WO2018145333A1 - 热塑性有机硅聚氨酯弹性体及其制备方法 - Google Patents

热塑性有机硅聚氨酯弹性体及其制备方法 Download PDF

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Publication number
WO2018145333A1
WO2018145333A1 PCT/CN2017/074660 CN2017074660W WO2018145333A1 WO 2018145333 A1 WO2018145333 A1 WO 2018145333A1 CN 2017074660 W CN2017074660 W CN 2017074660W WO 2018145333 A1 WO2018145333 A1 WO 2018145333A1
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Prior art keywords
parts
polyol
polyurethane elastomer
silicone
thermoplastic
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PCT/CN2017/074660
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English (en)
French (fr)
Inventor
王黑龙
宋红玮
刘德富
张生
王仁鸿
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Miracll Chemicals Co Ltd
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Miracll Chemicals Co Ltd
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Priority to US16/483,670 priority Critical patent/US11643498B2/en
Priority to MX2019009417A priority patent/MX2019009417A/es
Priority to KR1020197023764A priority patent/KR102224198B1/ko
Priority to EP17895997.9A priority patent/EP3581603A4/en
Publication of WO2018145333A1 publication Critical patent/WO2018145333A1/zh
Anticipated expiration legal-status Critical
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    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
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    • B29K2083/00—Use of polymers having silicon, with or without sulfur, nitrogen, oxygen, or carbon only, in the main chain, as moulding material

Definitions

  • the invention relates to a thermoplastic polyurethane elastomer, in particular to a thermoplastic silicone polyurethane elastomer and a preparation method thereof, and belongs to the technical field of polymer materials.
  • thermoplastic polyurethane elastomer (hereinafter referred to as TPU) is a linear polymer material obtained by polymerizing a macromolecular diol, a diisocyanate, and a small molecule diol or a diamine.
  • TPU is a block copolymer, which forms a soft segment from a macromolecular diol.
  • the diisocyanate reacts with a small molecule diol to form a hard segment.
  • the alternating molecular structure of the soft segment and the hard segment forms a microphase region and produces a microscopic phase.
  • TPU can form hydrogen bonds in the molecule and between molecules to form a physical cross-linking point, so that when deformed, the polymer chains do not slip between them, but exhibit elasticity. When heated, the cross-linking point melts and the polymer chain moves, and then flows.
  • TPU's unique structural features make it both plastic processing technology and physical and mechanical properties of rubber. TPU is soluble and fusible. It not only has excellent hardness range, high strength, wear resistance, oil resistance, low temperature flexibility, etc., but also can greatly change the performance and use of the product by adjusting the raw materials and their ratio. Widely used in medical and health, electronics, industrial and sports.
  • TPU has poor skin-friendly properties and is resistant to dirt and penetration.
  • Silicone rubber products have excellent skin-friendly, light-resistant, stain-resistant and penetration-resistant, but their mechanical strength, especially tensile strength and tear. Poor strength.
  • thermoplastic polyurethane elastomer which is good in skin-friendly and excellent in mechanical strength, and particularly provides high tensile strength and tear strength, no sensitization, yellowing resistance, and processability. It can be used in reproducible processing, and at the same time, it ensures that the production process is simple, efficient, and easy to automate. It can be widely used in smart wearable equipment, medical, industrial rubber, leather and other fields with high requirements for dirt and dirt resistance.
  • a thermoplastic silicone polyurethane elastomer A thermoplastic silicone polyurethane elastomer.
  • the invention aims to provide a thermoplastic silicone polyurethane elastomer and a preparation method thereof for the defects of the existing TPU materials in terms of skin-friendly, stain-resistant and penetration resistance and the mechanical strength of the silicone rubber.
  • thermoplastic silicone polyurethane elastomer the raw material of the elastomer comprising the following components:
  • the macropolyol is one of a silicon-free polyol having a molecular weight of 1000-4000 g/mol, a polyol modified by copolymerization or grafting of a silicone; the small molecule diol means A diol having 10 or less carbon atoms.
  • the macropolyol is a compound of one or more of a polyether polyol, a polyester polyol, a polycaprolactone polyol, a polycarbonate polyol, and a hydroxyl terminated polyolefin polyol, and
  • the above polyether polyol, polyester polyol, polycaprolactone polyol, polycarbonate polyol, and hydroxyl group-terminated polyolefin polyol are one of copolymerized or graft-modified polymers of silicone.
  • the silicone oil is an alcoholic hydroxyl group-containing silicone oil in which the number of functional groups of the alcoholic hydroxyl group is 1-3.
  • liquid silicone rubber is an industrialized room temperature curing silicone rubber, and the curing time is greater than 60 minutes.
  • diisocyanate is a combination of one or more of tolylene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate.
  • the small molecule diol is ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1, In 6-hexanediol, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, neopentyl glycol, dipropylene glycol, hydroquinone -bis( ⁇ -hydroxyethyl)ether One or more combinations.
  • auxiliary agent refers to one or more of an antioxidant, a light stabilizer, a lubricant, a catalyst, and an antistatic agent.
  • thermoplastic silicone polyurethane elastomer of the invention has the following excellent performance parameters: hardness ShoreA40-D80; tensile strength ⁇ 5 MPa; smooth hand feeling; dust and other dirt; liquid penetration resistance; no irritation to skin; TPU and other encapsulation effects are good, 180° peel strength >25N/25mm.
  • thermoplastic silicone polyurethane elastomer in the field of wearable devices, medical, industrial rubber, electronic injection molding, leather.
  • thermoplastic silicone polyurethane elastomer comprising the following steps:
  • the temperature of the twin-screw extruder in step 2) is set to 120-250 ° C
  • the granulation water temperature is controlled at 5-70 ° C
  • the drying drying temperature in step 3) is controlled at 50-90 ° C
  • the drying time is controlled at 0.5-4 h.
  • PTMG polytetrahydrofuran ether glycol
  • MDI Diphenylmethane diisocyanate
  • antioxidant Irganox 1010 0.6 parts
  • light stabilizer Tinuvin 622
  • thermoplastic silicone polyurethane elastomer The preparation method of the above thermoplastic silicone polyurethane elastomer is as follows:
  • the temperature of the twin-screw extruder is controlled to 120-250 ° C, and the polymer discharged from the die is subjected to underwater cutting and granulation to obtain elliptical pellets, and the temperature of the water is controlled to 20-30 ° C. ;
  • PTMG polytetrahydrofuran ether glycol
  • MDI Diphenylmethane diisocyanate
  • thermoplastic silicone polyurethane elastomer The preparation method of the above thermoplastic silicone polyurethane elastomer is as follows:
  • PEG polyethylene oxide diol
  • TDI Toluene diisocyanate
  • thermoplastic silicone polyurethane elastomer The preparation method of the above thermoplastic silicone polyurethane elastomer is as follows:
  • the temperature of the twin-screw extruder is controlled to be 120-250 ° C, and the polymer discharged from the die is subjected to underwater cutting and granulation to obtain round pellets, and the temperature of the water is controlled to be 5-15 ° C;
  • thermoplastic silicone polyurethane elastomer The preparation method of the above thermoplastic silicone polyurethane elastomer is as follows:
  • the heated polyester diol, 1,6-hexanediol, 45-50 ° C toluene diisocyanate (TDI), 60-120 ° C silicone oil is added to the twin-screw extruder in metered parts.
  • the temperature of the twin-screw extruder is controlled to be 120-250 ° C, and the polymer discharged from the die is subjected to underwater cutting and granulation to obtain round pellets, and the temperature of the water is controlled to be 5-15 ° C;
  • thermoplastic silicone polyurethane elastomer whose raw material composition is as follows: a polyester diol having a molecular weight of 3,500 g/mol (polymerized by adipic acid, 1,4-butanediol, 1,6-hexanediol), 25 a silicone oil terminated with PEG at both ends, having a hydroxyl value of 40 mg KOH/g, 15 parts; dicyclohexylmethane diisocyanate (H 12 MDI), 10 parts; ethylene glycol 3 parts; antioxidant Irganox 1010, 0.05 Parts; light stabilizer Tinuvin 770, 0.05 parts; lubricant erucamide, 0.05 parts, catalyst dibutyltin diacetate 0.1 parts, antistatic agent 0.05 parts.
  • a polyester diol having a molecular weight of 3,500 g/mol polymerized by adipic acid, 1,4-butanediol, 1,6-hexanediol
  • thermoplastic silicone polyurethane elastomer The preparation method of the above thermoplastic silicone polyurethane elastomer is as follows:
  • thermoplastic silicone polyurethane elastomer having a raw material composition as follows: a polycaprolactone diol having a molecular weight of 3000 g/mol, 35 parts; a silicone oil terminated with PEG at both ends, having a hydroxyl value of 40 mg KOH/g, 15 parts; Diphenylmethane diisocyanate (MDI), 15 parts; 1,4-butanediol 6 parts; antioxidant Irganox 1010, 0.05 parts; light stabilizer Tinuvin 770, 0.05 parts; lubricant erucamide, 0.05 parts, The catalyst was 0.05 parts of dibutyltin diacetate.
  • thermoplastic silicone polyurethane elastomer The preparation method of the above thermoplastic silicone polyurethane elastomer is as follows:
  • MDI diphenylmethane diisocyanate
  • thermoplastic silicone polyurethane elastomer The preparation method of the above thermoplastic silicone polyurethane elastomer is as follows:
  • the heated silicone-modified polyester polyol, 1,4-butanediol, and 45-50 ° C diphenylmethane diisocyanate (MDI) are added to the twin-screw extruder in metered portions.
  • MDI diphenylmethane diisocyanate
  • the temperature of the twin-screw extruder is controlled to be 120-250 ° C, and the polymer discharged from the die is subjected to underwater cutting and granulation to obtain round pellets, and the temperature of the water is controlled to be 15-25 ° C;
  • MDI diphenylmethane diisocyanate
  • Oxygen Irganox 1010 0.05 parts
  • light stabilizer Tinuvin 770 0.05 parts
  • thermoplastic silicone polyurethane elastomer The preparation method of the above thermoplastic silicone polyurethane elastomer is as follows:
  • the heated silicone-modified polyester polyol, 1,4-cyclohexanedimethanol, and 45-50 ° C diphenylmethane diisocyanate (MDI) are added to the twin-screw extrusion in parts by volume.
  • MDI diphenylmethane diisocyanate
  • the temperature of the twin-screw extruder is controlled to be 120-250 ° C, and the polymer discharged from the die is subjected to underwater cutting and granulation to obtain round pellets, and the temperature of the water is controlled to be 15-25 ° C;
  • PTMG polytetrahydrofuran ether glycol
  • MDI diphenylmethane diisocyanate
  • 1,4-butanediol 1,4-butanediol, in the total system
  • antioxidant Irganox 1010 0.6 parts
  • light stabilizer Tinuvin 622 0.5 parts, Tinuvin
  • TDI toluene diisocyanate
  • thermoplastic silicone polyurethane elastomer obtained in the present invention we conducted performance tests on Specific Examples 1-8 and Comparative Examples 1-2, wherein:
  • the tear strength is tested in accordance with ASTM D624;
  • the yellowing resistance level was tested according to ASTM D1148 for 48 hours, and the gray card was used for judgment;
  • the hand feel is smooth and tested according to the standards set by the company;
  • the specific test method is: according to the grinding tools made by the company, grinding three test piece cavities with different numbers of matte, one plane test piece cavity, using the same grinding tool
  • the standard samples are divided into five grades, and the observers respectively touch the test strips and compare them with the standard samples. When the four test strips are closest to a certain grade test strip standard, it is determined to be the grade;
  • the evaluation criteria are as follows: the smoothness of the hand is divided into 1, 2, 3, 4, and 5, with 1 being the worst and 5 being the best.
  • Level 1 The hand feels stagnation, and the test piece is completely stuck to the cavity
  • Level 3 general feel, the test piece is 1/2 or less stuck to the cavity
  • Level 4 The hand feels smooth and the test piece does not stick to the grinding cavity
  • Level 5 The hand feels smooth and slippery, and the test piece naturally falls off when the mold is opened;
  • the penetration resistance test is tested according to the enterprise standard; the test piece is coated with a marker, a gel pen, a ballpoint pen, ink, etc., or the test piece is immersed in juice, tea, etc., placed at rest for 96 hours, then taken out, and observed. Sheet penetration, trace removal;
  • the evaluation criteria are as follows: the penetration resistance is divided into 1, 2, and 3, with 1 being the worst and 3 being the best.
  • Level 1 The traces are completely infiltrated, the traces of the wipes are unchanged, and completely left;
  • Level 2 Part of the trace penetrates, the wiping marks are alleviated, but it cannot be completely wiped off;
  • thermoplastic silicone polyurethane elastomer provided by the present invention has several levels of hand and skin-friendly properties compared to conventional TPU, so that the silicone-containing TPU of the present invention can be applied to wear.

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Abstract

一种热塑性有机硅聚氨酯弹性体及其制备方法，弹性体的原料包括如下组分：大分子多元醇25-80份；有机硅油或液态硅橡胶0-60份；二异氰酸酯10-50份；扩链剂小分子二元醇3-20份；助剂0.1-3份；所述大分子多元醇为分子量介于1000-4000g/mol的无硅多元醇以及被有机硅通过共聚或接枝改性的多元醇；所述小分子二元醇小分子二元醇是指10个碳以下的小分子二元醇。热塑性有机硅聚氨酯弹性体具有如下优异的性能参数：硬度Shore A40-D80；拉伸强度≥5MPa；手感爽滑；耐灰尘等脏污；耐液体渗透；对皮肤无刺激；对PC、ABS、TPU等包胶效果好，180°剥离强度>25N/25mm。

Description

[根据细则37.2由ISA制定的发明名称]　热塑性有机硅聚氨酯弹性体及其制备方法 技术领域
本发明涉及一种热塑性聚氨酯弹性体，尤其涉及一种热塑性有机硅聚氨酯弹性体及其制备方法，属于高分子材料技术领域。
背景技术
热塑性聚氨酯弹性体(以下简称TPU)，是由大分子二元醇、二异氰酸酯和小分子二元醇或二元胺聚合而成的线性高分子材料。TPU是一种嵌段共聚物，由大分子二元醇形成软段，由二异氰酸酯和小分子二元醇反应形成硬段，软段和硬段交替的分子结构形成微相区并产生微观相分离；此外由于大量极性基团的存在，TPU的分子内和分子间可以形成氢键而产生物理交联点，因而在变形时，高分子链之间也不会发生滑动，而呈现弹性，而当加热时，交联点熔融后高分子链活动，便发生流动。TPU独特的结构特点使其兼具有塑料的加工工艺性能和橡胶的物理机械性能。TPU可溶可熔，不仅具有硬度范围宽、强度高、耐磨、耐油、低温柔韧性好等优良性能；而且通过调整原料及其配比可以大幅度的改变产品性能及用途。广泛应用于医疗卫生、电子电器、工业及体育等方面。
但是TPU亲肤性较差，耐脏污、耐渗透能力不足；而硅橡胶产品具有较优异的亲肤性，光稳定性，耐脏耐渗透，但是其力学强度尤其是拉伸强度和撕裂强度较差。
因此存在如下需求，提供一种亲肤性良好，力学强度优良的热塑性聚氨酯弹性体，特别是提供高抗张强度和撕裂强度、无致敏性、耐黄变、加工性 能好可重复加工使用的，同时保证生产工艺比较简单高效且便于自动化生产，并能广泛应用于智能穿戴设备、医疗、工业包胶、皮革等对手感和耐脏污性能要求较高领域的一种热塑性有机硅聚氨酯弹性体。
发明内容
本发明针对现有TPU材料在亲肤性、耐脏污、耐渗透能力方面存在的不足以及硅橡胶在力学强度方面存在的不足，提供一种热塑性有机硅聚氨酯弹性体及其制备方法。
本发明解决上述技术问题的技术方案如下：
一种热塑性有机硅聚氨酯弹性体，所述弹性体的原料包括如下组分：
大分子多元醇25-80份；
有机硅油或液态硅橡胶0-60份；
二异氰酸酯10-50份；
扩链剂小分子二元醇3-20份；
助剂0.1-3份；
其中，所述大分子多元醇为分子量介于1000-4000g/mol的无硅多元醇、被有机硅通过共聚或接枝改性的多元醇中的一种；所述小分子二元醇是指含有10个以下碳原子的二元醇。
进一步，所述大分子多元醇为聚醚多元醇、聚酯多元醇、聚己内酯多元醇、聚碳酸酯多元醇、端羟基聚烯烃多元醇中的一种或多种的复配，以及上述的聚醚多元醇、聚酯多元醇、聚己内酯多元醇、聚碳酸酯多元醇、端羟基聚烯烃多元醇被有机硅通过共聚或接枝改性的聚合物中的一种。
进一步，所述的有机硅油为含醇羟基的有机硅油，其中醇羟基的官能团数为1-3个。
进一步，所述的液态硅橡胶为工业化的室温固化硅橡胶，固化时间大于 60分钟。
进一步，所述的二异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯中的一种或多种的复配。
进一步，所述的小分子二元醇为乙二醇、1,3-丙二醇、2-甲基-1,3-丙二醇，1,3-丁二醇、1,4-丁二醇、1,6-己二醇、1,4-环己烷二甲醇、二乙二醇、三乙二醇、新戊二醇、一缩二丙二醇、氢醌-双(β-羟乙基)醚中的一种或多种的复配。
进一步，所述的助剂是指抗氧剂、光稳定剂、润滑剂、催化剂和抗静电剂中的一种或多种。
本发明的有益效果是：
本发明的热塑性有机硅聚氨酯弹性体具有如下优异的性能参数：硬度ShoreA40-D80；拉伸强度≥5MPa；手感爽滑；耐灰尘等脏污；耐液体渗透；对皮肤无刺激；对PC、ABS、TPU等包胶效果好，180°剥离强度>25N/25mm。
本发明还要求保护上述的热塑性有机硅聚氨酯弹性体在穿戴设备、医疗、工业包胶、电子注塑、皮革领域的应用。
本发明还提供了上述的热塑性有机硅聚氨酯弹性体的制备方法，包括如下步骤：
1)将称量好的助剂加入到大分子多元醇中，搅拌使助剂完全溶解；
2)后将步骤1)中所得的大分子多元醇与计量份的小分子多元醇、液体状态的二异氰酸酯以及液体状态的有机硅油或液态硅橡胶加入到双螺杆挤出机中，挤出后的物料经水下切割造粒；
3)将步骤2)所得的造粒后的产品干燥，即得。
进一步，步骤2)中所述双螺杆挤出机的温度设定为120-250℃，造粒水温控制在5-70℃，步骤3)中所述干燥的干燥温度控制在50-90℃，干燥时间控制在0.5-4h。
具体实施方式
以下结合实例对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
实施例1：
一种热塑性有机硅聚氨酯弹性体，其原料组成如下：分子量2000g/mol的聚四氢呋喃醚二醇(PTMG)，57份；两端由PEG封端的有机硅油，羟值为38mg KOH/g，15份；二苯基甲烷二异氰酸酯(MDI)，23份；1,4-丁二醇，总体系中R＝nNCO/nOH＝1.01，15份；抗氧剂Irganox 1010，0.6份；光稳定剂Tinuvin 622，0.5份，Tinuvin 328 0.8份；润滑剂EBO，0.3份，硅酮粉0.2份。
上述热塑性有机硅聚氨酯弹性体的制备方法如下：
1)将称量好的抗氧剂、光稳定剂、润滑剂加入到聚四氢呋喃醚二醇(PTMG)中，加热至100℃搅拌2小时使助剂彻底溶解；
2)后将加热的聚四氢呋喃醚二醇(PTMG)、1,4-丁二醇、45-50℃的二苯基甲烷二异氰酸酯(MDI)、60-120℃的有机硅油按计量份数加入到双螺杆挤出机中，双螺杆挤出机的温度控制为120-250℃，模头排出的聚合物经水下切割造粒制得椭圆形粒料，水的温度控制为20-30℃；
3)将步骤2)所得的粒料置于50℃下干燥2小时，后包装。
实施例2：
一种热塑性有机硅聚氨酯弹性体，其原料组成如下：分子量1800g/mol的聚四氢呋喃醚二醇(PTMG)，59份；两端由PEG封端的有机硅油，羟值为55mg KOH/g，30份；二苯基甲烷二异氰酸酯(MDI)，32份；1,4-丁二醇，总体系中R＝nNCO/nOH＝1.01，20份；抗氧剂Irganox 1010，0.2份，Irganox 1076，0.3份；光稳定剂Tinuvin 770，1.0份，Tinuvin P 0.5份；润滑剂EBS，0.5份，油酸酰胺0.5份。
上述热塑性有机硅聚氨酯弹性体的制备方法如下：
1)将称量好的抗氧剂、光稳定剂、润滑剂加入到聚四氢呋喃醚二醇(PTMG)中，加热至100℃搅拌2小时使助剂彻底溶解；
2)后将加热的聚四氢呋喃醚二醇(PTMG)、1,4-丁二醇、45-50℃的二苯基甲烷二异氰酸酯(MDI)、60-120℃的有机硅油按计量份数加入到双螺杆挤出机中，双螺杆挤出机的温度控制为120-250℃，模头排出的聚合物经水下切割造粒制得圆形粒料，水的温度控制为30-40℃；
3)将步骤2)所得的粒料置于60℃下干燥1.5小时，后包装。
实施例3：
一种热塑性有机硅聚氨酯弹性体，其原料组成如下：分子量2500g/mol的聚氧化乙烯二醇(PEG)，45份；两端由PEG封端的有机硅油，羟值为40mg KOH/g，30份；甲苯二异氰酸酯(TDI)，50份；1,3-丙二醇，总体系中R＝nNCO/nOH＝1.01，10份；抗氧剂Irganox 1010，0.2份，Irganox 1076，0.2份，Irganox 1098，0.2份；光稳定剂Tinuvin 770，1.5份，Tinuvin P 0.5份；润滑剂芥酸酰胺，0.6份，硬脂酸酰胺0.6份。
上述热塑性有机硅聚氨酯弹性体的制备方法如下：
1)将称量好的抗氧剂、光稳定剂、润滑剂加入到聚氧化乙烯二醇(PEG)中，加热至100℃搅拌2小时使助剂彻底溶解；
2)后将加热的聚氧化乙烯二醇(PEG)、1,3-丙二醇、45-50℃的甲苯二异氰酸酯(TDI)、60-120℃的有机硅油按计量份数加入到双螺杆挤出机中，双螺杆挤出机的温度控制为120-250℃，模头排出的聚合物经水下切割造粒制得圆形粒料，水的温度控制为5-15℃；
3)将步骤2)所得的粒料置于80℃下干燥0.5小时，后包装。
实施例4：
一种热塑性有机硅聚氨酯弹性体，其原料组成如下：分子量3000g/mol 的聚酯二元醇(己二酸、1，4-丁二醇、乙二醇聚合而成)，35份；两端由分子量500g/mol的聚酯二元醇(己二酸+1,4-丁二醇)封端的有机硅油，羟值为30mg KOH/g，45份；甲苯二异氰酸酯(TDI)，40份；1,6-己二醇，总体系中R＝nNCO/nOH＝1.01，8份；抗氧剂Irganox 1010，0.1份；光稳定剂Tinuvin  770，0.05份；润滑剂芥酸酰胺，0.05份，催化剂二月桂酸二丁基锡0.1份。
上述热塑性有机硅聚氨酯弹性体的制备方法如下：
1)将称量好的抗氧剂、光稳定剂、润滑剂、催化剂加入到聚酯二元醇中，加热至100℃搅拌2小时使助剂彻底溶解；
2)后将加热的聚酯二元醇、1,6-己二醇、45-50℃的甲苯二异氰酸酯(TDI)、60-120℃的有机硅油按计量份数加入到双螺杆挤出机中，双螺杆挤出机的温度控制为120-250℃，模头排出的聚合物经水下切割造粒制得圆形粒料，水的温度控制为5-15℃；
3)将步骤2)所得的粒料置于90℃下干燥0.5小时，后包装。
实施例5：
一种热塑性有机硅聚氨酯弹性体，其原料组成如下：分子量3500g/mol的聚酯二元醇(己二酸、1，4-丁二醇、1，6-己二醇聚合而成)，25份；两端由PEG封端的有机硅油，羟值为40mg KOH/g，15份；二环己基甲烷二异氰酸酯(H12MDI)，10份；乙二醇3份；抗氧剂Irganox 1010，0.05份；光稳定剂Tinuvin 770，0.05份；润滑剂芥酸酰胺，0.05份，催化剂二醋酸二丁基锡0.1份，抗静电剂0.05份。
上述热塑性有机硅聚氨酯弹性体的制备方法如下：
1)将称量好的抗氧剂、光稳定剂、润滑剂、催化剂、抗静电剂加入到聚酯二元醇中，加热至100℃搅拌2小时使助剂彻底溶解；
2)后将加热的聚酯二元醇、乙二醇、45-50℃的二环己基甲烷二异氰酸酯 (H12MDI)、60-120℃的有机硅油按计量份数加入到双螺杆挤出机中，双螺杆挤出机的温度控制为120-250℃，模头排出的聚合物经水下切割造粒制得圆形粒料，水的温度控制为15-25℃；
3)将步骤2)所得的粒料置于50℃下干燥4小时，后包装。
实施例6：
一种热塑性有机硅聚氨酯弹性体，其原料组成如下：分子量3000g/mol的聚己内酯二元醇，35份；两端由PEG封端的有机硅油，羟值为40mg KOH/g，15份；二苯基甲烷二异氰酸酯(MDI)，15份；1，4-丁二醇6份；抗氧剂Irganox 1010，0.05份；光稳定剂Tinuvin 770，0.05份；润滑剂芥酸酰胺，0.05份，催化剂二醋酸二丁基锡0.05份。
上述热塑性有机硅聚氨酯弹性体的制备方法如下：
1)将称量好的润滑剂、催化剂加入到聚己酯二元醇中，加热至100℃搅拌2小时使助剂彻底溶解；
2)后将加热的聚己酯二元醇、1，4-丁二醇、45-50℃的二苯基甲烷二异氰酸酯(MDI)、60-120℃的有机硅油按计量份数加入到双螺杆挤出机中，双螺杆挤出机的温度控制为120-250℃，模头排出的聚合物经水下切割造粒制得圆形粒料，水的温度控制为15-25℃；
3)将步骤2)所得的粒料置于50℃下干燥4小时，后包装。
实施例7：
一种热塑性有机硅聚氨酯弹性体，其原料组成如下：分子量3000g/mol的有机硅共聚改性的聚酯多元醇(己二酸+1,4-丁二醇+1，6-己二醇+有机硅)，其中有机硅含量为10％，80份；二苯基甲烷二异氰酸酯(MDI)，20份；1，4-丁二醇，总体系中R＝nNCO/nOH＝1.01，10份；抗氧剂Irganox 1010，0.05份；催化剂二醋酸二丁基锡0.05份。
上述热塑性有机硅聚氨酯弹性体的制备方法如下：
1)将称量好的抗氧剂、催化剂加入到有机硅改性的聚酯多元醇中，加热至100℃搅拌2小时使助剂彻底溶解；
2)后将加热的有机硅改性的聚酯多元醇、1，4-丁二醇、45-50℃的二苯基甲烷二异氰酸酯(MDI)按计量份数加入到双螺杆挤出机中，双螺杆挤出机的温度控制为120-250℃，模头排出的聚合物经水下切割造粒制得圆形粒料，水的温度控制为15-25℃；
3)将步骤2)所得的粒料置于50℃下干燥4小时，后包装。
实施例8：
一种热塑性有机硅聚氨酯弹性体，其原料组成如下：分子量4000g/mol的有机硅接枝改性的聚酯多元醇(己二酸+1,4-丁二醇+乙二醇+有机硅)，其中有机硅含量为20％，80份；二苯基甲烷二异氰酸酯(MDI)，16份；1,4-环己烷二甲醇，总体系中R＝nNCO/nOH＝1.01，20份；抗氧剂Irganox 1010，0.05份；光稳定剂Tinuvin 770，0.05份；润滑剂芥酸酰胺，0.05份；催化剂二醋酸二丁基锡0.05份。
上述热塑性有机硅聚氨酯弹性体的制备方法如下：
1)将称量好的抗氧剂、光稳定剂、润滑剂、催化剂加入到有机硅改性的聚酯多元醇中，加热至100℃搅拌2小时使助剂彻底溶解；
2)后将加热的有机硅改性的聚酯多元醇、1,4-环己烷二甲醇、45-50℃的二苯基甲烷二异氰酸酯(MDI)按计量份数加入到双螺杆挤出机中，双螺杆挤出机的温度控制为120-250℃，模头排出的聚合物经水下切割造粒制得圆形粒料，水的温度控制为15-25℃；
3)将步骤2)所得的粒料置于50℃下干燥4小时，后包装。
对比例1：
原料组成为：分子量为2000g/mol的聚四氢呋喃醚二醇(PTMG)，57份；二苯基甲烷二异氰酸酯(MDI)，23份；1,4-丁二醇，总体系中 R＝nNCO/nOH＝1.01，23份；抗氧剂Irganox 1010，0.6份；光稳定剂Tinuvin 622，0.5份，Tinuvin 328 0.8份；润滑剂EBO，0.3份，硅酮粉0.2份。
对比例2：
原料组成为：分子量3000g/mol的聚酯二元醇(己二酸、1，4-丁二醇、乙二醇聚合而成)，35份；甲苯二异氰酸酯(TDI)，40份；1,6-己二醇，总体系中R＝nNCO/nOH＝1.01，8份；抗氧剂Irganox 1010，0.1份；光稳定剂Tinuvin 770，0.05份；润滑剂芥酸酰胺，0.05份，催化剂二月桂酸二丁基锡0.1份。
为了验证本发明所得热塑性有机硅聚氨酯弹性体的性能，我们对具体实施例1～8和对比例1-2进行性能测试，其中：
硬度按ASTM D2240标准进行测试；
撕裂强度按ASTM D624标准进行测试；
耐黄等级按ASTM D1148测试48h，对比灰卡来进行判定；
致敏测试按ISO10993标准进行测试；
拉伸强度按ASTM D412标准进行测试；
手感爽滑按本公司规定标准进行测试；具体测试方法为：依照本公司制作的磨具，磨具有磨砂不同目数的3个试片模腔，1个平面试片模腔，使用同一磨具制作标样，分为5个等级，由观察者分别触摸试片，与标样进行比较，当4个试片都最接近某一等级试片标样时，确定其为此等级；
评价标准如下：手感爽滑度分为1、2、3、4、5五级，1为最差，5为最好。
1级：手感滞涩，试片完全粘于模腔；
2级：手感滞涩，试片有2/3粘于模腔；
3级：手感一般，试片1/2以下粘于模腔；
4级：手感爽滑，试片不粘于磨腔；
5级：手感爽滑，试片在开模时自然脱落；
耐渗透测试按照企业标准进行测试；将试片分别用记号笔、中性笔、圆珠笔、墨水等涂抹试片表面或者将试片浸泡于果汁、茶水等中，静止放置96h，然后取出，观察试片渗透情况，痕迹清理情况；
评价标准如下：耐渗透分为1、2、3三级，1为最差，3为最好。
1级：痕迹完全渗透，擦拭痕迹无变化，完全残留；
2级：痕迹部分渗透，擦拭痕迹减轻，但不能完全擦掉；
3级：痕迹无渗透，擦拭痕迹去除，无痕迹残留；
结果如表1所示：
表1 实施例1-8和对比例1-2所得产品的主要理化性能
Figure PCTCN2017074660-appb-000001
表1中的数据表明，本发明所提供的热塑性有机硅聚氨酯弹性体相对普通TPU来说在手感和亲肤性上提高了几个层级，从而使得本发明的含有机硅的TPU能够适用于在穿戴设备、医疗、工业包胶、电子注塑、皮革等对手感和耐脏污性能要求较高的领域。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种热塑性有机硅聚氨酯弹性体，其特征在于，所述弹性体的原料包括如下组分：
    大分子多元醇25-80份；
    有机硅油或液态硅橡胶0-60份；
    二异氰酸酯10-50份；
    扩链剂小分子二元醇3-20份；
    助剂0.1-3份；
    其中，所述大分子多元醇为分子量介于1000-4000g/mol的无硅多元醇、被有机硅通过共聚或接枝改性的多元醇中的一种；所述的小分子二元醇是指含有10个以下碳原子的二元醇。
  2. 根据权利要求1所述的热塑性有机硅聚氨酯弹性体，其特征在于，所述大分子多元醇为聚醚多元醇、聚酯多元醇、聚己内酯多远醇、聚碳酸酯多元醇、端羟基聚烯烃多元醇中的一种或多种的复配，以及上述的聚醚多元醇、聚酯多元醇、聚己内酯多元醇、聚碳酸酯多元醇、端羟基聚烯烃多元醇被有机硅通过共聚或接枝改性的聚合物中的一种。
  3. 根据权利要求1所述的热塑性有机硅聚氨酯弹性体，其特征在于，所述的有机硅油为含醇羟基的有机硅油，其中醇羟基的官能团数为1-3个。
  4. 根据权利要求1所述的热塑性有机硅聚氨酯弹性体，其特征在于，所述的液态硅橡胶为工业化的室温固化硅橡胶，固化时间大于60分钟。
  5. 根据权利要求1所述的热塑性有机硅聚氨酯弹性体，其特征在于，所述的二异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯中的一种或多种的复配。
  6. 根据权利要求1所述的热塑性有机硅聚氨酯弹性体，其特征在于， 所述的小分子二元醇为乙二醇、1,3-丙二醇、2-甲基-1,3-丙二醇1,3-丁二醇、1,4-丁二醇、1,6-己二醇、1,4-环己烷二甲醇、二乙二醇、三乙二醇、新戊二醇、一缩二丙二醇、氢醌-双(β-羟乙基)醚中的一种或多种的复配。
  7. 根据权利要求1所述的热塑性有机硅聚氨酯弹性体，其特征在于，所述的助剂包括抗氧剂、光稳定剂、润滑剂、催化剂和抗静电剂中的一种或多种。
  8. 一种权利要求1-7中任一项所述的热塑性有机硅聚氨酯弹性体在穿戴设备、医疗、工业包胶、电子注塑、皮革领域的应用。
  9. 一种权利要求1-7中任一项所述的热塑性有机硅聚氨酯弹性体的制备方法，其特征在于，包括如下步骤：
    1)将称量好的助剂加入到大分子多元醇中，搅拌使助剂完全溶解；
    2)后将步骤1)中所得的大分子多元醇与计量份的小分子多元醇、液体状态的二异氰酸酯以及液体状态的有机硅油或液态硅橡胶加入到双螺杆挤出机中，挤出后的物料经水下切割造粒；
    3)将步骤2)所得的造粒后的产品干燥，即得。
  10. 根据权利要求9所述的热塑性有机硅聚氨酯弹性体的制备方法，其特征在于，步骤2)中所述双螺杆挤出机的温度设定为120-250℃，造粒水温控制在5-70℃，步骤3)中所述干燥的干燥温度控制在50-90℃，干燥时间控制在0.5-4h。
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