CN107636036A - 包含管状颗粒的制品 - Google Patents
包含管状颗粒的制品 Download PDFInfo
- Publication number
- CN107636036A CN107636036A CN201680028639.8A CN201680028639A CN107636036A CN 107636036 A CN107636036 A CN 107636036A CN 201680028639 A CN201680028639 A CN 201680028639A CN 107636036 A CN107636036 A CN 107636036A
- Authority
- CN
- China
- Prior art keywords
- tpe
- foam
- thermoplastic elastomer
- product
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002245 particle Substances 0.000 title claims abstract description 132
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 206
- 229920000642 polymer Polymers 0.000 claims abstract description 112
- 239000006260 foam Substances 0.000 claims abstract description 99
- 239000000047 product Substances 0.000 claims description 74
- 239000012948 isocyanate Substances 0.000 claims description 37
- 229920001169 thermoplastic Polymers 0.000 claims description 35
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 35
- 239000004416 thermosoftening plastic Substances 0.000 claims description 35
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 32
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 26
- 150000002513 isocyanates Chemical class 0.000 claims description 25
- 229920001971 elastomer Polymers 0.000 claims description 22
- 239000000806 elastomer Substances 0.000 claims description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 238000005187 foaming Methods 0.000 claims description 14
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- 150000005846 sugar alcohols Polymers 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 6
- 101710130081 Aspergillopepsin-1 Proteins 0.000 claims description 5
- 102100031007 Cytosolic non-specific dipeptidase Human genes 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- GTACSIONMHMRPD-UHFFFAOYSA-N 2-[4-[2-(benzenesulfonamido)ethylsulfanyl]-2,6-difluorophenoxy]acetamide Chemical compound C1=C(F)C(OCC(=O)N)=C(F)C=C1SCCNS(=O)(=O)C1=CC=CC=C1 GTACSIONMHMRPD-UHFFFAOYSA-N 0.000 claims description 4
- 238000005336 cracking Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 238000009408 flooring Methods 0.000 claims 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 32
- -1 methylols Chemical class 0.000 description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 10
- 229920000728 polyester Polymers 0.000 description 9
- 229920000570 polyether Polymers 0.000 description 9
- 229920002397 thermoplastic olefin Polymers 0.000 description 7
- 229920006347 Elastollan Polymers 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- 229920006342 thermoplastic vulcanizate Polymers 0.000 description 5
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229920002633 Kraton (polymer) Polymers 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N ethyl trimethyl methane Natural products CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 2
- 229940051250 hexylene glycol Drugs 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920001281 polyalkylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 229920006345 thermoplastic polyamide Polymers 0.000 description 2
- 230000010415 tropism Effects 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- DTZHXCBUWSTOPO-UHFFFAOYSA-N 1-isocyanato-4-[(4-isocyanato-3-methylphenyl)methyl]-2-methylbenzene Chemical compound C1=C(N=C=O)C(C)=CC(CC=2C=C(C)C(N=C=O)=CC=2)=C1 DTZHXCBUWSTOPO-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- 125000004825 2,2-dimethylpropylene group Chemical group [H]C([H])([H])C(C([H])([H])[H])(C([H])([H])[*:1])C([H])([H])[*:2] 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- MXZROAOUCUVNHX-UHFFFAOYSA-N 2-Aminopropanol Chemical compound CCC(N)O MXZROAOUCUVNHX-UHFFFAOYSA-N 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical class CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- QOFLTGDAZLWRMJ-UHFFFAOYSA-N 2-methylpropane-1,1-diol Chemical class CC(C)C(O)O QOFLTGDAZLWRMJ-UHFFFAOYSA-N 0.000 description 1
- HUWXDEQWWKGHRV-UHFFFAOYSA-N 3,3'-Dichlorobenzidine Chemical compound C1=C(Cl)C(N)=CC=C1C1=CC=C(N)C(Cl)=C1 HUWXDEQWWKGHRV-UHFFFAOYSA-N 0.000 description 1
- NIQIPYGXPZUDDP-UHFFFAOYSA-N 3-aminocyclohexan-1-ol Chemical class NC1CCCC(O)C1 NIQIPYGXPZUDDP-UHFFFAOYSA-N 0.000 description 1
- YHFGMFYKZBWPRW-UHFFFAOYSA-N 3-methylpentane-1,1-diol Chemical class CCC(C)CC(O)O YHFGMFYKZBWPRW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- OCEINMLGYDSKFW-UHFFFAOYSA-N 4-(4-amino-3-nitrophenyl)-2-nitroaniline Chemical class C1=C([N+]([O-])=O)C(N)=CC=C1C1=CC=C(N)C([N+]([O-])=O)=C1 OCEINMLGYDSKFW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical class [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical group CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- 239000004425 Makrolon Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920002614 Polyether block amide Polymers 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229920006099 Vestamid® Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QTQUJRIHTSIVOF-UHFFFAOYSA-N amino(phenyl)methanol Chemical compound NC(O)C1=CC=CC=C1 QTQUJRIHTSIVOF-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- PGEAEAYLSCKCCO-UHFFFAOYSA-N benzene;n-methylmethanamine Chemical compound CNC.C1=CC=CC=C1 PGEAEAYLSCKCCO-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 229920002678 cellulose Chemical class 0.000 description 1
- 239000001913 cellulose Chemical class 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 239000006263 elastomeric foam Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002083 enediols Chemical class 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000011796 hollow space material Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000004005 microsphere Substances 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
- UOBSVARXACCLLH-UHFFFAOYSA-N monomethyl adipate Chemical class COC(=O)CCCCC(O)=O UOBSVARXACCLLH-UHFFFAOYSA-N 0.000 description 1
- 125000005487 naphthalate group Chemical group 0.000 description 1
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000058 polyacrylate Chemical class 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920003031 santoprene Polymers 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 229950006389 thiodiglycol Drugs 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/22—After-treatment of expandable particles; Forming foamed products
- C08J9/228—Forming foamed products
- C08J9/232—Forming foamed products by sintering expandable particles
-
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Abstract
该公开内容提供一种制品,其具有0.03至0.45g/cc的密度且包含在制品中随机取向的多个各向异性管状颗粒。管状颗粒包括热塑性弹性体泡沫和设置在热塑性弹性体泡沫外表面上作为颗粒的最外层的聚合物。热塑性弹性体泡沫和聚合物各自独立地具有根据DIN ISO306测定的软化温度。聚合物的软化温度比热塑性弹性体泡沫的软化温度低至少5℃。
Description
技术领域
本公开一般涉及具有特定密度并且包含多个各向异性管状颗粒的制品。更具体地,管状颗粒包括热塑性弹性体泡沫和设置在热塑性弹性体泡沫外表面上作为颗粒的最外层的聚合物。
背景
热塑性泡沫颗粒可以通过将颗粒松散地组合或将它们粘合在一起以形成连接的颗粒网络来用于形成垫状材料。颗粒的粘合可以通过使用热固性胶实现或使用温度和压力以及颗粒的固有热塑性(熔融)行为将它们彼此熔合而实现。在粘合过程中,颗粒通常在压力下放置在模具中以形成制品。如果使用温度来粘合颗粒(例如通过蒸汽箱裂化模制),则通常接近/超过颗粒的熔点以使得能够在模具中熔化。升高的温度结合模具中的压力可具有永久扭曲颗粒的不期望的结果,这导致制品的不希望的收缩。因此,仍有改进的机会。
发明概述
本公开提供了具有0.03至0.45g/cc的密度并且包含在制品中随机取向的多个各向异性管状颗粒的制品。管状颗粒包括热塑性弹性体泡沫和设置在热塑性弹性体泡沫外表面上作为颗粒的最外层的聚合物。热塑性弹性体泡沫和聚合物各自独立地具有根据DINISO306测定的软化温度。聚合物的软化温度比热塑性弹性体泡沫的软化温度低至少5℃。
本公开还提供了形成制品的方法。该方法包括提供热塑性弹性体和聚合物的步骤以及共挤出热塑性弹性体和聚合物以形成管状挤出物的步骤,其中热塑性弹性体在共挤出期间发泡以形成热塑性弹性体泡沫,并且聚合物设置在热塑性弹性体泡沫外表面上作为管状挤出物的最外层。该方法还包括将管状挤出物分段以形成多个各向异性管状颗粒的步骤。此外,该方法包括以下步骤:将多个各向异性管状颗粒设置在模具中并加热多个各向异性管状颗粒以形成制品,使得多个各向异性管状颗粒在制品中随机取向。
附图说明
本发明的其它优点将容易理解,因为在结合附图考虑时参考以下详细描述可以更好地理解本发明的其它优点,其中:
图1是本公开的颗粒的一个实施方案的侧视截面图;
图2是本公开的颗粒的另一个实施方案的侧视截面图;
图3是本公开的挤出物的一个实施方案的侧视截面图;
图4是本发明的多个颗粒的一个实施方案的侧视截面图;和
图5是本公开的制品的一个实施方案的侧视截面图。
本公开的详细描述
本公开提供了具有0.03至0.45g/cc的密度的制品(10),例如,如图5所示。制品(10)本身在维度,尺寸或类型上没有特别限制。在各种实施方案中,制品(10)是鞋底,家具垫,汽车垫,床垫,地板表面,地板基材等。在其他实施方案中,制品(10)的密度为0.03-0.4、0.05-0.4、0.1-0.35、0.15-0.3、0.2-0.25、0.03-0.1、0.03-0.25、0.03-0.2、0.03-0.15、0.03-0.05、0.04-0.09、0.05-0.08、0.06-0.07、0.1-0.45、0.15-0.4、0.2-0.35、0.25-0.3g/cc(或g/ml)。通过使用ASTM D 5035测定,制品(10)通常还具有0.1至4.0兆帕,0.4至3.0兆帕,或0.5至1.5兆帕的极限断裂强度。在各种另外的非限制性实施方案中,在此明确地考虑在上述值之间和包含上述值的所有值和值范围。
各向异性管状颗粒:
制品(10)包含多个各向异性管状颗粒(12),下文中描述为“颗粒(12)”,例如图4所示。术语“多个”描述了制品(10)包含多个颗粒(12),即三个或更多个。术语“各向异性”描述了当在不同方向上测量时,颗粒(12)表现出具有不同值的物理性质。例如,当将该力施加到颗粒的一侧时,颗粒可能需要特定量的力来使颗粒塌陷。当施加到颗粒的端部以使颗粒塌陷时,所需力的量可能是不同的。颗粒(12)是管状的并且可以是实心的或中空的。在一个实施方案中,颗粒(12)被描述为中空圆筒。在另一个实施方案中,颗粒(12)被描述为实心圆筒。
颗粒(12)的横截面可以是圆形,椭圆形,正方形,矩形或任何其它形状。换句话说,术语“管状”不限于圆形或椭圆形横截面。然而,在附图中,横截面近似为圆形。颗粒(12)可以被描述为具有长度和可以是任何形状的横截面的中空或实心形状。在其他实施方案中,颗粒(12)是弯曲/弯曲的管状或波纹/“手风琴”形状。颗粒(12)的弯曲/弯曲可导致不同的性质,如颗粒(12)所示。颗粒(12)可以替代地描述为管道,导管,管,圆柱体等。管状颗粒的使用通常允许实现制品的较低堆积密度。换句话说,颗粒的几何形状通常允许增加的密度降低,例如相对于不使用本公开技术形成的对比制品。
颗粒(12)在制品(10)中随机取向,例如,在三维取向上。换句话说,颗粒(12)在制品(10)中不是单向地或沿任何特定的一个或多个方向设置的。颗粒(12)通常在x,y和z维度上在制品(10)中随机取向或分散。通常,制品(10)的横截面不显示制品(10)中颗粒(12)的取向或分散的图案。
颗粒(12)通常熔合在一起,但是不一定必须“熔合”,只要制品具有上述密度即可。在一个实施方案中,一些颗粒(12)熔合在一起,而其它颗粒不是。通常,如果熔合,则使用下述方法使颗粒(12)熔合。颗粒(12)可以在多个点处熔合在一起,例如,沿着颗粒(12)的边缘或者沿着或跨过颗粒(12)的外表面(26)。或者,颗粒(12)可以在各种颗粒(12)的外层的一个或多个界面处熔合在一起。只要达到上述的密度,颗粒就可以以任何方式彼此融合或彼此粘合。
颗粒(12)包含热塑性弹性体泡沫(14)和设置在热塑性弹性体泡沫(14)的外表面(26)上作为颗粒(12)的最外层(24)的聚合物(16)。该聚合物(16)可以另外被描述为“外部”聚合物(16)。术语“最外面”或“外部”可以描述该层的一侧暴露于环境并且不与任何其它层接触。换句话说,最外层不夹在任何其它层之间。
颗粒(12)可以包含热塑性弹性体泡沫(14)和聚合物(16)、基本上由其组成或由其组成。术语“基本上由其组成”描述了在各实施方案中,颗粒(12)不含不是热塑性弹性体泡沫(14)或聚合物(16)的聚合物,并且可以不含或可以包含本领域已知的各种聚合物添加剂和/或加工助剂。
热塑性弹性体泡沫(14)和聚合物(16)都不特别限于颗粒(12)中的任何厚度,长度,宽度或高度。通常,热塑性弹性体泡沫(14)在颗粒(12)中的厚度为0.5至50,1至30,或1至10mm。类似地,聚合物(16)通常在颗粒(12)中具有0.001至10,0.005至5,或0.01至1mm的厚度。在各种另外的非限制性实施方案中,在此明确地考虑在上述值之间和包含上述值的所有值和值范围。
颗粒(12)本身也不特别限于任何厚度,长度,宽度或高度。在各种实施方案中,颗粒(12)的长度为1至50,1至40,或1.5至30mm。在其它实施方案中,颗粒(12)的直径为1至100,1至50,或1至30mm。在其它实施方案中,颗粒(12)的尺寸设计成使得它们具有约0.5mm至约25mm的直径。颗粒(12)的直径可以为约2mm至约10mm或约3mm至约8mm。在各种另外的非限制性实施方案中,在此明确地考虑在上述值之间和包含上述值的所有值和值范围。
热塑性弹性体泡沫:
热塑性弹性体泡沫(14)没有特别限制,只要它是泡沫即可。然而,热塑性弹性体泡沫(14)通常由非发泡热塑性弹性体形成。在一个实施方案中,如下所述,热塑性弹性体泡沫(14)通常在非发泡热塑性弹性体挤出期间发泡。例如,可将非发泡热塑性弹性体供至挤出机(例如以颗粒形式),然后在挤出过程中可以发泡以形成热塑性弹性体泡沫(14)。另外的方法步骤也可以是有用的,例如加入可膨胀微球,加入发泡剂,如NaHCO3或柠檬酸,或加入气体,例如CO2,N2或Ar,通过注入熔体中。也可以使用这些步骤的组合。如下所述,术语“热塑性弹性体”和“热塑性弹性体泡沫(14)”可以在各种非限制性实施方案中可互换使用。
在各种实施方案中,热塑性弹性体泡沫(14)使用非发泡热塑性弹性体制备,非发泡热塑性弹性体使用DIN ISO 7619-1测定具有肖氏40A至83D的硬度。在各种实施方案中,用于形成热塑性弹性体泡沫(14)的非发泡热塑性弹性体具有40A至83D,60A至70D或80A至95A的硬度,使用DIN ISO 7619-1测定。热塑性弹性体泡沫(14)本身通常具有0.1至0.6、0.15至0.55,0.2至0.5、0.25至0.45,0.3至0.4,0.3至0.35或0.35至0.4g/cc(或g/ml)的密度。在其他实施方案中,在此明确地考虑在上述值之间和包含上述值的所有值和值范围。
热塑性弹性体和/或热塑性弹性体泡沫(14)可以选自热塑性聚氨酯弹性体(TPU),热塑性共聚酯弹性体(TPC),热塑性苯乙烯弹性体(TPS),热塑性聚酰胺(TPA),热塑性硫化橡胶(TPV),热塑性聚烯烃(TPO)及其组合。
热塑性聚氨酯弹性体:
热塑性聚氨酯弹性体(例如发泡或非发泡)也可以在本文简单地描述为TPU,热塑性聚氨酯或TPE-U。热塑性聚氨酯弹性体通常包括线性分段聚合物嵌段,包括硬链段和软链段。不期望受任何特定理论的约束,认为软链段具有低极性并形成弹性体基质,其为热塑性聚氨酯提供弹性。硬链段被认为比软链段短,具有更高的极性,并且作为多功能连接点,其既作为物理交联又作为补强填充剂也起作用。认为物理交联在加热时消失,从而允许热塑性聚氨酯以各种加工方法使用。
热塑性聚氨酯可进一步定义为聚醚热塑性聚氨酯,聚酯热塑性聚氨酯或聚醚热塑性聚氨酯和聚酯热塑性聚氨酯的组合。也就是说,非发泡和/或发泡热塑性聚氨酯可以进一步被定义为包括或是异氰酸酯和聚醚多元醇,聚酯多元醇,脂族或烯属多元醇或这些多元醇的组合的反应产物。或者,非发泡和/或发泡热塑性聚氨酯可以进一步定义为由异氰酸酯与线性聚合二醇(例如重均分子量为500至8,000g/mol),低分子量二醇(例如重均分子量为50至600g/mol)和/或多元醇的聚加成反应产生的多嵌段共聚物。通常,如上所述,可以通过改变硬链段和软链段的比来获得非发泡和/或发泡热塑性聚氨酯。物理性质如肖氏硬度以及模量,承载能力(压缩应力),撕裂强度和比重通常随硬链段与软链段比的增加而增加。
在一个实施方案中,非发泡和/或发泡热塑性聚氨酯是聚酯热塑性聚氨酯,并且包括聚酯多元醇,异氰酸酯组分和增链剂的反应产物。合适的聚酯多元醇通常由二羧酸和具有至少一个伯羟基的二醇的反应制备。合适的二羧酸包括但不限于己二酸,己二酸甲酯,琥珀酸,辛二酸,癸二酸,草酸,戊二酸,庚二酸,壬二酸,邻苯二甲酸,对苯二甲酸,间苯二甲酸及其组合。适用于生产聚酯多元醇的二醇包括但不限于乙二醇,丁二醇,己二醇,双(羟甲基环己烷),1,4-丁二醇,二甘醇,2-甲基丙二醇,3-甲基戊二醇,2,2-二甲基丙二醇,1,3-丙二醇及其组合。
在替代实施方案中,非发泡和/或发泡热塑性聚氨酯是聚酯热塑性聚氨酯,并且包括合适的增链剂,异氰酸酯组分和聚合多元醇的反应产物。合适的增链剂包括但不限于二醇,包括乙二醇,丙二醇,丁二醇,1,4-丁二醇,丁烯二醇,丁炔二醇,2-乙基-1,3-己二醇,亚二甲苯基二甲醇,戊二醇,1,4-亚苯基-双-β-羟基乙基醚,1,3-亚苯基-双-β-羟基乙基醚,双-(羟基-甲基-环己烷),己二醇和硫二甘醇,二胺包括乙二胺,丙二胺,丁二胺,六亚甲基二胺,环己二胺,苯二胺,甲苯二胺,苯二甲胺,3,3'-二氯联苯胺,3,3'-二硝基联苯胺,链烷醇胺,包括乙醇胺,氨基丙醇,2,2-二甲基丙醇胺,3-氨基环己醇和对氨基苄醇,及其组合。可用于本发明的合适的聚酯热塑性聚氨酯的具体实例包括但不限于可从BASF公司购得的800、B、C和S系列聚酯热塑性聚氨酯。
在另一个实施方案中,非发泡和/或发泡热塑性聚氨酯是聚醚热塑性聚氨酯,并且包括聚醚多元醇,异氰酸酯组分和增链剂的反应产物。合适的聚醚多元醇包括但不限于聚四亚甲基二醇,聚乙二醇,聚丙二醇及其组合。在另一个实施方案中,非发泡和/或发泡热塑性聚氨酯是聚醚热塑性聚氨酯,并且包括增链剂和异氰酸酯组分的反应产物。应当理解,本领域技术人员可以根据热塑性聚氨酯的期望性质使用本领域已知的任何增链剂。可用于本发明的合适的聚醚热塑性聚氨酯的具体实例包括但不限于可从BASF公司购得的1000、1100和1200系列聚醚热塑性聚氨酯。
在另一个实施方案中,非发泡和/或发泡热塑性聚氨酯是脂族或烯属热塑性聚氨酯,并且包括脂族或烯属热塑性多元醇,异氰酸酯组分和增链剂的反应产物。合适的聚醚多元醇包括但不限于氢化聚丁二烯或非氢化聚丁二烯及其组合,或与聚酯和/或聚醚多元醇的组合。应当理解,本领域技术人员可以根据热塑性聚氨酯的期望性质使用本领域已知的任何增链剂。
通常,用于形成非发泡和/或发泡热塑性聚氨酯的聚醚,聚酯,脂族或烯属多元醇的重均分子量为600-3000g/mol。然而,多元醇不限于该分子量范围。在一个实施方案中,用于形成非发泡和/或发泡热塑性聚氨酯的原料(例如,线性聚合二醇,低分子量二醇和/或多元醇)具有约2的平均官能度。例如,任何预聚物或单体可以具有2个末端反应性基团以促进在非发泡和/或发泡热塑性聚氨酯中形成没有或具有很少分支点的高分子量线性链。
用于形成非发泡和/或发泡热塑性聚氨酯的异氰酸酯组分通常包括但不限于异氰酸酯,二异氰酸酯,多异氰酸酯及其组合。在一个实施方案中,异氰酸酯组分包括n-官能异氰酸酯。在该实施方案中,n是通常为2至5,更典型地为2至4,更典型地为2至3,最典型地为约2的数。应理解,n可以是整数或可以具有从2至5的中间值。异氰酸酯组分通常包括选自芳族异氰酸酯,脂族异氰酸酯及其组合的异氰酸酯。在另一个实施方案中,异氰酸酯组分包括脂族异氰酸酯如六亚甲基二异氰酸酯(HDI),二环己基-甲基-二异氰酸酯(H12MDI),异佛尔酮-二异氰酸酯及其组合。如果异氰酸酯组分包括脂族异氰酸酯,则异氰酸酯组分也可以包括改性的多价脂族异氰酸酯,即通过脂族二异氰酸酯和/或脂族多异氰酸酯的化学反应获得的产物。实例包括但不限于脲,缩二脲,脲基甲酸酯,碳二亚胺,脲酮亚胺(uretonimine),异氰脲酸酯,氨基甲酸酯基,二聚物,三聚物及其组合。异氰酸酯组分还可以包括但不限于单独使用的改性二异氰酸酯或与聚氧化烯二醇,二甘醇,二丙二醇,聚氧乙烯二醇,聚氧丙烯二醇,聚氧乙烯聚氧丙烯二醇,聚酯醇,聚己内酯及其组合的反应产物。
或者,异氰酸酯组分可以包括芳族异氰酸酯。如果异氰酸酯组分包括芳族异氰酸酯,则芳族异氰酸酯通常对应于式R'(NCO)z,其中R'是芳族的,z是对应于R'的化合价的整数。通常,z至少为2。芳族异氰酸酯的合适实例包括但不限于四甲基亚二甲苯基二异氰酸酯(TMXDI),1,4-二异氰酸酯基苯,1,3-二异氰酸-邻二甲苯,1,3-二异氰酸-对二甲苯,1,3-二异氰酸-间二甲苯,2,4-二异氰酸-1-氯苯,2,4-二异氰酸-1-硝基苯,2,5-二异氰酸-1-硝基苯,间苯二异氰酸酯,对苯二异氰酸酯,2,4-甲苯二异氰酸酯,2,6-甲苯二异氰酸酯,2,4-和2,6-甲苯二异氰酸酯的混合物,1,5-萘二异氰酸酯,1-甲氧基-2,4-亚苯基二异氰酸酯,4,4'-二苯基甲烷二异氰酸酯2,4'-二苯基甲烷二异氰酸酯,4,4'-联亚苯基二异氰酸酯,3,3'-二甲基-4,4'-二苯基甲烷二异氰酸酯,3,3'-二甲基二苯基甲烷-4,4'-二异氰酸酯,三异氰酸酯如4,4',4”-三苯甲烷三异氰酸酯多亚甲基多亚苯基多异氰酸酯和2,4,6-甲苯三异氰酸酯,四异氰酸酯如4,4'-二甲基-2,2'-5,5'-二苯基甲烷四异氰酸酯,甲苯二异氰酸酯,2,2'-二苯基甲烷二异氰酸酯,2,4'-二苯基甲烷二异氰酸酯,4,4'-二苯基甲烷二异氰酸酯,聚亚甲基聚亚苯基多异氰酸酯,其相应的异构体混合物,及其组合。或者,芳族异氰酸酯可以包括间-TMXDI和1,1,1-三羟甲基丙烷的三异氰酸酯产物,甲苯二异氰酸酯和1,1,1-三甲基丙烷的反应产物及其组合。在一个实施方案中,异氰酸酯组分包括选自亚甲基二苯基二异氰酸酯,甲苯二异氰酸酯,六亚甲基二异氰酸酯,H12MDI及其组合的二异氰酸酯。异氰酸酯组分也可以以本领域技术人员所确定的任何量与多元醇和/或增链剂反应。
热塑性聚酯弹性体:
热塑性弹性体泡沫可以替代地是热塑性聚酯弹性体,也称为TPC。热塑性弹性体也可以描述为热塑性橡胶,并且通常是具有热塑性和弹性性质的一类共聚物或聚合物(例如塑料和橡胶)的物理混合物。热塑性聚酯弹性体的非限制性实例是来自DSM的Arnitel和来自DuPont的Hytrel。
热塑性苯乙烯弹性体:
热塑性弹性体(泡沫)可以替代地是热塑性苯乙烯弹性体,也称为与乙烯,丙烯,丁二烯,异戊二烯单元或TPS的苯乙烯,苯乙烯嵌段共聚物。热塑性苯乙烯弹性体通常基于A-B-A型嵌段结构,其中A是硬相,B是弹性体。热塑性苯乙烯弹性体的非限制性实例是KratonD和Kraton G。
热塑性硫化橡胶弹性体:
热塑性弹性体(泡沫)可以是热塑性硫化橡胶弹性体,也称为TPV。热塑性硫化橡胶弹性体的非限制性实例是来自埃克森美孚的Santoprene。
热塑性聚酰胺弹性体:
热塑性弹性体(泡沫)也可以是热塑性聚酰胺弹性体,也称为TPA。热塑性聚酰胺弹性体的非限制性实例是来自Evonik的Vestamid E。
热塑性聚烯烃弹性体:
热塑性弹性体(泡沫)也可以是热塑性聚烯烃弹性体,也称为TPO。热塑性聚烯烃弹性体的非限制性实例是来自Dow的Engage。
聚合物:
回头看聚合物(16)本身,聚合物(16)设置在热塑性弹性体泡沫(14)的外表面(26)上,作为颗粒(12)的最外层(24)。聚合物(16)可以设置在热塑性弹性体泡沫(14)的外表面(26)上并且直接接触热塑性弹性体泡沫(14)的外表面(26)。如图1所示,或者可以设置在热塑性弹性体泡沫(14)的外表面(26)上并与之隔开,如图2所示。可以使用单个聚合物(16)或可以使用聚合物的组合。聚合物(16)可以在化学上与热塑性弹性体泡沫(14)相同,或者可以在化学上不同于热塑性弹性体泡沫(14)。
除了下面更详细描述的软化温度之外,聚合物(16)没有特别限制。聚合物(16)可以包括选自聚氨酯(发泡或非发泡),热塑性弹性体(发泡或非发泡),聚亚烷基,例如聚亚乙基,聚亚丙基,聚亚烷基萘二甲酸酯和对苯二甲酸酯,聚酰亚胺,聚酰胺,聚醚酰亚胺,聚苯乙烯,丙烯腈,聚碳酸酯,聚丙烯酸烷基酯,聚丙烯酸酯,纤维素衍生物,卤化聚合物,聚砜,聚醚砜,聚丙烯腈,聚硅氧烷,环氧树脂,聚乙酸乙烯酯,聚醚酰胺,离聚物树脂,弹性体,苯乙烯-丁二烯共聚物,苯乙烯-丙烯腈共聚物,聚酯,聚烯烃,聚苯乙烯,其异构体,其共聚物及其组合,基本上由其组成,或由其组成。在一个实施方案中,聚合物是发泡的。在另一个实施方案中,聚合物是非发泡的。在各种实施方案中,聚合物(16)选自Elastollan 880A13N,Elastollan ER368511及其组合。在其它实施方案中,聚合物(16)选自泡沫热塑性弹性体(不同于上述任何一种),非发泡热塑性弹性体(不同于上述任何一种),非发泡热塑性弹性体如TPS,TPV,TPO和TPA,及其组合。
在各种实施方案中,可以使用一种或多种上述聚合物,例如其量至多约50重量%的聚合物形成热塑性弹性体泡沫(14)。在各种实施方案中,热塑性弹性体泡沫(14)使用1,2,3,4,5,10,15,20,25,30,35,40,45或50重量%的一种或多种上述聚合物,余量为热塑性弹性体。在各种另外的非限制性实施方案中,在此明确地考虑在上述值之间和包含上述值的所有值和值范围。
软化温度:
热塑性弹性体泡沫(14)和聚合物(16)各自独立地具有根据ASTM DIN ISO 306测定的软化温度。聚合物(16)的软化温度比热塑性弹性体泡沫(14)的软化温度低至少5℃。不期望受任何特定理论的限制,认为聚合物的较低软化温度允许将颗粒加热至该较低的软化温度,从而使聚合物软化或塑化并使聚合物变粘,从而将颗粒粘附在一起。由于聚合物的软化温度低于热塑性弹性体泡沫(14)的软化温度,所以热塑性弹性体泡沫(14)本身不会熔化/软化,从而可以保持其性能和尺寸。这通常导致在从模具中移除之后不会随着致密化而遭受收缩的制品,即,由于热塑性弹性体泡沫(14)在颗粒本身中的压实/固结/附聚而导致的不希望的密度增加。
在各种实施方案中,聚合物(16)的软化温度比热塑性弹性体泡沫(14)的软化温度低至少5,10,15,20,25,30,35,40,45或50℃或甚至更高。在其它实施方案中,聚合物(16)的软化温度比热塑性弹性体泡沫(14)的软化温度低5至20,10至20,15至50,20至45,25至40,30至35,15至30,15至25,或15至20℃。在各种实施方案中,热塑性弹性体泡沫(14)的软化温度为80至180℃,90至160℃,100至160℃,或110℃至150℃。在其它实施方案中,聚合物(16)的软化温度为40至120,50至100,60至80,60至70,60至65,或60至70℃。可以通过各种分析程序,例如通过使用DSC仪器和程序来检测热塑性弹性体和聚合物的熔点或软化点的差异,或作为颗粒的一部分,或甚至在制品形成之后检测。在各种另外的非限制性实施方案中,在此明确地考虑在上述值之间和包含上述值的所有值和值范围。
其他聚合物:
在各种实施方案中,制品(10)和/或颗粒(12)还包括中间聚合物(18),例如如图2所示设置在“外部”聚合物(16)(即,设置在作为颗粒(12)的最外层(24)的热塑性弹性体外表面(26)上的聚合物)和热塑性弹性体泡沫(14)之间。该中间聚合物(18)可以夹在外部聚合物(16)和热塑性弹性体泡沫(14)之间。中间聚合物(18)可以设置在热塑性弹性体泡沫(14)和/或外部聚合物(16)上并与其直接接触。或者,中间聚合物(18)可以设置在热塑性弹性体泡沫(14)和/或外部聚合物(16)上但是与其隔开(图中未示出)。
在其它实施方案中,制品(10)和/或颗粒(12)包括内部聚合物(20),其可设置在热塑性弹性体泡沫(14)上并与热塑性弹性体泡沫(14)直接接触,使得热塑性弹性体泡沫14)设置在内部聚合物(20)和外部聚合物(16)之间,例如,如图2所示。在该实施方案中,热塑性弹性体泡沫(14)通常夹在内部聚合物(20)和外部聚合物(16)之间。在另一个实施方案中,中间聚合物(18)也可以存在并且设置在内部聚合物(20)和外部聚合物(16)之间的任何位置。例如,内部聚合物(20)可以设置在热塑性弹性体泡沫(14)和/或外部聚合物(16)上并与其直接接触。或者,内部聚合物(20)可以设置在热塑性弹性体泡沫(14)和/或外部聚合物(16)上但与之相隔开。预期可以使用一种或多种中间体聚合物(18),并且可以使用一种或多种内部聚合物(20)。预期内部聚合物(20)可以设置为颗粒(12)的最内层,使得内部聚合物(20)暴露于如图2所示的颗粒(12)的中空部分,以及不夹在任何层之间。例如,内部聚合物(20)可以仅在一侧与另一种聚合物(例如热塑性弹性体泡沫(14))接触。在另一个实例中,内部聚合物(20)限定了颗粒(12)的内表面。
中间聚合物(18)和/或内部聚合物(20)中的任何一种或多种可以如上文所述相对于外部聚合物(16)或不同。中间聚合物(18),内部聚合物(20)和/或外部聚合物(16)可以彼此相同或不同。在各种实施方案中,内部聚合物(20)选自热塑性聚氨酯(TPU),聚酰胺-6和热塑性酰胺(TPA)。在其它实施方案中,中间体聚合物(18)选自热塑性聚氨酯(TPU),聚酰胺-6(PA6)和热塑性酰胺(TPA)。
形成制品的方法:
本公开还提供了形成制品(10)的方法。该方法包括如上所述提供(非发泡)热塑性弹性体和上述“外部”聚合物的步骤。该方法还包括共挤出(非发泡)热塑性弹性体和外部聚合物(16)以形成管状挤出物(22)(例如图3所示)的步骤,其中(非发泡)热塑性弹性体在共挤出期间发泡(从而形成热塑性弹性体泡沫(14)),外部聚合物(16)设置在热塑性弹性体泡沫(14)上作为管状挤出物(22)的最外层(28)。共挤出步骤没有特别限制,可以是本领域已知的。换句话说,共挤出步骤可以包括本领域已知的一个或多个子步骤,温度,条件等。例如,在各种实施方案中,共挤出步骤利用可以如本领域技术人员所理解那样改进的以下参数:
模头类型:十字头;挤出机1(1-1/2“直径);1区340°F;2区360°F;3区370°F;
4区-370°F;夹具-370°F;适配器-370°F;压头-4000psi;螺杆RPM-12.5,螺杆扭矩-18.5%;挤出机2(3/4“直径);1区-275°F;2区320°F;3区340°F;夹具-340°F;适配器-340°F;压头-3800psi;螺杆RPM-15;螺杆扭矩-31.6%;机头-370°F;模头370°F;Take Off Motor230RPM;速率指示器21.3。或者,共挤出的一个或多个参数可以在实施例中描述。在各种另外的非限制性实施方案中,在此明确地考虑在上述值之间和包含上述值的所有值和值范围。
该方法还包括将管状挤出物(22)分段以形成多个颗粒(12)的步骤。分段步骤通常被进一步定义为切割或砍断,但没有特别限制。
该方法还包括将多个颗粒(12)设置在模具中的步骤。颗粒(12)通常以随机方式设置在模具中,例如倒入模具中。这通常允许最终产品中颗粒(12)的随机或三维取向。在各种实施方案中,颗粒(12)或者(1)通过手“手工”倒入模具中,或(2)使用空气输送系统注入模具中。通常,模具在处于打开位置时被填充,从而允许颗粒“过度填充”模具。在模具闭合之后,通常强制使颗粒在一起,这促进了更多的表面积接触。这是为了促进增加附着力。
该方法还包括加热多个颗粒(12)以形成制品(10),例如,使得多个颗粒(12)在制品(10)中随机取向。加热步骤没有特别限制,可以包括用电,气体,蒸汽等进行加热。在一个实施方案中,加热步骤进一步定义为用蒸汽(例如,在蒸汽箱裂化模制方法中)加热颗粒(12)和/或模具本身。在另一个实施方案中,加热步骤(和/或整个方法)可进一步定义为蒸汽箱裂化模制方法。具体步骤可以是本领域已知的和/或如上所述。
其它实施方案
在一个实施方案中,该方法包括使模具装载颗粒(12)并将蒸汽供给到模具中的颗粒(12)。蒸汽的供入加热颗粒(12)并且可以膨胀热塑性弹性体泡沫(14)。蒸汽的供入还可以熔化或软化外部聚合物(16),使得颗粒(12)彼此熔合,粘合或结合。本公开方法可以包括在US 2013/0291409中描述的一个或多个步骤,组件,条件或处理参数,其在各种非限制性实施方案中明确地并入本文。
在各种实施方案中,颗粒(12)以大气压装载到模具中,并且可以稍后在模具内加压。为此,可以使用各种不同的方法。例如,可以通过减小模具的体积来实现这些步骤。在一些实施方案中,为此,模具的可移动部分被移动,使得模具的体积减小。在另外的实施方案中,模具被设计成使得模具内的压力局部地变化。或者,可以将颗粒(12)装载到已经具有压力的模具中,例如,具有局部变化的压力。这样,可以加速制造方法。
颗粒(12)在模具中压缩的压力可影响最终制品(10)的密度和强度。颗粒(12)的直径可以通过施加的压力而减小。例如,在较高压力下,颗粒(12)可以被更强地压缩和致密化。通过减小压力,颗粒(12)可以重新扩大至其原始直径。外部聚合物(16)可以在该过程中发泡或不发泡,并且可能在该过程中崩塌或不崩塌。
在其他实施方案中,该方法可以包括关闭模具并用蒸汽预处理模具的步骤。该方法还可以包括用水和/或空气(其通过模具供应)冷却模具的步骤。因此,制品(10)和/或颗粒(12)可以经由模具间接冷却。在某些实施方案中,该方法的持续时间为约3-15分钟。对于较不精细的方法,持续时间可以为约3-6分钟。此外,该方法可以具有长于15分钟的持续时间。
本公开还提供挤出物或管状结构(在砍断或分割之前)本身,独立于任何颗粒或任何制品。类似地,本公开还提供多个颗粒本身,独立于任何挤出物或管状结构或制品。挤出物或管状结构可以是如上所述的任何一种。类似地,多个颗粒可以是如上所述的任何颗粒。
在其它实施方案中,颗粒覆盖或涂覆市售粘合剂(例如一种或两种组分),并在模具中压在一起以形成所需的制品。
本公开还提供了进一步定义为鞋底的制品。在各种实施方案中,鞋底包括使用一种或多种聚醚热塑性弹性体形成的颗粒。鞋底可以具有如US 2013/0291409中所述的一个或多个尺寸,属性或部件,其在各种非限制性实施方案中明确地并入本文。另外,软化温度的描述也可以描述为软化范围,如US 5,674,600中所述,其在一个或多个非限制性实施方案中通过引用将其全部内容明确地并入本文。在各种实施方案中,本公开提供了允许在低温下粘合颗粒的面料(例如,设置在外表面上的聚合物),而不会破坏颗粒和/或整个制品的其余结构。例如,这些优点可以通过上述一个或多个物理性质观察到,例如但不限于密度和极限断裂强度。
实施例
根据本公开形成一系列制品。更具体地,非发泡热塑性弹性体与外部聚合物一起提供。将热塑性弹性体和外部聚合物共挤出以形成管状挤出物,其中热塑性弹性体在共挤出期间发泡以形成热塑性弹性体泡沫,外部聚合物设置在热塑性弹性体泡沫上作为管状挤出物的最外层。然后将管状挤出物分段以形成多个各向异性管状颗粒,包括热塑性弹性体泡沫和设置在热塑性弹性体泡沫上作为管状颗粒的最外层的外部聚合物。然后将多个各向异性管状颗粒置于模具中并加热以形成制品。形成后,评估制品以确定密度。
使用1180A10作为热塑性弹性体(肖氏硬度为80A)和880A13N作为外部聚合物形成第一制品。将热塑性弹性体挤出和用发泡剂:3%负载的Elastollan Konz V2894和3%负载的Elastollan Konz V2893的组合发泡。热塑性弹性体的发泡比重为约0.4克/毫升。管的平均外径为0.125英寸。外部聚合物的平均壁厚为0.004英寸。发泡热塑性弹性体的平均壁厚为0.030英寸。多个各向异性颗粒的松散堆积密度为0.16克/毫升。将多个各向异性颗粒模制以形成密度为0.20至0.26克/毫升的制品。
使用1190A10作为热塑性弹性体(具有90A的肖氏硬度)和880A13N作为外部聚合物形成第二制品。将热塑性弹性体挤出和用发泡剂:3%负载的Elastollan Konz V2894和3%负载的Elastollan Konz V2893的组合发泡。热塑性弹性体的发泡比重为约0.4克/毫升。该管具有0.125英寸的平均外径。外部聚合物的平均壁厚为0.004英寸。发泡热塑性弹性体的平均壁厚为0.030英寸。多个各向异性颗粒具有0.16克/毫升的松散堆积密度。将多个各向异性颗粒模制以形成具有0.20至0.26克/毫升的密度的制品。
在各种实施方案中,热塑性弹性体泡沫的密度可以最小化,因为颗粒的性能可以取决于由外部聚合物获得的模量。外部聚合物的较低软化点/熔点可以允许在模制期间较低的加工温度以避免颗粒的永久变形和随后的制品致密化。此外,本公开可以允许形成低密度制品,同时保持性能(例如能量吸收和恢复)。较低的密度可以允许颗粒更好地与家具垫,床垫和汽车座椅中常见的传统热固性泡沫竞争。与热固性聚合物相比,热塑性弹性体也被认为是更“回收友好的”。本公开还可以使较低的加工温度能够用于在压力下热粘合颗粒而不使其永久变形。
在一个或多个非限制性实施方案中,整个公开的上述实施方案的所有组合在此明确地预期,即使这样的公开内容不是在上述单个段落或部分中逐字描述。换句话说,明确考虑的实施方案可以包括从本公开的任何部分选择并组合的上述任何一个或多个元素。
只要方差保持在本公开的范围内,上述值中的一个或多个可以在±5%,±10%,±15%,±20%,±25%等变化。可以从独立于所有其他成员的马库什组的每个成员获得预料不到的结果。可以单独地或组合地依赖每个成员,并且在所附权利要求的范围内为特定实施方案提供足够的支持。独立和从属权利要求的所有组合的主题,单一和多重从属的,在此明确地预期。本公开是说明性的,包括说明性而不是限制性的词语。根据上述教导,本公开的许多修改和变化是可能的,并且本公开可以以不同于本文具体描述的方式实施。
还应当理解,在描述本公开的各种实施方案中所依赖的任何范围和子范围独立地并且共同地落入所附权利要求的范围内,并且被理解为描述并考虑包含其中的全部和/或部分值的所有范围,即使这些值未在本文中明确写出。本领域技术人员容易认识到,枚举的范围和子范围充分地描述和实现本公开的各种实施方案,该范围和子范围可以被进一步描述为相关的一半,三分之一,四分之一,五分之一等等。仅仅作为一个例子,可以将“0.1至0.9”的范围进一步描述为下三分之一,即从0.1至0.3,中间的三分之一,即0.4至0.6,上三分之一,即0.7至0.9,其单独地和集体地在所附权利要求的范围内,并且可以单独地和/或集体地从属并为所附权利要求范围内的特定实施方案提供足够支持。此外,对于定义或修改范围的语言,例如“至少”,“大于”,“小于”,“不超过”等等,应当理解,这种语言包括子范围和/或上限或下限。作为另一示例,“至少10”的范围固有地包括从至少10到35的子范围,从至少10到25的子范围,从25到35的子范围等等,并且每个子范围可以单独地和/或集体地从属,并且为所附权利要求范围内特定实施方案提供足够支持。最后,在所公开的范围内的单个数字可以从属,并且为所附权利要求范围内特定实施方案提供足够支持。例如,“从1到9”的范围包括各种单个整数,例如3,以及包括小数点(或分数),例如4.1的单个数字,可以从属并为所附权利要求范围内特定实施方案提供足够支持。
Claims (21)
1.一种制品,其具有0.03至0.45g/cc的密度并且包含在所述制品中随机取向的多个各向异性管状颗粒,其中所述管状颗粒包含热塑性弹性体泡沫和设置在所述热塑性弹性体泡沫外表面上作为所述管状颗粒的最外层的聚合物,其中所述热塑性弹性体泡沫和所述聚合物各自独立地具有根据DIN ISO 306测定的软化温度,并且其中所述聚合物的软化温度比所述热塑性弹性体泡沫的软化温度低至少5℃。
2.根据权利要求1的制品,其中所述热塑性弹性体泡沫是热塑性聚氨酯泡沫。
3.根据权利要求2的制品,其中所述热塑性聚氨酯泡沫是聚醚多元醇、异氰酸酯组分和增链剂的发泡反应产物。
4.根据权利要求2的制品,其中所述热塑性聚氨酯泡沫是聚酯多元醇、异氰酸酯组分和增链剂的发泡反应产物。
5.根据权利要求1-4中任一项的制品,其中所述热塑性弹性体泡沫由热塑性聚氨酯形成,所述热塑性聚氨酯具有使用DIN ISO 7619-1测定的40A至83D的硬度。
6.根据权利要求2的制品,其中所述热塑性聚氨酯泡沫是脂族和/或烯属多元醇、异氰酸酯组分和增链剂的发泡反应产物。
7.根据权利要求1-4中任一项的制品,其中所述热塑性弹性体泡沫由热塑性聚氨酯形成,其具有使用DIN ISO 7619-1测定的80A至95A的硬度。
8.根据权利要求1的制品,其中所述热塑性弹性体泡沫选自热塑性聚酯弹性体(TPE)、热塑性苯乙烯弹性体(TPS)、热塑性聚酰胺(TPA)、热塑性硫化橡胶(TPV)、热塑性聚烯烃(TPO)及其组合。
9.根据权利要求1-8中任一项的制品,其中所述热塑性弹性体泡沫具有0.1-0.6g/cc的密度。
10.根据权利要求1-9中任一项的制品,其具有使用ASTM D 5035测定的0.1至4.0兆帕的极限断裂强度。
11.根据权利要求1-10中任一项的制品,其中所述管状颗粒在多个点处熔合在一起。
12.根据权利要求1-11中任一项的制品,其中设置在所述热塑性弹性体泡沫外表面上的所述聚合物设置在所述热塑性弹性体泡沫上并与所述热塑性弹性体泡沫直接接触。
13.根据权利要求1-12中任一项的制品,还包括设置在设置在所述热塑性弹性体泡沫外表面上的所述聚合物与所述热塑性弹性体泡沫之间的中间聚合物。
14.根据权利要求1-13中任一项的制品,还包括设置在所述热塑性弹性体泡沫上且与所述热塑性弹性体泡沫直接接触的内部聚合物,使得所述热塑性弹性体泡沫设置在所述内部聚合物和设置在所述热塑性弹性体泡沫外表面上的所述聚合物之间。
15.根据权利要求1-14中任一项的制品,其中设置在所述热塑性弹性体泡沫外表面上的所述聚合物是发泡的。
16.根据权利要求1-14中任一项的制品,其中设置在所述热塑性弹性体泡沫外表面上的所述聚合物是非发泡的。
17.根据权利要求1-16中任一项的制品,其中设置在所述热塑性弹性体泡沫外表面上的所述聚合物进一步被定义为热塑性聚氨酯。
18.根据权利要求1-17中任一项的制品,其中所述管状颗粒各自独立地具有1至30mm的长度和1至30mm的直径。
19.根据权利要求1-18中任一项的制品,其进一步被定义为鞋底、垫、地板材料或地板基材。
20.一种形成密度为0.03至0.45g/cc的制品的方法,所述方法包括以下步骤:
A.提供各自独立地具有根据DIN ISO 306测定的软化温度的热塑性弹性体和聚合物,其中聚合物的软化温度比热塑性弹性体的软化温度低至少5℃;
B.将热塑性弹性体和聚合物共挤出以形成管状挤出物,其中热塑性弹性体在共挤出过程中发泡以形成热塑性弹性体泡沫,并且聚合物设置在热塑性弹性体泡沫外表面上作为管状挤出物的最外层;
C.将管状挤出物分段以形成多个各向异性管状颗粒,其包含热塑性弹性体泡沫和设置在热塑性弹性体泡沫外部作为管状颗粒的最外层的聚合物;
D.将多个各向异性管状颗粒设置在模具中;和
E.将多个各向异性管状颗粒加热以形成制品,使得多个各向异性管状颗粒在制品中随机取向。
21.根据权利要求20的方法,其中将模具加热的步骤进一步定义为蒸汽箱裂化模制。
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CN107636036B (zh) | 2021-02-23 |
BR112017024625A2 (pt) | 2018-07-31 |
RU2017144274A3 (zh) | 2019-11-19 |
KR102524875B1 (ko) | 2023-04-25 |
EP3298054B1 (en) | 2019-07-10 |
BR112017023125A2 (pt) | 2018-07-10 |
US20180072861A1 (en) | 2018-03-15 |
CN107636052A (zh) | 2018-01-26 |
KR20180008482A (ko) | 2018-01-24 |
ES2749655T3 (es) | 2020-03-23 |
PL3298055T3 (pl) | 2020-01-31 |
US10829608B2 (en) | 2020-11-10 |
US20180112053A1 (en) | 2018-04-26 |
WO2016187438A1 (en) | 2016-11-24 |
US10662309B2 (en) | 2020-05-26 |
ES2748810T3 (es) | 2020-03-18 |
CN107636052B (zh) | 2021-02-19 |
JP6865693B2 (ja) | 2021-04-28 |
RU2017144275A3 (zh) | 2019-06-19 |
WO2016187442A1 (en) | 2016-11-24 |
JP6861647B2 (ja) | 2021-04-21 |
JP2018517026A (ja) | 2018-06-28 |
PL3298054T3 (pl) | 2019-11-29 |
JP2018517027A (ja) | 2018-06-28 |
EP3298055B1 (en) | 2019-07-10 |
KR102524876B1 (ko) | 2023-04-25 |
RU2017144274A (ru) | 2019-06-19 |
RU2017144275A (ru) | 2019-06-19 |
KR20180008483A (ko) | 2018-01-24 |
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