CN1183416A - 亚烷基桥接的膦酸烷基酯 - Google Patents
亚烷基桥接的膦酸烷基酯 Download PDFInfo
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- 125000005600 alkyl phosphonate group Chemical group 0.000 title claims abstract description 11
- 239000003063 flame retardant Substances 0.000 claims abstract description 23
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- 239000011496 polyurethane foam Substances 0.000 claims abstract description 13
- 239000003822 epoxy resin Substances 0.000 claims abstract description 3
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 3
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 3
- 239000002966 varnish Substances 0.000 claims abstract description 3
- 150000003008 phosphonic acid esters Chemical class 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 125000001118 alkylidene group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
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- 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 abstract description 3
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- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000003973 paint Substances 0.000 abstract 1
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- 150000003009 phosphonic acids Chemical class 0.000 description 5
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- 229910019142 PO4 Inorganic materials 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- -1 phosphonic acids hydrogen ester Chemical class 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
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- 229940051250 hexylene glycol Drugs 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical class [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 2
- VBUBYMVULIMEHR-UHFFFAOYSA-N propa-1,2-diene;prop-1-yne Chemical compound CC#C.C=C=C VBUBYMVULIMEHR-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- ZWVMLYRJXORSEP-LURJTMIESA-N (2s)-hexane-1,2,6-triol Chemical compound OCCCC[C@H](O)CO ZWVMLYRJXORSEP-LURJTMIESA-N 0.000 description 1
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 1
- FVHVJARLLUJUTI-UHFFFAOYSA-N 2-cyclooctylazocane Chemical compound C1CCCCCCC1C1NCCCCCC1 FVHVJARLLUJUTI-UHFFFAOYSA-N 0.000 description 1
- BYHQTRFJOGIQAO-GOSISDBHSA-N 3-(4-bromophenyl)-8-[(2R)-2-hydroxypropyl]-1-[(3-methoxyphenyl)methyl]-1,3,8-triazaspiro[4.5]decan-2-one Chemical compound C[C@H](CN1CCC2(CC1)CN(C(=O)N2CC3=CC(=CC=C3)OC)C4=CC=C(C=C4)Br)O BYHQTRFJOGIQAO-GOSISDBHSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000003197 gene knockdown Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 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
- 238000005809 transesterification reaction Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4075—Esters with hydroxyalkyl compounds
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- 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
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/025—Polyphosphazenes
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Abstract
不含卤素的具有下面通式的结构的亚烷基-桥接的膦酸烷基酯的低聚物或聚合物:式中n是1~20的整数;R1和R5每一个是C1~C6烷基;R2和R4每一个是C2~C10烷基和R3是C2~C10烷基。这种膦酸酯作为阻燃剂(例如用于聚氨基甲酸乙酯泡沫、树脂和组合物、环氧树脂、酚醛树脂、涂料、清漆和织物中)的应用或与阻燃剂结合的应用。
Description
本发明涉及亚烷基桥接的膦酸烷基酯,涉及特殊的我们相信是新的膦酸酯,涉及这类膦酸酯作为阻燃剂、或者与阻燃剂结合的应用并涉及其阻燃剂制作的制品。
为了安全,阻燃剂被加入到很多产品中,以便抑制火焰通过产品的蔓延。阻燃剂可以例如起迅速熄灭火焰的作用,或通过使产品难于点燃起作用。在阻燃剂被传统地用于处理纤维、软家具等的同时,尤其已经加入到泡沫、涂料和诸如环氧树脂之类的树脂中,很多其它的应用目前正在积极地开发之中,特别是在电子、汽车、航天和工业构件中。
聚氨基甲酸乙酯泡沫广泛地用于各种类型的座椅构件,尤其是汽车的座椅构件。这些聚氨酯泡沫不是固有的阻燃剂(实际上很多聚氨基甲酸乙酯泡沫的燃烧产物有剧毒)因而需要加入某种阻燃组分。
已经发现传统的与聚氨基甲酸乙酯泡沫座椅构件结合使用的很多阻燃剂有随着时间迁移和/或挥发的趋势。这种趋势对于汽车座椅的聚氨基甲酸乙酯泡沫构件的情形特别不利,在汽车里阻燃剂的迁移和/或挥发导致诸如窗户或仪表盘的玻璃表面“结雾”。
此外,使用含卤素的膦酸酯作为阻燃剂基于环境的理由是不希望的。
我们发现某些不含卤素的亚烷基-桥接的膦酸烷基酯的低聚物或聚合物,特别给予聚氨基甲酸乙酯泡沫以令人满意的阻燃特性。此外,这些膦酸酯已经表明当泡沫用作汽车座椅构件时已经极大地减小了“结雾”。
由此,本发明涉提供具有通式(I)结构的不含卤素的亚烷基-桥接的膦酸烷基酯的低聚物或聚合物:
式中:
n是1~20的整数;
R1和R5(它们可以相同或不同)每一个是有1~6个碳原子的烷基;
R2和R4(它们可以相同或不同)每一个是有2~10个碳原子的烷基;及
R3是起“亚烷基-桥接”基团作用的有2~10个碳原子的烷基。
本发明也提供作为一种新化合物的具有如上所述的通式(I)结构的膦酸酯,其中:
n的平均值是3;
R1和R5每一个是甲基;
R2和R4每一个是丁基;和
R3是己基。
本发明还提供作为一种新化合物的具有如上所述的通式(I)结构的膦酸酯,其中:
n的平均值是6;
R1和R5每一个是甲基;
R2和R4每一个是丁基;和
R3是亚己基。
本发明再提供作为一种新化合物的具有如上所述的通式(I)结构的膦酸酯,其中:
n的平均值是3;
R1和R5每一个是乙基;
R2和R4每一个是丁基;
R5是己基。
本发明还提供作为阻燃剂的具有如上所述的通式(I)结构的膦酸酯的应用。
最后,本发明提供通过使用具有如上所述的通式(I)结构的膦酸酯的阻燃剂制作的制品。
那么就具有通式(I)结构的膦酸酯而言,以下的变化可以在本发明的范围内。
n可以是3~8(例如3)的整数,
R1和R5每一个可以是甲基或乙基;
R2和R4每一个是有3~8个碳原子、例如4~6个碳原子的烷基,如R2和R4每一个是 丁基。
R3可以有4~8个碳原子并且可以例如是己基。
R3可以是直链或支链的,此外可以含有某些取代基例如氧或氮。
就根据本发明的膦酸酯作为阻燃剂的使用而言,这种使用包括提供对于泡沫,特别是聚氨基甲酸乙酯泡沫的阻燃性。尤其是,根据本发明的膦酸酯找到了作为阻燃剂用于由聚氨基甲酸乙酯泡沫制作的制品的特别的应用,例如作为汽车座椅构件,那里要求具有“低-结雾”的性质。
根据本发明的膦酸酯的其它应用,包括在环氧树酯、聚氨基甲酸乙酯树脂和组合物、酚醛树脂、涂料、清漆和织物的阻燃剂,或与它们结合的阻燃剂。
本发明的膦酸酯的低聚物或聚合物的“膦酸酯”组分是从磷酸(H3PO3)或从其烷基或芳基衍生物常规衍生的。
本发明将通过以下实施例具体说明:
制备膦酸烷基酯低聚物的常规工艺
1、将(Z+1)份亚磷酸二烷基酯与Z份多元醇在50~200℃在0~10摩尔%(优选0.1~2.0摩尔%)合适的酯基转移催化剂(例如甲醇钠)存在下混合并加热,用以形成单元长度=Z的H-膦酸酯低聚物。当蒸馏时回收到2Z单元的烷基醇。实际回收的醇将取决于所用的亚膦酸二烷基酯。
2、将H-膦酸酯低聚物在游离基加成条件下(例如140℃;1~2摩尔%二叔丁基过氧化物作为游离基引发剂)用(Z+1)份不饱和(优选α-不饱和)烃(例如烯烃或炔烃)处理,并且可任选地,在气态不饱和烃的情况,和在高于大气压的条件下(即在压力下反应)处理。
3、这样将生成一种粗制的高酸值膦酸烷基酯低聚物,然后将它用一种适当的方法/试剂(例如环氧丙烷)处理以便将酸值减小到适当的水平用于应用(例如作为聚氨基甲酸乙酯泡沫的阻燃剂,此时的酸值应该不超过1.0毫克KOH/g.cpd)。
4、产物用真空气提以便除去残留的挥发物,回收纯的产物。
实施例1
制备膦酸丁酯、二甲酯低聚物,n=6。10外形适于蒸馏的反应器,装入亚磷酸二甲酯(770克;7摩尔)、己烷-1,6-二醇(708克;6摩尔)和甲醇钠(0.035摩尔;7.6克25%甲醇溶液)。2)搅拌的反应混合物加热到90℃,在此温度馏出液开始出现。进一步加热至125℃收集到330克馏出液并导致膦酸氢酯低聚物的形成。3)装置的外形重新调整以适于回流和加热至135℃。然后在10小时的期间将丁烯与部分二叔丁基过氧化物(总共15克;1.5摩尔%)一起加到反应混合物里。4)在此之后,混合物被冷却至室温用以留下粗产物,该产物的酸值是83毫克KOH/g。cpd。5)在110℃在3小时的期间内将环氧丙烷(70克)加到粗产物混合物里,然后在110℃将该混合物再加热1小时,然后冷却至室温。6)将反应混合物真空气提(20mmHg;20~110℃;1小时)留下粘稠液体的产物(1210克),其酸值为0.11毫克KOH/g.cpd,理论的磷含量为14.6%。
实施例2
制备亚己基-桥接的膦酸丁酯、二乙酯低聚物1)外形适于蒸馏的反应器,装入1,6-己二醇(354克;3摩尔),然后在惰性气氛中熔融。2)往在60℃加热和搅拌的这种熔融混合物中加入焦磷酸甲酯(MAPP)作为催化剂(3滴),随后加入亚磷酸二乙酯(DEHP)(552克;4摩尔)。3)在搅拌下将该混合物缓慢加热至135℃,在此温度下开始收集馏出液。然后在3小时的期间内将该混合物从135℃加热至150℃,在此期间进一步收集馏出液。然后将混合物在150℃再加热1小时,在此期间将喷吹氮气通进该反应混合物中。在加热期间收集到总量258克的馏出液(主要含有乙醇)。4)将混合物冷却至140℃,改变装置外形使适于回流。在15小时的期间内将丁烯与部分二叔丁基过氧化物一起加到混合物中(总共12克;2摩尔%w.r.t.DEHP)。5)在此之后,混合物被冷却至室温用以留下粗产物,该产物的酸值是16.5毫克KOH/g.cpd。6)将该粗产物混合物在110℃加热。在3小时内加入环氧丙烷(60克)。该混合物在110℃再加热1小时,然后冷却至室温。7)将反应混合物真空气提(20mmHg;20~110℃;1小时)留下粘稠的、浅黄色的液体产物(844克),其酸值为0.6毫克KOH/g.cpd,理论的磷含量为14.5%。
实施例3
制备膦酸丁酯、二甲酯的亚己基-桥接低聚物1)外形适于蒸馏的反应器,装入1,6-己二醇(354克;3摩尔),然后在惰性气氛中熔化。2)往在60℃加热和搅拌的这种熔融混合物中加入焦磷酸甲酯(MAPP)作为催化剂(3滴),随后加入亚磷酸二甲酯(DMHP)(440克;4摩尔)。3)在搅拌下将该混合物缓慢加热至125℃,在此温度下开始收集馏出液。然后在3小时的期间内将该混合物从125℃加热至150℃,在此期间收集到更多的馏出液。然后将混合物在150℃再加热1小时,在此期间将喷吹氮气通进该反应混合物中。在加热期间收集到总量168克的馏出液(主要含有甲醇)。4)将混合物冷却至140℃,改变装置外形使适于回流。在15小时的期间内将丁烯与部分二叔丁基过氧化物一起加到混合物中(总共12克;2摩尔%w.r.t.DMHP)。5)在此之后,混合物被冷却至室温用以留下粗产物,该产物的酸值是29.6毫克KOH/g.cpd。6)将该粗产物混合物在110℃加热。在3小时内加入环氧丙烷(50克)。该混合物在110℃再加热1小时,然后冷却至室温。7)将反应混合物真空气提(20mmHg;20~110℃;1小时)留下粘稠的、浅黄色的液体产物(823克),其酸值为1.1毫克KOH/g.cpd,理论的磷含量为15.0%。
实施例4
使用一种传统的卤化膦酸烷基酯和实施例1(上述的)的产物,每种作为阻燃添加剂用于聚氮基甲酸乙酯泡沫的制备中。其用量和得到的结果列于表I中(下面)。
表I
聚酯泡沫 本发明的 对照物
配方 膦酸酯 磷酸酯聚醚多元醇 份数 100.00 100.00(OH值=48)水 份数 4.15 4.15(a)催化剂I 份数 0.04 0.04(b)催化剂II 份数 0.12 0.12(c)表面活性剂 份数 1.30 1.30辛酸亚锡 份数 0.25 0.25甲苯二异氰酸酯 指数 110 110(d)本发明的膦酸 份数 10.00 -酯(e)对照物 磷酸酯 份数 - 13.00呈乳油状时间 秒 19.00 20.00胀大时间 秒 105.00 111.00密度 kg/m3 23.60 26.20联邦汽车安全标准302性能 指标燃烧长度 mm - -燃烧时间 秒 - -速度 自己熄灭 自己熄灭DIN75201B部分的指标 结雾性能结雾 毫克/10毫米泡沫 0.45 1.18
表1的说明(a)一种胺催化剂,含有70%双(2-二甲基氨基乙基)醚和30%二丙二醇,以NIAX*Al购到。(b)一种胺催化剂,含有33%二-氮杂-二环-辛烷和67%二丙二醇,以DABCO*33LV购到。(c)一种聚醚改性的聚硅氧烷,以TEGOSTAB*BF2370购到。(d)实施例1的产物,即亚己基-桥接的膦酸丁酯(二甲酯)低聚物。(e)一种氯化的磷酸烷基酯,以AMGARD*V6购到。*NIAX、DABCO、TEGOSTAB和AMGARD是注册商标。
Claims (25)
2、根据权利要求1的膦酸酯,其中,在式(I)中,n是3~8的整数。
3、根据权利要求1或2的膦酸酯,其中,在式(I)中,n的平均值是3。
4、根据权利要求1、2或3的膦酸酯,其中,在式(I)中,R1和R5每一个是甲基。
5、根据权利要求1、2或3的膦酸酯,其中,在式(I)中,R1和R5每一个是乙基。
6、根据权利要求1~5中任一权利要求的膦酸酯,其中,在式(I)中,R2和R4(它们可以相同或不同)每一个是有3~8个碳原子的烷基。
7、根据权利要求6的膦酸酯,其中,在式(I)中,R2和R4(它们可以相同或不同)每一个是有4~6个碳原子的烷基。
8、根据权利要求6或7的膦酸酯,其中,在式(I)中,R2和R4每一个是丁基。
9、根据权利要求1~8中任一权利要求的膦酸酯,其中,在式(I)中,R5是有4~8个碳原子烷基。
10、根据权利要求9的膦酸酯,其中,在式(I)中,R3是己基。
11、根据权利要求9或10的膦酸酯,其中,R3是直链烷基。
12、根据权利要求9或10的膦酸酯,其中,R3是支链烷基。
13、根据权利要求1~12中任一权利要求的膦酸酯,其中,在式(I)中,R3含有1或多个取代基团。
14、根据权利要求13的膦酸酯,其中,该取代基团或每一个取代基团是氧或氮。
15、根据权利要求1的膦酸酯,其中,在式(I)中,
n的平均值是3;
R1和R5每一个是甲基;
R2和R4每一个是甲基, 和 R3是己基。
16、根据权利要求1的膦酸酯,其中,在式(I)中,
n的平均值是6;
R1和R5每一个是甲基;
R2和R4每一个是丁基;和 R3是亚己基。
17、根据权利要求1的膦酸酯,其中,在式(I)中,
n的平均值是3;
R1和R5每一个是乙基;
R2和R4每一个是丁基;和 R3是亚己基。
18、一种亚烷基-桥接的膦酸烷基酯的低聚物或聚合物,实质上如上文参照各实施例所述。
19、根据上述任一权利要求的膦酸酯作为阻燃剂的应用或与阻燃剂结合的应用。
20、根据权利要求19在聚氨基甲酸乙酯泡沫中的应用或与聚氨基甲酸乙酯泡沫结合的应用。
21、根据权利要求19在环氧树酯、聚氨基甲酸乙酯树脂、聚氨基甲酸乙酯组合物、酚醛树脂、涂料、清漆和织物中的应用,或与它们结合的应用。
22、具有下面通式结构的膦酸酯根据权利要求19、20或21的应用:
式中:
n=3;
R1和R5每一个是甲基或乙基;
R2和R4每一个是丁基;和 R3是己基。
23、通过根据权利要求1~18中任一权利要求的一种膦酸酯的根据利要求19~22中任一权利要求的应用的阻燃制作的制品。
24、根据权利要求23的制品,它是由聚氨基甲酸乙酯泡沫制成。
25、根据权利要求23或24的制品,它是一种汽车座椅的构件。
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CN100453620C (zh) * | 2003-08-01 | 2009-01-21 | 罗迪亚公司 | 用于热塑性材料的阻燃性膦酸酯添加剂 |
CN101346426B (zh) * | 2005-12-29 | 2011-05-04 | 第一毛织株式会社 | 阻燃热塑性树脂组合物 |
CN101248130B (zh) * | 2005-05-27 | 2011-11-09 | 苏普雷斯塔有限责任公司 | 阻燃软质聚氨酯泡沫 |
CN102250140A (zh) * | 2011-05-24 | 2011-11-23 | 北京化工大学 | 一种聚次膦酸酯单体、聚次膦酸酯及其制备方法 |
CN105189111A (zh) * | 2013-03-12 | 2015-12-23 | 乐金华奥斯有限公司 | 包含玻璃纤维的真空绝热材料用外皮材料及包含其的真空绝热材料 |
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EP1022315B1 (en) | 1999-01-19 | 2014-11-12 | Poly-Med Inc. | Phosphonylated derivatives of aliphatic heterochain and acrylate polymers and applications thereof |
EP1031574A1 (fr) * | 1999-02-26 | 2000-08-30 | Ucb S.A. | Polyol phosphoré, oligomère dérivé de ce polyol phosphoré, polymère dérivé de cet oligomère, procédés pour leur préparation et utilisations de ceux-ci |
KR100355807B1 (ko) * | 2000-05-17 | 2002-10-19 | 박홍수 | 인 함유 변성 폴리에스테르 프리폴리머, 이의 제조방법,이를 포함하는 속건성 2성분계 폴리우레탄 난연도료의제조방법 |
EP2166013B1 (en) * | 2001-10-04 | 2018-01-24 | Akzo Nobel N.V. | Oligomeric, hydroxy-terminated phosphonates |
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WO2008016632A1 (en) * | 2006-08-01 | 2008-02-07 | University Of Massachusetts | Deoxybenzoin-based anti-flammable polyphosphonate and poly(arylate-phosphonate) copolymer compounds, compositions and related methods of use |
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CN102250140A (zh) * | 2011-05-24 | 2011-11-23 | 北京化工大学 | 一种聚次膦酸酯单体、聚次膦酸酯及其制备方法 |
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CN105541902B (zh) * | 2014-10-08 | 2019-04-12 | 雅富顿化学公司 | 含磷化合物及其应用 |
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PL187503B1 (pl) | 2004-07-30 |
KR19980042404A (ko) | 1998-08-17 |
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AU721694B2 (en) | 2000-07-13 |
ZA9710217B (en) | 1998-06-03 |
JPH10147648A (ja) | 1998-06-02 |
NZ329153A (en) | 1998-07-28 |
CA2221079A1 (en) | 1998-05-13 |
GB2319251A (en) | 1998-05-20 |
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DE69719465T2 (de) | 2003-10-30 |
ATE233776T1 (de) | 2003-03-15 |
CN1109040C (zh) | 2003-05-21 |
PT845474E (pt) | 2003-07-31 |
DE69719465D1 (de) | 2003-04-10 |
GB9623584D0 (en) | 1997-01-08 |
HU9702004D0 (en) | 1998-01-28 |
HUP9702004A2 (hu) | 1998-07-28 |
GB2319251B (en) | 2000-05-03 |
ES2194161T3 (es) | 2003-11-16 |
HUP9702004A3 (en) | 2000-03-28 |
NO975194L (no) | 1998-05-14 |
US6043305A (en) | 2000-03-28 |
PL323099A1 (en) | 1998-05-25 |
EP0845474B1 (en) | 2003-03-05 |
GB9722741D0 (en) | 1997-12-24 |
DK0845474T3 (da) | 2003-07-07 |
AU4511997A (en) | 1998-05-21 |
TW438851B (en) | 2001-06-07 |
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