SE124278C1

SE124278C1 -

Info

Publication number: SE124278C1
Authority: SE
Publication date: 1949-01-01

Description

Uppfinnare: J. A. van Melsen. Inventor: J. A. van Melsen.

Prioritei begard frdn, derb 29 februari 1944 (Nederlanderna). Prioritei begard frdn, derb 29 February 1944 (Netherlands).

Det r kant att sammanfora kautschuk med snth mangder maleinsyraanhydrid blandningsvalsar vid rumstemperatur, Le Bras (C. r. 212, 616 (1941), Rev. Gen du Caoutchow, 19, 43 (1942). Darvid uppkomma pro- dukter med en starkt minskad affinilet liii de vanliga losningsmedlen for kautschuk. De walla daligt eller i mindre grad i alifatiska kolvaten och bensol, medan kautschuk, SOM plasticerats i valsverk utan maleinsyraanhyd- rid, loser sig fullstandigt dari. Detta andrade fOrhallande till kolvaten tyder p5, att bryggbindningar bildats mellan kautschukmolekylerna, yarigenom uppkommit ett material, vil- ket liksonu fenolformaldebydhartser ager en mer eller mindre tredimensionell struktur. Reaktionsprodukten är dá awn mycket mind-re omattad an kautschuk. It is possible to combine rubber with small amounts of maleic anhydride mixing rollers at room temperature, Le Bras (C. r. 212, 616 (1941), Rev. Gen du Caoutchow, 19, 43 (1942)). affinilet liii the usual solvents for rubber. the rubber molecules, resulting in a material which, like phenol-formaldehyde resins, forms a more or less three-dimensional structure, and the reaction product is then much less unsaturated than rubber.

Av brittiska patentet us 507 996 framgar, att lcautschuk och maleinsyraanhydrid Oxen kunna bringas att reagera i losningsmedel i narvaro av peroxider som katalysator, medan ej flagon reaktion intrader utan derma katalysator. British patent us 507 996 states that lcautschuk and maleic anhydride Taurus can be reacted in solvents in the presence of peroxides as catalyst, while no flake reaction enters without this catalyst.

R. G. R. Bacon och E. H. Farmer, Rubber Chem, and Techn. 12. 200-209 (1939) be- skriva narmare detta slags produkter, varvid del visar sig, att vid derma reaktion med kautschuk sons utgangsmaterial uppkommer en forlust av ()manacle bindningar, vilken Or ungelar ekvivalent med den i rimier uttryckta mangden av den upptagna maleinsyraanhyd- Aden. Reaktionsprodukten, som per grund- molekyl CJis bar upptagit en mol maleinsyraanhydrid, dr alltsa mattad, medan de pro- dukter, som ago mindre maleinsyra, visa en minskning av antalet omattade bindningar, vilken motsvarar mangden upptagen maleinsyraanbydrid. R. G. R. Bacon and E. H. Farmer, Rubber Chem, and Techn. 12. 200-209 (1939) describe this kind of product in more detail, in which case it appears that in this reaction with the starting material of the rubber son there arises a loss of () manacle bonds, which Or gels equivalent to the amount of the uptake of maleic anhydride. The reaction product, which has taken up one mole of maleic anhydride per basic molecule CJis, is thus saturated, while the products which previously had less maleic acid show a reduction in the number of unsaturated bonds, which corresponds to the amount of maleic anhydride taken up.

Det liar yisat sig, att ytterligare en annan reaktionsprodukt kan Midas Indian. a ena sidan kautschuk eller hogmolekylalra, omattade, kautschukartade kolvaten med en mole kylvikt av mer an 5000 och Sandra sidan maleinsvraanhydrid. Harfor bringas kautschuk oels maleinsyraanhydrid att reagera med varandra utan tillsats av 16sningsmcdel och/eller katalysator, yarvid man lampligen arbetar utan lufttilltrade for att forebygga oxideringsreaktioner. Reaktionen sker lampligen Triennia 120 och 220° C, doer: ej under 100° C och ej Over 2° C. Under 120° C sker -visserligen annu en reaktion, men denim fdrsig;gar ytterst langsamt, medan yid hogre temperatur den termiska stabilitelen inskranker fOrfarandets genomforbarhet. It liar yisat itself, that yet another reaction product may Midas Indian. on the one hand rubber or high molecular weight, unsaturated, rubbery hydrocarbons with a mole cooling weight of more than 5000 and Sandra side maleic anhydride. For this purpose, the maleic anhydride of the rubber and the reaction of the maleic anhydride are reacted without the addition of a solvent and / or catalyst, while operating without an air vent to prevent oxidation reactions. The reaction takes place suitably in Triennia 120 and 220 ° C, doer: not below 100 ° C and not above 2 ° C. restricts the feasibility of the procedure.

Utom med kautschuk kan maleinsyraanhydrid aven bringas att reagera med guttaperka eller andra naturliga eller syntetiska, omattade, kautschukartade, hOgmolekyliira kolvaten. Utom med maleinsyraanhydrid kan en liknande reaktion kamma till stand med andra omattade amuen, sons uppvisa en C—C eller CC-bindning i lionjugation med en eller flera C=0-bindningar, alltsâ gruppering- enellerC-0, sasom alfa-beta-omiittade aldehyder, ketoner, syror, syraanhydrider och estrar av acetylendikarbonsyra. In addition to rubber, maleic anhydride can also be reacted with gutta-percha or other natural or synthetic, unsaturated, rubber-like, high molecular weight carbohydrates. Except with maleic anhydride, a similar reaction may occur with other unsaturated amines, which may exhibit a C-C or CC bond in lion judging with one or more C = O bonds, i.e. grouping or C-0, such as alpha-beta aldehydes, ketones, acids, acid anhydrides and esters of acetylenedicarboxylic acid.

Exempel 1. Example 1.

ForsOk 1. 35 g Lint sdnderskuren kautschuk OverfOres i ett glasror med 98 g maleinsyraanhydrid °els Innen i roret uldrives med kvitve, varefter roret tillsmaltes och halles vid en temperatur av 150° C under lva Hinman Den erhallna rha reaktionsprodukten upphettas for avlagsnande av den icke omsatta maleinsyraanhydriden till 70-100° C vid 0,1 Min tryck tills konstant vikt uppnatts. Av elementaranalys framgick, att reaktionsprodukten inneballer 0,15 moles maleinsyraanbydrid per grundmolekyl kautschuk, d. v. s. grundmolekylen CH, med en dubbelbindning. Experiment 1. 35 g Lint sdnderskuren rubber Transfer to a glass tube with 98 g maleic anhydride ° Inside the tube is driven with wool with twine, after which the tube is melted and kept at a temperature of 150 ° C under Hinman. reacted the maleic anhydride to 70-100 ° C at 0.1 min pressure until constant weight is reached. Elemental analysis showed that the reaction product contained 0.15 moles of maleic acid anhydride per base molecule kautschuk, i.e. the base molecule CH, with a double bond.

Forsok 2. En upprepning av alla betingelser i f5rsok 1 med undantag av upphettningstiden, som okades till 4 timmar -yid 150° C, 9 — — mule en produkt med 0,4 moler inaleinsyraanhydrid per grundmolekyl kautschuk. Experiment 2. A repetition of all the conditions of Experiment 1 with the exception of the heating time, which was increased to 4 hours at 150 DEG C., a product containing 0.4 moles of inalic anhydride per base molecule of rubber.

Fors5k 1 Upphettning under 4 timmar 'id 1700 G lamnade en reaktionsprodukt med 1,o moler maleinsyraanhydrid per grundmolekyl kautschuk. Experiment 1 Heating for 4 hours at 1700 g left a reaction product with 10 moles of maleic anhydride per base molecule of rubber.

Exempel 2. 7 g kautschuk och 29 g acetylendikarbonsyradimetylester lions yid en temperatur av 160° C under en timme. Reaktionsprodukten renades genom losning i kloroform och utfallning med metylalkohol och torkades sedan yid 70° C och 0,i mm tryek. Av clementaranalys framgick, att slutprodukten innebailer 0,27 moler acetylendikarbonsyra per grundmolekyl kautschuk. Example 2. 7 g of rubber and 29 g of acetylenedicarboxylic acid dimethyl ester ions at a temperature of 160 ° C for one hour. The reaction product was purified by dissolving in chloroform and precipitating with methyl alcohol and then dried at 70 ° C and 0 mm in pressure. Clementar analysis showed that the final product contained 0.27 moles of acetylenedicarboxylic acid per base molecule of rubber.

Exempel 3. 35 g aggvitefattig kautschuk upphettades med 56 g akrolein, som stabiliserats med 0,19 g hydrokinon, i eft tillsmalt ror under 2 timmar i kyayeatmosfar yid 170° C. Darpâ uttvattades produk ten en gang med eter och torkades. Reaktionsprodukten inne 11611 0,35 moler akrolein per grundmolekyl kautschuk. Example 3. 35 g of low-grade white rubber was heated with 56 g of acrolein, stabilized with 0.19 g of hydroquinone, in a further stirred tube for 2 hours in a cooling atmosphere at 170 ° C. The product was then diluted once with ether and dried. The reaction product contains 11611 0.35 moles of acrolein per base molecule of rubber.

Liksom yid de produkter, som erhallits enligt de kanda forfarandena, aVtar jodtalet yid addition ay maleinsyraanhydrid till kautschuk enligt uppfinningen. I motsats till dessa produkter forblir antalet omattade‘ bindningar, raknat pa reaktionsproduktens grundmolekvl konstant, d. v. s. grundmolekylen innehaller en dubbelbindning, gar over i en grundmolekyl av reaktionsprodukten som likaledes ager en dubbelbindning. Produkternas struktur ãr analog med den, som de produkter aga, vilka erhallits genom inyerkan ay maleinsyraanhydrid ph lagmolekylara alkencr (franska patentet nr 713 802 och K. Alder, Ber. 76, 27 (1943)) och identifierats som alkenylbarnstenssyraanhydrider. Forloppet av reaktionen mellan kautschuk och maleinsyraanhydrid kan formuleras enligt foljande: CH3 [—CH, — C — CH --- CH, — CH, H I C3I1202 — CH2 C = C CH --0 C 0 11.2C o De erhallna produkterna aro alltefter den upptagna mangden maleinsyraanhydrid mjukt kautschukartade till myeket styya. Sistniimnda produkter uppvisa dock yid syallning i oil-ha vatskor eller id upphettning till Nigro temperatur a-ter elastiska egenskaper och bOra betecknas som termoelastiska. As with the products obtained according to the known procedures, the iodine value is added by the addition of maleic anhydride to the rubber according to the invention. In contrast to these products, the number of unsaturated 'bonds', calculated on the base molecule of the reaction product, remains constant, i.e. the base molecule contains a double bond, passes into a base molecule of the reaction product which likewise acts as a double bond. The structure of the products is analogous to that of the products obtained by inerting maleic anhydride with low molecular weight alkenes (French Patent Nos. 713,802 and K. Alder, Ber. 76, 27 (1943)) and identified as alkenyl succinic anhydrides. The course of the reaction between rubber and maleic anhydride can be formulated as follows: CH 3 [—CH, - C - CH --- CH, - CH, HI C the absorbed amount of maleic anhydride softly rubbery to much styya. The latter products, however, exhibit yid sewing in oil-ha waders or id heating to Nigro temperature a-ter elastic properties and bOra are termed thermoelastic.

De nya produkterna kunna anyandas direkt eller efter vulkanisering -yarvid kautschukartat material med sarskilda egenslcaper erhalles, eller efter upplosning, varyid produkterna anydndas for lackandamal. De kunna dessutom anyandas som rainaterial for framstallning av andra den-vat, varvid syraanhydridresten Juin omsattas med I. ex. rotten, alkohol, ammoniak, aminer o. dyl., medan yid dubbelbindningen additionsreaktioner kunna genomfOras eller genom reaktionsbendgna reagens nya element eller grupper inforas. The new products can be used directly or after vulcanization - in which case rubber-like material with special properties is obtained, or after dissolution, the products can be used for paint and paint. They can also be used as raw material for the production of other denvates, the acid anhydride residue Juin being reacted with I. ex. rat, alcohol, ammonia, amines and the like, while the double bond addition reactions can be carried out or new elements or groups are introduced by reactive reagents.

Claims

Patent claim:

1. Set up to produce reaction products from natural or synthetic rubber or high-polymer, rubber-like, natural or synthetic hydrocarbons having a molecular weight of more than 5000 on one side and unmalted substances on the other side, characterized therefrom, or containing one or more times In this case the grouping -C = C --- C = 0 or -C ETC and all are brought to react with each other at a temperature of 120 '- 220 ° C in the absence of catalysts and solvents.

Salt according to patent claim 1, characterized in that the unsaturated substances constitute anhydrides and unilated, dibasic acids, in particular maleic anhydrides. Stockholm 1349.Roktr. P. A. Norstctit & Socer 490099