CA1053826A - Nitrile-pvc blends - Google Patents
Nitrile-pvc blendsInfo
- Publication number
- CA1053826A CA1053826A CA232,795A CA232795A CA1053826A CA 1053826 A CA1053826 A CA 1053826A CA 232795 A CA232795 A CA 232795A CA 1053826 A CA1053826 A CA 1053826A
- Authority
- CA
- Canada
- Prior art keywords
- parts
- weight
- nitrile rubber
- modified nitrile
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—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 a halogen; Compositions of derivatives of such polymers
- C08L27/02—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Blends of polyvinyl chloride and modified nitrile rubber are provided which have superior physical properties to similar blends of polyvinyl chloried and normal nitrile rubber.
The modified nitrile rubber contain small amounts of tertiary amine groups, which may be incorporated by copolymerizing with the conjugated diolefin and unsaturated nitrile monomer a tertiary amine group containing monomer such as dimethylaminoethyl methacrylate. The blends can range from rigid or flexible uncured blends, of good impact strength, to rubber compositions of improved green strength, vulcanizable to yield vulcanizates of enhanced physical and abrasion properties. The rigid blends may be used in containers or pipes and the rubbery blends may be used in wire and cable jackets, hose covers and molded goods.
Blends of polyvinyl chloride and modified nitrile rubber are provided which have superior physical properties to similar blends of polyvinyl chloried and normal nitrile rubber.
The modified nitrile rubber contain small amounts of tertiary amine groups, which may be incorporated by copolymerizing with the conjugated diolefin and unsaturated nitrile monomer a tertiary amine group containing monomer such as dimethylaminoethyl methacrylate. The blends can range from rigid or flexible uncured blends, of good impact strength, to rubber compositions of improved green strength, vulcanizable to yield vulcanizates of enhanced physical and abrasion properties. The rigid blends may be used in containers or pipes and the rubbery blends may be used in wire and cable jackets, hose covers and molded goods.
Description
~(~538;~6 .
This invention relates to rubber and plastic compositions, of the type comprising blends of vinyl chloride polymers and an oil resistant nitrile rubber, for example a butadiene-acrylonitrile copolymer rubber.
Blends of nitrile rubbers and polyvinyl chloride are known, and have achieved fairly widespread commercial use.
Such blends can vary in properties from rigid plastics in which the polyvinyl chloride constitutes a large major proportion (85-95~ by weight of the blend) to rubbery material in which the nitrile rubber constitutes the major proportion (80-90% by weight) of the blend. The rigid plastic polyvinyl chloride-nitrile rubber blends comprise impact resistant plastic materials, ~ith the nitrile rubber constituting an impact modifier. Flexible plastic polyvinyl chloride-nitrile rubber blends are also known in which the nitrile rubber acts as a plasticizer. Such compositions are not generally cured.
The rubbery polyvinyl chloride-nitrile rubber blends are normally compounded and may be used as such, but they are generally vulcanized with conventional sulfur or peroxide vulcanizing systems, and the vulcanizates exhibit good storage and colour stability, good ozone and weather resistance, good oil resistance, heat resistance and abrasion resistance. They \ are thus used in wire and cable jackets, footwear, ho~e covers, printing roll covers and general moldings. They are generally prepared by dry mixing of the polymeric ingredients, along with other compounding ingredients, plasticizers and curatives as desired, at elevated temperatures~ for a time long enough and at a temperature high enough to ensure fluxing of the polyvinyl chloride and intimate mixing of the ingredients.
Alternatively the polyvinyl chloride and nitrile rubber may be latex blended. Then the blends are molded to the desired . :. .: . .... . . . . , ... : .. - :
- - -1~538~6 ~shape of the finished article and heated to vulcanize them.
In common with most other rubber compounds, such rubbery blends of nitrile rubber and polyvinyl chloride generally develop their desirable physical properties only upon vulcanization, and the vulcanizates are not sufficiently thermoplastic to allow satisfactory re-molding. As a consequence, rubber goods cannot satisfactorily be recycled and reshaped, and scraps of compounds trimmed from vulcanized rubber articles on manufacture are not reusable in high grade rubber articles.
Whilst the nitrile rubber-polyvinyl chloride blends are more thermoplastic than many rubber materials, on account of the thermoplastic nature of the polyvinyl chloride component, vulcanized scraps of these compositions are still not conveniently reusable.
The present invention provides blends of vinyl chloride polymers and modified nitrile rubbers which exhibit unusual properties. The rubbery compositions of the invention have a high degree of thermoplasticity along with good physical pro-perties without conventional vulcanization. The blends appear to contain chemical cross-links between the polymer molecules of the constituents of the blends which are labile in nature, being broken when the blends are subjected to shearing action or possibly heat, but subsequently being reformed. The rubbery blends have good physical properties without vulcanization, i.e. in the green state, whilst at the same timé exhibiting thermoplasticity, i.e. the ability to flow when heated, but solidify and re-develop their good physical properties on subsequent cooling. These properties and behaviou$ of the blends are consistent with the presence of labile chemical cross-links.
Thus according to the present invention, there is provided a polymer composition comprising from about 10 to ~5;~6 about 95 parts by weight of at least one vinyl chloride polymer and from about 90 to about 5 parts by weight of modified nitrile rubber, the modified nitrile rubber comprising an interpolymer of from about 80 to about 50 parts by weight of at least one polymerized conjugated diolefinic hydrocarbon having from 4 to 6 carbon atoms per molecule and from about 20 to about 50 parts by weight of at least one polymerized ethylenically unsaturated nitrile monomer, and containing from about 1.5 millimoles to about 30 millimoles per 100 grams of interpolymer of bound tertiary amine groups in the polymer molecule.
The bound tertiary amine groups are conveniently introduced into the modified nitrile rubber by copolymerizing with the conjugated diolefinic hydrocarbon and the ethylenically unsatu~ated nitrile a small amount of a copolymerizable monomer having tertiary amine groups in the molecule, which amine groups are substantially unaf~ected by the polymerization so that the modified nitrile rubber is an interpolymer of at least three monomers.
By the term "vinyl chloride polymers" as used herein, there is meant high molecular weight thermoplastic polymers or copolymers containing at least 75~ by weight of polymerized vinyl chloride. It thus includes copolymers of vinyl chloride with a monomer selected from vinyl acetate, propylene, vinylidene chloride and acrylic esters~ The most preferred vinyl chloride polymer is polyvinyl chloride, and so the invention will be further described with respect to polyvinyl chloride.
It appears that the tertiary amine groups in the nitrile rubber polymer chains react with some of the chlorine groups attached to the polyvinyl chloride chains, so as to form in the blend the aforementioned labile cross-links.
- ; .:. . ... : . - . . . -. . . ..
~053S~
This is surprising, since it has previously been considered that the chlorine groups present in polyvinyl chloride are chemically unreactive.
In the rigid or flexible uncured plastic blends according to the present inve~tion, where the polyvinyl chloride constitutes from about 65 to about 95 parts by weight and the modified nitrile rubber constitutes from about 35 to about 5 parts by weight of the blend, the chemical bonding apparently achieved between the modified nitrile rubber and the polyvinyl chloride serves to resist the tendency of the rubber to be removed from the blend. Thus the desirable impact resistant and plasticized properties of the blend according to the invent-ion are retained over extended periodsof time. Further, the impact modifier (modified nitrile rubber) is much less extractable from the blend by solvents, as compared with conventional nitrile rubber containing rigid polyvinyl chloride-nitrile rubber compositions, on account of these chemical bonds. This renders the rigid blends according to ~he present invention particularly useful in plastic containers or pipes, etc., for storing or transporting materials which are solvents for the nitrile rubber.
In the rubbery compositions of the invention wherein the polyvinyl chloride constitutes from about 10 to about ~5 parts by weic3ht and the modified nitrile rubber constitutes about 90 to about 35 parts by weight of the blend, the labile cross-links apparently formed between the polyvinyl chloride and the tertiary amine groups of the nitrile rubber cause the composition to exhibit thermoplastic and rubbery properties without vulcanization. In some instances, the resulting compositions can be used as such, but they may if desired subsequently be vulcanized, e.g. with sulfur or peroxide systems, .
10~;~82G
to ~btain novel vulcanizates. Since the formation of the labile cross-links as previously discussed does not utilize the carbon-to-carbon unsaturation of nitrile rubber in the composition to any significant extent, th~ compositions remain sulfur and peroxide vulcanizable in the same manner as previously known polyvinyl chloride-nitrile rubber compositions. Whether or not the compositions of the invention should be vulcanized depends to a large extent upon the use to which the compositions will eventually be put. Sulfur vulcanizates according to the present invention have enhanced physical and abrasion properties, as compared with sulfur vulcanizates of comparable polyvinyl chloride-nitrile rubber blends of the prior art. Vulcanization results in reduced thermoplasticity.
The modified nitrile rubbers used in compositions of the present invention are inter-polymers of a C4-C6 conjugated diolefinic hydrocarbon, and a C3-C5 ethylenically unsaturated nitrile group containing monomer, the interpolymer having from about 1.5 millimoles to about 30 millimoles per 100 grams of interpolymer of bound tertiary amine groups in the polymer molecule, the amine groups preferably being derived from polymerization of a tertiary amine group containing monomer with the diolefinic hydrocarbon and the nitrile monomer.
Preferred among such diolefins are butadiene, isoprene and hexadiene, with butadiene being the most preferred. The ethylenically unsaturated nitrile monomer is preferably acrylonitrile or methacrylonitrile or a similar polymerizable C2-C4 alkyl substituted acrylic acid nitrile derivative. Most preferred is acrylonitrile.
The preferred interpolymer is one comprising from but~ ne D about 50 to about 80 parts by weight of }~T~ke+~-1,3 and from about 20 to about 50 parts by weight of acrylonitrile, most ~IL0~38;~
preferred being those comprising from about 60 to about 75 parts by weight of butadiene-l r 3 and from about 25 to about 40 parts by weight of acrylonitrile.
Prefexably, the tertiary amine group containing monomer used to incorporate tertiary amine groups in the modified nitrile rubber is one which copolymerizes readily with butadiene and acrylonitrile in a conventional emulsion poly-merization system, and which has a copolymerization reàctivity similar to that of the copolymerizing monomers. With such a preferred monomer, a copolymer is obtained with tertiary amine groups distributed along and amongst the polymer chains.
~ xamples of class of suitable monomers are acrylates and methacrylates of general formula:
R O ~ 3 H C = C - C - O(X)N
where R represents H or CH3, and X represents an aliphatic hydrocarbon group of 2-4 carbon atoms. Specific preferred mem- -bers of this class are dimethylaminoethyl acrylate, dimethyl-aminoethyl methacrylate and dimethylaminobutyl methacrylate.
The most preferred such monomer is dimethylaminoethyl methacrylate, which is copolymerized with the other monomer in ~ a Cry~
amounts to provide a bound dimethylaminoethyl mcthy~o~ e content in the terpolymer of from about 0.25 wt.% to about 4.3 wt.%, which corresponds to about 1.5 to about 30 millimoles of tertiary amine groups per 100 g. of terpolymer. The preferred range of bound dimethylaminoethyl methacrylate content in the terpolymer is from about 0.5 to about 4.0 wt.%, corresponding to a tertiary amine group content of from about 3.5 to about ~053826 28 millimoles per 100 g. of terpolymer~
The blends of the present invention may be mixed with other compounds and ingredients, in accordance with known comparable blends of the prior art. Thus in the case of rigid blends of the invention, they may include suitable stabili-zers for the vinyl chloride polymers, in amounts of up to about 10% by weight of the blend. The rigid blends may also include lubricants (internal and external) to assis~ in fabri-cation, anti-static agents, and fillers or pigments such as carbon black, calcium carbonate or clay.
With the flexible or rubbery blends of the present `-invention, there may if desired be included at least one plasticizer for the polyvinyl chloride of the conventional type, such as phthalates (dioctyl phthalate, diisooctyl phthalate, dinonyl phthala~te, di-2-ethylhexyl phthalate, for example);
phosphates (e.g. tritolyl phosphate or trixylyl phosphate);
esters of aliphatic dibasic acids (e.g. sebacates, azelates or adipates); polyesters; chlorinated paraffins and mixtures of two or more of these types. In addition, the flexible blends of the present invention may include stabilizers and antioxidants for the polyvinyl chloride and the nitrile rubber, and in some instances for the plasticizer also. Plasticizers may be used in amounts of from about 2 to about 20 parts by weight per 100 parts per weight of polyvinyl chloride~ Fillers such as carbon blacks, silica, calcium carbonate, clays etc.
may be used in amounts from about 25 to about 150 parts by weight, per 100 parts by weight combined polyvinyl chloride and modified nitrile rubber. ~ther polymers may also be included, to modify the properties of the final composition.
- - . ~ , . ~ ~ . . . .
-1053~3~6 The mixing procedures for preparing the compositions of the present invention are generally in accordance with known procedures for making comparable compositions of the prior art. Polyvinyl chloride is commonly prepared by an emul-sion polymerization system, and may be mixed in latex form with the latex of the modified nitrile rubber. In the alternative, the polymers and other ingredients can be dry-mixed at elevated temperatures, e.g. on a mill or in a Banbury mixer. The tem-perature of mixing should be high enough to ensure fluxirlg of the polyvinyl chloride~ The time of mixing should be longenough!to ensure intimate admixing of the ingredients into a substantially homogeneous compound.
When, in the case of a rubbery composition according to the invention, the composition is to be vulcanized, this is best undertaken as a subsequent step following the compound-ing described above. Suitable curing recipes are those well known in the art for this type of compound, and may be based upon sulfur curatives or peroxide curatives. Normally, curing takes place in a press at elevated temperatures, the curing recipe including suitable accelerators, etc.
The compositions of the present invention can be fabricated in accordance with techniques known in the prior art for comparable compositions. Both the flexible and the rigid compounds can be extruded into a variety of shapes, inclu-ding profiles, tubes and sheets. By the use of crosshead dies they can be extruded as wire sheathing. They can be processed from either a powder blend or granulated material. Specific applications for the compositions of the present invention include wire and cable insulation, footwear, hoses, molded goods ~053826 and printing rollers.
The present invention is further described in the following specific examples. In all cases unless otherwise specified r amounts are reported in parts by weight.
A modified nitrile rubber, namely a terpolymer of butadiene, acrylonitrile and dimethylaminoethylmethacrylate was blended with polyvinyl ch]Loride to yield a ru~bery com-position. Physical properties of the resulting compounds, both initial and after remolding, were tested. A similar com-pound was prepared using polyvinyl chloride and a copolymer of butadiene and acrylonitrile, for control purposes. The ter-polymer had a Mooney viscosity (ML-4 at 100C? of 29, and had a bound butadiene content of 33 wt.%, and a bound dimethyi-aminoethyl methacrylate content of 4 wt.%. The polyvinyl chloride used was that available commercially under the designation OPALON 630*. The nitrile rubber copolymer used in the control compound was that available commercially under the designation KRYNAC 34.50*.
The compounds were prepared by mixing on a micromill.
Duplicate mixes of each compound were prepared. Antioxidant and stabilizer were added to the rubber on the mill at room temperature, followed by the polyvinyl chloride. The mill was then heated to 175C and the compound milled until the poly-vinyl chloride melted and was fluxed. Samples were then pre-pared for stress-strain testing, ~y molding for five minutes at 175C after a two minute preheat. The remainder of each compound was formed into a sheet, which was cooled, cut-up and then re-molded at 1i5C into samples for testing. Stress-strain *Trade Marks ,'- - - . : ~ : .'.
.. - - , .
10538~6 properties (at room temperature) were measured on the original-ly molded samples and on the remolded samples which had been stored for 7 days at room temperature and further remolded samples were used to determine the stress-strain properties at elevated temperatures. The tests on the remolded samples indicate the thermoplastic nature of the compounds, i.e. the ability of the compounds to r~ecover their physical properties after heating, molding and coolingO
- The compound details and results of stress-strain testing of the original compounds and remolded compounds at room temperature are given in Table 1. The tests were conducted according to standard ASTM procedur~es except for the elevated temperature stress-strain where the ASTM procedure was followed except that the sample being tested was enclosed in an oven at the temperature~ specified.
105;~8~6 Compound No.~- _ __ __ ~erpolymer 6 6 _ Bd-AcN copolymer __ Polyvinylchloride 4 . _ .
This invention relates to rubber and plastic compositions, of the type comprising blends of vinyl chloride polymers and an oil resistant nitrile rubber, for example a butadiene-acrylonitrile copolymer rubber.
Blends of nitrile rubbers and polyvinyl chloride are known, and have achieved fairly widespread commercial use.
Such blends can vary in properties from rigid plastics in which the polyvinyl chloride constitutes a large major proportion (85-95~ by weight of the blend) to rubbery material in which the nitrile rubber constitutes the major proportion (80-90% by weight) of the blend. The rigid plastic polyvinyl chloride-nitrile rubber blends comprise impact resistant plastic materials, ~ith the nitrile rubber constituting an impact modifier. Flexible plastic polyvinyl chloride-nitrile rubber blends are also known in which the nitrile rubber acts as a plasticizer. Such compositions are not generally cured.
The rubbery polyvinyl chloride-nitrile rubber blends are normally compounded and may be used as such, but they are generally vulcanized with conventional sulfur or peroxide vulcanizing systems, and the vulcanizates exhibit good storage and colour stability, good ozone and weather resistance, good oil resistance, heat resistance and abrasion resistance. They \ are thus used in wire and cable jackets, footwear, ho~e covers, printing roll covers and general moldings. They are generally prepared by dry mixing of the polymeric ingredients, along with other compounding ingredients, plasticizers and curatives as desired, at elevated temperatures~ for a time long enough and at a temperature high enough to ensure fluxing of the polyvinyl chloride and intimate mixing of the ingredients.
Alternatively the polyvinyl chloride and nitrile rubber may be latex blended. Then the blends are molded to the desired . :. .: . .... . . . . , ... : .. - :
- - -1~538~6 ~shape of the finished article and heated to vulcanize them.
In common with most other rubber compounds, such rubbery blends of nitrile rubber and polyvinyl chloride generally develop their desirable physical properties only upon vulcanization, and the vulcanizates are not sufficiently thermoplastic to allow satisfactory re-molding. As a consequence, rubber goods cannot satisfactorily be recycled and reshaped, and scraps of compounds trimmed from vulcanized rubber articles on manufacture are not reusable in high grade rubber articles.
Whilst the nitrile rubber-polyvinyl chloride blends are more thermoplastic than many rubber materials, on account of the thermoplastic nature of the polyvinyl chloride component, vulcanized scraps of these compositions are still not conveniently reusable.
The present invention provides blends of vinyl chloride polymers and modified nitrile rubbers which exhibit unusual properties. The rubbery compositions of the invention have a high degree of thermoplasticity along with good physical pro-perties without conventional vulcanization. The blends appear to contain chemical cross-links between the polymer molecules of the constituents of the blends which are labile in nature, being broken when the blends are subjected to shearing action or possibly heat, but subsequently being reformed. The rubbery blends have good physical properties without vulcanization, i.e. in the green state, whilst at the same timé exhibiting thermoplasticity, i.e. the ability to flow when heated, but solidify and re-develop their good physical properties on subsequent cooling. These properties and behaviou$ of the blends are consistent with the presence of labile chemical cross-links.
Thus according to the present invention, there is provided a polymer composition comprising from about 10 to ~5;~6 about 95 parts by weight of at least one vinyl chloride polymer and from about 90 to about 5 parts by weight of modified nitrile rubber, the modified nitrile rubber comprising an interpolymer of from about 80 to about 50 parts by weight of at least one polymerized conjugated diolefinic hydrocarbon having from 4 to 6 carbon atoms per molecule and from about 20 to about 50 parts by weight of at least one polymerized ethylenically unsaturated nitrile monomer, and containing from about 1.5 millimoles to about 30 millimoles per 100 grams of interpolymer of bound tertiary amine groups in the polymer molecule.
The bound tertiary amine groups are conveniently introduced into the modified nitrile rubber by copolymerizing with the conjugated diolefinic hydrocarbon and the ethylenically unsatu~ated nitrile a small amount of a copolymerizable monomer having tertiary amine groups in the molecule, which amine groups are substantially unaf~ected by the polymerization so that the modified nitrile rubber is an interpolymer of at least three monomers.
By the term "vinyl chloride polymers" as used herein, there is meant high molecular weight thermoplastic polymers or copolymers containing at least 75~ by weight of polymerized vinyl chloride. It thus includes copolymers of vinyl chloride with a monomer selected from vinyl acetate, propylene, vinylidene chloride and acrylic esters~ The most preferred vinyl chloride polymer is polyvinyl chloride, and so the invention will be further described with respect to polyvinyl chloride.
It appears that the tertiary amine groups in the nitrile rubber polymer chains react with some of the chlorine groups attached to the polyvinyl chloride chains, so as to form in the blend the aforementioned labile cross-links.
- ; .:. . ... : . - . . . -. . . ..
~053S~
This is surprising, since it has previously been considered that the chlorine groups present in polyvinyl chloride are chemically unreactive.
In the rigid or flexible uncured plastic blends according to the present inve~tion, where the polyvinyl chloride constitutes from about 65 to about 95 parts by weight and the modified nitrile rubber constitutes from about 35 to about 5 parts by weight of the blend, the chemical bonding apparently achieved between the modified nitrile rubber and the polyvinyl chloride serves to resist the tendency of the rubber to be removed from the blend. Thus the desirable impact resistant and plasticized properties of the blend according to the invent-ion are retained over extended periodsof time. Further, the impact modifier (modified nitrile rubber) is much less extractable from the blend by solvents, as compared with conventional nitrile rubber containing rigid polyvinyl chloride-nitrile rubber compositions, on account of these chemical bonds. This renders the rigid blends according to ~he present invention particularly useful in plastic containers or pipes, etc., for storing or transporting materials which are solvents for the nitrile rubber.
In the rubbery compositions of the invention wherein the polyvinyl chloride constitutes from about 10 to about ~5 parts by weic3ht and the modified nitrile rubber constitutes about 90 to about 35 parts by weight of the blend, the labile cross-links apparently formed between the polyvinyl chloride and the tertiary amine groups of the nitrile rubber cause the composition to exhibit thermoplastic and rubbery properties without vulcanization. In some instances, the resulting compositions can be used as such, but they may if desired subsequently be vulcanized, e.g. with sulfur or peroxide systems, .
10~;~82G
to ~btain novel vulcanizates. Since the formation of the labile cross-links as previously discussed does not utilize the carbon-to-carbon unsaturation of nitrile rubber in the composition to any significant extent, th~ compositions remain sulfur and peroxide vulcanizable in the same manner as previously known polyvinyl chloride-nitrile rubber compositions. Whether or not the compositions of the invention should be vulcanized depends to a large extent upon the use to which the compositions will eventually be put. Sulfur vulcanizates according to the present invention have enhanced physical and abrasion properties, as compared with sulfur vulcanizates of comparable polyvinyl chloride-nitrile rubber blends of the prior art. Vulcanization results in reduced thermoplasticity.
The modified nitrile rubbers used in compositions of the present invention are inter-polymers of a C4-C6 conjugated diolefinic hydrocarbon, and a C3-C5 ethylenically unsaturated nitrile group containing monomer, the interpolymer having from about 1.5 millimoles to about 30 millimoles per 100 grams of interpolymer of bound tertiary amine groups in the polymer molecule, the amine groups preferably being derived from polymerization of a tertiary amine group containing monomer with the diolefinic hydrocarbon and the nitrile monomer.
Preferred among such diolefins are butadiene, isoprene and hexadiene, with butadiene being the most preferred. The ethylenically unsaturated nitrile monomer is preferably acrylonitrile or methacrylonitrile or a similar polymerizable C2-C4 alkyl substituted acrylic acid nitrile derivative. Most preferred is acrylonitrile.
The preferred interpolymer is one comprising from but~ ne D about 50 to about 80 parts by weight of }~T~ke+~-1,3 and from about 20 to about 50 parts by weight of acrylonitrile, most ~IL0~38;~
preferred being those comprising from about 60 to about 75 parts by weight of butadiene-l r 3 and from about 25 to about 40 parts by weight of acrylonitrile.
Prefexably, the tertiary amine group containing monomer used to incorporate tertiary amine groups in the modified nitrile rubber is one which copolymerizes readily with butadiene and acrylonitrile in a conventional emulsion poly-merization system, and which has a copolymerization reàctivity similar to that of the copolymerizing monomers. With such a preferred monomer, a copolymer is obtained with tertiary amine groups distributed along and amongst the polymer chains.
~ xamples of class of suitable monomers are acrylates and methacrylates of general formula:
R O ~ 3 H C = C - C - O(X)N
where R represents H or CH3, and X represents an aliphatic hydrocarbon group of 2-4 carbon atoms. Specific preferred mem- -bers of this class are dimethylaminoethyl acrylate, dimethyl-aminoethyl methacrylate and dimethylaminobutyl methacrylate.
The most preferred such monomer is dimethylaminoethyl methacrylate, which is copolymerized with the other monomer in ~ a Cry~
amounts to provide a bound dimethylaminoethyl mcthy~o~ e content in the terpolymer of from about 0.25 wt.% to about 4.3 wt.%, which corresponds to about 1.5 to about 30 millimoles of tertiary amine groups per 100 g. of terpolymer. The preferred range of bound dimethylaminoethyl methacrylate content in the terpolymer is from about 0.5 to about 4.0 wt.%, corresponding to a tertiary amine group content of from about 3.5 to about ~053826 28 millimoles per 100 g. of terpolymer~
The blends of the present invention may be mixed with other compounds and ingredients, in accordance with known comparable blends of the prior art. Thus in the case of rigid blends of the invention, they may include suitable stabili-zers for the vinyl chloride polymers, in amounts of up to about 10% by weight of the blend. The rigid blends may also include lubricants (internal and external) to assis~ in fabri-cation, anti-static agents, and fillers or pigments such as carbon black, calcium carbonate or clay.
With the flexible or rubbery blends of the present `-invention, there may if desired be included at least one plasticizer for the polyvinyl chloride of the conventional type, such as phthalates (dioctyl phthalate, diisooctyl phthalate, dinonyl phthala~te, di-2-ethylhexyl phthalate, for example);
phosphates (e.g. tritolyl phosphate or trixylyl phosphate);
esters of aliphatic dibasic acids (e.g. sebacates, azelates or adipates); polyesters; chlorinated paraffins and mixtures of two or more of these types. In addition, the flexible blends of the present invention may include stabilizers and antioxidants for the polyvinyl chloride and the nitrile rubber, and in some instances for the plasticizer also. Plasticizers may be used in amounts of from about 2 to about 20 parts by weight per 100 parts per weight of polyvinyl chloride~ Fillers such as carbon blacks, silica, calcium carbonate, clays etc.
may be used in amounts from about 25 to about 150 parts by weight, per 100 parts by weight combined polyvinyl chloride and modified nitrile rubber. ~ther polymers may also be included, to modify the properties of the final composition.
- - . ~ , . ~ ~ . . . .
-1053~3~6 The mixing procedures for preparing the compositions of the present invention are generally in accordance with known procedures for making comparable compositions of the prior art. Polyvinyl chloride is commonly prepared by an emul-sion polymerization system, and may be mixed in latex form with the latex of the modified nitrile rubber. In the alternative, the polymers and other ingredients can be dry-mixed at elevated temperatures, e.g. on a mill or in a Banbury mixer. The tem-perature of mixing should be high enough to ensure fluxirlg of the polyvinyl chloride~ The time of mixing should be longenough!to ensure intimate admixing of the ingredients into a substantially homogeneous compound.
When, in the case of a rubbery composition according to the invention, the composition is to be vulcanized, this is best undertaken as a subsequent step following the compound-ing described above. Suitable curing recipes are those well known in the art for this type of compound, and may be based upon sulfur curatives or peroxide curatives. Normally, curing takes place in a press at elevated temperatures, the curing recipe including suitable accelerators, etc.
The compositions of the present invention can be fabricated in accordance with techniques known in the prior art for comparable compositions. Both the flexible and the rigid compounds can be extruded into a variety of shapes, inclu-ding profiles, tubes and sheets. By the use of crosshead dies they can be extruded as wire sheathing. They can be processed from either a powder blend or granulated material. Specific applications for the compositions of the present invention include wire and cable insulation, footwear, hoses, molded goods ~053826 and printing rollers.
The present invention is further described in the following specific examples. In all cases unless otherwise specified r amounts are reported in parts by weight.
A modified nitrile rubber, namely a terpolymer of butadiene, acrylonitrile and dimethylaminoethylmethacrylate was blended with polyvinyl ch]Loride to yield a ru~bery com-position. Physical properties of the resulting compounds, both initial and after remolding, were tested. A similar com-pound was prepared using polyvinyl chloride and a copolymer of butadiene and acrylonitrile, for control purposes. The ter-polymer had a Mooney viscosity (ML-4 at 100C? of 29, and had a bound butadiene content of 33 wt.%, and a bound dimethyi-aminoethyl methacrylate content of 4 wt.%. The polyvinyl chloride used was that available commercially under the designation OPALON 630*. The nitrile rubber copolymer used in the control compound was that available commercially under the designation KRYNAC 34.50*.
The compounds were prepared by mixing on a micromill.
Duplicate mixes of each compound were prepared. Antioxidant and stabilizer were added to the rubber on the mill at room temperature, followed by the polyvinyl chloride. The mill was then heated to 175C and the compound milled until the poly-vinyl chloride melted and was fluxed. Samples were then pre-pared for stress-strain testing, ~y molding for five minutes at 175C after a two minute preheat. The remainder of each compound was formed into a sheet, which was cooled, cut-up and then re-molded at 1i5C into samples for testing. Stress-strain *Trade Marks ,'- - - . : ~ : .'.
.. - - , .
10538~6 properties (at room temperature) were measured on the original-ly molded samples and on the remolded samples which had been stored for 7 days at room temperature and further remolded samples were used to determine the stress-strain properties at elevated temperatures. The tests on the remolded samples indicate the thermoplastic nature of the compounds, i.e. the ability of the compounds to r~ecover their physical properties after heating, molding and coolingO
- The compound details and results of stress-strain testing of the original compounds and remolded compounds at room temperature are given in Table 1. The tests were conducted according to standard ASTM procedur~es except for the elevated temperature stress-strain where the ASTM procedure was followed except that the sample being tested was enclosed in an oven at the temperature~ specified.
105;~8~6 Compound No.~- _ __ __ ~erpolymer 6 6 _ Bd-AcN copolymer __ Polyvinylchloride 4 . _ .
2(4-Hydroxy-3,5-t-butyl aniline)-4-6-bis(n-octylthio)l,3,5 triazine 0.10.1 0.1 __ Basic lead carbonate .
stabilizer 0.1 _ Tensile Original 125 118 63 (Kg/cm ) Remolded 163 175 84 Elongation Original ;690 640 530 (%) Remolded ~570 530 ~ 500 100% Modulus Original 40 40 34 (Kg/cm ) . .
. Remolded .58 56 42 300% Modulus Original 60 65 48 (Kg/cm2 ) _ Remolded 85 86 _ _ " ~os3~6 The results of stress-strain testing at elevated temperatures of the remolded samples after 7 days storage are given in Table 2.
Compound No. 1 2 (Control) Tensile Strength 25C 145 165 88 .
50C 82 98 33~
lQ (Kg/cm ) i0~T~ 20 46 18 Elongation (%) 25C 540 530 550 50C `500670 - - 570 100C 280390~ 160 .
125C ~ 280330 170 100% Modul~s25C 60 55 45 . 50C 36 22 20 (Kg/cm2)100-C 12 14 10 300~ Modulus25C 100135 65 2 50C 60 44 _ __ 26 (Kg/cm )~ 75C ~ 2024 ~ ~
lOOC ~ 1~ _ It will be noted from the foregoing Tables that -optimum properties in the compounds of this Example according to the invention were developed after remolding, perhaps due 30 to more complete fluxing of the polyvinyl chloride during the : .
remolding process. The tensile strengths of the remolded samples according to the present invention are much higher than those of the control. Overall, the properties of the control composition ar~ much inferior to those according to .
the present invention.
. ' , . ~ .. ; ~ '; ... . .
` ~5;~8;26 Compositions similar to that described in Example 1 were prepared using differentrelative amounts of modified nitrile rubber and polyvinyl chloride, within the general range to give rubbery compositions, and including plasticizer.
The modified nitrile terpolymer rubber used was a terpolymer containing 63.3 wt.% polymerized butadiene, 33 wt.%
polymerized acrylonitrile and 3.7 wt.% polymerized dimethyl-aminoethylmethacrylate. It contained 1% of a suitable stabi-lizer. The rubber was banded on a mill at room temperature,and the polyvinyl chloride added to it, along with plasticizer and additional stabilizers. The mill was then heated to 170C
and the compound fluxed for two minutes. Then the compound was removed in sheet form at 8GC.
For testing purposes, macro sheets (0.075" thick) were molded from each compound. Molding was e~fected at 175C
for five minutes after a two minute pre-heat. One such sheet from each compound was then remilled and remolded at 175C
for five minutes after a two minute preheat, to give a remolded sample for testing purposes. The compound details and test results are given below in Table 3.
~L~538~6 Compound No. 4 ~ _ 6 Terpolymer 200 240 280 __ _ Polyvinyl chloride 200 160 120 2,6-Di(t-amyl)-hydroquinone (stabilizer) 2 2.4 2.8 Barium-cadmium-zinc (stabilizer) 3 2.4 1.8 .
Phosphite chelator - 0.5 0.4 0.3 .. _ ._ Di-isooctyl phthalate (plasticizer) 10 8 . 6 .
. Soyabean oil epoxide (plasticizer) 10 .
TENSILE PROPERTIES
Tensile s2trength Original 155 130 96 (Kg/cm ) Remolded 160 129 91 Elongation Original 480 540 810 (%) Remolded3.80 510 650 300% Modulus Original 112 76 32 (Kg/cm2) Remolded 135 85 44 HOT TENSILE PROPERTIES
....
.25C 190 165 110 Tensile Strength 575OC 160 49 _ 20 (Kg/cm2) 100C 24 14 7 ...
Elongation (%) 25C 500 620 750 75C ~ 1080 1120 ---- 94-0 . 100C 1070 830 500 .
300% Modulus 25C 110 830 500 (Kg/cm ) -575oC 50 32 20 100C 14 10 ~- 6 iOS3~
In this example, rubbery compositions of polyvinyl chloride and modified nitrile rubber in accordance with the present invention were prepared and vulcanized with a sulfur curing system, and the properties of the vulcanizates com- -pared with those of blends of polyvinyl chloride and conven-tional nitrile rubber.
The modified nitrile rubber used was a terpolymer of butadiene ~66% by weight), acrylonitrile (31.8~ by weight) and dimethylaminoethylmethacrylate (2.2% by weightj, having a Mooney (ML-4 at 100C) of 31. The conventional nitrile rubber was butadiene (65 wt.%)-acrylonitrile (~5 wt.%) copoly-mer having Mooney (ML-4 at 100C) of 35. Suitable stabilizers and plasticizers were added to compositions, which were pre-pared on a mill as described in Example 2. Details of the compositions are given below in Table 4.
1~538~6 Compound No. 7 ~ 10 (control) (control) Polyvinyl chloride 250 150 150 Terpolymer rubber 250 350 Nitrile rubber 250 _ 350 _ Barium-cadmium-zinc - _ .
Stabilizer 3.75 3.75 2.25 2.25 Phosph',te chelator 0.625 0.625 0.375 0.375 2,6-Di (t-amyl)-hyd- _ roquinone (Stabilizer) 2.5 2.5 3.5 3.5 Di-isooctyl phthalate (plasticizer)~ 12.5 12.5 7.5 7.5 , Soyabean oil epoxide 12.5 12.5 7.5 7.5 Then the compositions were compounded in identical curing recipes (2.5 parts sulfur, 5.~ parts zinc oxide, 1.0 parts stearic acid and 1.5 parts 2-mercaptobenzothiazole accelerator). Curing temperature in each case was 153C.
The vulcanizates were tested for stress-strain properties according to standard procedures, before and after aging.
The vulcanizates were also tested for oil resistance, by immersing samples in ASTM Fuel B for 70 hrs. at 25C, and then testing their stress-strain properties. Ross Flex tests were also conducted on the samples using the procedure accord-ing to ASTM D1052.
NBS Abrasion was also determined according to pro-cedure ASTM D-1630 for the Ross Flex, the lower the 0~3~Z6 . . .
result, the better the product. For the NBS Abrasion, the higher the number the better the product. The.result. are . given in Table 5.
~053826 Compound Mo. 10 (control) (control~
Cure time at 153C (min.) 18 18 12 12 _ ;--Physical Properties-Unaged Tensile strength (Kg/cm ) 192 210 86 90 Elongation (%) 280 260 220 230 100% modulus (Kg/cm ) 76 95 34 37 Hardness (SHORE A) 79 81 65 64 _ Physical Properties-Aged 10 days in air at 100C
Tensile strength (Rg/cm ) 220 248 94 104 Elongation (%) 150 150 120 120 ' 2 ~
100% modulus (Kg/cm ) 180 198 73 81 Hardness (SHORE A) 94 93 72 74 ....
Physical Properties-Aged 70 hrs. ASTM Fuel B, 25C
_ Tensile strength (Kg/cm ) 43 62 20 22 Elongation (%) 110 120 90 90 100% modulus (Kg/cm ) 33 51 _ _ Hardness (SHORE A~ 59 62 53 50 _ % Volume increase after immersion, 70 hrs, ASTM .
Fuel B, 25C 26 26 33 33 -rA~ Ross Flex cm cut growth ~,O~
per Kc (cm/Kc) 0.15 0.04 0.160.3 . NBS Abrasion 188 217 67 58 .; . .. .- ..::., - .
. .
~0~31~Z6 The compositions according to the invention show overall improvement in physical properties as compared with the control vulcanizates. Particularly noteworthy is the improvement in Ross Flex, where the cut growth rate in vulcanizates according to the invention is decreased almost fourfold.
In this example, compositions according to the invention were prepared generally as described in Example 3, using a sample of the same modified nitrile terpolymer rubber, mixed with nitrile rubber and carbon black and cured with a peroxide curing system. A control was also prepared in which the modified nitrile terpolymer was replaced with a standard nitrile copolymer.
The compositions were prepared on a mill as previously described, using stabilizers and plasticizers. In detailr the compositions were as shown as in Table 6.
¦Compound No. 11 12 20 ¦ (control) IPolyvinyl chloride 250 250 ¦Nitrile terpolymer 250 jNitrile copolymer 250 Barium-cadmium-zinc Stabilizer 3.75 3O75 Phosphate chelator 0.625 0.625 .
2,6-Di~t-amyl) hydroquinone Stabilizer 2.5 2.5 .
Di-isooctyl phthalate Plasticizer 12.5 12.5 ._ Soyabean oil epoxide Plasticizer 12.5 12.5 5313Z~
Each of these masterbatch compositions was then mixed in a Banbury mixer with additional nitrile rubber in the following recipe:
masterbatch 65.0 nitrile rubber (butadiene 73%, acrylonitrile 27%, Mooney 83) 35.0 basic lead carbonate 1.5 stearic acid 1.0 FT Carbon black 15.0 Fatty acid coated calcium carbonate 90.0 Soyabean oil epoxide (plasticizer) 15.0 ~.4 parts of dicumyl peroxide was added to the com-pound on a cool mill. The compositions were cured at 166C
for 18 minr Samples were tested according to standard proce-dures, generally described as in Example 3. The results are given in Table 7. Additional samples were cured for 36 min. at 166C and the compression set was determined after 22 hrs. at 100C, using ASTM D 395.
153~3Z6 , Compound No. 11 12 (control) Physical Properties-Unaged Tensile strength (Kg/cm ) 110 83 _ Elongation (~) 320 340 100% modulus (Kg/cm ) 32 25 Hardness (SHORE A) 69 68 .
Physical Properties-Aged 70 hrs. in air, at 100C -Tensile strength (Kg/cm ) 100 74 -Elongation (%) ~ 250 280 .
100% modulus (Kg/cm ) 40 33 Hardness (SHORE A) 74 69 Physical Properties-Aged 70 hrs, in ASTM Fuel B, 25C
Tensile strength (Kg/cm ) 5~ 43 Elongation (%) 250 250 100% modulus (Kg/cm2) 22 18 Hardness (SHORE A) 54 50 Compression set (22hrs at 100C) %24 31 This example demonstrates the cross linking effect of polyvinyl chloride on modified nitrile rubber, in accordance with the invention. A composition of 9 0 parts by weight of modified nitrile rubber and 10 parts by weight of polyvinyl chloride was prepared, this polyvinyl chloride level being ~0538'~
insufficient for it to act as a reinforcing agent in the rubber. The terpolymer contained 63.3% butadiene, 33%
acrylonitrile and 3.7% dimethylaminoethylmethacrylate. It was banded on a micro mill at~room temperature and compounded with filler. The polyvinyl chloride was added and the mix fluxed for two min. at 150C on the mill. In one compound, 0.2 parts dicumyl peroxide was added to give a few additional crosslinks. This was added on a cool mill. The compounds were molded into macro-micro sheets for five min. at 175C
after a two min. preheat. Parts of the samples were tested for stress-strain properties, and other parts were remilled and remolded for five min. at 175C after a two min. preheat and then tested. The results are given in Table 8.
~ TABLE 8 Compound No. 13 14 15 Modified nitrile rubber Polyvinyl chloride ISAF Carbon black 5 Silica _ 5 Dicumyl peroxide _ 0.02 . . .
Physical Properti es Tensile strength original57 78 75 (Kg/cm2) remold 75 74 59 Elongation (%) original 720 580 1180 remold 760 750 ~60 __ 100~ modulus original 27 31 24 (Kg/cm2) remold 28 30 35 300% modulus oriqinal _45 58 34 (Kg/cm2) remold 32 50 54 Hardness oriqinal 72 75 69 (SHORE A) remold 74 69 g _ -)53~Z6 ' The physical properties indicate that the polyvinyl chloride acts as a crosslin]cer fox the modified nitrile rubber.
EXP~LE 6 In this example, flexible compositions of polyvinyl chloride with minor amounts of modified nitrile rubber were prepared, to show the effectiveness of the modified rubber as a plasticizer for the polyvinyl chloride. Control experiments were run, in which regular nitrile rubber and conventional plasticizers were used in polyvinyl chloride compositions.
Modified nitrile rubber A was a terpolymer containing 66% butadiene, 31.8~ acrylonitrile and 2.2~ dimethylamino-ethylmethacrylate. Modified nitrile rubber-B was a terpolymer containing 65.53% butadiene, 3~% acrylonitrile and 0.47%
dimethylaminoethylmethacrylate. In preparing the compositions, the polyvinyl chloride and stabilizers were pre-blended in a powder mixer at low speed, and the plasticizers were added drop-wise and mixed thoroughly. This mix was then melted and banded on a mill at 175-C, using slow roll speed, and additional 20 stabilizer and the various rubber ingredients were added, thoroughly blended, and the mix fluxed for two minutes at 175-C.
Then the mix was sheeted off the mill at macro thickness, cooled and chopped into granules.
Màcro tensile sheets were moulded from the compounds for five minutes at 175 C, using a two minute warm up time before applying pressure. The mould was cooled to room temperature before demoulding~ Test of physical properties were performed according to standard methods, as previously described, and the compound details and results of testing are given below in Table 9 30 ~ in which compounds number 16, ~7 and 18 are controls. The in-teraction of the modified nitrile rubber with polyvinyl chloride is indicated by the percent weight loss after ~05~8'~6 swelling ]6 hours in methylethyl ketone, in filled tubes in the dark. To conduct this test, the samples were recovered from the solvent, quickly blotted,and dried to constant weight in a vacuum oven at about 75 C. The dried weight was then compared with the original weight, to give a "methylethyl ketone extractable percent" as recorded in the table.
- . 24 .. - . . , -, , . ~ . .. .. . . . . .
' ~0~1326 T~BLE 9 Compound No. 16 17 18 19 20 2¦ 22 _ _ __ Polyvinyl chloride 40D 400 400 4nn 40n 4no 4no Nitrile copolymer rubber _ 80 170 _ _ _ _ Modifiea nitrile rubber A _ _ _ 80 120 _ _ Modified nitrile rubber B _ _ _ _ _ 80 ~20 2,6-Di-(t-amyl) hydroquinon _D.8 ].20.8 1.2 0.8].2 (Stabilizer) _ _ Barium-cadmium zinc 12 12 12 12 12 12 12 (Stabilizer) Phosphite chelator 2 2 2 2 2 2 2 Di-octyl phthalate ]40 60 60 60 60 60 60 (plasticizer) Soyabean oil epoxide20 20 20 20 20 20 20 (plasticizer) Acrylic ester polymer 4 4 4 4 4 4 4 Physical Properties-Unaged _ __ Tensile strength (kg/cm2) 169 185 160 187 180 180 172 Elongation (%) 210 200 260 240 70 200 320 100% modulus (kg/cm2) 147 18Z 136 174 158 172 l50 Hardness (SHORE A) 92 93 91 95 94 95 94 Physical Properties-Aged 24 hrs, ASTM oil 2, 100 C _ _ Tensile strength (kg/cm2) 155 163 137 173 L69 169 L38 Elongation (%~ 210 270 320 230 300 270 380 100% modulus ~kg/cm2j 120 153 107 160 L23 194 L40 Hardness (SHORE A) 88 86 82 90 84 88 88 MEK extractable % 56.9 54.2 60.6_ 40.4 ~h~l 50.2 ~ 7 Compression set 22 hrs at ]OO'C % 71 67 68 50 44 54 59 A sharp decrease in MER extractables is to be noted in the compounds containing modified nitrile rubber, as compared with those where the plasticizer was a conventional nitrile rubber. The use of the modified nitrile rubber also resulted in increased modulus and tensile strength of the compositions and lower compression set.
In this example, a series of rigid compounds of polyvinyl chloride and modified nitrile terpolymer rubber was prepared, to evaluate the use of the modified nitrile rubber as a non-extractable impact modifier for polyvinyl-chloride.
Modified nitrile rubber C contained approximately 65.5~ polymerized butadiene, 34% acrylonitrile and 0.47%
dimethylaminoethylmethacrylate. Modified nitrile rubber ~
contained about 64. 7~ polymerized butadiene, 34% acrylonitrile and 1.3% dimethylaminoethylmethacrylate. Modified nitrile rubber E contained about 66% polymerized butadiene, 31. 8%
acrylonitrile and 2.2~ dimethy~aminoethylmethacrylate.The ~looney ~iscosities (ML-4 at lOO C) of the rubber C, D and E
were respectively 45, 48.5 and 31-To prepare the compounds, the nitrile rubbar wasfirst blended on a micro mill with stabilizer and cut into small pieces. Polyvinyl chloride was ,melted and banded on :? cadml~n~
! ~ the mill at 175-C. A barium and c~dmium zinc stabilizer was mixed with the polyvinyl chloride powder before it was added to the mill, and liquid phosphate chelator was added to the molten PVC as soon as it was fluxed. Then the rubber was added and the mix was fluxed for two minutes at 175'C. The material was removed after fluxing, allowed to cool and then ground.
lOS;~ 6 Flex bars and macro dumbbells were made from each compound. The ground material was compressed between foil at 175'C and cut into rough bars~ The cavities of appropriate compression moulds, preheated, were filled with rough bars and loose ground material. These were then preheated 2 minutes at 175 C and pressed for 4-5 minutes at 175'C with bumping in the early stages of compression to remove air.
Physical tests on the samples were conducted according to standard procedures, and the results are given below in Table 10.
~LOS3~'~6 TAsLE 10 Compound No. 23 24 25 26 27 Polyvinyl chloride 200200 200 200 200 Standard nitrile copolymer _ 20 _ Modified nitrile C _ _ 20 Modified nitrile D _ _ 20 Modified nitrile E _ _ _ _ 20 2,6-di(t-amyl)hydroquinone stabilize: . _ 0.2 0.2 0.2 0.2 Barium-cadmium-zinc stabilizer 6 6 6 Phosphate chelator 1 1 1 1 1 Physical Properties .
"
Maximum tensile (kg/cm ) 490475 535 520 470 Elongation at break (%) 5 18 12 19 27 Hardness (SHORE D) 7877.5 79 82 80 Flexural strength (kg.cm ) . 780 770 810 835 770 Flexural modulus (kg/cm ) 24,700 25,000 2B,500 30,400 24,150 Izod impact (ft. lbs/inch notch)0.310.37 0.32 0.31 0.36 _ Deflection temp ( C) (0.01" defl.) 72.5 54.7 55.0 55.4 52.5 Vicat softening point ('C) 87.483.381.0 80.0 82.3 Methyl ethyl ketone extract % 1828 26 25 16 -~ 28 -10~3826 .
The tests for methylethyl ~etone extraction and swelling was conducted by immersing dry, weighed samples y ketone for ]6 hours at ro The swollen samples recovered were quickly blotted to remove then dried to constant he final dried weight w The results show that compositio~s containing the Ubber are less extracta her materials. The Othe the physical properties of the compositions according to the 10 - present invention are similar to those of compositions ing regular NBR
29 _
stabilizer 0.1 _ Tensile Original 125 118 63 (Kg/cm ) Remolded 163 175 84 Elongation Original ;690 640 530 (%) Remolded ~570 530 ~ 500 100% Modulus Original 40 40 34 (Kg/cm ) . .
. Remolded .58 56 42 300% Modulus Original 60 65 48 (Kg/cm2 ) _ Remolded 85 86 _ _ " ~os3~6 The results of stress-strain testing at elevated temperatures of the remolded samples after 7 days storage are given in Table 2.
Compound No. 1 2 (Control) Tensile Strength 25C 145 165 88 .
50C 82 98 33~
lQ (Kg/cm ) i0~T~ 20 46 18 Elongation (%) 25C 540 530 550 50C `500670 - - 570 100C 280390~ 160 .
125C ~ 280330 170 100% Modul~s25C 60 55 45 . 50C 36 22 20 (Kg/cm2)100-C 12 14 10 300~ Modulus25C 100135 65 2 50C 60 44 _ __ 26 (Kg/cm )~ 75C ~ 2024 ~ ~
lOOC ~ 1~ _ It will be noted from the foregoing Tables that -optimum properties in the compounds of this Example according to the invention were developed after remolding, perhaps due 30 to more complete fluxing of the polyvinyl chloride during the : .
remolding process. The tensile strengths of the remolded samples according to the present invention are much higher than those of the control. Overall, the properties of the control composition ar~ much inferior to those according to .
the present invention.
. ' , . ~ .. ; ~ '; ... . .
` ~5;~8;26 Compositions similar to that described in Example 1 were prepared using differentrelative amounts of modified nitrile rubber and polyvinyl chloride, within the general range to give rubbery compositions, and including plasticizer.
The modified nitrile terpolymer rubber used was a terpolymer containing 63.3 wt.% polymerized butadiene, 33 wt.%
polymerized acrylonitrile and 3.7 wt.% polymerized dimethyl-aminoethylmethacrylate. It contained 1% of a suitable stabi-lizer. The rubber was banded on a mill at room temperature,and the polyvinyl chloride added to it, along with plasticizer and additional stabilizers. The mill was then heated to 170C
and the compound fluxed for two minutes. Then the compound was removed in sheet form at 8GC.
For testing purposes, macro sheets (0.075" thick) were molded from each compound. Molding was e~fected at 175C
for five minutes after a two minute pre-heat. One such sheet from each compound was then remilled and remolded at 175C
for five minutes after a two minute preheat, to give a remolded sample for testing purposes. The compound details and test results are given below in Table 3.
~L~538~6 Compound No. 4 ~ _ 6 Terpolymer 200 240 280 __ _ Polyvinyl chloride 200 160 120 2,6-Di(t-amyl)-hydroquinone (stabilizer) 2 2.4 2.8 Barium-cadmium-zinc (stabilizer) 3 2.4 1.8 .
Phosphite chelator - 0.5 0.4 0.3 .. _ ._ Di-isooctyl phthalate (plasticizer) 10 8 . 6 .
. Soyabean oil epoxide (plasticizer) 10 .
TENSILE PROPERTIES
Tensile s2trength Original 155 130 96 (Kg/cm ) Remolded 160 129 91 Elongation Original 480 540 810 (%) Remolded3.80 510 650 300% Modulus Original 112 76 32 (Kg/cm2) Remolded 135 85 44 HOT TENSILE PROPERTIES
....
.25C 190 165 110 Tensile Strength 575OC 160 49 _ 20 (Kg/cm2) 100C 24 14 7 ...
Elongation (%) 25C 500 620 750 75C ~ 1080 1120 ---- 94-0 . 100C 1070 830 500 .
300% Modulus 25C 110 830 500 (Kg/cm ) -575oC 50 32 20 100C 14 10 ~- 6 iOS3~
In this example, rubbery compositions of polyvinyl chloride and modified nitrile rubber in accordance with the present invention were prepared and vulcanized with a sulfur curing system, and the properties of the vulcanizates com- -pared with those of blends of polyvinyl chloride and conven-tional nitrile rubber.
The modified nitrile rubber used was a terpolymer of butadiene ~66% by weight), acrylonitrile (31.8~ by weight) and dimethylaminoethylmethacrylate (2.2% by weightj, having a Mooney (ML-4 at 100C) of 31. The conventional nitrile rubber was butadiene (65 wt.%)-acrylonitrile (~5 wt.%) copoly-mer having Mooney (ML-4 at 100C) of 35. Suitable stabilizers and plasticizers were added to compositions, which were pre-pared on a mill as described in Example 2. Details of the compositions are given below in Table 4.
1~538~6 Compound No. 7 ~ 10 (control) (control) Polyvinyl chloride 250 150 150 Terpolymer rubber 250 350 Nitrile rubber 250 _ 350 _ Barium-cadmium-zinc - _ .
Stabilizer 3.75 3.75 2.25 2.25 Phosph',te chelator 0.625 0.625 0.375 0.375 2,6-Di (t-amyl)-hyd- _ roquinone (Stabilizer) 2.5 2.5 3.5 3.5 Di-isooctyl phthalate (plasticizer)~ 12.5 12.5 7.5 7.5 , Soyabean oil epoxide 12.5 12.5 7.5 7.5 Then the compositions were compounded in identical curing recipes (2.5 parts sulfur, 5.~ parts zinc oxide, 1.0 parts stearic acid and 1.5 parts 2-mercaptobenzothiazole accelerator). Curing temperature in each case was 153C.
The vulcanizates were tested for stress-strain properties according to standard procedures, before and after aging.
The vulcanizates were also tested for oil resistance, by immersing samples in ASTM Fuel B for 70 hrs. at 25C, and then testing their stress-strain properties. Ross Flex tests were also conducted on the samples using the procedure accord-ing to ASTM D1052.
NBS Abrasion was also determined according to pro-cedure ASTM D-1630 for the Ross Flex, the lower the 0~3~Z6 . . .
result, the better the product. For the NBS Abrasion, the higher the number the better the product. The.result. are . given in Table 5.
~053826 Compound Mo. 10 (control) (control~
Cure time at 153C (min.) 18 18 12 12 _ ;--Physical Properties-Unaged Tensile strength (Kg/cm ) 192 210 86 90 Elongation (%) 280 260 220 230 100% modulus (Kg/cm ) 76 95 34 37 Hardness (SHORE A) 79 81 65 64 _ Physical Properties-Aged 10 days in air at 100C
Tensile strength (Rg/cm ) 220 248 94 104 Elongation (%) 150 150 120 120 ' 2 ~
100% modulus (Kg/cm ) 180 198 73 81 Hardness (SHORE A) 94 93 72 74 ....
Physical Properties-Aged 70 hrs. ASTM Fuel B, 25C
_ Tensile strength (Kg/cm ) 43 62 20 22 Elongation (%) 110 120 90 90 100% modulus (Kg/cm ) 33 51 _ _ Hardness (SHORE A~ 59 62 53 50 _ % Volume increase after immersion, 70 hrs, ASTM .
Fuel B, 25C 26 26 33 33 -rA~ Ross Flex cm cut growth ~,O~
per Kc (cm/Kc) 0.15 0.04 0.160.3 . NBS Abrasion 188 217 67 58 .; . .. .- ..::., - .
. .
~0~31~Z6 The compositions according to the invention show overall improvement in physical properties as compared with the control vulcanizates. Particularly noteworthy is the improvement in Ross Flex, where the cut growth rate in vulcanizates according to the invention is decreased almost fourfold.
In this example, compositions according to the invention were prepared generally as described in Example 3, using a sample of the same modified nitrile terpolymer rubber, mixed with nitrile rubber and carbon black and cured with a peroxide curing system. A control was also prepared in which the modified nitrile terpolymer was replaced with a standard nitrile copolymer.
The compositions were prepared on a mill as previously described, using stabilizers and plasticizers. In detailr the compositions were as shown as in Table 6.
¦Compound No. 11 12 20 ¦ (control) IPolyvinyl chloride 250 250 ¦Nitrile terpolymer 250 jNitrile copolymer 250 Barium-cadmium-zinc Stabilizer 3.75 3O75 Phosphate chelator 0.625 0.625 .
2,6-Di~t-amyl) hydroquinone Stabilizer 2.5 2.5 .
Di-isooctyl phthalate Plasticizer 12.5 12.5 ._ Soyabean oil epoxide Plasticizer 12.5 12.5 5313Z~
Each of these masterbatch compositions was then mixed in a Banbury mixer with additional nitrile rubber in the following recipe:
masterbatch 65.0 nitrile rubber (butadiene 73%, acrylonitrile 27%, Mooney 83) 35.0 basic lead carbonate 1.5 stearic acid 1.0 FT Carbon black 15.0 Fatty acid coated calcium carbonate 90.0 Soyabean oil epoxide (plasticizer) 15.0 ~.4 parts of dicumyl peroxide was added to the com-pound on a cool mill. The compositions were cured at 166C
for 18 minr Samples were tested according to standard proce-dures, generally described as in Example 3. The results are given in Table 7. Additional samples were cured for 36 min. at 166C and the compression set was determined after 22 hrs. at 100C, using ASTM D 395.
153~3Z6 , Compound No. 11 12 (control) Physical Properties-Unaged Tensile strength (Kg/cm ) 110 83 _ Elongation (~) 320 340 100% modulus (Kg/cm ) 32 25 Hardness (SHORE A) 69 68 .
Physical Properties-Aged 70 hrs. in air, at 100C -Tensile strength (Kg/cm ) 100 74 -Elongation (%) ~ 250 280 .
100% modulus (Kg/cm ) 40 33 Hardness (SHORE A) 74 69 Physical Properties-Aged 70 hrs, in ASTM Fuel B, 25C
Tensile strength (Kg/cm ) 5~ 43 Elongation (%) 250 250 100% modulus (Kg/cm2) 22 18 Hardness (SHORE A) 54 50 Compression set (22hrs at 100C) %24 31 This example demonstrates the cross linking effect of polyvinyl chloride on modified nitrile rubber, in accordance with the invention. A composition of 9 0 parts by weight of modified nitrile rubber and 10 parts by weight of polyvinyl chloride was prepared, this polyvinyl chloride level being ~0538'~
insufficient for it to act as a reinforcing agent in the rubber. The terpolymer contained 63.3% butadiene, 33%
acrylonitrile and 3.7% dimethylaminoethylmethacrylate. It was banded on a micro mill at~room temperature and compounded with filler. The polyvinyl chloride was added and the mix fluxed for two min. at 150C on the mill. In one compound, 0.2 parts dicumyl peroxide was added to give a few additional crosslinks. This was added on a cool mill. The compounds were molded into macro-micro sheets for five min. at 175C
after a two min. preheat. Parts of the samples were tested for stress-strain properties, and other parts were remilled and remolded for five min. at 175C after a two min. preheat and then tested. The results are given in Table 8.
~ TABLE 8 Compound No. 13 14 15 Modified nitrile rubber Polyvinyl chloride ISAF Carbon black 5 Silica _ 5 Dicumyl peroxide _ 0.02 . . .
Physical Properti es Tensile strength original57 78 75 (Kg/cm2) remold 75 74 59 Elongation (%) original 720 580 1180 remold 760 750 ~60 __ 100~ modulus original 27 31 24 (Kg/cm2) remold 28 30 35 300% modulus oriqinal _45 58 34 (Kg/cm2) remold 32 50 54 Hardness oriqinal 72 75 69 (SHORE A) remold 74 69 g _ -)53~Z6 ' The physical properties indicate that the polyvinyl chloride acts as a crosslin]cer fox the modified nitrile rubber.
EXP~LE 6 In this example, flexible compositions of polyvinyl chloride with minor amounts of modified nitrile rubber were prepared, to show the effectiveness of the modified rubber as a plasticizer for the polyvinyl chloride. Control experiments were run, in which regular nitrile rubber and conventional plasticizers were used in polyvinyl chloride compositions.
Modified nitrile rubber A was a terpolymer containing 66% butadiene, 31.8~ acrylonitrile and 2.2~ dimethylamino-ethylmethacrylate. Modified nitrile rubber-B was a terpolymer containing 65.53% butadiene, 3~% acrylonitrile and 0.47%
dimethylaminoethylmethacrylate. In preparing the compositions, the polyvinyl chloride and stabilizers were pre-blended in a powder mixer at low speed, and the plasticizers were added drop-wise and mixed thoroughly. This mix was then melted and banded on a mill at 175-C, using slow roll speed, and additional 20 stabilizer and the various rubber ingredients were added, thoroughly blended, and the mix fluxed for two minutes at 175-C.
Then the mix was sheeted off the mill at macro thickness, cooled and chopped into granules.
Màcro tensile sheets were moulded from the compounds for five minutes at 175 C, using a two minute warm up time before applying pressure. The mould was cooled to room temperature before demoulding~ Test of physical properties were performed according to standard methods, as previously described, and the compound details and results of testing are given below in Table 9 30 ~ in which compounds number 16, ~7 and 18 are controls. The in-teraction of the modified nitrile rubber with polyvinyl chloride is indicated by the percent weight loss after ~05~8'~6 swelling ]6 hours in methylethyl ketone, in filled tubes in the dark. To conduct this test, the samples were recovered from the solvent, quickly blotted,and dried to constant weight in a vacuum oven at about 75 C. The dried weight was then compared with the original weight, to give a "methylethyl ketone extractable percent" as recorded in the table.
- . 24 .. - . . , -, , . ~ . .. .. . . . . .
' ~0~1326 T~BLE 9 Compound No. 16 17 18 19 20 2¦ 22 _ _ __ Polyvinyl chloride 40D 400 400 4nn 40n 4no 4no Nitrile copolymer rubber _ 80 170 _ _ _ _ Modifiea nitrile rubber A _ _ _ 80 120 _ _ Modified nitrile rubber B _ _ _ _ _ 80 ~20 2,6-Di-(t-amyl) hydroquinon _D.8 ].20.8 1.2 0.8].2 (Stabilizer) _ _ Barium-cadmium zinc 12 12 12 12 12 12 12 (Stabilizer) Phosphite chelator 2 2 2 2 2 2 2 Di-octyl phthalate ]40 60 60 60 60 60 60 (plasticizer) Soyabean oil epoxide20 20 20 20 20 20 20 (plasticizer) Acrylic ester polymer 4 4 4 4 4 4 4 Physical Properties-Unaged _ __ Tensile strength (kg/cm2) 169 185 160 187 180 180 172 Elongation (%) 210 200 260 240 70 200 320 100% modulus (kg/cm2) 147 18Z 136 174 158 172 l50 Hardness (SHORE A) 92 93 91 95 94 95 94 Physical Properties-Aged 24 hrs, ASTM oil 2, 100 C _ _ Tensile strength (kg/cm2) 155 163 137 173 L69 169 L38 Elongation (%~ 210 270 320 230 300 270 380 100% modulus ~kg/cm2j 120 153 107 160 L23 194 L40 Hardness (SHORE A) 88 86 82 90 84 88 88 MEK extractable % 56.9 54.2 60.6_ 40.4 ~h~l 50.2 ~ 7 Compression set 22 hrs at ]OO'C % 71 67 68 50 44 54 59 A sharp decrease in MER extractables is to be noted in the compounds containing modified nitrile rubber, as compared with those where the plasticizer was a conventional nitrile rubber. The use of the modified nitrile rubber also resulted in increased modulus and tensile strength of the compositions and lower compression set.
In this example, a series of rigid compounds of polyvinyl chloride and modified nitrile terpolymer rubber was prepared, to evaluate the use of the modified nitrile rubber as a non-extractable impact modifier for polyvinyl-chloride.
Modified nitrile rubber C contained approximately 65.5~ polymerized butadiene, 34% acrylonitrile and 0.47%
dimethylaminoethylmethacrylate. Modified nitrile rubber ~
contained about 64. 7~ polymerized butadiene, 34% acrylonitrile and 1.3% dimethylaminoethylmethacrylate. Modified nitrile rubber E contained about 66% polymerized butadiene, 31. 8%
acrylonitrile and 2.2~ dimethy~aminoethylmethacrylate.The ~looney ~iscosities (ML-4 at lOO C) of the rubber C, D and E
were respectively 45, 48.5 and 31-To prepare the compounds, the nitrile rubbar wasfirst blended on a micro mill with stabilizer and cut into small pieces. Polyvinyl chloride was ,melted and banded on :? cadml~n~
! ~ the mill at 175-C. A barium and c~dmium zinc stabilizer was mixed with the polyvinyl chloride powder before it was added to the mill, and liquid phosphate chelator was added to the molten PVC as soon as it was fluxed. Then the rubber was added and the mix was fluxed for two minutes at 175'C. The material was removed after fluxing, allowed to cool and then ground.
lOS;~ 6 Flex bars and macro dumbbells were made from each compound. The ground material was compressed between foil at 175'C and cut into rough bars~ The cavities of appropriate compression moulds, preheated, were filled with rough bars and loose ground material. These were then preheated 2 minutes at 175 C and pressed for 4-5 minutes at 175'C with bumping in the early stages of compression to remove air.
Physical tests on the samples were conducted according to standard procedures, and the results are given below in Table 10.
~LOS3~'~6 TAsLE 10 Compound No. 23 24 25 26 27 Polyvinyl chloride 200200 200 200 200 Standard nitrile copolymer _ 20 _ Modified nitrile C _ _ 20 Modified nitrile D _ _ 20 Modified nitrile E _ _ _ _ 20 2,6-di(t-amyl)hydroquinone stabilize: . _ 0.2 0.2 0.2 0.2 Barium-cadmium-zinc stabilizer 6 6 6 Phosphate chelator 1 1 1 1 1 Physical Properties .
"
Maximum tensile (kg/cm ) 490475 535 520 470 Elongation at break (%) 5 18 12 19 27 Hardness (SHORE D) 7877.5 79 82 80 Flexural strength (kg.cm ) . 780 770 810 835 770 Flexural modulus (kg/cm ) 24,700 25,000 2B,500 30,400 24,150 Izod impact (ft. lbs/inch notch)0.310.37 0.32 0.31 0.36 _ Deflection temp ( C) (0.01" defl.) 72.5 54.7 55.0 55.4 52.5 Vicat softening point ('C) 87.483.381.0 80.0 82.3 Methyl ethyl ketone extract % 1828 26 25 16 -~ 28 -10~3826 .
The tests for methylethyl ~etone extraction and swelling was conducted by immersing dry, weighed samples y ketone for ]6 hours at ro The swollen samples recovered were quickly blotted to remove then dried to constant he final dried weight w The results show that compositio~s containing the Ubber are less extracta her materials. The Othe the physical properties of the compositions according to the 10 - present invention are similar to those of compositions ing regular NBR
29 _
Claims (21)
1. A polymer composition comprising from about 10 to about 95 parts by weigh of at least one vinyl chloride polymer and from about 90 to about 5 parts by weight of modified nitrile rubber, the modified nitrile rubber comprising an interpolymer of from about 80 to about 50 parts by weight of at least one polymerized conju-gated diolefinic hydrocarbon having from 4 to 6 carbon atoms per molecule and from about 20 to about 50 parts by weight of at least one polymerized C3-C5 ethylenically unsaturated nitrile monomer, and containing in the polymer molecule from about 1.5 millimoles to about 30 millimoles per 100 grams of polymer of bound tertiary amine groups of copolymerized monomer of the formula where R represents H or CH3 and X represents an aliphatic hydrocarbon group of 2-4 carbon atoms.
2. The composition of claim 1, wherein the modified nitrile rubber is a terpolymer of a conjugated diolefin selected from butadiene, isoprene and hexadiene, and unsaturated nitrile monomer selected from acrylonitrile and methacrylonitrile, and a tertiary amine group containing monomer selected from dimethylaminoethyl-acrylate, dimethylaminoethylmethacrylate, and diethylaminobutyl-methacrylate.
3. The composition of claim 1, where the modified nitrile rubber is a terpolymer of butadiene, acrylonitrile and dimethylaminoethyl-methacrylate.
4. The composition of claim 3 comprising from about 35 to about 5 parts by weight of modified rubber and from 65 to about 95 parts by weight of polyvinyl chloride.
5. The composition of claim 4 wherein the modified nitrile rubber contains from about 3.5 to about 28 millimoles of bound dimethyl-aminoethylmethacrylate.
6. The composition of claim 5 wherein the modified nitrile rubber contains from about 60 to about 75 parts by weight of butadiene-1,3 and from about 40 to about 25 parts by weight of acrylonitrile.
7. A rubbery polymer composition according to claim 1 comprising about 90 to about 35 parts by weight of modified nitrile rubber and from about 10 to about 65 parts by weight of polyvinyl chloride.
8. The composition of claim 7 wherein the modified nitrile rubber is a terpolymer of a conjugated diolefin selected from butadiene, isoprene and hexadiene, an unsaturated nitrile monomer selected from acrylonitrile and methacrylonitrile, and a tertiary amine group containing monomer selected from dimethylaminoethylacrylate, dimethlaminoethylmethacrylate and diethylaminobutylmethacrylate.
9. The composition of claim 8 wherein the modified nitrile rubber is a terpolymer of butadiene, acrylonitrile and dimethylaminoethylmethacrylate.
10. The composition of claim 9 wherein the modified nitrile rubber contains from about 3.5 to about 28 millimoles of bound dimethylaminoethylmethacrylate.
11. The composition of cliam 10 wherein the modified nitrile rubber contains from about 60 to about 75 parts by weight of butadiene-1,3 and from about 40 to about 25 parts by weight of acrylonitrile.
12. The composition of claim 8, claim 10 or claim 11 also including from about 2 to about 20 parts by weight per 100 parts by weight of polyvinylchloride, of at least one plasticizer.
13. The composition of claim 8, claim 10 or claim 11 also including from about 25 to about 150 parts by weight, per 100 parts by weight combined polyvinylchloride and modified nitrile rubber,of at least one filler.
14. A vulcanizate comprising the reaction product of (a) a polymer composition comprising from about 90 to about 35 parts by weight of modified nitrile rubber and from about 10 to about 65 parts by weight of polyvinylchloride, said modified nitrile rubber comprising an interpolymer of from about 80 to 50 parts by weight of at least one polymerized conjugated diolefinic hydrocarbon having from 4 to 6 carbon atoms per molecule and from about 20 to about 50 parts by weight of at least one polymerized C3-C5 ethylenically unsaturated nitrile monomer, and containing in the polymer molecule from about 1.5 millimoles to about 30 millimoles per 100 grams of interpolymer of bound tertiary amine groups of copolymerized monomer of the formula where R represents H or CH3 and X represents an aliphatic hydrocarbon group of 2-4 carbon atoms, and (b) a vulcanization system for said modified nitrile rubber.
15. The vulcanizate of claim 14 wherein the modified nitrile rubber is a terpolymer of a conjugated diolefin selected from butadiene, isoprene and hexadiene, an unsaturated nitrile monomer selected from acrylonitrile and methacrylonitrile, and a tertiary amine group containing monomer selected from dimethylaminoethyl-acrylate, dimethylaminoethyl-methacrylate and diethylaminobutyl-methacrylate.
16. The vulcanizate of claim 15 wherein the vulcanization system is a sulfur vulcanization system.
17. The vulcanizate of claim 15 wherein the vulcanization system is a peroxide vulcanization system.
18. The vulcanizate of claim 15, claim 16 or claim 17 which also includes at least one plasticizer, in an amount of from about 2 to about 20 parts by weight of plasticizer per 100 parts by weight of polyvinylchloride.
19. The vulcanizate of claim 15, claim 16 or claim 17, which also includes at least one filler, in an amount of from about 25 to about 150 parts by weight of filler per 100 parts by weight of combined polyvinylchloride and modified nitrile rubber.
20. A process for preparing a polymeric composition which comprises intimately admixing from about 10 parts to about 95 parts by weight of at least one vinyl chloride polymer and from about 90 parts by weight to about 5 parts by weight of a modified nitrile rubber, the modified nitrile rubber comprising an interpolymer of from about 80 to about 50 parts by weight of at least one polymerized conjugated diolefinic hydrocarbon having from 4 to 6 carbon atoms per molecule; from about 20 to about 50 parts by weight of at least one polymerized C3-C5 ethylenically unsaturated nitrile mono-mer; and from about 0.5 to about 4 parts by weight of at least one polymerized ethylenically unsaturated tertiary amine group containing monomer selected from dimethylaminoethylmethacrylate, diethylaminobutylacrylate, dimethylaminoethylmethacrylate and at a temperature sufficient to cause fluxing of the vinyl chloride polyer, and recovering and cooling the blended composition so formed.
21. The process of claim 20 which includes the subsequent step of vulcanizing the vinyl chloride polymer - modified nitrile rubber composition with a peroxide or sulfur vulcanization system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA232,795A CA1053826A (en) | 1975-07-31 | 1975-07-31 | Nitrile-pvc blends |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA232,795A CA1053826A (en) | 1975-07-31 | 1975-07-31 | Nitrile-pvc blends |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1053826A true CA1053826A (en) | 1979-05-01 |
Family
ID=4103767
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA232,795A Expired CA1053826A (en) | 1975-07-31 | 1975-07-31 | Nitrile-pvc blends |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1053826A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0761749A1 (en) * | 1995-08-25 | 1997-03-12 | The Goodyear Tire & Rubber Company | Heat resistant butadiene/acrylonitrile-polyvinyl chloride blends |
| CN114196085A (en) * | 2022-01-28 | 2022-03-18 | 高科橡塑工业有限公司 | Elastic coupling rubber material |
| CN116589806A (en) * | 2023-06-19 | 2023-08-15 | 安庆市悦发管业有限公司 | Novel polyvinyl chloride composite material and preparation method thereof |
-
1975
- 1975-07-31 CA CA232,795A patent/CA1053826A/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0761749A1 (en) * | 1995-08-25 | 1997-03-12 | The Goodyear Tire & Rubber Company | Heat resistant butadiene/acrylonitrile-polyvinyl chloride blends |
| CN114196085A (en) * | 2022-01-28 | 2022-03-18 | 高科橡塑工业有限公司 | Elastic coupling rubber material |
| CN116589806A (en) * | 2023-06-19 | 2023-08-15 | 安庆市悦发管业有限公司 | Novel polyvinyl chloride composite material and preparation method thereof |
| CN116589806B (en) * | 2023-06-19 | 2024-07-30 | 安庆市悦发管业有限公司 | Polyvinyl chloride composite material and preparation method thereof |
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