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Publication numberCN100371374 C
Publication typeGrant
Application numberCN 02819265
PCT numberPCT/EP2002/010050
Publication date27 Feb 2008
Filing date3 Oct 2002
Priority date18 Oct 2001
Also published asCA2462137A1, CA2462137C, CN1561360A, DE60211545D1, DE60211545T2, EP1448681A1, EP1448681B1, US7279504, US20040242713, US20060058407, WO2003035728A1
Publication number02819265.6, CN 02819265, CN 100371374 C, CN 100371374C, CN-C-100371374, CN02819265, CN02819265.6, CN100371374 C, CN100371374C, PCT/2002/10050, PCT/EP/2/010050, PCT/EP/2/10050, PCT/EP/2002/010050, PCT/EP/2002/10050, PCT/EP2/010050, PCT/EP2/10050, PCT/EP2002/010050, PCT/EP2002/10050, PCT/EP2002010050, PCT/EP200210050, PCT/EP2010050, PCT/EP210050
InventorsA卡萨里尼, D戈多尼, G福里格里欧, R兰弗雷迪
Applicant波利玛利欧洲股份公司
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
Expandable vinylaromatic polymers and process for their preparation
CN 100371374 C
Abstract  translated from Chinese
可发性乙烯基芳族聚合物,其包括:a)通过聚合50-100wt%的一种或多种乙烯基芳族单体和0.50wt%的可共聚的单体得到的基质;b)以相对于聚合物(a)计的1-10wt%的包入聚合物基质中的发泡剂;c) 以相对于聚合物(a)计的0.05-25wt%的均匀分布在所述聚合物基质中的无机填料,该填料为基本上球形的颗粒,平均直径为0.01-100μm,折射率高于1.6,并且按照“Colour Index”(第三版,由“The Societyof Dyers and Colourists出版,1982)定义的白色指数等于或低于22。 Can be made of the vinyl aromatic polymer, which comprises: a) by polymerization of 50-100wt% of one or more vinyl aromatic monomers and 0.50wt% of copolymerizable monomers obtained matrix; b) to with respect to the polymer (a) meter 1-10wt% of the package into the polymer matrix of the blowing agent; c) with respect to the polymer (a) meter 0.05-25wt% of uniformly distributed in the polymer matrix inorganic filler, the filler is substantially spherical particles having an average diameter of 0.01-100μm, refractive index higher than 1.6, and in accordance with "Colour Index" (third edition, published by "The Societyof Dyers and Colourists, 1982) defines white index equal to or lower than 22.
Claims(23)  translated from Chinese
1.可发性乙烯基芳族聚合物,其包括: a)通过聚合50-100wt%的一种或多种乙烯基芳族单体和0-50wt%的可共聚的单体得到的基质; b)相对于聚合物(a)计的1-10wt%的包入聚合物基质中的发泡剂; c)相对于聚合物(a)计的0.5-8wt%的均匀分布在所述聚合物基质中的无机填料,该填料具有基本上球形的颗粒形态,平均直径为0.1-50μm,折射率为1.6至3,并且按照由The Society of Dyers andColourists 1982年出版的Colour Index第三版定义的白色指数为5-22,包括端值。 1 can be made of the vinyl aromatic polymer, which comprises: a) by polymerization of 50-100wt% of one or more vinyl aromatic monomers and matrix 0-50wt% of copolymerizable monomers obtained; b) with respect to the polymer (a) meter 1-10wt% of the package into the polymer matrix of the blowing agent; c) with respect to the polymer (a) meter 0.5-8wt% of uniformly distributed in the polymer inorganic filler matrix, the filler particles having substantially spherical morphology, an average diameter of 0.1-50μm, a refractive index of 1.6 to 3, and in accordance with by The Society of Dyers andColourists Colour Index Third Edition published in 1982 defined a white index of 5-22, inclusive.
2. 根据权利要求l的聚合物,其中乙烯基芳族单体选自对应于下面通式的那些单体:其中,R是氣或甲基,n是0或1-5的整数,Y是卤素或具有l-4 个碳原子的坑基或坑氧基。 2. The polymer according to claim l, wherein the vinyl aromatic monomer is selected from those corresponding to the monomer of the formula: wherein, R is a gas or a methyl group, n is 0 or an integer of 1-5, Y is group or a halogen or a pit group having pits l-4 carbon atoms.
3. 根据权利要求2的聚合物,其中作为Y的所述卣素是氟或溴。 3. The polymer according to claim 2, wherein said wine container as prime Y is fluorine or bromine.
4. 根据权利要求2的聚合物,其中具有通式(I)的乙烯基芳族单体是以与最高达50wt。 4. The polymer according to claim 2, wherein the vinyl aromatic monomer having the general formula (I) is based with up to 50wt. /。 /. 的其它可共聚单体的混合物形式使用,所述可共聚单体选自(甲基)丙烯酸、(甲基)丙烯酸的d-C4烷基酯、(甲基)丙烯酸的跣胺和腈、丁二烯、乙烯、二乙烯基苯、马来酸酐, The other copolymerizable monomer is used as a mixture, the copolymerizable monomers selected from (meth) acrylic acid, (meth) acrylic acid d-C4 alkyl ester, (meth) acrylic acid and Municipal amines and nitriles, D dienes, ethylene, divinylbenzene, maleic anhydride,
5. 根据权利要求3的聚合物,其中可共聚单体是丙烯精和曱基丙烯酸甲酯, 5. The polymer of claim 3, wherein the copolymerizable monomer is propylene refined and 曱 methacrylate,
6. 根据权利要求1或2的聚合物,其中无机填料的白色指数为21-5,包括端值。 6. The polymer according to claim 1 or claim 2, wherein the inorganic filler is a white index 21-5, inclusive.
7. 根据权利要求1或2的聚合物,其中无机填料是二氣化钛或疏酸钡。 7. The polymer according to claim 1 or claim 2, wherein the inorganic filler is titanium vaporized titanium or sparsely barium.
8. 用上述权利要求中任一項的可发性乙烯基芳族聚合物制成的发泡制品,其密度为5-50g/l,热导率为25-50mW/mK,通常比相当的非填充发泡材料的热导率甚至低10%以上。 8. The use as claimed in any one of the preceding claims can be made of the vinyl aromatic polymer made from foamed article having a density of 5-50g / l, a thermal conductivity of 25-50mW / mK, generally equivalent ratio Thermal conductivity of unfilled foam even lower than 10%.
9. 一种制备可发性乙烯基芳族聚合物的方法,该方法包括在基本上球形颗粒的、平均直径为0. l-50,、折射率为1. 6至3并且按照The Society of Dyers and Colourists 1982年出版的Colour Index第三版定义的白色指数为5-22的无机填料存在下,在含水悬浮液中聚合一种或多种乙烯基芳族单体及非必要的最高达5Owt %的至少一种可聚合共聚单体,聚合之前、期间或之后加入发泡剂。 9. A process for preparing a foamable vinyl aromatic polymer, the method comprising substantially, the average diameter of the spherical particles of 0. l-50 ,, a refractive index of 1.6 to 3 and in accordance with The Society of defined in the third edition of Colour Index Whiteness Index Dyers and Colourists 1982, published as an inorganic filler is present in 5-22, the polymerization in aqueous suspension one or more vinyl aromatic monomers and non-essential up 5Owt % of at least one polymerizable comonomer, before polymerization, during or after the addition of the blowing agent.
10. 根据权利要求9的方法,其中聚合结束时,得到了平均直径为0. 2-2咖的基本上球形的聚合物珠粒,其内均勻分散着无机添加刑。 10. The method according to claim 9, wherein the end of the polymerization, to obtain an average diameter of 0. 2-2 coffee substantially spherical polymer beads, uniformly dispersed within an inorganic add punishment.
11. 根据权利要求9或IO的方法,其中聚合过程中,加入以所得聚合物重量计为0. l-8wt。 11. The method according to claim 9 or IO, wherein during the polymerization, the polymer was added to the resulting weight of 0. l-8wt. /。 /. 的阻燃剂。 Flame retardants.
12. 根据权利要求11的方法,其中阻燃刑是溴化的脂肪族化合物、 淡化的环脂族化合物或溴化的芳族化合物, 12. The method according to claim 11, wherein the brominated flame retardant punishment is an aliphatic compound, aromatic compound dilution cycloaliphatic compounds or brominated,
13. 根据权利要求9或10的方法,其中聚合过程中加入发泡刑, 所述发泡刑选自含有3-6个碳原子的脂肪烃或脂环烃、含有1-3个碳原子的脂肪烃的囟代衍生物、二氣化碳和水, 13. The method according to claim 9 or claim 10, wherein the polymerization process by adding foaming sentence, the sentence is selected from foamed aliphatic hydrocarbon containing 3-6 carbon atoms or alicyclic hydrocarbon, containing 1 to 3 carbon atoms, a halogenated aliphatic hydrocarbon derivatives, two gas dioxide and water,
14. 根据权利要求9或10的方法,其中所述悬浮聚合通过乙烯基芳族聚合物在单体或者单体混合物中的溶液进行,其中聚合物的浓度为l-30wt%。 14. A method according to claim 9 or 10, wherein said suspension polymerization by a vinyl aromatic monomer or a polymer solution in the monomer mixture was, wherein the concentration of polymer is l-30wt%.
15. 大量和连续地制备可发性乙烯基芳族聚合物的方法,该方法包括下迷的连续步槺:i.将通过聚合50-100wt^的一种或多种乙烯基芳族单体和0-50wt% 的可共聚的单体得到的乙烯基芳族聚合物和无机填料一起加入到挤出机中,所述无机填料具有基本上球形的顆粒形态,平均直径为0. 1-50一,折射率为1.6至3并且按照The Society of Dyers and Colourists 1982年出版的Colour Index第三版定义的白色指数为5-22;ii. 将所述乙烯基芳族聚合物加热至高于相对熔点的温度;iii. 在通过模头挤出之前,将发泡剂和可能的添加刑注入到熔融的聚合物中;和iv. 通过模头形成基本上球形的平均直径为0.2-2咖的珠粒,该珠粒为可发性的。 15. A number of methods can be made continuously preparing vinyl aromatic polymers and, the method comprising the successive steps 槺 under fans: i 50-100wt ^ by polymerizing one or more vinyl aromatic monomers. and 0-50wt% of the copolymerizable monomers of the vinyl aromatic polymer and an inorganic filler is added to the extruder along with the inorganic filler particles having substantially spherical morphology, an average diameter of 0. 1-50 a refractive index of 1.6 to 3 and in accordance with The Society of Dyers and Colourists 1982, published in the third edition of Colour Index defined white index 5-22;. ii the vinyl aromatic polymer is heated to a temperature above the melting point of the relative temperature;. iii before extruded through a die, and possible to add a blowing agent injected into the molten criminal polymer; and iv substantially an average diameter of 0.2-2 coffee spherical beads are formed through the die. tablets, the beads can be made for nature.
16. 根据权利要求10的方法,其中对制成的可发性珠粒用一般用于常规方法制成的珠粒的方法进行预处理,该预处理方法基本上包括:a) 用液体抗静电刑涂復珠粒;b) 在这样处理的珠粒上涂布涂层,该涂层基本上由甘油与脂肪酸的单、二和三酯和硬脂酸金属盐的混合物组成。 With a liquid antistatic a): 16. The method of claim 10, wherein the pair made of foamable beads for beads with the general method of a conventional method of pretreatment, the pretreatment method essentially comprising Penalty coated beads; b) the beads thus treated in a coating a coating consisting essentially of glycerol and a fatty acid mono-, di- and tri-esters and a mixture of metal salts of stearic acid composition.
17. 根据权利要求16的方法,其中a)步稞中使用的液体抗静电刑是胺、叔乙氧基化烷基胺或环氣乙烷-环氣丙烷共聚物。 17. The method according to claim 16, wherein the liquid antistatic Penalty step a) wheat used are amines, tertiary ethoxylated alkylamines or cyclic gas ethane - ring gas oxide copolymer.
18. 根据权利要求16的方法,其中b)步稞中的硬脂酸盐是硬脂酸锌和/或硬脂酸镁。 18. The method according to claim 16, wherein step b) wheat in the stearate is zinc stearate and / or magnesium stearate.
19. 根据权利要求9或IO的方法,其中无机填料还与甘油与脂肪酸的单、二和三酯和硬脂酸金属盐的混合物一起加入到涂层中。 19. The method according to claim 9 or IO, wherein the inorganic filler further with glycerol and a fatty acid mono-, di- and tri-esters and a mixture of metal salts of stearic acid was added to the coating together.
20. 根据权利要求15的方法,其中对制成的可发性珠粒用一般用于常规方法制成的珠粒的方法进行预处理,该预处理方法基本上包括:a) 用液体抗静电刑涂復珠粒;b) 在这样处理的珠粒上涂布涂层,该涂层基本上由甘油与脂肪酸的单、二和三酯和硬脂酸金属盐的混合物组成。 With a liquid antistatic a): 20. The method according to claim 15, wherein the pair made of foamable beads for beads with the general method of a conventional method of pretreatment, the pretreatment method essentially comprising Penalty coated beads; b) the beads thus treated in a coating a coating consisting essentially of glycerol and a fatty acid mono-, di- and tri-esters and a mixture of metal salts of stearic acid composition.
21. 根据权利要求20的方法,其中a)步槺中使用的液体抗静电剂是胺、叔乙氧基化烷基胺或环氣乙烷-环氧丙烷共聚物. 21. The method of claim 20, wherein the liquid antistatic agent a) is used in step 槺 amines, tertiary ethoxylated alkylamines or cyclic gas oxide - propylene oxide copolymer.
22. 根据权利要求20的方法,其中b)步槺中的硬脂酸盐是硬脂酸锌和/或硬脂酸镁。 22. The method of claim 20, wherein step b) 槺 The stearate is zinc stearate and / or magnesium stearate.
23. 根据权利要求15的方法,其中无机填料还与甘油与脂肪酸的羊、二和三酯和硬脂酸金属盐的混合物一起加入到涂层中。 23. The method according to claim 15, wherein the inorganic filler is also a fatty acid with glycerol and sheep, and a mixture of di- and triesters of stearic acid metal salt is added to the coating together.
Description  translated from Chinese

可发性乙烯基芳族聚合物及其制备方法本发明涉及可发性乙烯基芳族聚合物及其制备方法。 Can be made of a vinyl aromatic polymer and preparation method of the present invention relates to hair vinyl aromatic polymers and their preparation methods. 更具体地说,本发明涉及制备可发性乙烯基芳族聚合物的方法以及由此得到的产品,所述聚合物在发泡之后,具有降低的导热性和低的密度。 More particularly, the present invention relates to the preparation can be made of a vinyl aromatic polymers and the thus obtained product, after foaming of the polymer, having reduced thermal conductivity and low density. 可发性乙烯基芳族聚合物,特别是其中的可发性聚苯乙烯是已知的产品,长期以来就被用于各种应用中,其中最重要的一种应用是绝热领域。 The expandable vinyl aromatic polymers, in particular of polystyrene are known products, has long been used in various applications, the most important field of application would be adiabatic. 这些发泡产品是通过下述方法制成的:在密闭模具中膨胀充满了气体的发泡聚合物珠粒,并将模具内含有的膨胀的颗粒通过压力和温度的共同作用成型。 These foam products are prepared by the following methods: in a closed mold filled with expandable gas foamed polymer beads, and expanded particles contained within the mold by the combined effect of pressure and temperature of molding. 颗粒的膨胀一般是用维持在比聚合物的玻璃化转变温度(Tg)稍高的温度下的蒸汽或其它气体进行。 Expansive particles is generally used to maintain in the vapor or other gases at temperatures higher than the polymer has a glass transition temperature (Tg) were. 发泡聚苯乙烯的一个具体应用领域是建筑业中的绝热领域,在此一般使用其平板形式。 A specific application area is expanded polystyrene insulation in the field of construction, this is generally used in its tablet form. 一般使用的发泡聚苯乙烯平板的密度约为30g/l,因为聚合物的导热性在这样的密度数值下是最小的。 Commonly used foamed polystyrene plates of a density of about 30g / l, because the thermal conductivity of the polymer in such density value is minimal. 即使从技术上讲是可能的,密度低于该极限也是不利的,这是由于这将引起板的导热性急剧增加,而这必须通过增加板的厚度进行补偿。 Even if technically possible with a density below this limit is unfavorable, because it will cause a sharp increase in the thermal conductivity of the plate, which must be compensated by increasing the thickness of the plate. 美国专利6,130,265描迷了一种制备可发性聚苯乙烯颗粒的方法, 它可以用于制备用于建筑业的密度低于30g/1,但是导热性却与常规板类似的绝热板。 US Patent 6,130,265 describe a process for preparing fans polystyrene particles, which can be used to prepare for the construction of a density of less than 30g / 1, but the thermal conductivity was similar to conventional board insulation board. 根据该方法,可以制备可发性聚苯乙烯颗粒,该颗粒能够制成密度为10-15g/l并且导热性满足DIN 18164, Part 1标准的035级要求的诸如板之类的产品,在颗粒本身内包入了0.05-25wt。 According to this method, can be prepared polystyrene particles which can be made into a density of 10-15g / l and a thermal conductivity meet DIN 18164, Part 1 standard requirements such as plate 035 categories of products, the particles within the package itself into 0.05-25wt. /。 /. 的基本上为球形颗粒形式的、平均直径为0.1-5(Hmi的石墨粉末。更具体地说,上述美国专利的方法包括在石墨颗粒和常规试剂和/或聚合添加剂存在下,聚合含水悬浮液中的苯乙烯单体,或者苯乙烯中的聚笨乙烯溶液。这样就制成了平均直径为0.2-2mm的可发性聚笨乙烯球形珠 The substantially spherical particle form, the average diameter of 0.1-5 (Hmi graphite powder. More specifically, the above-described method of U.S. Patent comprises graphite particles and conventional reagents and / or additives in the presence of a polymerization, aqueous suspension polymerization styrene monomer, styrene or polystyrene solution. This made the average diameter of 0.2-2mm can send spherical beads of polystyrene

粒,其中均匀分布着粉末形式的石墨。 Tablets, which uniformly distributed in the form of graphite powder. 申请人现已发现,可以得到能够提供低密度发泡材料的可发性苯乙烯聚合物,其性能与现有技术的方法所得到的材料相当,而无需使用诸如石墨的不透热添加剂,石墨除了其它缺点之外,在聚合物发泡之前和之后具有不美观的灰色,有时更严重。 Applicants have now discovered, capable of providing a low density foamed material can be made of styrene polymer, its performance and the prior art methods resulting material considerably, without the use of additives such as athermanous graphite, graphite Among other drawbacks, polymer foam before and after having unsightly gray, sometimes more serious. 事实上已经发现,通过用折射率充分高于聚合物的折射率并且由此能够有助于反射红外辐射的物质代替不透热的石墨(即能够吸收红外辐射),可以得到密度远远低于30g/1,并且导热性也能够满足DIN 18164, Part l标准的035 级的基于乙烯基芳族聚合物的产品。 In fact it has been found, by a refractive index sufficiently higher than the refractive index of the polymer and thus can contribute to the infrared radiation to be reflected instead of athermanous graphite (i.e. capable of absorbing infrared radiation), can be much lower than the density 30g / 1, and the thermal conductivity is also able to meet the DIN 18164, based on the vinyl aromatic polymer product of Part l standard 035's. 这个结果是非常令人感兴趣的, 因为这样允许选择诸如二氣化钛之类的材料,而由于二氧化钛是白色的,它不改变聚合物、特别是聚苯乙烯的颜色。 This result is very interesting, because it allows the selection of a material such as titanium bis gasification, and since titanium dioxide is white, it does not change the polymer, in particular polystyrene color. 因此,本发明的一个目的涉及可发性乙烯基芳族聚合物,其包括:a) 通过聚合50-100wt%的一种或多种乙烯基芳族单体和0-50wt% 的可共聚的单体得到的基质;b) 以相对于聚合物(a)计的l-10wt%的包入聚合物基质中的发泡剂;c) 以相对于聚合物(a)计的0.05-25wt。 Accordingly, an object of the present invention relates to a foamable vinyl aromatic polymer, which comprises: a) by polymerization of 50-100wt% of one or more vinyl aromatic monomers and copolymerizable 0-50wt% monomers matrix; b) with respect to the polymer (a) meter l-10wt% of the package into the polymer matrix of the blowing agent; c) with respect to the polymer (a) meter 0.05-25wt. /。 /. 的均匀分布在所述聚合物基质中的无机填料,该填料为基本上球形的颗粒,平均直径为O.Ol-lOOnm,折射率高于1.6,并且按照"Colour Index"(第三版,由"The Society of Dyers and Colourists出版,1982 )定义的白色指数等于或低于22。本说明书和权利要求书中使用的术语"乙烯基芳族单体"主要指对应于下面通式的产品:其中,R是氣或甲基,n是0或l-5的整数,Y是卤素如氯或溴, 或具有i-4个碳原子的烷基或烷氧基。<formula>formula see original document page 6</formula> Evenly distributed in the polymer matrix of an inorganic filler, the filler is substantially spherical particles having an average diameter of O.Ol-lOOnm, refractive index higher than 1.6, and in accordance with "Colour Index" (third edition, by "The Society of Dyers and Colourists Publishing, 1982) defines a white index equal to or lower than 22. In the present specification and claims, the terms used in the claims," vinyl aromatic monomer "mainly refers to the product corresponding to the following general formula: wherein , R is a gas or a methyl group, n is an integer of 0 or l-5, Y is a halogen such as chlorine or bromine, or an alkyl or alkoxy group i-4 carbon atoms. <formula> formula see original document page 6 </ formula>

具有上面定义的通式的乙烯基芳族单体的实例是:苯乙烯、oc-曱基苯乙烯、曱基苯乙烯、乙基苯乙烯、丁基苯乙烯、二甲基苯乙烯、 单、二、三、四和五氯苯乙烯、溴代苯乙烯、甲氧基苯乙烯、乙酰氧基苯乙烯等。 Examples of having the general formula defined above vinyl aromatic monomers are: styrene, oc- 曱 group styrene, 曱 group styrene, ethyl styrene, butyl styrene, dimethyl styrene, mono-, two, three, four and five-chlorostyrene, bromostyrene, methoxy styrene, acetoxy styrene. 优选的乙烯基芳族单体是苯乙烯和a-甲基苯乙烯。 Preferred vinyl aromatic monomers are styrene and a- methylstyrene. 具有通式(I)的乙烯基芳族单体可以单独使用,或者是以与最高达50wt。 Vinyl aromatic monomers having the general formula (I) can be used alone, or is with up 50wt. /。 /. 的其它可共聚单体的混合物形式使用。 Form of a mixture of other copolymerizable monomers. 这些单体的实例是: (甲基)丙烯酸;(甲基)丙烯酸的d-C4烷基酯,例如丙烯酸甲酯、 甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸异丙酯、丙烯酸丁酯;(甲基)丙烯酸的酰胺和腈,例如丙烯酰胺、甲基丙烯酰胺、丙烯腈、曱基丙烯腈;丁二烯;乙烯;二乙烯基苯;马来酸酐等。 Examples of these monomers are: (meth) acrylic acid; (meth) acrylic acid d-C4 alkyl esters, such as methyl acrylate, methyl methacrylate, ethyl acrylate, methyl methacrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate; (meth) acrylic acid amides and nitriles, such as acrylamide, methacrylamide, acrylonitrile, Yue-yl acrylonitrile; butadiene; ethylene; divinylbenzene; and maleic anhydride. 优选的可共聚单体是丙烯腈和曱基丙烯酸甲酯。 Preferred copolymerizable monomers are acrylonitrile and Yue methacrylate. 任何能够被包入乙烯基芳族聚合物基质中的发泡剂都可以与本发明的乙烯基芳族聚合物结合使用。 Any can be wrapped in a vinyl aromatic polymer matrix in the blowing agent are used in combination with the vinyl aromatic polymer of the present invention. 其典型实例是脂肪烃、氟利昂、二氧化碳、水等。 Typical examples are aliphatic hydrocarbons, freon, carbon dioxide, water and the like. 折射率高于1.6、优选为1.6-3 (包括端值)并且白色指数等于或低于22、优选为21-5 (包括端值)的无机填料,既可以通过悬浮聚合, 也可以通过连续质量才支术(continuous mass technique)加入到乙烯基芳族聚合物中,其加入量使其在聚合物中的最终浓度为0.05-25wt % , 优选0.5-8wt%。 A refractive index higher than 1.6, preferably 1.6-3 (inclusive) and the white index equal to or lower than 22, preferably 21-5 (inclusive) of the inorganic filler, either by suspension polymerization, or by continuous mass before performing surgery (continuous mass technique) was added to the vinyl aromatic polymer in an amount to give the final concentration in the polymer is 0.05-25wt%, preferably 0.5-8wt%. 填料的粒径优选为0.1-50pm。 The particle size of the filler is preferably 0.1-50pm. 优选的无机填料是二氧化钛和硫酸钡。 Preferred inorganic filler is titanium dioxide and barium sulfate. 加入填料之后,就得到了可发性聚合物,它可以被加工制成密度为5-50g/l、优选10-25g/l的发泡制品。 After addition of the filler, to obtain a foamable polymer which can be processed into a density of 5-50g / l, preferably 10-25g / l of the foamed article. 这些材料还具有优异的绝热能力,其热导率为25-50mW/mK,优选30-45mW/mK,这平均起来一般比目前市场上相当的非填充发泡材料,例如表1和2中所例举的来自EniChem SpA的EXTIR A-5000甚至还低10%以上。 These materials also have excellent thermal insulation capacity, the thermal conductivity of 25-50mW / mK, preferably 30-45mW / mK, which is generally on average than the corresponding unfilled foam material currently on the market, such as those in Tables 1 and 2 Exemplary from EniChem SpA of EXTIR A-5000 and even lower than 10%. 由于本发明可发性聚合物的这些特征,因此制备绝热制品时可以节约很多材料,或者例如可以制备比用常规非填充聚合物制成的板材更薄的板材,由此减少了空间。 Because of these features of the present invention can be made of polymer, and therefore can save a lot of material when the insulation products prepared, for example, or may be prepared by conventional sheet metal than a non-filled polymer sheet made thinner, thereby reducing the space. 一般用于传统材料中的常规添加剂,例如颜料、稳定剂、阻燃剂、 抗静电剂、分离剂(detaching agent)等也可以加入到本发明的可发性聚合物中。 Conventional materials generally used conventional additives, such as pigments, stabilizers, flame retardants, antistatic agents, separating agents (detaching agent), etc. may be added to the present invention can be made of polymers. 本发明的又一个目的涉及可发性聚合物的制备方法,所述可发性聚合物具有改善的热导率,膨胀之后密度低于30g/1。 A further object of the present invention relates to methods can be made of polymer, the polymer can be made with improved thermal conductivity, after expansion density of less than 30g / 1. 具体地说,本发明的又一个目的涉及可发性乙烯基芳族聚合物的制备方法,该方法包括在基本上为球形颗粒的、平均直径为O.Ol-lOOjim、折射率高于1.6并且按照"Colour Index"(第三版,由"The Society of Dyers and Colourists, 1982 )定义的白色指数等于或低于22的无机填料存在下,在含水悬浮液中聚合一种或多种乙烯基芳族单体及任选的最高达50wt。/。的至少一种可聚合共聚单体,聚合之前、之间或之后加入发泡剂。聚合结束时,得到了平均直径为0.2-2mm的基本上为球形的聚合物珠粒,其内均匀分散着无机添加剂。在悬浮聚合过程中,使用通常用于制备可发性乙烯基芳族聚合物的聚合添加剂,例如过氧化物引发剂、悬浮液稳定剂、链转移剂、发泡助剂、成核剂、增塑剂等。特别是,优选在聚合过程中加入所得聚合物重量的0.1-8wt。/。的阻燃剂。特别适合本发明的可发性乙烯基芳族聚合物的阻燃剂是溴化的脂肪族、环脂族、芳族化合物,例如六溴环十二烷、五溴一氯环己烷和五溴苯基烯丙基醚。发泡剂优选在聚合阶段加入,并且选自含有3-6个碳原子的脂肪族或环脂族烃,例如正戊烷、异戊烷、环戊烷或它们的混合物;含有1-3个碳原子的脂肪经的囟代衍生物,例如二氯二氟甲烷、1,2,2-三氟乙烷、1,1,2-三氟乙烷,二氧化碳和水。为了改善悬浮液稳定性,可以使用乙烯基芳族聚合物在单体或单体混合物中的溶液,其中聚合物浓度为l-30wt%,优选5-20wt。/。。该溶液可以通过如下方法得到:将预先制成的聚合物(例如新的聚合物, 或以前聚合和/或发泡的废料)溶解在单体中;或者预聚合单体或所有单体的混合物以达到上述浓度,然后在剩余添加剂存在下继续在含水悬浮液中聚合。 In particular, a further object of the present invention relates to a method for preparing a foamable vinyl aromatic polymer, which process comprises substantially spherical particles, the average diameter of O.Ol-lOOjim, refractive index higher than 1.6 and according to the following "Colour Index" (third edition, by "The Society of Dyers and Colourists, 1982) defines a white index equal to or lower than 22, the presence of an inorganic filler, one or more vinyl aromatic polymerization in aqueous suspension aromatic monomers and optionally up to 50wt. /. of at least one polymerizable comonomer, before polymerization, during or after adding a foaming agent. When the end of the polymerization, to obtain an average diameter of 0.2-2mm substantially spherical polymer beads, uniformly dispersed within an inorganic additive. In the suspension polymerization process, generally used for the preparation of polymeric additive can be made of a vinyl aromatic polymers, such as peroxide initiators, suspension stabilizers , chain transfer agents, foaming aids, nucleating agents, plasticizers, etc. In particular, the weight of the resulting polymer is preferably added during the polymerization of 0.1-8wt. / flame retardants. In particular the present invention may be suitable Hair vinyl aromatic polymer is a brominated flame retardant aliphatic, cycloaliphatic, aromatic compounds, such as six HBCD, penta-HCH and a five-bromophenyl allyl . ether blowing agent is preferably added in the polymerization stage, and is selected from an aliphatic or cycloaliphatic hydrocarbon of 3-6 carbon atoms, such as n-pentane, isopentane, cyclopentane or mixtures thereof; containing 1- 3 carbon atoms, aliphatic halogenated derivatives by, e.g., dichlorodifluoromethane, 1,2,2-trifluoroethane, 1,1,2-trifluoroethane, carbon dioxide and water. In order to improve the suspension stability, can use a solution of vinylaromatic polymer in the monomer or monomer mixture, wherein the polymer concentration of l-30wt%, preferably 5-20wt / .. The solution can be obtained by the following method: The pre- polymers (e.g., new polymers, or before the polymerization and / or waste foam) was dissolved in the monomer prepared; or a mixture of monomers or pre-polymerization of all monomers in order to achieve the above concentrations, and then in the presence of the remaining additives By continuing polymerization in an aqueous suspension.

本发明的另一个目的涉及大量和连续地制备可发性乙烯基芳族聚合物的方法,该方法包括下述的连续步骤:i.将上述乙烯基芳族聚合物和无机填料一起加入到挤出机中,所迷无机填料具有基本上球形的颗粒形态,平均直径为0.01-100^mi,折射率高于1.6并且按照"Colour Index"(第三版,由"The Society of Dyers and Colourists, 1982 )定义的白色指数等于或低于22;U.将所述乙烯基芳族聚合物加热至高于相对熔点的温度;iii.在通过^^莫头挤出之前,将发泡剂和可能的添加剂如阻燃剂注入到熔融的聚合物中;和W.通过模头形成基本上球形的可发性珠粒,其平均直径为0.2-2mm。大量和连续地制备乙烯基芳族聚合物的详细方法描述在欧洲专利EP126,459中。聚合结束时,或者在悬浮液中或者在连续物流中,对制成的可发性珠粒进行一般用于常规可发性珠粒的预处理,该预处理基本上包括:1.用液体抗静电剂如胺、叔乙氧基化烷基胺、环氧乙烷-环氧丙烷共聚物等涂覆珠粒。该试剂的目的既有助于"涂层,,的粘合,也有助于悬浮液中制成的珠粒的筛选。 Another object of the present invention relates to a method for continuously preparing a large number of foamable vinyl aromatic polymers and, the method comprising the following successive steps:. I The above vinyl aromatic polymer and an inorganic filler added together to squeeze the machine, the fans of the inorganic filler particles having substantially spherical morphology, an average diameter of 0.01-100 ^ mi, refractive index higher than 1.6 and in accordance with "Colour Index" (third edition, by "The Society of Dyers and Colourists, 1982) defines a white index equal to or lower than 22;. U the vinyl aromatic polymer is heated to a temperature higher than the relative melting point;. iii ^^ Mo before extruded through the blowing agent and the possible additives such as a flame retardant is injected into the molten polymer; and W. formed through a die can be made of substantially spherical beads having an average diameter of 0.2-2mm and a large number of continuous manufacture of vinyl aromatic polymers. The method is described in detail in European Patent No. EP126,459. When the end of the polymerization, or in suspension or in a continuous stream of foamable beads prepared are generally used for conventional pretreatment can be made of beads, the Pretreatment essentially comprises: 1 with a liquid antistatic agent such as amines, tertiary ethoxylated alkylamines, ethylene oxide - propylene oxide copolymer beads coated with the agent of such purposes only help. ". ,, coating adhesion, but also contribute to the screening of the beads prepared in suspension. 2,在上述珠粒上涂布"涂层,,,该涂层基本上由甘油(或其它醇) 与脂肪酸的单、二和三酯和硬脂酸金属盐例如硬脂酸锌和/或镁的混合物组成。或者,无机填料也可以同酯的混合物一起加入到涂层中。 为了更好地理解本发明和其实施方式,下面给出了一些说明性的而非限定性的实施例。 实施例1将150重量份水、0.1重量份焦磷酸钠、100重量份苯乙烯、0.15 重量份过氧化苯甲酰、0.25重量份过苯甲酸叔丁基酯和1重量份二氧化钛的混合物加入到密闭、搅拌的容器中,所述二氧化钛基本上为球形颗粒,平均直径约为0.2nm。将该混合物搅拌下加热至90'C。 90。C下约2小时后,加入4份10%的聚乙烯基吡咯烷酮溶液。搅拌下,将混合物再加热2小时至100。C,加入7份正戊烷和异戊烷的70/30的混合物,并将混合物再加热4小时至125C。随后收集这样制成的可发性聚合物珠粒,用去离子水洗涤,热空气流中干燥,加入0.02%的乙氧基化胺,过筛,分离出直径为l-1.5mm 的部分。然后向这一部分中加入0.2%的甘油基单硬脂酸酯和0.05%的硬脂酸镁。将该产物用100。C的蒸汽以三种接触时间进行预发泡,并熟化一天(密度见表1)。将一部分珠粒第二次发泡以达到更低的密度。将仅发泡一次和发泡两次的珠粒都用于在0.4巴压力下制成样块(尺寸1040 x 1030 x 550mm),并测试冷却时间(数据见表2-片材1)。然后评价该样块的收缩率(或样块体积与模具体积的差),并切开制成用于测试烧结和热导率的平板。其热导率为36.7mW/mK,而用传统非填充参考产品(EXTIR A-5000)制成的相同密度的板的热导率为42.5mW/mK。表2说明了用本发明的第一次发泡和第二次发泡的可发性珠粒制成的发泡聚苯乙烯样块的物理性能,并与市场上参考产品得到的类似样块进行了比较。令人惊奇的是,本发明珠粒制成的样块,其烧结度急剧增加。实施例2将单独与二氧化钛(2%和4% )预混合(在第一段),和单独与硫酸钡(2% )预混合(在第二段)的200'C/5kg条件下熔融指数为10g/10min的聚苯乙烯加入到装有加料漏斗的双螺杆挤出机中。聚合物变为熔融态后,注入6份重量比为70/30的正戊烷/异戊烷的混合物。将所得材料通过带有孔的挤出机头挤出。将从所述孔中出来的聚合物用一系列与模头表面接触的旋转刀切断,得到平均直径约为 2, the coating on the beads ",,, coating the coating consists essentially of glycerin (or other alcohols) with fatty acids, mono-, di- and tri-esters and stearic acid metal salts such as zinc stearate and / or a mixture of magnesium components. Alternatively, the inorganic filler may be added together with the mixture of esters into the coating. For a better understanding of the present invention and its embodiments, given below some embodiments as illustrative and not restrictive. 1 to 150 parts by weight of water in Example, 0.1 part by weight of sodium pyrophosphate, 100 parts by weight of styrene, 0.15 part by weight of benzoyl peroxide, 0.25 parts by weight of over-tert-butyl ester and titanium dioxide was added to a mixture of 1 part by weight sealed, stirred vessel, said titanium dioxide are substantially spherical particles having an average diameter of about 0.2nm. After the mixture was heated with stirring to about 2 hours 90'C. 90.C, the addition of 4 parts of 10% polyethylene vinylpyrrolidone solution. Under stirring, the mixture was heated for 2 hours to 100.C, was added a mixture of 7 parts of n-pentane and isopentane 70/30, and the mixture was heated for 4 hours to 125 C. followed by collection thus produced can be made of polymer beads, washed with deionized water, dried in a hot air flow, 0.02% of the ethoxylated amine and sieved, separating the l-1.5mm diameter part Then to This part was added 0.2% of glyceryl monostearate and 0.05% magnesium stearate. The product was 100.C vapor contact time in three pre-foaming, and curing a day (density in Table 1 ). A portion of the beads a second time in order to achieve a lower density foam. The foam and foam only once for the two beads are made at 0.4 bar pressure specimens (dimensions 1040 x 1030 x 550mm ), and cooling time test (2- sheet data in Table 1). Then evaluation shrinkage (or volume difference between the volume of the mold specimens) of the sample block and cut and prepared for testing the thermal conductivity of sintered plate. Its thermal conductivity of 36.7mW / mK, while the traditional non-filled reference product (EXTIR A-5000) made of a plate of the same density thermal conductivity of 42.5mW / mK. Table 2 illustrates the present invention first and second foamed foaming onset foaming polystyrene beads can be made of the physical properties of the specimens, and the specimens on the market similar to the reference product obtained were compared. Surprisingly that the present invention is made of beads specimens, a sharp increase in the sintering degree. Example 2 with titanium dioxide alone (2% and 4%) pre-mixed (in the first stage), and with barium sulfate alone (2% After) under premixed (second paragraph) of 200'C / 5kg conditions melt index of 10g / 10min polystyrene was added to an addition funnel fitted with a twin screw extruder. polymer into the molten state, injecting 6 parts by weight ratio of 70/30 n-pentane / isopentane mixtures. The resulting material was extruded through the extrusion head with holes. out from said bore and a die with a series of polymers surface of the contact rotating knife cut to obtain an average diameter of about

1.2mm的基本上球形的珠粒。 1.2mm of substantially spherical beads. 所述模头浸在水浴中。 The die is immersed in a water bath. 所述珠粒通过水流输送,冷却到35。 The beads are conveyed by the water flow, cooled to 35. C,并从水中分离出来,在热空气流中干燥。 C, and separated from water, dried in a stream of hot air. 然后按照实施例1所述方法,向珠粒中加入乙氧基化胺和涂层。 Then according to the method described in Example 1, was added to the beads and coating ethoxylated amines. 按照实施例l所述方法,进行发泡和成型。 According to the method described in Example l, foaming and molding. 对应于2%和4%的二氧化钛,其热导率分别约为36和35.5mW/mK。 Corresponding to the 2% and 4% titanium dioxide, its thermal conductivity was about 36 and 35.5mW / mK. 另一方面,含有2wt。 On the other hand, contains 2wt. /U危酸钡、密度为17g/l的平板的热导率达到了36.7mW/mK。 / U danger barium, a density of 17g / l of the thermal conductivity of the plate reached 36.7mW / mK. 表2说明了由用二氧化钛改性的可发性珠粒制成的发泡样块的物理性能。 Table 2 shows the physical properties of the foam specimens from modified with titanium dioxide can be made of beads made. 所有情况下,与参考样块相比,用本发明珠粒制成的样块的烧结度急剧增加。 In all cases, compared with the reference sample block, the sample block of sintered bead of the invention made with a sharp increase. 表l<table>table see original document page 11</column></row> <table> Table l <table> table see original document page 11 </ column> </ row> <table>

表2 -第一次发泡和第二次发泡珠粒制成的样块<table>table see original document page 12</column></row> <table> Table 2 - first and second foaming foam beads made of specimens <table> table see original document page 12 </ column> </ row> <table>

Classifications
International ClassificationC08J9/16, C08L25/06, C08J9/20, C08J9/00
Cooperative ClassificationC08J9/20, C08J2325/06, C08J9/0066, C08J9/16, C08J2201/03
European ClassificationC08J9/16, C08J9/00M, C08J9/20
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5 Jan 2005C06Publication
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27 Feb 2008C14Granted