CN109135033A - 高分子材料物理发泡方法及发泡制品 - Google Patents

高分子材料物理发泡方法及发泡制品 Download PDF

Info

Publication number
CN109135033A
CN109135033A CN201810699146.8A CN201810699146A CN109135033A CN 109135033 A CN109135033 A CN 109135033A CN 201810699146 A CN201810699146 A CN 201810699146A CN 109135033 A CN109135033 A CN 109135033A
Authority
CN
China
Prior art keywords
type embryo
supercritical fluid
foaming
polyolefin
embryo
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201810699146.8A
Other languages
English (en)
Inventor
罗振寰
刘伏奇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dongguan High Polymer Mstar Technology Ltd
Original Assignee
Dongguan High Polymer Mstar Technology Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dongguan High Polymer Mstar Technology Ltd filed Critical Dongguan High Polymer Mstar Technology Ltd
Priority to CN201810699146.8A priority Critical patent/CN109135033A/zh
Priority to US16/152,682 priority patent/US20200002499A1/en
Publication of CN109135033A publication Critical patent/CN109135033A/zh
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B11/00—Making preforms
    • B29B11/06—Making preforms by moulding the material
    • 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
    • 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
    • B29C44/3442—Mixing, kneading or conveying the foamable material
    • B29C44/3446—Feeding the blowing agent
    • B29C44/3453—Feeding the blowing agent to solid plastic material
    • 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
    • B29C44/3469—Cell or pore nucleation
    • B29C44/348—Cell or pore nucleation by regulating the temperature and/or the pressure, e.g. suppression of foaming until the pressure is rapidly decreased
    • 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
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • 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
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • 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
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
    • C08J9/0066—Use of inorganic compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • 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
    • B29C44/3488—Vulcanizing the material before foaming
    • 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
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B29K2023/0608—PE, i.e. polyethylene characterised by its density
    • B29K2023/0633—LDPE, i.e. low density polyethylene
    • 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
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/08—Copolymers of ethylene
    • B29K2023/083—EVA, i.e. ethylene vinyl acetate copolymer
    • 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
    • B29K2509/00—Use of inorganic materials not provided for in groups B29K2503/00 - B29K2507/00, as filler
    • B29K2509/02—Ceramics
    • 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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/026—Crosslinking before of after foaming
    • 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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/03—Extrusion of the foamable blend
    • 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
    • C08J2203/06—CO2, N2 or noble gases
    • 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
    • C08J2203/08—Supercritical fluid
    • 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
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/10—Rigid foams
    • 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
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/22—Thermoplastic 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
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/26—Elastomers
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; 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
    • 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
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • 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
    • C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
    • C08J2491/06—Waxes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides

Landscapes

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

Abstract

本发明涉及一种高分子材料物理发泡方法及发泡制品。本发明的高分子材料物理发泡方法包括：(1)使用射出机、挤出机或模压机，将热塑性弹性体或聚烯烃材料制作成异型型胚；(2)加热聚烯烃型胚使其发生交联反应，得到交联的聚烯烃型胚；(3)将热塑性弹性体型胚或交联的聚烯烃型胚在压力釜中用超临界流体进行高压浸渗，然后泄压至常压，得到超临界流体浸渗的型胚；(4)将超临界流体浸渗的型胚置于成品模具中，进行1:1模内发泡，即得成品的发泡制品。本发明利用超临界流体作为物理发泡剂，通过简单的模内发泡工艺，获得了低比重、环保无毒、弹性优良的发泡材料。

Description

高分子材料物理发泡方法及发泡制品
技术领域
本发明涉及高分子材料领域，特别涉及高分子材料物理发泡方法及发泡制品。
背景技术
发泡工艺是用于制作低比重材料的常用工艺之一。发泡工艺根据所使用的发泡剂可分为化学发泡工艺和物理发泡工艺。传统制作低比重聚烯烃化学发泡材料需使用化学发泡剂，通常有以下缺点：不符合环保要求；发泡剂分解物质存在有害物质，不符合相关的安全法规。传统制作聚烯烃物理发泡材料的主要方法为气辅注塑成型、挤出成型等方法，使用烷烃类气体、低挥发点化合物、CO2、N2(例如Mucell技术)等作为物理发泡剂。Mucell技术为美国Trexcel公司所建立，其技术乃将制造超临界流体的设备连结至注塑机或挤出机的料管，将超临界流体注入注塑机或挤出机的料管中与高分子材料在料管中进行混合，然后将混合超临界流体的高分子熔融塑料注塑到塑料模具中进行注塑成型或是挤出成型，以获得轻量化的注塑成品或挤出成品。
以上方法制作异型物理发泡材料通常有以下缺点：比重偏高(约0.4以上)、弹性低、触感较差、表面外观具有气痕不够平整光滑等问题，不适合制作鞋材以及具缓冲效果之地垫或运动器材等产品。以烷烃类气体(如丁烷、戊烷、己烷等)或低挥发点化合物作为物理发泡剂，亦不是完全符合环保需求的发泡剂。另外，传统制作聚烯烃物理或化学发泡制品为模外发泡后，再置入成品模具中进行二次加工，工艺较繁琐费时。
发明内容
本发明利用超临界流体作为物理发泡剂，通过简单的模内发泡工艺，获得了低比重、环保无毒、弹性优良的发泡材料。
本发明的一个方面提供一种高分子材料物理发泡方法，包括：
(1)使用射出机、挤出机或模压机，将热塑性弹性体或聚烯烃材料制作成异型型胚；
(2)使聚烯烃型胚发生交联反应，得到交联的聚烯烃型胚；
(3)将热塑性弹性体型胚或交联的聚烯烃型胚在压力釜中用超临界流体在10-50MPa压力下进行高压浸渗，然后泄压至常压，得到超临界流体浸渗的型胚；
(4)将超临界流体浸渗的型胚置于成品模具中，进行1:1模内发泡，即得成品的发泡制品。
本发明的另一个方面提供一种由上述高分子材料物理发泡方法获得的发泡制品，所述发泡制品具有按照ASTM D2632测量的50％以上的回弹性能。
本发明利用超临界流体作为物理发泡剂，通过简单的模内发泡工艺，获得了低比重、环保无毒、弹性优良且表面外观平整光滑的发泡材料。本发明的异型发泡材料完全符合环保无毒、可回收再利用的环境友好潮流趋势。由于利用一次发泡成型即可获得最终制品，无需进行二次加工，本发明可以同时达到减少人力及节省能源的目的。
具体实施方式
本发明的高分子材料物理发泡方法包括：制备热塑性弹性体或聚烯烃异型型胚(对于聚烯烃异型型胚，可以在制成型胚后使聚烯烃材料发生交联反应而得到交联的聚烯烃型胚)；用超临界流体对上述型胚进行高压浸渗，得到超临界流体浸渗的型胚；然后对超临界流体浸渗的型胚进行1:1模内发泡，得到成品的发泡制品。
-原料-
可用于本发明的分子材料物理发泡方法的原料包括热塑性弹性体和聚烯烃材料。
热塑性弹性体可以包括热塑性聚氨酯(TPU)、热塑性聚酯弹性体(TPEE)、嵌段聚醚酰胺弹性体(Pebax)中的一种或它们的混合物。
聚烯烃材料可以包括乙烯-乙酸乙烯酯共聚物(EVA)、聚烯烃弹性体(POE)、低密度聚乙烯(LDPE)中的一种或它们的混合物。例如，聚烯烃材料可以为EVA，其中乙酸乙烯酯的摩尔含量为5％-40％，或者可以为EVA/POE的混合物，掺混比例为100/0.1～0.1/100，或者可以为聚烯烃材料与橡胶材料的共混物，例如EVA/POE/EPDM(三元乙丙橡胶)共混物，掺混比例为100/0.1/0.1～0.1/100/20。
聚烯烃材料还可以掺杂有交联剂、填充剂和助剂中的至少一种。其中，以聚烯烃材料的重量份为100phr计，交联剂的量可以为1.2phr以下，例如0.15phr–1.1phr，优选0.25phr-1.0phr，填充剂的量可以为20phr以下，助剂的量可以为5phr以下。
交联剂可以包括过氧化物，例如过氧化二异丙苯(DCP),双叔丁基过氧化二异丙基苯(BIPB)。
填充剂可以包括碳酸钙、滑石粉、云母粉、陶土、锌氧粉、钛白粉中的至少一种。
助剂可以包括石蜡、硬脂酸及其盐(锌盐或钙盐)、其他长链脂肪酸中的至少一种。
-异型型胚的制备-
本发明的高分子材料物理发泡方法中，使用射出机、挤出机或模压机将上述的原料(热塑性弹性体或聚烯烃材料)制作成异型型胚。
异型型胚的制备可以在适宜的条件下进行，例如对于需进行交联反应的聚烯烃材料，可以在模具温度160-180℃，合适的合模压力例如10Mpa下成型400-550秒。
本发明对异型型胚的形状没有特别的限制，通常，异型型胚可以为片状、颗粒形状等。
在形成异型型胚后，为了提升聚烯烃材料的分子链强度，可以对聚烯烃材料进行交联反应。交联反应可以以化学交联方式和/或电子束辐照方式进行。例如，可以将聚烯烃型胚在170-180℃的温度进行模压交联成型(利用聚烯烃组合物中包含的交联剂使聚烯烃交联)，交联成型可以以硫变仪测试的硫化曲线作为参考依据。也可以采用电子束辐照方式，例如照射高能电子束，以20-50kGy(千戈瑞)的高能电子束辐照进行交联。
-超临界流体高压浸渗-
本发明的高分子材料物理发泡方法还包括：用超临界流体对上述型胚进行高压浸渗，以得到超临界流体浸渗的型胚。
例如，可以将热塑性弹性体型胚或交联的聚烯烃型胚在压力釜中用超临界流体进行高压浸渗，然后泄压至常压，得到超临界流体浸渗的型胚。
超临界流体可以包括二氧化碳超临界流体、氮气超临界流体等。
高压浸渗可以在10-50MPa压力、40-150℃进行0.5-8小时，优选1-5小时。
高压浸渗后的泄压通常控制在15-40分钟泄压至常压，以符合生产效率且控制预发泡(预发泡倍率控制为1-1.4倍，1倍代表无预发泡现象)。
在所得的超临界流体浸渗的型胚中，型胚的超临界流体渗透量以重量计为0.6％-15％，优选0.8％-10％。
-模内发泡-
本发明的高分子材料物理发泡方法还包括：将超临界流体浸渗的型胚通过一次发泡成型获得最终成品。
例如，可以将上述超临界流体浸渗的型胚置于成品模具中，进行1:1模内发泡，即得成品的发泡制品。
模内发泡的条件可以包括：温度为70-150℃，发泡时间为5-30分钟。
模内发泡前的型胚线性尺寸(通常以长度方向定义线性尺寸)与模内发泡后的成品尺寸的比例可以为1:1.5～1:3.5，优选1:1.7～1:2.5。
模内发泡后，发泡材料的比重可以由最初的约1.0g/cm3降低到0.30g/cm3以下，优选0.25g/cm3以下，更优选0.20g/cm3以下。
发泡制品具有按照ASTM D2632测量的50％以上的回弹性能。
-发泡制品-
本发明还提供由上述高分子材料物理发泡方法获得的发泡制品。
本发明的发泡制品的孔径尺寸为0.1-3mm，比重为0.03-0.30g/cm3。
本发明的发泡制品可用于地垫、鞋材、运动器材、玩具或包装材料。
本发明利用超临界流体作为物理发泡剂，通过简单的模内发泡工艺，获得了低比重、环保无毒、弹性优良、表面外观平整光滑的发泡材料。本发明利用一次发泡成型获得最终制品，无需进行二次加工，可以同时达到减少人力及节省能源的目的。
下面通过实施例及对比例来进一步说明本发明，但本发明不受这些实施例和对比例的任何限制。
实施例1
将100phr的EVA(台塑EVA7470，乙酸乙烯酯的摩尔含量为26％)、1phr的碳酸钙、0.5phr的石蜡和0.5phr的DCP在三泰机械公司的ST-75L密炼机中，在100℃和0.75Mpa压力条件下混合12min。卸料后以三泰机械公司ST-75L密炼机配套的挤出造粒机将上述混合物进行挤出与造粒(胶粒)。将该胶粒以巨闽机械公司KM-E308L3的EVA射出机中在模具温度180℃下进行模压交联成型。
将交联的聚烯烃型胚放入德阳四创公司的高压釜中，注入二氧化碳超临界流体，在温度50℃、压力40Mpa下维持2小时。然后，在30min时间内泄压至常压，得到超临界流体浸渗的型胚(预发泡倍率为1.5以下)，型胚的超临界流体渗透量以重量计为10％。
将上述超临界流体浸渗的型胚置于成型模具中，在140℃温度下进行模内发泡，发泡时间为15min，得到表面外观平整光滑的成品的发泡制品，发泡比例以发泡前型胚长度方向的线性尺寸与模内发泡后的成品尺寸的比例计为1.8。
成品的发泡制品的泡孔直径用光学显微镜测量，材料密度用比重天平测试；回弹性能按照ASTM D2632测试：将质量28±0.5g的标准锥形钢球在400mm高度上自由落在泡沫塑料试样上来进行测试，钢球回弹的最大高度与落下高度的比值为回弹百分率。
实施例1中，测得的成品的发泡制品的比重、泡孔直径、回弹性能分别为0.16、0.5-1.5mm和55％。
实施例2
除了用掺混比例为60/40的EVA/POE混合物(其中EVA的乙酸乙烯酯的摩尔含量为26％，且POE为陶氏化学公司的8150型号的POE)代替EVA之外，采用与实施例1相同的程序，获得成品的发泡制品。
该成品的发泡制品的比重、泡孔直径、回弹性能分别为0.13、0.5-1.5mm和60％。
实施例3
用掺混比例为60/40的EVA/POE混合物(其中EVA的乙酸乙烯酯的摩尔含量为26％，且POE为陶氏化学公司的8150型号的POE)代替EVA，以超临界氮气流体取代二氧化碳流体之外，采用与实施例1相同的程序，获得成品的发泡制品。
该成品的发泡制品的比重、泡孔直径、回弹性能分别为0.15、0.5-2.5mm和60％。
实施例4
除了用科思创公司的85AU10型号的TPU代替EVA组合物并省略混炼和交联步骤之外，采用与实施例1相同的程序，获得成品的发泡制品。
该成品的发泡制品的比重、泡孔直径、回弹性能分别为0.28、0.5-1.0mm和55％。
实施例5
配方除了不使用过氧化物交联剂外，其他成分实施例3，采用照射高能电子束方式进行交联，以20-50kGy(千戈瑞)的高能电子束辐照进行交联，采用与实施例3相同程序，获得成品的发泡制品。
该成品的发泡制品的比重、泡孔直径、回弹性能分别为0.14、0.5-2.5mm和60％。
对比例1
以传统Mucell技术使用超临界流体发泡设备制作TPU发泡成品，注塑机料管温度210℃，模具温度30℃，利用Mucell设备将超临界氮气流体注入注塑机的计量段与TPU融体混合，然后将此流体混合的TPU熔融体注塑到模具中成型，超临界流体于模具模穴中在TPU融体的内部与外部气化并产生内部泡孔，获得注塑发泡及尺寸同模穴尺寸但表面有气痕不光滑的TPU制品，其发泡成品的比重、泡孔直径、回弹性能分别为0.55、0.8-1.5mm和53％。
对比例2
除了超临界流体渗透后预发泡比例大于1.6外，采用与实施例1相同的程序，获得成品的发泡制品，其发泡成品的比重、泡孔直径、回弹性能分别为0.22、0.5-1.7mm和50％。
对比例3
除了将实施例1配方中的交联剂DCP改为1.25phr外，其他程序同实施例1，其发泡成品的比重、泡孔直径、回弹性能分别为0.32、0.2-0.8mm和40％。
对比例4
除了将实施例1配方中的交联剂DCP改为0.12phr外，其他程序同实施例1，其发泡成品的比重、泡孔直径、回弹性能分别为0.42、0.2-0.6mm和35％。
对比例5
除了将实施例2配方中的交联剂DCP改为0.12phr外，其他程序同实施例2，其发泡成品的比重、泡孔直径、回弹性能分别为0.35、0.1-0.8mm和42％。

Claims (10)

1.一种高分子材料物理发泡方法，包括：
(1)使用射出机、挤出机或模压机，将热塑性弹性体或聚烯烃材料制作成异型型胚；
(2)使聚烯烃型胚发生交联反应，得到交联的聚烯烃型胚；
(3)将热塑性弹性体型胚或交联的聚烯烃型胚在压力釜中用超临界流体在10-50MPa压力下进行高压浸渗，然后泄压至常压，得到超临界流体浸渗的型胚；
(4)将超临界流体浸渗的型胚置于成品模具中，进行1:1模内发泡，即得成品的发泡制品。
2.根据权利要求1所述的方法，其特征在于，所述热塑性弹性体包括热塑性聚氨酯(TPU)、热塑性聚酯弹性体(TPEE)、嵌段聚醚酰胺弹性体(Pebax)中的一种或它们的混合物。
3.根据权利要求2所述的方法，其特征在于，所述聚烯烃材料包括乙烯-乙酸乙烯酯共聚物(EVA)、聚烯烃弹性体(POE)、低密度聚乙烯(LDPE)中的一种或它们的混合物；或上述聚烯烃材料与橡胶材料的共混物，例如EVA/POE/EPDM(三元乙丙橡胶)共混物；并且所述聚烯烃材料任选地掺杂有交联剂、填充剂和助剂中的至少一种。
4.根据权利要求3所述的方法，其特征在于，所述交联剂包括过氧化物，例如过氧化二异丙苯(DCP)，双叔丁基过氧化二异丙基苯(BIPB)；所述的填充剂包括碳酸钙、滑石粉、云母粉、陶土、锌氧粉、钛白粉中的至少一种；所述助剂包括石蜡、硬脂酸及其盐、其他长链脂肪酸中的至少一种。
5.根据权利要求3所述的方法，其特征在于，在掺杂交联剂时，相对于100phr(重量份)的所述聚烯烃材料，所述交联剂的量为0.15phr–1.1phr，优选0.25phr-1.0phr；在不掺杂交联剂时，采用电子束辐照方式，以20-50kGy(千戈瑞)的高能电子束辐照使所述聚烯烃型胚发生交联反应。
6.根据权利要求1所述的方法，其特征在于，所述异型型胚包括片状、颗粒形状。
7.根据权利要求1所述的方法，其特征在于，所述超临界流体包括二氧化碳超临界流体、氮气超临界流体；优选地，所述超临界流体的高压浸渗在40-150℃进行0.5-8小时。
8.根据权利要求1所述的方法，其特征在于，所述模内发泡的条件包括：温度为70-150℃，发泡时间为5-30分钟。
9.根据权利要求1所述的方法，其特征在于，模内发泡前的型胚线性尺寸与模内发泡后的成品尺寸的比例为1:1.5～1:3.5，优选1:1.7～1:2.5。
10.一种由权利要求1-9中任一项所述的高分子材料物理发泡方法获得的发泡制品，所述发泡制品具有按照ASTM D2632测量的50％以上的回弹性能。
CN201810699146.8A 2018-06-29 2018-06-29 高分子材料物理发泡方法及发泡制品 Pending CN109135033A (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201810699146.8A CN109135033A (zh) 2018-06-29 2018-06-29 高分子材料物理发泡方法及发泡制品
US16/152,682 US20200002499A1 (en) 2018-06-29 2018-10-05 Method for physically foaming a polymer material and foamed article

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810699146.8A CN109135033A (zh) 2018-06-29 2018-06-29 高分子材料物理发泡方法及发泡制品

Publications (1)

Publication Number Publication Date
CN109135033A true CN109135033A (zh) 2019-01-04

Family

ID=64802491

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810699146.8A Pending CN109135033A (zh) 2018-06-29 2018-06-29 高分子材料物理发泡方法及发泡制品

Country Status (2)

Country Link
US (1) US20200002499A1 (zh)
CN (1) CN109135033A (zh)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110157086A (zh) * 2019-05-17 2019-08-23 东莞海瑞斯新材料科技有限公司 一种直接在模内形成发泡产品的物理发泡方法
CN110343330A (zh) * 2019-05-24 2019-10-18 天津市大林新材料科技股份有限公司 一种交联聚丙烯发泡材料及其制备方法
CN110539440A (zh) * 2019-09-02 2019-12-06 厦门市锋特新材料科技有限公司 一种eva注塑件发泡工艺
CN111808354A (zh) * 2019-04-10 2020-10-23 东莞市龙奕实业有限公司 一种超临界物理发泡粗孔运动器材生产工艺
CN112552546A (zh) * 2020-05-25 2021-03-26 江苏集萃先进高分子材料研究所有限公司 一种绿色环保eva发泡材料及制备方法
CN112795080A (zh) * 2021-02-03 2021-05-14 长链轻材(南京)科技有限公司 Eva/ldpe超临界固态发泡材料及其制备方法
CN113444363A (zh) * 2021-07-16 2021-09-28 福建三盛实业有限公司 一种tpe超临界微孔发泡物及其制备方法
CN113527865A (zh) * 2021-07-16 2021-10-22 福建三盛实业有限公司 一种高分子物理发泡物、方法及其发泡装置
CN114479235A (zh) * 2021-01-19 2022-05-13 杭州海虹精细化工有限公司 一种无毒无害环保运动垫的制造方法
CN114874524A (zh) * 2022-04-27 2022-08-09 中山大学 一种交联橡塑复合物微发泡卷材及其制备方法和应用
CN114921022A (zh) * 2022-05-31 2022-08-19 安踏（中国）有限公司 一种具有金属色彩外观的发泡材料、鞋底和相应的制备方法
CN115260565A (zh) * 2022-08-15 2022-11-01 青岛科技大学 一种tpee泡沫及其制备工艺

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108976584A (zh) * 2018-06-29 2018-12-11 东莞海锐思高分子材料科技有限公司 高分子物理发泡体及其制作方法
CN111849058A (zh) * 2020-07-16 2020-10-30 广东国立科技股份有限公司 一种eva/tpee超临界发泡复合鞋用材料及其制备方法
US11697227B2 (en) * 2020-09-10 2023-07-11 Guangzhou Green And Health Biotech Co., Ltd. Foaming and dyeing integrated production line for polymer material product, and method thereof
USD1022420S1 (en) 2020-12-03 2024-04-16 Puma SE Shoe
US20210114324A1 (en) * 2020-12-28 2021-04-22 Runhong Liu Process of making a sole having different properties
KR102374794B1 (ko) * 2020-12-31 2022-03-16 한국신발피혁연구원 이산화탄소 가스를 사용한 발포체 제조방법 및 이에 사용되는 발포용 컴파운드 조성물
CN115505161B (zh) * 2021-06-23 2024-01-19 华润化学材料科技股份有限公司 尼龙模压发泡材料及其制备方法
CN113337034A (zh) * 2021-07-16 2021-09-03 福建三盛实业有限公司 一种eva/poe超临界发泡复合材料、制备方法及装置
CN115466453B (zh) * 2022-09-22 2023-08-22 青岛昶捷科技有限公司 一种含有回收料的超临界发泡材料及其制备方法
CN116144065A (zh) * 2023-01-10 2023-05-23 安踏（中国）有限公司 一种高弹缓震发泡材料的制备方法和鞋底

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102504323A (zh) * 2011-11-07 2012-06-20 常州天晟新材料股份有限公司 可工业化的超临界流体技术制备聚合物发泡材料的方法
CN104194030A (zh) * 2014-08-08 2014-12-10 汕头市新力新材料科技有限公司 一种热塑性聚氨酯弹性体发泡珠粒及其制备方法
CN107082906A (zh) * 2017-03-21 2017-08-22 苏州诚和成新材料科技有限公司 一种易脱模逐级可控发泡制备tpu发泡材料的方法
CN108102338A (zh) * 2018-01-26 2018-06-01 青岛科技大学 一种发泡鞋中底

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5121243B2 (ja) * 2006-03-30 2013-01-16 Ｊｓｒ株式会社 ポリオレフィン系樹脂発泡体とその製造方法
EP3486277B1 (en) * 2015-08-19 2021-12-08 NIKE Innovate C.V. Process for preparing thermoplastic elastomer foam and foamed article
CN108976584A (zh) * 2018-06-29 2018-12-11 东莞海锐思高分子材料科技有限公司 高分子物理发泡体及其制作方法
US11318647B2 (en) * 2018-10-29 2022-05-03 Dongguan Hailex New Material Science And Technology Co., Ltd Method of microcellular foam molding

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102504323A (zh) * 2011-11-07 2012-06-20 常州天晟新材料股份有限公司 可工业化的超临界流体技术制备聚合物发泡材料的方法
CN104194030A (zh) * 2014-08-08 2014-12-10 汕头市新力新材料科技有限公司 一种热塑性聚氨酯弹性体发泡珠粒及其制备方法
CN107082906A (zh) * 2017-03-21 2017-08-22 苏州诚和成新材料科技有限公司 一种易脱模逐级可控发泡制备tpu发泡材料的方法
CN108102338A (zh) * 2018-01-26 2018-06-01 青岛科技大学 一种发泡鞋中底

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111808354A (zh) * 2019-04-10 2020-10-23 东莞市龙奕实业有限公司 一种超临界物理发泡粗孔运动器材生产工艺
CN110157086A (zh) * 2019-05-17 2019-08-23 东莞海瑞斯新材料科技有限公司 一种直接在模内形成发泡产品的物理发泡方法
CN110343330A (zh) * 2019-05-24 2019-10-18 天津市大林新材料科技股份有限公司 一种交联聚丙烯发泡材料及其制备方法
CN110539440A (zh) * 2019-09-02 2019-12-06 厦门市锋特新材料科技有限公司 一种eva注塑件发泡工艺
CN112552546A (zh) * 2020-05-25 2021-03-26 江苏集萃先进高分子材料研究所有限公司 一种绿色环保eva发泡材料及制备方法
CN112552546B (zh) * 2020-05-25 2022-07-01 江苏集萃先进高分子材料研究所有限公司 一种绿色环保eva发泡材料及制备方法
CN114479235A (zh) * 2021-01-19 2022-05-13 杭州海虹精细化工有限公司 一种无毒无害环保运动垫的制造方法
CN114479235B (zh) * 2021-01-19 2023-12-19 杭州海虹精细化工有限公司 一种无毒无害环保运动垫的制造方法
CN112795080A (zh) * 2021-02-03 2021-05-14 长链轻材(南京)科技有限公司 Eva/ldpe超临界固态发泡材料及其制备方法
CN113527865A (zh) * 2021-07-16 2021-10-22 福建三盛实业有限公司 一种高分子物理发泡物、方法及其发泡装置
CN113444363A (zh) * 2021-07-16 2021-09-28 福建三盛实业有限公司 一种tpe超临界微孔发泡物及其制备方法
CN113444363B (zh) * 2021-07-16 2023-03-10 福建三盛实业有限公司 一种tpe超临界微孔发泡物及其制备方法
CN114874524A (zh) * 2022-04-27 2022-08-09 中山大学 一种交联橡塑复合物微发泡卷材及其制备方法和应用
CN114874524B (zh) * 2022-04-27 2023-02-03 中山大学 一种交联橡塑复合物微发泡卷材及其制备方法和应用
CN114921022A (zh) * 2022-05-31 2022-08-19 安踏（中国）有限公司 一种具有金属色彩外观的发泡材料、鞋底和相应的制备方法
CN115260565A (zh) * 2022-08-15 2022-11-01 青岛科技大学 一种tpee泡沫及其制备工艺

Also Published As

Publication number Publication date
US20200002499A1 (en) 2020-01-02

Similar Documents

Publication Publication Date Title
CN109135033A (zh) 高分子材料物理发泡方法及发泡制品
CN108976584A (zh) 高分子物理发泡体及其制作方法
CN110157086A (zh) 一种直接在模内形成发泡产品的物理发泡方法
CN105451830B (zh) 形成高尔夫球或高尔夫球的一部分的方法及由此获得的高尔夫球
CN109485984A (zh) 一种高分子物理发泡材料的发泡方法
CN104877335B (zh) 一种热塑性聚氨酯弹性体发泡珠粒及其制备方法
TW201512263A (zh) 低密度發泡體、中底、鞋以及製造低密度發泡體的方法
CN102911430A (zh) 一种eva/tpu/poe复合发泡材料的制备方法
TW201512264A (zh) 低密度發泡物件及製造方法
US20180291194A1 (en) Composition and Process of Manufacture for a Shoe Sole Component for Footwear
US11318647B2 (en) Method of microcellular foam molding
US20090008829A1 (en) Applicator for cosmetics
US11458657B2 (en) Method of microcellular foam molding
CN105001505A (zh) 三元橡塑合成交联体的配方和制备工艺
CN109517262A (zh) 一种全程保压的超临界流体发泡方法
CN112646325A (zh) 一种tpee材质的发泡鞋中底材料及其制备工艺
CN106147036A (zh) 一种可回收循环使用的发泡材料及其制造方法
CN109504068A (zh) 一种热塑性聚氨酯共混发泡材料及其制备方法
CN105001506A (zh) 含已发泡eva废弃料的三元橡塑合成交联体
CN102924802B (zh) 一种poe／epdm／rec复合发泡材料及其制备方法
KR0139144B1 (ko) 발포체 프리폼을 이용한 신발중창의 제조방법
US20190322847A1 (en) Composition for manufacturing lightweight footwear having improved heat-resistance and lightweight footwear manufactured using the same
CN110128815A (zh) 一种高弹性蜂窝鞋底及其制作方法
US20200189155A1 (en) Process of foaming in a mold
CN109306106A (zh) 一种超轻质高耐磨橡塑鞋底及制备工艺

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20190104

RJ01 Rejection of invention patent application after publication