CN116917365A - 减轻聚合物材料腐蚀的聚氨酯泡沫 - Google Patents
减轻聚合物材料腐蚀的聚氨酯泡沫 Download PDFInfo
- Publication number
- CN116917365A CN116917365A CN202280013063.3A CN202280013063A CN116917365A CN 116917365 A CN116917365 A CN 116917365A CN 202280013063 A CN202280013063 A CN 202280013063A CN 116917365 A CN116917365 A CN 116917365A
- Authority
- CN
- China
- Prior art keywords
- anhydride
- polyurethane foam
- isocyanate
- component
- diisocyanate
- 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.)
- Pending
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- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 78
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 66
- 230000007797 corrosion Effects 0.000 title claims abstract description 35
- 238000005260 corrosion Methods 0.000 title claims abstract description 35
- 239000000463 material Substances 0.000 title claims abstract description 35
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 239000012948 isocyanate Substances 0.000 claims abstract description 24
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 20
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 20
- 239000011541 reaction mixture Substances 0.000 claims abstract description 17
- 239000004604 Blowing Agent Substances 0.000 claims abstract description 14
- 239000004970 Chain extender Substances 0.000 claims abstract description 13
- 239000000654 additive Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229920005862 polyol Polymers 0.000 claims description 33
- 150000003077 polyols Chemical class 0.000 claims description 33
- 239000004417 polycarbonate Substances 0.000 claims description 31
- 229920000515 polycarbonate Polymers 0.000 claims description 31
- -1 decyl anhydride Chemical class 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 12
- 150000001412 amines Chemical class 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 229920000570 polyether Polymers 0.000 claims description 12
- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical group CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-N 0.000 claims description 11
- 150000008065 acid anhydrides Chemical class 0.000 claims description 11
- 125000001931 aliphatic group Chemical group 0.000 claims description 11
- 239000004088 foaming agent Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 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 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 9
- FGQUIQAGZLBOGL-UHFFFAOYSA-N 3-non-1-enyloxolane-2,5-dione Chemical compound CCCCCCCC=CC1CC(=O)OC1=O FGQUIQAGZLBOGL-UHFFFAOYSA-N 0.000 claims description 8
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- 229920000728 polyester Polymers 0.000 claims description 6
- 229920005906 polyester polyol Polymers 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- HMMBJOWWRLZEMI-UHFFFAOYSA-N 4,5,6,7-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CCCC2=C1C(=O)OC2=O HMMBJOWWRLZEMI-UHFFFAOYSA-N 0.000 claims description 3
- MGICRVTUCPFQQZ-UHFFFAOYSA-N 4-methyloxane-2,6-dione Chemical compound CC1CC(=O)OC(=O)C1 MGICRVTUCPFQQZ-UHFFFAOYSA-N 0.000 claims description 3
- GRSMWKLPSNHDHA-UHFFFAOYSA-N Naphthalic anhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=CC3=C1 GRSMWKLPSNHDHA-UHFFFAOYSA-N 0.000 claims description 3
- VJDDQSBNUHLBTD-GGWOSOGESA-N [(e)-but-2-enoyl] (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(=O)\C=C\C VJDDQSBNUHLBTD-GGWOSOGESA-N 0.000 claims description 3
- 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 3
- VJDDQSBNUHLBTD-UHFFFAOYSA-N trans-crotonic acid-anhydride Natural products CC=CC(=O)OC(=O)C=CC VJDDQSBNUHLBTD-UHFFFAOYSA-N 0.000 claims description 3
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 3
- 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 claims 1
- YIDSTEJLDQMWBR-UHFFFAOYSA-N 1-isocyanatododecane Chemical compound CCCCCCCCCCCCN=C=O YIDSTEJLDQMWBR-UHFFFAOYSA-N 0.000 claims 1
- QWDQYHPOSSHSAW-UHFFFAOYSA-N 1-isocyanatooctadecane Chemical compound CCCCCCCCCCCCCCCCCCN=C=O QWDQYHPOSSHSAW-UHFFFAOYSA-N 0.000 claims 1
- DYQFCTCUULUMTQ-UHFFFAOYSA-N 1-isocyanatooctane Chemical compound CCCCCCCCN=C=O DYQFCTCUULUMTQ-UHFFFAOYSA-N 0.000 claims 1
- BHDCTKUOBUNTTP-UHFFFAOYSA-N 3-(isocyanatomethyl)heptane Chemical compound CCCCC(CC)CN=C=O BHDCTKUOBUNTTP-UHFFFAOYSA-N 0.000 claims 1
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 claims 1
- ANJPRQPHZGHVQB-UHFFFAOYSA-N hexyl isocyanate Chemical compound CCCCCCN=C=O ANJPRQPHZGHVQB-UHFFFAOYSA-N 0.000 claims 1
- YDNLNVZZTACNJX-UHFFFAOYSA-N isocyanatomethylbenzene Chemical compound O=C=NCC1=CC=CC=C1 YDNLNVZZTACNJX-UHFFFAOYSA-N 0.000 claims 1
- 239000004971 Cross linker Substances 0.000 abstract description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 21
- 239000004814 polyurethane Substances 0.000 description 16
- 229920002635 polyurethane Polymers 0.000 description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 239000006260 foam Substances 0.000 description 11
- 239000003063 flame retardant Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 239000007858 starting material Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 150000002191 fatty alcohols Chemical class 0.000 description 4
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000004072 triols Chemical class 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 3
- 229940035437 1,3-propanediol Drugs 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000004359 castor oil Substances 0.000 description 3
- 235000019438 castor oil Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004872 foam stabilizing agent Substances 0.000 description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000012766 organic filler Substances 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 125000001302 tertiary amino group Chemical group 0.000 description 3
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- FCQPNTOQFPJCMF-UHFFFAOYSA-N 1,3-bis[3-(dimethylamino)propyl]urea Chemical compound CN(C)CCCNC(=O)NCCCN(C)C FCQPNTOQFPJCMF-UHFFFAOYSA-N 0.000 description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- PGZVFRAEAAXREB-UHFFFAOYSA-N 2,2-dimethylpropanoyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC(=O)C(C)(C)C PGZVFRAEAAXREB-UHFFFAOYSA-N 0.000 description 2
- GXVUZYLYWKWJIM-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanamine Chemical compound NCCOCCN GXVUZYLYWKWJIM-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- OHKOAJUTRVTYSW-UHFFFAOYSA-N 2-[(2-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC=C1CC1=CC=CC=C1N OHKOAJUTRVTYSW-UHFFFAOYSA-N 0.000 description 2
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
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- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
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- 239000002253 acid Substances 0.000 description 2
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- 230000032683 aging Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
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- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
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- 150000003254 radicals Chemical class 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 150000003335 secondary amines Chemical group 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- NGEZPLCPKXKLQQ-VOTSOKGWSA-N (e)-4-(3-methoxyphenyl)but-3-en-2-one Chemical compound COC1=CC=CC(\C=C\C(C)=O)=C1 NGEZPLCPKXKLQQ-VOTSOKGWSA-N 0.000 description 1
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 1
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Abstract
本发明涉及可用于减轻或防止聚合物材料腐蚀的聚氨酯泡沫,其可通过以下方式得到:混合组分(a)至少一种多异氰酸酯、(b)至少一种具有至少两个对异氰酸酯有反应性的基团的化合物、(c)任选地扩链剂和/或交联剂、(d)发泡剂、(e)催化剂、(f)任选地助剂和添加剂,以及(g)至少一种酸酐来得到反应混合物,并固化所述反应混合物以得到聚氨酯泡沫,其中,基于组分(a)的重量计,以0.05wt%至5wt%的量添加酸酐。本发明还涉及通过上述聚氨酯泡沫减轻或防止聚合物材料腐蚀的方法,以及这种聚氨酯泡沫在某些应用中,例如在汽车内饰中,的用途。
Description
技术领域
本发明涉及可用于减轻或防止聚合物材料腐蚀的聚氨酯泡沫。本发明还涉及通过上述聚氨酯泡沫减轻或防止聚合物材料腐蚀的方法,及这种聚氨酯泡沫在某些应用中,例如在汽车内饰中的用途。
背景技术
聚氨酯泡沫适用于大量的应用,例如缓冲材料、隔热材料、包装材料、汽车仪表盘或建筑材料。聚氨酯泡沫,例如,当用于汽车内饰时,可应用于构成方向盘、音响系统、座椅、装饰板等部件。在这些应用中,聚氨酯泡沫经常与其他材料接触,如聚酯或聚碳酸酯(PC)。在制备聚氨酯泡沫时使用的某些成分或反应物可能作为残留物存在于最终的泡沫产品中,并且在实际使用中不可避免地泄漏到环境中。一些胺类化合物(例如,可以用作制备聚氨酯的催化剂),经常从泡沫中泄漏出来,并渗透到邻接的聚酯或聚碳酸酯中。这些胺类化合物可能对这些聚合物材料具有催化作用,从而引起其腐蚀或降解。这些聚合物材料的腐蚀或降解导致汽车零部件变色、开裂甚至功能异常。
因此,在本技术领域中需要制备新的聚氨酯泡沫,当在某些应用中与聚合物材料一起使用时,该泡沫大幅减轻聚合物材料的腐蚀或降解。这种需求到目前为止还没有得到满足。
发明内容
本发明的目的之一是提供在一起使用时可以减轻或防止聚合物材料腐蚀或降解的聚氨酯泡沫。这个目的由通过如下方式可获得或获得的聚氨酯泡沫来实现:混合以下组分以形成反应混合物:
(a)至少一种多异氰酸酯
(b)至少一种具有至少两个对异氰酸酯有反应性的氢原子的化合物,
(c)任选地扩链剂和/或交联剂,
(d)发泡剂,
(e)催化剂,
(f)任选地助剂和添加剂,以及
(g)至少一种酸酐,
并使所述反应混合物反应生成聚氨酯泡沫,其中,基于组分(a)的重量计,以0.05wt%至5wt%的量加入酸酐。
在一种实施方案中,基于组分(a)的重量计,以0.1wt%至3wt%,优选0.25wt%至2wt%的量加入酸酐。
在一种实施方案中,酸酐选自可以分散或溶解在异氰酸酯中的线性或环状、饱和或不饱和、芳香族或脂肪族的C4-C24羧酸酐或C4-C24二羧酸酐。
在另一种实施方案中,所述酸酐选自线性或环状C4-C24烯基琥珀酸酐,包括但不限于十二烯基琥珀酸酐、壬烯基琥珀酸酐;甲基降冰片烯-2,3-二羧酸酐;2,2-二甲基戊二酸酐;1,8-萘二甲酸酐;3,4,5,6-四氢邻苯二甲酸酐;3-甲基戊二酸酐;癸酸酐;巴豆酸酐。
在一种实施方案中,通过将包含(b)、任选地(c)、(d)、(e)和任选地(f)的组分(A)与包含(a)和(g)的组分(B)混合以产生反应混合物,并使所述反应混合物发生反应来制备聚氨酯泡沫。
在另一种实施方案中,发泡剂包括水或仅为水。
在另一种实施方案中,催化剂包括胺基催化剂。
本发明还涉及一种减轻聚合物材料腐蚀的方法,其包括使聚合物材料与根据本发明的聚氨酯泡沫接触。
本发明另外涉及所述聚氨酯泡沫用于减轻聚合物材料腐蚀的的用途。
与传统的聚氨酯泡沫相比,本发明的聚氨酯泡沫在例如汽车内饰(如方向盘、座椅、装饰板等)中可以直接与聚合物材料如聚碳酸酯或其他聚酯(PBT、PET等)接触,并且令人惊讶地发现从聚合物材料的表面可以看到显著减少的——甚至没有——腐蚀或降解。
附图说明
图1示出了PC板在与聚氨酯泡沫接触之前,在120℃烘箱中加热7天的照片。
图2示出了PC板在与不含酸酐或含0.5份壬烯基琥珀酸酐的聚氨酯泡沫接触之后,在120℃烘箱中加热7天的照片。
图3示出了PC板与包含不同含量壬烯基琥珀酸酐的聚氨酯泡沫接触后的照片。
图4示出了PET板与无酸酐(左)和由0.5%的DDSA(右)制备的聚氨酯泡沫接触后的照片。
图5示出了使用马赛克滤镜对图4中的照片进行Photoshop分析,以显示发黄面积的百分比。
具体实施方式
除非另有定义,本文使用的所有技术和科学术语具有本发明所属领域技术人员通常理解的含义。如本文所用,下列术语具有下文赋予它们的含义,除非另有说明。
如本文所用,冠词“一个(a)”和“一个(an)”是指一个或多个(即至少一个)该冠词的语法宾语。举例来说,“一个元素”是指一个元素或一个以上的元素。
如本文所用,术语“约”应理解为本领域普通技术人员在实现相同功能或结果的上下文中认为等同于所述值的数字范围。
如本文所用,术语“添加剂”是指包括在配方体系中以增强其物理或化学性质并提供预期结果的添加剂。这些添加剂包括但不限于染料、颜料、增韧剂、冲击改性剂、流变改性剂、增塑剂、触变剂、天然或合成橡胶、填充剂、增强剂、增稠剂、抑制剂、荧光或其他标记物、热降解还原剂、耐热性赋予剂、表面活性剂、润湿剂、消泡剂、分散剂、助流或助滑剂、杀虫剂和稳定剂。
除非另有说明,所有百分比(%)均为“重量百分比”。
上述在一般术语或优先领域内给出的基本定义或说明适用于最终产品,并相应地适用于原料和中间体。这些基本定义可以按需要彼此组合,即包括一般定义和/或各自的优选范围和/或实施方案之间的组合。
本文公开的所有实施方案和优选实施方案可以按需要组合,它们也被视为涵盖在本发明的范围内。
除非另有说明,温度是指室温,压力是指环境压力。
除非另有说明,溶剂是指本领域普通技术人员已知的所有有机和无机溶剂,并且不包括任何类型的单体分子。
本发明涉及聚氨酯泡沫,其可通过如下制备:混合以下组分以形成反应混合物:
(a)至少一种多异氰酸酯,
(b)至少一种具有至少两个对异氰酸酯有反应性的氢原子的化合物,
(c)任选地扩链剂和/或交联剂,
(d)发泡剂,
(e)催化剂,
(f)任选地助剂和添加剂,以及
(g)至少一种酸酐,
并使所述反应混合物反应生成聚氨酯泡沫,其中,基于组分(a)的重量计,以0.05wt%至5wt%的量加入酸酐。
(a)多异氰酸酯
用于制备根据本发明的聚氨酯泡沫的多异氰酸酯(a)包括所有已知用于制备聚氨酯的多异氰酸酯。这些多异氰酸酯包括从现有技术中已知的脂肪族、脂环族和芳香族二价或多价异氰酸酯及其任何所需混合物。使用的脂肪族二异氰酸酯是常规的脂肪族和/或脂环族二异氰酸酯,例如三、四、五、六、七和/或八亚甲基二异氰酸酯、2-甲基五亚甲基-1,5-二异氰酸酯、2-乙基四亚甲基-1,4-二异氰酸酯、六亚甲基-1,6-二异氰酸酯(HDI)、五亚甲基-1,5-二异氰酸酯、丁烯-1,4-二异氰酸酯、三甲基六亚甲基-1,6-二异氰酸酯、1-异氰酸酯基-3,3,5-三甲基-5-异氰酸酯基甲基环己烷(异氟尔酮二异氰酸酯,IPDI)、1,4-和/或1,3-双(异氰酸酯基甲基)环己烷(HXDI)、1,4-二异氰酸酯环己烷、1-甲基-2,4-和/或-2,6-二异氰酸酯环己烷、亚甲基-4,4'-、-2,4'-和/或-2,2'-二异氰酸酯(H12MDI)。合适的芳香族二异氰酸酯特别是亚萘基-1,5-二异氰酸酯(NDI)、甲苯-2,4-和/或-2,6-二异氰酸酯(TDI)、3,3'-二甲基-4,4'-二异氰酸酯(TODI)、对苯二异氰酸酯(PDI)、4,4'-二苯乙烷二异氰酸酯(EDI)、二苯甲烷二异氰酸酯、3,3'-二苯基联苯二异氰酸酯、1,2-二苯乙烷二异氰酸酯和/或二苯甲烷二异氰酸酯(MDI)。
本文优选使用的多异氰酸酯(a)是工业上容易获得的芳香族多异氰酸酯,特别优选二苯甲烷二异氰酸酯(MDI)和多苯基多亚甲基多异氰酸酯的混合物。
多异氰酸酯(a)也可以以多异氰酸酯预聚物的形式使用。这些多异氰酸酯预聚物可通过将过量的上述多异氰酸酯(成分(a-1))与具有异氰酸酯反应基团的聚合物(成分(a-2))和/或扩链剂(成分(a-3))例如在20℃至100℃下,优选在约80℃下反应,得到异氰酸酯预聚物。
具有异氰酸酯反应基团的聚合物(a-2)和扩链剂(a-3)为本领域普通技术人员已知,并且在例如"Kunststoffhandbuch[Plastics Handbook],volume 7,Polyurethane[Polyurethanes]",Carl Hanser Verlag,1993年第3版,第3.1章中描述。
(b)具有至少两个对异氰酸酯有反应性的氢原子的化合物
在这里使用的具有至少两个对异氰酸酯(b)反应性的氢原子的化合物可以是已知用于聚氨酯制备,并且具有至少两个反应性氢原子且具有至少500g/mol的摩尔质量的任何化合物。举例来说,它们的官能度从2到8,分子量从400到12000。例如,因此可以使用聚醚多胺和/或选自聚醚多元醇、聚酯多元醇、聚碳酸酯多元醇或其混合物的多元醇。
优选使用的多元醇为分子量在500至12000之间,优选为500至6000,以及优选平均官能度为2至6,优选为2至4的聚醚多元醇和/或聚酯多元醇。
可用于本发明的聚醚多元醇通过已知方法制备。举例来说,它们可以通过阴离子聚合来制备,使用碱金属氢氧化物(例如氢氧化钠或氢氧化钾)或使用碱金属醇化物(例如甲醇钠、乙醇钠或乙醇钾,或异丙醇钾)作为催化剂,并添加至少一种具有2至8个,优选为2至6个反应性氢原子的起始分子;或者通过阳离子聚合来制备,使用路易斯酸(例如五氯化锑、三氟化硼乙醚等)或漂白土作为催化剂。聚醚多元醇同样可以通过双金属氰化物催化,由在烯烃基部分中具有2至4个碳原子的一种或多种环氧烷烃来制备。叔胺也可以用作催化剂,例如三乙胺、三丁胺、三甲胺、二甲基乙醇胺、咪唑或二甲基环己胺。对于特定预期用途,也可以将单官能起始物包含到聚醚的结构中。
合适的环氧烷烃的例子有四氢呋喃、1,3-环氧丙烷、1,2-或2,3-环氧丁烷、氧化苯乙烯,优选环氧乙烷和1,2-环氧丙烷。环氧烷烃可以单独使用、交替连续使用或以混合物的形式使用。
可以使用的起始分子的例子有:水、脂肪族和芳香族的任选地N-单烷基取代二胺或N,N-二烷基取代二胺或N,N'-二烷基取代二胺,其在烷基部分具有1至4个碳原子,例如任选地单烷基取代乙二胺和二烷基取代乙二胺、二乙烯三胺、三乙烯四胺、1,3-丙烯二胺、1,3-或1,4-丁烯二胺、1,2-、1,3-、1,4-、1,5-和1,6-己烷二胺、苯二胺、2,3-、2,4-和2,6-甲苯二胺(TDA),以及4,4'-、2,4'-和2,2'-二氨基二苯甲烷(MDA)及聚MDA。其他可使用的起始分子有:烷醇胺,如乙醇胺、N-甲基乙醇胺和N-乙基乙醇胺;二烷醇胺,如二乙醇胺、N-甲基二乙醇胺和N-乙基二乙醇胺;三烷醇胺,如三乙醇胺和氨。优选使用多羟基醇,如乙二醇、1,2-和2,3-丙二醇、二甘醇、二丙二醇、1,4-丁二醇、1,6-己二醇、丙三醇、三羟甲基丙烷;季戊四醇、山梨糖醇和蔗糖及其混合物。聚醚多元醇可以单独使用或以混合物的形式使用。
聚酯多元醇例如由烷烃二羧酸和多元醇、聚硫醚多元醇、聚酯酰胺、羟基化聚缩醛和/或羟基化脂肪族聚碳酸酯,优选在酯化反应催化剂的存在下的制备。其他可能的多元醇例如在"Kunststoffhandbuch,Band 7,Polyurethane"[Plastics Handbook,volume 7,Polyurethanes],Carl Hanser Verlag,1993年第3版,第3.1章中给出。
优选使用的聚酯多元醇可例如通过具有2至12个碳原子,优选具有4至6个碳原子的二羧酸与多元醇来制备。可使用的二羧酸的例子有:脂肪族二羧酸,如丁二酸、戊二酸、己二酸、辛二酸、壬二酸和癸二酸,以及芳香族二羧酸,如邻苯二甲酸、间苯二甲酸和对苯二甲酸。二羧酸可单独使用或以混合物的形式使用,如以丁二酸、戊二酸和己二酸的混合物的形式使用。任选地,对于制备聚酯多元醇而言,用相应的二羧酸衍生物代替二羧酸,例如在醇部分中具有1至4个碳原子的二羧酸酯、二羧酸酐或二酰基氯化物是有利的。多元醇的例子是具有2至10个,优选具有2至6个碳原子的二醇,如乙二醇、二乙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,10-癸二醇、2,2-二甲基-1,3-丙二醇、1,3-丙二醇和二丙二醇;具有3至6个碳原子的三醇,例如丙三醇和三羟甲基丙烷,以及更高官能度的醇,如季戊四醇。根据所需要的性能,多元醇可以单独使用,也可以任选地与其他多元醇混合使用。在制备本发明的聚氨酯泡沫时,优选使用聚醚多元醇作为具有至少两个对异氰酸酯有反应性的氢原子的化合物(b)。特别优选的是,这些化合物包括至少一种羟值为20至40,且伯羟基比例大于70%的二官能团至三官能团聚氧化烯多元醇(b1)。聚氧化烯多元醇(b1)优选包含至少50重量%的环氧丙烷,特别是优选至少80重量%。
特别地,为了制备本发明的聚氨酯泡沫,除了聚氧化烯多元醇(b1)外,可以使用具有2至4官能度,羟值为25至60的聚氧化烯多元醇(b2),基于OH基团的总数计,其伯羟基的比例大于70%,优选大于80%,并且环氧乙烷的含量优选为至少50重量%,特别优选为60重量%至95重量%。
用于制备本发明的聚氨酯泡沫的其他原料是至少一种二羟基至四羟基聚氧化烯多元醇(b3),其羟值为150至650,且伯羟基的比例大于80%,其中多羟基化合物(b3)优选包含至少30重量%的环氧乙烷,特别优选包含至少50重量%。在一种实施方案中,多元醇(b1)-(b3)可一起用作组分(b)。组分(b1)的比例优选为15重量%至35重量%,组分(b2)的比例优选为15重量%至35重量%,组分(b3)的比例优选为20重量%至35重量%,在每种情况下均基于组分(b)的总重量计。
(c)任选扩链剂和/或交联剂
可使用的扩链剂和/或交联剂(c)是摩尔质量优选小于500g/mol的物质,特别优选60g/mol至400g/mol,其中扩链剂具有两个对异氰酸酯有反应性的氢原子,而交联剂具有三个对异氰酸酯有反应性的氢原子。这些可以单独使用或优选地以混合物的形式使用。优选使用分子量小于500的二醇和/或三醇,特别是60至400,尤其是60至350。可使用那些物质的例子是具有2至14个,优选为2至10个碳原子的脂肪族、脂环族和/或芳脂族二醇,如乙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇、1,10-癸二醇和双(2-羟乙基)对苯二酚、1,2-、1,3-和1,4-环己二醇、二乙二醇、二丙二醇、三丙二醇,三醇,如1,2,4-或1,3,5-环己三醇、丙三醇和三羟甲基丙烷,以及基于环氧乙烷和/或以1,2-环氧丙烷和基于上述二醇和/或三醇为起始分子的低分子量羟基化聚氧化烯。作为交联剂(c),特别优选使用基于环氧乙烷和/或基于1,2-环氧丙烷,特别是优选基于乙烯,以及基于三官能度的起始物(特别是丙三醇)的低分子量羟基化聚环氧烷。
基于组分(b)的重量计,扩链剂和/或交联剂(c)的比例,如果存在,优选为1重量%至35重量%,特别优选为3重量%至25重量%,尤其是5重量%至15重量%。
(d)发泡剂
此处使用的发泡剂(d)可以是在本技术领域中已知的可适用于制备聚氨酯泡沫的任何发泡剂。优选地,发泡剂(d)包括含水的发泡剂。所使用的发泡剂也可以包括具有化学和/或物理作用的众所周知的化合物,以及水。化学发泡剂是通过与异氰酸酯反应形成气态产物的化合物,例如水或甲酸。物理发泡剂是在聚氨酯制备的起始材料中溶解或乳化并在聚氨酯形成条件下蒸发的化合物。举例来说,这些是烃、卤化烃和其他化合物,例如全氟烷烃,如全氟己烷、氟氯碳和醚、酯、酮和/或缩醛,例如具有4至8个碳原子的(环)脂肪烃或碳氟化合物,例如来自Solvay Fluorides LLC的Solkane 365mfc。在一种优选实施方案中,水作为唯一发泡剂用作发泡剂(d)。
在一种优选实施方案中,基于组分(b)的重量计,发泡剂的含量为0.1重量%至10重量%,优选为0.2重量%至9重量%,特别优选为0.3重量%至7重量%。
(e)催化剂
催化剂(e)极大地加快了组分(b)和任选的扩链剂和交联剂(c)和发泡剂(d)与多异氰酸酯(a)的反应。催化剂(e)优选地包含胺基催化剂。
适用于制备聚氨酯的典型催化剂包括,例如脒,如2,3-二甲基-3,4,5,6-四氢嘧啶,叔胺,如三乙胺、三丁胺、二甲基苄胺、N-甲基吗啉、N-乙基吗啉和N-环己基吗啉、N,N,N',N'-四甲基乙二胺、N,N,N',N'-四甲基丁二胺、N,N,N',N'-四甲基己二胺、五甲基二乙烯三胺、四甲基二氨基乙醚、双(二甲氨基丙基)脲、二甲基哌嗪、1,2-二甲基咪唑、1-氮杂双环[3.3.0]辛烷和优选1,4-二氮杂双环[2.2.2]辛烷以及烷醇胺化合物,如三乙醇胺、三异丙醇胺、N-甲基二乙醇胺和N-乙基二乙醇胺和二甲基乙醇胺。同样考虑的是有机金属化合物,优选有机锡化合物,例如有机羧酸锡(II)盐,如乙酸锡(II)、辛酸锡(II)、乙基己酸锡(II)和月桂酸锡(II),有机羧酸的二烷基锡(IV)盐,如二乙酸二丁基锡、二月桂酸二丁基锡、顺丁烯二酸二丁基锡和二乙酸二辛基锡,以及羧酸铋,如新癸酸铋(III)、2-乙基己酸铋和辛酸铋,或者其混合物。所述有机金属化合物可单独使用或优选与强碱性胺组合使用。如果组分(b)是酯,则优选仅使用胺催化剂。
胺基催化剂具有至少一个,优选1至8个,特别优选1至2个对异氰酸酯有反应性的基团,如伯胺基、仲胺基、羟基、酰胺或脲基,优选伯胺基、仲胺基、羟基。胺基胺催化剂主要用于制备低排放聚氨酯,特别是用于汽车内饰的低排放聚氨酯。这种催化剂是已知,并记载在例如EP1888664中。这些催化剂包括除了对异氰酸酯有反应性的基团外,优选还包含一个或多个叔氨基的化合物。在可包含的催化剂中的至少一个叔氨基中优选地携带至少两个脂肪族烃基,优选每个烃基具有1至10个碳原子,特别优选每个烃基具有1至6个碳原子。尤其优选具有独立地选自甲基和乙基的两个自由基加上另一个有机自由基的叔氨基。可使用的胺基催化剂的例子有:双(二甲氨基丙基)脲、双(N,N-二甲氨基乙氧基乙基)氨基甲酸酯、二甲氨基丙基脲、N,N,N-三甲基-N-羟乙基双(氨基丙醚)、N,N,N-三甲基-N-羟乙基双(氨基乙醚)、二乙基乙醇胺、双(N,N-二甲基-3-氨丙基)胺、二甲氨基丙胺、3-二甲氨基丙基-N,N-二甲基丙烷-1,3-二胺、二甲基-2-(2-氨基乙氧基乙醇)、(1,3-双(二甲氨基)丙烷-2-醇)、N,N-双(3-二甲氨基丙基)-N-异丙醇胺、双(二甲氨基丙基)-2-羟乙胺、N,N,N-三甲基-N-(3-氨丙基)-双(氨乙基乙醚)、1,4-二氮杂二环[2.2.2]辛烷-2-甲醇和3-二甲氨基异丙基二异丙醇胺或其混合物。
基于组分(b)的总重量计,可使用的催化剂(e)的含量例如为0.005wt%至5wt%,优选为0.01wt%至3wt%,更优选为0.05wt%至2wt%。在一种特别优选的实施方案中,仅以胺基催化剂作为催化剂(e)。
(f)助剂和添加剂
可使用的助剂和添加剂(f)包括稳泡剂、阻燃剂、开孔调节剂、表面活性剂、反应阻滞剂、用于老化作用和风化作用方面的稳定剂、增塑剂、防霉和抑菌物质、颜料和染料,以及本身已知的常规有机和无机填料。
优选使用的稳泡剂包括硅酮基稳泡剂。所使用的稳泡剂还可以包括硅氧烷-聚氧化烯共聚物、有机聚硅氧烷、乙氧基化脂肪醇和烷基酚和蓖麻油酯和各自的蓖麻油酸酯。
开孔调节剂的例子有石蜡、聚丁二烯、脂肪醇和二甲基聚硅氧烷。
用于老化作用和风化作用方面的稳定剂主要包括抗氧化剂。例如,这些稳定剂可以是空间位阻酚、HALS稳定剂(受阻胺光稳定剂)、三嗪、二苯甲酮和苯并三唑。
可以使用的表面活性剂的例子为用于促进起始材料的均化和确保多元醇组分在长时间内的相稳定性的化合物。任选地,这些表面活性剂也适用于调节孔结构。举例来说,乳化剂,如蓖麻油硫酸钠盐或脂肪酸的钠盐,以及含胺脂肪酸的盐,如二乙胺油酸盐、二乙醇胺硬脂酸盐、二乙醇胺蓖麻油酸盐,磺酸盐,例如十二烷基苯-或二萘基甲烷二磺酸和蓖麻油酸的碱金属或铵盐;稳泡剂,如硅氧烷-氧化烯共聚物和其他有机聚硅氧烷、乙氧基化烷基酚、乙氧基化脂肪醇、石蜡油、蓖麻油酯和各自地,蓖麻油酸酯、土耳其红油和花生油,以及泡孔调节剂,如石蜡、脂肪醇和二甲基聚硅氧烷。用于改善乳化效果或孔结构和/或用于稳定泡沫的其他合适化合物是具有聚氧化烯和氟代烷烃基团作为悬垂基团的低聚的聚丙烯酸酯。
基于组分(b)的重量计,通常使用的表面活性剂的用量通常为0.01重量%至5重量%。
可添加的填料,特别是增强填料,包括本身已知的材料,该材料为常规有机和无机填料、增强剂和增重剂。具体来说,例子有:无机填料,例如硅酸盐矿物质,如层状硅酸盐,如叶蛇纹石、蛇纹石、角闪石、闪石、温石棉、沸石、滑石;金属氧化物,例如高岭土、氧化铝、硅酸铝、氧化钛和氧化铁,金属盐,例如白垩、重晶石和无机颜料,例如硫化镉、硫化锌,以及玻璃颗粒。可使用的有机填料的例子有:炭黑、三聚氰胺、松香、环戊二烯树脂和聚合物改性聚氧化烯多元醇。
所使用的阻燃剂包括包含可膨胀石墨和包含低聚有机磷阻燃剂的阻燃剂。可膨胀石墨是众所周知的。其包括一种或多种可膨胀材料,因此在火灾条件下会发生相当大的膨胀。可膨胀石墨是通过已知的工艺制备的。通常的方法为首先用氧化剂,如硝酸盐、铬酸盐或过氧化物对石墨进行改性,或通过电解作用对石墨进行改性,以打开晶体层,然后将硝酸盐或硫酸盐插入石墨中,可以在给定条件下引起膨胀。低聚有机磷阻燃剂优选包含不少于5重量%的磷含量,在优选实施方案中存在至少3个磷酸酯单元。这里的“磷酯单元”包括磷酸酯单元和膦酸酯单元。因此,本发明的低聚有机磷阻燃剂包括具有纯膦酸酯单元、具有纯磷酸酯单元以及具有膦酸酯单元和磷酸酯单元的结构。
对于聚氨酯,可以使用一种或多种通常与低聚有机磷阻燃剂和可膨胀石墨一起使用的任意阻燃剂。这些阻燃剂包括卤素取代磷酸酯,如磷酸三甲酚酯、三(2-氯乙基)磷酸酯、三(2-氯丙基)磷酸酯、三(1,3-二氯丙基)磷酸酯、三(2,3-二溴丙基)磷酸酯和四(2-氯乙基)亚乙基二磷酸酯,和/或无机阻燃剂,如红磷、水合氧化铝、三氧化二锑、氧化砷、聚磷酸铵和硫酸钙,和/或三聚氰酸衍生物,如三聚氰胺。优选的阻燃剂不包含具有卤素基团的化合物。
关于上述助剂和添加剂的使用方式和作用的更多信息,以及更多的例子,在例如"Kunststoffhandbuch,Band 7,Polyurethane"["Plastics handbook,volume 7,Polyurethanes"],Carl Hanser Verlag,1993年第3版,第3.4章中给出。
(g)酸酐
这里使用的酸酐可以是聚氨酯工业中通常已知的任何羧酸酐。这些酸酐包括可以适当地分散或溶解在异氰酸酯或其混合物中的线性或环状、饱和或不饱和、芳香族或脂肪族C4-C24羧酸酐或C4-C24二羧酸酐。可以提及的例子包括乙酸酐、丙酸酐、丁酸酐、异丁酸酐、戊酸酐、异戊酸酐、特戊酸酐(pivalic anhydride)、月桂酸酐、肉豆蔻酸酐、棕榈酸酐、硬脂酸酐、丙二酸酐、丁二酸酐、戊二酸酐、己二酸酐、庚二酸酐、辛二酸酐、壬二酸酐、癸二酸酐、苹果酸酐、酒石酸酐、外消旋酸酐、亚酒石酸酐(tartronic anhydride),或者丙酮二酸酐。特别地,这里可以提到的酸酐包括线性或环状、饱和或不饱和、芳香族或脂肪族C4-C20羧酸酐或C4-C20二羧酸酸酐,其为液体且摩尔质量小于600g/mol。优选的酸酐是线性或环状的C4-C24烯基琥珀酸酐,包括,例如十二烯基琥珀酸酐、壬烯基琥珀酸酐;甲基降冰片烯-2,3-二羧酸酐、2,2-二甲基戊二酸酐;1,8-萘二酸酐;3,4,5,6-四氢邻苯二甲酸酐;3-甲基戊二酸酐;癸酸酐;巴豆酸酐。
在一种实施方案中,将酸酐(g)与多异氰酸酯(a)混合形成组分B,然后将其与其他组分混合形成反应混合物。基于组分(a)的重量计,酸酐(g)的添加量可以为0.05wt%至5wt%,优选为0.5wt%至3wt%。
聚氨酯泡沫的制备
将多异氰酸酯(a)、具有至少两个对异氰酸酯有反应性的氢原子的化合物(b)、任选地扩链剂和/或交联剂(c)、发泡剂(d)、催化剂(e)、任选地助剂和添加剂(f)优选地以特定的量混合,使得异氰酸酯指数在60至400范围内,特别优选在80至150范围内。聚氨酯泡沫制备过程中的异氰酸酯指数优选为95至130,特别优选为98至118。在计算异氰酸酯指数时,酸酐(g)不计算在内。
为了本发明的目的,异氰酸酯指数是异氰酸酯基团对于与异氰酸酯有反应性的基团的化学计量比乘以100。本文中与异氰酸酯有反应性的基团是指存在于反应混合物中的任一与异氰酸酯有反应性的基团,包括化学发泡剂,但不包括异氰酸酯基团本身。
本发明的聚氨酯泡沫优选以大泡沫厚板的形式,连续地在厚板-泡沫系统中或分批地在开放式泡沫模具中通过一步法(one-shot process)制备。如果使用具有多个入口喷嘴的混合室,则可以单独引入起始组分并在混合室中进行集中混合。已证明,使用双组分方法,并使用所谓的组分A,即由具有至少两个对异氰酸酯有反应性的氢原子的化合物(b)、任选地扩链剂和/或交联剂(c)、发泡剂(d)、催化剂(e)和任选地助剂和添加剂(f)混合而成的混合物,以及使用所谓的组分B,即由多异氰酸酯(a)和酸酐(g)混合而成的混合物,是特别有利的。由于A和B组分具有很好的保质期,它们易于以这种形式运输,在加工之前只需适量集中混合。可使用高压或低压加工系统混合结构组分(a)至(g),或组分(A)和(B)。
本发明的聚氨酯泡沫是通过在约15℃至60℃,优选为20℃至40℃的温度下,混合(有利地为组分A和B形式的)所述起始材料,然后使反应混合物在开放的、任选地温度控制模具中或在连续运作的厚板-泡沫系统中发泡而制备的。
所得聚氨酯泡沫的密度取决于所用发泡剂的量,并且所述密度为50g/L至500g/L,优选为100g/L至450g/L,特别优选为250g/L至350g/L。同时,产品表现出很好的抗水解性能。
如果有必要,可由所得的聚氨酯泡沫板根据所要制备的模塑件的尺寸切割泡沫厚板,并将这些泡沫厚板分开,以获得厚度从1mm到50mm,优选从2mm到30mm,特别是从5mm到20mm的PU泡沫片材。任何常规的工业分割装置都适用于此目的,但在实际操作中,优选使用具有循环带刀的水平分割系统。
在所述制备中,优选先将酸酐与多异氰酸酯(a)混合形成组分B,再与其它组分混合。这将最大程度避免酸酐和作为发泡剂的水之间的副反应。
减轻聚合物材料的腐蚀
由此制备的本发明聚氨酯泡沫可用于许多应用领域。例如,本发明的聚氨酯泡沫可用于汽车内饰,如方向盘、座椅、汽车天窗、汽车地毯、装饰板,或用于家用电器、休闲用品或家具。在这些应用中,聚氨酯泡沫经常与其他聚合物材料接触,如聚碳酸酯或其他聚酯。某些成分,特别是胺基催化剂,从聚氨酯泡沫中泄漏出来,渗透到邻接的聚合物材料中,并可能对其腐蚀或降解有催化作用。因此,用于汽车内饰的聚合物材料在与聚氨酯泡沫接触后会遭受许多损害,例如开裂,变色甚至功能异常。通过使用本发明的聚氨酯泡沫,可以极大地减轻甚至防止聚合物材料的这种腐蚀,并且从聚合物材料的表面可以看到显著减少的腐蚀甚至是没有腐蚀。所述聚合物材料可以是常规使用的聚合物材料,包括但不限于芳香族PC、脂肪族-芳香族PC或PC与其他聚合物材料的共聚物,如PC/PE、PC/HDPE或其他聚酯,如PBT、PET等。
实施例
现在将参考实施例和未限定本发明的比较实施例来描述本发明。
使用的起始材料如下:
异氰酸酯A:Elastan 4510/102/1C-B,4,4'-MDI,BASF市售。
多元醇1:由丙三醇起始的聚醚醇,OH值为35mg KOH/g,Mw约为4800。
多元醇2:由丙三醇起始的聚醚醇,OH值为42mg KOH/g,Mw约为4000。
多元醇3:由丙三醇起始的聚醚醇,OH值为28mg KOH/g,Mw约为4000。
催化剂1:双(2-二甲氨基乙基)醚,CAS号3033-62-3,Envonik市售。
催化剂2:1,4-二氮杂二环[2.2.2]辛烷,CAS号280-57-9,Evonik市售。
乙二醇:Sinopec市售。
酸酐1:壬烯基琥珀酸酐,TRIGON市售。
酸酐2:十二烯基琥珀酸酐(DDSA),CAS号25377-73-5,Vertellus市售。
测量方法:
泡沫的密度按照DIN EN ISO 1183-1,A确定。
腐蚀面积计算方法:通过Photoshop区域颜色分析来分析样品的腐蚀面积,详细说明见以下步骤。
实施例1:
制备聚氨酯泡沫的步骤如下:将86重量份的多元醇1、2.5重量份的多元醇2、12重量份的多元醇3、8重量份的乙二醇、0.8重量份的催化剂1、0.8重量份的催化剂2和0.5重量份的水混合成组分A;如表1所示,将组分A与组分B(包括100份异氰酸酯A和0.05份壬烯基琥珀酸酐)混合成反应混合物;并将反应混合物在模具(50cm×50cm×10cm)中于40℃下固化6小时,得到聚氨酯泡沫。这里使用的异氰酸酯指数为102。
对比例1
重复与实施例1相同的步骤,除了未在组分B中添加酸酐。得到了尺寸相同的聚氨酯泡沫。
实施例2-5
在这些实施例中,重复与实施例1相同的步骤,除了每个实施例按表1所示的量添加酸酐。
腐蚀等级评价方法如下:
1.使用聚碳酸酯(以Covestro 2407销售)为每个实施例中制备的PU泡沫制备相同的PC板。这些PC板长14cm,最大宽度2cm,最小宽度1.2cm,厚0.5cm。
2.将PU泡沫切割成5cm×2cm×1cm的泡沫片材,并将其铺在PC板上。
3.将这些PC板和放在其上的聚氨酯泡沫一起放入120℃的烘箱中加热7天。
4.对以上得到的样品进行拍照,并用Photoshop进行分析。引入了马赛克滤镜,将图片变成只有颜色的马赛克。对样本图片中泛黄马赛克的面积计数,计算泛黄面积(即泛黄马赛克的数量)基于样本整体面积(即整个样本马赛克的数量)的百分比。计算出的百分比数定义为腐蚀等级,单位为%。
结果总结如下表1。
表1
在120℃的烘箱中一起加热7天后,分析了这些PC板的腐蚀情况,裸眼可见明显不同的外观(见图1和2)。如图1和2所示,PC板与对比PU泡沫(无酸酐制备)接触后,整个表面呈现明显腐蚀的外观。与此相反,在PC板右侧——与本发明PU泡沫(以0.5份酸酐制备)接触——可以清晰地看到几乎没有腐蚀的干净外观。确实,从上表中可以看出,与本发明PU泡沫接触的PC板的腐蚀等级明显降低,甚至基本没有腐蚀。这表明,根据本发明的聚氨酯泡沫在与聚碳酸酯相互接触时,对减轻聚碳酸酯的腐蚀有实质性的效果。如图3所示,随着酸酐含量的增加,PC板的腐蚀等级降低。当酸酐含量足够高时,PC板表面基本看不到腐蚀现象。
实施例6-8
在这些实施例中,重复与实施例1相同的步骤,除了使用十二烯基琥珀酸酐(DDSA)代替壬烯基琥珀酸酐。其组分及其添加量列于如下表2。
对比例2
重复与实施例6-8相同的步骤,除了未在组分B中添加酸酐。
对比例2和实施例6-8中制备的PU泡沫的腐蚀等级评价方法与上述相同,除了与这些PU泡沫接触的板是PET板而不是PC板。结果总结如下表2。
表2
由上表可以看出,在实施例6-8中,将PC板改为PET板,在减轻聚合物材料腐蚀方面的效果与上述实施例1-5相似。用一定量酸酐制备的PU泡沫代替不含酸酐的PU泡沫,PET板的腐蚀等级明显降低,如图4和图5所示。
实施例9
在实施例9中,重复与实施例6-8相同的步骤,除了十二烯基琥珀酸酐(DDSA)的添加量如下表3所示。
对比例3
重复与实施例9相同的步骤,除了未在组分B中添加酸酐。
对比例3和实施例9中制备的PU泡沫的腐蚀等级进行评价的方法与上述相同,除了与这些PU泡沫接触的板为PBT板。结果总结如下表3。
表3
同样的,从实施例9和对比例3在减轻PBT板腐蚀的比较中可以看到相似的效果。PBT板与加入一定量酸酐制备的聚氨酯泡沫(实施例9)接触后,其腐蚀等级与未加入酸酐的聚氨酯泡沫(对比例3)接触后的相比有显著地降低。
本文所述的结构、材料、组合物和方法旨在作为本发明的代表性实施例,并且应理解,本发明的范围不受实施例范围的限制。本领域普通技术人员将认识到,本发明可以通过公开的结构、材料、组合物和方法的变型来实践,并且这些变型被认为在本发明的范围内。因此,本发明旨在涵盖在所附权利要求书及其相对应范围内的条款修订和变型。
Claims (15)
1.聚氨酯泡沫,其通过以下方式可得到或得到:混合下列组分以形成反应混合物:
(a)至少一种多异氰酸酯,
(b)至少一种具有至少两个对异氰酸酯有反应性的氢原子的化合物,
(c)任选地扩链剂和/或交联剂,
(d)发泡剂,
(e)催化剂,
(f)任选地助剂和添加剂,以及
(g)至少一种酸酐,
并使所述反应混合物反应生成聚氨酯泡沫,其中,基于组分(a)的重量计,以0.05wt%至5wt%的量加入酸酐。
2.根据权利要求1所述的聚氨酯泡沫,其中基于组分(a)的重量计,酸酐以0.1wt%至3wt%,优选0.25wt%至2wt%的量存在。
3.根据权利要求1或2所述的方法,其中酸酐选自可以分散或溶解在异氰酸酯中的线性或环状、饱和或不饱和、芳香族或脂肪族C4-C24羧酸酐或C4-C24二羧酸酐。
4.根据权利要求1至3中的任何一项所述的方法,其中酸酐选自线性或环状、饱和或不饱和、芳香族或脂肪族C4-C20羧酸酐或C4-C20二羧酸酐,其为液体且摩尔质量小于600g/mol。
5.根据权利要求1至4中的任何一项所述的聚氨酯泡沫,其中酸酐选自十二烯基琥珀酸酐、壬烯基琥珀酸酐、甲基降冰片烯-2,3-二羧酸酐、2,2-二甲基戊二酸酐;1,8-萘二酸酐;3,4,5,6-四氢邻苯二甲酸酐;3-甲基戊二酸酐;癸酸酐;巴豆酸酐。
6.根据权利要求1至4中的任何一项所述的聚氨酯泡沫,其中组分(a)选自:正己基异氰酸酯、环己基异氰酸酯、六亚甲基异氰酸酯、2-乙基己基异氰酸酯、正辛基异氰酸酯、十二烷基异氰酸酯、十八烷基异氰酸酯、苄基异氰酸酯、4,4'-二苯基甲烷二异氰酸酯、2,4'-二苯基甲烷二异氰酸酯、单体二苯基甲烷二异氰酸酯与具有多环数的二苯基甲烷二异氰酸酯同系物(聚合物MDI)的混合物、四亚甲基二异氰酸酯、六亚甲基二异氰酸酯(HDI)、六亚甲基二异氰酸酯与六亚甲基二异氰酸酯的低聚或多聚同系物(多核HDI)的混合物、异氟尔酮二异氰酸酯(IPDI)、甲苯2,4-或2,6-二异氰酸酯(TDI),以及这些异氰酸酯中的两种或两种以上的混合物。
7.根据权利要求1至6中的任何一项所述的聚氨酯泡沫,其中组分(b)选自聚醚多胺和/或选自聚醚多元醇、聚酯多元醇、聚碳酸酯多元醇或其混合物的多元醇。
8.根据权利要求1至7中的任何一项所述的聚氨酯泡沫,其中发泡剂包含水,并且优选地仅为水。
9.根据权利要求1至8中的任何一项所述的聚氨酯泡沫,其中催化剂包含胺基催化剂。
10.根据权利要求1至9中的任何一项所述的聚氨酯泡沫,其中聚氨酯泡沫通过将包含(b)、任选地(c)、(d)、(e)和任选地(f)的组分(A)与包含(a)和(g)的组分(B)混合以产生反应混合物,并使所述反应混合物反应而制备。
11.根据权利要求10所述的聚氨酯泡沫,其中组分A和组分B混合使得异氰酸酯指数在60至400范围内,特别优选在98至118范围内。
12.一种用于减轻或防止聚合物材料腐蚀的方法,其包括使聚合物材料与权利要求1-11的任何一项中可获得或获得的聚氨酯泡沫接触。
13.根据权利要求12所述的方法,其中所述聚合物材料包括聚碳酸酯和聚酯,例如PBT和PET。
14.权利要求1-11的任何一项中可获得或获得的聚氨酯泡沫用于减轻或防止聚合物材料腐蚀的用途。
15.根据权利要求14所述的用途,其中聚氨酯泡沫和聚合物材料是用于汽车内饰、家用电器、休闲用品或家具。
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