NO120119B - - Google Patents
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- NO120119B NO120119B NO15903465A NO15903465A NO120119B NO 120119 B NO120119 B NO 120119B NO 15903465 A NO15903465 A NO 15903465A NO 15903465 A NO15903465 A NO 15903465A NO 120119 B NO120119 B NO 120119B
- Authority
- NO
- Norway
- Prior art keywords
- acetylene
- autoclave
- catalysts
- titanium
- compounds
- Prior art date
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- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 50
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 47
- 229920000642 polymer Polymers 0.000 claims description 43
- 239000003054 catalyst Substances 0.000 claims description 19
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 7
- -1 acetylene hydrocarbons Chemical class 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000007858 starting material Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- 229920006158 high molecular weight polymer Polymers 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 150000002430 hydrocarbons Chemical group 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- 238000005979 thermal decomposition reaction Methods 0.000 claims 1
- 229910052723 transition metal Inorganic materials 0.000 claims 1
- 150000003624 transition metals Chemical class 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 60
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 28
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 27
- 239000000047 product Substances 0.000 description 19
- 239000007787 solid Substances 0.000 description 18
- 239000000126 substance Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000012299 nitrogen atmosphere Substances 0.000 description 14
- 239000003245 coal Substances 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 150000002736 metal compounds Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical group CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 229920001197 polyacetylene Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 2
- CGHIBGNXEGJPQZ-UHFFFAOYSA-N 1-hexyne Chemical group CCCCC#C CGHIBGNXEGJPQZ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 1
- WXZIKFXSSPSWSR-UHFFFAOYSA-N [Li]CCCCC Chemical compound [Li]CCCCC WXZIKFXSSPSWSR-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- KDUIUFJBNGTBMD-VXMYFEMYSA-N cyclooctatetraene Chemical compound C1=C\C=C/C=C\C=C1 KDUIUFJBNGTBMD-VXMYFEMYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 description 1
- ZSSVQAGPXAAOPV-UHFFFAOYSA-K molybdenum trichloride Chemical compound Cl[Mo](Cl)Cl ZSSVQAGPXAAOPV-UHFFFAOYSA-K 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000052 poly(p-xylylene) Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J61/00—Gas-discharge or vapour-discharge lamps
- H01J61/84—Lamps with discharge constricted by high pressure
- H01J61/86—Lamps with discharge constricted by high pressure with discharge additionally constricted by close spacing of electrodes, e.g. for optical projection
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J61/00—Gas-discharge or vapour-discharge lamps
- H01J61/02—Details
- H01J61/12—Selection of substances for gas fillings; Specified operating pressure or temperature
- H01J61/18—Selection of substances for gas fillings; Specified operating pressure or temperature having a metallic vapour as the principal constituent
Landscapes
- Discharge Lamp (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Discharge Lamps And Accessories Thereof (AREA)
Description
Fremgangsmåte til fremstilling av høymolekylære polymerisater av acetylenkullvannstoffer. Process for the production of high molecular weight polymers of acetylene coal water substances.
Man har tidligere polymerisert acetylen og acetylenkullvannstoffer til lavmolekylære polymerisater som f. eks. vinylace-tylen, benzen og cyklooktatetraen. Det er også kjent at acetylen polymeriseres i nærvær av kobber under dannelse av høymole-kylære tredimensjonale uoppløselige forbindelser (Cupren). Acetylene and acetylene coal water substances have previously been polymerized into low molecular weight polymers such as e.g. vinylacetylene, benzene and cyclooctatetraene. It is also known that acetylene polymerises in the presence of copper to form high-molecular three-dimensional insoluble compounds (Cuprene).
Ifølge foreliggende oppfinnelse får According to the present invention,
man av acetylen og andre acetylenkullvannstoffer med den alminnelige formel CH = CR, i hvilken R betyr alkyl eller aryl, høymolekylære polymerisater med lineære kullstoff kjeder eller inneholdende stykker av lineære kullstoff kjeder. Disse polymerisater er alle unntatt polyacetylenet fullstendig oppløselige i passende organiske oppløsningsmidler. one of acetylene and other acetylene hydrocarbons with the general formula CH = CR, in which R means alkyl or aryl, high molecular weight polymers with linear carbon chains or containing pieces of linear carbon chains. These polymers are all, except the polyacetylene, completely soluble in suitable organic solvents.
Polymeriseringen utføres i nærvær av The polymerization is carried out in the presence of
katalysatorer som er forskjellig fra de katalysatorer som brukes i polymerisasjons-prosesser med fri radikaler, og de er også andre enn dem (etter Friedel-Crafts) som hittil er brukt for kationisk polymerisa-sjon. catalysts which are different from the catalysts used in polymerization processes with free radicals, and they are also different from those (according to Friedel-Crafts) which have been used so far for cationic polymerization.
Det ble nemlig funnet at den særlige polymerisering som fører til dannelse av høymolekylære oppløselige polymerisater foregår når man som katalysatorer bruker forbindelser av flerverdige metaller av den 4. til 8. gruppe av det periodiske system, inneholdende alkyl eller alkenylgrupper som er bundet umiddelbart til metallet. Namely, it was found that the particular polymerization that leads to the formation of high-molecular-weight soluble polymers occurs when compounds of polyvalent metals of the 4th to 8th group of the periodic table are used as catalysts, containing alkyl or alkenyl groups that are bound immediately to the metal.
Slike katalysatorer kan fremstilles ved Such catalysts can be produced by
reaksjon mellom forbindelser av metaller av den 4. til 8. gruppe av det periodiske sy- reaction between compounds of metals of the 4th to 8th group of the periodic table
stem og organiske metallforbindelser. I denne reaksjon brukes fordelaktig alkyl-aluminium, alkylsink, alkyllitiumforbindel-ser og liknende som organiske metallforbindelser, mens det som forbindelser av de nevnte flerverdige metaller foretrekkes å bruke halogenidene. Imidlertid kan der også brukes andre reaktive forbindelser av disse metaller, som f. eks. alkoholater og liknende. En meget aktiv katalysator kan fremstilles ved f. eks. å la titantriklorid reagere med trietylaluminium eller alumi-niumdietylmonoklofid. I stedet for titantriklorid kan der også brukes titantetraklorid eller et tetraalkoholat av titan, f. eks. titantetraisopropylat. stem and organometallic compounds. In this reaction, alkyl aluminum, alkyl zinc, alkyl lithium compounds and the like are advantageously used as organic metal compounds, while it is preferred to use the halides as compounds of the aforementioned polyvalent metals. However, other reactive compounds of these metals can also be used, such as e.g. alcoholates and the like. A very active catalyst can be produced by e.g. allowing titanium trichloride to react with triethylaluminum or aluminum diethylmonoclofide. Instead of titanium trichloride, titanium tetrachloride or a tetraalcoholate of titanium can also be used, e.g. titanium tetraisopropylate.
Særlige aktive katalysatorer kan også fåes ved anvendelse av halogenider av jern, vanadin, molybden og andre metaller. Special active catalysts can also be obtained by using halides of iron, vanadium, molybdenum and other metals.
Fremstillingen og anvendelsen av ka-talysatorene kan skje i oppløsning i et oppløsningsmiddel som er inert likeoverfor vedkommende katalysatorer, f. eks. i et parafinkullvannstoff eller et aromatisk kullvannstoff. The production and use of the catalysts can take place in solution in a solvent which is inert to the catalysts in question, e.g. in a paraffinic coal hydrogen or an aromatic coal hydrogen.
Katalysatorer fremstillet på denne måte kan polymerisere acetylenkullvannstoffer ved temperaturer som er lavere enn romtemperatur, f. eks. ved 0° C og ved høyere temperaturer opp til 150° C. Det fordelaktigste er imidlertid å bruke temperaturer mellom 20 og 80° C. Catalysts prepared in this way can polymerize acetylene coal water substances at temperatures lower than room temperature, e.g. at 0° C and at higher temperatures up to 150° C. However, it is most advantageous to use temperatures between 20 and 80° C.
Når gassformige acetylenkullvannstoffer brukes som utgangsmateriale er det ofte fordelaktig å arbeide ved trykk som er høy-ere enn atmosfæretrykk. Herved fortynnes fortrinnsvis vedkommende kullvannstoff med en inert gass for å unngå risiko for eksplosjoner. Således kan man ved anvendelse av f. eks. acetylen som utgangsmateriale bruke en blanding av acetylen og nitrogen.. Det er også mulig å fortynne ace-tylenet med en annen gass som ikke rea-gerer med den anvendte katalysator f. eks. hydrogen eller metan. Man kan derfor bruke som utgangsmateriale acetylen som er fremstillet ved termisk spaltning av kullvannstoffer, f. eks. av metan. When gaseous acetylene coal water substances are used as starting material, it is often advantageous to work at pressures that are higher than atmospheric pressure. Hereby, the coal hydrogen in question is preferably diluted with an inert gas to avoid the risk of explosions. Thus, by using e.g. acetylene as starting material use a mixture of acetylene and nitrogen. It is also possible to dilute the acetylene with another gas which does not react with the catalyst used, e.g. hydrogen or methane. One can therefore use as starting material acetylene, which is produced by thermal splitting of coal water substances, e.g. of methane.
De høymolekylære polymerisater som fåes ved anvendelsen av de nevnte katalysatorer er i alminnelighet sterkt farvet. Således gir f. eks. acetylen et sort polymerisat og fenylacetylen gir et rødt polymerisat. Etylacetylen gir et mørkebrunt og butylacetylen et grønt polymerisat. Polymerisatet av acetylen er bare delvis opp-løselig i organiske oppløsningsmidler, men polymerisatene av de høyere acetylenkullvannstoffer er i alminnelighet fullstendig oppløselige i benzen. The high molecular weight polymers obtained from the use of the aforementioned catalysts are generally strongly coloured. Thus, e.g. acetylene a black polymer and phenylacetylene gives a red polymer. Ethyl acetylene gives a dark brown and butyl acetylene a green polymer. The polymers of acetylene are only partially soluble in organic solvents, but the polymers of the higher acetylene coal water substances are generally completely soluble in benzene.
Acetylenpolymerisatene inneholder et stort antall dobbeltbindinger som kan på-vises f. eks. ved tilleiring av halogen. Når man underkaster et slikt polymerisat opp-løst i kullstofftetraklorid en klorering ved 0° C, får man et hvitt klorert polymerisat som omtrentlig tilsvarer formelen (-CHCI-)n, dvs. formelen for det produkt som kan dannes av et lineært polyacetylen vel tilleiring av 2 kloratomer på hver dob-beltbinding. Dette forhold og de bøynings-linjer som man får ved røntgenundersø-kelse i monokromatisk- lys, kan bare for-klares ved den antagelse at molekylet overveiende dannes av kjeder inneholdende lineære metingrupper. The acetylene polymers contain a large number of double bonds which can be detected, e.g. by adding halogen. When such a polymer dissolved in carbon tetrachloride is subjected to chlorination at 0° C, a white chlorinated polymer is obtained which roughly corresponds to the formula (-CHCI-), i.e. the formula for the product that can be formed from a linear polyacetylene well of 2 chlorine atoms on each double bond. This relationship and the bending lines obtained by X-ray examination in monochromatic light can only be explained by the assumption that the molecule is predominantly formed by chains containing linear methine groups.
For de høyere acetylenkullvannstoffers polymerisater som er oppløselige i organiske oppløsningsmidler, kan man på basis av hydrogenopptagelsen ved den katalyt-iske hydrering beregne et antall dobbeltbindinger som omtrentlig tilsvarer det antall som man kan forutse for lineære polymerisater av vedkommende kullvannstoff. Ved hydrering av et hexin-polymerisat i nærvær av Raney-nikkel ved en temperatur på 100° C og 200 atmosfærers over-trykk, danner det seg et oljeaktig produkt som i det infrarøde område viser et spektrum som ligner et sådant spektrum for et polymerisat som er polymerisert gjennom hele molekylet og som kan fåes ved polymerisering av hexon-1. Det må derfor an-tas at acetylenpolymerisatene overveiende dannes av metingrupper og at polymerisatene av høyere acetylenkullvannstoffer består av metingrupper sc-m veksler med grupper — CR =. For the higher acetylene coal hydrogen polymers that are soluble in organic solvents, on the basis of the hydrogen absorption during the catalytic hydrogenation, one can calculate a number of double bonds which roughly corresponds to the number that can be predicted for linear polymers of the coal hydrogen in question. During the hydration of a hexine polymer in the presence of Raney nickel at a temperature of 100° C and 200 atmospheres overpressure, an oily product is formed which in the infrared range shows a spectrum similar to such a spectrum for a polymer which is polymerized throughout the molecule and which can be obtained by polymerizing hexon-1. It must therefore be assumed that the acetylene polymers are predominantly formed by methine groups and that the polymers of higher acetylene coal water substances consist of methine groups sc-m alternating with groups — CR =.
Ved polymerisering av acetylen påvir-kes det resulterende polymerisats egenskaper i en meget vesentlig grad ved anvendelsen av særlige katalysatorer. Der danner seg nemlig et sort produkt med metallik-nende glinsende overflate og som ved rønt-genundersøkelser viser de bøyningslinjer som er karakteristiske for krystallinske stoffer. Egnede katalysatorer til fremstilling av et slikt produkt kan fremstilles under anvendelse av f. eks. titantetraalkoholat. During the polymerization of acetylene, the properties of the resulting polymer are affected to a very significant extent by the use of special catalysts. Namely, a black product with a metallic-like shiny surface forms there and which, in X-ray examinations, shows the bending lines that are characteristic of crystalline substances. Suitable catalysts for the production of such a product can be produced using e.g. titanium tetraalcoholate.
Polymerisater av acetylenkullvannstoffer fremstillet ved hjelp av fremgangs-måten ifølge oppfinnelsen er produkter av ' en helt ny art som blant annet på grunn lav deres sterke reaktivitet i kjemisk hen-seende egner seg for tallrike anvendelser. Hva acetylenpolymerisatet angår er dette også tilfelle på grunn av disse polymerisa-ters høye absorpsjonsevne. Polymers of acetylene coal water substances produced by means of the process according to the invention are products of a completely new type which, among other reasons, due to their low strong reactivity in chemical terms are suitable for numerous applications. As far as the acetylene polymer is concerned, this is also the case because of the high absorption capacity of these polymers.
En mulighet til nyttiggjørelse av disse egenskaper og en mulighet som er over-raskende når man tar i betraktning at det dreier seg om kullvannstoffer, er at pro-duktene i intim blanding med naturlig gummi eller kunstig fremstillet gummi gir en økning av gummiets fasthetsegenskaper ved den vanlige vulkanisasjon. An opportunity to make use of these properties, and an opportunity that is surprising when you take into account that these are coal-water substances, is that the products in an intimate mixture with natural rubber or artificially produced rubber give an increase in the rubber's firmness properties by ordinary vulcanization.
I det følgende beskrives som eksempler noen utførelsesformer for oppfinnelsen. In the following, some embodiments of the invention are described as examples.
Eksempel 1: Example 1:
I en autoklav med volum 2150 cm<:l> av rustfritt stål føres der i nitrogenatmosfære inn 7,5 g titantriklorid og en oppløsning av 5,7 g trietylaluminium i 425 cm<:s> benzen. Acetylen pumpes inn i autoklaven og den oppvarmes til 40° C. Der inntrer en stadig synkning av trykket og man pumper por-sjonsvis inn ytterligere mengder acetylen inntil der i det hele er tilført 40 liter beregnet på normalt trykk og normal<1> temperatur. In an autoclave with a volume of 2150 cm<:l> of stainless steel, 7.5 g of titanium trichloride and a solution of 5.7 g of triethylaluminum in 425 cm<:s> of benzene are introduced there in a nitrogen atmosphere. The acetylene is pumped into the autoclave and it is heated to 40° C. There is a constant decrease in pressure and further amounts of acetylene are pumped in in portions until a total of 40 liters calculated for normal pressure and normal<1> temperature have been supplied.
Omkring 30 timer etter forsøkets begynnelse suges de ikke reagerte gasser ut og metanol pumpes inn i autoklaven for å spalte de tilstedeværende organiske metallforbindelser. Derpå åpnes autoklaven. Reaksjonsproduktet i samme er et sort pulver som er suspendert i det anvendte oppløsningsmiddel. Dette polymerisat frafiltreres og befries fra de anorganiske forurensninger som skriver seg fra katalysato-rens spaltning. Dette oppnåes ved å suspen-dere polymerisatet flere ganger i varmen i metanol og saltsyre. Derpå frafiltreres polymerisatet, vaskes med metanol og tør-kes i varmen under vakuum. Man får på denne måte 17 g av et fast brunsort polymerisat som bare i meget begrenset grad er oppløselig i benzen. Around 30 hours after the start of the experiment, the unreacted gases are sucked out and methanol is pumped into the autoclave to split the organic metal compounds present. The autoclave is then opened. The reaction product in the same is a black powder which is suspended in the solvent used. This polymer is filtered off and freed from the inorganic contaminants that result from the decomposition of the catalyst. This is achieved by suspending the polymer several times in the heat in methanol and hydrochloric acid. The polymer is then filtered off, washed with methanol and dried in the heat under vacuum. In this way, 17 g of a solid brown-black polymer is obtained which is only soluble to a very limited extent in benzene.
Eksempel 2: Example 2:
I en fir-halset 1000 cm3 glasskolbe med mekanisk røreverk, termometer og dråpetrakt føres der i nitrogenatmosfære inn en oppløsning av 11,4 g trietylaluminium i 200 cm<*> normalt heptan. Acetylen ledes derpå langsomt inn i kolben og ved 20° C tilsettes dråpevis en oppløsning av 1,9 g titantetraklorid i 50 cm' normalt heptan. Der foregår spontant en liten temperatur-stigning (7° C). Mens blandingen ved omkring 50° C stadig holdes i bevegelse, fort-settes innledningen av acetylen med en hastighet på. omkring 3,0 liter pr. time, i det hele i 17 timer. Etter forløpet av dette tidsrom består reaksjonsproduktet av en væske i hvilken der er suspendert et fast sort pulver. I glasskolben tilsettes nu 100 cm<8> metanol for å spalte de tilstedeværende organiske metallforbindelser. Umiddelbart derpå behandles reaksjonsproduktet med saltsyre for å bringe i oppløsning de anorganiske stoffer som skriver seg fra spaltningen av katalysatoren. Derpå frafiltreres det faste stoff, vaskes flere ganger med metanol og tørkes i varmen under vakuum. ;Man får 12,5 g av et sort fast pulver-formig polymerisat, av hvilket 40 pst. kan ekstraheres med varm aceton. ;Eksempel 3: ;I en 1750 cm<3> autoklav føres der i nitrogenatmosfære inn 11 g vannfritt feri-klorid og en oppløsning av 11,4 g trietylaluminium i 500 cm3 normalt heptan. Der oppvarmes til 40° C, autoklaven settes i bevegelse og under opprettholdelse av den nevnte temperatur ledes der litt etter litt inn 15 liter (beregnet på normalt trykk og normal temperatur) acetylen. Derpå suges de ikke reagerte monomere .forbindelser ut av autoklaven og metanol pumpes inn i samme. Viderebehandlingen av reaksjonsproduktet skjer således som angitt i eksempel 1. ;Man får 5,5 g av et fast sort produkt hvis egenskaper ligner det ifølge eksempel 1 erholdte produkt. ;Eksempel 4: ;I en 1750 cm<3> autoklav føres der i ni trogenatmosfære inn 2,5 g vanadintriklorid ;og 11,4 g trietylaluminium oppløst i 5p0 cm3 normalt heptan. Man oppvarmer til 45° C under omrøring og under opprettholdelse av denne temperatur ledes der litt etter litt inn 20 liter acetylen. Temperaturen holdes i 20 timer på 40—45° C. Reaksjonsproduktet viderebehandles således som angitt i eksempel 1. Man får en meget liten mengde av et fast, sort polymerisat hvis egenskaper ligner de ifølge de foregående eksempler erholdte produkters egenskaper. ;Eksempel 5: ;I en 2150 cm3 autoklav føres der i nitrogenatmosfære inn 10 g av en blanding be-stående av 50 pst. molybdentriklorid og 50 pst. molybdenpentaklorid, samt 11,4 g tri-etylenaluminium oppløst i 500 cm<3> heptan. Man oppvarmer til 30—36° C og pumper litt etter litt inn 26 liter acetylen. Etter en reaksjonstid på 20 timer suges de ikke reagerte gasser ut og produktet viderebehandles således som angitt i eksempel 1. Man får 16,5 g av et fast, brunsort polymerisat av hvilket 42 pst. kan ekstraheres med varm aceton. ;Eksempel 6: ;I en 1780 cm3 autoklav føres der i nitrogenatmosfære inn 11,4 g Alj(C5H-,)a opp-løst i 400 cm<3> heptan. Acetylen pumpes inn i autoklaven til trykket er steget til 2 atmosfærer og der oppvarmes til 27° C. Ved denne temperatur sprøytes der under nitrogentrykk inn en oppløsning av 10 g (omkring 0,04 mol) titantetraisopropylat i 100 cm<3> heptan. Der pumpes derpå inn ytterligere mengder acetylen, hvorved temperaturen holdes på 50° C. Etter innpump-ning av i det hele 25 liter acetylen sprøytes der under nitrogentrykk inn i autoklaven en oppløsning av 5,5 g titantetraisopropylat i 70 cm<3> heptan. Der tilføres litt etter litt ytterligere mengder acetylen, hvorved der når temperaturen er nådd 55° C, observeres en stadig minskning av trykket. 20 timer etter forsøkets begynnelse og etter at i det hele 34 liter acetylen er ledet inn, suger man ut ikke reagerte monomere forbindelser og metanol pumpes inn i autoklaven. Etter at autoklaven er åpen taes der ut av denne en sort masse som! er svel-let ut ved oppløsningsmidlets innvirkning. ;Ved viderebehandling av produktet således som angitt i eksempel 1, får man 35 g av et fast. sort polymerisat. Ved ekstrak-sjon med aceton oppdeles dette produkt i en amorf oppløselig bestanddel og en uopp-løselig bestanddel. Den sistnevnte bestanddel viser ved røntgenundersøkelse i monokromatisk lys noen bøyningslinjer som må tilskrives tilstedeværelsen av krystallinske partikler. ;Eksempel 7: ;I en 2150 cm<3> rysteautoklav bringes der inn to kuler av rustfritt stål med diameter 25 mm og en glassampulle inneholdende 4 g titantetraklorid. I den lukkede autoklav føres der derpå i nitrogenatmosfære inn en oppløsning av 5,7 g trietylaluminium i 250 cm3 vannfritt benzen samt 78 g fenyl-acetylen. Man oppvarmer til 50° C og set-ter autoklaven i bevegelse, hvorved ampul-len knuses. Temperaturen måles i 48 timer mellom 45 og 50° C. Etter forløpet av dette tidsrom avbrytes varmetilførselen og metanol pumpes inn i autoklaven. Reaksjonsproduktet er en halvfast, sterkt orangerødt farvet masse. ;De anorganiske forurensninger som skriver seg fra spaltningen av katalysatoren fjernes ved behandling med eter og saltsyre i varmen og i nitrogenatmosfære. Derpå koaguleres polymerisatet fullstendig med metanol, filtreres og tørkes i varmen under vakuum. ;Man får på denne måte 51 g av et polymerisat, hva der tilsvarer en omsetning på 65,5 pst. av det anvendte monomere produkt. 30 pst. av polymerisatet består av et fast, lysegult stoff som er oppløselig i varm aceton. For øvrig består polymerisatet av en fast orangerød bestanddel som i varmen er uoppløselig i eter og heptan, men imidlertid kan ekstraheres fullstendig med varm benzen. Den aceton-uoppløse-lige men benzen-oppløselige fraksjon har i tetrahydronaftalinoppløsning ved 135° C en grenseviskositet på 0,077 og oppløst i toluen en grenseviskositet på 0,132 ved 25° C. ;Eksempel 8: ;I en 2150 cm<8> autoklav bringes der i nitrogenatmosfære inn 4,5 g titantetraklorid samt 5,7 g trietylaluminium oppløst i 400 cm3heptan. ;Autoklaven settes i bevegelse og straks etter sprøytes der under nitrogentrykk inn 50 g etylacetylen. Der oppvarmes til 52° C og denne temperatur opprettholdes i omkring 14 timer. Etter forløpet av dette tidsrom pumpes der metanol inn i autoklaven. Autoklavens innhold består da av en fly-tende, mørkerød masse, som etter tilset-ning av større mengder metanol avspalter et sortbrunt, fast stoff. Dette stoff kan fraskilles ved filtrering. Det oppløses lett i varm eter og kan således befris for tilstedeværende anorganiske stoffer ved behandling med eter og saltsyre med påføl-gende fullstendig koagulering med metanol. Polymerisatet frafiltreres, vaskes og tørkes i varmen under vakuum. Man får på denne måte 5 g av et fast, sortbrunt pulver som oppløst i toluen, viser en grenseviskositet på 0,085 ved 25° C. ;Eksevipel 9: ;I en 500 cm3 kolbe med mekanisk røre-verk føres der i nitrogenatmosfære inn 4 g titantriklorid samt 5 g dietylsink oppløst i 200 cm3 vannfri benzen og 36 g fenylacetylen. Man oppvarmer til 80—85° C og om-rører i 3 timer. Etter forløpet av dette tidsrom spaltes de tilstedeværende organiske metallforbindelser med metanol, hvorpå reaksjonsproduktet viderebehandles således som angitt i eksempel 7. ;Man får på denne måte 20 g av et fast, lysegult polymerisat med lignende egenskaper som det ifølge 7 erholdte reaksjons-produkt. ;Eksempel 10: ;I en 2 liters rysteautoklav, som er pum-pet lufttom og fylt med nitrogen, føres der inn en oppløsning av 5,7 g aluminiumtrietyl i 200 cm3 heptan. Ved hjelp av en passende kompressor føres der inn 12 g renset og tør-ket acetylen og autoklaven oppvarmes til 40° C. Under nitrogentrykk føres der derpå inn 0,02 mol vanadylisopropylat (VCKOC3H7)*) oppløst i 50 cm<3> heptan. Før forløpet av 20 minutter stiger reaksjons-massens temperatur spontant med omkring 10° C, mens der samtidig iakktas en stadig minskning av trykket. A solution of 11.4 g of triethylaluminum in 200 cm<*> of normal heptane is introduced into a four-necked 1000 cm3 glass flask with mechanical stirrer, thermometer and dropping funnel in a nitrogen atmosphere. The acetylene is then slowly led into the flask and at 20° C a solution of 1.9 g of titanium tetrachloride in 50 cm' of normal heptane is added dropwise. A slight rise in temperature (7° C) takes place spontaneously. While the mixture at about 50° C is kept constantly moving, the introduction of acetylene continues at a rate of around 3.0 liters per hour, for a total of 17 hours. After this period of time, the reaction product consists of a liquid in which a solid black powder is suspended. In the glass flask, 100 cm<8> of methanol is now added to decompose the organic metal compounds present. Immediately thereafter, the reaction product is treated with hydrochloric acid in order to dissolve the inorganic substances that are formed from the cleavage of the catalyst. The solid is then filtered off, washed several times with methanol and dried in the heat under vacuum. ;You get 12.5 g of a black solid powdery polymer, of which 40% can be extracted with hot acetone. Example 3: 11 g of anhydrous ferric chloride and a solution of 11.4 g of triethylaluminum in 500 cm3 of normal heptane are introduced into a 1750 cm<3> autoclave under a nitrogen atmosphere. It is heated to 40° C, the autoclave is set in motion and, while maintaining the aforementioned temperature, 15 liters (calculated at normal pressure and normal temperature) of acetylene are introduced little by little. The unreacted monomeric compounds are then sucked out of the autoclave and methanol is pumped into it. The further processing of the reaction product thus takes place as indicated in example 1. 5.5 g of a solid black product is obtained whose properties are similar to the product obtained according to example 1. ;Example 4: ;In a 1750 cm<3> autoclave, nine nitrogen atmosphere into 2.5 g of vanadium trichloride; and 11.4 g of triethylaluminum dissolved in 5p0 cm3 of normal heptane. It is heated to 45° C while stirring and, while maintaining this temperature, 20 liters of acetylene are introduced little by little. The temperature is maintained for 20 hours at 40-45° C. The reaction product is further processed as indicated in example 1. A very small amount of a solid, black polymer is obtained whose properties are similar to the properties of the products obtained according to the previous examples. ;Example 5: ;Into a 2150 cm3 autoclave, 10 g of a mixture consisting of 50% molybdenum trichloride and 50% molybdenum pentachloride, as well as 11.4 g of triethylene aluminum dissolved in 500 cm<3> heptane are introduced in a nitrogen atmosphere . It is heated to 30-36° C and little by little 26 liters of acetylene are pumped in. After a reaction time of 20 hours, the unreacted gases are sucked out and the product is further processed as indicated in example 1. 16.5 g of a solid, brown-black polymer is obtained, of which 42 per cent can be extracted with hot acetone. ;Example 6: ;Into a 1780 cm3 autoclave, 11.4 g of Alj(C5H-,)a dissolved in 400 cm<3> of heptane are introduced there in a nitrogen atmosphere. The acetylene is pumped into the autoclave until the pressure has risen to 2 atmospheres and is heated to 27° C. At this temperature, a solution of 10 g (around 0.04 mol) titanium tetraisopropylate in 100 cm<3> of heptane is injected under nitrogen pressure. Further amounts of acetylene are then pumped in, whereby the temperature is kept at 50° C. After pumping in a total of 25 liters of acetylene, a solution of 5.5 g of titanium tetraisopropylate in 70 cm<3> heptane is injected into the autoclave under nitrogen pressure. Little by little further amounts of acetylene are added, whereby when the temperature has reached 55° C, a steady reduction in pressure is observed. 20 hours after the start of the experiment and after a total of 34 liters of acetylene have been introduced, unreacted monomeric compounds are sucked out and methanol is pumped into the autoclave. After the autoclave is open, a black mass is taken out of it which! is swollen by the effect of the solvent. By further processing the product as indicated in example 1, 35 g of a solid is obtained. black polymer. Upon extraction with acetone, this product is divided into an amorphous soluble component and an insoluble component. The latter component shows, on X-ray examination in monochromatic light, some bending lines which must be attributed to the presence of crystalline particles. ;Example 7: ;Into a 2150 cm<3> shaking autoclave, two stainless steel spheres with a diameter of 25 mm and a glass ampoule containing 4 g of titanium tetrachloride are introduced. A solution of 5.7 g of triethylaluminum in 250 cm3 of anhydrous benzene and 78 g of phenyl-acetylene are then introduced into the closed autoclave in a nitrogen atmosphere. It is heated to 50° C and the autoclave is set in motion, whereby the ampoule is crushed. The temperature is measured for 48 hours between 45 and 50° C. After this period of time, the heat supply is interrupted and methanol is pumped into the autoclave. The reaction product is a semi-solid, strongly orange-red colored mass. ;The inorganic impurities that result from the splitting of the catalyst are removed by treatment with ether and hydrochloric acid in the heat and in a nitrogen atmosphere. The polymer is then coagulated completely with methanol, filtered and dried in the heat under vacuum. In this way, 51 g of a polymer is obtained, which corresponds to a conversion of 65.5 per cent of the monomeric product used. 30 percent of the polymer consists of a solid, pale yellow substance that is soluble in hot acetone. Otherwise, the polymerizate consists of a solid orange-red component which in the heat is insoluble in ether and heptane, but can however be extracted completely with hot benzene. The acetone-insoluble but benzene-soluble fraction has in tetrahydronaphthalene solution at 135° C a limiting viscosity of 0.077 and dissolved in toluene a limiting viscosity of 0.132 at 25° C. ;Example 8: ;In a 2150 cm<8> autoclave is brought there in a nitrogen atmosphere add 4.5 g of titanium tetrachloride and 5.7 g of triethylaluminum dissolved in 400 cm3 of heptane. The autoclave is set in motion and immediately afterwards 50 g of ethyl acetylene are injected under nitrogen pressure. It is heated to 52° C and this temperature is maintained for around 14 hours. After this period of time, methanol is pumped into the autoclave. The contents of the autoclave then consist of a flowing, dark red mass, which, after the addition of larger amounts of methanol, releases a black-brown, solid substance. This substance can be separated by filtration. It dissolves easily in hot ether and can thus be freed from inorganic substances present by treatment with ether and hydrochloric acid followed by complete coagulation with methanol. The polymer is filtered off, washed and dried in the heat under vacuum. In this way, 5 g of a solid, black-brown powder is obtained which, dissolved in toluene, shows an intrinsic viscosity of 0.085 at 25° C. ;Example 9: ;Into a 500 cm3 flask with a mechanical stirrer, introduce 4 g in a nitrogen atmosphere titanium trichloride and 5 g of diethylzinc dissolved in 200 cm3 of anhydrous benzene and 36 g of phenylacetylene. It is heated to 80-85° C and stirred for 3 hours. After this period of time has elapsed, the organic metal compounds present are cleaved with methanol, after which the reaction product is further processed as indicated in example 7. In this way, 20 g of a solid, light yellow polymer with similar properties to the reaction product obtained according to 7 is obtained. ;Example 10: ;A solution of 5.7 g of aluminum triethyl in 200 cm3 of heptane is introduced into a 2 liter shaking autoclave, which has been pumped out of air and filled with nitrogen. Using a suitable compressor, 12 g of purified and dried acetylene are introduced and the autoclave is heated to 40° C. Under nitrogen pressure, 0.02 mol of vanadyl isopropylate (VCKOC3H7)*) dissolved in 50 cm<3> of heptane is then introduced. Before the end of 20 minutes, the temperature of the reaction mass rises spontaneously by around 10° C, while at the same time a steady decrease in pressure is observed.
Man leder nu inn acetylen i flere porsjoner inntil den totale tilførsel av acetylen i løpet av omkring 5 timer er 27 g. Etter for-løpet av nevnte tidsrom pumpes metanol inn i autoklaven og produktet tas ut. Det befries derpå for vedheftende anorganiske forurensninger ved behandling med saltsyre. Etter filtrering og tørking i vakuum og i varmen får man 22 g av et fast, sort polymerisat i form av metallglinsende la-meller. Ved røntgenundersøkelse viser dette polymerisat seg å være krystallinsk. Acetylene is now introduced in several portions until the total supply of acetylene over the course of about 5 hours is 27 g. After the aforementioned period of time, methanol is pumped into the autoclave and the product is removed. It is then freed from adhering inorganic contaminants by treatment with hydrochloric acid. After filtration and drying in a vacuum and in the heat, 22 g of a solid, black polymer in the form of shiny metallic lamellae are obtained. On X-ray examination, this polymer is found to be crystalline.
De oppløsningsmidler som er brukt til polymeriseringen og rensningen konsentre-res i varmen, hvorved man får 2 g oljeaktig lavmolekylære produkter. The solvents used for the polymerization and purification are concentrated in the heat, whereby 2 g of oily low molecular weight products are obtained.
I det hele får man 24 g acetylenpolymerisater hva der tilsvarer en omsetning på 86 pst. av det anvendte monomere utgangsmateriale. In all, 24 g of acetylene polymers are obtained, which corresponds to a conversion of 86 per cent of the monomeric starting material used.
Eksempel 11: I en 500 cm3 glasskolbe med mekanisk røreverk, dråpetrakt og tilbakeløpskjøler føres der i nitrogenatmosfære inn 5,7 g aluminiumtrietyl oppløst i 200 cm<3> vannfri benzen samt 30 g fenylacetylen. Man oppvarmer til 55° C og drypper inn i massen under omrøring en oppløsning av 5,5 g titanisopropylat i 50 cm3 heptan. Temperaturen stiger spontant til omkring 80° C mens massen samtidig blir mere og mere viskos. Example 11: 5.7 g of aluminum triethyl dissolved in 200 cm<3> of anhydrous benzene and 30 g of phenylacetylene are introduced into a 500 cm3 glass flask with a mechanical stirrer, dropping funnel and reflux condenser in a nitrogen atmosphere. It is heated to 55° C and a solution of 5.5 g of titanium isopropylate in 50 cm3 of heptane is dripped into the mass while stirring. The temperature rises spontaneously to around 80° C while the mass simultaneously becomes more and more viscous.
Etter omkring 4 timer tilsettes 50 cm3 metanol og polymerisatet renses således som foran beskrevet. Etter fullstendig koagulering med større mengder metanol får man 21 g polyfenylacetylen. Av dette produkt er omkring 10 pst. uoppløselig i koken-de aceton, men oppløselig i benzen selv ved romtemperatur. After about 4 hours, 50 cm3 of methanol is added and the polymer is purified as described above. After complete coagulation with larger amounts of methanol, 21 g of polyphenylacetylene are obtained. About 10 per cent of this product is insoluble in boiling acetone, but soluble in benzene even at room temperature.
Eksempel 12: I en 2080 cm<3> autoklav føres der i nitrogenatmosfære inn 12 g aluminiumdietyl-monoklorid oppløst i 400 cm3 heptan, hvorpå der pumpes inn 20 g acetylen. Ved 25° C sprøytes der under omrøring inn i massen en oppløsning av 11 g titanisopropylat i 50 cm<3> heptan. Temperaturen stiger før for-løpet av 25 min. spontant fra 25° til 40° C, mens trykket samtidig avtar stadig. Det tilføres i flere porsjoner frisk acetylen til en total mengde på 46 g, mens temperaturen holdes mellom 40 og 50° C. 3 timer etter forsøkets begynnelse suges de ikke reagerte gasser bort og metanol pumpes inn i autoklaven. Viderebehandlingen av produktet skjer som beskrevet i det foregående. Example 12: In a 2080 cm<3> autoclave, 12 g of aluminum diethyl monochloride dissolved in 400 cm3 of heptane are introduced in a nitrogen atmosphere, after which 20 g of acetylene is pumped in. At 25° C, a solution of 11 g of titanium isopropylate in 50 cm<3> of heptane is injected into the mass while stirring. The temperature rises before the pre-run of 25 min. spontaneously from 25° to 40° C, while the pressure simultaneously decreases steadily. Fresh acetylene is added in several portions to a total amount of 46 g, while the temperature is kept between 40 and 50° C. 3 hours after the start of the experiment, the unreacted gases are sucked away and methanol is pumped into the autoclave. The further processing of the product takes place as described above.
Man får på denne måte 20,5 g av et fast, sort polymerisat som ved røntgen-undersøkelse viser seg å være krystallinsk. Av de anvendte oppløsningsmidler utskilles 2.8 g oljeaktig lavmolekylært polymerisat. In this way, 20.5 g of a solid, black polymer is obtained which, on X-ray examination, turns out to be crystalline. From the solvents used, 2.8 g of oily low molecular weight polymer is separated.
Eksempel 13: I en 250 cm3 glasskolbe med mekanisk røreverk, dråpetrakt og tilbakeløpskjøler føres i nitrogenatmosfære inn 3,2 g titantriklorid og 100 cm<3> normalt heptan som oppløst inneholder 5,7 g aluminiumtrietyl. Ved en temperatur på 20—25° C tilsettes under omrøring en oppløsning av 30 g hek-sin-(l) (normalt-butylacetylen) i 50 cm3 normalt heptan. Massen omrøres i omkring 6 timer. Etter forløpet av denne tid spaltes de tilstedeværende organiske metallforbindelser med metanol og produktet renses ved behandling i varmen med eter som er sur gjort med saltsyre og utkoagulering méd metanol. Example 13: In a 250 cm3 glass flask with a mechanical stirrer, dropping funnel and reflux condenser, 3.2 g of titanium trichloride and 100 cm<3> of normal heptane are introduced in a nitrogen atmosphere, which in solution contains 5.7 g of aluminum triethyl. At a temperature of 20-25° C is added with stirring a solution of 30 g of hexine-(1) (normal-butylacetylene) in 50 cm 3 of normal heptane. The mass is stirred for about 6 hours. After this time, the organic metal compounds present are decomposed with methanol and the product is purified by treatment in the heat with ether acidified with hydrochloric acid and coagulation with methanol.
Etter filtrering og tørking i vakuum i varmen får man 14 g av et fast, gummiaktig heksinpolymerisat som kan ekstraheres fullstendig med varmt tetraklorkullstoff. After filtration and drying in a vacuum in the heat, 14 g of a solid, rubbery hexine polymer is obtained which can be completely extracted with hot carbon tetrachloride.
I tetrahydronaftalin-oppløsning ved 135° C viser produktet en grenseviskositet på 1,2. In tetrahydronaphthalene solution at 135° C, the product shows a limiting viscosity of 1.2.
Eksempel 14: I en 2000 cm<3>'s autoklav føres der i nitrogenatmosfære inn 0,14 mol amyl-litium oppløst i 200 cm3 pentan. Der tilføres så 10 g acetylen fortynnet med nitrogen. Example 14: 0.14 mol of amyl lithium dissolved in 200 cm3 of pentane is introduced into a 2000 cm3 autoclave in a nitrogen atmosphere. 10 g of acetylene diluted with nitrogen is then added.
Autoklaven oppvarmes til 50° C og ved denne temperatur sprøytes der inn 50 cm<3 >pentan inneholdende oppløst 0,02 mol titantetraisopropylat. Der foregår da en tem-peraturstigning og en stadig minskning av trykket. Der tilsettes litt etter litt ytterligere mengder acetylen inntil man i det hele har tilført 18 g. The autoclave is heated to 50° C and at this temperature 50 cm<3 >pentane containing dissolved 0.02 mol of titanium tetraisopropylate is injected into it. There then takes place a rise in temperature and a constant reduction in pressure. Further amounts of acetylene are added little by little until a total of 18 g has been added.
Omkring 9 timer etter forsøkets begynnelse suges det ikke reagerte acetylen ut og metanol pumpes inn i autoklaven. About 9 hours after the start of the experiment, the unreacted acetylene is sucked out and methanol is pumped into the autoclave.
Reaksjonsproduktet viderebehandles således som angitt i de foregående eksempler. Man får 7 g acetylenpolymerisater. 80 pst. av disse er fast, sort polymerisat som ved røntgenundersøkelse viser seg å være krystallinsk. The reaction product is thus further processed as indicated in the preceding examples. 7 g of acetylene polymers are obtained. 80 per cent of these are solid, black polymer which, on X-ray examination, turns out to be crystalline.
Claims (6)
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Application Number | Priority Date | Filing Date | Title |
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NL6408551A NL6408551A (en) | 1964-07-25 | 1964-07-25 |
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NO120119B true NO120119B (en) | 1970-08-31 |
Family
ID=19790628
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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NO15903465A NO120119B (en) | 1964-07-25 | 1965-07-21 |
Country Status (10)
Country | Link |
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JP (1) | JPS5250468B1 (en) |
AT (1) | AT255562B (en) |
BE (1) | BE667253A (en) |
CH (1) | CH447374A (en) |
DE (1) | DE1994024U (en) |
DK (1) | DK112392B (en) |
ES (1) | ES315676A1 (en) |
GB (1) | GB1110018A (en) |
NL (1) | NL6408551A (en) |
NO (1) | NO120119B (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3521110A (en) * | 1967-09-25 | 1970-07-21 | Gen Electric | Mercury-metallic halide vapor lamp with regenerative cycle |
DE2826733C2 (en) * | 1977-07-05 | 1982-07-29 | General Electric Co., Schenectady, N.Y. | High pressure metal halide discharge lamp |
US4170746A (en) * | 1977-12-27 | 1979-10-09 | General Electric Company | High frequency operation of miniature metal vapor discharge lamps |
DD203430A1 (en) * | 1982-01-19 | 1983-10-19 | Kloss | ELECTRODE STABILIZED HIGH-PRESSURE DISCHARGE LAMP WITH LIGHTING ACCESSORIES |
US4605881A (en) * | 1984-11-29 | 1986-08-12 | General Electric Company | High pressure sodium iodide arc lamp with excess iodine |
KR100665779B1 (en) * | 1999-10-18 | 2007-01-09 | 마츠시타 덴끼 산교 가부시키가이샤 | High voltage mercury lamp, lamp unit and method for producing mercury lamp |
GB2420220B (en) * | 2004-11-10 | 2009-10-14 | Gen Electric | Ceramic metal halide lamps |
-
1964
- 1964-07-25 NL NL6408551A patent/NL6408551A/xx unknown
-
1965
- 1965-07-20 DE DE1965N0017762 patent/DE1994024U/en not_active Expired
- 1965-07-21 GB GB3100165A patent/GB1110018A/en not_active Expired
- 1965-07-21 CH CH1022465A patent/CH447374A/en unknown
- 1965-07-21 AT AT670665A patent/AT255562B/en active
- 1965-07-21 NO NO15903465A patent/NO120119B/no unknown
- 1965-07-21 JP JP4387565A patent/JPS5250468B1/ja active Pending
- 1965-07-21 DK DK375665A patent/DK112392B/en unknown
- 1965-07-22 ES ES0315676A patent/ES315676A1/en not_active Expired
- 1965-07-22 BE BE667253A patent/BE667253A/xx unknown
Also Published As
Publication number | Publication date |
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DK112392B (en) | 1968-12-09 |
AT255562B (en) | 1967-07-10 |
JPS5250468B1 (en) | 1977-12-24 |
BE667253A (en) | 1966-01-24 |
ES315676A1 (en) | 1965-11-01 |
NL6408551A (en) | 1966-01-26 |
GB1110018A (en) | 1968-04-18 |
DE1994024U (en) | 1968-09-19 |
CH447374A (en) | 1967-11-30 |
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