CN103073681B - Method for preparing soft-type amphoteric vinyl polymer retanning fixing agent - Google Patents
Method for preparing soft-type amphoteric vinyl polymer retanning fixing agent Download PDFInfo
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- CN103073681B CN103073681B CN201310014968.5A CN201310014968A CN103073681B CN 103073681 B CN103073681 B CN 103073681B CN 201310014968 A CN201310014968 A CN 201310014968A CN 103073681 B CN103073681 B CN 103073681B
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Abstract
The invention relates to a method for preparing a soft-type amphoteric vinyl polymer retanning fixing agent. The method comprises the following steps: adopting diallyl dimethyl ammonium chloride, flexible monomer long-chain acrylate and vinyl monomers as raw materials, and preparing the soft-type amphoteric vinyl polymer retanning fixing agent through a cyclization polymerization method. The soft-type amphoteric vinyl polymer retanning fixing agent is applied to a leather dyeing fat-liquoring section and can give leather a soft and full feel. After tanning, the thickening rate of the leather reaches 20.5 percent. The dyeing depth of the leather after retanning is greatly reduced, and the K/S value of the tanned leather is increased by 51.84 percent.
Description
Technical field
The present invention relates to a kind of preparation method of retanning laking agent, be specifically related to a kind of preparation method of soft type amphoteric ethylene base polymer retanning laking agent, adopt diallyldimethylammonium chloride and flexible monomer long-chain acrylate and vinyl monomer by cyclopolymerization legal system for a kind of soft type amphoteric ethylene base polymer retanning laking agent.
Background technology
Retanning is described as " Golden Touch " in process hides, can improve Leather Properties, and gives finished leather with specific style.In leather retanning processing, because acrylic polymers has good Selective filling performance, can improve the mechanical property of finished leather, and after tanning, waste liquid does not pollute to environment, be the most widely used retanning agent of a class.But conventional acrylic resin side chain contains a large amount of anionic groups, affect the combination of matching stain and leather in later stage dyeing process, cause dyestuff specific absorption reduce, dye shallow and dye inhomogeneously, this phenomenon is called " losing colour " phenomenon in process hides.
The major cause that causes " losing colour " is that anionic retanning agent and dye molecule are competed the cation activity center in leather jointly, affect the fixing absorption of dye molecule in leather, thereby reduce dye uptake [Zhang Biao, Jin Yong, Cao Zhifeng. western leather, 2010, (3): 32-37.].Closely during the last ten years, do a large amount of research for solving " losing colour " problem both at home and abroad, the people such as Peng Ying [Peng Ying, Li Zhiqiang, Cheng Haiming, Deng. leather science and chemical industry, 2004,14 (2): 34-36.] pass through aqueous solution copolymerization legal system for polymer Dyeing-retanning Agent, applied the retanning effect both in process hides process with traditional retanning agent, there is again dyeing, but due to molecular structure of dye more complicated simultaneously, expect that the Dyeing-retanning Agent with desirable percentage of grafting is more difficult.Amphoteric ethylene base polymer retanning agent is owing to containing a certain amount of cation group in molecule, can reduce " losing colour " problem that uses anionic materials to produce in retanning process, become the focus of current research and development, its route is mainly on carboxylic polymer segment, to introduce amino positively charged ion [Jin Liqiang simultaneously, Xing Cunzhang. leather chemical industry, 2001,18 (3): 18-21; Lv Shenghua, Ma Jianzhong, poplar ancestor is remote. leather chemical industry, 2000 (2): 10-12; Jin Liqiang, Yu Jing, Zhang Jing. fine chemistry industry, 2008,25 (4): 380-383; Dang Hongxin, Pan Hui, Zhang Zhijun. Chinese leather, 2004,33 (7): 1-4.].
Dimethyl diallyl ammonium chloride is the water-soluble cationic monomer with non-conjugated property diene key, in molecule, two two bond energys enough carry out homopolymerization or carry out copolyreaction with other containing double bond monomer, and the molecular chain of polymkeric substance is often with positive charge and nitrogenous five-ring or six-membered ring structure.Compare with the linear polymer that common polyreaction forms, the thermostability that the polymkeric substance that cyclopolymerization forms has had and high second-order transition temperature, research also finds that dimethyl diallyl ammonium chloride can improve character and performance [the Avei D of polymkeric substance with hydrophobicity or functional monomer copolymerization, Mol N, Dngasan L. 2002,48 (4-5): 353-359; Yildiz B, Isik B, Kis M, et al.. J Appl Polym Sci, 2003,88; 2028-2031].
Along with the raising of people's living standard, also more and more higher to the feel requirement of leatherware, soft type leatherware is more and more subject to liking of people.Although at present amphoteric retanning agent has solved the phenomenon of losing colour of negatively charged ion retanning agent to a certain extent, after the tanning of traditional both sexes acrylic acid double tanning agent, leather has and necessarily moulds sense, affects finished leather feel and quality.The present invention adopt diallyldimethylammonium chloride and flexible monomer long-chain acrylate and vinyl monomer by cyclopolymerization legal system for a kind of soft type amphoteric ethylene base polymer retanning laking agent, give the feel of leather softness in fixation simultaneously, the added value that increases leatherware, this method yet there are no relevant report.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the object of this invention is to provide a kind of preparation method of soft type amphoteric ethylene base polymer retanning laking agent, taking vinyl monomers such as functional type monomer dipropyl alkyl dimethyl ammonium chloride, soft type long-chain acrylate monomers as raw material, adopt cyclopolymerization legal system standby a kind of for leather coloring stuffing workshop section, can increase substantially after retanning and dye the degree of depth on leather.
For achieving the above object, the technical solution used in the present invention is:
A preparation method for soft type amphoteric ethylene base polymer retanning laking agent, is characterized in that, comprises the following steps:
1) 12 ~ 17g diallyldimethylammonium chloride, 10 ~ 15g methacrylic acid, 10 ~ 20g vinylformic acid, 2 ~ 5g long-chain acrylate (dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate, octadecyl acrylate) are mixed, as mix monomer;
2) in the 250mL there-necked flask that agitator and condensing works are housed, add 100 ~ 150g deionized water, stirring is warming up to 50 ~ 80 DEG C, add 0.5 ~ 2g sodium bisulfite, adopt constant pressure funnel to drip mix monomer and 2 ~ 5g initiator, 20 ~ 60min, insulation reaction 2 ~ 6h simultaneously;
3) reaction is cooled to room temperature after finishing, and adopting sodium hydroxide solution regulation system pH value is 4.0 ~ 6.0, and discharging, makes soft type amphoteric ethylene base polymer retanning laking agent.
The invention has the beneficial effects as follows:
The present invention is taking vinyl monomers such as functional type monomer diallyl alkyl dimethyl ammonium chloride, soft type long-chain acrylate monomers as raw material, adopt cyclopolymerization method synthetic a kind of for leather coloring stuffing workshop section, can give the soft body bone of leather and increase considerably the soft type amphoteric ethylene base polymer retanning laking agent of the leather coloring degree of depth.Adopt the present invention, give the feel of leather softness in fixation simultaneously, increase the added value of leatherware.
Embodiment
Below in conjunction with specific embodiments, the present invention is described further:
embodiment 1
A preparation method for soft type amphoteric ethylene base polymer retanning laking agent, comprises the following steps:
1) 12g diallyldimethylammonium chloride, 10g methacrylic acid, 10g vinylformic acid, 2g long-chain acrylate (dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate, octadecyl acrylate) are mixed, as mix monomer;
2) in the 250mL there-necked flask that agitator and condensing works are housed, add 100g deionized water, stir and be warming up to 60 DEG C, add 0.7g sodium bisulfite, adopt constant pressure funnel to drip mix monomer and 2.5g initiator 20min, insulation reaction 2h simultaneously;
3) reaction is cooled to room temperature after finishing, and adopting sodium hydroxide solution regulation system pH value is 4.0, and discharging, makes soft type amphoteric ethylene base polymer retanning laking agent.
embodiment 2
A preparation method for soft type amphoteric ethylene base polymer retanning laking agent, comprises the following steps:
1) 15g diallyldimethylammonium chloride, 12g methacrylic acid, 15g vinylformic acid, 3g long-chain acrylate (dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate, octadecyl acrylate) are mixed, as mix monomer;
2) in the 250mL there-necked flask that agitator and condensing works are housed, add 120g deionized water, stir and be warming up to 55 DEG C, add 1.0g sodium bisulfite, adopt constant pressure funnel to drip mix monomer and 3g initiator 30min, insulation reaction 3.5h simultaneously;
3) reaction is cooled to room temperature after finishing, and adopting sodium hydroxide solution regulation system pH value is 5.0, and discharging, makes soft type amphoteric ethylene base polymer retanning laking agent.
embodiment 3
A preparation method for soft type amphoteric ethylene base polymer retanning laking agent, comprises the following steps:
1) 17g diallyldimethylammonium chloride, 14g methacrylic acid, 13g vinylformic acid, 5g long-chain acrylate (dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate, octadecyl acrylate) are mixed, as mix monomer;
2) in the 250mL there-necked flask that agitator and condensing works are housed, add 130g deionized water, stir and be warming up to 65 DEG C, add 1.5g sodium bisulfite, adopt constant pressure funnel to drip mix monomer and 2g initiator 50min, insulation reaction 6h simultaneously;
3) reaction is cooled to room temperature after finishing, and adopting sodium hydroxide solution regulation system pH value is 5.5, and discharging, makes soft type amphoteric ethylene base polymer retanning laking agent.
embodiment 4
A preparation method for soft type amphoteric ethylene base polymer retanning laking agent, comprises the following steps:
1) 16g diallyldimethylammonium chloride, 13g methacrylic acid, 12g vinylformic acid, 4g long-chain acrylate (dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate, octadecyl acrylate) are mixed, as mix monomer;
2) in the 250mL there-necked flask that agitator and condensing works are housed, add 140g deionized water, stir and be warming up to 70 DEG C, add 2g sodium bisulfite, adopt constant pressure funnel to drip mix monomer and 5g initiator 60min, insulation reaction 4h simultaneously;
3) reaction is cooled to room temperature after finishing, and adopting sodium hydroxide solution regulation system pH value is 4.5, and discharging, makes soft type amphoteric ethylene base polymer retanning laking agent.
embodiment 5
A preparation method for soft type amphoteric ethylene base polymer retanning laking agent, comprises the following steps:
1) 13g diallyldimethylammonium chloride, 15g methacrylic acid, 18g vinylformic acid, 2.5g long-chain acrylate (dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate, octadecyl acrylate) are mixed, as mix monomer;
2) in the 250mL there-necked flask that agitator and condensing works are housed, add 150g deionized water, stir and be warming up to 75 DEG C, add 1.7g sodium bisulfite, adopt constant pressure funnel to drip mix monomer and 4g initiator 40min, insulation reaction 5h simultaneously;
3) reaction is cooled to room temperature after finishing, and adopting sodium hydroxide solution regulation system pH value is 6.0, and discharging, makes soft type amphoteric ethylene base polymer retanning laking agent.
What exist for conventional acrylic tanning agent moulds the strong and phenomenon of losing colour of sense, and the application of soft type amphoteric ethylene base polymer retanning laking agent prepared by the present invention can be given leather softness, plentiful feel, and after tanning, leather thickens rate and reaches 31.63%; Increase substantially after retanning simultaneously and dye the degree of depth on leather, after making to tan, leather K/S value increases by 51.84%.
Claims (6)
1. a preparation method for soft type amphoteric ethylene base polymer retanning laking agent, is characterized in that, comprises the following steps:
1) 12 ~ 17g diallyldimethylammonium chloride, 10 ~ 15g methacrylic acid, 10 ~ 20g vinylformic acid, 2 ~ 5g long-chain acrylate are mixed, as mix monomer, long-chain acrylate is dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate or octadecyl acrylate;
2) in the 250mL there-necked flask that agitator and condensing works are housed, add 100 ~ 150g deionized water, stirring is warming up to 50 ~ 80 DEG C, add 0.5 ~ 2g sodium bisulfite, adopt constant pressure funnel to drip mix monomer and 2 ~ 5g initiator, 20 ~ 60min, insulation reaction 2 ~ 6h simultaneously;
3) reaction is cooled to room temperature after finishing, and adopting sodium hydroxide solution regulation system pH value is 4.0 ~ 6.0, and discharging, makes soft type amphoteric ethylene base polymer retanning laking agent.
2. the preparation method of a kind of soft type amphoteric ethylene base polymer retanning laking agent according to claim 1, is characterized in that, comprises the following steps:
1) 12g diallyldimethylammonium chloride, 10g methacrylic acid, 10g vinylformic acid, 2g long-chain acrylate are mixed, as mix monomer, long-chain acrylate is dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate or octadecyl acrylate;
2) in the 250mL there-necked flask that agitator and condensing works are housed, add 100g deionized water, stir and be warming up to 60 DEG C, add 0.7g sodium bisulfite, adopt constant pressure funnel to drip mix monomer and 2.5g initiator 20min, insulation reaction 2h simultaneously;
3) reaction is cooled to room temperature after finishing, and adopting sodium hydroxide solution regulation system pH value is 4.0, and discharging, makes soft type amphoteric ethylene base polymer retanning laking agent.
3. the preparation method of a kind of soft type amphoteric ethylene base polymer retanning laking agent according to claim 1, is characterized in that, comprises the following steps:
1) 15g diallyldimethylammonium chloride, 12g methacrylic acid, 15g vinylformic acid, 3g long-chain acrylate are mixed, as mix monomer, long-chain acrylate is dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate or octadecyl acrylate;
2) in the 250mL there-necked flask that agitator and condensing works are housed, add 120g deionized water, stir and be warming up to 55 DEG C, add 1.0g sodium bisulfite, adopt constant pressure funnel to drip mix monomer and 3g initiator 30min, insulation reaction 3.5h simultaneously;
3) reaction is cooled to room temperature after finishing, and adopting sodium hydroxide solution regulation system pH value is 5.0, and discharging, makes soft type amphoteric ethylene base polymer retanning laking agent.
4. the preparation method of a kind of soft type amphoteric ethylene base polymer retanning laking agent according to claim 1, is characterized in that, comprises the following steps:
1) 17g diallyldimethylammonium chloride, 14g methacrylic acid, 13g vinylformic acid, 5g long-chain acrylate are mixed, as mix monomer, long-chain acrylate is dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate or octadecyl acrylate;
2) in the 250mL there-necked flask that agitator and condensing works are housed, add 130g deionized water, stir and be warming up to 65 DEG C, add 1.5g sodium bisulfite, adopt constant pressure funnel to drip mix monomer and 2g initiator 50min, insulation reaction 6h simultaneously;
3) reaction is cooled to room temperature after finishing, and adopting sodium hydroxide solution regulation system pH value is 5.5, and discharging, makes soft type amphoteric ethylene base polymer retanning laking agent.
5. the preparation method of a kind of soft type amphoteric ethylene base polymer retanning laking agent according to claim 1, is characterized in that, comprises the following steps:
1) 16g diallyldimethylammonium chloride, 13g methacrylic acid, 12g vinylformic acid, 4g long-chain acrylate are mixed, as mix monomer, long-chain acrylate is dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate or octadecyl acrylate;
2) in the 250mL there-necked flask that agitator and condensing works are housed, add 140g deionized water, stir and be warming up to 70 DEG C, add 2g sodium bisulfite, adopt constant pressure funnel to drip mix monomer and 5g initiator 60min, insulation reaction 4h simultaneously;
3) reaction is cooled to room temperature after finishing, and adopting sodium hydroxide solution regulation system pH value is 4.5, and discharging, makes soft type amphoteric ethylene base polymer retanning laking agent.
6. the preparation method of a kind of soft type amphoteric ethylene base polymer retanning laking agent according to claim 1, is characterized in that, comprises the following steps:
1) 13g diallyldimethylammonium chloride, 15g methacrylic acid, 18g vinylformic acid, 2.5g long-chain acrylate are mixed, as mix monomer, long-chain acrylate is dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate or octadecyl acrylate;
2) in the 250mL there-necked flask that agitator and condensing works are housed, add 150g deionized water, stir and be warming up to 75 DEG C, add 1.7g sodium bisulfite, adopt constant pressure funnel to drip mix monomer and 4g initiator 40min, insulation reaction 5h simultaneously;
3) reaction is cooled to room temperature after finishing, and adopting sodium hydroxide solution regulation system pH value is 6.0, and discharging, makes soft type amphoteric ethylene base polymer retanning laking agent.
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| CN111363865B (en) * | 2020-03-25 | 2021-12-07 | 陕西科技大学 | High-absorption inner salt type amphoteric leather retanning agent with filling, dyeing-assisting and greasing functions and preparation method thereof |
| CN116102681B (en) * | 2022-10-19 | 2024-01-30 | 陕西科技大学 | Preparation method of amphoteric wet finishing material with retanning, fatliquoring and dyeing functions |
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| CN101619366A (en) * | 2009-07-21 | 2010-01-06 | 陕西科技大学 | Preparation method of amphoteric vinyl polymer/ZnO nanocomposite tanning agent |
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| CN101619366A (en) * | 2009-07-21 | 2010-01-06 | 陕西科技大学 | Preparation method of amphoteric vinyl polymer/ZnO nanocomposite tanning agent |
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| 马建中，等.P(DMDAAC-AA-AM-HEA)的制备及在皮革鞣制中的应用.《功能材料信息》.2011,第8卷(第5期),13-16页. * |
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