DK155608B - THERMOPLASTIC COPOLYMER OR HIGH NITRIL CONTENT AND PODECOPOLYMER AND METHOD OF PRODUCING IT - Google Patents
THERMOPLASTIC COPOLYMER OR HIGH NITRIL CONTENT AND PODECOPOLYMER AND METHOD OF PRODUCING IT Download PDFInfo
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- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
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iin
DK 155608 BDK 155608 B
Opfindelsen angår en hidtil ukendt termoplastisk copolymer eller podecopolymer med højt nitri 1 indhold og med høje varmedekomponeringstemperaturer, gode gasspærreegenskaber og lave krybningsegenskaber samt en fremgangsmåde til fremstilling 5 heraf.The invention relates to a novel thermoplastic copolymer or graft copolymer with a high content of nitrogen and with high heat decomposition temperatures, good gas barrier properties and low creep properties, and a process for the preparation thereof.
Fra tysk fremlæggelsesskrift nr. 2.644.492 kendes slagfaste podecopolymeri sater opnået ved radikalpolymerisation af styren og/eller acrylonitril med maleinsyreanhydrid og/eller et male-10 imid i nærværelse af et terpolymerisat af ethylen, propylen og en polyen, som mindst indeholder én systemkonjugeret dobbeltbinding. Fra US patentskrift nr. 3.887.527 kendes det at modificere en polyisoprengummi med maleinsyreanhydrid uden nogen væsentlig forøgelse af gel indholdet ved omsætning heraf i 15 nærværelse af et inaktivt opløsningsmiddel under anvendelse af visse bestemte mængder af maleinsyreanhydrid og radikaldannen-de katalysator i et bestemt forhold derimellem.German Patent Specification No. 2,644,492 discloses impact-resistant graft copolymers obtained by radical polymerization of styrene and / or acrylonitrile with maleic anhydride and / or a maleimide in the presence of a terpolymer of ethylene, propylene and a polyene containing at least one system conjugate. . U.S. Patent No. 3,887,527 discloses modifying a polyisoprene rubber with maleic anhydride without substantially increasing the gel content by reaction thereof in the presence of an inert solvent using certain specific amounts of maleic anhydride and radical-forming catalyst in a given ratio. therebetween.
Fra US patentskrift nr. 3.998.907 kendes fremstillingen af 20 gummimodificerede copolymere indeholdende et imidderivat af en ethylenisk umættet di carboxyl syremonomer ved direkte omsætning af vandig ammoniak eller aminer ved 125-200*0 og under autogene tryk på mellem 0,4-1,1 MPa i 0,5-48 timer med en gummimodificeret copolymer indeholdende en ethylenisk umættet carboxyl-25 syre, dets anhydrid eller et halvsurt derivat af dicarboxylsy-ren. De opnåede copolymere har gode varmedekomponeringsegenskaber, opløsningsmiddelmodstandsdygtighed, fleksibilitet og krybningsegenskaber. Ingen af de nævnte kendte polymere materialer er opnået ved tilsætning af maleinsyreanhydrid til en 30 kendt høj ni trileopolymer, og det er ganske overraskende, at det hidtil ukendte polymere materiale ifølge den foreliggende opfindelse har den i beskrivelsen anførte gode kombination af fysiske og kemiske egenskaber.US Patent No. 3,998,907 discloses the preparation of 20 rubber-modified copolymers containing an imide derivative of an ethylenically unsaturated di-carboxylic acid monomer by direct reaction of aqueous ammonia or amines at 125-200 * 0 and under autogenous pressures of between 0.4-1. 1 MPa for 0.5-48 hours with a rubber modified copolymer containing an ethylenically unsaturated carboxylic acid, its anhydride or a semi-acidic derivative of the dicarboxylic acid. The copolymers obtained have good thermal composition properties, solvent resistance, flexibility and creep properties. None of the aforementioned known polymeric materials has been obtained by the addition of maleic anhydride to a known high nine trileopolymer, and it is quite surprising that the novel polymeric material of the present invention has the good combination of physical and chemical properties set forth in the specification.
35 Ansøgningen angår således en termoplastisk copolymer eller podecopolymer med højt nitril indhold og med høje varmedekomponeringstemperaturer, gode gasspærreegenskaber og lave krybningsegenskaber, hvilken copolymer eller podecopolymer er opnået ved DO1vmeri sat i on af 100 væatdala af an hlandinn omfattanda·Thus, the application relates to a thermoplastic copolymer or graft copolymer with high nitrile content and with high heat decomposition temperatures, good gas barrier properties and low creep properties, which copolymer or graft copolymer is obtained by DO1vmeri put on one of 100 wt.
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2 (A) mindst et nitril med formlen CH2=C-CN, hvori R er hydro-2 (A) at least one nitrile of formula CH 2 = C-CN wherein R
RR
gen, en alkylgruppe med 1-4 carbonatomer eller et halogen-5 atom og (C) mindst en bestanddel valgt blandt (1) styren eller α-methylstyren, 10 (2) en ester med formlen CH2=C-CQ0R2,gene, an alkyl group having 1-4 carbon atoms or a halogen atom and (C) at least one component selected from (1) styrene or α-methylstyrene, (2) an ester of the formula CH 2 = C-C
Ri hvori Ri er hydrogen, en alkylgruppe med 1-4"carbonatomer 15 eller et halogenatom, og R2 er en alkylgruppe med 1-5 car bonatomer, R'R1 is hydrogen, an alkyl group having 1-4 "carbon atoms or a halogen atom, and R2 is an alkyl group having 1-5 carbon atoms, R1
(3) en α-olefin med 4-10 carbonatomer og med formlen CH2=C(3) an α-olefin of 4-10 carbon atoms and of the formula CH 2 = C
20 j R" hvori R' og R" er alkylgrupper med 1-7 carbonatomer, (4) en vinylether valgt blandt methylvinylether, ethylvinylet- her, propylvinylethrene og butylvinylethrene, og 25 (5) vinylacetat, i nærværelse af 0-40 vægtdele af 30 (D) en gummiagtig polymer af en konjugeret dienmonomer valgt blandt butadien og isopren, og eventuelt mindst en comonomer valgt blandt styren, en nitriImonomer med formlen CH2=C-CN, i20 'R' wherein R 'and R' are alkyl groups of 1-7 carbon atoms, (4) a vinyl ether selected from methyl vinyl ether, ethyl vinyl ether, propyl vinyl ethers and butyl vinyl ethers, and 25 (5) vinyl acetate, in the presence of 0-40 parts by weight of (D) a rubbery polymer of a conjugated diene monomer selected from butadiene and isoprene, and optionally at least one comonomer selected from styrene, a nitrile monomer of the formula CH 2 = C-CN;
35 R35 R
hvori R har den ovenfor anførte betydning, og en ester med formlen 3wherein R is as defined above and an ester of formula 3
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ch2=c-coor2 hvori Ri og R2 har de ovenfor anførte betydninger, 5 idet nævnte gummiagtige polymer indeholder fra 0 til 50 vægt% comonomer, og den copolymere eller podecopolymere er ejendommelig ved, at der i nævnte blanding indgår 60-90 vægt% af bestanddelen (A), 5-25 vægt% af bestanddelen (C) og yderligere 10 1-30 vægt% ma 1 einsyreanhydrid (B), hvorhos vægtVerne af (A), (B) og (C) er baseret på den samlede vægt af (A) plus (B) plus (C) .ch 2 = c-coor 2 wherein R 1 and R 2 have the above meanings, said rubbery polymer containing from 0 to 50 wt% comonomer, and the copolymer or graft copolymer being characterized in that said mixture comprises 60 to 90 wt% of component (A), 5-25% by weight of component (C) and an additional 10 to 30% by weight of monoacetic anhydride (B), the weight values of (A), (B) and (C) based on the total weight of (A) plus (B) plus (C).
De hidtil ukendte polymere produkter ifølge opfindelsen frem-15 stilles ved at polymerisere en størstedel af en olefinisk umættet nitril, såsom acrylonitril og en mindre del af en anden monovinylmonomerkomponent, som skal omfatte maleinsyrean-hydrid, eventuelt i nærværelse af en præformet gummiagtig polymer sammensat af en konjugeret dienmonomer, såsom butadien.The novel polymeric products of the invention are prepared by polymerizing a majority of an olefinically unsaturated nitrile such as acrylonitrile and a minor portion of another monovinyl monomer component to comprise maleic anhydride, optionally in the presence of a preformed rubbery polymer composed of a conjugated diene monomer such as butadiene.
2020
De konjugerede diener, der er anvendelige i forbindelse med denne opfindelse er defineret i krav 1. Butadien og isopren anvendes på grund af deres lette tilgængelighed og deres fremragende copolymer isat ionsegenskaber.The conjugated dienes useful in this invention are defined in claim 1. Butadiene and isoprene are used because of their ease of availability and their excellent copolymer isation properties.
2525
De olefinisk umættede nitriler, der er anvendelige i forbindelse med opfindelsen, er de α,/J-olef inisk umættede mononitri-ler med formlenThe olefinically unsaturated nitriles useful in the invention are the α, β-olefinic unsaturated mononitriles of the formula
30 CHo=C-CN= C-CN
RR
hvori R er hydrogen, en lavere alkylgruppe med 1-4 carbonato-mer eller et halogenatom. Sådanne forbindelser omfatter acry-35 lonitril, α-chloracry1onitri 1, α-f1uoracry1 on itri 1, methacry-lonitril, ethacrylonitri 1 og lignende. Den mest foretrukne olefinisk umættede nitril er acrylonitril.wherein R is hydrogen, a lower alkyl group having 1-4 carbon atoms or a halogen atom. Such compounds include acrylonitrile, α-chloroacrylonitrile 1, α-fluoroacrylonitrile 1, methacrylonitrile, ethacrylonitrile 1 and the like. The most preferred olefinically unsaturated nitrile is acrylonitrile.
44
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Som de vinylaromatiske monomerer indgår styren og a-methylsty-ren.Like the vinyl aromatic monomers, styrene and the α-methyl styrene are included.
Estrene af olefinisk umættede carboxylsyrer er de med formlen 5 ch2=c-coor2 il hvori Ri er hydrogen, en alkylgruppe med 1-4 carbonatomer el-10 ler et halogenatom, og R2 er en alkylgruppe med 1-6 carbonatomer. I forbindelse med den foreliggende opfindelse foretrækkes specielt methy1 aery1 at, ethylacrylat, methylmethacrylat og ethyl methacry1 at.The esters of olefinically unsaturated carboxylic acids are those of the formula 5ch2 = c-coor2il wherein R 1 is hydrogen, an alkyl group of 1-4 carbon atoms or a halogen atom, and R2 is an alkyl group of 1-6 carbon atoms. In the present invention, especially methyl aryl, ethyl acrylate, methyl methacrylate and ethyl methacrylate are particularly preferred.
15 α-olefinerne, der er anvendelige i forbindelse med opfindelsen, er de med mindst 4 og højst 10 carbonatomer, og som har formlen R'The 15 olefins useful in the invention are those having at least 4 and at most 10 carbon atoms and having the formula R '
20 CH2=CCH2 = C
R" hvori R' og R" er alkylgrupper med 1-7 carbonatomer, og mere specielt foretrukne er α-olefiner, såsom isobutylen, 2-methyl-25 buten-1, 2-methylpenten-1, 2-methy1hexen-1, 2-methy1hepten-1, 2-methylocten-l, 2-ethylbuten-1 og 2-propylpenten-1. Isobutylen foretrækkes mest.R "wherein R 1 and R" are alkyl groups of 1-7 carbon atoms and more particularly preferred are α-olefins such as isobutylene, 2-methyl-butene-1,2-methylpenten-1,2-methylhexene-1,2 -methylhepten-1,2-methyloctene-1,2-ethylbutene-1 and 2-propylpenten-1. Isobutylene is most preferred.
Vinylethrene er methylvinylether, ethyl vinyl ether, propylvi- 3 0 nylethrene og butyl vi ny1ethrene.The vinyl ethers are methyl vinyl ether, ethyl vinyl ether, propyl vinyl ethers and butyl vinyl ethers.
Maleinsyreanhydrid er en essentiel komponent af de hidtil ukendte materialer i overensstemmelse med opfindelsen.Maleic anhydride is an essential component of the novel materials in accordance with the invention.
De polymere materialer ifølge den foreliggende opfindelse kan fremstilles ved hjælp af enhver af de almindeligt kendte polymerisationsmetoder inklusive massepolymerisation, opløsnings- 35The polymeric materials of the present invention can be prepared by any of the commonly known polymerization methods including mass polymerization,
DK 155608 BDK 155608 B
SS
polymerisation og emulsions- eller suspensionspolymerisation ved chargevis, kontinuerlig eller intermitterende tilsætning af de monomere og de andre komponenter. Den foretrukne metode er opløsningspolymerisation i nærværelse af et organisk opløs-5 ningsmiddel og en fri radikaldannende polymerisationsinitiator ved en temperatur i intervallet fra ca. 0 til 100°C i alt væsentligt uden nærværelse af molekylært oxygen.polymerization and emulsion or suspension polymerization by batchwise, continuous or intermittent addition of the monomers and other components. The preferred method is solution polymerization in the presence of an organic solvent and a free radical-forming polymerization initiator at a temperature in the range of from about. 0 to 100 ° C substantially without the presence of molecular oxygen.
De gummiagtige polymere, der kan indgå i harpikserne ifølge 10 opfindelsen, er homopolymere af de ovennævnte konjugerede di-enmonomere såvel som copolymere af disse diener og en anden monomerkomponent som defineret i krav 1, såsom acrylonitri1, styren, ethylacrylat og blandinger deraf, hvori der indgår mindst 50 vægt% beregnet på den samlede mængde monomere af den 15 konjugerede dienmonomer.The rubbery polymers which may be included in the resins of the invention are homopolymers of the aforementioned conjugated diene monomers as well as copolymers of these dienes and another monomer component as defined in claim 1, such as acrylonitrile, styrene, ethyl acrylate and mixtures thereof, wherein contains at least 50% by weight based on the total amount of monomer of the 15 conjugated diene monomer.
De hidtil ukendte polymere er let bearbejdelige termoplasti ske materialer, der kan termoformes til en lang række nyttige genstande ved hjælp af enhver af de sædvanlige metoder, som 20 anvendes i forbindelse med kendte termoplast i ske materialer, såsom ekstrusion, formaling, støbning, trækning, sprøjtning, etc. De polymere produkter ifølge opfindelsen har fremragende opløsningsmiddelmodstandsdygtighed og deres slagstyrke og lave permeabilitet over for gasser og dampe gør dem nyttige i em-25 bal 1ageindustrien, og de er særligt velegnede til fremstillingen af flasker, folier, plader, rør og andre typer af beholdere til væsker og faste stoffer.The novel polymers are readily processable thermoplastic materials which can be thermoformed into a wide variety of useful articles by any of the usual methods used in conjunction with known thermoplastic materials, such as extrusion, grinding, casting, drawing, spraying, etc. The polymeric products of the invention have excellent solvent resistance and their impact strength and low permeability to gases and vapors make them useful in the packaging industry and are particularly suitable for the manufacture of bottles, foils, sheets, tubes and others. types of containers for liquids and solids.
Opfindelsen belyses nærmere ved hjælp af de følgende eksemp-30 ler, hvori bestanddelene er angivet i vægtdele, medmindre andet er anført.The invention is further illustrated by the following examples, in which the components are given in parts by weight, unless otherwise stated.
Eksempel 1 35 A. En acrylonitril-styren-copolymer, som ikke falder inden for den foreliggende opfindelses omfang, blev fremstillet i en polymerisationsreaktor, hvortil der blev sat 75 dele acryloni-tril, 3 dele styren og 73 dele methyl ethyl keton. BlandingenExample 1 35 A. An acrylonitrile-styrene copolymer which does not fall within the scope of the present invention was prepared in a polymerization reactor to which 75 parts of acrylonitrile, 3 parts of styrene and 73 parts of methyl ethyl ketone were added. The mixture
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6 blev omrørt, og temperaturen indstilles på 76°C under en nitrogenatmosfære. En fødeblanding bestående af 22 dele styren, 25 dele methylethylketon og 0,3 dele azobisisobutyronitril blev tilsat kontinuerligt og jævnt i løbet af en periode på 4 5 1/2 time. Den endelige reaktionsblanding blev holdt ved 76 til 78eC i yderligere en time. Den samlede omdannelse af monomere til polymer var 68% af den teoretiske værdi.6 was stirred and the temperature was adjusted to 76 ° C under a nitrogen atmosphere. A feed mixture consisting of 22 parts styrene, 25 parts methyl ethyl ketone and 0.3 parts azobisisobutyronitrile was added continuously and evenly over a period of 45 1/2 hours. The final reaction mixture was kept at 76 to 78 ° C for an additional hour. The total conversion of monomers to polymer was 68% of theoretical value.
Reaktorindholdet blev hældt i en omrørt blanding af lige volu-10 mendele benzen og petroleumsether. Den faste polymer blev isoleret, og tørret under reduceret tryk og ved en temperatur på 45-60eC i 48 timer. Harpiksen viste sig at have en ASTM varmedekomponeringstemperatur på 84-94eC, en bøjningsstyrke på 11^,9 MPa, et bøjningsmodul på 3792,3 MPa, en trækstyrke på 15 97,2 MPa, en oxygentransmissionshastighed på 3,5 cm3-0,0254 mm/645,2 cm2/24 timer/atmosfære og en vanddampoverføringshastighed på 8,0 g-0,0254 mm/645,2 cm2/24 timer/atmosfære.The reactor contents were poured into a stirred mixture of equal volumes of benzene and petroleum ether. The solid polymer was isolated and dried under reduced pressure and at a temperature of 45-60 ° C for 48 hours. The resin was found to have an ASTM thermal decomposition temperature of 84-94eC, a bending strength of 11 ^, 9 MPa, a bending modulus of 3792.3 MPa, a tensile strength of 97 97 MPa, an oxygen transmission rate of 3.5 cm3-0.0254 mm / 645.2 cm2 / 24 hours / atmosphere and a water vapor transfer rate of 8.0 g-0.0254 mm / 645.2 cm2 / 24 hours / atmosphere.
B. En acrylonitril-styren-maleinsyreanhydrid-terpolymer, som 20 falder inden for den foreliggende opfindelses omfang, blev fremstillet ved hjælp af fremgangsmåde A fra dette eksempel bortset fra, at den kontinuerligt tilførte fødeblanding bestod af 5 dele maleinsyreanhydrid, 17 dele styren, 25 dele methylethylketon og 0,3 dele asobisisobutyronitril og at den konti-25 nuerlige tilsætning af fødebiandingen skete jævnt over en 5 timers periode. Den samlede omdannelse af monomere til polymer var 80% af den teoretiske værdi. Den dannede harpiks viste sig at have en ASTM varmedekomponeringstemperatur på 102°C, en bøjningsstyrke på 128,9 MPa, et bøjningsmodul på 4178,4 MPa, 30 en trækstyrke på 104,8 MPa, en oxygentransmissionshastighed på 4,6 cm3-o,0254 mm/645,2 cm2/24 timer/atmosfære og en vanddampoverføringshastighed på 0,9 g-0,0254 mm/645,2 cm2/24 timer/atmosfære.B. An acrylonitrile-styrene-maleic anhydride terpolymer, which falls within the scope of the present invention, was prepared by Method A of this example except that the continuously fed feed mixture consisted of 5 parts of maleic anhydride, 17 parts of styrene, 25 parts of methyl ethyl ketone and 0.3 parts of asobisisobutyronitrile and that the continuous addition of the food mixture occurred evenly over a 5 hour period. The total conversion of monomers to polymer was 80% of theoretical value. The resin formed was found to have an ASTM heat decomposition temperature of 102 ° C, a flexural strength of 128.9 MPa, a flexural modulus of 4178.4 MPa, a tensile strength of 104.8 MPa, an oxygen transmission rate of 4.6 cm 3 0254 mm / 645.2 cm2 / 24 hours / atmosphere and a water vapor transfer rate of 0.9 g-0.0254 mm / 645.2 cm2 / 24 hours / atmosphere.
35 735 7
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Eksempel 2Example 2
Fremgangsmåden fra eksempel 1A blev fulgt bortset fra, at reaktoren i begyndelsen indeholdt 70'dele acrylonitril, 2,8 dele 5 styren, 75 dele methylethylketon og at den kontinuerligt tilsatte fødeblanding bestod af 5 dele maleinsyreanhydrid, 22,2 dele styren, 25 dele methylethylketon og 0,3 dele azobisisobu-tyronitril. Den kontinuerligt tilførte fødeblanding blev tilsat jævnt i løbet af en 6 timers periode. Den samlede omdan-10 nelse af monomere til polymer var 81% af den teoretiske værdi.The procedure of Example 1A was followed except that the reactor initially contained 70 parts of acrylonitrile, 2.8 parts of 5 styrene, 75 parts of methyl ethyl ketone and the continuously added feed mixture consisted of 5 parts of maleic anhydride, 22.2 parts of styrene, 25 parts of methyl ethyl ketone. and 0.3 parts of azobisisobutyronitrile. The continuously fed food mixture was added evenly over a 6 hour period. The total conversion of monomers to polymer was 81% of theoretical value.
Den resulterende harpiksagtige polymer viste sig at have en ASTM varmedekomponeringstemperatur på 104°C, en bøjningsstyrke på 130,3 MPa, et bøjningsmodul på 4226,6 MPa og en trækstyrke på 97,9 MPa.The resulting resinous polymer was found to have an ASTM thermal decomposition temperature of 104 ° C, a flexural strength of 130.3 MPa, a flexural modulus of 4226.6 MPa, and a tensile strength of 97.9 MPa.
1515
Eksempel 3Example 3
Der blev fremstillet en polymer ved hjælp af fremgangsmåden, der er beskrevet i eksempel 2, idet der i begyndelsen i reak-20 toren blev tilsat 70 dele acrylonitril, 2,8 dele styren og 75 dele methylethylketon og idet den kontinuerligt tilsatte fødeblanding er fremstillet af 10 dele maleinsyreanhydrid, 17,8 dele styren, 25 dele methylethylketon og 0,3 dele azobisisobu-tyronitril. Den resulterende harpiks viste sig at have en ASTM 25 varmedekomponer i ngstemperatur på 107°C, et bøjningsmodul på 4157,7 MPa, en oxygentransmissionshastighed på 2,7 cm3-0,0254 mm/645,2 cma/24 timer/atmosfære og en vanddampoverføringshastighed på 5,4 g-0,0254 mm/645,2 cm2/24 timer/atmosfære.A polymer was prepared by the method described in Example 2, with 70 parts of acrylonitrile, 2.8 parts of styrene and 75 parts of methyl ethyl ketone being added initially in the reactor and the continuously added feed mixture made of 10 parts maleic anhydride, 17.8 parts styrene, 25 parts methyl ethyl ketone and 0.3 parts azobisisobutyronitrile. The resulting resin was found to have an ASTM 25 thermocouple at 107 ° C, a bending modulus of 4157.7 MPa, an oxygen transmission rate of 2.7 cm3-0.0254 mm / 645.2 cma / 24 h / atmosphere and a water vapor transfer rate of 5.4 g-0.0254 mm / 645.2 cm 2/24 h / atmosphere.
30 Eksempel 4 A. Der blev fremstillet en copolymer af acrylonitril og methylacrylat, som falder uden for den foreliggende opfindelses omfang ved til en polymerisationsreaktor at sætte 75 dele 35 acrylonitril, 25 dele methylacrylat, 100 dele methylethylketon og 0,1 dele azobisisobutyronitri1. Polymerisationsreaktionen blev gennemført i 2 timer ved 75°C under omrøring under en ni trogenatmosfære. Den polymere blev isoleret ved koaguleringExample 4 A. A copolymer of acrylonitrile and methyl acrylate was prepared which falls outside the scope of the present invention by adding to a polymerization reactor 75 parts 35 acrylonitrile, 25 parts methyl acrylate, 100 parts methyl ethyl ketone and 0.1 parts azobisisobutyronitrile. The polymerization reaction was carried out for 2 hours at 75 ° C with stirring under a nine trogen atmosphere. The polymer was isolated by coagulation
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US80657777A | 1977-06-15 | 1977-06-15 | |
| US80657777 | 1977-06-15 |
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| DK269978A DK269978A (en) | 1978-12-16 |
| DK155608B true DK155608B (en) | 1989-04-24 |
| DK155608C DK155608C (en) | 1989-10-16 |
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| DK269978A DK155608C (en) | 1977-06-15 | 1978-06-15 | THERMOPLASTIC COPOLYMER OR HIGH NITRIL CONTENT AND PODECOPOLYMER AND METHOD OF PRODUCING IT |
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| JP (1) | JPS546091A (en) |
| AT (1) | AT366708B (en) |
| AU (1) | AU518735B2 (en) |
| BE (1) | BE868108A (en) |
| CA (1) | CA1106536A (en) |
| CH (1) | CH637661A5 (en) |
| DE (1) | DE2824713A1 (en) |
| DK (1) | DK155608C (en) |
| FR (1) | FR2394577B1 (en) |
| GB (1) | GB1599360A (en) |
| IT (1) | IT1096376B (en) |
| NL (1) | NL7806484A (en) |
| SE (1) | SE443364B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE2747822C2 (en) * | 1977-10-26 | 1985-05-30 | Bayer Ag, 5090 Leverkusen | Thermoplastic molding compounds |
| JP4746684B2 (en) * | 2009-03-24 | 2011-08-10 | 有限会社長州電気 | Telescopic device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3887527A (en) * | 1972-06-16 | 1975-06-03 | Kuraray Co | Method of producing maleic anhydride modified polyisoprene rubber |
| US3998907A (en) * | 1972-08-29 | 1976-12-21 | Arco Polymers, Inc. | Rubber-modified dicarboxylic acid imide copolymers |
| DE2644492A1 (en) * | 1975-10-03 | 1977-04-07 | Anic Spa | IMPACT-RESISTANT GRAFT-COPOLYMERISATE |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2734888A (en) * | 1951-08-31 | 1956-02-14 | Projducts | |
| DE919140C (en) * | 1951-12-05 | 1954-10-14 | Roehm & Haas G M B H | Process for improving the properties of acrylonitrile copolymers |
| DD252541A5 (en) * | 1985-12-04 | 1987-12-23 | Max-Planck-Gesellschaft Zur Foerderung Der Wissenschaften E. V.,De | METHOD FOR PRODUCING PHOSPHOVER BINDINGS CONTAINING PHOSPHOVER BINDINGS FOR TUMOR TREATMENT |
-
1978
- 1978-05-12 CA CA303,189A patent/CA1106536A/en not_active Expired
- 1978-05-19 ZA ZA00782898A patent/ZA782898B/en unknown
- 1978-05-22 AU AU36323/78A patent/AU518735B2/en not_active Expired
- 1978-05-30 AT AT0393378A patent/AT366708B/en not_active IP Right Cessation
- 1978-05-31 GB GB25677/78A patent/GB1599360A/en not_active Expired
- 1978-06-06 DE DE19782824713 patent/DE2824713A1/en not_active Ceased
- 1978-06-06 IT IT24274/78A patent/IT1096376B/en active
- 1978-06-12 FR FR7817464A patent/FR2394577B1/en not_active Expired
- 1978-06-14 CH CH649078A patent/CH637661A5/en not_active IP Right Cessation
- 1978-06-14 BE BE188558A patent/BE868108A/en not_active IP Right Cessation
- 1978-06-14 JP JP7312778A patent/JPS546091A/en active Granted
- 1978-06-14 SE SE7806875A patent/SE443364B/en not_active IP Right Cessation
- 1978-06-15 DK DK269978A patent/DK155608C/en not_active IP Right Cessation
- 1978-06-15 NL NL7806484A patent/NL7806484A/en not_active Application Discontinuation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3887527A (en) * | 1972-06-16 | 1975-06-03 | Kuraray Co | Method of producing maleic anhydride modified polyisoprene rubber |
| US3998907A (en) * | 1972-08-29 | 1976-12-21 | Arco Polymers, Inc. | Rubber-modified dicarboxylic acid imide copolymers |
| DE2644492A1 (en) * | 1975-10-03 | 1977-04-07 | Anic Spa | IMPACT-RESISTANT GRAFT-COPOLYMERISATE |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2394577A1 (en) | 1979-01-12 |
| IT1096376B (en) | 1985-08-26 |
| NL7806484A (en) | 1978-12-19 |
| DE2824713A1 (en) | 1979-01-04 |
| JPS546091A (en) | 1979-01-17 |
| CA1106536A (en) | 1981-08-04 |
| FR2394577B1 (en) | 1985-11-15 |
| JPS6315286B2 (en) | 1988-04-04 |
| SE443364B (en) | 1986-02-24 |
| AU518735B2 (en) | 1981-10-15 |
| ZA782898B (en) | 1979-05-30 |
| AT366708B (en) | 1982-05-10 |
| CH637661A5 (en) | 1983-08-15 |
| DK155608C (en) | 1989-10-16 |
| ATA393378A (en) | 1981-09-15 |
| IT7824274A0 (en) | 1978-06-06 |
| DK269978A (en) | 1978-12-16 |
| BE868108A (en) | 1978-10-02 |
| GB1599360A (en) | 1981-09-30 |
| AU3632378A (en) | 1979-11-29 |
| SE7806875L (en) | 1978-12-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PBP | Patent lapsed |