CN105829378B - 制造阻燃聚氨酯泡沫的方法 - Google Patents
制造阻燃聚氨酯泡沫的方法 Download PDFInfo
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- CN105829378B CN105829378B CN201480070008.3A CN201480070008A CN105829378B CN 105829378 B CN105829378 B CN 105829378B CN 201480070008 A CN201480070008 A CN 201480070008A CN 105829378 B CN105829378 B CN 105829378B
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- polyalcohol
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- polyurethane foam
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- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 34
- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 29
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- 238000002485 combustion reaction Methods 0.000 title abstract description 12
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- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 26
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 16
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 239000003063 flame retardant Substances 0.000 claims description 27
- 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 description 15
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
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- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 239000012972 dimethylethanolamine Substances 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical group CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
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- BHNZEZWIUMJCGF-UHFFFAOYSA-N 1-chloro-1,1-difluoroethane Chemical compound CC(F)(F)Cl BHNZEZWIUMJCGF-UHFFFAOYSA-N 0.000 description 1
- PQXKWPLDPFFDJP-UHFFFAOYSA-N 2,3-dimethyloxirane Chemical compound CC1OC1C PQXKWPLDPFFDJP-UHFFFAOYSA-N 0.000 description 1
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- 239000004604 Blowing Agent Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical group CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Chemical group O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- RREGISFBPQOLTM-UHFFFAOYSA-N alumane;trihydrate Chemical compound O.O.O.[AlH3] RREGISFBPQOLTM-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
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- 238000010924 continuous production Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
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- 229940113088 dimethylacetamide Drugs 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
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- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 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
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 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 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- RDBMUARQWLPMNW-UHFFFAOYSA-N phosphanylmethanol Chemical class OCP RDBMUARQWLPMNW-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000126 substance Chemical group 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000012970 tertiary amine catalyst Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical group [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 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 1
- RMLPZKRPSQVRAB-UHFFFAOYSA-N tris(3-methylphenyl) phosphate Chemical compound CC1=CC=CC(OP(=O)(OC=2C=C(C)C=CC=2)OC=2C=C(C)C=CC=2)=C1 RMLPZKRPSQVRAB-UHFFFAOYSA-N 0.000 description 1
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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
- C08G18/16—Catalysts
- C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
- C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
- C08G18/165—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22 covered by C08G18/18 and C08G18/24
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4866—Polyethers having a low unsaturation value
-
- 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
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Abstract
一种用于制造阻燃聚氨酯泡沫的方法,所述方法包括使PO基多元醇与泡沫形成反应物反应以提供所述聚氨酯泡沫,其中所述多元醇通过环氧烷在复合金属氰化物络合物催化剂存在下的开环聚合制备,并且其中所述多元醇没有EO部分或者包含量最多为1重量%的EO部分。
Description
发明领域
本发明涉及柔性聚氨酯泡沫。特别是,虽然并非排他,但本发明涉及制造符合耐燃(flame resistant)标准的耐燃性聚氨酯泡沫的方法、可以由此获得的泡沫、和特定的聚醚多元醇帮助实现耐燃性的用途。
发明背景
柔性聚氨酯泡沫已经在众多的工业和消费者应用中发现广泛的用途。这种普遍性是因为它们宽泛的机械性质和易于制造的能力。主要应用行业是汽车和飞机工业、软垫家具和技术制品。例如,都是从柔性聚氨酯泡沫制造的全泡沫座椅、座椅的顶部垫和背部与头部的约束装置被广泛用于汽车和飞机。其他应用包括使用柔性聚氨酯泡沫作为地毯背衬、寝具和床垫、摩托车泡沫鞍座、车身与其灯之间的衬垫、发动机空气过滤器的唇形密封、和减少声音与震动的汽车零件与发动机零件上的隔绝层。
如本领域技术人员所公知的,聚氨酯从异氰酸酯基团与羟基基团的反应形成。最常见的聚氨酯生产方法是通过多元醇与异氰酸酯的反应。交联剂、发泡剂、催化剂和其他添加剂也可以在需要时包括在聚氨酯制剂中。
柔性聚氨酯生产中使用的多元醇通常来自于环氧烷(如环氧丙烷和环氧乙烷)和各种各样的起始物如乙二醇、丙二醇、甘油、蔗糖和山梨糖醇。已知用于生产多元醇的方法包括环氧烷在碱金属催化剂存在下的开环聚合,和环氧烷在复合金属氰化物络合物催化剂存在下的开环聚合。
对于许多应用,柔性聚氨酯泡沫要求是耐燃的,即符合一种或多种耐燃性标准。耐燃性标准的一个实例是英国标准BS 5852,第二部分,例如其中的Crib 5测试。该测试对泡沫的抗引燃性推行了严格的要求。众所周知的耐燃性标准的另一个实例是Cal 117SectionA—第一部分。
本领域已知生产为耐燃性和柔性二者的聚氨酯泡沫的各种各样的方法。一组方法涉及使用特别定制的多元醇,但这些趋于昂贵。另外地或替代性地,表现出耐燃性的柔性聚氨酯泡沫可以依赖于包含阻燃(flame retardant)添加剂。例如,可以包含的阻燃添加剂包括:矿物,如三水合铝;盐,如羟甲基鏻盐;含磷化合物;磷酸酯;和卤烃或其他卤代化合物,如包含溴和/或氯的那些。然而,期望限制使用这样的阻燃剂。阻燃添加剂是昂贵的,可以使柔性聚氨酯泡沫的生产/形成复杂化,并且可以负面地影响以此形成的柔性聚氨酯泡沫的物理性质。
本发明的一个目的是以低成本和/或使用降低的阻燃添加剂水平提供耐燃性聚氨酯泡沫。
发明内容
现已发现,没有环氧乙烷(EO)部分或仅含有低百分比的EO部分,并且已经通过环氧烷在复合金属氰化物络合物催化剂存在下的开环聚合产生的环氧丙烷(PO)基多元醇在制造阻燃聚氨酯泡沫的情况下提供了特别的益处。
根据本发明的第一方面,提供了一种用于制造阻燃聚氨酯泡沫的方法,所述方法包括使PO基多元醇与泡沫形成反应物反应以提供所述聚氨酯泡沫,其中所述多元醇通过环氧烷在复合金属氰化物络合物催化剂存在下的开环聚合制备,并且其中所述多元醇没有EO部分或者包含量最多为1重量%的EO部分。
进一步地,从第二方面,本发明在于可通过本发明的第一方面的方法获得的聚氨酯泡沫。再进一步地,从第三方面,本发明在于包含这样的聚氨酯泡沫的成型制品。
从第四方面,本发明在于多元醇用于制备聚氨酯泡沫以增强所述泡沫的耐燃性和/或降低所述泡沫中阻燃添加剂的量的用途,所述多元醇通过环氧烷在复合金属氰化物络合物催化剂存在下的开环聚合制备,并且没有EO部分或者包含量最多为1重量%的EO部分。该用途可以例如依照本文限定的或描述的任何方法。
具体实施方式
与现有技术如WO9951661A1的教导相反,已经发现没有EO部分或者含有最多1%EO部分的PO基多元醇提供了特别的优势。具体而言,已经发现这样的多元醇增强了耐燃性并且可以因此减少对泡沫中阻燃添加剂的需要。它们也是用于泡沫生产的有成本效益的材料,特别是因为它们可以在连续方法中生产。
PO基多元醇任选地含有量最多为1重量%的EO部分。在EO部分存在于多元醇中的情况下,它们可以优选与PO部分随机共聚。在一个实施方式中,多元醇任选地含有量最多为0.9重量%、最多0.8重量%、最多0.7重量%、最多0.6重量%或最多0.5重量%的EO部分(即,如果有的话)。多元醇可以有利地包含组成多元醇的剩余部分的余量的PO部分。在一个实施方式中,多元醇仅包含PO部分(与如将描述的起始物组合)。
EO部分以重量%表示的量是基于存在的总氧化烯单元,并且可以依照ASTM D4875进行测量。
要在本方法中制备的聚氨酯泡沫是柔性聚氨酯泡沫。适合于制备柔性聚氨酯泡沫的聚醚多元醇倾向于具有相对高的数均分子量和相对低的标称官能度。
在一个实施方式中,可用于本发明的PO基多元醇具有在2500至15000道尔顿、优选2750至4000道尔顿、最优选2800至3200道尔顿范围内的数均分子量。有利地,多元醇具有在2至4范围内、优选2至3.5范围内、最优选2.5至3范围内的标称官能度(Fn)。
PO基多元醇的羟值适合地是15至150mg KOH/g、更适合地是20至75mg KOH/g。
PO基多元醇通常通过使具有多个活性氢原子的起始化合物或引发剂与PO和任选的EO反应而获得。具有2至12个羟基基团和300至5,000道尔顿的数均分子量的多羟基醇,如乙二醇、丙二醇、二乙二醇、二丙二醇、三羟甲基丙烷或甘油、或聚醚一元醇或聚醚多元醇可以用作引发剂,其可以通过环氧烷与上述多羟基醇在碱性催化剂或阳离子催化剂存在下的开环聚合获得。上述多羟基醇中羟基基团的数量优选是2至8,特别优选2至3。最优选地,使用丙二醇(MPG)、甘油或二者的组合作为引发剂。
引发剂可以与环氧烷和/或催化剂一起连续引入反应器中以进行环氧烷的聚合。在这种情况下,可以使用具有低分子量的多羟基醇作为引发剂。就具有低分子量的多羟基醇而言,可以使用具有最多400的分子量的多羟基醇,如乙二醇、丙二醇、二乙二醇、二丙二醇、三羟甲基丙烷或甘油。最优选地,还是在这种情况下,使用丙二醇(MPG)、乙二醇(MEG)、二乙二醇(DEG)、甘油或其组合作为引发剂。
或者,分批式方法也是本领域所已知的,并且原则上可以用于制备PO基多元醇。然而,已经令人惊讶地发现通过连续方法生产的PO基多元醇在聚氨酯泡沫中提供了改善的耐燃性。因此,这样的通常具有更高多分散指数(重均分子量Mw/数均分子量Mn)的PO基多元醇是优选的。
在一个实施方式中,PO基多元醇具有在1.18至1.5范围内,如1.2至1.4范围内,特别是在1.22至1.3范围内的多分散指数(Mw/Mn)。
特别是在与碱金属催化的连续方法相比时,复合金属氰化物催化的聚合通常倾向于产生不利地影响耐燃性的少量低分子量化合物(特别是低分子量一元醇)。
用于生产PO基多元醇的复合金属氰化物络合物催化剂是本领域公知的。复合金属氰化物络合物催化剂还经常称为双金属氰化物(DMC)催化剂。复合金属氰化物络合物催化剂通常由下式(1)表示:
(1)M1 a[M2 b(CN)c]d.e(M1 fXg).h(H2O).i(R)
其中M1和M2各自是金属,X是卤原子,R是有机配体,a、b、c、d、e、f、g、h和i各自是可以根据金属的原子平衡、待配位的有机配体的数量等变化的数字。
在上式(1)中,M1优选是选自Zn(II)或Fe(II)的金属。在上式中,M2优选是选自Co(III)或Fe(III)的金属。然而,如本领域所已知的,也可以使用其他金属和氧化态。
在上式(1)中,R是有机配体并且优选是选自醇、醚、酮、酯、胺和酰胺的至少一种化合物。就有机配体而言,可以使用水溶性的有机配体。具体而言,可以使用选自叔丁基醇、正丁基醇、异丁基醇、叔戊基醇、异戊基醇、N,N-二甲基乙酰胺、甘醇二甲醚(乙二醇二甲基醚)、二甘醇二甲醚(二乙二醇二甲基醚)、三甘醇二甲醚(三乙二醇二甲基醚)、乙二醇单叔丁基醚、异丙基醇和二氧六环的一种或多种化合物作为一种或多种有机配体。二氧六环可以是1,4-二氧六环或1,3-二氧六环并且优选是1,4-二氧六环。最优选地,复合金属氰化物络合物催化剂中的有机配体或有机配体之一是叔丁基醇。进一步地,可以使用多元醇,优选聚醚多元醇,作为醇有机配体。更优选地,可以使用具有在500至2,500道尔顿、优选800至2,200道尔顿范围内的数均分子量的聚(丙二醇)作为有机配体或有机配体之一。最优选地,这样的聚(丙二醇)与叔丁基醇组合作为有机配体使用。复合金属氰化物络合物催化剂可以通过已知的生产方法产生。
通过这样的方法获得的反应产物可以洗涤然后经历过滤,由此获得的滤饼(固体组分)可以干燥以制备粉末形式的复合金属氰化物络合物催化剂。或者,在洗涤反应产物后含有有机配体和复合金属氰化物络合物催化剂的水性溶液可以分散到多元醇中,然后可以蒸馏掉过量的水和有机配体以制备浆料形式的复合金属氰化物络合物催化剂。就分散多元醇而言,可以使用聚醚多元醇。聚醚多元醇优选是具有2至12个羟基基团和300至5,000道尔顿的数均分子量的聚醚多元醇,其可通过环氧烷与多羟基醇如乙二醇、丙二醇、二乙二醇、二丙二醇、三羟甲基丙烷或甘油在碱性催化剂或阳离子催化剂存在下的开环聚合获得。这样的聚醚多元醇也可以在随后使用浆料形式的复合金属氰化物络合物催化剂产生聚醚多元醇时用作引发剂。
这样的分散多元醇中的羟基基团数量优选是2至8,特别优选2至3。要在制造所述多元醇中使用的环氧烷可以是环氧丙烷、1,2-环氧丁烷、2,3-环氧丁烷、环氧氯丙烷、氧杂环丁烷或四氢呋喃。它们可以作为它们中的两种或更多种的混合物组合使用。环氧丙烷是优选的。最优选地,所述分散多元醇是具有500至1,500道尔顿的数均分子量的聚(丙二醇)。
所述PO基多元醇可以有利地是用于制造阻燃泡沫的唯一多元醇。因此,泡沫可以从由PO基多元醇和泡沫形成反应物组成的反应物混合物制造。然而,如本领域所已知的,原则上PO基多元醇也可以与一种或多种其他多元醇组合使用。为了提供关于耐燃性的明显益处,所述PO基多元醇可以优选占用于制造阻燃泡沫的多元醇的总量的至少50重量%。
如本领域所已知的,泡沫形成反应物将通常包含在发泡剂存在下的多异氰酸酯。
多异氰酸酯可以例如是芳族多异氰酸酯,如甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯或聚亚甲基聚苯基异氰酸酯;脂族多异氰酸酯,如六亚甲基二异氰酸酯、亚二甲苯基二异氰酸酯、二环己基甲烷二异氰酸酯、赖氨酸二异氰酸酯或四甲基亚二甲苯基二异氰酸酯;脂环族多异氰酸酯,如异佛尔酮二异氰酸酯或其改性产物。在一个实施方式中,多异氰酸酯是80重量%的2,4-甲苯二异氰酸酯和20重量%的2,6-甲苯二异氰酸酯的混合物,该混合物作为“TDI-80”销售。
在本发明的聚氨酯制备方法中,多异氰酸酯中的异氰酸酯(NCO)基团与聚醚多元醇和任意水中的羟基(OH)基团的摩尔比率可以是使得最终聚氨酯泡沫不含有游离的末端NCO基团。
所述NCO/OH的摩尔比率优选是0.7/1至1.5/1。NCO/OH摩尔比率为1/1对应于异氰酸酯指数为100。
用于制备本发明的聚氨酯泡沫的发泡剂的类型并不关键。例如,适合的发泡剂包括水、丙酮、气体或液体二氧化碳、卤代烃、脂族烷和脂环族烷。由于全氯化的、氟化的烷(CFC)的臭氧耗竭作用,使用这种类型的发泡剂通常不是优选的,虽然有可能在本发明的范围内使用它们。其中至少一个氢原子尚未被卤原子取代的卤代烷(所谓的HCFC)不具有或几乎不具有任何臭氧耗竭作用,因此是要用于物理发泡泡沫中的优选卤代烃。非常适合的HCFC型发泡剂是1-氯-1,1-二氟乙烷。使用水作为(化学)发泡剂也是众所周知的。水与异氰酸酯基团依照公知的NCO/H2O反应进行反应,由此释放导致发泡发生的二氧化碳。最后,脂族和脂环族烷作为CFC的替代性发泡剂开发。这样的烷的实例是正戊烷与正己烷(脂族)和环戊烷与环己烷(脂环族)。应理解,上述发泡剂可以单独或以两种或更多种的混合物使用。发泡剂所要用的量是常规应用的那些,即:在水的情况下,0.1至10每百重量份聚醚多元醇(php)、优选0.1至5php;和在卤代烃、脂族烷和脂环族烷的情况下,0.1至50php、优选0.1至20php。
另外,其他组分也可以在本发明的聚氨酯制备方法过程中存在,如一种或多种聚氨酯催化剂、表面活性剂和/或交联剂。聚氨酯催化剂是本领域所已知的并且包括许多不同的化合物。出于本发明的目的,适合的催化剂包括锡、铅或钛基催化剂、优选锡基催化剂,如羧酸的锡盐和二烷基锡盐。具体实例是辛酸亚锡、油酸亚锡、二月桂酸二丁基锡、乙酸二丁基锡和二乙酸二丁基锡。其他适合的催化剂是叔胺,如双(2,2'-二甲基氨基)乙基醚、三甲基胺、三乙基胺、三亚乙基二胺和二甲基乙醇胺(DMEA)。可商购叔胺催化剂的实例是以商品名NIAX、TEGOAMIN和DABCO(均为商标)销售的那些。催化剂通常以0.01至2.0重量份每百重量份聚醚多元醇(php)的量使用。优选的催化剂量是0.05至1.0php。
使用泡沫稳定剂(表面活性剂)是众所周知的。有机硅氧烷表面活性剂最常规地作为泡沫稳定剂应用于聚氨酯生产中。各种各样的这样的有机硅氧烷表面活性剂是可商购的。通常,这样的泡沫稳定剂以0.01至5.0重量份每百重量份聚醚多元醇(php)的量使用。优选的稳定剂量是0.25至1.0php。
在聚氨酯泡沫生产中使用交联剂也是众所周知的。多官能二醇胺已知可用于该目的。最常使用的并且也可用于制备本发明柔性聚氨酯泡沫的多官能二醇胺是二乙醇胺,常缩写为DEOA。如果真的使用,那么交联剂以高至3.0重量份每百重量份聚醚多元醇(php)的量应用,但是在0.1至1.5php范围内的量是最适合应用的。
另外,其他众所周知的助剂,如填料和阻燃剂,也可以在聚氨酯制备方法过程中使用。
适合地,阻燃剂可以以“阻燃有效量”存在,即足以赋予聚氨酯泡沫足以通过耐燃性标准(例如BS 5852,第二部分,Crib 5或Cal 117Section A—第一部分)的耐燃性的总阻燃剂量。
在一个实施方式中,耐燃性泡沫在如下意义下是耐燃的:在BS5852,第二部分,Crib 5测试中,泡沫重量损失(由于燃烧)不超过60g,并且自熄灭时间(当冒烟/闷烧停止时)不超过10min。在一个实施方式中,泡沫重量损失不超过40g。
有利地,由于PO基多元醇的性质,本发明的方法倾向于需要减少量的阻燃剂。
阻燃剂总量优选以约10至约40重量份每百重量份聚醚多元醇(php)、优选约15至约30php的量使用。
在一个实施方式中,三聚氰胺用作主要阻燃剂。适合地,三聚氰胺可以与补充卤代磷酸酯阻燃剂一起使用。
更特别地,可用于本发明的三聚氰胺适合地以约5至约50重量份每百重量份聚醚多元醇(php)、优选约10至约20php的量在聚氨酯形成反应混合物中使用。补充阻燃剂适合地以2至约15重量份每百重量份聚醚多元醇(php)、优选3至约13php、更优选约4至约10php的量使用。
三聚氰胺可以以任何形式使用,如可以期望的,包括固体或液体形式、研磨(例如球磨)或未研磨的,如任何特定应用所可以期望的。补充卤代磷酸酯阻燃剂是可商购的,例如名称为的三-单-氯-丙基-磷酸酯(TMCP)。
在一个特定实施方式中,本发明使用与泡沫形成反应物组合的PO基多元醇来提供阻燃聚氨酯泡沫,所述泡沫形成反应物包含量为约10至约15重量份每百重量份聚醚多元醇(php)的三聚氰胺、量为4至约10php的卤代磷酸酯补充阻燃剂和量为约3至约6php的水,其中所述多元醇通过环氧烷在复合金属氰化物络合物催化剂存在下的开环聚合制备,并且其中所述多元醇没有EO部分或者包含量最多为1重量%的EO部分。
如前所述,已经发现PO基多元醇增强了泡沫的耐燃性。因此,使用PO基多元醇可以使得能够减少泡沫符合耐燃性标准所需要的阻燃添加剂的量。
泡沫的耐燃性可以相对于如下增强,和/或所需阻燃添加剂的量可以相对于如下减少:(i)使用通过环氧烷在碱金属催化剂存在下的开环聚合制备但其他均相同的多元醇在相同条件下制造的相同泡沫;和/或(ii)使用具有大于1重量%的EO含量但其他均相同的多元醇在相同条件下制造的相同泡沫。
在本申请文件的说明书和权利要求书通篇,词语“包含”和“含有”以及这些词语的变体,例如“包含(comprising)”和“包含(comprises)”,是指“包括但不限于”,并且不排除其他部分、添加剂、组分、整数或步骤。此外,除非上下文另外要求,否则单数包括复数:特别是,在使用不定冠词的情况下,除非上下文另外要求,否则本说明书应理解为考虑到复数以及单数。
本发明的每个方面的优选特征可以描述为与任意另外方面相关。本发明的其他特征从以下实施例来看将变得明显。一般而言,本发明延伸至本申请文件(包括任何随附权利要求)中公开的特征中的任何新颖的一者或者任何新颖的组合。因此,结合本发明的特定方面、实施方式或实施例描述的特征、整数、特性、化合物、化学部分或基团要理解为可应用至本文所述的任何其他方面、实施方式或实施例,除非与之不相容。此外,除非另有说明,否则本文公开的任何特征都可以由服务于相同或相似目的的替代性特征代替。
在针对性质而引述上下限的情况下,那么也暗示了由任意上限与任意下限的组合限定的范围值。
在本说明书中,除非另有说明,否则提到性质都是在环境条件下测量的性质,即在大气压力和约20℃温度下。
本发明现将参照以下非限制性实施例作进一步描述。
实施例
实施例1
测试了从第一组多元醇生产的泡沫的可燃性。
多元醇1(比较性)具有约3000道尔顿的数均分子量,3.0的标称官能度,并且完全是PO基的。它是通过环氧丙烷在碱金属催化剂(KOH)存在下的开环聚合产生的。
多元醇2具有约3000道尔顿的数均分子量,约2.8的标称官能度,并且完全是PO基的(0重量%EO)。它是通过环氧丙烷在复合金属氰化物络合物催化剂存在下的连续开环聚合产生的。
多元醇3具有约3000道尔顿的数均分子量,约2.8的标称官能度,并且包含PO与EO部分的混合物,EO部分占约1重量%。它是通过环氧丙烷在复合金属氰化物络合物催化剂存在下的连续开环聚合产生的。
多元醇4(比较性)具有约3000道尔顿的数均分子量,约2.8的标称官能度,并且包含PO与EO部分的混合物,EO部分占约3重量%。它是通过环氧丙烷在复合金属氰化物络合物催化剂存在下的连续开环聚合产生的。
多元醇1至4各自进而使用表1所示反应混合物在相同条件下加工成聚氨酯泡沫。
表1
每种泡沫都进行BS 5852,第二部分,Crib 5测试,重量损失结果在表2中示出(5次测试的平均):
表2
注意到,依照本发明制备的多元醇2和3显示出与多元醇1和4相比增强的耐燃性。
实施例2
实施例1的多元醇3与进一步的多元醇(多元醇5)进行比较。
多元醇5是以商标ARCOL 1105S销售的BAYER多元醇。它具有约3000道尔顿的数均分子量,并且包含PO与EO部分的混合物,EO部分占约1重量%。多元醇5据信已经通过环氧丙烷在复合金属氰化物络合物催化剂的存在下基于分批的开环聚合而产生。
多元醇3和5的多分散指数(Mw/Mn)分别测定为约1.25和1.15。
多元醇3和5各自进而使用表3所示反应混合物在相同条件下加工成聚氨酯泡沫。
表3
每种泡沫都进行BS 5852,第二部分,Crib 5测试,结果在表4中示出(5次测试的平均):
表4
注意到,用连续方法制备且具有更高多分散指数的多元醇3显示出与多元醇5相比增强的耐燃性。
Claims (11)
1.一种用于制造柔性阻燃聚氨酯泡沫的方法,所述方法包括使PO基多元醇与泡沫形成反应物反应以提供所述聚氨酯泡沫,其中所述多元醇通过环氧烷在复合金属氰化物络合物催化剂存在下的开环聚合制备,并且其中所述多元醇没有EO部分或者包含量最多为1重量%的EO部分;其中所述多元醇具有在1.18至1.5范围内的多分散指数。
2.权利要求1所述的方法,其中所述多元醇如果含有EO部分的话,含有量最多为0.8重量%的EO部分。
3.权利要求1或权利要求2所述的方法,其中所述多元醇仅包含PO部分。
4.权利要求1或2所述的方法,其中所述多元醇具有在2750至4000道尔顿范围内的数均分子量和在2至3.5范围内的标称官能度。
5.权利要求1或2所述的方法,其中所述多元醇通过使具有多个活性氢原子的引发剂与PO和任选的EO反应获得,所述引发剂与所述环氧烷和所述催化剂一起连续引入反应器中以进行所述环氧烷的聚合。
6.权利要求1或2所述的方法,其中所述多元醇具有在1.2至1.4范围内的多分散指数。
7.权利要求1或2所述的方法,其中所述泡沫包含阻燃有效量的阻燃剂,使得所述泡沫通过耐燃性标准BS 5852,第二部分,Crib 5。
8.权利要求1或2所述的方法,其中所述泡沫形成反应物包含量为10至15php的三聚氰胺、量为4至10php的卤代磷酸酯补充阻燃剂、和量为3至6php的水。
9.一种可通过任意前述权利要求所述的方法获得的柔性聚氨酯泡沫。
10.一种包含如权利要求9所述的柔性聚氨酯泡沫的成型制品。
11.PO基多元醇用于制备柔性聚氨酯泡沫以增强所得泡沫的耐燃性和/或降低所述泡沫中阻燃添加剂的量的用途,所述多元醇通过环氧烷在复合金属氰化物络合物催化剂存在下的开环聚合制备,并且没有EO部分或者包含量最多为1重量%的EO部分;其中所述多元醇具有在1.18至1.5范围内的多分散指数。
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CN101389678A (zh) * | 2006-02-28 | 2009-03-18 | 旭硝子株式会社 | 软质聚氨酯泡沫塑料及其制造方法 |
CN102574978A (zh) * | 2009-09-07 | 2012-07-11 | 国际壳牌研究有限公司 | 制备聚氨酯泡沫的方法 |
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US6066683A (en) | 1998-04-03 | 2000-05-23 | Lyondell Chemical Worldwide, Inc. | Molded and slab polyurethane foam prepared from double metal cyanide complex-catalyzed polyoxyalkylene polyols and polyols suitable for the preparation thereof |
US6028230A (en) * | 1998-06-05 | 2000-02-22 | Arco Chemical Technology, L.P. | Epoxide polymerization process |
US6491846B1 (en) * | 2001-06-21 | 2002-12-10 | Bayer Antwerpen, N.V. | Process for the in-situ production of polyol blends, the in-situ produced polyol blends, and their use in the production of viscoelastic foam |
DE10143195A1 (de) * | 2001-09-04 | 2003-03-20 | Basf Ag | Integriertes Verfahren zur Herstellung von Polyurethan-Schäumen |
US7601762B2 (en) * | 2007-02-26 | 2009-10-13 | Bayer Materialscience Llc | Polyvinylchloride/polyurethane hybrid foams with improved burn properties and reduced after-glow |
-
2014
- 2014-12-19 US US15/106,844 patent/US20170002128A1/en not_active Abandoned
- 2014-12-19 ES ES14827760.1T patent/ES2676041T3/es active Active
- 2014-12-19 KR KR1020167016372A patent/KR102305944B1/ko active IP Right Grant
- 2014-12-19 RU RU2016129746A patent/RU2679138C2/ru active
- 2014-12-19 WO PCT/EP2014/078900 patent/WO2015097109A1/en active Application Filing
- 2014-12-19 BR BR112016014640-9A patent/BR112016014640B1/pt active IP Right Grant
- 2014-12-19 SG SG11201604489RA patent/SG11201604489RA/en unknown
- 2014-12-19 EP EP14827760.1A patent/EP3087115B1/en active Active
- 2014-12-19 CN CN201480070008.3A patent/CN105829378B/zh active Active
Patent Citations (4)
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US5171758A (en) * | 1990-03-12 | 1992-12-15 | Olin Corporation | Flame retardant urethane foams made using propylene oxide-based polyols |
CN1299300A (zh) * | 1998-05-05 | 2001-06-13 | 拜尔安特卫普有限公司 | 酸处理双金属氰化物络合催化剂 |
CN101389678A (zh) * | 2006-02-28 | 2009-03-18 | 旭硝子株式会社 | 软质聚氨酯泡沫塑料及其制造方法 |
CN102574978A (zh) * | 2009-09-07 | 2012-07-11 | 国际壳牌研究有限公司 | 制备聚氨酯泡沫的方法 |
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RU2679138C2 (ru) | 2019-02-06 |
RU2016129746A3 (zh) | 2018-08-29 |
SG11201604489RA (en) | 2016-07-28 |
BR112016014640A2 (zh) | 2017-08-08 |
US20170002128A1 (en) | 2017-01-05 |
CN105829378A (zh) | 2016-08-03 |
KR20160102417A (ko) | 2016-08-30 |
EP3087115B1 (en) | 2018-04-18 |
EP3087115A1 (en) | 2016-11-02 |
KR102305944B1 (ko) | 2021-09-28 |
BR112016014640B1 (pt) | 2021-09-14 |
RU2016129746A (ru) | 2018-01-30 |
WO2015097109A1 (en) | 2015-07-02 |
ES2676041T3 (es) | 2018-07-16 |
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