CN110591133A - Environment-friendly production process for improving strength of regenerated cellulose membrane - Google Patents
Environment-friendly production process for improving strength of regenerated cellulose membrane Download PDFInfo
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- CN110591133A CN110591133A CN201910726931.2A CN201910726931A CN110591133A CN 110591133 A CN110591133 A CN 110591133A CN 201910726931 A CN201910726931 A CN 201910726931A CN 110591133 A CN110591133 A CN 110591133A
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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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- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/08—Heat treatment
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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
- C08J2301/22—Cellulose xanthate
- C08J2301/24—Viscose
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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
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
Abstract
The invention discloses an environment-friendly production process for improving the strength of a regenerated cellulose membrane. The regenerated cellulose membrane prepared by the method has better mechanical property, the crystallinity, the heat resistance, the strength and the elongation of the product are obviously improved, the biodegradability is basically kept unchanged, the membrane breaking times in production can be effectively reduced, and the continuous production is ensured.
Description
Technical Field
The invention belongs to the technical field of organic polymers, and particularly relates to an environment-friendly production process for improving the strength of a regenerated cellulose membrane.
Background
Cellulose is a natural polymer compound with the most abundant reserves in the world and is inexhaustible as a renewable resource. Compared with synthesized polymer, the material has the advantages of complete biodegradation, no toxicity and no pollution. The regenerated cellulose membrane takes cellulose as a raw material, has the environmental protection characteristic of the cellulose, is used as a transparent film material which can be completely biodegraded, has high transparency, strong glossiness, antistatic property, good printability and heat resistance, and is an excellent substitute of plastic film materials.
At the present stage, the industrial production of the regenerated cellulose membrane is mature, the process is stable, and the efficiency is high. However, in the actual production process, because of the particularity of the production process of the regenerated cellulose film and the low strength thereof, the film breaking phenomenon is easy to occur. The regenerated cellulose membrane can not be recycled, and a large amount of materials, energy and labor are wasted once the membrane is broken. On the basis of the existing production equipment, the development of the production process for enhancing the strength of the regenerated cellulose membrane is a reliable scheme for solving the problem of membrane breakage.
Disclosure of Invention
The purpose of the invention is as follows: in order to solve the defects of the prior art, the invention provides an environment-friendly production process for improving the strength of a regenerated cellulose membrane, and the process endows the regenerated cellulose membrane with better mechanical property by adding an auxiliary agent and improving the process, so that the regenerated cellulose membrane has better strength and toughness; meanwhile, the added auxiliary agent is environment-friendly and degradable, and the environment-friendly characteristic of the regenerated cellulose membrane is not influenced.
The technical scheme is as follows: an environment-friendly production process for improving the strength of a regenerated cellulose membrane comprises the steps of firstly preparing an auxiliary agent solution in advance, blending a cellulose viscose stock solution and the auxiliary agent solution, spraying out after mixing, regenerating and solidifying in a solidifying bath and a regenerating bath to form a film, and finally obtaining the regenerated cellulose membrane through wet treatment, drying and humidifying treatment, wherein the auxiliary agent is an alcohol polymer.
The environment-friendly production process for improving the strength of the regenerated cellulose membrane specifically comprises the following operations:
(1) accurately weighing an auxiliary agent, wherein the auxiliary agent is an alcohol polymer;
(2) accurately weighing desalted water, heating the desalted water to a certain temperature, adding the weighed auxiliary agent while stirring by using a stirrer, and continuously stirring the auxiliary agent in hot water for a period of time;
(3) blending the viscose stock solution and the auxiliary agent solution: fully mixing the auxiliary agent solution with the viscose stock solution;
(4) film forming: spraying the mixed viscose stock solution and the auxiliary agent solution through a spray seam, and then regenerating and solidifying the viscose stock solution and the auxiliary agent solution in a coagulating bath and a regenerating bath to form a film;
(5) wet treatment: washing, desulfurizing, washing, bleaching, dechlorinating, washing and plasticizing the solidified and formed film;
(6) drying with hot air;
(7) moisture conditioning: and (5) carrying out humidity conditioning treatment on the dried membrane.
As an optimization: the auxiliary agent in the step (1) is polyvinyl alcohol.
As an optimization: the step (2) is implemented specifically as follows: heating the desalted water which is accurately weighed to 65-90 ℃, adding the weighed auxiliary agent while stirring at the rotating speed of 1000r/min by using a stirrer, and after the addition of the auxiliary agent is finished, keeping the temperature and stirring for 1 hour to completely dissolve the auxiliary agent.
As an optimization: the desalted water which is 20 times of the weight of the auxiliary agent is accurately obtained in the step (2), the desalted water is heated to 80 ℃, and the temperature of the desalted water is kept at 80 ℃ at the rotating speed of 1000r/min, and the desalted water is stirred for 1 hour.
As an optimization: and (3) blending the viscose stock solution and the auxiliary agent solution: filtering the prepared solution by using a filter screen, adding the auxiliary agent into a viscose pipeline in an amount accounting for 0.5-3% of the content of the alpha cellulose, and mixing by using a static mixer and a homogenizing pump to ensure that the viscose and the auxiliary agent are uniformly mixed.
As an optimization: the step (4) is film forming: the bath liquid components of the coagulating bath are sulfuric acid concentration of 130-160g/L, sodium sulfate concentration of 230-270g/L and temperature of 40-50 ℃; the concentration of the regeneration bath sulfuric acid is 50-80g/L, and the temperature is 40-65 ℃.
As an optimization: the wet treatment in the step (5): the water washing step is carried out at water flow rate of 1-3m3H, the temperature is 20-80 ℃; the desulfurization step is that the concentration of NaOH is 3-6g/L, and the temperature is 60-90 ℃; the bleaching step is as follows: the concentration of the effective chlorine of the sodium hypochlorite is 0.5-4g/L, and the temperature is less than or equal to 40 ℃; the plasticizing treatment comprises the following steps: the concentration of the glycerol is 30-50g/L, the concentration of the antisticking agent is 5-15g/L, the temperature is 40-70 ℃, and the pH value is 7-10.
As an optimization: the step (6) is dried by hot air; hot air drying is adopted, the air temperature is 135-55 ℃, and the temperature is gradually reduced during the drying treatment.
As an optimization: the step (7) of humidifying: and (3) carrying out humidity regulation treatment on the dried membrane, wherein the humidity regulation temperature is 55-65 ℃, and the relative humidity is 60-75% RH.
Has the advantages that: the regenerated cellulose membrane prepared by the method has better mechanical property, the crystallinity, the heat resistance, the strength and the elongation of the product are obviously improved, the biodegradability is basically kept unchanged, the membrane breaking times in production can be effectively reduced, and the continuous production is ensured.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below so that those skilled in the art can better understand the advantages and features of the present invention, and thus the scope of the present invention will be more clearly defined. The embodiments described herein are only a few embodiments of the present invention, rather than all embodiments, and all other embodiments that can be derived by one of ordinary skill in the art without inventive faculty based on the embodiments described herein are intended to fall within the scope of the present invention.
Detailed description of the preferred embodiment 1
An environment-friendly production process for improving the strength of a regenerated cellulose membrane comprises the steps of firstly preparing an auxiliary agent solution in advance, blending a cellulose viscose stock solution and the auxiliary agent solution, spraying out after mixing, regenerating and solidifying in a solidifying bath and a regenerating bath to form a film, and finally obtaining the regenerated cellulose membrane through wet treatment, drying and humidifying treatment, wherein the auxiliary agent is an alcohol polymer.
The environment-friendly production process for improving the strength of the regenerated cellulose membrane specifically comprises the following operations:
(1) accurately weighing an auxiliary agent, wherein the auxiliary agent is polyvinyl alcohol;
(2) heating the desalted water which is accurately weighed to 65 ℃, adding the weighed auxiliary agent while stirring at the rotating speed of 1000r/min by using a stirrer, and after the addition of the auxiliary agent is finished, keeping the temperature and stirring for 1 hour to completely dissolve the auxiliary agent;
(3) blending the viscose stock solution and the auxiliary agent solution: filtering the prepared solution by using a filter screen, adding the auxiliary agent into a viscose pipeline in a proportion of 0.5 percent of the content of the alpha cellulose, and mixing by using a static mixer and a homogenizing pump to ensure that the viscose and the auxiliary agent are uniformly mixed;
(4) film forming: spraying the mixed viscose stock solution and the auxiliary agent solution through a spray seam, and then regenerating and solidifying the viscose stock solution and the auxiliary agent solution in a coagulating bath and a regenerating bath to form a film; the components of the bath liquid of the coagulating bath are that the concentration of sulfuric acid is 130g/L, the concentration of sodium sulfate is 230g/L, and the temperature is 40 ℃; the concentration of the sulfuric acid in the regeneration bath is 50g/L, and the temperature is 40 ℃;
(5) wet treatment: washing, desulfurizing, washing, bleaching, dechlorinating, washing and plasticizing the solidified and formed film; wherein the water washing step has water flow of 1m3H, the temperature is 20 ℃; the desulfurization step is that the concentration of NaOH is 3g/L and the temperature is 60 ℃; the bleaching step is as follows: the concentration of the effective chlorine of the sodium hypochlorite is 0.5g/L, and the temperature is less than or equal to 40 ℃; the plasticizing treatment comprises the following steps: glycerin concentration of 30g/L, anti-tack agent concentration5g/L, 40 ℃ and pH 7;
(6) and (3) hot air drying: drying with hot air at 135 deg.C, wherein the temperature is gradually reduced during drying treatment;
(7) moisture conditioning: and (3) carrying out humidity regulation treatment on the dried membrane, wherein the humidity regulation temperature is 55 ℃, and the relative humidity is 60% RH.
Specific example 2
An environment-friendly production process for improving the strength of a regenerated cellulose membrane comprises the steps of firstly preparing an auxiliary agent solution in advance, blending a cellulose viscose stock solution and the auxiliary agent solution, spraying out after mixing, regenerating and solidifying in a solidifying bath and a regenerating bath to form a film, and finally obtaining the regenerated cellulose membrane through wet treatment, drying and humidifying treatment, wherein the auxiliary agent is an alcohol polymer.
The environment-friendly production process for improving the strength of the regenerated cellulose membrane specifically comprises the following operations:
(1) accurately weighing an auxiliary agent, wherein the auxiliary agent is polyvinyl alcohol;
(2) heating the desalted water which is accurately weighed to 90 ℃, adding the weighed auxiliary agent while stirring at the rotating speed of 1000r/min by using a stirrer, and after the addition of the auxiliary agent is finished, keeping the temperature and stirring for 1 hour to completely dissolve the auxiliary agent;
(3) blending the viscose stock solution and the auxiliary agent solution: filtering the prepared solution by using a filter screen, adding the auxiliary agent into a viscose pipeline in a proportion of 3% of the content of the alpha cellulose, and mixing by using a static mixer and a homogenizing pump to ensure that the viscose and the auxiliary agent are uniformly mixed;
(4) film forming: spraying the mixed viscose stock solution and the auxiliary agent solution through a spray seam, and then regenerating and solidifying the viscose stock solution and the auxiliary agent solution in a coagulating bath and a regenerating bath to form a film; the bath liquid of the coagulating bath comprises 160g/L sulfuric acid, 270g/L sodium sulfate and 50 deg.C; the concentration of the sulfuric acid in the regeneration bath is 80g/L, and the temperature is 65 ℃;
(5) wet treatment: washing, desulfurizing, washing, bleaching, dechlorinating, washing and plasticizing the solidified and formed film; wherein the water washing step has water flow of 3m3H, the temperature is 80 ℃; the desulfurization step is that the concentration of NaOH is 6g/L and the temperature is 90 ℃; the bleaching step is as follows: concentration of sodium hypochlorite in available chlorineThe temperature is 4g/L and the temperature is less than or equal to 40 ℃; the plasticizing treatment comprises the following steps: the concentration of the glycerol is 50g/L, the concentration of the antisticking agent is 15g/L, the temperature is 70 ℃, and the pH value is 10;
(6) and (3) hot air drying: drying with hot air at 135-55 deg.C, wherein the temperature is gradually reduced during drying treatment;
(7) moisture conditioning: and (3) carrying out humidity regulation treatment on the dried membrane, wherein the humidity regulation temperature is 65 ℃, and the relative humidity is 75% RH.
Specific example 3
An environment-friendly production process for improving the strength of a regenerated cellulose membrane comprises the steps of firstly preparing an auxiliary agent solution in advance, blending a cellulose viscose stock solution and the auxiliary agent solution, spraying out after mixing, regenerating and solidifying in a solidifying bath and a regenerating bath to form a film, and finally obtaining the regenerated cellulose membrane through wet treatment, drying and humidifying treatment, wherein the auxiliary agent is an alcohol polymer.
The environment-friendly production process for improving the strength of the regenerated cellulose membrane specifically comprises the following operations:
(1) accurately weighing an auxiliary agent, wherein the auxiliary agent is polyvinyl alcohol;
(2) heating the desalted water which is accurately weighed to 80 ℃, adding the weighed auxiliary agent while stirring at the rotating speed of 1000r/min by using a stirrer, and after the addition of the auxiliary agent is finished, keeping the temperature and stirring for 1 hour to completely dissolve the auxiliary agent;
(3) blending the viscose stock solution and the auxiliary agent solution: filtering the prepared solution by using a filter screen, adding the auxiliary agent into a viscose pipeline in a proportion of 0.5-3% of the content of the alpha cellulose, and mixing by using a static mixer and a homogenizing pump to ensure that the viscose and the auxiliary agent are uniformly mixed;
(4) film forming: spraying the mixed viscose stock solution and the auxiliary agent solution through a spray seam, and then regenerating and solidifying the viscose stock solution and the auxiliary agent solution in a coagulating bath and a regenerating bath to form a film; the components of the bath liquid of the coagulating bath are that the concentration of sulfuric acid is 146g/L, the concentration of sodium sulfate is 250g/L, and the temperature is 46 ℃; the concentration of the sulfuric acid in the regeneration bath is 70g/L, and the temperature is 52 ℃;
(5) wet treatment: washing, desulfurizing, washing, bleaching, dechlorinating, washing and plasticizing the solidified and formed film; wherein the water washing step is carried out at a water flow rate of 2m3H, temperature 60DEG C; the desulfurization step is that the concentration of NaOH is 5g/L, and the temperature is 76 ℃; the bleaching step is as follows: the concentration of the effective chlorine of the sodium hypochlorite is 3g/L, and the temperature is less than or equal to 40 ℃; the plasticizing treatment comprises the following steps: the concentration of the glycerol is 40g/L, the concentration of the antisticking agent is 9g/L, the temperature is 60 ℃, and the pH value is 8;
(6) and (3) hot air drying: drying with hot air at 85 deg.C, and gradually reducing the temperature during drying treatment;
(7) moisture conditioning: and (3) carrying out humidity regulation treatment on the dried membrane, wherein the humidity regulation temperature is 59 ℃, and the relative humidity is 60-75% RH.
Through test tests, the strength index of the regenerated cellulose membrane obtained in the embodiment can be improved by about 10%, and the crystallinity is improved by about 8%. Meanwhile, the regenerated fiber membrane is softer and is not easy to break in the production process.
The regenerated cellulose membrane prepared by the method has better mechanical property, the crystallinity, the heat resistance, the strength and the elongation of the product are obviously improved, the biodegradability is basically kept unchanged, the membrane breaking times in production can be effectively reduced, and the continuous production is ensured.
The above disclosure is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and variations which do not require inventive efforts by those skilled in the art are still within the scope of the present invention.
Claims (10)
1. An environment-friendly production process for improving the strength of a regenerated cellulose membrane is characterized in that: firstly, preparing an auxiliary agent solution in advance, blending a cellulose viscose stock solution and the auxiliary agent solution, spraying out after mixing, regenerating and solidifying in a coagulating bath and a regenerating bath to form a film, and finally, carrying out wet treatment, drying and humidity adjustment treatment to obtain a regenerated cellulose film, wherein the auxiliary agent is an alcohol polymer.
2. The environment-friendly production process for improving the strength of a regenerated cellulose membrane according to claim 1, characterized in that: the specific operation is as follows:
(1) accurately weighing an auxiliary agent, wherein the auxiliary agent is an alcohol polymer;
(2) accurately weighing desalted water, heating the desalted water to a certain temperature, adding the weighed auxiliary agent while stirring by using a stirrer, and continuously stirring the auxiliary agent in hot water for a period of time;
(3) blending the viscose stock solution and the auxiliary agent solution: fully mixing the auxiliary agent solution with the viscose stock solution;
(4) film forming: spraying the mixed viscose stock solution and the auxiliary agent solution through a spray seam, and then regenerating and solidifying the viscose stock solution and the auxiliary agent solution in a coagulating bath and a regenerating bath to form a film;
(5) wet treatment: washing, desulfurizing, washing, bleaching, dechlorinating, washing and plasticizing the solidified and formed film;
(6) drying with hot air;
(7) moisture conditioning: and (5) carrying out humidity conditioning treatment on the dried membrane.
3. The environment-friendly production process for improving the strength of the regenerated cellulose membrane according to claim 2, characterized in that: the auxiliary agent in the step (1) is polyvinyl alcohol.
4. The environment-friendly production process for improving the strength of the regenerated cellulose membrane according to claim 2, characterized in that: the step (2) is implemented specifically as follows: heating the desalted water which is accurately weighed to 65-90 ℃, adding the weighed auxiliary agent while stirring at the rotating speed of 1000r/min by using a stirrer, and after the addition of the auxiliary agent is finished, keeping the temperature and stirring for 1 hour to completely dissolve the auxiliary agent.
5. The environment-friendly production process for improving the strength of the regenerated cellulose membrane according to claim 2, characterized in that: the desalted water which is 20 times of the weight of the auxiliary agent is accurately obtained in the step (2), the desalted water is heated to 80 ℃, and the temperature of the desalted water is kept at 80 ℃ at the rotating speed of 1000r/min, and the desalted water is stirred for 1 hour.
6. The environment-friendly production process for improving the strength of the regenerated cellulose membrane according to claim 2, characterized in that: and (3) blending the viscose stock solution and the auxiliary agent solution: filtering the prepared solution by using a filter screen, adding the auxiliary agent into a viscose pipeline in an amount accounting for 0.5-3% of the content of the alpha cellulose, and mixing by using a static mixer and a homogenizing pump to ensure that the viscose and the auxiliary agent are uniformly mixed.
7. The environment-friendly production process for improving the strength of the regenerated cellulose membrane according to claim 2, characterized in that: the step (4) is film forming: the bath liquid components of the coagulating bath are sulfuric acid concentration of 130-160g/L, sodium sulfate concentration of 230-270g/L and temperature of 40-50 ℃; the concentration of the regeneration bath sulfuric acid is 50-80g/L, and the temperature is 40-65 ℃.
8. The environment-friendly production process for improving the strength of the regenerated cellulose membrane according to claim 2, characterized in that: the wet treatment in the step (5): the water washing step is carried out at water flow rate of 1-3m3H, the temperature is 20-80 ℃; the desulfurization step is that the concentration of NaOH is 3-6g/L, and the temperature is 60-90 ℃; the bleaching step is as follows: the concentration of the effective chlorine of the sodium hypochlorite is 0.5-4g/L, and the temperature is less than or equal to 40 ℃; the plasticizing treatment comprises the following steps: the concentration of the glycerol is 30-50g/L, the concentration of the antisticking agent is 5-15g/L, the temperature is 40-70 ℃, and the pH value is 7-10.
9. The environment-friendly production process for improving the strength of the regenerated cellulose membrane according to claim 2, characterized in that: the step (6) is dried by hot air; hot air drying is adopted, the air temperature is 135-55 ℃, and the temperature is gradually reduced during the drying treatment.
10. The environment-friendly production process for improving the strength of the regenerated cellulose membrane according to claim 2, characterized in that: the step (7) of humidifying: and (3) carrying out humidity regulation treatment on the dried membrane, wherein the humidity regulation temperature is 55-65 ℃, and the relative humidity is 60-75% RH.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112046043A (en) * | 2020-08-24 | 2020-12-08 | 成都丽雅纤维股份有限公司 | Continuous production process of cellulose sponge |
| CN115976875A (en) * | 2023-03-17 | 2023-04-18 | 山东中科恒联生物基材料有限公司 | Continuous production method of solvent-method functional regenerated cellulose membrane |
| CN116970208A (en) * | 2023-07-19 | 2023-10-31 | 山东恒联新材料股份有限公司 | Precoated regenerated cellulose base film and preparation method and application thereof |
| WO2023236784A1 (en) * | 2022-06-08 | 2023-12-14 | 山东恒联新材料股份有限公司 | Barrier and heat-sealable cellulose film, preparation method therefor, and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112046043A (en) * | 2020-08-24 | 2020-12-08 | 成都丽雅纤维股份有限公司 | Continuous production process of cellulose sponge |
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| CN116970208A (en) * | 2023-07-19 | 2023-10-31 | 山东恒联新材料股份有限公司 | Precoated regenerated cellulose base film and preparation method and application thereof |
| CN116970208B (en) * | 2023-07-19 | 2024-03-08 | 山东恒联新材料股份有限公司 | Precoated regenerated cellulose base film and preparation method and application thereof |
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Application publication date: 20191220 |