CA1319772C - Elastomer modified blow moldable polyester - Google Patents
Elastomer modified blow moldable polyesterInfo
- Publication number
- CA1319772C CA1319772C CA000577283A CA577283A CA1319772C CA 1319772 C CA1319772 C CA 1319772C CA 000577283 A CA000577283 A CA 000577283A CA 577283 A CA577283 A CA 577283A CA 1319772 C CA1319772 C CA 1319772C
- Authority
- CA
- Canada
- Prior art keywords
- weight
- ethylene
- injection molding
- molding grade
- polyester
- 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 - Fee Related
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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
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
- C08L2666/18—Polyesters or polycarbonates according to C08L67/00 - C08L69/00; Derivatives thereof
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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
In general, blow moldable or extrusion grade polyesters are quite expensive. A relatively inexpensive blow moldable polyester composition can be produced by modifying a low or injection molding grade of polyester with sufficient elastomer to reduce the viscosity of the injection molding grade polyester to a level at which the latter can be blow molded. For example, a copolyester prepared by transesterification using readily available starting materials such as dimethyl terephthalate polytetramethylene ether glycol and 1,4-butanediol can be mixed with an elastomer selected from the group consisting of ethylenepropylene diene terpolymer, ethylenepropylene diene terpolymer in combination with high density polyethylene, ethylene-vinyl acetate thermoplastic copolymer, and styrene-ethylene-butylene-styrene block copolymer to yield a relative inexpensive molding grade polyester composition.
In general, blow moldable or extrusion grade polyesters are quite expensive. A relatively inexpensive blow moldable polyester composition can be produced by modifying a low or injection molding grade of polyester with sufficient elastomer to reduce the viscosity of the injection molding grade polyester to a level at which the latter can be blow molded. For example, a copolyester prepared by transesterification using readily available starting materials such as dimethyl terephthalate polytetramethylene ether glycol and 1,4-butanediol can be mixed with an elastomer selected from the group consisting of ethylenepropylene diene terpolymer, ethylenepropylene diene terpolymer in combination with high density polyethylene, ethylene-vinyl acetate thermoplastic copolymer, and styrene-ethylene-butylene-styrene block copolymer to yield a relative inexpensive molding grade polyester composition.
Description
~ 3 ~ s~
This invention relates to a polyester composition, and in particular to an elastomer modified polyester composition.
In general, injection molding grades of polyesters are not blow moldable. slow moldable or extrusion grade polyester is expensive. Obviously, if blow moldable polyesters can be rendered extrudable or blow moldable, a substantial cost saving can be realized.
The object of the present invention is to meet the above described need by providing a polyester composition including a low or injecti.on molding grade of polyester which is modified to be blow moldable.
Accordingly, the present invention relates to a blow moldable composition comprising a homogeneous mixture of an injection molding gxade polyester and sufficient elastomer to reduce the viscosity of the injection molding grade polyester to level at which the latter can be blow molded.
The following is a list of trade marks used in the detailed description of the invention.
Hytrel is an E.I. duPont de Nemours (hereinafter referred to simply as duPont) trade mark for a copolyester prepared by transesterification using readily available starting materials such as dimethyl terephthalate polytetramethylene ether glycol and 1,4-butanediol. The polymers are normally synthesized by conventional equilibrium melt condensation polymerization in the presence of an ester interchange catalyst. The resulting products are random block copolymers consisting of crystalline 1,4-butanediol hard segments and amorphous elastomeric poly-alkylene ether terephthalate soft segments. Hytrel provides excelIent resistance to non-polar materials such as oils and ' '~` -hydraulic fluids even at elevated temperatures, and is resistant to most polar fluids such as acids, bases, amines and glycols at room temperature. The resistance of Hytrel to hot moist enviroments is also good. In general, Hytrel is resistant to the same classes of chemicals and fluids as polyurethanes, both ester and ether based. However, Hytrel has better high temperature properties than polyurethanes. Hytrel polyester elastomers do not contain an extractable plasticizer as do flexible vinyls, certain grades of nylon and many rubber compounds.
Many fluids and chemi.cals will extract the plasticizer from these materials, causing a significant increase in stiffness and volume shrinkage. Hytrel has excellent flexibility at room temperature and low temperatures, excellent flex crack resistance, resistance to tear, abrasion and impact, and has a service temperature of -50 C to 110C.
Lomod B0100 and B0200 are General Electric trade marks for a polyester.
Admer L2100 is a Mitsui Petrochemical Industries ltd.
trade mark for a maleic anhydride modified polyolefin adhesive.
Surlyn 1705 is a duPont trade mark for an ionomer based on zinc salts of ethylene/(meth) acrylic acid copolymers.
The zinc ions neutralize from 10 to 90% of the acid groups, and the remaining unsaturated carboxylic acids can be either mono or dicarboxylic acids such as acrylic, methacrylic (preferred), ethacrylic, itaconic, maleic-fumaric acids, hydrogen maleate :
.
.
:~ 3 ~ 2 and methyl hydrogen fumarate. Surlyn provides thermal stability, excellent abrasion and impact resistance. Most ionomers are insoluble in common organic solvents at room temperature, and resist a~tack from most mild acids and bases. Outstanding low temperature flex and impact toughness are characteristic.
The brittleness temperature for the polymers is as low as -110C.
Finally, the change in modulus versus temeprature is relatively small.
Elvax 265 is an E.I. duPont de Nemours trade mark for an ethylene-vinyl acetate (EVA) thermoplastic copolymer including from 5 - 50~ by weight vinyl acetate in an ethylene chain. EVA copolymers are polymerized under high pressure using reactors of the type used to make conventional low density polyethylene to yield a highly branched, copolymer with acetoxy groups positioned randomly along the carbon chain. The vinyl acetate reduces the polymers crystallinity which increases flexibility, and improves low temperature flexibility, impact strength, weatherability, and oil and grease resistance.
Nordel 5892 is a du Pont trade mark for ethylenepropylene diene( EPDM), which is a terpolymer elastomer produced in several variations, the principle variant being the diene mentioned above. Dicyclopentadiene, ethylidene norbornene and 1,4-hexadiene are the types usually selected as the nonconjugated diene component.
The unsaturation remaining after the initial syntheses is utilized in classical sulfur type vulcanization. Nordel hydrocarbon ' ' '' . :
~ ' .
- .
~ 3 ~ 2 elastomers are extremely resistant to attack by ozone, oxygen and weather. Moreover, properly prepared vulcanizates of Nordel are outstanding in resistance to deterioration by heat, steam and many chemicals.
Kraton G1650 is a Shell trade mark for styrene-ethylene-butylene-styrene block copolymer of the A-s-A type, where A
represents polystyrene end blocks and s represents a polyolefin rubber midblock. Since Kraton G rubbers have a unique olefin rubber midblock, they are heat and shear stable at processing temperatures as high as 500F. Finished articles formed of Kraton G rubbers are highly resistant to ozone attack, oxidation and degradation from exposure to sunlight. The elastomers provide excellent resistance to water, acids and bases, and are flexible at low temperatures.
Kraton G7610X is a Shell trade mark for an experimental copolymer of the above-described type.
NDG 4167 is a duPont trade mark for a preblended com-bination of Nordel (EPDM) and high density polyethylene having outstanding low temperature toughness and high stiffness.
GEOLAST 703-40 is a Monsanto trade mark for a thermo-plastic elastomer with superior oil resistance and excellent heat aging.
Several compositions were produced in an effort to convert high viscosity injection molding grade material to a lower viscosity material for use in a wide range oE applications : ~
:
7 7 ?J
such as blow molding, extrusion and perhaps injection blow molding.
It has been found that the introduction of an elastomer into the polyester lowers the melt flow of the material and subsequently the viscosity. Several of the compositions were tested for blow moldability by producing parts using conventional blow molding techniques.
In general terms, the blow molding technique involves the extrusion of a tubular parison into a mold, closing of the mold, and blowing of air into the parison to conform the shape thereof to that of the mold. The temperatures used are dependent upon the combinations of materials in the parison, and a consideration of the melt temperatures at lowest possible processing temperature of the combinations. Some of the compositions were coextruded into three layer articles by coextruding three thermoplastic masses through a common extrusion nozzle, each mass being in the form of a layer, whereby a three layer body is formed. The three thermoplastic resins are fed from three separate hoppers, the thickness of each layer varying in accordance with the rate of revolution and dimensions of the three individual screws leading from the hoppers. The thickness of each layer can range from 2 - 98% of the total thickness of the coextrusion. All of the compositions tested for extrusion and blow molding proved to be quite successful.
Table 1 below provides three examples of compositions, which were blow molded using the above described technique at a melt temperature of 220C.
.:
, .
- . : . .
;
INGREDIENTS COMPOSITION
EX.l EX.2 EX.3 HYTREL 5556 40~ 40% 40%
NORDEL 5892 (EPDM) 40% 46%
NDG 4167 (EPDM) 40%
ELVAX 265 (EVA~ 20% 14% 20%
TEST RESULTS
Melt flow (g/lOmin) 1.64 1.03 3.98 Hardness (Shore D) 40 38 49 Specific gravity 1.010 1.003 1.100 Tensile Properties Type: Inj. Moulded Tensile strength (MPs) 15.7 13.5 11.0 Elongation, break (%) 480 400 475 Flexural Modulus (MPa) 46.3 43.7 67.9 In general, for a polymer to be blow moldable, the polymer must have a melt flow in the range of 0.8 - 6g/lOmin at the lower end of the polymers processing temperature range (without unmelted material being extruded). Although the above table provides a small sampling of compositions, which prove to be blow moldable, it is readily apparent that it should be possible to blow mold virtually any elastomer modified polyester,
This invention relates to a polyester composition, and in particular to an elastomer modified polyester composition.
In general, injection molding grades of polyesters are not blow moldable. slow moldable or extrusion grade polyester is expensive. Obviously, if blow moldable polyesters can be rendered extrudable or blow moldable, a substantial cost saving can be realized.
The object of the present invention is to meet the above described need by providing a polyester composition including a low or injecti.on molding grade of polyester which is modified to be blow moldable.
Accordingly, the present invention relates to a blow moldable composition comprising a homogeneous mixture of an injection molding gxade polyester and sufficient elastomer to reduce the viscosity of the injection molding grade polyester to level at which the latter can be blow molded.
The following is a list of trade marks used in the detailed description of the invention.
Hytrel is an E.I. duPont de Nemours (hereinafter referred to simply as duPont) trade mark for a copolyester prepared by transesterification using readily available starting materials such as dimethyl terephthalate polytetramethylene ether glycol and 1,4-butanediol. The polymers are normally synthesized by conventional equilibrium melt condensation polymerization in the presence of an ester interchange catalyst. The resulting products are random block copolymers consisting of crystalline 1,4-butanediol hard segments and amorphous elastomeric poly-alkylene ether terephthalate soft segments. Hytrel provides excelIent resistance to non-polar materials such as oils and ' '~` -hydraulic fluids even at elevated temperatures, and is resistant to most polar fluids such as acids, bases, amines and glycols at room temperature. The resistance of Hytrel to hot moist enviroments is also good. In general, Hytrel is resistant to the same classes of chemicals and fluids as polyurethanes, both ester and ether based. However, Hytrel has better high temperature properties than polyurethanes. Hytrel polyester elastomers do not contain an extractable plasticizer as do flexible vinyls, certain grades of nylon and many rubber compounds.
Many fluids and chemi.cals will extract the plasticizer from these materials, causing a significant increase in stiffness and volume shrinkage. Hytrel has excellent flexibility at room temperature and low temperatures, excellent flex crack resistance, resistance to tear, abrasion and impact, and has a service temperature of -50 C to 110C.
Lomod B0100 and B0200 are General Electric trade marks for a polyester.
Admer L2100 is a Mitsui Petrochemical Industries ltd.
trade mark for a maleic anhydride modified polyolefin adhesive.
Surlyn 1705 is a duPont trade mark for an ionomer based on zinc salts of ethylene/(meth) acrylic acid copolymers.
The zinc ions neutralize from 10 to 90% of the acid groups, and the remaining unsaturated carboxylic acids can be either mono or dicarboxylic acids such as acrylic, methacrylic (preferred), ethacrylic, itaconic, maleic-fumaric acids, hydrogen maleate :
.
.
:~ 3 ~ 2 and methyl hydrogen fumarate. Surlyn provides thermal stability, excellent abrasion and impact resistance. Most ionomers are insoluble in common organic solvents at room temperature, and resist a~tack from most mild acids and bases. Outstanding low temperature flex and impact toughness are characteristic.
The brittleness temperature for the polymers is as low as -110C.
Finally, the change in modulus versus temeprature is relatively small.
Elvax 265 is an E.I. duPont de Nemours trade mark for an ethylene-vinyl acetate (EVA) thermoplastic copolymer including from 5 - 50~ by weight vinyl acetate in an ethylene chain. EVA copolymers are polymerized under high pressure using reactors of the type used to make conventional low density polyethylene to yield a highly branched, copolymer with acetoxy groups positioned randomly along the carbon chain. The vinyl acetate reduces the polymers crystallinity which increases flexibility, and improves low temperature flexibility, impact strength, weatherability, and oil and grease resistance.
Nordel 5892 is a du Pont trade mark for ethylenepropylene diene( EPDM), which is a terpolymer elastomer produced in several variations, the principle variant being the diene mentioned above. Dicyclopentadiene, ethylidene norbornene and 1,4-hexadiene are the types usually selected as the nonconjugated diene component.
The unsaturation remaining after the initial syntheses is utilized in classical sulfur type vulcanization. Nordel hydrocarbon ' ' '' . :
~ ' .
- .
~ 3 ~ 2 elastomers are extremely resistant to attack by ozone, oxygen and weather. Moreover, properly prepared vulcanizates of Nordel are outstanding in resistance to deterioration by heat, steam and many chemicals.
Kraton G1650 is a Shell trade mark for styrene-ethylene-butylene-styrene block copolymer of the A-s-A type, where A
represents polystyrene end blocks and s represents a polyolefin rubber midblock. Since Kraton G rubbers have a unique olefin rubber midblock, they are heat and shear stable at processing temperatures as high as 500F. Finished articles formed of Kraton G rubbers are highly resistant to ozone attack, oxidation and degradation from exposure to sunlight. The elastomers provide excellent resistance to water, acids and bases, and are flexible at low temperatures.
Kraton G7610X is a Shell trade mark for an experimental copolymer of the above-described type.
NDG 4167 is a duPont trade mark for a preblended com-bination of Nordel (EPDM) and high density polyethylene having outstanding low temperature toughness and high stiffness.
GEOLAST 703-40 is a Monsanto trade mark for a thermo-plastic elastomer with superior oil resistance and excellent heat aging.
Several compositions were produced in an effort to convert high viscosity injection molding grade material to a lower viscosity material for use in a wide range oE applications : ~
:
7 7 ?J
such as blow molding, extrusion and perhaps injection blow molding.
It has been found that the introduction of an elastomer into the polyester lowers the melt flow of the material and subsequently the viscosity. Several of the compositions were tested for blow moldability by producing parts using conventional blow molding techniques.
In general terms, the blow molding technique involves the extrusion of a tubular parison into a mold, closing of the mold, and blowing of air into the parison to conform the shape thereof to that of the mold. The temperatures used are dependent upon the combinations of materials in the parison, and a consideration of the melt temperatures at lowest possible processing temperature of the combinations. Some of the compositions were coextruded into three layer articles by coextruding three thermoplastic masses through a common extrusion nozzle, each mass being in the form of a layer, whereby a three layer body is formed. The three thermoplastic resins are fed from three separate hoppers, the thickness of each layer varying in accordance with the rate of revolution and dimensions of the three individual screws leading from the hoppers. The thickness of each layer can range from 2 - 98% of the total thickness of the coextrusion. All of the compositions tested for extrusion and blow molding proved to be quite successful.
Table 1 below provides three examples of compositions, which were blow molded using the above described technique at a melt temperature of 220C.
.:
, .
- . : . .
;
INGREDIENTS COMPOSITION
EX.l EX.2 EX.3 HYTREL 5556 40~ 40% 40%
NORDEL 5892 (EPDM) 40% 46%
NDG 4167 (EPDM) 40%
ELVAX 265 (EVA~ 20% 14% 20%
TEST RESULTS
Melt flow (g/lOmin) 1.64 1.03 3.98 Hardness (Shore D) 40 38 49 Specific gravity 1.010 1.003 1.100 Tensile Properties Type: Inj. Moulded Tensile strength (MPs) 15.7 13.5 11.0 Elongation, break (%) 480 400 475 Flexural Modulus (MPa) 46.3 43.7 67.9 In general, for a polymer to be blow moldable, the polymer must have a melt flow in the range of 0.8 - 6g/lOmin at the lower end of the polymers processing temperature range (without unmelted material being extruded). Although the above table provides a small sampling of compositions, which prove to be blow moldable, it is readily apparent that it should be possible to blow mold virtually any elastomer modified polyester,
2~ i.e. to convert a injection molding grade polyester to a b].ow molding grade polyester by elastomeric modification thereof.
All of the compounds listed in Table 1 have similar basic physical properties. With the use of elastomers, hardness decreases so that any element produced with the compositions has increased flexibility. Because of the low tensile flexural modulus elongation and hardness values, the compositions could be used for articles such as strut covers, dust shields and .
~ 3 ~ 2 air ducts where flexibility is important. The use of EVA helps maintain the excellent physical properties exhibited by the base resin (polyester). The use of EPDM (Nordel 5892) results in a low blow molding melt flow range, and the use of EPDM
(NDG 4167) results in a high blow molding melt flow range.
The low blow molding melt flow range usually provides a more stable parison for use in the production of thick parts, while the higher melt flow materials are often used for the production of thin walled parts.
Table 2 lists a second set of compositions (Examples 4 to 7) of compositions produced in accordance with the present invention.
INGREDIENTS COMPOSITION
EX.4 EX.5EX.6 EX.7 15 HYTREL 4774 60% 60~ 60% 60~
NORDEL 58g2 (EPDM) 15~ 10% 14% 20%
ELVAX 265 (EVA) 25% 30% 20% 20 CaCO 6%
TEST RESULTS
Melt flow (g/lOmin) 6.77 8.54 6.10 5.27 Hardness (Shore D) 40 41 42-43 41 Specific gravity 1.070 1.0721.110 1.063 Tensile Properties Type: Inj. Moulded Tensile strength (MPa) 16.0 13.6 13.4 13.5 Elongation,break(%) 430 388 310 363 Flexural Modulus (MPa) 50.5 51.0 57.3 50.0 .
. . -.
:.
.
~3~7~
All of the compositions listed in Table 2 have similar basic physical properties. The hardness of the basic polyester is reduced providing increased flexibility. The high values for melt flow means that the compositions can be used for the production of thin-walled elements. The use of ethylene-vinyl acetate helps to maintain the excellent physical properties of the base resin (polyester).
A third set of three compositions having the same constituents as each other is listed in Table 3.
INGREDIENTS COMPOSITION
EX.8 EX.9 EX.10 HYTREL 5556 48% 46% 40~
NORDEL 5892 (EPDM)47% 44% 40%
SURLYN 1705 5% 10% 20%
TEST RESULTS
Melt flow (g/lOmin)1.04 1.13 1.18 Hardness (Shore D)42-43 45 44-46 Specific gravity1.018 1.020 0.996 Tensile Properties Type: Inj. Moulded Tensile strength (MPa) 13.6 15.1 17.5 Elongation, break (%) 405 430 445 Flexural Modulus (MPa) 56.3 60.7 79.8 Except for the one relating to the melt flow values, the comments with respect to Examples 4 to 7 are also applicable to Examples 8 to 10. The low melt flow values of the composition of Examples 8 to 10 provide a more stable parison for use in the production of thicker parts.
.
11 3~ ~7~f;~
Table 4 provides details of two examples oE modified polyesters which have similar physical properties, including low melt flows, reduced hardness, and good tensile, elongation and flexural modulus values. The dramatically reduced melt flow results in slow extrusion of material and minimum parison stretching, enabling the production of thick walled components.
The combination of low melt flow and low hardness means that the compositions can be used in the production of components which are expected to have a long life span (increased flexibility due to decreased hardness) and durability (thicker parts because of low melt flow). The good tensile, elongation and flexural modulus properties make the compositions useful for the production of constant velocity, stearing gear, suspension struts and shock absorber boots or covers.
INGREDIENTS COMPOSITION
EX.ll EX.12 HYTREL 5556 40% 40~
KRATON 1650 40% 46%
SURLYN 1705 20% 14%
TEST RES LTS
U
Melt flow (g/lOmin) 0.94 0.98 Hardness (Shore D) 49-50 43 Specific gravity 1.030 1.012 Tensile Properties Type: Inj. Moulded Tensile strength (MPa)22.5 21.0 Elongation, break (%) 530 550 Flexural Modulus (MPa)92.3 73.0 , ~ , , .
, '- : ~ ' ' ' ' ~ .
~: , - ~ .
7 ~ ~
The compositions listed in Table 5 also have similar physical properties.
INGREDIENTS COMPOSITION
EX.13 EX.14 EX.15 HYTREL 5556 50~ 50%
HYTREL 4774 60~
ELVAX 265 (EVA) 22% 30% 30%
KRATON G7610X 28~ 20~ 10%
TEST RESULTS
Melt flow (g/lOmin)17.5 7.16 16.33 Hardness (Shore D) 35 40 40 Specific gravity 1.075 1.070 1.085 Tensile Properties Type: Inj. Moulded Tensile strength (MPa) 11.0 11.2 14.9 Elongation,break (%) 310 380 410 Flexural Modulus (MPa) 60.9 63.7 49.4 The high melt flow, which is out of blow molding range means that the compositions can be used for injection blow molding. Reduced hardness leads to increased flexibility.
Tables 6 and 7 list additional compositions which have similar basic physical properties, including melt flows at the high end of the blow molding melt flow range enabling the production of thin-walled elements. Because of the low tensile and elongation (especially tensile) properties, the compositions are best suited for the production of flexible elements, e.g. dust covers and air ducts. For such elements, the tensile and elongation values need not be high, and the material must be sufficiently soft to flex under extreme temperature conditions.
, .- , . . .
., ,~- ' . ~- , :
' ~ ~31~772 INGREDIENTS COMPOSITION
EX.16 EX.17 LOMOD B0100 40%
LOMOD B0200 40%
NORDEL 5892 (EPDM) 40% 40%
ELVAX 265 (EVA) 20~ 20%
TEST RESULTS
Melt flow (g/lOmin) 4.28 4.05 Hardness (Shore D) 29 35 Specific gravity 0.093 1.000 Tensile Properties Type: Inj. Moulded Tensile strength (MPa) 6.7 10.4 Elonyation, break (%) 370 400 Flexural Modulus (MPa) 26.3 41.8 INGREDI_NTS COMPOSITION
EX.18 HYTREL 5556 40~
GEOLAST 703-40 40%
ELVAX 265 (EVA) 20%
TEST RESULTS
Melt flow (g/lOmin) 0.32 20 Hardness 31 Specific gravity 0.956 Tensile Properties Type: Inj. Moulded Tensile strength (MPa) 9.1 Elongation, break (~) 200 Flexural Modulus (MPa) 28.7 For comparison purposes, the characteristics of the basic polyesters and elastomers used in the above described compositions are listed in Table 8.
~ .
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~' ' ~, ' .' ~' . :
~L3~ ~72 ,~
All of the compounds listed in Table 1 have similar basic physical properties. With the use of elastomers, hardness decreases so that any element produced with the compositions has increased flexibility. Because of the low tensile flexural modulus elongation and hardness values, the compositions could be used for articles such as strut covers, dust shields and .
~ 3 ~ 2 air ducts where flexibility is important. The use of EVA helps maintain the excellent physical properties exhibited by the base resin (polyester). The use of EPDM (Nordel 5892) results in a low blow molding melt flow range, and the use of EPDM
(NDG 4167) results in a high blow molding melt flow range.
The low blow molding melt flow range usually provides a more stable parison for use in the production of thick parts, while the higher melt flow materials are often used for the production of thin walled parts.
Table 2 lists a second set of compositions (Examples 4 to 7) of compositions produced in accordance with the present invention.
INGREDIENTS COMPOSITION
EX.4 EX.5EX.6 EX.7 15 HYTREL 4774 60% 60~ 60% 60~
NORDEL 58g2 (EPDM) 15~ 10% 14% 20%
ELVAX 265 (EVA) 25% 30% 20% 20 CaCO 6%
TEST RESULTS
Melt flow (g/lOmin) 6.77 8.54 6.10 5.27 Hardness (Shore D) 40 41 42-43 41 Specific gravity 1.070 1.0721.110 1.063 Tensile Properties Type: Inj. Moulded Tensile strength (MPa) 16.0 13.6 13.4 13.5 Elongation,break(%) 430 388 310 363 Flexural Modulus (MPa) 50.5 51.0 57.3 50.0 .
. . -.
:.
.
~3~7~
All of the compositions listed in Table 2 have similar basic physical properties. The hardness of the basic polyester is reduced providing increased flexibility. The high values for melt flow means that the compositions can be used for the production of thin-walled elements. The use of ethylene-vinyl acetate helps to maintain the excellent physical properties of the base resin (polyester).
A third set of three compositions having the same constituents as each other is listed in Table 3.
INGREDIENTS COMPOSITION
EX.8 EX.9 EX.10 HYTREL 5556 48% 46% 40~
NORDEL 5892 (EPDM)47% 44% 40%
SURLYN 1705 5% 10% 20%
TEST RESULTS
Melt flow (g/lOmin)1.04 1.13 1.18 Hardness (Shore D)42-43 45 44-46 Specific gravity1.018 1.020 0.996 Tensile Properties Type: Inj. Moulded Tensile strength (MPa) 13.6 15.1 17.5 Elongation, break (%) 405 430 445 Flexural Modulus (MPa) 56.3 60.7 79.8 Except for the one relating to the melt flow values, the comments with respect to Examples 4 to 7 are also applicable to Examples 8 to 10. The low melt flow values of the composition of Examples 8 to 10 provide a more stable parison for use in the production of thicker parts.
.
11 3~ ~7~f;~
Table 4 provides details of two examples oE modified polyesters which have similar physical properties, including low melt flows, reduced hardness, and good tensile, elongation and flexural modulus values. The dramatically reduced melt flow results in slow extrusion of material and minimum parison stretching, enabling the production of thick walled components.
The combination of low melt flow and low hardness means that the compositions can be used in the production of components which are expected to have a long life span (increased flexibility due to decreased hardness) and durability (thicker parts because of low melt flow). The good tensile, elongation and flexural modulus properties make the compositions useful for the production of constant velocity, stearing gear, suspension struts and shock absorber boots or covers.
INGREDIENTS COMPOSITION
EX.ll EX.12 HYTREL 5556 40% 40~
KRATON 1650 40% 46%
SURLYN 1705 20% 14%
TEST RES LTS
U
Melt flow (g/lOmin) 0.94 0.98 Hardness (Shore D) 49-50 43 Specific gravity 1.030 1.012 Tensile Properties Type: Inj. Moulded Tensile strength (MPa)22.5 21.0 Elongation, break (%) 530 550 Flexural Modulus (MPa)92.3 73.0 , ~ , , .
, '- : ~ ' ' ' ' ~ .
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7 ~ ~
The compositions listed in Table 5 also have similar physical properties.
INGREDIENTS COMPOSITION
EX.13 EX.14 EX.15 HYTREL 5556 50~ 50%
HYTREL 4774 60~
ELVAX 265 (EVA) 22% 30% 30%
KRATON G7610X 28~ 20~ 10%
TEST RESULTS
Melt flow (g/lOmin)17.5 7.16 16.33 Hardness (Shore D) 35 40 40 Specific gravity 1.075 1.070 1.085 Tensile Properties Type: Inj. Moulded Tensile strength (MPa) 11.0 11.2 14.9 Elongation,break (%) 310 380 410 Flexural Modulus (MPa) 60.9 63.7 49.4 The high melt flow, which is out of blow molding range means that the compositions can be used for injection blow molding. Reduced hardness leads to increased flexibility.
Tables 6 and 7 list additional compositions which have similar basic physical properties, including melt flows at the high end of the blow molding melt flow range enabling the production of thin-walled elements. Because of the low tensile and elongation (especially tensile) properties, the compositions are best suited for the production of flexible elements, e.g. dust covers and air ducts. For such elements, the tensile and elongation values need not be high, and the material must be sufficiently soft to flex under extreme temperature conditions.
, .- , . . .
., ,~- ' . ~- , :
' ~ ~31~772 INGREDIENTS COMPOSITION
EX.16 EX.17 LOMOD B0100 40%
LOMOD B0200 40%
NORDEL 5892 (EPDM) 40% 40%
ELVAX 265 (EVA) 20~ 20%
TEST RESULTS
Melt flow (g/lOmin) 4.28 4.05 Hardness (Shore D) 29 35 Specific gravity 0.093 1.000 Tensile Properties Type: Inj. Moulded Tensile strength (MPa) 6.7 10.4 Elonyation, break (%) 370 400 Flexural Modulus (MPa) 26.3 41.8 INGREDI_NTS COMPOSITION
EX.18 HYTREL 5556 40~
GEOLAST 703-40 40%
ELVAX 265 (EVA) 20%
TEST RESULTS
Melt flow (g/lOmin) 0.32 20 Hardness 31 Specific gravity 0.956 Tensile Properties Type: Inj. Moulded Tensile strength (MPa) 9.1 Elongation, break (~) 200 Flexural Modulus (MPa) 28.7 For comparison purposes, the characteristics of the basic polyesters and elastomers used in the above described compositions are listed in Table 8.
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r~ u~ ~ ~ m In c~ u~o u~ ~H ~U ~) 0 H ~:1~ u~ ~ 0 h a ~ z ~i ~
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From the foregoing, it will be appreciated that preferred polyester compositions of the present invention include the following:
(i) a homogeneous mixture of from 40 to 60% by weight of an injection molding grade copolyester dimethyl terephthalate polytetramethylene ether glycol and 1,4-butanediol, from 10 to 50~ by weight of ethylene propylene diene terpolymer; and from 10 to 30% by weight of ethylene-vinyl acetate thermoplastic copolymer;
(ii) the composition of (i) above including 0 to 6%
by weight of calcium carbonate;
(iii) a homogeneous mixture of from 40 to ~0% by weight of an injection molding grade copolyester of dimethyl terephthalate polytetramethylene ether glycol and 1,4-butanediol, from 40 to 50% by weight of ethylenepropylene diene terpolymer and from 5 to 20% by weight of an ionomer based on zinc salts of ethylene/(meth) acrylic acid copolymers;
(iv) the composition of (iii) above containing approximately 40% by weight of the copolyester, from 40 to 50%
by weight of the terpolymer and from 10 to 20% by weight of the ionomer;
(v) a homogeneous mixture of from 50 to 60~ by weight of an in~ection molding grade copolyester of dimethyl terephthalate polytetramethylene ether glycol and 1,4-butanediol, from 20 to 30% by weight ethylene-vinyl acetate ~.
copolymer, and from 10 to 30% by weight styrene-ethylene-' :, ' . ' : . . . ~ , ' ~ ' ' ~ 3~7~
butylene-styrene block copolymer of the A-B-A type, where A
represents polystyrene end blocks and B represents a polyolefin rubber midblock;
(vi) a homogeneous mixture of approximately 40% by weight of an injection molding grade polyester, approximately 40% by weight of ethylene-propylene diene terpolymer and approximately 20% by weight of ethylene-vinyl acetate thermoplastic copolymer; and (vii) a homogeneous mixture of approximately 40% by weight of an injection molding grade copolyester of dimethyl terephthalate polytetramethylene ether glycol and 1,4-butanediol; approximately 40% by weight of a thermoplastic elastomer and approximately 20% by weight of ethylene-vinyl acetate thermoplastic copolymer.
Obviously, the ingredients of the various compositions must be compatible.
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m ,~ o o .c O ~D
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From the foregoing, it will be appreciated that preferred polyester compositions of the present invention include the following:
(i) a homogeneous mixture of from 40 to 60% by weight of an injection molding grade copolyester dimethyl terephthalate polytetramethylene ether glycol and 1,4-butanediol, from 10 to 50~ by weight of ethylene propylene diene terpolymer; and from 10 to 30% by weight of ethylene-vinyl acetate thermoplastic copolymer;
(ii) the composition of (i) above including 0 to 6%
by weight of calcium carbonate;
(iii) a homogeneous mixture of from 40 to ~0% by weight of an injection molding grade copolyester of dimethyl terephthalate polytetramethylene ether glycol and 1,4-butanediol, from 40 to 50% by weight of ethylenepropylene diene terpolymer and from 5 to 20% by weight of an ionomer based on zinc salts of ethylene/(meth) acrylic acid copolymers;
(iv) the composition of (iii) above containing approximately 40% by weight of the copolyester, from 40 to 50%
by weight of the terpolymer and from 10 to 20% by weight of the ionomer;
(v) a homogeneous mixture of from 50 to 60~ by weight of an in~ection molding grade copolyester of dimethyl terephthalate polytetramethylene ether glycol and 1,4-butanediol, from 20 to 30% by weight ethylene-vinyl acetate ~.
copolymer, and from 10 to 30% by weight styrene-ethylene-' :, ' . ' : . . . ~ , ' ~ ' ' ~ 3~7~
butylene-styrene block copolymer of the A-B-A type, where A
represents polystyrene end blocks and B represents a polyolefin rubber midblock;
(vi) a homogeneous mixture of approximately 40% by weight of an injection molding grade polyester, approximately 40% by weight of ethylene-propylene diene terpolymer and approximately 20% by weight of ethylene-vinyl acetate thermoplastic copolymer; and (vii) a homogeneous mixture of approximately 40% by weight of an injection molding grade copolyester of dimethyl terephthalate polytetramethylene ether glycol and 1,4-butanediol; approximately 40% by weight of a thermoplastic elastomer and approximately 20% by weight of ethylene-vinyl acetate thermoplastic copolymer.
Obviously, the ingredients of the various compositions must be compatible.
f '~;^, :
~ . -- . ' .
Claims (9)
EXCLUSIVE PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS
FOLLOWS:
1. A blow moldable polyester composition comprising a homogeneous mixture of an injection molding grade polyester and sufficient elastomer to reduce the viscosity of the injection molding grade polyester to a level at which the latter can be blow molded.
2. A composition according to claim 1 wherein said injection molding grade polyester is a copolyester of dimethyl terephthalate polytetramethylene ether glycol and 1,4-butanediol, and said elastomer is selected from the group consisting of ethylenepropylene diene terpolymer, ethylenepropylene diene terpolymer in combination with high density polyethylene, ethylene-vinyl acetate thermoplastic copolymer, and styrene-ethylene-butylene-styrene block copolymer.
3. A blow moldable polyester composition comprising a homogeneous mixture of from 40 to 60% by weight of an injection molding grade copolyester of dimethyl terephthalate polytetramethylene ether glycol and 1,4-butanediol, from 10 to 50% by weight of ethylenepropylene diene terpolymer and from 10 to 30% by weight of ethylene-vinyl acetate thermoplastic copolymer.
4. A composition according to claim 3, including from 0 to 6% by weight of calcium carbonate.
5. A blow moldable polyester composition comprising a homogeneous mixture of from 40 to 50% by weight of an injection molding grade copolyester of dimethyl terephthalate polytetramethylene ether glycol and 1,4-butanediol, from 40 to 50% by weight of ethylenepropylene diene terpolymer and from 5 to 20% by weight of an ionomer based on zinc salts of ethylene/(meth) acrylic acid copolymers.
6. A blow moldable polyester composition comprising a homogeneous mixture of approximately 40% by weight of an injection molding grade copolyester of dimethyl terephthalate polytetramethylene ether glycol and 1,4-butanediol, from 40 to 50% by weight of ethylenepropylene diene terpolymer and from 10 to 20% by weight of an ionomer based on zinc salts of ethylene/(meth) acrylic acid copolymers.
7. A blow moldable polyester composition comprising a homogeneous mixture of from 50 to 60% by weight of an injection molding grade copolyester of dimethyl terephthalate polytetramethylene ether glycol and 1,4-butanediol, from 20 to 30% by weight of ethylene-vinyl acetate thermoplastic copolymer, and from 10 to 30% by weight of styrene-ethylene-butylene-styrene block copolymer of the A-B-A type, where A
represents polystyrene end blocks and B represents a polyolefin rubber midblock.
represents polystyrene end blocks and B represents a polyolefin rubber midblock.
8. A blow moldable polyester composition comprising a homogeneous mixture of approximately 40% by weight of an injection molding grade polyester, approximately 40% by weight of ethylene-propylene diene terpolymer and approximately 20%
by weight of ethylene-vinyl acetate thermoplastic copolymer.
by weight of ethylene-vinyl acetate thermoplastic copolymer.
9. A blow moldable polyester composition comprising a homogeneous mixture of approximately 40% by weight of an injection molding grade copolyester of dimethyl terephthalate polytetramethylene ether glycol and 1,4-butanediol, approximately 40% by weight of thermoplastic elastomer and approximately 20% by weight of ethylene-vinyl acetate thermoplastic copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000577283A CA1319772C (en) | 1988-09-13 | 1988-09-13 | Elastomer modified blow moldable polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000577283A CA1319772C (en) | 1988-09-13 | 1988-09-13 | Elastomer modified blow moldable polyester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1319772C true CA1319772C (en) | 1993-06-29 |
Family
ID=4138719
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000577283A Expired - Fee Related CA1319772C (en) | 1988-09-13 | 1988-09-13 | Elastomer modified blow moldable polyester |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1319772C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2325257A1 (en) * | 2009-11-19 | 2011-05-25 | DSM IP Assets B.V. | Process for producing a shaped article |
| WO2014047173A1 (en) * | 2012-09-18 | 2014-03-27 | Ticona Llc | Polymer articles made from a blend of a copolyester elastomer and an alpha-olefin vinyl acetate copolymer |
-
1988
- 1988-09-13 CA CA000577283A patent/CA1319772C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2325257A1 (en) * | 2009-11-19 | 2011-05-25 | DSM IP Assets B.V. | Process for producing a shaped article |
| WO2014047173A1 (en) * | 2012-09-18 | 2014-03-27 | Ticona Llc | Polymer articles made from a blend of a copolyester elastomer and an alpha-olefin vinyl acetate copolymer |
| CN104540893A (en) * | 2012-09-18 | 2015-04-22 | 提克纳有限责任公司 | Polymer articles made from a blend of a copolyester elastomer and an alpha-olefin vinyl acetate copolymer |
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