WO2018036504A1 - 一种热塑性聚酯弹性体发泡用前体、发泡体及其制备方法 - Google Patents

一种热塑性聚酯弹性体发泡用前体、发泡体及其制备方法 Download PDF

Info

Publication number
WO2018036504A1
WO2018036504A1 PCT/CN2017/098595 CN2017098595W WO2018036504A1 WO 2018036504 A1 WO2018036504 A1 WO 2018036504A1 CN 2017098595 W CN2017098595 W CN 2017098595W WO 2018036504 A1 WO2018036504 A1 WO 2018036504A1
Authority
WO
WIPO (PCT)
Prior art keywords
thermoplastic polyester
polyester elastomer
parts
melt
foaming
Prior art date
Application number
PCT/CN2017/098595
Other languages
English (en)
French (fr)
Inventor
唐靖
胡晓华
李巡天
Original Assignee
唐靖
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 唐靖 filed Critical 唐靖
Publication of WO2018036504A1 publication Critical patent/WO2018036504A1/zh

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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/18—Binary blends of expanding agents
    • C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
    • 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
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • 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
    • 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
    • C08J2425/00—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 at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/04—Homopolymers or copolymers of styrene
    • C08J2425/08—Copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer

Definitions

  • the invention belongs to the technical field of thermoplastic elastomer foaming, and particularly relates to a thermoplastic polyester elastomer foaming precursor, a foam body and a preparation method thereof.
  • PS foam plastics are polystyrene (PS) foam, polyethylene (PE) foam, polypropylene (PP) foam and the like. 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 heat resistance and is not suitable for high temperature applications. Such products should have high surface hardness, easy to be crushed under pressure, and low resilience, which is difficult to be used for protective applications such as long-term buffer damping.
  • Polyurethane (PU) soft and rigid foam materials are prone to residual isocyanate during foaming, which is harmful to human body, and thermosetting foaming materials cannot be recycled.
  • VA foaming material low temperature resistance, easy to melt above 70 degrees, and easy to decompose to produce acid gas, polluted air and surrounding environment, and has poor resilience after compression.
  • SEBS Thermoplastic polyolefin elastomer
  • TPU thermoplastic polyurethane elastomer
  • thermoplastic polyurethane Moldable foam beads of thermoplastic polyurethane have been disclosed in WO2007082838.
  • the reported foamed thermoplastic polyurethane beads have the disadvantages of coarse cell structure, "wrinkles" on the surface of the particles, low product yield, and n-butane as a foaming agent in the foaming process, which is prone to environmental pollution. problem.
  • thermoplastic polyester elastomer (TPEE) has better mechanical properties than thermoplastic polyolefin elastomer (SEBS) and thermoplastic polyurethane elastomer (TPU), the structural characteristics of thermoplastic polyester elastomer determine its lower Melt viscosity and high melt flow are not conducive to foaming.
  • An object of the present invention is to provide a thermoplastic polyester elastomer foaming precursor, a foam, and a method for producing the same, which solve one or more of the above problems of the prior art.
  • thermoplastic polyester elastomer foaming precursor comprising the following components: a thermoplastic polyester elastomer, a melt melt viscosity modifier, and a cell size stabilizer.
  • the melt melt viscosity modifier comprises one or a combination of ethylene-acrylate-glycidyl methacrylate and polystyrene-polyethylene-polybutene copolymer.
  • the cell size stabilizer comprises one or more of dihydroxypropyl stearyl acid ester, sorbitan stearic acid monoester, and sorbitan palmitic acid monoester.
  • the following components are included by weight: 100 parts of the thermoplastic polyester elastomer, 2 to 10 parts of the melt melt viscosity modifier, and 0.2 to 1.2 parts of the cell size stabilizer.
  • the following components are included in parts by weight: 100 parts of the thermoplastic polyester elastomer, 2 to 10 parts of the melt melt viscosity modifier, and 2 to 12 parts of the cell size stabilizer.
  • thermoplastic polyester elastomer has a hardness in the range of Shore H25D to H45D.
  • thermoplastic polyester elastomer foaming precursor is a granular structure having a smooth surface and a particle diameter of 0.2 to 8.0 mm.
  • thermoplastic polyester elastomer foaming precursor has a melt flow rate of from 8 to 200 g/10 min.
  • thermoplastic polyester elastomer foaming precursor further comprises a UV stabilizer, and the UV stabilizer has a weight component of 0.1 to 0.5 parts.
  • thermoplastic polyester foam comprising the following components: a thermoplastic polyester elastomer, a melt melt viscosity modifier, a cell size stabilizer, and a volatile blowing agent.
  • thermoplastic polyester elastomer 100 parts of thermoplastic polyester elastomer, 2 to 10 parts of melt melt viscosity modifier, 0.2 to 1.2 parts of cell size stabilizer, and volatile foaming agent 10 to 200 copies.
  • thermoplastic polyester elastomer 100 parts of thermoplastic polyester elastomer, 2 to 10 parts of melt melt viscosity modifier, 2 to 12 parts of cell size stabilizer, and volatile foaming agent 10 to 50 copies.
  • the volatile blowing agent is one or a combination of two of carbon dioxide and nitrogen.
  • the melt melt viscosity modifier comprises one or a combination of ethylene-acrylate-glycidyl methacrylate and polystyrene-polyethylene-polybutene copolymer.
  • the cell size stabilizer comprises one or more of dihydroxypropyl stearyl acid ester, sorbitan stearic acid monoester, and sorbitan palmitic acid monoester.
  • thermoplastic polyester elastomer is based on a polyether polyol having a molar mass of from 600 g/mol to 2500 g/mol and/or a polyester polyol having a molar mass of from 600 g/mol to 2500 g/mol.
  • thermoplastic polyester elastomer has a hardness in the range of Shore H25D to H45D.
  • thermoplastic polyester foam further comprises a UV stabilizer, and the UV stabilizer has a weight component of 0.1 to 0.5 parts.
  • thermoplastic polyester foam has a density of 0.08 to 0.60 g/m 3 and a cell diameter of 10 to 800 ⁇ m.
  • thermoplastic polyester foam as described above, comprising the steps of:
  • thermoplastic polyester elastomer the melt melt viscosity modifier and the cell stabilizer are uniformly mixed, and melt-cooled to prepare a thermoplastic polyester elastomer foaming precursor;
  • Foaming agent penetration a thermoplastic polyester elastomer foaming precursor is added to a high pressure reaction vessel, a volatile foaming agent is added, and the temperature is raised to the softening point of the thermoplastic polyester elastomer foaming precursor, and the pressure is increased.
  • the volatile foaming agent is in a supercritical state, and the heat preservation pressure is maintained;
  • Foaming After the penetration of the foaming agent is completed, the pressure is lowered, and the thermoplastic polyester elastomer foaming precursor is foamed to form a thermoplastic polyester foam.
  • the "precursor preparation" step comprises:
  • thermoplastic polyester elastomer 100 parts by weight of thermoplastic polyester elastomer, 2-10 parts of melt melt viscosity modifier, 0.2-1.2 parts of cell size stabilizer and 0.1-0.5 part of UV stabilizer are added to a high-mixer and mixed uniformly. The mixture is melt-kneaded by a twin-screw extruder, cooled, and then cut into pellets by an extruder strand or underwater pelletizing to obtain a thermoplastic polyester elastomer foaming precursor.
  • the reaction temperature after the temperature rise is 100 to 175° C.
  • the holding time of the heat preservation is 2 to 3 hours.
  • the "foaming agent penetration” step includes:
  • thermoplastic polyester elastomer foaming precursor and water are added to the autoclave, the volatile foaming agent is added, and the aqueous suspension mixture is pressurized to raise the temperature to the thermoplastic polyester elastomer before foaming.
  • the softening point of the body is pressurized to make the volatile foaming agent in a supercritical state, and the pressure is maintained.
  • the present invention has the following advantages and beneficial effects:
  • the present invention employs a thermoplastic polyester elastomer as a foaming body, and a thermoplastic melt elastomer is modified by adding a melt melt viscosity modifier and a cell size stabilizer to obtain a melt viscosity and a melt.
  • the thermoplastic polyester elastomer foaming precursor with suitable flow rate is beneficial to ensure the dimensional stability of the foamed particles, and optimizes the elasticity and compression properties of the material, and significantly expands the temperature applicable range;
  • the invention has reasonable design, simple process, strong practicability, stable size, uniform cell diameter, high surface gloss and high product yield; the obtained foam product has small deformation, wide use temperature and shrinks with respect to the size of the mold.
  • the rate is low, the dimensional stability is excellent, and the surface is beautiful; in addition, since the molded foam article has a small deformation, the aging time can be shortened, and the lower pressure water vapor can be used for molding processing, which is suitable for economical industrial production;
  • the invention can be used for toys filling, cushion filling, cushions, pillows, solid tires, etc. Under the condition of high temperature gas heating, it can be directly die-casting, injection molding, used for shock absorbing packaging materials, anti-collision protection parts, shock absorption.
  • Mat subway track cushion
  • precision instrument packaging thermal insulation
  • sports protection products sports midsole, insoles, helmets
  • outdoor protective equipment floating equipment
  • baby stroller tires etc.
  • thermoplastic polyester elastomer foaming precursor comprising the following components: a thermoplastic polyester elastomer, a melt melt viscosity modifier and a cell size stabilizer;
  • the cell size stabilizer is used to reduce the surface tension of the thermoplastic polyester elastomer and improve the foaming stability.
  • the cell size stabilizer comprises one or more of dihydroxypropyl octadecanoate, sorbitan stearate, and sorbitan palmitic monoester.
  • the advantage is that a small amount of addition can stabilize the cell size after foaming in a relatively concentrated range, and reduce the problem that the cell size is too large to be easily broken.
  • the melt melt viscosity modifier comprises one or a combination of ethylene-acrylate-glycidyl methacrylate and polystyrene-polyethylene-polybutene copolymer. The advantage is that a small addition increases the viscosity of the melt and the melt viscosity value remains stable over a range of ⁇ 15 °C.
  • thermoplastic polyester elastomer is a block type structural copolymer composed of two segments of soft and hard structure, and the soft segment is a segment formed of a non-crystalline polyether polyol or a polyester polyol.
  • the segment determines the flexibility and elasticity of the material, and the hard segment is a segment formed of a relatively high hardness, crystalline polyparaphenylene terephthalate which determines the mechanical strength and stability of the material.
  • thermoplastic polyester elastomer having a molecular weight of 10,000 or more is used.
  • thermoplastic polyester elastomer is obtained by polymerizing terephthalic acid and a polyether polyol or a polyester polyol.
  • a chain extender such as 1,4-butanediol may also be added. .
  • the melt melt viscosity modifier selects ethylene-acrylate-glycidyl methacrylate; in some embodiments of the invention, the melt melt viscosity modifier selects polyphenylene Ethylene-polyethylene-polybutene copolymer.
  • thermoplastic polyester elastomer by weight, 100 parts by weight of the thermoplastic polyester elastomer, 2 to 10 parts of the melt melt viscosity modifier, and 0.2 to 1.2 parts of the cell size stabilizer are included.
  • thermoplastic polyester elastomer by weight, 100 parts by weight of the thermoplastic polyester elastomer, 2 to 10 parts of the melt melt viscosity modifier, and 2 to 12 parts of the cell size stabilizer are included.
  • melt viscosity adjustment effect is poor, which affects the foam molding of the foam;
  • the content of the melt melt viscosity modifier is too large, The melt viscosity of the obtained thermoplastic polyester elastomer foaming precursor is too large, which is also disadvantageous for foaming.
  • the thermoplastic polyester elastomer has a hardness in the range of Shore H25D to H45D, preferably H28D to H45D.
  • thermoplastic polyester elastomer has a melting point of not higher than 175 ° C in this hardness range, which is advantageous for stably adjusting the softening temperature in the pellet high pressure reactor.
  • thermoplastic polyester elastomer is based on a polyether polyol having a molar mass of from 600 g/mol to 2500 g/mol.
  • thermoplastic polyester elastomer is based on a polyester polyol having a molar mass of from 600 g/mol to 2500 g/mol, or a polyether polyol of from 600 g/mol to 2500 g/mol and from 600 g/mol to 2500 g/mol. Polyester polyol is mixed.
  • the thermoplastic polyester elastomer foaming precursor is a smooth, granular structure having a particle diameter of 0.2 to 8.0 mm, and more preferably a particle diameter of 2 to 5 mm.
  • thermoplastic polyester elastomer foaming precursor has a smooth surface-like granular structure.
  • the inventors have found through many experiments that when the thermoplastic polyester elastomer foaming precursor is foamed, The angular particles tend to cause uneven penetration of the foaming agent, resulting in uneven cell diameter and cell density, and it is easy to cause cell breakage at the angular position during foaming, affecting the expansion ratio of the particles and the appearance of the product.
  • the smooth granular structure of the surface is favorable for the penetration of the foaming agent, and the smooth granular structure of the surface may be an ellipsoidal shape, a drop shape or a spherical structure.
  • the particle diameter is too large, it will affect the full penetration of the foaming agent and affect the expansion. rate.
  • thermoplastic polyester elastomer foaming precursor has a melt flow rate of from 8 to 200 g/10 min.
  • MI test conditions ISO 1133 230 ° C / 2.16 kg, measured at 230 ° C constant temperature, load 2.16 kg conditions to determine the melt flow rate, the unit is g/10min, the time flowing out within 10 minutes The weight in grams of the polymer.
  • thermoplastic polyester elastomer foaming precursor further comprises a UV stabilizer.
  • the UV stabilizer is used to increase the stability of the thermoplastic polyester elastomer under ultraviolet irradiation.
  • the UV stabilizer has a weight component of 0.1 to 0.5 parts by weight.
  • the UV stabilizer is poly(dimethyl 4-hydroxy-2,2,6,6-tetramethyl-1-azetaneethanol).
  • the thermoplastic polyester elastomer foaming precursor component further comprises an auxiliary agent, which is a flame retardant, an antistatic agent, a pigment, a hydrolysis inhibitor, and an inorganic filler. Or organic filler.
  • an auxiliary agent which is a flame retardant, an antistatic agent, a pigment, a hydrolysis inhibitor, and an inorganic filler. Or organic filler.
  • the amount of the adjuvant added is determined according to actual use requirements. The advantage is that the thermoplastic polyester elastomer modified material foamed particles can be adapted for different applications.
  • an antistatic agent may be added to the component to lower the surface resistance of the product. Adding an antistatic agent can speed up the electrostatic discharge of the contact surface and avoid the risk of damage to the instrument or the formation of sparks due to static buildup.
  • thermoplastic polyester elastomer foaming precursor may be added to the component, which may be a toner or a color paste. Adding pigments to the components can obtain foamed particles of thermoplastic polyester elastomer modified materials with preset colors, and can be made into colorful products, which can help to mark different products and improve the aesthetics of the products.
  • thermoplastic polyester foam comprising the following components: a thermoplastic polyester elastomer, a melt melt viscosity modifier, a cell size stabilizer, and a volatile foaming agent.
  • thermoplastic polyester foam can be prepared by adding a volatile foaming agent to the thermoplastic polyester elastomer foaming precursor as described above.
  • thermoplastic polyester foam provided by the invention has excellent applicability in high temperature and low temperature environments, The foaming temperature range is wide, the yield is high, and the finished product has a wide processing temperature range and can be used over a very wide temperature range. It has excellent mechanical strength, water resistance, oil resistance and chemical resistance. It has high color retention under UV light, rich color, environmental friendliness and recyclability.
  • the following components are included in parts by weight: 100 parts of thermoplastic polyester elastomer, 2 to 10 parts of melt melt viscosity modifier, 0.2 to 1.2 parts of cell size stabilizer, and volatility
  • the foaming agent is 10 to 200 parts.
  • the following components are included in parts by weight: 100 parts of thermoplastic polyester elastomer, 2 to 10 parts of melt melt viscosity modifier, 2 to 12 parts of cell size stabilizer, and volatility 10 to 50 parts of foaming agent.
  • the volatile blowing agent is one or a combination of carbon dioxide and nitrogen, preferably carbon dioxide.
  • the advantage is that the two gases are easy to obtain and low in price, have no toxicity and flammable and explosive danger, and have no environmental pollution.
  • the operating temperatures of the two gas foaming processes are also favorable for the foaming stable operation of the high pressure reactor, wherein The use of carbon dioxide also contributes to the fixation of greenhouse gases and reduces the greenhouse effect.
  • the melt melt viscosity modifier comprises one or both combinations of ethylene-acrylate-glycidyl methacrylate and polystyrene-polyethylene-polybutene copolymer.
  • the cell size stabilizer comprises one of dihydroxypropyl octadecanoate, sorbitan stearate, and sorbitan palmitic monoester or A variety.
  • thermoplastic polyester elastomer is based on a polyether polyol having a molar mass of from 600 g/mol to 2500 g/mol and/or a polyester polyol having a molar mass of from 600 g/mol to 2500 g/mol.
  • thermoplastic polyester elastomer has a hardness in the range of Shore H25D to H45D.
  • the thermoplastic polyester foam further comprises a UV stabilizer having a weight component of from 0.1 to 0.5 parts by weight. In some embodiments of the invention, the thermoplastic polyester foam has a density of from 0.08 to 0.60 g/m 3 and a cell diameter of from 10 to 800 ⁇ m.
  • the invention also discloses a preparation method of a thermoplastic polyester foam as described above, comprising the following steps:
  • Precursor preparation 100 parts by weight of thermoplastic polyester elastomer, 2-10 parts of melt melt viscosity modifier, 0.2-1.2 parts of cell size stabilizer and 0.1-0.5 parts of UV stabilizer are added to the high-mixer Mix evenly, melt and knead by twin-screw extruder, cool and then pass through extruder bar or underwater pelletizing The pellets were cut into pellets to obtain a precursor for foaming a thermoplastic polyester elastomer.
  • the preparation of the particles by means of underwater pelletizing is preferably carried out.
  • the pressure of the water acts to form the droplets, and the edges of the particles are reduced, thereby facilitating the improvement. Subsequent foaming effect.
  • thermoplastic polyester elastomer foaming precursor may also be extruded through an extruder to form different shapes depending on the shape of the thermoplastic polyester foam.
  • thermoplastic polyester elastomer foaming precursor is added to the autoclave, the volatile foaming agent is added, and the temperature is raised to the softening point of the thermoplastic polyester elastomer foaming precursor, and the reaction temperature after the temperature rise
  • the pressure foaming agent is in a supercritical state at a temperature of 100 to 175 ° C, and the pressure is maintained for 2 to 3 hours.
  • thermoplastic polyester elastomer foaming precursor After the penetration of the foaming agent is completed, the pressure is lowered, and the solubility of the foaming agent in the thermoplastic polyester elastomer foaming precursor is lowered due to the pressure reduction, thereby producing in the thermoplastic polyester elastomer foaming precursor. The expansion action, the thermoplastic polyester elastomer foaming precursor is foamed to form a thermoplastic polyester foam.
  • the "foaming agent penetration” step comprises:
  • thermoplastic polyester elastomer foaming precursor and water are added to the autoclave, a volatile foaming agent is added, and the mixture is pressurized to form an aqueous suspension mixture, and the temperature is raised to the softening point of the thermoplastic polyester elastomer foaming precursor. Pressurizing the volatile blowing agent in a supercritical state, and maintaining the pressure.
  • thermoplastic polyester elastomer particulate material used in the following examples are:
  • thermoplastic polyester elastomer granular material can be produced by the company produced by Jiangyin and Chuang Elastomer New Material Technology Co., Ltd., produced by Taiwan Changchun Chemical Co., Ltd., produced by SK Corporation of Korea, DuPont of the United States, and the like.
  • Plastic polyester elastomer foamed particle density reference index 0.08-0.60g/cm 3 .
  • the density of EVA resin products widely used in the market is about 0.27 g/cm 3 , so the expected value of the foaming material in the footwear industry is less than or equal to the density, and the density is higher than 0.3 g/cm 3 to 0.6 g/cm 3 .
  • the products are used for other applications with higher load-bearing loads.
  • foaming granules can be prepared by a lower cost foaming method, which will not be elaborated here.
  • the uniformity of the cell diameter directly affects the performance of the product. If the diameter of the cell is too large, it may cause cooling or collapse during use, which may affect the function and appearance. If the cell diameter is too small, the degree of foaming is low or not foaming, and the density of foamed particles of plastic polyester elastomer cannot be effectively reduced. .
  • the invention has been experimentally verified that the foamed particles of the thermoplastic polyester elastomer modified material have excellent cell diameter in the range of 10 to 800 ⁇ m (preferably 10 to 100 ⁇ m), high surface gloss, good elasticity of the foamed particles, and good Industrial application prospects.
  • thermoplastic polyester elastomer particles A 100 kg of thermoplastic polyester elastomer particles A, 5 kg of ethylene-acrylate-glycidyl methacrylate, 8 kg of sorbitan monostearate, 0.25 kg of UV stabilizer were added to the mixer. After mixing, the mixture was introduced into a twin-screw extruder through a hopper for melt-kneading, and the melt flow rate was measured under the conditions of a constant temperature of 230 ° C and a load of 8.7 kg.
  • the melt-kneaded material conforming to the melt flow rate index is extruded into a strip shape from a die hole having an extruder diameter of 1.5 mm, cooled and formed in a cooling water tank of about 5 m length, and cut into 2.5 mm by a pelletizer. Long particles, thereby obtaining a thermoplastic polyester elastomer foaming precursor.
  • thermoplastic polyester elastomer foaming precursor 100 kg were mixed and added to the autoclave to form an aqueous suspension mixture. While stirring, 30 kg of a carbon dioxide volatile blowing agent was added, and the autoclave was heated to 155 °C.
  • the melt flow rate obtained in this example was 130 g/10 min, the density of the thermoplastic polyester elastomer foamed particles was 0.25 g/cm 3 , and the average diameter of the foamed cells was 270 ⁇ m.
  • Table 1 is an example of the preparation of the thermoplastic polyester elastomer-modified material foamed granules of Example 1 and other methods similar or similar to those of Example 1, thermoplastic polyester elastomer particles, melt melt viscosity modifier, hair The weight of the cell size stabilizer, the UV stabilizer and the blowing agent, and the melt flow rate and the high pressure reactor temperature, the density of the foamed particles of the thermoplastic polyester elastomer-modified material and the average diameter of the foamed cells.
  • thermoplastic polyester elastomer modified material foaming granules prepared in Examples 1-18 have the required composition: the thermoplastic polyester elastomer content is 100 parts, and the melt melt viscosity modifier content ranges from 2 to 10 parts, the cell size stabilizer content ranges from 2 to 10 parts, the UV stabilizer content ranges from 0.1 to 0.5 parts, and the volatile blowing agent content ranges from 10 to 50 parts. Therefore, the melt flow rate values measured after melt-kneading were all in the range of 40 to 200 g/10 min.
  • the temperature of the high temperature reactor is controlled between 110 and 175 ° C.
  • the mixed suspension is stably adjusted in this temperature range to uniformly foam.
  • the density of the foamed particles of the plastic polyester elastomer modified material is 0.08-0.30g. /cm 3 interval; the average diameter of the foamed holes is within 250-800 ⁇ m.
  • thermoplastic polyester elastomer foamed particles could not be formed.
  • thermoplastic polyester elastomer particles A 100 kg of thermoplastic polyester elastomer particles A, 5 kg of ethylene-acrylate-glycidyl methacrylate, 0.2 kg of sorbitan monostearate, 0.25 kg of UV stabilizer were added to the mixer. After mixing, the mixture was introduced into a twin-screw extruder through a hopper for melt-kneading, and the melt flow rate was measured at a constant temperature of 230 ° C under a load of 2.16 kg. The melt kneaded product conforming to the melt flow rate index was introduced from an extruder into an underwater pelletizer, and cut into ellipsoidal particles having a diameter of 2.5 mm to obtain a thermoplastic polyester elastomer foaming precursor.
  • thermoplastic polyester elastomer foaming precursor 100 kg was added to 50 kg of a carbon dioxide volatile foaming agent, and added to a high pressure reaction vessel to form a suspension mixture.
  • the autoclave was heated to 165 ° C while stirring.
  • the melt flow rate obtained in this example was 8 g/10 min, the density of the thermoplastic polyester elastomer foamed beads was 0.22 g/cm 3 , and the average diameter of the foamed cells was 70 ⁇ m.
  • Table 2 is an example of the preparation of the thermoplastic polyester elastomer-modified material expanded particles in the same manner as or in the same manner as in Example 29, in Example 29, the thermoplastic polyester elastomer particles, the melt melt viscosity modifier, and the hair
  • thermoplastic polyester elastomer modified material foaming granules prepared in Examples 29-36 have the required composition: the thermoplastic polyester elastomer content is 100 parts, and the melt melt viscosity modifier content ranges from 2 to 2 10 parts, the cell size stabilizer content ranges from 0.2 to 1.2 parts, the UV stabilizer content ranges from 0.1 to 0.5 parts, and the volatile blowing agent content ranges from 10 to 200 parts. Therefore, the melt flow rate values measured after melt-kneading were all in the range of 8 to 40 g/10 min.
  • the temperature of the high temperature reactor is controlled between 110 and 175 ° C.
  • the mixed suspension is stably adjusted in this temperature range to uniformly foam.
  • the density of the foamed particles of the plastic polyester elastomer modified material is 0.08-0.60g. /cm 3 interval; the average diameter of the foamed holes is within 10 - 800 ⁇ m.
  • the present invention requires that the thermoplastic polyester elastomer of the host material has a hardness between Shore H28D and H45D, and the thermoplastic polyester elastomer itself has a melting point of not higher than 175 ° C, and the melt flow is adjusted by using a melt melt conditioner.
  • the rate reaches the target range, which stabilizes the effective foaming, ensures the dimensional stability of the foamed particles, and optimizes the elastic and compressive properties of the material and the range of the post-processing temperature range, while significantly expanding the temperature range.

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)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

为克服现有热塑性聚酯弹性体难以发泡的问题，本发明提供了一种热塑性聚酯弹性体发泡用前体，包括以下组分：热塑性聚酯弹性体、熔体熔融粘度调节剂和泡孔尺寸稳定剂。同时，本发明还公开了一种热塑性聚酯发泡体及其制备方法。本发明提供的热塑性聚酯发泡体具有重量轻，外观优良，回弹性优异的优点，利于推广应用。

Description

一种热塑性聚酯弹性体发泡用前体、发泡体及其制备方法
本申请以2016年8月24日提交的申请号为201610715351.X，名称为“一种热塑性聚酯弹性体发泡颗粒及制备方法”的中国发明专利为基础，并要求其优先权。
技术领域
本发明属于热塑性弹性材料发泡技术领域，具体涉及一种热塑性聚酯弹性体发泡用前体、发泡体及其制备方法。
背景技术
目前常用的泡沫塑料品种聚苯乙烯(PS)泡沫塑料，聚乙烯(PE)泡沫塑料，聚丙烯(PP)泡沫塑料等。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，不适合在高温领域应用。此类产品的应为表面硬度高，受压易脆裂，回弹性很低，很难用于持续长期缓冲减震等保护性应用。聚氨酯(PU)软质和硬质泡沫材料，在发泡过程中容易残留异氰酸酯，对人体有害，并且热固性发泡材料无法回收利用。VA类发泡材料，耐温低，在70度以上易熔化，而且容易分解产生酸性气体、污染空气和周边环境，压缩后回弹性差。热塑性聚烯烃弹性体(SEBS)和热塑性聚氨酯弹性体(TPU)发泡材料，近年在市场上有部分应用，但耐高温和低温性能较差，产品易发黄变色，适用范围受限，压缩回弹性差，在表面受压或者压力释放后易褶皱，抗撕裂性能弱，易水解和降解造成产品综合性能差，部分着色性不好，紫外线下易变色，耐老化性能弱，生产效率低且成本高。热塑性聚氨酯的可模塑泡沫珠粒在W02007082838中已经被公开。但是该报道的发泡热塑性聚氨酯珠粒的缺点是泡孔结构尺寸较粗，颗粒表面出现“皱纹”，产品收率低，其发泡过程中采用正丁烷作为发泡剂，易产生环境污染问题。
热塑性聚酯弹性体(TPEE)虽然相对于热塑性聚烯烃弹性体(SEBS)和热塑性聚氨酯弹性体(TPU)具有更好的力学性能，然而热塑性聚酯弹性体的结构特点决定了其具有较低的熔体粘度和较高的熔体流动性，不利于发泡。
发明内容
本发明的目的是提供一种热塑性聚酯弹性体发泡用前体、发泡体及其制备方法，解决上述现有技术问题中的一个或者多个。
本发明解决上述技术问题所采用的技术方案如下：
提供一种热塑性聚酯弹性体发泡用前体，包括以下组分：热塑性聚酯弹性体、熔体熔融粘度调节剂和泡孔尺寸稳定剂。
可选地，所述熔体熔融粘度调节剂包括乙烯-丙烯酸酯-甲基丙烯酸缩水甘油酯和聚苯乙烯-聚乙烯-聚丁烯共聚物的一种或两种组合。
可选地，所述泡孔尺寸稳定剂包括二羟基丙基十八烷酸酯、失水山梨醇硬脂酸单酯和失水山梨醇棕榈酸单酯中的一种或多种。
可选地，按重量份计，包括以下组分：热塑性聚酯弹性体100份、熔体熔融粘度调节剂2～10份、泡孔尺寸稳定剂0.2～1.2份。
可选地，按重量份计，包括以下组分：热塑性聚酯弹性体100份、熔体熔融粘度调节剂2～10份、泡孔尺寸稳定剂2～12份。
可选地，所述热塑性聚酯弹性体的硬度范围为邵氏H25D～H45D。
可选地，所述热塑性聚酯弹性体发泡用前体为表面圆滑的颗粒状结构，其颗粒直径为0.2～8.0mm。
可选地，所述热塑性聚酯弹性体发泡用前体的熔体流动速率为8～200g/10min。
可选地，所述热塑性聚酯弹性体发泡用前体还包括UV稳定剂，所述UV稳定剂的重量组分为：0.1～0.5份。
一种热塑性聚酯发泡体，包括以下组分：热塑性聚酯弹性体、熔体熔融粘度调节剂、泡孔尺寸稳定剂和挥发性发泡剂。
可选地，按重量份计，包括以下组分：热塑性聚酯弹性体100份、熔体熔融粘度调节剂2～10份、泡孔尺寸稳定剂0.2～1.2份、挥发性发泡剂10～200份。
可选地，按重量份计，包括以下组分：热塑性聚酯弹性体100份、熔体熔融粘度调节剂2～10份、泡孔尺寸稳定剂2～12份、挥发性发泡剂10～50份。
可选地，所述挥发性发泡剂为二氧化碳和氮气中的一种或两种组合。
可选地，所述熔体熔融粘度调节剂包括乙烯-丙烯酸酯-甲基丙烯酸缩水甘油酯和聚苯乙烯-聚乙烯-聚丁烯共聚物的一种或两种组合。
可选地，所述泡孔尺寸稳定剂包括二羟基丙基十八烷酸酯、失水山梨醇硬脂酸单酯和失水山梨醇棕榈酸单酯中的一种或多种。
可选地，所述热塑性聚酯弹性体基于摩尔质量为600g/mol～2500g/mol的聚醚多元醇和/或摩尔质量为600g/mol～2500g/mol的聚酯多元醇。
可选地，所述热塑性聚酯弹性体的硬度范围为邵氏H25D～H45D。
可选地，所述热塑性聚酯发泡体还包括UV稳定剂，UV稳定剂的重量组分为：0.1～0.5份。
可选地，所述热塑性聚酯发泡体的密度为0.08～0.60g/m3，泡孔直径为10～800μm。
如上所述的一种热塑性聚酯发泡体的制备方法，包括以下步骤：
前体制备：将热塑性聚酯弹性体、熔体熔融粘度调节剂和泡孔稳定剂混合均匀，熔融冷却后制成热塑性聚酯弹性体发泡用前体；
发泡剂渗透：将热塑性聚酯弹性体发泡用前体加入高压反应釜中，加入挥发性发泡剂，升温至热塑性聚酯弹性体发泡用前体的软化点，加压使所述挥发性发泡剂处于超临界状态，保温保压；
发泡：发泡剂渗透完成后，降低压力，热塑性聚酯弹性体发泡用前体发泡，形成热塑性聚酯发泡体。
可选地，所述“前体制备”步骤包括：
按重量份计，将100份热塑性聚酯弹性体、2～10份熔体熔融粘度调节剂、0.2～1.2份泡孔尺寸稳定剂和0.1～0.5份UV稳定剂加入高混机中混合均匀，通过双螺杆挤出机进行熔融混炼，冷却后通过挤出机拉条或者水下切粒切成颗粒，得到热塑性聚酯弹性体发泡用前体。
可选地，所述“发泡剂渗透”步骤中，升温后的反应温度为100～175℃，保温保压的时间为2～3小时。
所述“发泡剂渗透”步骤包括：
可选地，将热塑性聚酯弹性体发泡用前体和水加入高压反应釜中，加入挥发性发泡剂，加压形成含水的悬浮混合液，升温至热塑性聚酯弹性体发泡用前体的软化点，加压使所述挥发性发泡剂处于超临界状态，保温保压。
同现有技术相比，本发明具有如下优点和有益效果：
1、本发明采用了热塑性聚酯弹性体作为发泡的主体，加入熔体熔融粘度调节剂和泡孔尺寸稳定剂对热塑性聚酯弹性体进行改性，得到了熔体粘度和熔体 流动速率合适的热塑性聚酯弹性体发泡前体，有利于保证发泡颗粒的尺寸稳定性，并优化了该材料的弹性及压缩性能，同时明显扩大了温度适用范围；
2、本发明设计合理，工艺简洁，实用性强，尺寸稳定，泡孔直径均匀，表面光泽度高，产品收率高；所得到的泡沫制品形变小，使用温度宽，相对于模具的尺寸收缩率低，尺寸稳定性优异，表面美观；此外，由于模塑泡沫制品形变小，因此还可以缩短陈化时间，同时可采用较低压力的水蒸气进行成型加工，适合经济型的工业生产；
3、本发明可用于玩具填充、缓冲垫填充、靠垫、枕头、实心轮胎等应用，在高温气体加热条件下，能够直接压铸、注塑成型，用于减震包装材料、防撞保护部件、减震垫(地铁轨道减震垫)、精密仪器包装、保温隔热、运动保护产品(运动鞋中底、鞋垫、头盔)，户外防护用品、水上漂浮用品，童车轮胎等。
具体实施方式
为了使本发明所解决的技术问题、技术方案及有益效果更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
本发明公开了一种热塑性聚酯弹性体发泡用前体，包括以下组分：热塑性聚酯弹性体、熔体熔融粘度调节剂和泡孔尺寸稳定剂；
所述泡孔尺寸稳定剂用于降低热塑性聚酯弹性体的表面张力，提高发泡稳定性。在一些实施例中，所述泡孔尺寸稳定剂包括二羟基丙基十八烷酸酯、失水山梨醇硬脂酸单酯和失水山梨醇棕榈酸单酯中的一种或多种。优点在于少量添加即可让发泡后的泡孔尺寸稳定在相对集中的范围，减少因泡孔尺寸过大而易破裂的问题。在一些实施例中，所述熔体熔融粘度调节剂包括乙烯-丙烯酸酯-甲基丙烯酸缩水甘油酯和聚苯乙烯-聚乙烯-聚丁烯共聚物的一种或两种组合。优点在于少量的添加即可增加熔体的粘度，并且在±15℃范围内，熔体粘度值保持稳定。
所述热塑性聚酯弹性体为嵌段型结构共聚物，由软硬两种结构不同的链段构成，软段为非结晶性的聚醚多元醇或聚酯多元醇形成的链段，该软段决定材料的柔韧性和弹性，硬段为硬度比较高、结晶性的聚对苯二甲丁二醇酯形成的链段，该硬段决定材料的力学强度和稳定性。
优选情况下，采用分子量1万以上的热塑性聚酯弹性体。
优选情况下，所述热塑性聚酯弹性体由对苯二甲酸和聚醚多元醇或聚酯多元醇聚合得到，在部分实施例中，还可加入扩链剂，如1,4-丁二醇。
在本发明的一些实施例中，所述熔体熔融粘度调节剂选择乙烯-丙烯酸酯-甲基丙烯酸缩水甘油酯；在本发明的一些实施例中，所述熔体熔融粘度调节剂选择聚苯乙烯-聚乙烯-聚丁烯共聚物。
在本发明的一些实施例中，按重量份计，包括以下组分：热塑性聚酯弹性体100份、熔体熔融粘度调节剂2～10份、泡孔尺寸稳定剂0.2～1.2份。
在本发明的一些实施例中，按重量份计，包括以下组分：热塑性聚酯弹性体100份、熔体熔融粘度调节剂2～10份、泡孔尺寸稳定剂2～12份。
当所述熔体熔融粘度调节剂的含量过小时，其起到的熔融粘度调节作用较差，影响发泡体的发泡成型；当所述熔体熔融粘度调节剂的含量过大时，则得到的热塑性聚酯弹性体发泡用前体的熔融粘度过大，同样不利于发泡。
在本发明的一些实施例中，所述热塑性聚酯弹性体的硬度范围为邵氏H25D～H45D，优选H28D～H45D。
优点在于在此硬度范围内，所述热塑性聚酯弹性体的熔点不高于175℃，有利于稳定地调节颗粒高压反应釜中的软化温度。
在本发明的一些实施例中，所述热塑性聚酯弹性体基于摩尔质量为600g/mol～2500g/mol的聚醚多元醇。
作为替换，所述热塑性聚酯弹性体基于摩尔质量为600g/mol～2500g/mol的聚酯多元醇，或是600g/mol～2500g/mol的聚醚多元醇与600g/mol～2500g/mol的聚酯多元醇混合。
在本发明的一些实施例中，所述热塑性聚酯弹性体发泡用前体为表面圆滑的颗粒状结构，其颗粒直径为0.2～8.0mm，进一步优选颗粒直径为2～5mm。
所述热塑性聚酯弹性体发泡用前体采用表面圆滑的颗粒状结构的目的在于：发明人通过多次实验发现，在进行热塑性聚酯弹性体发泡用前体发泡的时候，带有棱角的颗粒容易造成发泡剂的渗透不均，从而导致泡孔直径和泡孔密度的不均匀，在发泡时容易在棱角位置发生泡孔破裂漏气，影响颗粒的膨胀率和产品外观。同时还发现了，采用热塑性聚酯弹性体进行发泡时，表面圆滑的颗粒状结构有利于发泡剂的渗入，表面圆滑的颗粒状结构可以是椭球状、水滴状或是球形等结构，当颗粒直径太大时，会影响发泡剂的充分渗入，影响膨胀 率。
在本发明的一些实施例中，所述热塑性聚酯弹性体发泡用前体的熔体流动速率为8～200g/10min。
熔体流动速率(MI)测试条件：ISO 1133 230℃/2.16kg，指在230℃恒温，负荷2.16kg条件下测定熔体流动速率，其单位为g/10min，计时10分钟内流出来的高聚物的重量克数。
ISO 1133：“塑料—热塑性塑料熔体质量流动速率(MFR)和熔体体积流动速率(MVR)的测定”标准方法。
在本发明的一些实施例中，所述热塑性聚酯弹性体发泡用前体还包括UV稳定剂。
所述UV稳定剂用于提高热塑性聚酯弹性体在紫外线照射下的稳定性。
按重量份计，所述UV稳定剂的重量组分为0.1～0.5份。
在本发明的一些实施例中，所述UV稳定剂为聚丁二酸二甲基4-羟基-2,2,6,6-四甲基-1-氮杂环己烷乙醇酯。
在本发明的一些实施例中，所述热塑性聚酯弹性体发泡用前体的组分还包括辅剂，所述辅剂为阻燃剂、抗静电剂、颜料、抗水解剂、无机填料或有机填料。所述辅剂的添加量根据实际使用要求来决定。优点在于能使热塑性聚酯弹性体改性材料发泡颗粒适用于不同的用途。
如果需要把所述热塑性聚酯弹性体发泡用前体应用于安全鞋类产品或应用于精密仪表的保证，可在组分中添加抗静电剂，以降低产品的表面电阻。添加抗静电剂可以加快接触表面的静电释放速度，避免因静电积累造成仪表损坏或者形成火花的危险。
如果需要把所述热塑性聚酯弹性体发泡用前体应用于需要使用颜色的方面，例如生产鞋底和运动器材，可在组分中添加颜料，所述颜料可以为色粉或色浆。在组分中添加颜料可得到预设色彩的热塑性聚酯弹性体改性材料发泡颗粒，并制成色彩丰富的制品，有助于不同产品的标示及提高产品的美观性。
本发明还公开了一种热塑性聚酯发泡体，包括以下组分：热塑性聚酯弹性体、熔体熔融粘度调节剂、泡孔尺寸稳定剂和挥发性发泡剂。
所述热塑性聚酯发泡体可采用如上所述的热塑性聚酯弹性体发泡用前体加入挥发性发泡剂制备得到。
本发明提供的热塑性聚酯发泡体在高温和低温环境中都有优异的适用性， 发泡的温度范围宽，成品率高，成品有较宽的加工温度范围，可以在非常宽泛的温度范围内使用。机械强度高、耐水、耐油、耐化学性都非常优异，在紫外光下颜色保持性高，颜色丰富，对环境友好，可回收利用等优点。
在本发明的一些实施例中，按重量份计，包括以下组分：热塑性聚酯弹性体100份、熔体熔融粘度调节剂2～10份、泡孔尺寸稳定剂0.2～1.2份、挥发性发泡剂10～200份。
在本发明的一些实施例中，按重量份计，包括以下组分：热塑性聚酯弹性体100份、熔体熔融粘度调节剂2～10份、泡孔尺寸稳定剂2～12份、挥发性发泡剂10～50份。
在本发明的一些实施例中，所述挥发性发泡剂为二氧化碳和氮气中的一种或两种组合，优选采用二氧化碳。优点在于此两种气体容易获得且价格低廉，没有毒性和易燃易爆的危险性，没有环境污染，此两种气体发泡的操作温度也有利于高压反应釜的发泡稳定操作，其中，采用二氧化碳还有利于温室气体的固定，降低温室效应。
在本发明的一些实施例中，所述熔体熔融粘度调节剂包括乙烯-丙烯酸酯-甲基丙烯酸缩水甘油酯和聚苯乙烯-聚乙烯-聚丁烯共聚物的一种或两种组合。
在本发明的一些实施例中，所述泡孔尺寸稳定剂包括二羟基丙基十八烷酸酯、失水山梨醇硬脂酸单酯和失水山梨醇棕榈酸单酯中的一种或多种。
在本发明的一些实施例中，所述热塑性聚酯弹性体基于摩尔质量为600g/mol～2500g/mol的聚醚多元醇和/或摩尔质量为600g/mol～2500g/mol的聚酯多元醇。
在本发明的一些实施例中，所述热塑性聚酯弹性体的硬度范围为邵氏H25D～H45D。
在本发明的一些实施例中，所述热塑性聚酯发泡体还包括UV稳定剂，UV稳定剂的重量组分为：0.1～0.5份。在本发明的一些实施例中，所述热塑性聚酯发泡体的密度为0.08～0.60g/m3，泡孔直径为10～800μm。
本发明还公开了如上所述的一种热塑性聚酯发泡体的制备方法，包括以下步骤：
前体制备：按重量份计，将100份热塑性聚酯弹性体、2～10份熔体熔融粘度调节剂、0.2～1.2份泡孔尺寸稳定剂和0.1～0.5份UV稳定剂加入高混机中混合均匀，通过双螺杆挤出机进行熔融混炼，冷却后通过挤出机拉条或者水下切粒 切成颗粒，得到热塑性聚酯弹性体发泡用前体。
在本发明的一些实施例中，优选采用水下切粒的方式进行颗粒制备，采用水下切粒时，由于水的压力作用，有利于使颗粒形成水滴状，减少颗粒的棱边，从而有利于提高后续发泡效果。
在本发明的一些实施例中，根据热塑性聚酯发泡体的形状需要，还可以通过挤出机将热塑性聚酯弹性体发泡用前体挤出形成不同的形状。
发泡剂渗透：将热塑性聚酯弹性体发泡用前体加入高压反应釜中，加入挥发性发泡剂，升温至热塑性聚酯弹性体发泡用前体的软化点，升温后的反应温度为100～175℃，加压使所述挥发性发泡剂处于超临界状态，保温保压2～3小时。
发泡：发泡剂渗透完成后，降低压力，由于压力降低，发泡剂在热塑性聚酯弹性体发泡用前体中的溶解度减低，从而在热塑性聚酯弹性体发泡用前体中产生膨胀作用，热塑性聚酯弹性体发泡用前体发泡，形成热塑性聚酯发泡体。
作为本发明的一种可选择的实施方式，所述“发泡剂渗透”步骤包括：
将热塑性聚酯弹性体发泡用前体和水加入高压反应釜中，加入挥发性发泡剂，加压形成含水的悬浮混合液，升温至热塑性聚酯弹性体发泡用前体的软化点，加压使所述挥发性发泡剂处于超临界状态，保温保压。
以下通过实施例对本发明进行进一步的说明。
以下实施例中采用的热塑性聚酯弹性体颗粒材料物理指标为：
Figure PCTCN2017098595-appb-000001
以上热塑性聚酯弹性体颗粒材料可以采用购自江阴和创弹性体新材料科技有限公司生产的、台湾长春化工有限公司生产的、韩国SK公司生产的、美国杜邦公司生产的等等。
塑性聚酯弹性体发泡颗粒密度参考指标：0.08-0.60g/cm3。目前市面上广泛使用的EVA树脂产品的密度在0.27g/cm3左右，因此制鞋行业对发泡材料的期望值是小于或等于该密度，密度高于0.3g/cm3到0.6g/cm3的产品，则用于其他承重载荷更高要求的用途，对于高于0.7g/cm3的产品，可以采用成本更低的发泡 方式来制备发泡颗粒，在此不做详细阐述。
泡孔直径均匀程度，直接影响产品的使用性能。泡孔直径过大，易造成冷却或使用过程中塌陷，影响使用功能和外观；泡孔直径过小，则发泡程度低或不发泡，不能有效地降低塑性聚酯弹性体发泡颗粒密度。本发明经试验验证热塑性聚酯弹性体改性材料发泡颗粒泡孔直径在10～800μm区间(优选10-100μm区间)的稳定性优异，表面光泽度高，发泡颗粒弹性好，有良好的工业应用前景。
实施例1
a)将100kg热塑性聚酯弹性体颗粒A，5kg乙烯-丙烯酸酯-甲基丙烯酸缩水甘油酯，8kg失水山梨醇硬脂酸单酯，0.25kg UV稳定剂加入混合机里。混匀后，通过料斗导入双螺杆挤出机中进行熔融混炼，在230℃恒温，负荷8.7kg条件下测试熔体流动速率。将符合熔体流动速率指标的熔融混炼物从挤出机直径为1.5mm的模孔中挤出成长条形状，通过约5米长度冷却水槽中冷却成形，用切粒机进行切割成2.5mm长的颗粒，从而得到热塑性聚酯弹性体发泡用前体。
b)将得到的热塑性聚酯弹性体发泡用前体100kg与纯净水500kg混合加入到高压反应釜中，形成水悬浮混合液。在进行搅拌的同时，加入30kg二氧化碳挥发性发泡剂，将高压反应釜升温至155℃。
c)在充分混合和加热均匀的状态下，将水悬浮混合液在此温度下恒温3小时，最后打开高压釜底端放料阀门，使高压釜内混合液排放到常压环境中，从而得到热塑性聚酯弹性体发泡颗粒。
本实施例所得到的熔体流动速率是130g/10min，热塑性聚酯弹性体发泡颗粒的密度是0.25g/cm3，发泡孔平均直径是270μm。
表1是实施例1以及其它采用与实施例1相同或类似的方法制备热塑性聚酯弹性体改性材料发泡颗粒的实施例中，热塑性聚酯弹性体颗粒、熔体熔融粘度调节剂、发泡孔尺寸稳定剂、UV稳定剂和发泡剂的重量，以及熔体流动速率和高压反应釜温度，制备出的热塑性聚酯弹性体改性材料发泡颗粒的密度和发泡孔平均直径。
由表1可知，实施例1-18制备的热塑性聚酯弹性体改性材料发泡颗粒所需的组成成份:热塑性聚酯弹性体含量为100份，熔体熔融粘度调节剂含量范围 为2～10份，泡孔尺寸稳定剂含量范围为2～10份，UV稳定剂含量范围为0.1～0.5份，挥发性发泡剂含量范围为10～50份。因此熔融混炼后测定的熔体流动速率值均在40-200g/10min范围内。随之高温反应釜温度都控制在110～175℃之间，此温度区间内稳定地调节混合悬浮液，使其均匀发泡，塑性聚酯弹性体改性材料发泡颗粒密度在0.08-0.30g/cm3区间；发泡孔平均直径均在250-800μm内。
实施例19-28由于熔体熔融调节剂份量、高温反应釜温度过低或过高，会导致熔体流动速率过高或过低，因此无法稳定地通过对颗粒和水的混合悬浮液加温到颗粒的适合发泡的软化温度，均无法形成热塑性聚酯弹性体发泡颗粒。
实施例29
a)将100kg热塑性聚酯弹性体颗粒A，5kg乙烯-丙烯酸酯-甲基丙烯酸缩水甘油酯，0.2kg失水山梨醇硬脂酸单酯，0.25kg UV稳定剂加入混合机里。混匀后，通过料斗导入双螺杆挤出机中进行熔融混炼，在230℃恒温，负荷2.16kg条件下测试熔体流动速率。将符合熔体流动速率指标的熔融混炼物从挤出机导入水下切粒机，切割成2.5mm直径的椭球形的颗粒，从而得到热塑性聚酯弹性体发泡用前体。
b)将得到的热塑性聚酯弹性体发泡用前体100kg加入50kg二氧化碳挥发性发泡剂，加入到高压反应釜中，形成悬浮混合液。在进行搅拌的同时，将高压反应釜升温至165℃。
c)在充分混合和加热均匀的状态下，将水悬浮混合液在此温度下恒温3小时，最后打开高压釜底端放料阀门，使高压釜内混合液排放到常压环境中，从而得到热塑性聚酯弹性体发泡颗粒。
本实施例所得到的熔体流动速率是8g/10min，热塑性聚酯弹性体发泡颗粒的密度是0.22g/cm3，发泡孔平均直径是70μm。
表2是实施例29以及其它采用与实施例29相同或类似的方法制备热塑性聚酯弹性体改性材料发泡颗粒的实施例中，热塑性聚酯弹性体颗粒、熔体熔融粘度调节剂、发泡孔尺寸稳定剂、UV稳定剂和发泡剂的重量，以及熔体流动速率和高压反应釜温度，制备出的热塑性聚酯弹性体改性材料发泡颗粒的密度和发泡孔平均直径。
由表2可知，实施例29-36制备的热塑性聚酯弹性体改性材料发泡颗粒所需的组成成份:热塑性聚酯弹性体含量为100份，熔体熔融粘度调节剂含量范围 为2～10份，泡孔尺寸稳定剂含量范围为0.2～1.2份，UV稳定剂含量范围为0.1～0.5份，挥发性发泡剂含量范围为10～200份。因此熔融混炼后测定的熔体流动速率值均在8-40g/10min范围内。随之高温反应釜温度都控制在110～175℃之间，此温度区间内稳定地调节混合悬浮液，使其均匀发泡，塑性聚酯弹性体改性材料发泡颗粒密度在0.08-0.60g/cm3区间；发泡孔平均直径均在10-800μm内。
因此本发明要求主体材料热塑性聚酯弹性体的硬度在邵氏H28D～H45D之间,改性后热塑性聚酯弹性体材料本身熔点不高于175℃，并且使用熔融熔体调节剂调整熔体流动速率到目标范围，从而稳定有效的发泡，保证了发泡颗粒的尺寸稳定性，并优化了该材料的弹性及压缩性能和后加工温度范围区间，同时明显扩大了温度适用范围。
以上所述仅为本发明的较佳实施例而已，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、等同替换和改进等，均应包含在本发明的保护范围之内。
Figure PCTCN2017098595-appb-000002
Figure PCTCN2017098595-appb-000003
Figure PCTCN2017098595-appb-000004

Claims (23)

  1. 一种热塑性聚酯弹性体发泡用前体，其特征在于，包括以下组分：热塑性聚酯弹性体、熔体熔融粘度调节剂和泡孔尺寸稳定剂。
  2. 根据权利要求1所述的热塑性聚酯弹性体发泡用前体，其特征在于，所述熔体熔融粘度调节剂包括乙烯-丙烯酸酯-甲基丙烯酸缩水甘油酯和聚苯乙烯-聚乙烯-聚丁烯共聚物的一种或两种组合。
  3. 根据权利要求1所述的热塑性聚酯弹性体发泡用前体，其特征在于，所述泡孔尺寸稳定剂包括二羟基丙基十八烷酸酯、失水山梨醇硬脂酸单酯和失水山梨醇棕榈酸单酯中的一种或多种。
  4. 根据权利要求1所述的热塑性聚酯弹性体发泡用前体，其特征在于，按重量份计，包括以下组分：热塑性聚酯弹性体100份、熔体熔融粘度调节剂2～10份、泡孔尺寸稳定剂0.2～1.2份。
  5. 根据权利要求1所述的热塑性聚酯弹性体发泡用前体，其特征在于，按重量份计，包括以下组分：热塑性聚酯弹性体100份、熔体熔融粘度调节剂2～10份、泡孔尺寸稳定剂2～12份。
  6. 根据权利要求1所述的热塑性聚酯弹性体发泡用前体，其特征在于，所述热塑性聚酯弹性体的硬度范围为邵氏H25D～H45D。
  7. 根据权利要求1所述的热塑性聚酯弹性体发泡用前体，其特征在于，所述热塑性聚酯弹性体发泡用前体为表面圆滑的颗粒状结构，其颗粒直径为0.2～8.0mm。
  8. 根据权利要求1所述的热塑性聚酯弹性体发泡用前体，其特征在于，所述热塑性聚酯弹性体发泡用前体的熔体流动速率为8～200g/10min。
  9. 根据权利要求4所述的热塑性聚酯弹性体发泡用前体，其特征在于，所 述热塑性聚酯弹性体发泡用前体还包括UV稳定剂，UV稳定剂的重量组分为：0.1～0.5份。
  10. 一种热塑性聚酯发泡体，其特征在于，包括以下组分：热塑性聚酯弹性体、熔体熔融粘度调节剂、泡孔尺寸稳定剂和挥发性发泡剂。
  11. 根据权利要求10所述的热塑性聚酯发泡体，其特征在于，按重量份计，包括以下组分：热塑性聚酯弹性体100份、熔体熔融粘度调节剂2～10份、泡孔尺寸稳定剂0.2～1.2份、挥发性发泡剂10～200份。
  12. 根据权利要求10所述的热塑性聚酯发泡体，其特征在于，按重量份计，包括以下组分：热塑性聚酯弹性体100份、熔体熔融粘度调节剂2～10份、泡孔尺寸稳定剂2～12份、挥发性发泡剂10～50份。
  13. 根据权利要求10所述的热塑性聚酯发泡体，其特征在于，所述挥发性发泡剂为二氧化碳和氮气中的一种或两种组合。
  14. 根据权利要求10所述的热塑性聚酯发泡体，其特征在于，所述熔体熔融粘度调节剂包括乙烯-丙烯酸酯-甲基丙烯酸缩水甘油酯和聚苯乙烯-聚乙烯-聚丁烯共聚物的一种或两种组合。
  15. 根据权利要求10所述的热塑性聚酯发泡体，其特征在于，所述泡孔尺寸稳定剂包括二羟基丙基十八烷酸酯、失水山梨醇硬脂酸单酯和失水山梨醇棕榈酸单酯中的一种或多种。
  16. 根据权利要求10所述的热塑性聚酯发泡体，其特征在于，所述热塑性聚酯弹性体基于摩尔质量为600g/mol～2500g/mol的聚醚多元醇和/或摩尔质量为600g/mol～2500g/mol的聚酯多元醇。
  17. 根据权利要求10所述的热塑性聚酯发泡体，其特征在于，所述热塑性聚酯弹性体的硬度范围为邵氏H25D～H45D。
  18. 根据权利要求11所述的热塑性聚酯发泡体，其特征在于，所述热塑性聚酯发泡体还包括UV稳定剂，UV稳定剂的重量组分为：0.1～0.5份。
  19. 根据权利要求10所述的热塑性聚酯发泡体，其特征在于，所述热塑性聚酯发泡体的密度为0.08～0.60g/m3，泡孔直径为10～800μm。
  20. 如权利要求10～19中任意一项所述的一种热塑性聚酯发泡体的制备方法，其特征在于，包括以下步骤：
    前体制备：将热塑性聚酯弹性体、熔体熔融粘度调节剂和泡孔稳定剂混合均匀，熔融冷却后制成热塑性聚酯弹性体发泡用前体；
    发泡剂渗透：将热塑性聚酯弹性体发泡用前体加入高压反应釜中，加入挥发性发泡剂，升温至热塑性聚酯弹性体发泡用前体的软化点，加压使所述挥发性发泡剂处于超临界状态，保温保压；
    发泡：发泡剂渗透完成后，降低压力，热塑性聚酯弹性体发泡用前体发泡，形成热塑性聚酯发泡体。
  21. 根据权利要求20所述的热塑性聚酯发泡体的制备方法，其特征在于，所述“前体制备”步骤包括：
    按重量份计，将100份热塑性聚酯弹性体、2～10份熔体熔融粘度调节剂、0.2～1.2份泡孔尺寸稳定剂和0.1～0.5份UV稳定剂加入高混机中混合均匀，通过双螺杆挤出机进行熔融混炼，冷却后通过挤出机拉条或者水下切粒切成颗粒，得到热塑性聚酯弹性体发泡用前体。
  22. 根据权利要求20所述的热塑性聚酯发泡体的制备方法，其特征在于，所述“发泡剂渗透”步骤中，升温后的反应温度为100～175℃，保温保压的时间为2～3小时。
  23. 根据权利要求20所述的热塑性聚酯发泡体的制备方法，其特征在于，所述“发泡剂渗透”步骤包括：
    将热塑性聚酯弹性体发泡用前体和水加入高压反应釜中，加入挥发性发泡剂，加压形成含水的悬浮混合液，升温至热塑性聚酯弹性体发泡用前体的软化点，加压使所述挥发性发泡剂处于超临界状态，保温保压。
PCT/CN2017/098595 2016-08-24 2017-08-23 一种热塑性聚酯弹性体发泡用前体、发泡体及其制备方法 WO2018036504A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201610715351.XA CN106189103A (zh) 2016-08-24 2016-08-24 一种热塑性聚酯弹性体发泡颗粒及制备方法
CN201610715351.X 2016-08-24

Publications (1)

Publication Number Publication Date
WO2018036504A1 true WO2018036504A1 (zh) 2018-03-01

Family

ID=57524806

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/098595 WO2018036504A1 (zh) 2016-08-24 2017-08-23 一种热塑性聚酯弹性体发泡用前体、发泡体及其制备方法

Country Status (2)

Country Link
CN (2) CN106189103A (zh)
WO (1) WO2018036504A1 (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111961247A (zh) * 2020-08-20 2020-11-20 广东康诚新材料科技股份有限公司 一种运动鞋中底及其制备方法
CN113201166A (zh) * 2021-05-31 2021-08-03 江苏中科聚合新材料产业技术研究院有限公司 一种高倍率高刚性发泡非晶聚酯珠粒及其制备方法
CN113845768A (zh) * 2021-09-28 2021-12-28 福建鸿星尔克体育用品有限公司 一种高回复力软弹中底材料及其制备工艺

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106189103A (zh) * 2016-08-24 2016-12-07 深圳市传佳新材料有限公司 一种热塑性聚酯弹性体发泡颗粒及制备方法
CN107641293A (zh) * 2017-06-20 2018-01-30 唐靖 一种热塑性聚酯弹性体发泡用前体、发泡体及其制备方法
CN107828205B (zh) * 2017-11-02 2020-10-02 福建安达福新材料科技有限公司 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
CN108410061A (zh) * 2018-03-12 2018-08-17 常州晟润新材料科技有限公司 一种热塑性聚合物发泡珠粒及其制备方法
CN108688047A (zh) * 2018-05-10 2018-10-23 朱连成 生活用品的制作工艺、生活用品、枕头、抱枕及靠垫
CN108676329B (zh) * 2018-05-11 2021-01-08 唐靖 一种热塑性聚酯弹性体发泡用前体、发泡体及其制备方法
WO2019213945A1 (zh) * 2018-05-11 2019-11-14 Tang Jing 热塑性聚酯弹性体发泡用前体、发泡体及其制备方法
CN110760168B (zh) * 2019-10-11 2021-09-07 美瑞新材料股份有限公司 一种热塑性聚酯弹性体发泡颗粒及其制备方法
CN110894308A (zh) * 2019-11-08 2020-03-20 南雄九盾化工有限公司 一种热塑性聚氨酯弹性体超临界发泡方法
CN110791059B (zh) * 2019-11-12 2022-01-28 常州市顺祥新材料科技股份有限公司 一种热塑性聚酯弹性体发泡颗粒的低压釜式制备方法
CN111393830A (zh) * 2020-05-20 2020-07-10 安踏（中国）有限公司 一种彩色高弹发泡鞋中底材料及其制备方法
CN112646325A (zh) * 2020-12-23 2021-04-13 广东昂斯新材料技术有限公司 一种tpee材质的发泡鞋中底材料及其制备工艺
CN113945055B (zh) * 2021-10-25 2023-03-31 长虹美菱股份有限公司 一种冰箱抽屉及具有其的冰箱

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004202998A (ja) * 2002-12-26 2004-07-22 Du Pont Toray Co Ltd ブロー成形品の製造方法
CN101544812A (zh) * 2009-05-08 2009-09-30 四川省宜宾五粮液集团有限公司 发泡cpet片材及其制备方法
CN101550267A (zh) * 2009-05-19 2009-10-07 河北北田工程塑料有限公司 热塑性聚酯弹性体闭孔微发泡材料及其制备方法、减震用途
CN101608056A (zh) * 2008-06-17 2009-12-23 E.I.内穆尔杜邦公司 热塑性弹性体组合物和制品
CN103642200A (zh) * 2013-12-20 2014-03-19 烟台开发区新龙华包装材料有限公司 一种发泡热塑性聚氨酯珠粒及其制备方法
CN106189103A (zh) * 2016-08-24 2016-12-07 深圳市传佳新材料有限公司 一种热塑性聚酯弹性体发泡颗粒及制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101935405B (zh) * 2010-09-01 2012-07-11 上海俊尔新材料有限公司 一种热塑性聚酯弹性体闭孔微发泡制品的成型方法
CN104072881B (zh) * 2013-03-28 2018-03-06 滁州格美特科技有限公司 一种热塑性微发泡减震材料及其制备方法
CN103804889B (zh) * 2014-02-18 2016-01-27 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
CN104672788A (zh) * 2015-03-09 2015-06-03 上海材料研究所 一种微交联改性聚酯弹性体微发泡材料及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004202998A (ja) * 2002-12-26 2004-07-22 Du Pont Toray Co Ltd ブロー成形品の製造方法
CN101608056A (zh) * 2008-06-17 2009-12-23 E.I.内穆尔杜邦公司 热塑性弹性体组合物和制品
CN101544812A (zh) * 2009-05-08 2009-09-30 四川省宜宾五粮液集团有限公司 发泡cpet片材及其制备方法
CN101550267A (zh) * 2009-05-19 2009-10-07 河北北田工程塑料有限公司 热塑性聚酯弹性体闭孔微发泡材料及其制备方法、减震用途
CN103642200A (zh) * 2013-12-20 2014-03-19 烟台开发区新龙华包装材料有限公司 一种发泡热塑性聚氨酯珠粒及其制备方法
CN106189103A (zh) * 2016-08-24 2016-12-07 深圳市传佳新材料有限公司 一种热塑性聚酯弹性体发泡颗粒及制备方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111961247A (zh) * 2020-08-20 2020-11-20 广东康诚新材料科技股份有限公司 一种运动鞋中底及其制备方法
CN111961247B (zh) * 2020-08-20 2022-11-22 广东康诚新材料科技股份有限公司 一种运动鞋中底及其制备方法
CN113201166A (zh) * 2021-05-31 2021-08-03 江苏中科聚合新材料产业技术研究院有限公司 一种高倍率高刚性发泡非晶聚酯珠粒及其制备方法
CN113845768A (zh) * 2021-09-28 2021-12-28 福建鸿星尔克体育用品有限公司 一种高回复力软弹中底材料及其制备工艺

Also Published As

Publication number Publication date
CN106189103A (zh) 2016-12-07
CN107641294A (zh) 2018-01-30
CN107641294B (zh) 2020-08-28

Similar Documents

Publication Publication Date Title
WO2018036504A1 (zh) 一种热塑性聚酯弹性体发泡用前体、发泡体及其制备方法
WO2018232968A1 (zh) 一种热塑性聚酯弹性体发泡用前体、发泡体及其制备方法
US10035894B2 (en) Coloured TPU foam material, preparation method and use thereof, as well as method for preparing shaped body, sheet and shoe material by using same
CN103642200B (zh) 一种发泡热塑性聚氨酯珠粒及其制备方法
TWI624344B (zh) 膨脹丸粒之製備
CN112980040B (zh) 膨胀聚酰胺粒料及使用其制造模制部件的方法
KR20210151127A (ko) 내황변 열가소성 폴리우레탄 발포재료 및 이의 제조 방법
Tang et al. Autoclave preparation of expanded polypropylene/poly (lactic acid) blend bead foams with a batch foaming process
CN109551701A (zh) 一种半结晶聚合物原位发泡模塑成型方法
BR112017017662B1 (pt) Processo para produção de espumas com base em poliuretanos termoplásticos
CN110003644B (zh) 一种热塑性聚酰胺弹性体物理化学联合发泡材料及其制备方法
CN108676329B (zh) 一种热塑性聚酯弹性体发泡用前体、发泡体及其制备方法
CN104385479A (zh) 一种连续挤出发泡制备tpu发泡珠粒的方法
WO2020228541A1 (zh) 一种发泡热塑性聚硅氧烷-聚氨酯嵌段共聚物及其制备方法和应用
JP4138949B2 (ja) 無架橋ポリエチレン系樹脂発泡粒子及びその成型体
KR102562308B1 (ko) 올레핀계 열가소성 엘라스토머 발포 입자
CN109651695A (zh) 一种易熔结、高耐温性发泡聚乙烯珠粒及其制备方法
CN109679307A (zh) 一种可生物降解的珍珠棉及其制备方法
WO2019213945A1 (zh) 热塑性聚酯弹性体发泡用前体、发泡体及其制备方法
KR101802383B1 (ko) 코어-쉘 구조의 발포체
KR101928926B1 (ko) 내충격성이 우수한 폴리올레핀계 엘라스토머 발포입자
KR101825657B1 (ko) 올레핀계 발포 비드를 성형하여 제조되는 올레핀계 발포 비드 성형물의 제조방법 및 이 방법에 의해 제조된 올레핀계 발포 비드 성형물
KR20180133607A (ko) 내충격성이 우수한 에틸렌 비닐 아세테이트 발포입자
KR101928927B1 (ko) 내충격성이 우수한 올레핀 블럭 공중합체 발포입자
JP7425137B1 (ja) 発泡粒子及び発泡粒子成形体

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17842926

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17842926

Country of ref document: EP

Kind code of ref document: A1