EP0000429A1 - Thermoplastische Formmassen auf der Basis eines Copolymers von Styrol-Acrylonitril, eines Elastomers und eines Polyimids - Google Patents
Thermoplastische Formmassen auf der Basis eines Copolymers von Styrol-Acrylonitril, eines Elastomers und eines Polyimids Download PDFInfo
- Publication number
- EP0000429A1 EP0000429A1 EP78300104A EP78300104A EP0000429A1 EP 0000429 A1 EP0000429 A1 EP 0000429A1 EP 78300104 A EP78300104 A EP 78300104A EP 78300104 A EP78300104 A EP 78300104A EP 0000429 A1 EP0000429 A1 EP 0000429A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- material according
- moulding material
- weight
- moulding
- rubber
- 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.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 52
- 239000004642 Polyimide Substances 0.000 title claims abstract description 39
- 229920001721 polyimide Polymers 0.000 title claims abstract description 39
- 229920001971 elastomer Polymers 0.000 title claims abstract description 34
- 238000009757 thermoplastic moulding Methods 0.000 title claims abstract description 5
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 title claims description 23
- 239000000806 elastomer Substances 0.000 title abstract description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000000465 moulding Methods 0.000 claims abstract description 35
- 239000005060 rubber Substances 0.000 claims abstract description 28
- 239000003365 glass fiber Substances 0.000 claims abstract description 16
- 239000013536 elastomeric material Substances 0.000 claims abstract description 14
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 12
- 239000000945 filler Substances 0.000 claims abstract description 9
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 9
- 239000012763 reinforcing filler Substances 0.000 claims abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000005864 Sulphur Substances 0.000 claims abstract description 7
- 239000010445 mica Substances 0.000 claims abstract description 5
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 5
- 229920000768 polyamine Polymers 0.000 claims abstract description 5
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract 4
- 229920000459 Nitrile rubber Polymers 0.000 claims description 18
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 12
- 239000004416 thermosoftening plastic Substances 0.000 claims description 11
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 claims description 6
- 229920001748 polybutylene Polymers 0.000 claims description 5
- 229920001400 block copolymer Polymers 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- -1 polybutylene Polymers 0.000 claims description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001491 aromatic compounds Chemical class 0.000 claims description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 239000004634 thermosetting polymer Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 abstract description 18
- 229920003230 addition polyimide Polymers 0.000 abstract 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000002991 molded plastic Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 54
- 238000012360 testing method Methods 0.000 description 13
- 239000011521 glass Substances 0.000 description 9
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 229920013647 Krynac Polymers 0.000 description 6
- 239000012745 toughening agent Substances 0.000 description 6
- 150000003949 imides Chemical class 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 238000013329 compounding Methods 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 229920013646 Hycar Polymers 0.000 description 2
- 229920013648 Perbunan Polymers 0.000 description 2
- 229920013623 Solprene Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011369 resultant mixture Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- AQPHBYQUCKHJLT-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-(2,3,4,5,6-pentabromophenyl)benzene Chemical group BrC1=C(Br)C(Br)=C(Br)C(Br)=C1C1=C(Br)C(Br)=C(Br)C(Br)=C1Br AQPHBYQUCKHJLT-UHFFFAOYSA-N 0.000 description 1
- DMYOHQBLOZMDLP-UHFFFAOYSA-N 1-[2-(2-hydroxy-3-piperidin-1-ylpropoxy)phenyl]-3-phenylpropan-1-one Chemical compound C1CCCCN1CC(O)COC1=CC=CC=C1C(=O)CCC1=CC=CC=C1 DMYOHQBLOZMDLP-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 229920004939 Cariflex™ Polymers 0.000 description 1
- 229920013644 Chemigum Polymers 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 229920013649 Paracril Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920001079 Thiokol (polymer) Polymers 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000004989 dicarbonyl group Chemical group 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000013031 physical testing Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical group CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
Classifications
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08L79/085—Unsaturated polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
Definitions
- the invention is concerned with plastics moulding materials, and particularly moulding materials based on thermoplastics.
- thermoplastics materials such as polystyrene and styrene-acrylonitrile copolymer (SAN) have excellent moulding properties but are brittle so that the impact resistance of articles moulded from them is not good.
- SAN styrene-acrylonitrile copolymer
- brittle thermoplastics polymers such as polystyrene and SAN can be rendered less brittle by incorporation therein of rubber. This so called “toughening” can increase the impact strength over untreated polymer by a factor of from 2 to 6. However, it has been found that when the impact strength is increased in this way there is an accompanying undesirable decrease in strengths and moduli, which may be up to 50% lower than those of the unmodified polymer.
- the effect of the polyimide prepolymers in these compositions is to increase strength and impact resistance of mouldings produced therefrom.
- US Patent No.3,717,615 discloses polymer compositions based on a mixture of a mono-imide of specified general formula and a bis-imide of specified general formula. It also discloses that the mono- and bis-imides can be co-reacted with various thermoplastics during copolymerization of the imides and that the resulting compositions may be compounded with fillers including glass fibre, and with synthetic rubbers.
- the polyimides prepared in this specification are, however, the basis of the compositions described, and the final product in each case is a thermoset material. Where thermoplastics materials are used, their proportion is less than that of the mixture of imides and they are co-reacted in the polymerization of the imides.
- US Patent No.3,678,075 discloses reacting an organic diamine with an aliphatically unsaturated dicarbonyl reagent in a solvent system to produce a polyimide by a condensation reaction.
- the polyimide is said to be able to be employed in combination with various thermoplastics polymers and can be compounded with fillers including glass fibre.
- the compositions disclosed are thermosetting, and the polyimide is not an addition polymer, nor is the inclusion of rubbery polymers in the compositions disclosed.
- thermoplastic moulding material comprising a styrene/acrylonitrile copolymer, an elastomeric material having an elongation at break greater than the styrene/acrylonitrile copolymer, a polyimide prepolymer, said prepolymer being the reaction product of a polyamine and a bis-imide of an unsaturated carboxylic acid and being capable of reacting further to give a thermoset resin, and a reinforcing filler comprising glass fibres or mica.
- the styrene-acrylonitrile copolymer is a thermoplastic copolymer, containing a ratio of styrene to acrylonitrile in the range 85:15 to 60:40 by weight, and having a melt flow index (MFI) of 2 to 25gms/lOmins at 230°C under a 5kg load.
- MFI melt flow index
- the toughening agent is an elastomeric material having an elongation at break greater than the styrene/acrylonitrile copolymer. It is preferred that the elongation at break should be significantly greater than that of the styrene/acrylonitrile copolymer, for example at least 10 times as great.
- both sulphur vulcanizable rubbers and thermoplastic rubbers can be used, vulcanizable rubbers preferably being used in an uncured or partially cured state.
- the toughening agent is included in an amount of from 1 to 50% by weight (based on the weight of the total composition)preferably from 1 to 30% and more preferably from 5 to 20%.
- the toughening agent preferably has a glass transition temperature below 20 0 C.
- Preferred sulphur vulcanizable elastomeric materials are rubbers such as nitrile rubbers, polyacrylates and polyurethanes.
- thermoplastic rubbers are block copolymers containing styrene e.g. block copolymers of styrene and butadiene, which have been found particularly useful in the compositions of this invention although other thermoplastic rubbers such as polybutylene have also been found effective.
- the elastomeric material used must be compatible with the styrene/acrylonitrile copolymer i.e. able to be compounded with the SAN in a satisfactory manner, and should be an elastomer which improves the impact resistance of the copolymer when so compounded, in the absence of other materials.
- the polyimide prepolymer is preferably incorporated in the amount of from 0.1 to 10% by weight (based on the weight of the total composition) more preferably 0.5% to 5.0% by weight.
- Polyimides which can be used are described, inter alia, in British Patent Specifications Nos.1,190,718; 1,355,401; 1,355,402; 1,355,403; 1,355,405; 1,355,406 and 1,355,407, and are believed to be formed by an addition reaction between the polyamide and the unsaturated bis-imide, rather than by a condensation reaction, the latter being the case with other polyimides.
- the polyimide prepolymer is the reaction product of a primary diamine containing not more than 30 carbon atoms and an N,N bis imide of general formula in which D represents a divalent radical containing a carbon-carbon double bond, and A is a divalent radical containing at least two carbon atoms.
- the primary diamine is an aromatic compound, e.g. containing phenylene groups such as the compound of formula
- the N,N l bis imide is derived from an ⁇ unsaturated dicarboxylic acid such as maleic acid.
- the radical A is preferably an aromatic radical such as
- the number average molecular weight of the prepolymer is preferably no more than 5000.
- the amount of filler present preferably does not exceed 50% by weight of the total composition and preferably is not less than 15 per cent.
- the particularly preferred range is 20 to 40 per cent by weight of the total compositio
- the composition may optionally also include one or more other additives such as antioxidants, flame retardents, blowing agents, antistatic agents and pigments.
- the composition contains at least 30% by weight of styrene/acrylonitrile copolymer.
- the composition can be prepared by any suitable method such as by milling, extrusion, injection moulding all of which are known per se.
- the order in which the components of the composition are compounded together is not important.
- the polyimide prepolymer can be added to the base polymer and the resultant mixture combined with the toughening agent.
- the polyimide prepolymer can be added to the toughening agent and the resultant mixture combined with the base polymer.
- the polyimide prepolymer can be applied as a dressing to the filler prior to incorporation of the filler into the composition i.e. when glass fibre is used the polyimide prepolymer may be used in a dressing for the glass fibres.
- the materials were compounded on a twin-screw extruder at barrel temperatures of 200°C, 125°C, 125°C and 190°C (die) and the extruded composition was chopped into pellets.
- the resultant material was formed into test bars by injection moulding using conventional moulding conditions for reinforced styrene/acrylonitrile copolymer (220/250°C barrel temperatures).
- the test bars were tested for tensile strength, tensile modulus, flexural strength, flexural modulus and impact strength. The results are shown in the following Table 1.
- Example 2 The same procedure was followed as in Example 1 save that the amount of nitrile rubber was increased to 10% (Example 2) and 15% (Example 3). The products were tested and the results are set out in the Table 1.
- Example 2 A composition was made in the same manner as in Example 1 except that both "Kerimid 601" and the nitrile rubber "Krynac 802" were omitted. Test bars formed from the composition by injection moulding were tested for the same properties as in Example 1. The results are set out in Table 2.
- a composition was made in the same manner as in Example 1 except that the nitrile rubber "Krynac 802" was omitted.
- Example 2 A composition was made in the same way as in Example 1 but "Kerimid 601" was omitted. The results of tests made on test bars formed from the composition are shown in the Table 2.
- compositions of increasing glass fibre content were prepared each containing the styrene/acrylotrile copolymer of Example 1.
- compositions of corresponding glass content were prepared in which 2 parts SAN by weight per 100 of composition were replaced by the polyimide prepolymer KERIMID 601; further compositions of corresponding glass content were prepared in which 15 parts of SAN per 100 of composition were replaced by the nitrile rubber KRYNAC 802; and further compositions of corresponding glass content were prepared in which 17 parts of SAN by weight per 100 of composition were replaced by 2 parts by weight of the polyimide prepolymer KERIMID 601 and 15 parts by weight of the nitrile rubber KRYNAC 802.
- a composition was prepared by compounding together the following ingredients in a twin-screw extruder in the same manner as described in Example 1.
- the ingredients were 60 parts by weight of styrene/acrylonitrile copolymer (Monsanto QE1044 as in Example 1.) 15 parts by weight of glass fibres, (ECR 1346 as in Example 1). 15 parts by weight of talc and 10 parts by weight of fire retardants.
- the fire retardants consisted of a 3:1 w/w mixture of _decabromobiphenyl (Flammex B10 commercially available from Berk Ltd.) and Antimony Trioxide.
- Three comparable compositions were prepared by respectively replacing (i) 2 parts of the styrene/acrylonitrile copolymer (SAN) by 2 parts of the polyimide prepolymer KERIMID 601, (ii) 15 parts of the SAN by 15 parts of PERBUNAN N2810 (a nitrile rubber containing 28% by weight of acrylonitrile and commercially available from Wegner AG) and (iii) 7 parts of SAN by 2 parts of the KERIMID 601 and 5 parts of the PERBUNAN N2810.
- SAN styrene/acrylonitrile copolymer
- PERBUNAN N2810 a nitrile rubber containing 28% by weight of acrylonitrile and commercially available from Wegner AG
- compositions were prepared using SAN and glass as used in Example 1. Each composition contained 30% by weight of glass fibre.
- compositions contained 5% by weight of a nitrile rubber (KRYNAC 802) one having uncured rubber incorporated into it and the other having cured rubber incorporated into it.
- the other two compositions also contained 5% of uncured and cured rubber respectively but additionally contained 2% by weight of the polyimide prepolymer KERIMID 601.
- SAN made up the whole of the balance of the composition.
- the compounding was carried out in a twin screw extruder under the same conditions as in Example 1, and test mouldings were injection moulded from each of the four compositions.
- the cured rubber was a compounded rubber in which the following formulation was compounded on a mill and press cured for 10 minutes at 150°C in sheets 1.5mm thick. Under these conditions the rubber was substantially fully vulcanised i.e. 95% of available cross linking sites used up.
- the rubber formulation was:- (TMT is tetramethyl thiuram disulphide)
- Example 1 The following examples illustrate the use of the invention with various kinds of commercially available synthetic rubbers.
- the composition was compounded as in Example 1, using the same type of SAN, glass fibre and polyimide prepolymer as in Example 1, to the following formulation: Glass fibre 30 parts by weight, polyimide prepolymer 2pbw, Rubber 5pbw and SAN 63pbw.
- Test mouldings were made as before by injection moulding, and the properties of the mouldings were measured.
Landscapes
- 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)
- Materials For Medical Uses (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB2826077 | 1977-07-06 | ||
| GB2826077 | 1977-07-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0000429A1 true EP0000429A1 (de) | 1979-01-24 |
| EP0000429B1 EP0000429B1 (de) | 1981-10-28 |
Family
ID=10272836
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP78300104A Expired EP0000429B1 (de) | 1977-07-06 | 1978-06-29 | Thermoplastische Formmassen auf der Basis eines Copolymers von Styrol-Acrylonitril, eines Elastomers und eines Polyimids |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4212792A (de) |
| EP (1) | EP0000429B1 (de) |
| JP (1) | JPS5417962A (de) |
| DE (1) | DE2861259D1 (de) |
| DK (1) | DK153560C (de) |
| IT (1) | IT1106420B (de) |
| NO (1) | NO158748C (de) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2496109A1 (fr) * | 1980-12-11 | 1982-06-18 | Mitsubishi Monsanto Chem | Nouvelle resine resistant a la chaleur contenant le motif n-phenylmaleimide et son procede de preparation |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63184767U (de) * | 1987-05-19 | 1988-11-28 | ||
| AU2001233289A1 (en) * | 2000-03-23 | 2001-10-03 | Dow Global Technologies Inc. | Hydrogenated monovinylidene aromatic polymer compositions |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3717615A (en) * | 1969-04-25 | 1973-02-20 | Gen Electric | Polyimides |
| US3951906A (en) * | 1972-08-31 | 1976-04-20 | Uniroyal Inc. | Reinforced styrene-acrylonitrile polymers |
| GB1587820A (en) * | 1976-10-04 | 1981-04-08 | Tba Industrial Products Ltd | Manufacture of moulding materials |
-
1978
- 1978-06-27 US US05/919,565 patent/US4212792A/en not_active Expired - Lifetime
- 1978-06-29 EP EP78300104A patent/EP0000429B1/de not_active Expired
- 1978-06-29 DE DE7878300104T patent/DE2861259D1/de not_active Expired
- 1978-07-04 IT IT50159/78A patent/IT1106420B/it active
- 1978-07-05 JP JP8184178A patent/JPS5417962A/ja active Granted
- 1978-07-05 DK DK303378A patent/DK153560C/da not_active IP Right Cessation
- 1978-07-05 NO NO782343A patent/NO158748C/no unknown
Non-Patent Citations (1)
| Title |
|---|
| The search did not reveal any document. * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2496109A1 (fr) * | 1980-12-11 | 1982-06-18 | Mitsubishi Monsanto Chem | Nouvelle resine resistant a la chaleur contenant le motif n-phenylmaleimide et son procede de preparation |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5417962A (en) | 1979-02-09 |
| NO158748C (no) | 1988-10-26 |
| DK303378A (da) | 1979-01-07 |
| NO158748B (no) | 1988-07-18 |
| IT7850159A0 (it) | 1978-07-04 |
| JPS621974B2 (de) | 1987-01-17 |
| DK153560B (da) | 1988-07-25 |
| IT1106420B (it) | 1985-11-11 |
| US4212792A (en) | 1980-07-15 |
| DE2861259D1 (en) | 1982-01-07 |
| DK153560C (da) | 1988-11-28 |
| NO782343L (no) | 1979-01-09 |
| EP0000429B1 (de) | 1981-10-28 |
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