CN102643381B - Method for preparing polyacrylate/montmorillonite composite leather finishing agent by adopting reactive emulsifier - Google Patents
Method for preparing polyacrylate/montmorillonite composite leather finishing agent by adopting reactive emulsifier Download PDFInfo
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- CN102643381B CN102643381B CN201110350895.8A CN201110350895A CN102643381B CN 102643381 B CN102643381 B CN 102643381B CN 201110350895 A CN201110350895 A CN 201110350895A CN 102643381 B CN102643381 B CN 102643381B
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Abstract
The invention relates to a method for preparing a polyacrylate/montmorillonite composite leather finishing agent by adopting a reactive emulsifier. At present, studies on the preparation of organic/inorganic nano-composite leather finishing agents by using silicon dioxide, titanium dioxide and zinc oxide have been reported, but the studies on the modification of a polyacrylate leather finishing agent by adopting montmorillonite are rarely reported. The method disclosed by the invention comprises the following steps: adopting the reactive emulsifier, namely allyloxy nonylphenol propanol polyoxyethylene (10) ether ammonium sulfate (DNS-86) as the emulsifier, taking acrylate type monomers and the montmorillonite as raw materials, and performing polymerization through a soap-free emulsion to prepare the polyacrylate/montmorillonite composite leather finishing agent. After the finishing agent is used for finishing leather, the tensile strength of a leather sample is 3.31N/mm<2>, and the elongation at break is 90.1%, which are respectively upgraded by 8.5% and 53% in comparison with crust leather before finishing, and respectively upgraded by 14.1% and 21.8% in comparison with the leather sample finished by the polyacrylate finishing agent prepared by adopting the reactive emulsifier. The fastness to dry rubbing of the leather sample achieves grades 3-4, and the fastness to wet rubbing achieves grades 2-3.
Description
technical field:
The present invention relates to a kind of preparation method of polyacrylic ester/montmorillonite Composite hide finishes, particularly a kind of method that adopts reactive emulsifier to prepare polyacrylic ester/montmorillonite Composite hide finishes.
background technology:
Polyacrylic ester, owing to having good light stability, chemical-resistant and good adhesive property, is therefore widely used as the aspects such as tackiness agent, coating membrane-forming agent, daily-use chemical industry, chemical power source, functional membrane, medical polymer and water treatment.But polyacrylate dispersion also exists, and low temperature becomes fragile, high temperature becomes the glutinous shortcomings such as strong, easy after tack of losing, and has limited its range of application and use value.
Inorganic nano-particle is owing to having small-size effect, surface effects, quantum effect and macro quanta tunnel effect etc., when it is evenly distributed in polymer materials, can give intensity, modulus and excellent barrier, elasticity, wear resistance and ageing resistance etc. that matrix material is high, thereby standby being popular.At present, about use silicon-dioxide [Zhang Ting has for Jia Xingang ，Li Zheng army, Zhao Yaojie. nanometer SiO
2quaternary ammonium salt derivative is covered with paint, lacquer, colour wash, etc. for leather antibacterial. leather science and engineering, and 2008,18(6): 45-49; Zhang Zhijie, Ma Jianzhong, Hu Jing, etc. original position generates nanometer SiO
2the research of/Acrylic Resin Leather Finishing Agent. fine chemistry industry, 2006,23(11): 1112-1117.], titanium dioxide [Wang Quanjie, Zhu Fei, Sun Genhang, etc. the research of nanometer titanium dioxide blending method modified acrylic resin finish. Chinese leather, 2007,36(9): 9-12.], the zinc oxide research of preparing organic/inorganic nano composite leather finishing agent has been reported, but about the research of adopting montmorillonite modified polyacrylate hide finishes rarely seen report also.
Letex polymerization is to produce one of important method of polyacrylic ester, have heat radiation easily, unique advantage such as rate of polymerization is large, molecular weight is high, inexpensive, safety, environmental protection, be now widely used.But because emulsifying agent molecule is unbound state in polymeric film, easily move to glue-line surface, therefore the performance such as bonding, water-fast, heat-resisting of glued membrane has larger gap with solvent borne polymer phase ratio, thereby a large amount of emulsifying agents that use also can cause environmental pollution to limit the development space of polymer emulsion simultaneously.Reactive emulsifier refers to the tensio-active agent with reactive group, and it not only has surfactivity, and has higher rate of polymerization, can with adsorbed matrix generation chemical reaction, be for good and all bonded to the part that matrix surface becomes matrix.Therefore, the performance such as the electrical property of polymer emulsion, optical property, surface property and water tolerance will be improved.
summary of the invention:
The object of the present invention is to provide a kind of method that adopts reactive emulsifier to prepare polyacrylic ester/montmorillonite Composite hide finishes, adopt its hide finishes Leather Finishing sample of preparing, can promote elongation at break and the tensile strength of leather sample.
For achieving the above object, the technical solution used in the present invention is:
Under magnetic agitation, 0.087 ~ 0.779g organo montmorillonite is slowly added in 20g distilled water, magnetic agitation 10 ~ 20min, supersound process 20 ~ 30min, obtains the aqueous solution of organo montmorillonite.0.866 ~ 1.731g reactive emulsifier allyloxy nonyl phenol propyl alcohol polyoxyethylene (10) ether ammonium sulfate (DNS-86) and 0.173 ~ 0.519g assistant for emulsifying agent PEG-4000 (PEG-400) are dissolved in the hot water of 40 ℃ of 40g and form surfactant soln.
The aqueous solution of organo montmorillonite and surfactant soln are added in the 250mL there-necked flask that agitator and reflux condensing tube are housed and stir 20 ~ 30min at 40 ℃.Add 0.36 ~ 0.52g linking agent N, N'-methylene-bisacrylamide, 0.36 ~ 0.52g vinylformic acid, 5.143 ~ 5.893g butyl acrylate and 2.679 ~ 3.429g methyl methacrylate, be warming up to 75 ℃ and stir 10min, drip respectively the aqueous solution (0.392 ~ 0.478g ammonium persulphate is dissolved in 40g distilled water) of initiator and the mixed solution (20.573 ~ 23.573g butyl acrylate and 10.715 ~ 13.715g methyl methacrylate) of residual monomer, 1h dropwises, be warming up to 80 ℃, insulation reaction 2h.Under room temperature, regulate emulsion pH to 5.5 ~ 6, obtain polyacrylic ester/montmorillonite Composite hide finishes.
The present invention is with respect to prior art, and its advantage is as follows:
The present invention adopts reactive emulsifier to prepare polyacrylic ester/montmorillonite Composite hide finishes, and reactive emulsifier is bonded in the shortcoming of having avoided conventional surfactant easily to move in polymer chain on the one hand; The introducing of inorganic nano material polynite gets a promotion the application performance of polyacrylic ester hide finishes on the other hand, especially shows physical and mechanical properties aspect.Meanwhile, this material also can be used in the industries such as weaving, papermaking and coating as filmogen.
embodiment:
Embodiment 1:
Under magnetic agitation, 0.437g organo montmorillonite is slowly added in 20g distilled water, magnetic agitation 10min, supersound process 30min, obtains the aqueous solution of organo montmorillonite.1.731g reactive emulsifier allyloxy nonyl phenol propyl alcohol polyoxyethylene (10) ether ammonium sulfate (DNS-86) and 0.347g assistant for emulsifying agent PEG-4000 (PEG-400) are dissolved in the hot water of 40 ℃ of 40g and form surfactant soln.
The aqueous solution of organo montmorillonite and surfactant soln are added in the 250mL there-necked flask that agitator and reflux condensing tube are housed and stir 30min at 40 ℃.Add 0.428g linking agent N, N'-methylene-bisacrylamide, 0.428g vinylformic acid, 5.634g butyl acrylate and 2.938g methyl methacrylate, be warming up to 75 ℃ and stir 10min, drip respectively the aqueous solution (0.428g ammonium persulphate is dissolved in 40g distilled water) of initiator and the mixed solution (22.536g butyl acrylate and 11.752g methyl methacrylate) of residual monomer, 1h dropwises, be warming up to 80 ℃, insulation reaction 2h.Under room temperature, regulate emulsion pH to 6, obtain polyacrylic ester/montmorillonite Composite hide finishes.
Embodiment 2:
Under magnetic agitation, 0.087g organo montmorillonite is slowly added in 20g distilled water, magnetic agitation 10min, supersound process 20min, obtains the aqueous solution of organo montmorillonite.0.866g reactive emulsifier allyloxy nonyl phenol propyl alcohol polyoxyethylene (10) ether ammonium sulfate (DNS-86) and 0.519g assistant for emulsifying agent PEG-4000 (PEG-400) are dissolved in the hot water of 40 ℃ of 40g and form surfactant soln.
The aqueous solution of organo montmorillonite and surfactant soln are added in the 250mL there-necked flask that agitator and reflux condensing tube are housed and stir 20min at 40 ℃.Add 0.36g linking agent N, N'-methylene-bisacrylamide, 0.36g vinylformic acid, 5.143g butyl acrylate and 3.429g methyl methacrylate, be warming up to 75 ℃ and stir 10min, drip respectively the aqueous solution (0.392g ammonium persulphate is dissolved in 40g distilled water) of initiator and the mixed solution (20.573g butyl acrylate and 13.715g methyl methacrylate) of residual monomer, 1h dropwises, be warming up to 80 ℃, insulation reaction 2h.Under room temperature, regulate emulsion pH to 5.5, obtain polyacrylic ester/montmorillonite Composite hide finishes.
Embodiment 3:
Under magnetic agitation, 0.779g organo montmorillonite is slowly added in 20g distilled water, magnetic agitation 20min, supersound process 30min, obtains the aqueous solution of organo montmorillonite.1.731g reactive emulsifier allyloxy nonyl phenol propyl alcohol polyoxyethylene (10) ether ammonium sulfate (DNS-86) and 0.173g assistant for emulsifying agent PEG-4000 (PEG-400) are dissolved in the hot water of 40 ℃ of 40g and form surfactant soln.
The aqueous solution of organo montmorillonite and surfactant soln are added in the 250mL there-necked flask that agitator and reflux condensing tube are housed and stir 30min at 40 ℃.Add 0.52g linking agent N, N'-methylene-bisacrylamide, 0.52g vinylformic acid, 5.893g butyl acrylate and 2.679g methyl methacrylate, be warming up to 75 ℃ and stir 10min, drip respectively the aqueous solution (0.478g ammonium persulphate is dissolved in 40g distilled water) of initiator and the mixed solution (23.573g butyl acrylate and 10.715g methyl methacrylate) of residual monomer, 1h dropwises, be warming up to 80 ℃, insulation reaction 2h.Under room temperature, regulate emulsion pH to 6, obtain polyacrylic ester/montmorillonite Composite hide finishes.
Embodiment 4:
Under magnetic agitation, 0.315g organo montmorillonite is slowly added in 20g distilled water, magnetic agitation 15min, supersound process 20min, obtains the aqueous solution of organo montmorillonite.1.025g reactive emulsifier allyloxy nonyl phenol propyl alcohol polyoxyethylene (10) ether ammonium sulfate (DNS-86) and 0.427g assistant for emulsifying agent PEG-4000 (PEG-400) are dissolved in the hot water of 40 ℃ of 40g and form surfactant soln.
The aqueous solution of organo montmorillonite and surfactant soln are added in the 250mL there-necked flask that agitator and reflux condensing tube are housed and stir 30min at 40 ℃.Add 0.423g linking agent N, N'-methylene-bisacrylamide, 0.481g vinylformic acid, 5.511g butyl acrylate and 3.061g methyl methacrylate, be warming up to 75 ℃ and stir 10min, drip respectively the aqueous solution (0.416g ammonium persulphate is dissolved in 40g distilled water) of initiator and the mixed solution (22.042g butyl acrylate and 12.246g methyl methacrylate) of residual monomer, 1h dropwises, be warming up to 80 ℃, insulation reaction 2h.Under room temperature, regulate emulsion pH to 5.8, obtain polyacrylic ester/montmorillonite Composite hide finishes.
Embodiment 5:
Under magnetic agitation, 0.528g organo montmorillonite is slowly added in 20g distilled water, magnetic agitation 20min, supersound process 30min, obtains the aqueous solution of organo montmorillonite.1.547g reactive emulsifier allyloxy nonyl phenol propyl alcohol polyoxyethylene (10) ether ammonium sulfate (DNS-86) and 0.259g assistant for emulsifying agent PEG-4000 (PEG-400) are dissolved in the hot water of 40 ℃ of 40g and form surfactant soln.
The aqueous solution of organo montmorillonite and surfactant soln are added in the 250mL there-necked flask that agitator and reflux condensing tube are housed and stir 30min at 40 ℃.Add 0.498g linking agent N, N'-methylene-bisacrylamide, 0.367g vinylformic acid, 5.807g butyl acrylate and 2.765g methyl methacrylate, be warming up to 75 ℃ and stir 10min, drip respectively the aqueous solution (0.452g ammonium persulphate is dissolved in 40g distilled water) of initiator and the mixed solution (23.227g butyl acrylate and 11.061g methyl methacrylate) of residual monomer, 1h dropwises, be warming up to 80 ℃, insulation reaction 2h.Under room temperature, regulate emulsion pH to 5.5, obtain polyacrylic ester/montmorillonite Composite hide finishes.
Polyacrylic ester/montmorillonite Composite hide finishes excellent property of preparing according to preparation method of the present invention, after leather finish, the tensile strength of leather sample is 3.31N/mm
2, elongation at break is 90.1%, compares and has promoted respectively 8.5% and 53% with crust leather before covering with paint, compares and has promoted respectively 14.1% and 21.8% with the polyacrylic ester finishing agent Leather Finishing sample that adopts reactive emulsifier to prepare.Leather sample xerotripsis fastness reaches 3-4 level, and wet rubbing fastness reaches 2-3 level.
Table 1 is removed from office the physical and mechanical properties of sample after covering with paint, lacquer, colour wash, etc.
| ? | Tensile strength (N/mm 2） | Elongation at break (%) |
| Crust leather | 3.05 | 59.0 |
| Polyacrylic ester/montmorillonite Composite hide finishes | 3.31 | 90.1 |
| Polyacrylic ester hide finishes | 2.90 | 74.0 |
Claims (4)
1. a method that adopts reactive emulsifier to prepare polyacrylic ester/montmorillonite Composite hide finishes, it is characterized in that: under magnetic agitation, 0.087 ~ 0.779g organo montmorillonite is slowly added in 20g distilled water, magnetic agitation 10 ~ 20min, supersound process 20 ~ 30min, obtains the aqueous solution of organo montmorillonite; 0.866 ~ 1.731g reactive emulsifier allyloxy nonyl phenol propyl alcohol polyoxyethylene (10) ether ammonium sulfate and 0.173 ~ 0.519g assistant for emulsifying agent PEG-4000 are dissolved in the hot water of 40 ℃ of 40g and form surfactant soln;
The aqueous solution of organo montmorillonite and surfactant soln are added in the 250mL there-necked flask that agitator and reflux condensing tube are housed and stir 20 ~ 30min at 40 ℃; Add 0.36 ~ 0.52g linking agent N, N'-methylene-bisacrylamide, 0.36 ~ 0.52g vinylformic acid, 5.143 ~ 5.893g butyl acrylate and 2.679 ~ 3.429g methyl methacrylate, be warming up to 75 ℃ and stir 10min, drip respectively the mixed solution of the aqueous solution of initiator and 20.573 ~ 23.573g butyl acrylate of residual monomer and 10.715 ~ 13.715g methyl methacrylate, the aqueous solution of initiator is dissolved in 40g distilled water by 0.392 ~ 0.478g ammonium persulphate and makes, 1h dropwises, be warming up to 80 ℃, insulation reaction 2h; Under room temperature, regulate emulsion pH to 5.5 ~ 6, obtain polyacrylic ester/montmorillonite Composite hide finishes;
Above-mentioned organo montmorillonite is palmityl trimethyl ammonium chloride modified montmorillonoid, its preparation method is: sodium-based montmorillonite is scattered in in distilled water, to be mixed with massfraction be 5% suspension, at 25 ℃, stir 30min, according to the loading capacity 90mmol/100g of polynite, calculate and add palmityl trimethyl ammonium chloride, at 85 ℃, continue to stir 4h, centrifugal, gained precipitation is washed with distilled water to AgNO
3solution check is without Cl
-; By grinding after 65 ℃ of vacuum-drying 24h of products therefrom, obtain organo montmorillonite.
2. a kind of method that adopts reactive emulsifier to prepare polyacrylic ester/montmorillonite Composite hide finishes according to claim 1, is characterized in that:
Under magnetic agitation, 0.437g organo montmorillonite is slowly added in 20g distilled water, magnetic agitation 10min, supersound process 30min, obtains the aqueous solution of organo montmorillonite; 1.731g reactive emulsifier allyloxy nonyl phenol propyl alcohol polyoxyethylene (10) ether ammonium sulfate and 0.347g assistant for emulsifying agent PEG-4000 are dissolved in the hot water of 40 ℃ of 40g and form surfactant soln;
The aqueous solution of organo montmorillonite and surfactant soln are added in the 250mL there-necked flask that agitator and reflux condensing tube are housed and stir 30min at 40 ℃; Add 0.428g linking agent N, N'-methylene-bisacrylamide, 0.428g vinylformic acid, 5.634g butyl acrylate and 2.938g methyl methacrylate, be warming up to 75 ℃ and stir 10min, drip respectively the mixed solution of the aqueous solution of initiator and the 22.536g butyl acrylate of residual monomer and 11.752g methyl methacrylate, the aqueous solution of initiator is dissolved in 40g distilled water by 0.428g ammonium persulphate and makes, 1h dropwises, and is warming up to 80 ℃, insulation reaction 2h; Under room temperature, regulate emulsion pH to 6, obtain polyacrylic ester/montmorillonite Composite hide finishes.
3. a kind of method that adopts reactive emulsifier to prepare polyacrylic ester/montmorillonite Composite hide finishes according to claim 1, is characterized in that:
Under magnetic agitation, 0.087g organo montmorillonite is slowly added in 20g distilled water, magnetic agitation 10min, supersound process 20min, obtains the aqueous solution of organo montmorillonite; 0.866g reactive emulsifier allyloxy nonyl phenol propyl alcohol polyoxyethylene (10) ether ammonium sulfate and 0.519g assistant for emulsifying agent PEG-4000 are dissolved in the hot water of 40 ℃ of 40g and form surfactant soln;
The aqueous solution of organo montmorillonite and surfactant soln are added in the 250mL there-necked flask that agitator and reflux condensing tube are housed and stir 20min at 40 ℃; Add 0.36g linking agent N, N'-methylene-bisacrylamide, 0.36g vinylformic acid, 5.143g butyl acrylate and 3.429g methyl methacrylate, be warming up to 75 ℃ and stir 10min, drip respectively the mixed solution of the aqueous solution of initiator and the 20.573g butyl acrylate of residual monomer and 13.715g methyl methacrylate, the aqueous solution of initiator is dissolved in 40g distilled water by 0.392g ammonium persulphate and makes, 1h dropwises, and is warming up to 80 ℃, insulation reaction 2h; Under room temperature, regulate emulsion pH to 5.5, obtain polyacrylic ester/montmorillonite Composite hide finishes.
4. a kind of method that adopts reactive emulsifier to prepare polyacrylic ester/montmorillonite Composite hide finishes according to claim 1, is characterized in that:
Under magnetic agitation, 0.779g organo montmorillonite is slowly added in 20g distilled water, magnetic agitation 20min, supersound process 30min, obtains the aqueous solution of organo montmorillonite; 1.731g reactive emulsifier allyloxy nonyl phenol propyl alcohol polyoxyethylene (10) ether ammonium sulfate and 0.173g assistant for emulsifying agent PEG-4000 are dissolved in the hot water of 40 ℃ of 40g and form surfactant soln;
The aqueous solution of organo montmorillonite and surfactant soln are added in the 250mL there-necked flask that agitator and reflux condensing tube are housed and stir 30min at 40 ℃; Add 0.52g linking agent N, N'-methylene-bisacrylamide, 0.52g vinylformic acid, 5.893g butyl acrylate and 2.679g methyl methacrylate, be warming up to 75 ℃ and stir 10min, drip respectively the mixed solution of the aqueous solution of initiator and the 23.573g butyl acrylate of residual monomer and 10.715g methyl methacrylate, the aqueous solution of initiator is dissolved in 40g distilled water by 0.478g ammonium persulphate and makes, 1h dropwises, and is warming up to 80 ℃, insulation reaction 2h; Under room temperature, regulate emulsion pH to 6, obtain polyacrylic ester/montmorillonite Composite hide finishes.
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| CN103694402B (en) * | 2013-12-06 | 2016-01-20 | 四川达威科技股份有限公司 | A kind of water-soluble colloidality polyacrylic ester filling resin for leather and preparation technology thereof |
| CN104177537B (en) * | 2014-08-04 | 2016-05-18 | 陕西科技大学 | A kind of preparation method of polyacrylate/columnar hollow zinc oxide complex emulsions for leather |
| CN105113248A (en) * | 2015-09-11 | 2015-12-02 | 无锡市长安曙光手套厂 | High-temperature-resisting deodorant textile material finishing method |
| CN117801153B (en) * | 2024-02-29 | 2024-04-30 | 淄博宏阳新材料科技有限公司 | Preparation method of nano silicon dioxide-zinc oxide-montmorillonite modified acrylic resin |
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| CN101210391A (en) * | 2006-12-25 | 2008-07-02 | 杨耀荣 | UV-ultraviolet light solidified water dope printing adhesive |
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