GB2070612A - Method of producing O-trimethylsilyl celluloses - Google Patents
Method of producing O-trimethylsilyl celluloses Download PDFInfo
- Publication number
- GB2070612A GB2070612A GB8104148A GB8104148A GB2070612A GB 2070612 A GB2070612 A GB 2070612A GB 8104148 A GB8104148 A GB 8104148A GB 8104148 A GB8104148 A GB 8104148A GB 2070612 A GB2070612 A GB 2070612A
- Authority
- GB
- United Kingdom
- Prior art keywords
- celluloses
- cellulose
- ammonia
- trimethylchlorosilane
- reacting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920002678 cellulose Polymers 0.000 title claims abstract description 50
- 235000010980 cellulose Nutrition 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000001913 cellulose Substances 0.000 claims abstract description 27
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000005051 trimethylchlorosilane Substances 0.000 claims abstract description 12
- 239000000047 product Substances 0.000 claims abstract description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- 238000001556 precipitation Methods 0.000 claims abstract description 5
- 238000006467 substitution reaction Methods 0.000 claims abstract description 5
- 230000008961 swelling Effects 0.000 claims abstract description 5
- 239000003880 polar aprotic solvent Substances 0.000 claims abstract description 4
- 229920000742 Cotton Polymers 0.000 claims abstract description 3
- 239000002023 wood Substances 0.000 claims abstract description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 14
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- -1 aliphatic ethers Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 18
- 239000002904 solvent Substances 0.000 abstract description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 abstract description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 abstract description 3
- 229960001760 dimethyl sulfoxide Drugs 0.000 abstract description 3
- 229940113088 dimethylacetamide Drugs 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- OEERIBPGRSLGEK-UHFFFAOYSA-N carbon dioxide;methanol Chemical compound OC.O=C=O OEERIBPGRSLGEK-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- LWFWUJCJKPUZLV-UHFFFAOYSA-N n-trimethylsilylacetamide Chemical compound CC(=O)N[Si](C)(C)C LWFWUJCJKPUZLV-UHFFFAOYSA-N 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-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
- 229910008338 Si—(CH3) Inorganic materials 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 238000005828 desilylation reaction Methods 0.000 description 1
- 150000002016 disaccharides Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000001727 glucose Nutrition 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000001483 monosaccharide substituent group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000002166 wet spinning Methods 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
Landscapes
- 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)
Abstract
A method of producing O-trimethylsilyl celluloses having a degree of substitution of up to 2.0 includes the steps of swelling wood or cotton cellulose in anhydrous, liquid ammonia, reacting it with trimethylchlorosilane, dissolving the reaction product in a strongly polar aprotic solvent, and, if desired, processing it into a dry product by precipitation. Suitable solvents are dimethyl formamide, dimethyl acetamide, N-methyl pyrrolidone and dimethylsulphoxide.
Description
SPECIFICATION
Improvements in or relating to a method of producing novel O-trimethylsilyl celluloses
The invention relates to a method of producing novel O-trimethylsilyl celluloses having a degree of substitution of up to 2.0, preferably 1.4 to 1.6.
Various experiments have been carried out in order to silylate the free hydroxy groups of
cellulose in the positions 2,3 and 6 of the
anhydroglucose units.
The studies performed so far in this field were
aimed at obtaining trimethylsilyl and other di- and tri-organosilyl derivatives of cellulose, which are
soluble in apolar solvents. The desired solubility
properties could be observed only with products in which, in the statistical median, at least two
hydroxy groups per anhydroglucose units had
been silylated, i.e. with products having a mean
degree of substitution (DS) of 2 to 3, possibly
over 2.5.
G. Keilich et al. (Makromol. Chem. 120 (1968), 87-95) for the first time produced, among others, 2,3,6-tris-0-trimethylsilyl cellulose of
native cotton cellulose having a mean-weight
average degree of polymerisation (DPw) of about
5,800. After bucking the cellulose was reacted in
pyridine under nitrogen with a 0.5% aqueous
NaOH solution containing an excess of trimethylchlorosilane. The resulting tris-0trimethylsilyl cellulose (O--TMS cellulose, I) was soluble only in apolar solvents, such as n-hexane
and cyclohexane, and precipitable from these
solutions with ethanol. Tetrahydrofuran (THF),
dioxane, benzene, toluene and chloroform
merely cause a swelling of (I).Keilich et al. also
found out that this O--TMS cellulose is
considerably less sensitive to hydrolysis than e.g.
O--TMS glucoses. Thus, the hydrolysis of a TMS
group per unit in the O--TMS cellulose takes
place by K2CO3 in methanol only after 75 minutes
at 50 C. A complete desilylation under these
conditions occurs only after three hours of boiling
under reflux.
OTMS celluloses which are also soluble in
aliphatic and aromatic, if desired chlorinated,
hydrocarbons and which contain2 to 3 O-TMS groups per anhydroglucose unit are products from
the method according to U.S. Patent No.
3,418,312, according to which cellulose is added
to a mixture of trimethylchlorosilane, a mono or
disaccharide, a solvent and a tertiary amine.
U.S. Patent No. 3,418,313 relates to the
production of O--TMS celluloses with the same
solubility properties by the addition of pure trimethylchlorosilane - prepared by reacting
hexamethyldisilazane with anhydrous hydrogen chloride -- to a mixture of cellulose, a tertiary
amine, and a solvent.
According to U.S. Patent No. 3,432,488
organosilylated celluloses having a degree of
substitution (DS) of between 2 and 3 are obtained
by the reaction of a cellulose material with an
organosilylamide and/or a silazane in N
alkylpyrrolidone or hexamethyl phosphoric acid triamide; the actually produced O-trimethylsilyl celluloses had a DS of 2.6 and 2.73.
K. Bredereck and Colleagues (Makromolekulare
Chem. 126(1969), 139-146) equally used
N-trimethylsilylacetamide as a silylating agent in tetraline or cyclohexanon for cellulose regenerated from cellulose acetate or native cellulose. When reacting cellulose in an N-trimethylsilylacetamide melt, a DS of 2.95 was obtained. The unusual stability of the O--TMS celluloses against hydrolysis is stressed also by these authors.
J. Nagy et al. (Period. Polytechn. Chem. Eng.
18,91-98, 1972) chose hexamethyldisilazane in pyridine in the presence of catalytic amounts of trimethylchlorosilane for the silylation of
Cellophane (Registered Trade Mark) used as a model substance. The product obtained was soluble in toluene. In this publication the discrepancy of bibliographical data referring to the solubility behaviour of cellulose derivatives silylated with trialkylchlorosilanes in organic solvents was pointed out.
R. E. Harmon and Colleagues (Carbohydrate
Research, 81(1973), 407-409) reacted various polysaccharides with hexamethyldisilazane in formamide at 700C and, among others, obtained tris-0-trimethylsi lyl cellulose by precipitating the reaction products with anhydrous acetone, which cellulose was soluble in benzene, toluene and chloroform.
None of the O-trimethylsilyl celluloses produced so far was soluble in polar solvents. It has not been possible to seriously take into consideration the processing of such solutions into shaped bodies of regenerated cellulose on a larger scale, since solutions in apolar solvents cannot be processed, for instance, according to the conventional wet-spinning methods by using aqueous regenerating baths.
The invention has as its object to provide a method of producing O-trimethylsilyl celluloses that are soluble in polar solvents, in particular solvents mixable with water, and for which celluloses of different degrees of polymerisation and of any desired origin can be used as starting materials. The invention is based on the knowledge that O-trimethylsilyl celluloses with a
DS of up to 2.0, preferably 1.4 to 1.6, do meet the solubility demands mentioned.
The object set is achieved with a method of producing substituted celluloses of the indicated
DS in that wood or cotton celluloses are swollen in anhydrous, liquid ammonia, then reacted with trimethylchlorosilane, the reaction product is dissolved in a strongly polar aprotic solvent and, if desired, is processed to a dry product by precipitation.
As strongly polar aprotic solvents dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone (NMP), dimethylsulphoxide (DMSO) may be used.
The silylation reaction in the presence of ammonia occurs via the intermediarily forming hexamethyldisilazane [(CH3)3-Si-NH-Si-(CH3)31. An embodiment of the method according to the invention therefore may consist in adding preformed hexamethyidisilazane to the cellulose swollen with ammonia.
As precipitating agents water, aliphatic ethers or aromatic hydrocarbons may be used. Water is preferred.
However, it is also possible to obtain 0trimethylsilyl celluloses in a dry state by evaporating the solvent, instead of precipitating it from the solvent.
Suitably, ammonia is removed by heating and evacuation after the reaction of the swollen cellulose with trimethylchlorosilane. Ammonia may be removed also by neutralisation. An extensive removal of ammonia is significant for the hydrolytic stability and thus the handling ability of trimethylsilyl celluloses.
The reaction product advantageously is purified by being dissolved in dimethylacetamide or dimethylformamide and by separation of the insoluble ammonium chloride.
For the method of the invention, celluloses having a mean average degree of polymerisation of about 30 to about 3,000 may be used.
The amount of trimethylchlorosilane, based on the amount of cellulose used, is of no relevance; even with relatively large stoichiometric excesses of trimethylchlorosilane, products are obtained in any case whose DS is below 2.
The method according to the invention will now be explained in more detail by the following examples.
EXAMPLE 1
Production of O-trimethylsilyl cellulose with DS 1.46.
Into a three-necked flask having a volume of 100 ml and equipped with a stirrer, an introduction tube and a methanol dry-ice bath, 2 g (12.34 mmole) of cellulose are fed and 50 ml of ammonia dried over solid KOH and calcium chips are condensed in. Thereafter, swelling is allowed to take place at this temperature for another
1/2 hour to 1 hour. Then 4 g (37.04 mmole) of trimethylchlorosilane are added by dropping and the mixture is allowed to react over night at the same temperature. The ammonia is evaporated by slowly heating the mixture, the final residues are removed by appiying a water jet vacuum with a drying cartridge filled with KOH interposed during 3 to 4 hours. If there is still too much ammonia present, hydrolysis and precipitation may take place already during the subsequent dissolution procedure.
By the addition of 100 ml of DMA, the silyl cellulose is dissolved and the insoluble ammonium chloride is removed by centrifugation or filtering.
The product is precipitated with water, sucked off and washed with water to be free of chloride. If the chloride is not removed by washing, the silyl cellulose is at least partly hydrolysed during the subsequent drying step in a high vacuum.
Yield: 3 g (90% of theory), Si: 15.3%, DS: 1.46.
EXAMPLE 2
Into a three-necked flask having a volume of 200 ml and equipped with a stirrer, an introduction tube and a methanol dry-ice bather 2 g (12.34 mmole) of cellulose are fed and 50 ml of dry ammonia are condensed in. After half an hour of swelling, 12 g (111.12 mmole) of trimethylchlorosilane are added by dropping and the reaction mixture is allowed to react over night.
Excess ammonia is extensively evaporated by heating, the final residues are sucked off by a pump. By the addition of 100 ml of DMF the silyl cellulose is dissolved, filtered from insoluble ammonium chloride, precipitated with water, sucked off, and washed with water to be free of chloride.
Yield: 3.1 g (about 90% of theory), Si: 15.5%, DS: 1.50.
EXAMPLE 3
2 g (12.34 mmole) of cellulose were swollen in liquid ammonia in a manner analogous to
Examples 1 and 2, and reacted with 6 g (37.27 mmole) of hexamethyldisilazane. After the stripping of ammonia the remaining residue is dissolved in DMF for purification. From the filtered solution the silyl cellulose is obtained in a solid state by precipitation with water, washing, and drying.
Yield: 3.1 g (93% of theory), Si: 15.0%, DS:
1.42.
The silylated celluloses produced according to the invention are soluble in the polar solvents mentioned, up to concentrations of about 16% by weight. The viscosities of the solutions depend on the DPs of the celluloses used. With DP-values of about 400, they range between 30,000 and 32,000 cP, thus being excellently suited, for instance, for spinning.
Claims (8)
1. A method of producing novel O-trimethylsilyl celluloses having a degree of substitution of up to 2.0, preferably 1.4 to 1.6, which method comprises swelling wood or cotton celluloses in anhydrous, liquid ammonia, reacting it with trimethylchlorosilane, dissolving the reaction product in a strongly polar aprotic solvent, and, if desired, processing it into a dry product by precipitation.
2. A method according to claim 1, wherein water, aliphatic ethers, or aromatic hydrocarbons are used as precipitating agents.
3. A method according to claim 1, wherein, after reacting the swollen cellulose with trimethylchlorosilane, ammonia is removed by heating and evacuation.
4. A method according to claim 1, wherein, after reacting the swollen cellulose with trimethylchlorosilane, ammonia is removed by neutralisation.
5. A method according to claims 1 to 4, wherein the reaction product is purified by dissolution in dimethylacetamide and separation of the insoluble ammonium chloride.
6. A modified embodiment according to claim 1 , wherein celluloses swollen with ammonia are reacted with preformed hexamethyldisilazane.
7. A method substantially as hereinbefore described with reference to Examples 1 and 2.
8. A modified embodiment substantially as hereinbefore described with reference to
Example 3.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT0110680A AT364859B (en) | 1980-02-28 | 1980-02-28 | METHOD FOR PRODUCING NEW O-TRIMETHYLSILYL CELLULOSES |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2070612A true GB2070612A (en) | 1981-09-09 |
| GB2070612B GB2070612B (en) | 1983-09-01 |
Family
ID=3506714
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8104148A Expired GB2070612B (en) | 1980-02-28 | 1981-02-11 | Method of producing o-trimethylsilyl celluloses |
Country Status (5)
| Country | Link |
|---|---|
| AT (1) | AT364859B (en) |
| DE (1) | DE3104531A1 (en) |
| FR (1) | FR2477157A1 (en) |
| GB (1) | GB2070612B (en) |
| IT (1) | IT1170744B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4474950A (en) * | 1982-09-01 | 1984-10-02 | Hoechst Aktiengesellschaft | Cellulose ethers having improved dispersing properties |
| JPH06340687A (en) * | 1993-03-23 | 1994-12-13 | Rhone Poulenc Rhodia Ag | Silyation of carbohydrate and use of silylated carbohydrate |
| US6555678B1 (en) * | 1997-10-27 | 2003-04-29 | Rhodia Acetow | Method for preparing a regenerated cellulose fibre or yarn |
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 |
| EP1630280A1 (en) * | 2004-08-31 | 2006-03-01 | Ciba Spezialitätenchemie Pfersee GmbH | Process for the treatment of textile fabrics |
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 AT0110680A patent/AT364859B/en not_active IP Right Cessation
-
1981
- 1981-02-09 DE DE19813104531 patent/DE3104531A1/en not_active Withdrawn
- 1981-02-11 GB GB8104148A patent/GB2070612B/en not_active Expired
- 1981-02-20 IT IT47863/81A patent/IT1170744B/en active
- 1981-02-24 FR FR8103655A patent/FR2477157A1/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4474950A (en) * | 1982-09-01 | 1984-10-02 | Hoechst Aktiengesellschaft | Cellulose ethers having improved dispersing properties |
| JPH06340687A (en) * | 1993-03-23 | 1994-12-13 | Rhone Poulenc Rhodia Ag | Silyation of carbohydrate and use of silylated carbohydrate |
| JP2622666B2 (en) * | 1993-03-23 | 1997-06-18 | ローネ−ポウレンク ローディア アクチェンゲゼルシャフト | Carbohydrate silylation method |
| US6555678B1 (en) * | 1997-10-27 | 2003-04-29 | Rhodia Acetow | Method for preparing a regenerated cellulose fibre or yarn |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2070612B (en) | 1983-09-01 |
| IT8147863A0 (en) | 1981-02-20 |
| ATA110680A (en) | 1981-04-15 |
| AT364859B (en) | 1981-11-25 |
| DE3104531A1 (en) | 1981-12-03 |
| IT1170744B (en) | 1987-06-03 |
| FR2477157A1 (en) | 1981-09-04 |
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