NO834504L - PROPYLENE COPOLYMERS WITH IMPROVED IMPACT - Google Patents
PROPYLENE COPOLYMERS WITH IMPROVED IMPACTInfo
- Publication number
- NO834504L NO834504L NO834504A NO834504A NO834504L NO 834504 L NO834504 L NO 834504L NO 834504 A NO834504 A NO 834504A NO 834504 A NO834504 A NO 834504A NO 834504 L NO834504 L NO 834504L
- Authority
- NO
- Norway
- Prior art keywords
- approx
- propylene
- ethylene
- weight
- mixture according
- Prior art date
Links
- 229920001577 copolymer Polymers 0.000 title claims description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims description 6
- 239000000203 mixture Substances 0.000 claims description 25
- 229920005989 resin Polymers 0.000 claims description 22
- 239000011347 resin Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 12
- 229920001155 polypropylene Polymers 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 11
- 239000005977 Ethylene Substances 0.000 claims description 11
- 229920001400 block copolymer Polymers 0.000 claims description 11
- 229920001971 elastomer Polymers 0.000 claims description 11
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 8
- -1 ethylene, propylene Chemical group 0.000 claims description 8
- 238000010525 oxidative degradation reaction Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 6
- 150000002978 peroxides Chemical class 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 239000000806 elastomer Substances 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229920005606 polypropylene copolymer Polymers 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- 229920001384 propylene homopolymer Polymers 0.000 claims description 3
- 229920001897 terpolymer Polymers 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000001993 dienes Chemical class 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 238000000518 rheometry Methods 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims 1
- 239000005060 rubber Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- ZGXMNEKDFYUNDQ-GQCTYLIASA-N (5e)-hepta-1,5-diene Chemical compound C\C=C\CCC=C ZGXMNEKDFYUNDQ-GQCTYLIASA-N 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 description 1
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
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
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)
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
Description
Foreliggende oppfinnelse vedrører propylen-kopolymerer med forbedret slagfasthet. The present invention relates to propylene copolymers with improved impact resistance.
Et tradisjonelt problem som erfares med slagfaste polypropylen-kopolymerer, er at det typisk foreligger et bytteforhold for slagfasthet mot smelteflytj dvs. slag-fastheten avtar etterson smelteflyten øker. Som et resultat av dette er produkter med lave smelteflyt-egenskaper og med høy slagfasthet vanskelig å sprøytestøpe i tynne delerj f.eks. batterikasser. A traditional problem experienced with impact-resistant polypropylene copolymers is that there is typically a trade-off between impact resistance and melt flow, i.e. impact strength decreases as melt flow increases. As a result of this, products with low melt flow properties and with high impact resistance are difficult to injection mold into thin parts, e.g. battery boxes.
Den tidligere teknikk beskriver forskjellige metoder for å forbedre forholdet ame 11eflyt/slagfas thet ved oksydative nedbrytningsteknikker. F.eks. beskriver japansk publika-sjon nr. 21731/73 forbedrede resultater ved varme-behandling av en etylen-propylen-blokkopolymer i nærvær av et peroksyd. Også US-patenter 3.940.379 og 4.061.694 beskriver fremgangsmåter for oksydativ nedbrytning av for-i skjellige vesentlig krystallinske propylenpolymerer. Et nødvendig trekk ved de sistnevnte to prosesser er at den oksydative nedbrytning mi utføres i nærvær av oksygen eller et peroksyd. The prior art describes various methods for improving the flow/impact strength ratio by oxidative degradation techniques. E.g. Japanese publication No. 21731/73 describes improved results in the heat treatment of an ethylene-propylene block copolymer in the presence of a peroxide. US patents 3,940,379 and 4,061,694 also describe methods for oxidative degradation of various substantially crystalline propylene polymers. A necessary feature of the latter two processes is that the oxidative degradation is carried out in the presence of oxygen or a peroxide.
Selv om en vesentlig forbedring i smelteflythastigheter er blitt oppnådd gjennom disse tidligere kjente metoder, har de ikke kunnet fremstille harpikser som er egnet for sprøytestøping til stive tynnveggede gjenstander med høy slag- og strekkfasthet, spesielt ved lave temperaturer. Although a significant improvement in melt flow rates has been achieved through these prior art methods, they have failed to produce resins suitable for injection molding into rigid thin-walled articles with high impact and tensile strength, especially at low temperatures.
Ifølge foreliggende oppfinnelse er det tilveiebragt en polypropylen-kopolymerblanding med høy slagfasthet og med regulert reologi, som er fremstilt ved en fremgangsmåte omfattende: According to the present invention, a polypropylene copolymer mixture with high impact strength and with regulated rheology is provided, which is produced by a method comprising:
I Tilveiebringelse av en harpiksb1 and ing medI Providing a resin b1 and ing with
a) fra ca. 70 til ca. 99 vekt-% av en blokk- kopolymer inneholdende fra ca. 70 til ca. a) from approx. 70 to approx. 99% by weight of a block copolymer containing from approx. 70 to approx.
90 vekt-% av en propylen-polymerandel og fra 90% by weight of a propylene polymer portion and from
ca. 10 til ca. 30 vekt-% av en blokk-kopolymerandel av etylen-propylen, og about. 10 to approx. 30% by weight of a block copolymer proportion of ethylene-propylene, and
b) fra ca. 1 til ca. 30 vekt-% av en etylen- propy1en-elastornerkomponent, hvor totalinnholdet av etylen-avledede enheter av harpiksblandingen varierer mellom ca. 5 og ca. 20 vekt-%. II. Behandling av harpiksblandingen i fravær av tilsatt oksygen under regulerte oksydative ned-bryt ning s be t inge 1 s e r med en fri radikal-utviklende forbindelse ved en temperatur fra ca. 204,4 til ca. 287,8oC. b) from approx. 1 to approx. 30% by weight of an ethylene propylene elastomer component, where the total content of ethylene-derived units of the resin mixture varies between approx. 5 and approx. 20% by weight. II. Treatment of the resin mixture in the absence of added oxygen under regulated oxidative degradation conditions 1 s with a free radical-developing compound at a temperature from approx. 204.4 to approx. 287.8oC.
I foreliggende fremgangsmåte antas det at polypropylen-segmentene i både blokk-kopolymeren og elastomeren gjennomgår kjedespalting til en høyere smelteflyt, og etylenpolymer-segmentene til disse komponenter kryssbindes under dannelse av seigere segmenter med høyere molekylvekt. Med den samtidige dannelse av propylen-polymer-radikaler og etylenpolymer-radikaler vil også noen av disse reagere under dannelse av slagfasthets-modifiserende podningspolymerer. Den dominerende reaksjon vil være kjedespalting eller øket smelteflyt, mens tap av slagfasthet vil minimaliseres ved dannelse av mer "gummi" og "gummi" med høy molekylvekt fra podningen og kryss-bindingen. In the present method, it is assumed that the polypropylene segments in both the block copolymer and the elastomer undergo chain cleavage to a higher melt flow, and the ethylene polymer segments of these components are cross-linked to form tougher segments with a higher molecular weight. With the simultaneous formation of propylene polymer radicals and ethylene polymer radicals, some of these will also react to form impact strength-modifying graft polymers. The dominant reaction will be chain cleavage or increased melt flow, while loss of impact resistance will be minimized by the formation of more "rubber" and "rubber" with a high molecular weight from the grafting and cross-linking.
Fremgangsmåten resulterer i harpiksprodukter som har vesentlig forøket smelteflyt mens de stort sett bibeholder de fysikalske egenskapene hos den opprinnelige harpiks med lavere smeltefflyt. The process results in resin products that have substantially increased melt flow while largely retaining the physical properties of the lower melt flow original resin.
Propylenpolymerandelen som representerer ca. 70-90 vekt-% av blokk-kopolymerkomponenten, er enten propylen homopolymer eller en vilkårlig kopolymer av propylen og mindre mengder etylen. Opptil 8 vekt-% etylenavledede enheter kan være til stede i nevnte propylenandel. Mengden av etylenenheter i den totale blokk-kopolymeren er fortrinnsvis begrenset til et område fra ca. 4 til ca. The propylene polymer portion representing approx. 70-90% by weight of the block copolymer component is either propylene homopolymer or an arbitrary copolymer of propylene and smaller amounts of ethylene. Up to 8% by weight of ethylene-derived units can be present in said propylene portion. The amount of ethylene units in the total block copolymer is preferably limited to a range from approx. 4 to approx.
15 vekt%.15% by weight.
Blokk-kopolymerer av denne type kan fremstilles ved hjelp av hvilken som helst av de velkjente katalyttiske poly-mer i sas jons teknikker og er kommersielt tilgjengelig. Selvom for oppfinnelsens formål blokk-kopolymeren er definert som en enkelt forbindelse^ skal det forstås at blokk-kopolymeri sas jonsprosesser faktisk resulterer i blandinger av blokk-kopolymerer med mindre mengder av homopolymer og vilkårlig kopolymer av etylen og propylen. Block copolymers of this type can be prepared using any of the well-known catalytic polymers in sas ion techniques and are commercially available. Although for the purposes of the invention the block copolymer is defined as a single compound, it should be understood that block copolymerization processes actually result in mixtures of block copolymers with smaller amounts of homopolymer and random copolymer of ethylene and propylene.
Etylen-propylen-etastomerkomponenten kan også være en hvilken som helst av de velkjente kommersielt tilgjengelige EP-gummienej som er kopolymerer av etylen og propylen inneholdende typisk mellom ca. 30 og ca. 70 vekt-% polymerisert etylen. En tredje monomer kan, om ønsket, inkorporeres i etylen-propylen-gummien for å øke gummiens evne til kryssbinding. Den tredje monomeren er en ikke-konjugert dien inneholdende typisk fra 6 til 8 karbon-atomer og med en terminal og en ikke-terminal dobbeltbinding, f.eks. 1,4-heksadien , 1,5 heptadien osv. De resulterende terpolymerene er kjente innen teknikken som EDPM-gummier, og er kommersielt tilgjengelige. For å lette bearbeidelse og blanding, sammenblandes elasto-maren noen ganger med ca. 30-50 vekt-% polypropylen eller polyetylen basert på totalvekten. The ethylene-propylene-elastomer component can also be any of the well-known commercially available EP rubbers which are copolymers of ethylene and propylene typically containing between approx. 30 and approx. 70% by weight polymerized ethylene. A third monomer can, if desired, be incorporated into the ethylene-propylene rubber to increase the rubber's ability to cross-link. The third monomer is a non-conjugated diene containing typically from 6 to 8 carbon atoms and having a terminal and a non-terminal double bond, e.g. 1,4-hexadiene, 1,5 heptadiene, etc. The resulting terpolymers are known in the art as EDPM rubbers, and are commercially available. To facilitate processing and mixing, the elastomar is sometimes mixed with approx. 30-50% by weight polypropylene or polyethylene based on the total weight.
Mengden av elas tomerkomponenten, om det er ED-gummi, EPDM-gummi eller en blanding av disse forbindelser med enten polypropylen eller polyetylenj bør ikke overskride ca. 30 vekt-% basert på totalvekten av harpikskomponentene (a) og (b) 1 foreliggende blanding, og konsentrasjonen holdes fortrinnsvis mellom ca. 3 og ca. 15 vekt-%. The quantity of the elastomer component, whether it is ED rubber, EPDM rubber or a mixture of these compounds with either polypropylene or polyethylenej should not exceed approx. 30% by weight based on the total weight of the resin components (a) and (b) in the present mixture, and the concentration is preferably kept between approx. 3 and approx. 15% by weight.
Harpiksen som skal behandles ved den oksydative nedbrytning^ har vanligvis en lav smelteflythastighet fra ca. 0,1 til ca. 5 g/10 min ved 230°C og ca. 2,16 kg. The resin to be treated by the oxidative degradation usually has a low melt flow rate from approx. 0.1 to approx. 5 g/10 min at 230°C and approx. 2.16 kg.
Den frie radikal-initiatoren som benyttes i den regulerte oksydative nedbrytningsbehandling av harpiksblandingen, bør være en som dekomponerer normalt, dvs. har minst 3-6, men fortrinnsvis ikke mer enn omkring 15 halveringstider under typiske ekstruderingsbetingelser ved ca. 204,4-287 ,8°C. The free radical initiator used in the regulated oxidative degradation treatment of the resin mixture should be one that decomposes normally, i.e. has at least 3-6, but preferably no more than about 15 half-lives under typical extrusion conditions at approx. 204.4-287 .8°C.
Mange organiske peroksyder er nyttige for dette formål, enten alene eller i kombinasjon^ f.eks. dikumylperoksyd; di-t-butylperoksyd, t-butylhydroperoksyd; t-butyl-perben-soat; 2,5-dimetyl-2,5-di-t-butylperoksyheksan ; 2,5-di mety1-2~5-di-t-peroksyheksin og andre. Peroksydkonsen-trasjonen bør hovedsakelig varieres fra ca. 100 til ca. 1500 ppm og fortrinnsvis mellom ca. 300 og 1000 ppm, avhengig av den ønskede innledende smelteflyt og den sluttlige smelteflyt. Many organic peroxides are useful for this purpose, either alone or in combination^ e.g. dicumyl peroxide; di-t-butyl peroxide, t-butyl hydroperoxide; t-butyl perbensoate; 2,5-dimethyl-2,5-di-t-butylperoxyhexane; 2,5-di methy1-2~5-di-t-peroxyhexine and others. The peroxide concentration should mainly be varied from approx. 100 to approx. 1500 ppm and preferably between approx. 300 and 1000 ppm, depending on the desired initial melt flow and the final melt flow.
Den regulerte oksydative nedbrytning utføres i en ekstruder eller slik apparatur som omdanner harpiksen til pellets. The regulated oxidative breakdown is carried out in an extruder or similar apparatus which converts the resin into pellets.
Ekstruderen opereres under normale pelletiserings-betingelser, mellom ca. 204,4 og ca. 287,8°C. Typiske smelteoppholdstider i ekstruderen varierer fra ca. 0,5 til ca. 3 min. Ekstruderingsope rasjonen utfføres i en inert atmosfære, dvs. oksygen eller luft hindres i å komme inn i ekstruderen under dden oksydative nedbrytnings-behandling. Ekstrudatet pelletiseres med normal kommersiell apparatur. Fremgangsmåten kan lett styres og gir produkter med høye sme1teflythastigheter, f.eks. i området fra ca. 10 til ca. 75 g/10 min ved 230°Cj og enda høyere, og er spesielt egnet for sprøytestøping av tynnveggede gjenstander av ønsket stivhet og med god slagfasthet ved romtemperatur og lavere temperaturer. Harpiksen er fullstendig homogen og er særlig anvendbar for fremstilling av batterikasser, våpenkasser, bagas je beho Ider e , ' f enderf oringer o.l. The extruder is operated under normal pelletizing conditions, between approx. 204.4 and approx. 287.8°C. Typical melt residence times in the extruder vary from approx. 0.5 to approx. 3 min. The extrusion operation is carried out in an inert atmosphere, i.e. oxygen or air is prevented from entering the extruder during the oxidative degradation treatment. The extrudate is pelletized with normal commercial equipment. The process can be easily controlled and produces products with high slurry flow rates, e.g. in the area from approx. 10 to approx. 75 g/10 min at 230°Cj and even higher, and is particularly suitable for injection molding of thin-walled objects of the desired stiffness and with good impact resistance at room temperature and lower temperatures. The resin is completely homogeneous and is particularly useful for the production of battery cases, weapon cases, luggage, accessories, etc.
Følgende eksempler illustrerer oppfinnelsen ytterligere. The following examples further illustrate the invention.
Eksempel 1Example 1
Det ble foretatt en rekke forsøk ved forskjellige peroksydnivåer varierende fra 0 til 1000 ppm under anvendelse av en pelletisert harpiksblanding bestående av 5 vektdeler "Nordel™ NDG 4167";. en EPDM-elas to mersa mmen-setning (33 vekt-% HD-polyetylen67 vekt-% terpolymer av etylen og propylen i omtrent like mengder og i tillegg små mengder 1j4-heksadien) , og 95 deler av en blokk-kopolymer av polypropylen bestående av 86 vekt-% propylen-homopolymer og 14 vekt-% etylen-propylen-postblokk (etylen-innholdet i blokken var ca. 40%). I hvert av forsøkene ble harpiksblandingen ytterligere blandet med den mengde peroksyd som er angitt i tabell 1, og etter ekstrudering pelletisert i en 6,35 cm Prodeks-ekstruder ved 260°C. Resultatene fra forsøkene er oppsummert i tabell 1. A series of tests were carried out at different peroxide levels ranging from 0 to 1000 ppm using a pelletized resin mixture consisting of 5 parts by weight of "Nordel™ NDG 4167";. an EPDM elastomer compound (33% by weight HD-polyethylene 67% by weight terpolymer of ethylene and propylene in approximately equal amounts and in addition small amounts of 1j4-hexadiene), and 95 parts of a block copolymer of polypropylene consisting of 86% by weight propylene homopolymer and 14% by weight ethylene-propylene mail block (the ethylene content in the block was approx. 40%). In each of the experiments, the resin mixture was further mixed with the amount of peroxide indicated in Table 1, and after extrusion pelletized in a 6.35 cm Prodeks extruder at 260°C. The results from the experiments are summarized in table 1.
Som det fremgår fra de angitte data var det sma eller intet tap i egenskaper opp til 26 MF og selv ved 66 MF var det bare et lite tap i slagfasthet. As can be seen from the data provided, there was little or no loss in properties up to 26 MF and even at 66 MF there was only a small loss in impact strength.
Eksempel 2Example 2
En pelletisert harpiks av komponenter i likhet med de i eksempel 1, men blandet i et forhold på 90:10 blokk-kopolymer/elastomer, ble underkastet regulert nedbrytning i nærvær av 500 ppm di-t-butylperoksyd ved 260°C i en 6,35 cm Prodeks-ekstruder. A pelletized resin of components similar to those of Example 1, but mixed in a 90:10 block copolymer/elastomer ratio, was subjected to controlled degradation in the presence of 500 ppm di-t-butyl peroxide at 260°C in a 6, 35 cm Prodeks extruder.
Smmenligningsdata er vist i tabell 2. Comparison data is shown in Table 2.
Den regalerte nedbryting resulterte i en harpiks med en ønsket høy sme11ef lythastighet og en meget høy Gardener-slagfas thetsverdi som ikke varierte i betydelig grad fra den til den opprinnelige harpiks med lav smelteflyt. The regaled degradation resulted in a resin with a desired high melt velocity and a very high Gardener impact phase temperature value that did not vary significantly from that of the original low melt flow resin.
Claims (10)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US45942983A | 1983-01-20 | 1983-01-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NO834504L true NO834504L (en) | 1984-07-23 |
Family
ID=23824730
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO834504A NO834504L (en) | 1983-01-20 | 1983-12-07 | PROPYLENE COPOLYMERS WITH IMPROVED IMPACT |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS59145242A (en) |
| DE (1) | DE3401612A1 (en) |
| FR (1) | FR2539749B1 (en) |
| GB (1) | GB2134122B (en) |
| NO (1) | NO834504L (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH068375B2 (en) * | 1983-08-18 | 1994-02-02 | 三井東圧化学株式会社 | Method for producing polypropylene resin composition |
| JPS61233047A (en) * | 1985-04-09 | 1986-10-17 | Mitsui Toatsu Chem Inc | Polypropylene resin composition |
| US5210139A (en) * | 1988-01-04 | 1993-05-11 | Exxon Chemical Patents Inc. | Thermoplastic olefin alloys and method for producing the same |
| US5023300A (en) * | 1988-01-04 | 1991-06-11 | Exxon Chemical Patents Inc. | Thermoplastic olefin alloys and method for producing the same |
| AT403581B (en) * | 1993-06-07 | 1998-03-25 | Danubia Petrochem Polymere | METHOD FOR PRODUCING NEW POLYPROPYLENE BY CHEMICAL DEGRADING |
| AU705311B2 (en) * | 1995-01-23 | 1999-05-20 | Showa Denko Kabushiki Kaisha | Propylene resin composition and molded article thereof |
| FI104828B (en) * | 1996-04-19 | 2000-04-14 | Borealis As | New tubular polypropylene composition |
| FR2762932B1 (en) * | 1997-05-02 | 1999-07-23 | Alsthom Cge Alcatel | WATERPROOF ELECTROCHEMICAL GENERATOR |
| JP4031622B2 (en) † | 2001-05-30 | 2008-01-09 | バセル ポリオレフィン イタリア エス．アール．エル． | Polypropylene resin composition |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB975877A (en) * | ||||
| US4087486A (en) * | 1975-05-15 | 1978-05-02 | Standard Oil Company (Indiana) | Polypropylene composition containing EPR |
| US4061694A (en) * | 1976-12-21 | 1977-12-06 | Dart Industries Inc. | Low temperature impact strength molding compositions |
| JPS5450057A (en) * | 1977-09-29 | 1979-04-19 | Ube Ind Ltd | Preparation of polypropylene composition having improved impact resistance |
| JPS56125442A (en) * | 1980-03-10 | 1981-10-01 | Showa Denko Kk | Production of crystalline polypropylene composition |
| JPS582338A (en) * | 1981-06-29 | 1983-01-07 | Mitsubishi Petrochem Co Ltd | Method for manufacturing thermoplastic elastomer |
| JPS5825340A (en) * | 1981-08-07 | 1983-02-15 | Mitsui Petrochem Ind Ltd | Method for producing partially crosslinked rubber-resin composition |
-
1983
- 1983-12-07 NO NO834504A patent/NO834504L/en unknown
- 1983-12-15 FR FR8320107A patent/FR2539749B1/en not_active Expired
- 1983-12-22 GB GB08334132A patent/GB2134122B/en not_active Expired
-
1984
- 1984-01-10 JP JP59001428A patent/JPS59145242A/en active Pending
- 1984-01-18 DE DE19843401612 patent/DE3401612A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| GB2134122B (en) | 1986-06-18 |
| GB2134122A (en) | 1984-08-08 |
| FR2539749A1 (en) | 1984-07-27 |
| GB8334132D0 (en) | 1984-02-01 |
| JPS59145242A (en) | 1984-08-20 |
| FR2539749B1 (en) | 1987-11-20 |
| DE3401612A1 (en) | 1984-07-26 |
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