CA1084519A - Phenyl-containing organopolysiloxanes - Google Patents
Phenyl-containing organopolysiloxanesInfo
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- CA1084519A CA1084519A CA233,187A CA233187A CA1084519A CA 1084519 A CA1084519 A CA 1084519A CA 233187 A CA233187 A CA 233187A CA 1084519 A CA1084519 A CA 1084519A
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- phenyl
- weight
- content
- percent
- containing organopolysiloxane
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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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)
- Silicon Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Lubricants (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Phenyl-containing organopolysiloxane fluids of the formula,
Phenyl-containing organopolysiloxane fluids of the formula,
Description
1~ 45~9 8SI-1594 This invention relates to organopolysiloxane polymers and more particularly to phenyl-contaïning organopolysiloxane fluid polymers.
In the past, the:re were three major types of silicone polymers which comprise nearly all of the phenyl-containing organopolysiloxanes. These included ~1) those siloxanes with phenyl and methyl groups on the same si.licon atom, (:2) those : siloxanes with two phenyls on one silicon and two methyls on the next or subsequent silicon atom, and (3~ those. siloxanes containing phenyl trimethylsilyl units stopped with trimethylsilyl units.
An example of the first type includes polymers of the structure . CH3 ~ CH3 ~ ~ CH3 ~ C,H3 CH3 - Si - t si a ) -t si o ~ si CH
CH3 ~ Ph / ~CH3 J CH3 .
X Y
wherein Ph is phenyl and wherein, in general, x = 0.05 y to y= O.
The second major type includes those polymers having the structure, CIH3 /'C,H3 ~ ~ Ph ~ ,CH3 CH3 - Si _ o ~ Si - O - ~ Si- O ~- - Si - CH3 CH3 ~CH3 ~ ~ Ph J CH3 ;~
where Ph is phenyl and wherein, in general, x = 0.05 y to x = y. :
The third group of polymers has the structure -,CH3 , 3 ,CH3 3, 3 CH3Si CH3 CH -CH3 - Si _ o Si - O Si - O --- Si - CH
CH3 Ph Ph CH3 wherein the polymer length varies up to about 25 phenyl containing units.
~ 451 9 8SI-1594 ' ' .
For varicus reasons, these prior art silicone fluids are characterized with both technical and commercial problems.
For example, the first of the above-identified silicone fluidæ
are necessarily made from a ~tarting material, i.e., methyl-phenyldichlorosilane, which comes from an expen~ive Grignard process while the polymers associated with the other above-identified classic structure6 are characterized with processing problems. For example, those polymers containing both diphenyl and dimethyl units have been found to be excessively volatile and moreover are difficult to manufacture in low vooai~ form which i8 oftentimes desirable.
The uses for these hereinabove described silicone polymers are of course widespread, depending upon molecular weisht and structure, and are well known. Included among these uses are, for example, lubricity additives for plastics, high temperature grease components and general mechanical fluids.
; More specifically, one recently significant use of phenyl-containing organopolysiloxane fluids ha~ been a~ internal mold release agents in polycarbonates. See, for example, U.S.
Patent No. 3,751,519 isffued August 7, 1973. However, prior art phenyl organopolysiloxane fluids have not been totally ~ati~-factory for polycarbonates as a result of their low solubility in the polycarbonate. Moreover, transparency ueually desired in polycarbonate products is usually lost when these prior art phenyl-containing organopoly~iloxane fluids are added thereto.
Accordingly, it i~ one object of this invention to provide a novel class of phenyl-containing organopolysiloxane fluids.
Another object of this invention is to provide novel phenyl-containing organopolysiloxanes which are easily prepared in an economic manner.
10~34519 Still another object of this invantion i~ to provide novel phenyl-containing organopolysiloxane fluids having a high phenyl content, whicht if desired, may be prepared in low viscosity form and which are charac~erized witn low volatility.
Still another object of this invention i8 to provide phenyl-containing organopolysiloxane fluids, u~eful as internal mold release additives and having high solubility in polycarbonates.
A still further object of this invention is to provide novel phenyl-containing fluids of varied utilities, including additives for plastics, high temperature grease components, mechanical fluids and the like.
A still further object of this invention is to provide polycarbonate co~positions comprising the novel phenyl organo-polysiloxane fluid~ of this invention, said polycarbonate compositions being characterized with transparency and internal mold release properties.
These zlnd other ob~ects are accomplished herein by providing phenyl--containing organopolysiloxane fluids char-acterized by the following basic structure, CH3 ,Ph ~ CH3 ~ ~ ,Ph (I) CH3 - Si - OSi _ o ~ Si - 0 ~ Si - 0 ~ R
J y\~ ~ :
wherein x and y are values ~ufficient to provide a phenyl content of from about 7 weight percnnt to about 80 weight per-cent, and where Ph is phenyl, and wherein R is selected from the group consisting of hydrogen and trimethylsilyl, i.e., ,H3 Bi - CH3 and mixtures thereof.
The novel phenyl-containing organopolysiloxane fluids characterized by Formula I hereinabove are made by the solvent - , hydroly~is of diphenyldichlorosilane and dimethyldichlorosilane.
In general, this solvent hydrolysis process involves preparing a blend of diphenyldichlorosilane, dimethyldichlorosilane, and a water-immiscible organic solvent.
` Suitable organic solvent~ are, for example, any water-immiscible organic solvent which i~ inert to the hydrolysis reactants during hydrolysis, and in which the hydrolyzate i~
soluble 80 as to provide for its separation. More specifically, suitable organic solvents include benzene, toluene, xylene, and the li~e; esters such as butyl acetate, ethyl acetate and the like; and ethers such as diethyl ether, dioxane and the like.
A preferred organic ~olvent i8 toluene. The amount of or~anic solvent employed may vary within a wide range and is generally within the range of ~rom about 10~ to about 50h by weight of the total weight of the blend of organohalo~ilanes, preferably about 25% by weight. - -~
For purpoces of this invention, the ratio of diphenyl-~hlorosilane to dimethylchlorosilane in the organohalosilane blend which is subjected to hydrolysis i~ from about 1.5 to 1 to about 4 to 1 by weight, re~pectively. Preerably, the ratio of diphenylchlorosilane to dimethylchlorosilane i8 about 3 to 1.
The afore-described mixture of organohalosilanes in organic solvent is admixed with and agitated in water which ha~
been preheated to from about 20 to about 85 C, preferably from about 60 to about 65 , the addition being carried out slowly over a period of, for example, from about 1 to about 2 hours, while maintaining a temperature of from about 60C to about 85C, preferably from about 75C to about 85 C. The resultant hydrolysis mixture i8 allowed to ~ettle and the ~ aqueous acid layer (bottom) is separated and discardea. The remaining organic layer is generally washed several times with, for example, 15%
?
., . -i~845~9 8SI-1594 sodium sulfate sOlution, until the HCl content is below about 10 parts per million. At this point, the water i9 azeotropically removed from the hydrolysis mixture at a temperature which should not exceed about 115 C~ The material remaining, hereinafter referred to as the hydrolyzate, i8 a mixture o linear siloxanes (chainstopped with diphenyl silanol unit~), cyclic polymers, and organic solvent.
The hydrolyzats is then saturated with anhydrous ammonia and trimethylchlorosilane is slowly added thereto. The trimethylchlorosilane act~ as a chain~topping agent and replaces the silanol groups with trimethylsiloxy chain-stopping units.
The amount of trimethylchlorosilane which is employed varies with the amount of hydroxyl group replacement desired. For purposes of tnis invention, the trimethylchlorosilane is employed in amounts from about 9.5 to 25.5 weight percsnt of the weight of the hydrolyzate. More specifically, for polycarbonate additive purposes, the amount of trimethylchlorsilane chain-stopping agent w ed ranges from about 11.4% to 19% by woight of the total weight of the hydrolyzate, providing a trimethyl-siloxy unit content for the fluid of from about 12 to about 21percent by weight. ~ fter agitating the mixture for about one hour, the mixture is washed with, for example, 15% sodium sulfate until essentially neutral and the aqueous bo~Dm layer is ~eparated and di~carded. The remaining organic layer i8 wa~hed with, for example, sodium sulfate, and the organic ~olvent and residual water is stripped under vacuum, e.g., 25 to 30 mm Hg. at about 150 C. The remaining phenyl-containing organopolysiloxane fluid is characterized by Formula I hereinabove, wherein x and y are 3~ values sufficient to provide a phenyl content of from about 40 to 80 weight percent and i8 especially well suited a~ an internal _ 5 _ : ' ., -. : ' 11)845~9 8SI--1594 mold release additive for polycarbonates since the fluid is highly soluble in polycarbonates and moreover retains the desired transparency of the polycarbonates. In general, x and y have a value of from about 3 to 10 for this purpose.
To obtain particularly high phenyl content, low volatile organopolysiloxane fluids within ths scope of the present invention, and which are particularly well suited as a base stock for all mechanical or hydraulic phenyl silicone fluids, the afore-described phenyl-containing organopoly-~iloxane fluid is totally chain~toppsd by employing a sufficient amount of trimethylchlorosilane to do the same. The substantially all trimethylsiloxy chainstopped fluid is then subjected to an equilibration process involving admixing the same with potassium hydroxide and heating toabout 180 C for about 1 to 2 hours.
If desired, additional trimethylsiloxy chainstopping units may be added during eguilibration. Strippi~g the mixture at about 250-300C under high vacuum (3-5 mm ~g.) results in a high phenol content, low volatile, organopolysiloxane fluid characterized by Formula I above wherein x is about 3 to 10 and y i8 about 3 to 10 and the phenyl content iB from about 40 to 80 weight percent.
To obtain phenyl-containing organopolysiloxane fluids within the scope of this invention and which are especially suitable a~ mechanical fluids and high temperature grease components the afore-described hydrolysis process for preparing the polycarbonate additive i~ continued by completely chain-stopping the fluid by the addition of a sufficient ~uantity of trimethylchlorosilane. The resultant mixture is equilibrated with potassium hydroxide at a temperature in the range of from about 180 C to 200C for about one hour. During equilibration octamethylcyclotetra~iloxane and trimethylsiloxy containing units provided, for example, by linear decamethyltetrasiloxane, 1~45~L9 are added in sufficient quantity to reduce the phenyl content to a desired amount, generally in the range of from about 38 to 48 weight percent, and to a desired viscosity, generally 100 to 200 centistokes at 25C. In the preferred method of equilibration, the octamethyltetracyclosiloxane and trimethyl-siloxy unit material are equilibrated first, then the phenyl-containing stock i~ added and the equilibration co~tinued for like about 3 hours.
The resultant equilibrate is ~tripped to about 280C
under very high vacuum, e.g., 3-5 mm ~g.
To obtain a fluid especially useful for transparent greases and controlled den3ity greases, the fluid identified hereinabove, as being particularly useful às an internal mold release agent for polycarbonate~, is further modified by the addition thereto of octamethylcyclotetrasiloxane (sufficient to lower the phenyl content to about 30 weight percent) and equilibrating and stripping the resultant mixture as de~cribed hereinabove.
It is clear to those skilled in the art that the phenyl-containing organopolysiloxanes of this invention as particularly characterized by Formula I hereinabove are particularly di~tinguished over the prior art phenyl-containing silicone fluids in that the present fluids comprise trimethylsikxy chainstopping units which are directly attached primarily to diphenylsilo~y units. This accounts for the advantageous solubility properties of the present fluids in polycarbonates, in addition to accounting for the other advantageous properties ~-herebefore described.
The polycarbonates which are contemplated herein in admixture with the above-identified internal mold relea~e phenyl-containing organopolysiloxane additives of this invention include those aromatic polycarbonates prepared by reacting a , 845:~L9 dihydric phenol and a carbonate precur~or. The reaction mixture can also include minor amounts of other additives or other amounts of other reactive monomeric constituents. It can also include copolymers of two or more different dihydric phenols.
Specifically, examples of dihydric phenols that can be empl~yed to prepare the polycarbonates eontemplated herein are bis(4-hydroxyphenyl)-methane, 2,2-bis(4-hydroxyphenyl-propane, 2,2-bis(4-hydroxy-3-methylphenyl)-propane, 4,4-bis-(4-hydroxyphenyl)-heptane, 2,2-bis(4-hydroxy, 3,5-dichloro-phenyl)-propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)-propane, ete.; dihydrie phenol ethers sueh as bis(4-hydroxyphenyl)-ether, bis(3,5-dichloro-4-hydroxyphenyl)-ether, etc.; dihydroxydiphenyls such as p,p'-dihydroxy-diphenyl, 3,3'-dichloro-4,4'-dihydroxy-diphenyl, etc.; dihydroxyaryl sulfones ~uch as bis(4-hydroxy-phenyl)-sulfone, bis(3,5-dimethyl-4-hydroxyphenyl)-sulfone, etc.;
dihydroxy benzenes, resorcinol, hydroquinones, halo and alkyl-substituted dihydroxy benzenes ~uch as 1,4-dihydroxy-2-ehloro-benzene, 1,4-dihydroxy-2,5-diehlorobenzene, 1,4-dihydroxy-3-methylbenzene, etc.; and dihydroxy diphenyl qulfoxides such as bis(4-hydroxyphenyl)-sulfoxide, bis(3,5-dibromo-4-hydroxyphenyl)-sulfoxide, ete. A variety of additional dihydric phenols are also available to provide earbonate polymers and are disclosed in U.S. Patents 2,999,835 issued September 12, 1961; 3,028,365 issued April 3, 1962 and 3,153,008 issued October 13, 1964. It i8, of course, possible to employ two or more different dihydric phenols or a copolymer of a dihydric phenol with glycol or with hydroxy or aeid terminated polyester, or with a diboric acid in the event a carbonate copolymer or interpolymer rather than a homopolymer is desired for use in the preparation of the aromatic earbonate polymers of this invention.
1~845~9 Among the carbonate precursors employed in the afore-described polycarbonate preparation are included phosgene, dibromo and diiodocarbonyls as well as the bishaloformates of dihydric phenols (e.g. bischloroformates of hydroquinone, bisphenol-A, etc.) or glycols (e.g., bischloroformates of ethylene glycol, neopentyl glycol, polyethylene glycol, etc.) A preferred aromatic polycarbonate within the scope of this invention is prepared from the reaction of phosgene and
In the past, the:re were three major types of silicone polymers which comprise nearly all of the phenyl-containing organopolysiloxanes. These included ~1) those siloxanes with phenyl and methyl groups on the same si.licon atom, (:2) those : siloxanes with two phenyls on one silicon and two methyls on the next or subsequent silicon atom, and (3~ those. siloxanes containing phenyl trimethylsilyl units stopped with trimethylsilyl units.
An example of the first type includes polymers of the structure . CH3 ~ CH3 ~ ~ CH3 ~ C,H3 CH3 - Si - t si a ) -t si o ~ si CH
CH3 ~ Ph / ~CH3 J CH3 .
X Y
wherein Ph is phenyl and wherein, in general, x = 0.05 y to y= O.
The second major type includes those polymers having the structure, CIH3 /'C,H3 ~ ~ Ph ~ ,CH3 CH3 - Si _ o ~ Si - O - ~ Si- O ~- - Si - CH3 CH3 ~CH3 ~ ~ Ph J CH3 ;~
where Ph is phenyl and wherein, in general, x = 0.05 y to x = y. :
The third group of polymers has the structure -,CH3 , 3 ,CH3 3, 3 CH3Si CH3 CH -CH3 - Si _ o Si - O Si - O --- Si - CH
CH3 Ph Ph CH3 wherein the polymer length varies up to about 25 phenyl containing units.
~ 451 9 8SI-1594 ' ' .
For varicus reasons, these prior art silicone fluids are characterized with both technical and commercial problems.
For example, the first of the above-identified silicone fluidæ
are necessarily made from a ~tarting material, i.e., methyl-phenyldichlorosilane, which comes from an expen~ive Grignard process while the polymers associated with the other above-identified classic structure6 are characterized with processing problems. For example, those polymers containing both diphenyl and dimethyl units have been found to be excessively volatile and moreover are difficult to manufacture in low vooai~ form which i8 oftentimes desirable.
The uses for these hereinabove described silicone polymers are of course widespread, depending upon molecular weisht and structure, and are well known. Included among these uses are, for example, lubricity additives for plastics, high temperature grease components and general mechanical fluids.
; More specifically, one recently significant use of phenyl-containing organopolysiloxane fluids ha~ been a~ internal mold release agents in polycarbonates. See, for example, U.S.
Patent No. 3,751,519 isffued August 7, 1973. However, prior art phenyl organopolysiloxane fluids have not been totally ~ati~-factory for polycarbonates as a result of their low solubility in the polycarbonate. Moreover, transparency ueually desired in polycarbonate products is usually lost when these prior art phenyl-containing organopoly~iloxane fluids are added thereto.
Accordingly, it i~ one object of this invention to provide a novel class of phenyl-containing organopolysiloxane fluids.
Another object of this invention is to provide novel phenyl-containing organopolysiloxanes which are easily prepared in an economic manner.
10~34519 Still another object of this invantion i~ to provide novel phenyl-containing organopolysiloxane fluids having a high phenyl content, whicht if desired, may be prepared in low viscosity form and which are charac~erized witn low volatility.
Still another object of this invention i8 to provide phenyl-containing organopolysiloxane fluids, u~eful as internal mold release additives and having high solubility in polycarbonates.
A still further object of this invention is to provide novel phenyl-containing fluids of varied utilities, including additives for plastics, high temperature grease components, mechanical fluids and the like.
A still further object of this invention is to provide polycarbonate co~positions comprising the novel phenyl organo-polysiloxane fluid~ of this invention, said polycarbonate compositions being characterized with transparency and internal mold release properties.
These zlnd other ob~ects are accomplished herein by providing phenyl--containing organopolysiloxane fluids char-acterized by the following basic structure, CH3 ,Ph ~ CH3 ~ ~ ,Ph (I) CH3 - Si - OSi _ o ~ Si - 0 ~ Si - 0 ~ R
J y\~ ~ :
wherein x and y are values ~ufficient to provide a phenyl content of from about 7 weight percnnt to about 80 weight per-cent, and where Ph is phenyl, and wherein R is selected from the group consisting of hydrogen and trimethylsilyl, i.e., ,H3 Bi - CH3 and mixtures thereof.
The novel phenyl-containing organopolysiloxane fluids characterized by Formula I hereinabove are made by the solvent - , hydroly~is of diphenyldichlorosilane and dimethyldichlorosilane.
In general, this solvent hydrolysis process involves preparing a blend of diphenyldichlorosilane, dimethyldichlorosilane, and a water-immiscible organic solvent.
` Suitable organic solvent~ are, for example, any water-immiscible organic solvent which i~ inert to the hydrolysis reactants during hydrolysis, and in which the hydrolyzate i~
soluble 80 as to provide for its separation. More specifically, suitable organic solvents include benzene, toluene, xylene, and the li~e; esters such as butyl acetate, ethyl acetate and the like; and ethers such as diethyl ether, dioxane and the like.
A preferred organic ~olvent i8 toluene. The amount of or~anic solvent employed may vary within a wide range and is generally within the range of ~rom about 10~ to about 50h by weight of the total weight of the blend of organohalo~ilanes, preferably about 25% by weight. - -~
For purpoces of this invention, the ratio of diphenyl-~hlorosilane to dimethylchlorosilane in the organohalosilane blend which is subjected to hydrolysis i~ from about 1.5 to 1 to about 4 to 1 by weight, re~pectively. Preerably, the ratio of diphenylchlorosilane to dimethylchlorosilane i8 about 3 to 1.
The afore-described mixture of organohalosilanes in organic solvent is admixed with and agitated in water which ha~
been preheated to from about 20 to about 85 C, preferably from about 60 to about 65 , the addition being carried out slowly over a period of, for example, from about 1 to about 2 hours, while maintaining a temperature of from about 60C to about 85C, preferably from about 75C to about 85 C. The resultant hydrolysis mixture i8 allowed to ~ettle and the ~ aqueous acid layer (bottom) is separated and discardea. The remaining organic layer is generally washed several times with, for example, 15%
?
., . -i~845~9 8SI-1594 sodium sulfate sOlution, until the HCl content is below about 10 parts per million. At this point, the water i9 azeotropically removed from the hydrolysis mixture at a temperature which should not exceed about 115 C~ The material remaining, hereinafter referred to as the hydrolyzate, i8 a mixture o linear siloxanes (chainstopped with diphenyl silanol unit~), cyclic polymers, and organic solvent.
The hydrolyzats is then saturated with anhydrous ammonia and trimethylchlorosilane is slowly added thereto. The trimethylchlorosilane act~ as a chain~topping agent and replaces the silanol groups with trimethylsiloxy chain-stopping units.
The amount of trimethylchlorosilane which is employed varies with the amount of hydroxyl group replacement desired. For purposes of tnis invention, the trimethylchlorosilane is employed in amounts from about 9.5 to 25.5 weight percsnt of the weight of the hydrolyzate. More specifically, for polycarbonate additive purposes, the amount of trimethylchlorsilane chain-stopping agent w ed ranges from about 11.4% to 19% by woight of the total weight of the hydrolyzate, providing a trimethyl-siloxy unit content for the fluid of from about 12 to about 21percent by weight. ~ fter agitating the mixture for about one hour, the mixture is washed with, for example, 15% sodium sulfate until essentially neutral and the aqueous bo~Dm layer is ~eparated and di~carded. The remaining organic layer i8 wa~hed with, for example, sodium sulfate, and the organic ~olvent and residual water is stripped under vacuum, e.g., 25 to 30 mm Hg. at about 150 C. The remaining phenyl-containing organopolysiloxane fluid is characterized by Formula I hereinabove, wherein x and y are 3~ values sufficient to provide a phenyl content of from about 40 to 80 weight percent and i8 especially well suited a~ an internal _ 5 _ : ' ., -. : ' 11)845~9 8SI--1594 mold release additive for polycarbonates since the fluid is highly soluble in polycarbonates and moreover retains the desired transparency of the polycarbonates. In general, x and y have a value of from about 3 to 10 for this purpose.
To obtain particularly high phenyl content, low volatile organopolysiloxane fluids within ths scope of the present invention, and which are particularly well suited as a base stock for all mechanical or hydraulic phenyl silicone fluids, the afore-described phenyl-containing organopoly-~iloxane fluid is totally chain~toppsd by employing a sufficient amount of trimethylchlorosilane to do the same. The substantially all trimethylsiloxy chainstopped fluid is then subjected to an equilibration process involving admixing the same with potassium hydroxide and heating toabout 180 C for about 1 to 2 hours.
If desired, additional trimethylsiloxy chainstopping units may be added during eguilibration. Strippi~g the mixture at about 250-300C under high vacuum (3-5 mm ~g.) results in a high phenol content, low volatile, organopolysiloxane fluid characterized by Formula I above wherein x is about 3 to 10 and y i8 about 3 to 10 and the phenyl content iB from about 40 to 80 weight percent.
To obtain phenyl-containing organopolysiloxane fluids within the scope of this invention and which are especially suitable a~ mechanical fluids and high temperature grease components the afore-described hydrolysis process for preparing the polycarbonate additive i~ continued by completely chain-stopping the fluid by the addition of a sufficient ~uantity of trimethylchlorosilane. The resultant mixture is equilibrated with potassium hydroxide at a temperature in the range of from about 180 C to 200C for about one hour. During equilibration octamethylcyclotetra~iloxane and trimethylsiloxy containing units provided, for example, by linear decamethyltetrasiloxane, 1~45~L9 are added in sufficient quantity to reduce the phenyl content to a desired amount, generally in the range of from about 38 to 48 weight percent, and to a desired viscosity, generally 100 to 200 centistokes at 25C. In the preferred method of equilibration, the octamethyltetracyclosiloxane and trimethyl-siloxy unit material are equilibrated first, then the phenyl-containing stock i~ added and the equilibration co~tinued for like about 3 hours.
The resultant equilibrate is ~tripped to about 280C
under very high vacuum, e.g., 3-5 mm ~g.
To obtain a fluid especially useful for transparent greases and controlled den3ity greases, the fluid identified hereinabove, as being particularly useful às an internal mold release agent for polycarbonate~, is further modified by the addition thereto of octamethylcyclotetrasiloxane (sufficient to lower the phenyl content to about 30 weight percent) and equilibrating and stripping the resultant mixture as de~cribed hereinabove.
It is clear to those skilled in the art that the phenyl-containing organopolysiloxanes of this invention as particularly characterized by Formula I hereinabove are particularly di~tinguished over the prior art phenyl-containing silicone fluids in that the present fluids comprise trimethylsikxy chainstopping units which are directly attached primarily to diphenylsilo~y units. This accounts for the advantageous solubility properties of the present fluids in polycarbonates, in addition to accounting for the other advantageous properties ~-herebefore described.
The polycarbonates which are contemplated herein in admixture with the above-identified internal mold relea~e phenyl-containing organopolysiloxane additives of this invention include those aromatic polycarbonates prepared by reacting a , 845:~L9 dihydric phenol and a carbonate precur~or. The reaction mixture can also include minor amounts of other additives or other amounts of other reactive monomeric constituents. It can also include copolymers of two or more different dihydric phenols.
Specifically, examples of dihydric phenols that can be empl~yed to prepare the polycarbonates eontemplated herein are bis(4-hydroxyphenyl)-methane, 2,2-bis(4-hydroxyphenyl-propane, 2,2-bis(4-hydroxy-3-methylphenyl)-propane, 4,4-bis-(4-hydroxyphenyl)-heptane, 2,2-bis(4-hydroxy, 3,5-dichloro-phenyl)-propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)-propane, ete.; dihydrie phenol ethers sueh as bis(4-hydroxyphenyl)-ether, bis(3,5-dichloro-4-hydroxyphenyl)-ether, etc.; dihydroxydiphenyls such as p,p'-dihydroxy-diphenyl, 3,3'-dichloro-4,4'-dihydroxy-diphenyl, etc.; dihydroxyaryl sulfones ~uch as bis(4-hydroxy-phenyl)-sulfone, bis(3,5-dimethyl-4-hydroxyphenyl)-sulfone, etc.;
dihydroxy benzenes, resorcinol, hydroquinones, halo and alkyl-substituted dihydroxy benzenes ~uch as 1,4-dihydroxy-2-ehloro-benzene, 1,4-dihydroxy-2,5-diehlorobenzene, 1,4-dihydroxy-3-methylbenzene, etc.; and dihydroxy diphenyl qulfoxides such as bis(4-hydroxyphenyl)-sulfoxide, bis(3,5-dibromo-4-hydroxyphenyl)-sulfoxide, ete. A variety of additional dihydric phenols are also available to provide earbonate polymers and are disclosed in U.S. Patents 2,999,835 issued September 12, 1961; 3,028,365 issued April 3, 1962 and 3,153,008 issued October 13, 1964. It i8, of course, possible to employ two or more different dihydric phenols or a copolymer of a dihydric phenol with glycol or with hydroxy or aeid terminated polyester, or with a diboric acid in the event a carbonate copolymer or interpolymer rather than a homopolymer is desired for use in the preparation of the aromatic earbonate polymers of this invention.
1~845~9 Among the carbonate precursors employed in the afore-described polycarbonate preparation are included phosgene, dibromo and diiodocarbonyls as well as the bishaloformates of dihydric phenols (e.g. bischloroformates of hydroquinone, bisphenol-A, etc.) or glycols (e.g., bischloroformates of ethylene glycol, neopentyl glycol, polyethylene glycol, etc.) A preferred aromatic polycarbonate within the scope of this invention is prepared from the reaction of phosgene and
2,2,bis(4-hydroxyphenyl)propane), commonly referred to as bisphenol A.
The preparation of the polycarbonate is generally carried out in the presence of an acid ac¢eptor which may be either an organic or an inorganic compound. A suitable organic acid acceptor is a tertiary amine and includes materials such as pyridine, triethylamine, dimethylaniline, tributylamine, etc.
The inorganic acid acceptor may be one which can ~ither be a hydroxide, a carbonate, a dicarbonate ox a phosphate of an alkali or alkaline earth metal.
Molecul,~r weight regulations may ~180 be smployed in the preparation of the polycarbonate, such as phenol, cyclohexanol, methanol, para-tertiary-butylphenol, parabromophenol. Para-tertiary-butylphenol is preferred.
The phenyl-containing organopolysiloxane fluids of this invention, as identified by Formula I hereinabove, can be readily mixed in any convenient manner with the aromatic polycarbonate.
Becau~e the phenyl-containing organopolysiloxane fluids of this invention are compatible with and highly soluble in the poly-carbonate material, thorough mixing is easily accomplished with no difficulty of separation. Thus, when preparing injection molded pellets, the polycarbonate and the siloxane can be either premixed or fed independently to the feed hopper of an extruder.
.
,: iQ84519 8SI-1594 Small amounts of the present phenyl-containing organopolysiloxanes achieve excellent results of mold release during the molding of the composition. The amount of siloxane U8ed i8 generally from about 0.01 to about 2.0 weight percent based on the weight of the polycarbonate, and preferably from about 0.1 to about 1.0 weight percent thereof. The desired polycarbonate transparency is not lost by the presence of the present phenyl-containing organopolysiloxane.
In order that those skilled in the art may better understand how to practice the present invention, the following examples are given by way of illustration and not by way of limitation.
_ ~J EXamDle 1 ~
This example illustrates the preparation of a phenyl-containing organopolysiloxane fluid within the scope of Formula I of this invention e~pecially well suited as an internal mold release agent for aromatic polycarbonates.
There are blended in a vessel 57~7 parts by weight diphenyldichloro~Llane, 19.2 parts by weight di~ethyldichloro-silane and 23.1 parts by weight toluene. Water in an amountwhich i8 about 1-1/2 timos the total weight of the organo-halosilane weight is heated to about 60 C to 61 C in a separate ve~el. The blend of organohalosilane~ and toluene is slowly added to the water over a period of about 1-1/2 hours with agitation and maintaining the temperature at about 75-85 C.
The hydrolysis mixture is stirred for an additional 1/2 hour after the addition is complete. The bottom aqueous acid laysr is separated and discarded. The organic layer i8 washed two times with 15% sodium sulfate and checked for HCl acid content which sho~d be belo~ 10 parts per million water. The water i8 azeotropically removed at a temperature which does not exceed 115C. To the remaining hydrolyzate is added sufficient anhydrous ammonia to saturate the hydrolyzate and 12.7 partæ by weight trimethylchlorosilane, in that order. Care is taken not to lose any ammonia. The mixture i~ stirred for about one hour at 55 C and then washed with water to remove ammonium chloride.
The aqueous acid bottom layer is separated and discarded. The organic layer i~ washed with 15% sodium sulfate, until e~sentially neutral and the re~idual water and toluene is stripped at about 150 C under a vacuum of about 25-30 mm Hg. The remain-ing phenyl-containing organopolysiloxane is characterized by the structure of Formula I hereinabove and has a phenyl content of 68.85% by weight and the trimethylsiloxy content is 16% by weight. This material i8 extremely well suited as a poly-carbonate internal mold release agent.
Example 2 Thi~ example illustrates the preparation of a phenyl-containing organopolysiloxane fluid within the scope of Formula j I hereinabove which i~ particularly well suited as a component for high temperature and as a mechanical fluid.
To 56.65 parts by weight of the phenyl-containing organopoly~iloxane fluid prepared in Example 1 i~ added about 1.6 parts by weight of decamethyltrisiloxane chainstopper and 41.8 parts by weight octatetramethylcyclosiloxane. 600 parts per million of potassium hydroxide pellets are added to the reaction vessel and the resultant admixture i8 equilibrated at 180 C for about three hours. The reaction mixture is stripped up to about 280 at high vacuum, e.g., 3 to 5 mm ~g.
The remaining phenyl-containing organopolysiloxane fluid is characterized by Formula I hereinabove and has a phenyl content of 39 percent by weight and a trimethylsiloxy content of 18 percent by weight.
- .
i ~
Example 3 This example illustrates the preparation of a phenyl-containing organopolysiloxane flui~ within the scope of Formula I hereinabove which is particularly well suited as a transparent grease component.
To 42.4 parts of the phenyl-containing fluid prepared in Example 1 i8 added 57.6 parts of octamethylcyclotetra- -siloxane and 600 parts per million of potassium hydroxide ; pellets. The mixture is eguilibrated by heating to 180C for two hours and the refractive index is adjusted by increasing or decreasing the amount of phenyl content by adding octamethyl-l cyclotetrasiloxane or the phenyl containing fluid. When the .1 desired refracti,ve index is achieved, the mixture is cooled to 40C, Fuller's earth is added and the resultant mixture is filtered through Celite~545 (diatomaceous earth sold by Johns-1 Manville). The mixture is stripped of~ at a temperature of i~! about 250 C under high vacuum conditions, e.g., 3 mm Hg., leaving the desired transparent grease component which is characterized by Formula I h~reinabove and has a 30 weight per-cent content.
This example illustrates the preparation of a phenyl-containing organopolysiloxane within the scope of Formula I
hereinabove which is characterized with low volatility and high phenyl content.
The same procedure as in Example 1 is followed except that 9 parts by weight of trimethylchlorsilane is added to the hydrolyzate in order to completely chain4top and replace substantlally all the silanol units with trimethylsiloxy units.
The totally chainstopped material i8 then equilibrated with potassium hydroxide and stripped such as is done in Example 1.
The resultant material has a phenyl content of-65 weight percent 11~845~L~
and demonstrates only an 8% weight loss after being heated at 250 for 24 hours.
Example 5 This example illustrates the preparation of a poly-carbonate composition within the scope of this invention.
To 99 part~ by weight of a polycarbonate prepared by reacting essentially equimoles of bisphenol A, i.e., (2,2-bis-(4-hydroxyphenyl)propane) and phosgene in the presence of an acid acceptor and a cat~lyst, which polycarbonate has an intrinsic viscosity of about 0.50, iB added 1 part by weight of the phenyl-containing organopolysiloxane of Example 1. The mixture is fed to an extruder and pelletized. The pellets are thon injection molded into discs of about 3 inches in diameter and about 1/8 inch thick. The molded disc is easily released from the mold without sticking and the molded piece is transparent.
Obviously, other modifications and variations of the present invention are possible in light of the above teachings.
It i8 therefore t~D be understood that changes may be made in the particular embodiments of this invention which are within the full intended scope of the invention as defined by the appended claim~.
'
The preparation of the polycarbonate is generally carried out in the presence of an acid ac¢eptor which may be either an organic or an inorganic compound. A suitable organic acid acceptor is a tertiary amine and includes materials such as pyridine, triethylamine, dimethylaniline, tributylamine, etc.
The inorganic acid acceptor may be one which can ~ither be a hydroxide, a carbonate, a dicarbonate ox a phosphate of an alkali or alkaline earth metal.
Molecul,~r weight regulations may ~180 be smployed in the preparation of the polycarbonate, such as phenol, cyclohexanol, methanol, para-tertiary-butylphenol, parabromophenol. Para-tertiary-butylphenol is preferred.
The phenyl-containing organopolysiloxane fluids of this invention, as identified by Formula I hereinabove, can be readily mixed in any convenient manner with the aromatic polycarbonate.
Becau~e the phenyl-containing organopolysiloxane fluids of this invention are compatible with and highly soluble in the poly-carbonate material, thorough mixing is easily accomplished with no difficulty of separation. Thus, when preparing injection molded pellets, the polycarbonate and the siloxane can be either premixed or fed independently to the feed hopper of an extruder.
.
,: iQ84519 8SI-1594 Small amounts of the present phenyl-containing organopolysiloxanes achieve excellent results of mold release during the molding of the composition. The amount of siloxane U8ed i8 generally from about 0.01 to about 2.0 weight percent based on the weight of the polycarbonate, and preferably from about 0.1 to about 1.0 weight percent thereof. The desired polycarbonate transparency is not lost by the presence of the present phenyl-containing organopolysiloxane.
In order that those skilled in the art may better understand how to practice the present invention, the following examples are given by way of illustration and not by way of limitation.
_ ~J EXamDle 1 ~
This example illustrates the preparation of a phenyl-containing organopolysiloxane fluid within the scope of Formula I of this invention e~pecially well suited as an internal mold release agent for aromatic polycarbonates.
There are blended in a vessel 57~7 parts by weight diphenyldichloro~Llane, 19.2 parts by weight di~ethyldichloro-silane and 23.1 parts by weight toluene. Water in an amountwhich i8 about 1-1/2 timos the total weight of the organo-halosilane weight is heated to about 60 C to 61 C in a separate ve~el. The blend of organohalosilane~ and toluene is slowly added to the water over a period of about 1-1/2 hours with agitation and maintaining the temperature at about 75-85 C.
The hydrolysis mixture is stirred for an additional 1/2 hour after the addition is complete. The bottom aqueous acid laysr is separated and discarded. The organic layer i8 washed two times with 15% sodium sulfate and checked for HCl acid content which sho~d be belo~ 10 parts per million water. The water i8 azeotropically removed at a temperature which does not exceed 115C. To the remaining hydrolyzate is added sufficient anhydrous ammonia to saturate the hydrolyzate and 12.7 partæ by weight trimethylchlorosilane, in that order. Care is taken not to lose any ammonia. The mixture i~ stirred for about one hour at 55 C and then washed with water to remove ammonium chloride.
The aqueous acid bottom layer is separated and discarded. The organic layer i~ washed with 15% sodium sulfate, until e~sentially neutral and the re~idual water and toluene is stripped at about 150 C under a vacuum of about 25-30 mm Hg. The remain-ing phenyl-containing organopolysiloxane is characterized by the structure of Formula I hereinabove and has a phenyl content of 68.85% by weight and the trimethylsiloxy content is 16% by weight. This material i8 extremely well suited as a poly-carbonate internal mold release agent.
Example 2 Thi~ example illustrates the preparation of a phenyl-containing organopolysiloxane fluid within the scope of Formula j I hereinabove which i~ particularly well suited as a component for high temperature and as a mechanical fluid.
To 56.65 parts by weight of the phenyl-containing organopoly~iloxane fluid prepared in Example 1 i~ added about 1.6 parts by weight of decamethyltrisiloxane chainstopper and 41.8 parts by weight octatetramethylcyclosiloxane. 600 parts per million of potassium hydroxide pellets are added to the reaction vessel and the resultant admixture i8 equilibrated at 180 C for about three hours. The reaction mixture is stripped up to about 280 at high vacuum, e.g., 3 to 5 mm ~g.
The remaining phenyl-containing organopolysiloxane fluid is characterized by Formula I hereinabove and has a phenyl content of 39 percent by weight and a trimethylsiloxy content of 18 percent by weight.
- .
i ~
Example 3 This example illustrates the preparation of a phenyl-containing organopolysiloxane flui~ within the scope of Formula I hereinabove which is particularly well suited as a transparent grease component.
To 42.4 parts of the phenyl-containing fluid prepared in Example 1 i8 added 57.6 parts of octamethylcyclotetra- -siloxane and 600 parts per million of potassium hydroxide ; pellets. The mixture is eguilibrated by heating to 180C for two hours and the refractive index is adjusted by increasing or decreasing the amount of phenyl content by adding octamethyl-l cyclotetrasiloxane or the phenyl containing fluid. When the .1 desired refracti,ve index is achieved, the mixture is cooled to 40C, Fuller's earth is added and the resultant mixture is filtered through Celite~545 (diatomaceous earth sold by Johns-1 Manville). The mixture is stripped of~ at a temperature of i~! about 250 C under high vacuum conditions, e.g., 3 mm Hg., leaving the desired transparent grease component which is characterized by Formula I h~reinabove and has a 30 weight per-cent content.
This example illustrates the preparation of a phenyl-containing organopolysiloxane within the scope of Formula I
hereinabove which is characterized with low volatility and high phenyl content.
The same procedure as in Example 1 is followed except that 9 parts by weight of trimethylchlorsilane is added to the hydrolyzate in order to completely chain4top and replace substantlally all the silanol units with trimethylsiloxy units.
The totally chainstopped material i8 then equilibrated with potassium hydroxide and stripped such as is done in Example 1.
The resultant material has a phenyl content of-65 weight percent 11~845~L~
and demonstrates only an 8% weight loss after being heated at 250 for 24 hours.
Example 5 This example illustrates the preparation of a poly-carbonate composition within the scope of this invention.
To 99 part~ by weight of a polycarbonate prepared by reacting essentially equimoles of bisphenol A, i.e., (2,2-bis-(4-hydroxyphenyl)propane) and phosgene in the presence of an acid acceptor and a cat~lyst, which polycarbonate has an intrinsic viscosity of about 0.50, iB added 1 part by weight of the phenyl-containing organopolysiloxane of Example 1. The mixture is fed to an extruder and pelletized. The pellets are thon injection molded into discs of about 3 inches in diameter and about 1/8 inch thick. The molded disc is easily released from the mold without sticking and the molded piece is transparent.
Obviously, other modifications and variations of the present invention are possible in light of the above teachings.
It i8 therefore t~D be understood that changes may be made in the particular embodiments of this invention which are within the full intended scope of the invention as defined by the appended claim~.
'
Claims (9)
1. A phenyl-containing organopolysiloxane fluid characterized by the general formula:
wherein ph is phenyl, R is selected from the group consisting of hydrogen, trimethylsilyl and mixtures thereof, and wherein x and y have a combined value sufficient to provide a phenyl content of from about 7 weight percent to about 80 weight percent.
wherein ph is phenyl, R is selected from the group consisting of hydrogen, trimethylsilyl and mixtures thereof, and wherein x and y have a combined value sufficient to provide a phenyl content of from about 7 weight percent to about 80 weight percent.
2. The phenyl-containing organopolysiloxane fluid characterized by the general formula of claim 1, wherein x and y have a combined value sufficient to provide a phenyl content of from about 40 weight percent to about 80 weight percent and R is a mixture of hydrogen and trimethylsilyl sufficient to provide the fluid with a trimethylsiloxy content of from about 12 to 21 percent by weight.
3. The phenyl-containing organopolysiloxane fluid characterized by the general formula of Claim 1, wherein x and y have a combined value sufficient to provide a phenyl content of from about 40 weight percent to about 80 weight percent and R
is substantially all trimethylsilyl.
is substantially all trimethylsilyl.
4. The phenyl-containing organopolysiloxane fluid characterized by the general formula of Claim 1, wherein x and y have a combined value sufficient to provide a phenyl content of from about 38 weight percent to about 48 weight percent and having a viscosity of from about 100 to 200 centistokes at 25°c.
5. The phenyl-containing organopolysiloxane fluid characterized by the general formula of Claim 1, wherein x and y have a combined value sufficient to provide a phenyl content of about 68 percent by weight and further characterized by a trimethylsiloxy content of about 16% by weight.
6. A polycarbonate composition comprising an aromatic polycarbonate and in admixture therewith in a quantity sufficient to provide a suitable mold release characteristic the phenyl-containing organopolysiloxane defined in Claim 1, wherein x and y have a combined value sufficient to provide a phenyl content of from about 40 to about 80 percent by weight, and R is a mixture hydrogen and trimethylsilyl sufficient to provide the fluid with a trimethylsiloxy content of from about 12 to 21 percent by weight.
7. A polycarbonate composition according to Claim 6 wherein the phenyl containing organopolysiloxane is present in an amount of from about 0.01 to about 2.0 percent by weight based on the weight of the polycarbonate.
8. A polycarbonate composition according to Claim 6 wherein the aromatic polycarbonate is the reaction product of phosgene and 2,2-bis(4-hydroxyphenyl)propane.
9. A polycarbonate composition according to Claim 8 wherein the phenyl containing organopolysiloxane has a phenyl content of about 68 percent by weight and a trimethylsiloxy content of about 16 percent by weight.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US50600774A | 1974-09-16 | 1974-09-16 | |
| US506,007 | 1974-09-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1084519A true CA1084519A (en) | 1980-08-26 |
Family
ID=24012775
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA233,187A Expired CA1084519A (en) | 1974-09-16 | 1975-08-07 | Phenyl-containing organopolysiloxanes |
Country Status (6)
| Country | Link |
|---|---|
| JP (2) | JPS604213B2 (en) |
| CA (1) | CA1084519A (en) |
| DE (1) | DE2539569A1 (en) |
| FR (1) | FR2284630A1 (en) |
| GB (1) | GB1513310A (en) |
| NL (1) | NL7510804A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6216809Y2 (en) * | 1979-06-28 | 1987-04-28 | ||
| US4289859A (en) * | 1980-06-02 | 1981-09-15 | Dow Corning Corporation | Non-bleeding transparent silicone additives for plastics |
| JPH0733474B2 (en) * | 1988-03-29 | 1995-04-12 | 出光石油化学株式会社 | Polycarbonate resin composition |
| CN100506914C (en) * | 2007-04-09 | 2009-07-01 | 杭州师范学院 | Smoke-inhibition type halogen-free flame-proof polycarbonate |
| CN103304818B (en) * | 2013-06-26 | 2015-09-02 | 江苏大学 | A kind of preparation method of methyl phenyl silicone oil |
-
1975
- 1975-08-07 CA CA233,187A patent/CA1084519A/en not_active Expired
- 1975-08-07 GB GB32986/75A patent/GB1513310A/en not_active Expired
- 1975-09-05 DE DE19752539569 patent/DE2539569A1/en not_active Withdrawn
- 1975-09-12 NL NL7510804A patent/NL7510804A/en not_active Application Discontinuation
- 1975-09-15 FR FR7528201A patent/FR2284630A1/en active Granted
- 1975-09-16 JP JP50111018A patent/JPS604213B2/en not_active Expired
-
1981
- 1981-10-02 JP JP56157384A patent/JPS5939449B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2284630A1 (en) | 1976-04-09 |
| JPS604213B2 (en) | 1985-02-02 |
| FR2284630B1 (en) | 1981-12-31 |
| JPS5155399A (en) | 1976-05-15 |
| JPS5939449B2 (en) | 1984-09-22 |
| JPS5794020A (en) | 1982-06-11 |
| DE2539569A1 (en) | 1976-04-01 |
| NL7510804A (en) | 1976-03-18 |
| GB1513310A (en) | 1978-06-07 |
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