CA2014005C - Process for stabilising polyolefins - Google Patents
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- CA2014005C CA2014005C CA002014005A CA2014005A CA2014005C CA 2014005 C CA2014005 C CA 2014005C CA 002014005 A CA002014005 A CA 002014005A CA 2014005 A CA2014005 A CA 2014005A CA 2014005 C CA2014005 C CA 2014005C
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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
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- 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
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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
- 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
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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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
- 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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Abstract
A process for stabilising olefin polymers having a mean particle diameter of from 1 to 5 mm that have been polymerised on carrier catalysts, which comprises treating the polyolefins with a stabiliser mixture prepared by heating to from 120 to 260°C a mixture containing a) at least one carrier and/or b) at least one stabiliser that melts at from 20 to 120°C and c) at least one stabiliser that melts at from 120 to 260°C, and then cooling said mixture until solidified, components b) and c) being different.
Description
A process for stabilising polyolefins The present invention relates to a process for stabilising olefin polymers having a mean particle diameter of from 1 to 5 mm that have been polymerised on carrier catalysts.
JP-A-84/150 719 describes a process for stabilising polypropylene powder in which the polypropylene powder, the stabilisers and a carrier are homogenised in a mixer with the application of heat.
EP-A-281 189 describes a process for producing a hydrolysis-resistant stabiliser mixture consisting of a phosphate and a phenolic antioxidant, and the use of that stabiliser mixture for stabilising polypropylene powder. Pulverulent polyolefin has to be granulated in an extruder before being shaped. During the granulation, stabilisers and other processing auxiliaries are added to the polymer.
Unstabilised granular-type polyolefins that have been produced by polymerising olefins on solid carrier catalysts have been commercially available for some time. Since these polyolefins are obtained in granular form when manufactured, they do not need to be extruded in a subsequent processing step, unless incorporation of the stabilisers and the process-ing auxiliaries necessitates melting in order to ensure an adequate distribution of the additive in the polymer.
In many cases the addition of stabilisers during the olefin polymerisa-tion causes interference with the polymerisation and discolouration of the polymers.
JP-A-84/150 719 describes a process for stabilising polypropylene powder in which the polypropylene powder, the stabilisers and a carrier are homogenised in a mixer with the application of heat.
EP-A-281 189 describes a process for producing a hydrolysis-resistant stabiliser mixture consisting of a phosphate and a phenolic antioxidant, and the use of that stabiliser mixture for stabilising polypropylene powder. Pulverulent polyolefin has to be granulated in an extruder before being shaped. During the granulation, stabilisers and other processing auxiliaries are added to the polymer.
Unstabilised granular-type polyolefins that have been produced by polymerising olefins on solid carrier catalysts have been commercially available for some time. Since these polyolefins are obtained in granular form when manufactured, they do not need to be extruded in a subsequent processing step, unless incorporation of the stabilisers and the process-ing auxiliaries necessitates melting in order to ensure an adequate distribution of the additive in the polymer.
In many cases the addition of stabilisers during the olefin polymerisa-tion causes interference with the polymerisation and discolouration of the polymers.
The present invention relates to a process for stabilising olefin polymers having a mean particle diameter of from 1 to 5 mm that have been polymerised on carrier catalysts, which comprises treating the polyolefins with a stabiliser mixture prepared by heating to from 120 to 260°C a mixture containing components a), b) and c) or components b) and c) with component a) being at least one carrier, component b) being at least one stabiliser that melts at from 20 to 120°C, and component c) being at least one stabiliser that melts at from 120 to 260°C, and then cooling said mixture until solidified, components b) and c) being different.
Component b) can where appropriate assume the function of component a) as a carrier.
The ratio by weight of a:c is preferably from 0.1:1 to 4:1, especially from 0.5:1 to 2:1, and the ratio by weight of b:c is, for example, from 4:1 to 0.1:1 or from 2:1 to 0.1:1, preferably from 1:1 to 0.1:1.
A process in which the stabiliser mixture used contains components a), b) and c) is preferred.
The carrier is preferably a wax, paraffin oil or a glyceryl monocarboxylic acid ester. The following may be mentioned as examples of suitable carriers= polyethylene, polypropylene (for example atactic), olefinic copolymers (for example copolymers of propylene, such as propylene/ethylene copolymer or propylene/butene-1 copolymer), ethylene/vinyl acetate copolymers, ethylene/(unsaturated carboxylic acid 201 4flfl5 - 2a -ester) copolymers (for example ethylene/methyl methacrylate copolymer), ethylene/(unsaturated carboxylic acid metal salt) copolymers (for example ethylene/magnesium acrylate copolymer or ethylene/ainc acrylate copolymer), polyethylene or polypropylene each modified with unsaturated carboxylic acids, such as, for example, maleic acid anhydride, petroleum, paraffin oil, polyalkylene glycol, such as, for example, polyethylene glycol, polypropylene glycol etc., or glyceryl monocarboxylic acid ester, preferably glyceryl monostearate.
~f;
F
Component b) can where appropriate assume the function of component a) as a carrier.
The ratio by weight of a:c is preferably from 0.1:1 to 4:1, especially from 0.5:1 to 2:1, and the ratio by weight of b:c is, for example, from 4:1 to 0.1:1 or from 2:1 to 0.1:1, preferably from 1:1 to 0.1:1.
A process in which the stabiliser mixture used contains components a), b) and c) is preferred.
The carrier is preferably a wax, paraffin oil or a glyceryl monocarboxylic acid ester. The following may be mentioned as examples of suitable carriers= polyethylene, polypropylene (for example atactic), olefinic copolymers (for example copolymers of propylene, such as propylene/ethylene copolymer or propylene/butene-1 copolymer), ethylene/vinyl acetate copolymers, ethylene/(unsaturated carboxylic acid 201 4flfl5 - 2a -ester) copolymers (for example ethylene/methyl methacrylate copolymer), ethylene/(unsaturated carboxylic acid metal salt) copolymers (for example ethylene/magnesium acrylate copolymer or ethylene/ainc acrylate copolymer), polyethylene or polypropylene each modified with unsaturated carboxylic acids, such as, for example, maleic acid anhydride, petroleum, paraffin oil, polyalkylene glycol, such as, for example, polyethylene glycol, polypropylene glycol etc., or glyceryl monocarboxylic acid ester, preferably glyceryl monostearate.
~f;
F
Depending on the nature of the carrier, it melts, for example, at from 0 to 120°C, from 10 to 120°C or from 20 to 100°C. It is preferable to use a carrier that melts either at from 0 to 79°C (for example paraffin oil) or at from 80 to 105°C (for example wax).
Component b) is preferably a sterically hindered phenolic antioxidant, a phosphorus-containing stabiliser, a sterically hindered amine, a benzo-triazole, a benzophenone, a thiodicarboxylic acid diester and/or a dialkyl disulfide.
The following stabilisers are examples of component b):
Sterically hindered phenolic antioxidants:
A) 2,2-Bis(3',5'-di-tert-butyl-4'-hydroxyphenylpropionyloxyethoxyphenyl)-propane (H3C)3C~
HO-~\~ ~~~-CHZCHZ-~-0-CHZCHZ-0-~~~ ~j.
_. .-. ~H
(H3C)sC/~
melting point: 100-102°C
B) Tetrakis(3,5-di-tert-butyl-4-hydroxyphenylpropionyloxymethyl)methane (H3C)3C~
.-.
HO-~~ j~-CHZCHZ-~-0-CHz C
-.
(H3C)3C~.
Component b) is preferably a sterically hindered phenolic antioxidant, a phosphorus-containing stabiliser, a sterically hindered amine, a benzo-triazole, a benzophenone, a thiodicarboxylic acid diester and/or a dialkyl disulfide.
The following stabilisers are examples of component b):
Sterically hindered phenolic antioxidants:
A) 2,2-Bis(3',5'-di-tert-butyl-4'-hydroxyphenylpropionyloxyethoxyphenyl)-propane (H3C)3C~
HO-~\~ ~~~-CHZCHZ-~-0-CHZCHZ-0-~~~ ~j.
_. .-. ~H
(H3C)sC/~
melting point: 100-102°C
B) Tetrakis(3,5-di-tert-butyl-4-hydroxyphenylpropionyloxymethyl)methane (H3C)3C~
.-.
HO-~~ j~-CHZCHZ-~-0-CHz C
-.
(H3C)3C~.
melting point: 110-120°C
C) n-Octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate (H3C)3C~
HO-~\~ ~%~-CHZCHz-~-0-C1BH3~-n (H3C)aC~.-.
melting point: 50-55°C
D) Triethyleneglycol-bis(3-(3'-tert-butyl-4'-hydroxy-5'-methylphenyl)-propionate) (H3C)3C\ /C(CH3)3 HO-~~~ ~j~-CHZCHz-~-0-(CHZCHz-O~~-CHzCHz-~~~ ~j~-OH
-. ._.
HaC/~ \CH3 melting point: 67-79°C
E) 1,5-Bis(3',5'-di-tert-butyl-4'-hydroxyphenylpropionyloxy~-3'-thia-pentane (HaC)aC\ /C(CH3)a HO-~~~ ~j~-CHzCHz-~-O-CHzCHz-S-CHZCHz-0-~-CHzCHz-~~~ ~j~-OH
(HaC)3C/.-. ~=~\C(CH3)a melting point: 63-68°C
Phosphorus-containing stabilisers:
F) Tetrakis(2,4-di-tert-butylphenylj-diphenylene diphosphonite j (CH3)a (H3C)aC\
(H3C)aC-~~. .~ P-~~.-.\ ~/~-~\ _P 0-~/. ~~ -C(CHa)s \ /~ \ /~ \ /~ \ /~
.-. ._. ._. .-.
z z melting point: 75-95°C
G) Distearylpentaerythritol diphosphite /0-CHz\ /CHz 0\ _ Ha~Cla-0-P\ /C\ /P 0-C18H3~
O-CH z CH z-0 melting point: 40-60°C
C) n-Octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate (H3C)3C~
HO-~\~ ~%~-CHZCHz-~-0-C1BH3~-n (H3C)aC~.-.
melting point: 50-55°C
D) Triethyleneglycol-bis(3-(3'-tert-butyl-4'-hydroxy-5'-methylphenyl)-propionate) (H3C)3C\ /C(CH3)3 HO-~~~ ~j~-CHZCHz-~-0-(CHZCHz-O~~-CHzCHz-~~~ ~j~-OH
-. ._.
HaC/~ \CH3 melting point: 67-79°C
E) 1,5-Bis(3',5'-di-tert-butyl-4'-hydroxyphenylpropionyloxy~-3'-thia-pentane (HaC)aC\ /C(CH3)a HO-~~~ ~j~-CHzCHz-~-O-CHzCHz-S-CHZCHz-0-~-CHzCHz-~~~ ~j~-OH
(HaC)3C/.-. ~=~\C(CH3)a melting point: 63-68°C
Phosphorus-containing stabilisers:
F) Tetrakis(2,4-di-tert-butylphenylj-diphenylene diphosphonite j (CH3)a (H3C)aC\
(H3C)aC-~~. .~ P-~~.-.\ ~/~-~\ _P 0-~/. ~~ -C(CHa)s \ /~ \ /~ \ /~ \ /~
.-. ._. ._. .-.
z z melting point: 75-95°C
G) Distearylpentaerythritol diphosphite /0-CHz\ /CHz 0\ _ Ha~Cla-0-P\ /C\ /P 0-C18H3~
O-CH z CH z-0 melting point: 40-60°C
Stericallv hindered amines:
H) Bis(2,2,6,6-tetramethyl-4-piperidinyl]sebacate H3C~ /CH3 H3C~ /CH3 HN\~ ~ j~-0-~-(CHz ) s-~-0-.\. ~~H
H3C~~~CH3 H3C~~~~CH3 melting point: 82-86°C
I) Bis[1,2,2,6,6-pentamethyl-4-piperidinyl]sebacate H3C~ /CH3 H3C~ /CH3 H3C-N\. '~~-0-~-(CHz)s-~-0-.\.-.~-CH3 H3C~~~CH3 H3C~~~CH3 melting point: 20°C
J) Bis(2,2,6,6-tetramethyl-4-piperidinyl]succinate H3C~ /CH3 H3C~ /CH3 HN\~ ~ j~-0-~-( CHz ) z-~-0-.\. ~~H
H3C~~~CH3 H3C~~/~CH3 melting point: 120°C
K) Condensate of 1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol and succinic acid HaC~ j Ha ~/ H
HOCHZCHz-N\~ ~j~~ + HO-~-(CHz)z-~-OH
~ OH
H3C~~~CH3 melting point: 55-70°C
H) Bis(2,2,6,6-tetramethyl-4-piperidinyl]sebacate H3C~ /CH3 H3C~ /CH3 HN\~ ~ j~-0-~-(CHz ) s-~-0-.\. ~~H
H3C~~~CH3 H3C~~~~CH3 melting point: 82-86°C
I) Bis[1,2,2,6,6-pentamethyl-4-piperidinyl]sebacate H3C~ /CH3 H3C~ /CH3 H3C-N\. '~~-0-~-(CHz)s-~-0-.\.-.~-CH3 H3C~~~CH3 H3C~~~CH3 melting point: 20°C
J) Bis(2,2,6,6-tetramethyl-4-piperidinyl]succinate H3C~ /CH3 H3C~ /CH3 HN\~ ~ j~-0-~-( CHz ) z-~-0-.\. ~~H
H3C~~~CH3 H3C~~/~CH3 melting point: 120°C
K) Condensate of 1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol and succinic acid HaC~ j Ha ~/ H
HOCHZCHz-N\~ ~j~~ + HO-~-(CHz)z-~-OH
~ OH
H3C~~~CH3 melting point: 55-70°C
Benzotriazoles:
L) 2-(2'-Hydroxy-5'-tert-octyl)benzotriazolel ~~\
I I ~-.\./.\N .\.__ /
~\CeHl -t melting point: 103-104°C
M) 2-(2'-Hydroxy-3',5'-di-tert-pentyl)benzotriazole2 ./~\ QH j SH11-t I I ~- /~ ~\
~\CsHii-t melting point: 79-87°C
Benzophenone:
N) 2-Hydroxy-4-octyloxybenzophenone ~H
%.\ _ _ %.\
I II ~ I II
Hm C80/~~,/.
melting point: 47°C
Thiodicarboxvlic acid diesters:
0) Dilauryl thiodipropionate Hz5C1z00CCHzCHz-S-CHzCHZC00C1zHzs melting point: 40-45°C
1 tert-octyl = 1,1,3,3-tetramethyl-1-butyl tert-pentyl = 1,1-dimethyl-1-propyl P) Dimyristyl thiodipropionate Hz9C1400CCHZCHz-S-CHZCHZCOOC14Hz9 melting point: 44-48°C
Q) Distearyl thiodipropionate H37C1800CCHzCHz-S-CHZCHZCOOC18H37 melting point: 57-67°C
Dialkyl disulfides:
R) Distearyl disulfide H37C18-$$-C18H37 melting point: ~66°C
Component b) is especially preferably sterically hindered phenolic antioxidant.
Component c) is preferably a sterically hindered phenolic antioxidant, a metal deactivator, a sterically hindered amine, a benzotriazole, a phosphorus-containing stabiliser, a nickel-containing UV-absorber and/or a metal salt of a C16-Czz-fatty acid.
The following stabilisers are examples of component c):
_$_ Sterically hindered phenolic antioxidant:
a) 1,3,5-Trimethyl-2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)-benzene H3C ~ CH3 /C(CHa)s \ /.\ / -I II in which R = -CHz-~~~ ~j~-OH
R/'~ /'~ .-.\
1~ C(CH3)3 melting point: 242-245°C .
f3) 1,3,5-Tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)isocyanurate ~\ /R /C(CH3)a in which R = -CHz-~~1 ~j~-OH
._.\
C(CH3)3 melting point: 218-223°C
y) 1,3,5-Tris(2',6'-dimethyl-4'-tert-butyl-5'-hydroxybenzyl)isocyanurate /R H3C\ _ in which R = -CHz-~~~ ~j~-C(CH3)3 /'~~~ .-0 0 H3C/ ~\OH
melting point: 145-155°C
d) 1,2-Bis[3',3'-bis(4"-hydroxy-5"-tert-butylphenyl)butanoyloxy)ethane QH
/~\ /C(CH3)a I II
.\ /.
H3C-~-CHz-~-~CHz ~~\
I II
~\ /~\C(CHa)a ~H
z melting point: 170°C
e) Bis(3-tert-butyl-4-hydroxy-6-methylphenyl)sulfide (H3C)3C\ /C(CH3)3 HO-~\. .~.-S-,\._.~~-OH
._ ._.
melting point: 161°C
2-(2'-Hydroxy-3'-tert-butyl-5'-methylbenzyl)-4-methyl-6-tert-butyl-phenyl acrylate QH CHZ ~OCCH=CHz (HaC)aC\ /~\ / ~ /~\ /C(CHa)a I II I II
.\ /. .\ /.
melting point: 130-132°C
n) 1,1,3-Tris[3'-tert-butyl-4'-hydroxy-6'-methylphenyl]butane (H3C)3C\ /C(CH3)3 HO-.\._.~~ H ~\. ~~._OH
._. HZ ._.
H3C HCH3 C~3 H3C\ ~~\
I II
~\ /~\C(CHa)s ~H
melting point: 182.5-190°C
B) 2,4-Di-tert-butylphenyl-3',5'-di-tert-butyl-4'-hydroxybenzoate /C(CHs)s j (CHa)s (HaC)sC_~~._./~ ~~ ~\._~/~ OH
\C(CHs)a melting point: 190°C
Metal deactivators:
1) N,N-Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl]hydrazine (HaC)aC\ /C(CH3)a .-.
HO-~~ j~-(CHz)z-~-NHNH-~-(CHz)z-~~~ ~j~-OH
.-. ._ (H3C)3C/ ~\C(CH3)a melting point: 224-229°C
K) N,N-Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyloxyethyl]oxalic acid diamide (HaC)aC\
H~~~~ ~j~-(CHz)2-~-0-(CHz)z-~-(H3C)3C~~-.
melting point: 173°C
Sterically hindered amines:
Poly(2-(N,N-bis(2',2',6',6'-tetramethyl-4'-piperidinyl)hexamethylene-diamino-4-morpholino-1,3,5-triazin-6-yl]
(CHz)6 ~ ~N\
H3C\I/~\I% H3 H3C\I/~\I% H3 H3C~~~~\CH3 H3C~~~~\CH3 .\0/.
n melting point: 110-130°C
u) Poly[2-(N,N-bis(2',2',6',6'-tetramethyl-4'-piperidinyl)hexamethylene-diamino-4-tert-octyl-1,3,5-triazin-6-yl]
~T ( C H z ) s ~1 ~N\
H3C\I/~\I/CH3 H3C\I/~\I/CH3 \
HN-C8H1~-t H3C/~~~\CH3 H3C/~\~~\CH3 n melting point: 120-150°C
v) 1,5,8,12-Tetrakis[2',4'-bis(1",2",2",6",6"-pentamethyl-4"-piperidinyl-(butyl)amino)-1',3',5'-triazin-6'-yl]-1,5,8,12-tetraazadodecane H-~-(CHz)a-~-(CHz)zy-(CHz)a-yH
H3C\ /CH3 r4H9 /.-~NN' .~-CH
.
~ a \.
.
_ HaC/
~N .\ \CH3 R - . HaC\ /CH3 -.~-CHa H \.
9 \CH3 melting point: 150°C
Bis[1',2',2',6',6'-pentamethyl-4'-piperidinyl]-2-butyl-2-(3",5"-di-tert-butyl-4"-hydroxybenzyl)malonate HaC\ j H3 /
(H3C)aC\ ~~ ~\~- -CH3 /~\
HO-~~. ~~ -CHz- -C4H9 H3C CH3 \ -_~/~ H3C\ % Ha (HaC)aC/~ 00 /. .~-CH3 .\ _ H3C/~\CH3 melting point: 146-150°C
o) 1,2-Bis[3',3',5',5'-tetramethyl-2'-oxo-1',4'-diazinan-1'-yl]ethane HaC\ /CHa~% 0~ HaC\ j H3 HN\~ ~-(CHz)z-~~ ~/NH
H3C/~\CH3. .H3C/.\CH3 melting point: 136°C
~r ) HjC\ /CH3 0 - \~~
H3C CH3 \~ ~/~\~ ~\~ ~/NH
\ /_ / \ /~\~~ HjC/~\CH3 ~J ~\ _ _ HN\~ /~
~ ~ 0 H3C/~\CH3 melting point: 270°C
Benzotriazoles:
p) 2-(2'-Hydroxy-3,5-di-tert-butylphenyl)benzotriazole ~ H C(CH3)3 \ ~_ /
I I ~-~j~ ~~
\~/.\N \~- /.
~\C(CH3)a melting point: 150-155°C
Q) 2-(2'-Hydroxy-3'-tert-butyl-5'-methylphenyl)-5'-chlorobenzotriazole C1\ /~\ QH /C(CH3)a I j - /~
~~ /~~ ~\ _ /
~ ~\CH3 melting point: 137-140°C
i) 2-(2'-Hydroxy-3',5'-di-tert-butylphenyl)-5'-chlorobenzotriazole C1\ /~\ QH /C(CH3)a I j .\ /.\,. .\ /
\C(CHs)a melting point: 154-158°C
Phosphorus-containing stabilisers:
v) Tris[2,4-di-tert-butylphenyl]phosphite (H3C)3C-~~~ ~j'- P
~ ~\C(CH3)a melting point: 180-185°C
Bis[2,4-di-tert-butylphenyl]pentaerythritol diphosphite C(CH3)a (HaC)aC
_ / 0-. -0 \ _ (HaC)aC-'/~ ~\ -0P/ \~/~ \P-C-~~. '~ -C(CH3)a \._./~ \~~/ \~-Q/ \._~/.
melting point: 160-175°C
X) Bis[2,6-di-tert-butyl-4-methylphenyl]pentaerythritol diphosphite /C(CHa)a (HsC)3C\
~ -' 0- ~ -0 H3C-~j ~ -0-P/ \ /~ \P-~~/._.\ -CH3 \~_- /~ \~~/~\~-0/ \ -~/~
~\C(CH3)a (H3C)3C/~
melting point: 235°C
V~ ) ~Ha (H3C)3C~ ~'~ ~ ~ ~'~ /C(CH3)3 I II ~ II
.\ /.\0 O/.\ /.
(H3C)3~ \~/ ~(CH3)3 melting point: 200-201°C
cu) Calcium salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester (H3C)3C~
CzHs _ HO-'~~_./~ CHZ-~ 0 Ca2+
(H3C)3C/~-melting point: >150°C
A) Nickel salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester (H3C)jC~ _ CzHs _ HO-~~~ ~ j~-CH2- 0 Ni2+
(H3C)3C/~-.
melting point: >180°C
Nickel-containing UV-absorbers:
B) 2,2'-Thio-bis(4-tert-octylphenolato~-butylamino nickel (II) t-H17C8-.\._.~ 0 jS Ni-NHC4H9 t-H17C8-.\.-.~ 0 melting point: 258°C
Metal salts of C,s-C~~-fatty acids:
t) Ca palmitate, melting point: 150-155°C (decomposition) D) Mg palmitate, melting point: 121°C
E) Zn palmatate, melting point: 125°C
Z) Ca stearate, melting point: 180°C
H) Mg stearate, melting point: 145°C
A) Zn stearate, melting point: 130°C
I) Ca behenate, melting point: 150°C
K) Mg behenate, melting point: 150°C
A) Zn behenate, melting point: 125°C
A phosphorus-containing stabiliser, especially a phosphate, is of interest as component c).
The invention relates especially preferably to a process in which the stabiliser system used contains components a), b) and c) and in which component b) is a sterically hindered phenolic antioxidant and compo-nent c) is a phosphate.
According to another preference, component b) is n-octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate and/or tetrakis[3,5-di-tert-butyl-4-hydroxyphenylpropionyloxymethyl]methane and component c) is tras[2,4-di-tert-butylphenyl]phosphate.
Also preferred is a process in which component b) is a stabiliser that melts at from 50 to 120°C and component c) is a stabiliser that melts at from 180 to 200°C and the stabiliser mixture as heated to from 180 to 200°C.
Components a), b) and c) are known and are for the most part commercially available products.
Olefins that can be polymerised on carrier catalysts are, for example, ethylene or a-olefins, especially propylene, 1-butene, 4-methylpentene-1 or 5-methylhexene-1, and mixtures of olefins, such as, for example, ethylene/propylene or propylene in admixture with smaller amounts of higher a-olefins.
Polyethylene, polypropylene, copolymers of ethylene and copolymers of propylene, especially polyethylene and polypropylene, each applied to carrier catalysts, are of interest.
The polymerisation catalysts used, which are frequently referred to as third generation catalysts, are advantageously solid catalysts of a particular particle size, such as, for example, those described in DE-A-29 33 997 and DE-A-26 41 960. They consist, for example, of an anhydrous magnesium dihalide in active form and a titanium compound.
Magnesium dihalide in active form denotes one in the X-ray spectrum of which the line of strongest reflection is broadened compared with the corresponding line in the spectrum of inactive magnesium halide.
Preferably, magnesium dichloride or magnesium dibromide is used as magnesium dihalide. The titanium compound contains preferably at least one titanium-halogen bond, the use of titanium tetrachloride being especially preferred.
The titanium compound can be used in combination with an electron donor, for example a carboxylic acid ester, such as that described in EP-A-45 977.
After reaction of the magnesium halide component with the titanium compound and, where appropriate, with the electron donor, the excess titanium compound and the excess electron donor are advantageously washed out with an inert solvent, for example with hexane or heptane.
The catalyst prepared in this manner is activated by reaction with an aluminium alkyl, which is preferably used in the form of a solution in an alkane. Examples of suitable aluminium alkyls are A1(CzHs)a or A1(CaH9)3.
There may be added as coactivator an electron donor such as, for example, an organic silicon compound that contains at least one Si-0-C bond, such as that described, for example, in EP-A-45 977. Examples of such silicon compounds are phenyltriethoxysilane, phenyltrimethoxysilane, diphenyldi-methoxysilane, methyltriethoxysilane, dimethyldiethoxysilane and ethyl-trimethoxysilane.
The polymerisation with these catalysts can be carried out according to known methods in liquid or gaseous phase. The liquid phase may be, for example, an aliphatic hydrocarbon, or the liquid monomer itself.
Spherical polymerised polyolefins are also described, for example, in P. Galli, P.C. Barbe and L. Noristi; "High Yield Catalysts in Olefin Polymerization", Die Angewandte Makromolekulare Chemie 120 (1984), p. 73-90 (No. 1935).
The diameter of the olefin polymers polymerised on carrier catalysts is preferably from 2 to 5 mm, especially from 2 to 3 mm.
The melting point of these granular-type polyolefins is, for example, from 140 to 165°C.
The concentration of the stabiliser mixtures in the polyolefin to be stabilised is preferably from 0.01 to 5 % by weight, especially from 0.05 to 1 % by weight.
Before incorporation into the polyolefin, it is advantageous to heat the stabiliser system until a milky solution has formed. This milky solution is a suspension of component c) in a) and/or b). For stabilisation, the polyolefin is stirred, for example for from 2 to 10 minutes, in a suitable device (preferably a mixer) with the stabiliser system, which has a temperature of, for example, from 60 to 120°C, preferably from 100 to 120°C, especially from 100 to 110°C, and then cooled.
Advantage-ously, the polyolefin is heated, for example to approximately from 60 to 120°C, before stabilisation.
The temperature of the polyolefin may be, for example, from 60 to 79°C if the stabiliser system contains as carrier a substance that melts at approximately from 0 to 79°C, such as, for example, paraffin oil, or if the stabilizer system has subsequently been treated with paraffin oil.
The ratio by weight of stabiliser system to paraffin oil is in the latter case, for example, from 1:1 to 3:1. In the case of subsequent treatment of the stabiliser system with paraffin oil, the stabiliser system is advantageously stirred into hot paraffin oil (from 100 to 120°C) and then stirred (for example for from 15 to 30 minutes) until a homogeneous mixture is obtained which can be used for the stabilisation of the polyolefin.
If a substance that melts at approximately from 80 to 110°C is used as carrier, such as, for example, wax, it is advantageous if the temperature of the polyolefin is, for example, from 80 to 120°C, preferably from 80 to 110°C.
The preparation of the stabiliser system is advantageously carried out by mixing components a) and/or b) and c). The mixture is heated, for example to from 120 to 260°C, preferably with stirring. The resulting melt is stirred, for example, for from 2 to 15 minutes, preferably from 8 to 12 minutes, and then cooled until it solidifies, which occurs, for example, at a temperature of from 0 to 30°C. The cooling can be effected, for example, with cold water or some other inert liquid, or with nitrogen or some other inert gas. It is also possible to cool the melt, for example, using a cold metal plate.
The preparation of the stabiliser system can also be effected, for example, in a kneader, in which case the stabiliser mixture is obtained in the form of a granulate.
The following Examples further illustrate the invention.
Example 1: Preparation of the stabiliser mixtures.
Stabiliser mixture I:
20 g of n-octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, 50 g of tetrakis[3,5-di-tert-butyl-4-hydroxyphenylpropionyloxymethyl]-methane and 100 g of tris[2,4-di-tert-butylphenyl]phosphite as well as 200 g of polyethylene wax (melting point according to ASTM D-3104:
102°C, hardness according to ASTM D-5: 7.0 dmm, density according to ASTM D-1505: 0.91 g/cc, viscosity according to Brookfield at 140°C:
180 cps) are mixed together and heated to 200°C. The molten material is stirred at that temperature for 10 minutes. The mixture is subsequently cooled, also with stirring, and solidifies.
Stabiliser mixture II:
II is prepared analogously to I using glyceryl monostearate instead of the wax.
Stabiliser mixture III:
III is prepared analogously to I using distearyl thiodipropionate instead of the polyethylene wax.
Stabiliser mixture IV:
IV is prepared analogously to I using 50 g of polyethylene wax instead of 200 g of polyethylene wax.
Stabiliser mixture V:
V is prepared analogously to IV, the mixing and heating being effected in an extruder ( BUSS-KO-KNETER) and the additive mixture being prepared in the form of a granulate.
Examples 2a-2c: Stabilisation of spherical polypropylene pellets.
a) 1000 g of spherical polypropylene ( Moplen SPL 12) are heated to 104°C
for 7 minutes in a~enschel mixer (capacity: 5000 ml). 3.7 g of the stabiliser mixture given in Table la, which have previously been melted at 104°C, are added. The mixture is stirred for 2 minutes and then cooled. The stabilised polypropylene pellets are subjected to oven ageing at 149°C for 30 h. The test results are given in Table la.
Discolouration of the polypropylene pellets indicates inadequate stabili-sation.
Table la:
Stabilizer 30 h oven ageing at 149C
mixture discolouration I no discolouration II no discolouration III no discolouration b) 1000 g of spherical polypropylene ( Moplen SPL 12) are heated to 65°C
for 3 minutes in ~Henschel mixer (capacity: 5000 ml). 3.7 g of the stabiliser mixture given in Table lb, which have previously been heated to 104°C, are added. Further processing and testing are carried out as in a). The test results are given in Table lb.
Table lb:
Stabilizer 30 h oven ageing at 149C
mixture discolouration III no discolouration c) 1000 g of sphe ~ al polypropylene ( Moplen SPL 12) are heated to 65°C
for 3 minutes in a Henschel mixer (capacity: 5000 ml).
2.2 g of the stabiliser mixture given in Table lc are added to 1 g of hot paraffin oil (110°C) and the resulting mixture is stirred at that temperature for 20 minutes. The mixture is then added to the poly-propylene (65°C) and the mixture is stirred for 2 minutes and then cooled. The polypropylene pellets are tested as in a). The test results are given in Table lc.
Table lc:
Stabilizer 30 h oven ageing at 149C
mixture discolouration IV no discolouration V no discolouration
L) 2-(2'-Hydroxy-5'-tert-octyl)benzotriazolel ~~\
I I ~-.\./.\N .\.__ /
~\CeHl -t melting point: 103-104°C
M) 2-(2'-Hydroxy-3',5'-di-tert-pentyl)benzotriazole2 ./~\ QH j SH11-t I I ~- /~ ~\
~\CsHii-t melting point: 79-87°C
Benzophenone:
N) 2-Hydroxy-4-octyloxybenzophenone ~H
%.\ _ _ %.\
I II ~ I II
Hm C80/~~,/.
melting point: 47°C
Thiodicarboxvlic acid diesters:
0) Dilauryl thiodipropionate Hz5C1z00CCHzCHz-S-CHzCHZC00C1zHzs melting point: 40-45°C
1 tert-octyl = 1,1,3,3-tetramethyl-1-butyl tert-pentyl = 1,1-dimethyl-1-propyl P) Dimyristyl thiodipropionate Hz9C1400CCHZCHz-S-CHZCHZCOOC14Hz9 melting point: 44-48°C
Q) Distearyl thiodipropionate H37C1800CCHzCHz-S-CHZCHZCOOC18H37 melting point: 57-67°C
Dialkyl disulfides:
R) Distearyl disulfide H37C18-$$-C18H37 melting point: ~66°C
Component b) is especially preferably sterically hindered phenolic antioxidant.
Component c) is preferably a sterically hindered phenolic antioxidant, a metal deactivator, a sterically hindered amine, a benzotriazole, a phosphorus-containing stabiliser, a nickel-containing UV-absorber and/or a metal salt of a C16-Czz-fatty acid.
The following stabilisers are examples of component c):
_$_ Sterically hindered phenolic antioxidant:
a) 1,3,5-Trimethyl-2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)-benzene H3C ~ CH3 /C(CHa)s \ /.\ / -I II in which R = -CHz-~~~ ~j~-OH
R/'~ /'~ .-.\
1~ C(CH3)3 melting point: 242-245°C .
f3) 1,3,5-Tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)isocyanurate ~\ /R /C(CH3)a in which R = -CHz-~~1 ~j~-OH
._.\
C(CH3)3 melting point: 218-223°C
y) 1,3,5-Tris(2',6'-dimethyl-4'-tert-butyl-5'-hydroxybenzyl)isocyanurate /R H3C\ _ in which R = -CHz-~~~ ~j~-C(CH3)3 /'~~~ .-0 0 H3C/ ~\OH
melting point: 145-155°C
d) 1,2-Bis[3',3'-bis(4"-hydroxy-5"-tert-butylphenyl)butanoyloxy)ethane QH
/~\ /C(CH3)a I II
.\ /.
H3C-~-CHz-~-~CHz ~~\
I II
~\ /~\C(CHa)a ~H
z melting point: 170°C
e) Bis(3-tert-butyl-4-hydroxy-6-methylphenyl)sulfide (H3C)3C\ /C(CH3)3 HO-~\. .~.-S-,\._.~~-OH
._ ._.
melting point: 161°C
2-(2'-Hydroxy-3'-tert-butyl-5'-methylbenzyl)-4-methyl-6-tert-butyl-phenyl acrylate QH CHZ ~OCCH=CHz (HaC)aC\ /~\ / ~ /~\ /C(CHa)a I II I II
.\ /. .\ /.
melting point: 130-132°C
n) 1,1,3-Tris[3'-tert-butyl-4'-hydroxy-6'-methylphenyl]butane (H3C)3C\ /C(CH3)3 HO-.\._.~~ H ~\. ~~._OH
._. HZ ._.
H3C HCH3 C~3 H3C\ ~~\
I II
~\ /~\C(CHa)s ~H
melting point: 182.5-190°C
B) 2,4-Di-tert-butylphenyl-3',5'-di-tert-butyl-4'-hydroxybenzoate /C(CHs)s j (CHa)s (HaC)sC_~~._./~ ~~ ~\._~/~ OH
\C(CHs)a melting point: 190°C
Metal deactivators:
1) N,N-Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl]hydrazine (HaC)aC\ /C(CH3)a .-.
HO-~~ j~-(CHz)z-~-NHNH-~-(CHz)z-~~~ ~j~-OH
.-. ._ (H3C)3C/ ~\C(CH3)a melting point: 224-229°C
K) N,N-Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyloxyethyl]oxalic acid diamide (HaC)aC\
H~~~~ ~j~-(CHz)2-~-0-(CHz)z-~-(H3C)3C~~-.
melting point: 173°C
Sterically hindered amines:
Poly(2-(N,N-bis(2',2',6',6'-tetramethyl-4'-piperidinyl)hexamethylene-diamino-4-morpholino-1,3,5-triazin-6-yl]
(CHz)6 ~ ~N\
H3C\I/~\I% H3 H3C\I/~\I% H3 H3C~~~~\CH3 H3C~~~~\CH3 .\0/.
n melting point: 110-130°C
u) Poly[2-(N,N-bis(2',2',6',6'-tetramethyl-4'-piperidinyl)hexamethylene-diamino-4-tert-octyl-1,3,5-triazin-6-yl]
~T ( C H z ) s ~1 ~N\
H3C\I/~\I/CH3 H3C\I/~\I/CH3 \
HN-C8H1~-t H3C/~~~\CH3 H3C/~\~~\CH3 n melting point: 120-150°C
v) 1,5,8,12-Tetrakis[2',4'-bis(1",2",2",6",6"-pentamethyl-4"-piperidinyl-(butyl)amino)-1',3',5'-triazin-6'-yl]-1,5,8,12-tetraazadodecane H-~-(CHz)a-~-(CHz)zy-(CHz)a-yH
H3C\ /CH3 r4H9 /.-~NN' .~-CH
.
~ a \.
.
_ HaC/
~N .\ \CH3 R - . HaC\ /CH3 -.~-CHa H \.
9 \CH3 melting point: 150°C
Bis[1',2',2',6',6'-pentamethyl-4'-piperidinyl]-2-butyl-2-(3",5"-di-tert-butyl-4"-hydroxybenzyl)malonate HaC\ j H3 /
(H3C)aC\ ~~ ~\~- -CH3 /~\
HO-~~. ~~ -CHz- -C4H9 H3C CH3 \ -_~/~ H3C\ % Ha (HaC)aC/~ 00 /. .~-CH3 .\ _ H3C/~\CH3 melting point: 146-150°C
o) 1,2-Bis[3',3',5',5'-tetramethyl-2'-oxo-1',4'-diazinan-1'-yl]ethane HaC\ /CHa~% 0~ HaC\ j H3 HN\~ ~-(CHz)z-~~ ~/NH
H3C/~\CH3. .H3C/.\CH3 melting point: 136°C
~r ) HjC\ /CH3 0 - \~~
H3C CH3 \~ ~/~\~ ~\~ ~/NH
\ /_ / \ /~\~~ HjC/~\CH3 ~J ~\ _ _ HN\~ /~
~ ~ 0 H3C/~\CH3 melting point: 270°C
Benzotriazoles:
p) 2-(2'-Hydroxy-3,5-di-tert-butylphenyl)benzotriazole ~ H C(CH3)3 \ ~_ /
I I ~-~j~ ~~
\~/.\N \~- /.
~\C(CH3)a melting point: 150-155°C
Q) 2-(2'-Hydroxy-3'-tert-butyl-5'-methylphenyl)-5'-chlorobenzotriazole C1\ /~\ QH /C(CH3)a I j - /~
~~ /~~ ~\ _ /
~ ~\CH3 melting point: 137-140°C
i) 2-(2'-Hydroxy-3',5'-di-tert-butylphenyl)-5'-chlorobenzotriazole C1\ /~\ QH /C(CH3)a I j .\ /.\,. .\ /
\C(CHs)a melting point: 154-158°C
Phosphorus-containing stabilisers:
v) Tris[2,4-di-tert-butylphenyl]phosphite (H3C)3C-~~~ ~j'- P
~ ~\C(CH3)a melting point: 180-185°C
Bis[2,4-di-tert-butylphenyl]pentaerythritol diphosphite C(CH3)a (HaC)aC
_ / 0-. -0 \ _ (HaC)aC-'/~ ~\ -0P/ \~/~ \P-C-~~. '~ -C(CH3)a \._./~ \~~/ \~-Q/ \._~/.
melting point: 160-175°C
X) Bis[2,6-di-tert-butyl-4-methylphenyl]pentaerythritol diphosphite /C(CHa)a (HsC)3C\
~ -' 0- ~ -0 H3C-~j ~ -0-P/ \ /~ \P-~~/._.\ -CH3 \~_- /~ \~~/~\~-0/ \ -~/~
~\C(CH3)a (H3C)3C/~
melting point: 235°C
V~ ) ~Ha (H3C)3C~ ~'~ ~ ~ ~'~ /C(CH3)3 I II ~ II
.\ /.\0 O/.\ /.
(H3C)3~ \~/ ~(CH3)3 melting point: 200-201°C
cu) Calcium salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester (H3C)3C~
CzHs _ HO-'~~_./~ CHZ-~ 0 Ca2+
(H3C)3C/~-melting point: >150°C
A) Nickel salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester (H3C)jC~ _ CzHs _ HO-~~~ ~ j~-CH2- 0 Ni2+
(H3C)3C/~-.
melting point: >180°C
Nickel-containing UV-absorbers:
B) 2,2'-Thio-bis(4-tert-octylphenolato~-butylamino nickel (II) t-H17C8-.\._.~ 0 jS Ni-NHC4H9 t-H17C8-.\.-.~ 0 melting point: 258°C
Metal salts of C,s-C~~-fatty acids:
t) Ca palmitate, melting point: 150-155°C (decomposition) D) Mg palmitate, melting point: 121°C
E) Zn palmatate, melting point: 125°C
Z) Ca stearate, melting point: 180°C
H) Mg stearate, melting point: 145°C
A) Zn stearate, melting point: 130°C
I) Ca behenate, melting point: 150°C
K) Mg behenate, melting point: 150°C
A) Zn behenate, melting point: 125°C
A phosphorus-containing stabiliser, especially a phosphate, is of interest as component c).
The invention relates especially preferably to a process in which the stabiliser system used contains components a), b) and c) and in which component b) is a sterically hindered phenolic antioxidant and compo-nent c) is a phosphate.
According to another preference, component b) is n-octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate and/or tetrakis[3,5-di-tert-butyl-4-hydroxyphenylpropionyloxymethyl]methane and component c) is tras[2,4-di-tert-butylphenyl]phosphate.
Also preferred is a process in which component b) is a stabiliser that melts at from 50 to 120°C and component c) is a stabiliser that melts at from 180 to 200°C and the stabiliser mixture as heated to from 180 to 200°C.
Components a), b) and c) are known and are for the most part commercially available products.
Olefins that can be polymerised on carrier catalysts are, for example, ethylene or a-olefins, especially propylene, 1-butene, 4-methylpentene-1 or 5-methylhexene-1, and mixtures of olefins, such as, for example, ethylene/propylene or propylene in admixture with smaller amounts of higher a-olefins.
Polyethylene, polypropylene, copolymers of ethylene and copolymers of propylene, especially polyethylene and polypropylene, each applied to carrier catalysts, are of interest.
The polymerisation catalysts used, which are frequently referred to as third generation catalysts, are advantageously solid catalysts of a particular particle size, such as, for example, those described in DE-A-29 33 997 and DE-A-26 41 960. They consist, for example, of an anhydrous magnesium dihalide in active form and a titanium compound.
Magnesium dihalide in active form denotes one in the X-ray spectrum of which the line of strongest reflection is broadened compared with the corresponding line in the spectrum of inactive magnesium halide.
Preferably, magnesium dichloride or magnesium dibromide is used as magnesium dihalide. The titanium compound contains preferably at least one titanium-halogen bond, the use of titanium tetrachloride being especially preferred.
The titanium compound can be used in combination with an electron donor, for example a carboxylic acid ester, such as that described in EP-A-45 977.
After reaction of the magnesium halide component with the titanium compound and, where appropriate, with the electron donor, the excess titanium compound and the excess electron donor are advantageously washed out with an inert solvent, for example with hexane or heptane.
The catalyst prepared in this manner is activated by reaction with an aluminium alkyl, which is preferably used in the form of a solution in an alkane. Examples of suitable aluminium alkyls are A1(CzHs)a or A1(CaH9)3.
There may be added as coactivator an electron donor such as, for example, an organic silicon compound that contains at least one Si-0-C bond, such as that described, for example, in EP-A-45 977. Examples of such silicon compounds are phenyltriethoxysilane, phenyltrimethoxysilane, diphenyldi-methoxysilane, methyltriethoxysilane, dimethyldiethoxysilane and ethyl-trimethoxysilane.
The polymerisation with these catalysts can be carried out according to known methods in liquid or gaseous phase. The liquid phase may be, for example, an aliphatic hydrocarbon, or the liquid monomer itself.
Spherical polymerised polyolefins are also described, for example, in P. Galli, P.C. Barbe and L. Noristi; "High Yield Catalysts in Olefin Polymerization", Die Angewandte Makromolekulare Chemie 120 (1984), p. 73-90 (No. 1935).
The diameter of the olefin polymers polymerised on carrier catalysts is preferably from 2 to 5 mm, especially from 2 to 3 mm.
The melting point of these granular-type polyolefins is, for example, from 140 to 165°C.
The concentration of the stabiliser mixtures in the polyolefin to be stabilised is preferably from 0.01 to 5 % by weight, especially from 0.05 to 1 % by weight.
Before incorporation into the polyolefin, it is advantageous to heat the stabiliser system until a milky solution has formed. This milky solution is a suspension of component c) in a) and/or b). For stabilisation, the polyolefin is stirred, for example for from 2 to 10 minutes, in a suitable device (preferably a mixer) with the stabiliser system, which has a temperature of, for example, from 60 to 120°C, preferably from 100 to 120°C, especially from 100 to 110°C, and then cooled.
Advantage-ously, the polyolefin is heated, for example to approximately from 60 to 120°C, before stabilisation.
The temperature of the polyolefin may be, for example, from 60 to 79°C if the stabiliser system contains as carrier a substance that melts at approximately from 0 to 79°C, such as, for example, paraffin oil, or if the stabilizer system has subsequently been treated with paraffin oil.
The ratio by weight of stabiliser system to paraffin oil is in the latter case, for example, from 1:1 to 3:1. In the case of subsequent treatment of the stabiliser system with paraffin oil, the stabiliser system is advantageously stirred into hot paraffin oil (from 100 to 120°C) and then stirred (for example for from 15 to 30 minutes) until a homogeneous mixture is obtained which can be used for the stabilisation of the polyolefin.
If a substance that melts at approximately from 80 to 110°C is used as carrier, such as, for example, wax, it is advantageous if the temperature of the polyolefin is, for example, from 80 to 120°C, preferably from 80 to 110°C.
The preparation of the stabiliser system is advantageously carried out by mixing components a) and/or b) and c). The mixture is heated, for example to from 120 to 260°C, preferably with stirring. The resulting melt is stirred, for example, for from 2 to 15 minutes, preferably from 8 to 12 minutes, and then cooled until it solidifies, which occurs, for example, at a temperature of from 0 to 30°C. The cooling can be effected, for example, with cold water or some other inert liquid, or with nitrogen or some other inert gas. It is also possible to cool the melt, for example, using a cold metal plate.
The preparation of the stabiliser system can also be effected, for example, in a kneader, in which case the stabiliser mixture is obtained in the form of a granulate.
The following Examples further illustrate the invention.
Example 1: Preparation of the stabiliser mixtures.
Stabiliser mixture I:
20 g of n-octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, 50 g of tetrakis[3,5-di-tert-butyl-4-hydroxyphenylpropionyloxymethyl]-methane and 100 g of tris[2,4-di-tert-butylphenyl]phosphite as well as 200 g of polyethylene wax (melting point according to ASTM D-3104:
102°C, hardness according to ASTM D-5: 7.0 dmm, density according to ASTM D-1505: 0.91 g/cc, viscosity according to Brookfield at 140°C:
180 cps) are mixed together and heated to 200°C. The molten material is stirred at that temperature for 10 minutes. The mixture is subsequently cooled, also with stirring, and solidifies.
Stabiliser mixture II:
II is prepared analogously to I using glyceryl monostearate instead of the wax.
Stabiliser mixture III:
III is prepared analogously to I using distearyl thiodipropionate instead of the polyethylene wax.
Stabiliser mixture IV:
IV is prepared analogously to I using 50 g of polyethylene wax instead of 200 g of polyethylene wax.
Stabiliser mixture V:
V is prepared analogously to IV, the mixing and heating being effected in an extruder ( BUSS-KO-KNETER) and the additive mixture being prepared in the form of a granulate.
Examples 2a-2c: Stabilisation of spherical polypropylene pellets.
a) 1000 g of spherical polypropylene ( Moplen SPL 12) are heated to 104°C
for 7 minutes in a~enschel mixer (capacity: 5000 ml). 3.7 g of the stabiliser mixture given in Table la, which have previously been melted at 104°C, are added. The mixture is stirred for 2 minutes and then cooled. The stabilised polypropylene pellets are subjected to oven ageing at 149°C for 30 h. The test results are given in Table la.
Discolouration of the polypropylene pellets indicates inadequate stabili-sation.
Table la:
Stabilizer 30 h oven ageing at 149C
mixture discolouration I no discolouration II no discolouration III no discolouration b) 1000 g of spherical polypropylene ( Moplen SPL 12) are heated to 65°C
for 3 minutes in ~Henschel mixer (capacity: 5000 ml). 3.7 g of the stabiliser mixture given in Table lb, which have previously been heated to 104°C, are added. Further processing and testing are carried out as in a). The test results are given in Table lb.
Table lb:
Stabilizer 30 h oven ageing at 149C
mixture discolouration III no discolouration c) 1000 g of sphe ~ al polypropylene ( Moplen SPL 12) are heated to 65°C
for 3 minutes in a Henschel mixer (capacity: 5000 ml).
2.2 g of the stabiliser mixture given in Table lc are added to 1 g of hot paraffin oil (110°C) and the resulting mixture is stirred at that temperature for 20 minutes. The mixture is then added to the poly-propylene (65°C) and the mixture is stirred for 2 minutes and then cooled. The polypropylene pellets are tested as in a). The test results are given in Table lc.
Table lc:
Stabilizer 30 h oven ageing at 149C
mixture discolouration IV no discolouration V no discolouration
Claims (13)
1. A process for stabilising olefin polymers having a mean particle diameter of from 1 to 5 mm that have been polymerised on carrier catalysts, which comprises treating the polyolefins with a stabiliser mixture prepared by heating to from 120 to 260°C a mixture containing components a), b) and c) or components b) and c) with component a) being at least one carrier, component b) being at least one stabiliser that melts at from 20 to 120°C, and component c) being at least one stabiliser that melts at from 120 to 260°C, and then cooling said mixture until solidified, components b) and c) being different.
2. A process according to claim 1, wherein the stabiliser mixture contains components a), b) and c).
3. A process according to claim 1, wherein component a) is a wax, paraffin oil or a glyceryl monocarboxylic acid ester.
4. A process according to claim 3, wherein component a) is a polyethylene, a polypropylene, an olefinic copolymer, an ethylene/vinyl acetate copolymer, an ethylene/(unsaturated carboxylic acid ester) copolymer, an ethylene/(unsaturated carboxylic acid metal salt) copolymer, a polyethylene or polypropylene each modified with unsaturated carboxylic acids, petroleum, paraffin oil, a polyalkylene glycol or a glyceryl monocarboxylic acid ester.
5. A process according to claim 1, wherein component b) is a sterically hindered phenolic antioxidant, a phosphorus-containing stabiliser, a sterically hindered amine, a benzotriazole, a benzophenone, a thiodicarboxylic acid diester or a dialkyl disulfide.
6. A process according to claim 1, wherein component b) is a sterically hindered phenolic antioxidant.
7. A process according to claim 1, wherein component c) is a sterically hindered phenolic antioxidant, a metal deactivator, a sterically hindered amine, a benzotriazole, a phosphorus-containing stabiliser, a nickel-containing UV-absorber or a metal salt of a C16-C22 fatty acid.
8. A process according to claim 1, wherein component c) is a phosphorus-containing stabiliser.
9. A process according to claim 1, wherein component c) is a phosphite.
10. A process according to claim 2, wherein component b) is a sterically hindered phenolic antioxidant and component c) is a phosphite.
11. A process according to claim 10, wherein component b) is n-octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxy-phenyl)propionate or tetrakis[3,5-di-tert-butyl-4-hydroxy-phenylpropionyloxymethyl]methane, and component c) is tris[2,4-di-tert-butylphenyl]phosphate.
12. A process according to claim 1, wherein component b) is a stabiliser that melts at from 50 to 120°C and component c) is a stabiliser that melts at from 180 to 200°C and the stabiliser mixture is heated to from 180 to 200°C.
13. A process according to claim 1, wherein the polyolefins have a mean diameter of from 2 to 5 mm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH135189 | 1989-04-10 | ||
| CH1351/89-3 | 1989-04-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2014005A1 CA2014005A1 (en) | 1990-10-10 |
| CA2014005C true CA2014005C (en) | 2001-05-15 |
Family
ID=4208441
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002014005A Expired - Fee Related CA2014005C (en) | 1989-04-10 | 1990-04-06 | Process for stabilising polyolefins |
Country Status (16)
| Country | Link |
|---|---|
| EP (1) | EP0392392B1 (en) |
| JP (1) | JP2942997B2 (en) |
| KR (1) | KR0156249B1 (en) |
| CN (1) | CN1038595C (en) |
| AR (1) | AR246976A1 (en) |
| AT (1) | ATE131189T1 (en) |
| AU (1) | AU632553B2 (en) |
| BR (1) | BR9001671A (en) |
| CA (1) | CA2014005C (en) |
| DD (1) | DD294035A5 (en) |
| DE (1) | DE59009938D1 (en) |
| ES (1) | ES2081313T3 (en) |
| FI (1) | FI101806B1 (en) |
| MX (1) | MX171591B (en) |
| NO (1) | NO301021B1 (en) |
| ZA (1) | ZA902698B (en) |
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 (en) * | 1989-08-02 | 1991-12-21 | Himont Inc | PROCEDURE FOR THE STABILIZATION OF POLYOLEFINS AND PRODUCTS OBTAINED FROM IT. |
| IT1247941B (en) * | 1991-05-17 | 1995-01-05 | Enichem Sintesi | PROCESS FOR OBTAINING GRANULAR FORMS OF ADDITIVES FOR ORGANIC POLYMERS |
| IT1258271B (en) * | 1992-04-06 | 1996-02-22 | Enichem Sintesi | PROCESS FOR OBTAINING GRANULAR FORMS OF ADDITIVES FOR ORGANIC POLYMERS. |
| 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 |
| ES2131162T3 (en) * | 1993-07-22 | 1999-07-16 | Gen Electric | NEODIOLPHOSPHITES AS STABILIZERS OF POLYMERS. |
| US5605947A (en) * | 1993-07-22 | 1997-02-25 | General Electric Company | Amorphous neo-diol phosphite compositions |
| US5614571A (en) * | 1994-09-16 | 1997-03-25 | General Electric Company | Stabilizer blend containing phosphite |
| WO1998046342A2 (en) | 1997-04-15 | 1998-10-22 | Ciba Specialty Chemicals Holding Inc. | Preparation of low-dust stabilisers |
| DE19817257A1 (en) | 1998-04-19 | 1999-12-09 | Grace Gmbh | Granulate composition of antiblocking agents and additives for polymer production |
| PL2397510T3 (en) | 2006-09-14 | 2015-03-31 | Ingenia Polymers Inc | High concentration pelletized additive concentrates for polymer |
| KR101957865B1 (en) | 2012-02-01 | 2019-03-13 | 가부시키가이샤 아데카 | Resin additive master batch |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1940066A1 (en) * | 1968-08-08 | 1970-02-12 | Ici Ltd | Polymer stabilizers |
| 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 |
| ATE82762T1 (en) * | 1987-02-13 | 1992-12-15 | Enichem Sintesi | SOLID STABILIZER MIXTURE FOR ORGANIC POLYMERS AND PROCESS FOR THEIR PRODUCTION. |
| IT1202611B (en) * | 1987-03-03 | 1989-02-09 | Enichem Sintesi | SOLID STABILIZING COMPOSITION FOR SYNTHETIC POLYMERS |
-
1990
- 1990-04-06 AR AR90316580A patent/AR246976A1/en active
- 1990-04-06 ES ES90106660T patent/ES2081313T3/en not_active Expired - Lifetime
- 1990-04-06 AT AT90106660T patent/ATE131189T1/en active
- 1990-04-06 CA CA002014005A patent/CA2014005C/en not_active Expired - Fee Related
- 1990-04-06 DE DE59009938T patent/DE59009938D1/en not_active Expired - Fee Related
- 1990-04-06 FI FI901772A patent/FI101806B1/en not_active IP Right Cessation
- 1990-04-06 MX MX020221A patent/MX171591B/en unknown
- 1990-04-06 AU AU53031/90A patent/AU632553B2/en not_active Ceased
- 1990-04-06 EP EP90106660A patent/EP0392392B1/en not_active Expired - Lifetime
- 1990-04-09 ZA ZA902698A patent/ZA902698B/en unknown
- 1990-04-09 BR BR909001671A patent/BR9001671A/en not_active IP Right Cessation
- 1990-04-09 NO NO901605A patent/NO301021B1/en not_active IP Right Cessation
- 1990-04-09 DD DD90339599A patent/DD294035A5/en not_active IP Right Cessation
- 1990-04-10 KR KR1019900004889A patent/KR0156249B1/en not_active IP Right Cessation
- 1990-04-10 CN CN90101989A patent/CN1038595C/en not_active Expired - Fee Related
- 1990-04-10 JP JP2094911A patent/JP2942997B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| AU5303190A (en) | 1990-10-11 |
| NO301021B1 (en) | 1997-09-01 |
| AR246976A1 (en) | 1994-10-31 |
| JP2942997B2 (en) | 1999-08-30 |
| DE59009938D1 (en) | 1996-01-18 |
| MX171591B (en) | 1993-11-08 |
| KR900016347A (en) | 1990-11-13 |
| EP0392392A1 (en) | 1990-10-17 |
| AU632553B2 (en) | 1993-01-07 |
| FI101806B (en) | 1998-08-31 |
| CN1046537A (en) | 1990-10-31 |
| NO901605L (en) | 1990-10-11 |
| ES2081313T3 (en) | 1996-03-01 |
| CA2014005A1 (en) | 1990-10-10 |
| BR9001671A (en) | 1991-05-14 |
| DD294035A5 (en) | 1991-09-19 |
| CN1038595C (en) | 1998-06-03 |
| ZA902698B (en) | 1991-01-30 |
| FI101806B1 (en) | 1998-08-31 |
| JPH02294345A (en) | 1990-12-05 |
| ATE131189T1 (en) | 1995-12-15 |
| NO901605D0 (en) | 1990-04-09 |
| FI901772A0 (en) | 1990-04-06 |
| EP0392392B1 (en) | 1995-12-06 |
| KR0156249B1 (en) | 1998-12-01 |
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| MKLA | Lapsed |