CA1078088A - Filled polystyrene, san or abs blends with nitrile rubber or urethane rubber - Google Patents
Filled polystyrene, san or abs blends with nitrile rubber or urethane rubberInfo
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- CA1078088A CA1078088A CA250,824A CA250824A CA1078088A CA 1078088 A CA1078088 A CA 1078088A CA 250824 A CA250824 A CA 250824A CA 1078088 A CA1078088 A CA 1078088A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
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Abstract
ABSTRACT
Filled thermoplastic compositions comprising a rigid thermoplastic resin, a particulate filler and a thermoplastic rubber are extrudable and injection-moldable to give high tensile modulus, high impact strength parts.
The compositions comprise 100 parts thermoplastic resin, 5-250 phr particulate filler and 2-60 phr thermoplastic rubber.
Filled thermoplastic compositions comprising a rigid thermoplastic resin, a particulate filler and a thermoplastic rubber are extrudable and injection-moldable to give high tensile modulus, high impact strength parts.
The compositions comprise 100 parts thermoplastic resin, 5-250 phr particulate filler and 2-60 phr thermoplastic rubber.
Description
1078~
This invention relates to rigid filled thermo-plastic compositions having increased tensile modulus and high impact strength. More particularly, this invention relates to rigid thermoplastic compositions comprising a blend of a thermo-plastic resin, a particulate filler and a thermoplastic rubber having unexpectedly high impact strength and tensile modulus properties.
Prior art methods for improving the reinforcing characteristics of fillers have largely been directed to treatment of the particulate filler either with polymeric materials or poly-merizable monomers and oligomers. Thus, in U.S. Patent Number 3,471,439 there is disclosed an extensive pre-treatment of particulate fillers such as clay, talc, silica, asbestos and the like with ethylenically-unsaturated monomers and oligomers, preferably including a peroxide or equivalent free radical generator.
The pre-treated filler is then added to a matrix polymer such as polyethylene and melt-processed to polymerize and~or crosslink the pre-treating system at the particle surface. It is said to be essential that the pre-treating monomer or oligomer possess an affinity for ~he particle surface, and the materials disclosed are those having ester, carboxylic acid, hydroxy or amino functionality or the like. In U.S. Patent No. 3,519,594, is disclosed a method for coating asbestos fiber to improve dispersability and decrease the tendency of asbestos-filled polypropylene toward degradation and cracking. The method requires that the fiber be thoroughly pre-treated to place thereon a coating by polymerizing an ethyl-enically-unsaturated monomer or oligomer on the fiber surface.
cm/p~
1~7808~
The common thread running through these prior art methods is the pre-treatment of the particles preferably by polymerizing or crosslinking in place on the particle surfaces.
It has generally been thought that encapsulation of the filler particles with a tightly-adhering polymeric sheath is necessary to produce the desired reinforcing characteristics. Thus pre-treatment of the particulate fillers with polymers or poly-merizable monomers having a high affinity for the particle surface has been necessary.
A method of preparing filled thermoplastic compositio~s having usefully high impact strength directly from filler materials without requiring extensive pre-treatment of the fillers is clearly needed.
Detailed Description It has now been found that rigid thermoplastic compositions having high impact strength and improved tensile modulus result when a thermoplastic resin matrix is compounded with a particulate filler and a thermoplastic rubber. More particularly, compositions comprising 100 parts by weight of a rigid thermoplastic resin selected from polystyrene, styrene-acrylonitrile copolymers and graft polymers prepared by poly-merizing styrene or mixtures of styrene and at least one co-polymerizable vinyl monomer in the presence of a rubbery diene polymer or copolymer, togethér with from 2 to 60 parts by weight based on the rigid thermoplastic resin of a thermoplastic rubber and from 5 to 250 parts by weight based on the rigid thermoplastic resin of a particulate filler having an average particle size less than 2.0 micron, have unexpectedly high tensile modulus and toughness.
The rubber component is characterized as being thermoplastic. ~n the genersl sense, thermoplastic rubbers are those capa~le of being thermally processed by virtue of their 1078~88 generally linear molecular structure and only a very small amount of crosslin~ing is present if any. These materials may be capable of being cured, but for the purposes of this invention the rubbers are used in the uncured state. Typical rubbers useful for these purposes include the uncured nitrile rubbers, which are rubbery butadiene-acrylonitrile copolymers generally containing from 10 to 50% acrylonitrile component and having a low gel content, and urethane elastomer rubbers including polyether, polyester and polycaprolactone-based structures in the fully polymerized but essentially uncrosslinked form. Such materials are generally described as elastoplastic rubbers.
Thermoplastic urethane rubbers, or elasto-plastics, are linear polymers completely soluble in strong polar solvents and are thermally processable, unlike the crosslinked urethane rubbers. These materials are generally polyester or polyether based systems, prepared by first providing a linear macroglycol from the esterification of a dicarboxylic acid such as adipic acid with a slight excess of glycol, or by initiating the ring opening polymerization of a lactone such as caprolactone with a glycol. The resulting polyester segments containing terminal hydroxyl functionality are then reacted with a diiso-cyanate, as for example methylene di-p-phenylene diisocyanate or the like to introduce isocyanate terminal functionality, followed by reaction with a chain extender which is a low molecular weight glycol or diamine such as ethylene glycol, 1,4-butanediol, 1,4-diaminobutane and the like to produce linear, high molecular weight polyester-urethanes having urethane and urea segments in the chain which provide hydrogen-bonding associations ~etween chains thereby imparting elastomeric properties. Typical elas-toplastics and their preparations are set forth in papers by -- 3 --cm/p ~
1078~88 C.A. Waugaman, et al, _ b er World 144 72 (1961) and by C.S. Schollenberger, et al, R ber World 137 549 (1958). These and similar elastoplastics are widely available commercial products.
Other linear thermoplastic rubbers which may also be employed include acrylate rubbers, chlorinated poly-ethylene, uncured polydienes, and the like.
The amount of the rubber component in the blend will generally be in the range of from 2 to 60 parts by weight per hundred parts of the rigid thermoplastic resin. While greater amounts may be employed, the effect of adding uncrosslinked rubber to a rigid thermoplastic is generally to produce a lowering in tensile modulus and upper use temperature properties. Hence it will normally be desirable to hold the level of added rubber to the lowest level consistent with attaining the desired modification.
The fillers which are useful in the present invention are generally characterized as being non-reinforcing particulate fillers. The fillers must be in the form of finely divided particles, and the average particle size will be less than about 2.0 microns. It will be understood that inasmuch as filler particles are of irregular shape, the dimension referred to will be the greatest dimension of the individual particle, and the average dimension is the number average dimension, whereby 50% of the particles have a dimension equal to or smaller than the average dimension. Among the specific fillers are kaolin and other clay minerals, calcium carbonate (whiting), magnesium oxide, barium carbonate, barium sulfate, powdered glass, titanium dioxide, talc and the like. The total amount of filler may vary from about 5 to about 250 parts by weight per 100 parts of the rigid thermo-plastic resin.
cm/ ~
1078~88 The rigid thermoplastic resins useful in the practice of this invention include polystyrene, copolymers of styrene with acrylonitrile or methacrylonitrile, and qraft polymers prepared by polymerizing styrene or a mixture of styrene and at least one additional copolymerizable vinyl monomer selected from the group acrylonitrile, methacrylonitrile, methyl methacrylate, methylacrylate, ethylacrylate, and the like in the presence of a rubbery diene polymer such as polybutadiene, butadiene-styrene copolymer rubber con~aining up to 35~ styrene component, nitrile rubbers and acrylate rubbers. The amount of rubbery substrate employed for the preparation of these graft polymers will comprise from 5% to about 40% of the total thermoplastic resin.
It has also been found to be desirable to include a moderate amount of a processing aid, in particular magnesium stearate, to obtain optimum properties. However, impact modification will be obtained without including the magnesium stearate, and its addition is optional.
Examples The acrylonitrile-butadiene-styrene or ABS resins employed in the following Examples 1-14 were prepared by poly-merizing a mixture containing the indicated amounts of styrene and acrylonitrile in the presence of a polybutadiene rubber latex, substantially by the emulsion process disclosed in U.S. 3,238,275.
The styrene-acrylonitrile copolymers employed in Examples 15-20 were prepared.by an emulsion polymerization of 70 parts by weight styrene and 30 parts by weight acrylonitrile substantially as disclosed in U.S. 2,820,773.
The compositions described in Examples 1-22 were prepared by charging the Banbury mixer with the given amounts of thermoplastic resin, thermoplastic rubber, clay and processing cm/~
~ Trademark 107~088 aids, if employed, then melt mixing at 300-420F. for about 4 minutes. The compositions were then transferred to a two roll mill and milled for 2 minutes, sheeted out, cooled and diced.
The diced pellets were injection molded to provide plaques for testing.
In the following Examples, all parts are by weight, and the Compositions of Examples 1-20 contain from 0.5 to 2 parts by weight magnesium stearate.
~m~
ABS - Nitrile Rubber - Clay Blends .
Example No. 1 2 3- 4 5 6 7 8 Nitrile Rubber (phr) - 12.8 9.7 6.75 12.8 12.8 6.75 7.8 Clay4 (phr) 25.3 28.6 27.7 27.0 28.65 28.66 27.0 46.9 Tensile Str~
(psi) 6300 5600 5850 5800 5750 5550 5750 5670 Elongation (%) 7 10 10 7 10 10 15 5 Tensile Modulus (psixlO~5) 5~7 5.0 5.0 5.3 4.~ 4.6 5.2 5.8 Falling Dart Impact (Ft. lbs) <1 6-8 8-10 6 4-6 <1 8-10 6-8 _ Notes:
1. ABS prepared by graft polymerizing a mixture of 61 parts styrene and 24 parts acrylonitrile in the presence of 15 parts polybutadiene rubber; Tensile Modulus 3.4x10-5psi, Falling Dart Impact 16. ft. lbs.
This invention relates to rigid filled thermo-plastic compositions having increased tensile modulus and high impact strength. More particularly, this invention relates to rigid thermoplastic compositions comprising a blend of a thermo-plastic resin, a particulate filler and a thermoplastic rubber having unexpectedly high impact strength and tensile modulus properties.
Prior art methods for improving the reinforcing characteristics of fillers have largely been directed to treatment of the particulate filler either with polymeric materials or poly-merizable monomers and oligomers. Thus, in U.S. Patent Number 3,471,439 there is disclosed an extensive pre-treatment of particulate fillers such as clay, talc, silica, asbestos and the like with ethylenically-unsaturated monomers and oligomers, preferably including a peroxide or equivalent free radical generator.
The pre-treated filler is then added to a matrix polymer such as polyethylene and melt-processed to polymerize and~or crosslink the pre-treating system at the particle surface. It is said to be essential that the pre-treating monomer or oligomer possess an affinity for ~he particle surface, and the materials disclosed are those having ester, carboxylic acid, hydroxy or amino functionality or the like. In U.S. Patent No. 3,519,594, is disclosed a method for coating asbestos fiber to improve dispersability and decrease the tendency of asbestos-filled polypropylene toward degradation and cracking. The method requires that the fiber be thoroughly pre-treated to place thereon a coating by polymerizing an ethyl-enically-unsaturated monomer or oligomer on the fiber surface.
cm/p~
1~7808~
The common thread running through these prior art methods is the pre-treatment of the particles preferably by polymerizing or crosslinking in place on the particle surfaces.
It has generally been thought that encapsulation of the filler particles with a tightly-adhering polymeric sheath is necessary to produce the desired reinforcing characteristics. Thus pre-treatment of the particulate fillers with polymers or poly-merizable monomers having a high affinity for the particle surface has been necessary.
A method of preparing filled thermoplastic compositio~s having usefully high impact strength directly from filler materials without requiring extensive pre-treatment of the fillers is clearly needed.
Detailed Description It has now been found that rigid thermoplastic compositions having high impact strength and improved tensile modulus result when a thermoplastic resin matrix is compounded with a particulate filler and a thermoplastic rubber. More particularly, compositions comprising 100 parts by weight of a rigid thermoplastic resin selected from polystyrene, styrene-acrylonitrile copolymers and graft polymers prepared by poly-merizing styrene or mixtures of styrene and at least one co-polymerizable vinyl monomer in the presence of a rubbery diene polymer or copolymer, togethér with from 2 to 60 parts by weight based on the rigid thermoplastic resin of a thermoplastic rubber and from 5 to 250 parts by weight based on the rigid thermoplastic resin of a particulate filler having an average particle size less than 2.0 micron, have unexpectedly high tensile modulus and toughness.
The rubber component is characterized as being thermoplastic. ~n the genersl sense, thermoplastic rubbers are those capa~le of being thermally processed by virtue of their 1078~88 generally linear molecular structure and only a very small amount of crosslin~ing is present if any. These materials may be capable of being cured, but for the purposes of this invention the rubbers are used in the uncured state. Typical rubbers useful for these purposes include the uncured nitrile rubbers, which are rubbery butadiene-acrylonitrile copolymers generally containing from 10 to 50% acrylonitrile component and having a low gel content, and urethane elastomer rubbers including polyether, polyester and polycaprolactone-based structures in the fully polymerized but essentially uncrosslinked form. Such materials are generally described as elastoplastic rubbers.
Thermoplastic urethane rubbers, or elasto-plastics, are linear polymers completely soluble in strong polar solvents and are thermally processable, unlike the crosslinked urethane rubbers. These materials are generally polyester or polyether based systems, prepared by first providing a linear macroglycol from the esterification of a dicarboxylic acid such as adipic acid with a slight excess of glycol, or by initiating the ring opening polymerization of a lactone such as caprolactone with a glycol. The resulting polyester segments containing terminal hydroxyl functionality are then reacted with a diiso-cyanate, as for example methylene di-p-phenylene diisocyanate or the like to introduce isocyanate terminal functionality, followed by reaction with a chain extender which is a low molecular weight glycol or diamine such as ethylene glycol, 1,4-butanediol, 1,4-diaminobutane and the like to produce linear, high molecular weight polyester-urethanes having urethane and urea segments in the chain which provide hydrogen-bonding associations ~etween chains thereby imparting elastomeric properties. Typical elas-toplastics and their preparations are set forth in papers by -- 3 --cm/p ~
1078~88 C.A. Waugaman, et al, _ b er World 144 72 (1961) and by C.S. Schollenberger, et al, R ber World 137 549 (1958). These and similar elastoplastics are widely available commercial products.
Other linear thermoplastic rubbers which may also be employed include acrylate rubbers, chlorinated poly-ethylene, uncured polydienes, and the like.
The amount of the rubber component in the blend will generally be in the range of from 2 to 60 parts by weight per hundred parts of the rigid thermoplastic resin. While greater amounts may be employed, the effect of adding uncrosslinked rubber to a rigid thermoplastic is generally to produce a lowering in tensile modulus and upper use temperature properties. Hence it will normally be desirable to hold the level of added rubber to the lowest level consistent with attaining the desired modification.
The fillers which are useful in the present invention are generally characterized as being non-reinforcing particulate fillers. The fillers must be in the form of finely divided particles, and the average particle size will be less than about 2.0 microns. It will be understood that inasmuch as filler particles are of irregular shape, the dimension referred to will be the greatest dimension of the individual particle, and the average dimension is the number average dimension, whereby 50% of the particles have a dimension equal to or smaller than the average dimension. Among the specific fillers are kaolin and other clay minerals, calcium carbonate (whiting), magnesium oxide, barium carbonate, barium sulfate, powdered glass, titanium dioxide, talc and the like. The total amount of filler may vary from about 5 to about 250 parts by weight per 100 parts of the rigid thermo-plastic resin.
cm/ ~
1078~88 The rigid thermoplastic resins useful in the practice of this invention include polystyrene, copolymers of styrene with acrylonitrile or methacrylonitrile, and qraft polymers prepared by polymerizing styrene or a mixture of styrene and at least one additional copolymerizable vinyl monomer selected from the group acrylonitrile, methacrylonitrile, methyl methacrylate, methylacrylate, ethylacrylate, and the like in the presence of a rubbery diene polymer such as polybutadiene, butadiene-styrene copolymer rubber con~aining up to 35~ styrene component, nitrile rubbers and acrylate rubbers. The amount of rubbery substrate employed for the preparation of these graft polymers will comprise from 5% to about 40% of the total thermoplastic resin.
It has also been found to be desirable to include a moderate amount of a processing aid, in particular magnesium stearate, to obtain optimum properties. However, impact modification will be obtained without including the magnesium stearate, and its addition is optional.
Examples The acrylonitrile-butadiene-styrene or ABS resins employed in the following Examples 1-14 were prepared by poly-merizing a mixture containing the indicated amounts of styrene and acrylonitrile in the presence of a polybutadiene rubber latex, substantially by the emulsion process disclosed in U.S. 3,238,275.
The styrene-acrylonitrile copolymers employed in Examples 15-20 were prepared.by an emulsion polymerization of 70 parts by weight styrene and 30 parts by weight acrylonitrile substantially as disclosed in U.S. 2,820,773.
The compositions described in Examples 1-22 were prepared by charging the Banbury mixer with the given amounts of thermoplastic resin, thermoplastic rubber, clay and processing cm/~
~ Trademark 107~088 aids, if employed, then melt mixing at 300-420F. for about 4 minutes. The compositions were then transferred to a two roll mill and milled for 2 minutes, sheeted out, cooled and diced.
The diced pellets were injection molded to provide plaques for testing.
In the following Examples, all parts are by weight, and the Compositions of Examples 1-20 contain from 0.5 to 2 parts by weight magnesium stearate.
~m~
ABS - Nitrile Rubber - Clay Blends .
Example No. 1 2 3- 4 5 6 7 8 Nitrile Rubber (phr) - 12.8 9.7 6.75 12.8 12.8 6.75 7.8 Clay4 (phr) 25.3 28.6 27.7 27.0 28.65 28.66 27.0 46.9 Tensile Str~
(psi) 6300 5600 5850 5800 5750 5550 5750 5670 Elongation (%) 7 10 10 7 10 10 15 5 Tensile Modulus (psixlO~5) 5~7 5.0 5.0 5.3 4.~ 4.6 5.2 5.8 Falling Dart Impact (Ft. lbs) <1 6-8 8-10 6 4-6 <1 8-10 6-8 _ Notes:
1. ABS prepared by graft polymerizing a mixture of 61 parts styrene and 24 parts acrylonitrile in the presence of 15 parts polybutadiene rubber; Tensile Modulus 3.4x10-5psi, Falling Dart Impact 16. ft. lbs.
2. ABS prepared by graft polymerizing a mixture of 51 parts styrene and 29 parts acrylonitrile in the presence of 20 parts polybutadiene rubber; Tensile Modulus 3.2x10-5psi; Falling Dart Impact 20-25 ft. lbs.
3. Rubbery copolymer of butadiene and acrylonitrile with approximately 29% acrylonitrile, having a Mooney Viscosity (ML-4 @ 212F.) of 50-65; obtained from B F. Goodrich Company.
4. Clay is Georgia Kaolin, obtained as Harwick 50R, having average particle size=0.5 microns from Harwick Chemical Company, except where noted otherwise.
5. Clay average particle size 0.8 microns, Harwick #1.
- 6. Clay average particle size 4.8 microns, Harwick ~42.
cm/~ - 7 -Trademark It will be apparent from the property data for control Example 1 that althouqh the addition of clay alone to A~S improves the tensile modulus, impact properties are destroyed. However, when thermoplastic nitrile rubber is added with the clay, as in Examples 2-4, 7 and 8, the high modulus is retained, while the dart impact strength is markedly improved over that of the ABS-filler combination. The relative amounts of nitrile rubber and clay have some effect on final properties, as will be seen when the properties of Example 2 having a rubber/clay ratio of 1/2.2 are compared with those of Example 4, having a rubber/clay ratio of 1/4, and the particular ratios and amounts employed may be varied over a wide range to achieve the desired balance of property characteristics.
The particle size employed also has an effect on properties, as shown by a comparison of Examples 2, 5 and 6, where the average clay particle size increases from 0.5~ (2) through 0.8~ (5) to 4.8~ (6), and impact is correspondingly reduced. In general, average particle sizes below about 2.0 are more effective for the purposes of providing high impact strength and are therefore preferred.
TABLE II
ABS - Urethane Rubber - Clay Blends Example No. 9 10 11 12 13 14 _ Urethane3 (phr) 21.7 21.5 18.8 32.2 14.5 14.4 Clay4 (phr) 21.7 30.7 36.2 23.6 29 38.6 Tensile Str. (psi) 5600 5650 5850 5830 5840 5840 Elongation (%) 48 22 9 10 46 7 Tensile Modulus (psix10-5) 4.2 5.0 5.6 5.0 4.8 5.1 Falling Dart Impact (ft. lbs~ 12-14 8-12 10-12 10-12 8-10 2-4 Notes:
1, 2. See notes 1, 2, TABLE I.
3. Urethane elastoplastic based~on polycaprolactone, obtained from Upjohn Company as Pellethane ~ CRP 2102-80A.
4. See note 4, TABLE I.
cm/p~
Approximately the same effects on properties are noted when the modifying thermoplastic rubber component employed is a urethane elastoplastic. ABS com-positions with high impact strength and high modulus result from blends containing clay, urethane and ABS as is shown by Examples given in TABLE II. In general, higher levels of urethane elastomer are required to achieve results equivalent to those reported in TABLE I for nitrile rubber blends, as will be seen by comparing Example 7 with Example 13 and Example 2 with Example 10.
~078~
TABLE III
SAN - Rubber - Clay Blends . _ Example No. 15 16 17 18 19 20 _ SANl 100 100 100 100 100 100 Urethane2 25.4 33.9 43.6 42.4 42.3 Nitrile Rubber3 ~ - - - - 25.4 Clay4 31.7 33.9 36.4 25.4 48 31.7 Tensile Str (psi) 6750 5650 4900 4760 4800 5800 Elongation (%) 9 9 28 25 9 7 Tensile Modulus (p8ixl~ 5) 5 5 4 9 3.6 3.8 4.7 4.7 Falling Dart Impact (ft. lbs) <2 2-3 2-4 6 6-8 2-4 _ Notes:
1. Copolymer of 70~ styrene and 30% acrylonitrile; Dart Impact <1.0 ft. lb.
2. See note 3, TABLE II.
3. See note 3, TABLE 1.
4. See note 4, TABLE I.
cm/,-~l~
107808~
It will be apparent from the test data fox Examples 16-20 shown in TABLE III, that useful improvements in tensile modulus and impact result with clay-filled compositions based on SAN copolymers. Again, the ratio of rubber to clay has some effect on final properties, as does the total amount and type of rubber employed. A blend prepared as in Example 20, but having no rubber component present was too brittle for testing purposes.
A blend of 100 parts by weight of impact modified polystyrene having a tensile modulus of 2.9xlO 5 psi, a tensile strength of 3700 psi and a falling dart impact of <1 ft. lb. (obtained from Amoco Chemicals Co. as H4F) with 27.6 parts Harwick 50R clay, 7 parts nitrile rubber and 0.7 parts magnesium stearate was prepared by Banbury mixing the blend, then dicing and molding it to form test plaques as before. These test plaques had a tensile modulus of 4.5xlO 5 psi and a falling dart impact strength of 2-4 ft. lbs. A control blend prepared without nitrile rubber, and having 100 parts polystyrene and 25 parts clay had a tensile modulus of 4.5xlO psi and a falling dart impact of less than 1 foot pounds.
A blend of 100 parts by weight of the ABS
I employed in Example 2, 9.7 parts by weight nitrile rubber of Example 2 and 27.8 parts by weight calcium carbonate having an average particle size of 0.03 microns was prepared by Banbury mixing as described above. The test plaques had a falling dart impact value of 8-10 ft. lbs.
_ AMPLE 23 3~ A blend of 100 parts by weight of the ABS
I employed in Example 2, 9.7 parts by weight nitrile rubber of Example 2, 28 parts by weight titanium dioxide pigment having .
~ Trademark cm/ ~ h ~078088 an average particle size of 0.2 microns, and 1.4 parts by weight of magnesium stearate was prepared by Banbury mixing as described above. The test plaques had a falling dart impact of 20-26 ft. lbs., and a tensile modulus of 3.2xlO psi.
A blend of 100 parts by weight of the ABS
II employed in Example 7, 0.75 parts by weight magnesium stearate, 20.0 parts by weight brominated biphenyl (flame retardant), 7.5 parts by weight antimony oxide having an average particle size of 1.0 micron, 0.5 parts by weight polyether lubricant and 5.0 parts by weight of the nitrile rubber of Example 7 was prepared by Banbury mixing as before. The test plaques had a falling dart impact strength of 12-14 ft. lbs.
It will thus be seen that the method of the present invention may be employed to provide marked improve-ment in impact properties of-rigid, filled thermoplastic resins.
It will be apparent to one skilled in the art that it will be possible to extend the technology to include blends of the com-positions of this invention with other thermoplastic resins such as for example the well known blends of impact polystyrene with polyphenylene ethers, as well as blends of ABS with such thermo-plastics as PVC,- and the method may be used to overcome losses in impact properties of thermoplastic resin compositions which result when pigments, fiberous particles and similar materials are included at moderate to high loading levels.
The high impact, high modulus compositions of this invention may also be extruded into profiles or sheet material and subsequently thermoformed as well as being processed by injection molding methods. These materials are useful in molde~ articles for automotive, household and similar applications where low cost, high impact strength and dimensional stability are important.
* Trademar~
~ _ "~, 1078~88 The Examples are provided by way of illustration to better demonstrate the useful improvements in impact properties that result from the use of particulate fillers together with thermoplastic rubbers in preparing blend compositions with rigid thermoplastics, and the invention is not intended to be limited to the specific polymers and formulations disclosed herein. It will be further apparent that various modifications of these blends to include the use of mixed particulate fillers, processing aids, stabilizers and the like may be made without departing from the spirit of the invention, and the scope thereof is limited solely by the appended claims.
cm/~
cm/~ - 7 -Trademark It will be apparent from the property data for control Example 1 that althouqh the addition of clay alone to A~S improves the tensile modulus, impact properties are destroyed. However, when thermoplastic nitrile rubber is added with the clay, as in Examples 2-4, 7 and 8, the high modulus is retained, while the dart impact strength is markedly improved over that of the ABS-filler combination. The relative amounts of nitrile rubber and clay have some effect on final properties, as will be seen when the properties of Example 2 having a rubber/clay ratio of 1/2.2 are compared with those of Example 4, having a rubber/clay ratio of 1/4, and the particular ratios and amounts employed may be varied over a wide range to achieve the desired balance of property characteristics.
The particle size employed also has an effect on properties, as shown by a comparison of Examples 2, 5 and 6, where the average clay particle size increases from 0.5~ (2) through 0.8~ (5) to 4.8~ (6), and impact is correspondingly reduced. In general, average particle sizes below about 2.0 are more effective for the purposes of providing high impact strength and are therefore preferred.
TABLE II
ABS - Urethane Rubber - Clay Blends Example No. 9 10 11 12 13 14 _ Urethane3 (phr) 21.7 21.5 18.8 32.2 14.5 14.4 Clay4 (phr) 21.7 30.7 36.2 23.6 29 38.6 Tensile Str. (psi) 5600 5650 5850 5830 5840 5840 Elongation (%) 48 22 9 10 46 7 Tensile Modulus (psix10-5) 4.2 5.0 5.6 5.0 4.8 5.1 Falling Dart Impact (ft. lbs~ 12-14 8-12 10-12 10-12 8-10 2-4 Notes:
1, 2. See notes 1, 2, TABLE I.
3. Urethane elastoplastic based~on polycaprolactone, obtained from Upjohn Company as Pellethane ~ CRP 2102-80A.
4. See note 4, TABLE I.
cm/p~
Approximately the same effects on properties are noted when the modifying thermoplastic rubber component employed is a urethane elastoplastic. ABS com-positions with high impact strength and high modulus result from blends containing clay, urethane and ABS as is shown by Examples given in TABLE II. In general, higher levels of urethane elastomer are required to achieve results equivalent to those reported in TABLE I for nitrile rubber blends, as will be seen by comparing Example 7 with Example 13 and Example 2 with Example 10.
~078~
TABLE III
SAN - Rubber - Clay Blends . _ Example No. 15 16 17 18 19 20 _ SANl 100 100 100 100 100 100 Urethane2 25.4 33.9 43.6 42.4 42.3 Nitrile Rubber3 ~ - - - - 25.4 Clay4 31.7 33.9 36.4 25.4 48 31.7 Tensile Str (psi) 6750 5650 4900 4760 4800 5800 Elongation (%) 9 9 28 25 9 7 Tensile Modulus (p8ixl~ 5) 5 5 4 9 3.6 3.8 4.7 4.7 Falling Dart Impact (ft. lbs) <2 2-3 2-4 6 6-8 2-4 _ Notes:
1. Copolymer of 70~ styrene and 30% acrylonitrile; Dart Impact <1.0 ft. lb.
2. See note 3, TABLE II.
3. See note 3, TABLE 1.
4. See note 4, TABLE I.
cm/,-~l~
107808~
It will be apparent from the test data fox Examples 16-20 shown in TABLE III, that useful improvements in tensile modulus and impact result with clay-filled compositions based on SAN copolymers. Again, the ratio of rubber to clay has some effect on final properties, as does the total amount and type of rubber employed. A blend prepared as in Example 20, but having no rubber component present was too brittle for testing purposes.
A blend of 100 parts by weight of impact modified polystyrene having a tensile modulus of 2.9xlO 5 psi, a tensile strength of 3700 psi and a falling dart impact of <1 ft. lb. (obtained from Amoco Chemicals Co. as H4F) with 27.6 parts Harwick 50R clay, 7 parts nitrile rubber and 0.7 parts magnesium stearate was prepared by Banbury mixing the blend, then dicing and molding it to form test plaques as before. These test plaques had a tensile modulus of 4.5xlO 5 psi and a falling dart impact strength of 2-4 ft. lbs. A control blend prepared without nitrile rubber, and having 100 parts polystyrene and 25 parts clay had a tensile modulus of 4.5xlO psi and a falling dart impact of less than 1 foot pounds.
A blend of 100 parts by weight of the ABS
I employed in Example 2, 9.7 parts by weight nitrile rubber of Example 2 and 27.8 parts by weight calcium carbonate having an average particle size of 0.03 microns was prepared by Banbury mixing as described above. The test plaques had a falling dart impact value of 8-10 ft. lbs.
_ AMPLE 23 3~ A blend of 100 parts by weight of the ABS
I employed in Example 2, 9.7 parts by weight nitrile rubber of Example 2, 28 parts by weight titanium dioxide pigment having .
~ Trademark cm/ ~ h ~078088 an average particle size of 0.2 microns, and 1.4 parts by weight of magnesium stearate was prepared by Banbury mixing as described above. The test plaques had a falling dart impact of 20-26 ft. lbs., and a tensile modulus of 3.2xlO psi.
A blend of 100 parts by weight of the ABS
II employed in Example 7, 0.75 parts by weight magnesium stearate, 20.0 parts by weight brominated biphenyl (flame retardant), 7.5 parts by weight antimony oxide having an average particle size of 1.0 micron, 0.5 parts by weight polyether lubricant and 5.0 parts by weight of the nitrile rubber of Example 7 was prepared by Banbury mixing as before. The test plaques had a falling dart impact strength of 12-14 ft. lbs.
It will thus be seen that the method of the present invention may be employed to provide marked improve-ment in impact properties of-rigid, filled thermoplastic resins.
It will be apparent to one skilled in the art that it will be possible to extend the technology to include blends of the com-positions of this invention with other thermoplastic resins such as for example the well known blends of impact polystyrene with polyphenylene ethers, as well as blends of ABS with such thermo-plastics as PVC,- and the method may be used to overcome losses in impact properties of thermoplastic resin compositions which result when pigments, fiberous particles and similar materials are included at moderate to high loading levels.
The high impact, high modulus compositions of this invention may also be extruded into profiles or sheet material and subsequently thermoformed as well as being processed by injection molding methods. These materials are useful in molde~ articles for automotive, household and similar applications where low cost, high impact strength and dimensional stability are important.
* Trademar~
~ _ "~, 1078~88 The Examples are provided by way of illustration to better demonstrate the useful improvements in impact properties that result from the use of particulate fillers together with thermoplastic rubbers in preparing blend compositions with rigid thermoplastics, and the invention is not intended to be limited to the specific polymers and formulations disclosed herein. It will be further apparent that various modifications of these blends to include the use of mixed particulate fillers, processing aids, stabilizers and the like may be made without departing from the spirit of the invention, and the scope thereof is limited solely by the appended claims.
cm/~
Claims (4)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A filled thermoplastic composition characterized by the composition comprising 1) a thermoplastic resin selected from the group polystyrene, styrene-acrylonitrile copolymers, graft polymers prepared by polymerizing styrene in the presence of a diene rubber and graft polymers prepared by polymerizing a mixture of styrene and at least one additional vinyl monomer copolymerizable therewith in the presence of a diene rubber, 2) from 2.0 to 60 parts by weight, based on 100 parts by weight thermoplastic resin, of a thermoplastic rubber selected from the group consisting of butadiene-acrylonitrile copolymers and urethane elastoplastics, and 3) from 5 to 250 parts by weight based on 100 parts by weight thermoplastic resin of a particulate filler having an average particle size less than 2.0 microns.
2. The filled thermoplastic composition of claim 1 characterized by the composition containing from .1 to about 5 parts by weight magnesium stearate.
3. The filled thermoplastic composition of claim 1 characterized in that the thermoplastic resin is a copolymer of styrene and acrylonitrile.
4. The filled thermoplastic composition of claim 1 characterized in that the thermoplastic resin is a graft polymer prepared by polymerizing styrene and acrylonitrile in the presence of polybutadiene.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US58150775A | 1975-05-28 | 1975-05-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1078088A true CA1078088A (en) | 1980-05-20 |
Family
ID=24325474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA250,824A Expired CA1078088A (en) | 1975-05-28 | 1976-04-22 | Filled polystyrene, san or abs blends with nitrile rubber or urethane rubber |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS6038414B2 (en) |
| CA (1) | CA1078088A (en) |
| DE (1) | DE2624024B2 (en) |
| FR (1) | FR2312537A1 (en) |
| GB (1) | GB1537395A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5736141A (en) * | 1980-08-13 | 1982-02-26 | Asahi Chem Ind Co Ltd | Thermoplastic resin composition |
| DE3120831A1 (en) * | 1981-05-26 | 1982-12-16 | SKS-Technik Säure- und Korrosionsschutz GmbH, 7320 Göppingen | Plastic mortars for the production of screeds or concrete |
| EP0487124A1 (en) * | 1990-11-16 | 1992-05-27 | SOLVAY (Société Anonyme) | Gelified preblends based on thermoresistant polymers and PVC-based compositions containing them |
| CN109082101B (en) * | 2018-07-03 | 2020-11-27 | 阜南县创发工艺品有限公司 | High-strength artificial wood board for weaving and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51117747A (en) * | 1975-04-08 | 1976-10-16 | Sumitomo Naugatuck Co Ltd | Semi-rigid or flexible resin compositions |
| JPS51126245A (en) * | 1975-04-25 | 1976-11-04 | Sumitomo Naugatuck Co Ltd | Semi-rigid abs resin composition |
-
1976
- 1976-04-22 CA CA250,824A patent/CA1078088A/en not_active Expired
- 1976-05-13 GB GB19838/76A patent/GB1537395A/en not_active Expired
- 1976-05-24 JP JP51059927A patent/JPS6038414B2/en not_active Expired
- 1976-05-26 FR FR7616013A patent/FR2312537A1/en active Granted
- 1976-05-28 DE DE2624024A patent/DE2624024B2/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6038414B2 (en) | 1985-08-31 |
| GB1537395A (en) | 1978-12-29 |
| FR2312537B1 (en) | 1980-12-26 |
| DE2624024A1 (en) | 1976-12-09 |
| DE2624024B2 (en) | 1979-05-23 |
| JPS5281361A (en) | 1977-07-07 |
| FR2312537A1 (en) | 1976-12-24 |
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