CN1038595C - 一种使聚烯烃稳定的方法 - Google Patents
一种使聚烯烃稳定的方法 Download PDFInfo
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of 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
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Artificial Filaments (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
一种用以使在载体催化剂上聚合成的粒子平均直径为1至5mm的烯烃类聚合物稳定的方法,此方法是用一种稳定剂混合物处理聚烯烃。这种稳定剂混合物制备方法是将下列组成的混合物加热至120至260℃,
a)不少于一种载体和/或
b)不少于一种在20至120℃之间熔融的稳定剂和
c)不少于一种在120至260℃之间熔融的稳定剂,
然后将上述混合物冷却至固化,组分b)和c)是不同的。
Description
本发明涉及一种使在载体催化剂上聚合成的粒子平均直径在1至5mm的烯烃类聚合物稳定的方法。
JP-A-84/150719叙述了一种使聚丙烯粉末稳定的方法,它是将聚丙烯粉末、稳定剂和载体在热作用下在混合器中均匀混合。
EP-A-281189叙述了由亚磷酸酯和酚类抗氧剂组成的防水解的稳定剂的制备方法,并用此稳定剂的混合物使聚丙烯粉末稳定。粉末状的聚烯烃在成型前必须在挤出机中制粒。在制粒时,将稳定剂和其它加工助剂加入到聚合物中。
由烯烃在固体载体催化剂上聚合制得的不稳定粒型聚烯烃已在市场上出售了一段时间。由于这些聚烯烃在制造时已成粒状,除了为了保证添加剂在聚合物中均匀分布需将加入的稳定剂和加工助剂熔融外,它们在下一道工序中不需要挤出成型。
在多数情况下,在烯烃聚合作用时加入稳定剂会妨碍聚合作用和影响聚合物色相。
本发明涉及一种用以使在载体催化剂上聚合成的、粒子平均直径在1至5mm的烯烃类聚合物稳定的方法,该方法是用一种稳定剂混合物处理聚烯烃,该稳定剂混合物制备方法是将下列组成的混合物加热至120至260℃,
a)不少于一种载体和/或
b)不少于一种在20至120℃之间熔融的稳定剂和
c)不少于一种在120至260℃之间熔融的稳定剂,然后将上述混合物冷却至固化。组分b)和C)是不同的。
组分b)在适当场合下可作为载体使用,起到组分a)的作用。
a和c择优重量比为0.1∶1至4∶1,最好为0.5∶1至2∶1,b和c的重量比的例子是4∶1至0.1∶1或2∶1至0.1∶1,最好为1∶1至0.1∶1。
在使用稳定剂混合物的方法中,含组分a)、b)、c)的混合物是择优的。
蜡、石蜡油或单羧酸甘油酯是择优的载体。下列化合物可作为适宜载体的例子,它们是:聚乙烯、聚丙烯(例如无规的)、烯烃类共聚物(如丙烯类共聚物、例如丙烯/乙烯共聚物或丙烯/丁烯-1共聚物)、乙烯/乙酸乙烯酯共聚物、乙烯/不饱和羧酸酯共聚物(如乙烯/甲基丙烯酸甲酯共聚物)、乙烯/不饱和羧酸金属盐共聚物(如乙烯/丙烯酸镁共聚物或乙烯/丙烯酸锌共聚物)、用不饱和羧酸如顺式丁烯二酸酐改性的聚乙烯和聚丙烯、石油产品、石蜡油、聚烷撑二醇、如聚乙二醇、聚丙二醇等,或单羧酸甘油酯,最好为单硬脂酸甘油酯。
取决于载体的性质,它可在至120℃、10至120℃或20至100℃时熔融。较理想的是所使用的载体在0至79℃间熔融(如石蜡油)或在80至105℃间熔融(如蜡)。
组分b)最好是位阻型酚类抗氧剂、含磷的稳定剂、位阻型胺、苯并***、二苯甲酮、硫撑二羧酸二酯和/或二烷基二硫化物。
下列稳定剂是组成b)的例子:
位阻型酚类抗氧剂
A)2,2-双〔3′,5′-二叔丁基-4′-羟苯基丙酰氧基乙氧基苯基〕-丙烷
熔点:100-102℃
熔点:110-120℃
熔点:50-55℃
D)三乙二醇-双〔3-(3′-叔丁基-4′-羟基-5′-甲基苯基)丙酸酯〕
熔点:67-79℃
熔点:63-68℃
含磷稳定剂:
F)四〔2,4-二叔丁基苯基〕-联苯二亚膦酸酯
熔点:75-95℃
熔点:40-60℃
位阻型腕类:
熔点:82-86℃
熔点:20℃
熔点:120℃
K)1-(2′-羟乙基)-2,2,6,6-四甲基-4-哌啶醇和丁二酸的缩合物
熔点:55-70℃
苯并***:
L)2-(2′-羟基-5′-叔辛基)苯并***
熔点:103-104℃
M)2-(2′-羟基-3′,5′-二叔戊基)苯并***
(叔戊基=1,1-二甲基-1-丙基)
熔点:79-87℃
二苯甲酮:
熔点:47℃
硫撑二羧酸二酯类:
O)硫撑二丙酸二月桂酯
H25C12OOCCH2CH2-S-CH2CH2COOC12H25
熔点:40-45℃
P)硫撑二丙酸二肉豆蔻酯
H29C14OOCCH2CH2-S-CH2CH2COOC14H29
熔点:44-48℃
Q)硫撑二丙酸二硬脂酯
H37C18OOCCH2CH2-S-CH2CH2COOC18H37
熔点:57-67℃
二烷基二硫化物:
R)二硬脂基二硫
H37C16-SS-C18H37
熔点:~66℃
最理想的组分b)是位阻酚型抗氧剂。
较理想的组分c是位阻的酚类抗氧剂、金属减活化剂、位阻型胺、苯并***、含磷的稳定剂、含镍的紫外线吸收剂和/或C脂肪酸金属盐。
下列稳定剂是组分C)的例子:
位阻型酚类抗氧剂:
α)1,3,5-三甲基-2,4,6-三(3′,5′-二叔丁基-4′-羟苄基)-苯
熔点:242-245℃
β)1,3,5-三〔3′,5′-二叔丁基-4′-羟苄基)异氰脲酸酯
熔点:218-223℃
γ)1,3,5-三(2′,6′-二甲基-4′-叔丁基-5′-羟苄基)异氰脲酸酯
熔点:145-155℃
δ)1,2-双〔3′,3′-双(4″-羟基-5″-叔丁基苯基)丁酰氧基〕乙烷
熔点:170℃
熔点:161℃
熔点:130-132℃
η)1,1,3-三〔3-叔丁基-4′-羟基-6′-甲苯基〕丁烷
熔点:182.5-190℃
θ)3′,5′-二叔丁基-4′-羟基苯甲酸(2,4-二叔丁基苯基)酯
熔点:190℃
金属减活化剂:
熔点:224-229℃
x)N,N-双〔3,5-二叔丁基-4-羟苯基丙酰氧乙基〕草酸二酰胺
熔点:173℃
位阻型胺类:
熔点:110-130℃
熔点:120-150℃
熔点:150℃
ξ)2-丁基-2-(3″,5″-二叔丁基-4″-羟苄基)丙二酸双〔1′,2′,2′,6′,6′-五甲基-4′-吡啶〕酯
熔点:146-150℃
熔点:136℃
熔点:270℃
苯并***类:
熔点:150-155℃
δ)2-(2′-羟基-3′-叙丁基-5′-甲基苯基)-5′-氯代苯并***
熔点:137-140℃
熔点:154-158℃
含磷稳定剂类:
熔点:180-185℃
熔点:160-175℃
x)季戊四醇二亚磷酸双〔2,6-二叔丁基-4-甲基苯基〕酯
熔点:235℃
ψ)
熔点:200-201℃
熔点:>150℃
A)3,5-二叔丁基-4-羟苄基膦酸单乙酯的镍盐
熔点:>180℃
含镍的紫外线吸收剂:
熔点:258℃
C16-C22的脂肪酸金属盐类:
γ)棕榈酸钙,熔点:150-155℃(分解)
Δ)棕榈酸镁,熔点:121℃
E)棕榈酸锌:熔点:~125℃
Z)硬脂酸钙,熔点:180℃
H)硬脂酸镁,熔点:145℃
θ)硬脂酸锌,熔点:130℃
I)二十二碳烷酸钙,熔点:~150℃
K)二十二碳烷酸镁,熔点:~150℃
Λ)二十二碳烷酸锌,熔点:~125℃
含磷的稳定剂,特别是亚磷酸酯用作组分C)是值得注意的。稳定
本发明涉及的优先方法中所使用的稳定剂体系包含组分a)、b)和c)并且其中组分B)为位阻型酚型抗氧剂和组分C)为亚磷酸酯。
根据另一种择优法,组分b)是3-(3′,5′-二叔丁基-4′-羟苯基)丙酸正十八酯和/或四〔3,5-二叔丁基-4-羟苯基丙酰氧甲基〕甲烷和组份C)是亚磷酸三〔2,4-二叔丁基苯基〕酯。
此外,择优的方法中组分b)是在50至120℃熔融的稳定剂,组分C)是在180至200℃熔融的稳定剂以及将稳定剂混合物加热至180至200℃。
组分a)、b)和c)是已知的并且是大多数是商售产品。
能在载体催化剂上聚合的烯烃的例子是乙烯或α-烯烃,尤其是丙烯、1-丁烯、4-甲基戊烯-1或5-甲基己烯-1,以及烯烃的混合物,如乙烯/丙烯或丙烯与较小量的较高碳原子的α-烯烃的混合物。
聚乙烯、聚丙烯、乙烯类共聚物和丙烯类共聚物,尤其是聚乙烯和聚丙烯为分别采用载体催化剂是值得注意的。
使用常称为第三代聚合催化剂是-种有特殊粒子大小的有效的固体催化剂,有关它们的例子在DE-A-2933997和DE-A-2641960中已有叙述。例如它们可由活性的无水的二卤化镁和钛的化合物组成。活性二卤化镁与非活性二卤化镁相比较,在相应的X-射线光谱中,其最强的反射线变宽了。
二氯化镁或二溴化镁是较理想的二卤化镁。钛化合物最好至少含一个钛-卤键,其中四氯化钛尤为理想。
钛化合物可与电子给予体如羧酸酯在一起使用,这一点在EP-A-45977中已有叙述。
在卤化镁与钛的化合物,适当场合下还可与电子给予体等反应后,过剩的钛化合物和过剩的电子给予体应使用如己烷或庚烷这样的惰性溶剂洗去。
以这种方法制得的催化剂通过与烷基铝反应加以活化,它们最好从烷烃溶液的形式使用。适宜的烷基铝的例子是Al(C2H5)3或Al(C4H9)3。也可加入作为共活化剂用的电子给予体,至少含有一个Si-O-C键的有机硅化合物,有关于此的例子在EP-A-45977中已有叙述。这类硅化合物的例子是苯基三乙氧基硅烷、苯基三甲氧基硅烷、二苯基二甲氧基硅烷、甲基三乙氧基硅烷、二甲基二乙氧基硅烷和乙基三甲氧基硅烷。
使用这些催化剂的聚合作用可按已知的方法在液相或气相中实现。液相可以是如脂肪烃或聚合用单体液体本身。
聚合所得的球状的聚烯烃也已在P.Galli,P.C.Barbe和L.Noristi的“High YieldEatalysts in Olefin Polymerization”Die Angewandte Makromolekulare Chime120(1984),P.7 3-90(№1935)中已有叙述。
在载体催化剂上聚合的烯烃类聚合物的直径以2至5mm较为理想,2至3mm最为理想。
这些颗粒型聚烯烃的熔点的例子为140至165℃。
能使聚烯烃稳定的稳定剂混合物在聚烯烃中的浓度以0.01至5%(重量)较为理想,以0.05至1%(重量)最为理想。
在加入聚烯烃中前,将稳定剂体系加热使其形成乳状的溶液是有利的。这种乳状的溶液是组分C)分散在a)和/或b)中的悬浮液。为了达到稳定作用,将聚烯烃与稳定剂体系在适当装置(最好是混合器)中搅拌2至10分钟,温度为60至120℃,较理想的为100至120℃,并以100至110℃为最好,随后冷却。在稳定处理前,如将聚烯烃加热至约60至120℃是有益的。
如果稳定剂体系中含有作为载体的物质,其熔点在0至70℃如石蜡油,或者如果稳定剂体系接着要用石蜡油处理时,聚烯烃的温度可在60至79℃。在后一情况下稳定剂体系对石蜡油的重量比的例子为1∶1至3∶1。在接着用石蜡油处理稳定剂体系的情况中,是将稳定体系在搅拌下加入到热石蜡油中(100至120℃),然后搅拌(如15至30分钟)直到形成一可用于使聚烯烃稳定的均匀混合物。
如果用作载体的物质在约80至110℃时熔融,如蜡,则聚烯烃的温度为80至120℃是有益的,最好为80至110℃。
稳定剂体系通常是将组分a)和/或b)和c)混合而制得。最好是在搅拌下将混合物加热至如120至260℃。将所得的熔融物搅拌约2至15分钟,以8至12分钟为好,随后冷却至固化使其温度为0至30℃。冷却可使用冷水或其它惰性液体,或用氮气或某些惰性气体,也可用一冷金属板来溶体冷却。
也可在捏和机中制备稳定剂体系,这种情况下得到的是颗粒状的稳定剂混合物。
下列实施例进一步说明本发明。
实施例1:稳定剂混合物的制备
稳定剂混合物I:
将20g的3-(3′,5′-二叔丁基-4′-羟苯基)丙酸正十八烷酯、50g的四〔3,5-二叔丁基-4-羟苯基丙酰氧甲基〕甲烷、100g的亚磷酸三〔2,4-二叔丁基苯基〕酯以及200g的聚乙烯蜡〔按ASTM D-3104熔点:102℃,按ASTM D-5硬度:7.0dmm,按ASTMD-1505密度:0.91g/cc.按Brookfield粘度计140℃:180LPS〕混合在一起并加热至200℃。并将该熔融物质在此温度下搅拌10分钟。接着在搅拌下冷却,并固化。
稳定剂混合物II:
制备II和I相似,只是用单硬脂酸甘油酯代替蜡。
稳定剂混合物III:
制备III和II相似,只是用硫撑二丙酸二(十八)酯代替聚乙烯蜡。
稳定剂混合物IV:
制备IV和I相似,只是用50g的聚乙烯蜡代替200g的聚乙烯蜡。
稳定剂混合V:
制备V和IV相似,但在挤出机(BUSS-KO-KNETER)中进行混合和加热并且所制得的组合混合物是颗粒状的。
实施例2a-2c:球状聚丙烯颗粒的稳定作用
a)将1000g球状聚丙烯(Moplen SPL12)在Henschel混合机(容量5000ml)中加热至104℃并保温7分钟。并加入3.7g事先已在104℃下熔融的表1a所给出的稳定剂混合物。将所得之混合物搅拌2分钟,然后冷却。经稳定处理的聚丙烯颗粒在烘箱中于149℃下老化30小时。试验结果列于表1a。聚丙烯颗粒的变色表明稳定处理不当。
表1a
稳定剂 烘箱中149℃
混合物 下老化30小时
- 变色
I 不变色
II 不变色
III 不变色
b)将1000g球状聚丙烯(Moplen SPL12)在Henschel混合机(容量:5000ml)中加热至65℃并保温3分钟。随后加入3.7g事先加热到104℃的表1b中给出的稳定剂混合物。进一步加工和按a)中方法进行测试。试验结果列于表1b。
表1b
稳定剂 烘箱中149℃
混合物 下老化30小时
- 变色
III 不变色
C)将1000g球状聚丙烯(Moplen SPL12)在Henschel混合机(容量:5000ml)中加热至65℃并保温3分钟。
将2.2g的表1c所列的稳定剂混合物加入到1g热石蜡油(110℃)中,并将得到的混合物在该温度下搅拌20分钟。然后将此混合物加入到聚丙烯(65℃)中,并搅拌2分钟,然后冷却。聚丙烯颗粒按a)的方法试验,其结果列于表1c。
稳定剂 烘箱中149℃
混合物 下老化30小时
- 变色
IV 不变色
V 不变色
Claims (14)
1.一种使在载体催化剂上聚合成的粒子平均直径为1至5mm的烯烃类聚合物稳定的方法,此方法是用一种稳定剂混合物处理聚烯烃,这种稳定剂混合物制备方法是将由组分a)、b)和c)或由组分b)和c)组成的混合物加热至120至260℃,其中,
组分a)为至少一种载体,
组分b)为至少一种在20至120℃之间熔融的稳定剂,
组分c)为至少一种在120至260℃之间熔融的稳定剂,
然后将上述混合物冷却至固化,组分b)和c)是不同的。
2.根据权利要求1中所述的方法,其中稳定剂混合物含有组分a),b)和c)。
3.根据权利要求1中所述的方法,其中组分a)是蜡、石蜡油或单羧酸甘油酯。
4.根据权利要求3中所述的方法,其中组分a)是聚乙烯、聚丙烯、烯烃类共聚物、乙烯/乙酸乙烯酯共聚物、乙烯/不饱和羧酸酯共聚物、乙烯/不饱和羧酸金属盐共聚物、用不饱和羧酸改性的聚乙烯或聚丙烯、石油制品、石蜡油、聚烷撑乙二醇或单羧酸甘油酯。
5.根据权利要求1中所述的方法,其中组分b)是位阻型酚类抗氧剂、含磷的稳定剂、位阻型胺、苯并***、三苯甲酮、硫撑二羧酸二酯和/或二烷基二硫化物。
6.根据权利要求1中所述的方法,其中组分b)是位阻型酚类抗氧剂。
7.根据权利要求1中所述的方法,其中组分C)是位阻型酚类抗氧剂、金属减活化剂、位阻型胺、苯并***、含磷的稳定剂、含镍的紫外线吸收剂和/或C16-C22的脂肪酸金属盐。
8.根据权利要求1中所述的方法,其中组分C)是含磷的稳定剂。
9.根据权利要求1中所述的方法,其中组分C)是亚磷酸酯。
10.根据权利要求2中所述的方法,其中组分b)是位阻型酚类抗氧剂和组分C)是亚磷酸酯。
11.根据权利要求10中所述的方法,其中组分b)是3-(3′,5′-二叔丁基-4′-羟苯基)丙酸正十八酯和/或四〔3,5-二叔丁基-4-羟苯基丙酰氧甲基〕甲烷,以及组分C)是亚磷酸三〔2,4-二叔丁基苯基〕酯。
12.根据权利要求1中所述的方法,其中组分b)是在50至120℃间熔融的稳定剂和组分C)是在180至200℃间熔融的稳定剂并且将稳定剂混合物加热至180至200℃。
13.根据权利要求1中所述的方法,其中聚烯烃粒子的平均直径为2至5mm。
14.根据权利要求1的方法中所述的稳定的聚烯烃。
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Family
ID=4208441
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN90101989A Expired - Fee Related CN1038595C (zh) | 1989-04-10 | 1990-04-10 | 一种使聚烯烃稳定的方法 |
Country Status (16)
Country | Link |
---|---|
EP (1) | EP0392392B1 (zh) |
JP (1) | JP2942997B2 (zh) |
KR (1) | KR0156249B1 (zh) |
CN (1) | CN1038595C (zh) |
AR (1) | AR246976A1 (zh) |
AT (1) | ATE131189T1 (zh) |
AU (1) | AU632553B2 (zh) |
BR (1) | BR9001671A (zh) |
CA (1) | CA2014005C (zh) |
DD (1) | DD294035A5 (zh) |
DE (1) | DE59009938D1 (zh) |
ES (1) | ES2081313T3 (zh) |
FI (1) | FI101806B1 (zh) |
MX (1) | MX171591B (zh) |
NO (1) | NO301021B1 (zh) |
ZA (1) | ZA902698B (zh) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU630179B2 (en) * | 1989-04-06 | 1992-10-22 | Montell North America Inc. | Polyolefins suitable for spinning and thermoweldable fibers obtained from them |
IT1231769B (it) * | 1989-08-02 | 1991-12-21 | Himont Inc | Procedimento per la stabilizzazione di poliolefine e prodotti da esso ottenuti. |
IT1247941B (it) * | 1991-05-17 | 1995-01-05 | Enichem Sintesi | Processo per l'ottenimento di forme granulari di additivi per polimeri organici |
IT1258271B (it) * | 1992-04-06 | 1996-02-22 | Enichem Sintesi | Processo per l'ottenimento di forme granulari di addittivi per polimeri organici. |
US5844042A (en) * | 1993-04-06 | 1998-12-01 | Great Lakes Chemical Italia S.R.L. | Process for obtaining granular forms of additives for organic polymers |
US5605947A (en) * | 1993-07-22 | 1997-02-25 | General Electric Company | Amorphous neo-diol phosphite compositions |
ES2131162T3 (es) * | 1993-07-22 | 1999-07-16 | Gen Electric | Neodiolfosfitos como estabilizadores de polimeros. |
US5614571A (en) * | 1994-09-16 | 1997-03-25 | General Electric Company | Stabilizer blend containing phosphite |
EP1264822A3 (en) | 1997-04-15 | 2003-01-29 | Ciba SC Holding AG | Stabiliser modification |
DE19817257A1 (de) | 1998-04-19 | 1999-12-09 | Grace Gmbh | Granulatzusammensetzung aus Antiblockingmitteln und Additiven für Polymerherstellung |
CA2663432C (en) | 2006-09-14 | 2015-03-31 | Ingenia Polymers Inc. | High concentration pelletized additive concentrates for polymer |
WO2013114652A1 (ja) * | 2012-02-01 | 2013-08-08 | 株式会社Adeka | 樹脂添加剤マスターバッチ |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ZA695633B (en) * | 1968-08-08 | 1971-03-31 | Ici Ltd | Polymer stabilisers |
US4647608A (en) * | 1986-03-21 | 1987-03-03 | The Dow Chemical Company | Process for the production of polyolefin resins containing an amide and a zinc compound |
EP0278579B1 (en) * | 1987-02-13 | 1992-11-25 | ENICHEM SYNTHESIS S.p.A. | Solid stabilizer composition for organic polymers, and process for preparing it |
IT1202611B (it) * | 1987-03-03 | 1989-02-09 | Enichem Sintesi | Composizione solida stabilizzante per polimeri sintetici |
-
1990
- 1990-04-06 AU AU53031/90A patent/AU632553B2/en not_active Ceased
- 1990-04-06 FI FI901772A patent/FI101806B1/fi not_active IP Right Cessation
- 1990-04-06 AR AR90316580A patent/AR246976A1/es active
- 1990-04-06 ES ES90106660T patent/ES2081313T3/es not_active Expired - Lifetime
- 1990-04-06 MX MX020221A patent/MX171591B/es unknown
- 1990-04-06 AT AT90106660T patent/ATE131189T1/de active
- 1990-04-06 EP EP90106660A patent/EP0392392B1/de not_active Expired - Lifetime
- 1990-04-06 CA CA002014005A patent/CA2014005C/en not_active Expired - Fee Related
- 1990-04-06 DE DE59009938T patent/DE59009938D1/de not_active Expired - Fee Related
- 1990-04-09 BR BR909001671A patent/BR9001671A/pt not_active IP Right Cessation
- 1990-04-09 DD DD90339599A patent/DD294035A5/de not_active IP Right Cessation
- 1990-04-09 ZA ZA902698A patent/ZA902698B/xx unknown
- 1990-04-09 NO NO901605A patent/NO301021B1/no not_active IP Right Cessation
- 1990-04-10 CN CN90101989A patent/CN1038595C/zh not_active Expired - Fee Related
- 1990-04-10 KR KR1019900004889A patent/KR0156249B1/ko not_active IP Right Cessation
- 1990-04-10 JP JP2094911A patent/JP2942997B2/ja not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
ES2081313T3 (es) | 1996-03-01 |
DE59009938D1 (de) | 1996-01-18 |
JPH02294345A (ja) | 1990-12-05 |
NO901605D0 (no) | 1990-04-09 |
DD294035A5 (de) | 1991-09-19 |
CN1046537A (zh) | 1990-10-31 |
MX171591B (es) | 1993-11-08 |
FI101806B (fi) | 1998-08-31 |
CA2014005A1 (en) | 1990-10-10 |
NO301021B1 (no) | 1997-09-01 |
NO901605L (no) | 1990-10-11 |
EP0392392B1 (de) | 1995-12-06 |
JP2942997B2 (ja) | 1999-08-30 |
AU632553B2 (en) | 1993-01-07 |
BR9001671A (pt) | 1991-05-14 |
AU5303190A (en) | 1990-10-11 |
CA2014005C (en) | 2001-05-15 |
KR900016347A (ko) | 1990-11-13 |
ATE131189T1 (de) | 1995-12-15 |
FI901772A0 (fi) | 1990-04-06 |
AR246976A1 (es) | 1994-10-31 |
KR0156249B1 (ko) | 1998-12-01 |
FI101806B1 (fi) | 1998-08-31 |
EP0392392A1 (de) | 1990-10-17 |
ZA902698B (en) | 1991-01-30 |
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