NO142233B - INSTALLATION FOR GASING OF LIQUID NATURAL GAS - Google Patents
INSTALLATION FOR GASING OF LIQUID NATURAL GAS Download PDFInfo
- Publication number
- NO142233B NO142233B NO763250A NO763250A NO142233B NO 142233 B NO142233 B NO 142233B NO 763250 A NO763250 A NO 763250A NO 763250 A NO763250 A NO 763250A NO 142233 B NO142233 B NO 142233B
- Authority
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- Norway
- Prior art keywords
- products
- anhydride
- mixture
- polyvinyl chloride
- gasing
- Prior art date
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- 238000009434 installation Methods 0.000 title 1
- 239000003949 liquefied natural gas Substances 0.000 title 1
- 239000000203 mixture Substances 0.000 claims description 24
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 13
- 239000004800 polyvinyl chloride Substances 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000005056 polyisocyanate Substances 0.000 claims description 8
- 229920001228 polyisocyanate Polymers 0.000 claims description 8
- 150000008064 anhydrides Chemical class 0.000 claims description 6
- 239000004604 Blowing Agent Substances 0.000 claims description 5
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000002685 polymerization catalyst Substances 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- 210000005056 cell body Anatomy 0.000 claims 1
- 239000006260 foam Substances 0.000 claims 1
- 239000000047 product Substances 0.000 description 29
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 7
- 239000012948 isocyanate Substances 0.000 description 7
- 150000002513 isocyanates Chemical class 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 150000008065 acid anhydrides Chemical class 0.000 description 5
- 230000001413 cellular effect Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- -1 maleic anhydride Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- RVZNTKZAFRNXIK-UHFFFAOYSA-N 1,3-dichloro-5-ethenylbenzene Chemical compound ClC1=CC(Cl)=CC(C=C)=C1 RVZNTKZAFRNXIK-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- KNIUHBNRWZGIQQ-UHFFFAOYSA-N 7-diethoxyphosphinothioyloxy-4-methylchromen-2-one Chemical compound CC1=CC(=O)OC2=CC(OP(=S)(OCC)OCC)=CC=C21 KNIUHBNRWZGIQQ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical class C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 150000005671 trienes Chemical class 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
- F01K23/00—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids
- F01K23/02—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled
- F01K23/06—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled combustion heat from one cycle heating the fluid in another cycle
- F01K23/10—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled combustion heat from one cycle heating the fluid in another cycle with exhaust fluid of one cycle heating the fluid in another cycle
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C9/00—Methods or apparatus for discharging liquefied or solidified gases from vessels not under pressure
- F17C9/02—Methods or apparatus for discharging liquefied or solidified gases from vessels not under pressure with change of state, e.g. vaporisation
- F17C9/04—Recovery of thermal energy
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2265/00—Effects achieved by gas storage or gas handling
- F17C2265/05—Regasification
Description
Fremgangsmåte ved fremstilling av stive celleprodukter. Procedure for the production of rigid cell products.
Denne oppfinnelse angår en forbedret fremgangsmåte for fremstilling av stive cellegjenstander av plast. Oppfinnelsen anvendes spesielt i forbindelse med den arbeidsmåte som er beskrevet i U.S. patentskrift nr. 2 576 749, ved hvilken et stivt, celleformet plastmateriale fremstilles i to arbeidstrinn, nemlig, This invention relates to an improved method for the production of rigid cellular objects made of plastic. The invention is used in particular in connection with the working method described in U.S. Pat. patent document no. 2 576 749, whereby a rigid, cellular plastic material is produced in two working steps, namely,
1) Man oppheter i en trykkform en 1) One heats up in a pressure mold
blanding som består av polyvinylklorid, et isocyanat (eller et polyisocyanat) og et termisk spaltbart blåsemiddel, slik at det dannes et celleholdig råemne, hvorpå trykkformen avkjøles. 2) Råemnet tas ut av formen og opp-hetes i nærvær av vann eller vanndamp, hvorved legemets dimensjoner økes samtidig som materialet herdner. mixture consisting of polyvinyl chloride, an isocyanate (or a polyisocyanate) and a thermally decomposable blowing agent, so that a cellular blank is formed, upon which the printing mold is cooled. 2) The raw material is taken out of the mold and heated in the presence of water or steam, whereby the dimensions of the body are increased at the same time as the material hardens.
Ved denne arbeidsmåte kan det fås By this way of working it can be obtained
materialer som har utmerkede mekaniske egenskaper, men som likevel har den ulempe at de trekker seg sammen etter noen tids forløp, særlig hvis de utsettes for moderat høye temperaturer. materials which have excellent mechanical properties, but which nevertheless have the disadvantage that they contract after some time, especially if they are exposed to moderately high temperatures.
Prosessens forløp er illustrert i US-patentskrift nr. 2 525 965. I dette tilfelle anvendes det imidlertid ikke isocyanat og vanndamp, og det inntrer derfor ingen herdning. The course of the process is illustrated in US Patent No. 2,525,965. In this case, however, isocyanate and steam are not used, and therefore no hardening occurs.
Fra fransk patentskrift nr. 946 720, 2<= Addition, (nr. 60 022) er det kjent å an-vende utgangsblandinger som foruten termisk spaltbart blåsemiddel og diisocyanat inneholder et syreansydrid, f. eks. maleinsyreanhydrid, som under prosessens annet trinn reagerer med H20 og diiso-cyanatet og bindes til sistnevnte over en amid-bro. From French patent document no. 946 720, 2<= Addition, (no. 60 022) it is known to use starting mixtures which, in addition to thermally cleavable blowing agent and diisocyanate, contain an acid anhydride, e.g. maleic anhydride, which during the second step of the process reacts with H2O and the diisocyanate and binds to the latter via an amide bridge.
Et av formålene ved den foreliggende oppfinnelse er å unngå den nevnte mangel på dimensjonsstabilitet og å skaffe kom-posisjoner som i denne henseende er meget gode, selv ved høye temperaturer. Oppfinnerne fant overraskende, at hvis man i utgangs-blandingen av polyvinylklorid, et isocyanat, et etylenisk umettet syreanhydrid og et blåsemiddel, innfører minst en annen etylenisk umettet monomer som er i stand til å fastpodes til PVC-kj edene samt å sampolymere seg med anhydridet, har de resulterende celleformede produkter en betydelig større dimensjonsstabilitet enn de produkter som fås ved hjelp av den hittil anvendte teknikk, spesielt når produktene utsettes for høye temperaturer. One of the purposes of the present invention is to avoid the aforementioned lack of dimensional stability and to obtain compositions which in this respect are very good, even at high temperatures. The inventors surprisingly found that if one introduces into the starting mixture of polyvinyl chloride, an isocyanate, an ethylenically unsaturated acid anhydride and a blowing agent, at least one other ethylenically unsaturated monomer is able to be grafted onto the PVC chains and to copolymerize with the anhydride , the resulting cellular products have a significantly greater dimensional stability than the products obtained by means of the technique used up to now, especially when the products are exposed to high temperatures.
Med «polyvinylklorid» skal det i dette patenskrift forstås både homopolymerisa-ter, sampolymerisater i hvilke vinylklorid dominerer, og blandinger av sådanne poly-merisater. In this patent, "polyvinyl chloride" is understood to mean both homopolymers, copolymers in which vinyl chloride predominates, and mixtures of such polymers.
De produkter som fås i henhold til den foreliggende oppfinnelse, har altså god dimensjonsstabilitet, de er videre usmeltbare, er uoppløselige i alle slags oppløsningsmid-ler, og de har meget gode mekaniske egenskaper. The products obtained according to the present invention thus have good dimensional stability, they are also infusible, are insoluble in all kinds of solvents, and they have very good mechanical properties.
Deres gode dimensjonsstabilitet fremgår av følgende: Hvis de etter den tid-ligere arbeidsmåte fremstilte produkter blir holdt i lengre tid ved moderat temperatur, f. eks. 90°C, har de tilbøyelighet til å trekke seg sammen, slik at deres volum minskes med ca. 60. Under de samme be-tingelser vil produkter som er blitt fremstilt i henhold til den foreliggende oppfinnelse, bare trekke seg ca. 5 pst. sammen. Their good dimensional stability is evident from the following: If the products manufactured according to the time-lier working method are kept for a longer time at a moderate temperature, e.g. 90°C, they tend to contract, so that their volume is reduced by approx. 60. Under the same conditions, products which have been manufactured according to the present invention will only withdraw approx. 5 percent together.
Usmeltbarheten av produktene som fås i henhold til oppfinnelsen, fremgår av deres oppførsel ved høyere temperaturer, f. eks. som følger: Ved temperaturer på 150—160°C vil de produkter som er blitt fremstilt i henhold til det ovennevnte U.S. patent, synke sammen, idet deres cellestruktur begynner å forsvinne, mens derimot produkter som er blitt fremstilt i henhold til den foreliggende oppfinnelse, ved samme behandlingsmåte bibeholder sin cellestruktur uforandret. The infusibility of the products obtained according to the invention is evident from their behavior at higher temperatures, e.g. as follows: At temperatures of 150-160°C, the products which have been manufactured according to the above U.S. patent, sink together, as their cell structure begins to disappear, while, on the other hand, products which have been produced according to the present invention, by the same method of treatment, retain their cell structure unchanged.
De produkter som fås i henhold til oppfinnelsen, er uoppløselige i vanlige oppløsningsmidler for polyvinylklorid, f. eks. i dimetylformamid, og i de kjente opp-løsningsmidler for sampolymere av maleinsyreanhydrid, samt i alkaliske vandige oppløsninger. Går man derimot ut fra blandinger som ikke inneholder alle de ingredienser som den foreliggende oppfinnelse foreskriver, vil produktene bli opp-løselige i allfall ett av de nevnte oppløs-ningsmidler. The products obtained according to the invention are insoluble in common solvents for polyvinyl chloride, e.g. in dimethylformamide, and in the known solvents for copolymers of maleic anhydride, as well as in alkaline aqueous solutions. If, on the other hand, we proceed from mixtures which do not contain all the ingredients prescribed by the present invention, the products will become soluble in at least one of the mentioned solvents.
Oppløselighetsforholdene belyses av den følgende tabell, hvor blandingen 4 er den som benyttes i henhold til den foreliggende oppfinnelse. The solubility conditions are illustrated by the following table, where mixture 4 is the one used according to the present invention.
Det er ved å behandle blandingen 3 med alkalisk vann umulig å ekstrahere den nevnte sampolymere av maleinsyreanhydrid, fordi denne sampolymere ved en pod-ningsreaksjon er blitt festet til polyvinyl-kloridets molekyler (den sampolymere i ikke podet tilstand er oppløselig i alkalisk vann, som angitt i tabellen). By treating the mixture 3 with alkaline water, it is impossible to extract the aforementioned copolymer of maleic anhydride, because this copolymer has been attached to the molecules of the polyvinyl chloride by a grafting reaction (the copolymer in the ungrafted state is soluble in alkaline water, as stated in the table).
Ennvidere viser det faktum at det er umulig å oppløseliggjøre selv små fraksjo-ner av det polyvinylklorid som foreligger i cellematerialet fra blanding 4 (hvilket cellemåteriale utgjør et reaksjonsprodukt mellom et polyisocyanat og blandingen 3), at alt polyvinylkloridet podes med maleinsyreanhydridsampolymeren. Denne sampolymer undergår ved vanndamp-behandlingen hydrolyse under dannelse av en syre, som altså også er bundet til polyvinylkloridet, således at det etter konden-sasjon av den dannede syre med polyisocyanat inntrer fullstendig fornetting av hele produktet. (Hvis anhydrid-bæreren ikke podes på polyvinylkloridet, vil det resulterende, celleformige reaksjonsprodukt med polyisocyanat forbli oppløselig i dimetylformamid, svarende til hva blandingen 1 angir). Furthermore, the fact that it is impossible to solubilize even small fractions of the polyvinyl chloride present in the cell material from mixture 4 (which cell material constitutes a reaction product between a polyisocyanate and mixture 3) shows that all the polyvinyl chloride is grafted with the maleic anhydride copolymer. During the steam treatment, this copolymer undergoes hydrolysis to form an acid, which is therefore also bound to the polyvinyl chloride, so that after condensation of the formed acid with polyisocyanate, complete cross-linking of the entire product occurs. (If the anhydride carrier is not grafted onto the polyvinyl chloride, the resulting cellular reaction product with polyisocyanate will remain soluble in dimethylformamide, corresponding to what mixture 1 indicates).
At alle disse produkter til og med blandingen 3 er oppløselige, og at blandingen 4 er uoppløselig, kan konstateres ved at man erstatter dimetylformamidet med andre oppløsningsmidler for polyvinylklorid, f. eks. med tetrahydrofuran, nitroben-zen og lignende. That all these products, including mixture 3, are soluble, and that mixture 4 is insoluble, can be ascertained by replacing the dimethylformamide with other solvents for polyvinyl chloride, e.g. with tetrahydrofuran, nitrobenzene and the like.
Uoppløseligheten av de i henhold til oppfinnelsen fremstilte produkter atskiller dem tydelig fra alle de før fremstilte. Det må derfor være tillatt å anta at disse nye produkter er fornettet, altså inneholder et tredimensjonalt nettverk. The insolubility of the products produced according to the invention clearly distinguishes them from all those previously produced. It must therefore be permissible to assume that these new products are networked, i.e. contain a three-dimensional network.
Denne fornetnings-reaksjon innebærer dannelsen av amidbroer mellom de forskjellige makromolekyler. Da isocyanatet er et polyisocyanat og altså inneholder to eller flere grupper — N = C = O pr. mo-lekyl, vil nemlig en kondensasjonsreaksjon mellom disse grupper og de påpodede syre-grupper føre til en brodannelse. This cross-linking reaction involves the formation of amide bridges between the different macromolecules. Since the isocyanate is a polyisocyanate and therefore contains two or more groups — N = C = O per molecule, namely a condensation reaction between these groups and the grafted acid groups will lead to a bridge formation.
For å oppnå de største fordeler ved den foreliggende oppfinnelse bør det anvendes nøye avveide mengder av de stof-fer som tilblandes til utgangsblandingen. In order to achieve the greatest advantages of the present invention, carefully weighed amounts of the substances that are mixed into the starting mixture should be used.
Den mengde polyvinylklorid som skal anvendes, er avhengig av den tethet man ønsker å få hos sluttproduktet; den ligger fortrinnsvis på 30—70 pst. av utgangsblandingen. The amount of polyvinyl chloride to be used depends on the density you want to achieve in the final product; it is preferably 30-70 percent of the starting mixture.
Det anvendte polyisicyanat er fortrinnsvis et triisocyanat, som f. eks. tri-fenylmetan-p,p'p"-triisocyanat (som selges under varemerkebetegnelsen «Desmodur L» av Farbenfabriken Bayer), eller også et diisocyanat som f. eks. difenylmetan-p,p'-diisocyanat, 2,4-toluen-diisocyanat, 2,6-toluendiisocyanat eller lignende. Disse isocyanater kan også anvendes i form av blandinger av to eller flere sådanne. Den samlede mengde isocyanater som anvendes, utgjør mellom 5 og 30 pst. av utgangsblandingen, avhengig av isocyanatets art og av det sluttresultat man ønsker å oppnå. The polyisocyanate used is preferably a triisocyanate, such as e.g. tri-phenylmethane-p,p'p"-triisocyanate (which is sold under the trade name "Desmodur L" by Farbenfabriken Bayer), or also a diisocyanate such as e.g. diphenylmethane-p,p'-diisocyanate, 2,4-toluene- diisocyanate, 2,6-toluene diisocyanate or the like. These isocyanates can also be used in the form of mixtures of two or more such. The total amount of isocyanates used is between 5 and 30 percent of the starting mixture, depending on the nature of the isocyanate and on the end result one wants to achieve.
Syreanhydridet som anvendes, skal være etylenisk umettet således at det er sampolymeriserbart med en annen umettet monomer. Man kan bruke f. eks. akryl-syreanhydrid, citrakonsyreanhydrid, ita-konsyreanhydrid, maleinsyreanhydrid eller lignende. Mengden av anhydrid avhenger av hvilken tetthet man ønsker at sluttproduktet skal ha etter ekspansjonen, og utgjør 5—30 vektspst. av utgangsblandingen. The acid anhydride used must be ethylenically unsaturated so that it is copolymerizable with another unsaturated monomer. You can use e.g. acrylic anhydride, citraconic anhydride, itaconic anhydride, maleic anhydride or the like. The amount of anhydride depends on the density you want the final product to have after expansion, and amounts to 5-30% by weight. of the starting mixture.
De sampolymeriserbare monomere som kan anvendes, er alle slike som kan poly-meriseres eller sampolymeriseres ved en radikal-reaksjon, og som inneholder minst en gruppe CH2=C-< (Det er klart at det også kan benyttes en blanding av slike monomere). Blant slike monomere kan nevnes butadien-1,3, isopren, dimetylbuta-dien-1,3, kloropren, 3-cyan-butadien-l,3, piperylen, triener som f. eks. mycen, vinylklorid, vinylidenklorid, styren, p-klorsty-ren, 3,5-diklorstyren, p-metoksystyren; estere, nitriler og amider av akrylsyrer og a-alkyl-akrylsyre, vinylpyridin, vinylben-zoat, vinyl-ketoner og -etere, vinylkarbazol og lignende, etylen, propylen og lignende, isobutylen, divinylbenzen, og lignende stof-fer som samtidig inneholder olefiniske og acetyleniske grupper som f. eks. vinylace-tylen. The copolymerizable monomers that can be used are all those that can be polymerized or copolymerized by a radical reaction, and which contain at least one group CH2=C-< (It is clear that a mixture of such monomers can also be used). Among such monomers can be mentioned butadiene-1,3, isoprene, dimethylbutadiene-1,3, chloroprene, 3-cyano-butadiene-1,3, piperylene, trienes such as e.g. mycene, vinyl chloride, vinylidene chloride, styrene, p-chlorostyrene, 3,5-dichlorostyrene, p-methoxystyrene; esters, nitriles and amides of acrylic acids and α-alkyl acrylic acid, vinyl pyridine, vinyl benzoate, vinyl ketones and ethers, vinyl carbazole and the like, ethylene, propylene and the like, isobutylene, divinylbenzene, and similar substances which simultaneously contain olefinic and acetylenic groups such as vinylace-tylene.
Foruten monomere som inneholder gruppen CH2 = C<, kan det også benyttes monomere som inneholder gruppen CF2 = C =, f. eks. tetrafluoretylen og lignende. Besides monomers containing the group CH2 = C<, monomers containing the group CF2 = C = can also be used, e.g. tetrafluoroethylene and the like.
Det anvendes 5—30 vektpst. etylenisk umettet monomer beregnet på utgangs-blandingen; i mange tilfeller er det fordelaktig å tilsette omtrent like mange molekyler av denne eller disse som av syreanhydridet. 5-30% by weight is used. ethylenically unsaturated monomer calculated on the starting mixture; in many cases it is advantageous to add approximately the same number of molecules of this or these as of the acid anhydride.
Det er i henhold til oppfinnelsen også fordelaktig å tilsette blandingen et stoff som katalyserer polymerisasjonen eller sampolymerisasjonen av den monomere og anhydridet. For dette formål kjennes det mange egnede katalysatorer. According to the invention, it is also advantageous to add to the mixture a substance which catalyzes the polymerization or copolymerization of the monomer and the anhydride. Many suitable catalysts are known for this purpose.
Den anvendte katalysatormengde avhenger av katalysatorens kvalitet og av mengden av monomer som skal polymeri-seres, som regel ligger katalysatormengden mellom 0,1 og 10 vektspst. av utgangsblandingen. Ofte utgjør blåsemidlet, som tjener til dannelsen av «kim»-cellene, samtidig en polymerisasjonskatalysator, og kan følgelig anvendes så det spiller begge disse roller samtidig. The amount of catalyst used depends on the quality of the catalyst and on the amount of monomer to be polymerised, as a rule the amount of catalyst is between 0.1 and 10% by weight. of the starting mixture. Often the blowing agent, which serves for the formation of the "germ" cells, is also a polymerization catalyst, and can therefore be used so that it plays both of these roles at the same time.
De nedenstående eksempler belyser fordelene ved oppfinnelsen ved sammenligning av den termiske stabilitet og den kjemiske motstandsevne hos produkter som er fremstilt i henhold til oppfinnelsen, med de tilsvarende egenskaper hos produkter som er fremstilt på før kjent måte. Under utførelsen av de forskjellige eksempler ble det valgt slike forhold at man i hvert eksempel til slutt skulle få celleprodukter av samme tetthet, da produktenes egenskaper i høy grad avhenger av deres tetthet. The following examples illustrate the advantages of the invention by comparing the thermal stability and the chemical resistance of products manufactured according to the invention, with the corresponding properties of products manufactured in a previously known manner. During the execution of the various examples, conditions were chosen such that in each example cell products of the same density should eventually be obtained, as the properties of the products depend to a large extent on their density.
I disse eksempler ble forbedringen av produktenes termiske oppførsel påvist ved å anbringe plater av 200 mm lengde, 100 mm bredde og 40 mm tykkelse i en ovn ved 80°C, og måle volumforandringen et-tersom tiden skred frem. In these examples, the improvement in thermal behavior of the products was demonstrated by placing plates of 200 mm length, 100 mm width and 40 mm thickness in an oven at 80°C, and measuring the volume change as time progressed.
I de nedenstående eksempler er vo-lumvariasj onene angitt ved forholdet In the examples below, the volume variations are indicated by the ratio
etter 200 timers opphold i en ovn av 80° C. after 200 hours in an oven at 80°C.
Jo nærmere verdien ligger 100, desto større er produktets stabilitet. The closer the value is to 100, the greater the product's stability.
For å sammenligne de forskjellige celleprodukters mekaniske egenskaper ved To compare the mechanical properties of the different cell products at
høyere temperatur bestemtes den kritiske trykkfasthet ved 80°C. higher temperature, the critical compressive strength was determined at 80°C.
Motstandsevnen mot oppløsningsmid-ler ble bestemt ved å måle den kritiske The resistance to solvents was determined by measuring the critical
trykkfasthet ved 20°C etter 24 timers ned-drypping ved 20°C i benzen og i styren. compressive strength at 20°C after 24 hours of immersion at 20°C in benzene and in styrene.
Disse trykkfasthetmålinger ble utført i henhold til DIN 53421, hvis intet annet er spesielt angitt. These compressive strength measurements were carried out in accordance with DIN 53421, if nothing else is specifically stated.
Eksempler : Examples:
Serie nr. 1: eksemplene I—XIV. Series No. 1: Examples I—XIV.
I den vedføyede tabell er det i vektpst. angitt mengdeforholdene av de forskjellige ingredienser som ble benyttet i hvert av de enkelte forsøk. De forskjellige ingredienser ble innført i et blandeappa-rat av Werner-typen og ble blandet i 3—5 min. inntil man fikk en homogen og glatt pasta. Denne ble anbrakt i en form av dimensjonene 20 x 20 x 2 cm, som ble luk-ket hermetisk og opphetet under trykk mellom plater i en presse. Temperaturen ble hevet til 175°C og holdt på denne høyde i 10 minutter. In the attached table, it is in weight indicated the proportions of the different ingredients that were used in each of the individual experiments. The various ingredients were introduced into a Werner-type mixer and were mixed for 3-5 min. until a homogeneous and smooth paste was obtained. This was placed in a mold of dimensions 20 x 20 x 2 cm, which was closed hermetically and heated under pressure between plates in a press. The temperature was raised to 175°C and held at this height for 10 minutes.
Deretter ble formen avkjølt, fremdeles under trykk. Det celle-«kim»-produkt som deretter ble tatt ut av formen, ble i et fuk-tig rom opphetet til 100°C. Produktet ble holdt i dette rom inntil det hadde inntatt et stabilt volum, hvilket tok ca. 2—3 timer. The mold was then cooled, still under pressure. The cell "germ" product which was then removed from the mold was heated to 100°C in a humid room. The product was kept in this room until it had reached a stable volume, which took approx. 2-3 hours.
Tabell nr. I. Forsøk I—XIV. Table No. I. Trials I—XIV.
Forsøkene I—VIII gjelder ikke selve Trials I-VIII do not apply themselves
den foreliggende oppfinnelse, men er bare anført som sammenligning for å vise de forbedringer som oppnås ved at man, i henhold til oppfinnelsen, anvender malein- the present invention, but is only listed as a comparison to show the improvements that are achieved by using, according to the invention, malein-
syreanhydrid, en eahpolymeriserbar mono- acid anhydride, an eahpolymerizable mono-
mer og et polyisocyanat samtidig (forsøk more and a polyisocyanate at the same time (experiment
IX—XIV). IX—XIV).
Det sees at etter 200 timer i en til 80°C It is seen that after 200 hours in a to 80°C
opphetet ovn har de første produkter et volum som bare utgjør 30—40 pst. av det opprinnelige, mens ingen av de produkter som er fremstilt i henhold til den forelig- heated oven, the first products have a volume that is only 30-40 per cent of the original, while none of the products manufactured according to the existing
gende oppfinnelse, har avtatt mere enn 7 ing invention, has decreased by more than 7
pst. i volum. percent in volume.
Alle prøvestykkene ble fremstilt slik at All the test pieces were prepared so that
de fikk en volumvekt av ca. 30 kg/m<3>. they received a volumetric weight of approx. 30 kg/m<3>.
Tabell nr. II. Forsøk XV—XVIII. Table No. II. Attempts XV—XVIII.
Forsøkene i tabell I ble gjentatt, med The experiments in Table I were repeated, with
den forskjell at det ble fremstilt prøvestyk- the difference that samples were produced
ker av volumvekt 45 kg/m<3>. ker of volume weight 45 kg/m<3>.
Forsøkene XV og XVI, som ikke om- Experiments XV and XVI, which do not re-
fattes av den foreliggende oppfinnelse og som bare tjener til sammenligning, viser en volumforminskelse på ca. 60 pst., mens de forsøk, XVII og XVIII, som gjelder oppfin- understood by the present invention and which only serves for comparison, shows a volume reduction of approx. 60 per cent, while the attempts, XVII and XVIII, which concern invention
nelsen, bare viser en volumforminskelse på nelsen, only shows a volume reduction of
2 pst. etter 200 timers opphold i en ovn av 90°C. 2 percent after 200 hours in a furnace of 90°C.
Disse forsøk viser tydelig at produkter These trials clearly show that products
som er fremstilt i henhold til den forelig- which is produced in accordance with the present
gende oppfinnelse, har både mekaniske egenskaper og motstandsevne mot hydro- invention, has both mechanical properties and resistance to hydrogen
karboner (styren, benzen), ved en gitt tem- carbons (styrene, benzene), at a given temperature
peratur, som er langt bedre enn hos tid- perature, which is far better than at time-
ligere fremstilte materialer. lower manufactured materials.
Eksemplene XIX og XX, i hvilke det Examples XIX and XX, in which it
ble anvendt de ovennevnte blandinger, ga celleprodukter med volumvekt 38 resp. 120 the above-mentioned mixtures were used, yielded cell products with a volume weight of 38 resp. 120
kg/m<3>, som også hadde meget gode egen- kg/m<3>, which also had very good
skaper. Disse to eksempler viser oppfinnel- creates. These two examples show inventive
sens store rekkevidde. sen's large range.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT27680/75A IT1042793B (en) | 1975-09-26 | 1975-09-26 | LIQUEFIED NATURAL GAS REGASIFICATION PLANT WITH ELECTRICITY PRODUCTION |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO763250L NO763250L (en) | 1977-03-29 |
| NO142233B true NO142233B (en) | 1980-04-08 |
| NO142233C NO142233C (en) | 1980-07-16 |
Family
ID=11222114
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO763250A NO142233C (en) | 1975-09-26 | 1976-09-22 | INSTALLATION FOR GASING OF LIQUID NATURAL GAS |
Country Status (27)
| Country | Link |
|---|---|
| JP (2) | JPS5241603A (en) |
| AR (1) | AR208145A1 (en) |
| AU (1) | AU507151B2 (en) |
| BE (1) | BE846592A (en) |
| BG (1) | BG31508A3 (en) |
| CA (1) | CA1069711A (en) |
| DD (1) | DD126910A5 (en) |
| DE (1) | DE2642667A1 (en) |
| DK (1) | DK411476A (en) |
| EG (1) | EG12641A (en) |
| ES (1) | ES452270A1 (en) |
| FI (1) | FI762506A (en) |
| FR (1) | FR2325877A1 (en) |
| GB (1) | GB1560096A (en) |
| IN (1) | IN145374B (en) |
| IT (1) | IT1042793B (en) |
| MX (1) | MX145533A (en) |
| NL (1) | NL180133C (en) |
| NO (1) | NO142233C (en) |
| NZ (1) | NZ181951A (en) |
| PL (1) | PL121010B1 (en) |
| PT (1) | PT65640B (en) |
| RO (1) | RO71062A (en) |
| SE (1) | SE428950B (en) |
| TR (1) | TR19131A (en) |
| YU (1) | YU232776A (en) |
| ZA (1) | ZA765182B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HU182479B (en) * | 1978-10-31 | 1984-01-30 | Energiagazdalkodasi Intezet | Method and apparatus for increasing the capacity and/or energetics efficiency of pressure-intensifying stations of hydrocarbon pipelines |
| GB2239489A (en) * | 1989-09-26 | 1991-07-03 | Roger Stuart Brierley | Harnessing of low grade heat energy |
| DE4102204A1 (en) * | 1991-01-25 | 1992-07-30 | Linde Ag | METHOD FOR EVAPORATING LIQUID NATURAL GAS |
| US6298671B1 (en) | 2000-06-14 | 2001-10-09 | Bp Amoco Corporation | Method for producing, transporting, offloading, storing and distributing natural gas to a marketplace |
| WO2007039480A1 (en) * | 2005-09-21 | 2007-04-12 | Exmar | Liquefied natural gas regasification plant and method with heat recovery |
| ITMI20061149A1 (en) * | 2006-06-14 | 2007-12-15 | Eni Spa | PROCEDURE AND PLANT FOR THE REGASIFICATION OF NATURAL LIQUEFIED GAS AND THE SUOM STORAGE |
| EP2123968A1 (en) * | 2008-05-20 | 2009-11-25 | Sincron S.r.l. | Gasification plant, in particular for methane, comprising a Stirling engine |
| NO332708B1 (en) * | 2009-05-14 | 2012-12-17 | Sevan Marine Asa | Regassification with power plants |
| US8943836B2 (en) * | 2009-07-10 | 2015-02-03 | Nrg Energy, Inc. | Combined cycle power plant |
| CN107636263A (en) | 2015-05-08 | 2018-01-26 | 约翰·里佐普洛斯 | Carburetion system and the method using the carburetion system |
| CN113233410B (en) * | 2021-05-27 | 2022-01-25 | 江苏斯凯德流体装备有限公司 | Full-flow circulation tank car filling equipment for liquid medium easy to self-gather |
-
1975
- 1975-09-26 IT IT27680/75A patent/IT1042793B/en active
-
1976
- 1976-01-01 AR AR264811A patent/AR208145A1/en active
- 1976-08-30 ZA ZA765182A patent/ZA765182B/en unknown
- 1976-09-01 FI FI762506A patent/FI762506A/fi not_active Application Discontinuation
- 1976-09-02 AU AU17383/76A patent/AU507151B2/en not_active Expired
- 1976-09-06 NZ NZ181951A patent/NZ181951A/en unknown
- 1976-09-06 IN IN1629/CAL/76A patent/IN145374B/en unknown
- 1976-09-10 DK DK411476A patent/DK411476A/en unknown
- 1976-09-14 CA CA261,133A patent/CA1069711A/en not_active Expired
- 1976-09-15 GB GB38296/76A patent/GB1560096A/en not_active Expired
- 1976-09-21 TR TR19131A patent/TR19131A/en unknown
- 1976-09-21 EG EG579/76A patent/EG12641A/en active
- 1976-09-22 YU YU02327/76A patent/YU232776A/en unknown
- 1976-09-22 DE DE19762642667 patent/DE2642667A1/en not_active Ceased
- 1976-09-22 NO NO763250A patent/NO142233C/en unknown
- 1976-09-23 ES ES452270A patent/ES452270A1/en not_active Expired
- 1976-09-24 BE BE170945A patent/BE846592A/en not_active IP Right Cessation
- 1976-09-24 FR FR7628711A patent/FR2325877A1/en active Granted
- 1976-09-24 BG BG7634276A patent/BG31508A3/en unknown
- 1976-09-24 DD DD194984A patent/DD126910A5/xx unknown
- 1976-09-24 SE SE7610618A patent/SE428950B/en not_active IP Right Cessation
- 1976-09-24 JP JP51113806A patent/JPS5241603A/en active Pending
- 1976-09-24 PT PT65640A patent/PT65640B/en unknown
- 1976-09-25 RO RO7687803A patent/RO71062A/en unknown
- 1976-09-25 PL PL1976192652A patent/PL121010B1/en unknown
- 1976-09-27 NL NLAANVRAGE7610708,A patent/NL180133C/en not_active IP Right Cessation
- 1976-09-27 MX MX166446A patent/MX145533A/en unknown
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1985
- 1985-09-25 JP JP1985145256U patent/JPS6163100U/ja active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| PT65640B (en) | 1978-04-07 |
| CA1069711A (en) | 1980-01-15 |
| SE7610618L (en) | 1977-03-27 |
| DK411476A (en) | 1977-03-27 |
| PT65640A (en) | 1976-10-01 |
| NL7610708A (en) | 1977-03-29 |
| ZA765182B (en) | 1977-08-31 |
| SE428950B (en) | 1983-08-01 |
| NZ181951A (en) | 1978-07-28 |
| NL180133B (en) | 1986-08-01 |
| AU1738376A (en) | 1978-03-09 |
| AR208145A1 (en) | 1976-11-30 |
| DD126910A5 (en) | 1977-08-24 |
| MX145533A (en) | 1982-03-03 |
| EG12641A (en) | 1979-06-30 |
| JPS5241603A (en) | 1977-03-31 |
| NL180133C (en) | 1987-01-02 |
| IT1042793B (en) | 1980-01-30 |
| IN145374B (en) | 1978-09-30 |
| GB1560096A (en) | 1980-01-30 |
| NO763250L (en) | 1977-03-29 |
| NO142233C (en) | 1980-07-16 |
| YU232776A (en) | 1982-02-28 |
| FR2325877B1 (en) | 1979-01-12 |
| AU507151B2 (en) | 1980-02-07 |
| FR2325877A1 (en) | 1977-04-22 |
| RO71062A (en) | 1981-06-22 |
| BE846592A (en) | 1977-03-24 |
| ES452270A1 (en) | 1977-11-01 |
| JPS6163100U (en) | 1986-04-28 |
| PL121010B1 (en) | 1982-04-30 |
| TR19131A (en) | 1978-05-16 |
| FI762506A (en) | 1977-03-27 |
| BG31508A3 (en) | 1982-01-15 |
| DE2642667A1 (en) | 1977-03-31 |
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