CN1665866A - 开孔聚丙烯泡沫颗粒 - Google Patents
开孔聚丙烯泡沫颗粒 Download PDFInfo
- Publication number
- CN1665866A CN1665866A CN038159937A CN03815993A CN1665866A CN 1665866 A CN1665866 A CN 1665866A CN 038159937 A CN038159937 A CN 038159937A CN 03815993 A CN03815993 A CN 03815993A CN 1665866 A CN1665866 A CN 1665866A
- Authority
- CN
- China
- Prior art keywords
- pearl
- open celled
- pore
- celled foam
- propene polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 26
- 239000006260 foam Substances 0.000 title claims description 33
- -1 polypropylene Polymers 0.000 title claims description 12
- 239000002245 particle Substances 0.000 title abstract description 11
- 239000004743 Polypropylene Substances 0.000 title description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 239000011324 bead Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000004088 foaming agent Substances 0.000 claims description 4
- 238000001228 spectrum Methods 0.000 claims description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 4
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 229910003480 inorganic solid Inorganic materials 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920006324 polyoxymethylene Polymers 0.000 claims description 3
- 229920001169 thermoplastic Polymers 0.000 claims description 3
- 239000004416 thermosoftening plastic Substances 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 229910001872 inorganic gas Inorganic materials 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 2
- 239000011118 polyvinyl acetate Substances 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 229920003169 water-soluble polymer Polymers 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims 1
- 239000008187 granular material Substances 0.000 abstract description 4
- 239000007900 aqueous suspension Substances 0.000 abstract 1
- 239000003380 propellant Substances 0.000 abstract 1
- 239000000454 talc Substances 0.000 description 8
- 235000012222 talc Nutrition 0.000 description 8
- 229910052623 talc Inorganic materials 0.000 description 8
- 238000007598 dipping method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 101100276036 Arabidopsis thaliana CTL1 gene Proteins 0.000 description 3
- 101100408822 Schizosaccharomyces pombe (strain 972 / ATCC 24843) pom1 gene Proteins 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 102000046669 Surf-1 Human genes 0.000 description 2
- 102100030638 Surfeit locus protein 2 Human genes 0.000 description 2
- 101710093351 Surfeit locus protein 2 Proteins 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000002902 bimodal effect Effects 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 230000006353 environmental stress Effects 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000006261 foam material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 101150081019 surf1 gene Proteins 0.000 description 2
- 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 2
- 229940078499 tricalcium phosphate Drugs 0.000 description 2
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 2
- 235000019731 tricalcium phosphate Nutrition 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical class CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920005027 Ultraform® Polymers 0.000 description 1
- 229920006097 Ultramide® Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 206010000269 abscess Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 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
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002984 plastic foam Substances 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
-
- 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
- C08J9/16—Making expandable particles
- C08J9/20—Making expandable particles by suspension polymerisation in the presence of the blowing agent
-
- 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
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- 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
- C08J9/16—Making expandable particles
- C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
-
- 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
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/05—Open cells, i.e. more than 50% of the pores are open
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明涉及含有大于40％的开孔的丙烯聚合物泡沫颗粒。这些颗粒通过用挥发性发泡剂将含有1－40重量％开孔剂的丙烯聚合物微粒浸渍在水悬浮液中，然后发泡来生产。
Description
本发明涉及基于丙烯聚合物的开孔泡沫珠。
由丙烯聚合物生产的泡沫制件越来越广泛地用于汽车内部制件，作为包装材料和作为消费品。它们通过相应泡沫珠的后膨胀和烧结来获得。这些泡沫珠又通过公知的方法获得(例如EP-A 95109)，其中用挥发性发泡剂在压力容器中将聚丙烯颗粒浸渍在水悬浮液中，然后将该混合物解压缩。以此方式生产的泡沫珠在DSC热图谱中显示所谓的双峰，即至少有一个处于比所用丙烯聚合物的熔点峰更高温度下的高温峰(参见例如EP-A415744)。它们的特点是特别好的加工性能和机械性能，例如耐热变形性。这种泡沫珠通常具有闭孔；例如，根据EP-A 95109的泡沫珠具有至少65％的闭孔。这在大多数应用中也是希望的。
EP-A 1016690描述了由丙烯聚合物制备的泡沫珠，其包含水作为发泡剂和0.05-10重量％的亲水性聚合物，例如聚酰胺、聚酯或聚乙烯醇。但是，它们包含至少85％的闭孔，即不是开孔的。
开孔塑料泡沫通常比闭孔泡沫塑料具有更高的弹性，和具有隔音作用，这是有利的，例如用于汽车内饰和一些包装材料中。WO00/15700描述了开孔聚烯烃泡沫材料，其具有良好的吸音性能。它们是通过聚烯烃熔体与挥发性有机发泡剂一起挤出获得的板、膜或管。在这种泡沫材料的挤出中，仅仅可能生产具有简单几何形状的模制品。另外，这些泡沫材料没有上述在DSC热图谱中的双峰，所以例如它们的耐热变形性对于一些应用而言是不足的。
本发明的目的是提供基于丙烯聚合物的开孔泡沫珠，其特别显示良好的机械性能和能进一步以各种方式加工。
我们发现该目的通过开孔泡沫珠来达到，该开孔泡沫珠具有1-10mm的平均珠尺寸和基于丙烯聚合物的5-200g/l的堆积密度，和具有大于40％比例的开孔(根据DIN ISO 4590)。
一种生产这种开孔泡沫珠的优选方法包括用挥发性发泡剂在压力容器中在高温下将丙烯聚合物珠粒浸渍在水悬浮液中，然后将该混合物解压缩。丙烯聚合物珠包含1-40重量％的开孔剂，例如极性的水不溶性热塑体、水溶性的聚合物或针状无机固体。
为了本发明的目的，丙烯聚合物是：
a.丙烯均聚物，
b.丙烯与最多15重量％的乙烯和/或1-丁烯的无规共聚物，优选丙烯与0.5-6重量％的乙烯或与0.5-12重量％1-丁烯的共聚物，或者丙烯、0.5-6重量％乙烯和0.5-6重量％1-丁烯的三元共聚物，
c.a.或b.与0.1-75重量％、优选3-50重量％的聚烯烃弹性体的混合物，例如乙烯-丙烯嵌段共聚物。
用齐格勒催化剂或用茂金属催化剂生产的丙烯聚合物是合适的。
丙烯聚合物的结晶熔点(DSC峰最大值)是120-170℃。通过DSC方法测定的熔融焓优选是50-110J/g，根据DIN 53735测定的熔体流动指数(MFI)(230℃，2.16kp)是2-25g/10分钟。
根据本发明的开孔泡沫珠是从颗粒生产，优选这些颗粒具有0.2-10mm的平均直径，特别是0.5-5mm。这些颗粒通常是圆柱形或球形的微粒，通过将丙烯聚合物与混合的开孔剂和其它添加剂一起挤出并将该混合物强制通过挤出机来获得，如果需要的话可以将该混合物冷却，和将该混合物造粒。
必要的是这些微粒含有1-40重量％、优选5-35重量％的开孔剂。优选的开孔剂是极性的水不溶性热塑体，优选聚酰胺(PA)或聚甲醛(POM)；水溶性聚合物，优选聚乙烯吡咯烷酮(PVP)，聚乙酸乙烯酯和聚氧化乙烯；还可以是针状无机固体，优选具有0.25-5mm长度的雕玻璃。另外，微粒可以含有常规添加剂，例如抗氧化剂、稳定剂、阻燃剂、蜡、颜料、染料和特别是成核剂，例如滑石、石墨粉、热解硅酸、沸石、膨润土和聚烯烃蜡。
微粒分散在搅拌型反应器中的悬浮介质中。优选的悬浮介质是水。在这种情况下，必须加入悬浮助剂以保证微粒在悬浮介质中的均匀分布。合适的悬浮助剂是水不溶性无机稳定剂，例如磷酸三钙、焦磷酸镁和碳酸钙；还有聚乙烯醇和表面活性剂，例如芳基磺酸盐和脂肪醇氧基化物。它们的用量是0.05-5重量％，基于微粒计。挥发性发泡剂向悬浮介质中的添加量是2-50重量％，优选5-30重量％，基于微粒计。发泡剂可以在反应器内容物的加热之前、期间或之后加入。合适的发泡剂是沸点为-5至150℃的有机化合物，例如烷烃、酮和醚，以及无机气体，例如氮气和二氧化碳。特别优选C4-C6烃。
在浸渍期间，温度应该在大约丙烯聚合物的软化点附近。该温度可以是从比熔点(结晶熔点)低40℃至比该熔点高15℃。优选的浸渍温度是120-160℃。根据发泡剂的类型和用量以及根据温度，在反应器内的压力通常大于2巴，但不超过40巴。浸渍时间应该通常是0.5-10小时，在此之后，反应器快速解压。在该操作期间，被发泡剂浸渍的丙烯聚合物珠膨胀。由于开孔剂的作用，在该过程中形成根据本发明的开孔泡沫珠。在解压和从反应器排出之后，将泡沫珠从悬浮介质中分离出来并洗涤。如果使用水溶性开孔剂，将该开孔剂同时基本上洗掉。在水不溶性开孔剂的情况下，这些开孔剂保留在泡沫珠中。
根据本发明的开孔泡沫珠具有特别好的机械性能，如果它们在DSC熔融谱中具有至少一个比所用丙烯聚合物的熔融峰更高温度的高温峰的话。这些泡沫珠的平均珠尺寸是1-10mm，优选2-8mm；它们的堆积密度可以是5-200g/l，优选10-100g/l。它们的特征在于开孔的比例(根据DIN ISO4590)大于40％，优选大于50％和特别是大于75％。在理想的情况下，基本上所有的孔都是开放的，也就是说，泡沫结构仅仅由泡孔网组成。平均泡孔直径优选是0.01-0.5mm，特别是0.05-0.3mm。
泡沫模制品可以从根据本发明的泡沫珠按照公知的包括后膨胀和烧结的方法生产。
在下面实施例中的份(P)是按重量计。
实施例
P表示重量份。
原料：
PP1：Novolen 3200MC；来自Basell GmbH的聚丙烯
POM1：Ultraform N 2320(BASFAG)
PA1：Ultramid B3(BASF AG)
PS1：标准聚苯乙烯，Mw＝195000g/mol，MVR＝10cm3/10分钟(BASFAG)
PVP1：聚乙烯吡咯烷酮，Kollidon K 30，来自BASFAG
玻璃：雕玻璃3786
Wax1：Luwax AF 31；聚乙烯(Mn＝3000)，来自BASF AG
滑石：HP 325
s-Pentane：工业级戊烷异构体混合物
正-/异-丁烷：工业级丁烷异构体混合物
Antiblock1：CaCO3；
Antiblock2：磷酸三钙；
Surf1：脂肪醇氧基化物
Surf2：芳基磺酸盐
颗粒的生产：
为了生产颗粒，将原料混合，加入挤出机和转化成微粒(d：0.8-1.2mm；I：1.8-3mm)。
Gran1(G1)：100P的PP1、20P的POM1、1P的滑石、0.5P的Wax1
Gran2(G2)：100P的PP1、34P的POM1、2.8P的滑石、0.5P的Wax1
Gran3(G3)：100P的PP1、25P的玻璃、0.5P的Wax1
Gran4(G4)：100P的PP1、20P的PA1、1P的滑石、0.5P的Wax1
Gran5(G5)：100P的PP1、25P的PVP1、1.25P的滑石、0.6P的Wax1
Gran6(G6)：100P的PP1、20P的滑石、0.5P的Wax1
Gran7(G7)：100P的PP1、20P的PS1、1P的滑石、0.5P的Wax1
颗粒的发泡
表中显示了在这些泡沫珠上测定的堆积密度和开孔比例。开孔比例按照DIN ISO 4590对泡沫珠检测得到。
实施例1-4
在每种情况下，将100P的颗粒、6.7P的Antiblock1、0.13P的Surf1、230P的水和表中所示量的正-/异-丁烷加入密闭的搅拌釜中。该釜然后在约55分钟内加热到表中显示的浸渍温度(IMT)，当达到该温度后，通过将内容物解压到环境压力而将颗粒发泡。
实施例5-10
在每种情况下，将100P的颗粒、8.75P的Antiblock2、0.33P的Surf2、234P的水和表中所示量的正-/异-丁烷加入密闭的搅拌釜中。该釜然后在约55分钟内加热到表中显示的浸渍温度(IMT)，当达到该温度后，通过将内容物解压到环境压力而将颗粒发泡。
表
| 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 实施例6 | 实施例7 | 实施例8 | 实施例9 | 实施例10 | |
| 颗粒 | G1 | G1 | G1 | G1 | G2 | G3 | G4 | G5 | G6 | G7 |
| IMT[℃] | 129.0 | 129.0 | 128.7 | 127.6 | 128.0 | 127.5 | 130.0 | 129.0 | 130.0 | 136.0 |
| 发泡剂[P] | 24 | 20 | 20 | 20 | 24 | 24 | 35 | 24 | 35 | 16 |
| 堆积密度[g/l] | 18 | 31 | 30 | 37 | 15 | 11 | 14 | 9 | 15 | 13 |
| 开孔[％] | 43 | 42 | 51 | 65 | 80 | 59 | 79 | 65 | 10 | 9 |
[P]＝重量份/100重量份PP微粒
实施例9-10是对比例。
Claims (11)
1、开孔泡沫珠，具有1-10mm的平均珠尺寸和基于丙烯聚合物的5-200g/l的堆积密度，和具有大于40％比例的开孔(根据DIN ISO 4590)。
2、根据权利要求1的开孔泡沫珠，其中丙烯聚合物是丙烯的均聚物或者丙烯与最多15重量％的乙烯和/或1-丁烯的共聚物。
3、根据权利要求1的开孔泡沫珠，其在DSC热图谱中具有至少一个在比所用丙烯聚合物的熔融峰温度更高温度下的高温峰。
4、根据权利要求1的开孔泡沫珠，其中平均泡孔直径是0.01-0.5mm。
5、根据权利要求1的开孔泡沫珠，其具有1-40重量％的开孔剂含量。
6、一种生产根据权利要求1的开孔泡沫珠的方法，其中用挥发性发泡剂在压力容器中在高温下将丙烯聚合物泡沫珠浸渍在悬浮液中，然后将该混合物解压，其中丙烯聚合物珠含有1-40重量％的开孔剂。
7、根据权利要求6的方法，其中发泡剂是沸点为-5至150℃的有机化合物，优选C4-C6烃，或是无机气体。
8、根据权利要求6的方法，其中开孔剂是极性的水不溶性热塑体，优选聚酰胺或聚甲醛。
9、根据权利要求6的方法，其中开孔剂是针状无机固体，优选长度为0.25-5mm的雕玻璃。
10、根据权利要求6的方法，其中开孔剂是水溶性聚合物，优选聚乙烯吡咯烷酮、聚乙酸乙烯酯或聚氧化乙烯。
11、通过将权利要求1的泡沫珠进行后膨胀和烧结而生产的开孔泡沫模制品。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10230583.8 | 2002-07-05 | ||
| DE10230583A DE10230583A1 (de) | 2002-07-05 | 2002-07-05 | Offenzellige Polypropylen-Partikelschäume |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1665866A true CN1665866A (zh) | 2005-09-07 |
| CN100528944C CN100528944C (zh) | 2009-08-19 |
Family
ID=29723784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB038159937A Expired - Fee Related CN100528944C (zh) | 2002-07-05 | 2003-06-30 | 开孔聚丙烯泡沫颗粒 |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US20050236728A1 (zh) |
| EP (1) | EP1521799B1 (zh) |
| JP (1) | JP4128177B2 (zh) |
| KR (1) | KR100988407B1 (zh) |
| CN (1) | CN100528944C (zh) |
| AU (1) | AU2003250861A1 (zh) |
| DE (1) | DE10230583A1 (zh) |
| PL (1) | PL206014B1 (zh) |
| WO (1) | WO2004005383A1 (zh) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531770B (zh) * | 2008-05-15 | 2011-11-23 | 上海高分子功能材料研究所 | 开孔发泡聚烯烃的制备与应用 |
| CN109415529A (zh) * | 2016-06-23 | 2019-03-01 | 巴斯夫欧洲公司 | 制备由具有聚酰胺链段的热塑性弹性体制成的泡沫颗粒的方法 |
| CN113045827A (zh) * | 2020-12-17 | 2021-06-29 | 株式会社Jsp | 聚丙烯系树脂发泡颗粒以及发泡颗粒成形体 |
| CN113754954A (zh) * | 2021-08-24 | 2021-12-07 | 无锡敬仁电子材料科技有限公司 | 一种兼具高通孔率和高闭孔率的发泡聚合物吸波材料及其制备方法 |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200517426A (en) | 2003-08-25 | 2005-06-01 | Dow Global Technologies Inc | Aqueous dispersion, its production method, and its use |
| DE10360398A1 (de) * | 2003-12-19 | 2005-07-14 | Basf Ag | Schaumstoffformteile aus offenzelligem EPP |
| DE102004002367A1 (de) * | 2004-01-15 | 2005-08-11 | Basf Ag | Expandierte Polyolefinpartikel enthaltend spezielle Keimbildner |
| US8357727B2 (en) | 2004-02-27 | 2013-01-22 | Dow Global Technologies Llc | Durable foam of olefin polymers, methods of making foam and articles prepared from same |
| US7361694B2 (en) | 2004-02-27 | 2008-04-22 | Dow Global Technologies Inc. | Durable foam of olefin polymers, methods of making foam and articles prepared from same |
| DE102005055076A1 (de) * | 2005-11-16 | 2007-05-24 | Basf Ag | Verfahren zur Herstellung von Polyolefin-Schaumpartikeln mit hoher Schüttdichte und enger Schüttdichtenverteilung |
| DE102006000363A1 (de) | 2006-07-21 | 2008-01-24 | Hilti Ag | Befestigungselement |
| BRPI0603479A (pt) * | 2006-08-14 | 2008-04-01 | Maria Isabel Pinto Koleski | espuma de polipropileno expandida |
| CN105849167B (zh) * | 2013-12-27 | 2020-04-14 | 株式会社钟化 | 聚烯烃系树脂发泡粒子及聚烯烃系树脂模内发泡成型体 |
| KR102141993B1 (ko) | 2018-11-26 | 2020-08-06 | 롯데케미칼 주식회사 | Voc 방출이 저감된 사출용 폴리프로필렌계 수지 조성물 |
| US11780981B2 (en) * | 2018-12-06 | 2023-10-10 | Exxonmobil Chemical Patents Inc. | Foam beads and method of making the same |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2044597A (en) * | 1996-04-05 | 1997-10-29 | Kaneka Corporation | Hydrous polyolefin resin composition, preexpanded particles produced therefrom, process for producing the same, and expanded moldings |
| DE19638039A1 (de) * | 1996-09-18 | 1998-03-19 | Basf Ag | Verfahren zur Herstellung von expandierten Polyolefin-Partikeln |
| GB2324798B (en) * | 1997-05-01 | 1999-08-18 | Ici Plc | Open celled cellular polyurethane products |
| SG77671A1 (en) * | 1998-03-23 | 2001-01-16 | Jsp Corp | Foamed and expanded beads of polypropylene resin for molding |
| DE19921386A1 (de) * | 1999-05-10 | 2000-11-16 | Basf Ag | Offenzellig Partikelschaumstoffe |
| DE19950420A1 (de) | 1999-10-20 | 2001-04-26 | Basf Ag | Partikelförmige, expandierbare Olefinpolymerisate |
-
2002
- 2002-07-05 DE DE10230583A patent/DE10230583A1/de not_active Withdrawn
-
2003
- 2003-06-30 US US10/519,801 patent/US20050236728A1/en not_active Abandoned
- 2003-06-30 WO PCT/EP2003/006895 patent/WO2004005383A1/de active Application Filing
- 2003-06-30 KR KR1020057000106A patent/KR100988407B1/ko active IP Right Grant
- 2003-06-30 PL PL374820A patent/PL206014B1/pl unknown
- 2003-06-30 EP EP03762546.4A patent/EP1521799B1/de not_active Expired - Lifetime
- 2003-06-30 JP JP2004518621A patent/JP4128177B2/ja not_active Expired - Fee Related
- 2003-06-30 AU AU2003250861A patent/AU2003250861A1/en not_active Abandoned
- 2003-06-30 CN CNB038159937A patent/CN100528944C/zh not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531770B (zh) * | 2008-05-15 | 2011-11-23 | 上海高分子功能材料研究所 | 开孔发泡聚烯烃的制备与应用 |
| CN109415529A (zh) * | 2016-06-23 | 2019-03-01 | 巴斯夫欧洲公司 | 制备由具有聚酰胺链段的热塑性弹性体制成的泡沫颗粒的方法 |
| CN109415529B (zh) * | 2016-06-23 | 2022-08-30 | 巴斯夫欧洲公司 | 制备由具有聚酰胺链段的热塑性弹性体制成的泡沫颗粒的方法 |
| CN113045827A (zh) * | 2020-12-17 | 2021-06-29 | 株式会社Jsp | 聚丙烯系树脂发泡颗粒以及发泡颗粒成形体 |
| CN113754954A (zh) * | 2021-08-24 | 2021-12-07 | 无锡敬仁电子材料科技有限公司 | 一种兼具高通孔率和高闭孔率的发泡聚合物吸波材料及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1521799A1 (de) | 2005-04-13 |
| AU2003250861A1 (en) | 2004-01-23 |
| WO2004005383A1 (de) | 2004-01-15 |
| KR100988407B1 (ko) | 2010-10-18 |
| PL206014B1 (pl) | 2010-06-30 |
| PL374820A1 (en) | 2005-10-31 |
| EP1521799B1 (de) | 2019-04-10 |
| CN100528944C (zh) | 2009-08-19 |
| JP2006509051A (ja) | 2006-03-16 |
| US20050236728A1 (en) | 2005-10-27 |
| KR20050025580A (ko) | 2005-03-14 |
| DE10230583A1 (de) | 2004-01-15 |
| JP4128177B2 (ja) | 2008-07-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100528944C (zh) | 开孔聚丙烯泡沫颗粒 | |
| KR101514094B1 (ko) | 폴리올레핀/스티렌 중합체 혼합물 기재의 탄성 입자 발포체 | |
| CN101243122B (zh) | 聚烯烃泡沫 | |
| BE1010400A3 (fr) | Composition a base de polyolefines et de copolymere ethylene-acetate de vinyle. | |
| US8729143B2 (en) | Elastic particle foam based on polyolefin/styrene polymer mixtures | |
| WO2008127544A2 (en) | Fine cell foamed polyolefin film or sheet | |
| CA2388134C (en) | Particle-shaped, expandable olefin polymers | |
| CA2817678A1 (en) | Process for producing expandable thermoplastic beads with improved expandability | |
| EP4112678A1 (en) | Polypropylene-based resin foamed particles, method for producing same, and polypropylene-based resin foam molded body | |
| US20120121905A1 (en) | Process for producing expandable thermoplastic beads with improved expandability | |
| EP0575958B1 (en) | Pre-expanded particles of LLDPE | |
| CN112521690A (zh) | 一种发泡聚丙烯复合材料的制备方法 | |
| KR20180133607A (ko) | 내충격성이 우수한 에틸렌 비닐 아세테이트 발포입자 | |
| WO2023120237A1 (ja) | 樹脂発泡体 | |
| JPH0649256A (ja) | ポリスチレン系樹脂発泡体 | |
| KR101674610B1 (ko) | 고분자 발포 입자 및 이의 제조 방법 | |
| CN115850783A (zh) | 低密度增韧聚丙烯发泡材料组合物以及低密度增韧聚丙烯发泡材料及其制备方法 | |
| KR101928927B1 (ko) | 내충격성이 우수한 올레핀 블럭 공중합체 발포입자 | |
| JP2024506230A (ja) | ポリオレフィン発泡体ビーズ及びその製造方法 | |
| CN112469774A (zh) | 可发泡聚烯烃组合物及其方法 | |
| JP2024075550A (ja) | ポリオレフィン系樹脂発泡体及び止水材 | |
| CN117480203A (zh) | 可膨胀树脂组合物、其制备方法和由其制造的泡沫模制品 | |
| JP2000336129A (ja) | 押出発泡成形用エチレン−プロピレンブロック共重合体 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090819 Termination date: 20210630 |