CN1494548A - 新的含磷单体和由其衍生的阻燃耐冲击性单亚乙烯基芳香聚合物组合物 - Google Patents
新的含磷单体和由其衍生的阻燃耐冲击性单亚乙烯基芳香聚合物组合物 Download PDFInfo
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- CN1494548A CN1494548A CNA018132308A CN01813230A CN1494548A CN 1494548 A CN1494548 A CN 1494548A CN A018132308 A CNA018132308 A CN A018132308A CN 01813230 A CN01813230 A CN 01813230A CN 1494548 A CN1494548 A CN 1494548A
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- multipolymer
- compound
- monovinylidene aromatic
- sulphur
- oxygen
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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 title claims description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 title claims description 5
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
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- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
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- 239000005977 Ethylene Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
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- KHMYONNPZWOTKW-UHFFFAOYSA-N pent-1-enylbenzene Chemical compound CCCC=CC1=CC=CC=C1 KHMYONNPZWOTKW-UHFFFAOYSA-N 0.000 description 1
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- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
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- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
-
- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657181—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonic acid derivative
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明公开了富马酸或马来酸的环磷酸酯,适于用作共聚单体,能够与单亚乙烯基芳香化合物共聚以赋予合成的共聚物阻燃性能。
Description
本发明涉及许多新的含磷单体,该含磷单体能够赋予使用这种单体合成的某些耐冲击性聚合物组合物阻燃性能。
由单亚乙烯基芳香化合物如苯乙烯衍生的聚合物已多年来成功地工业化应用于许多最终应用中。这些聚合物包括它的耐冲击性改性物,其中通过在聚合反应期间引入少量增韧剂如适宜的橡胶而改善耐冲击强度。这些聚合物的一个主要缺点是它们固有的高度易燃性。一种处理易燃性的已知方法是往聚合物中引入许多阻燃添加剂。一组已知的添加剂是某些卤代阻燃有机化合物如十溴二苯醚。
当这些卤代有机化合物与由单亚乙烯基芳香化合物衍生的聚合物混合时,合成的聚合物组合物的易燃性显著减小。但是,这些卤代化合物还表现出与毒性和环境影响相关的潜在问题。为了克服这些问题,已使用某些含磷化合物如磷酸三苯酯代替卤代化合物。尽管证明它们用作单亚乙烯基芳香化合物的聚合物的阻燃添加剂,这种含磷化合物具有许多已知的缺点。更为具体地,这种化合物趋于挥发,因而当将混入的聚合物制成有用的物品时这种化合物丧失其作为阻燃添加剂的总体有效性。这些化合物还趋于迁移至制品表面并从聚合物加工设备的表面析出,这种现象在本行业中已知为“出汁”。而且,由于已知的挥发性而在聚合物混合物中使用任何额外数量的这种化合物以补偿它们的有效性,经常趋于将聚合物混合物增塑,从而不利地影响它的某些物理性能如耐热性。
因此,仍然非常需要获得一种具有无先前为此尝试的缺点的有效阻燃性和现有技术领域中已知的相关阻燃添加剂的单亚乙烯基芳香聚合物组合物。
本发明的一方面是适于用作共聚单体,能够与单亚乙烯基芳香化合物共聚以赋予其合成的共聚物阻燃性能的含磷化合物,所述化合物包括以下通式的化合物:
其中:
R1为氢或烷基;
R2为烷氧羰基;
X为氧、硫或烷基胺;
P为三价磷;和
n为2或3。
本发明的另一方面是以上通式的含磷化合物,其中R2为具有以下通式的基团:
其中:
R1为氢或烷基;
X为氧、硫或烷基胺;
P为三价磷;和
n为2或3。
本发明的又另一方面是适于用作共聚单体,能够与单亚乙烯基芳香化合物共聚以赋予其合成的共聚物阻燃性能的含磷化合物,所述化合物包括以下通式的化合物:
其中:
R1为氢或烷基;
R2为烷氧羰基;
X为氧、硫或烷基胺;
Y为氧或硫;
P为五价磷;和
n为2或3。
本发明的另一方面是以上通式的含磷化合物,其中R2为具有以下通式的基团:
其中:
R1为氢或烷基;
X为氧、硫或烷基胺;
Y为氧或硫;
P为五价磷;和
n为2或3。
本发明的又一方面是一种单亚乙烯基芳香化合物和所述通式的含磷化合物的阻燃(共)聚合物组合物,所述聚合物组合物可以被橡胶或其它弹性体增韧或改性。
本发明的含磷单体一般可以归类为富马酸或马来酸的环亚膦酸酯或膦酸酯。本发明的相关单体或化合物的合成也在本领域熟练技术人员的能力范围内。
根据化学文摘命名系统确定的本发明的有用化合物的实例包括但不限于:2-丁烯二酸(2E)-,双[(5,5-二甲基-1,3,2-dioxaphosphorinan-2-基)甲基]酯;2-丁烯二酸:2-甲基-,4-[(5,5-二甲基-1,3,2-dioxaphosphorinan-2-基)甲基]1-甲酯,(2E)-;2-丙烯酸,(5,5-二甲基-2-环氧-1,3,2-dioxaphosphorinan-2-基)甲酯;2-丙烯酸,2-甲基-,(4,4,5,5-四甲基-1,3,2-dioxaphosphorlan-2-基)甲酯;2-丙烯酸,1-(5,5-二甲基-2-sulfido-1,3,2-dioxaphosphorinan-2-基)乙酯;和2-丙烯酸,(四氢-1,3,5,5-四甲基-2-环氧-1,3,2-diaxaphosphorin-2(1H)-基)甲酯。
适于用作制备橡胶改性的单亚乙烯基芳香聚合物的基体的单亚乙烯基芳香聚合物是通过乙烯基芳香单体的聚合而生产的聚合物。乙烯基芳香单体包括但不限于在US-A-4,666,987,US-A-4,572,819和US-A-4,585,825中所述的单体。优选单体具有下式:
其中R为氢或甲基,Ar为具有1-3个被烷基、卤素或卤烷基取代或未取代的芳环的芳环结构,其中任何烷基包含1-6个碳原子,而卤烷基指卤素取代的烷基。优选地,Ar为苯基或烷基苯基,其中烷基苯基指烷基取代的苯基,最优选为苯基。可以使用的典型的乙烯基芳香单体包括:苯乙烯、α-甲基苯乙烯、所有乙烯基甲苯的异构体,特别是对乙烯基甲苯、所有乙基苯乙烯的异构体、丙基苯乙烯、乙烯基二苯基、乙烯基萘、乙烯基蒽和它们的混合物。乙烯基芳香单体还可以与其它可聚合的单体组合。这些单体的实例包括但不限于丙烯酸单体如丙烯腈、甲基丙烯腈、甲基丙烯酸、甲基丙烯酸甲酯、丙烯酸和丙烯酸甲酯;马来酰亚胺、正苯基马来酰亚胺和马来酐。这些可共聚的单体可以单独或组合使用。例如,本发明的含磷化合物可以与结合至少一种可共聚单体的单亚乙烯基芳香化合物共聚,以生产本发明的共聚物。优选的可共聚单体为丙烯腈。优选的可共聚单体的组合包括丙烯腈和正苯基马来酰亚胺。
乙烯基芳香单体的聚合可以在预溶解的弹性体存在下完成,以制备冲击改性或含有接枝橡胶的产物。橡胶改性的乙烯基芳香聚合物可以通过以下方法制备:在预溶解的橡胶存在下聚合乙烯基芳香单体以制备冲击改性或含有接枝橡胶的产物,其实例描述在US-A-3,123,655,US-A-3,346,520,US-A-3,639,522和US-A-4,409,369中。橡胶一般为丁二烯或异戊二烯橡胶,优选聚丁二烯。优选橡胶改性的乙烯基芳香聚合物为耐冲击聚苯乙烯(HIPS)或丙烯腈-丁二烯-苯乙烯(ABS),最优选HIPS。
橡胶颗粒的体积平均粒径一般为0.2-3.0微米。如果生产双峰粒径,则橡胶一般包含80-85wt%的上述颗粒和5-20wt%的体积平均粒径为2-6微米的颗粒。
聚合反应优选在引发剂存在下完成。适宜的引发剂包括任何能够在聚合反应条件下给橡胶颗粒赋予目标聚合物接枝并加速乙烯基芳香单体聚合反应的引发剂。代表性的引发剂包括过氧化物引发剂如过酸酯,例如过氧苯甲酸叔丁酯和过氧乙酸叔丁酯、过氧辛酸叔丁酯、过氧化二苯甲酰、过氧化二月桂酰、1.1-双叔丁基过氧环己烷、1-3-双叔丁基过氧-3,3,5-三甲基环己烷和过氧化二枯基。如果需要,可以使用光化学引发技术。优选的引发剂包括过氧辛酸叔丁酯、叔丁基异丙基过碳酸酯、过氧化二苯甲酰、过氧苯甲酸叔丁酯、1,1-双叔丁基过氧环己烷和过氧乙酸叔丁酯。
可以在一定的浓度范围内使用引发剂,所述浓度依赖于多种因素,包括所用的特定引发剂、目标聚合物接枝水平和完成本体聚合的条件。一般地,每百万重量份乙烯基芳香单体所用引发剂可以为0-2000,优选100-1500重量份。
此外,可以在聚合反应中使用溶剂。可接受的溶剂包括与橡胶、乙烯基芳香单体和由其制备的聚合物形成溶液的常规液体有机物质。代表性的溶剂包括取代的芳烃如乙苯、甲苯、二甲苯或类似物;取代或未取代的、直链或支链饱和的5个或更多个碳原子的脂肪族化合物,如庚烷、己烷、辛烷或类似物;具有5或6个碳原子的脂环烃或取代的脂环烃,如环己烷。优选的溶剂包括取代的芳香族化合物,最优选乙苯和甲苯。一般地,使用的溶剂的数量足以改善聚合反应期间的加工性能和热传递。这种数量将随所用的橡胶、单体和溶剂、加工设备和目标聚合反应程度而变化。如果使用的话,溶剂一般以至多35wt%的数量,优选2-25wt%数量使用,以溶液的总重为基数。
在橡胶改性的单亚乙烯基芳香聚合物组合物的制备过程中还可以存在其它材料,包括增塑剂如矿物油;流动助剂,润滑剂,抗氧化剂,催化剂,脱模剂或聚合反应助剂如链转移试剂,包括烷基硫醇,如正十二烷硫醇。如果使用的话,可以存在0.001-0.5wt%数量的链转移试剂,以其加入的聚合反应混合物的总重为基数。
聚合反应进行的温度将根据特定的组分,特定的引发剂而变,但一般范围为60-190℃。
采用常规技术有利地完成合成产物中橡胶的交联和未反应的单体、可能使用的任何溶剂以及其它挥发性物质的除去,例如将聚合反应混合物引入脱挥发分器,高温如200-300℃和真空下闪蒸出单体和其它挥发物,然后从脱挥发分器中将它们除去。
通常,通过在一系列反应器中聚合目标组分的进料和接枝引发剂来生产双峰组合物,其中在第一反应器内形成并稳定橡胶颗粒,然后将其供给第二反应器的顶部,其中加入第二进料。第二进料可以已经包含分级的橡胶颗粒或可以是另一种单体/生产大颗粒的橡胶原材料进料。制备双峰粒径聚合物的方法公开在US-A-5,240,993和EP-0096447中。
本文所用的体积平均粒径指橡胶颗粒,包括在橡胶颗粒内的所有包藏的乙烯基芳香聚合物的直径。体积平均粒径和分布可以使用常规技术如Coulter CounterTM,透射式电子显微镜测定。
本发明阻燃共聚物中的含磷化合物使用的数量为至少一(1)重量份,优选至少二(2)重量份,更优选至少五(5)重量份,以100重量份的本发明聚合物组合物为基数。一般地,本发明阻燃共聚物中的含磷化合物的数量小于或等于三十(30)重量份,优选小于或等于十五(15)重量份,更优选小于或等于13重量份,最优选小于或等于十(10)重量份,以100重量份的本发明共聚物为基数。
此外,该阻燃聚合物组合物还可以任选地包含一种或多种在这种类型的聚合物中常用的添加剂。这种类型的优选添加剂包括但不限于:抗氧化剂;冲击改性剂;增塑剂如矿物油;抗静电剂;流动增强剂;脱模剂;填充剂如碳酸钙、滑石、粘土、云母、硅灰石、中空玻璃珠、氧化钛、二氧化硅、碳黑、玻璃纤维、钛酸钾、单层阳离子交换多层硅酸盐材料或它们的混合物,以及全氟化烷烃低聚物和用于改善UL 94的滴注性能的聚合物(如聚四氟乙烯)。而且,可以使用稳定阻燃聚合物组合物对抗由于但不限于热、光和氧导致的降解的化合物或它们的混合物。
如果使用的话,这些添加剂的数量是变化的且需要根据确定的最终应用的具体需求而进行控制,这些可以由本领域技术人员容易和适宜地实施。
本发明的阻燃共聚物是热塑性的。当应用热来软化或熔化时,它可以形成本发明的阻燃聚合物组合物,或可以使用常规技术如单独如组合使用压模法、注模法、气体辅助的注模法、压延法、真空成型法、热成型法、挤压和/或吹塑法进行模制。该阻燃聚合物组合物还可以成型、纺熔或拉伸成膜、纤维、多层层压材料或挤压片,或者可以在任何适于这种目的的机械中与一种或多种有机或无机物质化合。
本发明的共聚物用于制造多种有用的物品和部件。特别良好地适合的物品包括电视柜,计算机监视器,一般要求具有优良的可燃性等级的相关的打印机外壳。
提供以下实施例以进一步例示本发明,不应将其认为限定其范围。
实施例
实施例1:双(2-氧代-5,5-二甲基-1,3,2-dioxaphosphorinanyl甲基)
富马酸酯(ODDPM富马酸酯)
将ODDPM醇(36.03g,02.00mole)加到在3颈、250ml圆底烧瓶中的100mL无水氯仿中。中部瓶颈配备回流冷凝器,该冷凝器配备含有硫酸钠的干燥管。外部瓶颈配备玻璃塞。用磁搅拌棒搅拌混合物,并在ODDPM醇已完全溶于氯仿时,立即将富马酰氯(15.30g,0.100mole)全部加到溶液。通过对配有pHydrion试纸(pH 0-13)的冷凝器上方的大气进行取样而检测混合物。pH试验变深红色表明pH为0。而且,在5小时的反应时间之后,观察到相对于最初溶液而言溶液的粘度增大。然后将溶液冷却至室温,并将75mL氯仿加到烧瓶中。将溶液转入250mL分液漏斗,并滴加至大量过量的苯中。用苯沉淀白色半透明固体,通过平底漏斗过滤收集沉淀,用苯洗涤,并在60℃的真空烘箱中干燥过夜。ODDPM甲基丙烯酸酯的产量为39.0g(89%)。通过苯/氯仿重结晶而纯化ODDPM甲基丙烯酸酯(熔点149.5-150℃)。
实施例2:苯乙烯和双(2-氧代-5,5-二甲基
-1,3,2-dioxaphosphorinanyl甲基)富马酸酯的共聚反应
ODDPM富马酸酯不溶于非极性烃溶剂,但在卤代溶剂如氯仿中具有充足的溶解度。通过以下方法在圆底烧瓶中制备共聚反应溶液:首先加入来自由0.200g AIBN和29.8g氯仿制备的AIBN标准溶液的适量AIBN。然后加入单体,随后用氯仿稀释(表1)。仅可以在高温下实现大于10摩尔百分率的ODDPM富马酸酯的共聚单体的进料组合物的均匀溶液的共聚反应。圆底烧瓶用橡胶隔膜盖上,用铜线将其紧密栓到烧瓶上。在聚合反应之前,每份溶液用N2喷雾10分钟,同时用冰水急冷。然后将烧瓶在60℃(+/-0.5℃)的油浴中放置表1中给出的时间。共聚反应溶液用旋转蒸发器浓缩并加到大量过量的甲醇以沉淀出共聚物。通过重力过滤收集共聚物,用甲醇洗涤,并在大约80℃下的真空熔炉中干燥过夜。将聚(苯乙烯-共-ODDPM富马酸酯)样品溶于氯仿,并进一步用二乙醚再沉淀而纯化。最后,通过重力过滤收集共聚物,用二乙醚洗涤,并在大约80C的真空熔炉中干燥过夜。共聚物都具有粉状结构。
表1
60℃下苯乙烯和ODDPM富马酸酯的共聚反应1的配方
进料中ODDPM 苯乙烯 ODDPM富马酸 CHCl3(g) 反应时间
富马酸酯的 (g)/(mol) 酯(g)/(模) (小时)
摩尔百分率
5 2.47/2.38×10-2 0.55/1.25×10-3 25.7 7.5
10 2.34/2.25×10-2 1.10/2.50×10-3 25.3 9.0
15 2.21/2.13×10-2 1.65/3.75×10-3 24.9 7.5
20 2.08/2.00×10-2 2.20/5.00×10-3 24.5 7.0
30 1.82/1.75×10-2 3.30/7.50×10-3 23.6 6.5
1各系统包含0.008g(0.20摩尔百分率)AIBN
Claims (16)
1.一种含磷化合物,适于用作共聚单体,能够与单亚乙烯基芳香化合物共聚以赋予其合成的共聚物阻燃性能,所述化合物包括以下通式的化合物:
其中:
R1为氢或烷基;
R2为烷氧羰基;
X为氧、硫或烷基胺;
Y为氧或硫;
P为五价磷;和
n为2或3。
3.权利要求1的含磷化合物,其中R2为以下通式的基团:
其中:
R1为氢或烷基;
X为氧、硫或烷基胺;
Y为氧或硫;
P为五价磷;和
n为2或3。
5.权利要求1的含磷化合物,所述化合物为双(2-氧代-5,5-二甲基-1,3,2-dioxaphosphorinanyl甲基)富马酸酯。
6.一种共聚物,其中包含单亚乙烯基芳香化合物和权利要求1、2、3或4的含磷化合物。
7.权利要求6的共聚物,其中所述单亚乙烯基芳香化合物为苯乙烯。
8.权利要求6的共聚物,所述共聚物被橡胶改性。
9.权利要求8的共聚物,其中该橡胶为聚丁二烯。
10.权利要求7的共聚物,该共聚物被橡胶改性。
11.权利要求10的共聚物,其中该橡胶为聚丁二烯。
12.一种共聚物,所述共聚物包含单亚乙烯基芳香化合物和权利要求1、2、3或4的含磷化合物,以及至少一种选自以下的可共聚的化合物:丙烯腈、甲基丙烯腈、甲基丙烯酸、甲基丙烯酸甲酯、丙烯酸和丙烯酸甲酯;马来酰亚胺、正苯基马来酰亚胺和马来酐。
13.一种共聚物,其中包含单亚乙烯基芳香化合物和权利要求1、2、3或4的含磷化合物,丙烯腈和正苯基马来酰亚胺。
14.由权利要求8的橡胶改性的共聚物生产的物品。
15.由权利要求12的共聚物生产的物品。
16.由权利要求13的共聚物生产的物品。
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US22092700P | 2000-07-26 | 2000-07-26 | |
US60/220,927 | 2000-07-26 |
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CN1260235C CN1260235C (zh) | 2006-06-21 |
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US (2) | US6503992B2 (zh) |
EP (1) | EP1303526B1 (zh) |
CN (1) | CN1260235C (zh) |
AU (1) | AU2001280737A1 (zh) |
BR (1) | BR0112991A (zh) |
DE (1) | DE60107574T2 (zh) |
MX (1) | MXPA03000752A (zh) |
WO (1) | WO2002008233A2 (zh) |
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CN101586032B (zh) * | 2009-06-17 | 2012-08-08 | 东华大学 | 一种含p-s的阻燃剂的制备方法 |
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US8093332B2 (en) * | 2003-09-29 | 2012-01-10 | Fina Technology, Inc. | High impact polystyrene and process for preparing same |
KR20120076274A (ko) * | 2010-12-29 | 2012-07-09 | 제일모직주식회사 | 환형 포스페이트 n-페닐 말레이미드, 그 제조방법, 이를 포함한 공중합체 및 이를 포함하는 수지 조성물 |
EP2945994B1 (en) | 2013-01-18 | 2018-07-11 | Basf Se | Acrylic dispersion-based coating compositions |
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US3123655A (en) | 1964-03-03 | Process for extruding high impact thermoplastic | ||
US3346520A (en) | 1965-01-25 | 1967-10-10 | Dow Chemical Co | Process for making high impact styrene polymers in aqueous suspension |
US3639522A (en) | 1969-06-04 | 1972-02-01 | Dow Chemical Co | Self-extinguishing high impact styrene polymers |
AU8671075A (en) * | 1974-12-06 | 1977-05-26 | Gen Electric | Flame retardant, non-dripping composition of polyphenylene ether and acrylonitrile - butadiene-styrene |
US4409369A (en) | 1980-03-03 | 1983-10-11 | The Dow Chemical Company | Transparent impact resin and process for the preparation thereof |
US4427813A (en) * | 1981-12-14 | 1984-01-24 | The Dow Chemical Co. | Polycarbonate containing a bis(cyclic phosphate) as a thermal stabilizer |
NL8202281A (nl) | 1982-06-04 | 1984-01-02 | Dow Chemical Nederland | Met rubber versterkte polymeren van aromatische monovinylideenverbindingen en werkwijze voor de bereiding daarvan. |
US4572819A (en) | 1983-08-24 | 1986-02-25 | The Dow Chemical Company | Apparatus for anionic polymerization wherein the molecular weight of the polymer is closely controlled |
US4585825A (en) | 1983-09-30 | 1986-04-29 | The Dow Chemical Company | Monovinylidene aromatic polymer resins having added amounts of high molecular weight polymer |
US4666987A (en) | 1985-02-22 | 1987-05-19 | The Dow Chemical Company | In-mold polymerization of vinyl aromatic compound |
GB8918157D0 (en) | 1989-08-09 | 1989-09-20 | Dow Benelux | A process for the preparation of rubber-reinforced monovinylidene aromatic polymers |
SG85605A1 (en) * | 1997-10-16 | 2002-01-15 | Gen Electric | Flame resistant compositions of polycarbonate and monovinylidene aromatic compounds |
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2001
- 2001-07-24 BR BR0112991-0A patent/BR0112991A/pt not_active Application Discontinuation
- 2001-07-24 WO PCT/US2001/023300 patent/WO2002008233A2/en active IP Right Grant
- 2001-07-24 CN CN01813230.8A patent/CN1260235C/zh not_active Expired - Fee Related
- 2001-07-24 EP EP01959152A patent/EP1303526B1/en not_active Expired - Lifetime
- 2001-07-24 AU AU2001280737A patent/AU2001280737A1/en not_active Abandoned
- 2001-07-24 MX MXPA03000752A patent/MXPA03000752A/es active IP Right Grant
- 2001-07-24 DE DE60107574T patent/DE60107574T2/de not_active Expired - Lifetime
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CN101586032B (zh) * | 2009-06-17 | 2012-08-08 | 东华大学 | 一种含p-s的阻燃剂的制备方法 |
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DE60107574D1 (de) | 2005-01-05 |
BR0112991A (pt) | 2003-06-24 |
US20020040120A1 (en) | 2002-04-04 |
DE60107574T2 (de) | 2005-11-24 |
MXPA03000752A (es) | 2004-11-01 |
CN1260235C (zh) | 2006-06-21 |
US20030055188A1 (en) | 2003-03-20 |
AU2001280737A1 (en) | 2002-02-05 |
WO2002008233A2 (en) | 2002-01-31 |
EP1303526B1 (en) | 2004-12-01 |
EP1303526A2 (en) | 2003-04-23 |
US6503992B2 (en) | 2003-01-07 |
WO2002008233A3 (en) | 2003-01-03 |
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