WO2018214208A1 - Composition pour matériau moussant présentant une élasticité de rebondissement élevée et procédé de préparation associé - Google Patents

Composition pour matériau moussant présentant une élasticité de rebondissement élevée et procédé de préparation associé Download PDF

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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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Prior art keywords
foaming
composition
parts
foamed
mixture
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PCT/CN2017/089278
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English (en)
Chinese (zh)
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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/fr

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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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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

L'invention concerne une composition pour un matériau moussant ayant une élasticité de rebondissement élevée et un procédé de préparation associé. La composition comprend les constituants suivants en parties en poids : de 5 à 95 parties de polymère d'oléfine, de 5 à 95 parties d'élastomère de polyuréthane thermoplastique (TPU), de 0,1 à 45 parties d'agent de compatibilité, de 0,1 à 10 parties d'agent moussant, de 0,01 à 5 parties d'agent de réticulation, de 0 à 5 parties d'additif de réticulation, et de 0 à 10 parties d'un autre additif. L'utilisation de l'agent de compatibilité comprenant un groupe polaire ou un groupe actif double produit un effet de compatibilisation, de telle sorte qu'une tension interfaciale entre le polymère d'oléfine et le TPU est réduite, une structure de polymère d'oléfine/réseau polymère interpénétrant (IPN) de TPU est formée, et ainsi le problème de compatibilité entre deux types de matériaux est résolu ; grâce à une introduction réussie du constituant TPU dans le polymère d'oléfine, des propriétés d'un matériau polymère d'oléfine moussant, telle qu'une élasticité de rebondissement et une déformation permanente à la compression, sont considérablement améliorées en raison de l'excellente résilience du TPU.
PCT/CN2017/089278 2017-05-22 2017-06-21 Composition pour matériau moussant présentant une élasticité de rebondissement élevée et procédé de préparation associé WO2018214208A1 (fr)

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