CN108239386A - A kind of extrusion foaming thermoplastic polyurethane elastomer particle and preparation method thereof - Google Patents

A kind of extrusion foaming thermoplastic polyurethane elastomer particle and preparation method thereof Download PDF

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CN108239386A
CN108239386A CN201611218436.3A CN201611218436A CN108239386A CN 108239386 A CN108239386 A CN 108239386A CN 201611218436 A CN201611218436 A CN 201611218436A CN 108239386 A CN108239386 A CN 108239386A
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thermoplastic polyurethane
thermoplastic
polymer
foaming
polyurethane elastomer
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CN108239386B (en
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付小亮
杨永柱
黄岐善
陈玉兵
翟志斌
咸鹤武
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Wanhua Chemical Group Co Ltd
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Wanhua Chemical Group Co Ltd
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/08—Polyurethanes from polyethers
    • 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
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles
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    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
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    • C08J2203/00—Foams characterized by the expanding agent
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/06—Polyurethanes from polyesters
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    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers
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    • 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
    • C08J2423/06—Polyethene
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    • 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
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/14—Copolymers of propene
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    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2477/06—Polyamides derived from polyamines and polycarboxylic acids
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K2201/003—Additives being defined by their diameter
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    • C08L2203/00—Applications
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Abstract

The present invention relates to a kind of extrusion foaming thermoplastic polyurethane elastomer particles and preparation method thereof.Include the component of following mass percent, (A) 65 90% thermoplastic polyurethane elastomer, (B) 2 30% thermoplastic resin polymer, the compatilizer of (C) 0.5 15%, the foaming nucleation agent of (D) 0.1 5%.The TPU expanded particles preparation method includes：Thermoplastic polyurethane elastomer, thermoplastic resin polymer, compatilizer and foaming nucleation agent are uniformly mixed input melting extrusion equipment, blend alloy particle is obtained by granulation；Blend alloy particle is put into foaming extrusion equipment, fusion plastification obtains melt, supercritical carbon dioxide is dissolved in melt, and expanded particle is obtained by underwater cutpellet after mouth mold foams.The thermoplastic polyurethane foam particle size of preparation is stablized, and does not shrink substantially, surface-brightening is full, cell diameter is uniform.

Description

A kind of extrusion foaming thermoplastic polyurethane elastomer particle and preparation method thereof
Technical field
The present invention relates to a kind of extrusion foaming thermoplastic polyurethane elastomer particles and preparation method thereof, belong to expanded material Field.
Background technology
Expanded material has the performances such as density is low, specific strength is high, heat-insulating sound-insulating and buffering, be widely used in packaging, industry, The fields such as agricultural, transportation, military affairs, aerospace and daily civil goods.Common expanded material has polystyrene (PS) foam, polyethylene (PE) foam, polypropylene (PP) foam and polyurethane (PU) is soft and rigid foam etc., prepare hair at present The method of foam material in plastics inner mainly by either physically or chemically filling a large amount of bubble.
Thermoplastic polyurethane (TPU) have good physical mechanical property, low-temperature flexibility, hydrolysis, ageing-resistant performance, The advantages that environmentally friendly, recoverable, is retaining foaming TPU particles by the foaming product that steam compression molding obtains Except the excellent performance of base-material, while there is excellent resiliency energy, low-density, therefore the TPU products that foam are in footwear material field, automobile It is with a wide range of applications in field, packaging field and daily life.
The foam structure that TPU expanded materials are prepared using chemical foaming agent is rougher, and abscess-size is uneven, exists serious And steep and hole defect, the density for the sample that foams is big, and expansion multiplying power is relatively low.
International monopoly WO2000/44821A and WO2004/108811A disclose expended microsphere and prepare TPU expanded materials Method, abscess-size caused by can effectively reducing chemical foaming agent is uneven, and steeps and hole defect, but expansion density is general In 0.4g/cm3More than, while will appear surface indentation defect.
Chinese patent CN101370861, CN103642200, CN103804889 are disclosed with organic solvent or inert gas As physical blowing agent, the method that TPU expanded particle materials are prepared by suspension process.Prepared TPU expanded particle abscesses Small and be evenly distributed, density can be down to 0.1-0.5g/cm3, but this method by TPU particles in temperature is 100-150 DEG C of water Boiling, and TPU resins particularly polyester-type TPU resins are susceptible to hydrolysis, long-time boiling easily leads to it and degradation and xanthochromia, shadow occurs The follow-up use of TPU materials is rung, and organic solvent is not environmentally, while inflammable and explosive.
Chinese patent CN103804890, which is disclosed, uses the alkane of saturation as physical blowing agent, by continuously squeezing out and water The method that lower pelletizing prepares TPU expanded particles.Foaming agent used equally exists environmental issue and safety problem, while melt state Under, the viscosity of TPU and intensity relative reduction cause the foam structure of expanded material to be difficult to control, abscess-size is larger.
The critical-temperature of supercritical carbon dioxide is bordering on room temperature (31.1 DEG C), and critical pressure is not high (7.3MPa), is easy to make It is standby while nontoxic, non-ignitable, chemical inertness, no solvent residue, cheap and easy to get, safe to use, free from environmental pollution while overcritical State makes its solubility and diffusivity in the polymer significantly increase, and is gradually used as a kind of efficient physical blowing agent at present It is widely used.
Chinese patent CN104130439, which is disclosed, a kind of uses supercritical carbon dioxide to pass through two steps for physical blowing agent The method that method decompression foaming prepares TPU expanded particles.This method technological process and equipment are complicated, while TPU base materials need in water Boiling is impregnated, and easily leads to material degradation.
Chinese patent CN103951965 discloses a kind of colour TPU expanded material preparation methods, using overcritical titanium dioxide Carbon is physical blowing agent, a step foaming is carried out, then carry out second time of foaming by hot-air by water-bath or steam, finally by height Pressure air or nitrogen carry out foaming three times and prepare expanded material, and this method technological process and equipment are complicated, and cost is higher.
Chinese patent CN103709726 and CN104385479 disclose one kind using supercritical fluid as physical blowing agent, with Inorganic filler is nucleating agent, the method that TPU expanded particles are prepared by continuous extrusion foaming, but under melt state, and TPU's is viscous Degree and intensity relative reduction, cause the foam structure of expanded material to be difficult to control, and abscess-size is larger, easily shrink.
TPU texture materials are soft, the particle after foaming there are problems that serious contraction (dimensional contraction rate be up to 50% with On), this significant shrinkage not only dramatically increases the density of expanded material, also results in expanded material surface and apparent fold occurs And recess, appearance is shrivelled, seriously affects the follow-up use of expanded material.
Chinese patent CN103642200 and CN103804889 is adjusted by introducing abscess-size stabilizer and melt viscosity Agent adjusts abscess-size and shrinks problem, but effect is still not ideal enough, while TPU particles are 100- in temperature by the patented method Boiling in 150 DEG C of water, and TPU resins particularly polyester-type TPU resins are susceptible to hydrolysis, long-time boiling easily leads to it and drops Solution and xanthochromia.
Therefore prepare it is a kind of environmental protection, stability it is good, shrinking percentage is low, and appearance is full, the foaming TPU particles of excellent combination property With extensive market prospects.
Invention content
The shortcomings that it is an object of the present invention to overcoming existing foaming TPU particles, provides a kind of environmental protection, shrinks low, ruler The extrusion foaming thermoplastic polyurethane elastomer particle that very little stability is good, appearance is full, mechanical performance is excellent.
Another object of the present invention is to provide the preparation method of above-mentioned extrusion foaming thermoplastic polyurethane elastomer particle.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of extrusion foaming thermoplastic polyurethane elastomer particle based on raw material gross mass, includes following mass percent Component：
(A) thermoplastic polyurethane elastomer of 65-90%, preferably 80-85%,
(B) thermoplastic resin polymer of 2-30%, preferably 8-15%,
(C) compatilizer of 0.5-15%, preferably 4-10%,
(D) the foaming nucleation agent of 0.1-5%, preferably 0.2-1%.
The shore hardness of thermoplastic polyurethane elastomer of the present invention is 60A-90A (ASTM D2240), selected from poly- It is one or more in ether-based polyurethane, polyester polyurethane, polycarbonate polyurethane and polylactone polyurethane, it is preferably poly- Ether-based polyurethane and/or polyester polyurethane.
Thermoplastic polyurethane elastomer of the present invention is by least one polyisocyanates, at least one polyalcohol and extremely It is prepared by a kind of few chain extender reaction.
One kind in aromatic polyisocyanate and aliphatic polyisocyante of polyisocyanates of the present invention or It is a variety of；The polyisocyanates includes but not limited to 4,4'- methyl diphenylene diisocyanates (4,4'-MDI), 2,4'- hexichol Dicyclohexylmethane diisocyanate (2,4'-MDI), 2,2'- methyl diphenylene diisocyanates (2,2'-MDI), phenylenedimethylidyne two are different It is cyanate (XDI), 1,5- naphthalene diisocyanates (NDI), paraphenylene diisocyanate (PPDI), toluene di-isocyanate(TDI) (TDI), different Isophorone diisocyanate (IPDI), 1,4- cyclohexyl diisocyanates (CHDI), hexamethylene diisocyanate (HDI), the last of the ten Heavenly stems Alkane -1,10- diisocyanate and dicyclohexyl methyl hydride -4,4'- diisocyanate (H12MDI it is one or more in), preferably 4, 4'- methyl diphenylene diisocyanates.
Polyalcohol of the present invention is selected from polyester polyol, poly-lactone polyol, polycarbonate polyol and polyether polyols It is one or more in alcohol, preferably polyester polyol and/or polyether polyol.
Polyester polyol of the present invention can by dihydric alcohol and dicarboxylic acids, dicarboxylic acids acid anhydrides or dicarboxylic esters into Row esterification or ester exchange reaction are prepared.The number-average molecular weight (Mn) of the polyester polyol is 500-10000, preferably 700-5000, more preferably 750-4000；Acid value is 0-1.0mgKOH/g, preferably 0.1-0.5mgKOH/g.
Polyester polyol of the present invention prepare used in dihydric alcohol be aliphatic and/or aromatic diol, it is excellent It is selected as one or more in the dihydric alcohol with 2 to 12 carbon atoms, more preferable ethylene glycol, 1,2-PD, 1,3- the third two Alcohol, 1,3 butylene glycol, 1,4- butanediols, 1,5- pentanediols, 1,6-HD, 2,2- dimethyl -1,3- propylene glycol, 1,4- hexamethylenes It is one or more in dimethanol, decanediol and dodecanediol, further preferred 1,4-butanediol.
Dicarboxylic acids, dicarboxylic acids acid anhydrides or dicarboxylic esters used in polyester polyol preparation of the present invention are It is one or more in aliphatic and aromatic dicarboxylate or dicarboxylic acids acid anhydrides or dicarboxylic esters；Preferably have 4 to 15 It is one or more in the dicarboxylic acids of a carbon atom, dicarboxylic acids acid anhydrides or dicarboxylic esters, more preferably phthalic acid, benzene Dicarboxylic acid anhydride, repefral, dimethyl terephthalate (DMT), succinic acid, glutaric acid, adipic acid, pimelic acid, pungent two Acid, azelaic acid, decanedioic acid, dodecanedioic acid, M-phthalic acid, terephthalic acid (TPA), cyclohexyl dicarboxylic acid, phthalic anhydride and four It is one or more in hydrogen phthalic anhydride；Further preferably adipic acid, phthalic anhydride and tetrahydrophthalic acid It is one or more in acid anhydride.
In the preparation process of polyester polyol of the present invention, the dihydric alcohol and dicarboxylic acids, dicarboxylic acids acid anhydrides or The molar ratio of dicarboxylic esters is preferably 1.0-3.0, more preferable 1.02-2.0.
Poly-lactone polyol of the present invention is preferably polycaprolactone polyol, is existed by 6-caprolactone monomer and initiator It is prepared under catalyst initiation.The number-average molecular weight (Mn) of the polycaprolactone polyol is preferably 500-3000, more Preferably 1000-2000.
Used initiator in prepared by poly-lactone polyol of the present invention is glycol, diamines, hydramine and polyalcohol In one or more, preferably ethylene glycol, 1,2-PD, 1,3-PD, diethylene glycol, 1,3-BDO, Isosorbide-5-Nitrae-fourth Glycol, 1,5- pentanediols, neopentyl glycol, 1,6-HD, 1,4- cyclohexanediols, trimethylolpropane, pentaerythrite, 3,3 '- It is one or more in two chloro- 4,4 '-diaminodiphenylmethane, diethyl toluene diamine, monoethanolamine and diethanol amine；It is more excellent Be selected as ethylene glycol, 1,4- butanediols, neopentyl glycol, diethylene glycol, trimethylolpropane (TMP) and one kind in pentaerythrite or It is a variety of.
Phosgenation has can be used in polycarbonate polyol of the present invention, carbon dioxide adjusts copolymerization method, cyclic carbonate Ring-opening polymerisation method or ester-interchange method synthesis obtain.
Polycarbonate polyol of the present invention preferably carries out ester exchange reaction synthesis by dihydric alcohol and carbonic ester.
During ester-interchange method polycarbonate synthesis polyalcohol of the present invention, the dihydric alcohol is preferably 1,2- second two It is one or more in alcohol, 1,4- butanediols (BDO), 1,5- pentanediols (PDO) and 1,6-HD (HDO)；More preferably 1, 4- butanediols (BDO) and/or 1,5- pentanediols (PDO).The carbonic ester is preferably dimethyl carbonate and diethyl carbonate；It is more excellent It is selected as dimethyl carbonate.
The number-average molecular weight (Mn) of polycarbonate polyol of the present invention is 500-4000, preferably 1000-3000.
Polyether polyol of the present invention is to be reacted by initiator with the epoxide containing 2 to 6 carbon atoms, is prepared Obtained polyether polyol.
The number-average molecular weight (Mn) of polyether polyol of the present invention is 500 to 10000, preferably 700-4000.
The initiator used in polyether polyol preparation process of the present invention is small molecule polyol, small molecule polyamine With it is one or more in small molecule hydramine；The initiator preferably is selected from water, propylene glycol, glycerine, trimethylolpropane, ethylenediamine It is one or more in pentaerythrite, xylitol, triethylene diamine, sorbierite, ethylene glycol, bisphenol-A and toluenediamine；More preferably It is one or more in water, propylene glycol and glycerine.
The epoxide used in polyether polyol preparation process of the present invention is preferably ethylene oxide, propylene oxide With it is one or more in tetrahydrofuran (THF).
Polyether polyol of the present invention preferably is selected from polyethylene glycol, the propylene oxide that ethylene oxide is prepared with glycol reaction The polypropylene glycol prepared is reacted with propylene glycol or water reacts the polytetramethylene ether diol prepared with tetrahydrofuran (THF) (PTMEG), the reaction product copolyether of THF and ethylene oxide or THF and propylene oxide；Preferred polyether polyol is poly- four Methylene ether glycol (PTMEG).
The molar ratio of polyisocyanates and polyalcohol of the present invention is 0.95-1.10, preferably 0.96-1.02.
Chain extender of the present invention is one or more in the glycol with 2 to 10 carbon atoms, preferably ethylene glycol, Diethylene glycol, propylene glycol, dipropylene glycol, 1,4- butanediols, 1,6-HD, 1,3 butylene glycol, 1,5- pentanediols, 1,4- hexamethylenes One or more, further preferred 1,4-butanediol in glycol, quinhydrones two (ethoxy) ether and neopentyl glycol.
The dosage of chain extender of the present invention is the 3%-25% based on polyisocyanates Yu polyalcohol gross mass, preferably 5%-20%.
The present invention improves the contraction problem and stability of expanded particle by introducing thermoplastic resin polymer, is shunk Smaller, the preferable expanded particle of stability is substantially reduced the stable density of expanded particle.
Thermoplastic resin polymer of the present invention is selected from thermoplastic polyester elastomer, low melting polyester polymer, gathers Butylene terephthalate (PBT), polyamide thermoplastic polymer, polyethylene, polypropylene, one kind in polystyrene or more Kind, preferred thermoplastic polyesters elastomer, polybutylene terephthalate (PBT), polypropylene and one kind or more in polystyrene Kind.
Thermoplastic polyester elastomer of the present invention is preferably derived from phthalic acid or phthalic acid ester, at least one are polynary The reaction of alcohol and at least one chain extender.Wherein the selection of polyalcohol and chain extender is the same as aforementioned preparation thermoplastic polyurethane elastomer Polyalcohol and chain extender.Thermoplastic polyester elastomer preferably fusing point of the present invention is 170-230 DEG C, more preferable 190-220 ℃。
Low melting polyester polymer of the present invention is preferably derived from former with carbon based on terephthalic acid (TPA) and ethylene glycol The small molecule binary acid of subnumber 2~20, the polyethylene terephthalate copolymer of the small molecule dihydric alcohol or combination object reaction of carbon atom number 2~20 Object.The low melting polyester polymer preferably fusing point is 120-240 DEG C, more preferable 185-220 DEG C.
Polyamide thermoplastic polymer of the present invention is the group of fatty polyamide, semiaromatic polyamide composition or both Close object, preferred fat polyamide.Preferably, polyamide thermoplastic polymer of the present invention be selected from PA6, PA510, PA512、PA69、PA610、PA612、PA613、PA615、PA1010、PA1012、PA7、PA8、PA9、PA11、PA12、PA13、 It is one or more in PA1212 and PA1313, preferably PA6, PA69, PA610, PA612, PA1010, PA1012, PA13 and It is one or more in PA1212, it is one or more in further preferred PA6, PA1010 and PA1012.
Preferably, the fusing point of polyamide thermoplastic polymer of the present invention is 180-240 DEG C, preferably 190-220 DEG C.
Preferably, the inherent viscosity of polybutylene terephthalate (PBT) of the present invention is 0.55-1.5dl/g, excellent Select 0.8-1.0dl/g.
Polyethylene of the present invention is in high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene It is one or more, preferred high density polyethylene (HDPE)；It is common that the polypropylene is selected from homopolypropylene, atactic copolymerized polypropene, block It is one or more in poly- polypropylene, preferred atactic copolymerized polypropene；The polystyrene be selected from general purpose polystyrene and/or High impact polystyrene, preferred generic polystyrene.
Compatilizer of the present invention is selected from ethylene-octene copolymer (POE) grafted maleic anhydride polymer, polyethylene (HDPE, LDPE) grafted maleic anhydride polymer, polypropylene (PP) grafted maleic anhydride polymer, ethylene propylene diene rubber (EPDM) Grafted maleic anhydride polymer, hydrogenated styrene-butadiene-styrene block copolymer (SEBS) grafted maleic anhydride polymerization Object, styrene-butadiene-styrene block copolymer (SBS) grafted maleic anhydride polymer and polystyrene (PS) grafting It is one or more in maleic anhydride polymer, optimal ethylene-octene copolymer (POE) grafted maleic anhydride polymer, poly- second It is one or more in alkene (PE) grafted maleic anhydride polymer, ethylene propylene diene rubber (EPDM) grafted maleic anhydride polymer.
Preferably, in compatilizer of the present invention the content of maleic anhydride for 0.5-5wt%, preferably 0.8-1.5wt%, Based on compatilizer quality meter.
Foaming nucleation agent of the present invention is calcium carbonate, talcum powder, silica, zeolite, montmorillonite, carbon black, kaolinite It is one or more in soil, wollastonite, diatomite, mica sheet and titanium dioxide；It is preferred that calcium carbonate, talcum powder, montmorillonite and kaolinite It is one or more in soil；Its average particle diameter size is 10nm-10um, preferably 50nm-5um.
The density of extrusion foaming thermoplastic polyurethane elastomer particle of the present invention is between 0.06-0.4g/cm3, bubble Pore size is between 100-300um.
The preparation method of extrusion foaming thermoplastic polyurethane elastomer particle of the present invention comprises the steps of：(1) Proportionally thermoplastic polyurethane elastomer, thermoplastic resin polymer, compatilizer and foaming nucleation agent are uniformly mixed, passed through Extrusion equipment melting extrusion wire drawing granulation or underwater cutpellet obtain thermoplastic polyurethane blend alloy particle；
(2) the thermoplastic polyurethane blend alloy particle for obtaining step (1) puts into foaming extrusion equipment, and material is squeezing Go out fusion plastification in equipment, obtain thermoplastic polyurethane blend alloy melt, the melting temperature is 140-220 DEG C, preferably 160-200℃；
(3) supercritical carbon dioxide is injected into thermoplastic polyurethane blend alloy melt, it is made to be dissolved in melt, it is overcritical The meter pressure of carbon dioxide is 10-30MPa, preferably 15-25MPa, and the quality of supercritical carbon dioxide is total to for thermoplastic polyurethane The 1-20%, preferably 5-15% of the golden melt quality of mixing；
(4) expanded particle is obtained by underwater cutpellet after mouth mold foams, die temperature is 100-160 DEG C, preferably 120-140 ℃；Mouth mold meter pressure is 10-30MPa, preferably 15-25MPa；Underwater cutpellet temperature is 5-80 DEG C, preferably 30-60 DEG C；
(5) by expanded particle, drying obtains product at 50-65 DEG C.
Compared with prior art, beneficial effects of the present invention are as follows：
1) using supercritical carbon dioxide as foaming agent, production process environmental protection, preparation process is simple, is easy to industrial metaplasia Production.
2) introducing of thermoplastic resin polymer improves the ability that expanded material resists deformation, makes the contraction of expanded particle Problem is obviously improved, and shrinking percentage is low, dimensionally stable, and particle surface light is full, corrugationless.
3) compatilizer improves the compatibility of alloy material, and abscess defect is less, cell morphology even compact, expanded material Mechanical strength and elasticity it is higher.
4) introducing of foaming nucleation agent improves expanded particle cell morphology regularity, and abscess quantity increases, uniform foam cell It is fine and close.
Description of the drawings
Fig. 1 is 7 expanded particle section light microscope collection of illustrative plates of embodiment.
Specific embodiment
The present invention is described further with reference to embodiments, and following example is intended only as saying to the present invention It is bright, it is not used in and limits the scope of the invention.
Exemplary composition described below is being prepared, is using following material：
Thermoplastic polyurethane elastomer：The trade mark：WHT-1560IC, thermoplastic polyester type polyurethane, hardness 60A, factory Family：Wanhua Chemical Group Co., Ltd..
Thermoplastic polyurethane elastomer：The trade mark：WHT-8185RV, thermoplastic polyether urethane, hardness 85A, factory Family：Wanhua Chemical Group Co., Ltd..
Thermoplastic polyurethane elastomer：The trade mark：WHT-8190RV, thermoplastic polyether urethane, hardness 90A, factory Family：Wanhua Chemical Group Co., Ltd..
Polybutylene terephthalate：The trade mark：1200-211L, inherent viscosity 0.8dl/g, manufacturer：Taiwan Changchun Enterprise group.
Polybutylene terephthalate：The trade mark：1100-211MD, inherent viscosity 1.0dl/g, manufacturer：Taiwan is long Spring enterprise group.
Thermoplastic polyester elastomer (TPEE)：The trade mark：7246, about 220 DEG C of fusing point, manufacturer：It shuts out in the U.S. Nation.
Thermoplastic polyester elastomer (TPEE)：The trade mark：4069, about 190 DEG C of fusing point, manufacturer：It shuts out in the U.S. Nation.
Nylon 6 (PA6)：The trade mark：B30S, fusing point：220 DEG C, manufacturer：Germany is bright to contain chemistry.
Nylon 1012 (PA1012)：Fusing point：190 DEG C, manufacturer：Dupont.
High density polyethylene (HDPE)：The trade mark：8010, manufacturer：Formosa Plastics.
Atactic copolymerized polypropene：The trade mark：SEP750, manufacturer：Carefree chemistry.
General purpose polystyrene：The trade mark：1441, manufacturer：Total France.
Compatilizer：EPDM-G-MAH, the trade mark：DM-7, maleic anhydride grafting ratio about 0.8wt%, manufacturer：DOW of America Chemistry.
Compatilizer：POE-G-MAH, the trade mark：8842, maleic anhydride grafting ratio about 1.2wt%, manufacturer：DOW of America Chemistry.
Compatilizer：HDPE-G-MAH, the trade mark：1040, maleic anhydride grafting ratio about 1.5wt%, manufacturer：The U.S. angstrom gram Gloomy Mobil.
Foaming nucleation agent (nano-calcium carbonate), the trade mark：NPCC-201, grain size：D50≤10nm, manufacturer：Warner Nano material Co., Ltd.D50 represents that cumulative particle sizes percentile reaches grain size corresponding when 50%, is commonly used to represent powder The average grain diameter of body.
Foaming nucleation agent (nano-calcium carbonate), the trade mark：NPCC-501, grain size：D50≤50nm, manufacturer：Warner Nano material Co., Ltd.
Foaming nucleation agent (talcum powder), the trade mark：SG-95, grain size：D50≤2um, manufacturer：Japanese talcum strain formula Commercial firm.
Foaming nucleation agent (kaolin), the trade mark：70C, grain size：D50≤5.0um, manufacturer：U.S. KaMin LLC companies.
Foaming nucleation agent (montmorillonite), the trade mark：1.44P grain size：D50≤10um, manufacturer：NANOCOR is public Department.
The expanded particle of acquisition investigates abscess according to ASTM D792 test densitys by light microscope or scanning electron microscope Cross-section morphology determines abscess-size；Expanded particle is prepared by the foaming sample with certain size by steam compression molding, According to the mechanical strength of 1798 test samples of ISO, according to the resilience performance of 8307 test samples of ISO, surveyed according to ISO 1856 It has a try the Compression Set of sample.
Embodiment 1
(1) according to mass percent, by 90% thermoplastic polyether urethane (8190RV), 9.4% it is poly- to benzene two Formic acid fourth diester (1200-211L), the talcum powder of 0.5% compatilizer EPDM-G-MAH and 0.1% are uniformly mixed.It will mixing Good composition existsMelt blending, 175-235 DEG C of blending temperature are carried out in co-rotating twin screw extruder.Through water Thermoplastic polyurethane blend alloy particle is obtained after lower pelletizing, drying；
(2) the thermoplastic polyurethane blend alloy particle of acquisition is put into foaming extrusion equipment, material is in extrusion equipment Middle fusion plastification, obtains thermoplastic polyurethane blend alloy melt, and the melting temperature is 160-200 DEG C；
(3) supercritical carbon dioxide is injected into blend alloy melt, the pressure of supercritical carbon dioxide is 10MPa, dosage 5% for blend alloy melt quality；
(4) expanded particle is obtained by underwater cutpellet after mouth mold foams, underwater cutpellet temperature is 80 DEG C；Die temperature is 160 DEG C, mouth mold pressure is 10MPa.
(5) by expanded particle, drying obtains product at 50-65 DEG C.
Embodiment 2
(1) according to mass percent, by 82.8% thermoplastic polyether urethane (8190RV), 15% it is poly- to benzene two Formic acid fourth diester (1100-211MD), nano-calcium carbonate (NPCC-201, the D50 of 2% compatilizer POE-G-MAH and 0.2% =10nm) it is uniformly mixed.The composition mixed is existedMelt blending is carried out in co-rotating twin screw extruder, 175-235 DEG C of blending temperature.Thermoplastic polyurethane blend alloy particle is obtained after underwater cutpellet, drying；
(2) the thermoplastic polyurethane blend alloy particle of acquisition is put into foaming extrusion equipment, material is in extrusion equipment Middle fusion plastification, obtains thermoplastic polyurethane blend alloy melt, and the melting temperature is 170-220 DEG C；
(3) supercritical carbon dioxide is injected into blend alloy melt, the pressure of supercritical carbon dioxide is 15MPa, dosage 10% for blend alloy melt quality；
(4) expanded particle is obtained by underwater cutpellet after mouth mold foams, underwater cutpellet temperature is 60 DEG C；Die temperature is 140 DEG C, mouth mold pressure is 15MPa.
(5) by expanded particle, drying obtains product at 50-65 DEG C.
Embodiment 3
(1) according to mass percent, by 87.5% thermoplastic polyether urethane (8185RV), 2% thermoplastic poly Ester elastomer (7246), the talcum powder of 10% compatilizer HDPE-G-MAH and 0.5% is uniformly mixed.It will mixing Good composition existsMelt blending, 175-230 DEG C of blending temperature are carried out in co-rotating twin screw extruder.Through water Thermoplastic polyurethane blend alloy particle is obtained after lower pelletizing, drying；
(2) the thermoplastic polyurethane blend alloy particle of acquisition is put into foaming extrusion equipment, material is in extrusion equipment Middle fusion plastification, obtains thermoplastic polyurethane blend alloy melt, and the melting temperature is 160-200 DEG C；
(3) supercritical carbon dioxide is injected into blend alloy melt, the pressure of supercritical carbon dioxide is 25MPa, dosage 15% for blend alloy melt quality；
(4) expanded particle is obtained by underwater cutpellet after mouth mold foams, underwater cutpellet temperature is 30 DEG C；Die temperature is 120 DEG C, mouth mold pressure is 25MPa.
(5) by expanded particle, drying obtains product at 50-65 DEG C.
Embodiment 4
(1) according to mass percent, by 65% thermoplastic polyether urethane (8185RV), 30% thermoplastic polyester Elastomer (4069), the kaolin of 4.5% compatilizer POE-G-MAH and 0.5% is uniformly mixed.It will mix Composition existMelt blending, 175-210 DEG C of blending temperature are carried out in co-rotating twin screw extruder.Through underwater Thermoplastic polyurethane blend alloy particle is obtained after pelletizing, drying；
(2) the thermoplastic polyurethane blend alloy particle of acquisition is put into foaming extrusion equipment, material is in extrusion equipment Middle fusion plastification, obtains thermoplastic polyurethane blend alloy melt, and the melting temperature is 150-190 DEG C；
(3) supercritical carbon dioxide is injected into blend alloy melt, the pressure of supercritical carbon dioxide is 30MPa, dosage 20% for blend alloy melt quality；
(4) expanded particle is obtained by underwater cutpellet after mouth mold foams, underwater cutpellet temperature is 5 DEG C；Die temperature is 100 DEG C, mouth mold pressure is 30MPa.
(5) by expanded particle, drying obtains product at 50-65 DEG C.
Embodiment 5
(1) according to mass percent, by 80% thermoplastic polyester type polyurethane (1560IC), 4.5% nylon 6 (B30S), nano-calcium carbonate (NPCC-501, the D50=50nm) mixing of 15% compatilizer HDPE-G-MAH and 0.5% is equal It is even.The composition mixed is existedMelt blending, blending temperature 175- are carried out in co-rotating twin screw extruder 230℃.Thermoplastic polyurethane blend alloy particle is obtained after underwater cutpellet, drying；
(2) the thermoplastic polyurethane blend alloy particle of acquisition is put into foaming extrusion equipment, material is in extrusion equipment Middle fusion plastification, obtains thermoplastic polyurethane blend alloy melt, and the melting temperature is 140-180 DEG C；
(3) by supercritical carbon dioxide injection of polymer melt, the pressure of supercritical carbon dioxide is 20MPa, and dosage is The 10% of blend alloy melt quality；
(4) expanded particle is obtained by underwater cutpellet after mouth mold foams, underwater cutpellet temperature is 50 DEG C；Die temperature is 100 DEG C, mouth mold pressure is 20MPa.
(5) by expanded particle, drying obtains product at 50-65 DEG C.
Embodiment 6
(1) according to mass percent, by 87% thermoplastic polyester type polyurethane (1560IC), 8% Nylon 1012 (PA1012), the talcum powder of 4% compatilizer EPDM-G-MAH and 1% is uniformly mixed.The composition mixed is existedMelt blending, 175-210 DEG C of blending temperature are carried out in co-rotating twin screw extruder.Through underwater cutpellet, drying Thermoplastic polyurethane blend alloy particle is obtained afterwards；
(2) the thermoplastic polyurethane blend alloy particle of acquisition is put into foaming extrusion equipment, material is in extrusion equipment Middle fusion plastification, obtains thermoplastic polyurethane blend alloy melt, and the melting temperature is 140-180 DEG C；
(3) by supercritical carbon dioxide injection of polymer melt, the pressure of supercritical carbon dioxide is 20MPa, and dosage is The 8% of blend alloy melt quality；
(4) expanded particle is obtained by underwater cutpellet after mouth mold foams, underwater cutpellet temperature is 25 DEG C；Die temperature is 100 DEG C, mouth mold pressure is 20MPa.
(5) by expanded particle, drying obtains product at 50-65 DEG C.
Embodiment 7
(1) according to mass percent, by 85% thermoplastic polyether urethane (8185RV), 10% high-density polyethylene Alkene (8010), nano-calcium carbonate (NPCC-201, the D50=10nm) mixing of 4% compatilizer HDPE-G-MAH and 1% are equal It is even.The composition mixed is existedMelt blending, blending temperature 170- are carried out in co-rotating twin screw extruder 200℃.Thermoplastic polyurethane blend alloy particle is obtained after underwater cutpellet, drying；
(2) the thermoplastic polyurethane blend alloy particle of acquisition is put into foaming extrusion equipment, material is in extrusion equipment Middle fusion plastification, obtains thermoplastic polyurethane blend alloy melt, and the melting temperature is 160-190 DEG C；
(3) supercritical carbon dioxide is injected into blend alloy melt, the pressure of supercritical carbon dioxide is 20MPa, dosage 18% for blend alloy melt quality；
(4) expanded particle is obtained by underwater cutpellet after mouth mold foams, underwater cutpellet temperature is 45 DEG C；Die temperature is 100 DEG C, mouth mold pressure is 20MPa.
(5) by expanded particle, drying obtains product at 50-65 DEG C.
Embodiment 8
(1) according to mass percent, by 80% thermoplastic polyether urethane (8185RV), 10.5% random copolymerization Polypropylene (SEP750), the montmorillonite of 4.5% compatilizer POE-G-MAH and 5% are uniformly mixed.The composition that will be mixed Melt blending, 175-200 DEG C of blending temperature are carried out in co-rotating twin screw extruder.Through underwater cutpellet, do Thermoplastic polyurethane blend alloy particle is obtained after dry；
(2) the thermoplastic polyurethane blend alloy particle of acquisition is put into foaming extrusion equipment, material is in extrusion equipment Middle fusion plastification, obtains thermoplastic polyurethane blend alloy melt, and the melting temperature is 160-190 DEG C；
(3) supercritical carbon dioxide is injected into blend alloy melt, the pressure of supercritical carbon dioxide is 20MPa, dosage 1% for blend alloy melt quality；
(4) expanded particle is obtained by underwater cutpellet after mouth mold foams, underwater cutpellet temperature is 40 DEG C；Die temperature is 120 DEG C, mouth mold pressure is 20MPa.
(5) by expanded particle, drying obtains product at 50-65 DEG C.
Embodiment 9
(1) according to mass percent, by 84.5% thermoplastic polyester type polyurethane (1560IC), 5% general polyphenyl Ethylene (1441), the nano-calcium carbonate (NPCC-201, D50=10nm) of 10% compatilizer EPDM-G-MAH and 0.5% are mixed It closes uniform.The composition mixed is existedMelt blending, blending temperature are carried out in co-rotating twin screw extruder 175-220℃.Thermoplastic polyurethane blend alloy particle is obtained after underwater cutpellet, drying；
(2) the thermoplastic polyurethane blend alloy particle of acquisition is put into foaming extrusion equipment, material is in extrusion equipment Middle fusion plastification, obtains thermoplastic polyurethane blend alloy melt, and the melting temperature is 140-180 DEG C；
(3) supercritical carbon dioxide is injected into blend alloy melt, the pressure of supercritical carbon dioxide is 20MPa, dosage 12% for blend alloy melt quality；
(4) expanded particle is obtained by underwater cutpellet after mouth mold foams, underwater cutpellet temperature is 30 DEG C；Die temperature is 100 DEG C, mouth mold pressure is 20MPa.
(5) by expanded particle, drying obtains product at 50-65 DEG C.
Comparative example 1
(1) thermoplastic polyether urethane 8185RV particles are put into foaming extrusion equipment, material is in extrusion equipment Fusion plastification, the melting temperature are 160-190 DEG C；
(2) supercritical carbon dioxide is injected into 8185RV melts, the pressure of supercritical carbon dioxide is 20MPa, and dosage is The 18% of 8185RV melt qualities；
(3) expanded particle is obtained by underwater cutpellet after mouth mold foams, underwater cutpellet temperature is 45 DEG C；Die temperature is 100 DEG C, mouth mold pressure is 20MPa.
(4) by expanded particle, drying obtains product at 50-65 DEG C.
Comparative example 2
(1) according to mass percent, by 99% thermoplastic polyether urethane 8185RV particles and 1% nano-sized carbon Sour calcium (NPCC-201, D50=10nm) puts into foaming extrusion equipment, material fusion plastification in extrusion equipment, the melting Temperature is 160-190 DEG C；
(2) supercritical carbon dioxide is injected into blend alloy melt, the pressure of supercritical carbon dioxide is 20MPa, dosage 18% for blend alloy melt quality；
(3) expanded particle is obtained by underwater cutpellet after mouth mold foams, underwater cutpellet temperature is 45 DEG C；Die temperature is 100 DEG C, mouth mold pressure is 20MPa.
(4) by expanded particle, drying obtains product at 50-65 DEG C.
Comparative example 3
(1) according to mass percent, by 85% thermoplastic polyether urethane (8185RV), 14% EVA resin (V6110M, Yangtze petrochemical industry BASF Co., Ltd) and the mixing of 1% nano-calcium carbonate (NPCC-201, D50=10nm) are equal It is even.The composition mixed is existedMelt blending, blending temperature 175- are carried out in co-rotating twin screw extruder 200℃.Thermoplastic polyurethane blend alloy particle is obtained after underwater cutpellet, drying；
(2) the thermoplastic polyurethane blend alloy particle of acquisition is put into foaming extrusion equipment, material is in extrusion equipment Middle fusion plastification, obtains thermoplastic polyurethane blend alloy melt, and the melting temperature is 160-190 DEG C；
(3) supercritical carbon dioxide is injected into blend alloy melt, the pressure of supercritical carbon dioxide is 20MPa, dosage 18% for blend alloy melt quality；
(4) expanded particle is obtained by underwater cutpellet after mouth mold foams, underwater cutpellet temperature is 45 DEG C；Die temperature is 100 DEG C, mouth mold pressure is 20MPa.
(5) by expanded particle, drying obtains product at 50-65 DEG C.
The particle to have foamed and sample are subjected to dependence test, specific test result such as table 1：
Table 1
It can be obtained by test result, comparing embodiment 7 and comparative example 1, comparative example 2, under the conditions of same process, thermoplastic resin The introducing of polymer and compatilizer is substantially reduced the stable density of TPU expanded particles, and shrinking percentage reduces, and surface is more smooth, Corrugationless.
Comparing embodiment 7 and comparative example 3, identical B, C, D amounts of components and in the case of, this patent alloy system it is initial close Degree and stable density are significantly lower than the initial density and stable density of the alloy system of existing patent, and drawing due to compatilizer Enter, the mechanical strength of alloy is better than existing patent system.
The appearance of this patent expanded particle is full, and surface is smooth, corrugationless, but the appearance of existing patent formulation system have it is recessed Sunken and fold simultaneously for comparative example 3, contains a large amount of and bubble and hole defect in expanded particle.

Claims (11)

1. a kind of extrusion foaming thermoplastic polyurethane elastomer particle, which is characterized in that based on raw material gross mass, include following matter Measure the component of percentage：
(A) thermoplastic polyurethane elastomer of 65-90%, preferably 80-85%,
(B) thermoplastic resin polymer of 2-30%, preferably 8-15%,
(C) compatilizer of 0.5-15%, preferably 4-10%,
(D) the foaming nucleation agent of 0.1-5%, preferably 0.2-1.0%.
2. extrusion foaming thermoplastic polyurethane elastomer particle according to claim 1, which is characterized in that the thermoplastic Property polyurethane elastomer shore hardness for 60A-90A, gather selected from polyether polyurethane, polyester polyurethane, polycarbonate type It is one or more in urethane and polylactone polyurethane, preferred, polyethers type polyurethane and/or polyester polyurethane.
3. extrusion foaming thermoplastic polyurethane elastomer particle according to claim 1, which is characterized in that the thermoplastic Property resinous polymer be selected from thermoplastic polyester elastomer, low melting polyester polymer, polybutylene terephthalate, thermoplastic poly One or more in amide polymer, polyethylene, polypropylene, polystyrene, preferred thermoplastic polyesters elastomer gathers to benzene two It is one or more in formic acid fourth diester, polypropylene and polystyrene.
4. extrusion foaming thermoplastic polyurethane elastomer particle according to claim 3, which is characterized in that the thermoplastic Property polyester elastomer fusing point be 170-230 DEG C, preferably 190-220 DEG C；The low melting polyester polymer fusing point is 120-240 DEG C, preferably 185-220 DEG C；The fusing point of the polyamide thermoplastic polymer is 180-240 DEG C, preferably 190-220 DEG C； The inherent viscosity of the polybutylene terephthalate is 0.55-1.5dl/g, preferably 0.8-1.0dl/g.
5. extrusion foaming thermoplastic polyurethane elastomer particle according to claim 3, which is characterized in that the poly- second Alkene is one or more in high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene, preferably high-density polyethylene Alkene；The polypropylene is one or more in homopolypropylene, atactic copolymerized polypropene, block copolymerization polypropylene, excellent Select atactic copolymerized polypropene；The polystyrene is selected from general purpose polystyrene and/or high impact polystyrene, and preferred generic is gathered Styrene.
6. extrusion foaming thermoplastic polyurethane elastomer particle according to claim 1, which is characterized in that described is compatible Agent is selected from ethylene-octene copolymer grafted maleic anhydride polymer, Research of Grafting Malaic Anhydride Onto Polyethylene polymer, polypropylene grafted horse It is common to come anhydride polymer, grafting maleic anhydride with ethylene propylene terpolymer polymer, hydrogenated styrene-butadiene-styrene block Polymers grafted maleic anhydride polymer, styrene-butadiene-styrene block copolymer grafted maleic anhydride polymer and poly- It is one or more in styrene-grafted maleic anhydride polymer, optimal ethylene-octene copolymer grafted maleic anhydride polymer, It is one or more in Research of Grafting Malaic Anhydride Onto Polyethylene polymer, grafting maleic anhydride with ethylene propylene terpolymer polymer, it is described The content of maleic anhydride is 0.5-5wt%, preferably 0.8-1.5wt% in compatilizer, based on compatilizer quality meter.
7. the extrusion foaming thermoplastic polyurethane elastomer particle according to any one of claim 1-6, which is characterized in that The foaming nucleation agent is calcium carbonate, talcum powder, silica, zeolite, montmorillonite, carbon black, kaolin, wollastonite, diatom It is one or more in soil, mica sheet and titanium dioxide；It is preferred that one kind or more in calcium carbonate, talcum powder, montmorillonite and kaolin Kind；Its average particle diameter size is 10nm-10um, preferably 50nm-5um.
8. according to claim 1-7 any one of them extrusion foaming thermoplastic polyurethane elastomer particles, density 0.06- 0.4g/cm3, cell diameter 100-300um.
9. a kind of method for preparing claim 1-8 any one of them extrusion foaming thermoplastic polyurethane elastomer particles, It is characterized in that, comprises the steps of：
(1) proportionally thermoplastic polyurethane elastomer, thermoplastic resin polymer, compatilizer and foaming nucleation agent are mixed equal It is even, it is granulated and obtains thermoplastic polyurethane blend alloy particle；
(2) the thermoplastic polyurethane blend alloy particle for obtaining step (1) puts into foaming extrusion equipment, and material is set in extrusion Standby middle fusion plastification, obtains thermoplastic polyurethane blend alloy melt；
(3) supercritical carbon dioxide is injected into thermoplastic polyurethane blend alloy melt, it is made to be dissolved in melt；
(4) expanded particle is obtained by underwater cutpellet after mouth mold foams.
10. according to the method described in claim 9, it is characterized in that, in step (3), the meter pressure of supercritical carbon dioxide is 10-30MPa, preferably 15-25MPa, the 1-20%, excellent of the quality of supercritical carbon dioxide for polyurethane comixing alloy melt quality Select 5-15%.
11. method according to claim 9 or 10, which is characterized in that in step (4) die temperature for 100-160 DEG C, it is excellent 120-140 DEG C is selected, mouth mold meter pressure is 10-30MPa, preferably 15-25MPa, and underwater cutpellet temperature is 5-80 DEG C, preferably 30-60 ℃。
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CN111303617A (en) * 2018-12-12 2020-06-19 万华化学集团股份有限公司 Low-density thermoplastic polyurethane elastomer particles for plastic track and products thereof
CN111303548A (en) * 2020-04-02 2020-06-19 福建安达福新材料科技有限公司 PS/TPU supercritical foaming composite material and preparation method thereof
CN111675896A (en) * 2020-06-30 2020-09-18 四川大学 Method for improving retraction behavior of thermoplastic elastomer microcellular foam material cells
CN111690253A (en) * 2020-07-27 2020-09-22 江苏绿艳高分子材料有限公司 Ethylene propylene diene monomer modified polyurethane elastomer foam material and preparation method thereof
CN113316600A (en) * 2018-12-28 2021-08-27 巴斯夫欧洲公司 High strength ETPU
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CN111303617A (en) * 2018-12-12 2020-06-19 万华化学集团股份有限公司 Low-density thermoplastic polyurethane elastomer particles for plastic track and products thereof
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CN113316600A (en) * 2018-12-28 2021-08-27 巴斯夫欧洲公司 High strength ETPU
CN111253722B (en) * 2019-03-11 2022-10-04 汕头市三马塑胶制品有限公司 Foaming-grade modified polylactic acid and preparation method thereof
CN111253722A (en) * 2019-03-11 2020-06-09 汕头市三马塑胶制品有限公司 Foaming-grade modified polylactic acid and preparation method thereof
CN110003635A (en) * 2019-03-29 2019-07-12 江南大学 A kind of foamed thermoplastic polyurethane elastomer, preparation method and application
CN110256720A (en) * 2019-07-01 2019-09-20 黄山美森新材料科技有限公司 The wear-resisting resistance to cigarette calcination type foamed polystyrene composite material of one kind and preparation method
CN110405978B (en) * 2019-07-19 2021-12-14 南京法宁格节能科技股份有限公司 Continuous production method of modified EPDM/PP physical foaming material
CN110405978A (en) * 2019-07-19 2019-11-05 南京法宁格节能科技股份有限公司 A kind of continuous producing method of modified epdm/PP physical foaming material
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CN110819099A (en) * 2019-11-14 2020-02-21 丰县建鑫泡沫制品有限公司 Heat conduction cystosepiment
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CN111690253A (en) * 2020-07-27 2020-09-22 江苏绿艳高分子材料有限公司 Ethylene propylene diene monomer modified polyurethane elastomer foam material and preparation method thereof
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