CN111670206A - 改善的泡沫配方 - Google Patents
改善的泡沫配方 Download PDFInfo
- Publication number
- CN111670206A CN111670206A CN201780093135.9A CN201780093135A CN111670206A CN 111670206 A CN111670206 A CN 111670206A CN 201780093135 A CN201780093135 A CN 201780093135A CN 111670206 A CN111670206 A CN 111670206A
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- phosphate
- foam
- blowing agent
- trans
- 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
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 159
- 239000006260 foam Substances 0.000 title claims abstract description 153
- 238000009472 formulation Methods 0.000 title description 12
- 229920005862 polyol Polymers 0.000 claims abstract description 124
- 150000003077 polyols Chemical class 0.000 claims abstract description 123
- 239000003063 flame retardant Substances 0.000 claims abstract description 89
- 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 claims abstract description 88
- 239000004604 Blowing Agent Substances 0.000 claims abstract description 78
- 238000000034 method Methods 0.000 claims abstract description 66
- 230000032683 aging Effects 0.000 claims abstract description 49
- 239000011495 polyisocyanurate Substances 0.000 claims abstract description 49
- 229920000582 polyisocyanurate Polymers 0.000 claims abstract description 49
- LDTMPQQAWUMPKS-OWOJBTEDSA-N (e)-1-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)\C=C\Cl LDTMPQQAWUMPKS-OWOJBTEDSA-N 0.000 claims abstract description 38
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 35
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 35
- 239000010452 phosphate Substances 0.000 claims abstract description 35
- 239000012948 isocyanate Substances 0.000 claims abstract description 26
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 25
- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 claims abstract description 18
- NLOLSXYRJFEOTA-OWOJBTEDSA-N (e)-1,1,1,4,4,4-hexafluorobut-2-ene Chemical compound FC(F)(F)\C=C\C(F)(F)F NLOLSXYRJFEOTA-OWOJBTEDSA-N 0.000 claims abstract description 10
- KVMPUXDNESXNOH-UHFFFAOYSA-N tris(1-chloropropan-2-yl) phosphate Chemical compound ClCC(C)OP(=O)(OC(C)CCl)OC(C)CCl KVMPUXDNESXNOH-UHFFFAOYSA-N 0.000 claims description 45
- 239000003054 catalyst Substances 0.000 claims description 28
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 28
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 25
- 239000011496 polyurethane foam Substances 0.000 claims description 25
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 20
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- -1 polysiloxane Polymers 0.000 claims description 17
- 229920001296 polysiloxane Polymers 0.000 claims description 17
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims description 16
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 claims description 16
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 16
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 16
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 claims description 16
- 239000004094 surface-active agent Substances 0.000 claims description 16
- 150000001412 amines Chemical class 0.000 claims description 15
- CCJKFLLIJCGHMO-UHFFFAOYSA-N 2-[diethoxyphosphorylmethyl(2-hydroxyethyl)amino]ethanol Chemical compound CCOP(=O)(OCC)CN(CCO)CCO CCJKFLLIJCGHMO-UHFFFAOYSA-N 0.000 claims description 13
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 13
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 10
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 10
- YFMFNYKEUDLDTL-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)C(F)C(F)(F)F YFMFNYKEUDLDTL-UHFFFAOYSA-N 0.000 claims description 9
- WZLFPVPRZGTCKP-UHFFFAOYSA-N 1,1,1,3,3-pentafluorobutane Chemical compound CC(F)(F)CC(F)(F)F WZLFPVPRZGTCKP-UHFFFAOYSA-N 0.000 claims description 8
- 229940051271 1,1-difluoroethane Drugs 0.000 claims description 8
- 239000001273 butane Substances 0.000 claims description 8
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 8
- 239000001282 iso-butane Substances 0.000 claims description 8
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- KFUSEUYYWQURPO-OWOJBTEDSA-N trans-1,2-dichloroethene Chemical group Cl\C=C\Cl KFUSEUYYWQURPO-OWOJBTEDSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- NLOLSXYRJFEOTA-UPHRSURJSA-N (z)-1,1,1,4,4,4-hexafluorobut-2-ene Chemical compound FC(F)(F)\C=C/C(F)(F)F NLOLSXYRJFEOTA-UPHRSURJSA-N 0.000 claims description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 6
- 239000011493 spray foam Substances 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 150000002902 organometallic compounds Chemical class 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- DHNUXDYAOVSGII-UHFFFAOYSA-N tris(1,3-dichloropropyl) phosphate Chemical compound ClCCC(Cl)OP(=O)(OC(Cl)CCCl)OC(Cl)CCCl DHNUXDYAOVSGII-UHFFFAOYSA-N 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- 229920001400 block copolymer Polymers 0.000 claims description 4
- 239000011135 tin Substances 0.000 claims description 4
- CJWBPEYRTPGWPF-UHFFFAOYSA-N 2-[bis(2-chloroethoxy)phosphoryloxy]ethyl bis(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCOP(=O)(OCCCl)OCCCl CJWBPEYRTPGWPF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 claims description 3
- 229920005903 polyol mixture Polymers 0.000 claims description 3
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 claims description 3
- GTRSAMFYSUBAGN-UHFFFAOYSA-N tris(2-chloropropyl) phosphate Chemical compound CC(Cl)COP(=O)(OCC(C)Cl)OCC(C)Cl GTRSAMFYSUBAGN-UHFFFAOYSA-N 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 2
- ASLWPAWFJZFCKF-UHFFFAOYSA-N tris(1,3-dichloropropan-2-yl) phosphate Chemical compound ClCC(CCl)OP(=O)(OC(CCl)CCl)OC(CCl)CCl ASLWPAWFJZFCKF-UHFFFAOYSA-N 0.000 claims 1
- 239000004814 polyurethane Substances 0.000 abstract description 15
- 229920002635 polyurethane Polymers 0.000 abstract description 12
- 239000005056 polyisocyanate Substances 0.000 description 19
- 229920001228 polyisocyanate Polymers 0.000 description 19
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 15
- 230000000694 effects Effects 0.000 description 15
- 238000009413 insulation Methods 0.000 description 12
- 210000004027 cell Anatomy 0.000 description 11
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 238000001422 normality test Methods 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 8
- 239000007921 spray Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
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- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 5
- 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 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 4
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- 239000004615 ingredient Substances 0.000 description 4
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- ZUFQCVZBBNZMKD-UHFFFAOYSA-M potassium 2-ethylhexanoate Chemical compound [K+].CCCCC(CC)C([O-])=O ZUFQCVZBBNZMKD-UHFFFAOYSA-M 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- 238000005829 trimerization reaction Methods 0.000 description 4
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
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- 150000001735 carboxylic acids Chemical class 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
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- FYIRUPZTYPILDH-UHFFFAOYSA-N 1,1,1,2,3,3-hexafluoropropane Chemical compound FC(F)C(F)C(F)(F)F FYIRUPZTYPILDH-UHFFFAOYSA-N 0.000 description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 2
- WXGNWUVNYMJENI-UHFFFAOYSA-N 1,1,2,2-tetrafluoroethane Chemical compound FC(F)C(F)F WXGNWUVNYMJENI-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
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- 125000003710 aryl alkyl group Chemical group 0.000 description 2
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- BXYVQNNEFZOBOZ-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]-n',n'-dimethylpropane-1,3-diamine Chemical compound CN(C)CCCNCCCN(C)C BXYVQNNEFZOBOZ-UHFFFAOYSA-N 0.000 description 2
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- 238000011160 research Methods 0.000 description 2
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- 229910052708 sodium Inorganic materials 0.000 description 2
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- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
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- HOVAGTYPODGVJG-UVSYOFPXSA-N (3s,5r)-2-(hydroxymethyl)-6-methoxyoxane-3,4,5-triol Chemical compound COC1OC(CO)[C@@H](O)C(O)[C@H]1O HOVAGTYPODGVJG-UVSYOFPXSA-N 0.000 description 1
- LNVRXFUZNCFBBU-IJRZPAASSA-L (z)-2,3-bis(6-methylheptyl)but-2-enedioate;dibutyltin(2+) Chemical compound CCCC[Sn+2]CCCC.CC(C)CCCCC\C(C([O-])=O)=C(C([O-])=O)/CCCCCC(C)C LNVRXFUZNCFBBU-IJRZPAASSA-L 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
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Images
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Abstract
本发明公开了改善聚氨酯或聚异氰脲酸酯泡沫老化后的耐热性的方法,所述方法包括由包含异氰酸酯和多元醇预混组合物的可发泡组合物产生所述泡沫,其中所述多元醇预混组合物包含多元醇或多元醇的混合物、发泡剂和阻燃剂,所述发泡剂选自1,3,3,3‑四氟丙烯(1234ze)、1,1,1,4,4,4‑六氟‑2‑丁烯(1336mzzzm)和/或1‑氯‑3,3,3‑三氟丙烯(1233zd),其中所述阻燃剂包括25phpp或更少的磷酸酯基阻燃剂。
Description
本发明涉及提供随时间推移表现出减轻的λ老化的聚氨酯泡沫、聚异氰脲酸酯泡沫或它们的混合物,并且涉及可发泡组合物和用于制备其的发泡方法。
在商业、住宅和工业建筑物中使用由聚异氰脲酸酯(PIR)或聚氨酯(PU)泡沫制成的绝热板作为建筑物围护结构或覆面在本领域中众所周知的。聚异氰脲酸酯(PIR)或聚氨酯(PU)泡沫的使用允许生产具有优异热导率的板,使得它们能够用于为建筑物提供热绝缘。此外,此类板的泡沫芯密度低,具有优异的耐火特性,并且具有较高的强度-重量比。
通过在一种或多种发泡剂、一种或多种催化剂、一种或多种表面活性剂和任选的其他成分的存在下使多异氰酸酯与一种或多种多元醇反应来产生聚氨酯泡沫。就聚异氰脲酸酯泡沫而言,泡沫由多异氰酸酯与其自身反应形成环状三聚体结构而形成。实际上,常常被描述为聚异氰脲酸酯的泡沫含有聚氨酯和聚异氰脲酸酯结构两者,并且被描述为聚氨酯的泡沫通常结合了一些聚异氰脲酸酯结构。因此,本申请涉及聚氨酯泡沫、聚异氰脲酸酯泡沫以及它们的混合物。发泡剂可以是物理发泡剂或化学发泡剂。物理发泡剂由于多异氰酸酯与多元醇反应时所产生的热量在其中形成气泡而通过挥发及膨胀在液体混合物中形成气泡。就化学发泡剂(也称为气体生成材料)而言,通过热分解或与用于产生聚氨酯和/或聚异氰脲酸酯泡沫的成分中的一者或多者反应来生成气态物质。随着聚合反应继续进行,液体混合物变成多孔固体,从而使发泡剂包埋在泡沫的泡孔中。
通常使用液体氟碳化合物发泡剂,因为除其他因素外它们易于使用。氟碳化合物不仅由于其挥发性而充当物理发泡剂,而且被包封或夹带在硬质泡沫的闭孔结构中,并且通常是泡沫的导热特性的主要贡献者。在泡沫形成后,与所产生的泡沫相关联的k系数或λ提供泡沫抵抗热传递通过泡沫材料的能力的量度。所产生的具有较低k系数的泡沫更耐热传递,并因此是用于绝缘目的更好的泡沫。因此,产生较低k系数的泡沫通常是期望且有利的。
近年来,对气候变化的关注推动了同时符合臭氧损耗和气候变化规定要求的新一代氟碳化合物的发展。其中包括某些氢卤烯烃,包括某些氢氟烯烃(其中1,3,3,3-四氟丙烯(1234ze)和1,1,1,4,4,4-六氟-2-丁烯(1336mzzm)是特别感兴趣的)以及氢氯氟烯烃(其中1-氯-3,3,3-三氟丙烯(1233zd)是特别感兴趣的)。用于制造反式-1,3,3,3-四氟丙烯的方法公开于美国专利7,230,146和7,189,884中。用于制造反式-1-氯-3,3,3-三氟丙烯的方法公开于美国专利6,844,475和6,403,847中。
聚异氰脲酸酯(PIR)或聚氨酯(PU)泡沫绝热板可原位作为建筑物的一部分长期存在。由于泡沫的K系数(或λ)主要由夹带在泡沫泡孔中的发泡剂的绝热特性来确定,因此发泡剂组成的任何变化都将影响随时间推移泡沫的平均λ值。可使用针对工厂生产的用作建筑物隔热板的硬质聚氨酯和聚异氰脲酸酯泡沫产品的欧洲标准EN13165(2010)以及针对原位形成的喷涂硬质聚氨酯和聚异氰脲酸酯泡沫产品的欧洲标准EN14315(2013)(两者均以引用方式并入)对在工作条件下经25年使用期的平均热导率(λ值或k系数)进行估算。
因此,本领域期望一种防止发泡剂的组成随时间推移而发生此类变化并由此防止绝热板的热导率劣化的方法。本领域的这种期望通过如下所述的本发明来解决。
本发明的第一方面涉及减轻聚氨酯泡沫、聚异氰脲酸酯泡沫或它们的混合物的λ老化的方法,所述方法包括由包含异氰酸酯和多元醇预混组合物的可发泡组合物产生所述泡沫;其中所述多元醇预混组合物包含:多元醇或多元醇的混合物;发泡剂,该发泡剂选自1,3,3,3-四氟丙烯(1234ze)、1,1,1,4,4,4-六氟-2-丁烯(1336mzzm)和/或1-氯-3,3,3-三氟丙烯(1233zd);以及阻燃剂,其中该阻燃剂包括25phpp或更少的磷酸酯基阻燃剂。
术语phpp将阻燃剂的量定义为按重量计“每百份多元醇的份数”。
将阻燃剂添加到泡沫绝热板中,以通过抑制火焰中的化学反应或通过在材料表面上形成保护性炭层来抑制或延迟火焰蔓延。一般来讲,将阻燃剂以液体或固体形式添加到多元醇预混组合物中。另选地阻燃剂可与异氰脲酸酯一起添加,或者可在形成泡沫之前作为单独的流添加。一般来讲,阻燃剂可以是矿物质类、有机卤素化合物或有机磷化合物。用于泡沫绝热板的常规阻燃剂包括磷酸三(2-氯乙基)酯、磷酸三(2-氯丙基)酯、磷酸三(1,3-二氯丙基)酯、磷酸三(2-氯异丙基)酯、磷酸三甲苯酯、磷酸三(2,2-二氯异丙基)酯、N,N-双(2-羟乙基)氨甲基膦酸二乙酯、甲基膦酸二甲酯、磷酸三(1,3-二氯丙基)酯和二磷酸四(2-氯乙基)亚乙基酯、磷酸三乙酯、磷酸铵、各种卤代芳族化合物、三水合铝、N,N-双(2-羟乙基)氨甲基膦酸二乙酯(Fyrol 6)和三聚氰胺。
出于本发明的目的,磷酸酯基阻燃剂选自磷酸三(2-氯乙基)酯、磷酸三(2-氯丙基)酯、磷酸三(1,3-二氯丙基)酯、磷酸三(2-氯异丙基)酯、磷酸三甲苯酯、磷酸三(2,2-二氯异丙基)酯、N,N-双(2-羟乙基)氨甲基膦酸二乙酯、甲基膦酸二甲酯、磷酸三(1,3-二氯丙基)酯、N,N-双(2-羟乙基)氨甲基膦酸二乙酯(Fyrol 6)、二磷酸四(2-氯乙基)亚乙基酯、磷酸三乙酯和磷酸铵,更优选地磷酸三(1-氯-2-丙基)酯(TCPP)、磷酸三乙酯(TEP)和N,N-双(2-羟乙基)氨甲基膦酸二乙酯(Fyrol 6)。
多元醇预混组合物中磷酸酯基阻燃剂的量为25phpp或更少、优选地20phpp或更少、优选地15phpp或更少、优选地10phpp或更少、优选地5phpp或更少。优选地,可发泡组合物不包含磷酸酯基阻燃剂。
阻燃剂可与多元醇共混,并且因此在产生可发泡组合物之前,与多元醇或多元醇的混合物一起提供在多元醇预混组合物中。另选地,阻燃剂可在可发泡组合物形成期间作为单独的流添加。出于本发明的目的,磷酸酯基阻燃剂的量包括所有的磷酸酯基阻燃剂,即多元醇预混组合物中存在的量或在可发泡组合物形成期间作为单独的流添加的磷酸酯基阻燃剂的量。
本发明人出乎意料地发现,通过将多元醇预混组合物中磷酸酯基阻燃剂的量限制为25phpp或更少,可减轻由该多元醇预混组合物产生的聚氨酯泡沫、聚异氰脲酸酯泡沫或它们的混合物在70℃下老化21天后的λ老化。因此,在第一方面的特别优选的特征中,聚氨酯泡沫、聚异氰脲酸酯泡沫或它们的混合物在70℃下老化21天后具有6mW/mK或更小的λ变化。
EN13165(2010)和EN14315(2013)的附录C列出了“正态性检验”(参见EN13165(2010)和EN14315(2013)的C.2和C.3章节)和任选的“加速试验”(参见C.4.4)。出于本发明的目的,取决于泡沫类型,可使用EN13165(2010)和EN14315(2013)的C.2和C.3章节中列出的“正态性检验”来估算平均λ值,优选地,取决于泡沫类型,使用EN13165(2010)和EN14315(2013)的C.2和C.3章节中列出的“正态性检验”来估算平均λ值。
在第一方面的优选特征中,泡沫λ老化的减轻可通过使用如在实施例章节和EN13165(2010)的C.2和C.3章节中针对除喷涂泡沫之外的所有泡沫列出的“正态性检验”进行测量,或者如通过EN14315(2013)的C.2和C.3章节进行测量。因此,聚氨酯泡沫、聚异氰脲酸酯泡沫或它们的混合物在70℃下老化21天后具有λ老化减轻,如使用在实施例章节和EN13165(2010)的C.2和C.3章节中针对除喷涂泡沫之外的所有泡沫列出的“正态性检验”所测量的,或如通过EN14315(2013)的C.2和C.3章节所测量的。优选地,聚氨酯泡沫、聚异氰脲酸酯泡沫或它们的混合物在70℃下老化21天后具有6mW/mK或更小的λ变化,如使用在实施例章节和EN13165(2010)的C.2和C.3章节中针对除喷涂泡沫之外的所有泡沫列出的“正态性检验”所测量的,或如通过EN14315(2013)的C.2和C.3章节所测量的。
发明人已发现,当多元醇预混组合物中磷酸酯基阻燃剂的量优选地为15phPP或更小时,使用第一方面的方法产生的泡沫显示出改善的λ变化特性和阻燃特性。因此,第一方面提供了一种减轻聚氨酯泡沫、聚异氰脲酸酯泡沫或它们的混合物的λ老化的方法,所述方法包括由包含异氰酸酯和多元醇预混组合物的可发泡组合物产生所述泡沫;其中所述多元醇预混组合物包含:多元醇或多元醇的混合物;发泡剂,该发泡剂选自1,3,3,3-四氟丙烯(1234ze)、1,1,1,4,4,4-六氟-2-丁烯(1336mzzm)和/或1-氯-3,3,3-三氟丙烯(1233zd);以及阻燃剂;其中该磷酸酯基阻燃剂包括15phpp或更少的阻燃剂。
如上所述,磷酸酯基阻燃剂仅为一种类型的阻燃剂。发明人已确定,多元醇预混组合物可另外包含溴化反应性阻燃剂,特别是与磷酸酯基阻燃剂组合的溴化多元醇化合物。获得必要阻燃性所需的溴化阻燃剂的量可由技术人员使用其公知常识来确定,因为溴化阻燃剂的存在不影响由多元醇预混物产生的泡沫的λ老化。
此类溴化反应性阻燃剂的示例包括Saytex RB-79(四溴邻苯二甲酸酐与二甘醇和丙二醇的羟基封端酯)或Saytex RB-9170的反应性阻燃剂。
出于本发明的目的,发泡剂包括氢卤烯烃发泡剂中的至少一种或组合,该氢卤烯烃发泡剂选自1,3,3,3-四氟丙烯(1234ze)、1,1,1,4,4,4-六氟-2-丁烯(1336mzzm)和/或1-氯-3,3,3-三氟丙烯(1233zd)。
1,3,3,3-四氟丙烯(1234ze)可作为顺式异构体、反式异构体或它们的组合提供。优选地,1,3,3,3-四氟丙烯作为反式异构体提供。1-氯-3,3,3-三氟丙烯(1233zd)可作为顺式异构体、反式异构体或它们的组合提供。优选地,1-氯-3,3,3-三氟丙烯作为反式异构体提供。1,1,1,4,4,4-六氟-2-丁烯(1336mzzm)可作为顺式异构体、反式异构体或它们的组合提供。优选地,1,1,1,4,4,4-六氟-2-丁烯作为顺式异构体提供。
因此,发泡剂优选地包括反式-1,3,3,3-四氟丙烯(反式1234ze)、顺式1,1,1,4,4,4-六氟-2-丁烯(顺式1336mzzm)和/或反式1-氯-3,3,3-三氟丙烯(反式1233zd)中的至少一种或组合。发泡剂优选地包括顺式1,1,1,4,4,4-六氟-2-丁烯(顺式1336mzzm)和/或反式1-氯-3,3,3-三氟丙烯(反式1233zd)。发泡剂最优选地包括反式1-氯-3,3,3-三氟丙烯(反式1233zd)。
发泡剂可包括1,3,3,3-四氟丙烯(1234ze)、1,1,1,4,4,4-六氟-2-丁烯(1336mzzm)和/或1-氯-3,3,3-三氟丙烯(1233zd),优选地反式1,3,3,3-四氟丙烯(反式1234ze)、顺式1,1,1,4,4,4-六氟-2-丁烯(顺式1336mzzm)和/或反式1-氯-3,3,3-三氟丙烯(反式1233zd),基本上由其组成或由其组成。
因此,本发明的第一方面特别涉及减轻聚氨酯泡沫、聚异氰脲酸酯泡沫或它们的混合物的λ老化的方法,所述方法包括由包含异氰酸酯和多元醇预混组合物的可发泡组合物产生所述泡沫;其中所述多元醇预混组合物包含多元醇或多元醇的混合物、包括反式1-氯-3,3,3-三氟丙烯(反式1233zd)的发泡剂以及阻燃剂,其中该阻燃剂包括25phpp或更少的磷酸酯基阻燃剂。优选地,本发明的第一方面特别涉及减轻聚氨酯泡沫、聚异氰脲酸酯泡沫或它们的混合物的λ老化的方法,所述方法包括由包含异氰酸酯和多元醇预混组合物的可发泡组合物产生所述泡沫;其中所述多元醇预混组合物包含多元醇或多元醇的混合物、包括反式1-氯-3,3,3-三氟丙烯(反式1233zd)的发泡剂以及阻燃剂,其中该阻燃剂包括15phpp或更少的磷酸酯基阻燃剂。
发泡剂可另外包括一种或多种额外的共发泡剂,诸如烃、氟碳化合物、氯烃、氟氯烃、氢氯氟烃、氢氟烃、卤代烃、醚、氟化醚、酯、缩醛、醇、醛、酮、有机酸、气体生成材料、水、二氧化碳(CO2)或它们的组合。优选的发泡剂具有不大于150、更优选地不大于100、并且甚至更优选地不大于75的全球变暖潜能值(GWP)。如本文所用,“GWP”是相对于二氧化碳的GWP并且在100年的时间范围内测量的,如“The Scientific Assessment of OzoneDepletion,2002,a report of the World Meteorological Association's GlobalOzone Research and Monitoring Project”中所定义的,该文献以引用方式并入本文。优选的发泡剂具有不大于0.05、更优选地不大于0.02、并且甚至更优选地约零的臭氧消耗潜值(ODP)。如本文所用,“ODP”如“The Scientific Assessment of Ozone Depletion,2002,A report of the World Meteorological Association's Global Ozone Research andMonitoring Project”中所定义,该文献以引用方式并入本文。
优选的任选共发泡剂包括水、产生CO2和/或CO的有机酸;CO2、醚、卤代醚;酯、醇、醛、酮;反式-1,2-二氯乙烯;甲缩醛、甲酸甲酯;氢氟烃,诸如1,1,1,2-四氟乙烷(134a);1,1,2,2-四氟乙烷(134);1,1,1,3,3-五氟丁烷(365mfc);1,1,1,2,3,3,3-七氟丙烷(227ea)、1,1,1,3,3,3-六氟丙烷(236fa);1,1,1,2,3,3-六氟丙烷(236ea);1,1,1,2,3,3,3-七氟丙烷(227ea)、1,1-二氟乙烷(152a);1,1,1,3,3-五氟丙烷(245fa);烃类,诸如丁烷;异丁烷;正戊烷;异戊烷;环戊烷,或它们的组合。
更优选地,共发泡剂是选自以下中的一种或多种:水、产生CO2和/或CO的有机酸、反式-1,2二氯乙烯;甲缩醛、甲酸甲酯;1,1,1,2-四氟乙烷(134a);1,1,1,3,3-五氟丁烷(365mfc);1,1,1,2,3,3,3-七氟丙烷(227ea)、1,1-二氟乙烷(152a);1,1,1,3,3-五氟丙烷(245fa);丁烷;异丁烷;正戊烷;异戊烷;环戊烷,或它们的组合。
因此,本发明的第一方面特别涉及减轻聚氨酯泡沫、聚异氰脲酸酯泡沫或它们的混合物的λ老化的方法,所述方法包括由包含异氰酸酯和多元醇预混组合物的可发泡组合物产生所述泡沫;其中所述多元醇预混组合物包含:多元醇或多元醇的混合物;包括反式1-氯-3,3,3-三氟丙烯(反式1233zd)的发泡剂;以及一种或多种共发泡剂,该一种或多种共发泡剂选自水、产生CO2和/或CO的有机酸、反式-1,2二氯乙烯;甲缩醛、甲酸甲酯;1,1,1,2-四氟乙烷(134a);1,1,1,3,3-五氟丁烷(365mfc);1,1,1,2,3,3,3-七氟丙烷(227ea)、1,1-二氟乙烷(152a);1,1,1,3,3-五氟丙烷(245fa);丁烷;异丁烷;正戊烷;异戊烷;环戊烷或它们的组合;以及阻燃剂,其中该阻燃剂包括25phpp或更少的磷酸酯基阻燃剂。
优选地,本发明的第一方面特别涉及减轻聚氨酯泡沫、聚异氰脲酸酯泡沫或它们的混合物的λ老化的方法,所述方法包括由包含异氰酸酯和多元醇预混组合物的可发泡组合物产生所述泡沫;其中所述多元醇预混组合物包含:多元醇或多元醇的混合物;包括反式1-氯-3,3,3-三氟丙烯(反式1233zd)的发泡剂;以及一种或多种共发泡剂,该一种或多种共发泡剂选自水、产生CO2和/或CO的有机酸、反式-1,2二氯乙烯;甲缩醛、甲酸甲酯;1,1,1,2-四氟乙烷(134a);1,1,1,3,3-五氟丁烷(365mfc);1,1,1,2,3,3,3-七氟丙烷(227ea)、1,1-二氟乙烷(152a);1,1,1,3,3-五氟丙烷(245fa);丁烷;异丁烷;正戊烷;异戊烷;环戊烷或它们的组合;以及阻燃剂,其中该阻燃剂包括15phpp或更少的磷酸酯基阻燃剂。
该一种或多种共发泡剂特别包括水和/或正戊烷、异戊烷或环戊烷中的一种或组合,它们可与本文所讨论的氢卤烯烃发泡剂中的一种或组合一起提供,具体地与反式1-氯-3,3,3-三氟丙烯(反式1233zd)组合提供。
发泡剂特别包括1,3,3,3-四氟丙烯(1234ze)、1,1,1,4,4,4-六氟-2-丁烯(1336mzzm)和/或1-氯-3,3,3-三氟丙烯(1233zd),优选地与水组合的反式1,3,3,3-四氟丙烯(反式1234ze)、顺式1,1,1,4,4,4-六氟-2-丁烯(顺式1336mzzzm)和/或反式1-氯-3,3,3-三氟丙烯(反式1233zd)。具体地,发泡剂包括反式1-氯-3,3,3-三氟丙烯(反式1233zd)和水,基本上由其组成或由其组成。
因此,本发明的第一方面特别涉及减轻聚氨酯泡沫、聚异氰脲酸酯泡沫或它们的混合物的λ老化的方法,所述方法包括由包含异氰酸酯和多元醇预混组合物的可发泡组合物产生所述泡沫;其中所述多元醇预混组合物包含多元醇或多元醇的混合物、包括反式1-氯-3,3,3-三氟丙烯(反式1233zd)和水的发泡剂以及阻燃剂,其中该阻燃剂包括25phpp或更少的磷酸酯基阻燃剂。
优选地,本发明的第一方面特别涉及减轻聚氨酯泡沫、聚异氰脲酸酯泡沫或它们的混合物的λ老化的方法,所述方法包括由包含异氰酸酯和多元醇预混组合物的可发泡组合物产生所述泡沫;其中所述多元醇预混组合物包含多元醇或多元醇的混合物、包括反式1-氯-3,3,3-三氟丙烯(反式1233zd)和水的发泡剂以及阻燃剂,其中该阻燃剂包括15phpp或更少的磷酸酯基阻燃剂。
更优选地,发泡剂基本上由反式1-氯-3,3,3-三氟丙烯(反式1233zd)和水组成。
发泡剂组分(即氢卤烯烃和任选的共发泡剂)优选地以按多元醇预混组合物的重量计约1重量%至约30重量%、优选地约3重量%至约25重量%、并且更优选地约5重量%至约25重量%的量存在于多元醇预混组合物中。
当氢卤烯烃和任选的发泡剂同时存在时,氢卤烯烃组分优选地以按发泡剂的重量计约5重量%至约99重量%、优选地约7重量%至约98重量%、并且更优选地约10重量%至约95重量%的量存在于发泡剂中;并且任选的发泡剂优选地以按发泡剂的重量计约95重量%至约1重量%、优选地约93重量%至约2重量%、并且更优选地约90重量%至约5重量%的量存在于发泡剂中。
多元醇预混组合物包含多元醇或多元醇的混合物。多元醇或多元醇混合物可以是以已知方式与异氰酸酯反应以制备聚氨酯泡沫、聚异氰脲酸酯泡沫或它们的混合物的任何多元醇或多元醇混合物。可用的多元醇包括以下中的一种或多种:含蔗糖的多元醇;含苯酚、苯酚甲醛的多元醇;含葡萄糖的多元醇;含山梨糖醇的多元醇;含甲基葡糖苷的多元醇;芳族聚酯多元醇;甘油;乙二醇;二甘醇;丙二醇;与(b)中的一种或多种缩合的(a)中的一种或多种,其中(a)选自甘油、乙二醇、二甘醇、三羟甲基丙烷、乙二胺、季戊四醇、大豆油、卵磷脂、妥尔油、棕榈油和蓖麻油;并且(b)选自环氧乙烷、环氧丙烷、环氧乙烷和环氧丙烷的混合物;以及它们的组合。
多元醇或多元醇的混合物通常以按多元醇预混组合物的重量计约50重量%至约95重量%、优选地约50重量%至约85重量%、并且更优选地约55重量%至约80重量%的量存在于多元醇预混组合物中。
多元醇预混组合物还可包含一种或多种额外的材料,该一种或多种额外的材料选自硅氧烷表面活性剂、非硅氧烷表面活性剂、金属催化剂、胺催化剂以及它们的组合,如下文所详述。
多元醇预混组合物可包含表面活性剂,优选地硅氧烷表面活性剂。硅氧烷表面活性剂优选地有助于泡沫的形成以及控制泡沫的气泡尺寸,以便获得具有期望泡孔结构的泡沫。优选地,其中具有均匀尺寸的小泡或泡孔的泡沫是期望的,因为它具有最期望的物理特性,诸如压缩强度和热导率。此外,具有在形成之前或在泡沫上升期间不塌缩的稳定泡孔的泡沫是至关重要的。还期望具有“封闭的”泡孔,即泡孔的壁是完整的并且不对大气开放以允许泡孔中的气体与大气气体容易地交换。
用于制备聚氨酯和/或聚异氰脲酸酯泡沫的硅氧烷表面活性剂可以本领域技术人员已知的许多商品名获得。已发现此类材料可适用于广泛的配方,从而允许均匀泡孔的形成和最大的气体截留以实现极低密度的泡沫结构。优选的硅氧烷表面活性剂包括聚硅氧烷聚氧化烯嵌段共聚物。可用于本发明的一些代表性硅氧烷表面活性剂为:Momentive的L-5130、L-5180、L-5340、L-5440、L-6100、L6124、L-6900、L-6980、L-6988和Y10762;AirProducts(现为Evonik)Dabco193、Dabco197、Dabco5582、Dabco5598、Dabco SI 3504、DabcoSI3102以及得自德国埃森的Evonik Industries AG的B-8404、B-8407、B-8409、B84205、B84210、B84501、B-8462、B8465、B84701、B84704、B8490和B8496。其他公开于美国专利2,834,748、2,917,480、2,846,458和4,147,847中,这些专利以引用方式并入本文。
硅氧烷表面活性剂组分通常以按多元醇预混组合物的重量计约0.5重量%至约5.0重量%、优选地约1.0重量%至约4.0重量%、并且更优选地约1重量%至约3.0重量%的量存在于多元醇预混组合物中
多元醇预混组合物可任选地包含非硅氧烷表面活性剂,诸如非硅氧烷非离子表面活性剂。这可包括乙氧基化烷基酚、乙氧基化脂肪醇、石蜡油、蓖麻油酯、蓖麻油酸酯、土耳其红油、花生油、石蜡和脂肪醇。优选的非硅氧烷非离子表面活性剂为可从Air ProductsCorporation商购获得的LK-443或得自DOW的Vorasurf 504。
当使用非硅氧烷非离子表面活性剂时,其通常以按多元醇预混组合物的重量计约0.25重量%至约3.0重量%、优选地约0.5重量%至约2.5重量%、并且更优选地约0.75重量%至约2.0重量%的量存在于多元醇预混组合物中。
多元醇预混组合物还包含一种或多种催化剂,具体地为胺催化剂和/或金属催化剂。胺催化剂可包括但不限于伯胺、仲胺或叔胺。可用的叔胺催化剂非排他性地包括N,N-二甲基环己胺、N,N-二甲基乙醇胺、二甲基氨基乙氧基乙醇、N,N,N'-三甲基氨乙基-乙醇胺、N,N,N'-三甲基-N'-羟乙基双氨基乙醚、四甲基亚氨基双丙胺、2-[[2-[2-(二甲基氨基)乙氧基]乙基]甲基氨基]乙醇、五甲基二亚乙基三胺、五甲基二亚丙基三胺、N,N,N',N”-五甲基-二亚丙基三胺、1,1,4,7,10,10-六甲基三亚乙基四胺、N,N-双(3-二甲基氨基丙基)-N-异丙醇胺、N'-(3-(二甲基氨基)丙基)-N,N-二甲基-1,3-丙二胺、双(3-二甲基氨基丙基)-n,n-二甲基丙二胺、双-(2-二甲基氨乙基)醚、N,N',N”-二甲基氨基丙基六氢三嗪、四甲基亚氨基双丙胺、三甲基-n',2-羟乙基-丙二胺、双-(3-氨基丙基)-甲胺、N,N-二甲基-1,3-丙二胺、1-(二甲基氨基)十六烷、苄基二甲胺、3-二甲基氨基丙基脲、二环己基甲胺;二异丙基乙胺;二甲基异丙胺;甲基异丙基苄胺;甲基环戊基苄胺;异丙基-仲丁基-三氟乙胺;二乙基-(α-苯乙基)胺、三正丙胺或它们的组合。可用的仲胺催化剂非排他性地包括:二环己胺;叔丁基异丙胺;二叔丁胺;环己基-叔丁胺;二仲丁胺、二环戊胺;二-(α-三氟甲基乙基)胺;二-(α-苯乙基)胺;或它们的组合。
其他可用的胺包括吗啉、咪唑和含醚化合物。这些包括
二吗啉二乙醚
N-乙基吗啉
N-甲基吗啉
双(二甲基氨乙基)醚
咪唑
n甲基咪唑
1,2-二甲基咪唑
二吗啉基二甲基醚
N,N,N',N',N",N"-五甲基二亚乙基三胺
N,N,N',N',N",N"-五乙基二亚乙基三胺
N,N,N',N',N",N"-五甲基二亚丙基三胺
双(二乙基氨乙基)醚
双(二甲氨基丙基)醚。
当使用胺催化剂时,其以按多元醇预混组合物的重量计约0.1重量%至约8重量%、优选地约0.1重量%至约7重量%、并且更优选地约0.2重量%至约6重量%的量存在于多元醇预混组合物中
多元醇预混组合物可任选地还包含非胺催化剂。合适的非胺催化剂可包括含铋、铅、锡、钛、锑、铀、镉、钴、钍、铝、汞、锌、镍、铈、钼、钒、铜、锰、锆、钠、钾、锂、镁、钡、钙、铪、镧、铌、钽、碲、钨、铯或它们的组合的有机金属化合物。优选地,非胺催化剂包括含铋、铅、锡、锌、钠、钾或它们的组合的有机金属化合物。
非胺催化剂包括2-乙基己酸铋、2-乙基己酸铅、苯甲酸铅、羧酸的亚锡盐、羧酸的锌盐、羧酸的二烷基锡盐(例如二月桂酸二丁基锡、二新癸酸二甲基锡、二新癸酸二辛基锡、二月桂基硫醇二丁基锡、二异辛基马来酸二丁基锡、二月桂基硫醇二甲基锡、二月桂基硫醇二辛基锡、二硫代乙醇酸二丁基锡、二硫代乙醇酸二辛基锡)、乙酸钾、辛酸钾、2-乙基己酸钾、甘氨酸盐、季铵羧酸盐、碱金属羧酸盐和2-乙基己酸锡(II)或它们的组合。非胺催化剂优选地以按多元醇预混组合物的重量计约0.01重量%至约2.5重量%、优选地约0.02重量%至约2.5重量%、并且更优选地约0.05重量%至约2重量%的量存在于多元醇预混组合物中。
在聚异氰脲酸酯泡沫的制备中,三聚催化剂可用于将共混物与过量异氰酸酯一起转化成聚异氰脲酸酯-聚氨酯泡沫的目的。所采用的三聚催化剂可以是本领域技术人员已知的任何催化剂,包括但不限于甘氨酸盐、叔胺三聚催化剂、季铵羧酸盐和碱金属羧酸盐以及各种类型催化剂的混合物。优选的三聚催化剂是乙酸钾、辛酸钾和N-(2-羟基-5-壬基苯酚)甲基-N-甲基甘氨酸酯。
因此,本发明的第一方面特别涉及减轻聚氨酯泡沫、聚异氰脲酸酯泡沫或它们的混合物的λ老化的方法,所述方法包括由包含异氰酸酯和多元醇预混组合物的可发泡组合物产生所述泡沫;其中所述多元醇预混组合物包含:多元醇或多元醇的混合物;包括反式1-氯-3,3,3-三氟丙烯(反式1233zd)的发泡剂;以及一种或多种共发泡剂,该一种或多种共发泡剂选自水、产生CO2和/或CO的有机酸、反式-1,2二氯乙烯;甲缩醛、甲酸甲酯;1,1,1,2-四氟乙烷(134a);1,1,1,3,3-五氟丁烷(365mfc);1,1,1,2,3,3,3-七氟丙烷(227ea)、1,1-二氟乙烷(152a);1,1,1,3,3-五氟丙烷(245fa);丁烷;异丁烷;正戊烷;异戊烷;环戊烷或它们的组合;聚硅氧烷聚氧化烯嵌段共聚物表面活性剂,其量为多元醇预混组合物的0.5重量%至约5.0重量%;胺催化剂,其量为多元醇预混组合物的0.1重量%至8重量%;以及/或者包括含有铋、铅、锑、锡、锌、钾或它们的组合的有机金属化合物的金属催化剂,其量为多元醇预混组合物的0.01重量%至2.5重量%;以及阻燃剂,其中该阻燃剂包括25PHPP或更少的磷酸酯基阻燃剂。
第一方面特别涉及减轻聚氨酯泡沫、聚异氰脲酸酯泡沫或它们的混合物的λ老化的方法,所述方法包括由包含异氰酸酯和多元醇预混组合物的可发泡组合物产生所述泡沫;其中所述多元醇预混组合物包含:多元醇或多元醇的混合物;包括反式1-氯-3,3,3-三氟丙烯(反式1233zd)的发泡剂;以及一种或多种共发泡剂,该一种或多种共发泡剂选自水、产生CO2和/或CO的有机酸、反式-1,2二氯乙烯;甲缩醛、甲酸甲酯;1,1,1,2-四氟乙烷(134a);1,1,1,3,3-五氟丁烷(365mfc);1,1,1,2,3,3,3-七氟丙烷(227ea)、1,1-二氟乙烷(152a);1,1,1,3,3-五氟丙烷(245fa);丁烷;异丁烷;正戊烷;异戊烷;环戊烷或它们的组合;聚硅氧烷聚氧化烯嵌段共聚物表面活性剂,其量为多元醇预混组合物的0.5重量%至约5.0重量%;胺催化剂,其量为多元醇预混组合物的0.1重量%至8重量%;以及/或者包括含有铋、铅、锑、锡、锌、钾或它们的组合的有机金属化合物的金属催化剂,其量为多元醇预混组合物的0.01重量%至2.5重量%;以及阻燃剂,其中该阻燃剂包括15PHPP或更少的磷酸酯基阻燃剂。
此外,多元醇预混组合物中可包含其他成分,诸如染料、填料、颜料等。可将分散剂和泡孔稳定剂掺入到多元醇预混组合物中。用于本文的常规填料包括例如硅酸铝、硅酸钙、硅酸镁、碳酸钙、硫酸钡、硫酸钙、玻璃纤维、炭黑和二氧化硅。填料(如果使用)通常以按重量计每100份多元醇约5份至100份范围内的量存在。可用于本文的颜料可以是任何常规颜料诸如二氧化钛、氧化锌、氧化铁、氧化锑、铬绿、铬黄、铁蓝黄土、钼橙,以及有机颜料诸如对位红、联苯胺黄、甲苯胺红、调色剂和酞菁。
将多元醇预混物与异氰酸酯混合以形成可发泡组合物,所述可发泡组合物用于产生聚氨酯泡沫、聚异氰脲酸酯泡沫或它们的混合物。
出于本发明的目的,异氰酸酯可以是可用于聚氨酯和/或聚异氰脲酸酯泡沫合成的任何有机多异氰酸酯,包括脂族和芳族多异氰酸酯。合适的有机多异氰酸酯包括聚氨酯化学领域公知的脂族、脂环族、芳脂族、芳族和杂环异氰酸酯。这些描述于例如美国专利4,868,224、3,401,190、3,454,606、3,277,138、3,492,330、3,001,973、3,394,164、3,124.605和3,201,372,这些专利以引用方式并入本文。优选的一类是芳族多异氰酸酯。
代表性的有机多异氰酸酯对应于下式:
R(NCO)z
其中R是多价有机基团,该多价有机基团是脂族、芳烷基、芳族或它们的混合物,并且z是对应于R的化合价的整数且至少为二。本文所设想的有机多异氰酸酯的代表包括例如芳族二异氰酸酯,诸如2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、2,4-甲苯二异氰酸酯和2,6-甲苯二异氰酸酯的混合物、粗甲苯二异氰酸酯、亚甲基二苯基二异氰酸酯、粗亚甲基二苯基二异氰酸酯;芳族三异氰酸酯,诸如4,4',4"-三苯基甲烷三异氰酸酯、2,4,6-甲苯三异氰酸酯;芳族四异氰酸酯,诸如4,4'-二甲基二苯基甲烷-2,2'5,5'-四异氰酸酯;芳烷基多异氰酸酯,诸如亚二甲苯基二异氰酸酯;脂族多异氰酸酯,诸如六亚甲基-1,6-二异氰酸酯、赖氨酸二异氰酸酯甲酯;以及它们的混合物。其他有机多异氰酸酯包括多亚甲基多苯基异氰酸酯、氢化亚甲基二苯基异氰酸酯、间亚苯基二异氰酸酯、亚萘基-1,5-二异氰酸酯、1-甲氧基亚苯基-2,4-二异氰酸酯、4,4'-亚联苯基二异氰酸酯、3,3'-二甲氧基-4,4'-联苯基二异氰酸酯、3,3'-二甲基-4,4'-联苯基二异氰酸酯和3,3'-二甲基二苯基甲烷-4,4'-二异氰酸酯;典型的脂族多异氰酸酯是亚烷基二异氰酸酯,诸如三亚甲基二异氰酸酯、四亚甲基二异氰酸酯和六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯和4,4'-亚甲基双(环己基异氰酸酯)等;典型的芳族多异氰酸酯包括间亚苯基二异氰酸酯和对亚苯基二异氰酸酯、多亚甲基多苯基异氰酸酯、2,4-甲苯二异氰酸酯和2,6-甲苯二异氰酸酯、联茴香胺二异氰酸酯、二亚氨基异氰酸酯、亚萘基1,4-二异氰酸酯、双(4-异氰酸基苯基)亚甲基、双(2-甲基-4-异氰酸基苯基)甲烷。优选的多异氰酸酯是多亚甲基多苯基异氰酸酯,特别是含有约30-约85重量%的亚甲基双(苯基异氰酸酯)的混合物,其中该混合物的其余部分包含官能度大于2的多亚甲基多苯基多异氰酸酯。这些多异氰酸酯通过本领域已知的常规方法制备。在本发明中,多异氰酸酯和多元醇的使用量将产生在约0.9至约5.0范围内的NCO/OH化学计量比。在本发明中,NCO/OH当量比率优选地为约1或更大且约4或更小,理想范围为约1.1至约3。特别合适的有机多异氰酸酯包括多亚甲基多苯基异氰酸酯、亚甲基双(苯基异氰酸酯)、甲苯二异氰酸酯或它们的组合。
使用多元醇预混组合物和异氰酸酯制备聚氨酯和/或聚异氰脲酸酯泡沫可遵循本领域公知的任何方法进行,参见Saunders和Frisch,第I卷和第II卷,PolyurethanesChemistry and Technology,1962;John Wiley和Sons,New York,N.Y.;或者Gum、Reese、Ulrich,Reaction Polymers,1992,Oxford University Press,New York,N.Y.;或者Klemnner和Sendijarevic,Polymeric Foams and Foam Technology,2004,HanserGardner Publications,Cincinnati,OH,所有这些文献均以引用方式并入本文。一般来讲,聚氨酯和/或聚异氰脲酸酯泡沫通过特别是将异氰酸酯和多元醇预混组合物混合来制备。所产生的泡沫优选地为闭孔泡沫,其可为硬质的或半硬质的。优选地,所产生的泡沫为硬质泡沫。
出于本发明的目的,异氰酸酯可与其他组分诸如某些硅氧烷表面活性剂组合提供。异氰酸酯可与发泡剂混合,但在本专利申请中设想,发泡剂将至少主要构成第一方面的多元醇预混组合物。然而,本发明确实包括其中发泡剂的至少一部分与异氰酸酯组合的选项。
聚氨酯泡沫、聚异氰脲酸酯泡沫或它们的混合物通过将异氰酸酯和多元醇预混组合物放在一起来制备,或通过手动混合用于小制备,以及优选地通过机器混合连续或不连续生产技术以形成板、块、平板、层合物、现场灌注面板和其他物品、喷涂泡沫、泡沫等。任选地,可将其他成分诸如着色剂、辅助发泡剂、水、催化剂和甚至其他多元醇作为流添加到混合头或反应部位中。然而,最便利的是将它们全部掺入到如上所述的多元醇预混组合物中。
出于本发明的目的,聚氨酯泡沫、聚异氰脲酸酯泡沫或它们的混合物被生产为连续或不连续的现场灌注面板、板或喷涂泡沫。
具体地,当泡沫以板或面板的形式提供时,泡沫可通过以下方式来产生:将可发泡混合物倾倒在面板的两个面层之间,从而允许泡沫上升以产生“泡沫夹层”,其被切割成期望长度。面板的面层可以是铝箔、屋顶纸、金属、木材等。然后,可将所得的板或面板施加到现有的建筑物围护结构或用于形成建筑物围护结构。这些面板可通过连续或不连续方法两者来产生。
本发明的第二方面提供了由本发明第一方面的方法产生的聚氨酯泡沫、聚异氰脲酸酯泡沫或它们的混合物。
出于本发明的目的,泡沫含有1-15重量%、优选地2-13重量%、更优选地4-12重量%的发泡剂。发泡剂如本发明的第一方面所定义。
制得的聚氨酯泡沫、聚异氰脲酸酯泡沫或它们的混合物的密度可在约0.5磅/立方英尺至约60磅/立方英尺、优选地约1.0至20.0磅/立方英尺以及最优选地约1.5至6.0磅/立方英尺内变化。所得密度是发泡剂或发泡剂混合物的量加上用于制备泡沫的辅助发泡剂(诸如水或其他共发泡剂)的量的函数。
在许多用途中,本发明的泡沫可用于隔离建筑物(例如建筑物围护结构)或其中期望能量管理和/或隔离其外侧上的温度波动的任何构造。此类结构包括本领域已知的任何标准结构,包括但不限于由粘土、木材、石材、金属、塑料、混凝土等制造的那些,包括但不限于房屋、办公楼或住宅、商业、工业、农业或可能期望能量效率和绝热的其他结构。
因此,本发明的第二方面涉及通过本发明第一方面的方法产生的板泡沫、泡沫芯面板或喷涂泡沫。
本发明第二方面的泡沫提供了λ老化随时间推移减轻的特别优点。具体地,泡沫在70℃下老化21天后显示出λ老化的减轻。更具体地,泡沫在70℃下老化21天后的Δλ小于或等于6mW/mK。
具体地,该泡沫显示在70℃下老化21天后λ老化的减轻,如根据EN13165(2010)的C.2和C.3章节中针对除喷涂泡沫之外的所有泡沫列出的“正态性检验”测量的,或如根据EN14315(2013)的C.2或C.3章节中针对喷涂泡沫所列出的“正态性检验”测量的。更具体地,该泡沫在70℃下老化21天后具有小于或等于6mW/mK的Δλ,如根据EN13165(2010)的C.2和C.3章节中针对除喷涂泡沫之外的所有泡沫所列出的“正态性检验”测量的,或如根据EN14315(2013)的C.2或C.3章节中针对喷涂泡沫所列出的“正态性检验”测量的。
本发明的第三方面涉及形成制品的方法,该制品用于建筑物围护结构中或作为建筑物围护结构的一部分,该制品包括基板和在此类基板上和/或附接到此类基板的泡沫,其中该方法包括根据本发明第一方面的方法形成所述泡沫,所述泡沫与待安装在所述建筑物围护结构中的制品相关联和/或与已经安装在建筑物围护结构中的诸如墙壁、天花板或屋顶部件的结构物体或基板相关联。
安装步骤可包括诸如通过形成面板或绝热板而预先形成泡沫,并将所述预先形成的泡沫安装在建筑物围护结构之上或之中。另选地或除此之外,安装步骤可包括在建造围护结构时或之后将泡沫形成到建筑物围护结构的基板或部件之中或之上。
当泡沫作为喷涂泡沫提供时,可将可发泡混合物施加到建筑物围护结构(例如施加到墙壁、屋顶、基础结构等),其中泡沫发泡以提供原位绝热。然后可用保护性涂层或内墙或外墙饰面来覆盖该泡沫。
针对本发明的每个方面描述的所有优选特征加以必要的变更适用于所有其他方面。
附图说明
图1是Δλ对TCPP剂量的依赖性的图形表示。
图2是TCPP和TEP的70℃/21天的老化比较的图形表示。
图3是RB-79对λ老化的影响的图形表示。
图4是TCPP与RB-79的组合对初始λ的影响的图形表示。
图5是TCPP与RB-79的组合对λ老化的影响的图形表示
图6是TCPP和RB-9170的FR组合对初始λ的影响的图形表示
图7是TCPP和RB-9170的FR组合对λ老化的影响的图形表示。
图8是相比于1233zd(E)泡沫(顶部线)而言,TCPP对1336mzz(Z)发泡泡沫(底部线)的λ老化的影响的图形表示。
实验
原材料:
Stepanpol PS 2352(Stepan):聚酯多元醇,羟基值:240mgKOH/g,官能度:2
NIAX硅氧烷L-6900:得自Momentive的不可水解的硅表面活性剂
Dabco K15:得自Air Products(现为Evonik)的辛酸钾二甘醇溶液
Polycat8:得自Air Products的N,N-二甲基环己胺
Lupranate M 20S:聚合异氰酸酯,31.5%NCO,官能度:2.7,得自BASF
Desmodur MDI 44V20L:聚合异氰酸酯,31.5%NCO,官能度:2.7,得自Covestro
磷酸三(1-氯-2-丙基)酯(TCPP),得自江苏雅克
磷酸三甲酯(TEP),得自江苏雅克
Saytex RB-79(溴基反应性阻燃剂,溴含量:45%,羟基值:210mgKOH/g,得自Albermarle)
Saytex RB-9170:溴基反应性阻燃剂,溴含量:43%,羟基值:170mgKOH/g,得自Albermarle
多元醇共混物:通过混合基于以下配方的材料来产生共混物。
发泡:基于以下列出的配方,通过手工混合来产生泡沫。使用模具(30cm*30cm*10cm)。
λ值:使用LaserComp FOX50记录λ值,样本尺寸为20cm*20cm*2cm。
泡沫的平均λ值的测定
泡沫热导率根据EN13165:2008的5.3.2章节和EN14135-1:2013的4.2.2章节的要求来测量。这两个标准都需要EN12667或对于厚产品的EN12939的热导率测试。对于该文献中给出的数据,样本厚度不超过测试装置的测试能力,因此遵循EN 12667(参见EN12939,第1章节“范围”)。EN 12667允许使用两种类型的用于测量热导率的装置,即防护热板或热流计。对于本文中给出的数据,使用热流计(Fox 314)。该装置符合EN12667附录D。
通过测量热通量、样本厚度和跨样本的温差来确定样本的热导率。在热导率公式的每个分量中,FOX仪器提供了非常精确的读数,累计高输出热通量换能器的分辨率为6mV,厚度测量的精度为0.001”,温度控制和分辨率为0.01℃。
对于每项单独的测试,在制备泡沫之后,从泡沫块切割下来尺寸为300mm×300mm×20mm的泡沫样本,并使其在室温下固化24小时。将泡沫样本置于平均温度设为10℃(热板温度15.6℃,冷板温度4.4℃)的Fox314热流计中,并测量热导率。该测量结果被称为初始λ。在测试完成后,将样本从装置中取出,并放入设定为70℃的烘箱中。在70℃下老化21天后,将样本从烘箱中取出,并在室温下放置16小时。在该室温老化之后,使用上述程序再次测试样本的热导率。其被称为老化的λ。
结果与讨论
1。磷酸三(1-氯-2-丙基)酯(TCPP)对1233zd(E)发泡泡沫的λ老化的影响
为了评估TCPP在PIR泡沫中对λ老化性能的影响,在配方中使用不同剂量的TCPP,如表2所示。泡沫具有约33kg/m3的自由发泡密度。模制泡沫具有约41kg/m3的芯密度。
表2。具有不同剂量的TCPP的PIR配方
TCPP剂量(phpp)的影响列于下表3中。
表3 TCPP对λ老化的影响
TCPP剂量(phpp) | 0 | 10 | 20 | 30 |
初始λ(10℃,mW/mK) | 18.32 | 18.76 | 18.60 | 18.51 |
老化λ(10℃,mW/mK) | 23.48 | 24.14 | 24.38 | 24.81 |
初始λ值表明,与含TCP的PIR泡沫的初始λ值相比,在不存在TCPP下产生的PIR泡沫显示出稍好的初始λ值。将泡沫在70℃下老化21天后,所有λ值均增加,正如预期的那样。如图1所示,Δλ随着TCPP剂量的增加而增加。
2。磷酸三(1-氯-2-丙基)酯(TCPP)相比于磷酸三乙酯(TEP)
由含有20份TEP(表4)的多元醇共混物制备的PIR泡沫具有19.47mW/mK的初始λ。将该泡沫在70℃下老化21天后,所得的Δλ为6.93mW/mK,大于含TCPP的泡沫的Δλ(如图2所示)。
表4用于比较TCPP和TEP的配方
3。TCPP相比于SaytexRB-79
研究了Saytex RB-79(四溴邻苯二甲酸酐与二甘醇和丙二醇的羟基封端酯)对λ老化的影响。具有10phpp RB-79(表5)的PIR泡沫的初始λ为18.41mW/mK(10℃)。将泡沫在70℃老化21天后,λ变为23.48mW/mK。Δλ仅为5.08mW/mK,优于含有10phpp TCPP的泡沫(图3)并且优于不含任何阻燃剂的泡沫,5.16mW/mK。(参见图1)
表5用于比较TCPP和RB79的配方
4。TCPP与RB-79或RB-9170组合的影响
为了满足EN13165测试,发现TCPP的剂量必须受到限制。在这种情况下,除了TCPP之外,可能还需要采用第二阻燃剂。该第二阻燃剂可提供所需的泡沫防火性能,而不会不利地影响λ老化。基于上述结果,RB 79或类似的溴化阻燃剂RB-9170可能是用于本专利申请以解决λ老化问题的潜在候选物。
表6示出了其中将低剂量的TCPP(10phpp)与分别在3phpp和5phpp下的RB-79或RB-9170组合使用的配方。
表6用于研究TCPP与第二阻燃剂的影响的配方
据发现,向TCPP添加RB-79或RB-9170不仅减轻了初始λ,而且还改善了泡沫的λ老化(图4和图5)。
反应性阻燃剂RB-9170的粘度比RB-79低得多(3000cps相比于100000cps)。它应有利于PIR制造中的流动性。当与TCPP组合使用时,该反应性阻燃剂对于初始λ和老化λ表现出与RB-79类似的效果(图6和图7)。需注意,初始λ值在RB 9170的剂量为3phpp时比为5phpp时低。
5。TCPP对1336mzz(Z)发泡泡沫的λ老化的影响
当含有不同剂量的TCPP(表7)的1336mzz(Z)发泡泡沫老化时,Δλ随着TCPP剂量的增加而增加,如1233zd(E)发泡泡沫的情况(图8)。然而,在每种TCPP剂量下,1336mzz(Z)发泡泡沫的Δλ总是小于1233zd(E)发泡泡沫的Δλ。
表7用于研究TCPP对1336mzz(Z)发泡泡沫的λ老化的影响的配方
Claims (28)
1.一种减轻聚氨酯泡沫、聚异氰脲酸酯泡沫或它们的混合物的λ老化的方法,所述方法包括由包含异氰酸酯和多元醇预混组合物的可发泡组合物产生所述泡沫;
其中所述多元醇预混组合物包含:多元醇或多元醇的混合物;发泡剂,所述发泡剂选自1,3,3,3-四氟丙烯(1234ze)、1,1,1,4,4,4-六氟-2-丁烯(1336mzzm)和/或1-氯-3,3,3-三氟丙烯(1233zd);以及阻燃剂,其中所述阻燃剂包括25phpp或更少的磷酸酯基阻燃剂。
2.根据权利要求1所述的方法,其中所述泡沫在70℃下老化21天后具有小于或等于6mW/mK的Δλ。
3.根据权利要求1或权利要求2所述的方法,其中所述阻燃剂包括20phpp或更少的磷酸酯基阻燃剂。
4.根据权利要求1或权利要求2所述的方法,其中所述阻燃剂包括15phpp或更少的磷酸酯基阻燃剂。
5.根据权利要求1或权利要求2所述的方法,其中所述阻燃剂包括10phpp或更少的磷酸酯基阻燃剂。
6.根据权利要求1或权利要求2所述的方法,其中所述阻燃剂包括5phpp或更少的磷酸酯基阻燃剂。
7.根据权利要求1至6中任一项所述的方法,其中所述磷酸酯基阻燃剂为以下中的一种或多种:磷酸三(2-氯乙基)酯、磷酸三(2-氯丙基)酯、磷酸三(1,3-二氯丙基)酯、磷酸三(2-氯异丙基)酯、磷酸三甲苯酯、磷酸三(2,2-二氯异丙基)酯、N,N-双(2-羟乙基)氨甲基膦酸二乙酯、甲基膦酸二甲酯、磷酸三(1,3-二氯异丙基)酯、N,N-双(2-羟乙基)氨甲基膦酸二乙酯(Fyrol 6)、二磷酸四(2-氯乙基)亚乙基酯、磷酸三乙酯和磷酸铵,更优选地磷酸三(1-氯-2-丙基)酯(TCPP)、磷酸三乙酯(TEP)和N,N-双(2-羟乙基)氨甲基膦酸二乙酯(Fyrol6)。
8.根据权利要求1至7中任一项所述的方法,其中所述阻燃剂还包括溴化反应性阻燃剂。
9.权利要求8所述的方法,其中所述溴化反应性阻燃剂是Saytex RB-79或Saytex RB-9170。
10.根据权利要求1至9中任一项所述的方法,其中所述发泡剂包括反式-1,3,3,3-四氟丙烯(1234ze(E))、顺式-1,1,1,4,4,4-六氟-2-丁烯(1336mzzm(Z))或反式-1-氯-3,3,3-三氟丙烯(1233zd(E))中的一种或多种。
11.根据权利要求1至10中任一项所述的方法,其中所述发泡剂包括反式-1-氯-3,3,3-三氟丙烯(1233zd(E))。
12.根据权利要求1至11中任一项所述的方法,其中所述发泡剂包括共发泡剂。
13.根据权利要求12所述的方法,其中所述共发泡剂是选自以下中的一种或多种:水、产生CO2和/或CO的有机酸、反式-1,2二氯乙烯;甲缩醛、甲酸甲酯;1,1,1,2-四氟乙烷(134a);1,1,1,3,3-五氟丁烷(365mfc);1,1,1,2,3,3,3-七氟丙烷(227ea)、1,1-二氟乙烷(152a);
1,1,1,3,3-五氟丙烷(245fa);丁烷;异丁烷;正戊烷;异戊烷;环戊烷,或它们的组合。
14.根据权利要求12或13中任一项所述的方法,其中所述共发泡剂是水和/或正戊烷、异戊烷或环戊烷中的一种或组合。
15.根据权利要求1至14中任一项所述的方法,其中所述发泡剂包括反式-1-氯-3,3,3-三氟丙烯(1233zd(E))和水。
16.根据权利要求15所述的方法,其中所述发泡剂基本上由反式-1-氯-3,3,3-三氟丙烯(1233zd(E))和水组成。
17.根据权利要求1至16中任一项所述的方法,其中所述发泡剂具有不大于150、优选地不大于100并且更优选地不大于75的全球变暖潜能值。
18.根据权利要求1至17中任一项所述的方法,其中所述发泡剂具有不大于0.05、优选地不大于0.02并且更优选地约零的臭氧消耗潜能值(ODP)。
19.根据权利要求1至18中任一项所述的方法,其中所述发泡剂组分以按所述多元醇预混组合物的重量计约1重量%至约30重量%、优选地约3重量%至约25重量%、并且更优选地约5重量%至约25重量%的量存在于所述多元醇预混组合物中。
20.根据权利要求12至19中任一项所述的方法,其中所述反式-1,3,3,3-四氟丙烯(1234ze(E))、顺式-1,1,1,4,4,4-六氟-2-丁烯(1336mzzm(Z))或反式-1-氯-3,3,3-三氟丙烯(1233zd(E))以按所述发泡剂的重量计约5重量%至约99重量%、优选地约7重量%至约98重量%、并且更优选地约10重量%至约95重量%的量存在于所述发泡剂中;并且任选的发泡剂优选地以按所述发泡剂的重量计约95重量%至约1重量%、优选地约93重量%至约2重量%、并且更优选地约90重量%至约5重量%的量存在于所述发泡剂中。
21.根据权利要求1至20中任一项所述的方法,其中所述多元醇或多元醇混合物以按所述多元醇预混组合物的重量计约50重量%至约95重量%、优选地约50重量%至约85重量%、并且更优选地约55重量%至约80重量%的量存在于所述多元醇预混组合物中。
22.根据权利要求1所述的方法,其中所述多元醇预混组合物包含:多元醇或多元醇的混合物;包括反式1-氯-3,3,3-三氟丙烯(反式1233zd)的发泡剂;以及一种或多种共发泡剂,所述一种或多种共发泡剂选自水、产生CO2和/或CO的有机酸、反式-1,2二氯乙烯;甲缩醛、甲酸甲酯;1,1,1,2-四氟乙烷(134a);1,1,1,3,3-五氟丁烷(365mfc);1,1,1,2,3,3,3-七氟丙烷(227ea)、1,1-二氟乙烷(152a);
1,1,1,3,3-五氟丙烷(245fa);丁烷;异丁烷;正戊烷;异戊烷;环戊烷或它们的组合;聚硅氧烷聚氧化烯嵌段共聚物表面活性剂,其量为所述多元醇预混组合物的0.5重量%至约5.0重量%;胺催化剂,其量为所述多元醇预混组合物的0.1重量%至8重量%;以及/或者包括含有铋、铅、锑、锡、锌、钾或它们的组合的有机金属化合物的金属催化剂,其量为所述多元醇预混组合物的0.01重量%至2.5重量%;以及阻燃剂,其中所述阻燃剂包括25PHPP或更少的磷酸酯基阻燃剂。
23.根据权利要求22所述的方法,其中所述阻燃剂包括20phpp或更少的磷酸酯基阻燃剂。
24.根据权利要求23所述的方法,其中所述阻燃剂包括15phpp或更少的磷酸酯基阻燃剂。
25.根据权利要求24所述的方法,其中所述阻燃剂包括10phpp或更少的磷酸酯基阻燃剂。
26.根据权利要求25所述的方法,其中所述阻燃剂包括5phpp或更少的磷酸酯基阻燃剂。
27.根据权利要求1至26中任一项所述的方法,其中所述泡沫为面板、板或喷涂泡沫的形式。
28.一种用于形成制品的方法,所述制品用于建筑物围护结构中或作为所述建筑物围护结构的一部分,所述制品包括基板和在此类基板上和/或附接到此类基板的泡沫,其中所述方法包括通过权利要求1至27中任一项所述的方法形成泡沫,所述泡沫与待安装在所述建筑物围护结构中的制品相关联和/或与已经安装在所述建筑物围护结构中的诸如墙壁、天花板或屋顶部件的结构物体或基板相关联。
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CN101896525A (zh) * | 2007-10-12 | 2010-11-24 | 霍尼韦尔国际公司 | 包含卤代烯烃发泡剂的聚氨酯泡沫多元醇预混物的稳定 |
CN102532582A (zh) * | 2010-10-28 | 2012-07-04 | 霍尼韦尔国际公司 | 包含1,1,1,3,3,3-六氟丁烯和1-氯-3,3,3-三氟丙烯的混合物 |
WO2013082964A1 (en) * | 2011-12-09 | 2013-06-13 | Honeywell International Inc. | Foams and articles made from foams containing hcfo or hfo blowing agents |
CN106700119A (zh) * | 2016-12-26 | 2017-05-24 | 青岛海尔股份有限公司 | 发泡剂组合物和聚氨酯硬质泡沫 |
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JP2020533420A (ja) | 2020-11-19 |
JP7350661B2 (ja) | 2023-09-26 |
MX2019014811A (es) | 2020-02-10 |
CA3066294A1 (en) | 2018-12-20 |
JP2023175797A (ja) | 2023-12-12 |
TW201903046A (zh) | 2019-01-16 |
WO2018227358A1 (en) | 2018-12-20 |
KR20200030030A (ko) | 2020-03-19 |
KR20220121262A (ko) | 2022-08-31 |
EP3638707A1 (en) | 2020-04-22 |
US20240076463A1 (en) | 2024-03-07 |
EP3638707A4 (en) | 2021-01-20 |
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