SE204433C1

SE204433C1 -

Info

Publication number: SE204433C1
Authority: SE
Publication date: 1965-01-01

Description

Uppfinnare: I Haidasch och J Voss Prioritet begdrd fain den 23 juni ocIt 27 augusti 1959 (Farb undsrepubliken Tyskland) Foreliggande uppfinning avser ett forfarande for framstallning av blandetrar av cellulosa, vilka innehalla allylgrupper. Uppfinningen avser isynnerhet ett forfarande for framstallning av lagringsbestandiga, vattenlosliga cellulosablandetrar, vilka innehalla saval karboximetylgrupper som allylgrupper och som aro polymeriserbara genom tillsattning av katalysatorer. Inventors: In Haidasch and J Voss Priority Required from June 23 and August 27, 1959 (Color Republic of Germany) The present invention relates to a process for the preparation of cellulose blenders containing allyl groups. In particular, the invention relates to a process for the preparation of storage-resistant, water-soluble cellulose blenders which contain both carboxymethyl groups as allyl groups and which are polymerizable by the addition of catalysts.

Det är kant att framstdlla vattenlosliga, polymeriserbara blandetrar av cellulosa pa sá salt, att man fOrst omsatter alkalicellulosa med ett avsevart overskott av etylenoxid och darefter bringar de erhallna vattenlosliga, i utspadd natronlut losta oxietyletrarna av cellulosa, att reagera med allylbromid. Detta forfarande fir ofordelaktigt, emedan till foljd av den avsevarda fortvalningen av allylbromiden genom den vattenhaltiga alkaliska losningen endast en liten del av den insatta allylbromiden tas i ansprak for f8retringen av cellulosan. Dessutom erfordras stora mangder losningsmedel, for att allylblandetrarna av cellulosan skola erhallas ur losningarna i vdI filtrerbar form. De sh utvunna blandetrarna aro ej bestandiga i luft och bli redan efter fa dagar vattenolosliga ph grand av polymerisation. Viskositeten hos de vattenhaltiga losningarna av dessa etrar är lag. It is possible to prepare water-soluble, polymerizable mixtures of cellulose on the salt by first reacting alkali cellulose with a considerable excess of ethylene oxide and then causing the resulting water-soluble, in dilute sodium hydroxide solution to dissolve the oxyethyl ethers of cellulose to react with allyl bromide. This process is disadvantageous, because due to the considerable pre-digestion of the allyl bromide by the aqueous alkaline solution, only a small part of the inserted allyl bromide is used for the digestion of the cellulose. In addition, large amounts of solvents are required for the allyl mixers of the cellulose to be obtained from the solutions in a filterable form. The mixed meters are not resistant to air and become water-insoluble in polymerization after only a few days. The viscosity of the aqueous solutions of these ethers is low.

Foreliggande uppfinning avser ett satt att i hogt utbyte framstalla allylgrupphaltiga cellulosa-blandetrar, som ge hogviskOsa vattenlosningar. Enligt det nya flirfarandet erhaller man utan svarighet cellulosa-blandetrar, av vilka en 2-proc. losning i vatten vid unders8kning i en Hoppler-viskosimeter vid 20°C upp visar en viskositet mellan 500 och 20000 cP. Farfarandet enligt uppfinningen lannetecknas ddrav, att man samtidigt eller i godtycklig ordningsfoljd efter varandra bringar cellulosa och alkalihydroxid att reagera med a ena sidan halogendttiksyra eller ett vattenlosligt salt av denna syra och ft andra sidan med en allylhalogenid, vid temperaturer under 110°C. The present invention relates to a process for producing, in high yield, allyl group-containing cellulose mixtures which give highly viscous aqueous solutions. According to the new procedure, cellulose mixers are obtained without responsibility, of which a 2-percent. solution in water when examined in a Hoppler viscometer at 20 ° C shows a viscosity between 500 and 20,000 cP. The process according to the invention is characterized in that cellulose and alkali hydroxide are reacted simultaneously or in any order one after the other with haloacetic acid or a water-soluble salt of this acid and on the other hand with an allyl halide, at temperatures below 110 ° C.

De enligt fOreliggande fOrfarande framstallda cellulosablandetrarna utmArka sig for god vattenloslighet och hog viskositet. Vid lagring forbli de vattenlosliga under rang tid, och ej heller forandras deras losningar vid staende i luften, utan gelatinera forst efter tillsattning av ldmpliga katalysatorer, t. ex. redoxsystemet kaliumperoxisulfatnatriumsulfit. Pa grund av dessa egenskaper kunna forfarandeprodukterna med fordel finna anvandning inom mainings- och tryckeritekniken, liksom aven for framstallningen av vattenfasta impregneringar av vdvnader. The cellulose blends prepared according to the present process are characterized by good water solubility and high viscosity. During storage, they remain water-soluble for a long time, nor do their solutions change when standing in the air, but gelatinize only after the addition of suitable catalysts, e.g. redox system potassium peroxysulfate sodium sulfite. Due to these properties, the process products can be used to advantage in the maintenance and printing technology, as well as for the production of waterproof impregnations of fabrics.

Vid arbete enligt forfarandet enligt uppfinningen gar man till vaga pa sa satt, att man forst framstaller alkalisaltet av karboximetylcellulosa och ddrefter omsatter delta med allylhalogenid i narvaro av alkali. Man kan emellertid dven forst framstalla en allylcellulosa och darefter i nOrvaro av alkali ater omsatta denna med alkalisalter av en halogendttiksyra. Enligt uppfinningen dr del dven mojligt att i narvaro av alkali omsatta cellulosan. samtidigt med allylhalogenid och ett alkalisalt av en halogenattiksyra. When working according to the process according to the invention, care is taken in such a way that the alkali salt of carboxymethylcellulose is first prepared and then the delta is reacted with allyl halide in the presence of alkali. However, one can first prepare an allyl cellulose and then in the presence of alkali aters react it with alkali metal salts of a haloacetic acid. According to the invention, it is also possible to react the cellulose in the presence of alkali. simultaneously with allyl halide and an alkali salt of a haloacetic acid.

Om man som utgangsmaterial for allyleringen valjer natriumkarboximetylcellulosa, kan detta pa kant salt framstallas genom hop- 2 blandning av alkalicellulosa med exempelvis natriumhalogenacetat under langre tid vid 30-40°C eller ur alkalicellulosa och natriumkloracetat under tillsattning av losningsmedel, t. ex. butanol. Allyleringen for inforande av allylgrupper genomfores darefter omedelbart i anslutning till reaktionen mellan alkalicellulosa och ett alkalisalt av en halogenattiksyra, t. ex. natriumkloracetat, eller sedan karboximetylcellulosan isolerats i form av sitt natriumsalt, renats och Ater forsatts med alkali. If sodium carboxymethylcellulose is chosen as the starting material for the allylation, this edge salt can be prepared by mixing alkali cellulose with, for example, sodium haloacetate for a long time at 30-40 ° C or from alkali cellulose and sodium chloroacetate with the addition of solvents, e.g. butanol. The allylation for the introduction of allyl groups is then carried out immediately in connection with the reaction between alkali cellulose and an alkali salt of a haloacetic acid, e.g. sodium chloroacetate, or after the carboxymethylcellulose has been isolated in the form of its sodium salt, purified and Ater is added with alkali.

De enligt uppfinningen framstallda karboximetylcellulosaallyletrarna skola lampligen innehalla 0,2-1,0 karboximetylgrupper pa varje glykosenhet, och allylhalten skall lampligen ej Overstiga 1,0 allylgrupper per glykosenhet. The carboxymethylcellulose allylates prepared according to the invention should suitably contain 0.2-1.0 carboxymethyl groups per each glucose unit, and the allyl content should suitably not exceed 1.0 allyl groups per glucose unit.

Karboximetylcellulosaallyletrarna och deras vattenlosliga salter aro polymeriserbara i narvaro av katalysatorer, out de innehalla minst 0,1 allylgrupp per glykosenhet. Det Or fordelaktigt att Oka blandetrarnas halt av allylgrupper utover den minsta mangden, och narmare bestamt desto mera, ju hogre substitutionen av cellulosan tined karboximetylresten Or. Hos en blandeter, som innehMler 1 karboximetylgrupp per glykosenhet, Or det darfor lampligt att infora 0,5-0,8 allylgrupper. For uppnaende av tillracklig vattenloslighet är det lampligt att ej overskrida en viss total substitution av cellulosan. Per glykosenhet skola 0,5 OHgrupper vara besatta av allyl- och karboximetylgrupper, darav minst 0,2 OH-grupper per glykosenhet med karboximetylgrupperna. Sat.- deles gynnsamma loslighets- och polymerisationsforhallanden uppnas hos blandetrar, som i bunden form innehalla 0,2-0,6 karboximetylgrupper och 0,3-0,6 allylgrupper per glykosenhet. The carboxymethylcellulose allyl ethers and their water-soluble salts are polymerizable in the presence of catalysts, provided they contain at least 0.1 allyl group per glucose unit. It Or advantageous to Increase the content of allyl groups of the mixers beyond the minimum amount, and more precisely the more, the higher the substitution of the cellulose tined carboxymethyl residue Or. In a mixed ether containing 1 carboxymethyl group per glucose unit, it is therefore appropriate to introduce 0.5-0.8 allyl groups. In order to achieve sufficient water solubility, it is appropriate not to exceed a certain total substitution of the cellulose. Per glucose unit 0.5 OH groups must be occupied by allyl and carboxymethyl groups, of which at least 0.2 OH groups per glucose unit with the carboxymethyl groups. The favorable solubility and polymerization ratios are obtained in mixed meters, which in bound form contain 0.2-0.6 carboxymethyl groups and 0.3-0.6 allyl groups per glucose unit.

Bildningen av karboximetyleellulosa-allylblandetrar med en bestamd halt av allylgrupper uppnas saval genom anvandning av en bestamd mangd allylhalogenid vid ett Overskott av alkali som genom anvandning av en bestamd alkalimangd med ett overskott av allylhalogenid. Man erhOler cellulosablandetrar med en halt av exempelvis 0,1-0,8 allylgrupper per glykosenhet, om man omsatter ett alkalisalt av en karboximetylcellulosa i narvaro av alkali i overskott, t. ex. 0,3-5,0 mol Na0I-I, med 0,2-2,5 mol allylhalogenid, allt raknat pa en glykosenhet. Alternativt behandlar man alkalisaltet av en karboximetylcellulosa forst med 0,2-2,5 mol alkali och omsatter det darefter med allylhalogenid i godtyckligt overskott. Det ax Oven mojligt att arbeta med ekvimolara mangder av alkali och allylhalogenid, varvid 0,3-2,5 mol av vardera av de hada reaktionskomponenterna anvandas. The formation of carboxymethylellulose-allyl mixtures with a certain content of allyl groups is achieved by the use of a certain amount of allyl halide in an excess of alkali as by the use of a certain amount of alkali with an excess of allyl halide. Cellulose blenders with a content of, for example, 0.1-0.8 allyl groups per glucose unit are obtained if an alkali salt of a carboxymethylcellulose is reacted in the presence of excess alkali, e.g. 0.3-5.0 moles of NaOI-I, with 0.2-2.5 moles of allyl halide, all concentrated on one glucose unit. Alternatively, the alkali salt of a carboxymethylcellulose is first treated with 0.2-2.5 moles of alkali and then reacted with allyl halide in any excess. It is also possible to work with equimolar amounts of alkali and allyl halide, using 0.3-2.5 moles of each of the reactants.

I stallet fOr att utga frau karboximetylcellulosa med en substitutionsgrad av 0,2-1,0 och foretra denna eter vidare med en allylhalogenid, kan man forst ur cellulosa och fritt alkali och allylhalogenid framstalla en cellu- losaallyleter och i narvaro av fritt alkali omsatta denna med ett alkalisalt av en halogen- attiksyra i sadana mangder, att en cellulosa- blandeter med en halt av 0,2-1,0 karboximetylgrupper bildas. Endr allylcellulosor med hogre substitutionsgrad, vilka ej foreligga sa- som blandetrar, ha benagenhet till bryggbildning, Or det lampligt att harfor insatta cellu- losaallyletrar, som ej innehalla mer an 0,a allylgrupper per glykosenhet. Man kan Oven ga tillvaga pa sa satt, att man samtidigt later ett alkalisalt av halogenattiksyra och allylhalogenid, i detta fall lampligen allylbromid, inverka pa cellulosa och fritt alkali. Instead of starting from carboxymethylcellulose having a degree of substitution of 0.2-1.0 and preferring this ether further with an allyl halide, it is first possible to prepare a cellulose allyl from cellulose and free alkali and allyl halide and reacting it in the presence of free alkali. with an alkali salt of a haloacetic acid in such amounts that a cellulose mixture ether with a content of 0.2-1.0 carboxymethyl groups is formed. Allyl celluloses with a higher degree of substitution, which are not present as mixed meters, have a tendency to form bridges. It is appropriate to have cellulose allyl ethers which do not contain more than 0, a allyl groups per glucose unit. It is also possible to proceed in such a way that at the same time an alkali salt of haloacetic acid and allyl halide, in this case suitably allyl bromide, is allowed to act on cellulose and free alkali.

Foretringen av cellulosan intrader, out reaktionskomponenterna blandas vid forhojd, temperatur. Det Or mojligt att till reaktions- komponenterna satta organiska losningsmedel, t. ex. kolvaten, alkoholer med 3-5 kol- atomer, klorerade kolvaten, alkyletrar. Forhal- landet mellan den tillsatta mangden losningsmedel och mangden allylhalogenid bor dock ej valjas alit fOr stort, emedan reaktionstiden blir starkt forlangd, om onodigt mycket losningsmedel finns narvarande 1 reaktions- blandningen. Forfarandet genomfores med fordel vid forhojd temperatur. Vid anvandning av allylbromid Or det lampligt att arbeta vid temperaturer av 45-70°C, i synnerhet Indian 50 och 60°C. Out man sasom fen-- etringsmedel anvander allylklorid, arbetar man med fordel vid hogre temperaturer upp till 110°C och darover, och erhaller sardeles goda resultat vid 70-90°C. Emedan polyme- risation i sarskilt hog grad intrader redan vid temperaturer Over 110°C, ifragakomma fOr forfarandet endast temperaturer upp till 110° C. The etherification of the cellulose enters, the reactants are mixed at elevated temperature. It is possible to add organic solvents to the reactants, e.g. the hydrocarbons, alcohols having 3-5 carbon atoms, chlorinated hydrocarbons, alkyl ethers. However, the ratio between the added amount of solvent and the amount of allyl halide should not be chosen too large, since the reaction time is strongly required if an unnecessary amount of solvent is present in the reaction mixture. The process is advantageously carried out at elevated temperature. When using allyl bromide Is it appropriate to work at temperatures of 45-70 ° C, especially Indian 50 and 60 ° C. When using allyl chloride as a fencing agent, it works advantageously at higher temperatures up to 110 ° C and above, and obtains extremely good results at 70-90 ° C. Since polymerization to a particularly high degree already occurs at temperatures above 110 ° C, only temperatures up to 110 ° C are eligible for the process.

Exempel 1. Till en suspension av 32,4 g pulverformig cellulosa i en av 50 ml vatten och 450 ml isopropanol framstalld losningsmedels- blandning sattes 20 ml 30-viktproc. natronlut och darefter 9,3 g natriummonokloracetat, och reaktionsblandningen varmes under standig omroring 1/2 timme vid 60°C. Sedan reaktionsblandningen avkylts, forsatter man den under ornroring med 48 ml 30-viktproc natronlut och avsuger efter tillrOcklig genomblandningav innehallet 400 ml isopropanol frau reaktionskarlet. Efter tillsattning ay 34,6 ml allylbromid ornrores reaktionsblandningen :niter 3 timmar vid 60°C. Den aterigen avkylda reaktionsblandningen neutraliseras med isattika, avsuges, tvattas saltfri med 80-proc. metanoT och torkas darefter yid 60°C. Utbytet av cel- lulosa-blandeter utgor 36 g. Reaktionsprodukten innehaller 0,22 karboximetylgrupper och 3 0,75 allylgrupper per glykosenhet och kan 10- sas i vatten till en Mar lOsning med hog viskositet. Example 1. To a suspension of 32.4 g of powdered cellulose in a solvent mixture prepared from 50 ml of water and 450 ml of isopropanol was added 20 ml of 30% by weight. sodium hydroxide solution and then 9.3 g of sodium monochloroacetate, and the reaction mixture was heated with constant stirring for 1/2 hour at 60 ° C. After the reaction mixture has cooled, it is continued with stirring with 48 ml of 30% strength by weight sodium hydroxide solution and, after sufficient mixing, 400 ml of isopropanol are filtered off with suction from the reaction vessel. After addition of 34.6 ml of allyl bromide, the reaction mixture is stirred: rivets for 3 hours at 60 ° C. The reactivated reaction mixture is neutralized with glacial acetic acid, filtered off with suction, washed salt-free with 80%. methanoT and then dried at 60 ° C. The yield of cellulose mixtures is 36 g. The reaction product contains 0.22 carboxymethyl groups and 0.75 allyl groups per glucose unit and can be dissolved in water to a high viscosity Mar solution.

Genom tillsattning av redoxkatalysatorer, t. ex. en blandning av kaliumpersulfat och natriumsulfit, till en vattenlosning av blandetern utloses polymerisation. Vid tillsattning av en stone mangd av en lamplig redoxkatalysator undergar vattenlosningen gelbildning. Vid anyandning av mindre mangder forblir vattenlosningen flytande under viss tid, men en ur denna losning, t. ex. paen glasplatta, utgjuten vatskefilm blir daremot vattenolOslig vid torkning men forblir svallbar i vatten. By adding redox catalysts, e.g. a mixture of potassium persulphate and sodium sulphite, to an aqueous solution of the mixture ether polymerization is triggered. Upon addition of a stone amount of a suitable redox catalyst, the aqueous solution undergoes gel formation. When inhaling small amounts, the aqueous solution remains liquid for a certain time, but one from this solution, e.g. on a glass plate, poured liquid film, on the other hand, becomes water-insoluble on drying but remains swellable in water.

Exempel 2. 39 g av den enligt uppgifterna i exempel 1 framstallda, renade och torkade natriumkarboximetylcellulosan dispergeras i en blandning av 450 ml isopropanol och 50 ml vatten. Man tillsatter 20 ml av en 30-viktproc. natronlut och later natronluten inverka 10 min pa karboximetylcellulosan. Darefter avsuges 400 ml isopropanol fran reaktionsblandningen, den alkalihaltiga karboximetylcellulosan utrores med 51,5 ml allylbromid, varefter blandningen, under standig genomblandning varmes 3 tim vid 60°C. Den orena foretringsprodukten upptas i metanol, avsuges och tvattas saltfri med metanol. Man erhaller c:a 41 g av en cellulosa-blandeter med 0,21 karboximetylgrupper och 0,72 allylgrupper per glykosenhet. Cellulosa-blandetern ger med vatten en klar 16sning. Example 2. 39 g of the sodium carboxymethylcellulose prepared, purified and dried according to the data of Example 1 are dispersed in a mixture of 450 ml of isopropanol and 50 ml of water. 20 ml of a 30% by weight process are added. sodium hydroxide solution and allow the sodium hydroxide solution to act on the carboxymethylcellulose for 10 minutes. Then 400 ml of isopropanol are filtered off with suction from the reaction mixture, the alkali-containing carboxymethylcellulose is stirred with 51.5 ml of allyl bromide, after which the mixture is heated for 3 hours at 60 [deg.] C. with continuous mixing. The crude ether product is taken up in methanol, filtered off with suction and washed salt-free with methanol. About 41 g of a cellulose mixture ether with 0.21 carboxymethyl groups and 0.72 allyl groups per glucose unit are obtained. The cellulose mixer gives a clear solution with water.

Exempel 3. 42 g natriumkarboximetylcellulosa med en foretringsgrad av 0,49 karboximetylgrupper per glykosenhet utrores med 300 ml isopropanol och alkaliseras med 44 ml 30-yiktproc. natronlut. Darefter avsuges 200 ml isopropanol. Efter iroring av 75 g allylklorid varmes reaktionsblandningen 1 tim yid 90°C i ett tryckkarl med vent!!. Efter avslutad reaktion avtappas overskottet av allylklorid genom ventilen, varefter reaktionsprodukten avkyles i tryckkarlet. Den bildade cellulosablandetern upptas i metanol, aysuges, tvattas saltfri med metanol och torkas vid 60°C. Man erhaller 40 g av en cellulosa-blandeter med 0,62 allylgrupper och 0,49 karboximetylgrupper per glykosenhet. Cellulosa-blandetern ger i vatten en klar losning. Example 3. 42 g of sodium carboxymethylcellulose with a degree of etherification of 0.49 carboxymethyl groups per glucose unit are stirred with 300 ml of isopropanol and alkalized with 44 ml of 30-strength process. baking soda. Then 200 ml of isopropanol are filtered off with suction. After stirring 75 g of allyl chloride, the reaction mixture is heated for 1 hour at 90 ° C in a pressurized pressure vessel. After completion of the reaction, the excess allyl chloride is drained through the valve, after which the reaction product is cooled in the pressure vessel. The cellulose blender formed is taken up in methanol, aysuges, washed salt-free with methanol and dried at 60 ° C. 40 g of a cellulose mixture ether with 0.62 allyl groups and 0.49 carboxymethyl groups per glucose unit are obtained. The cellulose mixer gives a clear solution in water.

Exempel 4. 35 g cellulosa-allyleter med en halt av 0,3 allylgrupper per glykosenhet uppslammas i en blandning av 450 ml isopropanol och 50 ml vatten och alkaliseras genom tillsattning av 26 ml 30-viktproc. natronlut. Darefter tillsatter man 9,3 g natriummonokloracetat och varmer reaktionsblandningen 1 tim. vid 65°C. Efter avkylning neutraliseras reaktionsblandningen med isattika, aysuges, tvattas saltfri med metanol och torkas yid 60°C. Man erhaller 36 g cellulosa-blandeter med 0,3 allylgrupper och 0,22 karboximetylgrupper per glykosenhet. Cellulosablandetern ger i vat-ten en klar losning. Example 4. 35 g of cellulose allyl ether having a content of 0.3 allyl groups per glucose unit are slurried in a mixture of 450 ml of isopropanol and 50 ml of water and alkalized by adding 26 ml of 30% by weight. baking soda. Then 9.3 g of sodium monochloroacetate are added and the reaction mixture is heated for 1 hour. at 65 ° C. After cooling, the reaction mixture is neutralized with glacial acetic acid, aspirated, washed salt-free with methanol and dried at 60 ° C. 36 g of cellulose mixture ether with 0.3 allyl groups and 0.22 carboxymethyl groups per glucose unit are obtained. The cellulose blender gives a clear solution in the water.

Claims

Patent claim: Process for the preparation of water-soluble, polymerizable mixtures of cellulose, characterized therefrom, all of which, simultaneously or in any order, the cellulose and alkali hydroxide are reacted with A on one side of haloacetic acid or a water-soluble salt of this acid and A on the other side with an allyl halide at temperatures below 110 ° C. Request publications: Patents Iran UK 654 014; USA 2 891 056.