CN112166157B - 发泡热塑性聚氨基甲酸酯及其微波成型体 - Google Patents
发泡热塑性聚氨基甲酸酯及其微波成型体 Download PDFInfo
- Publication number
- CN112166157B CN112166157B CN201880093761.2A CN201880093761A CN112166157B CN 112166157 B CN112166157 B CN 112166157B CN 201880093761 A CN201880093761 A CN 201880093761A CN 112166157 B CN112166157 B CN 112166157B
- Authority
- CN
- China
- Prior art keywords
- microwave
- thermoplastic polyurethane
- weight
- parts
- molded body
- 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.)
- Active
Links
Classifications
-
- 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
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
-
- 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
- C08J9/14—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 organic
- C08J9/141—Hydrocarbons
-
- 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
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
-
- 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
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
-
- 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
-
- 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
- B29C44/3415—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
- B29C44/3461—Making or treating expandable particles
-
- 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
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- 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
- C08J3/28—Treatment by wave energy or particle radiation
-
- 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
- C08J9/0066—Use of inorganic compounding ingredients
-
- 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
-
- 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
- C08J9/14—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 organic
-
- 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
- C08J9/16—Making expandable particles
-
- 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
-
- 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
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
-
- 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
- C08K3/34—Silicon-containing compounds
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
-
- 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
-
- 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
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
- B29C2035/0855—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using microwave
-
- 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
-
- 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
- C08G2110/0066—≥ 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
- 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
- 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
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Toxicology (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Thermal Sciences (AREA)
- Mechanical Engineering (AREA)
- Electromagnetism (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Emergency Medicine (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明涉及一种可发泡组合物用以制作发泡热塑性聚氨基甲酸酯及其微波成型体,该可发泡组合物包括未发泡热塑性聚氨基甲酸酯粒子、增黏剂或架桥剂,以及发泡剂,其中该未发泡热塑性聚氨基甲酸酯粒子具有1,000泊至9,000泊的黏度,该黏度以JISK 7311测试方法在170℃测得。
Description
技术领域
本发明涉及一种发泡热塑性聚氨基甲酸酯以及其经微波所制成的成型体。
背景技术
热塑性聚氨基甲酸酯(thermoplastic polyurethane,TPU)为热塑性弹性体(thermoplastic elastomer,TPE)的原材料。以TPU制成的TPE具备黏性、高弹性、耐磨性、耐冲击性、耐曲折性、高延伸性、耐候性、耐化学性、无毒性及高抗撕裂强度等诸多优点,故已被广泛应用于如鞋子、汽车、包装材料、绝热材料等产品中。
射出成型是现有技术中制备TPU发泡成型体最常用的方法。射出成型的制程涉及塑橡胶粒在射出成型机内加热熔化,然后压缩熔融使其移动通过喷嘴注入温度较低的模具内,生产流程长甚为耗时。而且射出用的模具重量相当重,导致更换模具相当不便。现有技术另有一种采用水蒸气成型法制备TPU发泡成型体。然而,水蒸气成型法需涉及高温或高压制程,往往需消耗更多的能源,导致成本增加。有别于射出成型法及水蒸气成型法,以微波方法所制造的成型体制程简单且省时省能源。微波TPU发泡成型体已可应用于各类产品。举例而言,微波TPU发泡成型体已成功地应用于鞋子上,其能兼具舒适性、灵活性及轻质等优点。
然而,可发泡组合物中所含未发泡热塑性聚氨基甲酸酯粒子,其黏度通常限制在10,000泊以上,才适用于形成微波TPU发泡成型体。若使用黏度低于10,000泊的未发泡粒子,其所形成的发泡粒子经微波后,具有低劣发泡的现象,导致微波成型体有成型不良(如外观易变型、塌陷、粒子间黏着不佳、成型稳定性不佳)的问题。
发明内容
本发明意外地发现可使用增黏剂或架桥剂来改善上述的问题。添加增黏剂或架桥剂,可使聚氨基甲酸酯粒子的黏弹性质或分子键结结构的改变,进而增强分子链间结构强度。本发明提供一种适用于微波成型体的可发泡组合物,包含1,000泊至9,000泊的黏度的未发泡热塑性聚氨基甲酸酯粒子,及增黏剂或架桥剂,该黏度以JISK 7311测试方法在170℃测得。
本发明于一方面提供制作发泡热塑性聚氨基甲酸酯的可发泡组合物(也可称作配方)、将上述组合物经过发泡造粒所制成的发泡热塑性聚氨基甲酸酯,以及其发泡造粒的方法。本发明的发泡热塑性聚氨基甲酸酯具有经微波可再次发泡的特性,因此本发明还提供将上述之发泡热塑性聚氨基甲酸酯微波后二次发泡的微波成型体及其制造方法。本发明之发泡热塑性聚氨基甲酸酯具有更具轻质之优点,藉由微波加热发泡热塑性聚氨基甲酸酯后各粒子表面将产生黏合作用,且同时再次发泡以形成微波成型体(或称为热塑性聚氨基甲酸酯发泡材料)。有别于现有的射出成型法及水蒸气成型法,以微波方法所制造的成型体制程简单且省时省能源。
于一实施例,本发明提供一种可发泡组合物用以制作发泡热塑性聚氨基甲酸酯,该可发泡组合物包括100重量份之一未发泡热塑性聚氨基甲酸酯粒子、5重量份至25重量份之一发泡剂,及0.5重量份至5重量份之一增黏剂或一架桥剂,其中该未发泡热塑性聚氨基甲酸酯粒子具有1,000泊至9,000泊的黏度,该黏度以JISK 7311测试方法在170℃测得。
于一实施例,本发明提供如上述的可发泡组合物,其中该增黏剂系选自无机增稠剂、聚丙烯酸类增稠剂、或纤维素类增稠剂。
于一实施例,本发明提供如上述的可发泡组合物,其中架桥剂系选自过氧化二异丙苯(DCP)、过氧化苯甲酰、二叔丁基过氧化物、或过氧化氢二异丙苯2,5-二甲基-2,5二叔丁基过氧化己烷。
于一实施例,本发明提供如上述的可发泡组合物,其中该无机增稠剂系选自膨润土或硅酸铝,该聚丙烯酸类增稠剂系选自丙烯酸、马来酸、马来酸酐或甲基丙烯酸之羧酸类单体形成的增稠剂,该聚丙烯酸类增稠剂系选自甲基纤维素、羧甲基纤维素、羟乙基纤维素、或羟丙基甲基纤维素所形成的增稠剂。
于一实施例,本发明提供如上述的可发泡组合物,其中该未发泡热塑性聚氨基甲酸酯粒子具有2.5mm至4.5mm的粒径。
于一实施例,本发明提供如上述的可发泡组合物,其中该未发泡热塑性聚氨基甲酸酯粒子具有40A至64D的肖氏硬度。
于一实施例,本发明提供如上述之可发泡组合物,其中该未发泡热塑性聚氨基甲酸酯粒子具有1.0g/cm3至1.25g/cm3的密度。
于一实施例,本发明提供如上述的可发泡组合物,包含100重量份之该未发泡热塑性聚氨基甲酸酯粒子及5重量份至20重量份的该发泡剂。
于一实施例,本发明提供如上述的可发泡组合物,其中该发泡剂为膨胀性微球、二氧化碳(CO2)、或碳数为4至10之烃类化合物。
于一实施例,本发明提供如上述的可发泡组合物,还包含0.1重量份至5重量份之滑石粉。
于一实施例,本发明提供如上述的可发泡组合物,还包含1重量份至20重量份之可塑剂,该可塑剂为苯甲酸酯或其衍生物。
于一实施例,本发明提供如上述之可发泡组合物,还包含色粉,基于100重量份的该未发泡热塑性聚氨基甲酸酯粒子,该色粉含有0.1重量份至5重量份。
于一实施例,本发明提供如上述的可发泡组合物,更包含1重量份至5重量份之该增黏剂或该架桥剂。
于一实施例,本发明提供一种发泡热塑性聚氨基甲酸酯,是采用上述任一项所述的可发泡组合物经一螺杆造粒机发泡造粒制成。
于一实施例,本发明提供如上述的发泡热塑性聚氨基甲酸酯,其中该发泡热塑性聚氨基甲酸酯具有残留的该发泡剂。
于一实施例,本发明提供如上述的发泡热塑性聚氨基甲酸酯,其中该发泡热塑性聚氨基甲酸酯具有3mm至7.5mm的粒径。
于一实施例,本发明提供如上述的发泡热塑性聚氨基甲酸酯,其中该发泡热塑性聚氨基甲酸酯具有40C至80C的肖氏硬度。
于一实施例,本发明提供如上述的发泡热塑性聚氨基甲酸酯,其中该发泡热塑性聚氨基甲酸酯具有0.2g/cm3至0.8g/cm3的密度。
于一实施例本发明提供一种微波成型体,其是将上述的发泡热塑性聚氨基甲酸酯经微波而成。
于一实施例,本发明提供如上述的微波成型体,其中该微波成型体的密度为0.15g/cm3至0.6g/cm3。
于一实施例,本发明提供如上述的微波成型体,其中该微波成型体的肖氏硬度为40C至80C。
于一实施例,本发明提供如上述的微波成型体,其中该微波成型体是经由500W至30,000W微波功率制成。
于一实施例,本发明提供如上述的微波成型体,其中该微波的过程中不加水。
于一实施例,本发明提供如上述的微波成型体,其中该微波的过程中加水或醇类,以该发泡热塑性聚氨基甲酸酯的总重为100重量份,该水或醇类的用量为1重量份至10重量份。
本发明尚包含其他各方面及各种微波成型体,以解决其他问题并合并上述的各方面详细揭露于以下实施方式中。
具体实施方式
为使本发明及其所要主张的申请专利范围能被充分地理解,以下将示范本发明之较佳实施例。为避免模糊本发明之内容,以下说明可能会省略本领域技术人员公知的组件、相关材料、及其相关处理技术。
制作发泡热塑性聚氨基甲酸酯的可发泡组合物
本发明制作发泡热塑性聚氨基甲酸酯的可发泡组合物主要包含未发泡热塑性聚氨基甲酸酯粒子、增黏剂或架桥剂、及发泡剂。组合物中未发泡热塑性聚氨基甲酸酯粒子具有在1,000泊至9,000泊的黏度,可使首次发泡的粒子具有良好的再次发泡功能。黏度是以JISK 7311测试方法在170℃度测得。未发泡热塑性聚氨基甲酸酯粒子具有在3,000泊至8,000泊的黏度者为更佳,其除可使首次发泡的粒子达成良好的再次发泡功能外,再次发泡后材料将有更佳的机械强度。
100重量份的未发泡热塑性聚氨基甲酸酯粒子中,增黏剂或架桥剂的含量以0.5重量份至5重量份为较佳。100重量份的未发泡热塑性聚氨基甲酸酯粒子中,发泡剂的含量以5重量份至25重量份为较佳,若要有更佳的机械强度,以5重量份至20重量份为更佳。依据本发明的各实施例,组合物中未发泡热塑性聚氨基甲酸酯粒子优选具有2.5mm至4.5mm(millimeter即毫米)的粒径者。本发明所述的粒径是指量测粒子的最长轴。依据本发明的其他实施例,组合物中未发泡热塑性聚氨基甲酸酯粒子优选具有40A至64D的肖氏硬度者。依据本发明的再其他的实施例,组合物中未发泡热塑性聚氨基甲酸酯粒子优选具有1.0g/cm3至1.25g/cm3的密度者。本文所指密度均以阿基米得原理(浮力法)测得。
本发明的发泡热塑性聚氨基甲酸酯具有良好的再次发泡特性。所谓『再次发泡』特性是指经过首次发泡所形成的发泡热塑性聚氨基甲酸酯,本身可再次(二次)发泡,特别是经由微波来再次发泡。此类发泡热塑性聚氨基甲酸酯再次发泡后其粒子明显膨胀且粒子间可黏合紧密而呈现形状饱满的发泡成型体,此为良好再次发泡。
可发泡组合物中未发泡热塑性聚氨基甲酸酯粒子可为酯类、醚类、聚己内酯类或聚碳酸酯类。未发泡热塑性聚氨基甲酸酯粒子的作法,举例而言,可将二异氰酸酯、聚酯多元醇、增链剂、催化剂和其他的添加剂相混合在约200~300℃下反应并通过熟知的注塑或挤出处理以获得未发泡热塑性聚氨基甲酸酯粒子。二异氰酸酯可选自4,4_亚甲基双(苯基异氰酸酯)(MDI)、间-亚二甲苯基二异氰酸酯(XDI)、亚苯基-1,4-二异氰酸酯、1,5-萘二异氰酸酯、甲苯二异氰酸酯(TDI)、异佛尔酮二异氰酸酯(IPDI)、六亚甲基二异氰酸酯(HDI)和二环己基甲烷-4,4-二异氰酸酯。较佳为MDI或TDI。聚酯多元醇为二元酸和二元醇的聚酯类,二元醇可为具有2-10个碳原子的二元醇,二元酸可为具有4-12个碳原子的直链或支链的二元酸。较佳为己二酸1,4-丁二醇酯。增链剂是具有2-12个碳原子的二醇;例如:乙二醇、二甘醇、丙二醇、二丙二醇、1,4-丁二醇、1,6-己二醇、1,3-丁二醇、1,5-戊二醇、1,4-环己烷二甲醇、新戊二醇、苯二醇和二甲苯二醇中的至少一种。催化剂可选自三乙胺、二甲基环己胺、二辛酸亚锡、二辛酸二丁基锡、二月桂酸二丁基锡、二乙酸二丁基锡中的至少一种。注塑或挤出处理过程中也可使用各种添加剂、譬如颜料、填料、抗氧剂、增强剂、润滑剂或增塑剂等等。
可发泡组合物含有增黏剂或架桥剂。增黏剂可为无机增稠剂(例如;膨润土、硅酸铝等)、聚丙烯酸类增稠剂(例如:羧酸类单体,如丙烯酸、马来酸或马来酸酐、甲基丙烯酸等)、纤维素类增稠剂(甲基纤维素、羧甲基纤维素、羟乙基纤维素、羟丙基甲基纤维素等)。架桥剂可为过氧化二异丙苯(DCP)、过氧化苯甲酰、二叔丁基过氧化物、过氧化氢二异丙苯2,5-二甲基-2,5二叔丁基过氧化己烷等。
可发泡组合物中发泡剂可为有机发泡剂或无机发泡剂。有机发泡剂的实例,譬如偶氮化合物(例如:偶氮二甲酰胺、偶氮二异丁腈、偶氮二甲酸二异丙酯)、磺酰胺类化合物(例如:4,4-氧代双苯磺酰肼、对苯磺酰肼、1,4-苯二磺酰肼)、亚硝基化合物(例如:二亚硝基对苯二甲酰胺、N,N’-二亚硝基五次甲基四胺)、二氧化碳(CO2)、碳数为4至10之烃类化合物(例如:正戊烷、异戊烷与环戊烷)或膨胀性微球(例如:可膨胀性微胶囊、微球发泡粉)。其中以可膨胀性微球为更佳。
本发明制作发泡热塑性聚氨基甲酸酯的可发泡组合物除了未发泡热塑性聚氨基甲酸酯粒子、增黏剂或架桥剂、以及发泡剂外,还可视需要包含无机填充物及可塑剂。无机填充物例如用作脱模剂的滑石粉、云母粉、硫代硫酸钠等。较佳地使用滑石粉。依据各种实施例,基于100重量份的未发泡热塑性聚氨基甲酸酯粒子,较佳地含有0.1重量份至5重量份的滑石粉为更佳。可塑剂可为安息香酸类化合物(例如:苯甲酸酯、如苯甲酸甲酯、苯甲酸乙酯、二苯甲酸二丙二醇酯等、及其衍生物)、酯类化合物(例如:柠檬酸三乙酯、柠檬酸三甲酯、柠檬酸乙酰基三乙酯、及其衍生物)、醚类化合物(例如:己二酸醚酯、乙二醇丁醚酯、及其衍生物)、聚己内酯类化合物(例如:聚己内酯二醇、及其衍生物)或聚碳酸酯类化合物(例如:聚碳酸甲酯、聚碳酸苯酯、及其衍生物)。较佳使用苯甲酸酯或其衍生物。依据各种实施例,基于100重量份的未发泡热塑性聚氨基甲酸酯粒子,较佳地含有1重量份至20重量份的可塑剂。
于一较佳实施例,本发明制作发泡热塑性聚氨基甲酸酯的可发泡组合物具有以下配比:100重量份的未发泡热塑性聚氨基甲酸酯粒子;0.5重量份至5重量份之增黏剂或架桥剂;0.1重量份至5重量份之滑石粉;1重量份至20重量份之可塑剂;以及5重量份至25重量份的发泡剂,组合物中未发泡热塑性聚氨基甲酸酯粒子具有在1,000泊至9,000泊的黏度,该黏度以JISK 7311测试方法在170℃测得。在滑石粉及可塑剂皆有需要加入组合物的状况下,上述配比有助于形成具有孔洞大小均匀及粒径一致的发泡热塑性聚氨基甲酸酯。
此外,可发泡组合物中也可以添加各种颜色的色粉。依据各种实施例,基于100重量份的未发泡热塑性聚氨基甲酸酯粒子,较佳地含有0.1重量份至5重量份的色粉。
制作发泡热塑性聚氨基甲酸酯的方法
以下举例说明进行发泡造粒以制作发泡热塑性聚氨基甲酸酯的方法。首先将符合前述的可发泡组合物(含未发泡热塑性聚氨基甲酸酯粒子、增黏剂或架桥剂、及发泡剂、或可视需要添加无机填料、可塑剂、色料等等)投入一单螺杆造粒机中以进行发泡造粒。所述的单螺杆造粒机的模头温度可为100℃至180℃,挤压速度可为50kg/h至70kg/h,模头压力可为35kgf/cm2至65kgf/cm2,水中造粒温度可为10℃至20℃;再更佳的,所述的单螺杆造粒机的模头温度可为110℃至165℃,或再更佳110℃到150℃。可使用上述的发泡造粒法或其他合适方法制作发泡热塑性聚氨基甲酸酯。注意挤压速度过低将可能导致造粒发泡粒子过发(称螺杆过发),造成无法再经微波发泡。
可依据上述的方法配制发泡热塑性聚氨基甲酸酯具有多种颜色的单一粒子。举例而言,可先准备多种含单色料的可发泡组合物,每种颜色不同,譬如第一可发泡组合物(含黑色料)及第二可发泡组合物(含红色料)。然后,将第一组合物分多次投入单螺杆造粒机中,在该第一组合物的该多次投入中任选两次,在所任选的两次之间投入一部分的该第二可发泡组合物。以此方法类推可配制发泡热塑性聚氨基甲酸酯具有多种颜色的单一粒子。
发泡热塑性聚氨基甲酸酯
可依据前述的可发泡组合物与方法制造本发明的发泡热塑性聚氨基甲酸酯,但不此为限。较佳而言,本发明的发泡热塑性聚氨基甲酸酯具有可再发泡性质,换言之,本发明的发泡热塑性聚氨基甲酸酯可透过譬如微波等合适方法再次发泡,而产生更低密度。具体而言,在各较佳实例中,本发明提供具有一密度范围为0.2g/cm3至0.8g/cm3的发泡热塑性聚氨基甲酸酯,将此发泡热塑性聚氨基甲酸酯施以微波可使其再次发泡而产生比首次发泡的密度更低的再次发泡的密度,范围为0.15g/cm3至0.6g/cm3。在本文中,前述组合物经造粒发泡形成发泡热塑性聚氨基甲酸酯,此段制程称为第一段发泡。第一段发泡所制得的发泡热塑性聚氨基甲酸酯再进行发泡,此段制程称为第二段发泡。在一较佳实施例中,第一段发泡的发泡热塑性聚氨基甲酸酯是残留发泡剂,但本发明不以此为限。调整可发泡组合物的配方或控制造粒发泡的制程而使发泡热塑性聚氨基甲酸酯中残留尚未完全失效的发泡剂,将可加强其再次发泡的能力。依据本发明的实施例,第一段发泡的发泡热塑性聚氨基甲酸酯较佳具有3mm至7.5mm的粒径。依据本发明的其他实施例,第一段发泡的发泡热塑性聚氨基甲酸酯较佳具有40C至80C的肖氏硬度。依据本发明的再其他的实施例,第一段发泡的发泡热塑性聚氨基甲酸酯较佳具有0.2g/cm3至0.8g/cm3的密度。第一段发泡的发泡热塑性聚氨基甲酸酯可有各种外型,譬如球状、薄片状、非球状的不规则状等等。
微波成型体及其方法
本发明微波成型体系以微波方式进行第二段发泡而成,其经微波所制得的发泡材料中形成的孔洞将比未经过微波的更加均匀细致,更具有轻质的优点。此外,通过微波也使发泡热塑性聚氨基甲酸酯的各个粒子表面产生相互黏合作用,进而成为微波成型体。依据各种实施例,本发明所制作的微波成型体可优选地具有以下物性:较佳硬度肖氏为40C至80C;较佳密度为0.15g/cm3至0.6g/cm3。
依据各种实施例,本发明微波成型体制法可为:取适当量的第一段发泡的发泡热塑性聚氨基甲酸酯置入一容器中,然后照射微波,此容器可为各种模具。陶瓷模具、塑料模具、玻璃模具或金属与塑料复合模具,于较佳实施例容器为金属与塑料复合材。本发明于进行微波发泡制程中,频率为2450MHz微波,较佳的微波功率为500瓦(W)至30,000W,更佳为5,000W至25,000W,微波时间为3秒至300秒,更佳为5秒到120秒。依据某些实施例,微波过程中不需加水。于某些实施例微波过程中可加入水或醇类等作为微波介质。在此等实施例中,基于100重量份的发泡热塑性聚氨基甲酸酯,该介质的用量为1重量份至10重量份。该介质可为极性介质,可选用的醇类包括一级醇(例如:甲醇或乙醇)及二级醇(例如:乙二醇或丙二醇),但并非仅限于此。
综上所述,通过提供有合适配比的可发泡组合物,依序进行第一段发泡造粒制程及第二段微波发泡制程,即可产出兼具轻质(发泡倍率高)、质量稳定、孔洞分布均匀等优点的热塑性聚氨基甲酸酯发泡材料。
以下列举各种实例详细说明本发明的实施方式。本领域技术人员可经由本说明书的内容轻易地了解本发明所能达成之优点与功效,并且于不悖离本发明的精神下进行各种修饰与变更,以施行或应用本创作之内容。
第一段造粒发泡:实例1a、实例2a及比较例1a’
实例1a:将100重量份的未发泡热塑性聚氨基甲酸酯粒子(商品名称:T955PLVM2,肖氏硬度为50A,黏度为9000泊(170℃),由三晃股份有限公司制造)、2.5重量份的苯甲酸甲酯(作为可塑剂)、2.5重量份的硅酸铝(作为增黏剂)、0.1重量份的滑石粉及15重量份的膨胀性微球(商品名称:Expancel 930DU-120,购自Matsumoto,作为发泡剂)均匀混合后,投入单螺杆造粒机,以物料挤压速度为50kg/h、模头压力为50kgf/cm2、模头温度为155℃、螺杆温度120-170℃及水中造粒温度为20℃的条件进行第一段发泡造粒制程,以获得一次发泡热塑性聚氨基甲酸酯。此一次发泡热塑性聚氨基甲酸酯的密度为0.33g/cm3,为粒状。
实例2a:将100重量份的未发泡热塑性聚氨基甲酸酯粒子(商品名称:T955PLVM2,肖氏硬度为50A,黏度为9000泊(170℃),由三晃股份有限公司制造)、2.5重量份的苯甲酸甲酯(作为可塑剂)及1.0重量份的过氧化二异丙苯(作为架桥剂)、0.1重量份的滑石粉及15重量份的膨胀性微球(商品名称:Expancel 930DU-120,购自Matsumoto,作为发泡剂)均匀混合后,投入单螺杆造粒机,以物料挤压速度为50kg/h、模头压力为50kgf/cm2、模头温度为155°C、螺杆温度120-170℃及水中造粒温度为20℃的条件进行第一段发泡造粒制程,以获得一次发泡热塑性聚氨基甲酸酯。此一次发泡热塑性聚氨基甲酸酯的密度为0.32g/cm3,为粒状。
比较例1a’:将100重量份的未发泡热塑性聚氨基甲酸酯粒子(T955PLVM2,肖氏硬度为50A,黏度为9000泊(170度),由三晃股份有限公司制造)、2.5重量份的苯甲酸甲酯(作为可塑剂)、0.1重量份的滑石粉及15重量份的膨胀性微球(商品名称:Expancel 930DU-120,购自Matsumoto,作为发泡剂)均匀混合后,投入单螺杆造粒机,以物料挤压速度为50kg/h、模头压力为35kgf/cm2、模头温度为155℃、螺杆温度120-170℃及水中造粒温度为20°C的条件进行第一段发泡造粒制程进行第一段发泡造粒制程,未加入增黏剂、架桥架,此一次发泡热塑性聚氨基甲酸酯的密度为0.48g/cm3,为粒状。
第二段微波发泡:实例1b、实例2b及比较例1b’
实例1b:将前述实例1a所制得的发泡热塑性聚氨基甲酸酯(名称为1a)取72重量份并加入3重量份的水置入模具中,该模具的长度为20公分、宽度为12公分、高度为1.2公分,再以微波频率为2450MHz,微波功率为8000W、微波时间为35秒进行第二段微波发泡制程,待模具降温冷却后,即完成热塑性聚氨基甲酸酯微波成型体,平均密度为0.27g/cm3。
实例2b、实例2b及比较例1b’可参考实例1b的作法。各实例的条件可参考表1及表2的说明。
实例与比较例的分析讨论
实例1a/1b、2a/2b、与比较例1a/1b(添加增稠剂/架桥剂)
比较例1a’与实例1a的差异在于实例1a有使用增稠剂。比较例1a’与实例2a的差异在于实例2a有使用架桥剂。由于比较例1a无使用增稠剂或架桥剂,因此发泡热塑性聚氨基甲酸酯在一次发泡阶段由于黏度过低,强度不足,导致发泡粒子无法稳定成型,造成冷却时粒子有明显收缩现象,因而密度提升。比较例1a虽可顺利获得已发泡热塑性聚氨基甲酸酯(密度0.48g/cm3),但此粒子经微波后膨胀性不佳,因而塌陷无法呈现形状饱满的微波发泡成型体。
表1
表2
Claims (16)
1.一种微波成型体,其特征在于,将发泡热塑性聚氨基甲酸酯经微波而成,所述发泡热塑性聚氨基甲酸酯是由可发泡组合物经螺杆造粒机发泡造粒制成,所述可发泡组合物包括:100重量份的未发泡热塑性聚氨基甲酸酯粒子、5重量份至25重量份的发泡剂,及0.5重量份至5重量份的增黏剂或架桥剂,其中所述未发泡热塑性聚氨基甲酸酯粒子具有1,000泊至9,000泊的黏度,所述黏度以JISK 7311测试方法在170℃测得;
其中所述增黏剂选自无机增稠剂、聚丙烯酸类增稠剂、或纤维素类增稠剂,
其中所述无机增稠剂选自膨润土或硅酸铝,所述聚丙烯酸类增稠剂选自丙烯酸、马来酸、马来酸酐或甲基丙烯酸的羧酸类单体形成的增稠剂,所述纤维素类增稠剂选自甲基纤维素、羧甲基纤维素、羟乙基纤维素、或羟丙基甲基纤维素所形成的增稠剂,
其中架桥剂选自过氧化二异丙苯、过氧化苯甲酰、二叔丁基过氧化物、或过氧化氢二异丙苯。
2.如权利要求1所述的微波成型体,其特征在于,其中所述微波成型体的密度为0.15g/cm3至0.6g/cm3。
3.如权利要求1所述的微波成型体,其特征在于,其中所述微波成型体的硬度为肖氏硬度C 40至肖氏硬度C 80。
4.如权利要求1所述的微波成型体,其特征在于,其中所述未发泡热塑性聚氨基甲酸酯粒子具有2.5mm至4.5mm的粒径。
5.如权利要求1所述的微波成型体,其特征在于,其中所述未发泡热塑性聚氨基甲酸酯粒子具有肖氏硬度A 40至肖氏硬度D 64的硬度。
6.如权利要求1所述的微波成型体,其特征在于,其中所述未发泡热塑性聚氨基甲酸酯粒子具有1.0g/cm3至1.25g/cm3的密度。
7.如权利要求1所述的微波成型体,其特征在于,包含100重量份的所述未发泡热塑性聚氨基甲酸酯粒子及5重量份至20重量份的所述发泡剂。
8.如权利要求1所述的微波成型体,其特征在于,其中所述发泡剂为膨胀性微球、二氧化碳、或碳数为4至10的烃类化合物。
9.如权利要求1所述的微波成型体,其特征在于,还包含0.1重量份至5重量份的滑石粉。
10.如权利要求1所述的微波成型体,其特征在于,还包含1重量份至20重量份的可塑剂,所述可塑剂为苯甲酸酯或其衍生物。
11.如权利要求1所述的微波成型体,其特征在于,还包含色粉,基于100重量份的所述未发泡热塑性聚氨基甲酸酯粒子,所述色粉含有0.1重量份至5重量份。
12.如权利要求1所述的微波成型体,其特征在于,还包含1重量份至5重量份的所述增黏剂或所述架桥剂。
13.如权利要求1所述的微波成型体,其特征在于,其中所述微波成型体是经由500W至30,000W微波功率制成。
14.如权利要求1所述的微波成型体,其特征在于,其中所述微波的过程中不加水。
15.如权利要求1所述的微波成型体,其特征在于,其中所述微波的过程中加水或醇类,以所述发泡热塑性聚氨基甲酸酯的总重为100重量份,所述水或醇类的用量为1重量份至10重量份。
16.如权利要求1所述的微波成型体,所述二叔丁基过氧化物为2,5-二甲基-2,5-二叔丁基过氧化己烷。
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/CN2018/091068 WO2019237280A1 (zh) | 2018-06-13 | 2018-06-13 | 发泡热塑性聚氨基甲酸酯及其微波成型体 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN112166157A CN112166157A (zh) | 2021-01-01 |
CN112166157B true CN112166157B (zh) | 2021-10-29 |
Family
ID=68841710
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201880093761.2A Active CN112166157B (zh) | 2018-06-13 | 2018-06-13 | 发泡热塑性聚氨基甲酸酯及其微波成型体 |
Country Status (7)
Country | Link |
---|---|
US (1) | US11993689B2 (zh) |
EP (1) | EP3808814A4 (zh) |
JP (1) | JP7090749B2 (zh) |
KR (1) | KR20210028187A (zh) |
CN (1) | CN112166157B (zh) |
TW (1) | TWI756530B (zh) |
WO (1) | WO2019237280A1 (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20230365776A1 (en) * | 2020-09-29 | 2023-11-16 | Sunko Ink Co., Ltd. | Regenerated foamed particles, regenerated foamed and molded body, and manufacturing method therefor |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015123960A1 (zh) * | 2014-02-18 | 2015-08-27 | 山东美瑞新材料有限公司 | 一种发泡热塑性聚氨酯粒子及其制备方法和应用 |
CN107022185A (zh) * | 2015-09-11 | 2017-08-08 | 三晃股份有限公司 | 发泡热塑性聚氨基甲酸酯及其微波成型体 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001089594A (ja) * | 1999-09-21 | 2001-04-03 | Achilles Corp | 熱可塑性発泡ポリウレタン樹脂組成物 |
CN102971146B (zh) * | 2010-07-12 | 2016-01-20 | 可乐丽股份有限公司 | 被膜形成方法及被膜 |
CN102504688B (zh) * | 2011-11-23 | 2014-01-29 | 万华化学(广东)有限公司 | 一种合成革用水性聚氨酯发泡层及其制备方法 |
US9375866B2 (en) * | 2013-03-15 | 2016-06-28 | Nike, Inc. | Process for foaming thermoplastic elastomers |
TWI667285B (zh) * | 2013-10-18 | 2019-08-01 | 德商巴斯夫歐洲公司 | 膨脹熱塑性彈性體之製造 |
JP6548481B2 (ja) * | 2015-06-29 | 2019-07-24 | 株式会社荏原製作所 | 洗浄装置、洗浄方法、洗浄液製造装置および洗浄液製造方法 |
EP3181620A1 (en) * | 2015-12-17 | 2017-06-21 | Sunko Ink Co., Ltd. | Microwave molded article and manufacturing method thereof |
JP2018075753A (ja) * | 2016-11-08 | 2018-05-17 | 株式会社ジェイエスピー | 熱可塑性エラストマー発泡粒子成形体の製造方法 |
-
2018
- 2018-06-13 JP JP2020568978A patent/JP7090749B2/ja active Active
- 2018-06-13 WO PCT/CN2018/091068 patent/WO2019237280A1/zh unknown
- 2018-06-13 CN CN201880093761.2A patent/CN112166157B/zh active Active
- 2018-06-13 EP EP18922192.2A patent/EP3808814A4/en not_active Withdrawn
- 2018-06-13 US US17/251,171 patent/US11993689B2/en active Active
- 2018-06-13 KR KR1020217000869A patent/KR20210028187A/ko not_active IP Right Cessation
-
2019
- 2019-04-08 TW TW108112156A patent/TWI756530B/zh active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015123960A1 (zh) * | 2014-02-18 | 2015-08-27 | 山东美瑞新材料有限公司 | 一种发泡热塑性聚氨酯粒子及其制备方法和应用 |
CN107022185A (zh) * | 2015-09-11 | 2017-08-08 | 三晃股份有限公司 | 发泡热塑性聚氨基甲酸酯及其微波成型体 |
Also Published As
Publication number | Publication date |
---|---|
US11993689B2 (en) | 2024-05-28 |
EP3808814A1 (en) | 2021-04-21 |
JP2021526577A (ja) | 2021-10-07 |
EP3808814A4 (en) | 2022-02-23 |
CN112166157A (zh) | 2021-01-01 |
TW202000769A (zh) | 2020-01-01 |
JP7090749B2 (ja) | 2022-06-24 |
WO2019237280A1 (zh) | 2019-12-19 |
KR20210028187A (ko) | 2021-03-11 |
US20210214515A1 (en) | 2021-07-15 |
TWI756530B (zh) | 2022-03-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI675868B (zh) | 微波成型體及其製造方法 | |
EP3181620A1 (en) | Microwave molded article and manufacturing method thereof | |
KR100611686B1 (ko) | 발포 열가소성 폴리우레탄 | |
JP6691754B2 (ja) | ポリ乳酸発泡成形材料、その発泡成形品と製造方法 | |
CN107828205B (zh) | 一种可硫化交联的发泡聚氨酯混炼胶粒子及其制备方法和成型工艺 | |
CN108884260B (zh) | 热塑性聚氨酯发泡粒子 | |
WO2017077764A1 (ja) | 発泡成形品の製造方法及び発泡成形品 | |
CN112166157B (zh) | 发泡热塑性聚氨基甲酸酯及其微波成型体 | |
CN101341201B (zh) | 化学组合物与方法 | |
KR20130123297A (ko) | 발포 플라스틱 재료, 특히 pvc계 폴리머 폼의 생성을 위한 공정 및 상기 공정을 수행하기 위한 폴리머 혼합물의 제제 | |
JP2007186692A (ja) | ポリ乳酸系樹脂発泡性粒子の製造方法 | |
JP3825702B2 (ja) | 生分解性ポリエステル樹脂組成物、その製造方法、及びそれより得られる発泡体 | |
TW201938347A (zh) | 依高頻輻射的方法經由熱塑性彈性體鍵結固態主體 | |
CN107685413B (zh) | 一种由低温热膨胀微球发泡聚丙烯塑料的方法 | |
JP6043897B1 (ja) | 発泡成形品の製造方法及び発泡成形品 | |
JPH06298983A (ja) | 発泡性熱可塑性樹脂粒子の製造法 | |
JPH04345637A (ja) | 発泡性エラストマーパウダー組成物、発泡成形体及びその製造法 | |
KR940000116B1 (ko) | 구상화된 가교폴리에틸렌 수지의 팽창입자 제조방법 | |
JP2022515854A (ja) | 芳香族ポリエステル-ポリウレタンマルチブロックコポリマーからなる発泡性粒子 | |
JPH07138397A (ja) | プロピレン系樹脂発泡成形体およびその製造方法 | |
TW202212445A (zh) | 再生發泡粒子、再生發泡成型體及其製造方法 | |
JPH08157635A (ja) | 熱可塑性ポリウレタン発泡成形体の製造方法 |
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 | ||
GR01 | Patent grant | ||
GR01 | Patent grant |