CN106497008A - A kind of ultralight PU foaming composite sheet and preparation method thereof - Google Patents
A kind of ultralight PU foaming composite sheet and preparation method thereof Download PDFInfo
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- CN106497008A CN106497008A CN201610905272.5A CN201610905272A CN106497008A CN 106497008 A CN106497008 A CN 106497008A CN 201610905272 A CN201610905272 A CN 201610905272A CN 106497008 A CN106497008 A CN 106497008A
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- Prior art keywords
- polyurethane foam
- composite sheet
- ultralight
- particle
- thermoplastic polyurethane
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- 239000002131 composite material Substances 0.000 title claims abstract description 77
- 238000005187 foaming Methods 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 88
- 239000006260 foam Substances 0.000 claims abstract description 83
- 229920005830 Polyurethane Foam Polymers 0.000 claims abstract description 74
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims abstract description 74
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 74
- 239000004814 polyurethane Substances 0.000 claims abstract description 66
- 239000000463 material Substances 0.000 claims abstract description 58
- 239000011496 polyurethane foam Substances 0.000 claims abstract description 54
- 239000011159 matrix material Substances 0.000 claims abstract description 46
- 238000000748 compression moulding Methods 0.000 claims abstract description 3
- 239000005056 polyisocyanate Substances 0.000 claims description 27
- 229920001228 polyisocyanate Polymers 0.000 claims description 27
- 239000004970 Chain extender Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- 239000003054 catalyst Substances 0.000 claims description 24
- 150000005846 sugar alcohols Polymers 0.000 claims description 19
- 238000000465 moulding Methods 0.000 claims description 18
- 239000004088 foaming agent Substances 0.000 claims description 17
- 239000000654 additive Substances 0.000 claims description 16
- 238000007664 blowing Methods 0.000 claims description 2
- 229920001169 thermoplastic Polymers 0.000 claims 1
- 239000004416 thermosoftening plastic Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 6
- 229920001940 conductive polymer Polymers 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 229920005983 Infinergy® Polymers 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- -1 polymethylene Polymers 0.000 description 7
- 229920002635 polyurethane Polymers 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920000909 polytetrahydrofuran Polymers 0.000 description 6
- 239000004604 Blowing Agent Substances 0.000 description 5
- PTIXVVCRANICNC-UHFFFAOYSA-N butane-1,1-diol;hexanedioic acid Chemical compound CCCC(O)O.OC(=O)CCCCC(O)=O PTIXVVCRANICNC-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- FZWBABZIGXEXES-UHFFFAOYSA-N ethane-1,2-diol;hexanedioic acid Chemical compound OCCO.OC(=O)CCCCC(O)=O FZWBABZIGXEXES-UHFFFAOYSA-N 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- FRXFBIWLAJRBQW-UHFFFAOYSA-N hexanedioic acid;2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCCO.OC(=O)CCCCC(O)=O FRXFBIWLAJRBQW-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 210000003739 neck Anatomy 0.000 description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 229940058015 1,3-butylene glycol Drugs 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 description 2
- GGBJHURWWWLEQH-UHFFFAOYSA-N butylcyclohexane Chemical compound CCCCC1CCCCC1 GGBJHURWWWLEQH-UHFFFAOYSA-N 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- REZQBEBOWJAQKS-UHFFFAOYSA-N triacontyl alcohol Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCO REZQBEBOWJAQKS-UHFFFAOYSA-N 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- USEBIPUIVPERGC-UHFFFAOYSA-N Dibutylone Chemical compound CCC(N(C)C)C(=O)C1=CC=C2OCOC2=C1 USEBIPUIVPERGC-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 206010000269 abscess Diseases 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 210000004177 elastic tissue Anatomy 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
-
- 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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to a kind of ultralight PU foaming composite sheet and preparation method thereof, belongs to conductive polymer composite technical field.The composite sheet is counted by volume including 20 99% thermoplastic polyurethane foam's particles and 1 80% polyurethane foam matrix；Polyurethane foam matrix is coated on thermoplastic polyurethane foam's particle surface and compression molding obtains ultralight PU foaming composite sheet；Or polyurethane foam matrix is laminated to obtain ultralight PU foaming composite sheet with sheet material respectively with thermoplastic polyurethane foam's particle.The density of ultralight PU foaming composite sheet is 0.10 2.50g/cm3, the thickness of the composite sheet is 3mm 5cm.The present invention is obtained by thermoplastic polyurethane foam's particle and polyurethane foam matrix are compound, have the advantages that lightweight, high resilience, good impact resistance, high-wearing feature, high tensile, good chemical stability and resistance to low temperature.
Description
Technical field
The present invention relates to a kind of ultralight PU foaming composite sheet and preparation method thereof, belongs to polymer composite technology neck
Domain.
Background technology
Polyurethane material (PU) is that the one kind being made up of isocyanates and polyol reaction has carbamate segment weight
The polymer of complex structure unit.Polyurethane material excellent performance, of many uses, its a variety of product can be applicable to numerous necks
Domain.Polyurethane product generally can be divided into two big class of foamed product and non foamed product, non foamed product include coating, adhesive,
Elastomer and elastic fiber etc., and foamed product then includes flexible foam, rigid foam, semi-rigid foam and other Special Foams
Plastics (such as microporous foaming elastomer, skinned foam plastics).
PU foams have been widely used as padded coaming, packaging material, heat preserving and insulating material, ornament materials etc., with lightweight,
The characteristics such as resilience and durability are good, density and hardness scalable, impact resistance is good, heat-proof quality is good, while also have
The advantages of good biocompatibility, easy bonding processing, degradable.
Foamed thermoplastic polyurethane elastomer (E-TPU) has been provided simultaneously with the excellent properties of TPU and conventional expanded material.With
Soft PU foams are compared, and this expanded particle has the foam structure of closing, thus with higher resilience.Additionally, E-TPU
Material also has low-density, high-wearing feature, high tensile, good chemical stability and resistance to low temperature, in numerous areas
There is great application potential.At present, E-TPU materials using more moulding process mostly be vapor molding/hot-forming, excellent
Gesture is that operation is simple, without the need for other chemical assistants, clean and effective.And limit to part and be：1) as current E-TPU particles are more
For white, also color is single for resulting product；2) E-TPU particle prices are received, and production cost is higher；3) different material is obtained
E-TPU particles physical property is different, and under the conditions of moulding process is jejune, defect rate is higher, also considerably increases production cost.
Therefore, by expanded particle is combined with PU foam plasticss, E-TPU usage amounts are reduced while being had
Ultralight low-density and the composite of excellent properties, and reduce production cost.
Content of the invention
A kind of high resilience of above-mentioned problem offer, good impact resistance, high-wearing feature, the height of being directed to of the invention is stretched by force
The ultralight PU foaming composite sheet of degree, good chemical stability and resistance to low temperature.
For achieving the above object, the technical solution used in the present invention is as follows：A kind of ultralight PU foaming composite sheet, described multiple
Close sheet material to be counted including 20-99% thermoplastic polyurethane foams particle and 1-80% polyurethane foam matrixes by volume.
Described polyurethane foam matrix is coated on thermoplastic polyurethane foam's particle surface and compression molding obtains ultralight PU
Foaming composite sheet；
Or polyurethane foam matrix and thermoplastic polyurethane foam's particle respectively with sheet material be laminated ultralight PU foaming is multiple
Close sheet material.
The basic recipe of polyurethane foam matrix is close with the composition of thermoplastic polyurethane foam's particle, and then improves each other
Between bonding force and integral foam mechanical performance.Sheet properties with cladding form are more uniform.
Preferably, the composite sheet is counted by volume including 50-99% thermoplastic polyurethane foams particle and 1-
50% polyurethane foam matrix.
The density of the ultralight PU foaming composite sheet of the present invention is 0.10-2.50g/cm3.Composite sheet is close in the present invention
Spend little, the expansion ratio of material is big, and abscess-size is big, can reduce intensity and resilience of material etc., if conversely, density mistake
Greatly, the expansion ratio of material is low, then do not reach the purpose of the present invention.
Preferably, the density of ultralight PU foaming composite sheet is 0.2-1.5g/cm3, the thickness of the composite sheet is
3mm-5cm.According to the difference that Application Design is required, the cross sectional shape of composite sheet can for rectangle, arc and other do not advise
Then shape.
The inside of thermoplastic polyurethane foam's particle has the foam structure of closing, is spherical, oval or cylinder
Shape granule.
Preferably, the particle diameter of thermoplastic polyurethane foam's particle is 2mm-2cm.The too little granule of particle diameter, prepares difficult；
Particle diameter is too big, the contact area increase between two granules, and overall contact area in material reduces, and reduces material on the contrary
The intensity of material.
The density of thermoplastic polyurethane foam's particle is 0.05-0.25g/cm3.Thermoplastic polyurethane foam's particle
Density is excessive, illustrates that expansion ratio is low, and hardness is high, and the pressure and temperature that molding needs can also be improved；Otherwise thermoplastic polyurethane
Expanded particle density is low, and the performance such as the intensity of material, elasticity can then be deteriorated.
Preferably, the density of thermoplastic polyurethane foam's particle is 0.15-0.25g/cm3.
The foaming method of thermoplastic polyurethane foam's particle is：Thermoplastic polyurethane particle based on polyhydric alcohol utilizes
The method of physical blowing makes thermoplastic polyurethane foam's particle.
Preferably, described polyhydric alcohol be PTMEG, one or more in polyester-diol.Further preferably, institute
The PTMEG that states is PTMG, and the molecular weight of PTMG is 500-2500g/mol.Still further preferably,
Described polyester-diol is adipic acid-ethylene glycol system, adipic acid-butanediol system, the one kind or many in adipic acid-diethylene glycol system
Kind, the molecular weight of the polyester-diol is 500-2000g/mol.Still more preferably, described polyester-diol is adipic acid-fourth
Glycol system, the molecular weight of the polyester-diol is 600-1000g/mol.
The material of the polyurethane foam matrix include soft PU foams, hard PU foams, semi-rigid PU foam, from skinning
One or more in PU foams.
Preferably, the material of the polyurethane foam matrix is soft PU foams, semi-rigid PU foam, steeps from skinning PU
One or more in foam.
The density of the polyurethane foam matrix is 0.05-1.5g/cm3.The density of polyurethane foam matrix is excessive, matrix
Hardness can improve, and do not reach the purpose of the present invention, but if polyurethane foam matrix density is too small, just reduce wear-resisting
The performances such as property, intensity.
Preferably, the density of the polyurethane foam matrix is 0.15-0.25g/cm3.
The preparation method of above-mentioned ultralight PU foaming composite sheet is：
Polyisocyanates, polyhydric alcohol, chain extender, catalyst, foaming agent, other additives and thermoplastic polyurethane are sent out
Bubble mix particles are uniform, inject the mixture into cure under pressure molding in mould and obtain ultralight PU foaming composite sheet；
Or first polyisocyanates, polyhydric alcohol, chain extender, catalyst, foaming agent and other additives are mixed, evenly laid out
Form polyurethane foam matrix sheet material in a mold, then send out in polyurethane foam matrix sheet material upper berth last layer thermoplastic polyurethane
Bubble particle, then tile on thermoplastic polyurethane foam's particle polyurethane foam matrix sheet material, is layering successively, and pressurization is solid
Change ultralight PU foaming composite sheet of shaping to obtain.
In polyurethane foam matrix, the mass percent of each composition is respectively：Polyisocyanates 45%-55%, polyhydric alcohol
The addition of 40%-55%, chain extender 2%-8%, catalyst 2%-8%, foaming agent 0.2%-0.8% and other additives
0.5%-2%.
Described mixing can pass through prepolymer method or semi-prepolymer process or one-step method mixing.
Preferably, described polyisocyanates is fat/ring race and aromatic difunctional or multi-functional different
Cyanate and its mixture.Further preferably, described polyisocyanates be diphenyl-methane -4,4 '-diisocyanate, hexichol first
Alkane -2,4 ' -- diisocyanate, polymeric MDI (mixture of monomer MDI and polyphenyl polymethylene polyisocyanates), six methylenes
One or more in group diisocyanate (HDI), isophorone diisocyanate (IPDI), toluene di-isocyanate(TDI) (TDI).
Still further preferably, described polyisocyanates is 4,4 '-diisocyanate I and/or polymeric MDI.Still more preferably, described
Polyisocyanates be 4,4 ' -- diisocyanate and polymeric MDI 1-3 in mass ratio:1 mixture.
Preferably, described polyhydric alcohol be PTMEG, one or more in polyester-diol.Further preferably, institute
The PTMEG that states is PTMG, and the molecular weight of PTMG is 500-2500g/mol.Further preferably, institute
The polyester-diol that states is adipic acid-ethylene glycol system, adipic acid-butanediol system, the one kind or many in adipic acid-diethylene glycol system
Kind, the molecular weight of the polyester-diol is 500-2000g/mol.Still further preferably, described polyester-diol is adipic acid-fourth
Glycol system, the molecular weight of the polyester-diol is 600-1000g/mol.
Preferably, described chain extender is one or more that molecular weight is less than in the dihydroxylic alcohols of 400g/mol.Enter one
Preferably, described chain extender is one or more in the dihydroxylic alcohols of molecular weight 50-300g/mol to step.Still further preferably, institute
The chain extender that states be ethylene glycol, 1,2-PD, 1,3-PD, 1,3 butylene glycol, BDO, 1,6- hexanediol, neighbour/
One kind in a right/dihydroxy butylcyclohexane, diethylene glycol, dipropylene glycol.Still more preferably, described chain extender is Isosorbide-5-Nitrae-fourth
Glycol and/or 1,6- hexanediol.
Preferably, the catalyst is in tertiary amine compounds, triacontanol amine compound and organo-metallic compound
Plant or multiple.Further preferably, described organo-metallic compound is organo-tin compound.Further preferably, described catalysis
Agent is the mixture of organo-tin compound or organo-tin compound and tertiary amine compound.Still further preferably, described catalyst
It is 1.2-2.5 in mass ratio for organo-tin compound and tertiary amine compound:1 mixture.Still more preferably, described tertiary amine
Compound be triethylamine, tri-n-butylamine, dimethyl benzylamine, N-methylmorpholine, one or more in triethanolamine；Described is organic
Tin compound is stannous octoate, dibutyl tin laurate, one or more in dibutyitin maleate.
Preferably, described foaming agent be physical blowing agent, one or more in CBA.Further excellent
Choosing, described CBA are that water and isocyanates react the compound or formic acid of generation gas and isocyanates reaction is generated
The compound of gas.Described physical blowing agent is one or more in low-boiling compound, further, described physics
Foaming agent is the low-boiling compounds such as hydrocarbon, halogenated hydrocarbons, ether, ester, ketone.
Preferably, other described additives include foam stabiliser, releasing agent, cell modifiers, filler, pigment,
Color inhibition agent, hydrolysis inhibitor and true/bacterial inhibitor.
Preferably, described mould is first preheated to 20-90 DEG C.Further preferably, mould is first preheated to 30-80 DEG C.
The forming method of polyurethane foam matrix sheet material can for cast molding, calendering formation, laminated into type, be extruded into
Any one in type.
Preferably, the temperature in cure under pressure molding is 20-90 DEG C, pressure is 0.1-10MPa.Further preferably, plus
Temperature in cured molding is 50-80 DEG C, and pressure is 0.5-5MPa.Can improve under the temperature and pressure of above range compound
The intensity of sheet material, if temperature is too high or pressure is excessive in forming process, the density of composite sheet becomes big, and surface property is bad；If
In forming process, temperature is too low or pressure is too small, the low intensity of the composite sheet that molding is obtained, poor performance.
Compared with expanded material of the prior art, the present invention is by thermoplastic polyurethane foam's particle and polyurethane foam
The compound obtained ultralight PU of matrix foams composite sheet, with lightweight, high resilience, good impact resistance, high-wearing feature,
The advantages of high tensile, good chemical stability and resistance to low temperature, and E-TPU material usages and defect rate is reduced,
Effectively reduce production cost.
Description of the drawings
The sectional view of ultralight PU foaming composite sheet in Fig. 1 embodiment of the present invention 1.
The sectional view of ultralight PU foaming composite sheet in Fig. 2 embodiment of the present invention 2.
In figure, 1, thermoplastic polyurethane foam's particle；2nd, polyurethane foam matrix.
Specific embodiment
The specific embodiment of the present invention is the following is, technical scheme is further described, but the present invention is simultaneously
It is not limited to these embodiments.
Embodiment 1
A kind of ultralight PU foaming composite sheet, composite sheet are counted by volume including 60% thermoplastic polyurethane foam's particle
With 40% polyurethane foam matrix.The thickness of the ultralight PU foaming composite sheet is 2cm, and density is 0.12g/cm3.
The material of the polyurethane foam matrix is from skinning PU foams；The inside of thermoplastic polyurethane foam's particle has
The foam structure of closing；Thermoplastic polyurethane foam's particle is spherical, and its particle diameter is 2mm-2cm；Thermoplastic polyurethane foam's grain
The density of son is 0.15-0.25g/cm3.
The foaming method of thermoplastic polyurethane foam's particle is：Physics is utilized based on polyester-diol thermoplastic polyurethane particle
The method of foaming makes thermoplastic polyurethane foam's particle.Described polyester-diol be adipic acid-butanediol system, the polyester two
The molecular weight of alcohol is 600-1000g/mol.
Embodiment 2
A kind of ultralight PU foaming composite sheet, composite sheet are counted by volume including 80% thermoplastic polyurethane foam's particle
With 20% polyurethane foam matrix.The thickness of the ultralight PU foaming composite sheet is 3cm, and density is 0.25g/cm3.
The material of the polyurethane foam matrix is soft PU foams；The inside of thermoplastic polyurethane foam's particle has envelope
The foam structure for closing；Thermoplastic polyurethane foam's particle is ellipse, and its particle diameter is 2mm-2cm；Thermoplastic polyurethane foam's grain
The density of son is 0.15-0.25g/cm3.
The foaming method of thermoplastic polyurethane foam's particle is：Physics is utilized based on polyester-diol thermoplastic polyurethane particle
The method of foaming makes thermoplastic polyurethane foam's particle.Described described polyester-diol be adipic acid-ethylene glycol system, its point
Son amount is 500-2000g/mol.
Embodiment 3
A kind of ultralight PU foaming composite sheet, composite sheet are counted by volume including 90% thermoplastic polyurethane foam's particle
With 10% polyurethane foam matrix.The thickness of the ultralight PU foaming composite sheet is 4cm, and density is 0.38g/cm3.
The material of the polyurethane foam matrix is hard PU foams；The inside of thermoplastic polyurethane foam's particle has envelope
The foam structure for closing；Thermoplastic polyurethane foam's particle is cylindrical particle, and its particle diameter is 2mm-2cm；Thermoplastic polyurethane is sent out
The density of bubble particle is 0.15-0.25g/cm3.
The foaming method of thermoplastic polyurethane foam's particle is：Physics is utilized based on PTMEG thermoplastic polyurethane particle
The method of foaming makes thermoplastic polyurethane foam's particle.Described PTMEG be PTMG, PTMG
Molecular weight be 500-2500g/mol.
Embodiment 4
A kind of ultralight PU foaming composite sheet, composite sheet are counted by volume including 20% thermoplastic polyurethane foam's particle
With 80% polyurethane foam matrix.The thickness of the ultralight PU foaming composite sheet is 5cm, and density is 0.68g/cm3.
The material of the polyurethane foam matrix is semi-rigid PU foam；The inside of thermoplastic polyurethane foam's particle has
The foam structure of closing；Thermoplastic polyurethane foam's particle is spherical, and its particle diameter is 0.5mm-3cm；Thermoplastic polyurethane foam
The density of particle is 0.05-1.5g/cm3.
The foaming method of thermoplastic polyurethane foam's particle is：Physics is utilized based on the thermoplastic polyurethane particle of polyhydric alcohol
The method of foaming makes thermoplastic polyurethane foam's particle.
The foaming method of thermoplastic polyurethane foam's particle is：Physics is utilized based on polyester-diol thermoplastic polyurethane particle
The method of foaming makes thermoplastic polyurethane foam's particle.Described described polyester-diol is adipic acid-diethylene glycol system, its
Molecular weight is 500-2000g/mol.
Embodiment 5
In the present embodiment, the preparation method of ultralight PU foaming composite sheet as shown in Figure 1 is：By polyisocyanates, polynary
Thermoplastic polyurethane foam's mix particles described in alcohol, chain extender, catalyst, foaming agent, other additives and embodiment 1
Uniformly, inject the mixture in the mould for be preheated to 40 DEG C curing molding under conditions of 60 DEG C, 8MPa and obtain ultralight PU foaming
Composite sheet.
Described polyisocyanates is 4,4 '-diisocyanate and polymeric MDI 1-3 in mass ratio:1 mixture；Described
Polyhydric alcohol for molecular weight 600-1000g/mol adipic acid-butanediol system；Described chain extender is BDO and 1,6-
Hexanediol 1.2-1.6 in mass ratio:1 mixture for being formed；Described catalyst for stannous octoate with triethylamine is in mass ratio
2:1 mixture.
Embodiment 6
In the present embodiment, the preparation method of ultralight PU foaming composite sheet as shown in Figure 1 is：By polyisocyanates, polynary
Thermoplastic polyurethane foam's mix particles described in alcohol, chain extender, catalyst, foaming agent, other additives and embodiment 2
Uniformly, inject the mixture in the mould for be preheated to 30 DEG C curing molding under conditions of 50 DEG C, 6MPa and obtain ultralight PU foaming
Composite sheet.
Described polyisocyanates be diphenyl-methane -4,4 '-diisocyanate；Described polyhydric alcohol is molecular weight 500-
The PTMG of 2500g/mol；Described chain extender is BDO；Described catalyst is di lauric dibutyl
Stannum is 1.5 with N-methylmorpholine in mass ratio:1 mixture.
Embodiment 7
In the present embodiment, the preparation method of ultralight PU foaming composite sheet as shown in Figure 1 is：By polyisocyanates, polynary
Thermoplastic polyurethane foam's mix particles described in alcohol, chain extender, catalyst, foaming agent, other additives and embodiment 3
Uniformly, inject the mixture in the mould for be preheated to 70 DEG C curing molding under conditions of 70 DEG C, 5MPa and obtain ultralight PU foaming
Composite sheet.
Described polyisocyanates be diphenyl-methane -2,4 '-diisocyanate；Described polyhydric alcohol is molecular weight 500-
The adipic acid of 2000g/mol-ethylene glycol system；Described chain extender is 1,6- hexanediol；Described catalyst is tri-n-butylamine.
Embodiment 8
In the present embodiment, the preparation method of ultralight PU foaming composite sheet as shown in Figure 1 is：By polyisocyanates, polynary
Thermoplastic polyurethane foam's mix particles described in alcohol, chain extender, catalyst, foaming agent, other additives and embodiment 4
Uniformly, inject the mixture in the mould for be preheated to 20 DEG C curing molding under conditions of 90 DEG C, 2MPa and obtain ultralight PU foaming
Composite sheet.
Described polyisocyanates is isophorone diisocyanate；Described polyhydric alcohol is molecular weight 500-2000g/
The adipic acid of mol-diethylene glycol system；Described chain extender is 1,3 butylene glycol；Described catalyst is stannous octoate.
Embodiment 9
In the present embodiment, the preparation method of ultralight PU foaming composite sheet as shown in Figure 2 is：First by polyisocyanates, many
The mixing of first alcohol, chain extender, catalyst, foaming agent and other additives, evenly laid out casting in 60 DEG C of mould is pre-heated to
Molding obtains polyurethane foam matrix sheet material, then the heat in polyurethane foam matrix sheet material upper berth last layer as described in example 1 above
Plastic polyurethane expanded particle sheet material, then tile on thermoplastic polyurethane foam's particle sheet material polyurethane foam base sheet
Material, is layering successively, and under conditions of 4 DEG C, 5MPa, solidifying and setting obtains ultralight PU foaming composite sheet.
Described polyisocyanates is 4,4 '-diisocyanate and polymeric MDI 1-3 in mass ratio:1 mixture；Described
Polyhydric alcohol for molecular weight 600-1000g/mol adipic acid-butanediol system；Described chain extender is BDO；Described
Catalyst be dibutyitin maleate and dimethyl benzylamine be 1.2 in mass ratio:1 mixture.
Embodiment 10
In the present embodiment, the preparation method of ultralight PU foaming composite sheet as shown in Figure 2 is：First by polyisocyanates, many
The mixing of first alcohol, chain extender, catalyst, foaming agent and other additives, evenly laid out calendering in 40 DEG C of mould is pre-heated to
Molding obtains polyurethane foam matrix sheet material, then the heat in polyurethane foam matrix sheet material upper berth last layer as described in example 2 above
Plastic polyurethane expanded particle sheet material, then tile on thermoplastic polyurethane foam's particle sheet material polyurethane foam base sheet
Material, is layering successively, and under conditions of 50 DEG C, 6MPa, solidifying and setting obtains ultralight PU foaming composite sheet.
Described polyisocyanates is polymeric MDI；Poly- tetrahydrochysene furan of the described polyhydric alcohol for molecular weight 500-2500g/mol
Mutter ether；Described chain extender is 1,6- hexanediol；Described catalyst is dibutyitin maleate.
Embodiment 11
In the present embodiment, the preparation method of ultralight PU foaming composite sheet as shown in Figure 2 is：First by polyisocyanates, many
The mixing of first alcohol, chain extender, catalyst, foaming agent and other additives, evenly laid out lamination in 90 DEG C of mould is pre-heated to
Molding obtains polyurethane foam matrix sheet material, then the heat in polyurethane foam matrix sheet material upper berth last layer as described in example 3 above
Plastic polyurethane expanded particle sheet material, then tile on thermoplastic polyurethane foam's particle sheet material polyurethane foam base sheet
Material, is layering successively, and under conditions of 3 DEG C, 10MPa, solidifying and setting obtains ultralight PU foaming composite sheet.
Described polyisocyanates is toluene di-isocyanate(TDI)；Described polyhydric alcohol is molecular weight 500-2000g/mol's
Adipic acid-ethylene glycol system；Described chain extender is 1,6- hexanediol；Described catalyst is dibutyl tin laurate.
Embodiment 12
In the present embodiment, the preparation method of ultralight PU foaming composite sheet as shown in Figure 2 is：First by polyisocyanates, many
The mixing of first alcohol, chain extender, catalyst, foaming agent and other additives, evenly laid out extrusion in 20 DEG C of mould is pre-heated to
Molding obtains polyurethane foam matrix sheet material, then the heat in polyurethane foam matrix sheet material upper berth last layer as described in example 4 above
Plastic polyurethane expanded particle sheet material, then tile on thermoplastic polyurethane foam's particle sheet material polyurethane foam base sheet
Material, is layering successively, and under conditions of 90 DEG C, 2MPa, solidifying and setting obtains ultralight PU foaming composite sheet.
Described polyisocyanates is hexamethylene diisocyanate；Described polyhydric alcohol is molecular weight 500-2000g/
The adipic acid of mol-diethylene glycol system；Described chain extender is diethylene glycol；Described catalyst is triacontanol amine compound.
Mixing in above-described embodiment can pass through prepolymer method or semi-prepolymer process or one-step method mixing.Polyurethane foam
In matrix, the mass percent of each composition is respectively：Polyisocyanates 45%-55%, polyhydric alcohol 40%-55%, chain extender 2%-
8%th, the addition 0.5%-2% of catalyst 2%-8%, foaming agent 0.2%-0.8% and other additives.Described foaming agent
For one or more in physical blowing agent, CBA；Further preferably, described CBA is water and Carbimide.
Ester reaction generates the compound or formic acid of gas and isocyanates react the compound for generating gas.Described physical blowing agent is
One or more in low-boiling compound；Further preferably, described physical blowing agent is hydrocarbon, halogenated hydrocarbons, ether, ester, ketone etc.
Low-boiling compound.Preferably, other described additives include foam stabiliser, releasing agent, cell modifiers, filler,
Pigment, color inhibition agent, hydrolysis inhibitor and true/bacterial inhibitor.
Ultralight PU foaming composite sheet obtained in embodiment 5-12 is carried out performance test
Table 1：The performance test of ultralight PU foaming composite sheet obtained in embodiment 5-12
In sum, the present invention is compound obtained ultralight by thermoplastic polyurethane foam's particle and polyurethane foam matrix
PU foams composite sheet, with lightweight, high resilience, good impact resistance, high-wearing feature, high tensile, good
The advantages of chemical stability and resistance to low temperature, and E-TPU material usages and defect rate is reduced, effectively reduce and produce into
This.
Specific embodiment described herein is only to the spiritual explanation for example of the present invention.Technology neck belonging to of the invention
The technical staff in domain can be made various modifications or supplement or substituted using similar mode to described specific embodiment, but simultaneously
Do not deviate by the spirit of the present invention or surmount scope defined in appended claims.
Although having made a detailed description and being cited some specific embodiments to the present invention, skilled to this area
For technical staff, as long as it is obvious that can make various changes without departing from the spirit and scope of the present invention or revise.
Claims (10)
1. a kind of ultralight PU foams composite sheet, it is characterised in that the composite sheet is counted by volume including 20-99% thermoplastics
Property polyurethane foam particle and 1-80% polyurethane foam matrixes.
2. ultralight PU according to claim 1 foams composite sheet, it is characterised in that described polyurethane foam matrix bag
Overlay on thermoplastic polyurethane foam's particle surface and compression molding obtains ultralight PU foaming composite sheet.
3. ultralight PU according to claim 1 foams composite sheet, it is characterised in that polyurethane foam matrix and thermoplasticity
Polyurethane foam particle is laminated to obtain ultralight PU foaming composite sheet with sheet material respectively.
4. ultralight PU according to claim 1 foams composite sheet, it is characterised in that described ultralight PU foaming composite sheet
The density of material is 0.10-2.50g/cm3, the thickness of the composite sheet is 3mm-5cm.
5. the ultralight PU foaming composite sheet according to claim 1 or 2 or 3, it is characterised in that the thermoplastic polyurethane
The inside of expanded particle has the foam structure of closing, is spherical, oval or cylindrical particle.
6. ultralight PU according to claim 5 foams composite sheet, it is characterised in that thermoplastic polyurethane foam's grain
The particle diameter of son is 2mm-2cm, and density is 0.05-0.25g/cm3.
7. ultralight PU according to claim 6 foams composite sheet, it is characterised in that thermoplastic polyurethane foam's particle
Foaming method is：Thermoplastic polyurethane particle based on polyhydric alcohol makes thermoplastic polyurethane foam using the method for physical blowing
Particle.
8. the ultralight PU foaming composite sheet according to claim 1 or 2 or 3, it is characterised in that the polyurethane foam base
The material of body be soft PU foams, hard PU foams, semi-rigid PU foam, one or more from skinning PU foams, described
The density of polyurethane foam matrix is 0.05-1.5g/cm3.
9. a kind of ultralight PU foams the preparation method of composite sheet, it is characterised in that described preparation method is：
By polyisocyanates, polyhydric alcohol, chain extender, catalyst, foaming agent, other additives and thermoplastic polyurethane foam's grain
Sub- mix homogeneously, injects the mixture into cure under pressure molding in mould and obtains ultralight PU foaming composite sheet；
Or first polyisocyanates, polyhydric alcohol, chain extender, catalyst, foaming agent and other additives are mixed, evenly laid out in mould
Polyurethane foam matrix sheet material is formed in tool, then in polyurethane foam matrix sheet material upper berth last layer thermoplastic polyurethane foam's grain
Son, then tile on thermoplastic polyurethane foam's particle polyurethane foam matrix sheet material, is layering successively, and cure under pressure is fixed
Type obtains ultralight PU foaming composite sheet.
10. ultralight PU according to claim 9 foams the preparation method of composite sheet, it is characterised in that cure under pressure into
Temperature in type is 20-90 DEG C, and pressure is 0.1-10MPa.
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| CN107199832A (en) * | 2017-05-23 | 2017-09-26 | 宁波格林美孚新材料科技有限公司 | A kind of inflation-free solid tyre |
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| CN109337343A (en) * | 2018-09-03 | 2019-02-15 | 美瑞新材料股份有限公司 | A kind of top load padded coaming and preparation method thereof |
| CN109456589A (en) * | 2018-09-03 | 2019-03-12 | 美瑞新材料股份有限公司 | A kind of solid tyre |
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| CN110678097A (en) * | 2017-06-01 | 2020-01-10 | 耐克创新有限合伙公司 | Method of making articles from foam particles |
| CN110678097B (en) * | 2017-06-01 | 2021-11-05 | 耐克创新有限合伙公司 | Method of making articles from foam particles |
| CN111225579A (en) * | 2017-10-13 | 2020-06-02 | 株式会社爱世克私 | Outsole and shoe |
| CN108264754B (en) * | 2017-12-29 | 2021-01-01 | 美瑞新材料股份有限公司 | Thermoplastic polyurethane elastomer foam material with density gradient and preparation method thereof |
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| CN109456589A (en) * | 2018-09-03 | 2019-03-12 | 美瑞新材料股份有限公司 | A kind of solid tyre |
| CN109337343A (en) * | 2018-09-03 | 2019-02-15 | 美瑞新材料股份有限公司 | A kind of top load padded coaming and preparation method thereof |
| CN112622392A (en) * | 2019-09-20 | 2021-04-09 | 美瑞新材料股份有限公司 | Thermoplastic polyurethane foam product with surface coating and preparation method thereof |
| CN111117206A (en) * | 2019-12-20 | 2020-05-08 | 美瑞新材料股份有限公司 | Conductive foamed thermoplastic polyurethane elastomer bead as well as preparation method and application thereof |
| CN116234687A (en) * | 2020-12-24 | 2023-06-06 | 井上株式会社 | Sheet and method for producing sheet |
| CN115286888A (en) * | 2022-09-02 | 2022-11-04 | 合肥维信诺科技有限公司 | Buffer material and preparation method and application thereof |
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Application publication date: 20170315 |