NO163620B - ETHYLENE POLYMERS CONTAINING UNITS DERIVED FROM MALEIC ACID ANHYRIDE, PROCEDURE FOR PREPARING THE PYLYMERS AND THEIR USE FOR PREPARATION OF FILES. - Google Patents
ETHYLENE POLYMERS CONTAINING UNITS DERIVED FROM MALEIC ACID ANHYRIDE, PROCEDURE FOR PREPARING THE PYLYMERS AND THEIR USE FOR PREPARATION OF FILES. Download PDFInfo
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- NO163620B NO163620B NO820224A NO820224A NO163620B NO 163620 B NO163620 B NO 163620B NO 820224 A NO820224 A NO 820224A NO 820224 A NO820224 A NO 820224A NO 163620 B NO163620 B NO 163620B
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- ethylene
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- terpolymer
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- 238000000034 method Methods 0.000 title claims description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 title 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 title 1
- 239000011976 maleic acid Substances 0.000 title 1
- 229920000573 polyethylene Polymers 0.000 title 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 title 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 34
- 239000005977 Ethylene Substances 0.000 claims description 34
- 229920000642 polymer Polymers 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 23
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 19
- 229920001897 terpolymer Polymers 0.000 claims description 17
- 229920006029 tetra-polymer Polymers 0.000 claims description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical group CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 7
- 239000011888 foil Substances 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 7
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical group CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000002688 maleic acid derivatives Chemical class 0.000 claims description 4
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- -1 2-ethylhexyl Chemical group 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 claims 1
- 239000004711 α-olefin Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- UUPWEGAONCOIFJ-UHFFFAOYSA-N CCCCC(CC)COC(=O)OOC(O)=O Chemical compound CCCCC(CC)COC(=O)OOC(O)=O UUPWEGAONCOIFJ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000012169 petroleum derived wax Substances 0.000 description 1
- 235000019381 petroleum wax Nutrition 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- UWNNZXDNLPNGQJ-UHFFFAOYSA-N tert-butyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OC(C)(C)C UWNNZXDNLPNGQJ-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Description
Denne oppfinnelse angår terpolymerer og tetrapolymerer av ethylen, som inneholder enheter avledet fra maleinsyreanhydrid, samt en fremgangsmåte for fremstilling av polymerene og deres anvendelse for fremstilling,av folier. This invention relates to terpolymers and tetrapolymers of ethylene, which contain units derived from maleic anhydride, as well as a method for producing the polymers and their use for the production of foils.
I fransk patentskrift nr. 1.323.379 beskrives terpolymerer av ethylen, et alkylacrylat og maleinsyreanhydrid, som har lav krystallinitet, og som anvendes som modifiseringsmid-ler for petroleumvoks i en mengde av fra 5 til 10 vekt% av voksen, for belegning av papir. French patent document no. 1,323,379 describes terpolymers of ethylene, an alkyl acrylate and maleic anhydride, which have low crystallinity, and which are used as modifiers for petroleum wax in an amount of from 5 to 10% by weight of the wax, for coating paper.
Det er nu, i henhold til oppfinnelsen, frembragt forbed-rede polymerer som inneholder enheter avledet fra ethylen som en hovedmonomer, og som dessuten inneholder enheter avledet fra to eller tre comonomerer, av hvilke den første er en (meth)acrylsyreester og den andre er maleinsyreanhydrid. Now, according to the invention, improved polymers have been produced which contain units derived from ethylene as a main monomer, and which also contain units derived from two or three comonomers, of which the first is a (meth)acrylic acid ester and the second is maleic anhydride.
Med oppfinnelsen tilveiebringes det således en terpolymer eller tetrapolymer av ethylen, med en smelteindeks på 1-500 dg/mn, som består av fra 88 til 98,7 mol% enheter avledet fra ethylen, fra 1 til 10 mol% enheter avledet fra minst én ester valgt blant alkylacrylater og -methacrylater, hvor alkylgruppen har 1-6 carbonatomer, og fra 0,3 til 3 mol% enheter avledet fra maleinsyreanhydrid, samt eventuelt en fjerde monomer. Den nye polymer er særpreget ved at dens polydispersitet er høyere enn 6, og at den lar seg fremstille ved at man i nærvær av minst én fri-radikal-initiator copolymeriserer en blanding bestående av 94-99 vekt% ethylen, 0,7-5 vekt% av minst én (meth)acrylsyreester og 0,2-0,9 vekt% maleinsyreanhydrid i en reaktor som holdes ved et trykk på The invention thus provides a terpolymer or tetrapolymer of ethylene, with a melt index of 1-500 dg/mn, which consists of from 88 to 98.7 mol% units derived from ethylene, from 1 to 10 mol% units derived from at least one ester selected from among alkyl acrylates and -methacrylates, where the alkyl group has 1-6 carbon atoms, and from 0.3 to 3 mol% units derived from maleic anhydride, as well as optionally a fourth monomer. The new polymer is characterized by the fact that its polydispersity is higher than 6, and that it can be produced by copolymerizing, in the presence of at least one free-radical initiator, a mixture consisting of 94-99% by weight ethylene, 0.7-5 wt% of at least one (meth)acrylic acid ester and 0.2-0.9 wt% maleic anhydride in a reactor maintained at a pressure of
fra 1000 til 3000 bar og ved en temperatur fra 170° til 280°C, avlaster trykket, derefter separerer den i reaktoren dannede blanding av monomer og terpolymer eller tetrapolymer og tilslutt resirkulerer til reaktoren den utskilte blanding av ethylen og monomerer, idet det til reaktoren resirkuleres en blanding som inneholder fra 99 til 99,8% ethylen og fra 0,2 til 1% (meth)acrylsyreester. Fortrinnsvis er polymerens Vicat-temperatur mellom 30 og 85°C. from 1000 to 3000 bar and at a temperature from 170° to 280°C, relieves the pressure, then separates the mixture of monomer and terpolymer or tetrapolymer formed in the reactor and finally recycles the separated mixture of ethylene and monomers to the reactor, a mixture containing from 99 to 99.8% ethylene and from 0.2 to 1% (meth)acrylic acid ester is recycled. Preferably, the Vicat temperature of the polymer is between 30 and 85°C.
Når polymerene ifølge oppfinnelsen omfatter enheter avledet fra en fjerde comonomer, er denne valgt blant ot-olefiner med 3-8 carbonatomer, monoalkylmaleater og dialkylmale-ater hvor alkylgruppene har 1-6 carbonatomer, vinylacetat og carbonmonoxyd, og den kan være tilstede i en mengde av inntil 5 mol%, idet mengden av ethylen i tetrapolymeren i det tilfelle reduseres tilsvarende i forhold til det ovenfor angitte område. When the polymers according to the invention comprise units derived from a fourth comonomer, this is selected from o-olefins with 3-8 carbon atoms, monoalkyl maleates and dialkyl maleates where the alkyl groups have 1-6 carbon atoms, vinyl acetate and carbon monoxide, and it can be present in an amount of up to 5 mol%, the amount of ethylene in the tetrapolymer in that case being reduced correspondingly in relation to the range indicated above.
Med oppfinnelsen tilveiebringes det dessuten en fremgangsmåte for fremstilling av den nye terpolymer eller tetrapolymer av ethylen, ved hvilken man i nærvær av minst én fri-radikal-initiator copolymeriserer en blanding bestående av 94-99 vekt% ethylen, 0,7-5 vekt% av minst én (meth)acryl-syreester, 0,2-0,9 vekt% maleinsyreanhydrid og eventuelt en fjerde monomer i en reaktor som holdes ved et trykk på fra 1000 til 3000 bar og ved en temperatur fra 170°C til 280°C, avlaster trykket, derefter separerer den i reaktoren dannede blanding av monomer og terpolymer eller tetrapolymer og tilslutt resirkulerer til reaktoren den utskilte blanding av ethylen og monomerer. Fremgangsmåten utmerker seg ved The invention also provides a method for the production of the new terpolymer or tetrapolymer of ethylene, in which, in the presence of at least one free-radical initiator, a mixture consisting of 94-99% by weight ethylene, 0.7-5% by weight is copolymerized of at least one (meth)acrylic acid ester, 0.2-0.9% by weight maleic anhydride and optionally a fourth monomer in a reactor which is maintained at a pressure of from 1000 to 3000 bar and at a temperature of from 170°C to 280° C, relieves the pressure, then separates the mixture of monomer and terpolymer or tetrapolymer formed in the reactor and finally recycles to the reactor the separated mixture of ethylene and monomers. The procedure is distinguished by
at der til reaktoren resirkuleres en blanding som inneholder fra 99 til 99,8% ethylen og fra 0,2 til 1% (meth)acarylsyre-ester. that a mixture containing from 99 to 99.8% ethylene and from 0.2 to 1% (meth)acarylic acid ester is recycled to the reactor.
Sluttelig angår oppfinnelsen en anvendelse av den nye terpolymer eller tetrapolymer for fremstilling av folier Finally, the invention concerns a use of the new terpolymer or tetrapolymer for the production of foils
av tykkelse mellom 10 og 500^um. of thickness between 10 and 500 µm.
Ved fremgangsmåten ifølge oppfinnelsen kan det benyttes en separat tilførsel av friskt ethylen på den ene side, og en tilførsel av comonomerene og det resirkulerte ethylen på den annen side. Innføringen av comonomerene i reaktoren foretaes fortrinnsvis ved at en oppløsning av maleinsyreanhydrid i (meth)acrylsyreester anbringes under trykk og blandes med strømmen av ethylen, hvoretter den erholdte blanding homogeniseres før den tilføres reaktoren. Eksempelvis kan blandingen og homogeniseringen utføres samtidig i en innretning av Venturi-typen. Selvfølgelig kan man overveie en sepa-rasjon av det resirkulerte ethylen og (meth)acrylsyreesteren. men en slik operasjon gir ingen fordeler som kompenserer for den økning i fremstillingskostnadene som dette medfører. In the method according to the invention, a separate feed of fresh ethylene can be used on the one hand, and a feed of the comonomers and the recycled ethylene on the other hand. The introduction of the comonomers into the reactor is preferably carried out by placing a solution of maleic anhydride in (meth)acrylic acid ester under pressure and mixing with the stream of ethylene, after which the resulting mixture is homogenised before it is fed to the reactor. For example, the mixing and homogenization can be carried out simultaneously in a Venturi-type device. Of course, one can consider a separation of the recycled ethylene and the (meth)acrylic acid ester. but such an operation provides no advantages that compensate for the increase in manufacturing costs that this entails.
Eksempler på fri-radikal-initiatorer som kan anvendes ved fremgangsmåten ifølge oppfinnelsen, er 2-ethylhexyl-peroxy-dicarbonat, di-tert.-butyl-peroxyd, tert.-butyl-perbenzoat og tert.-butyl-2-ethyl-hexanoat. Det er også mulig ved fremgangsmåten ifølge oppfinnelsen å anvende på i og for seg kjent måte ett eller flere overføringsmidler, som f.eks. hyd-rogen, for å regulere polymerens egenskaper, spesielt dens smelteindeks. Examples of free-radical initiators that can be used in the method according to the invention are 2-ethylhexyl-peroxy-dicarbonate, di-tert-butyl-peroxide, tert-butyl-perbenzoate and tert-butyl-2-ethyl-hexanoate . It is also possible with the method according to the invention to use in a known manner one or more transfer agents, such as e.g. hydrogen, to regulate the polymer's properties, especially its melt index.
Fremgangsmåten ifølge oppfinnelsen utføres kontinuerlig, enten i en omrørt autoklavreaktor som omfatter én eller ,flere soner, eller i en rørreaktor, som beskrevet f.eks. i DD-patentskrift nr. 58.387. På nedstrømssiden av reaktoren er det montert en ekspansjonsventil, som etterfølges av en sepa-rator som drives under et trykk på fra 200 til 500 bar. Ved fremgangsmåten ifølge oppfinnelsen kan det foretas kjøling av blandingen av polymer og av monomerer mellom ekspansjonsventilen og separatoren, f.eks. i henhold til fransk patentskrift nr, 2.313.399, ved injisering av ethylen ved et trykk som er lavere enn trykket i separatoren, hvilket ethylen kan oppsamles på nedstrømssiden av en varmeveksler i resirkulasjons-kretsløpet. The method according to the invention is carried out continuously, either in a stirred autoclave reactor comprising one or more zones, or in a tube reactor, as described e.g. in DD patent document no. 58,387. An expansion valve is mounted on the downstream side of the reactor, which is followed by a separator which is operated under a pressure of from 200 to 500 bar. With the method according to the invention, the mixture of polymer and monomers can be cooled between the expansion valve and the separator, e.g. according to French patent document no, 2,313,399, by injecting ethylene at a pressure lower than the pressure in the separator, which ethylene can be collected on the downstream side of a heat exchanger in the recirculation circuit.
Polymerene ifølge oppfinnelsen kan anvendes for mange formål, enten alene eller blandet med andre materialer eller polymerer. På samme måte som for copolymerene av ethylen og The polymers according to the invention can be used for many purposes, either alone or mixed with other materials or polymers. In the same way as for the copolymers of ethylene and
(meth)acrylsyreester, hvis egenskaper de forbedrer, vil deres anvendelse avhenge av smelteindeksen som oppnåes ved anvendelse av kjedeoverføringsmidletAnvendelsen avhenger likeledes av innholdet av enheter avledet fra maleinsyreanhydrid. En viktig anvendelse av polymerene ifølge oppfinnelsen med en smelteindeks i området fra 1 til 10 dg/mn og med fra 0,3 til 1 mol% enheter avledet fra maleinsyreanhydrid er således fremstilling av folier. Disse folier kan ha en tykkelse av mellom 10 og 500 fm. når de fremstilles gjennom en spalteformet dyse, og en tykkelse av fra 25 til 200 / m når de fremstilles ved blåse- (meth)acrylic acid esters, whose properties they improve, their use will depend on the melting index obtained by using the chain transfer agent The use likewise depends on the content of units derived from maleic anhydride. An important application of the polymers according to the invention with a melt index in the range from 1 to 10 dg/mn and with from 0.3 to 1 mol% units derived from maleic anhydride is thus the production of foils. These foils can have a thickness of between 10 and 500 fm. when produced through a slit-shaped nozzle, and a thickness of from 25 to 200 / m when produced by blowing
ekstrudering. De anvendes for fremstilling av poser, emballasje for næringsmidler, emballasje for tyngre gods og som folier for anvendelse i jordbruket. Blåseekstruderingen av disse folier foretas ved hjelp av konvensjonelle maskiner og med et oppblåsningsforhold på mellom 1 og 3, og en uttaksha-stighet som kan nå opp i noen titall meter pr. minutt. extrusion. They are used for the production of bags, packaging for foodstuffs, packaging for heavier goods and as foils for use in agriculture. The blow extrusion of these foils is carried out using conventional machines and with an inflation ratio of between 1 and 3, and a withdrawal speed that can reach up to a few tens of meters per second. minute.
De følgende eksempler illustrerer oppfinnelsen. The following examples illustrate the invention.
EKSEMPLER 1- 4 EXAMPLES 1-4
Det benyttes en sylindrisk autoklavreaktor omfattende tre soner, hver med et volum på 1 liter og utstyrt med en bladrører. Sonene er adskilt ved hjelp av ventilskjermer. Det friske ethylen som komprimeres i en første kompressor, tilføres den første sone. Den annen sone tilføres en homogen blanding av ethylen, maleinsyreanhydrid (AM) og ethylacrylat (AE). Sluttelig innføres en oppløsning av tertiært butyl-2-ethyl-perhexanoat i en hydrocarbonfraksjon i den tredje sone. Denne sone utgjør følgelig den eneste reaksjonssone, fordi den bringer sammen de tre comonomerer og en fri-radikal-ini--tiator. Tabell I nedenfor angir på den ene side vektmengden av maleinsyreanhydrid og ethylacrylat i forhold til ethylen i reaksjonssonen, og på den annen side temperaturen i denne sone. Reaktoren holdes ved et trykk på 1600 bar. I bunnen av reaktorens tredje sone er det anordnet en ekspansjonsventil som tillater reduksjon av trykket til 300 bar. Blandingen av den smeltede polymer og de gassformige monomerer vil, etter å ha passert gjennom ekspansjonsventilen, strømme inn i en skilletrakt. Mens polymeren oppsamles i bunnen av trak-ten, føres monomerene, etter at de har passert gjennom en av-setningstrakt, til en andre kompressor. På den annen side blir en oppløsning av maleinsyreanhydrid i ethylacrylat satt under trykk og ført til innløpet av en homogenisator av Venturi-typen, hvor den blandes med strømmen av resirkulerte monomerer som kommer fra den annen kompressor. Fra utløpet av denne Venturi-innretning føres blandingen av de tre monomerer til en spiralhomogenisator, fra hvilken den føres til A cylindrical autoclave reactor comprising three zones, each with a volume of 1 liter and equipped with a blade stirrer, is used. The zones are separated by means of valve screens. The fresh ethylene that is compressed in a first compressor is supplied to the first zone. The second zone is supplied with a homogeneous mixture of ethylene, maleic anhydride (AM) and ethyl acrylate (AE). Finally, a solution of tertiary butyl-2-ethyl-perhexanoate is introduced in a hydrocarbon fraction in the third zone. This zone therefore constitutes the only reaction zone, because it brings together the three comonomers and a free-radical initiator. Table I below indicates on the one hand the amount by weight of maleic anhydride and ethyl acrylate in relation to ethylene in the reaction zone, and on the other hand the temperature in this zone. The reactor is kept at a pressure of 1600 bar. At the bottom of the reactor's third zone, an expansion valve is arranged which allows the pressure to be reduced to 300 bar. The mixture of the molten polymer and the gaseous monomers will, after passing through the expansion valve, flow into a separatory funnel. While the polymer is collected at the bottom of the funnel, the monomers, after they have passed through a settling funnel, are led to a second compressor. On the other hand, a solution of maleic anhydride in ethyl acrylate is pressurized and fed to the inlet of a Venturi-type homogenizer, where it is mixed with the stream of recycled monomers coming from the second compressor. From the outlet of this Venturi device, the mixture of the three monomers is fed to a spiral homogenizer, from which it is fed to
reaktorens andre sone. the reactor's second zone.
Ved utløpet fra skilletrakten analyseres den fremstilte terpolymer ved infrarød spektrofotometri, og mengden av ethyl-acrylatenheter og maleinsyreanhydridenheter i mol bestemmes. Disse er oppført i tabell I nedenfor. Polymerens smelteindeks bestemmes i henhold til Standard ASTM D 1238-73 og ut-trykkes i dg/mn. At the outlet from the separating funnel, the produced terpolymer is analyzed by infrared spectrophotometry, and the amount of ethyl acrylate units and maleic anhydride units in moles is determined. These are listed in Table I below. The melt index of the polymer is determined according to Standard ASTM D 1238-73 and is expressed in dg/min.
Derefter måles de følgende egenskaper av polymeren: tettheten S, uttrykt i g/cm og bestemt i henhold til Standard ASTM D 2839, The following properties of the polymer are then measured: the density S, expressed in g/cm and determined according to Standard ASTM D 2839,
den antallsmidlere molekylvekt Mn, bestemt ved gelgjen-nomtrengningskromatografi, the number average molecular weight Mn, determined by gel permeation chromatography,
polydispersiteten, som bestemmes etter samme metode, og som er lik forholdet Mw/Mn, hvor Mw er den vektmidlere molekylvekt, the polydispersity, which is determined according to the same method, and which is equal to the ratio Mw/Mn, where Mw is the weight average molecular weight,
Vicat-temperaturen, uttrykt i grader C og bestemt i henhold til Standard NF T 51-012 (1). The Vicat temperature, expressed in degrees C and determined according to Standard NF T 51-012 (1).
Resultatene av disse målinger er oppført i tabell II nedenfor . The results of these measurements are listed in table II below.
EKSEMPEL 5 EXAMPLE 5
Innretningen ifølge de foregående eksempler anvendes The device according to the preceding examples is used
for polymerisering av ethylen, maleinsyreanhydrid og ethylacrylat under de følgende betingelser: Reaktortrykk: 1200 bar Reaksjonssonens temperatur: 180°C . for the polymerization of ethylene, maleic anhydride and ethyl acrylate under the following conditions: Reactor pressure: 1200 bar Reaction zone temperature: 180°C.
Sammensetningen på vektbasis av monomerblandingen i reaksjonssonen, sammensetningen i mol av den fremstilte terpolymer og terpolymerens smelteindeks er oppført i tabell I nedenfor. Polymeren blir heretter analysert og karakterisert ved sin tetthet, sin molekylvekt Mn og sin polydispersitet, bestemt som beskrevet ovenfor. Verdiene for disse egenskaper fremgår av tabell II nedenfor. The composition by weight of the monomer mixture in the reaction zone, the composition in moles of the terpolymer produced and the melt index of the terpolymer are listed in Table I below. The polymer is then analyzed and characterized by its density, its molecular weight Mn and its polydispersity, determined as described above. The values for these characteristics appear in table II below.
EKSEMPEL 6 EXAMPLE 6
Innretningen ifølge de foregående eksempler anvendes for copolymerisering av ethylen, maleinsyreanhydrid og butylmeth-acrylat (BMA) under de følgende betingelser: The device according to the preceding examples is used for the copolymerization of ethylene, maleic anhydride and butyl methacrylate (BMA) under the following conditions:
Mengden av comonomerene i reaksjonssonen regnet på vektbasis, er som følger: The amount of the comonomers in the reaction zone, calculated on a weight basis, is as follows:
4,8 % BMA, 0,38 % MA 4.8% BMA, 0.38% MA
Den erholdte polymer har en smelteindeks på 30 dg/mn (bestemt i henhold til Standard ASTM D 1238-73). The obtained polymer has a melt index of 30 dg/mn (determined according to Standard ASTM D 1238-73).
EKSEMPEL 7 EXAMPLE 7
Den i det foregående anvendte innretning anvendes for copolymerisering av ethylen, maleinsyreanhydrid og butylacrylat (BA) under de følgende betingelser: The device used above is used for the copolymerization of ethylene, maleic anhydride and butyl acrylate (BA) under the following conditions:
Mengden av comonomerene i reaksjonssonen, regnet på vektbasis, er som følger: 1,3 % BA, 0,23 % MA The amount of comonomers in the reaction zone, calculated on a weight basis, is as follows: 1.3% BA, 0.23% MA
Den erholdte polymer har en smelteindeks på 2 dg/mn (bestemt i henhold til Standard ASTM D 12 38-7 3), en Vicat temperatur på 65°C og en tetthet på 0,935 g/cm . Analyse av polymeren ved spektrofotometri i det infrarøde område viste til-stedeværelse av: The obtained polymer has a melt index of 2 dg/mn (determined according to Standard ASTM D 12 38-7 3), a Vicat temperature of 65°C and a density of 0.935 g/cm. Analysis of the polymer by spectrophotometry in the infrared range showed the presence of:
2,0 mol% enheter avledet fra butylacrylat, 2.0 mol% units derived from butyl acrylate,
0,8 mol% enheter avledet fra maleinsyreanhydrid. 0.8 mol% units derived from maleic anhydride.
EKSEMPEL 8 EXAMPLE 8
Den i eksempel 2 erholdte terpolymer formes ved blåseeks-trudering ved temperatur 140°C til en film av tykkelse 100 /im, idet uttagningshastigheten er 2,5 m/minutt og oppblåsnings-forholdet er 2. De følgende egenskaper måles for den erholdte film: strekkgrensen, uttrykt i kg/cm 2 og bestemt i henhold til Standard NF T 51-034, The terpolymer obtained in example 2 is formed by blow extrusion at a temperature of 140°C into a film of thickness 100 µm, the removal speed being 2.5 m/minute and the inflation ratio being 2. The following properties are measured for the obtained film: the tensile strength, expressed in kg/cm 2 and determined according to Standard NF T 51-034,
strekkstyrken, uttrykt i kg/cm 2 og bruddforlengelse uttrykt i prosent og bestemt i henhold til Standard ASTM D 882-67. the tensile strength, expressed in kg/cm 2 and elongation at break expressed as a percentage and determined according to Standard ASTM D 882-67.
De følgende verdier, som er de samme i tverretningen som i lengderetningen, finnes: The following values, which are the same in the transverse direction as in the longitudinal direction, are found:
o o
Strekkgrense = 51 kg/cm Tensile strength = 51 kg/cm
Strekkfasthet = 112 kg/cm<2>Tensile strength = 112 kg/cm<2>
Bruddforlengelse = 540 % Elongation at break = 540%
EKSEMPEL 9 EXAMPLE 9
Den i eksempel 1 erholdte terpolymer formes til en film av tykkelse 100 ^m under de samme betingelser som i eksempel 8. Egenskapene som måles for denne film, er som følger: The terpolymer obtained in example 1 is formed into a film of thickness 100 µm under the same conditions as in example 8. The properties measured for this film are as follows:
Strekkgrense = 5 9 kg/cm<2>Tensile strength = 5 9 kg/cm<2>
Strekkfasthet = 100 kg/cm<2>Tensile strength = 100 kg/cm<2>
Bruddforlengelse = 450 % Elongation at break = 450%
Claims (10)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8101430A FR2498609B1 (en) | 1981-01-27 | 1981-01-27 | ETHYLENE TERPOLYMERS, THEIR MANUFACTURING PROCESS AND THEIR APPLICATION TO THE MANUFACTURE OF FILMS |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO820224L NO820224L (en) | 1982-07-28 |
| NO163620B true NO163620B (en) | 1990-03-19 |
| NO163620C NO163620C (en) | 1990-06-27 |
Family
ID=9254524
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO820224A NO163620C (en) | 1981-01-27 | 1982-01-26 | ETHYLENE POLYMERS CONTAINING UNITS DERIVED FROM MALEIC ACID ANHYRIDE, PROCEDURE FOR PREPARING THE PYLYMERS AND THEIR USE FOR PREPARATION OF FILES. |
Country Status (14)
| Country | Link |
|---|---|
| AT (1) | AT383813B (en) |
| BE (1) | BE891751A (en) |
| CH (1) | CH650520A5 (en) |
| DE (1) | DE3202545A1 (en) |
| DK (1) | DK161651C (en) |
| FR (1) | FR2498609B1 (en) |
| GB (1) | GB2091745B (en) |
| GR (1) | GR74724B (en) |
| IE (1) | IE52360B1 (en) |
| IT (1) | IT1149318B (en) |
| LU (1) | LU83894A1 (en) |
| NL (1) | NL190898C (en) |
| NO (1) | NO163620C (en) |
| SE (1) | SE452769B (en) |
Families Citing this family (36)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2505731A1 (en) * | 1981-05-15 | 1982-11-19 | Charbonnages Ste Chimique | COMPLEX THERMOPLASTIC FILMS AND PROCESS FOR OBTAINING THEM |
| DE3404744A1 (en) * | 1984-02-10 | 1985-08-14 | Basf Ag, 6700 Ludwigshafen | COPOLYMERISATES OF ETHYLENE WITH COMONOMERS CONTAINING CARBOXYL GROUPS |
| DE3404743A1 (en) * | 1984-02-10 | 1985-08-14 | Basf Ag, 6700 Ludwigshafen | COPOLYMERISATES OF ETHYLENE WITH COMONOMERS CONTAINING CARBOXYL GROUPS |
| GB8405877D0 (en) * | 1984-03-06 | 1984-04-11 | Dermil Research Ltd | Adhesives |
| FR2566288B1 (en) * | 1984-06-21 | 1991-10-18 | Elf Aquitaine | POLYMERIC ADDITIVES FOR USE INHIBITING THE DEPOSITION OF PARAFFINS IN RAW OILS |
| FR2569411B1 (en) * | 1984-08-23 | 1986-11-21 | Charbonnages Ste Chimique | NOVEL PROCESS FOR THE MANUFACTURE OF ETHYLENE RADICAL TERPOLYMERS AND ETHYLENE RADICAL COPOLYMERS |
| FR2569412B1 (en) * | 1984-08-23 | 1986-11-21 | Charbonnages Ste Chimique | NOVEL PROCESS FOR THE MANUFACTURE OF ETHYLENE RADICAL TERPOLYMERS AND ETHYLENE RADICAL COPOLYMERS |
| DE3444094A1 (en) * | 1984-12-04 | 1986-06-12 | Basf Ag, 6700 Ludwigshafen | COPOLYMERISATE OF ETHYLENE |
| DE3444096A1 (en) * | 1984-12-04 | 1986-06-05 | Basf Ag, 6700 Ludwigshafen | COPOLYMERISATE OF ETHYLENE AND THE USE THEREOF AS AN IMPACT MODIFIER IN THERMOPLASTICS |
| US4833224A (en) * | 1985-10-11 | 1989-05-23 | Idemitsu Kosan Company Limited | Ethylene copolymers and process for production |
| JPS636011A (en) * | 1986-06-25 | 1988-01-12 | Sumitomo Chem Co Ltd | Vinyl chloride-grafted ethylene copolymer and its production |
| US5191050A (en) * | 1987-10-14 | 1993-03-02 | Norsolor | Functionalized ethylene polymers useful for metal coating, and process for their preparation |
| FR2625508B1 (en) * | 1987-12-30 | 1992-05-22 | Charbonnages Ste Chimique | FLAME RETARDANT POLYMER COMPOSITIONS AND THEIR APPLICATION TO THE COATING OF ELECTRIC CABLES |
| FR2660660B1 (en) * | 1990-04-09 | 1993-05-21 | Norsolor Sa | IMPROVEMENT IN THE PROCESS FOR THE MANUFACTURE OF ETHYLENE RADICAL POLYMERS FOR USE IN THE COATING OF A METAL. |
| EP1664875B1 (en) | 2003-08-28 | 2011-01-12 | Prysmian S.p.A. | Optical cable and optical unit comprised therein |
| EP1803011B1 (en) | 2004-09-27 | 2019-06-12 | Prysmian S.p.A. | Optical cable for communication |
| EP1803010A1 (en) | 2004-09-27 | 2007-07-04 | Prysmian Cavi e Sistemi Energia S.r.l. | Water-resistant optical cable and manufacturing method |
| ES2714554T3 (en) * | 2007-02-23 | 2019-05-29 | Basf Se | Composite materials and procedure for their production |
| FR2938261B1 (en) | 2008-11-13 | 2010-11-19 | Arkema France | MANUFACTURE OF CARBOXYLIC ACID VINYL ETHYLENE / ESTER COPOLYMERS FROM RENEWABLE MATERIALS, COPOLYMERS OBTAINED AND USES THEREOF |
| FR2938262B1 (en) | 2008-11-13 | 2010-11-19 | Arkema France | FABRICATION OF ETHYLENE / CARBOXYLIC ACID COPOLYMERS FROM RENEWABLE MATERIALS, COPOLYMERS OBTAINED AND USES THEREOF |
| FR2946653B1 (en) | 2009-06-15 | 2012-08-03 | Arkema France | PROCESS FOR PRODUCING A MIXED-MASTER COMPOSITION COMPRISING AN ORGANIC PEROXIDE |
| BR112012001132A2 (en) | 2009-07-17 | 2016-02-23 | Arkema France | process for manufacturing polyester composition having improved impact resistance properties |
| FR2950352A1 (en) | 2009-09-21 | 2011-03-25 | Arkema France | MIXER-MASTER COMPOSITION USEFUL IN PHOTOVOLTAIC MODULES |
| FR2953524B1 (en) | 2009-12-03 | 2012-12-14 | Arkema France | HIGH SPEED CROSSLINKING SYSTEM |
| FR2953525B1 (en) | 2009-12-03 | 2013-01-25 | Arkema France | USEFUL COMPOSITION AS A CROSSLINKING MIXTURE COMPRISING A FUNCTIONAL POLYOLEFIN |
| FR2958939B1 (en) | 2010-04-14 | 2013-08-09 | Arkema France | IMPER-BREATHABLE FILM BASED ON ETHYLENE COPOLYMER |
| EP2444980B1 (en) | 2010-10-21 | 2014-03-26 | Borealis AG | A cable comprising a layer which is formed of a composition containing epoxy-groups |
| EP2444455A1 (en) | 2010-10-21 | 2012-04-25 | Borealis AG | A semiconductive polymer composition which contains epoxy-groups |
| FR2985731B1 (en) | 2012-01-17 | 2014-01-10 | Arkema France | HIGH TEMPERATURE MECHANICAL THERMOPLASTIC COMPOSITIONS, ESPECIALLY FOR ELECTRIC CABLES |
| FR3009562B1 (en) | 2013-08-06 | 2017-12-08 | Arkema France | THERMOMECHANICAL HIGH THERMOPLASTIC FLEXIBLE THERMOPLASTIC COMPOSITIONS, IN PARTICULAR FOR ELECTRIC CABLES. |
| FR3014893B1 (en) | 2013-12-18 | 2016-01-01 | Arkema France | FLAME RETARDANT THERMOPLASTIC COMPOSITIONS, ESPECIALLY FOR ELECTRIC CABLES |
| EP3511391A4 (en) | 2016-09-12 | 2020-05-06 | Unitika Ltd. | Sealing material, production method therefor, and coating composition for sealing material |
| FR3061189B1 (en) | 2016-12-22 | 2020-10-30 | Michelin & Cie | REINFORCED RUBBER COMPOSITION |
| EP3476885B1 (en) | 2017-10-31 | 2020-06-17 | Borealis AG | A cross-linkable ethylene polymer composition comprising epoxy-groups and a cross-linking agent |
| FR3081602B1 (en) | 2018-05-22 | 2020-05-01 | Arkema France | MULTILAYER CABLES FOR OFFSHORE ENVIRONMENT |
| EP3797135A1 (en) | 2018-05-23 | 2021-03-31 | Borealis AG | A cross-linkable polyolefin composition comprising a first and a second olefin polymer |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1323379A (en) * | 1961-06-21 | 1963-04-05 | Du Pont | New ethylene copolymers |
| US3925326A (en) * | 1971-04-07 | 1975-12-09 | Du Pont | Alternating copolymers of ethylene/alkyl acrylates/cure-site monomers and a process for their preparation |
| DE2236471A1 (en) * | 1971-08-06 | 1973-02-15 | Dow Chemical Co | TERPOLYMERES |
| US4065613A (en) * | 1975-03-17 | 1977-12-27 | E. I. Du Pont De Nemours And Company | Alternating copolymers of alkyl acrylate/ethylene/branching agents |
| DD137443B5 (en) * | 1978-06-27 | 1993-12-16 | Leuna Werke Ag | PROCESS FOR THE PREPARATION OF TERPOLYMERS |
-
1981
- 1981-01-27 FR FR8101430A patent/FR2498609B1/en not_active Expired
-
1982
- 1982-01-07 NL NL8200045A patent/NL190898C/en not_active IP Right Cessation
- 1982-01-11 BE BE0/207031A patent/BE891751A/en not_active IP Right Cessation
- 1982-01-14 CH CH200/82A patent/CH650520A5/en not_active IP Right Cessation
- 1982-01-25 LU LU83894A patent/LU83894A1/en unknown
- 1982-01-25 GB GB8201981A patent/GB2091745B/en not_active Expired
- 1982-01-25 IT IT47643/82A patent/IT1149318B/en active
- 1982-01-26 SE SE8200402A patent/SE452769B/en not_active IP Right Cessation
- 1982-01-26 NO NO820224A patent/NO163620C/en unknown
- 1982-01-26 GR GR67123A patent/GR74724B/el unknown
- 1982-01-26 AT AT0026382A patent/AT383813B/en not_active IP Right Cessation
- 1982-01-26 IE IE158/82A patent/IE52360B1/en not_active IP Right Cessation
- 1982-01-26 DK DK034582A patent/DK161651C/en not_active IP Right Cessation
- 1982-01-27 DE DE19823202545 patent/DE3202545A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| FR2498609B1 (en) | 1985-12-27 |
| IT8247643A0 (en) | 1982-01-25 |
| DK161651B (en) | 1991-07-29 |
| LU83894A1 (en) | 1982-06-30 |
| NO163620C (en) | 1990-06-27 |
| IE52360B1 (en) | 1987-09-30 |
| IT1149318B (en) | 1986-12-03 |
| NO820224L (en) | 1982-07-28 |
| SE452769B (en) | 1987-12-14 |
| AT383813B (en) | 1987-08-25 |
| DK34582A (en) | 1982-07-28 |
| SE8200402L (en) | 1982-07-28 |
| GB2091745B (en) | 1984-10-17 |
| GR74724B (en) | 1984-07-10 |
| DE3202545C2 (en) | 1992-09-03 |
| IE820158L (en) | 1982-07-27 |
| NL190898C (en) | 1994-10-17 |
| CH650520A5 (en) | 1985-07-31 |
| DK161651C (en) | 1992-01-06 |
| ATA26382A (en) | 1987-01-15 |
| NL190898B (en) | 1994-05-16 |
| DE3202545A1 (en) | 1982-08-26 |
| NL8200045A (en) | 1982-08-16 |
| BE891751A (en) | 1982-07-12 |
| FR2498609A1 (en) | 1982-07-30 |
| GB2091745A (en) | 1982-08-04 |
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