing the mixture by twin-screw reaction extrusion.

[0022] Or in one embodiment of the present invention, the method is a prepolymerization method, comprising the following steps: premixing a polyol component with a diisocyanate in a single-screw mixing device to obtain a preliminary reaction mixture, and injecting the reaction mixture with a small molecule diol and a small molecule diamine into a twin-screw continuous reaction extruder for reaction.

[0023] Another object of the present invention is to provide a use of a thermoplastic polyurethane elastomer.

[0024] A use of a thermoplastic polyurethane elastomer, wherein the elastomer is the above-mentioned elastomer, or is an elastomer prepared by the above-mentioned method, and the elastomer is used to prepare a high-resilience thermoplastic polyurethane elastomer, preferably used to prepare a high-resilience film, fine wire, and a net woven with the wire.

[0025] Another object of the present invention is to provide a thermoplastic polyurethane product.

[0026] A thermoplastic polyurethane product is prepared by using the above elastomer or the elastomer prepared by the above method. The product is a high-resilience thermoplastic polyurethane elastomer and is preferably used for high-resilience films, fine wires, and nets woven with wires.

[0027] Compared with the prior art, the positive effects of the present invention are:

[0028] (1) It has a lower processing temperature, with the initial flow temperature between 110-132°C;

[0029] (2) Maintain excellent rebound performance, the 300% rebound rate can be between 75% and 100%. DETAILED DESCRIPTION

[0030] The implementation method of the present invention is described in detail below, but the present invention is not limited thereto, and the changes made by professionals in the field to the technical solution of the present invention all belong to the protection scope of the present invention. The raw materials used in the examples are all commercially available raw materials unless otherwise specified.

[0031] Polybutylene adipate hexanediol ester diol (Mw = 1500), Wanhua Chemical Group Co., Ltd., WHP-1546.

[0032] Polybutylene adipate hexanediol ester diol (Mw = 2000), Wanhua Chemical Group Co., Ltd., WHP-2046.

[0033] Polybutylene adipate diol (Mw=1200), Wanhua Chemical Group Co., Ltd., WHP-124.

[0034] Polycaprolactone diol (Mw = 500), Hunan Juren New Materials Co., Ltd., PCL-500

[0035] Polycaprolactone diol (Mw = 800), Hunan Juren New Materials Co., Ltd., PCL-800

[0036] Polycaprolactone diol (Mw = 400), Hunan Juren New Materials Co., Ltd., PCL-4500

[0037] Poly(hexanediol adipate neopentyl glycol) (Mw=4000), Wanhua Chemical Group Co., Ltd., WHP-4056.

[0038] Poly(ethylene glycol) butanediol adipate diol (Mw=1500), Wanhua Chemical Group Co., Ltd., WHP-1524.

[0039] 4,4'-Diphenylmethane diisocyanate: CAS101-68-8, Wanhua Chemical Group Co., Ltd.;

[0040] Hexamethylene diisocyanate: CAS 822-06-0, Wanhua Chemical Group Co., Ltd.

[0041] Toluene diisocyanate: CAS 584-84-9, Wanhua Chemical Group Co., Ltd.

[0042] 1,4-Butanediol: CAS110-63-4, Wanhua Chemical Group Co., Ltd.

[0043] 1,6-Hexanediol: CAS 629-11-8, Shanghai MacLean Biochemical Technology Co., Ltd.;

[0044] 1,10-Decanediol: CAS112-47-0, Shanghai MacLean Biochemical Technology Co., Ltd.;

[0045] 1,12-Dodecanediol: 5675-51-4, Shanghai MacLean Biochemical Technology Co., Ltd.;

[0046] Diethyltoluenediamine (DETDA): Shanghai MacLean Biochemical Technology Co., Ltd.;

[0047] Biuret, N,N',2-trimethyl: CAS 816-00-2, Hubei Yangxin Pharmaceutical Technology Co., Ltd.;

[0048] Urea, N,N'-dimethyl-N'-[(methylamino)(methyl)methyl]: CAS 780717-00-2, Shenzhen Aituo Chemical Co., Ltd.;

[0049] Methoxyamine: CAS 67-62-9, Aibixin (Shanghai) Biotechnology Co., Ltd.;

[0050] Propyl isocyanate: CAS110-78-1, Shanghai Aladdin Biochemical Technology Co., Ltd.;

[0051] N,N-Diethylhydrazine: CAS1615-80-1, Shaanxi Didu Pharmaceutical Chemical Co., Ltd.;

[0052] Cyclohexyl isocyanate: CAS 3173-53-3, Shanghai Aladdin Biochemical Technology Co., Ltd.;

[0053] 2-Methoxy-N, N'-dipropyl: CAS 5710-24-7, synthesized according to the following method: 1L of frozen benzene is used as solvent, 1mol of methoxyamine and 2mol of propyl isocyanate are added in proportion, reacted at 10°C for 1h, and then the unreacted raw materials and solvent benzene in the system are distilled off, and the temperature is gradually increased from 40°C to 80°C. The obtained product is tested by NMR carbon spectrum analysis, and the purity is 99.6%.

[0054] 1,2-Hydrazine dicarboxyl, N,N'-dicyclohexyl-1,2-diethyl: CAS 40028-64-6, synthesized according to the following method: 1L of room temperature benzene is used as solvent, 1mol N,N-diethylhydrazine and 2mol cyclohexyl isocyanate are added in proportion, reacted at 50℃ for 2h, and then the unreacted raw materials and solvent benzene in the system are removed by reduced pressure distillation, and the temperature is gradually increased from 40℃ to 80℃. The obtained product is tested by nuclear magnetic resonance carbon spectrum analysis, and the purity is 99.2%. Diethyltoluenediamine: CAS 68479-98-1, Shanghai MacLean Biochemical Technology Co., Ltd.

[0055] The initial flow temperature was tested using a Shimadzu CFT-500D rheometer, with the initial temperature set at 40°C and the heating rate set at 3°C / min.

[0056] Example 1

[0057] 200 kg of thermoplastic polyurethane elastomer was prepared by a one-step method using the following raw materials in parts by weight:

[0058] 80wt% of polybutylene adipate hexanediol diol-1500 accounting for 80wt% of the total mass of raw materials and 19wt% of 4,4'-diphenylmethane diisocyanate, 1wt% of aminodicarbonyl diamine, N,N',2-trimethylolpropane are subjected to twin-screw reaction extrusion (extruder temperature feed section: 130°C, compression section 170°C, metering section 185°C, die head 180°C) to obtain a high-resilience thermoplastic polyurethane elastomer, which is pelletized under cooling water at 10°C and then dried at 30°C to a moisture content of less than 0.1%.

[0059] Example 2

[0060] 200 kg of thermoplastic polyurethane elastomer was prepared by a two-step method using the following raw materials in parts by weight:

[0061] 80wt% of polybutylene adipate hexanediol diol-1500 accounting for 80wt% of the total mass of the raw materials and 19wt% of 4,4'-diphenylmethane diisocyanate are premixed in a single-screw device, and 1wt% of aminodicarbonyl diamine, N,N',2-trimethylol is poured into a twin-screw continuous reaction extruder through a mass flow meter for reaction (feeding section: 130°C, compression section 180, metering section 190°C, die head 180°C) to obtain a high-resilience thermoplastic polyurethane elastomer, which is pelletized under cooling water at 10°C and then dried at 30°C to a moisture content of less than 0.1%.

[0062] Example 3

[0063] 200 kg of thermoplastic polyurethane elastomer was prepared by a one-step method using the following raw materials in parts by weight:

[0064] 72wt% of polybutylene adipate diol-1200 accounting for 72wt% of the total mass of raw materials, 19.5wt% of hexamethylene diisocyanate, 8.5wt% of aminodicarbonyl diamine, N,N',2-trimethylolpropane are reacted and extruded by a twin-screw extruder (extruder temperature feed section: 120°C, compression section 160°C, metering section 175°C, die head 170°C) to obtain a high-resilience thermoplastic polyurethane elastomer, which is pelletized under cooling water at 10°C and then dried at 30°C to a moisture content of less than 0.1%.

[0065] Example 4

[0066] 200 kg of thermoplastic polyurethane elastomer was prepared by a one-step method using the following raw materials in parts by weight:

[0067] 75wt% of the total mass of raw materials, polybutylene adipate hexanediol ester diol-2000, 20wt% of 4,4'-dicyclohexylmethane diisocyanate, 2.5wt% of 1,4-butanediol, 2.5wt% of aminodicarbonylamine, N,N',2-trimethylol, are subjected to twin-screw reaction extrusion (feeding section: 130°C, compression section 170, metering section 180°C, die head 175°C) to obtain a high-resilience thermoplastic polyurethane elastomer, which is pelletized under cooling water at 10°C and then dried at 30°C to a moisture content of less than 0.1%.

[0068] Example 5

[0069] 200 kg of thermoplastic polyurethane elastomer was prepared by a one-step method using the following raw materials in parts by weight:

[0070] 65wt% of polycaprolactone diol-500 accounting for the total mass of raw materials is mixed evenly with 28.3wt% of toluene diisocyanate, 6.7wt% of urea, and N,N'-dimethyl-N'-[(methylamino)(methyl)methyl], and then subjected to twin-screw reaction extrusion (feeding section: 130°C, compression section 170, metering section 180°C, die head 175°C) to obtain a high-resilience thermoplastic polyurethane elastomer, which is pelletized under cooling water at 10°C and then dried at 30°C to a moisture content of less than 0.1%.

[0071] Example 6

[0072] 200 kg of thermoplastic polyurethane elastomer was prepared by a two-step method using the following raw materials in parts by weight:

[0073] 60wt% of polycaprolactone diol-800 accounting for the total mass of raw materials and 30wt% of 4,4'-diphenylmethane diisocyanate are premixed in a single-screw device, and then 5wt% of 2-methoxy-N,N'-dipropyl and 5wt% of 1,6-hexanediol are poured into a twin-screw continuous reaction extruder through a mass flow meter for reaction (feeding section: 130°C, compression section 180, metering section 190°C, die head 180°C) to obtain a high-resilience thermoplastic polyurethane elastomer, which is pelletized under cooling water at 10°C and then dried at 30°C to a moisture content of less than 0.1%.

[0074] Example 7

[0075] 200 kg of thermoplastic polyurethane elastomer was prepared by a one-step method using the following raw materials in parts by weight:

[0076] The polycaprolactone diol-4500 accounting for 60wt% of the total mass of the raw materials is mixed with 19wt% of 4,4'-diphenylmethane diisocyanate, 1wt% of 1,2-hydrazine dicarboxyl, N,N'-dicyclohexyl-1,2-diethyl and 20wt% of 1,12-dodecanediol through a twin-screw reaction extruder (feeding section: 130°C, compression section 170, metering section 180°C, die head 175°C) to obtain a high-resilience thermoplastic polyurethane elastomer, which is pelletized under cooling water at 10°C and then dried at 30°C to a moisture content of less than 0.1%.

[0077] Example 8

[0078] 200 kg of thermoplastic polyurethane elastomer was prepared by a one-step method using the following raw materials in parts by weight:

[0079] 60wt% of the total mass of raw materials, poly(hexanediol adipate neopentyl glycol) ester diol-4000, 19wt% of 4,4'-dicyclohexylmethane diisocyanate, 21wt% of aminodicarbonylamine, N,N',2-trimethylolpropane, were extruded through a twin-screw reaction extruder (feeding section: 130°C, compression section 170, metering section 180°C, die head 175°C) to obtain a high-resilience thermoplastic polyurethane elastomer, which was pelletized under cooling water at 10°C and then dried at 30°C to a moisture content of less than 0.1%.

[0080] Comparative Example 1

[0081] Compared with Example 3, the only difference is that aminodicarbonyl diamine, N,N',2-trimethyl is replaced by 1,10-decanediol.

[0082] 72wt% of polybutylene adipate diol-1200 accounting for 72wt% of the total mass of raw materials, 19.5wt% of hexamethylene diisocyanate and 8.5wt% of 1,10-decanediol are subjected to twin-screw reaction extrusion (extruder temperature feeding section: 120°C, compression section 160°C, metering section 175°C, die head 170°C) (extruder temperature 160°C) to obtain a high-resilience thermoplastic polyurethane elastomer, which is pelletized under cooling water at 10°C and then dried at 30°C to a moisture content of less than 0.1%.

[0083] Comparative Example 2

[0084] Compared with Example 6, the only difference is that 2-methoxy-N,N'-dipropyl is replaced by diethyltoluenediamine.

[0085] 60wt% of polycaprolactone diol-800 accounting for the total mass of raw materials and 30wt% of 4,4'-diphenylmethane diisocyanate are premixed in a single-screw device, and then 5wt% of 1,6-hexanediol and 5wt% of diethyltoluenediamine are poured into a twin-screw continuous reaction extruder through a mass flow meter for reaction (feeding section: 130°C, compression section 180, metering section 190°C, die head 180°C) to obtain a high-resilience thermoplastic polyurethane elastomer, which is pelletized under cooling water at 10°C and then dried at 30°C to a moisture content of less than 0.1%.

[0086] Thermoplastic polyurethane elastomer performance tests are as follows:

[0087] Hardness is tested according to ASTM D2240 standard; tensile strength is tested according to ASTM D412_16e1 standard, tensile speed is 100mm / min;

[0088] Rebound resilience refers to HG / T3322-1981 standard for determination of permanent deformation of vulcanized rubber at fixed elongation, and the 100% and 300% fixed elongation rebound retention rates are tested respectively: a film with a width of 30mm×length of 127mm×thickness of 0.2mm is stretched to 100% and 300%, maintained for 5min and 1min respectively, then the tension is removed, and the product is recovered at room temperature for 5min and 1min, the recovery length of the product is tested, and the fixed elongation deformation rate is confirmed. The test result is the average value of 3 parallel splines.

[0089] The performance data of the TPU provided by the above examples and comparative examples are shown in Table 1.

[0090] It can be seen from the data in Table 1 that the present invention introduces the small molecule diamine structure into the TPU structure, adds multiple hydrogen bond structures to the TPU, improves the resilience of the film, and can obtain a film with good resilience by using either a one-step method or a prepolymerization method. At the same time, TPU has a lower initial flow temperature and is easy to process.

[0091] Table 1

[0092]

[0093] Table 2

[0094] project Comparative Example 1 Comparative Example 2 Polyols PBA-1200 PCL-800 Isocyanate HDI MDI Chain Extender 1,10-Decanedioic acid HDO+Diethyltoluenediamine Process One-step method Two-step method Hardness(Shore A) 82 62 Tensile strength(MPa) 39.6 22.8 100% deformation retention 57％ 82％ 300% deformation retention 50％ 75％ Initial flow temperature (℃) 106 146

[0095] From the above data, it can be seen that the difference between Comparative Example 1 and Example 3 is that aminodicarbonyl diamine, N,N',2-trimethyl is replaced by 1,10-decanediol. Although the flow point of Comparative Example 1 is lower than that of Example 3, the resilience is poor; the difference between Comparative Example 2 and Example 6 is that 2-methoxy-N,N'-dipropyl is replaced by diethyltoluenediamine, and it can be seen that its resilience is reduced, while the flow point is high.

[0096] It is easy to understand that the above embodiments are only examples for clear explanation and do not mean that the present invention is limited thereto. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived from this are still within the protection scope of the present invention.

Claims

1. A thermoplastic polyurethane elastomer, characterized in that: The elastomer is prepared by comprising the following raw materials in parts by weight: Polyol 60-80wt%, preferably 60-75wt%, Isocyanate 19-39wt%, preferably 20-35wt%, Small molecule diol 0-20wt%, preferably 0-10wt%, 1-21wt% of small molecule diamine, preferably 2-20wt%; Wherein, the small molecule diamine comprises the following structure: Wherein, R1 and R2 independently represent O, S, -NR 1 One of them, R 1 It is linear C1-C 30 Alkyl or branched C1-C 30 Alkyl; R3 independently represents a linear C1-C 30 Alkyl, branched C1-C 30 Alkyl, C6-C 10 Aryl, -OR 2 One of them, R 2 It is linear C1-C 30 Alkyl, branched C1-C 30 Alkyl; n is an integer of 1-3; R4 and R5 independently represent C1-C 30 Alkyl, preferably C1-C 15 alkyl.

2. The elastic body according to claim 1, characterized in that The polyol is a polyester polyol, preferably one or more of polyethylene adipate diol, polypropylene adipate diol, polybutylene adipate diol, polyhexylene adipate diol, polyethylene adipate diol, polybutylene adipate hexylene adipate diol, and polycaprolactone diol, more preferably one or more of polybutylene adipate diol, polyethylene adipate diol, polybutylene adipate hexylene adipate diol, and polycaprolactone diol; Preferably, the molecular weight of the polyol is 400-4500, preferably 500-2500.

3. The elastic body according to claim 1 or 2, characterized in that: The diisocyanate is an aromatic diisocyanate and / or an aliphatic diisocyanate, preferably one or more of diphenylmethane diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, isophorone diisocyanate, meta-xylylene diisocyanate, 1,5-naphthalene diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate, more preferably one or more of hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, diphenylmethane diisocyanate, and isophorone diisocyanate.

4. The elastomer according to any one of claims 1 to 3, characterized in that The small molecule diol is a C2-C12 small molecule diol, preferably one or more of ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, methyl propanediol, diethylene glycol, 1,4-cyclohexanol, neopentyl glycol, 1,6-hexanediol, and 1,10-decanediol.

5. A method for preparing a thermoplastic polyurethane elastomer, wherein the method prepares the elastomer according to any one of claims 1 to 4, characterized in that: The method is a one-step method, comprising the following steps: uniformly mixing a polyol component with a diisocyanate component, a small molecule diol and a small molecule diamine, and extruding the mixture through a twin-screw reaction; Alternatively, the method is a prepolymerization method, comprising the following steps: premixing the polyol component and the diisocyanate in a single-screw mixing device to obtain a preliminary reaction mixture, and injecting the reaction mixture, small molecule diols and small molecule diamines into a twin-screw continuous reaction extruder for reaction.

6. Use of a thermoplastic polyurethane elastomer, wherein the elastomer is the elastomer described in any one of claims 1 to 4, or the elastomer prepared by the method described in claim 5, and the elastomer is used to prepare a high-resilience thermoplastic polyurethane elastomer, preferably used to prepare a high-resilience film, fine wire, and a net woven with the wire.

7. A thermoplastic polyurethane product, which is prepared using the elastomer described in any one of claims 1 to 4, or the elastomer prepared by the method described in claim 5, and the product is a high-resilience thermoplastic polyurethane elastomer, preferably used for high-resilience films, fine wires, and nets woven with wires.

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