IT8147864A1 - PROCEDURE FOR THE PRODUCTION OF 0-TRIMETHYLSYL CELLULOSE. - Google Patents
PROCEDURE FOR THE PRODUCTION OF 0-TRIMETHYLSYL CELLULOSE. Download PDFInfo
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- IT8147864A1 IT8147864A1 IT1981A47864A IT4786481A IT8147864A1 IT 8147864 A1 IT8147864 A1 IT 8147864A1 IT 1981A47864 A IT1981A47864 A IT 1981A47864A IT 4786481 A IT4786481 A IT 4786481A IT 8147864 A1 IT8147864 A1 IT 8147864A1
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- Prior art keywords
- cellulose
- production
- solution
- trimethylchlorosilane
- trimethylsilylcellulose
- Prior art date
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- 229920002678 cellulose Polymers 0.000 title claims description 31
- 239000001913 cellulose Substances 0.000 title claims description 28
- 238000000034 method Methods 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 230000008961 swelling Effects 0.000 claims description 7
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 7
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 229920000742 Cotton Polymers 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 235000010980 cellulose Nutrition 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000012454 non-polar solvent Substances 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical compound CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- -1 tettahydrofuran Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Description
D E S C R I Z I O N E D E L L ' I N V E N Z I O N E D E S C R I Z I O N E D E L L 'I N V E N Z I O N E
A V E N T E P E R T I T O L O A V E N T E P E R T I T O L O
"Procedimento per la produzione di "Process for the production of
O-trimetilsililcellulose." O-trimethylsilylcellulose. "
La presente invenzione si riferisce ad un procedimento per la produzi?ne di O-trimetilsililcellulose attraverso il trattamento di cellulosa di cotone o di legno con mez zi di rigonfiamento della cellulosa, in particolare basi contenenti azoto attraverso la reazione con trimetilc?orosilano ed il di scioglimento del prodotto ottenuto in un solvente organico come pure l'utilizzazione del procedimento nella produzione di nuove O-trimetilsililcellulose con un grado di sostituzione (DS) al di sotto di 2. The present invention relates to a process for the production of O-trimethylsilylcellulose through the treatment of cotton or wood cellulose with cellulose swelling means, in particular nitrogen-containing bases through the reaction with trimethyl? Orosilane and di dissolution of the product obtained in an organic solvent as well as the use of the process in the production of new O-trimethylsilylcelluloses with a degree of substitution (DS) below 2.
Vennero gi? effettuate diverse prove sperimentali per la si1i1izzazione di gruppi ossidrilici liberi della cellulo sa nelle posizioni 2, 3 e 6 delle unit? di anidroglucosio, Did they come already? carried out several experimental tests for the si1i1ization of free hydroxyl groups of the cell in the positions 2, 3 and 6 of the units. of anhydroglucose,
I procedimenti fino ad ora noti miravano allo scopo di ottenere trimetilsilil rispettivamente altri di - e triorganosilderivati della cellulosa, che sono solubili in solventi non polari. Questo scopo pu?1 essere ottenuto soltanto attraverso la produzione di prodotti aventi un DS medio per quanto possibile elevato, vale a dire attraverso la sililizzazione possibilmente di tutti e tre i gruppi ossidrilici per unit? di anidroglucosio. The up to now known processes aimed at obtaining trimethylsilyl respectively other di- and triorganosyl derivatives of cellulose, which are soluble in non-polar solvents. This aim can only be achieved through the production of products having an average DS as high as possible, that is to say through the sililization, if possible, of all three hydroxyl groups per unit. of anhydroglucose.
G. Keilich ed altri (Makromol Chem. 120 (1968) 87-95) pro ducevano fra l'altro per la prima volta 2,3,6-tris-0-trimetilsilil-cellulosa a partire da cellulosa di cotone nativa di un grado di polimerizzazione media di peso medio (DPw) di approssimetivamente 5800. La cellulosa veniva fatta reagire dopo il rigonfiamento in atmosfera di azoto G. Keilich et al. (Makromol Chem. 120 (1968) 87-95) produced among other things for the first time 2,3,6-tris-0-trimethylsilyl-cellulose from native cotton cellulose of one grade average weight polymerization (DPw) of approximately 5800. The cellulose was reacted after swelling in a nitrogen atmosphere
con una soluzi?ne acquosa di NaOH dello 0,5% con eccesso with an aqueous solution of NaOH of 0.5% with excess
di trimetilclorosilano in piridina. La risultante tris-O-trimetil -cel lulosa (0-TMS-cellulosa, I) era solubile soltanto in solventi non polari, come ad esempio n-esano of trimethylchlorosilane in pyridine. The resulting tris-O-trimethyl-cellulose (0-TMS-cellulose, I) was soluble only in non-polar solvents, such as n-hexane
e cicloesano e poteva essere separata per precipitazione and cyclohexane and could be separated by precipitation
da questa soluzione con etanolo. Tetraidrofurano (THF), diossano, benzolo, toluolo e cloroformio determinavano soltanto un rigonfiamento di (I). Keilich ed altri ha nno anche gi? constatato che questa 0-TMS-ce-lulosa ? sostanzialmente meno sensibile all'idrolisi che non eventualmen te gli 0-TMS-glucosi. Cosi' ad esempio l'idrolisi di un from this solution with ethanol. Tetrahydrofuran (THF), dioxane, benzene, toluene and chloroform caused only a swelling of (I). Keilich and others have already nno already? found that this 0-TMS-ce-lulosa? substantially less sensitive to hydrolysis than possibly 0-TMS-glucoses. Thus for example the hydrolysis of a
gruppo TMS per componente nella O-TMS-cellulosa avviene attraverso K2CO3 in metanolo soltanto dopo 75 minuti alla temperatura di 50?C. Una completa desililizzazione avviene in queste condizioni soltanto dopo una bollitura per TMS group by component in O-TMS-cellulose occurs through K2CO3 in methanol only after 75 minutes at a temperature of 50 ° C. A complete desililization takes place in these conditions only after boiling for
tre ore in condizioni a ricadere. three hours in reflux conditions.
Ugualmente 0-TMS-cellulose solubili in idrocarburi alifatici e aromatici, eventualmente clorurati, che contengono Equally 0-TMS-cellulose soluble in aliphatic and aromatic hydrocarbons, possibly chlorinated, which contain
per unit? di anidroglucosio da 2 a 3 gruppi di 0-TMS, sono prodotti del procedimento secondo la US-PS 3418312, se condo il quale la cellulosa viene aggiunta ad una miscela composta di trimetilclorosilano, di una mono- o disaccar per unit? of anhydroglucose from 2 to 3 groups of 0-TMS, are products of the process according to US-PS 3418312, according to which the cellulose is added to a mixture composed of trimethylchlorosilane, a mono- or disacchar
de, di un solvente e di una ammina terziaria. de, a solvent and a tertiary amine.
La US-PS 3418313 si riferisce alla produzione di 0-TMS-cellulosa con le medesime caratteristiche di solubilit? attraverso 1'aggiunta di trimetilclorosilano puro - ottenuto attraverso la reazione di esametildisilazano con acido cloridrico anidro - ad una miscela di cellulosa, di una ammina terziaria e di un solvente. US-PS 3418313 refers to the production of 0-TMS-cellulose with the same characteristics of solubility? through the addition of pure trimethylchlorosilane - obtained through the reaction of hexamethyldisilazane with anhydrous hydrochloric acid - to a mixture of cellulose, a tertiary amine and a solvent.
J. Nagy ed altri (Period. Poiytechn.Che; Eng. 18? 91-98 (1972)) sceglievano per la si1i1izzazione di cellofane utilizzato come una sostanza di modello esametildisilazano in piridina in presenza di quantitativi catalitici di trimetilclorosilano . Il prodotto ottenuto era solubile in toluolo. I dati contrastanti nella letteratura in riguardo al comportamento di solubilit? di derivati cellulosici sililizzati con trialchilclorosilani in solventi organici vengono indicati in questa pubblicazione. J. Nagy et al. (Period. Poiytechn.Cche; Eng. 18? 91-98 (1972)) chose for the silization of cellophane used as a model substance hexamethyldisilazane into pyridine in the presence of catalytic quantities of trimethylchlorosilane. The obtained product was soluble in toluene. The conflicting data in the literature regarding the solubility behavior? of cellulosic derivatives sililized with trialkylchlorosilanes in organic solvents are indicated in this publication.
Nel corso delle proprie ricerche venne riconosciuto il fatto che 0-trimetilsilil-cellulose vengono idrolizzate attraverso quantitativi di piccola entit?, ancora presenti nelle condizioni della produzione di sali acidi in pre senza dell'umidit? dell'aria in maniera rapida ed in conseguenza di ci?' diventano insolubili. Siffatti prodotti per questa ragione non sono capaci di resistere al magazzinaggio e pertanto sono inappropriati per l'impiego ind? striale. Soluzioni di cellulose sililizzate, che possono essere utilizzate ad esempio eventualmente per la produzione di articoli sagomati da cellulosa rigenerata, sono troppo instabili e sono soggette ad alterazioni. In the course of his research it was recognized that 0-trimethylsilyl-cellulose are hydrolyzed through small quantities, still present in the conditions of the production of acid salts in the presence of humidity. of the air quickly and as a result of that? ' become insoluble. For this reason, such products are not capable of withstanding storage and are therefore inappropriate for industrial use. strial. Solutions of sililized cellulose, which can be used for example possibly for the production of shaped articles from regenerated cellulose, are too unstable and are subject to alterations.
La presente invenzione si pone il problema di evitare gli inconvenienti in precedenza descritti e creare 0-trimetilsilil-cellulose che si possono maneggiare in maniera non complicata con caratteristiche di solubilit? riproducibili. The present invention poses the problem of avoiding the drawbacks described above and creating 0-trimethylsilyl-cellulose which can be handled in an uncomplicated manner with solubility characteristics. reproducible.
Per la soluzione di questo problema nel caso di un procedimento del genere in precedente definito si procede in tale maniera che al prodotto di reazione grezzo disciolto nel solvente organico viene aggiunto un reagente basico, preferibilmente carbonato di sodio, per neutralizzare i sali acidi ancora presenti in piccoli quantitativi, dopo di che le sostanze solide vengono rimosse dalla soluzione e viene fatta precipitare eventualmente dalla soluzione di trimetilsilil-cellulosa e viene elaborata per ottenere un preparato solido. For the solution of this problem, in the case of a procedure of the kind defined above, one proceeds in such a way that a basic reagent, preferably sodium carbonate, is added to the raw reaction product dissolved in the organic solvent, to neutralize the acid salts still present in small quantities, after which the solid substances are removed from the solution and eventually precipitated from the trimethylsilyl-cellulose solution and processed to obtain a solid preparation.
Le O-TMS-cellulose con un DS al di sotto di 2 sono nuove. Queste nuove O-TMS-cellulose vengono prodotte con applica zione del procedimento secondo l'invenzione per il fatto che la cellulosa fatta rigonfiare viene fatta reagire con meno di 2,0 mol di trimetilclorosilano per mol di unit? di anidroglucosio della cellulosa. O-TMS-celluloses with a SD below 2 are new. These new O-TMS-celluloses are produced by applying the process according to the invention in that the swollen cellulose is reacted with less than 2.0 mol of trimethylchlorosilane per mol of unit. of anhydroglucose of cellulose.
Sono noti appropriati mezzi di rigonfiamento della cellulosa, in qualit? di base contenente azoto viene vantaggio semente utilizzata la piridina. Suitable cellulose swelling means are known, in quality? pyridine is advantageously used as a nitrogen-containing base.
In qualit? di solventi per le cellulose sililizzate grezze vanno presi in considerazione solventi polari, come ad esempio dimetilformammide (DMF), dimetilacetammide (DMA), N-meti1pirrol idone (NMP), dimeti1solfossido (DMSO), tetra idrofurano (THF), ma anche idrocarburi non polari come ad esmepio quelli alitatici e aromatici, eventualmente aloge nati. Pi? ? elevato il valore di DS di 0-TMS cellulose, tanto migliore sar? la solubilit? delle medesime in sol-, venti non polari rispettivamente solventi debolmente pola ri. Prodotti con un valore di DS intorno a 2 si disciolgo no in solventi debolmente polari, come THF, mentre cellulose sililizzate, che presentano un DS di approssimativamente 1,5 e al di sotto di esso, si sciolgono soltanto ancora in solventi fortemente polari. In quality? of solvents for crude sililized cellulose polar solvents, such as dimethylformamide (DMF), dimethylacetamide (DMA), suitable N-methyl pyrrol (NMP), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), but also non-hydrocarbons polar such as alitatic and aromatic ones, possibly halogenated. Pi? ? the higher the DS value of 0-TMS cellulose, the better it will be? the solubility? of the same in non-polar solvents respectively weakly polar solvents. Products with a DS value of around 2 dissolve in weakly polar solvents, such as THF, while sililized celluloses, which have a DS of approximately 1.5 and below it, only dissolve again in strongly polar solvents.
All'infuori del carbonato di sodio possono venire utilizzati per la neutralizzazione anche altri reagenti basici, come ad esempio carbonati dei metalli alcalini residui, dei carbonati acidi di metalli alcalino-terrosi come pure carbonati o ossidi di metalli alcalino-terrosi. Other than sodium carbonate, other basic reagents can also be used for neutralization, such as carbonates of residual alkali metals, acid carbonates of alkaline earth metals as well as carbonates or oxides of alkaline earth metals.
In qualit? di precipitanti vengono utilizzati opportunamente alcooli, preferibilmente alcanoli, come metanolo, e tanolo, n- e o-propanolo come pure butanoli. Per la separazione per precipitazione di 'prodotti di alta siiilizzazione ? ad esempio appropriato anche acetone. In quality? of precipitants, alcohols, preferably alkanols, such as methanol, and tanol, n- and o-propanol as well as butanols, are suitably used. For the separation by precipitation of high siiilization products? for example acetone is also appropriate.
Nei seguenti esempi il procedimento secondo la presente invenzione verr? illustrato pi? dettagliatamente. In the following examples the process according to the present invention will be described illustrated more? in detail.
ESEMPIO 1: EXAMPLE 1:
Produzione di O-trimetilsilil-cellulosa con DS 2,65. Production of O-trimethylsilyl-cellulose with DS 2.65.
In un matraccio a tre colli avente una capacit? di 100 ml, attrezzato con elementi di agitazione e di organi di raffreddamento a ricadere, che si trova in cominicazione attraverso un tubo a secco con l'atmosfera circostante, vengono preparati 2 g (12,34 mMol) di cellulosa e 50 mi di piridina anidra e la miscela viene riscaldata per la dura ta di quattro ore a ricadere. Dopo di ci? 6 g (55,6 mMol) di trimetilclorosilano vengono aggiunti goccia a goccia alla temperatura ambiente ed il contenuto del matraccio viene agitato per la durate di tre ore. Attraverso l'aggiunta di metanolo viene ridotto il rigonfiamento della sililcellulosa e la sostanza sililizzata viene sottoposta ad un lavaggio con metanolo dopo l'aspirazione. Il prodot^ to grezzo cosi' ottenuto viene disciolto in petroletere e viene ripreso con approssimativamente 0,1 g di carbonato di sodio per neutralizzare i piccoli quantitativi ancora presenti di idrocloruro di'piridinio, che altrimenti sareb bero sufficienti per determinare l'idrolizzazione della cellulosa siiliizzata. La soluzione viene sottoposta ad u ne centrifugazione o filtraggio sotto pressione e la 0-TMS cellulosa viene fatta precipitare dalla soluzione chiara risultante con etanolo. Dopo l'essiccamento sotto vuoto spinto si ottiene un prodotto di colore bianco solubile in solventi non polari, come ad esempio idrocarburi, o in eteri, come ad esempio tettaidrofurano. In a three-necked flask having a capacity of 100 ml, equipped with stirring elements and reflux cooling elements, which is in communication through a dry tube with the surrounding atmosphere, 2 g (12.34 mMol) of cellulose and 50 ml of pyridine are prepared anhydrous and the mixture is heated for the duration of four hours under reflux. After that? 6 g (55.6 mMol) of trimethylchlorosilane are added drop by drop at room temperature and the contents of the flask are shaken for three hours. Through the addition of methanol the swelling of the silylcellulose is reduced and the sililized substance is subjected to a washing with methanol after aspiration. The crude product thus obtained is dissolved in petroleum jets and taken up with approximately 0.1 g of sodium carbonate to neutralize the small quantities of pyridinium hydrochloride still present, which would otherwise be sufficient to determine the hydrolyzation of the cellulose. siiliized. The solution is subjected to centrifugation or filtration under pressure and the 0-TMS cellulose is precipitated from the resulting clear solution with ethanol. After drying under high vacuum, a white colored product is obtained which is soluble in non-polar solvents, such as hydrocarbons, or in ethers, such as tettahydrofuran, for example.
Resa: 3,75 g (85% del teorico), Analisi: Si: 21%, DS: 2,65. Yield: 3.75 g (85% of theoretical), Analysis: Yes: 21%, DS: 2.65.
ESEMPIO 2: EXAMPLE 2:
2 g (12,34 mMol) di cellulosa di piridina vengono riscaldati fino al punto di ebollizione a ricadere per la durata di 4 ore allo scopo di ottenere il rigonfiamento. Immediatamente dopo vengono aggiunti 2,2 g (20,37 mMol) di trimetilclorosi lano goccia a goccia e si protrae la reazione per la durata di 3 ore alla temperatura ambiente. Attraverso l'aggiunta di metanolo viene ridotto il rigonfiamento, il prodotto viene sottoposto ad aspirazione e viene lav?to con metanolo. Per la depurazione il prodotto viene disciolto in DMF. I piccoli quantitativi ancora pre senti di idrocloruro di piridinio vengono neutralizzati attraverso l'aggiunta di carbonato di potassio e la soluzione viene sottoposta ad una centrifugazione e filtraggio sotto pressione. La sililcellulosa viene fatta precipitare con acqua dalla soluzione chiara e viene essiccata. 2 g (12.34 mMol) of pyridine cellulose is heated to the reflux boiling point for the duration of 4 hours in order to achieve swelling. Immediately afterwards 2.2 g (20.37 mMol) of trimethylchlorosis are added drop by drop and the reaction is continued for the duration of 3 hours at room temperature. By adding methanol, swelling is reduced, the product is subjected to suction and washed with methanol. For purification the product is dissolved in DMF. The small quantities still present of pyridinium hydrochloride are neutralized by adding potassium carbonate and the solution is subjected to centrifugation and filtration under pressure. The silylcellulose is precipitated with water from the clear solution and dried.
Resa: 2,9 g (88% del teorico), Si: 14,7 DS: 1,37. Yield: 2.9 g (88% of theoretical), Si: 14.7 SD: 1.37.
La presente invenzione ? stata illustrata e descritta in alcune sue preferite forme di pratica realizzazione, ma si intende che varianti esecutive potranno ad essa in pratica apportarsi senza peraltro uscire dall?ambito di protezione del presente brevetto per invenzione industriale. The present invention? has been illustrated and described in some of its preferred embodiments, but it is understood that executive variations may in practice be applied to it without however departing from the scope of protection of the present patent for industrial invention.
Claims (3)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT0110780A AT364860B (en) | 1980-02-28 | 1980-02-28 | METHOD FOR PRODUCING O-TRIMETHYLSILYL CELLULOSES |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| IT8147864A0 IT8147864A0 (en) | 1981-02-20 |
| IT8147864A1 true IT8147864A1 (en) | 1982-08-20 |
| IT1170745B IT1170745B (en) | 1987-06-03 |
Family
ID=3506736
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IT47864/81A IT1170745B (en) | 1980-02-28 | 1981-02-20 | PROCEDURE FOR THE PRODUCTION OF O-TRIMETILSILICELLULOSE |
Country Status (5)
| Country | Link |
|---|---|
| AT (1) | AT364860B (en) |
| DE (1) | DE3104530A1 (en) |
| FR (1) | FR2477158A1 (en) |
| GB (1) | GB2070613B (en) |
| IT (1) | IT1170745B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4390692A (en) * | 1982-06-21 | 1983-06-28 | The Dow Chemical Company | Trimethylsilylation of cellulose |
| DE3232467A1 (en) * | 1982-09-01 | 1984-03-01 | Hoechst Ag, 6230 Frankfurt | METHOD FOR PRODUCING CELLULOSE ETHERS WITH IMPROVED DISPERSION BEHAVIOR |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2562955A (en) * | 1948-05-07 | 1951-08-07 | Hartwig A Schuyten | Silicon containing derivatives of cellulosic material |
| GB671721A (en) * | 1949-02-23 | 1952-05-07 | Dow Corning Ltd | Improvement in organo-silicon derivatives of cellulose |
-
1980
- 1980-02-28 AT AT0110780A patent/AT364860B/en not_active IP Right Cessation
-
1981
- 1981-02-09 DE DE19813104530 patent/DE3104530A1/en not_active Withdrawn
- 1981-02-11 GB GB8104183A patent/GB2070613B/en not_active Expired
- 1981-02-20 IT IT47864/81A patent/IT1170745B/en active
- 1981-02-24 FR FR8103656A patent/FR2477158A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| IT1170745B (en) | 1987-06-03 |
| GB2070613B (en) | 1983-09-01 |
| ATA110780A (en) | 1981-04-15 |
| AT364860B (en) | 1981-11-25 |
| FR2477158A1 (en) | 1981-09-04 |
| IT8147864A0 (en) | 1981-02-20 |
| GB2070613A (en) | 1981-09-09 |
| DE3104530A1 (en) | 1981-12-03 |
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