GB2065545A - Coagulating regenerated cellulose fibres and films - Google Patents
Coagulating regenerated cellulose fibres and films Download PDFInfo
- Publication number
- GB2065545A GB2065545A GB8038039A GB8038039A GB2065545A GB 2065545 A GB2065545 A GB 2065545A GB 8038039 A GB8038039 A GB 8038039A GB 8038039 A GB8038039 A GB 8038039A GB 2065545 A GB2065545 A GB 2065545A
- Authority
- GB
- United Kingdom
- Prior art keywords
- cellulose
- process according
- regenerated
- tertiary amine
- alcoholic groups
- 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.)
- Withdrawn
Links
- 230000001112 coagulating effect Effects 0.000 title claims abstract description 14
- 239000004627 regenerated cellulose Substances 0.000 title claims abstract description 7
- 229920003043 Cellulose fiber Polymers 0.000 title 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 48
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920002678 cellulose Polymers 0.000 claims abstract description 19
- 239000001913 cellulose Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 15
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 18
- 238000009835 boiling Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229940113088 dimethylacetamide Drugs 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 230000008929 regeneration Effects 0.000 abstract description 6
- 238000011069 regeneration method Methods 0.000 abstract description 6
- 229920001223 polyethylene glycol Polymers 0.000 abstract description 2
- 239000002202 Polyethylene glycol Substances 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 25
- 229910001868 water Inorganic materials 0.000 description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 235000019256 formaldehyde Nutrition 0.000 description 11
- 150000001412 amines Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920002556 Polyethylene Glycol 300 Polymers 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000001143 conditioned effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- -1 e.g. methanol Chemical compound 0.000 description 1
- JUWSSMXCCAMYGX-UHFFFAOYSA-N gold platinum Chemical compound [Pt].[Au] JUWSSMXCCAMYGX-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001976 hemiacetal group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing 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
- C08B16/00—Regeneration of cellulose
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Textile Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Artificial Filaments (AREA)
- Detergent Compositions (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
In a process for the preparation of formed bodies of regenerated cellulose from solutions of methylol derivatives of cellulose in an organic solvent, (eg dimethyl formamide, dimethylacetamide, dimethylsulphoxide and N-methylpyrrolidone) the cellulose derivative is coagulated and partially or totally regenerated, from its solution in the solvent, in a coagulating bath which comprises a tertiary amine and a component having free alcoholic groups in its molecule, e.g. a polyethylene glycol or methanol. The presence of the tertiary amines permits to increase the speed of cellulose regeneration from the methylol derivative.
Description
SPECIFICATION
Process for the preparation of formed bodies of regenerated cellulose from solutions of cellulose derivatives in organic solvents
In British Application No. 80 1 2765 of the same Applicant a process has been described and claimed for the preparation of formed bodies of regenerated cellulose from solutions of methylol derivatives of cellulose in an organic solvent chosen among dimethylformamide (DMF), dimethylacetamide (DMAC), dimethylsulphoxide and N-methylpyrrolidone, characterized in that the cellulose derivative is coagulated, from said solutions, in a coagulating bath comprising as main component a high boiling alcohol which is capable of combining with free (para)formaldehyde and with combined (para)formaldehyde contained in the methylol derivative, to a degree which varies depending on the temperature.
As preferred high boiling alcohols, polyethylene glycols have been indicated.
It has now been found, and this is the object of the present invention, that if tertiary amines, i.e. amines which do not contain reactive hydrogen atoms, are present in the coagulating bath, the speed of the regeneration of the cellulose from the methylol derivative is considerably increased, which is extremely advantageous from a process viewpoint. Further, it is clearly advantageous from a general technical viewpoint to be table to control the regeneration speed of the cellulose and this is made possible from its methylol derivative, by the use of tertiary amines together with coagulating and regenerating agents.
The invention is therefore characterized in that, in a process of the aforementioned type, a coagulating bath is employed which contains as active component, or as an element of a mixture of active components, a tertiary amine, in the additional presence of free alcoholic groups. Said alcoholic groups may derive from another component of the bath, such as one of the alcohols indicated in the previously cited application or an alcohol which is not high boiling, such as e.g. methanol, which is indicated as component of regenerating and coagulating baths in said copending Application or said alcoholic groups may be included together with the amino groups of the tertiary amine, in a single molecule.
A typical tertiary amine not containing alcoholic groups is triethylamine, while a typical tertiary amine containing alcholic group is triethanolamine.
The percentages of amine contained in the bath in which it is mixed with alcohols, depends from the desired regeneration speed and may vary within very wide limits, e.g., from 1 to 50%.
On the other hand, if a tertiary amine is employed which already contains alcoholic groups, such as triethanolamine, the bath may contain from 1 to 99 of amine.
Of course, the coagulating baths always contain a more or less high percentage of the spinning solvent, which may be one those previously indicated in said copending Application although dimethylacetamide is preferred in principle, and they may contain amounts of water between 0 and 50%.
If the alcoholic groups are carried by a high boiling alcohol, the advantage is obtained that the formaldehyde may be recovered more easily from the coagulating baths, merely by the thermal decomposition of the hemiacetal which forms from formaldehyde and alcoholic groups.
The coagulating temperatures vary according to the components emplyed. If e.g. a trimaine is employed in combination with a high boiling alcohol, the temperatures vary from about 65'C to the boiling temperature of the amine.
If a triamine is employed in combination with a low boiling alcohol, such as e.g. methanol, the temperatures vary from O"C to 50"C.
If a trimaine is employed which contains free alcoholic groups, such as triethanolamine, the temperatures vary from 65"C to 160"C.
A number of embodiments of the invention will now be described for illustrative purposes, without intending any limitation of the invention.
EXAMPLES 1-12
40.5 parts of prehydrolized cellulose obtained by the sulphite process (DP=500), dried to a water content below 0.6%, and 90 part of (para)formaldehyde containing 95% of CH2O, are charged into a closed laboratory reactor with 370 parts of DMAC containing less than 0.07% of water, and are brought to about 140"C, under efficient stirring, for 30-60 minutes. A clear solution is obtained, from which part of the formaldehyde and of the DMAC are eliminated by heating to 115-1 20 C while maintaining the reactor open.
Viscous solutions are obtained with cellulose contents varying from 9 to 1 1% and CH2O contents varying from 4 to 8%, depending on the time during which formaldehyde and DMAC have been eliminated, which time may vary from 30 to 90 minutes.
Said viscous solutions are cooled and filtered, and are extruded through gold-platinum spinnerets having 1 20 orifices with a diameter of 80 micron, into baths having variable compositions and temperatures. The filaments obtained are drawn in air at room temperature, and are washed in H20 at different temperatures, until the CK2O and DMAC are totally eliminated.
Hereinafter the compositions of a number of spinning, drawing and post-treatment (regeneration and/or washing) baths are indicated.
Composition and temperature
Example ("C) of the spinning bath % Drawing Post-treatment 1) Triethanolamine 80 up to 90% H20, 25 C DMAC 20 90"C 2) Triethanolamine 70 up to 80% H2O, 60 C DMAC 30
100 C 3) Methanol 80 up to 50% H20, 50 C Triethanolamine 20 30"C 4) Methanol 70 up to 100% H20, 25 C
Triethanolamine 15
DMAC 15 20 C 5) Triethanolamine 20 up to 110% H20, 50 C DMAC 20
Methanol 60 25 C 6) Triethylamine 10 up to 40% H2O, 60 C
DMAC 45
Methanol 45 25 C 7) Triethylamine 10 up to 100% H2O, 80 C PEG 300 90 65"C 8) Triethylamine 10 up to 300% H20, 70 C PEG 300 60
DMAC 30 65"C 9) Triethanolamine 50 up to 120% H20, boiling
H20 50 95 C 10) Triethanolamine 65,8 up to 380% H2O, 50 C H20 28
DMAC 6,2
80 C 11) Triethanolamine 3
H20 3 up to 400% H20 boiling
DMAC 3 80 C 12) PEG 300 65 up to 320% H20 60 C Triethanolamine 10
DMAC 25
80 C
The yarns obtained according to examples 1-12 have round cross-sections and good mechanical characteristics.
Typicai numerical characteristics of the products obtained are:
Count 1.5-3 deniers
Tenacity in che conditioned state . up to 2 g/den
Elongation in the conditioned state 20-30%
Tenacity in the wet state up to 1 g/den
Elongation in the wet state 30-50%
Loop tenacity up to 0.7 g/den
EXAMPLES 13-17
A viscous solution of cellulose having a concentration of about 10% in DMAC, prepared substantially as described in the preceding examples, has been smeared to form a thin layer on glass plates, and the plates have been subsequently immersed at room temperature into coagulating baths containing various ratios of methanol to triethanolamine content, until the coagulated films become completely detached from the glass plates. It has been possible to detach ail films after 10-30 seconds of immersion.
Said films have been then washed twice with cooled methanol and the molar ratio CH2O/cellulose has been determined thereon by titrating the total CH2O with sodium sulphite and weighing said films after treatment with sulphite and drying.
Said molar ratio may be taken as an inverse index of the cellulose regeneration speed.
The results are tabulated hereinafter.
CH20 (Mols)
Example Coagulating bath on coagulated films
CELLULOSE
(anhydroglucosidic units) 13) CH30H 100% 2.68-2.69 14) CH30H 95% 1.17-1.22
Triethanolamine 5% 15) CH3OH 80% 0.89-0.64
Triethanolamine 20% 16) CHH 70% 0.54-0.58
Triethanolamine 30% 17) CH3OH 50% 0.40-0.25
Triethanolamine 50%
Claims (11)
1. A process for the preparation of formed bodies of regenerated cellulose from solutions of methylol derivatives of the cellulose in an organic solvent chosen in the group consisting of dimethylformamide, dimethyl-acetamide, dimethylsulphoxide and N-methylpirrolidone, characterized in that the cellulose derivative is coagulated and partially or totally regenerated, from its solution in said solvent, in a coagulating bath comprising a tertiary amine and further a component having free alcoholic groups in its molecule.
2. A process according to Claim 1, characterized in that the tertiary amine and the component which comprises alcoholic groups are two different substances.
3. A process according to Claim 1, characterized in that the component containing alcoholic groups is chosen in the group consisting of polyethylenglycols and methanol.
4. A process according to Claim 1, characterized in that the tertiary amine is also the component having alcoholic groups in its molecule.
5. A process according to Claim 4, characterized in that the tertiary amine is triethanolamine.
6. A process according to Claim 1, characterized in that the alcoholic groups are contained in a high boiling alcohol.
7. A process for the preparation of formed bodies of regenerated cellulose, substantially as described.
8. Regenerated bodies of cellulose, obtained by the process according to Claim 1.
9. A process for the preparation of a formed body of regenerated cellulose from a solution of a methylol derivative of the cellulose in an organic solvent, wherein the cellulose derivative is coagulated and partially or totally regenerated, from its solution in said solvent, in a coagulating bath comprising a tertiary amine and a compound having one or more free alcoholic groups in its molecule.
10. A process according to claim 9, wherein the organic solvent is dimethylformamide, dimethylacetamide, dimethylsulphoxide or N-methylpyrrolidone.
11. A process according to claim 9 or 10, which process includes the limitation(s) of one or more of claims 2 to 6.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT28306/79A IT1194603B (en) | 1979-12-21 | 1979-12-21 | PROCEDURE FOR THE PREPARATION OF BODIES FORMED OF CELLULOSE REGENERATED FROM SOLUTIONS OF CELLULOSE DERIVATIVES IN ORGANIC SOLVENTS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB2065545A true GB2065545A (en) | 1981-07-01 |
Family
ID=11223329
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8038039A Withdrawn GB2065545A (en) | 1979-12-21 | 1980-11-27 | Coagulating regenerated cellulose fibres and films |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS56120701A (en) |
| DE (1) | DE3046676A1 (en) |
| FR (1) | FR2471985A1 (en) |
| GB (1) | GB2065545A (en) |
| IT (1) | IT1194603B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0185813A1 (en) * | 1983-06-03 | 1986-07-02 | Exxon Research And Engineering Company | Method for preparing thin regenerated cellulose membranes of high flux and selectivity for organic liquids separations |
| AT401063B (en) * | 1994-09-05 | 1996-06-25 | Chemiefaser Lenzing Ag | METHOD FOR PRODUCING CELLULOSIC SHAPED BODIES |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0781154B2 (en) * | 1992-08-14 | 1995-08-30 | オイレス工業株式会社 | Sliding member |
| CN101921402B (en) * | 2010-09-21 | 2012-06-27 | 武汉大学 | Method for preparing cellulose membrane by hot-water coagulating bath |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4022631A (en) * | 1975-05-19 | 1977-05-10 | International Telephone And Telegraph Corporation | Process for producing regenerated cellulosic articles |
| US4097666A (en) * | 1976-04-29 | 1978-06-27 | The Institute Of Paper Chemistry | Solvent system for polysaccharides |
-
1979
- 1979-12-21 IT IT28306/79A patent/IT1194603B/en active
-
1980
- 1980-11-27 GB GB8038039A patent/GB2065545A/en not_active Withdrawn
- 1980-12-11 DE DE19803046676 patent/DE3046676A1/en not_active Withdrawn
- 1980-12-17 FR FR8026809A patent/FR2471985A1/en not_active Withdrawn
- 1980-12-18 JP JP17962780A patent/JPS56120701A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0185813A1 (en) * | 1983-06-03 | 1986-07-02 | Exxon Research And Engineering Company | Method for preparing thin regenerated cellulose membranes of high flux and selectivity for organic liquids separations |
| AT401063B (en) * | 1994-09-05 | 1996-06-25 | Chemiefaser Lenzing Ag | METHOD FOR PRODUCING CELLULOSIC SHAPED BODIES |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56120701A (en) | 1981-09-22 |
| IT1194603B (en) | 1988-09-22 |
| FR2471985A1 (en) | 1981-06-26 |
| IT7928306A0 (en) | 1979-12-21 |
| DE3046676A1 (en) | 1981-08-27 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |