CA1083283A - Minimizing oil exudation from hydrogenated block copolymer compositions - Google Patents
Minimizing oil exudation from hydrogenated block copolymer compositionsInfo
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- CA1083283A CA1083283A CA262,208A CA262208A CA1083283A CA 1083283 A CA1083283 A CA 1083283A CA 262208 A CA262208 A CA 262208A CA 1083283 A CA1083283 A CA 1083283A
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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
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
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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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
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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
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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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
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
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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
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
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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
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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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
- C08L25/00—Compositions 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; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
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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
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
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- Oil, Petroleum & Natural Gas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Abstract
A B S T R A C T
The bleeding of oil from a composition containing a selectively hydrogenated block copolymer of a mono-alkenyl or mono-alkenylidene aromatic hydrocarbon and an aliphatic conjugated diene hydrocarbon, a polyolefin and oil is minimized by the presence of a sterically hindered phenol, a benzotriazole or a mixture of these compounds.
The bleeding of oil from a composition containing a selectively hydrogenated block copolymer of a mono-alkenyl or mono-alkenylidene aromatic hydrocarbon and an aliphatic conjugated diene hydrocarbon, a polyolefin and oil is minimized by the presence of a sterically hindered phenol, a benzotriazole or a mixture of these compounds.
Description
The invention relates to a composition comprising a selectively hydrogenated block copolymer. It also relates to shaped articles which are obtained by using such compositions.
It is known that selectively hydrogenated block co-polymers having at least two polymer blocks of a mono-alkenyl or mono-alkenylidene aromatic hydrocarbon and at least one partially or completely hydrogenated polymer block of an aliphatic conjugated diene hydro-carbon have certain advantages. However, their processability ; leaves something to be desired. It may be improved by extending the block copolymers with certain olefinic polymers. Furthermore, the blends may be extended with rubber extending oils in order to both improve ,t, 15 processability and reduce the cost of the final compo-sition. However, the resulting composltions show bleed-out of oil following exposure to actinic radiation.
Oil bleed-out appears to occur with the compositions comprising a selectively hydrogenated block copolymer, 3 20 a polyolefin and oil after injection moulding operation which unavoidably results in surface stresses. No adverse phenomena occur during the initial period~
Eventually, a thin film of oil, which is lar~ely identical ;~
with the extending oil, exudes to the surface and forms , 25 a tacky surface film which gradually thickens under continued ageing or exposure to light. Upon still further -:
. ' .
. ~,.. . . ~ . . . - . . . . .
. . ; ., , : . .
exposure, the oil appears to be absorbed into the shaped article. It would be recognized by experts in the art, that even a temporary pre-sence of an oily surface could result in a substantial technical dis-advantage. The presence of the oil not only is unsightly, but causes difficulty with adhesion to substrates or to paint films.
The object of the invention is to reduce or to eliminate oil bleed-out from oil-extended compositions comprising a selectively hydro-genated block copolymer and a polyolefin.
It has been found that oil bleed-out is minimized or prevented by the presence of sterically hindered phenols and benzotriazoles.
Now, in accordance with the invention a composition is provided comprising (a) 100 parts by weight of a selectively hydrogenated block copoly-, mer having at least two polymer blocks A, having a number average 3 molecular weight between 7,500 and 50,000, of a mono-alkenyl or mono-alkenylidene aromatic hydrocarbon, and at least one ;,l partially or completely hydrogenated polymer block B, having a I number average molecular weight between 10,000 and 125,000, of an i aliphatic conjugated diene hydrocarbon;
~ 20 (b) 5-150 parts by weight of a polyolefin;
! (c) 10-175 parts by weight of a rubber extending oil; and ;'~
.. '~ ' ~ ' ~ . .
. .~ , . , ,:, . . .
(d) 0.2-5 parts by wei~ht of a sterically hindered phenol, a benzotriazole or a mixturf~ of these oil bleed-out reducing agents.
The selectively hydrogenated block copolymer present in the composition according to the invention may have a linear, branched or radial structure. It may be produced by sequential block polymerization utilizing a lithium initiator such as a lithium alkyl. Alternatively, a coupling agent may be used in the production of the block copolymer resulting in either a linear or a branched or radial product. The resulting block copolymer ~ is then selectively hydrogenated.
t The polymer blocks A formed from a mono-alkenyl or a mono-alkenylidene aromatic hydrocarbon ma~ have a number average molecular weight between 7,500 and 50,000. The ; ~
polymer block B formed from an aliphatic conjugated diene ~ -Z hydrocarbon may have a number average molecular weight between 10,000 and 12,f,000. At least 90% of the residual ~i aliphatic double bonds of the diene polymer block B may ,~l 20 be hydrogenated. Preferably at least 98% of these double bonds are hydrogenated.
~1 The polymer blocks A may be formed from styrene, alpha- ;~
,l methyl styrene or tert-butyl styrene. The polymer block B may be formed from butadiene or isoprène. The Z 25 block copolymer may have the linear structure polystyrene-polybutadiene-polystyrene or polystyrene-polyisoprene-polyetyrene.
.
.
:' .
.
- , , . . . .
As used herein the term "a sterically hindered phenol" is intended to include a phenol or alkylene bisphenol of the formula:
OH
R ~ R
R ~ R
R
wherein R represents a hydrogen atom or an alkyl group having from 1-20 carbon atoms, provided that at least one R ortho to the OH-group is an alkyl or substituted alkylene group, and wherein, additionally one R may be a group of the formula OH OH OH
R ~ Rl-- or R--~R or R --~ R
R ' R R1 wherein R1 is an alkylene group having from 1 to 3 carbon atoms in the chain and from 1 to 8 carbon atoms in the group and R is a group as defined above.
:l Examples of these phenols are:
It is known that selectively hydrogenated block co-polymers having at least two polymer blocks of a mono-alkenyl or mono-alkenylidene aromatic hydrocarbon and at least one partially or completely hydrogenated polymer block of an aliphatic conjugated diene hydro-carbon have certain advantages. However, their processability ; leaves something to be desired. It may be improved by extending the block copolymers with certain olefinic polymers. Furthermore, the blends may be extended with rubber extending oils in order to both improve ,t, 15 processability and reduce the cost of the final compo-sition. However, the resulting composltions show bleed-out of oil following exposure to actinic radiation.
Oil bleed-out appears to occur with the compositions comprising a selectively hydrogenated block copolymer, 3 20 a polyolefin and oil after injection moulding operation which unavoidably results in surface stresses. No adverse phenomena occur during the initial period~
Eventually, a thin film of oil, which is lar~ely identical ;~
with the extending oil, exudes to the surface and forms , 25 a tacky surface film which gradually thickens under continued ageing or exposure to light. Upon still further -:
. ' .
. ~,.. . . ~ . . . - . . . . .
. . ; ., , : . .
exposure, the oil appears to be absorbed into the shaped article. It would be recognized by experts in the art, that even a temporary pre-sence of an oily surface could result in a substantial technical dis-advantage. The presence of the oil not only is unsightly, but causes difficulty with adhesion to substrates or to paint films.
The object of the invention is to reduce or to eliminate oil bleed-out from oil-extended compositions comprising a selectively hydro-genated block copolymer and a polyolefin.
It has been found that oil bleed-out is minimized or prevented by the presence of sterically hindered phenols and benzotriazoles.
Now, in accordance with the invention a composition is provided comprising (a) 100 parts by weight of a selectively hydrogenated block copoly-, mer having at least two polymer blocks A, having a number average 3 molecular weight between 7,500 and 50,000, of a mono-alkenyl or mono-alkenylidene aromatic hydrocarbon, and at least one ;,l partially or completely hydrogenated polymer block B, having a I number average molecular weight between 10,000 and 125,000, of an i aliphatic conjugated diene hydrocarbon;
~ 20 (b) 5-150 parts by weight of a polyolefin;
! (c) 10-175 parts by weight of a rubber extending oil; and ;'~
.. '~ ' ~ ' ~ . .
. .~ , . , ,:, . . .
(d) 0.2-5 parts by wei~ht of a sterically hindered phenol, a benzotriazole or a mixturf~ of these oil bleed-out reducing agents.
The selectively hydrogenated block copolymer present in the composition according to the invention may have a linear, branched or radial structure. It may be produced by sequential block polymerization utilizing a lithium initiator such as a lithium alkyl. Alternatively, a coupling agent may be used in the production of the block copolymer resulting in either a linear or a branched or radial product. The resulting block copolymer ~ is then selectively hydrogenated.
t The polymer blocks A formed from a mono-alkenyl or a mono-alkenylidene aromatic hydrocarbon ma~ have a number average molecular weight between 7,500 and 50,000. The ; ~
polymer block B formed from an aliphatic conjugated diene ~ -Z hydrocarbon may have a number average molecular weight between 10,000 and 12,f,000. At least 90% of the residual ~i aliphatic double bonds of the diene polymer block B may ,~l 20 be hydrogenated. Preferably at least 98% of these double bonds are hydrogenated.
~1 The polymer blocks A may be formed from styrene, alpha- ;~
,l methyl styrene or tert-butyl styrene. The polymer block B may be formed from butadiene or isoprène. The Z 25 block copolymer may have the linear structure polystyrene-polybutadiene-polystyrene or polystyrene-polyisoprene-polyetyrene.
.
.
:' .
.
- , , . . . .
As used herein the term "a sterically hindered phenol" is intended to include a phenol or alkylene bisphenol of the formula:
OH
R ~ R
R ~ R
R
wherein R represents a hydrogen atom or an alkyl group having from 1-20 carbon atoms, provided that at least one R ortho to the OH-group is an alkyl or substituted alkylene group, and wherein, additionally one R may be a group of the formula OH OH OH
R ~ Rl-- or R--~R or R --~ R
R ' R R1 wherein R1 is an alkylene group having from 1 to 3 carbon atoms in the chain and from 1 to 8 carbon atoms in the group and R is a group as defined above.
:l Examples of these phenols are:
2-methylphenol 2,6-ditert.-butyl-4-methylphenol 2-methyl-6-isopropylphenol 2-tert.-butyl-4-methylphenol 2-amylphenol ~, :
~, .
, , . ~ . . . .
2-nonylphenol 2-dodecylphenol 2-tetradecylphenol methylenebis-2(2,6-ditert.-butyl)phenol : 5 t2,2-bis(2-hydroxyphenyl)~propane 2-eicosylphenol 2,4,6-triicosylphenol 1,3-bis(2-hydroxyphenyl)-2-methyl-2-t-butylpropane ;
. and mixtures Or these phenols.
j 10~ Preferred hindered phenols include methylene bisphenols having the general configuration OH ,OH
~ CH ~ R
:, wherein R and R are alkyl radicals having 2-5 carbon .
atoms each. The preferred species is 2,2-methylene ;
bis(4-ethyl-6-tert.-but~phenol).
The benzotriazole which may be present in the composition according to the invention can comprise -any benzotriazole which has the general formula ' ~ / N ~ ;:
wherein R1 is an alkyl radical having from one-six carbon atoms and R2 is an alkyl radical having from 20 one-six oarbon ~toms or hydrogen. Examples are:
' . ' ~ . .
~, ,:" . .
.i . .
,.. . .
2(2-hydr~xy-3,5-di-n-hexylphenyl)benzotriazole 2(2-hydroxy-5-methylphenyl)benzotriazole 2(2-hydroxy-5-tert-buty~henyl)benzotriazole 2(2-hydroxy-3-methyl-5-isoamylphenyl)benzotriazole 2(2-hydroxy-3-hexyl-5-isopropylphenyl)benzotriazole t 2(2-hydroxy-3,5-dimethylphenyl)benzotriazole.
In a specific embodiment 2~2-hydroxy-5-methylphenyl) benzotriazole produced outstanding results.
Preferred benzotriazoles are chlorinated, having the general configuration C~ ~ \ N
~, I /
~ N R4 wherein R 3and R4 are alkyl radicals having from j 2-5 carbon atoms each. The preferred species is 2-(3',5'-ditert.-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole.
The sterically hindered phenols and benzotriazoles are preferably present in an amount of 0.75-2 part by weight per 100 parts by weight of the block copolymers.
;l~ The rubber extending oil which is present in the composition according to the invention may be hydro-carbon oils which may be paraffinic, naphthenic, or ., aromatic, relatively nonvolatile oils, at least under the physical conditions to which the composition ;~ ~ would normally be exposed. It is preferably present in an amount of 50-125 parts by weight per 100 parts by weight of the block copolymer.
.'j ; .
. ' ,. l -' .
.: . .
: , . :-. .:
~083283 The polyolefin which is present in the composition according to the invention may be a homopolymer such as polyethylene and polypropylene o~ a copolymer which may be a tapered, random or block copolymer.
The polyolefin is preferably present in an amount of 10-125 parts by weight per 100 parts by weight of the block copolymer.
A preferred composition is as follows:
a) a block copolymer having the configuration polystyrene-completely hydrogenated poly- -~
butadiene-polystyrene b) Polypropylene ~
c) Mineral rubber extending oil -d) 2,2'-methylene bis[4-ethyl-6-tert.-butylphenol]
e) 2-(3~,5'-ditert.-butyl-2'-hydroxyphenyl-5-chlorobenzotriazole.
It is emphasized that the present invention relates ~ -, to compositions comprising at least the three essential -components including the selectively hydrogenated block , copolymer. Since the diene blocks have been substantially completely hydrogenated, the normal stability problems encountered with non-hydrogenated diene polymers are at a minimum. Thus, normal oxygen, ozone and light sensitivity in the bulk properties ttensile strength, viscosity and melt flow) are of little concern in the hydrogenated block copolymers. On the other hand, the :
.
,, ~
~., , :
g .
oil bleed-out problem has been f'ound to be of major concern in the utility of the hydrogenated block copolymer compounds, but it does not affect the utility, to any appreciable extent, of compositions comprising the non-hydrogenated block copolymers.
Other compounding ingredients may be present~
such as resins, fillers, pigment and stabilizers.
The ingredients may be mixed by dry blending procedures, or in a typical Banbury mixing operation and the mixture so formed is then subjected to shaping operation such ` as compression moulding or some form of extrusion moulding or extrusion.
The following examples illustrate the reduction in oil bleed-out effected by th~ use of the present invention.
The basic composition was as follows:
Block copolymers 100 parts by weight ~ :
~ Polypropylene 40 ; A Penrico EX26~ Oil 150 1 20 The block copolymer had the structure polystyrene-completely hydrogenated polybutadiene-polystyrene with block molecular weight of 25,000-100,000-25,000. ~-~; Plaques.measuring 10 cm x lO.cm x 0.16 cm were . `
, 25 injection moulded and exposed to GE Sunlamps in equipment 'I ~
~; resembling that required in the Fadeometer test, ~ .
~ ~ Tr~dQ~s , ~
., , ,. . .` ` ~ ` . .
1~)83Z83 -- ~ o --ASTM 0928 Method B until maximum oil bleed-out occurred.
For these tests, samples of the basic composition were modified with one or more of th_ following additives, wi~h the changes in maximum oil bleed-out noted below:
Table 1 Parts by Weight Sample A B C D E
Additive;
Tetrakis ~methylene 3-(3',5'-10 di-tert.butyl-4'hydroxyphenyl) propionate~methane 1.0 1.0 Dilaurylthiodipropionate 1.72 1.0 2,2'-bis(4-methyl-6-tert. -butylhydroxyphenyl)methane o ~ 58 2(3',5'-di-tert.butyl-2'-hydroxyphenyl)-5-chloro- `~ ;~
~¦ benzotriazole 1.22 Max.~il Bleed-Out, mg/6.45 cm2 1.2 1.5 2.1 0.6 1.0 Note the low level of oil bleed-out especially in ?~ 20 Samples D and E, which are according to this invention.
The amount of oil bleed-out was determined by weighing the plaque, blotting off the oil from the surface with ~-~ paper and re-weighing the sample to determine weight loss due to oil removal.
A second series of samples were prepared wherein Q : ~ ~ ' the basic composition noted above was modified with . ;~
.
"
' ' " ' . ' ' .... . .
~083Z83 180 parts of calcium carbonate and 2 parts by weight of a polyepoxide. Injection moulded plaques of the above dimensions were conta ning the same series of additives listed in Table 1. The samples were exposed to a fluorescent UV source and maximum oil bleed-out was determined as described above. Table 2 lists the results obtalned.
Table 2 Parts by Weight Sample F ~ ~ I
Tetrakis rmethylene 3-(3',5'-di-tert.
butyl-4'hydroxyphenyl)propionate~
methane 0.
Dilaurylthiodipropionate 0.5 2,2~-bis(4-methyl-6-tert.butyl-hydroxyphenyl)methane 1.0 1.0 2(3',5'-di-tert.butyl--2'-hydroxy-phenyl3-5-chloro-benzotriazole 1.0 1.0 Max.Oil Bleed-out, mg/6.45 cm2 1.8 0.2 0.1 0.0 Note that samples G, H, and I, all according to this invention, showed exceptionally low oil bleed-out.
(QUV) Testing was carried out in a temperature controlled circulating air accelerated weathering environment chamber employing fluorescent light bulbs the output of which closely matches that of unfiltered sunlight at the short waveIength end of the spectrum, producing virtually no radiation shorter than 295 nm.
-; ,. .. . .
. , , . , . , ~.
~, .
, , . ~ . . . .
2-nonylphenol 2-dodecylphenol 2-tetradecylphenol methylenebis-2(2,6-ditert.-butyl)phenol : 5 t2,2-bis(2-hydroxyphenyl)~propane 2-eicosylphenol 2,4,6-triicosylphenol 1,3-bis(2-hydroxyphenyl)-2-methyl-2-t-butylpropane ;
. and mixtures Or these phenols.
j 10~ Preferred hindered phenols include methylene bisphenols having the general configuration OH ,OH
~ CH ~ R
:, wherein R and R are alkyl radicals having 2-5 carbon .
atoms each. The preferred species is 2,2-methylene ;
bis(4-ethyl-6-tert.-but~phenol).
The benzotriazole which may be present in the composition according to the invention can comprise -any benzotriazole which has the general formula ' ~ / N ~ ;:
wherein R1 is an alkyl radical having from one-six carbon atoms and R2 is an alkyl radical having from 20 one-six oarbon ~toms or hydrogen. Examples are:
' . ' ~ . .
~, ,:" . .
.i . .
,.. . .
2(2-hydr~xy-3,5-di-n-hexylphenyl)benzotriazole 2(2-hydroxy-5-methylphenyl)benzotriazole 2(2-hydroxy-5-tert-buty~henyl)benzotriazole 2(2-hydroxy-3-methyl-5-isoamylphenyl)benzotriazole 2(2-hydroxy-3-hexyl-5-isopropylphenyl)benzotriazole t 2(2-hydroxy-3,5-dimethylphenyl)benzotriazole.
In a specific embodiment 2~2-hydroxy-5-methylphenyl) benzotriazole produced outstanding results.
Preferred benzotriazoles are chlorinated, having the general configuration C~ ~ \ N
~, I /
~ N R4 wherein R 3and R4 are alkyl radicals having from j 2-5 carbon atoms each. The preferred species is 2-(3',5'-ditert.-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole.
The sterically hindered phenols and benzotriazoles are preferably present in an amount of 0.75-2 part by weight per 100 parts by weight of the block copolymers.
;l~ The rubber extending oil which is present in the composition according to the invention may be hydro-carbon oils which may be paraffinic, naphthenic, or ., aromatic, relatively nonvolatile oils, at least under the physical conditions to which the composition ;~ ~ would normally be exposed. It is preferably present in an amount of 50-125 parts by weight per 100 parts by weight of the block copolymer.
.'j ; .
. ' ,. l -' .
.: . .
: , . :-. .:
~083283 The polyolefin which is present in the composition according to the invention may be a homopolymer such as polyethylene and polypropylene o~ a copolymer which may be a tapered, random or block copolymer.
The polyolefin is preferably present in an amount of 10-125 parts by weight per 100 parts by weight of the block copolymer.
A preferred composition is as follows:
a) a block copolymer having the configuration polystyrene-completely hydrogenated poly- -~
butadiene-polystyrene b) Polypropylene ~
c) Mineral rubber extending oil -d) 2,2'-methylene bis[4-ethyl-6-tert.-butylphenol]
e) 2-(3~,5'-ditert.-butyl-2'-hydroxyphenyl-5-chlorobenzotriazole.
It is emphasized that the present invention relates ~ -, to compositions comprising at least the three essential -components including the selectively hydrogenated block , copolymer. Since the diene blocks have been substantially completely hydrogenated, the normal stability problems encountered with non-hydrogenated diene polymers are at a minimum. Thus, normal oxygen, ozone and light sensitivity in the bulk properties ttensile strength, viscosity and melt flow) are of little concern in the hydrogenated block copolymers. On the other hand, the :
.
,, ~
~., , :
g .
oil bleed-out problem has been f'ound to be of major concern in the utility of the hydrogenated block copolymer compounds, but it does not affect the utility, to any appreciable extent, of compositions comprising the non-hydrogenated block copolymers.
Other compounding ingredients may be present~
such as resins, fillers, pigment and stabilizers.
The ingredients may be mixed by dry blending procedures, or in a typical Banbury mixing operation and the mixture so formed is then subjected to shaping operation such ` as compression moulding or some form of extrusion moulding or extrusion.
The following examples illustrate the reduction in oil bleed-out effected by th~ use of the present invention.
The basic composition was as follows:
Block copolymers 100 parts by weight ~ :
~ Polypropylene 40 ; A Penrico EX26~ Oil 150 1 20 The block copolymer had the structure polystyrene-completely hydrogenated polybutadiene-polystyrene with block molecular weight of 25,000-100,000-25,000. ~-~; Plaques.measuring 10 cm x lO.cm x 0.16 cm were . `
, 25 injection moulded and exposed to GE Sunlamps in equipment 'I ~
~; resembling that required in the Fadeometer test, ~ .
~ ~ Tr~dQ~s , ~
., , ,. . .` ` ~ ` . .
1~)83Z83 -- ~ o --ASTM 0928 Method B until maximum oil bleed-out occurred.
For these tests, samples of the basic composition were modified with one or more of th_ following additives, wi~h the changes in maximum oil bleed-out noted below:
Table 1 Parts by Weight Sample A B C D E
Additive;
Tetrakis ~methylene 3-(3',5'-10 di-tert.butyl-4'hydroxyphenyl) propionate~methane 1.0 1.0 Dilaurylthiodipropionate 1.72 1.0 2,2'-bis(4-methyl-6-tert. -butylhydroxyphenyl)methane o ~ 58 2(3',5'-di-tert.butyl-2'-hydroxyphenyl)-5-chloro- `~ ;~
~¦ benzotriazole 1.22 Max.~il Bleed-Out, mg/6.45 cm2 1.2 1.5 2.1 0.6 1.0 Note the low level of oil bleed-out especially in ?~ 20 Samples D and E, which are according to this invention.
The amount of oil bleed-out was determined by weighing the plaque, blotting off the oil from the surface with ~-~ paper and re-weighing the sample to determine weight loss due to oil removal.
A second series of samples were prepared wherein Q : ~ ~ ' the basic composition noted above was modified with . ;~
.
"
' ' " ' . ' ' .... . .
~083Z83 180 parts of calcium carbonate and 2 parts by weight of a polyepoxide. Injection moulded plaques of the above dimensions were conta ning the same series of additives listed in Table 1. The samples were exposed to a fluorescent UV source and maximum oil bleed-out was determined as described above. Table 2 lists the results obtalned.
Table 2 Parts by Weight Sample F ~ ~ I
Tetrakis rmethylene 3-(3',5'-di-tert.
butyl-4'hydroxyphenyl)propionate~
methane 0.
Dilaurylthiodipropionate 0.5 2,2~-bis(4-methyl-6-tert.butyl-hydroxyphenyl)methane 1.0 1.0 2(3',5'-di-tert.butyl--2'-hydroxy-phenyl3-5-chloro-benzotriazole 1.0 1.0 Max.Oil Bleed-out, mg/6.45 cm2 1.8 0.2 0.1 0.0 Note that samples G, H, and I, all according to this invention, showed exceptionally low oil bleed-out.
(QUV) Testing was carried out in a temperature controlled circulating air accelerated weathering environment chamber employing fluorescent light bulbs the output of which closely matches that of unfiltered sunlight at the short waveIength end of the spectrum, producing virtually no radiation shorter than 295 nm.
-; ,. .. . .
. , , . , . , ~.
Claims (11)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS;
1. A composition which comprises:
(a) 100 parts by weight of a selectively hydrogenated block copolymer having at least two polymer blocks A, having a number average molecular weight between 7,500 and 50,000, of a mono-alkenyl or mono-alkenylidene aromatic hydrocarbon, and at least one partially or completely hydrogenated polymer block B, having a number average molecular weight between 10,000 and 125,000, of an aliphatic con-jugated diene hydrocarbon;
(b) 5-150 parts by weight of a polyolefin;
(c) 10-175 parts by weight of a rubber extending oil; and (d) 0.2 5 parts by weight of a sterically hindered phenol, a benzotri-azole or a mixture of these oil bleed-out reducing agents.
(a) 100 parts by weight of a selectively hydrogenated block copolymer having at least two polymer blocks A, having a number average molecular weight between 7,500 and 50,000, of a mono-alkenyl or mono-alkenylidene aromatic hydrocarbon, and at least one partially or completely hydrogenated polymer block B, having a number average molecular weight between 10,000 and 125,000, of an aliphatic con-jugated diene hydrocarbon;
(b) 5-150 parts by weight of a polyolefin;
(c) 10-175 parts by weight of a rubber extending oil; and (d) 0.2 5 parts by weight of a sterically hindered phenol, a benzotri-azole or a mixture of these oil bleed-out reducing agents.
2. A composition as claimed in claim 1, wherein at least 98% of the residual aliphatic double bonds of the diene polymer block B are hydrogenated.
3. A composition as claimed in claim 1, wherein the sterically hin-dered phenol is a phenol or alkylene bisphenol of the formula:
wherein R represents a hydrogen atom or an alkyl group having from 1 to 20 carbon atoms, provided that at least one R ortho to the OH-group is an alkyl or substituted alkylene group, and wherein, additionally one R may be a group of the formula or or wherein R1 is an alkylene group having from 1 to 3 carbon atoms in the chain and from 1 to 8 carbon atoms in the group and R is an atom or group as de-fined above.
wherein R represents a hydrogen atom or an alkyl group having from 1 to 20 carbon atoms, provided that at least one R ortho to the OH-group is an alkyl or substituted alkylene group, and wherein, additionally one R may be a group of the formula or or wherein R1 is an alkylene group having from 1 to 3 carbon atoms in the chain and from 1 to 8 carbon atoms in the group and R is an atom or group as de-fined above.
4. A composition as claimed in claim 3, wherein the sterically hin-dered phenol is a methylene phenol having the general formula wherein R1 and R2 are alkyl radicals having 2-5 carbon atoms each.
5. A composition as claimed in claim 1, wherein the benzotriazole is one having the general formula wherein R1 is an alkyl radical having from 1 to 6 carbon atoms and R2 is an alkyl radical having from 1 to 6 carbon atoms or hydrogen.
6. A composition as claimed in claim 1, wherein the benzotriazole is a chlorinated one having the general configuration wherein R3 and R4 are alkyl radicals having from 2 to 5 carbon atoms each.
7. A composition as claimed in claim 1, 2 or 3, wherein the oil bleed-out reducing agent is present in an amount of 0.75-2 parts by weight per 100 parts by weight of the block copolymer.
8. A composition as claimed in claim 1, 2 or 3, wherein the rubber extending oil is a hydrocarbon oil.
9. A composition as claimed in claim 1, 2 or 3, wherein the rubber extending oil is present in an amount of 50-125 parts by weight per 100 parts by weight of the block copolymer.
10. A composition as claimed in claim 1, 2 or 3, wherein the poly-olefin is present in an amount of 10-125 parts by weight per 100 parts by weight of the block copolymer.
11. Moulded or extruded articles formed of a composition as claimed in claim 1, 2 or 3.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US62601775A | 1975-10-28 | 1975-10-28 | |
US626,017 | 1975-10-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1083283A true CA1083283A (en) | 1980-08-05 |
Family
ID=24508611
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA262,208A Expired CA1083283A (en) | 1975-10-28 | 1976-09-28 | Minimizing oil exudation from hydrogenated block copolymer compositions |
Country Status (12)
Country | Link |
---|---|
JP (1) | JPS5931540B2 (en) |
AU (1) | AU500861B2 (en) |
BE (1) | BE847613A (en) |
CA (1) | CA1083283A (en) |
DE (1) | DE2648452A1 (en) |
ES (1) | ES452730A1 (en) |
FR (1) | FR2329708A1 (en) |
GB (1) | GB1560896A (en) |
IT (1) | IT1069029B (en) |
NL (1) | NL183093C (en) |
SE (1) | SE411913B (en) |
ZA (1) | ZA766398B (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58206644A (en) * | 1982-05-27 | 1983-12-01 | Mitsubishi Petrochem Co Ltd | Elastomer composition |
JPS6072953A (en) * | 1983-09-30 | 1985-04-25 | Asahi Chem Ind Co Ltd | Block copolymer composition |
JPS6134049A (en) * | 1984-07-27 | 1986-02-18 | Asahi Chem Ind Co Ltd | Hydrogenated block copolymer composition |
JPH064745B2 (en) * | 1985-10-03 | 1994-01-19 | 住友化学工業株式会社 | Thermoplastic elastomer composition |
JPH0446778Y2 (en) * | 1986-03-14 | 1992-11-04 | ||
JPS62240342A (en) * | 1986-03-18 | 1987-10-21 | Chisso Corp | Elastomeric composition for molding |
WO1996007702A1 (en) * | 1994-09-09 | 1996-03-14 | Shell Internationale Research Maatschappij B.V. | Block copolymer containing binder composition and electrophotographic toner composition derived therefrom |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3239478A (en) * | 1963-06-26 | 1966-03-08 | Shell Oil Co | Block copolymer adhesive compositions and articles prepared therefrom |
US3779965A (en) * | 1971-12-17 | 1973-12-18 | Grace W R & Co | Extruded disc gasket for alcoholic beverage bottle caps |
US3830767A (en) * | 1973-05-02 | 1974-08-20 | Shell Oil Co | Block copolymer compositions |
-
1976
- 1976-09-28 CA CA262,208A patent/CA1083283A/en not_active Expired
- 1976-10-25 BE BE1007718A patent/BE847613A/en not_active IP Right Cessation
- 1976-10-26 FR FR7632211A patent/FR2329708A1/en active Granted
- 1976-10-26 SE SE7611890A patent/SE411913B/en not_active IP Right Cessation
- 1976-10-26 DE DE19762648452 patent/DE2648452A1/en active Granted
- 1976-10-26 NL NLAANVRAGE7611829,A patent/NL183093C/en not_active IP Right Cessation
- 1976-10-26 ZA ZA766398A patent/ZA766398B/en unknown
- 1976-10-26 ES ES452730A patent/ES452730A1/en not_active Expired
- 1976-10-26 AU AU19002/76A patent/AU500861B2/en not_active Expired
- 1976-10-26 IT IT28712/76A patent/IT1069029B/en active
- 1976-10-26 GB GB44427/76A patent/GB1560896A/en not_active Expired
- 1976-10-26 JP JP51127900A patent/JPS5931540B2/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
ES452730A1 (en) | 1977-10-01 |
JPS5931540B2 (en) | 1984-08-02 |
NL183093C (en) | 1988-07-18 |
JPS5253957A (en) | 1977-04-30 |
FR2329708B1 (en) | 1981-05-29 |
NL183093B (en) | 1988-02-16 |
AU500861B2 (en) | 1979-06-07 |
IT1069029B (en) | 1985-03-21 |
ZA766398B (en) | 1977-10-26 |
NL7611829A (en) | 1977-05-02 |
DE2648452C2 (en) | 1987-04-02 |
GB1560896A (en) | 1980-02-13 |
BE847613A (en) | 1977-04-25 |
SE7611890L (en) | 1977-04-29 |
FR2329708A1 (en) | 1977-05-27 |
SE411913B (en) | 1980-02-11 |
DE2648452A1 (en) | 1977-05-05 |
AU1900276A (en) | 1978-05-04 |
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