WO2018133157A1 - 一种原位增容制备tpu合金材料的工艺 - Google Patents

一种原位增容制备tpu合金材料的工艺 Download PDF

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Publication number
WO2018133157A1
WO2018133157A1 PCT/CN2017/074659 CN2017074659W WO2018133157A1 WO 2018133157 A1 WO2018133157 A1 WO 2018133157A1 CN 2017074659 W CN2017074659 W CN 2017074659W WO 2018133157 A1 WO2018133157 A1 WO 2018133157A1
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WIPO (PCT)
Prior art keywords
parts
tpu
screw extruder
twin
group
Prior art date
Application number
PCT/CN2017/074659
Other languages
English (en)
French (fr)
Inventor
战振生
宋红玮
赵庆波
张生
任光雷
Original Assignee
美瑞新材料股份有限公司
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Filing date
Publication date
Application filed by 美瑞新材料股份有限公司 filed Critical 美瑞新材料股份有限公司
Priority to MX2019008646A priority Critical patent/MX2019008646A/es
Priority to EP17892533.5A priority patent/EP3549983B1/en
Priority to ES17892533T priority patent/ES2823196T3/es
Priority to KR1020197020584A priority patent/KR102189552B1/ko
Priority to US16/477,894 priority patent/US11274203B2/en
Publication of WO2018133157A1 publication Critical patent/WO2018133157A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0895—Manufacture of polymers by continuous processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L75/04—Polyurethanes
    • C08L75/06—Polyurethanes from polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B01J2/20—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by expressing the material, e.g. through sieves and fragmenting the extruded length
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B29B9/065—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion under-water, e.g. underwater pelletizers
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    • B29B9/12—Making granules characterised by structure or composition
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    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
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    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
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    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92904—Die; Nozzle zone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the invention relates to a TPU material and a preparation process thereof, in particular to a TPU alloy material and a preparation process thereof, and belongs to the technical field of polymer materials.
  • Thermoplastic polyurethane elastomer is a kind of polyurethane which can be plasticized by heating and has no or little chemical cross-linking in chemical structure. It has high strength, high modulus, good elasticity and excellent in a wide hardness range. Wear resistance and good oil resistance. Excellent performance of TPU in terms of elasticity, wear resistance, etc. can often be used to improve the performance of other materials.
  • thermoplastic polyurethane elastomer TPU
  • PP polypropylene
  • SEBS polypropylene
  • EVA ethylene-octene copolymer
  • POE ethylene-octene copolymer
  • the general method is Firstly, the TPU is synthesized, and the modified material is grafted with a compatibilizing agent, such as SEBS-g-MAH, EVA-g-MAH, POE-g-MAH, etc., and then the modified material and TPU are uniformly mixed in a high-speed mixer. Granulation was carried out by extrusion through a twin-screw extruder. Since the grafting ratio in the compatibilizer is generally low and physically compatible, a relatively large amount of compatibilizer is generally required to obtain a relatively good effect, and at the same time, the production process and equipment are required to be high.
  • a compatibilizing agent such as SEBS-g-MAH, EVA-g-MAH, POE-g-MAH, etc.
  • the invention aims at the deficiencies in the preparation process of the existing TPU modified materials, and provides a process for preparing TPU alloy materials by in-situ compatibilization.
  • a process for preparing a TPU alloy material by in-situ compatibilization characterized in that the method comprises the following steps:
  • the TPU raw material 100 parts by weight of the TPU raw material is premixed and added to the feed port of the twin-screw extruder, and 5 to 95 parts by weight of the alloy component and 0.1 to 10 parts by weight of the double active material are injected through the side feed.
  • the twin-screw extruder there is no order, 0.1-5 parts by weight of the auxiliary agent is added to the TPU raw material or the mixture of the alloy component and the double active material, wherein the alloy component is a polyolefin material
  • the alloy component is a polyolefin material
  • a reactive thermoplastic polymer material which is a substance containing both a group reactive with a TPU raw material and a group reactive with the alloy component, the auxiliary agent Including an initiator;
  • the bi-active material is a compound containing one or more of an acid anhydride group, a carboxyl group-COOH, a hydroxyl group-OH, an amino-NH or -NH 2 , an isocyanate group-NCO, and an epoxy group.
  • the double active substance is maleic anhydride, glycidyl methacrylate, acrylic acid, methyl methacrylate, butyl acrylate, acrylamide, allyl polyethylene glycol, amino acid, epoxy resin.
  • maleic anhydride glycidyl methacrylate, acrylic acid, methyl methacrylate, butyl acrylate, acrylamide, allyl polyethylene glycol, amino acid, epoxy resin.
  • the reactive thermoplastic polymer material means one of polyamide, ABS resin, TPE, and polyacrylate.
  • polyolefin material is one of SEBS, SBS, PP, PE, EVA, POE, and EPDM.
  • the TPU raw material includes a polymer polyol, a chain extender, and an isocyanate.
  • the polymer polyol is a compound of one or more of a polyester polyol, a polyether polyol, and a hydroxyl terminated polybutadiene diol, and the chain extender contains 12 or less.
  • chain extender is ethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexane.
  • Dimethanol diethylene glycol, triethylene glycol, neopentyl glycol, one a compounding of one or more of dipropylene glycol; the isocyanate is toluene diisocyanate TDI, diphenylmethane diisocyanate MDI, hexamethylene diisocyanate HDI, dicyclohexylmethane diisocyanate H12MDI, sulphur A combination of one or more of ketone diisocyanate IPDI, benzene dimethylene diisocyanate XDI.
  • the auxiliary agent further includes an antioxidant, a lubricant, and a UV-resistant auxiliary.
  • the rotational speed of the screw extruder in the step 2) is controlled to be 80-400 rpm, and the temperature in the cooling zone is controlled to be 90-110 °C.
  • a process for preparing a TPU alloy material by in-situ compatibilization includes the following steps:
  • the TPU modified material prepared in this example has a hardness of 75 A, a tensile strength of 10.2 MPa, a DIN abrasion of 55 mm 3 , and a ball rebound of 55%.
  • a process for preparing a TPU alloy material by in-situ compatibilization includes the following steps:
  • the TPU modified material prepared in this example has a hardness of 82 A, a tensile strength of 9.9 MPa, a DIN abrasion of 43 mm 3 , and a falling ball rebound of 50%.
  • a process for preparing a TPU alloy material by in-situ compatibilization includes the following steps:
  • the TPU modified material prepared in this example has a hardness of 81 A, a tensile strength of 12.9 MPa, a DIN abrasion of 66 mm 3 , and a falling ball rebound of 53.9%.
  • a process for preparing a TPU alloy material by in-situ compatibilization includes the following steps:
  • the TPU modified material prepared in this example has a hardness of 79 A, a tensile strength of 7.6 MPa, a DIN abrasion of 44.2 mm 3 , and a ball rebound rebound of 59.1%.
  • a process for preparing a TPU alloy material by in-situ compatibilization includes the following steps:
  • the TPU modified material prepared in this example has a hardness of 73 A, a tensile strength of 13.4 MPa, a DIN abrasion of 56.1 mm 3 , and a ball rebound rebound of 53.1%.
  • a process for preparing a TPU alloy material by in-situ compatibilization includes the following steps:
  • the TPU modified material prepared in this example has a hardness of 78 A, a tensile strength of 13.4 MPa, a DIN abrasion of 56.1 mm 3 , and a ball rebound rebound of 52.9%.
  • a process for preparing a TPU alloy material by in-situ compatibilization includes the following steps:
  • the TPU modified material prepared in this example has a hardness of 78 A, a tensile strength of 13.4 MPa, a DIN abrasion of 56.1 mm 3 , and a ball rebound rebound of 52.9%.
  • a process for preparing a TPU alloy material by in-situ compatibilization includes the following steps:
  • the TPU modified material prepared in this example has a hardness of 82 A, a tensile strength of 13.3 MPa, a DIN abrasion of 56.1 mm 3 , and a falling ball rebound of 53.5%.
  • Example 3 The TPU alloy material obtained in Example 3 was applied to EVA foaming to obtain an EVA foamed material, and the results were as shown in Table 1 as compared with the EVA foamed material obtained by separately using TPU and EVA-g-MAH. Show.
  • Table 1 Performance test data of materials obtained by the process of the present invention and materials obtained by conventional processes
  • the EVA foamed material obtained by the TPU material of the present invention can be increased by 2.3 MPa in tensile strength, the tear strength can be increased by 3 KN/m, the rebound rebound can be increased by 5.6%, and compression set is obtained. It can be reduced by 6.9%. From this data, it can be seen that the process of this patent has obvious advantages in improving the performance of the final product compared with the conventional process.

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Abstract

本发明涉及一种原位增容制备TPU合金材料的工艺，在制备过程中通过引入双活性物质，实现了TPU材料与其它材料如聚烯烃、TPE或聚酰胺的化学键连接，提高了材料间的相容性，制备的合金材料既具有TPU材料优良的力学性能、耐磨性能、耐化学性能、耐高低温性能、易加工性能等各方面的性能，同时也提高了与其它材料的结合性能，扩大了TPU的应用范围。

Description

一种原位增容制备TPU合金材料的工艺 技术领域
本发明涉及一种TPU材料及其制备工艺，尤其涉及一种TPU合金材料及其制备工艺，属于高分子材料技术领域。
背景技术
热塑性聚氨酯弹性体(TPU)是一类加热可以塑化，化学结构上没有或很少有化学交联的聚氨酯，在宽广的硬度范围内具有高强度、高模量、较好的弹性、优良的耐磨性和良好的耐油性。由于TPU在弹性、耐磨性等方面的优异表现通常可以用于改善其它材料的性能。
但热塑性聚氨酯弹性体(TPU)与聚丙烯(PP)、SEBS、EVA、乙烯-辛烯共聚物(POE)等进行改性时存在相容性差的问题，需要使用相容剂，一般的方法是先合成TPU，将改性材料接枝上相容剂，如SEBS-g-MAH，EVA-g-MAH，POE-g-MAH等，然后将改性材料、TPU在高速混合机中混合均匀后通过双螺杆挤出机挤出后进行造粒。由于相容剂中接枝率一般很低，且为物理相容，一般需要较大量的相容剂才能取得比较好的效果，同时对生产工艺和设备要求较高。
发明内容
本发明针对现有TPU改性材料的制备工艺存在的不足，提供一种原位增容制备TPU合金材料的工艺。
本发明解决上述技术问题的技术方案如下：
一种原位增容制备TPU合金材料的工艺，其特征在于，包括如下步骤：
1)将100重量份的TPU原料经预混后加入到双螺杆挤出机的进料口，将5-95重量份的合金组分和0.1-10重量份的双活性物质通过侧喂料注入到双螺杆挤出机中，二者无先后顺序，0.1-5重量份的助剂加入到TPU原料中或合金组分与双活性物质的混合物中，其中，所述合金组分为聚烯烃材料、具有反应活性的热塑性高分子材料中的一种，所述双活性物质为既含有能与TPU原料反应的基团又含有能与所述合金组分反应的基团的物质，所述助剂包括引发剂；
2)控制双螺杆挤出机的反应区温度为50-250℃，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，所述的双活性物质为含有酸酐基团、羧基-COOH、羟基-OH、氨基-NH或-NH2、异氰酸酯基-NCO、环氧基团中的一种或多种的化合物。
进一步，所述的双活性物质为马来酸酐、甲基丙烯酸缩水甘油酯、丙烯酸、甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸酰胺、烯丙基聚乙二醇、氨基酸、环氧树脂中的一种。
进一步，所述具有反应活性的热塑性高分子材料是指聚酰胺、ABS树脂、TPE、聚丙烯酸酯中的一种。
进一步，所述的聚烯烃材料为SEBS、SBS、PP、PE、EVA、POE、EPDM中的一种。
进一步，所述的TPU原料包括聚合物多元醇、扩链剂和异氰酸酯。
进一步，所述的聚合物多元醇为聚酯多元醇、聚醚多元醇、端羟基聚丁二烯二醇中的一种或多种的复配，所述的扩链剂为含12个以下碳原子的小分子二元醇或二元胺类。
进一步，所述的扩链剂为乙二醇、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 缩二丙二醇中的一种或多种的复配；所述的异氰酸酯为甲苯二异氰酸酯TDI、二苯基甲烷二异氰酸酯MDI、六亚甲基二异氰酸酯HDI、二环己基甲烷二异氰酸酯H12MDI、异弗尔酮二异氰酸酯IPDI、苯二亚甲基二异氰酸酯XDI中的一种或多种的复配。
进一步，所述的助剂还包括抗氧剂、润滑剂和耐UV助剂。
进一步，步骤2)中所述螺杆挤出机的转速控制为80-400rpm，降温区温度控制为90-110℃。
本发明的有益效果是：
1)TPU与合金材料之间通过双活性物质的化学键连接，从根本上解决了TPU与合金材料的相容性问题，使得产品既具有TPU优良的力学性能、耐磨性能、耐化学性能、耐高低温性能、易加工性能等各方面的性能，也能提高与其他材料的结合性能，并能够提高最终制品的性能。
2)TPU的合成、双活性组分的原位增容过程、TPU与合金材料的混合过程，均在双螺杆反应挤出过程中一步实现，简化了生产工艺流程。
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：
一种原位增容制备TPU合金材料的工艺，包括如下步骤：
1)将分子量为2000g/mol的聚酯多元醇68份、BDO 6份、二苯基甲烷二异氰酸酯MDI 26份置于反应釜内预混合，后加入到双螺杆挤出机的进料口，将95份SEBS(岳阳石化的YH-503T)、MAH(马来酸酐)10份和引发剂DCP(过氧化二异丙苯)0.1份通过侧喂料注入到双螺杆挤出机中；
2)控制双螺杆挤出机的反应区温度为140-200℃，降温区温度为90-110℃， 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。
本实施例所制备的TPU改性材料，其硬度为75A，拉伸强度为10.2MPa，DIN磨耗为55mm3，落球回弹为55％。
实施例2：
一种原位增容制备TPU合金材料的工艺，包括如下步骤：
1)将0.3份的Irganox 1010、0.2份的Irganox 1076、0.5份的Tinuvin B900、0.3份的E蜡、0.2份的油酸酰胺加入到分子量为1500g/mol的聚酯多元醇55份、BDO 7份、二苯基甲烷二异氰酸酯MDI 38份置于反应釜内预混合，后加入到双螺杆挤出机的进料口，将75份SEBS(科腾的G1650)、MAH(马来酸酐)5份和引发剂DCP(过氧化二异丙苯)0.2份通过侧喂料注入到双螺杆挤出机中；
2)控制双螺杆挤出机的反应区温度为50-250℃，降温区温度为90-110℃，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。
本实施例所制备的TPU改性材料，其硬度为82A，拉伸强度为9.9MPa，DIN磨耗为43mm3，落球回弹为50％。
实施例3：
一种原位增容制备TPU合金材料的工艺，包括如下步骤：
1)将0.3份的Irganox 1010、0.1份的Irganox 1076、0.7份的Tinuvin B900、0.2份的硬脂酸酰胺、0.4份的EBS加入到70重量份的分子量为1800g/mol的聚醚多元醇中，后与BDO 5份、甲苯二异氰酸酯TDI 25份置于反应釜内预混合，后加入到双螺杆挤出机的进料口，将65份EVA(三井化学的Evaflex 150Y)、丙烯酸0.1份和引发剂DCP(过氧化二异丙苯)0.1份通过侧喂料注入到双螺杆挤出机中；
2)控制双螺杆挤出机的反应区温度为140-180℃，降温区温度为90-110℃，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。
本实施例所制备的TPU改性材料，其硬度为81A，拉伸强度为12.9MPa，DIN磨耗为66mm3，落球回弹为53.9％。
实施例4：
一种原位增容制备TPU合金材料的工艺，包括如下步骤：
1)将0.35份的Irganox 1010、0.2份的Irganox 1098、0.2份的Tinuvin 770、0.4份的
Figure PCTCN2017074659-appb-000001
 0.4份的油酸酰胺、0.1份的硬脂酸酰胺加入到45重量份的分子量为1000g/mol的聚醚多元醇中，后与BDO 8份、甲苯二异氰酸酯TDI 47份置于反应釜内预混合，后加入到双螺杆挤出机的进料口，将34份POE(Dow化学的8130)、丙烯酸酰胺0.5份和引发剂DCP(过氧化二异丙苯)0.15份通过侧喂料注入到双螺杆挤出机中；
2)控制双螺杆挤出机的反应区温度为140-170℃，降温区温度为90-110℃，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。
本实施例所制备的TPU改性材料，其硬度为79A，拉伸强度为7.6MPa，DIN磨耗为44.2mm3，落球回弹为59.1％。
实施例5：
一种原位增容制备TPU合金材料的工艺，包括如下步骤：
1)将0.35份的Irganox 1010、0.2份的Irganox 1098、0.3份的Tinuvin 770、0.2份的
Figure PCTCN2017074659-appb-000002
 0.4份的油酸酰胺、0.1份的硬脂酸酰胺加入到45重量份的分子量为1800g/mol的聚醚多元醇中，后与BDO 8份、六亚甲基二异氰酸酯HDI 47份置于反应釜内预混合，后加入到双螺杆挤出机的进料口，将45份POE(Dow化学的8130)、丙烯酸酰胺1.5份和引发剂 DCP(过氧化二异丙苯)0.25份通过侧喂料注入到双螺杆挤出机中；
2)控制双螺杆挤出机的反应区温度为140-170℃，降温区温度为90-110℃，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。
本实施例所制备的TPU改性材料，其硬度为73A，拉伸强度为13.4MPa，DIN磨耗为56.1mm3，落球回弹为53.1％。
实施例6：
一种原位增容制备TPU合金材料的工艺，包括如下步骤：
1)将0.55份的Irganox 1010、0.2份的Irganox 1098、0.25份的Tinuvin 770、0.5份的
Figure PCTCN2017074659-appb-000003
 0.4份的油酸酰胺、0.1份的硬脂酸酰胺加入到45重量份的分子量为1800g/mol的聚醚多元醇中，后与BDO 8份、六亚甲基二异氰酸酯HDI 47份置于反应釜内预混合，后加入到双螺杆挤出机的进料口，将5份聚酰胺、甲基丙烯酸甲酯0.1份和引发剂DCP(过氧化二异丙苯)1份通过侧喂料注入到双螺杆挤出机中；
2)控制双螺杆挤出机的反应区温度为140-170℃，降温区温度为90-110℃，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。
本实施例所制备的TPU改性材料，其硬度为78A，拉伸强度为13.4MPa，DIN磨耗为56.1mm3，落球回弹为52.9％。
实施例7：
一种原位增容制备TPU合金材料的工艺，包括如下步骤：
1)将0.55份的Irganox 1010、0.2份的Irganox 1098、0.25份的Tinuvin 770、0.5份的
Figure PCTCN2017074659-appb-000004
 0.4份的油酸酰胺、0.1份的硬脂酸酰胺加入到45重量份的分子量为1800g/mol的聚醚多元醇中，后与BDO 8份、六亚甲基二异氰酸酯HDI 47份置于反应釜内预混合，后加入到双螺杆挤出 机的进料口，将75份ABS树脂、丙烯酸丁酯6份和引发剂DCP(过氧化二异丙苯)1份通过侧喂料注入到双螺杆挤出机中；
2)控制双螺杆挤出机的反应区温度为140-170℃，降温区温度为90-110℃，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。
本实施例所制备的TPU改性材料，其硬度为78A，拉伸强度为13.4MPa，DIN磨耗为56.1mm3，落球回弹为52.9％。
实施例8：
一种原位增容制备TPU合金材料的工艺，包括如下步骤：
1)将0.55份的Irganox 1010、0.2份的Irganox 1098、0.25份的Tinuvin 770、0.5份的
Figure PCTCN2017074659-appb-000005
 0.4份的油酸酰胺、0.1份的硬脂酸酰胺加入到45重量份的分子量为1800g/mol的聚醚多元醇中，后与BDO 8份、六亚甲基二异氰酸酯HDI 47份置于反应釜内预混合，后加入到双螺杆挤出机的进料口，将25份TPE、环氧树脂2份和引发剂DCP(过氧化二异丙苯)0.8份通过侧喂料注入到双螺杆挤出机中；
2)控制双螺杆挤出机的反应区温度为140-170℃，降温区温度为90-110℃，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。
本实施例所制备的TPU改性材料，其硬度为82A，拉伸强度为13.3MPa，DIN磨耗为56.1mm3，落球回弹为53.5％。
将实施例3中所得到的TPU合金材料应用于EVA发泡中制得EVA发泡材料，与单独将TPU和EVA-g-MAH制得的EVA发泡材料相比，其结果如表1所示。
表1：本发明工艺所得材料与传统工艺制得材料的性能测试数据
  单位 实施例3 传统工艺
拉伸强度 MPa 8.4 6.1
撕裂强度 KN/m 13.2 10.2
落球回弹 ％ 69.2 63.6
压缩永久变形 ％ 26.3 33.2
由表1中数据可以看出，本发明的TPU材料得到的EVA发泡材料在拉伸强度上可以提高2.3MPa，撕裂强度可以提高3KN/m,落球回弹可以提高5.6％，压缩永久变形可以降低6.9％，由此数据可以看出本专利的工艺与传统工艺相比在提升最终制品性能方面具有比较明显的优势。
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. 一种原位增容制备TPU合金材料的工艺，其特征在于，包括如下步骤：
    1)将100重量份的TPU原料经预混后加入到双螺杆挤出机的进料口，将5-95重量份的合金组分和0.1-10重量份的双活性物质通过侧喂料注入到双螺杆挤出机中，二者无先后顺序，0.1-5重量份的助剂加入到TPU原料中或合金组分与双活性物质的混合物中，其中，所述合金组分为聚烯烃材料、具有反应活性的热塑性高分子材料中的一种，所述双活性物质为既含有能与TPU原料反应的基团又含有能与所述合金组分反应的基团的物质，所述助剂包括引发剂；
    2)控制双螺杆挤出机的反应区温度为50-250℃，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。
  2. 根据权利要求1所述的工艺，其特征在于，所述的双活性物质为含有酸酐基团、羧基-COOH、羟基-OH、氨基-NH或-NH2、异氰酸酯基-NCO、环氧基团中的一种或多种的化合物。
  3. 根据权利要求2所述的工艺，其特征在于，所述的双活性物质为马来酸酐、甲基丙烯酸缩水甘油酯、丙烯酸、甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸酰胺、烯丙基聚乙二醇、氨基酸、环氧树脂中的一种。
  4. 根据权利要求1所述的工艺，其特征在于，所述具有反应活性的热塑性高分子材料是指聚酰胺、ABS树脂、TPE、聚丙烯酸酯中的一种。
  5. 根据权利要求1所述的工艺，其特征在于，所述的聚烯烃材料为SEBS、SBS、PP、PE、EVA、POE、EPDM中的一种。
  6. 根据权利要求1所述的工艺，其特征在于，所述的TPU原料包括聚 合物多元醇、扩链剂和异氰酸酯。
  7. 根据权利要求6所述的工艺，其特征在于，所述的聚合物多元醇为聚酯多元醇、聚醚多元醇、端羟基聚丁二烯二醇中的一种或多种的复配，所述的扩链剂为含12个以下碳原子的小分子二元醇或二元胺类。
  8. 根据权利要求6或7所述的工艺，其特征在于，所述的扩链剂为乙二醇、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、一缩二丙二醇中的一种或多种的复配；所述的异氰酸酯为甲苯二异氰酸酯TDI、二苯基甲烷二异氰酸酯MDI、六亚甲基二异氰酸酯HDI、二环己基甲烷二异氰酸酯H12MDI、异弗尔酮二异氰酸酯IPDI、苯二亚甲基二异氰酸酯XDI中的一种或多种的复配。
  9. 根据权利要求1所述的工艺，其特征在于，所述的助剂还包括抗氧剂、润滑剂和耐UV助剂。
  10. 根据权利要求1所述的工艺，其特征在于，步骤2)中所述螺杆挤出机的转速控制为80-400rpm，降温区温度控制为90-110℃。
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