阅读说明：本技术 一种阳离子表面活性剂的制备方法及其应用 (Preparation method and application of cationic surfactant ) 是由 蔡熙扬 卢志敏 郭晓丹 刘保 陈奕 何辉 张世林 潘宇鹏 黄煜璇 戴殷 于 2020-04-30 设计创作，主要内容包括：本发明涉及一种阳离子表面活性剂的制备方法,其中所述阳离子表面活性剂为(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,其制备方法包括以下步骤：将乙烯基吡咯烷酮水溶液在催化剂、引发剂的作用下发生聚合反应,加入(4-乙烯基苯基-4’-亚甲基羧基苯基)碘鎓,封端,干燥后即得。所述阳离子表面活性剂能与阴离子表面活性剂兼容的阳离子表面活性剂的制备方法；该阳离子表面活性剂能应用到特定改性纤维素的制备,该改性纤维素能同时具有吸附染料和抑菌衣物的功效。(The invention relates to a preparation method of a cationic surfactant, wherein the cationic surfactant is (4-vinyl phenyl-4' -methylene carboxyl phenyl) iodonium terminated polyvinylpyrrolidone, and the preparation method comprises the following steps: 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. A process for preparing a cationic surfactant which is compatible with an anionic surfactant; the cationic surfactant can be applied to the preparation of specific modified cellulose, and the modified cellulose can simultaneously have the effects of adsorbing dye and inhibiting bacteria of clothes.)

1. A preparation method of a cationic surfactant is characterized in that the cationic surfactant is (4-vinyl phenyl-4' -methylene carboxyl phenyl) iodonium terminated polyvinylpyrrolidone, and the preparation method comprises the following steps: 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.

2. The method according to claim 1, wherein the mass ratio of the vinylpyrrolidone aqueous solution, the catalyst, and the initiator to the 4-vinylphenyl-4' -methylenecarboxyphenyl) iodonium is 100: (0.2-0.5): (0.3-0.6): (0.5-2).

3. The method of claim 1, wherein the catalyst is hydrogen peroxide; preferably, the initiator is azobisisobutyronitrile.

4. The preparation method according to claim 1, 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 after adding the (4-vinylphenyl-4' -methylenecarboxyphenyl) iodonium is 0.2-0.8 h.

5. The method according to claim 1, wherein after the (4-vinylphenyl-4' -methylenecarboxyphenyl) iodonium-terminated polyvinylpyrrolidone is obtained, 0.2 to 0.6 mass% of ammonia water is added to the polymer; preferably, the drying is spray drying, and the hot air temperature range of the spray drying is 120-180 ℃.

6. The method according to claim 1, wherein the (4-vinylphenyl-4' -methylenecarboxyphenyl) iodonium is prepared by: reacting diphenyl iodonium salt with ethylene under the action of a molecular sieve catalyst to obtain 4,4 '-divinyl diphenyl iodonium, and then carrying out catalytic oxidation to obtain (4-vinylphenyl-4' -methylene carboxyl phenyl) iodonium.

7. The preparation method of claim 6, wherein the mass ratio of the diphenyliodonium 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 ℃.

8. The method of claim 7, wherein the molecular sieve catalyst is selected from a magnesium, calcium, or barium exchanged sodium ZSM-5 type molecular sieve.

9. The method according to claim 6, wherein the catalyst used 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.

10. Use of the cationic surfactant according to any one of claims 1 to 9 for the color-absorbing and stain-proofing of fabric washing.

Technical Field

The invention belongs to the field of textile engineering, and particularly relates to a preparation method and application of a cationic surfactant, and particularly relates to a preparation method and application of (4-vinylphenyl-4' -methylenecarboxyphenyl) iodonium terminated polyvinylpyrrolidone.

Background

The existing dye capture agent is a cationic surfactant which is incompatible with an anionic surfactant in a detergent, and the anionic surfactant is dominant in the washing process, so that the cationic surfactant and the anionic surfactant are directly formed into a salt to be solubilized in a system, the consumed anionic surfactant influences the detergency of the detergent, and the reacted cationic surfactant loses the capability of capturing the dye.

Disclosure of Invention

In order to solve the technical problems in the prior art, the invention provides a cationic surfactant compatible with an anionic surfactant, and the prepared modified cellulose has the effects of adsorbing dye and inhibiting bacteria of clothes.

The preparation method of the cationic surfactant is characterized in that the cationic surfactant is (4-vinyl phenyl-4' -methylene carboxyl phenyl) iodonium terminated polyvinylpyrrolidone, and the preparation method comprises the following steps: 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): (0.5-2).

Preferably, the catalyst of the present invention 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 after adding the (4-vinylphenyl-4' -methylenecarboxyphenyl) iodonium is 0.2-0.8 h.

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: reacting diphenyl iodonium salt with ethylene under the action of a molecular sieve catalyst to obtain 4,4 '-divinyl diphenyl iodonium, and then carrying out catalytic oxidation to obtain 4-vinylphenyl-4' -methylene carboxyl phenyl) iodonium.

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 of the present invention is selected from the group consisting of magnesium, calcium or barium exchanged sodium ZSM-5 type molecular sieves.

Further, the catalyst used for oxidizing 4,4' -divinyldiphenyliodonium according to the present invention is a supported palladium (Pd) heteropoly acid (hetetopolyacid) 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.

The invention also aims to provide the application of the cationic surfactant in fabric washing, color absorbing and dye preventing.

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

. The invention provides a preparation method of a cationic surfactant compatible with an anionic surfactant; the cationic surfactant can be applied to the preparation of specific modified cellulose, and the cellulose can simultaneously have the effects of adsorbing dye and inhibiting bacteria.

When clothes are washed, the modified cellulose is hydrolyzed, the (4-vinylphenyl-4-methylenecarboxyphenyl) iodonium terminated polyvinylpyrrolidone is dissociated again, the polyvinylpyrrolidone is a high-efficiency dye capture agent, and the iodonium compound is a surfactant with cationic property, can be compatible with an anionic surfactant, and can still exert an effective antibacterial effect in the washing process. The modified cellulose prepared by the (4-vinylphenyl-4' -methylenecarboxyphenyl) iodonium terminated polyvinylpyrrolidone has the bacteriostatic effect and the dye adsorption effect.

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 mono- (4-vinylphenyl-4' -methylenecarboxyphenyl) iodonium

The method comprises the following steps of (1) reacting diphenyl iodonium salt with ethylene by using a molecular sieve as a catalyst to obtain 4,4' -divinyl diphenyl iodonium (shown in a formula (I) (the reaction conditions of examples 1-1, 1-2 and 1-3 are shown in a table 1), and partially oxidizing the 4,4' -divinyl diphenyl iodonium with a supported palladium (Pd) heteropoly acid (hetetopolyacid) catalyst system to obtain 4-vinylphenyl-4 ' -methylene carboxyl phenyl) iodonium (shown in a formula (II)) (the reaction conditions of examples 1-1, 1-2 and 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