US3719449A - Crosslinked hetercyclic cellulosic products - Google Patents
Crosslinked hetercyclic cellulosic products Download PDFInfo
- Publication number
- US3719449A US3719449A US00248181A US3719449DA US3719449A US 3719449 A US3719449 A US 3719449A US 00248181 A US00248181 A US 00248181A US 3719449D A US3719449D A US 3719449DA US 3719449 A US3719449 A US 3719449A
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- United States
- Prior art keywords
- cotton
- reacted
- cellulose
- crosslinked
- fabrics
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- 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.)
- Expired - Lifetime
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- 229920002678 cellulose Polymers 0.000 abstract description 16
- 239000001913 cellulose Substances 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 abstract description 9
- OGNCVVRIKNGJHQ-UHFFFAOYSA-N 4-(3-pyridin-4-ylpropyl)pyridine Chemical compound C=1C=NC=CC=1CCCC1=CC=NC=C1 OGNCVVRIKNGJHQ-UHFFFAOYSA-N 0.000 abstract description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001294 propane Substances 0.000 abstract description 3
- 229930192474 thiophene Natural products 0.000 abstract description 2
- 229920000742 Cotton Polymers 0.000 description 40
- 241000219146 Gossypium Species 0.000 description 40
- 239000004744 fabric Substances 0.000 description 29
- 238000000034 method Methods 0.000 description 21
- 230000037303 wrinkles Effects 0.000 description 11
- 125000000623 heterocyclic group Chemical class 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000011084 recovery Methods 0.000 description 9
- 239000007921 spray Substances 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- ATSGLBOJGVTHHC-UHFFFAOYSA-N bis(ethane-1,2-diamine)copper(2+) Chemical compound [Cu+2].NCCN.NCCN ATSGLBOJGVTHHC-UHFFFAOYSA-N 0.000 description 6
- 239000004753 textile Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000001143 conditioned effect Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001720 carbohydrates Chemical class 0.000 description 4
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QLVNUZPODFIOGC-UHFFFAOYSA-N 5-bromofuran-2-carbonyl chloride Chemical compound ClC(=O)C1=CC=C(Br)O1 QLVNUZPODFIOGC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- -1 for example Chemical compound 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OFTKFKYVSBNYEC-UHFFFAOYSA-N 2-furoyl chloride Chemical compound ClC(=O)C1=CC=CO1 OFTKFKYVSBNYEC-UHFFFAOYSA-N 0.000 description 1
- LHKORVGWWVBBPJ-UHFFFAOYSA-N 3-(5-bromothiophen-2-yl)prop-2-enoyl chloride Chemical compound ClC(=O)C=CC1=CC=C(Br)S1 LHKORVGWWVBBPJ-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- QIQITDHWZYEEPA-UHFFFAOYSA-N thiophene-2-carbonyl chloride Chemical compound ClC(=O)C1=CC=CS1 QIQITDHWZYEEPA-UHFFFAOYSA-N 0.000 description 1
- QERYCTSHXKAMIS-UHFFFAOYSA-N thiophene-2-carboxylic acid Chemical class OC(=O)C1=CC=CS1 QERYCTSHXKAMIS-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/35—Heterocyclic compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
- D06M13/21—Halogenated carboxylic acids; Anhydrides, halides or salts thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/46—Compounds containing quaternary nitrogen atoms
- D06M13/47—Compounds containing quaternary nitrogen atoms derived from heterocyclic compounds
- D06M13/477—Compounds containing quaternary nitrogen atoms derived from heterocyclic compounds having six-membered heterocyclic rings
Definitions
- This invention relates to a process for the preparation of cotton and other cellulosic textile products. More specifically, this invention relates to a single-bath process wherein cellulose chemically reacts through a multistep reaction to produce crosslinked heterocyclic cellulosic furoates and thenoates.
- the cotton fabric derivatives produced by the process of this invention have good wrinkle recovery angles and spray ratings.
- the first object of this invention is to provide a process for improving wrinkle resistance of cotton and other cellulosic fabrics.
- the second object of this invention is to provide new and useful cotton derivatives with water repellency.
- Cotton is the most widely used textile in the world today. However, in order to add additional properties to the natural properties of cotton and to maintain cottons competitive position with the man-made textile fibers in the market place, numerous treatments and modifications have been proposed.
- textile uses in which cotton must compete with other textiles are out-of-door uses, such as awnings or sand bags, which require rot resistance and water resistance and clothing uses which require improved wrinkle recovery from deformation.
- the instant invention defines a distinct impro'vemnt in that rot resistant heterocyclic cellulose esters of cotton, in yarn and in fabric forms, by raction with furoyl chlorides or with thenoyl chlorides and then crosslinking the derived heterocyclic cellulose esters of cotton with the difunctional chemical, 1,3-di-(4-pyridyl)propane by the sequence of reactions shown in Scheme A to yield a textile cotton product with improved rot resistance with improved wrinkle recovery angles from deformation and "ice with improved water resistance, as evidenced by increased spray ratings.
- EXAMPLE 1 Cotton cellulose (4 grams, 0.022 mole of glucose residue) in the form of yarn, which had been predried in air at 60 C. for 2 hours, was added to a homogeneous solution composed of N,N-dimethylformamide (200 milliliters), 5-bromo-2-furoyl chloride (0.089 mole), and 1,3- di-(4-pyridyl) propane (0.178 mole). The mixture was heated at 80 C. in absence of moisture for 16 hours. The reacted yarn was washed at 25 C. twice with N,N-dimethylformamide milliliters each time); immersed in methanol at 50 C. for 30 minutes; then kept in 10 percent potassium hydrogen carbonate solution at 25 C.
- Control cotton yarns were soluble in 0.5 M cupriethylenediamine at 25 C.; the reacted cotton yarns were insoluble in 0.5 M cupriethylenediamine at 25 C., which indicated crosslinking of the reacted cotton yarns.
- Example 2 The method of Example 1, except that S-bromo-Z- thenoyl chloride (0.089 mole) was used as the acid chloride. After 20 hours of reaction the extent of reaction was determined to be 31 percent add-on. Control cotton yarns were soluble in 0.5 M cupriethylenediamine at 25 (3.; the reacted cotton yarns were insoluble in 0.5 M cupriethylenediamine at 25 C., which indicated crosslinking of the reacted cotton yarns.
- EXAMPLE 3 The method of Example 1, except that S-bromo-Z-thiopheneacryloyl chloride (0.089 mole) was used as the acid chloride. After 20 hours of reaction the extent of reaction was determined to be 11 percent add-on. Control cotton yarns were soluble in 0.5 M cupriethylenediamine at 25 C.; the reacted cotton yarns were insoluble in 0.5 M cupriethylenediamine at 25 C., which indicated crossliuking of the reacted cotton yarns.
- EXAMPLE 4 The method of Example 1, except that cotton cellulose in the form of fabric (printcloth, 80 x 80) was used. The extent of reaction was determined to be 22 percent. The wrinkle recovery angles of control fabrics were 188 (conditioned) and 193 (wet); the wrinkle recovery angles of reacted fabrics were 242 (conditioned) and 216 (wet). This indicated crosslinking of the reacted cotton fabric. The spray rating of control fabric was zero; the spray rating of the reacted cotton fabric (the product by the process of this invention) was 50. This indicates that the cover factors of the reacted cotton fabrics were better since they were higher than those of the control cotton fabrics.
- EXAMPLE 5 The method of Example 2, except that cotton cellulose in the form of fabric (printcloth, 80 x 80) was used. The extent of reaction was determined to be 20 percent. The wrinkle recovery angles of control fabrics were 167 (conditioned) and 183 (wet). The wrinkle recovery angles of reacted fabrics were 234 (conditioned) and 225 (wet). This indicated crosslinking of the reacted cotton fabric. The spray rating of control fabric was zero; the spray rating of the reacted cotton fabric (the product by the process of this invention) was 70. This indicates that the cover factors of the reacted cotton fabrics were better since they were higher than those of the control cotton fabrics.
- EXAMPLE 6 The method of Example 3, except that cotton cellulose in the form of fabric (printcloth, 80 x 80) was used. The extent of reaction was determined to be 5 percent. The wrinkle recovery angles of control fabrics were 159 (con- 4 ditioned) and 135 (wet); the wrinkle recovery angles of reacted fabrics were 192 (conditioned) and 197 (wet). This indicated crosslinking of the reacted cotton fabrics. The spray rating of the untreated control fabric was zero; the spray rating of the reacted cotton fabric (the product by the process of this invention) was 50. This indi cates that the cover factors of the reacted cotton fabrics were better since they were higher than those of the control cotton fabrics.
- a process for imparting to cotton and other cellulosic fabrics the desirable properties of wrinkle resistance and water repellency comprising:
- heterocyclic acid chloride is S-bromo-Z-furoyl chloride.
- heterocyclic acid chloride is 5-bromo-2-thiopheneacryloy1 chloride.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Coloring (AREA)
Abstract
FIBROUS CELLULOSIC MATERIAL IS REACTED WITH SOLUTIONS CONTAINING A HALO-SUBSTITUTED HETEROCYCLIC (FURAN AND THIOPHENE) ACID CHLORIDE AND 1,3-BIS(4-PYRIDYL) PROPANE. CROSS-LINKKING IS EFFECTED BY REACTION BETWEEN THE CELLULOSE HALO-ESTERGROUPS FORMED AND THE PROPANE.
Description
United States Patent 3,719,449 CROSSLINKED HETEROCYCLIC CELLULOSIC PRODUCTS Jett C. Arthur, Jr., Metairie, La., Sujan Singh, Varanasi,
India, and Ricardo H. Wade, New Orleans, La., assiguors to the United States of America as represented by the Secretary of Agriculture No Drawing. Filed Apr. 27, 1972, Ser. No. 248,181 Int. Cl. D06m 13/20, 13/22, 13/34 US. Cl. 8--120 7 Claims ABSTRACT OF THE DISCLOSURE Fibrous cellulosic material is reacted with solutions containing a halo-substituted heterocyclic (furan and thiophene) acid chloride and 1,3-bis(4-pyridyl) propane. Cross-linking is effected by reaction between the cellulose halo-ester groups formed and the propane.
A non-exclusive, irrevocable, royalty-free license in the invention herein described throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of Amer- 'ica.
This invention relates to a process for the preparation of cotton and other cellulosic textile products. More specifically, this invention relates to a single-bath process wherein cellulose chemically reacts through a multistep reaction to produce crosslinked heterocyclic cellulosic furoates and thenoates. The cotton fabric derivatives produced by the process of this invention have good wrinkle recovery angles and spray ratings.
The first object of this invention is to provide a process for improving wrinkle resistance of cotton and other cellulosic fabrics.
The second object of this invention is to provide new and useful cotton derivatives with water repellency.
Cotton is the most widely used textile in the world today. However, in order to add additional properties to the natural properties of cotton and to maintain cottons competitive position with the man-made textile fibers in the market place, numerous treatments and modifications have been proposed. Among the textile uses in which cotton must compete with other textiles are out-of-door uses, such as awnings or sand bags, which require rot resistance and water resistance and clothing uses which require improved wrinkle recovery from deformation.
The cellulose furoate and Z-thenoates, which could be considered as intermediates produced in the reaction of this invention, have been disclosed in Carbohydrate Research [14 (1970) 73-82 and 17 (1971) 353463] by authors Sujan Singh and lett C. Arthur, Jr. The title of the one is Synthesis and Properties of Cellulose Furoate. The title of the second paper is Synthesis and Properties of Cellulose 2-Thenoates. These compounds are represented by the chemical equations of Scheme A. The products produced by the process of the present invention are represented by the last line of the said scheme.
The instant invention defines a distinct impro'vemnt in that rot resistant heterocyclic cellulose esters of cotton, in yarn and in fabric forms, by raction with furoyl chlorides or with thenoyl chlorides and then crosslinking the derived heterocyclic cellulose esters of cotton with the difunctional chemical, 1,3-di-(4-pyridyl)propane by the sequence of reactions shown in Scheme A to yield a textile cotton product with improved rot resistance with improved wrinkle recovery angles from deformation and "ice with improved water resistance, as evidenced by increased spray ratings.
Cl Cell- 0 H \N HCl SCHEME A Generally, the reactions were conducted in N,N-dimethyl formamide at to C. The desired amount of heterocyclic acid chloride, for example, furoyl chloride or thenoyl chloride, was added. Then the cross-linking agent, 1,3-di-(4-pyridyl)propane was added, and the mixture stirred until a homogeneous solution was obtained. Predried cotton yarn or cotton fabric was added to the solution. Then the formation of heterocyclic esters of cotton cellulose and the formation of crosslinkages of 1,3-di-(4-pyridyl)propane occurred in the absence of water.
The following examples are provided to facilitate the comprehension of the invention and should not be construed as limiting the invention in any manner whatever.
EXAMPLE 1 Cotton cellulose (4 grams, 0.022 mole of glucose residue) in the form of yarn, which had been predried in air at 60 C. for 2 hours, was added to a homogeneous solution composed of N,N-dimethylformamide (200 milliliters), 5-bromo-2-furoyl chloride (0.089 mole), and 1,3- di-(4-pyridyl) propane (0.178 mole). The mixture was heated at 80 C. in absence of moisture for 16 hours. The reacted yarn was washed at 25 C. twice with N,N-dimethylformamide milliliters each time); immersed in methanol at 50 C. for 30 minutes; then kept in 10 percent potassium hydrogen carbonate solution at 25 C. for 30 minutes; (restretching to about 80-85 percent of its initial dimension before reaction); followed by washing with water and drying to equilibrium weight at 25 C. and 50 percent relative humidity. The extent of reaction was ascertained by determining the increase in weight (add-on) of these reacted yarns over those of control yarns to be 35 percent. Control cotton yarns were soluble in 0.5 M cupriethylenediamine at 25 C.; the reacted cotton yarns were insoluble in 0.5 M cupriethylenediamine at 25 C., which indicated crosslinking of the reacted cotton yarns.
3 EXAMPLE 2 The method of Example 1, except that S-bromo-Z- thenoyl chloride (0.089 mole) was used as the acid chloride. After 20 hours of reaction the extent of reaction was determined to be 31 percent add-on. Control cotton yarns were soluble in 0.5 M cupriethylenediamine at 25 (3.; the reacted cotton yarns were insoluble in 0.5 M cupriethylenediamine at 25 C., which indicated crosslinking of the reacted cotton yarns.
EXAMPLE 3 The method of Example 1, except that S-bromo-Z-thiopheneacryloyl chloride (0.089 mole) was used as the acid chloride. After 20 hours of reaction the extent of reaction was determined to be 11 percent add-on. Control cotton yarns were soluble in 0.5 M cupriethylenediamine at 25 C.; the reacted cotton yarns were insoluble in 0.5 M cupriethylenediamine at 25 C., which indicated crossliuking of the reacted cotton yarns.
EXAMPLE 4 The method of Example 1, except that cotton cellulose in the form of fabric (printcloth, 80 x 80) was used. The extent of reaction was determined to be 22 percent. The wrinkle recovery angles of control fabrics were 188 (conditioned) and 193 (wet); the wrinkle recovery angles of reacted fabrics were 242 (conditioned) and 216 (wet). This indicated crosslinking of the reacted cotton fabric. The spray rating of control fabric was zero; the spray rating of the reacted cotton fabric (the product by the process of this invention) was 50. This indicates that the cover factors of the reacted cotton fabrics were better since they were higher than those of the control cotton fabrics.
EXAMPLE 5 The method of Example 2, except that cotton cellulose in the form of fabric (printcloth, 80 x 80) was used. The extent of reaction was determined to be 20 percent. The wrinkle recovery angles of control fabrics were 167 (conditioned) and 183 (wet). The wrinkle recovery angles of reacted fabrics were 234 (conditioned) and 225 (wet). This indicated crosslinking of the reacted cotton fabric. The spray rating of control fabric was zero; the spray rating of the reacted cotton fabric (the product by the process of this invention) was 70. This indicates that the cover factors of the reacted cotton fabrics were better since they were higher than those of the control cotton fabrics.
EXAMPLE 6 The method of Example 3, except that cotton cellulose in the form of fabric (printcloth, 80 x 80) was used. The extent of reaction was determined to be 5 percent. The wrinkle recovery angles of control fabrics were 159 (con- 4 ditioned) and 135 (wet); the wrinkle recovery angles of reacted fabrics were 192 (conditioned) and 197 (wet). This indicated crosslinking of the reacted cotton fabrics. The spray rating of the untreated control fabric was zero; the spray rating of the reacted cotton fabric (the product by the process of this invention) was 50. This indi cates that the cover factors of the reacted cotton fabrics were better since they were higher than those of the control cotton fabrics.
We claim:
1. A process for imparting to cotton and other cellulosic fabrics the desirable properties of wrinkle resistance and water repellency, the process comprising:
(a) immersing a fibrous cellulosic material in a solution containing a heterocyclic acid chloride selected from the group consisting of: 5-bromo-2-furoyl chloride, 5-brom0-2-thenoyl chloride, and 5-bromo-2-thiopheneacryloyl chloride; and 1,3-di-(4-pyridyl) propane in a molar ration of about 1:2, respectively, and
(b) heating the immersed cellulosic material in the solution of (a), in the absence of moisture, to a temperature of about to C., for about 16 to 20 hours, thereby reacting the cellulosic material with the chloride reagent to form the cellulosic furoate or the Z-thenoate as an intermediate product which subsequently is converted into the crosslinked fibrous cellulose derivatives as it reacts with the propane.
2. The process of claim 1 wherein the heterocyclic acid chloride is S-bromo-Z-furoyl chloride.
3. The process of claim 1 wherein the heterocyclic acid chloride is 5-'bromo-2-thenoyl chloride.
4. The process of claim 1 wherein the heterocyclic acid chloride is 5-bromo-2-thiopheneacryloy1 chloride.
5. The crosslinked fibrous cellulose derivative produced by the process of claim 2.
6. The crosslinked fibrous cellulosic derivative produced by the process of claim 3.
7. The crosslinked fibrous cellulose derivative produced by the process of claim 4.
References Cited Singh et al., Carbohydrate Research, 14 (1970), 73-82.
Singh et al., Carbohydrate Research, 17 (1971), 353- 363.
Singh et al., Carbohydrate Research, 18 (1971), 449- 452.
GEORGE F. LESMES, Primary Examiner J. CANNON, Assistant Examiner US. Cl. X.R.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US24818172A | 1972-04-27 | 1972-04-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3719449A true US3719449A (en) | 1973-03-06 |
Family
ID=22938043
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00248181A Expired - Lifetime US3719449A (en) | 1972-04-27 | 1972-04-27 | Crosslinked hetercyclic cellulosic products |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3719449A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0882836A2 (en) * | 1997-06-04 | 1998-12-09 | Ciba SC Holding AG | Process for crosslinking cellulose containing fibrous materials |
-
1972
- 1972-04-27 US US00248181A patent/US3719449A/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0882836A2 (en) * | 1997-06-04 | 1998-12-09 | Ciba SC Holding AG | Process for crosslinking cellulose containing fibrous materials |
| TR199801002A3 (en) * | 1997-06-04 | 1999-10-21 | Ciba Specialty Chemicals Holding Inc. | Cross-linking of cellulosic fiber materials. |
| EP0882836A3 (en) * | 1997-06-04 | 2000-11-22 | Ciba SC Holding AG | Process for crosslinking cellulose containing fibrous materials |
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