WO2018129791A1 - 一种膨胀型热塑性聚氨酯弹性体制品的制备方法 - Google Patents

一种膨胀型热塑性聚氨酯弹性体制品的制备方法 Download PDF

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WO2018129791A1
WO2018129791A1 PCT/CN2017/074658 CN2017074658W WO2018129791A1 WO 2018129791 A1 WO2018129791 A1 WO 2018129791A1 CN 2017074658 W CN2017074658 W CN 2017074658W WO 2018129791 A1 WO2018129791 A1 WO 2018129791A1
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Prior art keywords
thermoplastic polyurethane
polyurethane elastomer
expanded thermoplastic
binder
preparation
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PCT/CN2017/074658
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English (en)
French (fr)
Inventor
王光阜
宋红玮
杨冲冲
任光雷
王仁鸿
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美瑞新材料股份有限公司
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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 ES17891752T priority Critical patent/ES2933100T3/es
Priority to EP17891752.2A priority patent/EP3569647B1/en
Priority to MX2019008486A priority patent/MX2019008486A/es
Priority to US16/478,290 priority patent/US11530310B2/en
Priority to KR1020197023983A priority patent/KR102291202B1/ko
Publication of WO2018129791A1 publication Critical patent/WO2018129791A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products
    • C08J9/236—Forming foamed products using binding agents
    • 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
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
    • B29C44/04—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles consisting of at least two parts of chemically or physically different materials, e.g. having different densities
    • B29C44/0407—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles consisting of at least two parts of chemically or physically different materials, e.g. having different densities by regulating the temperature of the mould or parts thereof, e.g. cold mould walls inhibiting foaming of an outer layer
    • 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
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
    • B29C44/04—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles consisting of at least two parts of chemically or physically different materials, e.g. having different densities
    • B29C44/0415—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles consisting of at least two parts of chemically or physically different materials, e.g. having different densities by regulating the pressure of the material during or after filling of the mould, e.g. by local venting
    • 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
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3415—Heating or cooling
    • 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
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/36—Feeding the material to be shaped
    • B29C44/38—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length
    • B29C44/44—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length in solid form
    • B29C44/445—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length in solid form in the form of expandable granules, particles or beads
    • 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
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/60—Measuring, controlling or regulating
    • 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
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/20—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored
    • B29C67/207—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored comprising impregnating expanded particles or fragments with a binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/224—Surface treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3415—Heating or cooling
    • B29C44/3426—Heating by introducing steam in the mould
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/005—< 50kg/m3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/0058—≥50 and <150kg/m3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/22—Expandable microspheres, e.g. Expancel®
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/53—Core-shell polymer

Definitions

  • the invention relates to a preparation method of a thermoplastic polyurethane elastomer product, in particular to a preparation method of an expanded thermoplastic polyurethane elastomer product, belonging to the field of lightweight materials.
  • the polymer foaming material is a polymer-based material which physically or chemically generates a large number of cell structures inside the polymer matrix. Because the unique cell structure of the foaming material gives it a series of excellent properties, such as low density, thermal insulation, high specific strength, buffering, etc., in the packaging industry, industry, agriculture, transportation, military industry, aerospace It has a wide range of applications in the fields of industry and daily necessities.
  • Commonly used foam materials are polyurethane (PU) soft and rigid foam, polystyrene (PS) foam, polyethylene (PE) foam, polypropylene (PP) foam, foamed ethylene-vinyl acetate ( EVA) and so on.
  • Polyurethane foams tend to remain isocyanate during the foaming process, which is harmful to the human body and the foamed material cannot be recycled. Styrofoam products are difficult to degrade and are prone to "white pollution" problems.
  • the UN Environment Organization has decided to stop using PS foam products.
  • Polyethylene foam has poor temperature resistance and is not suitable for high temperature applications.
  • Foamed EVA is processed by molding foaming process. This process equipment is quite mature, but the loss of elasticity of foamed EVA during long-term use is serious, and Not environmentally friendly during the preparation process.
  • Thermoplastic polyurethane elastomer (TPU) materials have a wide range of hardness, excellent wear resistance, mechanical strength, water resistance, oil resistance, chemical resistance, mold resistance, environmental friendliness, and recycling.
  • the expanded thermoplastic polyurethane elastomer particles have excellent resilience, shape diversity, and low density while retaining the excellent properties of the thermoplastic polyurethane matrix, and can be used over a wide temperature range. Based on the above advantages, TPU foaming materials are used in many industrial fields (automotive industry, Packaging materials) as well as daily life areas (shoe materials, pillows, mattresses) have a very broad application prospects.
  • CN103371564A discloses a method for producing midsole and insole articles using expanded thermoplastic polyurethane elastomer particles (E-TPU) materials, which are processed using a water vapor molding apparatus in which foam is sprayed by water vapor in a specially designed mold.
  • Thermoplastic polyurethane particles are sintered, but the production equipment is complicated in process, high in equipment cost, complicated in mold design and low in yield, which severely limits the promotion and application of this material. Therefore, the development of an expanded thermoplastic polyurethane elastomer material suitable for general-purpose molding foaming equipment and a preparation method have become targets of many companies and research institutions.
  • the present invention provides a method for preparing an expanded thermoplastic polyurethane elastomer product in view of the deficiencies in the existing expansion type thermoplastic polyurethane processing and molding method.
  • a method for preparing an expanded thermoplastic polyurethane elastomer product comprising the steps of:
  • step 2) Curing molding: the product obtained in step 1) is added to a molding die and then placed in a vulcanizer to be molded and cured;
  • the binder described in the step 1) is a heat-fusible resin having a melting point of 40 to 200 ° C, and the form thereof is one of a powder and a liquid.
  • the binder described in the step 1) is one of a thermoplastic polyurethane elastomer, an acrylate, an epoxy resin, a one-component polyurethane, a two-component polyurethane, and an aqueous polyurethane.
  • the powder form of the hot meltable resin has a particle diameter of 30 to 5000 mesh, preferably 50 to 3000 mesh, particularly preferably 300 to 2500 mesh; and the liquid form of the hot meltable resin has an effective solid content of 5-100% by weight, preferably 10-80%, particularly preferably 20-50%.
  • the density of the expanded thermoplastic polyurethane elastomer particles described in the step 1) is from 0.001 to 0.6 g/cm 3 , preferably from 0.05 to 0.3 g/cm 3 , particularly preferably from 0.15 to 0.25 g/cm 3 , according to ASTM- D792 test was obtained.
  • the method of attaching the binder to the surface of the expanded thermoplastic polyurethane elastomer particles in the step 1) is one of electrostatic adsorption, spray coating, dry mixing, and a simple mixer such as a drum mixer or a high mixer may be used.
  • the mixture is mechanically mixed or manually mixed in a plastic container to obtain an expanded thermoplastic polyurethane elastomer particle having a surface-attached binder.
  • the mass ratio of the binder to the expanded thermoplastic polyurethane elastomer particles described in the step 1) is from 1:1 to 1:10000.
  • step 2) the vulcanization temperature of the vulcanizer is 40-200 ° C, the vulcanization pressure is 0.01-1 MPa, and the vulcanization time is 1-30 minutes.
  • the temperature of cooling in the step 3) is 10-40 ° C, and the cooling time is 1-20 min.
  • the method of the invention adopts a universal mature molding foaming process equipment, and adjusts the mixing ratio of the binder and the expanded thermoplastic polyurethane particles and the curing temperature to maintain the elasticity of the expanded thermoplastic polyurethane particles under the premise of retaining the elasticity of the expanded thermoplastic polyurethane particles.
  • the foamed thermoplastic polyurethane particles are bonded to each other, so that the prepared article has excellent resilience, resistance to tortuosity and compression deformation, thereby avoiding expansion thermoplasticity due to uneven heating of water vapor in the steam molding process. Defects such as poor adhesion between polyurethane particles.
  • the binder is cured to form expanded thermoplastic polyurethane particles, and it is not necessary to weld the expanded thermoplastic polyurethane particles through a high-pressure high-temperature steam medium, thereby avoiding high-cost water.
  • the investment in steam molding equipment and the development of corresponding molds and equipments do not require equipment reinvestment and transformation, the production process is simple, the production cost is low, the control is easy, the process is mature, and the yield is high;
  • the article prepared by the method of the invention has excellent elasticity, tensile strength and flexural bending resistance, and is unmatched by the material of the expanded thermoplastic polyurethane article prepared by the steam molding process.
  • a method for preparing an expanded thermoplastic polyurethane elastomer article comprising the steps of:
  • thermoplastic polyurethane powder by electrostatic adsorption Coated on the surface of 1 part by weight of the expanded thermoplastic polyurethane particles, wherein the thermoplastic polyurethane powder has a melting point of 80-100 ° C and a particle diameter of 30 mesh; the foamed thermoplastic polyurethane particles have a density of 0.6 g/cm 3 and a white appearance.
  • the product mold of the step (2) is placed in a flat vulcanizing machine for molding and solidification molding, the vulcanization temperature of the flat vulcanizing machine is 100 ° C, the vulcanization pressure is 0.01 Mpa, and the vulcanization time is 2 minutes;
  • a method for preparing an expanded thermoplastic polyurethane elastomer article comprising the steps of:
  • acrylate glue (TA-868) is coated on the surface of 10,000 parts by weight of expanded thermoplastic polyurethane particles by a spraying process, wherein the acrylate has a solid content of 5% in the acrylate glue solution;
  • the polyurethane particles have a density of 0.25 g/cm 3 , a fluorescent yellow appearance, and a cylindrical shape;
  • the product mold of the step (2) is placed in a flat vulcanizing machine for molding and solidification molding, the vulcanization temperature of the flat vulcanizing machine is 200 ° C, the vulcanization pressure is 1 Mpa, and the vulcanization time is 30 minutes;
  • a method for preparing an expanded thermoplastic polyurethane elastomer article comprising the steps of:
  • the appearance is sapphire blue and the shape is cylindrical;
  • the product mold of the step (2) is placed in a flat vulcanizing machine for molding and solidification molding, the vulcanization temperature of the flat vulcanizing machine is 150 ° C, the vulcanization pressure is 0.5 Mpa, and the vulcanization time is 10 minutes;
  • a method for preparing an expanded thermoplastic polyurethane elastomer article comprising the steps of:
  • the product mold of the step (2) is placed in a flat vulcanizing machine for molding and solidification molding, the vulcanization temperature of the flat vulcanizing machine is 60 ° C, the vulcanization pressure is 1 Mpa, and the vulcanization time is 5 minutes;
  • a method for preparing an expanded thermoplastic polyurethane elastomer article comprising the steps of:
  • the product mold of the step (2) is placed in a flat vulcanizing machine for molding and solidification molding, the vulcanization temperature of the flat vulcanizing machine is 70 ° C, the vulcanization pressure is 0.8 Mpa, and the vulcanization time is 10 minutes;
  • a method for preparing an expanded thermoplastic polyurethane elastomer article comprising the steps of:
  • the product mold of the step (2) is placed in a flat vulcanizing machine for molding and solidification molding, the vulcanization temperature of the flat vulcanizing machine is 70 ° C, the vulcanization pressure is 0.8 Mpa, and the vulcanization time is 10 minutes;
  • test standard for tensile strength is ISO179:2008; the test standard for ball rebound is ISO830:2007; the test standard for tortuosity is ASTM D1052 (100,000 times); the test standard for compression deformation is SATRA TM64.

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

本发明涉及一种膨胀型热塑性聚氨酯弹性体制品的制备方法，包括如下步骤：1)涂覆粘结剂：使膨胀型热塑性聚氨酯弹性体粒子的表面附着粘结剂；2)固化成型：步骤1)中所得产品加入到成型模具中后置于硫化机内模压固化成型；3)冷却定型：将步骤2)中成型后的成型模具冷却，即得。本发明的通过在膨胀型热塑性聚氨酯弹性体粒子表面预先附着粘结剂的方式，可以减少粘结剂添加的比例，最大程度地利用膨胀型热塑性聚氨酯弹性体粒子的特性。

Description

一种膨胀型热塑性聚氨酯弹性体制品的制备方法 技术领域
本发明涉及一种热塑性聚氨酯弹性体制品的制备方法，尤其涉及一种膨胀型热塑性聚氨酯弹性体制品的制备方法，属于轻量化材料领域。
背景技术
聚合物发泡材料是以聚合物为基体材料，通过物理或化学方法使聚合物基体内部产生大量的泡孔结构。由于发泡材料独特的泡孔结构赋予了其一系列优良的性能，如密度低、隔热隔音、比强度高、缓冲等，因此在包装业、工业、农业、交通运输业、军事工业、航天工业以及日用品等领域具有广泛的应用。常用的泡沫材料种类有聚氨酯(PU)软质和硬质泡沫塑料、聚苯乙烯(PS)泡沫塑料、聚乙烯(PE)泡沫塑料、聚丙烯(PP)泡沫塑料、发泡乙烯-醋酸乙烯(EVA)等。聚氨酯泡沫塑料在发泡过程中容易残留异氰酸酯，对人体有害，并且发泡材料无法回收利用。聚苯乙烯泡沫塑料产品降解困难，易产生“白色污染”问题，***环境组织已决定停止使用PS泡沫塑料产品。聚乙烯泡沫塑料耐高温性能较差，不适合在高温领域内应用，发泡EVA采用模压发泡工艺加工，此种工艺设备已经相当成熟，但发泡EVA长时间使用过程中弹性损失严重，并且制备过程中不环保。
热塑性聚氨酯弹性体(TPU)材料具有较宽泛的硬度范围，优异的耐磨性、机械强度、耐水、耐油、耐化学腐蚀、耐霉菌，对环境友好，可回收利用等优点。膨胀型热塑性聚氨酯弹性体粒子在保留热塑性聚氨酯基体优异的性能之外，同时具有优异的回弹性，形状多样性，低密度，可以在较宽的温度范围内使用。基于上述优点，TPU发泡材料在许多工业领域(汽车工业、 包装材料)以及日常生活领域(鞋材、枕头、床垫)具有非常广泛的应用前景。
CN103371564A公开了采用膨胀型热塑性聚氨酯弹性体粒子(E-TPU)材料生产中底和鞋内底制品的方法，其采用水蒸气模塑设备加工，在特殊设计的模具中，通过水蒸气将发泡热塑性聚氨酯粒子烧结成型，但是此种生产设备工艺复杂，设备成本高，模具设计复杂，成品率低，严重限制了此材料的推广与应用。因而开发一种适用于通用模发泡设备的膨胀型热塑性聚氨酯弹性体材料以及制备方法成为许多公司和研究机构的目标。
发明内容
本发明针对现有膨胀型热塑性聚氨酯加工成型方法上存在的不足，提供一种膨胀型热塑性聚氨酯弹性体制品的制备方法。
本发明解决上述技术问题的技术方案如下：
一种膨胀型热塑性聚氨酯弹性体制品的制备方法，其特征在于，包括如下步骤：
1)附着粘结剂：使膨胀型热塑性聚氨酯弹性体粒子的表面附着粘结剂；
2)固化成型：步骤1)中所得产品加入到成型模具中后置于硫化机内模压固化成型；
3)冷却定型：将步骤2)中成型后的成型模具冷却，即得。
进一步，步骤1)中所述的粘结剂为熔点处于40-200℃的可热熔树脂，其形态为粉体、液体中的一种。
进一步，步骤1)中所述的粘结剂为热塑性聚氨酯弹性体、丙烯酸酯、环氧树脂、单组份聚氨酯、双组份聚氨酯、水性聚氨酯中的一种。
进一步，所述粉体形态的可热熔树脂的粒径为30-5000目，优选50-3000目，特别优选300-2500目；所述液体形态的可热熔树脂其有效固含量为 5-100wt％，优选10-80％，特别优选20-50％。
进一步，步骤1)中所述的膨胀型热塑性聚氨酯弹性体粒子的密度为0.001-0.6g/cm3，优选0.05-0.3g/cm3,特别优选0.15-0.25g/cm3，其根据ASTM-D792测试得到。
进一步，步骤1)中于膨胀型热塑性聚氨酯弹性体粒子的表面附着粘结剂的方法为静电吸附、喷涂、干混中的一种，可以采用简单混合器如转鼓式混合器或高混机中进行机械混合或在塑料容器中手动进行混合，得到表面附着粘结剂的膨胀型热塑性聚氨酯弹性体粒子。
进一步，步骤1)中所述的粘结剂与膨胀型热塑性聚氨酯弹性体粒子的质量比为1:1到1：10000。
进一步，步骤2)中硫化机的硫化温度为40-200℃，硫化压力为0.01-1MPa，硫化时间为1-30分钟。
进一步，步骤3)中冷却的温度为10-40℃，冷却时间为1-20min。
本发明的方法采用通用成熟的模压发泡工艺设备，通过调整粘结剂与膨胀热塑性聚氨酯粒子的混合比例以及固化温度，在保留膨胀热塑性聚氨酯粒子优异弹性的前提下，通过粘结剂的固化作用使发泡热塑性聚氨酯粒子相互粘结在一起，使得所制备的制品具有优异的回弹性，耐曲折和压缩变形等性能，从而避免了水蒸气模塑成型工艺中由于水蒸气加热不均匀导致膨胀热塑性聚氨酯粒子之间粘结不牢等缺陷问题。
本发明的有益效果是：
1)通过在膨胀型热塑性聚氨酯弹性体粒子表面预先附着粘结剂的方式，可以减少粘结剂添加的比例，最大程度地利用膨胀型热塑性聚氨酯弹性体粒子的特性；
2)通过控制固化温度，使粘结剂固化膨胀型热塑性聚氨酯粒子成型，无需通过高压高温水蒸气介质熔接膨胀型热塑性聚氨酯粒子，避免了高成本的水 蒸气模塑成型设备的投资与相应模具和设备的研发，无需进行设备再投资与改造，生产工艺简单，生产成本低；便于控制，工艺成熟，成品率高；
3)本发明的方法所制备的制品具有优异弹性，拉伸强度，抗曲折弯曲性能，是目前通过水蒸气模塑成型工艺制备的膨胀型热塑性聚氨酯制品材料无法比拟的。
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：
一种膨胀型热塑性聚氨酯弹性体制品的制备方法，包括如下步骤：
(1)采用静电吸附方式将1重量份的热塑性聚氨酯粉末
Figure PCTCN2017074658-appb-000001
涂覆在1重量份的膨胀热塑性聚氨酯粒子表面，其中热塑性聚氨酯粉末的熔点为80-100℃，粒径为30目；发泡热塑性聚氨酯粒子的密度为0.6g/cm3,外观为白色，形状为椭圆形；
(2)称取100g上述表面附着粘结剂的膨胀型热塑性聚氨酯弹性体粒子并装填到制品模具中；
(3)将步骤(2)的制品模具置于平板硫化机中进行模压固化成型，平板硫化机的硫化温度为100℃，硫化压力为0.01Mpa,硫化时间为2分钟；
(4)将上述步骤(3)的制品模具采用冷却水冷却，冷却温度为10℃，冷却时间为1分钟，得到最终的膨胀型热塑性聚氨酯弹性体制品。
实施例2：
一种膨胀型热塑性聚氨酯弹性体制品的制备方法，包括如下步骤：
(1)采用喷涂工艺将1重量份的丙烯酸酯胶(TA-868)涂覆在10000重量份的膨胀热塑性聚氨酯粒子表面，其中丙烯酸酯胶溶液中丙烯酸酯的固含量 为5％；发泡热塑性聚氨酯粒子的密度为0.25g/cm3,外观为荧光黄，形状为圆柱形；
(2)称取100g上述表面涂覆粘结剂的膨胀型热塑性聚氨酯弹性体粒子并装填到制品模具中；
(3)将步骤(2)的制品模具置于平板硫化机中进行模压固化成型，平板硫化机的硫化温度为200℃，硫化压力为1Mpa,硫化时间为30分钟；
(4)将上述步骤(3)的制品模具采用冷却水冷却，冷却温度为40℃，冷却时间为20分钟，得到最终的膨胀型热塑性聚氨酯弹性体制品。
实施例3：
一种膨胀型热塑性聚氨酯弹性体制品的制备方法，包括如下步骤：
(1)采用干混工艺将1重量份的环氧树脂胶
Figure PCTCN2017074658-appb-000002
涂覆在500重量份的膨胀型热塑性聚氨酯粒子表面，其中所使用的环氧树脂胶的有效固含量为100％，粒径为5000目，膨胀型热塑性聚氨酯粒子的密度为0.3g/cm3,外观为宝石蓝，形状为圆柱形；
(2)称取100g上述表面附着粘结剂的膨胀型热塑性聚氨酯弹性体粒子并装填到制品模具中；
(3)将步骤(2)的制品模具置于平板硫化机中进行模压固化成型，平板硫化机的硫化温度为150℃，硫化压力为0.5Mpa,硫化时间为10分钟；
(4)将上述步骤(3)的制品模具采用冷却水冷却，冷却温度为20℃，冷却时间为5分钟，得到最终的膨胀型热塑性聚氨酯弹性体制品。
实施例4：
一种膨胀型热塑性聚氨酯弹性体制品的制备方法，包括如下步骤：
(1)采用喷涂工艺将1重量份的单组份聚氨酯胶
Figure PCTCN2017074658-appb-000003
涂覆在100重量份的膨胀型热塑性聚氨酯粒子表面，其中所使用的单组份聚氨酯胶液体的有效固含量为80％，膨胀型热塑性聚氨酯粒子的密度为0.05g/cm3,外 观为荧光黄，形状为圆柱形；
(2)称取100g上述表面涂覆粘结剂的膨胀型热塑性聚氨酯弹性体粒子并装填到制品模具中；
(3)将步骤(2)的制品模具置于平板硫化机中进行模压固化成型，平板硫化机的硫化温度为60℃，硫化压力为1Mpa,硫化时间为5分钟；
(4)将上述步骤(3)的制品模具采用冷却水冷却，冷却温度为30℃，冷却时间为5分钟，得到最终的膨胀型热塑性聚氨酯弹性体制品。
实施例5：
一种膨胀型热塑性聚氨酯弹性体制品的制备方法，包括如下步骤：
(1)采用喷涂工艺将1重量份的双组份聚氨酯胶
Figure PCTCN2017074658-appb-000004
涂覆在800重量份的膨胀型热塑性聚氨酯粒子表面，其中双组份聚氨酯胶液体的有效固含量为50％，膨胀热塑性聚氨酯粒子的密度为0.15g/cm3,外观为桃红，形状为圆形；
(2)称取100g上述表面涂覆粘结剂的膨胀型热塑性聚氨酯弹性体粒子并装填到制品模具中；
(3)将步骤(2)的制品模具置于平板硫化机中进行模压固化成型，平板硫化机的硫化温度为70℃，硫化压力为0.8Mpa,硫化时间为10分钟；
(4)将上述步骤(3)的制品模具采用冷却水冷却，冷却温度为25℃，冷却时间为10分钟，得到最终的膨胀型热塑性聚氨酯弹性体制品。
实施例6：
一种膨胀型热塑性聚氨酯弹性体制品的制备方法，包括如下步骤：
(1)采用喷涂工艺将1重量份的水性聚氨酯
Figure PCTCN2017074658-appb-000005
涂覆在1000重量份的膨胀型热塑性聚氨酯粒子表面，其中水性聚氨酯乳液的有效固含量为20％，膨胀热塑性聚氨酯粒子的密度为0.25g/cm3,外观为桃红，形状为圆形；
(2)称取100g上述表面涂覆粘结剂的膨胀型热塑性聚氨酯弹性体粒子并装填到制品模具中；
(3)将步骤(2)的制品模具置于平板硫化机中进行模压固化成型，平板硫化机的硫化温度为70℃，硫化压力为0.8Mpa,硫化时间为10分钟；
(4)将上述步骤(3)的制品模具采用冷却水冷却，冷却温度为25℃，冷却时间为10分钟，得到最终的膨胀型热塑性聚氨酯弹性体制品。
为了验证本发明所得的膨胀型热塑性聚氨酯弹性体制品的性能，我们将实施例1-6所得的产品与水蒸汽模塑制品进行了如下测试，具体测试结果数据如表1所示：
表1：实施例1-6所得产品与水蒸汽模塑制品的性能测试数据
Figure PCTCN2017074658-appb-000006
其中，拉伸强度的测试标准为ISO179：2008；落球回弹的测试标准为ISO830：2007；耐曲折的测试标准为ASTM D1052(10万次)；压缩变形的测试标准为SATRA TM64。
由表1中的数据可以看出，本发明所制备的产品在拉伸强度，落球回弹性，耐曲折和压缩变形方面都优于市场同类产品。
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. 一种膨胀型热塑性聚氨酯弹性体制品的制备方法，其特征在于，包括如下步骤：
    1)附着粘结剂：使膨胀型热塑性聚氨酯弹性体粒子的表面附着粘结剂；
    2)固化成型：步骤1)中所得产品加入到成型模具中后置于硫化机内模压固化成型；
    3)冷却定型：将步骤2)中成型后的成型模具冷却，即得。
  2. 根据权利要求1所述的制备方法，其特征在于，步骤1)中所述的粘结剂为熔点处于40-200℃的可热熔树脂，其形态为粉体、液体中的一种。
  3. 根据权利要求2所述的制备方法，其特征在于，步骤1)中所述的粘结剂为热塑性聚氨酯弹性体、丙烯酸酯、环氧树脂、单组份聚氨酯、双组份聚氨酯、水性聚氨酯中的一种。
  4. 根据权利要求2所述的制备方法，其特征在于，所述粉体形态的可热熔树脂的粒径为30-5000目，所述液体形态的可热熔树脂其有效固含量为5-100wt％。
  5. 根据权利要求3所述的制备方法，其特征在于，所述粉体形态的可热熔树脂的粒径为50-3000目，所述液体形态的可热熔树脂其有效固含量为10-80wt％。
  6. 根据权利要求1所述的制备方法，其特征在于，步骤1)中所述的膨胀型热塑性聚氨酯弹性体粒子的密度为0.001-0.6g/cm3。
  7. 根据权利要求6所述的制备方法，其特征在于，步骤1)中所述的膨胀型热塑性聚氨酯弹性体粒子的密度为0.05-0.3g/cm3。
  8. 根据权利要求1所述的制备方法，其特征在于，步骤1)中所述的粘结剂与膨胀型热塑性聚氨酯弹性体粒子的质量比为1:1到1:10000。
  9. 根据权利要求1所述的制备方法，其特征在于，步骤1)中于膨胀型热塑性聚氨酯弹性体粒子的表面附着粘结剂的方法为静电吸附、喷涂、干混中的一种。
  10. 根据权利要求1-9中任一项所述的制备方法，其特征在于，步骤2)中硫化机的硫化温度为40-200℃，硫化压力为0.01-1MPa，硫化时间为1-30分钟，步骤3)中冷却的温度为10-40℃，冷却时间为1-20min。
PCT/CN2017/074658 2017-01-16 2017-02-24 一种膨胀型热塑性聚氨酯弹性体制品的制备方法 WO2018129791A1 (zh)

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US20190367698A1 (en) 2019-12-05
PT3569647T (pt) 2022-12-13
EP3569647A1 (en) 2019-11-20
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