CN113121706A - Preparation method of molten cellulose mixed ester, fiber and film - Google Patents
Preparation method of molten cellulose mixed ester, fiber and film Download PDFInfo
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- CN113121706A CN113121706A CN202110434390.3A CN202110434390A CN113121706A CN 113121706 A CN113121706 A CN 113121706A CN 202110434390 A CN202110434390 A CN 202110434390A CN 113121706 A CN113121706 A CN 113121706A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/16—Preparation of mixed organic cellulose esters, e.g. cellulose aceto-formate or cellulose aceto-propionate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B13/00—Preparation of cellulose ether-esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
- D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
- D01F2/28—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/14—Mixed esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/32—Cellulose ether-esters
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- Polymers & Plastics (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
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Abstract
The invention discloses a preparation method of molten cellulose mixed ester, belonging to the field of fibers and comprising the following steps: obtaining a cellulose raw material, dissolving the cellulose raw material in a solvent, wherein the solvent contains one or more of OAc-, HCOO-, Cl-, (Me O)2PO2-, and obtaining a solution; adding an organic monomer into the solution, and reacting to obtain a first reactant A; adding an oligomer B into the first reactant A, and reacting to obtain a cellulose mixed ester, wherein the oligomer B simultaneously contains-OH and-COOH; the invention also discloses a fiber or film, which is characterized in that the preparation method comprises the following steps: preparing cellulose mixed ester, heating and melting the cellulose mixed ester, and drawing to obtain the fiber or the film.
Description
Technical Field
The present invention relates to the field of fiber preparation.
Background
Cellulose has high polymerization degree, a main chain contains a large amount of hydroxyl, a large amount of hydrogen bonds exist among molecules and in molecules, and a large number of physical crosslinking points exist, so that the melting temperature is higher than the decomposition temperature, and the application and the processing of the cellulose are limited.
The traditional cellulose fiber production method is a solvent method, has many defects, long flow, large energy consumption and serious environmental pollution. Therefore, the development of a new production process of the cellulose fiber which is environment-friendly is generally concerned at home and abroad, the Japan company prepares the cellulose fiber by a melt spinning method at home and abroad, and related researches are rarely carried out at home.
Because the traditional production process of the cellulose fiber has the defects of long process, large energy consumption, environmental pollution and the like, researchers at home and abroad also develop and research some new processes on the cellulose fiber.
1. Organic solvent NMMO spinning, an amine oxide system developed by Courtaulds (cowerlz) in the uk, is a new cellulose organic solvent, and the NMMO spinning process is a physical process of dissolution and coagulation, a method for producing cellulose fibers without chemical reaction, and also involves the problem of solvent recovery, and the production of by-products increases the cost of the solvent and causes difficulty in the dyeing process of regenerated cellulose.
2. The method is characterized in that the inorganic solvent NaOH dilute solution spinning appears in the 90 s of the twentieth century, Chevalier and the like adopt a steam flash explosion technology to process wood pulp fibers, SO that cellulose can be directly dissolved in the NaOH dilute solution, a production process of a wet technology is adopted, acidic solutions such as H2SO4, HCl, CH3COOH, H3PO4 and sodium salt and ammonium salt with certain concentration can be used as coagulating baths, the problem of solvent recovery also exists, and the spinning pretreatment process of the NaOH solution is complex and difficult.
3. The spinning in ionic liquid is to dissolve cellulose with ionic liquid or its mixture with other proper agent and to spin in dry-wet method. The Donghua university of Zhutianxiang researches the dissolution and spinning forming of cellulose in ionic liquid, and the research researches the dissolution kinetics and the forming kinetics of the cellulose by taking 1-butyl-3-methylimidazolium chloride as a solvent and carries out a spinning test. Zhang Hui et al prepared a cellulose/[ Bmin ] Cl solution with a concentration of 8% using [ Bmin ] Cl as a solvent, followed by dry-wet spinning under a constant pressure. The Denkendorf institute of textile chemistry and chemical fiber in Germany adopts solvents such as chlorinated 1-butyl-3-methylimidazolium salt ([ Bmin ] Cl) and chlorinated 1-ethyl-3-methylimidazolium salt ([ Emin ] Cl) to dissolve cellulose and successfully spin cellulose fiber.
The ionic solvent is also removed in the ionic liquid spinning solidification process, and the spinnability is poor when the cellulose concentration is high; the cellulose concentration is low, and the ionic liquid is not easy to be quickly removed, so that the phenomenon of fiber adhesion is easily caused.
Therefore, the process flow is short, the three wastes pollution is avoided, and the efficient melt spinning method for producing the cellulose fiber is an urgent need for reducing the energy consumption and the cost and being environment-friendly, and is also a research trend in recent years.
Disclosure of Invention
The invention discloses a preparation method of molten cellulose mixed ester, which comprises the following steps:
obtaining a cellulose raw material, dissolving the cellulose raw material in a solvent, wherein the solvent contains one or more of OAc-, HCOO-, Cl-, (Me O)2PO2-, and obtaining a solution;
adding an organic monomer into the solution, and reacting to obtain a first reactant A;
and adding an oligomer B into the first reactant A, and reacting to obtain a cellulose mixed ester, wherein the melting temperature of the obtained cellulose mixed ester is 270-320 ℃, the oligomer B simultaneously contains-OH and-COOH, such as an oligomer formed by 2-hydroxypropionic acid and the like, the preferable ratio of-OH to-COOH in the oligomer B is 1:1, and the modification effect is better.
In a preferred embodiment, the organic monomer is one or more of organic acid, organic alcohol and ester monomer.
In a preferred embodiment, the organic monomer is selected from one or a mixture of acetic acid, propionic acid, butyric acid, ethylene glycol, hexanediol and acrylic esters.
In a preferred embodiment, the average degree of substitution of the first reactant a is below 2.6.
In a preferred embodiment, the reaction molar ratio of the first reactant A and the oligomer B is 1 (1-9), and the organic metal salt added in the reaction is used as a catalyst.
In a preferred embodiment, the organometallic salt is an organic carboxylic acid metal salt.
The invention also discloses a molten cellulose mixed ester prepared by the preparation method.
The invention also discloses a fiber or film, and the preparation method comprises the following steps:
step 1: preparing a cellulose mixed ester according to the process of any one of the preceding claims;
step 2: heating and melting cellulose mixed ester;
and step 3: stretching to obtain the fiber or the film.
In a preferred embodiment, the heating melting or/and drawing temperature is 10 to 40 ℃ or higher than the endothermic peak temperature at the time of temperature rise in differential scanning calorimetry of the cellulose mixed ester.
The invention modifies cellulose, destroys hydrogen bonds thereof, changes intermolecular force, reduces melting point thereof and realizes the preparation of cellulose fiber by melting and plasticizing through chemical modification and blending modification. Compared with the traditional solvent method, the method for preparing the cellulose fiber by the melt spinning method has the advantages of short process flow, no three-waste pollution, small shrinkage during fiber forming, high fiber section uniformity and capability of applying high-power drawing, thereby obtaining the fiber with higher performance.
Detailed Description
The present invention will be described in detail below.
Example 1: the embodiment discloses a preparation method of molten cellulose mixed ester, which comprises the following steps: purchasing or self-making a cellulose raw material, drying and other treatment, dissolving the cellulose raw material in a solvent, wherein the solvent contains OAc-, and then obtaining a solution; adding acetic acid into the solution, reacting to obtain a first reactant A, wherein the average substitution degree of the first reactant A is about 2.5, adding an oligomer B into the first reactant A, and adding an organic metal salt as a catalyst, wherein the organic metal salt is an organic carboxylic acid metal salt. The first reactant A and the oligomer B are reacted at a molar ratio of 1:2 to obtain the cellulose mixed ester, wherein the oligomer B contains-OH and-COOH at the same time. The invention also discloses the molten cellulose mixed ester prepared by the method. When preparing fiber or film, heating and melting the cellulose mixed ester; stretching to obtain the fiber or the film. The heating melting or/and stretching temperature is 30-40 ℃ above the endothermic peak temperature point at the time of temperature rise in differential scanning calorimetry of the cellulose mixed ester.
Example 2: the embodiment discloses a preparation method of molten cellulose mixed ester, which comprises the following steps: purchasing or self-making a cellulose raw material, drying and other treatment, dissolving the cellulose raw material in a solvent, wherein the solvent contains HCOO-, and then obtaining a solution; adding propionic acid into the solution, reacting to obtain a first reactant A, wherein the average substitution degree of the first reactant A is 2, adding an oligomer B into the first reactant A, and adding an organic metal salt as a catalyst, wherein the organic metal salt is an organic carboxylic acid metal salt. The first reactant A and the oligomer B are reacted at a molar ratio of 1:3 to obtain the cellulose mixed ester, wherein the oligomer B contains-OH and-COOH at the same time. The invention also discloses the molten cellulose mixed ester prepared by the method. When preparing fiber or film, heating and melting the cellulose mixed ester; stretching to obtain the fiber or the film. The heating melting or/and stretching temperature is 10-30 ℃ above the endothermic peak temperature point at the time of temperature rise in differential scanning calorimetry of the cellulose mixed ester.
Example 3: the embodiment discloses a preparation method of molten cellulose mixed ester, which comprises the following steps: purchasing or self-making a cellulose raw material, drying and other treatment, dissolving the cellulose raw material in a solvent, wherein the solvent contains Cl < - > to obtain a solution; adding ethylene glycol into the solution, reacting to obtain a first reactant A, wherein the average substitution degree of the first reactant A is 2.4, adding an oligomer B into the first reactant A, and adding an organic metal salt as a catalyst, wherein the organic metal salt is an organic carboxylic acid metal salt. The first reactant A and the oligomer B are reacted at a molar ratio of 1:8 to obtain the cellulose mixed ester, wherein the oligomer B contains-OH and-COOH at the same time. The invention also discloses the molten cellulose mixed ester prepared by the method. When preparing fiber or film, heating and melting the cellulose mixed ester; stretching to obtain the fiber or the film. The heating melting or/and stretching temperature is 20-40 ℃ above the endothermic peak temperature point at the time of temperature rise in differential scanning calorimetry of the cellulose mixed ester.
Example 4: the embodiment discloses a preparation method of molten cellulose mixed ester, which comprises the following steps: purchasing or self-making a cellulose raw material, drying and other treatment, dissolving the cellulose raw material in a solvent, wherein the solvent contains (Me O)2PO2 < - > so as to obtain a solution; adding acrylate into the solution, reacting to obtain a first reactant A, wherein the average substitution degree of the first reactant A is 2.2, adding an oligomer B into the first reactant A, and adding an organic metal salt as a catalyst, wherein the organic metal salt is an organic carboxylic acid metal salt. The first reactant A and the oligomer B are reacted at a molar ratio of 1:9 to obtain the cellulose mixed ester, wherein the oligomer B contains-OH and-COOH at the same time. The invention also discloses the molten cellulose mixed ester prepared by the method. When preparing fiber or film, heating and melting the cellulose mixed ester; stretching to obtain the fiber or the film. The heating melting or/and stretching temperature is 20-30 ℃ above the endothermic peak temperature point at the time of temperature rise in differential scanning calorimetry of the cellulose mixed ester.
Example 5: the embodiment discloses a preparation method of a molten cellulose mixed ester mixture, which comprises the following steps: purchasing or self-making a cellulose raw material, drying and other treatment, dissolving the cellulose raw material in a solvent, wherein the solvent contains (Me O)2PO2 < - > so as to obtain a solution; adding hexanediol into the solution, reacting to obtain a first reactant A, wherein the average substitution degree of the first reactant A is 2.6, adding an oligomer B and an oligomer C into the first reactant A, and adding an organic metal salt serving as a catalyst, wherein the organic metal salt is an organic carboxylic acid metal salt. The reaction molar ratio of the first reactant A to the oligomer B is 1:7, cellulose mixed ester is obtained through reaction, the melting temperature of the obtained cellulose mixed ester is 270-320 ℃, the oligomer B contains-OH and-COOH, and the oligomer C is an acrylonitrile oligomer. Mixing the prepared cellulose mixed ester and the cellulose nano raw material in a mass ratio of 2:1 to form a mixture. In the spinning and film forming processes, the cellulose mixed ester can be used as a continuous phase, the unmelted cellulose nano-raw material (the melting temperature of which is more than 350 ℃) is used as a disperse phase, the low melting temperature of the cellulose mixed ester and the high performance of the cellulose nano-raw material are utilized, so that the performance of the cellulose can not be greatly changed in the spinning process, the cellulose can reinforce the mixed ester, the interface bonding performance of the cellulose mixed ester and the cellulose nano-raw material is good, and the prepared fiber and film have high toughness. The invention also discloses the molten cellulose mixed ester prepared by the method. When preparing fiber or film, heating and melting the cellulose mixed ester mixture; stretching to obtain the fiber or the film. The heating melting or/and stretching temperature is 10-40 ℃ above the endothermic peak temperature point at the time of temperature rise in differential scanning calorimetry of the cellulose mixed ester.
Claims (9)
1. A method for preparing molten cellulose mixed ester is characterized by comprising the following steps:
obtaining a cellulosic feedstock, dissolving the cellulosic feedstock in a solvent comprising OAc-、HCOO-、Cl-、(Me O)2PO2 -To obtain a solution;
adding an organic matter monomer into the solution, and carrying out graft modification reaction to obtain a first reactant A;
adding oligomer B into the first reactant A, blending and plasticizing to obtain cellulose mixed ester; the oligomer B contains-OH and-COOH at the same time.
2. A method as claimed in claim 1, wherein the organic monomer is a mixture of one or more of organic acid, organic alcohol, and ester monomer.
3. A method of producing molten cellulose mixed ester according to claim 1, wherein the organic monomer is selected from one or a mixture of acetic acid, propionic acid, butyric acid, ethylene glycol, hexylene glycol, and acrylates.
4. A process for preparing a molten cellulose mixed ester according to claim 3, wherein the average degree of substitution of the first reactant a is less than 2.6.
5. A molten cellulose mixed ester production method according to claim 4, wherein the reaction molar ratio of the first reactant A and the oligomer B is 1 (1-9), and an organic metal salt is added as a catalyst in the reaction.
6. A molten cellulose mixed ester preparation method according to claim 4 wherein the organometallic salt is an organic carboxylic acid metal salt.
7. A molten cellulose mixed ester produced by the production method according to any one of claims 1 to 6.
8. A fiber or film, characterized in that the preparation method is as follows:
preparing a cellulose mixed ester according to the process of any one of claims 1-6;
heating and melting cellulose mixed ester;
stretching to obtain the fiber or the film.
9. The fiber or film according to claim 8, wherein the heating melting or/and stretching temperature is 10 to 40 ℃ or higher than the endothermic peak temperature at the time of temperature rise in differential scanning calorimetry of the cellulose mixed ester.
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| CN202110434390.3A CN113121706A (en) | 2021-04-22 | 2021-04-22 | Preparation method of molten cellulose mixed ester, fiber and film |
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| CN202110434390.3A CN113121706A (en) | 2021-04-22 | 2021-04-22 | Preparation method of molten cellulose mixed ester, fiber and film |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1062740A (en) * | 1990-11-30 | 1992-07-15 | 伊斯曼柯达公司 | The blend composition of aliphatic-Aromatic copolyesters and cellulose ester/polymkeric substance |
| CN101215725A (en) * | 2007-12-27 | 2008-07-09 | 天津工业大学 | A kind of cellulose solvent and the method for preparing spinning liquid with it |
| CN103193964A (en) * | 2012-01-10 | 2013-07-10 | 中国科学院化学研究所 | Method for preparing cellulose ester grafted aliphatic polyester copolymer |
| CN103290504A (en) * | 2013-06-19 | 2013-09-11 | 东华大学 | Cellulose in-situ chemical modification and plasticizing melt spinning method thereof |
| CN105199001A (en) * | 2014-06-19 | 2015-12-30 | 南通醋酸纤维有限公司 | Preparation method of cellulose long-chain aliphatic ester or long-chain and short-chain mixed acid ester |
-
2021
- 2021-04-22 CN CN202110434390.3A patent/CN113121706A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1062740A (en) * | 1990-11-30 | 1992-07-15 | 伊斯曼柯达公司 | The blend composition of aliphatic-Aromatic copolyesters and cellulose ester/polymkeric substance |
| CN101215725A (en) * | 2007-12-27 | 2008-07-09 | 天津工业大学 | A kind of cellulose solvent and the method for preparing spinning liquid with it |
| CN103193964A (en) * | 2012-01-10 | 2013-07-10 | 中国科学院化学研究所 | Method for preparing cellulose ester grafted aliphatic polyester copolymer |
| CN103290504A (en) * | 2013-06-19 | 2013-09-11 | 东华大学 | Cellulose in-situ chemical modification and plasticizing melt spinning method thereof |
| CN105199001A (en) * | 2014-06-19 | 2015-12-30 | 南通醋酸纤维有限公司 | Preparation method of cellulose long-chain aliphatic ester or long-chain and short-chain mixed acid ester |
Non-Patent Citations (1)
| Title |
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| 陈佳月 等: ""低熔点纤维的研究进展"", 《纺织科技进展》 * |
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