Modification method of cellulosic fiber cheese

Abstract

The invention belongs to the technical field of textile material modification, and particularly relates to a modification method of cellulosic fiber cheese. Comprising the following steps: activating the fiber surface of a cellulosic fiber cheese through cationization pretreatment, and then grafting an alkene monomer to the surface of the cellulosic fiber in a cheese dyeing machine by adopting an emulsion graft polymerization or sol-gel method principle, and finally, carrying out post-treatment to obtain the modified cellulosic fiber cheese. According to the method, the cellulosic fiber cheese is finally modified by selecting the types of the alkene monomers and designing a novel modification process, the method is simple in process, convenient to operate and high in industrialization realizability, the cellulosic fiber yarn modified through the method is obviously increased in weight, and the apparent morphology of the fiber is obviously changed.

Description

Technical Field

[0001] The invention belongs to the technical field of textile material modification, and in particular relates to a method for modifying anti-cellulose fiber cheese yarn. Background Art

[0002] There are many patents or literatures on the grafting modification of various types of fibers with unsaturated olefin monomers, but there are relatively few reports on the grafting modification of cellulose fiber cheese yarns with olefin monomers. In addition, the modification process often involves problems such as large amounts of olefin monomers and low prospects for industrial application.

[0003] Patent CN113897714B discloses a lyocell / cotton fiber blended yarn and a preparation method thereof, wherein the cotton fiber modification treatment steps are: immersing the cotton fiber in a swelling agent, then treating it with helium plasma, and finally reacting it in an alcohol solution of glycidyl methacrylate in an oxygen-free environment. In the invention, glycidyl methacrylate is used as the monomer for modifying the cotton fiber, and the modification process is complicated and the modification time is long (swelling time is 18-25h, modification temperature is 120-130°C, and modification time is 5-8h), and the grafting modification efficiency of glycidyl methacrylate of cotton fiber described in the invention is low.

[0004] The paper "Grafting Modification of Silk Fabrics with Glycidyl Methacrylate" discloses a method for grafting modification of silk fabrics with glycidyl methacrylate. The amount of glycidyl methacrylate used in the paper is high (50% of the weight of the fabric), and the industrial feasibility is poor. More importantly, the method in the document was used to graft modify cellulose fibers such as cotton, and it was found that the fibers / yarns did not gain weight.

[0005] Patent CN109967008B discloses a hemicellulose-based hydrogel, a preparation method and an application thereof, wherein viscose fiber waste liquid is grafted and modified with glycidyl acrylate or glycidyl methacrylate, and then an initiator and a cross-linking agent are sequentially added to react to obtain a primary hydrogel. The amount of olefin monomers used in the invention reaches 350-700 g / L. The amount of olefin monomers used in the invention is large and the reaction time is long. Summary of the invention

[0006] In view of the deficiencies in the prior art, the purpose of the present invention is to provide a method for modifying cellulose fiber cheese yarn, which promotes the grafting modification of olefin monomers to cellulose fibers by performing cationic pretreatment on the cellulose fiber cheese yarn, thereby achieving modification and significantly changing the apparent morphological characteristics of the fibers.

[0007] The technical solution adopted by the present invention is as follows:

[0008] The method for modifying cellulose fiber cheese yarn comprises the following steps:

[0009] (1) Cationic pretreatment:

[0010] The cellulose fiber cheese yarn is placed in a cationic pretreatment liquid for pretreatment, and then washed with water after the pretreatment, wherein the cationic pretreatment liquid comprises: a cationic auxiliary agent, a penetrant and solvent water;

[0011] (2) Graft modification:

[0012] A neutralizing acid, an emulsifier, an initiator and an unsaturated olefin monomer are added to a solvent water to obtain a graft modification solution, and then the graft modification solution is added to the cellulose fiber cheese yarn pretreated by cationization to perform graft modification;

[0013] (3) Post-processing:

[0014] The modification of the cellulose fiber cheese yarn is completed by sequentially washing with water, soaping and drying.

[0015] The modification method of the cellulose fiber cheese yarn is characterized in that the cellulose fiber is one of cotton fiber, tencel fiber, flax fiber, viscose fiber and bamboo fiber, the yarn fineness of the cheese yarn is 6-60tex, and the weight of the cheese yarn is 0.3-1.0kg / piece.

[0016] The mass ratio of the cellulose fiber cheese yarn to the solvent water in the steps (1) and (2) is 1:(6-20), and the mass ratio of the cellulose fiber cheese yarn to water in the washing and soaping process of the step (3) is 1:(6-20).

[0017] The cationic auxiliary agent in step (1) is a quaternary ammonium salt compound containing an epoxy group, preferably 3-chloro-2-hydroxypropyltrimethylammonium chloride or a chitosan quaternary ammonium salt, and more preferably a chitosan quaternary ammonium salt modifier BS, which is purchased from Changzhou Meisheng Biomaterials Co., Ltd.

[0018] In the step (1), the penetrant is a polyoxyethylene ether compound, preferably, the penetrant is JFC, purchased from Zibo Lurui Fine Chemical Co., Ltd.

[0019] In the step (1), the amount of the cationizing agent is 6-15 g / L, the amount of the penetrant is 0.5-1.5 g / L, the pretreatment temperature is 65-85° C., and the time is 30-60 min.

[0020] The water washing in step (1) includes hot water washing and cold water washing, wherein the temperature of the hot water washing is 80-90°C and the time is 10-15 minutes, and the temperature of the cold water washing is 25-35°C and the time is 5-10 minutes.

[0021] The neutralizing acid in the step (2) is a mixture of citric acid and maleic acid, the emulsifier is fatty alcohol polyoxyethylene ether, the initiator is one or more of ammonium persulfate or potassium persulfate, and the unsaturated olefin monomer is one or more of glycidyl methacrylate, methylenebispropionamide or vinyltrimethoxysilane; preferably, the neutralizing acid is PH-N and the emulsifier is WA-M, both of which are purchased from Zibo Lurui Fine Chemical Co., Ltd.

[0022] In the step (2), the amount of neutralizing acid is 0.5-5g / L, the amount of emulsifier is 0.5-1.5g / L, the amount of unsaturated olefin monomer is 5-20g / L, and the amount of initiator is 0-2% of the mass of the unsaturated olefin monomer. Preferably, the amount of neutralizing acid is 0.5-2g / L, the amount of emulsifier is 0.75-1g / L, the amount of unsaturated olefin monomer is 6-12g / L, and the amount of initiator is 0-1.5% of the mass of the unsaturated olefin monomer.

[0023] The process conditions for grafting modification in step (2) are: temperature 70-90°C, time 20-60 min, preferably, temperature 70-80°C, time 30-50 min.

[0024] In the step (3), the water washing temperature is 60-90°C, and the water washing time is 5-15min; the amount of soaping agent used in soap washing is 1-3g / L, the soap washing temperature is 85-98°C, and the soap washing time is 10-30min; and a radio frequency dryer is used for drying;

[0025] The modification of the cellulose fiber cheese yarn is carried out in a cheese yarn dyeing machine, and the pump speed of the dyeing machine is set to 80-95%.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] (1) The modification method of the present invention is carried out in a cheese dyeing machine, which has simple process, convenient operation and strong industrial feasibility;

[0028] (2) Compared with the conventional olefin monomer modification process, the modification method of the present invention requires a smaller amount of monomer to be added, which can effectively reduce the modification cost;

[0029] (3) The graft modification reaction time of the unsaturated olefin monomers described in the present invention is short and the production and processing efficiency is high;

[0030] (4) The cellulose fiber cheese yarn obtained by the modification method described in the present invention has a significant weight gain, and the apparent morphology of the fiber changes significantly; the yarn modified by grafting with unsaturated olefin monomers can be improved in properties such as strength and hydrophobicity, and can be used as a bridging group to further react with other functional compounds. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 is a scanning electron micrograph of untreated cotton fiber (×3000);

[0032] Figure 2 is the scanning electron micrograph of cotton fiber after cationic pretreatment (×3000 times);

[0033] Figure 3 is a scanning electron micrograph of untreated Tencel fiber (×3000);

[0034] Figure 4 is a scanning electron microscope image (×2000 times) of the cellulose fiber modified with the unsaturated olefin monomer in Example 1;

[0035] Figure 5 is a scanning electron microscope image (×3000 times) of the cellulose fiber modified with the unsaturated olefin monomer in Example 2;

[0036] Figure 6 This is a scanning electron microscope image (×2000 times) of the cellulose fiber modified with the unsaturated olefin monomer in Example 3. DETAILED DESCRIPTION

[0037] The present invention is further described below with reference to the embodiments, but they do not limit the implementation of the present invention.

[0038] Example 1

[0039] The cellulose fiber is cotton fiber, the cheese yarn fineness is 11.81tex, the cheese yarn weight is 0.6kg / piece, and the specific modification process is as follows:

[0040] (1) Cationic pretreatment of cotton fiber, the dosage of cationic auxiliary agent BS is 15g / L, the dosage of penetrant JFC is 1g / L, the pump speed of the dyeing machine is 85%, the mass ratio of cheese yarn to water is 1:10, the pretreatment temperature is 65°C, the time is 60min, and after the pretreatment, the pure cotton cheese yarn is washed with hot water (temperature 80°C, time 15min) and cold water (temperature 35°C, time 5min) respectively;

[0041] (2) Grafting modification of unsaturated olefin monomers: fix the pretreated cotton fiber cheese on a yarn carrier and put it into a dyeing machine. The pump speed of the dyeing machine is set to 85%, and the flow direction is from inside to outside. After the dyeing machine runs for 10 minutes, a mixed solution of 0.5g / L neutralizing acid PH-N and 1g / L fatty alcohol polyoxyethylene ether emulsifier WA-M is injected into the main cylinder of the dyeing machine from a small auxiliary cylinder in sequence. The mass ratio of cheese to water is 1:10. After heating to 60°C and maintaining for 30 minutes, 20g / L vinyl trimethoxysilane is added to the main cylinder of the dyeing machine. After heating to 80°C and maintaining for 40 minutes, the grafting reaction is completed by draining.

[0042] (3) The modified cotton fiber cheese yarn was post-treated by washing, soaping and drying in sequence: the washing temperature was 90°C, the washing time was 5 min, and the above conditions were used for washing twice; the amount of soaping agent used in soaping was 1 g / L, the soaping temperature was 98°C, and the time was 10 min; the mass ratio of cheese yarn to water during washing and soaping was 1:10, and after soaping, it was dried in a radio frequency dryer.

[0043] Example 2

[0044] The cellulose fiber is Tencel fiber, the cheese yarn fineness is 14.76tex, the cheese yarn weight is 0.3kg / piece, and the specific modification process is as follows:

[0045] (1) cationic pretreatment of Tencel fiber, the amount of cationic auxiliary agent BS is 8g / L, the amount of penetrant JFC is 0.75g / L, the pump speed of the dyeing machine is 95%, the mass ratio of cheese yarn to water is 1:20, the pretreatment temperature is 85°C, the time is 40min, and after the pretreatment, the Tencel fiber cheese yarn is washed with hot water (temperature 90°C, time 10min) and cold water (temperature 25°C, time 10min) respectively;

[0046] (2) Grafting modification of unsaturated olefin monomers: fix the pretreated Tencel fiber cheese on a yarn carrier and put it into a dyeing machine. The pump speed of the dyeing machine is set to 95%, and the flow direction is from inside to outside. After the dyeing machine has been running for 10 minutes, a mixed solution of 2g / L neutralizing acid PH-N, 1.5g / L fatty alcohol polyoxyethylene ether emulsifier WA-M and 0.12g / L initiator ammonium persulfate is injected into the main cylinder of the dyeing machine from a small auxiliary cylinder in sequence. The mass ratio of cheese yarn to water is 1:20. After heating to 60°C and maintaining for 30 minutes, a mixed emulsion of 6g / L methacrylate glycidyl ester and 0.3g / L methylenebisacrylamide is added to the main cylinder of the dyeing machine. After heating to 70°C and maintaining for 60 minutes, the mixed emulsion is drained to complete the grafting reaction.

[0047] (3) The modified Tencel fiber cheese yarn was post-treated by washing, soaping and drying in sequence: the washing temperature of the water washing was 75°C, and the washing time was 10 min; the amount of soaping agent used in the soap washing was 2 g / L, the soaping temperature was 90°C, and the time was 20 min; the mass ratio of the cheese yarn to water during the water washing and soaping process was 1:20, and the radio frequency dryer was used for drying after soaping.

[0048] Example 3

[0049] The cellulose fiber is made of cotton fiber, the fineness of the cheese yarn is 60tex, and the weight of the cheese yarn is 1kg / piece. The specific modification process is as follows:

[0050] (1) Cationic pretreatment of cotton fiber, the dosage of cationic auxiliary agent BS is 6g / L, the dosage of penetrant JFC is 0.5g / L, the pump speed of the dyeing machine is 80%, the mass ratio of cheese yarn to water is 1:20, the pretreatment temperature is 75°C, the time is 60min, and after the pretreatment, the pure cotton cheese yarn is washed with hot water (temperature 85°C, time 12min) and cold water (temperature 30°C, time 8min) respectively;

[0051] (2) Grafting modification of unsaturated olefin monomers: fix the pretreated cotton fiber cheese on a yarn carrier and put it into a dyeing machine. The pump speed of the dyeing machine is set to 80%, and the flow direction is from inside to outside. After the dyeing machine has been running for 10 minutes, a mixed solution of 1g / L neutralizing acid PH-N and 0.5g / L fatty alcohol polyoxyethylene ether emulsifier WA-M is injected into the main cylinder of the dyeing machine from a small auxiliary cylinder in sequence. The mass ratio of cheese to water is 1:20. After heating to 90°C and holding for 20 minutes, 12g / L glycidyl methacrylate is added to the main cylinder of the dyeing machine. After heating to 80°C and holding for 30 minutes, drain the water to complete the grafting reaction.

[0052] (3) The modified cotton fiber cheese yarn was post-treated by hot water washing, soap washing and drying in sequence: the washing temperature was 60°C, the washing time was 15 min; the amount of soaping agent was 3 g / L, the soap washing temperature was 85°C, and the time was 30 min; the mass ratio of cheese yarn to water during the washing and soap washing process was 1:20, and after soap washing, a radio frequency dryer was used for drying.

[0053] Comparative Example 1

[0054] The cellulose fiber is cotton fiber, the cheese yarn fineness is 11.81tex, the cheese yarn weight is 0.6kg / piece, and the specific modification process is as follows:

[0055] (1) Grafting modification of unsaturated olefin monomers: fix cotton fiber cheese on a yarn carrier and put it into a dyeing machine. The pump speed of the dyeing machine is set to 85%, and the flow direction is from inside to outside. After the dyeing machine runs for 10 minutes, a mixed solution of 0.5 g / L neutralizing acid PH-N and 1 g / L fatty alcohol polyoxyethylene ether emulsifier WA-M is injected into the main cylinder of the dyeing machine from a small auxiliary cylinder in sequence. The mass ratio of cheese to water is 1:10. After heating to 60°C and holding for 30 minutes, 20 g / L vinyl trimethoxy silane is added to the main cylinder of the dyeing machine. After heating to 80°C and holding for 40 minutes, the grafting reaction is completed by draining.

[0056] (2) The modified cotton fiber cheese yarn was post-treated by washing, soaping and drying in sequence: the washing temperature was 90°C, the washing time was 5 min, and the above conditions were used for washing twice; the amount of soaping agent used in soaping was 1 g / L, the soaping temperature was 98°C, and the time was 10 min; the mass ratio of cheese yarn to water during washing and soaping was 1:10, and after soaping, it was dried in a radio frequency dryer.

[0057] Comparative Example 2

[0058] The cellulose fiber is Tencel fiber, the cheese yarn fineness is 14.76tex, the cheese yarn weight is 0.3kg / piece, and the specific modification process is as follows:

[0059] (1) Grafting modification of unsaturated olefin monomers: fix the tencel fiber cheese on a yarn carrier and put it into a dyeing machine. The pump speed of the dyeing machine is set to 95%, and the flow direction is from inside to outside. After the dyeing machine runs for 10 minutes, a mixed solution of 2g / L neutralizing acid PH-N, 1.5g / L fatty alcohol polyoxyethylene ether emulsifier WA-M and 0.12g / L initiator ammonium persulfate is injected into the main cylinder of the dyeing machine from a small auxiliary cylinder in sequence. The mass ratio of cheese yarn to water is 1:20. After heating to 60°C and holding for 30 minutes, a mixed emulsion of 6g / L methacrylate glycidyl ester and 0.3g / L methylenebisacrylamide is added to the main cylinder of the dyeing machine. After heating to 70°C and holding for 60 minutes, the mixed emulsion is drained to complete the grafting reaction.

[0060] (2) The modified Tencel fiber cheese yarn was post-treated by washing, soaping and drying in sequence: the washing temperature was 75°C, and the washing time was 10 min; the amount of soaping agent was 2 g / L, the soaping temperature was 90°C, and the time was 20 min; the mass ratio of cheese yarn to water during washing and soaping was 1:20, and after soaping, it was dried in a radio frequency dryer.

[0061] Comparative Example 3

[0062] The cellulose fiber is made of cotton fiber, the fineness of the cheese yarn is 60tex, and the weight of the cheese yarn is 1kg / piece. The specific modification process is as follows:

[0063] (1) Grafting modification of unsaturated olefin monomers: fix cotton fiber cheese on a yarn carrier and put it into a dyeing machine. The pump speed of the dyeing machine is set to 80%, and the flow direction is from inside to outside. After the dyeing machine runs for 10 minutes, a mixed solution of 1g / L neutralizing acid PH-N and 0.5g / L fatty alcohol polyoxyethylene ether emulsifier WA-M is injected into the main cylinder of the dyeing machine from a small auxiliary cylinder in sequence. The mass ratio of cheese to water is 1:20. After heating to 60°C and holding for 20 minutes, 12g / L glycidyl methacrylate is added to the main cylinder of the dyeing machine. After heating to 90°C and holding for 20 minutes, the mixture is drained to complete the grafting reaction.

[0064] (2) The modified cotton fiber cheese yarn was post-treated by hot water washing, soap washing and drying in sequence: the washing temperature was 60°C, the washing time was 15 min; the amount of soaping agent was 3 g / L, the soap washing temperature was 85°C, and the time was 30 min; the mass ratio of cheese yarn to water during the washing and soap washing process was 1:20, and after soap washing, a radio frequency dryer was used for drying.

[0065] Test method:

[0066] The weight gain rate of the yarns before and after modification of Examples 1-3 and Comparative Examples 1-3 was tested; the wicking performance of the yarns obtained after post-treatment in Example 1 and Comparative Example 1 was tested using FZ / T01071-2008 "Test method for capillary effect of textiles"; the yarn strength of the yarns obtained after post-treatment in Examples 2-3 and Comparative Examples 2-3 was tested using GB / T3916-1997 "Determination of breaking strength and breaking elongation of a single yarn"; the test results are shown in Table 1; at the same time, the morphology of the cellulose fiber before and after modification and the cotton fiber after cationization pretreatment was tested using a scanning electron microscope, and the results are shown in Table 1. Figure 1-6 shown.

[0067] The calculation formula of the yarn weight gain rate after modification is as follows:

[0068]

[0069] Where: GR is the weight gain rate of the modified yarn; N m is the mass of the modified yarn after drying; N0 is the mass of the unmodified yarn after drying.

[0070] Table 1 Comparison of yarn properties

[0071]

[0072]

[0073] According to the data in Table 1 and Figure 1-6It can be seen from the electron microscope pictures that the modified yarns obtained by Examples 1-3 of the present invention have gained significant weight compared to the original yarns, and the surface morphology of the modified yarns has changed significantly; while the yarns treated by the methods of Comparative Examples 1-3 have no weight gain. From the above data analysis, it can be seen that the modification method of the present invention can successfully graft olefin monomers to the surface of cellulose fibers. The wicking height of the yarn obtained after post-treatment in Example 1 is 0, while the wicking height of the yarn obtained after post-treatment in Comparative Example 1 is 8.5, indicating that the hydrophobicity of the yarn obtained after post-treatment in Example 1 is significantly improved compared to Comparative Example 1. The strength of the yarns obtained after post-treatment in Examples 2-3 is significantly improved compared to Comparative Examples 2-3, which are increased by 13.05% and 22.6%, respectively. From the above data analysis, it can be seen that the modification method of the present invention can successfully graft olefin monomers to the surface of cellulose fibers and can bring about significant performance improvement effects.

Claims

1. A method for modifying cellulose fiber cheese yarn, characterized in that: The following steps are involved: (1) Cationic pretreatment: The cellulose fiber cheese yarn is placed in a cationic pretreatment liquid for pretreatment, and then washed with water after the pretreatment, wherein the cationic pretreatment liquid comprises: a cationic auxiliary agent, a penetrant and solvent water; (2) Graft modification: A neutralizing acid, an emulsifier, an initiator and an unsaturated olefin monomer are added to a solvent water to obtain a graft modification solution, and then the graft modification solution is added to the cellulose fiber cheese yarn pretreated by cationization to perform graft modification; (3) Post-processing: The modification of the cellulose fiber cheese yarn is completed by washing with water, soaping and drying in sequence.

2. The method for modifying cellulose fiber cheese yarn according to claim 1, characterized in that: The cellulose fiber is one of cotton fiber, tencel fiber, flax fiber, viscose fiber and bamboo fiber. The yarn fineness of the cheese yarn is 6-60tex, and the weight of the cheese yarn is 0.3-1.0kg / piece.

3. The method for modifying cellulose fiber cheese yarn according to claim 1, characterized in that: The mass ratio of the cellulose fiber cheese yarn to the solvent water in the steps (1) and (2) is 1:(6-20), and the mass ratio of the cellulose fiber cheese yarn to water in the washing and soaping process of the step (3) is 1:(6-20).

4. The method for modifying cellulose fiber cheese yarn according to claim 1, characterized in that: In the step (1), the cationic auxiliary agent is a quaternary ammonium salt compound containing an epoxy group, and the penetrant is a polyoxyethylene ether compound.

5. The method for modifying cellulose fiber cheese yarn according to claim 1, characterized in that: In the step (1), the amount of the cationizing agent is 6-15 g / L, the amount of the penetrant is 0.5-1.5 g / L, the pretreatment temperature is 65-85° C., and the time is 30-60 min.

6. The method for modifying cellulose fiber cheese yarn according to claim 1, characterized in that: The water washing in step (1) includes hot water washing and cold water washing, wherein the temperature of the hot water washing is 80-90°C and the time is 10-15 minutes, and the temperature of the cold water washing is 25-35°C and the time is 5-10 minutes.

7. The method for modifying cellulose fiber cheese yarn according to claim 1, characterized in that: The neutralizing acid in step (2) is a mixture of citric acid and maleic acid, the emulsifier is fatty alcohol polyoxyethylene ether, the initiator is one or more of ammonium persulfate or potassium persulfate, and the unsaturated olefin monomer is one or more of glycidyl methacrylate, methylenebispropionamide or vinyl trimethoxysilane.

8. The method for modifying cellulose fiber cheese according to claim 1, characterized in that: In the step (2), the amount of neutralizing acid is 0.5-5 g / L, the amount of emulsifier is 0.5-1.5 g / L, the amount of unsaturated olefin monomer is 5-20 g / L, and the amount of initiator is 0-2% of the mass of the unsaturated olefin monomer.

9. The method for modifying cellulose fiber cheese according to claim 1, characterized in that: The process conditions for grafting modification in step (2) are: temperature 70-90° C., time 20-60 min.

10. The method for modifying cellulose fiber cheese yarn according to claim 1, characterized in that: In the step (3), the water washing temperature is 60-90°C, and the water washing time is 5-15min; the amount of soaping agent used in soap washing is 1-3g / L, the soap washing temperature is 85-98°C, and the soap washing time is 10-30min; and a radio frequency dryer is used for drying; The modification of the cellulose fiber cheese yarn is carried out in a cheese yarn dyeing machine, and the pump speed of the dyeing machine is set to 80-95%.

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