CN101115788B - 涂覆可发苯乙烯聚合物颗粒的方法 - Google Patents

涂覆可发苯乙烯聚合物颗粒的方法 Download PDF

Info

Publication number
CN101115788B
CN101115788B CN2006800040197A CN200680004019A CN101115788B CN 101115788 B CN101115788 B CN 101115788B CN 2006800040197 A CN2006800040197 A CN 2006800040197A CN 200680004019 A CN200680004019 A CN 200680004019A CN 101115788 B CN101115788 B CN 101115788B
Authority
CN
China
Prior art keywords
coating
forming agent
water
styrene polymer
paraffin
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.)
Expired - Fee Related
Application number
CN2006800040197A
Other languages
English (en)
Other versions
CN101115788A (zh
Inventor
M·阿尔门丁格尔
K·哈恩
J·鲁赫
G·埃尔曼
B·施密德
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of CN101115788A publication Critical patent/CN101115788A/zh
Application granted granted Critical
Publication of CN101115788B publication Critical patent/CN101115788B/zh
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • 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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/03—Extrusion of the foamable blend
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • 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
    • C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof

Landscapes

  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (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)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Paints Or Removers (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

一种通过使包含发泡剂的苯乙烯聚合物熔体挤出通过模板，随后在水下造粒而生产涂覆的可发苯乙烯聚合物(EPS)颗粒的方法，其中所述EPS颗粒用可溶解、可乳化或可悬浮于水中的涂层剂在水下造粒机的循环水路中涂覆。

Description

涂覆可发苯乙烯聚合物颗粒的方法
本发明涉及一种通过使包含发泡剂的苯乙烯聚合物熔体挤出通过模板，随后在水下造粒而生产涂覆的可发苯乙烯聚合物(EPS)颗粒的方法，其中所述EPS颗粒用可溶解、可乳化或可悬浮于水中的涂层剂在水下造粒机的循环水路中涂覆。
用于周界绝热的疏水处理的可发聚苯乙烯颗粒例如由WO97/4334和EP-A913423已知。在这些情况下使疏水化剂吸附在硅胶上并在紧邻后处理和干燥后以该形式施加至EPS颗粒。
本发明的目的为发现一种均匀涂覆EPS颗粒的简单廉价的方法，该方法还可在不对基材产生吸附下进行。
因此我们已发现了开头所述的方法。
合适的涂层剂为两亲或疏水有机化合物。在疏水有机化合物中，尤其可提及C10-C30石蜡，N-羟甲基胺和脂肪酸衍生物的反应产物，C9-C11羰基合成醇和氧化乙烯、氧化丙烯或氧化丁烯的反应产物或聚(甲基)丙烯酸氟代烷基酯或其混合物。这些涂层剂可优选以含水乳液形式使用。
优选的疏水化剂为碳链中具有10-30个碳原子且优选具有10-70℃，尤其是25-60℃熔点的石蜡。这类石蜡例如包含在市售BASF产品RAMASIT KGT、PERSISTOL E和PERSISTOL HP以及购自Henkel的AVERSIN HY-N和购自Sandoz的CEROL ZN中。
另一类合适的疏水化剂由N-羟甲基胺与脂肪酸衍生物如脂肪酸酰胺、胺或醇的树脂状反应产物组成，这例如描述在US-A2927090或GB-A475170中。其熔点通常为50-90℃。这类树脂例如包含在市售BASF产品PERSISTOL HP和购自Hoechst的ARCOPHOB EFM中。
最后，聚(甲基)丙烯酸氟代烷基酯如聚丙烯酸全氟辛基酯也是适合的。后一物质包含在市售BASF产品PERSISTOL O和购自Pfersee的OLEOPHOBOL C中。
可行的两亲涂层剂为抗静电剂如乳化剂K30(仲链烷磺酸钠)或甘油硬脂酸酯如甘油单硬脂酸酯GMS或甘油三硬脂酸酯。
为生产本发明的可发苯乙烯聚合物，将发泡剂混入聚合物熔体中。本方法包括步骤a)生产熔体，b)混合，c)冷却，d)传输和e)造粒。这些步骤中的每个均可借助塑料加工中已知的设备或设备的组合而进行。为了混合，合适的是静态或动态混合器如挤出机。可将聚合物熔体由聚合反应器中直接取出或可在混合挤出机或单独的熔体挤出机中通过熔融聚合物颗粒而直接生产。熔体的冷却可在混合设备或单独的冷却器中进行。可行的造粒方法例如为加压水下造粒法、用旋转刀并借助喷雾雾化冷却液体或雾化颗粒而冷却的造粒法。适合进行该方法的设备排列例如为：
a)聚合反应器-静态混合器/冷却器-造粒机
b)聚合反应器-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
包含发泡剂的苯乙烯聚合物熔体通常在140-300℃，优选160-240℃的温度下挤出通过模板。不必冷却至玻璃化转变温度区域。
根据本发明，所得可发苯乙烯聚合物(EPS)颗粒的涂覆借助可溶解、可乳化或可悬浮于水中的涂层剂在造粒机中进行。
一种尤其优选的生产可发苯乙烯聚合物的方法包括如下步骤：
a)聚合苯乙烯单体和如果合适的话可共聚单体，
b)使所得苯乙烯聚合物熔体脱气，
c)借助静态或动态混合器在至少150℃，优选180-260℃的温度下将发泡剂和如果合适的话添加剂混入苯乙烯聚合物熔体中，
d)使包含发泡剂的苯乙烯聚合物熔体冷却至至少120℃，优选150-200℃的温度，
e)如果合适的话加入添加剂或填料，
f)通过具有洞的模板排出，其中所述洞在模板出口侧的直径不超过1.5mm，和
g)在涂层剂的溶液、乳液或悬浮液存在下将包含发泡剂的熔体直接在模板之后在水下造粒。
在UWP中的可变反压力使得可以特定的方式产生压缩颗粒和部分发泡的颗粒。通常而言，造粒在1-25巴，优选5-15巴的压力下进行。甚至当使用成核剂时，在UWP的模板处的部分发泡仍保持可控。
EPS颗粒通常用0.01-0.5重量％，优选0.1-0.3重量％涂层剂涂覆，其中在每种情况下所述量均基于固体含量。施加的涂层剂的量例如可经由循环水路中的浓度设定。基于水中的固体含量，通常用于水下造粒机的循环水路中的涂层剂的量为0.05-20重量％，优选0.1-10重量％。为获得恒定的涂覆质量，循环水路中涂层剂的浓度例如应借助恒定计量加入与涂覆EPS的量对应的涂层剂而保持恒定。
水下造粒机中的循环水路的温度应低于苯乙烯聚合物的玻璃化转变温度，以使EPS颗粒仅在表面上被涂覆且不被完全浸渍。温度优选为5-80℃，尤其是10-60℃。
有利的是本发明的可发聚苯乙烯颗粒可用于生产持续暴露于水的模制品，例如用于屋顶绝热或周界绝热的板，用于漂浮体或水敏感性包装材料如鱼箱。
实施例中的份数和百分数基于重量。
吸水率根据DIN53433测定，透水性通过如下方法测定：将直径为100mm的管粘至厚度为100mm的泡沫板上并充入100mm高的水柱。
24小时后，进行检查以测定在泡沫板的下面是否可观察到水的出口。水平面的下降以mm测定。在实验之前，将泡沫板在干燥箱中在60℃下调节24小时。然后借助硅橡胶粘上所述管。
实施例：
涂层剂：
Persistol HP＝购自BASF的疏水化剂，包含22.8％石蜡(熔点52-54℃)和9.6％源自N-羟甲基密胺和硬脂酰胺的树脂(熔点70℃)的含水乳液
Ramasit KGT＝购自BASF的疏水化剂，包含16.6％石蜡(熔点52-54℃)的含水乳液
Plurafac LF＝氧化乙烯和氧化丁烯与C9-C11羰基合成醇的反应产物
实施例1-3
将包含其中已混入6重量％正戊烷的粘数为75ml/g的聚苯乙烯(Mw＝185000g/mol，多分散性Mw/Mn＝2.6)的聚苯乙烯熔体用于实施例。将包含发泡剂的熔体由起初的260℃冷却至190℃。
将包含聚苯乙烯熔体、发泡剂和阻燃剂的混合物以60kg/h挤压通过具有32个洞的模板(每个洞的直径：0.75mm)。借助加压水下造粒设备生产具有窄粒度分布的压缩颗粒。
水下造粒的冷却水呈示于表1的浓度为0.5-10重量％的液体涂层剂或疏水化剂的含水乳液形式。为获得恒定的涂覆质量，必须保持水中涂层剂的浓度恒定。这可通过借助活塞膜式泵直接将涂层剂以对应于损失料流的量恒定计量加入循环水路而实现。借助直接进入水箱的节流流动补偿水损失。
将这些颗粒在蒸汽流中预发泡以生产发泡的珠粒(20g/l)，储存24小时，然后在气密模具中借助蒸汽熔融生产发泡体。
对比实验C1
与实施例类似进行对比实验，但是水下造粒在循环水路中在不存在疏水化剂下进行。
表1
 
实施例 疏水化剂[基于原始EPS产品的重量％] 吸水率[体积％] 不透水性[mm]
C1 － 5.8 28
1 0.1的Persistol HP 0.9 5
2 0.25的Persistol HP 0.2 2
3 0.25的Ramasit KGT 0.2 0.5
4 0.2的Plurafac LF120 0.9 9

Claims (6)

1.一种通过使包含发泡剂的苯乙烯聚合物熔体挤出通过模板，随后在水下造粒而生产涂覆的可发苯乙烯聚合物颗粒的方法，其中所述可发苯乙烯聚合物颗粒用两亲或疏水有机化合物作为可溶解、可乳化或可悬浮于水中的涂层剂在水下造粒机的循环水路中涂覆，其中所述涂层剂选自C10-C30石蜡，N-羟甲基胺和脂肪酸衍生物的反应产物或聚(甲基)丙烯酸氟代烷基酯或其混合物，或选自C9-C11羰基合成醇和氧化乙烯、氧化丙烯或氧化丁烯的反应产物或甘油硬脂酸酯，并且基于水中的固体含量，水下造粒机的循环水路中的涂层剂的量为0.05-20重量％。
2.根据权利要求1的方法，其中将C10-C30石蜡，N-羟甲基胺和脂肪酸衍生物的反应产物或聚(甲基)丙烯酸氟代烷基酯或其混合物的含水乳液用作涂层剂。
3.根据权利要求1或2的方法，其中将具有10-70℃熔点的石蜡用作涂层剂。
4.根据权利要求3的方法，其中将具有25-60℃熔点的石蜡用作涂层剂。
5.根据权利要求2的方法，其中基于水中的固体含量，水下造粒机的循环水路中的涂层剂的量为0.1-10重量％。
6.根据权利要求1-4中任一项的方法，其中水下造粒机的循环水路的温度为10-60℃。
CN2006800040197A 2005-02-04 2006-02-03 涂覆可发苯乙烯聚合物颗粒的方法 Expired - Fee Related CN101115788B (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102005005495.1 2005-02-04
DE102005005495A DE102005005495A1 (de) 2005-02-04 2005-02-04 Verfahren zur Beschichtung von expandierbaren Styrolpolymeren-Granulaten
PCT/EP2006/050649 WO2006082232A1 (de) 2005-02-04 2006-02-03 Verfahren zur beschichtung von expandierbaren styrolpolymeren-granulaten

Publications (2)

Publication Number Publication Date
CN101115788A CN101115788A (zh) 2008-01-30
CN101115788B true CN101115788B (zh) 2010-07-28

Family

ID=36061311

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2006800040197A Expired - Fee Related CN101115788B (zh) 2005-02-04 2006-02-03 涂覆可发苯乙烯聚合物颗粒的方法

Country Status (10)

Country Link
EP (1) EP1846485B1 (zh)
KR (1) KR101196173B1 (zh)
CN (1) CN101115788B (zh)
AT (1) ATE398647T1 (zh)
BR (1) BRPI0607101A2 (zh)
DE (2) DE102005005495A1 (zh)
MX (1) MX2007008745A (zh)
MY (1) MY143600A (zh)
PL (1) PL1846485T3 (zh)
WO (1) WO2006082232A1 (zh)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2671396A1 (en) 2006-12-18 2008-06-26 Basf Se Expandable styrene polymers and foams with decreased water absorption
DE102007050681A1 (de) * 2007-10-22 2009-04-23 Coperion Werner & Pfleiderer Gmbh & Co. Kg Verfahren und Vorrichtung zur Herstellung eines Polymergranulats
DE102011119939A1 (de) * 2011-12-01 2013-06-06 Technische Universität Hamburg-Harburg Verfahren zur Herstellung eines Verbundwerkstoffs, der Verbundwerkstoff und die Verwendung des Verbundwerkstoffs zur Herstellung bestimmter Produkte
KR101584133B1 (ko) * 2015-03-17 2016-01-11 (주)폴머 이종 발포입자를 이용한 복합발포성형물 및 그 제조방법
DE102015220203A1 (de) * 2015-10-16 2017-04-20 Alois Edler Verfahren und Vorrichtung zum Herstellen eines Polystyrol-Granulats

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0305862A1 (en) * 1987-09-04 1989-03-08 General Electric Company One-step process for the production of expandable foam beads
US5124365A (en) * 1990-03-28 1992-06-23 Basf Aktiengesellschaft Finely divided, expandable styrene polymers
EP0912620B1 (en) * 1996-07-04 2000-12-20 Nova Chemicals (International) S.A. Process for the preparation of polymer particles

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0305862A1 (en) * 1987-09-04 1989-03-08 General Electric Company One-step process for the production of expandable foam beads
US5124365A (en) * 1990-03-28 1992-06-23 Basf Aktiengesellschaft Finely divided, expandable styrene polymers
EP0449065B1 (de) * 1990-03-28 1995-11-15 BASF Aktiengesellschaft Feinteilige expandierbare Styrolpolymerisate
EP0912620B1 (en) * 1996-07-04 2000-12-20 Nova Chemicals (International) S.A. Process for the preparation of polymer particles

Also Published As

Publication number Publication date
EP1846485B1 (de) 2008-06-18
DE102005005495A1 (de) 2006-08-10
WO2006082232A1 (de) 2006-08-10
DE502006000957D1 (de) 2008-07-31
PL1846485T3 (pl) 2008-11-28
ATE398647T1 (de) 2008-07-15
BRPI0607101A2 (pt) 2010-03-09
KR20070108217A (ko) 2007-11-08
KR101196173B1 (ko) 2012-11-01
MX2007008745A (es) 2007-08-06
CN101115788A (zh) 2008-01-30
EP1846485A1 (de) 2007-10-24
MY143600A (en) 2011-06-15

Similar Documents

Publication Publication Date Title
CN101115788B (zh) 涂覆可发苯乙烯聚合物颗粒的方法
RU2451038C2 (ru) Частицы пенопласта с нанесенным покрытием и способ получения не содержащих галоидов огнестойких формованных изделий из пенопласта в виде частиц
JP5165991B2 (ja) ポリマー粒子を製造するための方法及びプラント
CN102812101B (zh) 热膨胀性微囊
RU2671722C2 (ru) Способ рециклирования вспениваемых пластических материалов и вспениваемый или вспененный пластический материал, который может быть получен с его помощью
PL206013B1 (pl) Sposób wytwarzania spienialnych polimerów styrenu i spienialne polimery styrenu (EPS)
ITMI20071005A1 (it) Procedimento per la preparazione di granuli a base di polimeri termoplastici espandibili e relativo prodotto
JP2007514027A (ja) ペレット状の発泡性フィラー含有熱可塑性ポリマー材料から構成される成形用発泡成形体
CN1890307A (zh) 由可膨胀聚苯乙烯及热塑性聚合物的混合物组成的膨胀珠粒模塑件
JP2008529859A (ja) 発泡性スチレンポリマー顆粒の製造方法
TWI820295B (zh) 熱膨脹性微膠囊及發泡成形用組成物
CN1984948A (zh) 用于聚苯乙烯泡沫的增效防火混合物
KR100948122B1 (ko) 화학적 조성물 및 공정
JP2024015416A (ja) 発泡性塩素化塩化ビニル系樹脂粒子、その発泡粒子、およびこれを用いた塩素化塩化ビニル系樹脂発泡成形体
KR20110120929A (ko) 저배성형용 발포성 폴리스티렌계 수지 입자와 그 제조방법, 저배발포 입자, 저배발포 성형체 및 흄관용 쿠션재, 저배발포 성형체 및 흄관용 쿠션재의 제조방법
JP2020519717A (ja) ポリスチレンを含む熱可塑性ポリマーを発泡させるためのＺ−ＨＦＯ−１３３６ｍｚｚ発泡剤配合物
JP2014145066A (ja) 難燃性スチレン系樹脂粒子、その製造方法、発泡性粒子、発泡粒子及び発泡成形体
CZ20032168A3 (cs) Expandovatelné částice polyolefinů
US9695295B2 (en) Compositions of self-extinguishing expandable vinyl aromatic (co)polymers and process for their preparation
DE102004034527A1 (de) Verfahren zur Herstellung von expandierbaren Styrolpolymeren mit verbesserter Expandierbarkeit
JPS6328888A (ja) 防錆性能を有する発泡性熱可塑性樹脂粒子の製造方法
JP2005297464A (ja) 廃発泡ポリオレフィン系樹脂成形体を利用した発泡ポリオレフィン系樹脂成型体の製造方法
CN101778890B (zh) 用于可发性苯乙烯聚合物颗粒的涂料制剂
US20150197612A1 (en) Novel Blowing Agents and Process
JPH0741586A (ja) 発泡体の製造方法

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
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20100728

Termination date: 20140203