CA2133208A1 - A polymer composition comprising a mixture of a crystalline or semi/crystalline polyolefin and a polymer based on vinylaromatic and dicarboxylic acid anhydride monomer units - Google Patents
A polymer composition comprising a mixture of a crystalline or semi/crystalline polyolefin and a polymer based on vinylaromatic and dicarboxylic acid anhydride monomer unitsInfo
- Publication number
- CA2133208A1 CA2133208A1 CA002133208A CA2133208A CA2133208A1 CA 2133208 A1 CA2133208 A1 CA 2133208A1 CA 002133208 A CA002133208 A CA 002133208A CA 2133208 A CA2133208 A CA 2133208A CA 2133208 A1 CA2133208 A1 CA 2133208A1
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- Prior art keywords
- polymer
- polymer composition
- polyolefin
- crystalline
- dicarboxylic acid
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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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L35/00—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 carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L35/06—Copolymers with vinyl aromatic monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Abstract
A polymer composition comprising a mixture of a crystalline or semi-crystalline polyolefin A and a polymer B based on vinyl-aromatic and dicarboxylic acid anhydride monomer units. The polymer B
is chemically crosslinked with a compound which contains at least two functional groups which are able to react with the dicarboxylic acid anhydride group of the polymer B; polymer B can also be physically crosslinked.
is chemically crosslinked with a compound which contains at least two functional groups which are able to react with the dicarboxylic acid anhydride group of the polymer B; polymer B can also be physically crosslinked.
Description
WO 93/20144 ~ PCI`/I~iL93/00068 `, i , :
P(:)LYMER COMPOSITION COMPRISING A MIXTURE OF A ~RYSTALLINE OR SEMI~
CRYSTALLINE POLYOLEFIN ANr) A POLYMER BASED ON VINYLAROMATI(:` ANI) RBOXYLlC A~ ANHYr3Rll~E MONOMER UNITS
The invention relat~s to a polymer composition comprising a mixture of a crystalline or semi-crystalline polyolefin (A) and a polymer (B) based on vinyl-aromatic and dicarboxylic acid anhydride monomer units.
A polymer composition of this type is known from WO-A-9005759. In WO-A-9005759 a polymer mixture of a crystalline or semi-crystalline polyole~in and a second polymer, such as a copolymer of styrene and maleic anhydride, is described. Since the polyolefin ancl the second polymer are not miscible, the polymer mixture contains a compatibiliser. According to this publication, the compatibiliser is a block copolymer of a vinyl-aromatic -compound and a conjugated diene or partially hydrogenated derivatives thereof. Here and hereafter a compatibiliser is understood to be a compound which improves the compatibility of A and B and is primarily located at the interface of the `
polyolefin A and the polymer B.
It is known from JP-A-63.2050341 to use styrene-containing rubber-like copolymers as compatibilisers in polymer compositions consisting of polypropene and styrene/maleic anhydride copolymers. A drawback of these polymer compositions is, however, that the impact strength/rigidity combinatisn (Izod vs. modulus of elas-- ticity) is poor, as a result of which the polymer com-positions are unsuitable for structural moulded components which are used in, for example, cars and furniture.
The aim of the invention is to provide a polymer composition of a~ polyolefin A and a polymer B based onvinyl-aromatic monomer units and dicarboxylic acid anhydride WO93/201~ PCT/NL93/00068 , _ ~
monomer units, which has a good impact strength/rigidity combination.
The invention is characterised in that the polymer B is crosslinked. The crosslinking of the polymer B can be either of the chemical or the physical type. Physical crosslinking is effected under the influence of Van der Waals forces, dipole-dipole interactions and ionogenic interactions.
Polymer B can be chemically crosslinked by a reaction with a compound which contains at least two functional groups which are able to react with the dicarboxylic acid anhydride group of the polymer.
A further advantage of the polymer composition according to the invention is that the elongation at break of the polymer composition increases.
Another advantage of the polymer composition according to the invention is that the said composition also `
has good scratch resistance and paintability~
Compounds containing two or more alcohol or thiol functional groups form a first group of possible compounds suitable for crosslinking the polymer B. lhe combination of alcohol and thiol functional groups in a compound is also possible. Compounds containing two or more alcohol functional groups, such as 1,4-butanediol, 1,6-hexanediol, pentaerythritol, ethyiene glycol and propylene glycol and polymers thereof are preferred. Polyhydroxy ethers can also be used, for example polyhydroxy ethers based on bisphenol A.
Compounds containing two or more primary or secondary amine functional groups, preferably primary amine groups, form a second group of compounds suitable for crosslinking the polymer B. llhe following may be mentioned as examples of these compounds containing amine functional ~roups: alkane diamines containing a C~-C20 alkylene group, such as 1,4-diaminobutane and 1,6-diaminohexane, polyoxy-ethylene diamine, polyoxypropylene diamine, polyoxypropylene triamine, diphenyl sulphone diamine, 1,3-phenylene-diamine WO93/201~ ~ J ~ ' PCT/NL93/()006X
and 1,4-phenylene diamine. The combination of one or more primary amine groups with one or more secondary amine groups in a compound is possible. Polyamides can also be used. The compound suitable for crosslinking the polymer B can also contain at least one alcohol or thiol group and also at least one amine group. Diethanolamine and monoethanolamine are examples of this type of compound.
Compounds containing two or more epoxide functional groups having the general formula: ~
:
( CR------CHR ) n .
\ O ~
-in which n22 and R is a hydrocarbon radical or a hydrogen ;;
atom form a third group of compounds suitable for cross-linking the polymer B. Examples of such compounds are: -polyglycidyl ethers of polyhydroxyl-substituted compounds.
These compounds can be subdivided into polyepoxide compounds of the aromatic type, such as can be obtained from bisphenol A, and polyepoxide compounds of the aliphatic type, such as -polyglycidyl ethers of polyalcohols. The following may be -mentioned as examples of the latter type of polyepoxide compounds: diglycidyl ethers of -~ diols, such as butanediol diglycidyl çther, hexanediol diglycidyl ether, paracyclohexyldimethanol diglycidyl ether, neopentyl glycol di~lycidyl ether and bisphenol A diglycidyl ether.
Preferably, compounds are used which are the result of the 30 epoxidation of olefins, such as epoxidised soya oil. ~ -When crosslinking with an epoxide compound it is usually desirable to use an activator, such as an imidazole, a quaternary ammonium salt or a tertiary amine.
- ~ Compounds containing 2 or more oxazoline groups form a fourth group of compounds suitable for crosslinking the polymer B. 1,3-phenylenebisoxazoline may be mentioned a~
an example of these compounds.
Compounds containing 2 or more isocyanate groups form a fifth group of compounds suitable for crosslinking -`
WO93/201~ ; !? ~ 4 _ PCT/NL93/0006X
the polymer s. Examples of these compounds are toluene 2,4-diisocyanate, benzene 1,3,5-triisocyanate and methanediphenyl diisocyanate.
Salts of metal atoms from groups 2-lO of the Periodic System of the Elements (Handbook of Chemistry and Physics, 70th Edition, CRC Press, 1989-1990) form a sixth group of compounds suitable for crosslinking the polymer B.
Preferably, metal alkoxides and salts of divalent positive ions are used, such as tetrabutoxytitanium, zinc oxide and zinc acetate.
A compound containing two or more functional groups, chosen from the abovementioned groups, is also suitable for crosslinking the polymer B.
A mixture of compounds suitable for crosslinkinq the polymer B, chosen from one or more of the abovementioned ~-groups of compounds, can also be used.
The compound suitable for crosslinking the polymer B is present in an amount of 0.1-20 mol~ with respect to the amount of dicarboxylic acid anhydride groups present in polymer B. ~`
Crystalline or semi-crystalline polyolefins A which `-can be used in a polymer composition according to the invention are homopolymers, copolymers or terpolymers or mixtures thereo~. Polymers of -olefins are preferably used and these -olefins generally have 2 to 20 carbon atoms. The use of polymers of -olefins having 2-6 carbon atoms is particularly preferred.
The crystalline or semi-crystalline polyolefins are derived from olefins, such as ethylene, propylene, l-butene, 1-pentene, 4 methyl-1-pentene, l-octene, l-decene, 4-ethyl-l-hexene, etc. Examples of particularly suitable polyolefins - are: low density polyethylene, high density polyethylene, linear low density polyethylene, ultra-low density poly-ethylene, polypropylene, (high and low density) poly(l-butene), poly(4-methyl-1-pentene), ethylene/propylene copolymers and copolymers of ethylene and/or propylene with other copolymerisable monomers, such as ethylene/l-butene WO93/201~ PCT/NL93/00068 copolymer, ethylene/vinyl acrylate copolymer or ethylene/-vinyl acetate. Polymers and copolymers of halogenated olefins can also be used.
An amount of 30-95 parts by weight of polyolefin A
is present in the polymer composition, based on the sum of polyolefin A and polymer B. The amount of polyolefin is preferably 60-80 parts by weight. The amount of polyolefin A
in the polymer composition can proportionally be lowered when a functionalised polyolefin A is used as compatibiliser (see below).
- Polymer B comprises vinyl-aromatic monomer units and dicarboxylic acid anhydride monomer units. Suitable vinyl-aromatic monomers for use in the polymer B are,- for example, styrene, alpha-methyl-styrene, para-methylstyrene and mixtures thereof. Styrene is preferably used.-Suitable dicarboxylic acid anhydrides are, for ;~
example, maleic anhydride, chloromaleic anhydride, citraco-nic anhydride, cyclohexylmaleic anhydrids, benzyl maleic anhydride, phenyl maleic anhydride, aconitic anhydride, propyl maleic anhydride and mixtures thereof. Maleic anhy-dride (MA) is preferably used.
Polymer B preferably consists of styrene and maleic anhydride and can contain 5-40 mol~ of maleic anhydride. In particular, polymer B~contains 22-32 mol~ of maleic anhydride.
Polymer B can also contain imide monomer units or spirodilactone units. Imide monomer units which can be 30 present in polymer B are N-phenylmaleimide, maleimide, -~
citraconimide, itaconimide, aconimide, N-methylmaleimide or mixtures thereof. The spirodilactone units can be formed by heating the polymer B. The dicarboxylic acid anhydride content of polymer B must remain at least 5 mol~.
Polymer B can be prepared by copolymerising the vinyl-aromatic monomer units and the dicarboxylic acid anhydride monomer units and/or the imide monomer units in a known manner.
Imide units can also be obtained by reacting some WO93/20~ PCT/~L93/00068 of the dicarboxylic dcid anhydride units in the polymer B
with a primary amine or ammonia. Examples of amines which can ~e used are: aniline and methylamine.
Polymer B is present in the polymer composition in an amount of 5-70 parts by weight based on the sum of polyolefin A and polymer B, preferably 20-40 parts by weight.
The amount of polymer B in the polymer composition can proportionally be lowered when a functionalised polymer B is used as compatibiliser (see below).
- A functionalised polyolefin A and/or a functiona-lised polymer B can be added to the polymer composition in 15 order to obtain an even better compatibility. To this end, a ~`
portion of the amount of polyolefin A or the amount of -~
polymer B present in the polymer mixture can be replaced by, respectively, the functionalised polyolefin A or the functionalised polymer B. The portion which can be replaced is 0-lO0~, with a preference for 50-100~ for the replacement of polymer B and a preference for 0.5-30% for the replacement of polyolefin A. Combinations of the functionalised polyolefins A and functionalised polymers B
can also be used.
A functionalised polyolefin A c- a functionalised polymer B is understoQd to be: a polyolefin A or a polymer B
which contains groups which are compatible or reactive with, respectively, the polymer B or the polyolefin A.
The functionalised polyolefin A contains one or more functional groups, such as:
- a hydroxyl group, -- a thiol group, - an amine group, - an amide group, - an epoxide group, - an oxazolîne group, - an isocyanate group or - an alkoxide group.
Preferably, the functional polyolefin A contains WO93~201~ ~ PCT/NL93/00068 one or more isocyanate groups, one or more oxazoline groups or one or more amine groups.
The functionalised polymer B contains one or more linear or branched alkyl ~roups with 10-200 carbon atoms.
The functionalised polyolefin A is, for example, prepared starting from a polyolefin grafted with a dicarboxylic acid or anhydride, like maleic anhydride or acrylic acid. Such a grafted polyolefin preferably contains 0.01-10 parts by weight of anhydride groups or acid groups. -~
Preferably, the polyolefin is grafted with maleic anhydride - or acrylic acid and contains 0.1-7% by weight of maleic anhydride groups or acrylic acid groups.
The polyolefin grafted with an anhydride or with an acid can hereafter be reacted with one or more of the compounds listed below, or combinations of these compounds, in order to obtain the functionalised polyolefin A. The compound to be used contains 2 or more:
- hydroxyl-groups, - thiol-groups, - amine-~roups, - amide-groups, - epoxide-groups, - oxazoline groups, - isocyanate groups.
The compound can also be an alkoxide of a metal from group 4-13 of the Periodic System of the Elements (Handbook of Chemistry and Physics, 70th Edition, CRC Press, 1989-1990).
Examples of such compounds are: 1,3-phenylene-bisoxazoline, 1,4-phenylene diamine, 1,3-phenylene diamine, methane-diphenyl diisocyanate, tetrabutyl titanate and ethanolamine.
- During these reactions preferably at least 70~ of the anhydride groups or acid groups are reacted.
Crosslinking of the functionalised polyolefin should be -- avoided. Particularly prefered, 100~ of the anhydride or acid groups are converted~
The functionalised polyolefin A can also be WO93/201~ PCT/NL93/0006X
prepared by grafting non-functionalised polyolefin A with for example hydroxyethyl methacrylate, glycidyl methacrylate, acrylamide, isopropenyloxa~oline and dimethyl methaisopropenyl benzylisocyanate.
The functionalised polymer B is, for example, synthesised by grafting the polymer B with a compound which contains a linear or branched alkylgroup with 10-200 carbon atoms and having a terminal functional group which is able to react with the dicarboxylic acid anhydride groups in the polymer B. Preferably, 20-90~ of the dicarboxylic acid - anhydride units are converted.
- The functionalised polymer B can be grafted with a linear or branched alkyl compound containing as the terminal functional group:
- a primary or secondary amine group, - a primary alcohol group, - a primary thiol group, - an oxazoline group, - an epoxide group and/or - an isocyanate group. ~
These compounds are, for example: l-dodecylamine, 1-octa- -decylamine, l-nonadecyl alcohol, epoxydodecane, OLOA 1200R
from Chevron (an amine-terminated polybutene having about 70 ~;
carbon atoms).
When grafting polymer B with an epoxide compound it is usually necessary to use an activator, such as an imida-zole, a quaternary ammonium salt or a tertiary amine.
Preferably, a compound which contains a linear or branched alkylgroup with 10-200 carbon atoms and a primary amine functional group is used as the compound for grafting -~
polymer B.
The grafting reactions are performed by known methods for a person skilled in the art.
A polymer composition according to the invention can also contain an elastomer or an elastomer-containing composition as an impact modifier. Examples of suitable elastomers or elastomer-containing compositions are~
WO93/201~ ~ ~` PCT/NL93/00068 _ g _ ~ .
polybutadiene, ethylene-propylene rubber (EPR), ethylene-propylene-diene rubber (EPDM), functionalised EPDM, acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-ethylene-styrene copolymer (AES) and silicone elastomer. 0-50~ by weight of the elastomer or of the elastomer-containing composition can be added to the polymer composition. Preferably, 0-30 parts by weight are added.
The polymer composition can be obtained by mixing all components in arbitrary sequence. The polymer composi-tion can preferably be obtained by dynamic crosslinking, that is ~o say, the composition is mixed and/or kneaded, with heating, in equipment customary for this purpose, for example in a Brabender mixer or on rollers or in an extruder. The polyolefin A, the polymer B and, where appropriate, the compatibiliser are mixed at a temperature at which all three of the materials flow readily. This temperature is higher than the glass transition temperature of the polymer B and higher than the glass transition temperature or the melting point of the polyolefin ~, depending on the polyolefin A used and the polymer B used.
It is preferred that the crosslinkin~ compound is added after the polyolefin A and the polymer B have been mixed well. The time which is needed to carry out the crosslinking reaction varies with the compounding conditions (such as temperature and shear rate) and the type of polymer and crosslinking agent used. Suitable temperatures are between the melting point of the polyolefin (175C for polypropylene) and 300C, while specifically the limits are 180-260~C.
The polymer composition according to the invention can also contain the customary additives, such as fibres, fillers, plasticisers, flame retardants and stabilisers.
The invention is further illustrated with the aid of the following examples, without being restricted thereto.
The Izod is determined in accordance with ISO R180/4A (23C; measured parallel to the direction of injection-moulding).
WO93/201~ ~ PCT/NL93/00068 The modulus of elasticity is determined in accordance with ISO 178 (23C; measured parallel to the direction of injection-moulding).
The elongation at break is determined in accordance with ISO 37-2 (23C), Example 1 Mixtures of polypropylene (PP), styrene maleic acid anhydride copolymer (SMA) and crosslinking agent were prepared in a Berstorff twin-screw extruder. -~
Blending conditions: cylinder temperature 215-240C; screw Be 07; speed of rotation 150 rpm; yield: 5 kg/h.
As reference, the same amounts of polypropylene and SMA were "~
mixed without crosslinking agent being added.
The polypropylene which was used is Stamylan P 8:3EOOR.
The SMA which was used is 5tapron 28110R (both products of DSM).
The crosslinking agents used were 1.3 mol~ of 1,3-phenylene- ;-bisoxazoline (PBO) from Takeda Chemicals and 1.5 mol% of pentaerythritol (PTA) from Aldrich Chemie. The amount of crosslinking agent which is added is related to the amount of anhydride groups present in polymer B. `~
Sheets were prepared from these mixtures by means of injection-moulding Properties were determined on these``~
sheets.
The results are shown in Table 1.
`` `, '",' WO93/201~ PCT/NL93/00068 Without crosslinking agent PP/SMA Izod Modulus ofElongation at elasticitybreak (parts by weight) (kJ/m2) (N/mm2) (~) 95/5 35.2 1320 90/10 12.4 1350 80/20 5.9 1490 70/30 3.0 1750 5.3 With PBO ~
95/5 - 29.1 1300 -90/10 ~1.7 1360 -80/20 17.8 1480 70/30 8.5 1680 48.4 With PTA
70/30 9.3 1750 53.3 ;~
It can clear;y be seen that over a broad range of compositions the impact strength is increased by adding the crosslinking agent to the mixture of polypropylene and SMA, whilst the rigidity is largely retained in comparison with the mixture of polypropylene and SMA without crosslinking agent. The elongation at break also increases by adding the crosslinking agent.
Comparative ExPeriment A
On the basis of JP-A-63.205.341 mixtures of polypropylene, SMA and a compatibiliser were prepared. The polypropylene and SMA type-Q are the same as were used in Example 1.
WO93/201~ PCT/~L93/00068 ~ .;
The mixtures were prepared using the same process as in Example 1. The sheets were injection-moulded.
The compatibilisers used were: `
A. Kraton G 1652~ (a styrene/ethylene/butene/styrene block copolymer; product from Mitsui Petrochemical).
B. Kraton G 1702 XR (a styrene/ethylene/propene block `
copolymer; product from Mitsui Petrochemical).
C. Kraton FG 1901 XR (a maleic anhydride-modified styrene/-olefin block copolymer; product from Mitsui Petrochemical).
- ~he mixtures consist of PP/SMA/Kraton 63/27/10 ','~. ~
Kraton Izod Modulus of elasticity -~
type kJ/m2 N/mm ...
A 3.8 1470 B 4.6 1400 C 3.2 1460 - .
Compared with a crosslinked polypropylene/SMA
mixture containing 70~ by weight of polypropylene and 30% by weight of SM~ according to Example 1, the mixtures containing Kraton as compatibiliser show both a poorer impact strength and a poorer rigidity.
Example II
Process for the preparation of an a-octadecylamine-modified styrene/maleic anhydride copolymer.
150.0 g of Stapron 28110R (SMA) were dissolved in ~`-1 dm3 of methyl ethyl ketone (MER) t with stirring and heating under a N2 atmosphere. `";
28.6 g of ~-octadecylamine were then added to the "',-' ~ ' ~
WO93/201~ ~ PCT/NL93/0006X
- 13 - .
solution. The mixture was then heated to 67C, with stirring. After the amine had dissolved, the reaction mixture was stirred for a further 5 hours at 67C under N2.
2.4 g of sodium acetate and 24 ml of acetic anhydride were then added to the pale yellow, clear reaction mixture, after which the mixture was stirred for 5~ hours at 80~ under N2.
After cooling to room temperature, the mixture was coagulated in methanol. The precipitated SMA-g-Cl~H3 ~NH2 was filtered off, washed with methanol and dried under vacuum at 6C~C~ 25% of the original amount of MA groups in the SMA had been converted to imide groups (determined by FTIR and elementary analysis).
30 parts by weight of the so obtained SMA-g-Cl8H3~NX2 by the process described above were mixed with 70 parts by weight of Stamylan P 83ElOR (PP) under the conditions indicated in Example 1~ The crosslinking agent used was 1.3 mol~ of PBO~
TABLE 3 ~ -Pp/sMA-g-cl~H37NH2 Izod Modulus of elasticity (parts by weight) (kJ/m2) (N/mm2) . .
70/30 13.1 1650 Compared with a mixture of 70 parts by weight of polypropylene with 30 parts by weight of non~modified SMA
which has been crosslinked using PB0, as described in - Example 1, the impact strength is even further improved.
P(:)LYMER COMPOSITION COMPRISING A MIXTURE OF A ~RYSTALLINE OR SEMI~
CRYSTALLINE POLYOLEFIN ANr) A POLYMER BASED ON VINYLAROMATI(:` ANI) RBOXYLlC A~ ANHYr3Rll~E MONOMER UNITS
The invention relat~s to a polymer composition comprising a mixture of a crystalline or semi-crystalline polyolefin (A) and a polymer (B) based on vinyl-aromatic and dicarboxylic acid anhydride monomer units.
A polymer composition of this type is known from WO-A-9005759. In WO-A-9005759 a polymer mixture of a crystalline or semi-crystalline polyole~in and a second polymer, such as a copolymer of styrene and maleic anhydride, is described. Since the polyolefin ancl the second polymer are not miscible, the polymer mixture contains a compatibiliser. According to this publication, the compatibiliser is a block copolymer of a vinyl-aromatic -compound and a conjugated diene or partially hydrogenated derivatives thereof. Here and hereafter a compatibiliser is understood to be a compound which improves the compatibility of A and B and is primarily located at the interface of the `
polyolefin A and the polymer B.
It is known from JP-A-63.2050341 to use styrene-containing rubber-like copolymers as compatibilisers in polymer compositions consisting of polypropene and styrene/maleic anhydride copolymers. A drawback of these polymer compositions is, however, that the impact strength/rigidity combinatisn (Izod vs. modulus of elas-- ticity) is poor, as a result of which the polymer com-positions are unsuitable for structural moulded components which are used in, for example, cars and furniture.
The aim of the invention is to provide a polymer composition of a~ polyolefin A and a polymer B based onvinyl-aromatic monomer units and dicarboxylic acid anhydride WO93/201~ PCT/NL93/00068 , _ ~
monomer units, which has a good impact strength/rigidity combination.
The invention is characterised in that the polymer B is crosslinked. The crosslinking of the polymer B can be either of the chemical or the physical type. Physical crosslinking is effected under the influence of Van der Waals forces, dipole-dipole interactions and ionogenic interactions.
Polymer B can be chemically crosslinked by a reaction with a compound which contains at least two functional groups which are able to react with the dicarboxylic acid anhydride group of the polymer.
A further advantage of the polymer composition according to the invention is that the elongation at break of the polymer composition increases.
Another advantage of the polymer composition according to the invention is that the said composition also `
has good scratch resistance and paintability~
Compounds containing two or more alcohol or thiol functional groups form a first group of possible compounds suitable for crosslinking the polymer B. lhe combination of alcohol and thiol functional groups in a compound is also possible. Compounds containing two or more alcohol functional groups, such as 1,4-butanediol, 1,6-hexanediol, pentaerythritol, ethyiene glycol and propylene glycol and polymers thereof are preferred. Polyhydroxy ethers can also be used, for example polyhydroxy ethers based on bisphenol A.
Compounds containing two or more primary or secondary amine functional groups, preferably primary amine groups, form a second group of compounds suitable for crosslinking the polymer B. llhe following may be mentioned as examples of these compounds containing amine functional ~roups: alkane diamines containing a C~-C20 alkylene group, such as 1,4-diaminobutane and 1,6-diaminohexane, polyoxy-ethylene diamine, polyoxypropylene diamine, polyoxypropylene triamine, diphenyl sulphone diamine, 1,3-phenylene-diamine WO93/201~ ~ J ~ ' PCT/NL93/()006X
and 1,4-phenylene diamine. The combination of one or more primary amine groups with one or more secondary amine groups in a compound is possible. Polyamides can also be used. The compound suitable for crosslinking the polymer B can also contain at least one alcohol or thiol group and also at least one amine group. Diethanolamine and monoethanolamine are examples of this type of compound.
Compounds containing two or more epoxide functional groups having the general formula: ~
:
( CR------CHR ) n .
\ O ~
-in which n22 and R is a hydrocarbon radical or a hydrogen ;;
atom form a third group of compounds suitable for cross-linking the polymer B. Examples of such compounds are: -polyglycidyl ethers of polyhydroxyl-substituted compounds.
These compounds can be subdivided into polyepoxide compounds of the aromatic type, such as can be obtained from bisphenol A, and polyepoxide compounds of the aliphatic type, such as -polyglycidyl ethers of polyalcohols. The following may be -mentioned as examples of the latter type of polyepoxide compounds: diglycidyl ethers of -~ diols, such as butanediol diglycidyl çther, hexanediol diglycidyl ether, paracyclohexyldimethanol diglycidyl ether, neopentyl glycol di~lycidyl ether and bisphenol A diglycidyl ether.
Preferably, compounds are used which are the result of the 30 epoxidation of olefins, such as epoxidised soya oil. ~ -When crosslinking with an epoxide compound it is usually desirable to use an activator, such as an imidazole, a quaternary ammonium salt or a tertiary amine.
- ~ Compounds containing 2 or more oxazoline groups form a fourth group of compounds suitable for crosslinking the polymer B. 1,3-phenylenebisoxazoline may be mentioned a~
an example of these compounds.
Compounds containing 2 or more isocyanate groups form a fifth group of compounds suitable for crosslinking -`
WO93/201~ ; !? ~ 4 _ PCT/NL93/0006X
the polymer s. Examples of these compounds are toluene 2,4-diisocyanate, benzene 1,3,5-triisocyanate and methanediphenyl diisocyanate.
Salts of metal atoms from groups 2-lO of the Periodic System of the Elements (Handbook of Chemistry and Physics, 70th Edition, CRC Press, 1989-1990) form a sixth group of compounds suitable for crosslinking the polymer B.
Preferably, metal alkoxides and salts of divalent positive ions are used, such as tetrabutoxytitanium, zinc oxide and zinc acetate.
A compound containing two or more functional groups, chosen from the abovementioned groups, is also suitable for crosslinking the polymer B.
A mixture of compounds suitable for crosslinkinq the polymer B, chosen from one or more of the abovementioned ~-groups of compounds, can also be used.
The compound suitable for crosslinking the polymer B is present in an amount of 0.1-20 mol~ with respect to the amount of dicarboxylic acid anhydride groups present in polymer B. ~`
Crystalline or semi-crystalline polyolefins A which `-can be used in a polymer composition according to the invention are homopolymers, copolymers or terpolymers or mixtures thereo~. Polymers of -olefins are preferably used and these -olefins generally have 2 to 20 carbon atoms. The use of polymers of -olefins having 2-6 carbon atoms is particularly preferred.
The crystalline or semi-crystalline polyolefins are derived from olefins, such as ethylene, propylene, l-butene, 1-pentene, 4 methyl-1-pentene, l-octene, l-decene, 4-ethyl-l-hexene, etc. Examples of particularly suitable polyolefins - are: low density polyethylene, high density polyethylene, linear low density polyethylene, ultra-low density poly-ethylene, polypropylene, (high and low density) poly(l-butene), poly(4-methyl-1-pentene), ethylene/propylene copolymers and copolymers of ethylene and/or propylene with other copolymerisable monomers, such as ethylene/l-butene WO93/201~ PCT/NL93/00068 copolymer, ethylene/vinyl acrylate copolymer or ethylene/-vinyl acetate. Polymers and copolymers of halogenated olefins can also be used.
An amount of 30-95 parts by weight of polyolefin A
is present in the polymer composition, based on the sum of polyolefin A and polymer B. The amount of polyolefin is preferably 60-80 parts by weight. The amount of polyolefin A
in the polymer composition can proportionally be lowered when a functionalised polyolefin A is used as compatibiliser (see below).
- Polymer B comprises vinyl-aromatic monomer units and dicarboxylic acid anhydride monomer units. Suitable vinyl-aromatic monomers for use in the polymer B are,- for example, styrene, alpha-methyl-styrene, para-methylstyrene and mixtures thereof. Styrene is preferably used.-Suitable dicarboxylic acid anhydrides are, for ;~
example, maleic anhydride, chloromaleic anhydride, citraco-nic anhydride, cyclohexylmaleic anhydrids, benzyl maleic anhydride, phenyl maleic anhydride, aconitic anhydride, propyl maleic anhydride and mixtures thereof. Maleic anhy-dride (MA) is preferably used.
Polymer B preferably consists of styrene and maleic anhydride and can contain 5-40 mol~ of maleic anhydride. In particular, polymer B~contains 22-32 mol~ of maleic anhydride.
Polymer B can also contain imide monomer units or spirodilactone units. Imide monomer units which can be 30 present in polymer B are N-phenylmaleimide, maleimide, -~
citraconimide, itaconimide, aconimide, N-methylmaleimide or mixtures thereof. The spirodilactone units can be formed by heating the polymer B. The dicarboxylic acid anhydride content of polymer B must remain at least 5 mol~.
Polymer B can be prepared by copolymerising the vinyl-aromatic monomer units and the dicarboxylic acid anhydride monomer units and/or the imide monomer units in a known manner.
Imide units can also be obtained by reacting some WO93/20~ PCT/~L93/00068 of the dicarboxylic dcid anhydride units in the polymer B
with a primary amine or ammonia. Examples of amines which can ~e used are: aniline and methylamine.
Polymer B is present in the polymer composition in an amount of 5-70 parts by weight based on the sum of polyolefin A and polymer B, preferably 20-40 parts by weight.
The amount of polymer B in the polymer composition can proportionally be lowered when a functionalised polymer B is used as compatibiliser (see below).
- A functionalised polyolefin A and/or a functiona-lised polymer B can be added to the polymer composition in 15 order to obtain an even better compatibility. To this end, a ~`
portion of the amount of polyolefin A or the amount of -~
polymer B present in the polymer mixture can be replaced by, respectively, the functionalised polyolefin A or the functionalised polymer B. The portion which can be replaced is 0-lO0~, with a preference for 50-100~ for the replacement of polymer B and a preference for 0.5-30% for the replacement of polyolefin A. Combinations of the functionalised polyolefins A and functionalised polymers B
can also be used.
A functionalised polyolefin A c- a functionalised polymer B is understoQd to be: a polyolefin A or a polymer B
which contains groups which are compatible or reactive with, respectively, the polymer B or the polyolefin A.
The functionalised polyolefin A contains one or more functional groups, such as:
- a hydroxyl group, -- a thiol group, - an amine group, - an amide group, - an epoxide group, - an oxazolîne group, - an isocyanate group or - an alkoxide group.
Preferably, the functional polyolefin A contains WO93~201~ ~ PCT/NL93/00068 one or more isocyanate groups, one or more oxazoline groups or one or more amine groups.
The functionalised polymer B contains one or more linear or branched alkyl ~roups with 10-200 carbon atoms.
The functionalised polyolefin A is, for example, prepared starting from a polyolefin grafted with a dicarboxylic acid or anhydride, like maleic anhydride or acrylic acid. Such a grafted polyolefin preferably contains 0.01-10 parts by weight of anhydride groups or acid groups. -~
Preferably, the polyolefin is grafted with maleic anhydride - or acrylic acid and contains 0.1-7% by weight of maleic anhydride groups or acrylic acid groups.
The polyolefin grafted with an anhydride or with an acid can hereafter be reacted with one or more of the compounds listed below, or combinations of these compounds, in order to obtain the functionalised polyolefin A. The compound to be used contains 2 or more:
- hydroxyl-groups, - thiol-groups, - amine-~roups, - amide-groups, - epoxide-groups, - oxazoline groups, - isocyanate groups.
The compound can also be an alkoxide of a metal from group 4-13 of the Periodic System of the Elements (Handbook of Chemistry and Physics, 70th Edition, CRC Press, 1989-1990).
Examples of such compounds are: 1,3-phenylene-bisoxazoline, 1,4-phenylene diamine, 1,3-phenylene diamine, methane-diphenyl diisocyanate, tetrabutyl titanate and ethanolamine.
- During these reactions preferably at least 70~ of the anhydride groups or acid groups are reacted.
Crosslinking of the functionalised polyolefin should be -- avoided. Particularly prefered, 100~ of the anhydride or acid groups are converted~
The functionalised polyolefin A can also be WO93/201~ PCT/NL93/0006X
prepared by grafting non-functionalised polyolefin A with for example hydroxyethyl methacrylate, glycidyl methacrylate, acrylamide, isopropenyloxa~oline and dimethyl methaisopropenyl benzylisocyanate.
The functionalised polymer B is, for example, synthesised by grafting the polymer B with a compound which contains a linear or branched alkylgroup with 10-200 carbon atoms and having a terminal functional group which is able to react with the dicarboxylic acid anhydride groups in the polymer B. Preferably, 20-90~ of the dicarboxylic acid - anhydride units are converted.
- The functionalised polymer B can be grafted with a linear or branched alkyl compound containing as the terminal functional group:
- a primary or secondary amine group, - a primary alcohol group, - a primary thiol group, - an oxazoline group, - an epoxide group and/or - an isocyanate group. ~
These compounds are, for example: l-dodecylamine, 1-octa- -decylamine, l-nonadecyl alcohol, epoxydodecane, OLOA 1200R
from Chevron (an amine-terminated polybutene having about 70 ~;
carbon atoms).
When grafting polymer B with an epoxide compound it is usually necessary to use an activator, such as an imida-zole, a quaternary ammonium salt or a tertiary amine.
Preferably, a compound which contains a linear or branched alkylgroup with 10-200 carbon atoms and a primary amine functional group is used as the compound for grafting -~
polymer B.
The grafting reactions are performed by known methods for a person skilled in the art.
A polymer composition according to the invention can also contain an elastomer or an elastomer-containing composition as an impact modifier. Examples of suitable elastomers or elastomer-containing compositions are~
WO93/201~ ~ ~` PCT/NL93/00068 _ g _ ~ .
polybutadiene, ethylene-propylene rubber (EPR), ethylene-propylene-diene rubber (EPDM), functionalised EPDM, acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-ethylene-styrene copolymer (AES) and silicone elastomer. 0-50~ by weight of the elastomer or of the elastomer-containing composition can be added to the polymer composition. Preferably, 0-30 parts by weight are added.
The polymer composition can be obtained by mixing all components in arbitrary sequence. The polymer composi-tion can preferably be obtained by dynamic crosslinking, that is ~o say, the composition is mixed and/or kneaded, with heating, in equipment customary for this purpose, for example in a Brabender mixer or on rollers or in an extruder. The polyolefin A, the polymer B and, where appropriate, the compatibiliser are mixed at a temperature at which all three of the materials flow readily. This temperature is higher than the glass transition temperature of the polymer B and higher than the glass transition temperature or the melting point of the polyolefin ~, depending on the polyolefin A used and the polymer B used.
It is preferred that the crosslinkin~ compound is added after the polyolefin A and the polymer B have been mixed well. The time which is needed to carry out the crosslinking reaction varies with the compounding conditions (such as temperature and shear rate) and the type of polymer and crosslinking agent used. Suitable temperatures are between the melting point of the polyolefin (175C for polypropylene) and 300C, while specifically the limits are 180-260~C.
The polymer composition according to the invention can also contain the customary additives, such as fibres, fillers, plasticisers, flame retardants and stabilisers.
The invention is further illustrated with the aid of the following examples, without being restricted thereto.
The Izod is determined in accordance with ISO R180/4A (23C; measured parallel to the direction of injection-moulding).
WO93/201~ ~ PCT/NL93/00068 The modulus of elasticity is determined in accordance with ISO 178 (23C; measured parallel to the direction of injection-moulding).
The elongation at break is determined in accordance with ISO 37-2 (23C), Example 1 Mixtures of polypropylene (PP), styrene maleic acid anhydride copolymer (SMA) and crosslinking agent were prepared in a Berstorff twin-screw extruder. -~
Blending conditions: cylinder temperature 215-240C; screw Be 07; speed of rotation 150 rpm; yield: 5 kg/h.
As reference, the same amounts of polypropylene and SMA were "~
mixed without crosslinking agent being added.
The polypropylene which was used is Stamylan P 8:3EOOR.
The SMA which was used is 5tapron 28110R (both products of DSM).
The crosslinking agents used were 1.3 mol~ of 1,3-phenylene- ;-bisoxazoline (PBO) from Takeda Chemicals and 1.5 mol% of pentaerythritol (PTA) from Aldrich Chemie. The amount of crosslinking agent which is added is related to the amount of anhydride groups present in polymer B. `~
Sheets were prepared from these mixtures by means of injection-moulding Properties were determined on these``~
sheets.
The results are shown in Table 1.
`` `, '",' WO93/201~ PCT/NL93/00068 Without crosslinking agent PP/SMA Izod Modulus ofElongation at elasticitybreak (parts by weight) (kJ/m2) (N/mm2) (~) 95/5 35.2 1320 90/10 12.4 1350 80/20 5.9 1490 70/30 3.0 1750 5.3 With PBO ~
95/5 - 29.1 1300 -90/10 ~1.7 1360 -80/20 17.8 1480 70/30 8.5 1680 48.4 With PTA
70/30 9.3 1750 53.3 ;~
It can clear;y be seen that over a broad range of compositions the impact strength is increased by adding the crosslinking agent to the mixture of polypropylene and SMA, whilst the rigidity is largely retained in comparison with the mixture of polypropylene and SMA without crosslinking agent. The elongation at break also increases by adding the crosslinking agent.
Comparative ExPeriment A
On the basis of JP-A-63.205.341 mixtures of polypropylene, SMA and a compatibiliser were prepared. The polypropylene and SMA type-Q are the same as were used in Example 1.
WO93/201~ PCT/~L93/00068 ~ .;
The mixtures were prepared using the same process as in Example 1. The sheets were injection-moulded.
The compatibilisers used were: `
A. Kraton G 1652~ (a styrene/ethylene/butene/styrene block copolymer; product from Mitsui Petrochemical).
B. Kraton G 1702 XR (a styrene/ethylene/propene block `
copolymer; product from Mitsui Petrochemical).
C. Kraton FG 1901 XR (a maleic anhydride-modified styrene/-olefin block copolymer; product from Mitsui Petrochemical).
- ~he mixtures consist of PP/SMA/Kraton 63/27/10 ','~. ~
Kraton Izod Modulus of elasticity -~
type kJ/m2 N/mm ...
A 3.8 1470 B 4.6 1400 C 3.2 1460 - .
Compared with a crosslinked polypropylene/SMA
mixture containing 70~ by weight of polypropylene and 30% by weight of SM~ according to Example 1, the mixtures containing Kraton as compatibiliser show both a poorer impact strength and a poorer rigidity.
Example II
Process for the preparation of an a-octadecylamine-modified styrene/maleic anhydride copolymer.
150.0 g of Stapron 28110R (SMA) were dissolved in ~`-1 dm3 of methyl ethyl ketone (MER) t with stirring and heating under a N2 atmosphere. `";
28.6 g of ~-octadecylamine were then added to the "',-' ~ ' ~
WO93/201~ ~ PCT/NL93/0006X
- 13 - .
solution. The mixture was then heated to 67C, with stirring. After the amine had dissolved, the reaction mixture was stirred for a further 5 hours at 67C under N2.
2.4 g of sodium acetate and 24 ml of acetic anhydride were then added to the pale yellow, clear reaction mixture, after which the mixture was stirred for 5~ hours at 80~ under N2.
After cooling to room temperature, the mixture was coagulated in methanol. The precipitated SMA-g-Cl~H3 ~NH2 was filtered off, washed with methanol and dried under vacuum at 6C~C~ 25% of the original amount of MA groups in the SMA had been converted to imide groups (determined by FTIR and elementary analysis).
30 parts by weight of the so obtained SMA-g-Cl8H3~NX2 by the process described above were mixed with 70 parts by weight of Stamylan P 83ElOR (PP) under the conditions indicated in Example 1~ The crosslinking agent used was 1.3 mol~ of PBO~
TABLE 3 ~ -Pp/sMA-g-cl~H37NH2 Izod Modulus of elasticity (parts by weight) (kJ/m2) (N/mm2) . .
70/30 13.1 1650 Compared with a mixture of 70 parts by weight of polypropylene with 30 parts by weight of non~modified SMA
which has been crosslinked using PB0, as described in - Example 1, the impact strength is even further improved.
Claims (9)
1. A polymer composition comprising a mixture of a crystalline or semi-crystalline polyolefin A and a polymer B based on vinyl-aromatic and dicarboxylic acid anhydride monomer units, characterised in that polymer B
is crosslinked.
is crosslinked.
2. A polymer composition according to claim 1, characterised in that polymer B is crosslinked with a crosslinking agent being a compound which contains at least two functional groups which are able to react with the dicarboxylic acid anhydride group of polymer B.
3. A polymer composition according to claim 2, characterised in that the functional groups are selected from alcohol, thiol, amine, amide, epoxide, oxazoline isocyanate or mixtures thereof.
4. A polymer composition according to claim 2, characterised in that polymer B is crosslinked with a salt of a metal atom from group 4-13 of the Periodic System of the Elements.
5. A polymer composition according to anyone of claims 1-4, characterised in that 0.1-20 parts by weight of the crosslinking agent is present with respect to the amount of dicarboxylic acid anhydride monomers present in polymer B.
6. A polymer composition according to anyone of claims 1-5, characterised in that a compatibiliser consisting of a functionalised polyolefin A and/or a functionalised polymer B is also present.
7. Process for obtaining a polymer composition according to anyone of claims 1-6, characterized in that polyolefin A, polymer B, the crosslinking compound and, where appropriate, the compatibilizer are added to a mixing equipment and are mixed and/or kneaded with heating, so that dynamic crosslinking takes place.
8. Products entirely or partially formed from a polymer composition as described in anyone of claims 1-6 or produced by a process of claim 7.
9. Polymer composition, process and products as essentially described and/or illustrated in more detail in the examples.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL9200603A NL9200603A (en) | 1992-03-31 | 1992-03-31 | A POLYMER COMPOSITION CONTAINING A MIXTURE OF A POLYOLEFINE AND A POLYMER BASED ON VINYLAROMATIC AND DICARBONIC ACID ANHYDRIDE MONOMERS. |
| NL9200603 | 1992-03-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2133208A1 true CA2133208A1 (en) | 1993-10-14 |
Family
ID=19860643
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002133208A Abandoned CA2133208A1 (en) | 1992-03-31 | 1993-03-25 | A polymer composition comprising a mixture of a crystalline or semi/crystalline polyolefin and a polymer based on vinylaromatic and dicarboxylic acid anhydride monomer units |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0633910A1 (en) |
| JP (1) | JPH07505428A (en) |
| AU (1) | AU3907993A (en) |
| CA (1) | CA2133208A1 (en) |
| NL (1) | NL9200603A (en) |
| WO (1) | WO1993020144A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA976110B (en) | 1996-07-12 | 1999-01-11 | Dow Chemical Co | Elastomers processes for their manufacture and articles made from these elastomers |
| MY117913A (en) * | 1996-07-12 | 2004-08-30 | Dow Global Technologies Inc | Elastomers, processes for their manufacture, and articles made from these elastomers |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL8303377A (en) * | 1983-10-01 | 1985-05-01 | Stamicarbon | PROCESS FOR PREPARING AN IMPACT-RESISTANT THERMOPLASTIC FORMING MASS. |
| FR2628115B1 (en) * | 1988-03-04 | 1990-07-13 | Atochem | COMPOSITION FOR MAKING COMPATIBLE WITH AT LEAST TWO INCOMPATIBLE THERMOPLASTIC POLYMERS, ITS APPLICATION TO THE MANUFACTURE OF THERMOPLASTIC ALLOYS, THERMOPLASTIC ALLOYS OBTAINED |
| US5212239A (en) * | 1991-02-22 | 1993-05-18 | Arco Chemical Technology, L.P. | Resin blends containing crystalline propylene polymers and styrenic copolymers |
-
1992
- 1992-03-31 NL NL9200603A patent/NL9200603A/en not_active Application Discontinuation
-
1993
- 1993-03-25 EP EP93908156A patent/EP0633910A1/en not_active Withdrawn
- 1993-03-25 AU AU39079/93A patent/AU3907993A/en not_active Abandoned
- 1993-03-25 JP JP5517314A patent/JPH07505428A/en active Pending
- 1993-03-25 CA CA002133208A patent/CA2133208A1/en not_active Abandoned
- 1993-03-25 WO PCT/NL1993/000068 patent/WO1993020144A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| AU3907993A (en) | 1993-11-08 |
| EP0633910A1 (en) | 1995-01-18 |
| JPH07505428A (en) | 1995-06-15 |
| WO1993020144A1 (en) | 1993-10-14 |
| NL9200603A (en) | 1993-10-18 |
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