WO2018214208A1 - Composition for foaming material with high rebound resilience and preparation method therefor - Google Patents

Composition for foaming material with high rebound resilience and preparation method therefor Download PDF

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Publication number
WO2018214208A1
WO2018214208A1 PCT/CN2017/089278 CN2017089278W WO2018214208A1 WO 2018214208 A1 WO2018214208 A1 WO 2018214208A1 CN 2017089278 W CN2017089278 W CN 2017089278W WO 2018214208 A1 WO2018214208 A1 WO 2018214208A1
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WIPO (PCT)
Prior art keywords
foaming
composition
parts
foamed
mixture
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PCT/CN2017/089278
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French (fr)
Chinese (zh)
Inventor
王光阜
战振生
张生
王仁鸿
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美瑞新材料股份有限公司
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Publication of WO2018214208A1 publication Critical patent/WO2018214208A1/en

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Definitions

  • the invention relates to a composition for a high resilience foaming material and a preparation method thereof, and belongs to the field of lightweight materials.
  • Olefin polymer foam materials such as EVA, SEBS, POE, etc.
  • EVA, SEBS, POE, etc. have good flexibility, rubber-like elasticity, and can have good flexibility, chemical stability, anti-aging and resistance at temperatures below 0 °C.
  • Ozone is good in strength and is widely used in foaming shoe materials, luggage linings, toy materials, sporting goods materials, building materials, and various emerging applications including electronic components and automotive interiors.
  • the high expansion ratio olefin polymer foamed material has poor resilience, large permanent deformation, severe deterioration of mechanical properties, and poor wear resistance, which greatly reduces the performance of the product and seriously affects its application range. Therefore, the development of an olefin polymer/TPU composition foaming material having high resilience and maintaining excellent properties has been pursued by many universities and enterprises.
  • the present invention provides a composition for a foamed material having high resilience and a method for producing the same, in view of the deficiencies of the existing high expansion ratio olefin polymer.
  • a composition for foaming materials having high resilience comprising parts by weight, as follows:
  • the olefin-based polymer refers to a polymer obtained by homopolymerization or copolymerization of an olefin monomer having a carbon-carbon double bond, and has a glass transition temperature of less than 0 ° C, and is heated at 20 K/min according to DSC.
  • the olefin monomer structure is shown in the figure below:
  • R 1 , R 2 , R 3 , R 4 are any known chemical group or segment structure.
  • the olefin polymer refers to an ethylene-vinyl acetate copolymer, a styrene-ethylene-butadiene-styrene block copolymer, an ethylene-propylene binary or multicomponent copolymer, and an ethylene-octene copolymer.
  • One or more mixtures preferably ethylene-vinyl acetate copolymer, styrene-ethylene-butadiene-styrene block copolymer, most preferably ethylene-vinyl acetate copolymer, when ethylene-vinyl acetate is selected
  • EVA copolymer
  • EVA copolymer having a VA content of 15% or more is preferable.
  • thermoplastic polyurethane elastomer refers to a mixture of one or more of a polyester type, a polyether type, a polycarbonate type, a polycaprolactone type, and a polyester ether type thermoplastic polyurethane elastomer, and the hardness thereof Is Shore A 50-Shore D 80, preferably Shore A 50-Shore A 90, most preferably Shore A 60-Shore A 85; melting point 80-200 ° C, preferably 80-190 ° C, most preferably 100-180 ° C; vitrification
  • the transition temperature is below 0 ° C, preferably below 20 ° C under zero, as measured by DSC at 20 K/min ramp.
  • the compatibilizing agent is selected from one or more of two types of substances having the following structure;
  • A a substance containing both a polar group and a non-polar segment
  • the polar group is preferably a hydroxyl group -OH, an amino group -NH 2 or -NH-, a urethane group -NHCO0-, an amide group -NHCO- One or more of a ureido-NHCONH-, a carboxyl-COOH, an acid anhydride-COOCO-, an epoxy group, an isocyanate group
  • the non-polar segment means a fatty chain having a carbon number of 2 or more or a large
  • the compatibilizer refers to EVA grafted maleic anhydride, SEBS grafted maleic anhydride, POE grafted maleic anhydride, higher fatty alcohol, higher fatty acid, ring One or more of an oxidized polyolefin resin, a hydroxylated resin, a carboxylated resin, and an aminated resin.
  • the compatibilizing agent is
  • the compatibilizing agent is preferably Is maleic anhydride, glycidyl methacrylate, acrylic acid, methyl methacrylate, butyl acrylate, acrylamide, hydroxyethyl acrylate, hydroxypropyl acrylate, methacrylic acid, hydroxyethyl methacrylate, methyl One or more of hydroxypropyl acrylate, divinyl benzene, N-methylol acrylamide, diacetone acrylamide, allyl poly
  • the foaming agent refers to a mixture of one or more of an exothermic foaming agent, an endothermic foaming agent, and foamed microspheres.
  • the foaming agent refers to azo two. Formamide, azobisisobutyronitrile, cesium azodicarboxylate, 4,4'-oxobisbenzenesulfonyl hydrazide, p-toluenesulfonylhydrazide, sodium hydrogencarbonate, sodium citrate, ammonium hydrogencarbonate, expandable micro a mixture of one or more of the balls.
  • the crosslinking agent is one of a peroxide or an azo compound
  • the co-crosslinking agent is a compound containing two or more carbon-carbon double bonds, and preferably, the co-crosslinking agent is butyl.
  • the other auxiliary agent refers to a mixture of one or more of an anti-UV agent, an antioxidant, and a cell stabilizer.
  • the base material can be prepared by any of the following methods:
  • a part of the olefin polymer, a part of the compatibilizer and some other auxiliary agents are fed into the extruder according to the ratio side by the side feeding method, and after extrusion granulation Obtaining a primary base material; and then granulating the primary base material with the remaining part of the olefin polymer, the compatibilizer, and other auxiliary agents by using one or more of an extruder or a training or compacting form. , obtaining a base material;
  • TPU Production of TPU according to a one-step or two-step process well known in the art, and then using TPU with all olefin polymers, compatibilizers, and other auxiliaries in an extruder or in a form of training or compacting. One or several combinations of processed granulation to obtain a base;
  • the TPU is produced according to a one-step or two-step process well known in the art, and then the TPU and a part of the olefin polymer, a part of the compatibilizer, and some other auxiliary agents are extruded and granulated by an extruder to obtain a primary group. Then, the primary base material and the remaining part of the olefin polymer, the compatibilizer, and other auxiliary agents are processed by one or more of an extruder or a form of grinding or compacting, and then granulated to obtain a base. material;
  • the base material is uniformly mixed with the foaming agent, the crosslinking agent and the auxiliary crosslinking agent, and a high resilience foaming product is obtained by using one of the following production processes:
  • A The mixture is placed in a product mold, the product mold is placed in a flat vulcanizer, and the foam is molded at 100-200 ° C for 1-60 minutes, and then the mold is cooled to 5-60 ° C to obtain a high rebound.
  • the invention utilizes a compatibilizing agent containing a polar group or a double reactive group to compatibilize, reduce the interfacial tension between the olefin polymer and the TPU, and form an olefin polymer/TPU interpenetrating network structure (IPN) to solve
  • IPN interpenetrating network structure
  • a composition for foaming materials having high resilience comprising parts by weight, as follows:
  • the foamed article was prepared as follows:
  • Base preparation In the process of producing TPU by a one-step method well known in the art, EVA-1, EVA-2, EVA grafted maleic anhydride was added to the extruder through a side feed screw to control the extrusion screw. The temperature is 100-190 ° C, the temperature of the die is controlled to 150 ° C, and the base material is obtained by extrusion granulation;
  • step 2) Preparation of high resilience foaming material: the base material obtained in step 1), 0.1 part azodicarbonamide, 0.01 part DCP is uniformly mixed by high mixing machine and put into the product mold, and the temperature of the flat vulcanizing machine is 100 ° C. The foam was molded for 1 minute, and then the mold was cooled to 5 ° C to obtain a final high resilience foamed article material.
  • a composition for foaming materials having high resilience comprising parts by weight, as follows:
  • the foamed article was prepared as follows:
  • Base preparation In the process of producing TPU by a one-step method well known in the art, EVA-1, EVA-2, EVA grafted maleic anhydride was added to the extruder through a side feed screw to control the extrusion screw. The temperature is 100-190 ° C, the temperature of the die is controlled to 150 ° C, and the base material is obtained by extrusion granulation;
  • step 2) Preparation of high resilience foaming material: the base material obtained in step 1), 1 part azodicarbonamide, 0.05 part DCP are uniformly mixed by high mixing machine and put into the product mold, and the temperature of the flat vulcanizing machine is 100 ° C. The foam was molded for 1 minute, and then the mold was cooled to 5 ° C to obtain a final high resilience foamed article material.
  • a composition for foaming materials having high resilience comprising parts by weight, as follows:
  • the foamed article was prepared as follows:
  • TPU particles are produced by a one-step method well known in the art, and TPU particles and EVA-1, EVA grafted maleic anhydride are mixed in a high-mixer and then added to a twin-screw extruder to control extrusion.
  • the temperature of the screw is 100-190 ° C, the temperature of the die is controlled to 150 ° C, and the base material 1 is obtained by extrusion granulation; the base material 1 and EVA-2 are mixed by a high mixer and then added to a twin screw or an internal mixer. Medium, after uniform mixing, extrusion granulation, to obtain the final base 2;
  • base material 2 1.5 parts of azodicarbonamide prepared in step 1), 0.1 part of DCP are uniformly mixed by high-mixer, and then put into a product mold, and the temperature of the flat vulcanizing machine is 100. °C, molded and foamed for 1 minute, and then the mold was cooled to 5 ° C to obtain a final high resilience foamed article material.
  • a composition for foaming materials having high resilience comprising parts by weight, as follows:
  • the foamed article was prepared as follows:
  • the die temperature is controlled to 150 ° C, extrusion granulation to obtain a primary base, wherein the amount of TPU added is 95 parts by weight, the amount of SEBS added is 3 parts by weight, and the amount of SEBS grafted maleic anhydride is 20 parts by weight, the anti-UV agent is added in an amount of 1 part by weight; then the primary base and 2 parts by weight of SEBS, 25 parts by weight of SEBS grafted maleic anhydride, 1 part by weight of antioxidant After processing by an open mill, granulation is carried out to obtain a base material.
  • step 2) Preparation of high resilience foaming material: the base material prepared in step 1), 10 parts by weight of sodium hydrogencarbonate, 5 parts of BPO, 0.2 parts by weight of the cross-linking agent TAIC are uniformly mixed by a high-mixer and then put into EVA injection molding. In the foaming equipment, the injection temperature is 150-220 ° C, and the final high-rebound foaming material is obtained.
  • Example 4 product Market SEBS foam products density ASTM-D792 g/cm 3 0.18 0.25 hardness GB/T10807-2006 Shore 45 45 Tensile Strength ISO1798-2008 MPa 7.5 1.2 Elongation at break ISO1798-2008 % 580 330 Tear strength GB/T10808-2006 N/mm 12.4 5.2 Falling ball back elasticity ISO8307 % 58 52 Compression set GB/T6669-2008 % 18 35 Wear resistance DIN53516 Mm 3 380 500
  • a composition for foaming materials having high resilience comprising parts by weight, as follows:
  • the foamed article was prepared as follows:
  • Base preparation a polycarbonate type TPU elastomer is produced by a one-step method well known in the art, and then 75 parts by weight of polycarbonate type TPU particles, 50 parts by weight of POE, and 0.5 part by weight of maleic anhydride are put into an extruder. Performing granulation, controlling the temperature of the extrusion screw to be 150-220 ° C, and controlling the temperature of the die to 200 ° C to obtain a base material;
  • step 2) Preparation of high-rebound foaming material: the base material prepared in step 1), 3 parts by weight of expandable microspheres, uniformly mixed by a high-mixer, and then put into an extruder, and the screw temperature of the extruder is set to 150- At 220 ° C, the die temperature was set at 180 ° C, and a high resilience foamed product was obtained by extrusion.
  • a composition for foaming materials having high resilience comprising parts by weight, as follows:
  • the foamed article was prepared as follows:
  • TPU elastomer is produced by a two-step method well known in the art, and then TPU, ethylene-propylene binary copolymer, epoxidized polyolefin resin, anti-UV agent Antioxidants Adding to the twin-screw extruder, controlling the screw temperature of the extruder to be 150-220 ° C, the die temperature is 220 ° C, and extruding and granulating to obtain a base material;
  • step 2) Preparation of high-rebound foaming material: the base material prepared in step 1), 10 parts by weight of azobisisobutyronitrile, and 2 parts of DTBP are uniformly mixed by high-mixer and put into EVA injection foaming equipment, and the injection temperature is The final high resilience foamed article material is obtained at 100-150 °C.
  • a composition for foaming materials having high resilience comprising parts by weight, as follows:
  • the foamed article was prepared as follows:
  • Base preparation In the process of producing TPU by a one-step method well known in the art, EVA-1, EVA-2, maleic anhydride is added to the extruder through a side feed screw to control the temperature of the extruder. The temperature is 100-200 ° C, the die temperature is 160 ° C, and the base material is obtained by extrusion granulation;
  • step 2) Preparation of high resilience foaming material: the base prepared in step 1), 5 parts of azobisisobutyronitrile, 3 parts of BPO, 2 parts by weight of triallyl cyanurate are mixed by high mixing machine After evenly, it was put into a product mold, the plate vulcanizer was heated at 150 ° C, molded and foamed for 20 minutes, and then the mold was cooled to 5 ° C to obtain a final high resilience foamed product material.
  • a composition for foaming materials having high resilience comprising parts by weight, as follows:
  • the foamed article was prepared as follows:
  • step 2) Preparation of high resilience foaming material: base 1 and base 2 obtained in step 1), 3 parts azobisisobutyronitrile, 3 parts BPO, 2 parts by weight of triallyl cyanurate After mixing by a high-mixer, it was put into a product mold, the plate vulcanizer was heated at 150 ° C, molded and foamed for 20 minutes, and then the mold was cooled to 5 ° C to obtain a final high-rebound foamed product material.
  • a composition for foaming materials having high resilience comprising parts by weight, as follows:
  • the foamed article was prepared as follows:
  • Base preparation SEBS, hydroxyethyl acrylate, anti-UV agent is produced by a side feed screw during the production of TPU by a one-step method well known in the art. Antioxidants It was added to an extruder, the screw temperature of the extruder was controlled to 160-220 ° C, the die temperature was controlled to 200 ° C, and the base material was obtained by extrusion granulation.
  • a composition for foaming materials having high resilience comprising parts by weight, as follows:
  • Base preparation a polycarbonate type TPU elastomer is produced by a two-step process well known in the art, and then TPU, ethylene-octene binary copolymer, N-methylol acrylamide is added to the twin-screw extruder.
  • the screw temperature is controlled to be 100-160 ° C
  • the die temperature is controlled to 150 ° C
  • the base material is obtained by extrusion granulation;
  • step 2) Preparation of high resilience foaming material: the base material prepared in step 1), 0.1 part by weight of expandable microspheres, 0.01 part of dicumyl peroxide DCP, and 5 parts of divinylbenzene are uniformly mixed by a high mixer. It is put into the EVA injection foaming equipment, and the injection temperature is 100-150 ° C to obtain the final high rebound foaming material.
  • a composition for foaming materials having high resilience comprising parts by weight, as follows:
  • the foamed article was prepared as follows:
  • Base preparation a polycaprolactone type TPU elastomer is produced by a two-step method well known in the art, and then TPU, ethylene-propylene terpolymer, SEBS grafted maleic anhydride, anti-UV agent Antioxidants Adding to the twin-screw extruder, the screw temperature of the extruder is controlled to be 100-160 ° C, the temperature of the die is controlled to 150 ° C, and the base material is obtained by extrusion granulation;
  • step 2) Preparation of high-rebound foaming material: the base material prepared in step 1), 2 parts by weight of azobisisobutyronitrile, and 3 parts of BPO are uniformly mixed by a high-mixer and then put into an extruder, and the extruder screw The temperature was set to 150-220 ° C, the die temperature was set to 180 ° C, and a high resilience foamed product was obtained by extrusion.

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Abstract

A composition for a foaming material with high rebound resilience and a preparation method therefor. The composition comprises the following components in parts by weight: 5-95 parts of olefin polymer, 5-95 parts of thermoplastic polyurethane (TPU) elastomer, 0.1-45 parts of compatibilizer, 0.1-10 parts of foaming agent, 0.01-5 parts of crosslinking agent, 0-5 parts of crosslinking additive, and 0-10 parts of other additive. Using of the compatibilizer having a polar group or a double active group yields a compatibilization effect, such that an interfacial tension between the olefin polymer and TPU is reduced, an olefin polymer/TPU interpenetrating polymer network (IPN) structure is formed, and thus the problem of compatibility between two types of materials is solved; by means of successful introduction of the TPU component into the olefin polymer, properties of a foaming olefin polymer material, such as rebound resilience and compression permanent deformation, are greatly improved by virtue of the excellent resilience of TPU.

Description

一种具有高回弹性的发泡材料用组合物及其制备方法Composition for foaming material with high resilience and preparation method thereof 技术领域Technical field
本发明涉及一种高回弹发泡材料用组合物及其制备方法，属于轻量化材料领域。The invention relates to a composition for a high resilience foaming material and a preparation method thereof, and belongs to the field of lightweight materials.
背景技术Background technique
烯烃类聚合物发泡材料(如EVA，SEBS，POE等)具有良好的柔软性，橡胶般的弹性，在0℃以下仍能够具有较好的可挠性，化学稳定性良好，抗老化和耐臭氧强度好，被广泛应用于发泡鞋材，箱包内衬，玩具用材，体育用品材料，建材，以及各类新兴应用包括电子配件和汽车内饰等。Olefin polymer foam materials (such as EVA, SEBS, POE, etc.) have good flexibility, rubber-like elasticity, and can have good flexibility, chemical stability, anti-aging and resistance at temperatures below 0 °C. Ozone is good in strength and is widely used in foaming shoe materials, luggage linings, toy materials, sporting goods materials, building materials, and various emerging applications including electronic components and automotive interiors.
但是高发泡倍率烯烃类聚合物发泡材料回弹性较差，永久变形大，力学性能下降严重，且存在耐磨性差等问题，大大降低其使用性能，严重影响其应用范围。因而，开发一种具有高回弹性，并可保持优异性能的烯烃类聚合物/TPU组合物发泡材料成为许多高校和企业所追求的目标。However, the high expansion ratio olefin polymer foamed material has poor resilience, large permanent deformation, severe deterioration of mechanical properties, and poor wear resistance, which greatly reduces the performance of the product and seriously affects its application range. Therefore, the development of an olefin polymer/TPU composition foaming material having high resilience and maintaining excellent properties has been pursued by many universities and enterprises.
发明内容Summary of the invention
本发明针对现有高发泡倍率的烯烃类聚合物存在的不足，提供一种具有高回弹性的发泡材料用组合物及其制备方法。The present invention provides a composition for a foamed material having high resilience and a method for producing the same, in view of the deficiencies of the existing high expansion ratio olefin polymer.
本发明解决上述技术问题的技术方案如下：The technical solution of the present invention to solve the above technical problems is as follows:
一种具有高回弹性的发泡材料用组合物，按重量份计，包括如下组份：A composition for foaming materials having high resilience, comprising parts by weight, as follows:
Figure PCTCN2017089278-appb-000001
Figure PCTCN2017089278-appb-000001
Figure PCTCN2017089278-appb-000002
Figure PCTCN2017089278-appb-000002
进一步，所述烯烃类聚合物是指由含碳碳双键的烯烃单体经由均聚或共聚反应得到的聚合物，并且其玻璃化转变温度低于0℃，按照DSC在20K/min升温法测得，这些烯烃单体结构如下图所示：Further, the olefin-based polymer refers to a polymer obtained by homopolymerization or copolymerization of an olefin monomer having a carbon-carbon double bond, and has a glass transition temperature of less than 0 ° C, and is heated at 20 K/min according to DSC. The olefin monomer structure is shown in the figure below:
Figure PCTCN2017089278-appb-000003
Figure PCTCN2017089278-appb-000003
其中R1、R2、R3、R4为任一已知的化学基团或链段结构。Wherein R 1 , R 2 , R 3 , R 4 are any known chemical group or segment structure.
进一步，所述烯烃类聚合物是指乙烯-醋酸乙烯共聚物、苯乙烯-乙烯-丁二烯-苯乙烯嵌段共聚物、乙烯-丙烯二元或多元共聚物、乙烯-辛烯共聚物中的一种或几种的混合物，优选方案为乙烯-醋酸乙烯共聚物、苯乙烯-乙烯-丁二烯-苯乙烯嵌段共聚物，最优选乙烯-醋酸乙烯共聚物，当选用乙烯-醋酸乙烯共聚物(EVA)时，则优选VA含量在15％以上的EVA，当选用不同VA含量的EVA混合物时，优选其中含有VA含量大于25％的EVA聚合物，并且此EVA占EVA混合物总量的5％以上。Further, the olefin polymer refers to an ethylene-vinyl acetate copolymer, a styrene-ethylene-butadiene-styrene block copolymer, an ethylene-propylene binary or multicomponent copolymer, and an ethylene-octene copolymer. One or more mixtures, preferably ethylene-vinyl acetate copolymer, styrene-ethylene-butadiene-styrene block copolymer, most preferably ethylene-vinyl acetate copolymer, when ethylene-vinyl acetate is selected In the case of copolymer (EVA), EVA having a VA content of 15% or more is preferable. When an EVA mixture having a different VA content is selected, it is preferable to contain an EVA polymer having a VA content of more than 25%, and this EVA accounts for the total amount of the EVA mixture. More than 5%.
进一步，所述热塑性聚氨酯弹性体是指聚酯型、聚醚型、聚碳酸酯型、聚己内酯型、聚酯醚型热塑性聚氨酯弹性体中的一种或几种的混合物，且其硬度为Shore A 50-Shore D 80，优选Shore A 50-Shore A 90，最优选Shore A 60-Shore A 85；熔点为80-200℃，优选80-190℃，最优选100-180℃；玻璃化转变温度低于0℃，优选低于零下20℃，按照DSC在20K/min升温法测得。Further, the thermoplastic polyurethane elastomer refers to a mixture of one or more of a polyester type, a polyether type, a polycarbonate type, a polycaprolactone type, and a polyester ether type thermoplastic polyurethane elastomer, and the hardness thereof Is Shore A 50-Shore D 80, preferably Shore A 50-Shore A 90, most preferably Shore A 60-Shore A 85; melting point 80-200 ° C, preferably 80-190 ° C, most preferably 100-180 ° C; vitrification The transition temperature is below 0 ° C, preferably below 20 ° C under zero, as measured by DSC at 20 K/min ramp.
进一步，所述相容剂选自具有如下结构的两类物质中的一种或多种；Further, the compatibilizing agent is selected from one or more of two types of substances having the following structure;
A：同时含有极性基团和非极性链段的物质，所述极性基团优选为羟基 -OH、氨基-NH2或-NH-、氨酯基-NHCO0-、酰胺基-NHCO-、脲基-NHCONH-、羧基-COOH、酸酐-COOCO-、环氧基、异氰酸酯基中的一种或多种，所述非极性链段是指碳原子数大于等于2的脂肪链或大分子聚合物中的一种或多种，优选地，所述相容剂是指EVA接枝马来酸酐、SEBS接枝马来酸酐、POE接枝马来酸酐、高级脂肪醇、高级脂肪酸、环氧化聚烯烃树脂、羟基化树脂、羧基化树脂、氨基化树脂中的一种或多种，此类相容剂的加入量为10-45重量份，优选15-40重量份，特别优先20-35重量份。A: a substance containing both a polar group and a non-polar segment, and the polar group is preferably a hydroxyl group -OH, an amino group -NH 2 or -NH-, a urethane group -NHCO0-, an amide group -NHCO- One or more of a ureido-NHCONH-, a carboxyl-COOH, an acid anhydride-COOCO-, an epoxy group, an isocyanate group, and the non-polar segment means a fatty chain having a carbon number of 2 or more or a large One or more of the molecular polymers, preferably, the compatibilizer refers to EVA grafted maleic anhydride, SEBS grafted maleic anhydride, POE grafted maleic anhydride, higher fatty alcohol, higher fatty acid, ring One or more of an oxidized polyolefin resin, a hydroxylated resin, a carboxylated resin, and an aminated resin. The compatibilizing agent is added in an amount of 10 to 45 parts by weight, preferably 15 to 40 parts by weight, particularly preferably 20 - 35 parts by weight.
B：含有双活性基团的物质，能够同时与热塑性聚氨酯弹性体中的基团以及烯烃类聚合物中的基团发生反应，所述双活性基团优选为酸酐基团-COOCO-、羧基-COOH、羟基-OH、氨基-NH或-NH2、异氰酸酯基-NCO、环氧基、脲基-NHCONH-、碳碳双键中的一种或多种，优选地，所述相容剂优选为马来酸酐、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、丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、二乙烯基苯、N-羟甲基丙烯酰胺、双丙酮丙烯酰胺、烯丙基聚乙二醇、氨基酸、环氧树脂中的一种或多种，此类相容剂的加入量为0.5-10重量份。B: a substance containing a bis-reactive group capable of simultaneously reacting with a group in the thermoplastic polyurethane elastomer and a group in the olefin-based polymer, which is preferably an acid anhydride group -COOCO-, a carboxyl group - One or more of COOH, hydroxy-OH, amino-NH or -NH 2 , isocyanate-NCO, epoxy, ureido-NHCONH-, carbon-carbon double bond, preferably, the compatibilizing agent is preferably Is maleic anhydride, glycidyl methacrylate, acrylic acid, methyl methacrylate, butyl acrylate, acrylamide, hydroxyethyl acrylate, hydroxypropyl acrylate, methacrylic acid, hydroxyethyl methacrylate, methyl One or more of hydroxypropyl acrylate, divinyl benzene, N-methylol acrylamide, diacetone acrylamide, allyl polyethylene glycol, amino acid, epoxy resin, such compatibilizer The amount added is from 0.5 to 10 parts by weight.
进一步，所述发泡剂是指放热型发泡剂、吸热型发泡剂、发泡微球中的一种或几种的混合物，优选地，所述发泡剂是指偶氮二甲酰胺，偶氮二异丁腈，偶氮二甲酸钡，4,4’-氧代双苯磺酰肼，对甲苯磺酰肼，碳酸氢钠，柠檬酸钠，碳酸氢铵，可膨胀微球中的一种或多种的混合物。Further, the foaming agent refers to a mixture of one or more of an exothermic foaming agent, an endothermic foaming agent, and foamed microspheres. Preferably, the foaming agent refers to azo two. Formamide, azobisisobutyronitrile, cesium azodicarboxylate, 4,4'-oxobisbenzenesulfonyl hydrazide, p-toluenesulfonylhydrazide, sodium hydrogencarbonate, sodium citrate, ammonium hydrogencarbonate, expandable micro a mixture of one or more of the balls.
进一步，所述交联剂为过氧化物或偶氮化合物中的一种，所述助交联剂为含有2个及以上碳碳双键的化合物，优选地，所述助交联剂为丁二烯、戊二烯、辛二烯、二乙烯基苯、三烯丙基异氰脲酸酯TAIC、三烯丙基三聚氰酸酯TAC、三羟甲基丙烷中的一种或多种的混合物，所述其他助剂是指抗UV剂、抗氧剂、泡孔稳定剂中的一种或多种的混合物。 Further, the crosslinking agent is one of a peroxide or an azo compound, and the co-crosslinking agent is a compound containing two or more carbon-carbon double bonds, and preferably, the co-crosslinking agent is butyl. One or more of diene, pentadiene, octadiene, divinylbenzene, triallyl isocyanurate TAIC, triallyl cyanurate TAC, trimethylolpropane The mixture, the other auxiliary agent refers to a mixture of one or more of an anti-UV agent, an antioxidant, and a cell stabilizer.
本发明提供的发泡材料用组合物的制备方法如下：The preparation method of the composition for foaming materials provided by the present invention is as follows:
1)基料的制备，基料可采用如下方法中的任意一种制备得到：1) Preparation of the base material, the base material can be prepared by any of the following methods:
A：在采用一步法生产TPU的过程中，采用侧喂料方式将所有烯烃类聚合物、相容剂、其他助剂按照配比侧喂到挤出机中，经挤出造粒后得到基料；A: In the process of one-step production of TPU, all olefin polymers, compatibilizers and other auxiliaries are fed to the extruder according to the ratio side by side feeding method, and the base is obtained by extrusion granulation. material;
B：在采用一步法生产TPU的过程中，采用侧喂料方式将一部分烯烃类聚合物、一部分相容剂、一部分其他助剂按照配比侧喂到挤出机中，经挤出造粒后得到初级基料；再将初级基料与剩余部分的烯烃类聚合物、相容剂、其他助剂利用挤出机或开练或密练等形式中的一种或几种组合加工后造粒，得到基料；B: In the process of producing TPU by one-step method, a part of the olefin polymer, a part of the compatibilizer and some other auxiliary agents are fed into the extruder according to the ratio side by the side feeding method, and after extrusion granulation Obtaining a primary base material; and then granulating the primary base material with the remaining part of the olefin polymer, the compatibilizer, and other auxiliary agents by using one or more of an extruder or a training or compacting form. , obtaining a base material;
C：按照本领域内公知的一步法或两步法工艺生产TPU，再将TPU与全部烯烃类聚合物、相容剂、其他助剂利用挤出机或开练或密练等形式中的一种或几种组合加工后造粒，得到基料；C: Production of TPU according to a one-step or two-step process well known in the art, and then using TPU with all olefin polymers, compatibilizers, and other auxiliaries in an extruder or in a form of training or compacting. One or several combinations of processed granulation to obtain a base;
D：按照本领域内公知的一步法或两步法工艺生产TPU，再将TPU与一部分烯烃类聚合物、部分相容剂、部分其他助剂利用挤出机挤出造粒后，得到初级基料；再将初级基料与剩余部分的烯烃类聚合物、相容剂、其他助剂利用挤出机或开练或密练等形式中的一种或几种组合加工后造粒，得到基料；D: The TPU is produced according to a one-step or two-step process well known in the art, and then the TPU and a part of the olefin polymer, a part of the compatibilizer, and some other auxiliary agents are extruded and granulated by an extruder to obtain a primary group. Then, the primary base material and the remaining part of the olefin polymer, the compatibilizer, and other auxiliary agents are processed by one or more of an extruder or a form of grinding or compacting, and then granulated to obtain a base. material;
2)将基料与发泡剂、交联剂、助交联剂混合均匀，采用如下生产过程中的一种得到高回弹发泡制品：2) The base material is uniformly mixed with the foaming agent, the crosslinking agent and the auxiliary crosslinking agent, and a high resilience foaming product is obtained by using one of the following production processes:
A：将混合物置于制品模具中，将制品模具置于平板硫化机中，在100-200℃下进行模压发泡1-60分钟，然后将模具冷却至5-60℃，得到高回弹发泡制品；A: The mixture is placed in a product mold, the product mold is placed in a flat vulcanizer, and the foam is molded at 100-200 ° C for 1-60 minutes, and then the mold is cooled to 5-60 ° C to obtain a high rebound. Foam product
B：将混合物加入到EVA注塑发泡机中，在100-220℃下进行注塑发泡，经冷却、定型后得到高回弹发泡制品；B: adding the mixture to the EVA injection foaming machine, performing injection foaming at 100-220 ° C, and obtaining a high rebound foamed product after cooling and setting;
C：将混合物加入到挤出机中，在100-220℃下进行挤出发泡，经冷却、定型后得到高回弹发泡制品。 C: The mixture was added to an extruder, and extrusion foaming was carried out at 100-220 ° C, and after cooling and setting, a high-rebound foamed product was obtained.
本发明提供的发泡材料用组合物的有益效果是：The beneficial effects of the composition for foaming materials provided by the present invention are:
本发明利用含有极性基团或双活性基团的相容剂起到增容作用，降低烯烃类聚合物与TPU的界面张力，形成烯烃类聚合物/TPU互穿网络结构(IPN)，解决两种材料间相容性问题；通过在烯烃类聚合物中成功的引入TPU组份，利用TPU优异的弹性，大大改善发泡烯烃类聚合物材料的回弹性，压缩永久变形等性能。工艺流程简单，生产成本低，适合工业化生产。The invention utilizes a compatibilizing agent containing a polar group or a double reactive group to compatibilize, reduce the interfacial tension between the olefin polymer and the TPU, and form an olefin polymer/TPU interpenetrating network structure (IPN) to solve The problem of compatibility between the two materials; by the successful introduction of the TPU component in the olefin polymer, the excellent elasticity of the TPU is utilized to greatly improve the resilience, compression set and the like properties of the foamed olefin polymer material. The process is simple, the production cost is low, and it is suitable for industrial production.
具体实施方式detailed description
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。The principles and features of the present invention are described in the following examples, which are intended to illustrate the invention and are not intended to limit the scope of the invention.
实施例1：Example 1:
一种具有高回弹性的发泡材料用组合物，按重量份计，包括如下组份：A composition for foaming materials having high resilience, comprising parts by weight, as follows:
Figure PCTCN2017089278-appb-000004
Figure PCTCN2017089278-appb-000004
采用如下方法制备发泡制品：The foamed article was prepared as follows:
1)基料制备：采用本领域公知的一步法生产TPU的过程中，通过侧喂料螺杆将EVA-1、EVA-2，EVA接枝马来酸酐加入到挤出机中，控制挤出螺杆的温度为100-190℃，模头温度控制为150℃，经挤出造粒得到基料；1) Base preparation: In the process of producing TPU by a one-step method well known in the art, EVA-1, EVA-2, EVA grafted maleic anhydride was added to the extruder through a side feed screw to control the extrusion screw. The temperature is 100-190 ° C, the temperature of the die is controlled to 150 ° C, and the base material is obtained by extrusion granulation;
2)高回弹发泡材料制备：将步骤1)制得的基料，0.1份偶氮二甲酰胺，0.01份DCP通过高混机混合均匀后投入到制品模具中，平板硫化机温度100℃，模压发泡1分钟，然后将模具冷却至5℃，得到最终的高回弹发泡制品材料。 2) Preparation of high resilience foaming material: the base material obtained in step 1), 0.1 part azodicarbonamide, 0.01 part DCP is uniformly mixed by high mixing machine and put into the product mold, and the temperature of the flat vulcanizing machine is 100 ° C. The foam was molded for 1 minute, and then the mold was cooled to 5 ° C to obtain a final high resilience foamed article material.
本实施例所制得的发泡制品材料与现有市场上EVA发泡制品的物性测试数据如表1所示。The physical property test data of the foamed product material obtained in this embodiment and the EVA foamed product on the existing market are shown in Table 1.
实施例2：Example 2:
一种具有高回弹性的发泡材料用组合物，按重量份计，包括如下组份：A composition for foaming materials having high resilience, comprising parts by weight, as follows:
Figure PCTCN2017089278-appb-000005
Figure PCTCN2017089278-appb-000005
采用如下方法制备发泡制品：The foamed article was prepared as follows:
1)基料制备：采用本领域公知的一步法生产TPU的过程中，通过侧喂料螺杆将EVA-1、EVA-2，EVA接枝马来酸酐加入到挤出机中，控制挤出螺杆的温度为100-190℃，模头温度控制为150℃，经挤出造粒得到基料；1) Base preparation: In the process of producing TPU by a one-step method well known in the art, EVA-1, EVA-2, EVA grafted maleic anhydride was added to the extruder through a side feed screw to control the extrusion screw. The temperature is 100-190 ° C, the temperature of the die is controlled to 150 ° C, and the base material is obtained by extrusion granulation;
2)高回弹发泡材料制备：将步骤1)制得的基料，1份偶氮二甲酰胺，0.05份DCP通过高混机混合均匀后投入到制品模具中，平板硫化机温度100℃，模压发泡1分钟，然后将模具冷却至5℃，得到最终的高回弹发泡制品材料。2) Preparation of high resilience foaming material: the base material obtained in step 1), 1 part azodicarbonamide, 0.05 part DCP are uniformly mixed by high mixing machine and put into the product mold, and the temperature of the flat vulcanizing machine is 100 ° C. The foam was molded for 1 minute, and then the mold was cooled to 5 ° C to obtain a final high resilience foamed article material.
本实施例所制得的发泡制品材料与现有市场上EVA发泡制品的物性测试数据如表1所示。The physical property test data of the foamed product material obtained in this embodiment and the EVA foamed product on the existing market are shown in Table 1.
实施例3：Example 3:
一种具有高回弹性的发泡材料用组合物，按重量份计，包括如下组份：A composition for foaming materials having high resilience, comprising parts by weight, as follows:
Figure PCTCN2017089278-appb-000006
Figure PCTCN2017089278-appb-000006
Figure PCTCN2017089278-appb-000007
Figure PCTCN2017089278-appb-000007
采用如下方法制备发泡制品：The foamed article was prepared as follows:
1)基料制备：采用本领域公知的一步法生产TPU颗粒，再将TPU颗粒与EVA-1、EVA接枝马来酸酐经高混机混合后加入到双螺杆挤出机中，控制挤出螺杆的温度为100-190℃，模头温度控制为150℃，经挤出造粒得到基料1；再将基料1、EVA-2经高混机混合后加入到双螺杆或密炼机中，混合均匀后挤出造粒，得到最终基料2；1) Preparation of base material: TPU particles are produced by a one-step method well known in the art, and TPU particles and EVA-1, EVA grafted maleic anhydride are mixed in a high-mixer and then added to a twin-screw extruder to control extrusion. The temperature of the screw is 100-190 ° C, the temperature of the die is controlled to 150 ° C, and the base material 1 is obtained by extrusion granulation; the base material 1 and EVA-2 are mixed by a high mixer and then added to a twin screw or an internal mixer. Medium, after uniform mixing, extrusion granulation, to obtain the final base 2;
2)高回弹发泡材料制备：将步骤1)制得的基料2，1.5份偶氮二甲酰胺，0.1份DCP通过高混机混合均匀后投入到制品模具中，平板硫化机温度100℃，模压发泡1分钟，然后将模具冷却至5℃，得到最终的高回弹发泡制品材料。2) Preparation of high resilience foaming material: base material 2, 1.5 parts of azodicarbonamide prepared in step 1), 0.1 part of DCP are uniformly mixed by high-mixer, and then put into a product mold, and the temperature of the flat vulcanizing machine is 100. °C, molded and foamed for 1 minute, and then the mold was cooled to 5 ° C to obtain a final high resilience foamed article material.
本实施例所制得的发泡制品材料与现有市场上EVA发泡制品的物性测试数据如表1所示：The physical property test data of the foamed product obtained in this embodiment and the EVA foamed product on the existing market are shown in Table 1:
表1实施例1-3所得产品与市场上EVA发泡制品的物性数据比较Table 1 Comparison of physical properties of products obtained in Examples 1-3 and EVA foamed products on the market
Figure PCTCN2017089278-appb-000008
Figure PCTCN2017089278-appb-000008
实施例4：Example 4:
一种具有高回弹性的发泡材料用组合物，按重量份计，包括如下组份：A composition for foaming materials having high resilience, comprising parts by weight, as follows:
Figure PCTCN2017089278-appb-000009
Figure PCTCN2017089278-appb-000009
采用如下方法制备发泡制品：The foamed article was prepared as follows:
1)基料制备：采用本领域公知的一步法生产TPU过程中，通过侧喂料螺杆将SEBS，SEBS接枝马来酸酐，抗UV剂，加入到挤出机中，控制挤出螺杆温度为100-150℃，模头温度控制为150℃，经挤出造粒得到初级基料，其中，TPU加入量为95重量份，SEBS加入量为3重量份，SEBS接枝马来酸酐加入量为20重量份，抗UV剂加入量为1重量份；然后将初级基料和2重量份SEBS，25重量份SEBS接枝马来酸酐，1重量份抗氧化剂
Figure PCTCN2017089278-appb-000010
采用开炼机加工后造粒，得到基料。1) Preparation of base material: In the process of producing TPU by a one-step method well known in the art, SEBS, SEBS grafted maleic anhydride and anti-UV agent are added to the extruder through a side feed screw to control the extrusion screw temperature. 100-150 ° C, the die temperature is controlled to 150 ° C, extrusion granulation to obtain a primary base, wherein the amount of TPU added is 95 parts by weight, the amount of SEBS added is 3 parts by weight, and the amount of SEBS grafted maleic anhydride is 20 parts by weight, the anti-UV agent is added in an amount of 1 part by weight; then the primary base and 2 parts by weight of SEBS, 25 parts by weight of SEBS grafted maleic anhydride, 1 part by weight of antioxidant
Figure PCTCN2017089278-appb-000010
After processing by an open mill, granulation is carried out to obtain a base material.
2)高回弹发泡材料制备：将步骤1)制备的基料，10重量份碳酸氢钠，5份BPO，0.2重量份助交联剂TAIC通过高混机混合均匀后投入到EVA注塑发泡设备中，注塑温度为150-220℃，得到最终的高回弹发泡制品材料。2) Preparation of high resilience foaming material: the base material prepared in step 1), 10 parts by weight of sodium hydrogencarbonate, 5 parts of BPO, 0.2 parts by weight of the cross-linking agent TAIC are uniformly mixed by a high-mixer and then put into EVA injection molding. In the foaming equipment, the injection temperature is 150-220 ° C, and the final high-rebound foaming material is obtained.
本实施例所制得的发泡制品材料与现有市场上SEBS发泡制品的物性测试数据如表2所示：The physical property test data of the foamed product obtained in this embodiment and the SEBS foamed product on the market are shown in Table 2:
表2实施例4所得产品与市场上SEBS发泡制品的物性数据比较 Table 2 Comparison of physical properties of the products obtained in Example 4 and SEBS foamed products on the market
项目project 测试标准standard test 单位unit 实施例4产品Example 4 product 市场SEBS发泡产品Market SEBS foam products
密度density ASTM-D792ASTM-D792 g/cm3 g/cm 3 0.180.18 0.250.25
硬度hardness GB/T10807-2006GB/T10807-2006 ShoreShore 4545 4545
拉伸强度Tensile Strength ISO1798-2008ISO1798-2008 MPaMPa 7.57.5 1.21.2
断裂伸长率Elongation at break ISO1798-2008ISO1798-2008 ％% 580580 330330
撕裂强度Tear strength GB/T10808-2006GB/T10808-2006 N/mmN/mm 12.412.4 5.25.2
落球回弹性Falling ball back elasticity ISO8307ISO8307 ％% 5858 5252
压缩永久变形Compression set GB/T6669-2008GB/T6669-2008 ％% 1818 3535
耐磨性Wear resistance DIN53516DIN53516 Mm3 Mm 3 380380 500500
实施例5：Example 5:
一种具有高回弹性的发泡材料用组合物，按重量份计，包括如下组份：A composition for foaming materials having high resilience, comprising parts by weight, as follows:
Figure PCTCN2017089278-appb-000011
Figure PCTCN2017089278-appb-000011
采用如下方法制备发泡制品：The foamed article was prepared as follows:
1)基料制备：采用本领域公知的一步法生产聚碳酸酯型TPU弹性体，然后将75重量份聚碳酸酯型TPU颗粒，50重量份POE，0.5重量份马来酸酐投入挤出机中进行造粒，控制挤出螺杆温度为150-220℃，模头温度控制为200℃，得到基料；1) Base preparation: a polycarbonate type TPU elastomer is produced by a one-step method well known in the art, and then 75 parts by weight of polycarbonate type TPU particles, 50 parts by weight of POE, and 0.5 part by weight of maleic anhydride are put into an extruder. Performing granulation, controlling the temperature of the extrusion screw to be 150-220 ° C, and controlling the temperature of the die to 200 ° C to obtain a base material;
2)高回弹发泡材料制备：将步骤1)制备的基料，3重量份可膨胀微球，通过高混机混合均匀后投入到挤出机中，挤出机螺杆温度设定150-220℃，模头温度设定180℃，挤出得到高回弹发泡制品。2) Preparation of high-rebound foaming material: the base material prepared in step 1), 3 parts by weight of expandable microspheres, uniformly mixed by a high-mixer, and then put into an extruder, and the screw temperature of the extruder is set to 150- At 220 ° C, the die temperature was set at 180 ° C, and a high resilience foamed product was obtained by extrusion.
本实施例所制得的发泡制品材料与现有市场上POE发泡制品的物性测试数据如表3所示：The physical property test data of the foamed product obtained in this embodiment and the POE foamed product on the existing market are shown in Table 3:
表3实施例5所得产品与市场上POE发泡制品的物性数据比较Table 3 Comparison of physical properties of the products obtained in Example 5 and POE foamed products on the market
项目project 测试标准standard test 单位unit 实施例5产品Example 5 product 市场POE发泡产品Market POE foam products
密度density ASTM-D792ASTM-D792 g/cm3 g/cm 3 0.220.22 0.250.25
硬度hardness GB/T10807-2006GB/T10807-2006 ShoreShore 4545 4545
拉伸强度Tensile Strength ISO1798-2008ISO1798-2008 MPaMPa 1010 11
断裂伸长率Elongation at break ISO1798-2008ISO1798-2008 ％% 710710 350350
撕裂强度Tear strength GB/T10808-2006GB/T10808-2006 N/mmN/mm 5.85.8 3.53.5
落球回弹性Falling ball back elasticity GB/T6670-2008GB/T6670-2008 ％% 6161 5252
压缩永久变形Compression set GB/T6669-2008GB/T6669-2008 ％% 22twenty two 3838
耐磨性Wear resistance DIN53516DIN53516 Mm3 Mm 3 350350 550550
实施例6：Example 6
一种具有高回弹性的发泡材料用组合物，按重量份计，包括如下组份：A composition for foaming materials having high resilience, comprising parts by weight, as follows:
Figure PCTCN2017089278-appb-000012
Figure PCTCN2017089278-appb-000012
采用如下方法制备发泡制品：The foamed article was prepared as follows:
1)基料制备：采用本领域公知的两步法生产聚己内酯型TPU弹性体，然后将TPU，乙烯-丙烯二元共聚物，环氧化聚烯烃树脂，抗UV剂
Figure PCTCN2017089278-appb-000013
抗氧化剂
Figure PCTCN2017089278-appb-000014
加入到双螺杆挤出机中，控制挤出机的螺杆温度为150-220℃，模头温度为220℃，经挤出造粒得到基料；1) Base preparation: Polycaprolactone type TPU elastomer is produced by a two-step method well known in the art, and then TPU, ethylene-propylene binary copolymer, epoxidized polyolefin resin, anti-UV agent
Figure PCTCN2017089278-appb-000013
Antioxidants
Figure PCTCN2017089278-appb-000014
Adding to the twin-screw extruder, controlling the screw temperature of the extruder to be 150-220 ° C, the die temperature is 220 ° C, and extruding and granulating to obtain a base material;
2)高回弹发泡材料制备：将步骤1)制备的基料，10重量份偶氮二异丁腈，2份DTBP通过高混机混合均匀后投入到EVA注塑发泡设备中，注塑温度为100-150℃，得到最终的高回弹发泡制品材料。2) Preparation of high-rebound foaming material: the base material prepared in step 1), 10 parts by weight of azobisisobutyronitrile, and 2 parts of DTBP are uniformly mixed by high-mixer and put into EVA injection foaming equipment, and the injection temperature is The final high resilience foamed article material is obtained at 100-150 °C.
本实施例所制得的发泡制品材料与现有市场上乙烯丙烯共聚物发泡制品的物性测试数据如表4所示：The physical property test data of the foamed product obtained in this embodiment and the ethylene propylene copolymer foamed product on the existing market are shown in Table 4:
表4实施例6所得产品与市场上乙烯丙烯共聚物发泡制品的物性数据比较Table 4 Comparison of physical properties of the products obtained in Example 6 and the foamed articles of ethylene propylene copolymer on the market
Figure PCTCN2017089278-appb-000015
Figure PCTCN2017089278-appb-000015
Figure PCTCN2017089278-appb-000016
Figure PCTCN2017089278-appb-000016
实施例7：Example 7
一种具有高回弹性的发泡材料用组合物，按重量份计，包括如下组份：A composition for foaming materials having high resilience, comprising parts by weight, as follows:
Figure PCTCN2017089278-appb-000017
Figure PCTCN2017089278-appb-000017
采用如下方法制备发泡制品：The foamed article was prepared as follows:
1)基料制备：采用本领域公知的一步法生产TPU的过程中，通过侧喂料螺杆将EVA-1、EVA-2，马来酸酐，加入到挤出机中，控制挤出机的温度为100-200℃，模头温度为160℃，经挤出造粒得到基料；1) Base preparation: In the process of producing TPU by a one-step method well known in the art, EVA-1, EVA-2, maleic anhydride is added to the extruder through a side feed screw to control the temperature of the extruder. The temperature is 100-200 ° C, the die temperature is 160 ° C, and the base material is obtained by extrusion granulation;
2)高回弹发泡材料制备：将步骤1)制得的基料，5份偶氮二异丁腈，3份BPO，2重量份三烯丙基三聚氰酸酯通过高混机混合均匀后投入到制品模具中，平板硫化机温度150℃，模压发泡20分钟，然后将模具冷却至5℃，得到最终的高回弹发泡制品材料。2) Preparation of high resilience foaming material: the base prepared in step 1), 5 parts of azobisisobutyronitrile, 3 parts of BPO, 2 parts by weight of triallyl cyanurate are mixed by high mixing machine After evenly, it was put into a product mold, the plate vulcanizer was heated at 150 ° C, molded and foamed for 20 minutes, and then the mold was cooled to 5 ° C to obtain a final high resilience foamed product material.
本实施例所制得的发泡制品材料与现有市场上EVA发泡制品的物性测试数据如表5所示。The physical property test data of the foamed product material obtained in this embodiment and the EVA foamed product on the existing market are shown in Table 5.
实施例8：Example 8
一种具有高回弹性的发泡材料用组合物，按重量份计，包括如下组份： A composition for foaming materials having high resilience, comprising parts by weight, as follows:
Figure PCTCN2017089278-appb-000018
Figure PCTCN2017089278-appb-000018
采用如下方法制备发泡制品：The foamed article was prepared as follows:
1)基料制备：1) Base preparation:
A：采用本领域公知的一步法生产TPU的过程中，通过侧喂料螺杆将EVA-1，马来酸酐，加入到挤出机中，控制挤出机的温度为100-200℃，模头温度为160℃，经挤出造粒得到基料1；A: In the process of producing TPU by a one-step method well known in the art, EVA-1, maleic anhydride is added to the extruder through a side feeding screw, and the temperature of the extruder is controlled to be 100-200 ° C, the die The temperature is 160 ° C, extruded granulation to obtain a base 1;
B：将基料1、EVA-2混合后加入到双螺杆挤出机或密炼机中，混合均匀后挤出造粒，得到基料2；B: the base material 1, EVA-2 is mixed and added to a twin-screw extruder or an internal mixer, mixed uniformly and then extruded and granulated to obtain a base material 2;
2)高回弹发泡材料制备：将步骤1)制得的基料1和基料2，3份偶氮二异丁腈，3份BPO，2重量份三烯丙基三聚氰酸酯通过高混机混合均匀后投入到制品模具中，平板硫化机温度150℃，模压发泡20分钟，然后将模具冷却至5℃，得到最终的高回弹发泡制品材料。2) Preparation of high resilience foaming material: base 1 and base 2 obtained in step 1), 3 parts azobisisobutyronitrile, 3 parts BPO, 2 parts by weight of triallyl cyanurate After mixing by a high-mixer, it was put into a product mold, the plate vulcanizer was heated at 150 ° C, molded and foamed for 20 minutes, and then the mold was cooled to 5 ° C to obtain a final high-rebound foamed product material.
本实施例所制得的发泡制品材料与现有市场上EVA发泡制品的物性测试数据如表5所示。The physical property test data of the foamed product material obtained in this embodiment and the EVA foamed product on the existing market are shown in Table 5.
表5实施例7、8所得产品与市场上现有EVA发泡制品的物性测试数据Table 5 Physical property test data of the products obtained in Examples 7 and 8 and existing EVA foamed products on the market
Figure PCTCN2017089278-appb-000019
Figure PCTCN2017089278-appb-000019
Figure PCTCN2017089278-appb-000020
Figure PCTCN2017089278-appb-000020
实施例9：Example 9
一种具有高回弹性的发泡材料用组合物，按重量份计，包括如下组份：A composition for foaming materials having high resilience, comprising parts by weight, as follows:
Figure PCTCN2017089278-appb-000021
Figure PCTCN2017089278-appb-000021
采用如下方法制备发泡制品：The foamed article was prepared as follows:
1)基料制备：采用本领域公知的一步法生产TPU过程中，通过侧喂料螺杆将SEBS，丙烯酸羟乙酯，抗UV剂
Figure PCTCN2017089278-appb-000022
抗氧化剂
Figure PCTCN2017089278-appb-000023
加入到挤出机中，挤出机的螺杆温度控制为160-220℃，模头温度控制为200℃，经挤出造粒得到基料。1) Base preparation: SEBS, hydroxyethyl acrylate, anti-UV agent is produced by a side feed screw during the production of TPU by a one-step method well known in the art.
Figure PCTCN2017089278-appb-000022
Antioxidants
Figure PCTCN2017089278-appb-000023
It was added to an extruder, the screw temperature of the extruder was controlled to 160-220 ° C, the die temperature was controlled to 200 ° C, and the base material was obtained by extrusion granulation.
2)高回弹发泡材料制备：将步骤1)制备的基料，8重量份对甲苯磺酰肼，5份2,5-二甲基-2,5二叔丁基过氧化己烷，3重量份助交联剂三烯丙基异氰脲酸酯TAIC通过高混机混合均匀后投入到EVA注塑发泡设备中，注塑温度为150-220℃，得到最终的高回弹发泡制品材料。2) Preparation of high resilience foaming material: the base prepared in the step 1), 8 parts by weight of p-toluenesulfonylhydrazide, 5 parts of 2,5-dimethyl-2,5 di-tert-butylperoxyhexane, 3 parts by weight of the cross-linking agent, triallyl isocyanurate, TAIC, is uniformly mixed by a high-mixer and then put into an EVA injection foaming equipment at an injection temperature of 150-220 ° C to obtain a final high-rebound foaming product. material.
本实施例所制得的发泡制品材料与现有市场上SEBS发泡制品的物性测 试数据如表6所示：The properties of the foamed product obtained in this embodiment and the physical properties of SEBS foamed products on the market The test data is shown in Table 6:
表6实施例9所得产品与市场上SEBS发泡制品的物性数据比较Table 6 Comparison of physical properties of the products obtained in Example 9 with SEBS foamed products on the market
项目project 测试标准standard test 单位unit 实施例9产品Example 9 product 市场SEBS发泡产品Market SEBS foam products
密度density ASTM-D792ASTM-D792 g/cm3 g/cm 3 0.170.17 0.250.25
硬度hardness GB/T10807-2006GB/T10807-2006 ShoreShore 4545 4545
拉伸强度Tensile Strength ISO1798-2008ISO1798-2008 MPaMPa 7.07.0 1.21.2
断裂伸长率Elongation at break ISO1798-2008ISO1798-2008 ％% 560560 330330
撕裂强度Tear strength GB/T10808-2006GB/T10808-2006 N/mmN/mm 12.012.0 5.25.2
落球回弹性Falling ball back elasticity ISO8307ISO8307 ％% 5858 5252
压缩永久变形Compression set GB/T6669-2008GB/T6669-2008 ％% 1818 3535
耐磨性Wear resistance DIN53516DIN53516 Mm3 Mm 3 380380 500500
实施例10：Example 10:
一种具有高回弹性的发泡材料用组合物，按重量份计，包括如下组份：A composition for foaming materials having high resilience, comprising parts by weight, as follows:
Figure PCTCN2017089278-appb-000024
Figure PCTCN2017089278-appb-000024
采用如下方法制备：Prepared by the following method:
1)基料制备：采用本领域公知的两步法生产聚碳酸酯型TPU弹性体，然后将TPU，乙烯-辛烯二元共聚物，N-羟甲基丙烯酰胺加入到双螺杆挤出机中，挤出机的螺杆温度控制为100-160℃，模头温度控制为150℃，经挤出造粒得到基料；1) Base preparation: a polycarbonate type TPU elastomer is produced by a two-step process well known in the art, and then TPU, ethylene-octene binary copolymer, N-methylol acrylamide is added to the twin-screw extruder. In the extruder, the screw temperature is controlled to be 100-160 ° C, the die temperature is controlled to 150 ° C, and the base material is obtained by extrusion granulation;
2)高回弹发泡材料制备：将步骤1)制备的基料，0.1重量份可膨胀微球，0.01份过氧化二异丙苯DCP、5份二乙烯基苯通过高混机混合均匀后投入到EVA注塑发泡设备中，注塑温度为100-150℃，得到最终的高回弹发泡制品材料。2) Preparation of high resilience foaming material: the base material prepared in step 1), 0.1 part by weight of expandable microspheres, 0.01 part of dicumyl peroxide DCP, and 5 parts of divinylbenzene are uniformly mixed by a high mixer. It is put into the EVA injection foaming equipment, and the injection temperature is 100-150 ° C to obtain the final high rebound foaming material.
本实施例所制得的发泡制品材料与现有市场上POE发泡制品的物性测试 数据如表7所示：The physical property test of the foamed product material obtained in this embodiment and the POE foamed product on the existing market The data is shown in Table 7:
表7实施例10所得产品与现有市场上POE发泡制品的物性测试数据Table 7 Physical property test data of the product obtained in Example 10 and the POE foamed product on the market
Figure PCTCN2017089278-appb-000025
Figure PCTCN2017089278-appb-000025
实施例11：Example 11
一种具有高回弹性的发泡材料用组合物，按重量份计，包括如下组份：A composition for foaming materials having high resilience, comprising parts by weight, as follows:
Figure PCTCN2017089278-appb-000026
Figure PCTCN2017089278-appb-000026
采用如下方法制备发泡制品：The foamed article was prepared as follows:
1)基料制备：采用本领域公知的两步法生产聚己内酯型TPU弹性体，然后将TPU，乙烯-丙烯三元共聚物，SEBS接枝马来酸酐，抗UV剂
Figure PCTCN2017089278-appb-000027
抗氧化剂
Figure PCTCN2017089278-appb-000028
加入到双螺杆挤出机中，挤出机的螺杆温度控制为100-160℃，模头温度控制为150℃，经挤出造粒得到基料；1) Base preparation: a polycaprolactone type TPU elastomer is produced by a two-step method well known in the art, and then TPU, ethylene-propylene terpolymer, SEBS grafted maleic anhydride, anti-UV agent
Figure PCTCN2017089278-appb-000027
Antioxidants
Figure PCTCN2017089278-appb-000028
Adding to the twin-screw extruder, the screw temperature of the extruder is controlled to be 100-160 ° C, the temperature of the die is controlled to 150 ° C, and the base material is obtained by extrusion granulation;
2)高回弹发泡材料制备：将步骤1)制备的基料，2重量份偶氮二异丁腈，3份BPO通过高混机混合均匀后投入到挤出机中，挤出机螺杆温度设定150-220℃，模头温度设定180℃，挤出得到高回弹发泡制品。 2) Preparation of high-rebound foaming material: the base material prepared in step 1), 2 parts by weight of azobisisobutyronitrile, and 3 parts of BPO are uniformly mixed by a high-mixer and then put into an extruder, and the extruder screw The temperature was set to 150-220 ° C, the die temperature was set to 180 ° C, and a high resilience foamed product was obtained by extrusion.
本实施例所制得的发泡制品材料与现有市场上乙烯-丙烯共聚物发泡制品的物性测试数据如表8所示：The physical property test data of the foamed product material obtained in this embodiment and the ethylene-propylene copolymer foamed product on the existing market are shown in Table 8:
表8实施例11所得产品与现有市场上乙烯-丙烯共聚物发泡制品的物性测试数据Table 8 Physical property test data of the product obtained in Example 11 and the existing ethylene-propylene copolymer foamed product on the market
Figure PCTCN2017089278-appb-000029
Figure PCTCN2017089278-appb-000029
通过表1-表8中的数据对比可以看出，本发明所制备的产品在落球回弹性不低于45％，机械性能，压缩永久变形和耐磨性方面都优于市场现有的发泡材料，并且发泡密度更低。其原因主要在于我们利用相容剂起到增容作用，促进了烯烃类聚合物与TPU两种聚合物的相容和分散，形成了烯烃/TPU互穿网络结构(IPN)；另一面利用TPU优异的回弹性，耐磨性，机械性能，大大改善发泡烯烃类材料的回弹性，压缩永久变形等性能，简化工艺流程，生产成本降低。It can be seen from the comparison of the data in Tables 1 to 8 that the products prepared by the invention are superior to the existing foam in the market in terms of falling ball resilience not less than 45%, mechanical properties, compression set and wear resistance. Material and foam density is lower. The main reason is that we use compatibilizer to compatibilize, promote the compatibility and dispersion of olefin polymer and TPU polymer, form olefin/TPU interpenetrating network structure (IPN); use TPU on the other side. Excellent resilience, wear resistance, mechanical properties, greatly improve the resilience of the foamed olefinic materials, compression and other properties, simplify the process, and reduce production costs.
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。 The above are only the preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalents, improvements, etc., which are within the spirit and scope of the present invention, should be included in the protection of the present invention. Within the scope.

Claims (10)

  1. 一种具有高回弹性的发泡材料用组合物，其特征在于，按重量份计，包括如下组份：A composition for foaming materials having high resilience, characterized in that, by weight parts, the following components are included:
    Figure PCTCN2017089278-appb-100001
    Figure PCTCN2017089278-appb-100001
  2. 根据权利要求1所述的发泡材料用组合物，其特征在于，所述烯烃类聚合物是指由含碳碳双键的烯烃单体经均聚或共聚反应得到的聚合物，并且其玻璃化转变温度低于0℃，按照DSC在20K/min升温法测得。The composition for a foaming material according to claim 1, wherein the olefin polymer refers to a polymer obtained by homopolymerization or copolymerization of an olefin monomer having a carbon-carbon double bond, and the glass thereof The transformation temperature was lower than 0 ° C and measured according to DSC at 20 K/min.
  3. 根据权利要求2所述的发泡材料用组合物，其特征在于，所述烯烃类聚合物是指乙烯-醋酸乙烯共聚物、苯乙烯-乙烯-丁二烯-苯乙烯嵌段共聚物、乙烯-丙烯二元或多元共聚物、乙烯-辛烯共聚物中的一种或几种的混合物。The composition for a foamed material according to claim 2, wherein the olefin polymer refers to an ethylene-vinyl acetate copolymer, a styrene-ethylene-butadiene-styrene block copolymer, and ethylene. a mixture of one or more of a propylene binary or multicomponent copolymer, an ethylene-octene copolymer.
  4. 根据权利要求1所述的发泡材料用组合物，其特征在于，所述热塑性聚氨酯弹性体是指聚酯型、聚醚型、聚碳酸酯型、聚己内酯型、聚酯醚型热塑性聚氨酯弹性体中的一种或几种的混合物，且其硬度为Shore A50-Shore D 80，熔点为80-200℃，玻璃化转变温度低于0℃，按照DSC在20K/min升温法测得。The composition for a foamed material according to claim 1, wherein the thermoplastic polyurethane elastomer is a polyester type, a polyether type, a polycarbonate type, a polycaprolactone type, or a polyester ether type thermoplastic. a mixture of one or more of polyurethane elastomers having a hardness of Shore A50-Shore D 80, a melting point of 80-200 ° C, a glass transition temperature of less than 0 ° C, measured by DSC at 20 K/min. .
  5. 根据权利要求1所述的发泡材料用组合物，其特征在于，所述相容剂是指同时含有极性基团和非极性链段的物质，所述极性基团优选为羟基 -OH、氨基-NH2或-NH-、氨酯基-NHCO0-、酰胺基-NHCO-、脲基-NHCONH-、羧基-COOH、酸酐-COOCO-、环氧基、异氰酸酯基中的一种或多种，所述非极性链段是指碳原子数大于等于2的脂肪链或大分子聚合物中的一种或多种，优选地，所述相容剂是指EVA接枝马来酸酐、SEBS接枝马来酸酐、POE接枝马来酸酐、高级脂肪醇、高级脂肪酸、环氧化聚烯烃树脂、羟基化树脂、羧基化树脂、氨基化树脂中的一种或多种。The composition for a foamed material according to claim 1, wherein the compatibilizing agent means a substance containing both a polar group and a non-polar segment, and the polar group is preferably a hydroxyl group - One of OH, amino-NH 2 or -NH-, urethane-NHCO0-, amide-NHCO-, ureido-NHCONH-, carboxy-COOH, anhydride-COOCO-, epoxy, isocyanate or In many cases, the non-polar segment refers to one or more of an aliphatic chain or a macromolecular polymer having 2 or more carbon atoms. Preferably, the compatibilizing agent refers to EVA-grafted maleic anhydride. And one or more of SEBS grafted maleic anhydride, POE grafted maleic anhydride, higher fatty alcohol, higher fatty acid, epoxidized polyolefin resin, hydroxylated resin, carboxylated resin, and aminated resin.
  6. 根据权利要求1所述的发泡材料用组合物，其特征在于，所述相容剂是指含有双活性基团的物质，能够同时与热塑性聚氨酯弹性体中的基团以及烯烃类聚合物中的基团发生反应，所述双活性基团优选为酸酐基团-COOCO-、羧基-COOH、羟基-OH、氨基-NH或-NH2、异氰酸酯基-NCO、环氧基、脲基-NHCONH-、碳碳双键中的一种或多种，优选地，所述相容剂是指马来酸酐、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、丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、二乙烯基苯、N-羟甲基丙烯酰胺、双丙酮丙烯酰胺、烯丙基聚乙二醇、氨基酸、环氧树脂中的一种或多种。The composition for foaming materials according to claim 1, wherein the compatibilizing agent refers to a substance containing a double reactive group, which is capable of simultaneously reacting with a group in the thermoplastic polyurethane elastomer and an olefin polymer. The group is reactive, preferably the acid group -COOCO-, carboxyl-COOH, hydroxy-OH, amino-NH or -NH 2 , isocyanate-NCO, epoxy, ureido-NHCONH One or more of carbon-carbon double bonds, preferably, the compatibilizer means maleic anhydride, glycidyl methacrylate, acrylic acid, methyl methacrylate, butyl acrylate, acrylamide, Hydroxyethyl acrylate, hydroxypropyl acrylate, methacrylic acid, hydroxyethyl methacrylate, hydroxypropyl methacrylate, divinyl benzene, N-methylol acrylamide, diacetone acrylamide, allyl polymerization One or more of ethylene glycol, amino acid, and epoxy resin.
  7. 根据权利要求1所述的发泡材料用组合物，其特征在于，所述发泡剂是指放热型发泡剂、吸热型发泡剂、发泡微球中的一种或几种的混合物，优选地，所述发泡剂是指偶氮二甲酰胺，偶氮二异丁腈，偶氮二甲酸钡，4,4’-氧代双苯磺酰肼，对甲苯磺酰肼，碳酸氢钠，柠檬酸钠，碳酸氢铵，可膨胀微球中的一种或多种的混合物。The composition for a foaming material according to claim 1, wherein the foaming agent is one or more of an exothermic foaming agent, an endothermic foaming agent, and foamed microspheres. Mixture, preferably, the blowing agent means azodicarbonamide, azobisisobutyronitrile, hydrazine azodicarboxylate, 4,4'-oxobisbenzenesulfonyl hydrazide, p-toluenesulfonyl hydrazide a mixture of one or more of sodium bicarbonate, sodium citrate, ammonium bicarbonate, and expandable microspheres.
  8. 根据权利要求1所述的发泡材料用组合物，其特征在于，所述交联剂为过氧化物或偶氮化合物中的一种，所述助交联剂为含有2个及以上碳碳双键的化合物，优选地，所述助交联剂为丁二烯、戊二烯、辛二烯、二乙烯基苯、三烯丙基异氰脲酸酯、三烯丙基三聚氰酸酯、三羟甲基丙烷中的一种或多种的混合物，所述其他助剂是指抗UV剂、抗氧剂中的一种或两种的混 合物。The composition for a foamed material according to claim 1, wherein the crosslinking agent is one of a peroxide or an azo compound, and the crosslinking agent contains two or more carbons and carbons. A compound of a double bond, preferably, the co-crosslinking agent is butadiene, pentadiene, octadiene, divinylbenzene, triallyl isocyanurate, triallyl cyanuric acid a mixture of one or more of an ester, trimethylolpropane, which refers to a mixture of one or both of an anti-UV agent and an antioxidant Compound.
  9. 一种权利要求1-8中任一项所述的发泡材料用组合物的制备方法，其特征在于，包括如下步骤：A method for preparing a composition for a foamed material according to any one of claims 1 to 8, which comprises the steps of:
    1)将称量好的烯烃类聚合物、热塑性聚氨酯弹性体、相容剂和其他助剂混合均匀后造粒得基料，将所得基料与发泡剂、交联剂、助交联剂混合均匀；1) The weighed olefin polymer, thermoplastic polyurethane elastomer, compatibilizer and other auxiliaries are uniformly mixed and granulated to obtain a base material, and the obtained base material is combined with a foaming agent, a crosslinking agent and a co-crosslinking agent. well mixed;
    2)将步骤1)中所得混合物进行发泡，经冷却、定型后得到高回弹发泡制品。2) The mixture obtained in the step 1) is foamed, and after cooling and setting, a high resilience foamed product is obtained.
  10. 根据权利要求9所述的发泡材料用组合物的制备方法，其特征在于，步骤2)中发泡的具体步骤为如下方法中的一种：The method for producing a composition for a foamed material according to claim 9, wherein the specific step of foaming in the step 2) is one of the following methods:
    A：将混合物置于制品模具中，将制品模具置于平板硫化机中，在100-200℃下进行模压发泡1-60分钟，然后将模具冷却至5-60℃，得到高回弹发泡制品；A: The mixture is placed in a product mold, the product mold is placed in a flat vulcanizer, and the foam is molded at 100-200 ° C for 1-60 minutes, and then the mold is cooled to 5-60 ° C to obtain a high rebound. Foam product
    B：将混合物加入到EVA注塑发泡机中，在100-220℃下进行注塑发泡，经冷却、定型后得到高回弹发泡制品；B: adding the mixture to the EVA injection foaming machine, performing injection foaming at 100-220 ° C, and obtaining a high rebound foamed product after cooling and setting;
    C：将混合物加入到挤出机中，在100-220℃下进行挤出发泡，经冷却、定型后得到高回弹发泡制品。 C: The mixture was added to an extruder, and extrusion foaming was carried out at 100-220 ° C, and after cooling and setting, a high-rebound foamed product was obtained.
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