阅读说明：本技术 聚二甲基二烯丙基氯化胺聚合物及其制备方法和应用 (Polydimethy diallyl amine chloride polymer and preparation method and application thereof ) 是由 刘振波 任春平 李瑶 彭洪刚 乔德川 黄紫微 张有志 于 2019-11-28 设计创作，主要内容包括：本发明公开了聚二甲基二烯丙基氯化胺聚合物及其制备方法和应用。本发明利用二甲基二稀丙基氯化铵、二烯丙基胺和引发剂为原料通过聚合反应合成共聚物,加入交联剂得到一种新型的聚阳离子型耐汗渍固色剂。所述共聚物与超细纤维PU革所用阴离子染料反应生成色淀,同时形成的高分子网状结构在革表面形成一种薄膜,包覆染料和纤维,从而提高了革的耐汗渍色牢度。本发明制备的固色剂在生产过程中不使用有机溶剂,绿色环保,不含甲醛,耐汗渍效果优异,稳定性好,且制备工艺简单,所需时间短,能耗少,为工业化生产提供了重要保障。(The invention discloses a polydimethyl diallyl amine chloride polymer and a preparation method and application thereof. The invention utilizes dimethyl diallyl ammonium chloride, diallyl amine and an initiator as raw materials to synthesize a copolymer through a polymerization reaction, and a crosslinking agent is added to obtain the novel polycation type sweat stain-resistant fixing agent. The copolymer reacts with anionic dye used by superfine fiber PU leather to generate lake, and a high molecular net structure formed at the same time forms a film on the surface of the leather to coat the dye and the fiber, so that the color fastness to perspiration of the leather is improved. The color fixing agent prepared by the invention does not use an organic solvent in the production process, is green and environment-friendly, does not contain formaldehyde, has excellent sweat resistance effect, good stability, simple preparation process, short required time and low energy consumption, and provides an important guarantee for industrial production.)

1. A polydimethyldiallylamine chloride polymer characterized by the structural formula (I) or (II):

wherein m and n are positive integers, m is more than or equal to 400 and less than or equal to 500, and n is more than or equal to 400 and less than or equal to 500.

2. The preparation method of the polydimethy diallyl amine chloride polymer is characterized by comprising the following steps:

1) reacting dimethyl diallyl ammonium chloride, diallyl amine and an initiator according to a mass ratio of 100: 5-25: 0.5 to 1.5, adding into a reaction kettle, adding glacial acetic acid to adjust the pH value of the reaction system to be 4.5 to 6.5, controlling the reaction temperature to be 65 to 90 ℃, reacting for 1 to 4 hours to obtain reaction liquid,

the initiator is any one of ammonium persulfate, sodium sulfite, azobisisobutyramidine hydrochloride, azobisisobutyrimidazoline hydrochloride, azobisisobutyroline sulfate, azobiscyanovaleric acid, azobisisobutyronitrile, azobis (1-imino-1-pyrrolidinyl-2-ethylpropyl) hydrochloride and azobis (ethoxy) imidazoline hydrochloride;

2) adding a cross-linking agent into the reaction liquid prepared in the step 1), wherein the mass of the added cross-linking agent is 5-7 times of that of the initiator prepared in the step 1), reacting for 30-90 min to obtain a polydimethyldiallylammonium chloride polymer,

wherein the cross-linking agent is any one of ethyl orthosilicate, methyl orthosilicate, trimethoxysilane, benzoyl peroxide, dicumyl peroxide, diethylenetriamine and epichlorohydrin.

3. The method for preparing polydiallyldimethylammonium chloride polymer of claim 2 wherein in step 1) diallylamine is replaced with methyldiallylamine.

4. The application of the polydimethy diallyl amine chloride polymer as the color fixing agent of superfine fiber PU leather.

Technical Field

The invention relates to the field of polymers, in particular to a poly (dimethyl diallyl ammonium chloride) polymer, a preparation method and application of a color fixing agent, which are applied to the field of subsequent treatment of superfine fiber PU leather fabrics and are suitable for a polycation type sweat-resistant color fixing agent for superfine fiber PU leather, a preparation method and application thereof.

Background

Sweat stains have obvious influence on fabric fading. But the market is fresh to have a special sweat stain fixing agent with good effect. Especially, the color loss of the water bubbles is serious. Based on the reasons, the subject group invents a novel color fixing agent which can resist sweat stain and effectively improve the soaking effect, and related literature data are consulted, and no similar synthesis method is found.

After the superfine fiber PU leather is dyed by dye, the color fixing effect is needed to prevent the superfine fiber PU leather from being decolored, and the development of a color fixing agent is a main method for solving the problems. The early color fixing agent is a cationic surfactant, the earliest color fixing agent in China is dicyandiamide type resin developed in the early 50 th of the 20 th century, the color fixing agent can cause color change of fabrics and reduce the color fastness to sunlight, and the color fixing agent contains free formaldehyde and is harmful to human bodies. At present, with the enhancement of environmental awareness and the regulation of various indexes of textiles, an aldehyde-free color fixing agent gradually enters the public visual field, and with the continuous appearance of more types of color fixing agents, the research on the color fixing agent is also continuously developed.

In order to solve the problem of poor color fastness to sweat stain of PU leather, the development and the use of a color fixing agent are an effective way for improving the color fastness to sweat stain. Research shows that the existing dye fixing agents are dicyandiamide type dye fixing agents, polycation type dye fixing agents, environment-friendly double-active-group dye fixing agents, reactive dye fixing agents, composite type and mixed type dye fixing agents, dye fixing agents containing ultraviolet absorption functional groups, waterborne polyurethane dye fixing agents and the like, the variety of the dye fixing agents is wide, and the research on novel and environment-friendly dye fixing agents is a current hotspot. According to survey results, almost no color fixing agent capable of solving the color fastness to perspiration is available.

The polycation color fixing agent is an aldehyde-free color fixing agent, has the characteristics of no toxicity, environmental protection, low energy consumption, no side reaction and the like, replaces an organic solvent with water, accords with the concept of environmental protection, and has high-density positive charge and good water solubility. Cationic groups in the polycation color fixing agent generate color lake through the action with anions in dyes to be fixed on fabrics, and a film is formed on the surface of the fabrics by a reticular structure of the polycation color fixing agent, and the color fixing is simultaneously performed on the fabrics through the interaction of the film forming effect and static electricity, so that the color fixing efficiency is improved.

Disclosure of Invention

The invention provides a non-toxic polycation type color fixing agent poly-dimethyl diallyl ammonium chloride polymer which is free of aldehyde and good in stability, is environment-friendly and greatly improves the color fastness to perspiration of PU leather based on the deepening of an environment-friendly concept, and solves a series of problems that the color fastness to perspiration of superfine fiber PU leather is poor, and a traditional color fixing agent uses a toxic solvent and causes pollution to the environment. The invention also provides a preparation method and application of the color fixing agent.

To achieve one of the objects of the invention, the present invention provides a novel polymer:

a polydimethyidiallylamine chloride polymer characterized by a structural formula (I) or (II):

wherein m and n are positive integers, m is more than or equal to 400 and less than or equal to 500, and n is more than or equal to 400 and less than or equal to 500.

In order to achieve the second object, the present invention provides a method for preparing a polymer, comprising:

the preparation method of the polymer comprises the following steps:

(1) reacting dimethyl diallyl ammonium chloride, diallyl amine and an initiator according to a mass ratio of 100: 5-25: 0.5 to 1.5, adding into a reaction kettle, adding glacial acetic acid to adjust the pH value of the reaction system to be 4.5 to 6.5, controlling the reaction temperature to be 65 to 90 ℃, reacting for 1 to 4 hours to obtain reaction liquid,

the initiator is any one of ammonium persulfate, sodium sulfite, azobisisobutyramidine hydrochloride, azobisisobutyrimidazoline hydrochloride, azobisisobutyroline sulfate, azobiscyanovaleric acid, azobisisobutyronitrile, azobis (1-imino-1-pyrrolidinyl-2-ethylpropyl) hydrochloride and azobis (ethoxy) imidazoline hydrochloride;

(2) adding a cross-linking agent into the reaction liquid prepared in the step 1), wherein the mass of the added cross-linking agent is 5-7 times of that of the initiator prepared in the step 1), reacting for 30-90 min to obtain a polydimethyldiallylammonium chloride polymer,

wherein the cross-linking agent is any one of ethyl orthosilicate, methyl orthosilicate, trimethoxysilane, benzoyl peroxide, dicumyl peroxide, diethylenetriamine and epichlorohydrin.

Preferably, in step 1) the diallylamine is replaced by methyldiallylamine.

To achieve the third object, the present invention provides the use of a novel polymer:

the application of the copolymer is the application of the superfine fiber PU leather color fixing agent.

Adding deionized water to dilute the synthesized polymer so that the solid content of the polymer is 25-40 percent, thus obtaining the superfine fiber PU leather color fixing agent.

The color fixing agent applied to the polymer is characterized in that a long-chain structure of the poly dimethyl diallyl ammonium chloride polymer has a large number of positive ammonium ions which react with anionic dyes in fabrics to form color lakes, and meanwhile, a net structure formed by the long-chain structure can form a film on the surface of leather to coat dye molecules so as to prevent the dye molecules from losing and play a role in fixing color.

When the dye fixing agent is used, the obtained sample solution and deionized water are uniformly mixed according to the mass ratio of 3: 100-8: 100, the pH value of the dye fixing agent solution is controlled to be 3-7, a dye sample with the same size is soaked in the dye fixing agent solution for 3-5 min, and the dye sample is dried in an oven at 100-120 ℃ and is baked at 120-145 ℃ for 5-20 min. FIG. 3 is a graph showing the effect of perspiration on the white sample cloth caused by fading of red and blue dyed samples of the superfine fiber PU leather (after the treatment of the example product), and the perspiration-resistant color fixing effect is excellent.

The invention has the prominent substantive characteristics that the linear long chain structure of the synthesized polydimethyldiallylamine chloride polymer can maximally graft positive charge ammonium ions, so that the polymer is combined with anions on dyes to form difficultly compatible solid precipitates (lakes) to be deposited on the surface of the fabric when being used as a color fixing agent; meanwhile, when the poly dimethyl diallyl amine chloride compound is used as a color fixing agent at high temperature, long chains can be solidified into a film, namely, polymers interact with active groups on leather and dye matrixes to form a compact net-shaped structure in a crosslinking manner, the compact net-shaped structure is tightly covered on the surfaces of fabrics and dyes to lock the color lake, and further, a better color fixing effect is obtained.

The beneficial effects are as follows:

the poly dimethyl diallyl amine chloride polymer is in a linear structure, the overall effect of improving the wet fastness is similar to that of a resin type, sometimes is slightly poorer, but the hand feeling and the dyeing vividness of the fabric are not influenced, and the fastness to perspiration, sunlight and chlorine is not reduced. The polydimethyldiallylamine chloride polymer can effectively improve the sweat-resistant color-fixing capacity, so that the problem that the fabric fades when meeting sweat is solved, and the water-resistant color-fixing effect of the fabric can be improved. In addition, the polydimethyldiallylamine chloride polymer prepared by the invention does not contain formaldehyde, and deionized water is used for replacing an organic solvent, so that the polymer is low in harm to a human body, green and environment-friendly, and excellent in color fixing effect.

Meanwhile, the preparation method of the invention has short time and low energy consumption, and can be used for industrial mass production.

Drawings

The accompanying drawings are included to provide a further understanding of the present invention and are not to be construed as limiting the present invention.

FIG. 1 is an infrared spectrum of the product of example 1.

FIG. 2 is an infrared spectrum of the product of example 3.

FIG. 3 is an infrared spectrum of the product of example 4.

FIG. 4 is a graph of the effect of sweat stain on a white swatch before and after treatment with the fixing agents of examples 1-6.

Wherein a is not treated by a color fixing agent; b is the fading effect of the treated commercial color fixing agent; c is the fading effect after the treatment of the example 1; d is the fading effect after the treatment of the example 2; e is the fading effect after the treatment of the embodiment 3; f is the fading effect after the treatment of the embodiment 4; g is the fading effect after the treatment of example 5; h is the fading effect after the treatment of example 6.

FIG. 5 is typical electron micrographs of a colored fabric before and after treatment with a polydiallyldimethylammonium chloride polymer product, wherein a and b are electron micrographs of effects before and after treatment, respectively.

Detailed Description

The present invention will now be described in more detail with reference to the accompanying drawings, in which preferred embodiments of the invention are shown, it being understood that one skilled in the art may modify the invention herein described while still achieving the beneficial results of the present invention. Accordingly, the following description should be construed as broadly as possible to those skilled in the art and not as limiting the invention.

In order to make the objects and features of the present invention more comprehensible, embodiments of the present invention are described in detail below with reference to the accompanying drawings. It is noted that the drawings are in greatly simplified form and that non-precision ratios are used for convenience and clarity in aiding in the description of the embodiments of the invention.