CN107325193B - Synthetic method of cellulose carbamate - Google Patents
Synthetic method of cellulose carbamate Download PDFInfo
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- CN107325193B CN107325193B CN201710607953.8A CN201710607953A CN107325193B CN 107325193 B CN107325193 B CN 107325193B CN 201710607953 A CN201710607953 A CN 201710607953A CN 107325193 B CN107325193 B CN 107325193B
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Abstract
The invention discloses a synthetic method of cellulose carbamate, which comprises the following steps: (1) pretreating, namely putting the cellulose raw material into a grinder to be ground to obtain cellulose powder; (2) ball milling, namely, mixing cellulose powder, a catalyst and urea according to the mass ratio of 100: 0.001-0.5: 0.5-5, sequentially putting into a ball mill for ball milling to obtain mixed powder; (3) pre-reaction, namely heating the mixed powder subjected to ball milling treatment in an oven to melt urea; (4) performing microwave reaction, namely performing microwave irradiation on the mixed powder obtained by the pre-reaction to initiate powder reaction; (5) removing impurities, drying, cleaning reactant obtained by microwave irradiation, and drying to obtain the product. The cellulose carbamate prepared by the method has good performance and can be used for preparing regenerated cellulose fiber. The reaction process does not use organic solvent and alkali liquor, so that the production cost is reduced, and the method is more environment-friendly; the reaction is initiated by microwaves, so that the reaction speed is improved, the production period is shortened, and the production cost is reduced.
Description
Technical Field
The invention relates to a synthetic method of a cellulose derivative, in particular to a synthetic method of cellulose formate.
Background
With the continuous improvement of the environmental awareness of human beings, the traditional production mode with high pollution and high energy consumption is gradually eliminated, and the green technology is gradually developed. In the field of rayon, the viscose process, as a more traditional old technology, is still adopted by many enterprises. Because the process uses a large amount of CS in the production process2Causing great pollution to the environment and damaging the health of people. Environmental concerns in most developed countries have prohibited the use of viscose processes for production. China gradually undertakes most of the viscose process production in the world after the reform and the opening of the last century and also becomes a main victim country of the pollution. Nowadays, the development of new green technologies is imminent.
Currently, the cellulose carbamate process is one of the most promising technologies for replacing the viscose process, but it is limited by that the industrial level still cannot meet the industrial demand. The general cellulose activation adopts chemical methods, such as alkali soaking, liquid ammonia soaking and the like, and the use of the reagents increases the production cost and has certain influence on the environment. The solvent is selected from either organic solvent or supercritical liquid in the synthesis process, the former is unfavorable to the environment and easy to remain in the product, and the latter has higher equipment construction cost. A plurality of patent documents related to the preparation of cellulose carbamate are found through searching, for example, the patent CN1687137 uses a common organic solvent xylene as a solvent, and the use of the solvent has large influence on the environment and is difficult to separate from the product.
Disclosure of Invention
The invention aims to provide a method for synthesizing a cellulose derivative, which is free of solvent and alkali liquor, reduces industrial cost, is beneficial to environmental protection, and can be used for preparing regenerated cellulose fibers by dissolving and spinning prepared cellulose carbamate.
The technical scheme provided by the invention is as follows.
A synthetic method of cellulose carbamate comprises the following steps:
(1) pretreating, namely putting the cellulose raw material into a grinder to be ground to obtain cellulose powder;
(2) ball milling, namely, mixing cellulose powder, a catalyst and urea according to the mass ratio of 100: 0.001-0.5: 0.5-5, sequentially putting into a ball mill for ball milling to obtain mixed powder;
(3) pre-reaction, namely placing the mixed powder subjected to ball milling treatment in an oven for heating to melt urea; the temperature of the oven is 110-150 ℃, and the heating time is 5-30 minutes;
(4) performing microwave reaction, namely performing microwave irradiation on the mixed powder obtained by the pre-reaction to initiate the powder to perform substitution reaction;
(5) removing impurities, drying, cleaning reactant obtained by microwave irradiation, and drying to obtain the product.
The cellulose material is selected from one of cotton pulp, wood pulp, bamboo pulp or reed pulp.
The catalyst is selected from nano-ZnO, CuO or Al2O3One kind of powder.
The length of the fiber raw material powder in the step (1) is 0.1-10 mm.
The ball milling parameters in the step (2) are as follows: the size of the grinding ball is 1-10 mm, the rotating speed is 300-1000 rpm, the ball milling time is 30-120 minutes, and the temperature of circulating water is lower than 80 ℃.
In the step (4), the microwave power is 50-1000 watts, the irradiation time is 5-100 minutes, and the irradiation frequency is 1-10 seconds per 10 seconds.
And (3) in the step (5), the cleaning reagent is soft water, the cleaning times are 3-5 times, and the drying method is drying or airing.
The synthesis reaction is as follows:
NH2-CO-NH2→HN＝C＝O+NH3(1)
Cell-OH+HN＝C＝O→Cell-O-CO-NH2(2)
the cellulose groups may be activated by ball milling the cellulosic feedstock using a ball mill. Urea is decomposed at high temperature to isocyanic acid, which reacts with hydroxyl groups on activated cellulose to form carbamate. The urea can be melted at high temperature and can be fully mixed with cellulose molecular chains, and then the reaction is fully carried out. The catalyst is a common catalyst for synthesizing the carbamate organic matter. The microwave irradiation activates the hydroxyl groups of the cellulose molecules, and then the cellulose molecules react with urea.
The invention has the beneficial effects that:
(1) the reaction process does not use organic solvent and alkali liquor, so that the production cost is reduced, and the method is more environment-friendly;
(2) the microwave is adopted to initiate polymerization, so that the polymerization reaction speed is improved, the production period is shortened, the production efficiency is improved, the production cost is reduced, the use of an initiator is reduced, the pollution is reduced, and the cost is reduced;
(3) the post-treatment is simple, the synthesis period is short, the cleaning time of the equipment is greatly shortened compared with the cleaning time of the equipment taking an organic solvent as a medium, the preparation time is greatly shortened compared with the preparation time of the equipment taking supercritical carbon dioxide as a medium, and the reaction conditions are simpler.
Drawings
FIG. 1 is a flow chart of the synthesis process of the present invention.
Detailed Description
The invention is further illustrated by the following examples, to which the present invention is not at all restricted.
Example 1
(1) Pretreating, namely putting the cotton pulp into a crusher to crush the cotton pulp into cellulose powder with the length of 5 mm;
(2) ball milling, namely putting 100g of cotton pulp powder, 0.001g of ZnO nano powder and 0.5g of urea into a ball mill in sequence for ball milling to obtain mixed powder, wherein the size of the ball mill is 1mm, the rotating speed is 300rpm, the ball milling time is 30 minutes, and the circulating water temperature is 60 ℃;
(3) pre-reaction, namely heating the powder subjected to ball milling treatment in an oven at 110 ℃ for 5 minutes;
(4) performing microwave reaction, namely performing microwave irradiation on the raw material obtained by the pre-reaction, wherein the microwave power is 50 watts, the irradiation time is 100 minutes, and the irradiation frequency is 10 seconds per 10 seconds;
(4) removing impurities, drying, cooling reactant obtained by microwave irradiation, cleaning with hot water for 3 times, and drying to obtain the final product.
The nitrogen content of the product is 0.12% by detection. 1 part of reaction product is taken and mixed with 39 parts of NaOH solution (7%) uniformly, then the mixture is frozen to-15 ℃ in a freezer, then the mixture is unfrozen to obtain a cellulose carbamate solution with the concentration of 2.5%, wet spinning can be carried out after filtration and defoaming, and the fiber strength is 0.8-0.9 cN/dtex.
Example 2
(1) Pretreating, namely putting wood pulp into a grinder to be ground into cellulose powder with the length of 0.1 mm;
(2) ball milling, namely, mixing 100g of cotton pulp powder and 0.5g of Al2O3Sequentially adding the nano powder and 5g of urea into a ball mill for ball milling to obtain mixed powder, wherein the ball mill is 5mm zirconium dioxide balls, the rotating speed is 500rpm, the ball milling time is 60 minutes, and the circulating water temperature is 70 ℃;
(3) pre-reaction, namely heating the powder subjected to ball milling treatment in an oven at 130 ℃ for 30 minutes;
(4) performing microwave reaction, namely performing microwave irradiation on the raw material obtained by the pre-reaction, wherein the microwave power is 300 watts, the irradiation time is 60 minutes, and the irradiation frequency is 5 seconds per 10 seconds;
(4) removing impurities, drying, cooling reactant obtained by microwave irradiation, cleaning for 3 times, and drying to obtain the product.
The nitrogen content of the product is 2.8% by detection. And (3) uniformly mixing 1 part of reaction product with 13 parts of NaOH solution (7.5%), freezing to-15 ℃ in a freezer, thawing to obtain a 7.1% cellulose carbamate solution, filtering, defoaming and carrying out wet spinning, wherein the fiber strength is 1.9-2.0 cN/dtex.
Example 3
(1) Preprocessing, namely putting the reed pulp into a crusher to be crushed into cellulose powder with the length of 5 mm;
(2) ball milling, namely putting 100g of reed pulp powder, 0.2g of CuO nano powder and 2.5g of urea into a ball mill in sequence for ball milling to obtain mixed powder, wherein the ball milling is 6mm zirconium dioxide balls, the rotating speed is 500rpm, the ball milling time is 60 minutes, and the circulating water temperature is 50 ℃;
(3) pre-reaction, namely heating the powder subjected to ball milling treatment in an oven at 120 ℃ for 15 minutes;
(4) performing microwave reaction, namely performing microwave irradiation on the raw material obtained by the pre-reaction, wherein the microwave power is 1000 watts, the irradiation time is 5 minutes, and the irradiation frequency is 1 second every 10 seconds;
(4) removing impurities, drying, cooling reactant obtained by microwave irradiation, cleaning for 3 times, and drying to obtain the product.
The nitrogen content of the product is 1.9% by detection. And (3) uniformly mixing 1 part of reaction product with 19 parts of NaOH solution (7.0%), freezing to-15 ℃ in a freezer, thawing to obtain a cellulose carbamate solution with the concentration of 5%, filtering, defoaming and carrying out wet spinning, wherein the fiber strength is 1.6-1.7 cN/dtex.
Example 4
(1) Pretreating, namely putting the bamboo pulp into a grinder to be ground into cellulose powder with the length of 1 mm;
(2) ball milling, 100g of bamboo pulp powder and 0.1g of Al2O3The nanometer powder and 3g of urea are sequentially put into a ball millGrinding to obtain mixed powder, wherein the grinding ball is a 10mm zirconium dioxide ball, the rotating speed is 1000rpm, the ball milling time is 90 minutes, and the circulating water temperature is 60 ℃;
(3) pre-reaction, namely heating the powder subjected to ball milling treatment in an oven at 150 ℃ for 5 minutes;
(4) performing microwave reaction, namely performing microwave irradiation on the raw material obtained by the pre-reaction, wherein the microwave power is 500 watts, the irradiation time is 60 minutes, and the irradiation frequency is 5 seconds per 10 seconds;
(4) removing impurities, drying, cooling reactant obtained by microwave irradiation, cleaning for 3 times, and drying to obtain the product.
The nitrogen content of the product is 2.0 percent through detection. And (3) uniformly mixing 1 part of reaction product with 19 parts of NaOH solution (7.2%), freezing to-15 ℃ in a freezer, thawing to obtain a cellulose carbamate solution with the concentration of 5%, filtering, defoaming and carrying out wet spinning, wherein the fiber strength is 1.7-1.8 cN/dtex.
The nitrogen content of the cellulose carbamate prepared by the method is 0.1-3%, which is equivalent to 0.1-4% reported in China. The non-liquid phase method is adopted for preparation, so that the urea consumption is less, the substitution degree is lower than that of a liquid phase method, and certain advantages are achieved in the aspects of cost control and environmental protection. The cellulose fiber obtained by wet spinning has better fiber strength and can be used for preparing regenerated cellulose fiber.
Claims (7)
1. A synthetic method of cellulose carbamate is characterized by comprising the following steps:
(1) pretreating, namely putting the cellulose raw material into a grinder to be ground to obtain cellulose powder;
(2) ball milling, namely, mixing cellulose powder, a catalyst and urea according to the mass ratio of 100: 0.001-0.5: 0.5-5, sequentially putting into a ball mill for ball milling to obtain mixed powder;
(3) pre-reaction, namely placing the mixed powder subjected to ball milling treatment in an oven for heating to melt urea; the temperature of the oven is 110-150 ℃, and the heating time is 5-30 minutes;
(4) performing microwave reaction, namely performing microwave irradiation on the mixed powder obtained by the pre-reaction to initiate the powder to perform substitution reaction;
(5) removing impurities, drying, cleaning reactant obtained by microwave irradiation, and drying to obtain the product.
2. The method for synthesizing cellulose carbamate according to claim 1, wherein: the cellulose raw material is selected from one of cotton pulp, wood pulp, bamboo pulp or reed pulp.
3. The method for synthesizing cellulose carbamate according to claim 1, wherein: the catalyst is selected from nano-scale ZnO or CuO or Al2O3One kind of powder.
4. The method for synthesizing cellulose carbamate according to claim 1, wherein: the length of the cellulose powder obtained in the step (1) is 0.1-10 mm.
5. The method for synthesizing cellulose carbamate according to claim 1, wherein: in the step (2), the ball milling parameters are that the size of the milling ball is 1-10 mm, the rotating speed is 300-1000 rpm, the ball milling time is 30-120 minutes, and the temperature of circulating water is lower than 80 ℃.
6. The method for synthesizing cellulose carbamate according to claim 1, wherein: in the step (4), the microwave power is 50-1000 watts, the irradiation time is 5-100 minutes, and the irradiation frequency is 1-10 seconds per 10 seconds.
7. The method for synthesizing cellulose carbamate according to claim 1, wherein: and (3) using soft water as a reagent for cleaning in the step (5), wherein the cleaning times are 3-5 times, and the drying method is drying or airing.
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