CN1556225A - Preparation technology of ving/polymer/modified montmorillonoid nano composite tanoing agent - Google Patents
Preparation technology of ving/polymer/modified montmorillonoid nano composite tanoing agent Download PDFInfo
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- CN1556225A CN1556225A CNA200410025819XA CN200410025819A CN1556225A CN 1556225 A CN1556225 A CN 1556225A CN A200410025819X A CNA200410025819X A CN A200410025819XA CN 200410025819 A CN200410025819 A CN 200410025819A CN 1556225 A CN1556225 A CN 1556225A
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- trimethylammonium bromide
- cetyl trimethylammonium
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Abstract
A process for preparing the nano-class composite tanning agent includes using ammonium hexadecane bromide to modify Na-base montmorillonite, using vinyl monomer (acrylic acid, acrylonitrile, or ethyl acrylate) to prepare vinyl polymer, and combounding them together by solution stripping-adsorption method. Its advantages are high effect on raising the shrinking temp of sheep leather to 76 deg.C and increasing leather thickness, and high air and moisture permeability of leather.
Description
Technical field
The present invention relates to a kind ofly has the preparation technology of the nano composite material of tanning effect, the preparation technology of particularly a kind of vinyl polymer/ester/modified montmorillonite nano composite tanning agent to rawhide.
Background technology
Leather industry and human lives and development and national economy are closely bound up.Two during the last ten years leather industry both brought wealth in the tremendous development of China to us, make us see startling numeral simultaneously: about 7,000 ten thousand tons of China's tanning industry year waste discharge (wherein 1.4 ten thousand tons of sulfur compounds, 3.8 ten thousand tons of chromic salts, 210,000 tons of suspended substances, COD
Cr350,000 tons, BOD
S940,000 tons), about 700,000 tons of protein solid waste (see Liu Bailing, Zhang Mingrang. realize the Green Chemistry research in China's tanning industry ecology. Beijing leather .2000 (22): 50～52).In these pollutents, the toxicity maximum of chromium.No matter take what way,, just caused the permanent pollution of chromium ion inevitably, simultaneously attached to the Cr that is not reduced on the leather goods as long as the intervention of chromium is arranged
6+Can directly cause damage, bring out various diseases human body skin.In some process hides factory area of concentrations, the phenomenon of teratogenesis birth has appearred causing owing to the pollution of chromium water source.The basic way that solves pollution of chromium can only be thoroughly to abandon chrome tanning, adopt the linking agent that do not contain chromium (see Qin Shufa. clean the technology and the strategy of sustainable development.The scientific and technological Conference Papers collection of 21 century first Chinese leather.2001:33～35), the elimination curriery is polluted, realize that process hides cleans extremely urgent, this class problem has become one of focus of global process hides circle research and (has seen Luisa.F.Cabeza, Maryann M.Taylor, Gary L.Dimaio, etc.Processing of leather waste:pilot scale studies on chrome shavings.Part IIpurification of chrome calce and tanning trials.J Amer.Leather Chem.Assoc.1998 (93): 83～98;
Chen?Wuyong，H.Cooke.Peter，Gay?L.Dimaio，etc..Modified?collagen?hydrolysatepotentiall?for?use?as?a?filler?for?leather.J?Amer.Leather?Chem.Assoc.2001(96)：263～267；
Cantera?C.S.，Giuste?M.DE.，Sofia?A.，Hydrolysis?of?chrome?shavings：Application?ofcollagen?hydrolysate?and“A?crylic-protein”in?post?tanning?operations，J.Soc.LeatherTechnol.Chem..1998(81)：183～191)。In the research of Chrome-free or few chrome tanning system, most researchers all is conceived to improvement (the Covington A.D. of the development and application technology of conventional tanning agent both at home and abroad, Lampard G.S., Pennington M., An investigation of titanium (III) as a tanning agnet.J.Soc.Leather Technol.Chem.1999 (82): 78～80;
Brown?Eleanor?M..Effects?of?neutral?salts?on?collagen?structure?andchromium-collagen?interactions.J.Amer.Leather?Chem.Assoc.1999(94)：59～66；
M.H.Cuq，C.Palevody，M.Delmas.Fundamental?study?of?cross-linking?ofcollagenwith?chrome?tanning?agents?in?traditional?and?Cr.A.B.processes.J.Soc.LeatherTechnol.Chem.2000(83)：233～238；
Price?David?N..Recent?advancees?in?soft-touch?acrylic?technology.J.Amer.LeatherChem.Assoc..2001(96)：54～60)。Because non-chrome tanning agent and the molecule crosslinked Stability Analysis of Structures degree of collagen are not enough, still there is not a kind of novel tanning agent that can replace chromium to occur at present.The chrome-free tanning agent that the utilization traditional method is developed is difficult to satisfy the requirement of the good use properties of finished leather.The key that realizes chrome-free tanning is to improve the stability of tanning agent and collagen crosslinking structure and give finished leather certain filling effect, this also have now just synthetic tanning agent can not have both.
The traditional tanning industry of transformation that develops into of nano composite material provides a kind of new possibility.Particularly Organic is because its excellent performance has become one of the focus in nano materials research field.Polynite is a kind of layered silicate, and interlamellar spacing is approximately about 1nm, and polynite alumina octahedral top trivalent aluminium is made a layer internal surface have negative charge by divalence magnesium isomorphous substitution, and superfluous negative charge compensates by the positively charged ion of interlayer absorption, as: Na
+, K
+, Ca
2+Deng.These positively charged ions be can with the organic or inorganic cationic exchange.Compound nylon-type, polystyrene, Resins, epoxy, ethene--polymer-based carbon Nano composite material of montmorillonite such as vinyl acetate copolymer, the polyacrylic acid (Ke Yangchuan that knows clearly that successfully prepared of modified montmorillonoid and polymkeric substance, the Pi Te Strong. polymkeric substance-inorganic nano composite material. Chemical Industry Press, 2003.; Wang Lixin, Li Junfeng, Zhang Hongbo etc. the preparation of nm-class unsaturated polyester/montmorillonite composition and friction and Wear Study thereof. tribology journal .2003,5 (3): 197～200).But the polymer-based carbon Nano composite material of montmorillonite is introduced the leather tanning field yet there are no relevant report.
Summary of the invention
The object of the present invention is to provide a kind of consumption that can reduce chromium, reduce pollution of chromium, can make the lamb skin post shrinkage temperature of tanning reach 76 ℃, use 0.5% chrome tanning agent again (with Cr
2O
3Meter) tanning can make leather shrinking temperature reach 96 ℃, and chroming waste liquor exhaustion rate height, and the back finished leather of tanning thickens obviously the preparation technology of the vinyl polymer that the finished leather permeability to water vapour is good/ester/modified montmorillonite nano composite tanning agent.
For achieving the above object, the preparation technology that the present invention adopts is:
1) cetyl trimethylammonium bromide modified montmorillonoid:
At first polynite is added in the deionized water with 5～15% mass percent, stir the Colloidal fluid that makes polynite form homogeneous,, add cetyl trimethylammonium bromide then with 90-120mmol/100g polynite metering with ultrasonication 30～60 minutes; Stirred 2-6 hour down at 70-90 ℃, use ultrasonication 30-60 minute at last once more, be the polynite of cetyl trimethylammonium bromide modification;
2) preparation of vinyl polymer:
At first with vinylformic acid, vinyl cyanide, ethyl propenoate and Virahol mixing are dissolved in the deionized water, make and contain the vinylformic acid that mass percent is 8-12%, the vinyl cyanide of 8-12%, the mixed solution of the ethyl propenoate of 1-2% and the Virahol of 1-4%, half mixed solution is added in the deionized water of mixed solution total mass 70-80%, after being warming up to 75-80 ℃, drip second half mixed solution simultaneously and account for vinylformic acid, ethyl propenoate, the concentration of vinyl cyanide and Virahol total mass 4-10% is 10% water soluble starter ammonium persulphate initiated polymerization, the control dropping time is 30-40 minute, be warming up to 85-90 ℃ at last, insulated and stirred 2-3 hour, regulate pH value to 5.0, discharging with sodium hydroxide;
3) cetyl trimethylammonium bromide modified montmorillonoid and vinyl polymer are compound:
With cetyl trimethylammonium bromide modified montmorillonoid and vinyl polymer with solid content in the liquid than 1: 0.8-2 mixed, with ultrasonication 0.5-1.5 hour; Be warming up to 75-85 ℃ again, stirred 2-4 hour, regulate pH value to 6.0 with sodium hydroxide, discharging promptly gets vinyl polymer/cetyl trimethylammonium bromide Nano composite material of montmorillonite modified.
The present invention adopts hexadecyl brometo de amonio modification sodium-based montmorillonite, prepare vinyl polymer with vinyl monomer vinylformic acid, vinyl cyanide, ethyl propenoate, adopt then solution peel off-absorption method is the two compound preparation vinyl polymer/montmorillonite nano-composite tanning agent.This composite tanning agent can make the post shrinkage temperature of tanning reach 76 ℃; Re-use 0.5% chrome tanning agent (with Cr
2O
3Meter) tanning can make the shrinkage temperature of leather reach 96 ℃, can satisfy in the present production requirement to the crust leather shrinkage temperature fully.While chroming waste liquor exhaustion rate height; The back finished leather of tanning thickens obviously, and the permeability to water vapour of finished leather is good.Therefore this tanning agent is a kind of functional, and environment amenable nano-composite tanning agent.
Embodiment
Embodiment 1,1) cetyl trimethylammonium bromide modified montmorillonoid: at first polynite is added in the deionized water with 5% mass percent, stirring makes polynite form the Colloidal fluid of homogeneous, with ultrasonication 60 minutes, add cetyl trimethylammonium bromide then with 90mmol/100g polynite metering; Stirred 2 hours down at 90 ℃, use ultrasonication 30 minutes at last once more, be the polynite of cetyl trimethylammonium bromide modification;
2) preparation of vinyl polymer: at first with vinylformic acid, vinyl cyanide, ethyl propenoate and Virahol mix in molten and the deionized water, make that to contain mass percent be 8% vinylformic acid, 12% vinyl cyanide, the mixed solution of 1% ethyl propenoate and 1% Virahol, half mixed solution is added in the deionized water of mixed solution total mass 78%, after being warming up to 75 ℃, drip second half mixed solution simultaneously and account for vinylformic acid, ethyl propenoate, the concentration of vinyl cyanide and Virahol total mass 10% is 10% water soluble starter ammonium persulphate initiated polymerization, the control dropping time is 40 minutes, be warming up to 85 ℃ at last, insulated and stirred 3 hours, regulate pH value to 5.0, discharging with sodium hydroxide;
3) cetyl trimethylammonium bromide modified montmorillonoid and vinyl polymer are compound:
Cetyl trimethylammonium bromide modified montmorillonoid and vinyl polymer are mixed than 1: 0.8 with solid content in the liquid, use ultrasonication 0.5 hour; Be warming up to 75 ℃ again, stirred 2 hours, regulate pH value to 6.0 with sodium hydroxide, discharging promptly gets vinyl polymer/cetyl trimethylammonium bromide Nano composite material of montmorillonite modified.
Embodiment 2:1) cetyl trimethylammonium bromide modified montmorillonoid: at first polynite is added in the deionized water with 15% mass percent, stirring makes polynite form the Colloidal fluid of homogeneous, with ultrasonication 45 minutes, add cetyl trimethylammonium bromide then with 110mmol/100g polynite metering; Stirred 3 hours down at 70 ℃, use ultrasonication 55 minutes at last once more, be the polynite of cetyl trimethylammonium bromide modification;
2) preparation of vinyl polymer: at first with vinylformic acid, vinyl cyanide, ethyl propenoate and Virahol mix in molten and the deionized water, make that to contain mass percent be 12% vinylformic acid, 10% vinyl cyanide, the mixed solution of 1.2% ethyl propenoate and 1.8% Virahol, half mixed solution is added in the deionized water of mixed solution total mass 75%, after being warming up to 76 ℃, drip second half mixed solution simultaneously and account for vinylformic acid, ethyl propenoate, the concentration of vinyl cyanide and Virahol total mass 8% is 10% water soluble starter ammonium persulphate initiated polymerization, the control dropping time is 30 minutes, be warming up to 88 ℃ at last, insulated and stirred 2.8 hours, regulate pH value to 5.0, discharging with sodium hydroxide;
3) cetyl trimethylammonium bromide modified montmorillonoid and vinyl polymer are compound:
Cetyl trimethylammonium bromide modified montmorillonoid and vinyl polymer are mixed than 1: 2 with solid content in the liquid, use ultrasonication 1.5 hours; Be warming up to 85 ℃ again, stirred 3 hours, regulate pH value to 6.0 with sodium hydroxide, discharging promptly gets vinyl polymer/cetyl trimethylammonium bromide Nano composite material of montmorillonite modified.
Embodiment 3:1) cetyl trimethylammonium bromide modified montmorillonoid: at first polynite is added in the deionized water with 8% mass percent, stirring makes polynite form the Colloidal fluid of homogeneous, with ultrasonication 30 minutes, add cetyl trimethylammonium bromide then with 100mmol/100g polynite metering; Stirred 4 hours down at 85 ℃, use ultrasonication 40 minutes at last once more, be the polynite of cetyl trimethylammonium bromide modification;
2) preparation of vinyl polymer: at first with vinylformic acid, vinyl cyanide, ethyl propenoate and Virahol mix in molten and the deionized water, make that to contain mass percent be 9% vinylformic acid, 11% vinyl cyanide, the mixed solution of 1.5% ethyl propenoate and 4% Virahol, half mixed solution is added in the deionized water of mixed solution total mass 74.5%, after being warming up to 77 ℃, drip second half mixed solution simultaneously and account for vinylformic acid, ethyl propenoate, the concentration of vinyl cyanide and Virahol total mass 4% is 10% water soluble starter ammonium persulphate initiated polymerization, the control dropping time is 38 minutes, be warming up to 90 ℃ at last, insulated and stirred 2 hours, regulate pH value to 5.0, discharging with sodium hydroxide;
3) cetyl trimethylammonium bromide modified montmorillonoid and vinyl polymer are compound:
Cetyl trimethylammonium bromide modified montmorillonoid and vinyl polymer are mixed than 1: 1.2 with solid content in the liquid, use ultrasonication 1 hour; Be warming up to 77 ℃ again, stirred 4 hours, regulate pH value to 6.0 with sodium hydroxide, discharging promptly gets vinyl polymer/cetyl trimethylammonium bromide Nano composite material of montmorillonite modified.
Embodiment 4:1) cetyl trimethylammonium bromide modified montmorillonoid: at first polynite is added in the deionized water with 12% mass percent, stirring makes polynite form the Colloidal fluid of homogeneous, with ultrasonication 55 minutes, add cetyl trimethylammonium bromide then with 115mmol/100g polynite metering; Stirred 5 hours down at 75 ℃, use ultrasonication 35 minutes at last once more, be the polynite of cetyl trimethylammonium bromide modification;
2) preparation of vinyl polymer: at first with vinylformic acid, vinyl cyanide, ethyl propenoate and Virahol mix in molten and the deionized water, make that to contain mass percent be 11% vinylformic acid, 11% vinyl cyanide, the mixed solution of 2% ethyl propenoate and 3% Virahol, half mixed solution is added in the deionized water of mixed solution total mass 73%, after being warming up to 79 ℃, drip second half mixed solution simultaneously and account for vinylformic acid, ethyl propenoate, the concentration of vinyl cyanide and Virahol total mass 9% is 10% water soluble starter ammonium persulphate initiated polymerization, the control dropping time is 32 minutes, be warming up to 86 ℃ at last, insulated and stirred 2.5 hours, regulate pH value to 5.0, discharging with sodium hydroxide;
3) cetyl trimethylammonium bromide modified montmorillonoid and vinyl polymer are compound:
Cetyl trimethylammonium bromide modified montmorillonoid and vinyl polymer are mixed than 1: 1.5 with solid content in the liquid, use ultrasonication 1.3 hours; Be warming up to 83 ℃ again, stirred 2.5 hours, regulate pH value to 6.0 with sodium hydroxide, discharging promptly gets nano composite material in vinyl polymer/cetyl trimethylammonium bromide modified montmorillonoid.
Embodiment 5:1) cetyl trimethylammonium bromide modified montmorillonoid: at first polynite is added in the deionized water with 7% mass percent, stirring makes polynite form the Colloidal fluid of homogeneous, with ultrasonication 40 minutes, add cetyl trimethylammonium bromide then with 120mmol/100g polynite metering; Stirred 6 hours down at 83 ℃, use ultrasonication 60 minutes at last once more, be the polynite of cetyl trimethylammonium bromide modification;
2) preparation of vinyl polymer: at first with vinylformic acid, vinyl cyanide, ethyl propenoate and Virahol mix in molten and the deionized water, make that to contain mass percent be 10% vinylformic acid, 9.5% vinyl cyanide, the mixed solution of 1.5% ethyl propenoate and 3% Virahol, half mixed solution is added in the deionized water of mixed solution total mass 76%, after being warming up to 80 ℃, drip second half mixed solution simultaneously and account for vinylformic acid, ethyl propenoate, the concentration of vinyl cyanide and Virahol total mass 6% is 10% water soluble starter ammonium persulphate initiated polymerization, the control dropping time is 35 minutes, be warming up to 89 ℃ at last, insulated and stirred 2.7 hours, regulate pH value to 5.0, discharging with sodium hydroxide;
3) cetyl trimethylammonium bromide modified montmorillonoid and vinyl polymer are compound:
Cetyl trimethylammonium bromide modified montmorillonoid and vinyl polymer are mixed than 1: 1.9 with solid content in the liquid, use ultrasonication 0.8 hour; Be warming up to 80 ℃ again, stirred 3.8 hours, regulate pH value to 6.0 with sodium hydroxide, discharging promptly gets vinyl polymer/cetyl trimethylammonium bromide Nano composite material of montmorillonite modified.
Embodiment 6:1) cetyl trimethylammonium bromide modified montmorillonoid: at first polynite is added in the deionized water with 14% mass percent, stirring makes polynite form the Colloidal fluid of homogeneous, with ultrasonication 35 minutes, add cetyl trimethylammonium bromide then with 95mmol/100g polynite metering; Stirred 4.5 hours down at 78 ℃, use ultrasonication 45 minutes at last once more, be the polynite of cetyl trimethylammonium bromide modification;
2) preparation of vinyl polymer: at first with vinylformic acid, vinyl cyanide, ethyl propenoate and Virahol mix in molten and the deionized water, make that to contain mass percent be 10.5% vinylformic acid, 9% vinyl cyanide, the mixed solution of 1.8% ethyl propenoate and 2.7% Virahol, half mixed solution is added in the deionized water of mixed solution total mass 76%, after being warming up to 78 ℃, drip second half mixed solution simultaneously and account for vinylformic acid, ethyl propenoate, the concentration of vinyl cyanide and Virahol total mass 7% is 10% water soluble starter ammonium persulphate initiated polymerization, the control dropping time is 37 minutes, be warming up to 87 ℃ at last, insulated and stirred 2.2 hours, regulate pH value to 5.0, discharging with sodium hydroxide;
3) cetyl trimethylammonium bromide modified montmorillonoid and vinyl polymer are compound:
Cetyl trimethylammonium bromide modified montmorillonoid and vinyl polymer are mixed than 1: 1.7 with solid content in the liquid, use ultrasonication 0.7 hour; Be warming up to 81 ℃ again, stirred 3.4 hours, regulate pH value to 6.0 with sodium hydroxide, discharging promptly gets vinyl polymer/cetyl trimethylammonium bromide Nano composite material of montmorillonite modified.
Chrome tanning agent exists serious pollution and chromium resource relative shortage, and the application of the tanning agent of the present invention's preparation is significant for the consumption that reduces chromium, reduction pollution of chromium.When modified montmorillonoid and vinyl polymer compound tense, the effect of composite tanning agent and leather is obvious, can improve to maximum amplitude the shrinkage temperature of the back leather of tanning.Vinyl polymer/cetyl trimethylammonium bromide ester/modified montmorillonite nano composite tanning agent can make the lamb skin post shrinkage temperature of tanning reach 76 ℃, uses 0.5% chrome tanning agent (with Cr again
2O
3Meter) tanning can make leather shrinking temperature reach 96 ℃, can satisfy in the present production requirement to the crust leather shrinkage temperature fully.While chroming waste liquor exhaustion rate height; The back finished leather of tanning thickens obviously, and the finished leather permeability to water vapour is good.Therefore this tanning agent is a kind of functional, and environment amenable nano-composite tanning agent.
Claims (7)
1, the preparation technology of a kind of vinyl polymer/ester/modified montmorillonite nano composite tanning agent is characterized in that:
1) cetyl trimethylammonium bromide modified montmorillonoid:
At first polynite is added in the deionized water with 5～15% mass percent, stir the Colloidal fluid that makes polynite form homogeneous,, add cetyl trimethylammonium bromide then with 90-120mmol/100g polynite metering with ultrasonication 30～60 minutes; Stirred 2-6 hour down at 70-90 ℃, use ultrasonication 30-60 minute at last once more, be the polynite of cetyl trimethylammonium bromide modification;
2) preparation of vinyl polymer:
At first with vinylformic acid, vinyl cyanide, ethyl propenoate and Virahol mixing are dissolved in the deionized water, make and contain the vinylformic acid that mass percent is 8-12%, the vinyl cyanide of 8-12%, the mixed solution of the ethyl propenoate of 1-2% and the Virahol of 1-4%, half mixed solution is added in the deionized water of mixed solution total mass 70-80%, after being warming up to 75-80 ℃, drip second half mixed solution simultaneously and account for vinylformic acid, ethyl propenoate, the concentration of vinyl cyanide and Virahol total mass 4-10% is 10% water soluble starter ammonium persulphate initiated polymerization, the control dropping time is 30-40 minute, be warming up to 85-90 ℃ at last, insulated and stirred 2-3 hour, regulate pH value to 5.0, discharging with sodium hydroxide;
3) cetyl trimethylammonium bromide modified montmorillonoid and vinyl polymer are compound:
With cetyl trimethylammonium bromide modified montmorillonoid and vinyl polymer with solid content in the liquid than 1: 0.8-2 mixed, with ultrasonication 0.5-1.5 hour; Be warming up to 75-85 ℃ again, stirred 2-4 hour, regulate pH value to 6.0 with sodium hydroxide, discharging promptly gets vinyl polymer/cetyl trimethylammonium bromide Nano composite material of montmorillonite modified.
2, the preparation technology of vinyl polymer according to claim 1/ester/modified montmorillonite nano composite tanning agent, it is characterized in that: 1) cetyl trimethylammonium bromide modified montmorillonoid: at first polynite is added in the deionized water with 5% mass percent, stirring makes polynite form the Colloidal fluid of homogeneous, with ultrasonication 60 minutes, add cetyl trimethylammonium bromide then with 90mmol/100g polynite metering; Stirred 2 hours down at 90 ℃, use ultrasonication 30 minutes at last once more, be the polynite of cetyl trimethylammonium bromide modification;
2) preparation of vinyl polymer: at first with vinylformic acid, vinyl cyanide, ethyl propenoate and Virahol mix in molten and the deionized water, make that to contain mass percent be 8% vinylformic acid, 12% vinyl cyanide, the mixed solution of 1% ethyl propenoate and 1% Virahol, half mixed solution is added in the deionized water of mixed solution total mass 78%, after being warming up to 75 ℃, drip second half mixed solution simultaneously and account for vinylformic acid, ethyl propenoate, the concentration of vinyl cyanide and Virahol total mass 10% is 10% water soluble starter ammonium persulphate initiated polymerization, the control dropping time is 40 minutes, be warming up to 85 ℃ at last, insulated and stirred 3 hours, regulate pH value to 5.0, discharging with sodium hydroxide;
3) cetyl trimethylammonium bromide modified montmorillonoid and vinyl polymer are compound:
Cetyl trimethylammonium bromide modified montmorillonoid and vinyl polymer are mixed than 1: 0.8 with solid content in the liquid, use ultrasonication 0.5 hour; Be warming up to 75 ℃ again, stirred 2 hours, regulate pH value to 6.0 with sodium hydroxide, discharging promptly gets vinyl polymer/cetyl trimethylammonium bromide Nano composite material of montmorillonite modified.
3, the preparation technology of vinyl polymer according to claim 1/ester/modified montmorillonite nano composite tanning agent, it is characterized in that: 1) cetyl trimethylammonium bromide modified montmorillonoid: at first polynite is added in the deionized water with 15% mass percent, stirring makes polynite form the Colloidal fluid of homogeneous, with ultrasonication 45 minutes, add cetyl trimethylammonium bromide then with 110mmol/100g polynite metering; Stirred 3 hours down at 70 ℃, use ultrasonication 55 minutes at last once more, be the polynite of cetyl trimethylammonium bromide modification;
2) preparation of vinyl polymer: at first with vinylformic acid, vinyl cyanide, ethyl propenoate and Virahol mix in molten and the deionized water, make that to contain mass percent be 12% vinylformic acid, 10% vinyl cyanide, the mixed solution of 1.2% ethyl propenoate and 1.8% Virahol, half mixed solution is added in the deionized water of mixed solution total mass 75%, after being warming up to 76 ℃, drip second half mixed solution simultaneously and account for vinylformic acid, ethyl propenoate, the concentration of vinyl cyanide and Virahol total mass 8% is 10% water soluble starter ammonium persulphate initiated polymerization, the control dropping time is 30 minutes, be warming up to 88 ℃ at last, insulated and stirred 2.8 hours, regulate pH value to 5.0, discharging with sodium hydroxide;
3) cetyl trimethylammonium bromide modified montmorillonoid and vinyl polymer are compound:
Cetyl trimethylammonium bromide modified montmorillonoid and vinyl polymer are mixed than 1: 2 with solid content in the liquid, use ultrasonication 1.5 hours; Be warming up to 85 ℃ again, stirred 3 hours, regulate pH value to 6.0 with sodium hydroxide, discharging promptly gets vinyl polymer/cetyl trimethylammonium bromide Nano composite material of montmorillonite modified.
4, the preparation technology of vinyl polymer according to claim 1/ester/modified montmorillonite nano composite tanning agent, it is characterized in that: 1) cetyl trimethylammonium bromide modified montmorillonoid: at first polynite is added in the deionized water with 8% mass percent, stirring makes polynite form the Colloidal fluid of homogeneous, with ultrasonication 30 minutes, add cetyl trimethylammonium bromide then with 100mmol/100g polynite metering; Stirred 4 hours down at 85 ℃, use ultrasonication 40 minutes at last once more, be the polynite of cetyl trimethylammonium bromide modification;
2) preparation of vinyl polymer: at first with vinylformic acid, vinyl cyanide, ethyl propenoate and Virahol mix in molten and the deionized water, make that to contain mass percent be 9% vinylformic acid, 11% vinyl cyanide, the mixed solution of 1.5% ethyl propenoate and 4% Virahol, half mixed solution is added in the deionized water of mixed solution total mass 74.5%, after being warming up to 77 ℃, drip second half mixed solution simultaneously and account for vinylformic acid, ethyl propenoate, the concentration of vinyl cyanide and Virahol total mass 4% is 10% water soluble starter ammonium persulphate initiated polymerization, the control dropping time is 38 minutes, be warming up to 90 ℃ at last, insulated and stirred 2 hours, regulate pH value to 5.0, discharging with sodium hydroxide;
3) cetyl trimethylammonium bromide modified montmorillonoid and vinyl polymer are compound:
Cetyl trimethylammonium bromide modified montmorillonoid and vinyl polymer are mixed than 1: 1.2 with solid content in the liquid, use ultrasonication 1 hour; Be warming up to 77 ℃ again, stirred 4 hours, regulate pH value to 6.0 with sodium hydroxide, discharging promptly gets vinyl polymer/cetyl trimethylammonium bromide Nano composite material of montmorillonite modified.
5, the preparation technology of vinyl polymer according to claim 1/ester/modified montmorillonite nano composite tanning agent, it is characterized in that: 1) cetyl trimethylammonium bromide modified montmorillonoid: at first polynite is added in the deionized water with 12% mass percent, stirring makes polynite form the Colloidal fluid of homogeneous, with ultrasonication 55 minutes, add cetyl trimethylammonium bromide then with 115mmol/100g polynite metering; Stirred 5 hours down at 75 ℃, use ultrasonication 35 minutes at last once more, be the polynite of cetyl trimethylammonium bromide modification;
2) preparation of vinyl polymer: at first with vinylformic acid, vinyl cyanide, ethyl propenoate and Virahol mix in molten and the deionized water, make that to contain mass percent be 11% vinylformic acid, 11% vinyl cyanide, the mixed solution of 2% ethyl propenoate and 3% Virahol, half mixed solution is added in the deionized water of mixed solution total mass 73%, after being warming up to 79 ℃, drip second half mixed solution simultaneously and account for vinylformic acid, ethyl propenoate, the concentration of vinyl cyanide and Virahol total mass 9% is 10% water soluble starter ammonium persulphate initiated polymerization, the control dropping time is 32 minutes, be warming up to 86 ℃ at last, insulated and stirred 2.5 hours, regulate pH value to 5.0, discharging with sodium hydroxide;
3) cetyl trimethylammonium bromide modified montmorillonoid and vinyl polymer are compound:
Cetyl trimethylammonium bromide modified montmorillonoid and vinyl polymer are mixed than 1: 1.5 with solid content in the liquid, use ultrasonication 1.3 hours; Be warming up to 83 ℃ again, stirred 2.5 hours, regulate pH value to 6.0 with sodium hydroxide, discharging promptly gets vinyl polymer/cetyl trimethylammonium bromide Nano composite material of montmorillonite modified.
6, the preparation technology of vinyl polymer according to claim 1/ester/modified montmorillonite nano composite tanning agent, it is characterized in that: 1) cetyl trimethylammonium bromide modified montmorillonoid: at first polynite is added in the deionized water with 7% mass percent, stirring makes polynite form the Colloidal fluid of homogeneous, with ultrasonication 40 minutes, add cetyl trimethylammonium bromide then with 120mmol/100g polynite metering; Stirred 6 hours down at 83 ℃, use ultrasonication 60 minutes at last once more, be the polynite of cetyl trimethylammonium bromide modification;
2) preparation of vinyl polymer: at first with vinylformic acid, vinyl cyanide, ethyl propenoate and Virahol mix in molten and the deionized water, make that to contain mass percent be 10% vinylformic acid, 9.5% vinyl cyanide, the mixed solution of 1.5% ethyl propenoate and 3% Virahol, half mixed solution is added in the deionized water of mixed solution total mass 76%, after being warming up to 80 ℃, drip second half mixed solution simultaneously and account for vinylformic acid, ethyl propenoate, the concentration of vinyl cyanide and Virahol total mass 6% is 10% water soluble starter ammonium persulphate initiated polymerization, the control dropping time is 35 minutes, be warming up to 89 ℃ at last, insulated and stirred 2.7 hours, regulate pH value to 5.0, discharging with sodium hydroxide;
3) cetyl trimethylammonium bromide modified montmorillonoid and vinyl polymer are compound:
Cetyl trimethylammonium bromide modified montmorillonoid and vinyl polymer are mixed than 1: 1.9 with solid content in the liquid, use ultrasonication 0.8 hour; Be warming up to 80 ℃ again, stirred 3.8 hours, regulate pH value to 6.0 with sodium hydroxide, discharging promptly gets vinyl polymer/cetyl trimethylammonium bromide Nano composite material of montmorillonite modified.
7, the preparation technology of vinyl polymer according to claim 1/ester/modified montmorillonite nano composite tanning agent, it is characterized in that: 1) cetyl trimethylammonium bromide modified montmorillonoid: at first polynite is added in the deionized water with 14% mass percent, stirring makes polynite form the Colloidal fluid of homogeneous, with ultrasonication 35 minutes, add cetyl trimethylammonium bromide then with 95mmol/100g polynite metering; Stirred 4.5 hours down at 78 ℃, use ultrasonication 45 minutes at last once more, be the polynite of cetyl trimethylammonium bromide modification;
2) preparation of vinyl polymer: at first with vinylformic acid, vinyl cyanide, ethyl propenoate and Virahol mix in molten and the deionized water, make that to contain mass percent be 10.5% vinylformic acid, 9% vinyl cyanide, the mixed solution of 1.8% ethyl propenoate and 2.7% Virahol, half mixed solution is added in the deionized water of mixed solution total mass 76%, after being warming up to 78 ℃, drip second half mixed solution simultaneously and account for vinylformic acid, ethyl propenoate, the concentration of vinyl cyanide and Virahol total mass 7% is 10% water soluble starter ammonium persulphate initiated polymerization, the control dropping time is 37 minutes, be warming up to 87 ℃ at last, insulated and stirred 2.2 hours, regulate pH value to 5.0, discharging with sodium hydroxide;
3) cetyl trimethylammonium bromide modified montmorillonoid and vinyl polymer are compound:
Cetyl trimethylammonium bromide modified montmorillonoid and vinyl polymer are mixed than 1: 1.7 with solid content in the liquid, use ultrasonication 0.7 hour; Be warming up to 81 ℃ again, stirred 3.4 hours, regulate pH value to 6.0 with sodium hydroxide, discharging promptly gets vinyl polymer/cetyl trimethylammonium bromide Nano composite material of montmorillonite modified.
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