阅读说明：本技术 一种非织布材料及其应用 (Non-woven fabric material and application thereof ) 是由 陆业昌 甘静 姚泽伟 蔡熙扬 郭晓丹 黄煜璇 卢志敏 张世林 刘保 于 2020-04-30 设计创作，主要内容包括：本发明公开了一种非织布材料及其应用。其中所述非织布材料通过如下步骤制备而成：S1、将纤维素氧化得2,3-双羧基纤维素,在加热及脱水剂的作用下与(4-乙烯基苯基-4’-亚甲基羧基苯基)碘鎓封端聚乙烯吡咯烷酮发生缩合反应得改性纤维素A；S2、将纤维素经氧化得6-羧基纤维素,再经阳离子改性,得改性纤维素B；S3、混合改性纤维素A和改性纤维素B得混合纤维,经预处理,成网、加固、化学后整理后即得。该非织布材料在不影响洗涤剂的去污效果下增加吸色纤维的吸色能力,从而有效防止织物洗涤过程中的串色问题。(The invention discloses a non-woven fabric material and application thereof. Wherein the non-woven fabric material is prepared by the following steps: s1, oxidizing cellulose to obtain 2, 3-dicarboxyl cellulose, and carrying out condensation reaction with (4-vinylphenyl-4' -methylenecarboxyphenyl) iodonium terminated polyvinylpyrrolidone under the action of heating and a dehydrating agent to obtain modified cellulose A; s2, oxidizing cellulose to obtain 6-carboxyl cellulose, and modifying by cations to obtain modified cellulose B; s3, mixing the modified cellulose A and the modified cellulose B to obtain mixed fibers, and carrying out pretreatment, web formation, reinforcement and chemical after-treatment to obtain the composite fiber. The non-woven fabric material increases the color absorbing capacity of the color absorbing fiber under the condition of not influencing the decontamination effect of a detergent, thereby effectively preventing the color cross problem in the fabric washing process.)

1. A non-woven fabric material is characterized by being prepared by the following steps:

s1, oxidizing cellulose to obtain 2, 3-dicarboxyl cellulose, and carrying out condensation reaction with (4-vinylphenyl-4' -methylenecarboxyphenyl) iodonium terminated polyvinylpyrrolidone under the action of heating and a dehydrating agent to obtain modified cellulose A;

s2, oxidizing cellulose to obtain 6-carboxyl cellulose, and modifying by cations to obtain modified cellulose B;

s3, mixing the modified cellulose A and the modified cellulose B to obtain mixed fibers, and carrying out pretreatment, web formation, reinforcement and chemical after-treatment to obtain the composite fiber.

2. The nonwoven fabric material according to claim 1, wherein the mass ratio of the (4-vinylphenyl-4 '-methylenecarboxyphenyl) iodonium-terminated polyvinylpyrrolidone to the 2, 3-biscarboxy cellulose is in the range of (1:9) to (6:4), and the amount of the dehydrating agent is 3 to 8% of the total mass of the 2, 3-biscarboxy cellulose and the (4-vinylphenyl-4' -methylenecarboxyphenyl) iodonium-terminated polyvinylpyrrolidone; preferably, the dehydrating agent is selected from phosphorus pentoxide, acetic anhydride, acetyl chloride or phosphorus oxychloride; preferably, the heating temperature range is 50-65 ℃.

3. The nonwoven material of claim 1, wherein the (4-vinylphenyl-4' -methylenecarboxyphenyl) iodonium terminated polyvinylpyrrolidone is prepared by the following method: performing polymerization reaction on vinyl pyrrolidone aqueous solution under the action of a catalyst and an initiator, adding (4-vinylphenyl-4' -methylene carboxyl phenyl) iodonium, sealing, and drying to obtain the catalyst.

4. The nonwoven material of claim 3, wherein the mass ratio of the aqueous vinylpyrrolidone solution, the catalyst, the initiator, and the 4-vinylphenyl-4' -methylenecarboxyphenyl) iodonium is 100: (0.2-0.5): (0.3-0.6): (0.5 to 2); preferably, the catalyst is hydrogen peroxide; preferably, the initiator is azobisisobutyronitrile.

5. The non-woven fabric material according to claim 3, wherein the temperature of the polymerization reaction of the vinyl pyrrolidone aqueous solution, the catalyst and the initiator is 40-80 ℃, and the reaction time is 2-5 h; preferably, the reaction time is 0.2-0.8 h after the (4-vinylphenyl-4' -methylenecarboxyphenyl) iodonium is added; preferably, after the (4-vinylphenyl-4' -methylenecarboxyphenyl) iodonium terminated polyvinylpyrrolidone is obtained, 0.2-0.6 mass percent of ammonia water is added into the polymer; preferably, the drying is spray drying, and the hot air temperature range of the spray drying is 120-180 ℃.

6. The nonwoven material of claim 3, wherein the (4-vinylphenyl-4' -methylenecarboxyphenyl) iodonium is prepared by: the diphenyl iodonium salt reacts with ethylene under the action of a molecular sieve catalyst to obtain 4,4 '-divinyl diphenyl iodonium, and then (4-vinyl phenyl-4' -methylene carboxyl phenyl) iodonium is obtained through catalyst oxidation.

7. The non-woven fabric material according to claim 6, wherein the mass ratio of the diphenyl iodonium salt to the ethylene is (7:1) - (9:1), and the amount of the molecular sieve catalyst is 0.05-0.2% of the mass of the ethylene; preferably, the reaction pressure is 0.8-2.0 MPa, and the reaction temperature is 120-220 ℃; preferably, the molecular sieve catalyst is selected from a magnesium, calcium or barium exchanged sodium ZSM-5 type molecular sieves.

8. The nonwoven material of claim 6, wherein the catalyst employed for oxidizing 4,4' -divinyldiphenyliodonium is a supported palladium heteropolyacid catalyst; preferably, the amount of the catalyst is 0.02-0.1% of the mass of 4,4' -divinyl diphenyl iodonium; preferably, the reaction temperature is 140-260 ℃ and the reaction pressure is 0.3-1.5 MPa.

9. The nonwoven material of claim 1, wherein the 2, 3-dicarboxy cellulose is prepared by the following method:

1) dialdehyde cellulose: sodium acetate and HIO for cellulose₄Oxidizing at 35-45 ℃ for 40-60 h;

2) 2, 3-dicarboxylcellulose: dripping an acidic potassium permanganate solution (5% aqueous solution) into dialdehyde cellulose at the temperature of 47-53 ℃ until the acidic potassium permanganate does not fade, recrystallizing and drying to obtain the dialdehyde cellulose.

10. The nonwoven material of claim 7, wherein the concentration of sodium acetate is in the range of 0.03-0.08 g/mL, preferably, the HIO₄In the concentration range ofIs 0.08-0.2 g/mL; preferably, the concentration of the cellulose is 0.03-0.06 g/mL; preferably, the cellulose is soaked in a methanol-water solution with the mass ratio of 0.2-5 for 2-6 h.

11. The nonwoven fabric material according to claim 1, wherein the oxidizing agent used in step S2 is 2,2,6, 6-tetramethylpiperidinyloxy/NaClO/NaBr reagent; preferably, the mass ratio of the cellulose to the 2,2,6, 6-tetramethylpiperidine oxide to the NaClO to the NaBr is in the range of 1: (0.01-0.025): (2-4): (0.08-0.12); preferably, the reaction temperature is 0-5 ℃, the reaction time is 10-20 h, and the pH is 9-11.

12. The nonwoven fabric material of claim 1, wherein the mass ratio of 6-carboxyl cellulose to cation addition reaction in step S2 is 1: (1-4), and the reaction temperature is 40-60 ℃.

13. The nonwoven material of claim 1, wherein the cationic structure is as follows:

wherein R1 is a linear chain saturated alkyl with the chain length of C1-C3, preferably methyl; r2 is a straight chain alkyl with the chain length of C1-C18 and at most one unsaturated bond.

14. The nonwoven material of claim 1 or 13, wherein the cation is selected from the group consisting of a glycidyltrimethylquaternary ammonium salt, a 1, 2-epoxybutanetriethylquaternary ammonium salt, a 1, 2-epoxydecanetripropylquaternary ammonium salt, and a 1, 2-epoxyoctadecane-N-methyl-N-ethyl-N-propyl quaternary ammonium salt; preferably, after the reaction in step S2 is completed, the mixture is washed to be neutral, filtered and dried.

15. The nonwoven fabric material according to claim 1, wherein the mixing mass ratio of the modified cellulose a and the modified cellulose B in step S3 is in the range of (80:20) to (20: 80); preferably, the mixing mass ratio of the modified cellulose A to the modified cellulose B is in the range of (60:40) to (40: 60).

16. The nonwoven material of claim 1, wherein the cellulose is selected from natural cellulose and/or regenerated cellulose.

17. Use of the nonwoven material according to any of claims 1 to 16 for the color-absorbing and stain-proofing of textiles in washing.

Technical Field

The invention belongs to the field of textile engineering, and particularly relates to a non-woven fabric material and application thereof.

Background

During the washing process of daily worn fabrics, dyes on the surfaces of the fabrics can fall off into the washing solution and are transferred to the surfaces of other fabrics in the washing solution along with the stirring of the washing operation, so that the color cross phenomenon seen by the naked eyes of people is caused. Generally, dyes used for textiles have a strong affinity for textiles, and the dyes can be bound to textile fibers by van der waals forces, hydrogen bonds, and chemical bonds, so that dye molecules are fixed on the fibers, a so-called dyeing process. The dyeing process is reversible, in which part of the dye linkage to the fabric fibers can be broken during washing, the dye molecules are restored to free molecules, but the total amount of broken free dye molecules is small. Therefore, once the cross-color phenomenon occurs, the dye molecules are stained on other fabrics, and the dye molecules in the stained positions are difficult to fall off completely by a rewashing method. However, the color of the fabric surface is changed remarkably, which affects the evaluation of the fabric look and feel of consumers.

Generally, light-colored clothes are stained with dark-colored dye strings, and then the visual effect is greatly influenced, so that consumers are used to sort the light-colored clothes and the dark-colored clothes and then wash the light-colored clothes and the dark-colored clothes respectively, and the risk that the light-colored clothes are stained is effectively reduced. However, this does not completely prevent light-colored clothes from being stained, because the clothes washed together may not always be the same color. In addition, sorting and washing the laundry increases the amount of labor of the washer, and requires more water, electricity, detergent, and labor time to be consumed.

At present, color absorbing sheets with the function of preventing color cross talk have been developed in the industry to achieve the purpose that the fabric does not cross talk when in shuffling. CN103132276A discloses a viscose non-woven fabric modified by 2, 3-epoxypropyltrimethylammonium chloride; CN106319760B discloses a non-woven fabric formed by combining anion modified fibers and cation modified fibers; CN107474178A discloses an acrylate copolymer containing a cationic monomer copolymer. The core ideas of the patent applications are as follows: a water-insoluble substrate is loaded with charged ionic groups, and free dye molecules with opposite charges are adsorbed on the substrate through electrostatic adsorption, so that the dye molecules cannot move freely in the washing process, and the cross-color phenomenon is prevented.

However, the imbibition film based on this idea has two serious drawbacks: firstly, in the actual washing process, the distance between the fabrics is very small, even the surfaces of two fabrics are often tightly attached, but the electrostatic adsorption depended on in the above thought is a passive adsorption method, which just can adsorb dye molecules near the color absorbing sheet like the function of a filter screen, but cannot effectively adsorb dye molecules far away from the color absorbing sheet; therefore, the dye falling off from the fabric is often dyed on the fabric at a closer distance before being absorbed by the color absorbing sheet. Secondly, detergent is usually required to be added in the washing process to improve the effect of washing stains, the detergent often contains a large amount of anionic surfactant and sometimes also contains a small amount of cationic surfactant, and the ionic surfactants can be strongly adsorbed by the color absorbing sheet. When the color absorbing sheet absorbs the surfactant instead of the target dye, the color absorbing capacity of the color absorbing sheet is reduced, and the color cross-color preventing effect of the color absorbing sheet is reduced. In addition, the color absorbing sheet absorbs the surfactant, so that the concentration of effective substances of the detergent is reduced, and the decontamination effect of the detergent is also reduced.

Therefore, it is necessary to prepare more effective anti-cross-color materials to solve the cross-color problem more effectively.

Disclosure of Invention

In order to solve the above technical problems in the prior art, the present invention provides a nonwoven fabric material that more effectively solves the problem of cross-color, and that increases the color absorbing ability of the color absorbing fiber without affecting the stain removing effect of the detergent.

The first technical purpose of the invention is realized by the following technical scheme:

the invention provides a non-woven fabric material which is prepared by the following steps:

s1, oxidizing cellulose to obtain 2, 3-dicarboxyl cellulose, and carrying out condensation reaction with (4-vinylphenyl-4' -methylenecarboxyphenyl) iodonium terminated polyvinylpyrrolidone and a dehydrating agent under the action of heating and the dehydrating agent to obtain modified cellulose A;

s2, oxidizing cellulose to obtain 6-carboxyl cellulose, and modifying by cations to obtain modified cellulose B;

s3, mixing the modified cellulose A and the modified cellulose B to obtain mixed fibers, and carrying out pretreatment, web formation, reinforcement and chemical after-treatment to obtain the composite fiber.

Further, the mass ratio of the (4-vinylphenyl-4 '-methylenecarboxyphenyl) iodonium terminated polyvinylpyrrolidone to the 2, 3-dicarboxy cellulose ranges from (1:9) to (6:4), and the amount of the dehydrating agent is 3-8% of the total mass of the 2, 3-dicarboxy cellulose and the (4-vinylphenyl-4' -methylenecarboxyphenyl) iodonium terminated polyvinylpyrrolidone; preferably, the dehydrating agent is selected from phosphorus pentoxide, acetic anhydride, acetyl chloride or phosphorus oxychloride; preferably, the heating temperature range is 50-65 ℃.

Further, the (4-vinylphenyl-4' -methylenecarboxyphenyl) iodonium terminated polyvinylpyrrolidone of the present invention is prepared by the following method: performing polymerization reaction on vinyl pyrrolidone aqueous solution under the action of a catalyst and an initiator, adding (4-vinylphenyl-4' -methylene carboxyl phenyl) iodonium, sealing, and drying to obtain the catalyst.

Furthermore, the mass ratio of the vinyl pyrrolidone aqueous solution, the catalyst and the initiator to the 4-vinylphenyl-4' -methylenecarboxyphenyl) iodonium is 100: (0.2-0.5): (0.3-0.6): (0.5 to 2); preferably, the catalyst is hydrogen peroxide; preferably, the initiator is azobisisobutyronitrile.

Further, the temperature of the polymerization reaction of the vinyl pyrrolidone aqueous solution, the catalyst and the initiator is 40-80 ℃, and the reaction time is 2-5 h; preferably, the reaction time is 0.2-0.8 h after the (4-vinylphenyl-4' -methylenecarboxyphenyl) iodonium is added; preferably, after the (4-vinylphenyl-4' -methylenecarboxyphenyl) iodonium terminated polyvinylpyrrolidone is obtained, 0.2-0.6 mass percent of ammonia water is added into the polymer; preferably, the drying is spray drying, and the hot air temperature range of the spray drying is 120-180 ℃.

Further, the (4-vinylphenyl-4' -methylenecarboxyphenyl) iodonium of the present invention is prepared by the following method: the diphenyl iodonium salt reacts with ethylene under the action of a molecular sieve catalyst to obtain 4,4 '-divinyl diphenyl iodonium, and then (4-vinyl phenyl-4' -methylene carboxyl phenyl) iodonium is obtained through catalyst oxidation.

Furthermore, the mass ratio of the diphenyl iodonium salt to the ethylene is (7:1) - (9:1), and the dosage of the molecular sieve catalyst is 0.05-0.2% of the mass of the ethylene; preferably, the reaction pressure is 0.8-2.0 MPa, and the reaction temperature is 120-220 ℃; preferably, the molecular sieve catalyst is selected from a magnesium, calcium or barium exchanged sodium ZSM-5 type molecular sieves.

Preferably, the catalyst used for oxidizing 4,4' -divinyldiphenyliodonium in the invention is a supported palladium heteropolyacid catalyst; preferably, the amount of the catalyst is 0.02-0.1% of the mass of 4,4' -divinyl diphenyl iodonium; preferably, the reaction temperature is 140-260 ℃ and the reaction pressure is 0.3-1.5 MPa.

Further, the 2, 3-dicarboxyl cellulose is prepared by the following method:

1) dialdehyde cellulose: sodium acetate and HIO for cellulose₄Oxidizing at 35-45 ℃ for 40-60 h;

2) 2, 3-dicarboxylcellulose: dripping an acidic potassium permanganate solution (5% aqueous solution) into dialdehyde cellulose at the temperature of 47-53 ℃ until the acidic potassium permanganate does not fade, recrystallizing and drying to obtain the dialdehyde cellulose.

Preferably, the concentration range of the sodium acetate is 0.03-0.08 g/mL, and the HIO is preferably₄The concentration range of (A) is 0.08-0.2 g/mL; preferably, the concentration of the cellulose is 0.03-0.06 g/mL; preferably, the cellulose is soaked in a methanol-water solution with the mass ratio of 0.2-5 for 2-6 h.

Further, the oxidant adopted in step S2 of the present invention is 2,2,6, 6-tetramethylpiperidine oxide/NaClO/NaBr reagent; preferably, the mass ratio of the cellulose to the 2,2,6, 6-tetramethylpiperidine oxide to the NaClO to the NaBr is in the range of 1: (0.01-0.025): (2-4): (0.08-0.12); preferably, the reaction temperature is 0-5 ℃, the reaction time is 10-20 h, and the pH is 9-11.

Further, in step S2 of the present invention, the mass ratio of the 6-carboxyl cellulose to the cation addition reaction is 1: (1-4), and the reaction temperature is 40-60 ℃.

Further, the cation structure of the invention is as follows:

wherein R1 is a linear chain saturated alkyl with the chain length of C1-C3, preferably methyl; r2 is a straight chain alkyl with the chain length of C1-C18 and at most one unsaturated bond.

Further, the cation of the invention is selected from propylene oxide trimethyl quaternary ammonium salt, 1, 2-butylene oxide triethyl quaternary ammonium salt, 1, 2-epoxy decane tripropyl quaternary ammonium salt or 1, 2-epoxy octadecane-N-methyl-N-ethyl-N-propyl quaternary ammonium salt which is commercially available as a cation surfactant with a glycidyl ether structure); preferably, after the reaction in step S2 is completed, the mixture is washed to be neutral, filtered and dried.

Further, in step S3 of the present invention, the mixing mass ratio of the modified cellulose a to the modified cellulose B is in the range of (80:20) to (20: 80); preferably, the mixing mass ratio of the modified cellulose A to the modified cellulose B is in the range of (60:40) to (40: 60).

The invention also aims to provide the application of the non-woven fabric material in fabric washing, color absorbing and dye preventing.

The invention adopts the technical proposal to achieve the following beneficial effects:

1. the cellulose is subjected to cationic modification after oxidation, and cations are grafted on ester bonds of carboxyl obtained after oxidation, so that the effects of dye adsorption, antistatic property, antibiosis and mildew resistance can be achieved.

2. The modified cellulose A obtained by modification of iodonium salt has an acid anhydride functional group, is hydrolyzed when clothes are washed, the (4-vinylphenyl-4' -methylenecarboxyphenyl) iodonium terminated polyvinylpyrrolidone is liberated again, the polyvinylpyrrolidone is a high-efficiency dye capture agent, the iodonium compound is a cationic surfactant and is compatible with an anionic surfactant (generally, a mixture of the cationic surfactant and the anionic surfactant has higher surface activity, but phase separation is often carried out above the critical micelle concentration, the solution becomes turbid or pearlescent, even precipitation is generated), and the antimicrobial effect is achieved.

3. The non-woven fabric can be compatible with a detergent of an anionic surfactant system and simultaneously has an excellent pigment adsorption effect by grafting the cationic surfactant on the cellulose.

4. The existing color absorbing fiber is a dye trapping agent which is dissolved and adsorbed on non-woven fabric, is a physical adsorption and generates friction loss part in the production, packaging and use processes, thereby influencing the product effect. According to the invention, the dye capture agent is grafted on the cellulose in a chemical modification manner, so that the use effect of the product is ensured.

Detailed Description

The present invention will be described in more detail with reference to specific preferred embodiments, but the present invention is not limited to the following embodiments.

Preparation of (4-vinylphenyl-4' -methylenecarboxyphenyl) iodonium the supported palladium (Pd) heteropolyacid (heteropolyacid) catalyst may be selected from the national distributors company, the StandoilCo, USA, Halcon International Inc, France institute Francasdu Petrol, Japan catalytic industry or Japan Showa and electrician.

The diphenyliodonium salt used in the preparation of (4-vinylphenyl-4' -methylenecarboxyphenyl) iodonium can be selected from the group consisting of Shanghai-sourced Biotech Co., Ltd, Shanghai Henfei Biotech Co., Ltd, Shanghai-Yoghei Biotech Co., Ltd, Shanghai-minghai-Biotech Co., Ltd and the like, having CAS number 722-56-5 (including, but not limited to, the above-mentioned companies), which are not listed herein.

Preparation of modified cellulose A

Preparation of mono), (4-vinylphenyl-4' -methylenecarboxyphenyl) iodonium

1. Using a molecular sieve as a catalyst, reacting diphenyl iodonium salt with ethylene to obtain 4,4' -divinyl diphenyl iodonium (shown in a formula (I) (the reaction conditions of examples 1-1-1, 1-1-2 and 1-1-3 are shown in a table 1), and partially oxidizing 4,4' -divinyl diphenyl iodonium with a supported palladium (Pd) heteropolyacid (hetetopolyacid) catalyst system to obtain 4-vinylphenyl-4 ' -methylenecarboxyphenyl) iodonium (shown in a formula (II)) (the reaction conditions of examples 1-1-1, 1-1-2 and 1-1-3 are shown in a table 2):

wherein the molecular sieve is selected from sodium ZSM-5 type molecular sieve exchanged by magnesium, calcium or barium.

TABLE 1 reaction conditions and material amounts of diphenyliodonium salts with ethylene

TABLE 24, 4' -Divinyldiphenyliodonium partial catalytic Oxidation conditions and amounts of materials