CN1491253A - 可发泡聚烯烃颗粒 - Google Patents
可发泡聚烯烃颗粒 Download PDFInfo
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- CN1491253A CN1491253A CNA028046099A CN02804609A CN1491253A CN 1491253 A CN1491253 A CN 1491253A CN A028046099 A CNA028046099 A CN A028046099A CN 02804609 A CN02804609 A CN 02804609A CN 1491253 A CN1491253 A CN 1491253A
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- 239000003795 chemical substances by application Substances 0.000 claims abstract description 39
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- 150000003839 salts Chemical class 0.000 claims abstract description 8
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000008116 calcium stearate Substances 0.000 claims abstract description 5
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- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 claims description 4
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- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical group CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Chemical group CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- 238000001938 differential scanning calorimetry curve 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
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- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical group CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
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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
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
-
- 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
- C08J9/22—After-treatment of expandable particles; Forming foamed products
- C08J9/224—Surface treatment
-
- 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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/044—Elimination of an inorganic solid phase
-
- 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
- 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
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- Engineering & Computer Science (AREA)
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- 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
本发明涉及含有发泡剂的可发泡聚烯烃颗粒，其中所述颗粒涂覆有0.01－3重量％长链脂肪酸的盐和/或酯，优选硬脂酸钙，以防止在发泡过程中结块。
Description
本发明涉及一种为防止在发泡过程中结块而被涂敷的可发泡聚烯烃颗粒。
聚烯烃泡沫颗粒以日益增长的量用于生产汽车结构、包装和休闲领域中的泡沫模制品。发泡聚丙烯泡沫颗粒(EPP)在工业上通过在超计大气压下用挥发性发泡剂在水悬浮液中浸渍聚丙烯粒料，然后减压来生产，当减压时浸渍过的颗粒发泡。工业上使用的发泡剂是丁烷、二氯二氟甲烷和CO2。由于这些发泡剂较快地再次从聚丙烯中渗出，因此人们认为包含发泡剂且以此方式生产的聚丙烯颗粒不能储存。
德国专利申请199 50 420和100 03 021第一次描述了包含发泡剂且堆积密度大于400g/l的可发泡聚烯烃颗粒，其能够长期储存而不会发生任何显著量发泡剂的逃逸。因此可以使用过热蒸汽将它们在超计大气压下发泡至堆积密度低于200g/l。DE 199 50 420通过在高温下在压力容器中使用有机发泡剂、优选戊烷将聚烯烃粒料浸渍在水悬浮液中并在减压前将该混合物冷却至100℃以下来生产颗粒。DE 100 03 021将聚丙烯粒料与有机发泡剂和成核剂在挤出机中混合，并在避免发泡的温度和压力条件下进行挤出和造粒。
现已发现可发泡聚烯烃颗粒在发泡过程中趋于结块和团集，尤其当在较高温度下，即在高蒸汽压力下进行操作以获得低于100g/l的堆积密度时。由于通过利用发泡剂在水悬浮液中浸渍来生产可发泡颗粒总是需要加入较大量的金属碳酸盐或金属磷酸盐作为分散剂以防止所用聚烯烃粒料在该悬浮液内结块，因此显而易见的方法是要避免除去这些分散剂并允许它们保留在所得可发泡颗粒中。然而，金属碳酸盐和金属磷酸盐会损害发泡后所得泡沫颗粒的熔合，因此必须将它们通过复杂的酸洗方法从泡沫颗粒中除去，从而产生其中存在盐的废水。
因此，本发明的目的是提供不会在发泡过程中结块且可以毫无困难地熔合得到泡沫模制品的可发泡聚烯烃颗粒。
我们发现该目的通过用0.01-3重量％长链脂肪酸的盐和/或酯涂敷可发泡聚烯烃颗粒而实现。该涂层可以在发泡之后保留在泡沫颗粒上，因为它不会或仅非常小地损害为得到泡沫体而进行的熔合工艺。
DE-C 19541725描述了可发泡苯乙烯聚合物，其上涂敷有三硬脂酸甘油酯和疏水性硅酸盐的混合物以降低吸水性。
对本发明而言，聚烯烃是
a)均聚丙烯，
b)含0.1-15重量％、优选0.5-12重量％乙烯和/或C4-C10α-烯烃的丙烯无规共聚物，优选含0.5-6重量％乙烯或含0.5-15重量％1-丁烯的丙烯共聚物，或由丙烯、0.5-6重量％乙烯和0.5-6重量％1-丁烯制成的三元共聚物，或
c)a)或b)与0.1-75重量％、优选3-50重量％聚烯烃弹性体(例如含有30-70重量％丙烯的乙烯-丙烯嵌段共聚物)的混合物，或
d)聚乙烯(LLDPE、LDPE、MDPE、HDPE)，或
e)在a)-d)下提到的聚烯烃的混合物(或合适的话，加入有相容剂)。
在a)-e)下所列的聚烯烃的结晶熔点(DSC最大值)通常为90-170℃，通过DSC测定的其熔化焓优选为20-300J/g，并且熔体流动指数MFI(对丙烯聚合物为230℃和2.16kp，对乙烯聚合物为190℃和2.16kp)根据DIN 53 735优选为0.1-100g/10min。
优选的聚烯烃是含至多15重量％乙烯和/或1-丁烯的丙烯均聚物或丙烯共聚物，特别优选含1-5重量％乙烯的丙烯-乙烯共聚物。它们的熔点为130-160℃且密度(在室温下)为约900g/l。
烯烃聚合物可以与基于其重量为至多50％的玻璃化转变温度(DSC曲线中的拐点)低于180℃且不同类型的热塑性塑料共混。合适的热塑性塑料的实例是聚酰胺，其量为5-40重量％。可以向该混合物中加入常用相容剂，例如嵌段共聚物如Exxelor P 1015(EXXON)。
已发现本发明也可不混入任何不同类型的热塑性塑料而实施。这是优选的，因为外来热塑性塑料的存在损害聚烯烃的重复利用能力以及由其生产的泡沫体的重复利用能力。对本发明而言，不认为可加入用来增塑的弹性乙烯-丙烯共聚物是不同类型的。
聚烯烃可以包含常用添加剂，如抗氧化剂、稳定剂、阻燃剂、蜡、成核剂、填料、颜料和染料。
制备本发明可发泡聚烯烃颗粒的原料是聚烯烃粒料，其优选具有的平均直径为0.2-10mm，尤其是0.5-5mm。这些大多数情况下呈圆柱形或圆形的小粒料通过挤出聚烯烃，合适的话与待混入的热塑性塑料和其它添加剂一起挤出，以及合适的话进行冷却和造粒而制备。
小粒料应优选包含0.001-10重量％、优选0.1-5重量％、尤其0.5-3重量％的成核剂。这些合适成核剂的实例是滑石和/或蜡，以及还有碳黑、石墨和热解法二氧化硅。它们使得能够生产小孔泡沫体且在很多情况下不使用它们将不能进行很好的发泡。
在制备可发泡颗粒的优选方法中，在搅拌反应器中将粒料分散在悬浮介质中。优选的悬浮介质是水。在此必须加入悬浮剂以确保小粒料在悬浮介质中均匀分布。合适的悬浮剂是水不溶性无机稳定剂，如磷酸三钙、焦磷酸镁、金属碳酸盐以及还有聚乙烯醇和表面活性剂如十二烷基芳基磺酸钠。它们的常用量为0.05-10重量％。像WO-A 99/10419中一样若悬浮介质的密度低于悬浮粒料的密度，则可以省去加入悬浮稳定剂。例如在悬浮介质为乙醇或乙醇与至多50％水的混合物时情况就是如此。
发泡剂的沸点应为-5℃至150℃，尤其是25-125℃。发泡剂优选为链烷烃、链烷醇、酮、醚或酯。特别优选戊烷类和己烷类，尤其是仲戊烷、3，3-二甲基-2-丁酮和4-甲基-2-戊酮。还可以使用发泡剂混合物。发泡剂优选不含卤素。然而，不应排除包含少量、优选低于10重量％、尤其低于5重量％的含卤素发泡剂如二氯甲烷或氟代烃的发泡剂混合物。
发泡剂的用量基于粒料优选为2-50重量％，尤其是5-30重量％。发泡剂可以在加热反应器内容物之前、之中或之后加入。可以一次或分批引入。
在浸渍工艺过程中，温度应处于聚烯烃软化点附近。该温度可以比聚烯烃的熔点(结晶熔点)高40-25℃，但优选应低于该熔点。在聚丙烯的情况下，优选的浸渍温度为120-160℃。
取决于发泡剂的用量和性质以及温度，在反应器中建立的压力通常高于2巴，但不高于40巴。
浸渍时间通常为0.5-10小时。在减压和从搅拌的反应器中取出之前，例如通过将冷却水通入反应器夹套而将悬浮液冷却至100℃以下，优选冷却至10-50℃。然后有利地通过加入酸而溶解低溶解性悬浮剂。一旦压力降低并从反应器中排出批料，就从悬浮介质中分离出包含发泡剂的颗粒并进行洗涤。
在制备可发泡颗粒的另一方法中，将100重量份聚烯烃粒料与3-30重量份挥发性有机发泡剂和0.01-8、优选0.1-5重量份细颗粒成核剂以及合适的话还有其它常规添加剂一起引入挤出机中，并在挤出机中于包含发泡剂的混合物熔融的温度下、优选于160-220℃下混合。
合适成核剂的实例是滑石、聚烯烃蜡、石墨粉末、热解法二氧化硅、柠檬酸酯以及还有未改性或改性的膨润土。其它可以使用的添加剂是抗氧化剂、稳定剂、阻燃剂、填料和颜料。借助位于挤出机下游的泵计量加入3-30、优选5-25重量份挥发性有机发泡剂。还可以将成核剂和合适的话，其它添加剂与发泡剂一起在该点而不是上游加入，在这种情况下有利的是添加剂在发泡剂中呈悬浮液或溶液状态。
根据本发明，为了防止熔体在从挤出机中排出的过程中发泡，挤出和挤出物的造粒在实际上粒料不发生发泡的温度和压力条件下进行。这些条件可以因烯烃聚合物的性质、添加剂的性质以及尤其是所用发泡剂的性质和用量而异。理想的条件可以通过研究性试验而容易地确定。
有用的工业方法是在温度低于100℃且压力大于2巴的水浴中进行水下造粒。温度必须不能太低，否则熔体在口模板上凝结，而且温度必须不能太高，否则熔体会发泡。提高发泡剂的沸点或降低发泡剂的用量允许使用更高的水温和更低的压力。在特别优选的仲戊烷发泡剂的情况下，水浴的理想温度为30-60℃且水压力为8-12巴。
根据本发明，将可发泡颗粒基于其重量用0.01-3％、优选0.1-1.0％抗结块剂涂敷。该方法可以在常规混合设备如桨式混合器中进行。合适的抗结块剂是金属皂类，即长链、未支化或支化的脂族或脂环族羧酸的金属盐(见Szczepanek+Knen的“金属皂类”，Ullmann’s Encyclopedia(Ullmann百科全书)，第6版，Wiley VCH)，优选二价或三价金属的脂族C16-C36单羧酸盐。特别优选硬脂酸钙。其它合适的物质是蜡和脂肪，即所述长链羧酸的酯，优选甘油酯，尤其是硬脂酸甘油酯。还可以使用所述盐和酯的混合物。其它合适的物质是长链脂肪酸的酰胺。已发现疏水性抗结块剂特别合适。
除了本发明的抗结块剂外，该涂层优选还包含0.01-0.5重量％防粘连剂和/或0.01-0.3重量％抗静电剂，每种情况下都基于颗粒。防粘连剂防止粉状抗结块剂发生粘连。合适防粘连剂的实例是细颗粒硅石、滑石和膨润土。抗静电剂防止抗结块剂带静电并从而防止与混合设备的壁或搅拌器粘附。合适抗静电剂的实例是烷基磺酸盐、烷基硫酸盐和烷基磷酸盐，脂肪醇乙氧基化物和季铵化合物。
包含发泡剂的颗粒可以使用热空气或蒸汽在加压预发泡器中通过常规方法发泡。在使用蒸汽发泡的情况下，取决于发泡剂的类型和聚合物基体的类型以及所需堆积密度，所用蒸汽压力为2-4.5巴且发泡时间为3-30秒，而发泡过程中的温度应高于100℃，在聚丙烯情况下尤其为130-160℃。在简单发泡工序的情况下，所获得的堆积密度低于200g/l。因技术或经济原因，合适的是发泡两次或更多次以获得低堆积密度。
所得泡沫颗粒可以用于通过已知方法生产泡沫模制品。
实施例中提到的份数和百分数均基于重量。
实施例
A.生产包含发泡剂的聚丙烯粒料
原料：
PP1：Novolen 3200 MC；Targor GmbH的聚丙烯
PP2：Novolen 3300；Targor GmbH的聚丙烯
蜡：Luwax AF31；BASF AG的聚乙烯(Mn 3000)
滑石：Grade HF 325
碳黑：Elftex 570(Cabott)
稳定剂1：Ultranox 626(General Electric)
稳定剂2：Lowinox TBM 6(Great Lakes Chem.)
GTS：三硬脂酸甘油酯
GMS：单硬脂酸甘油酯
防粘连剂：Aerosil R 972；Degussa AG
抗静电剂：Armostat 3002；Akzo Chemie GmbH
ZnS：硬脂酸锌
MgS：硬脂酸镁
CaS：硬脂酸钙
AIS：二硬脂酸铝
StS：硬脂酸硬脂基酯
NaS：硬脂酸钠
粒料的生产：
粒料G1
将100份PP1与1份滑石和0.5份蜡混合并通过双螺杆挤出机加工得到l∶d为3∶1且重量为1.3mg的粒料。
粒料G2
将100份PP2与2份碳黑、1份滑石、0.5份蜡和各为0.05份的稳定剂1和稳定剂2混合并加工得到l∶d为2.1∶1且重量为1.3mg的粒料。
浸渍用材料量：
粒料： 296.1kg
水： 658.1kg
仲戊烷：62.2kg
碳酸钙：13.3kg(Calcilit1 G；Alfa)
Lutensol AO 3109：53.3g(BASF AG)
浸渍：
将原料加入装有横桨式搅拌器和挡板的1.36m3搅拌容器中。在2.5小时内将混合物升至浸渍温度(对粒料1为140℃，而对粒料2为133℃)并在该温度下保持30分钟，然后冷却至室温并使用18.3升65％浓度的硝酸溶解碳酸钙。洗涤浸渍过的粒料并离心分离除去水，然后借助气流干燥器进行干燥。在干燥过程之前立即施涂市购抗静电剂以防止任何带静电。发泡剂含量在粒料1中为11.0％，在粒料2中为10.8％。DSC在熔融范围内具有双峰，粒料1的高温峰位于166.2℃，而粒料2的高温峰位于160.8℃。
B.涂料组合物的制备
将表1所给百分数的各涂料组合物的各组分相互非常均匀地混合数分钟。所得涂料组合物(B1-B10)呈具有良好流动性能的粉状。
表1
| B1 | B2 | B3 | B4 | B5 | B6 | B7 | B8 | B9 | B10 | |
| ZnS | 46 | |||||||||
| MgS | 46 | |||||||||
| AlS | 46 | |||||||||
| CaS | 46 | 46 | 77 | |||||||
| NaS | 77 | |||||||||
| StS | 77 | |||||||||
| GMS | 40 | 77 | ||||||||
| GTS | 40 | 40 | 40 | 40 | 77 | |||||
| 防粘连剂 | 10 | 10 | 10 | 10 | 10 | 16 | 16 | 16 | 16 | 16 |
| 抗静电剂 | 4 | 4 | 4 | 4 | 4 | 7 | 7 | 7 | 7 | 7 |
C.涂敷
将涂料组合物在桨式混合器中与在A下所述的可发泡粒料均匀混合，由此使前者施涂于该粒料上。表2所给量为每100份PP粒料对应的份数。混合时间为2-3分钟。
D.发泡和力学性能
将常用于EPS加工的蒸汽操作的加压预发泡器用于该发泡工艺。逐步增加蒸汽压力，蒸汽施加时间在每种情况下为12秒。在泡沫颗粒干燥后使用筛网测定结块程度和堆积密度。表2给出了结块程度保持在1％以下的最大蒸汽压力。对于一些样本测定其根据DIN 53571的拉伸强度以作为其熔合质量的量度。
可以使用的最大蒸汽压力越高，可以获得的堆积密度就越低。因此使用硬脂酸钙得到最低的堆积密度(实施例6-8)。由于使用了不同品级的聚丙烯来生产粒料1和2，因此可获得的最大蒸汽压力和模制品的力学质量具有差异。
表2
| 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 | 实施例11 | 实施例12 | 实施例13 | 实施例14 | 实施例15 | |
| 涂层 | |||||||||||||||
| 粒料 | G1 | G1 | G1 | G1 | G1 | G1 | G1 | G1 | G2 | G2 | G2 | G2 | G2 | G2 | G2 |
| 涂层 | 无 | B1 | B1 | B2 | B3 | B4 | B4 | B8 | B4 | B8 | B5 | B6 | B7 | B9 | B10 |
| 量[Pts] | --- | 0.5 | 0.7 | 0.5 | 0.5 | 0.5 | 0.7 | 0.3 | 0.7 | 0.2 | 0.7 | 0.3 | 0.3 | 0.3 | 0.3 |
| 发泡* | |||||||||||||||
| 蒸汽压[巴] | 2.3** | 2.4 | 2.6 | 3.0 | 2.9 | 3.4 | 4.0 | 4.0 | 3.5 | 3.2 | 3.3 | 2.5 | 2.1 | 2.5 | 2.1 |
| 堆积密度[g/l] | 222 | 182 | 121 | 82 | 90 | 65 | 53 | 53 | 54 | 65 | 52 | 72 | 78 | 107 | 91 |
| 力学性能 | |||||||||||||||
| 模制品密度[g/l] | 77 | 79 | 58 | ||||||||||||
| 拉伸强度[kPa] | 915 | 816 | 815 | ||||||||||||
*所列实验是具有其中结块程度保持低于1％的最大蒸汽压力的实验；
**在该情况下结块程度甚至在2.3巴下也远大于1％。
Claims (8)
1.一种堆积密度大于400g/l的可发泡聚烯烃颗粒，包含1-40重量％的挥发性有机发泡剂，并且基于其重量涂覆有0.01-3％长链羧酸的盐和/或酯和/或酰胺以防止结块。
2.如权利要求1所要求的颗粒，其中所述抗结块剂为具有16-36个碳原子的脂族单羧酸的盐或酯，优选硬脂酸的盐或酯。
3.如权利要求2所要求的颗粒，其中所述抗结块剂为二-或三价金属的盐，优选硬脂酸钙。
4.如权利要求2所要求的颗粒，其中所述抗结块剂为甘油酯，优选三硬脂酸甘油酯。
5.如权利要求1所要求的颗粒，其中所述抗结块剂为疏水性的。
6.如权利要求1所要求的颗粒，其中所述涂层还包含抗静电剂和/或防粘连剂。
7.如权利要求1所要求的可发泡聚烯烃颗粒，其中所述聚烯烃为丙烯聚合物，优选含至多15重量％乙烯和/或1-丁烯的丙烯共聚物。
8.如权利要求1所要求的可发泡聚烯烃颗粒在生产泡沫体中的用途。
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| US9359481B2 (en) | 2003-11-26 | 2016-06-07 | Owens Corning Intellectual Capital, Llc | Thermoplastic foams and method of forming them using nano-graphite |
| US8568632B2 (en) * | 2003-11-26 | 2013-10-29 | Owens Corning Intellectual Capital, Llc | Method of forming thermoplastic foams using nano-particles to control cell morphology |
| DE102005039976A1 (de) * | 2005-08-23 | 2007-03-08 | Basf Ag | Partikel aus expandierbarem Polystyrol und daraus erhältliche Formteile mit verbessertem Brandverhalten |
| WO2007023092A1 (de) * | 2005-08-23 | 2007-03-01 | Basf Se | Verfahren zur herstellung von schaumstoffplatten |
| PL2591044T3 (pl) | 2011-06-23 | 2014-10-31 | Total Res & Technology Feluy | Ulepszone spienialne polimery winyloaromatyczne |
| KR101886435B1 (ko) | 2012-03-08 | 2018-08-07 | 현대자동차주식회사 | 팽창 그라파이트에 팽창 고분자 비드가 충전된 하이브리드 필러를 함유한 고방열 복합재 및 그 제조방법 |
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| JPS52892A (en) * | 1975-06-24 | 1977-01-06 | Teijin Ltd | Process for producing polyesters |
| JPS58152027A (ja) * | 1982-03-06 | 1983-09-09 | Kanegafuchi Chem Ind Co Ltd | ポリオレフイン系樹脂発泡体の製造方法 |
| JPS60181139A (ja) * | 1984-02-28 | 1985-09-14 | Japan Styrene Paper Co Ltd | ポリプロピレン系樹脂発泡粒子 |
| JPS63130646A (ja) * | 1986-11-21 | 1988-06-02 | Sekisui Plastics Co Ltd | 発泡性熱可塑性合成樹脂の製造方法 |
| JPH05200892A (ja) * | 1992-01-28 | 1993-08-10 | Mitsubishi Yuka Badische Co Ltd | 多孔質構造体の製造方法 |
| US5623012A (en) * | 1995-12-19 | 1997-04-22 | Shell Oil Company | Pelletizing aid for polymers |
| DE19950420A1 (de) | 1999-10-20 | 2001-04-26 | Basf Ag | Partikelförmige, expandierbare Olefinpolymerisate |
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2001
- 2001-02-08 DE DE10105618A patent/DE10105618A1/de not_active Withdrawn
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- 2002-01-25 TW TW091101241A patent/TW593473B/zh not_active IP Right Cessation
- 2002-02-06 PL PL363262A patent/PL205204B1/pl unknown
- 2002-02-06 CN CNB028046099A patent/CN1254497C/zh not_active Expired - Fee Related
- 2002-02-06 RU RU2003127369/04A patent/RU2311430C2/ru not_active IP Right Cessation
- 2002-02-06 CA CA002437344A patent/CA2437344C/en not_active Expired - Fee Related
- 2002-02-06 HU HU0302848A patent/HU226851B1/hu not_active IP Right Cessation
- 2002-02-06 KR KR1020037010407A patent/KR100837979B1/ko not_active IP Right Cessation
- 2002-02-06 MX MXPA03006492 patent/MX237418B/es active IP Right Grant
- 2002-02-06 AT AT02702347T patent/ATE440895T1/de not_active IP Right Cessation
- 2002-02-06 WO PCT/EP2002/001192 patent/WO2002062882A1/de active Application Filing
- 2002-02-06 CZ CZ20032168A patent/CZ300732B6/cs not_active IP Right Cessation
- 2002-02-06 EP EP02702347A patent/EP1368420B1/de not_active Expired - Lifetime
- 2002-02-06 JP JP2002563228A patent/JP4070606B2/ja not_active Expired - Fee Related
- 2002-02-06 ES ES02702347T patent/ES2330311T3/es not_active Expired - Lifetime
- 2002-02-06 DE DE50213796T patent/DE50213796D1/de not_active Expired - Lifetime
- 2002-02-06 BR BRPI0206981-4A patent/BR0206981B1/pt not_active IP Right Cessation
- 2002-02-06 US US10/466,479 patent/US6864298B2/en not_active Expired - Lifetime
- 2002-02-06 AU AU2002235896A patent/AU2002235896A1/en not_active Abandoned
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101248122B (zh) * | 2005-08-23 | 2012-07-04 | 巴斯夫欧洲公司 | 生产泡沫板的方法 |
| CN105647040A (zh) * | 2014-11-10 | 2016-06-08 | 天津麦索节能科技有限公司 | 具有泡孔结构的xps板材配方及其制备工艺 |
Also Published As
| Publication number | Publication date |
|---|---|
| CZ20032168A3 (cs) | 2004-01-14 |
| DE50213796D1 (de) | 2009-10-08 |
| NO20033503L (no) | 2003-10-07 |
| KR20030074800A (ko) | 2003-09-19 |
| BR0206981B1 (pt) | 2010-12-28 |
| WO2002062882A1 (de) | 2002-08-15 |
| TW593473B (en) | 2004-06-21 |
| CN1254497C (zh) | 2006-05-03 |
| DE10105618A1 (de) | 2002-08-22 |
| HUP0302848A2 (hu) | 2003-11-28 |
| MX237418B (es) | 2006-06-02 |
| HU226851B1 (en) | 2009-12-28 |
| PL205204B1 (pl) | 2010-03-31 |
| CZ300732B6 (cs) | 2009-07-29 |
| NO20033503D0 (no) | 2003-08-07 |
| AU2002235896A1 (en) | 2002-08-19 |
| US6864298B2 (en) | 2005-03-08 |
| MXPA03006492A (es) | 2003-10-15 |
| CA2437344A1 (en) | 2002-08-15 |
| US20040054020A1 (en) | 2004-03-18 |
| RU2311430C2 (ru) | 2007-11-27 |
| HUP0302848A3 (en) | 2007-09-28 |
| EP1368420A1 (de) | 2003-12-10 |
| EP1368420B1 (de) | 2009-08-26 |
| ES2330311T3 (es) | 2009-12-09 |
| CA2437344C (en) | 2009-07-14 |
| PL363262A1 (en) | 2004-11-15 |
| JP4070606B2 (ja) | 2008-04-02 |
| KR100837979B1 (ko) | 2008-06-13 |
| ATE440895T1 (de) | 2009-09-15 |
| BR0206981A (pt) | 2004-07-06 |
| RU2003127369A (ru) | 2005-03-27 |
| JP2005505637A (ja) | 2005-02-24 |
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