CN101014650B - 不含卤素的阻燃聚合物泡沫材料 - Google Patents
不含卤素的阻燃聚合物泡沫材料 Download PDFInfo
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- CN101014650B CN101014650B CN2005800303107A CN200580030310A CN101014650B CN 101014650 B CN101014650 B CN 101014650B CN 2005800303107 A CN2005800303107 A CN 2005800303107A CN 200580030310 A CN200580030310 A CN 200580030310A CN 101014650 B CN101014650 B CN 101014650B
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- -1 phosphorus compound Chemical class 0.000 claims description 41
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- 229910052736 halogen Inorganic materials 0.000 claims description 25
- 150000002367 halogens Chemical class 0.000 claims description 24
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- 239000011574 phosphorus Substances 0.000 claims description 23
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
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- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical group C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 1
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
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- CYQFCXCEBYINGO-IAGOWNOFSA-N delta1-THC Chemical group C1=C(C)CC[C@H]2C(C)(C)OC3=CC(CCCCC)=CC(O)=C3[C@@H]21 CYQFCXCEBYINGO-IAGOWNOFSA-N 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- XZTWHWHGBBCSMX-UHFFFAOYSA-J dimagnesium;phosphonato phosphate Chemical compound [Mg+2].[Mg+2].[O-]P([O-])(=O)OP([O-])([O-])=O XZTWHWHGBBCSMX-UHFFFAOYSA-J 0.000 description 1
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 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
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000003643 water by type Substances 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0038—Use of organic additives containing phosphorus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0012—Combinations of extrusion moulding with other shaping operations combined with shaping by internal pressure generated in the material, e.g. foaming
-
- 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
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明涉及一种不含卤素的阻燃聚合物泡沫材料,特别是由发泡的聚苯乙烯(EPS)或挤出的聚苯乙烯泡沫片材(XPS)制备的聚苯乙烯颗粒泡沫材料,其含有通式(I)的磷化合物或通式(I)磷化合物的水解产物或金属盐作为阻燃剂,其中R1、R2和R3各自独立地是H,取代或未取代的C1-C15烷基,取代或未取代的C1-C15链烯基,取代或未取代的C3-C8环烷基,取代或未取代的C6-C18芳基,或者取代或未取代的C7-C30烷基芳基;本发明还涉及上述材料的制备方法。
Description
本发明涉及一种不含卤素的阻燃聚合物泡沫材料,其含有通式(I)的磷化合物或通式(I)的磷化合物的水解产物或金属盐作为阻燃剂:
其中R1、R2和R3各自独立地是H,取代或未取代的C1-C15烷基,取代或未取代的C1-C15链烯基,取代或未取代的C3-C8环烷基,取代或未取代的C6-C18芳基,或者取代或未取代的C7-C30烷基芳基,和涉及它们的制备方法。
在聚合物泡沫材料中提供阻燃性对于各种应用而言是重要的,例如用于由可发泡性聚苯乙烯(EPS)组成的模塑聚苯乙烯泡沫或用于建筑物隔热的挤出的聚苯乙烯泡沫片材(XPS)。迄今为止,含卤素的、特别是溴化的有机化合物主要用于这些聚苯乙烯均聚物和共聚物。但是,许多这些溴化物质是不利的,因为它们对环境和健康有潜在危害。
EP-A-834 529描述了可发泡的苯乙烯聚合物,其含有一种由磷化合物和用于清除水的金属氢氧化物作为不含卤素的阻燃剂。5-10重量%的Mg(OH)2和5-10重量%的磷酸三苯酯(TPP)优选被引入在挤出机中的熔融的聚苯乙烯中,并且该材料优选进行造粒,在水悬浮液中的粒料优选用发泡剂进行后浸渍。
WO 00/34342描述了一种经由苯乙烯在5-50重量%可发泡性石墨和如果合适的2-20重量%的作为阻燃剂的磷化合物的存在下悬浮聚合来制备可发泡性聚苯乙烯的方法。
JP-A 2002-06913描述了9,10-二氢-9-氧杂-磷杂菲10-氧化物(DOP)及其衍生物用于制备透明的阻燃塑料模制品的用途,例如由环氧树脂、由聚酯(例如PET)和由聚苯乙烯(例如ABS)制备。
用于实现通过含卤阻燃剂达到的相同阻燃效果所必须的不含卤素的阻燃剂的量通常显著更高。所以,能用于热塑性聚合物(例如聚苯乙烯)的含卤素的阻燃剂通常不能用于聚合物泡沫材料,因为它们会破坏发泡工艺或者影响聚合物泡沫材料的机械性能和热性能。当经由悬浮聚合制备可发泡性聚苯乙烯时,大量的阻燃剂还会降低悬浮液的稳定性。
通常不能预测在热塑性聚合物中所用的阻燃剂在聚合物泡沫材料中的有效性,因为燃烧行为是不同的,并且燃烧实验是不同的。
所以,本发明的目的是发现一种用于聚合物泡沫材料、特别是用于可发泡性聚苯乙烯(EPS)或挤出的聚苯乙烯泡沫片材(XPS)的不含卤素的阻燃剂,且该阻燃剂不会显著影响发泡工艺或机械性能,并且特别允许制备主要闭孔的聚合物泡沫材料。
因此,已经发现上述通式(I)的磷化合物用作聚合物泡沫材料的阻燃剂。基团R1、R2和R3优选各自独立地是H、甲基、乙基、叔丁基、戊基、己基、乙烯基、环己基、α-甲基苄基、苯基、1,4-二羟基苯基、1,4-二羟基-5-(叔丁基)苯基、1,4-二羟基萘基。特别优选9,10-二氢-9-氧杂-10-磷杂菲 10-氧化物(6H-二苯并[c,e]氧杂磷-6-氧化物,DOP,CASreg.no.35948-25-5),或其水解产物或金属盐。通式(I)的磷化合物及其水解产物或金属盐可以例如如JP-A 2004-035495、JP-A 2002-069313或JP-A 2001-115047所述制备。
通式(I)磷化合物的用量通常是0.5-25重量%,优选5-15重量%,基于聚合物泡沫材料计。
通式(I)磷化合物的效果可以进一步通过加入合适的阻燃协同剂改进,例如热自由基产生剂过氧化二枯基、过氧化二叔丁基或二枯基。
也可以使用其它阻燃剂,例如蜜胺、氰脲酸蜜胺酯、金属氧化物或金属氢氧化物,磷酸盐,次膦酸盐,或协同剂,例如Sb2O3或锌化合物。
如果在聚合物泡沫材料中不需要完全不含卤素,则可以经由使用通式(I)的磷化合物和添加较少量、优选0.05-1重量%、特别是0.1-0.5重量%的含卤素的、特别是溴化的阻燃剂(例如六溴环癸烷(HBCD))来制备卤素含量低的泡沫材料。
不含卤素的阻燃聚合物泡沫材料的密度优选是8-200g/l,特别优选10-50g/l,它们的闭孔比例优选大于80%,特别优选是95-100%。
不含卤素的阻燃聚合物泡沫材料优选含有热塑性聚合物,特别是苯乙烯聚合物。
本发明的不含卤素的可发泡性阻燃聚苯乙烯(EPS)和挤出的阻燃聚苯乙烯泡沫片材(XPS)可以通过混合以将发泡剂和通式(I)的磷化合物或通式(I)磷化合物的水解产物或金属盐引入聚合物熔体中、然后挤出得到泡沫片材、泡沫挤出物或可发泡性粒料来制备。
可发泡性苯乙烯聚合物的摩尔质量优选是190 000-400 000g/mol,特别优选220 000-300 000g/mol。可发泡性聚苯乙烯的摩尔质量通常比所用聚苯乙烯的摩尔质量低10000g/mol,因为摩尔质量由于剪切和/或加热而降低。
所用的苯乙烯聚合物优选含有玻璃透明的聚苯乙烯(GPPS)、抗冲击性聚苯乙烯(HIPS)、阴离子聚合的聚苯乙烯或抗冲聚苯乙烯(A-IPS)、苯乙烯/α-甲基苯乙烯共聚物、丙烯腈/丁二烯/苯乙烯聚合物(ABS)、苯乙烯/丙烯腈共聚物(SAN)、丙烯腈/苯乙烯/丙烯酸酯聚合物(ASA)、甲基丙烯酸酯/丁二烯/苯乙烯聚合物(MBS)、甲基丙烯酸甲酯/丙烯腈/丁二烯/苯乙烯聚合物(MABS),或它们的混合物,或它们与聚苯醚(PPE)的混合物。
为了改进机械性能或耐热性,所述苯乙烯聚合物可以在合适时和相容剂一起与热塑性聚合物共混,热塑性聚合物例如是聚酰胺(PA),聚烯烃例如聚丙烯(PP)或聚乙烯(PE),聚丙烯酸酯例如聚甲基丙烯酸甲酯(PMMA),聚碳酸酯(PC),聚酯例如聚对苯二甲酸乙二酯(PET)或聚对苯二甲酸丁二酯(PBT),聚醚砜(PES),聚醚酮,或聚醚硫化物(PES),或它们的混合物,通常总比例为至多30重量%,优选1-10重量%,基于聚合物熔体计。这些混合物也可以与例如疏水改性的或官能化的聚合物或低聚物、橡胶例如聚丙烯酸酯或聚二烯(例如苯乙烯-丁二烯嵌段共聚物)或可生物降解的脂族或脂族/芳族共聚酯一起在特定的用量范围内。
合适的相容剂例如是有机硅烷或含有环氧基的聚合物,或马来酸酐改性的苯乙烯共聚物。
苯乙烯聚合物熔体也可以含有从上述热塑性聚合物得到的再循环聚合物,特别是苯乙烯聚合物和可发泡性聚苯乙烯(EPS),其混合量不会显著影响它们的性能,通常是至多50重量%,特别是1-20重量%。
含有发泡剂的苯乙烯聚合物熔体通常含有按照2-10重量%、优选3-7重量%的总比例均匀分散的一种或多种发泡剂,基于含有发泡剂的苯乙烯聚合物熔体计。合适的发泡剂是在EPS中通常使用的物理发泡剂,例如具有2-7个碳原子的脂族烃,醇,酮,醚,或卤代烃。优选使用异丁烷、正丁烷、异戊烷或正戊烷。对于XPS,优选使用二氧化碳或二氧化碳与醇或与酮的混合物。
为了改进发泡性,细分散的内部水滴可以被引入苯乙烯聚合物基体中。例如,这可以通过将水加入到熔融的苯乙烯聚合物基体中来实现。加入水可以在与发泡剂进料位置相对而言的上游、相同位置或下游的位置进行。水的均匀分散可以通过动态或静态混合器来实现。
基于苯乙烯聚合物计,足量的水通常是0-2重量%,优选0.05-1.5重量%。
可发泡性苯乙烯聚合物(EPS)与至少90%的直径0.5-15微米的内部水液滴形式的内部水一起在发泡时形成具有足够数量的泡孔和均匀泡沫结构的泡沫材料。
选择发泡剂和水的用量,使得可发泡性苯乙烯聚合物(EPS)具有发泡系数α为至多125,优选25-100,发泡系数α定义为发泡前的堆积密度/发泡后的堆积密度。
本发明的可发泡性苯乙烯聚合物粒料(EPS)的堆积密度通常是至多700g/l,优选590-660g/l。如果使用填料,则堆积密度会在590-1200g/l范围内,这取决于填料的性质和用量。
其它可以加入苯乙烯聚合物熔体中的材料是添加剂、成核剂、填料、增塑剂、可溶性和不溶性的有机和/或无机染料和颜料,例如IR吸收剂,例如碳黑、石墨或铝粉,它们可以例如通过混合器或辅助挤出机一起或分别加入。染料和颜料的添加量通常是0.01-30重量%,优选1-5重量%。为了得到颜料在苯乙烯聚合物内的均匀和微分散分布,可以有利地(特别在极性颜料的情况下)使用分散剂,例如有机硅烷、含有环氧基的聚合物或马来酸酐接枝的苯乙烯聚合物。优选的增塑剂是矿物油或邻苯二甲酸酯,其用量可以是0.05-10重量%,基于苯乙烯聚合物计。
为了制备本发明的可发泡性苯乙烯聚合物,发泡剂通过混入聚合物熔体中而被引入。该方法包括以下步骤:a)熔体的制备,b)混合,c)冷却,d)输送,和e)造粒。每个步骤可以经由在塑料加工中已知的设备或设备组合来进行。合适的用于混合引入的设备是静态或动态混合器,例如挤出机。聚合物熔体可以直接从聚合反应器取出或直接在混合挤出机中或在单独的熔融挤出机中经由聚合物粒料的熔融来制备。熔体的冷却可以在混合组件或在单独的冷却器中进行。可以使用的造粒方法的例子是在压力下进行水下造粒,用旋转刮刀造粒和用温度受控的液体通过喷雾雾化而冷却,或喷雾造粒。合适的用于进行该工艺的设备排列例如是:
a)聚合物反应器一静态混合器/冷却器一造粒机
b)聚合物反应器-挤出机-造粒机
c)挤出机-静态混合器-造粒机
d)挤出机-造粒机
所述排列也可以具有用于引入添加剂(例如溶剂或热敏性添加剂)的辅助挤出机。
含有发泡剂的苯乙烯聚合物熔体通常在140-300℃、优选160-240℃的温度经由模板输送。不需要冷却到玻璃化转变温度的区域。
模板被至少加热到含有发泡剂的聚苯乙烯熔体的温度。模板的温度优选比含有发泡剂的聚苯乙烯熔体的温度高20-100℃。这抑制了在模口中形成聚合物沉积物,并确保造粒不被中断。
为了获得可出售的粒料尺寸,在模口出口处的口型槽口的直径(D)应该在0.2-1.5mm的范围内,优选0.3-1.2mm,特别优选0.3-0.8mm。该方法也可以在模口膨胀后获得精确调节到低于2mm的粒料尺寸,特别是0.4-1.4mm。
特别优选一种制备不含卤素的可发泡性阻燃苯乙烯聚合物(EPS)的方法,包括以下步骤:
a)通过静态或动态混合器在至少150℃的温度向聚合物熔体中混合引入有机发泡剂和1-25重量%的通式(I)磷化合物或通式(I)磷化合物的水解产物或金属盐,
b)将含有发泡剂的苯乙烯聚合物熔体冷却到至少120℃的温度,
c)通过模板排料,其中模板具有在模口出口处的直径至多为1.5mm的孔,和
d)直接在模板的下游在水下在1-20巴的压力下将含有发泡剂的熔体造粒。
还可以通过悬浮聚合制备本发明的可发泡性苯乙烯聚合物(EPS)。
在悬浮聚合中,所用的单体优选仅仅含有苯乙烯。但是其重量的至多20%已经被其它烯属不饱和单体代替,例如烷基苯乙烯、二乙烯基苯、丙烯腈、1,1-二苯基醚或α-甲基苯乙烯。
在悬浮聚合方法中,可以加入常用的助剂,例如过氧化物引发剂、悬浮稳定剂、发泡剂、链转移剂、发泡助剂、成核剂和增塑剂。在聚合过程中加入的通式(I)磷化合物的量是0.5-25重量%,优选5-15重量%。发泡剂的添加量是基于单体计的3-10重量%。它们可以在悬浮聚合之前、期间或之后加入。合适的发泡剂是具有4-6个碳原子的脂族烃。有利的是,所用的悬浮稳定剂含有无机Pickering分散剂,例如焦磷酸镁或磷酸钙。
悬浮聚合获得了珠粒状的基本上圆形的颗粒,平均直径为0.2-2mm。
为了改进加工性,最终的可发泡性苯乙烯聚合物粒料可以被甘油酯、抗静电剂或抗结块剂涂覆。
EPS粒料可以用单硬脂酸甘油酯GMS(通常是0.25%)、三硬脂酸甘油酯(通常是0.25%)、Aerosil R972细粒二氧化硅(通常是0.12%)或硬脂酸锌(通常是0.15%)或用抗静电剂涂覆。
在第一步中,热空气或水蒸气可以用于将本发明的可发泡性苯乙烯聚合物粒料预发泡,得到密度为8-100g/l的泡沫珠粒;在第二步中,该材料可以在闭模中熔化,得到模塑的泡沫材料。
可发泡性聚苯乙烯珠粒可以加工得到密度为8-200g/l、优选10-50g/l的聚苯乙烯泡沫材料。为此,将可发泡性珠粒进行预发泡。这大多数通过将这些珠粒用水蒸气在预发泡剂中加热来进行。所得的经过预发泡的珠粒然后熔化,得到模制品。为此,将经过预发泡的珠粒引入模具中(这些模具不会关闭以得到气密性密封),并用水蒸气处理。在冷却之后,除去模具。
实施例
实施例1-3:
将预先混合在聚苯乙烯熔体中的9,10-二氢-9-氧杂-磷杂菲10-氧化物(DOP)如表1所示(加入量按照基于聚苯乙烯计的重量百分比表示)通过侧流挤出机在从初始的260℃冷却到190℃之后加入含有发泡剂的聚苯乙烯熔体主料流(PS 148G,来自BASF Aktiengesellschaft,粘数VN为83ml/g,Mw=220000g/mol,多分散指数Mw/Mn=2.8,和7重量%的正戊烷)中。所得的聚苯乙烯熔体以60kg/h输送通过具有32个孔(直径0.75mm)的模板。通过在压力下的水下造粒制得了具有窄尺寸分布的密实粒料。
实施例4
重复进行实施例3,不同的是六溴环癸烷(HBCD,0.2重量%,基于EPS粒料计)也通过侧流挤出机加入。
实施例5
重复进行实施例3,不同的是过氧化二枯基(0.5重量%,基于EPS粒料计)也通过侧流挤出机加入。
实施例6
将4.55kg的聚苯乙烯(PS 158K,来自BASF)溶解在15.03kg的苯乙烯中,并用9,10-二氢-9-氧杂-磷杂菲10-氧化物(DOP)(10重量%,基于苯乙烯和聚苯乙烯的总量计)处理。还加入45.6g的过氧化二枯基和18.1g的过氧化二苯甲酰。该有机相被引入在50L搅拌釜中的19.5升去离子水中。水相含有69.8g的焦磷酸钠和129.5g的硫酸镁。然后将该悬浮液加热到80℃。在140分钟之后,加入3.51g的乳化剂K30(Bayer AG)。在30分钟之后,加入1175g的戊烷,并在134℃完成聚合。所得的EPS珠粒具有1.2mm的平均直径。
将上述实施例中获得的EPS粒料在水蒸气流中预发泡,得到密度为约15g/l的泡沫珠粒,静置中间储存24小时,然后使用水蒸气在气密性模具中熔化,得到泡沫模塑品。
在研究燃烧性能之前,将试验样品储存至少72小时。为了评价燃烧行为,将泡沫模塑品在水平燃烧试验中暴露于Bunsen燃烧器火焰达2秒,然后从火焰中移开。测定余焰时间。
表1泡沫模塑品的燃烧行为
实施例 | DOP[%] | 余焰时间[秒] |
1 | 25 | 1 |
2 | 15 | 3 |
3 | 10 | 10 |
4 | 10 | 3 |
5 | 10 | 6 |
实施例 | DOP[%] | 余焰时间[秒] |
6 | 10 | 10 |
Claims (11)
2.根据权利要求1的不含卤素的阻燃聚合物泡沫材料,其包含9,10-二氢-9-氧杂-磷杂菲10-氧化物或其水解产物或金属盐作为阻燃剂。
3.根据权利要求1或2的不含卤素的阻燃聚合物泡沫材料,其包含基于聚合物泡沫材料计0.5-25重量%的通式(I)磷化合物。
4.根据权利要求1或2的不含卤素的阻燃聚合物泡沫材料,其密度在8-200g/l的范围内。
5.根据权利要求1或2的不含卤素的阻燃聚合物泡沫材料,其中大于80%的泡孔是闭孔。
6.根据权利要求1或2的不含卤素的阻燃聚合物泡沫材料,其含有作为聚合物的苯乙烯聚合物。
7.一种制备不含卤素的可发泡性阻燃苯乙烯聚合物或挤出的阻燃苯乙烯聚合物泡沫片材的方法,包括使用如权利要求1所定义的通式(I)的磷化合物或通式(I)磷化合物的水解产物或金属盐作为阻燃剂。
8.一种制备不含卤素的可发泡性阻燃苯乙烯聚合物的方法,包括以下步骤:
a)通过静态或动态混合器在至少150℃的温度向苯乙烯聚合物熔体中混合引入有机发泡剂和1-25重量%的如权利要求1所定义的通式(I)磷化合物或通式(I)磷化合物的水解产物或金属盐,
b)将含有发泡剂的苯乙烯聚合物熔体冷却到至少120℃的温度,
c)通过模板排料,其中模板具有在模口出口处的直径至多为1.5mm的孔,和
d)直接在模板的下游在水下在1-20巴的压力下将含有发泡剂的熔体造粒。
9.一种通过苯乙烯在有机发泡剂和阻燃剂的存在下在水悬浮液中聚合来制备不含卤素的可发泡性阻燃苯乙烯聚合物的方法,包括使用如权利要求1所定义的通式(I)的磷化合物或通式(I)磷化合物的水解产物或金属盐作为阻燃剂。
10.一种不含卤素的可发泡性阻燃苯乙烯聚合物,其可以通过权利要求7-9中任一项的方法获得。
11.一种制备根据权利要求1的不含卤素的阻燃聚合物泡沫材料的方法,包括在第一步中使用热空气或水蒸气将权利要求10所述的可发泡性苯乙烯聚合物预发泡,得到密度为8-200g/l的泡沫珠粒;和在第二步中,将该材料闭模中熔化。
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DE102004044380A DE102004044380A1 (de) | 2004-09-10 | 2004-09-10 | Halogenfreie, flammgeschützte Polymerschaumstoffe |
DE102004044380.7 | 2004-09-10 | ||
PCT/EP2005/009652 WO2006027241A1 (de) | 2004-09-10 | 2005-09-08 | Halogenfreie, flammgeschützte polymerschaumstoffe |
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US (1) | US20080058435A1 (zh) |
EP (1) | EP1791896B8 (zh) |
KR (1) | KR20070105963A (zh) |
CN (1) | CN101014650B (zh) |
AT (1) | ATE386071T1 (zh) |
BR (1) | BRPI0515029A (zh) |
DE (2) | DE102004044380A1 (zh) |
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- 2005-09-08 EP EP05778134A patent/EP1791896B8/de not_active Not-in-force
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- 2005-09-08 WO PCT/EP2005/009652 patent/WO2006027241A1/de active IP Right Grant
- 2005-09-08 CN CN2005800303107A patent/CN101014650B/zh not_active Expired - Fee Related
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Publication number | Publication date |
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KR20070105963A (ko) | 2007-10-31 |
PL1791896T3 (pl) | 2008-07-31 |
WO2006027241A1 (de) | 2006-03-16 |
DE102004044380A1 (de) | 2006-03-30 |
EP1791896B8 (de) | 2008-04-02 |
EP1791896A1 (de) | 2007-06-06 |
DE502005002859D1 (de) | 2008-03-27 |
EP1791896B1 (de) | 2008-02-13 |
US20080058435A1 (en) | 2008-03-06 |
CN101014650A (zh) | 2007-08-08 |
ATE386071T1 (de) | 2008-03-15 |
BRPI0515029A (pt) | 2008-07-01 |
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