NO136988B - DOOR FURNITURE. - Google Patents
DOOR FURNITURE. Download PDFInfo
- Publication number
- NO136988B NO136988B NO2574/72A NO257472A NO136988B NO 136988 B NO136988 B NO 136988B NO 2574/72 A NO2574/72 A NO 2574/72A NO 257472 A NO257472 A NO 257472A NO 136988 B NO136988 B NO 136988B
- Authority
- NO
- Norway
- Prior art keywords
- polymerization
- vinyl acetate
- polyvinyl alcohols
- vinyl
- formate
- Prior art date
Links
- 238000006116 polymerization reaction Methods 0.000 claims description 21
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 20
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 16
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 16
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229920001290 polyvinyl ester Polymers 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 11
- 230000008961 swelling Effects 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000029142 excretion Effects 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16H—GEARING
- F16H21/00—Gearings comprising primarily only links or levers, with or without slides
- F16H21/02—Gearings comprising primarily only links or levers, with or without slides the movements of two or more independently-moving members being combined into a single movement
-
- E—FIXED CONSTRUCTIONS
- E05—LOCKS; KEYS; WINDOW OR DOOR FITTINGS; SAFES
- E05F—DEVICES FOR MOVING WINGS INTO OPEN OR CLOSED POSITION; CHECKS FOR WINGS; WING FITTINGS NOT OTHERWISE PROVIDED FOR, CONCERNED WITH THE FUNCTIONING OF THE WING
- E05F15/00—Power-operated mechanisms for wings
- E05F15/50—Power-operated mechanisms for wings using fluid-pressure actuators
Landscapes
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Actuator (AREA)
- Securing Of Glass Panes Or The Like (AREA)
- Fertilizers (AREA)
- Air-Flow Control Members (AREA)
- Gates (AREA)
- Power-Operated Mechanisms For Wings (AREA)
- Looms (AREA)
- Toys (AREA)
Description
Fremgangsmåte til fremstilling av polyvinylestere. Process for the production of polyvinyl esters.
Foreliggende oppfinnelse angår en fremgangsmåte til fremstilling av polyvinylestere ved polymerisering av vinylformiat ved lave temperaturer. The present invention relates to a method for producing polyvinyl esters by polymerization of vinyl formate at low temperatures.
Det er funnet at polyvinylalkoholer It has been found that polyvinyl alcohols
erholdt ved forsåpning av polyvinylformiat, særlig polyvinylalkoholer fremstillet av polyvinylformiat som er erholdt ved å polymerisere vinylformiat ved temperaturer som er lavere enn romtemperatur, har et mindre innhold av 1,2-glycol-bindinger og et større innhold av krystallinske be-standdeler i sammenligning med polyvinylalkoholer erholdt ved forsåpning av nor-malt polyvinylacetat. obtained by saponification of polyvinyl formate, in particular polyvinyl alcohols produced from polyvinyl formate which are obtained by polymerizing vinyl formate at temperatures lower than room temperature, have a lower content of 1,2-glycol bonds and a higher content of crystalline components in comparison with polyvinyl alcohols obtained by saponification of normal polyvinyl acetate.
Når imidlertid vinylformiat polymeriseres til temperaturer som er lavere enn ca. 30° C inntreffer det fenomener som forårsaker besværligheter. Ved polymerisering av vinylformiat ved lave temperaturer inntreffer der en rask økning av reaksjonsblandingens viskositet, geldannelse, utskillelse av polymerisat osv. Særlig når der inntreffer utskillelse av uoppløselig polymerisat i en bomullsaktig form, økes polymeriseringshastigheten raskt, så at utskillelse av polymerisat økes plutselig, hvorved regulering av polymeriseringsreak-sjonen blir ytterst vanskelig. Videre akku-muleres den varme som utvikles under polymeriseringen så at det ikke blir mulig å utføre denne ved lave temperaturer. Når f. eks. masse-polymerisering av vinylformiat utføres ved 0° C, utskilles et ugjen-nomsiktig bomullslignende polymerisat However, when vinyl formate is polymerized to temperatures lower than approx. 30° C, phenomena occur which cause difficulties. During the polymerization of vinyl formate at low temperatures, there occurs a rapid increase in the viscosity of the reaction mixture, gel formation, excretion of polymer, etc. Especially when excretion of insoluble polymer in a cotton-like form occurs, the rate of polymerization is increased rapidly, so that excretion of polymer is increased suddenly, whereby regulation of the polymerization reaction becomes extremely difficult. Furthermore, the heat developed during the polymerization is accumulated so that it is not possible to carry it out at low temperatures. When e.g. mass polymerization of vinyl formate is carried out at 0° C, an opaque cotton-like polymer is secreted
ved en omdannelse på 10 pst. Dette forhold at a conversion of 10 per cent. This ratio
kan forenkles ved å anta at polyvinylformiat ved lave temperaturer blir mindre oppløselig i de monomere og oppløsnings-midler, og at mengden av 1,2-glycol-bindinger avtar ved lavere temperaturer og at selve polymerisatet blir mindre oppløse-lig på grunn av økning av sidekj edenes steriske regelmessighet. can be simplified by assuming that polyvinyl formate at low temperatures becomes less soluble in the monomers and solvents, and that the amount of 1,2-glycol bonds decreases at lower temperatures and that the polymer itself becomes less soluble due to an increase in the steric regularity of the side chains.
Ved hjelp av fremgangsmåten ifølge oppfinnelsen forhindres geldannelse i reak-sj onsblandingen under polymeriseringens forløp, så at polymeriseringen lar seg ut-føre jevnt og man får et sampolymerisat fra hvilket der kan fremstilles i høy grad krystallinske polyvinylalkoholer. With the help of the method according to the invention, gel formation in the reaction mixture is prevented during the course of the polymerization, so that the polymerization can be carried out evenly and a copolymer is obtained from which highly crystalline polyvinyl alcohols can be produced.
Det karakteristiske hovedtrekk ved fremgangsmåten ifølge oppfinnelsen er at man sampolymeriserer vinylformiatet med opptil 25 molpst. vinylactat. Herved opp-nås at polymeriseringen selv ved lave temperaturer foregår jevnt og gir et produkt fra hvilket der kan fåes i høy grad krystallinske polyvinylalkoholer. The characteristic main feature of the method according to the invention is that the vinyl formate is copolymerized with up to 25 mole parts. vinyl acetate. Hereby it is achieved that the polymerization takes place evenly even at low temperatures and gives a product from which highly crystalline polyvinyl alcohols can be obtained.
Det er funnet at når vinylformiat til-settes små mengder vinylacetat forhindres ikke alene de ovenfor nevnte uheldige fenomener som en rask økning av viskosi-teten, geldannelse, utskillelse av polymerisat så at polymeriseringen foregår på en jevn måte, men dertil påvirkes ikke de krystallinske egenskaper hos polyvinylalkoholer erholdt ved å forsåpe de på denne måte fremstilte sampolymerisater i ugunstig retning. Videre finner der ikke sted noen forandring i de erholdte polyvinylalkoho-lers polymerisasjonsgrad. Således viser f. eks. måling av svellingen i vann av film fremstillet av sådanne polyvinylalkoholer ved konstant romtemperatur at svellegraden ikke undergår noen vesentlig forandring ved tilsetning av vinylacetat i mengder opp til 25 pst. og at hvis man tilset-ter mere enn 25 pst. vinylacetat, øker svellegraden gradvis proporsjonalt med den tilsatte mengde vinylacetat inntil den nær-mer seg svellegraden for polyvinylalkoholer erholdt fra polyvinylacetat. Videre er det, som nevnt, fastslått at polyvinylalkohole-nes polymerisasj onsgrad praktisk talt ikke viser noen forandring ved tilsetning av vinylacetat til det vinylformiat som skal polymeriseres. It has been found that when small amounts of vinyl acetate are added to vinyl formate, not only are the above-mentioned unfortunate phenomena such as a rapid increase in viscosity, gel formation, excretion of polymer so that the polymerization takes place in a uniform manner, but also the crystalline properties are not affected in the case of polyvinyl alcohols obtained by saponifying the copolymers produced in this way in an unfavorable direction. Furthermore, there is no change in the degree of polymerization of the polyvinyl alcohols obtained. Thus, e.g. measurement of the swelling in water of film made from such polyvinyl alcohols at constant room temperature that the degree of swelling does not undergo any significant change when vinyl acetate is added in quantities of up to 25 per cent and that if more than 25 per cent vinyl acetate is added, the degree of swelling gradually increases proportionally with the added amount of vinyl acetate until it approaches the degree of swelling for polyvinyl alcohols obtained from polyvinyl acetate. Furthermore, as mentioned, it has been established that the degree of polymerization of the polyvinyl alcohols practically shows no change when vinyl acetate is added to the vinyl formate that is to be polymerized.
I det følgende beskrives som eksempler to utførelsesformer for oppfinnelsen. In the following, two embodiments of the invention are described as examples.
Eksempel 1 Example 1
100 vektsdeler vinylformiat ble tilsatt 0,1 del 2,2-azo-bis-isobutyronitril og henholdsvis 0,1, 2, 3 og 5 vektpst. vinylacetat. De således erholdte blandinger ble polymerisert ved 30° C i nitrogenatmosfære. Når vinylacetat ikke ble tilsatt inntraff geldannelse. Ved tilsetningen av vinylacetat øket ikke reaksjonsblandingens viskositet og når der ble tilsatt mere enn 3 vektpst. vinylacetat, var det erholdte polymerisat flytende selv etter 24 timer. Ut-byttet ved disse polymeriseringer var henholdsvis 68,1, 62,8, 63,2, 58,5 Og 52,7 pst. Polymeriseringshastigheten avtok ganske lite ved økende mengder tilsatt vinylacetat, så lite at dette var uten betydning. Oppløsninger av de erholdte polymerisater i aceton og med en konsentrasjon 0,5 pst. ble hensatt ved —40° C. Endringen i viskositet som funksjon av tiden ved hen-stand ved —40° C representeres av forme-len )]t —. i]0 (1 + at''»), hvor i|t betegner viskositet etter t timer, t|0 opprinnelig viskositet, t betegner tiden og a er en konstant som bestemmes ved forsøk, a er et mål for geldannelse i det erholdte polymerisat. a var 2,75, 1,47, 0,51, 0,12 og 0 i avhengighet av den tilsatte mengde vinylacetat, dvs. henholdsvis 0, 1, 2, 3, og 5 pst. 100 parts by weight of vinyl formate were added to 0.1 part of 2,2-azo-bis-isobutyronitrile and respectively 0.1, 2, 3 and 5 parts by weight. vinyl acetate. The mixtures thus obtained were polymerized at 30° C. in a nitrogen atmosphere. When vinyl acetate was not added gelation occurred. The addition of vinyl acetate did not increase the viscosity of the reaction mixture and when more than 3 wt. vinyl acetate, the polymer obtained was liquid even after 24 hours. The yield in these polymerizations was respectively 68.1, 62.8, 63.2, 58.5 and 52.7 percent. The rate of polymerization decreased quite a bit with increasing amounts of added vinyl acetate, so little that this was insignificant. Solutions of the polymers obtained in acetone and with a concentration of 0.5% were stored at -40° C. The change in viscosity as a function of time during storage at -40° C is represented by the formula )]t -. i]0 (1 + at''"), where i|t denotes viscosity after t hours, t|0 initial viscosity, t denotes time and a is a constant determined by experiment, a is a measure of gel formation in the obtained polymerized. a was 2.75, 1.47, 0.51, 0.12 and 0 depending on the added amount of vinyl acetate, i.e. 0, 1, 2, 3 and 5 per cent respectively.
Det fremgår klart at desto større den tilsatte mengde vinylacetat er, jo mindre geldannelse fnner der sted. Svellegraden for polyvinylalkoholer erholdt fra polymerisatet var henholdsvis 1,48, 1,30, 1,36, It is clear that the greater the added amount of vinyl acetate, the less gelation takes place there. The degree of swelling for polyvinyl alcohols obtained from the polymerizate was respectively 1.48, 1.30, 1.36,
1,34 og 1,31, hva der viser at noen vesentlig forandring i svellegraden ikke forårsakes ved tilsetning av vinylacetat. De fremstilte poly vinylalkoholers polymerisasj onsgrad var henholdsvis 910, 899, 908, 911 og 901, hva der viser at noen vesentlig forandring i polymeriseringsgraden ikke forårsakes ved tilsetning av vinylacetat. 1.34 and 1.31, which shows that no significant change in the degree of swelling is caused by the addition of vinyl acetate. The degree of polymerization of the produced polyvinyl alcohols was respectively 910, 899, 908, 911 and 901, which shows that no significant change in the degree of polymerization is caused by the addition of vinyl acetate.
Eksempel 2 Example 2
En blanding av 100 vektsdeler vinylformiat og 2,5 henholdsvis 10 vektpst. vinylacetat ble tilsatt 0,275 vektsdel triethyl-bor og 0,656 vektsdel benzoylperoxyd. De erholdte blandinger ble polymerisert ved 0° C i nitrogenatmosfære i 17 timer. Omdannelse var henholdsvis 44,2 pst., 35,7 eller 34,9 pst. Reaksjonsblandingens fluidi-tet under polymeriseringen ble i høy grad øket ved tilsetning av en liten mengde vinylacetat og polymeriseringen lot seg gjennomføre under opprettholdelse av fluiditeten og uten at der utfeltes polymerisat under polymeriseringens forløp. Av de erholdte polymerisater ble der fremstillet polyvinylalkoholer og film bestående av disse viste en svellegrad i vann ved 30° C på henholdsvis 1,09 og 1,15 eller 1,13. Disse verdier er praktisk talt de samme som svellegraden (0,94) for polyvinylalkoholer erholdt fra samme polymerisater fremstillet uten tilsetning av vinylacetat. Når polymeriseringen ble fortsatt opp til en omdannelse på 68,5 pst. uten tilsetning av vinylacetat, var svellegraden for polyvinylalkoholer erholdt fra polymerisatene så høy som 2,21 på grunn av geldannelse. i A mixture of 100 parts by weight of vinyl formate and 2.5 and 10 parts by weight respectively. vinyl acetate was added 0.275 part by weight of triethyl boron and 0.656 part by weight of benzoyl peroxide. The mixtures obtained were polymerized at 0° C. in a nitrogen atmosphere for 17 hours. Conversion was respectively 44.2 per cent, 35.7 or 34.9 per cent. The fluidity of the reaction mixture during the polymerization was greatly increased by adding a small amount of vinyl acetate and the polymerization could be carried out while maintaining the fluidity and without precipitation polymerized during the course of the polymerization. Polyvinyl alcohols were produced from the polymers obtained and films consisting of these showed a degree of swelling in water at 30° C of 1.09 and 1.15 or 1.13, respectively. These values are practically the same as the degree of swelling (0.94) for polyvinyl alcohols obtained from the same polymers produced without the addition of vinyl acetate. When the polymerization was continued up to a conversion of 68.5% without the addition of vinyl acetate, the degree of swelling of polyvinyl alcohols obtained from the polymers was as high as 2.21 due to gelation. in
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT5181571 | 1971-07-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| NO136988B true NO136988B (en) | 1977-08-29 |
| NO136988C NO136988C (en) | 1977-12-07 |
Family
ID=11275784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO2574/72A NO136988C (en) | 1971-07-22 | 1972-07-19 | DOOR FURNITURE. |
Country Status (16)
| Country | Link |
|---|---|
| US (1) | US3823510A (en) |
| JP (1) | JPS4835504A (en) |
| AR (1) | AR198288A1 (en) |
| AT (1) | AT329634B (en) |
| BE (1) | BE786569A (en) |
| BR (1) | BR7204855D0 (en) |
| CA (1) | CA987357A (en) |
| CH (1) | CH560293A5 (en) |
| DE (1) | DE2235909A1 (en) |
| ES (1) | ES405039A1 (en) |
| FI (1) | FI53611C (en) |
| FR (1) | FR2146888A5 (en) |
| GB (1) | GB1355597A (en) |
| NL (1) | NL7210159A (en) |
| NO (1) | NO136988C (en) |
| SE (1) | SE391555B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5071994A (en) * | 1973-11-09 | 1975-06-14 | ||
| JPS5824547B2 (en) * | 1974-03-29 | 1983-05-21 | シノダ シロウ | Zenji Douna Senki |
| JPS5124353U (en) * | 1974-07-30 | 1976-02-23 | ||
| DE2448043C2 (en) * | 1974-10-09 | 1982-08-26 | Dr. C. Otto & Comp. Gmbh, 4630 Bochum | Mobile service trolleys on the coke side of coking furnace batteries |
| US4133140A (en) * | 1975-11-14 | 1979-01-09 | Devices Development Corporation | Safety mechanism for highway exit ramp |
| US5466088A (en) * | 1994-01-24 | 1995-11-14 | Nasatka; Ralph G. | Vehicle barrier having a pivotal vehicle barricade and a cooperating pivotal signal barrier |
| US5440838A (en) * | 1994-05-24 | 1995-08-15 | Lesser; Christopher M. | Motorized vertical lift gate |
| DE10222633C1 (en) * | 2002-05-17 | 2003-08-21 | Dieter Funke | Access barrier for restricted area has barrier elements pivoted between closed and open positions by displacement of spring-loaded rod coupled between operating axes of associated pivot levers |
| IL160055A (en) * | 2004-01-26 | 2006-07-05 | Moshe Levy | Adjustable safety gate which can be opened to the upward direction of a stairway |
| WO2017064540A1 (en) * | 2015-10-16 | 2017-04-20 | Gomez, Oscar | Retractable vehicle barrier |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US592013A (en) * | 1897-10-19 | martin | ||
| US1997199A (en) * | 1930-11-20 | 1935-04-09 | Louis H Pranger | Railway crossing gate |
| US2606022A (en) * | 1948-05-18 | 1952-08-05 | Nat Pneumatic Co Inc | Door operation and control |
| FR1234259A (en) * | 1959-05-13 | 1960-10-17 | Mineur Becourt | Barrier or swing door control device |
-
1972
- 1972-07-19 GB GB3383072A patent/GB1355597A/en not_active Expired
- 1972-07-19 NO NO2574/72A patent/NO136988C/en unknown
- 1972-07-20 FI FI2066/72A patent/FI53611C/en active
- 1972-07-20 SE SE7209545A patent/SE391555B/en unknown
- 1972-07-20 BE BE786569A patent/BE786569A/en unknown
- 1972-07-20 AR AR243175A patent/AR198288A1/en active
- 1972-07-21 ES ES405039A patent/ES405039A1/en not_active Expired
- 1972-07-21 CA CA147,716A patent/CA987357A/en not_active Expired
- 1972-07-21 CH CH1093972A patent/CH560293A5/xx not_active IP Right Cessation
- 1972-07-21 NL NL7210159A patent/NL7210159A/xx not_active Application Discontinuation
- 1972-07-21 DE DE2235909A patent/DE2235909A1/en active Pending
- 1972-07-21 BR BR004855/72A patent/BR7204855D0/en unknown
- 1972-07-21 JP JP47072638A patent/JPS4835504A/ja active Pending
- 1972-07-24 US US00274421A patent/US3823510A/en not_active Expired - Lifetime
- 1972-07-24 AT AT635372A patent/AT329634B/en not_active IP Right Cessation
- 1972-07-24 FR FR7226592A patent/FR2146888A5/fr not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| AU4484472A (en) | 1974-01-24 |
| NO136988C (en) | 1977-12-07 |
| CH560293A5 (en) | 1975-03-27 |
| JPS4835504A (en) | 1973-05-25 |
| BR7204855D0 (en) | 1973-07-19 |
| AR198288A1 (en) | 1974-06-14 |
| NL7210159A (en) | 1973-01-24 |
| FI53611C (en) | 1978-06-12 |
| FI53611B (en) | 1978-02-28 |
| CA987357A (en) | 1976-04-13 |
| FR2146888A5 (en) | 1973-03-02 |
| US3823510A (en) | 1974-07-16 |
| ES405039A1 (en) | 1975-07-16 |
| ATA635372A (en) | 1975-08-15 |
| BE786569A (en) | 1972-11-16 |
| SE391555B (en) | 1977-02-21 |
| DE2235909A1 (en) | 1973-02-15 |
| AT329634B (en) | 1976-05-25 |
| GB1355597A (en) | 1974-06-05 |
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