CN110536913A - 弹性体、其制备方法及其用途 - Google Patents
弹性体、其制备方法及其用途 Download PDFInfo
- Publication number
- CN110536913A CN110536913A CN201780087084.9A CN201780087084A CN110536913A CN 110536913 A CN110536913 A CN 110536913A CN 201780087084 A CN201780087084 A CN 201780087084A CN 110536913 A CN110536913 A CN 110536913A
- Authority
- CN
- China
- Prior art keywords
- diisocyanate
- glycol
- elastomer
- polyurethane
- diamines
- 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
- 229920001971 elastomer Polymers 0.000 title claims abstract description 28
- 239000000806 elastomer Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims description 8
- 239000004814 polyurethane Substances 0.000 claims abstract description 51
- 229920002635 polyurethane Polymers 0.000 claims abstract description 47
- 150000002009 diols Chemical class 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 35
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 27
- 229920000098 polyolefin Polymers 0.000 claims abstract description 26
- 150000004985 diamines Chemical class 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 18
- 229920002396 Polyurea Polymers 0.000 claims abstract description 13
- 229920003226 polyurethane urea Polymers 0.000 claims abstract description 13
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 103
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 43
- 239000000203 mixture Substances 0.000 claims description 42
- 238000005984 hydrogenation reaction Methods 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 20
- 230000005855 radiation Effects 0.000 claims description 16
- -1 Butylene diamines Chemical class 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 15
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- IIGAAOXXRKTFAM-UHFFFAOYSA-N N=C=O.N=C=O.CC1=C(C)C(C)=C(C)C(C)=C1C Chemical compound N=C=O.N=C=O.CC1=C(C)C(C)=C(C)C(C)=C1C IIGAAOXXRKTFAM-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 8
- 239000002685 polymerization catalyst Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 7
- 239000005062 Polybutadiene Substances 0.000 claims description 7
- 229920002857 polybutadiene Polymers 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910000510 noble metal Inorganic materials 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 5
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 claims description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 5
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 229960005082 etohexadiol Drugs 0.000 claims description 5
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 229920002367 Polyisobutene Polymers 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- QVTWBMUAJHVAIJ-UHFFFAOYSA-N hexane-1,4-diol Chemical compound CCC(O)CCCO QVTWBMUAJHVAIJ-UHFFFAOYSA-N 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229960003511 macrogol Drugs 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims description 4
- 229920001083 polybutene Polymers 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N dodecahydrosqualene Natural products CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001195 polyisoprene Polymers 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 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 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims 3
- 125000000217 alkyl group Chemical group 0.000 claims 3
- HDONYZHVZVCMLR-UHFFFAOYSA-N N=C=O.N=C=O.CC1CCCCC1 Chemical class N=C=O.N=C=O.CC1CCCCC1 HDONYZHVZVCMLR-UHFFFAOYSA-N 0.000 claims 2
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 125000000753 cycloalkyl group Chemical group 0.000 claims 1
- 150000002083 enediols Chemical class 0.000 claims 1
- 239000006261 foam material Substances 0.000 claims 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims 1
- 229920001223 polyethylene glycol Polymers 0.000 claims 1
- 230000000717 retained effect Effects 0.000 claims 1
- 239000012948 isocyanate Substances 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- 150000002513 isocyanates Chemical class 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000001993 dienes Chemical class 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- 229920000515 polycarbonate Polymers 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- 125000000739 C2-C30 alkenyl group Chemical group 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical group NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004845 hydriding Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- UWJRJUDLJQOQSP-UHFFFAOYSA-N N=C=O.N=C=O.CC1=CC=CC(C)=C1C Chemical compound N=C=O.N=C=O.CC1=CC=CC(C)=C1C UWJRJUDLJQOQSP-UHFFFAOYSA-N 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical group [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000000655 anti-hydrolysis Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 230000003280 chronobiological effect Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- QPBQEXGQGCAOKS-UHFFFAOYSA-N cyclohexa-2,4-diene-1,1-diol Chemical compound OC1(O)CC=CC=C1 QPBQEXGQGCAOKS-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- JXCHMDATRWUOAP-UHFFFAOYSA-N diisocyanatomethylbenzene Chemical compound O=C=NC(N=C=O)C1=CC=CC=C1 JXCHMDATRWUOAP-UHFFFAOYSA-N 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- SVTBMSDMJJWYQN-UHFFFAOYSA-N hexylene glycol Natural products CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 1
- IHPDTPWNFBQHEB-UHFFFAOYSA-N hydrobenzoin Chemical compound C=1C=CC=CC=1C(O)C(O)C1=CC=CC=C1 IHPDTPWNFBQHEB-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N n-Butanol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
公开了分段式热塑性弹性体,其可以是聚氨酯、聚脲或聚氨酯‑脲,其包含软段和硬段,其中,软段由聚烯烃二醇或聚烯烃二胺制成,所述聚烯烃二醇或聚烯烃二胺的主链中可以具有0至1000个碳原子,其中,主链中的每个碳原子可以具有0至2个侧链,并且每个侧链可以具有0至30个碳原子,硬段由二异氰酸酯和增链剂制成,硬段占弹性体的10‑60%,而软段占剩余部分,弹性体的数均分子量是5×103‑1000×103克/摩尔;弹性体的极限伸长率是100‑1000%;杨氏模量是1‑3,000MPa;并且极限拉伸强度是10‑100MPa。还公开了用于制备所述分段式热塑性弹性体的方法及所述分段式热塑性弹性体的用途。
Description
技术领域
本发明属于大分子材料领域,涉及包含聚烯烃软段的聚氨酯。更具体地,本发明涉及聚氨酯、其制备方法及其用途。
背景技术
聚烯烃是一类聚合材料,其链具有软段和硬段。由于这一特殊的结构,聚氨酯材料具有许多优异的性质,例如抗低温、耐磨损、在生物环境中的稳定性高,因此其广泛用于航空产品、医疗装置、涂料、纺织品和皮革。目前,用于医疗装置的聚氨酯材料常具有以下结构:软段和硬段,所述软段由低聚多元醇形成,所述低聚多元醇例如聚四氢呋喃(PTMO)、聚二甲基硅氧烷(PDMS)或脂族聚碳酸酯,而所述硬段由二异氰酸酯[例如4,4’-二苯甲烷二异氰酸酯(MDI)或氢化MDI(HMDI)]和增链剂[例如1,4-丁二醇(BDO)]形成。然而,在长期的使用期间,聚醚型或聚碳酸酯型聚氨酯可通过氧化、水解或酶促反应而化学降解,这可导致材料失效,或者在某些条件下甚至使装置失效。例如,当聚醚型聚氨酯材料用于长期植入物时,其可氧化。在与组织接触的装置表面处常发生由炎性反应造成的氧化。这被称为环境应力开裂。在与某些金属表面(例如钴及其合金)接触的装置表面处所发生的氧化反应被称为金属离子诱导的氧化。
一般来说,醚键易氧化降解。不幸的是,在患者的生物体内存在氧化性化学物质。因此,解决这一问题的关键在于开发出由抗氧化反应比聚醚更强的软段所组成的聚氨酯材料。过去已经开发出了具有新型软段的多种聚氨酯,例如聚碳酸酯型聚氨酯[路博润公司(Lubrizol)的CarbothaneTM、DSM公司的BionateTM等)、PDMS聚氨酯(Biomerics公司的ElastEonTM、DSM公司的PursilTM等)等。这些新材料已经证明了具有改进的抗氧化降解性。然而,它们具有水解降解的问题。
最近,由聚异丁烯软段制成的聚氨酯材料显示出优异的抗氧化和水解降解性。然而,合成这种材料需要复杂的过程。以相当的成本生产商业规模的材料仍然是一个问题。在过去建议使用聚乙烯二醇[参考文献1:M.D.Benz,K.Bonnema,E.Didomenico,C.Hobot,D.Miller,“Medical devices constaining segmented polyurethane biomaterials”(含有分段式聚氨酯生物材料的医疗装置),US 6,915,168]。假设由聚乙烯段制成的聚氨酯会具有良好的抗氧化和水解反应。与聚异丁烯聚氨酯类似,聚乙烯聚氨酯的合成工艺仍存在技术挑战,这继续推迟了材料的商业化。
因此,仍需要开发用于生产聚烯烃二醇以制造聚氨酯材料的有效方法。
发明内容
本发明为一种有效的制备聚烯烃聚氨酯的方法。所述方法由两部分组成。第一部分是通过对二烯进行聚合随后氢化来制造聚烯烃二醇。第二部分是通过使用微波加热来制造聚氨酯材料。以这种方式制造的聚烯烃聚氨酯预计具有优异的性质以用于长期生物医学植入应用。
技术方案
本发明的目的可通过以下内容来实现:
{1}聚氨酯、聚脲或聚氨酯-脲弹性组合物可以定义为以下物质的反应产物:
1)大分子二醇或大分子二胺,包括氢化聚烯烃二醇、氢化聚烯烃二胺或者氢化聚烯烃二醇、氢化聚烯烃二胺、聚醚二醇和/或聚碳酸酯二醇的混合物,其中,聚烯烃二醇或聚烯烃二胺的主链中可以具有0至1000个碳原子,其中,主链中的每个碳原子可以具有0至2个侧链,并且每个侧链可以具有0至30个碳原子,
2)二异氰酸酯,和
3)增链剂;
{2}根据{1}所述的聚氨酯、聚脲或聚氨酯-脲弹性组合物,其特征在于,所述弹性组合物的数均分子量是5×103-1000×103克/摩尔;所述弹性组合物的极限伸长率是100-1000%;挠曲模量是1-3,000MPa;并且所述弹性组合物的极限拉伸强度是10-100MPa。
{3}根据{1}所述的聚氨酯、聚脲或聚氨酯-脲弹性组合物,其特征在于,所述大分子二醇优选地选自聚丁二烯二醇、聚异戊二烯二醇、聚丁烯二醇、聚乙烯二醇、聚丙烯二醇、聚(乙烯-丙烯)共聚物二醇、聚异丁烯二醇及其混合物;
所述二异氰酸酯选自甲苯-2,4-二异氰酸酯(TDI)、其异构体或其混合物;4,4’-二苯甲烷二异氰酸酯(MDI)、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、亚甲基双(环己基)二异氰酸酯(HMDI)、反-1,4-环己烷二异氰酸酯(CHDI)、对苯二异氰酸酯、赖氨酸二异氰酸酯、对苯二亚甲基二异氰酸酯、1,5-环戊烷二异氰酸酯、对四甲基二甲苯二异氰酸酯、间四甲基二甲苯二异氰酸酯及其混合物;其中,特别优选MDI;并且
增链剂选自乙二醇、1,3-丙二醇、1,4-丁二醇、1,4-己二醇、1,4-环己二醇、1,6-己二醇、1,8-辛二醇、1,9-壬二醇(nondadiol)、1,10-癸二醇、乙二胺、丙二胺、丁二胺、己二胺、环己二胺及其混合物;其中,特别优选1,4-丁二醇。
{4}根据{3}所述的聚氨酯、聚脲或聚氨酯-脲弹性组合物,其特征在于,所述大分子二醇是氢化聚丁二烯二醇或氢化聚异戊二烯二醇。
{5}一种用于制备聚氨酯、聚脲或聚氨酯-脲弹性组合物的方法,其包括以下步骤:
(i)制备具有不饱和键的二醇,随后对二醇进行氢化以获得氢化二醇,其中,所述二醇具有以下结构:
其中,n是1-1000的整数;并且R1和R2独立地为H、C1-30烷基、C3-30环烷基或C2-30烯基;
(ii)使用微波辐射,利用二异氰酸酯和聚合催化剂,对步骤(i)中获得的氢化二醇进行预聚合以获得聚氨酯预聚物;以及
(iii)将增链剂添加到聚氨酯预聚物中,并且使用微波辐射持续进行聚合以获得聚氨酯。
{6}根据{5}所述的方法,其特征在于,在步骤(i)中,将二醇和贵金属氢化催化剂添加到氢化反应器中以使二醇氢化。
{7}根据{6}所述的方法,其特征在于,反应温度是0-200℃,反应压力是0.1-100MPa,并且反应时间是1-24h;并且所述贵金属氢化催化剂是Pt族金属中的一种。
{8}根据{5}所述的方法,其特征在于,在步骤(ii)中,二异氰酸酯选自甲苯-2,4-二异氰酸酯(TDI)、其异构体或其混合物;4,4’-二苯甲烷二异氰酸酯(MDI)、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、亚甲基双(环己基)二异氰酸酯(HMDI)、反-1,4-环己烷二异氰酸酯(CHDI)、对苯二异氰酸酯、赖氨酸二异氰酸酯、对苯二亚甲基二异氰酸酯、1,5-环戊烷二异氰酸酯、对四甲基二甲苯二异氰酸酯、间四甲基二甲苯二异氰酸酯及其混合物;
聚合催化剂选自:三亚乙基二胺、二月桂酸二丁基锡、辛酸亚锡及其混合物;并且
预聚合温度是50-200℃,预聚合时间是1-5h;调整微波辐射功率以使温度保持在预计范围内,例如,对50mL至800mL的反应物混合物施加300-600W。
{9}根据{8}所述的方法,其特征在于,预聚合温度是65℃至95℃。
{10}根据{5}所述的方法,其特征在于,在步骤(iii)中,增链剂选自乙二醇、1,3-丙二醇、1,4-丁二醇、1,4-己二醇、1,4-环己二醇、1,6-己二醇、1,8-辛二醇、1,9-壬二醇、1,10-癸二醇、对二苯基乙二醇、松脂二甲醇(colophony dimethol)、乙二胺、丙二胺、丁二胺、己二胺、环己二胺及其混合物;并且
聚合温度是50-250℃,聚合时间是2-3h;调整微波辐射功率以使反应混合物的温度保持在预计范围内,例如,对50mL至800mL的反应物混合物施加300-600W。
{11}根据{10}所述的方法,其特征在于,预聚合温度是65℃至95℃。
{12}根据{5}所述的方法,其特征在于,在溶剂的存在下进行步骤(i)-(iii),其中,所述溶剂选自甲苯、二甲苯、四氢呋喃、氯仿、N,N-二甲基甲酰胺、乙酸乙酯、N,N-二甲基乙酰胺、二甲基亚砜及其混合物。
{13}一种用于制备相同的聚氨酯、聚脲或聚氨酯-脲弹性组合物的替代方法,其包括以下步骤:(1)通过对二烯进行聚合来制备不饱和二醇,(2)制备聚氨酯和(3)将聚合物氢化成饱和聚氨酯。
{14}根据{1}-{4}中任一项所述的聚氨酯在医疗装置、涂料、纤维、粘合剂或泡沫材料中的用途。
有益效果
本发明提供了一种生产方法,其为制备饱和聚乙烯二醇和其他聚烯烃二醇提供了可行的途径。该方法简单并且高效。特别地,相比于传统方法,可以更低的仪器成本、更短的反应时间、更高的产率、更少的副产物和更低的能耗来实现所述方法。其适于大规模连续生产。
用所述方法制造的产品可用于医疗装置、涂料、纤维、粘合剂或泡沫材料。
附图说明
图1示出了实施例1中的氢化前和氢化后的聚丁二醇的UV吸收光谱。
图2示出了实施例1中获得的聚氨酯的IR光谱。
具体实施方式
术语的定义
本申请中的术语定义如下:
聚合是一种或多种类型的许多单体之间的化学反应。该反应使得形成了长链分子。单体的反应基团化学连接在一起并变成不同基团。例如,一个单体的羟基与另一个单体的异氰酸酯可反应并形成氨基甲酸酯基团。氨基甲酸酯基团存在于聚合物链中并起到键合的作用。
二醇是具有两个羟基的有机化合物,所述羟基可与其他化合物的异氰酸酯基团反应。
二异氰酸酯是具有两个异氰酸酯基团的有机化合物,所述异氰酸酯基团可与羟基反应形成氨基甲酸酯基团。
增链剂是分子量小于200D并且具有两个可与异氰酸酯反应的羟基的化合物。增链剂也可以是二胺或者一端具有胺另一端具有羟基的化合物,例如4-氨基-1-丁醇。
催化剂是可加速反应但不是反应产物的一部分的化合物。
不饱和软段二醇是包含C=C双键或其他不饱和烃键的软段二醇。
氢化是通过加入氢原子将不饱和烃基转换成饱和基团的反应,例如将C=C转换成C-C。该反应通常需要氢气和催化剂。
聚氨酯预聚物是具有如下性质的聚合物:分子量为50D至10,000D并且在每个分子的末端具有两个异氰酸酯基团,该异氰酸酯基团可与增链剂反应形成氨基甲酸酯基团。
聚氨酯是通过二醇与二异氰酸酯化合物之间的反应所形成的聚合物。所形成的氨基甲酸酯基团是单体之间的键合物。
支链是作为侧基化学连接到主链结构的化学基团。聚合物链可具有1个或超过1个支链。支链可以相同或不同。支链的一些实例是甲基、乙基、丙基、丁基、异丁基等。
微波辐射反应器是一种化学反应器,在该反应器中可在微波辐射下进行反应。通常的微波辐射反应器具有非接触式红外温度传感器,其可用于监测反应混合物的温度并根据实时情况控制温度。
在一个实施方式中,上述聚氨酯可以下述方式以两步来制造。
在第一步中,制造具有以下结构的二醇:
其中,n是1-1000的整数;R1和R2独立地为H、C1-30烷基、C3-30环烷基或C2-30烯基。
为了获得第一步中的结构,选择适当的二烯单体或适当的二烯单体组。二烯单体单独聚合或与其他烯单体共聚,对于这两种情况,使用过氧化氢作为催化剂。二烯包括但不限于丁二烯、异戊二烯等。烯单体包括但不限于乙烯、丙烯、丁烯、异丁烯及其组合。通过调整总的双键与过氧化氢的比值可控制聚二烯的分子量。也可通过阴离子聚合、活性自由基聚合和/或其他聚合反应并随后用羟基终止两个链端形成二醇结构来制造聚二烯。
在第二步中,将第一步中制得的结构(I)氢化成以下饱和二醇(II):
其中,n是1-1000的整数;R3和R4独立地为H、C1-30烷基或C3-30环烷基。
结构(II)的二醇是氢化聚乙烯二醇、氢化聚丙烯二醇、氢化聚丁烯二醇、氢化聚丁二烯二醇、氢化聚戊烯二醇、氢化聚(4-甲基-1-戊烯)二醇、氢化聚己烯二醇、氢化聚(乙烯-丙烯)共聚物二醇或者氢化聚异丁烯二醇。
在制备聚氨酯期间,先去除水和/或其他杂质再进行氢化,以避免氢化催化剂中毒。本领域技术人员应知晓去除杂质的方法。一种方法可以是一边加热混合物一边施加真空,进行适当的持续时间。
在第一个方面中,本发明提供了由软段二醇或二胺制成的聚氨酯、聚脲或聚氨酯-脲弹性体,所述软段二醇或二胺包括但不限于氢化聚烯烃二醇、氢化聚烯烃二胺或者氢化聚烯烃二醇、氢化聚烯烃二胺、聚醚二醇和/或聚碳酸酯二醇的混合物。聚烯烃二醇或聚烯烃二胺的主链中可以具有0至1000个碳原子,其中,主链中的每个碳原子可以具有0至2个侧链,并且每个侧链可以具有0至30个碳原子。
在本发明中,弹性体的数均分子量是5×103-1,000×103克/摩尔,优选100×103-600×103克/摩尔;弹性体的极限伸长率是100-1000%;杨氏模量是1-3,000MPa;并且弹性体的极限拉伸强度是10-100MPa。
在第二方面中,本发明提供了制备上述聚氨酯的方法,所述方法包括以下步骤:
(i)对二醇进行氢化以获得氢化二醇;
(ii)使用微波辐射,利用二异氰酸酯和聚合催化剂,对步骤(i)中获得的氢化二醇进行预聚合以获得聚氨酯预聚物;以及
(iii)将增链剂添加到聚氨酯预聚物中,并且使用微波辐射持续进行聚合以获得聚氨酯。
在本发明中,在步骤(i)中,将二醇和溶剂添加到反应器(例如氢化反应器)中;待二醇溶解后,将贵金属氢化催化剂和氢气添加到反应器中;将温度和压力控制在预计范围内并使反应继续直到反应完成;以及分离、纯化并干燥氢化二醇。
在本发明中,在步骤(i)中,氢化反应器的体积是1-3L,反应温度是0-200℃,优选50-150℃,反应压力是0.1-100MPa,反应时间是1-24h;并且所述贵金属氢化催化剂是Pt族金属(即,Ru、Rh、Pd、Os、Ir和Pt)载体催化剂中的一种。
在本发明中,在步骤(ii)中,在进行预聚合之前,在真空中对步骤(i)中获得的氢化软段进行加热和脱水,其中,加热和脱水的温度是80-120℃,并且加热和脱水的时间是1-6h。
在本发明中,在步骤(ii)中,二异氰酸酯选自甲苯-2,4-二异氰酸酯(TDI)、其异构体或其混合物;4,4’-二苯甲烷二异氰酸酯(MDI)、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、亚甲基双(环己基)二异氰酸酯(HMDI)、反-1,4-环己烷二异氰酸酯(CHDI)、对苯二异氰酸酯、赖氨酸二异氰酸酯、对苯二亚甲基二异氰酸酯、1,5-环戊烷二异氰酸酯、对四甲基二甲苯二异氰酸酯、间四甲基二甲苯二异氰酸酯及其混合物。
在本发明中,在步骤(ii)中,聚合催化剂选自:三亚乙基二胺、二月桂酸二丁基锡、辛酸亚锡及其混合物。
在本发明中,在步骤(ii)中,预聚合的温度是50-200℃,优选65-95℃,并且预聚合的时间是1-5h。
在本发明中,在步骤(ii)中,对于10mL至2L的反应物混合物,微波辐射功率是100-800W。
在本发明中,在步骤(iii)中,增链剂选自乙二醇、1,3-丙二醇、1,4-丁二醇、1,4-己二醇、1,4-环己二醇、1,6-己二醇、1,8-辛二醇、1,9-壬二醇、1,10-癸二醇、对二苯基乙二醇、松脂二甲醇(colophony dimethol)、乙二胺、丙二胺、丁二胺、己二胺、环己二胺及其混合物;
在本发明中,在步骤(iii)中,聚合的温度是50-250℃,并且聚合的时间是1-5h,优选2-3h。
在本发明中,在溶剂的存在下进行步骤(i)-(iii),其中,所述溶剂选自甲苯、二甲苯、四氢呋喃、氯仿、N,N-二甲基甲酰胺、乙酸乙酯、N,N-二甲基乙酰胺、二甲基亚砜及其混合物。
实施例
下文给出实施例以具体描述本发明,然而,本发明不限于下文所述的实施例。在以下的实施例中,在所有情况中,量值或量的比值是基于重量计。
实施例1:制备氢化二醇
将50g聚丁二烯二醇和600mL THF添加到氢化釜中;待聚丁二烯二醇溶解后,将12g的Pt氢化催化剂和氢气添加到氢化釜中;将温度控制在60℃并将压力控制在2MPa,继续反应20小时直到反应完成;分离、纯化并干燥所获得的氢化二醇。
实施例2:
过程:
在100mL的玻璃反应器中加入30mL甲苯和3.7g氢化聚丁二烯二醇(H-HTPB)。搅拌混合物直到H-HTPB溶解在甲苯中。然后加入1.5g 4,4’-二苯甲烷二异氰酸酯,随后加入40μL二月桂酸二丁基锡催化剂。接着利用微波辐射(400W)加热反应混合物以将其温度保持在65℃,同时进行搅拌。反应2小时后,0.36g增链剂BDO(根据滴定的异氰酸酯的量来计算,以使OH的总摩尔与异氰酸酯的相同);然后通过将微波功率增大到500W来将温度升高到80℃。使反应再继续2小时。基于FI-IR测试,当异氰酸酯完全反应时,终止反应。将反应溶液倒到甲醇中以使聚合物产物沉淀。将混合物放置在冰箱中24小时。通过离心混合物获得固体聚合物产物。在真空炉中干燥产物24小时。
结果:
反应的收率为75%。用凝胶渗透色谱法(GPC)测得数均分子量Mn=30×103克/摩尔,并且重均分子量Mw=50×103克/摩尔。
图1示出了在氢化之前和氢化之后的聚丁二醇UV吸收光谱。氢化后,HTPB的双键在288nm的特征吸收峰消失,表明HTPB中的全部双键均被氢化。
图2示出了得到的聚氨酯的IR光谱。异氰酸酯基团–NCO在2,270cm-1处的特征峰消失,表明全部的残余异氰酸酯基团在最后一步中均反应掉。3,327cm-1和1,538cm-1处的峰指示氨基甲酸酯基团的–NH–,并且1,710cm-1处的峰指示氨基甲酸酯基团的–C=O。这两组峰提示形成了氨基甲酸酯。
实施例3
过程:
在100mL玻璃反应器中加入30mL甲苯并加热到65℃。在反应器中加入3.7g氢化聚丁二烯二醇(H-HTPB)。搅拌混合物直到H-HTPB溶解在甲苯中。然后加入1.5g 4,4’-二苯甲烷二异氰酸酯,随后加入40μL二月桂酸二丁基锡催化剂。用常规加热器加热反应混合物以将其温度保持在65℃,同时搅拌。反应5小时后,0.36g增链剂BDO(根据滴定的异氰酸酯的量来计算,以使OH的总摩尔与异氰酸酯的相同);然后通过增大加热功率来将温度升高到80℃。使反应再继续5小时。基于FI-IR测试,当异氰酸酯完全反应时,终止反应。将反应溶液倒到甲醇中以使聚合物产物沉淀。将混合物放置在冰箱中24小时。通过离心混合物获得固体聚合物产物。在真空炉中干燥产物24小时。
结果:
反应的收率是70%,用凝胶渗透色谱法(GPC)测得数均分子量Mn=15×103克/摩尔,并且重均分子量Mw=30×103克/摩尔。
实施例4:机械测试(GB/T 528-2009)
测试条件:
仪器:英斯特朗(Instron)5567电子万能测试机(美国英斯特朗公司);
标距长度:50mm;十字头速度:5mm min-1。35mm×2mm×0.5mm的试样用于该评估。
出于精确,从至少五个试样的平均值获取数据。
结果:
聚氨酯的机械性质包括下述:
在实施例2中,聚氨酯的极限伸长率是500%;杨氏模量是380MPa;并且极限拉伸强度是33MPa。
在实施例3中,聚氨酯的极限伸长率是70%;杨氏模量是25MPa;并且极限拉伸强度是10MPa。
工业适用性
在本发明中,在微波辐射下合成聚烯烃聚氨酯的时间不超过5h,而传统加热方式的反应时间约为10h。微波辐射显著地缩短了反应时间,并且降低了能耗,从而为合成聚烯烃聚氨酯提供了高效且环境友好的途径。工业适用性几乎涵盖了聚烯烃聚氨酯的所有潜在用途,尤其是用于医疗装置、涂料、纤维、粘合剂或泡沫材料。
Claims (19)
1.一种分段式热塑性弹性体,其可以是聚氨酯、聚脲或聚氨酯-脲,其由软段和硬段组成,其中
软段由聚烯烃二醇或聚烯烃二胺制成,所述聚烯烃二醇或聚烯烃二胺的主链中可以具有0至1000个碳原子,其中,主链中的每个碳原子可以具有0至2个侧链,并且每个侧链可以具有0至30个碳原子,
硬段由二异氰酸酯和增链剂制成,
硬段占弹性体的10-60%,而软段占剩余部分,
弹性体的数均分子量是5×103-1000×103克/摩尔;弹性体的极限伸长率是100-1000%;杨氏模量是1-3,000MPa;并且极限拉伸强度是10-100MPa。
2.根据权利要求1所述的弹性体,其特征在于,数均分子量是10×103-300×103克/摩尔;极限伸长率是200-700%;杨氏模量是10-2,000MPa;并且极限拉伸强度是10-100MPa。
3.根据权利要求1所述的弹性体,其中,软段由以下物质形成:聚丁二烯二醇、聚异戊二烯二醇、聚丁烯二醇、聚乙烯二醇、聚丙烯二醇、聚(乙烯-丙烯)共聚物二醇、聚异丁烯二醇、支化聚乙烯二醇、聚丁烯二胺、聚乙烯二胺、聚丙烯二胺、聚(乙烯-丙烯)共聚物二胺、聚异丁烯二胺、支化聚乙烯二胺及其混合物。
4.根据权利要求1所述的弹性体,其中,二异氰酸酯选自甲苯-2,4-二异氰酸酯、其异构体或其混合物;4,4’-二苯甲烷二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、4,4’-二(环己基)甲烷二异氰酸酯、亚甲基双(环己基)二异氰酸酯、反-1,4-环己烷二异氰酸酯、对苯二异氰酸酯、赖氨酸二异氰酸酯、对苯二亚甲基二异氰酸酯、1,5-环戊烷二异氰酸酯、对四甲基二甲苯二异氰酸酯、间四甲基二甲苯二异氰酸酯及其混合物。
5.根据权利要求1所述的弹性体,其中,增链剂选自乙二醇、1,3-丙二醇、1,4-丁二醇、1,4-己二醇、1,4-环己二醇、1,6-己二醇、1,8-辛二醇、1,9-壬二醇、1,10-癸二醇、乙二胺、丙二胺、丁二胺、己二胺、环己二胺及其混合物。
6.如权利要求3所述的弹性体,其特征在于,软段是氢化聚丁二烯二醇。
7.根据权利要求3所述的弹性体,其特征在于,软段是氢化聚异戊二烯二醇。
8.一种制备弹性体的方法,所述方法包括以下步骤:
(i)制备具有不饱和键的二醇,随后氢化该二醇以获得氢化二醇,其中,二醇的主链中具有1至1000个碳原子,其中,主链中的每个碳原子具有0至2个侧链,并且每个侧链具有0至30个碳原子,所述侧链是烷基或环烷基;
(ii)使用微波辐射,利用二异氰酸酯和聚合催化剂,对步骤(i)中获得的氢化二醇进行预聚合以获得聚氨酯预聚物;以及
(iii)将增链剂添加到聚氨酯预聚物中,并且使用微波辐射持续进行聚合以获得聚氨酯。
9.根据权利要求8所述的方法,其特征在于,在步骤(i)中,将二醇和贵金属氢化催化剂添加到氢化反应器中以使二醇氢化。
10.根据权利要求9所述的方法,其特征在于,反应温度是0-200℃,反应压力是0.1-100MPa,并且反应时间是1-24h;并且所述贵金属氢化催化剂是Pt族金属中的一种。
11.根据权利要求8所述的方法,其特征在于,在步骤(ii)中,二异氰酸酯选自甲苯-2,4-二异氰酸酯、其异构体或其混合物;4,4’-二苯甲烷二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、4,4’-二(环己基)甲烷二异氰酸酯、亚甲基双(环己基)二异氰酸酯、反-1,4-环己烷二异氰酸酯、对苯二异氰酸酯、赖氨酸二异氰酸酯、对苯二亚甲基二异氰酸酯、1,5-环戊烷二异氰酸酯、对四甲基二甲苯二异氰酸酯、间四甲基二甲苯二异氰酸酯及其混合物;
聚合催化剂选自:三亚乙基二胺、二月桂酸二丁基锡、辛酸亚锡及其混合物;并且
预聚合温度是50-200℃,预聚合时间是1-5h;调整微波辐射功率以使反应温度保持在预计范围内。
12.根据权利要求11所述的方法,其特征在于,预聚合温度是65℃至95℃。
13.根据权利要求8所述的方法,其特征在于,在步骤(iii)中,增链剂选自乙二醇、1,3-丙二醇、1,4-丁二醇、1,4-己二醇、1,4-环己二醇、1,6-己二醇、1,8-辛二醇、1,9-壬二醇、1,10-癸二醇、乙二胺、丙二胺、丁二胺、己二胺、环己二胺及其混合物;并且
聚合温度是50-250℃,聚合时间是1-5h;并且调整微波辐射功率以使反应混合物的温度可保持在预计范围内。
14.根据权利要求12所述的方法,其特征在于,预聚合温度是65℃至95℃。
15.根据权利要求8所述的方法,其特征在于,在溶剂的存在下进行步骤(i)-(iii),其中,所述溶剂选自甲苯、二甲苯、四氢呋喃、氯仿、N,N-二甲基甲酰胺、乙酸乙酯、N,N-二甲基乙酰胺、二甲基亚砜及其混合物。
16.一种制备弹性体的方法,所述方法包括以下步骤:
(i)制备具有不饱和键的二醇和/或二胺,随后氢化该二醇和/或二胺以获得氢化二醇和/或二胺,其中,二醇和/或二胺的主链中具有1至1000个碳原子,其中,其中,主链中的每个碳原子具有0至2个侧链,并且每个侧链具有0至30个碳原子,其中,所述侧链是烷基或环烷基;
(ii)使用微波辐射,利用二异氰酸酯和聚合催化剂,对步骤(i)中获得的氢化二醇、二胺或其混合物进行预聚合以获得预聚物;以及
(iii)将增链剂添加到预聚物中,并且使用微波辐射持续进行聚合以获得弹性体。
17.一种制备弹性体的方法,所述方法包括以下步骤:
(i)制备具有不饱和键的二醇或二胺;
(ii)使用微波辐射,利用二异氰酸酯和聚合催化剂,对步骤(i)中获得二醇或二胺进行预聚合以获得聚氨酯或聚脲预聚物;以及
(iii)将增链剂添加到聚氨酯或聚脲预聚物中,并且使用微波辐射持续进行聚合以获得聚氨酯或聚脲;以及
(iv)在催化剂的存在下氢化聚氨酯或聚脲。
18.根据权利要求1-7中任一项所述的聚氨酯在医疗装置、涂料、纤维、粘合剂或泡沫材料中的用途。
19.一种医疗装置,其包括如权利要求1所述的弹性体。
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