CN104892989A - Aqueous carboxymethylcellulose nitrate ester resin dispersion - Google Patents
Aqueous carboxymethylcellulose nitrate ester resin dispersion Download PDFInfo
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- CN104892989A CN104892989A CN201510272016.2A CN201510272016A CN104892989A CN 104892989 A CN104892989 A CN 104892989A CN 201510272016 A CN201510272016 A CN 201510272016A CN 104892989 A CN104892989 A CN 104892989A
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- carboxymethyl cellulose
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Abstract
The invention discloses an aqueous carboxymethylcellulose nitrate ester resin dispersion and aims at solving the problem that relatively serious pollution and injury to the environment and human health are caused because the dosage of traditional organic nitrocellulose paint solvents and particularly benzene solvents is superhigh and achieving the aim that a stable emulsion can also be obtained without additionally adding water-based polymer resin. The aqueous carboxymethylcellulose nitrate ester resin dispersion comprises carboxymethylcellulose nitrate, resin, a cellosolve, deionized water, an emulsifying agent and a plasticizer. The aqueous carboxymethylcellulose nitrate ester resin dispersion prepared by the invention is simple in process, uniform in emulsion dispersion, good in storage stability and film forming property, environment-friendly because of replacing part of organic solvent with water, very high in industrial production capacity and very wide in application prospect.
Description
Technical field
The present invention relates to a kind of water-based Nitro cellulose resin material of paint field, be specifically related to a kind of carboxymethyl cellulose nitrate resin aqueous dispersion.
Background technology
Along with the development of society, environmental pollution especially recently causes the concern of people day by day, more and more higher to coating industry requirement, particularly requires that the pollution of application of paints to environment is little.Solvent in traditional solvent-borne coating is everlasting more than 60%, and the solvent of pyroxylin(e)finish when constructing more can up to 80%, and the solvent-borne type metallic color white spirit content of painting dressing automobiles is up to 85%.
These volatile organic solvents (VOC) enter air, can cause environmental pollution.In addition, fit up the coating used at home, also can produce VOC, thus cause the pollution of indoor environment, and then affect HUMAN HEALTH.
Reduce the volatilization of coating organic compound in use (VOC), development environment friendly coating especially water-borne coatings has become the focus of coating research field.The use history of pyroxylin(e)finish is existing century-old, and because of its abundant raw material source, preparation is simple, and the huge advantage especially in woodenware industry, also cannot be substituted in a short time.But take nitro-cotton as the traditional nitro paint coating of representative, be faced with huge environmental protection pressure, the environmental-friendly nitryl coating of development water soluble green, become the good recipe of rescue pyroxylin(e)finish industry.
Pyroxylin(e)finish is also known as celluloid lacquer, lacquer paint, because it has the features such as quick-drying, with low cost, easy construction and paint film property be good, be widely used in vehicle, machinery, electrical instrument, light industrial goods, plastics, leather, fabric, furniture etc., as priming paint, finish paint and enamel paint, be subject to the favor of market and consumers in general.
Traditional solvent-borne pyroxylin(e)finish is for dispersion medium with organic solvents such as alcohols, ester class, benzene,toluene,xylenes, wherein benzene kind solvent (toluene, dimethylbenzene) account for the over half of solvent total amount, but these benzene kind solvents do not play solvency action, be just used as dispersion agent to reduce the viscosity of pyroxylin(e)finish.These organic solvents not only contaminate environment, more can damage the healthy of the mankind.The benzene kind solvent of dispelling in traditional solvent-borne pyroxylin(e)finish is feasible, and on this basis, further modification obtains water-based pyroxylin(e)finish, will greatly reduce the consumption of organic solvent, and reduce the pollution to environment.
In recent years, Chinese scholars is done a lot in pyroxylin(e)finish modification, is divided into two classes substantially: one is physical method, namely realizes its emulsifying water by the additional hydrophilic polymer of physical blending; Two is chemical processes, is namely introduced on soluble cotton skeleton by chemical modification and has hydrophilic polymer segment and realize its emulsifying water.Such as, Synolac Phase inversion emulsification and acrylic ester monomer interpenetrating polymer networks polymerization are prepared modification nitrocellulose emulsion by Zeng Chaoxia, and the method is essentially physical mixing processes.The homemade self-emulsifying type urethane of Li little Rui carries out emulsification and modification to nitro-cotton brightening agent, obtain polyurethane modified nitrocellulose luster emulsion, the method is also adopt self-emulsifying urethane and soluble cotton to carry out physical blending and obtain nitrocellulose emulsion, not single nitrocellulose emulsion.Xu Min adopts organic silicon-acrylate graft modification soluble cotton to make DX-8502 silicon third nitrocellulose emulsion type brightening agent, the method is chemic modified method, but graft modification chemical time is long, and technique is wayward, and this emulsion particle is comparatively large, stability is bad.Chinese patent CN200910092647.0 discloses a kind of water-emulsifiable nitrolacquer and preparation method thereof, but it remains the emulsion that Malin's acid resin and soluble cotton physical blending are made, and soluble cotton is not unique raw material.Above-mentioned application document is as follows:
[1] Zeng Chaoxia, Bao Huichuan, Fu Heqing, etc. Modification of Waterborne Nitrocellulose Emulsion research [J]. coatings industry, 2007,37 (2): 33-35.
[2] Li little Rui. the preparation [J] of polyurethane modified nitrocellulose luster emulsion. Chinese leather, 2009,29 (17): 19-21.
[3] research [J] of Xu Min .DX-8502 silicon third nitro-cotton brightening agent. Chinese leather, 1998,27 (8): 8-9.
[4] Chen Bing, Chen Shousheng. water-emulsifiable nitrolacquer and preparation method thereof: China, CN200910092647.0 [P] .2012.2.17.
As can be seen from above-mentioned document, the emulsion modified treatment process of current aqueous nitrocellulose element has a variety of, and majority carries out aqueous dispersion for nitrocellulose cellulose and one or more aqueous polymer resin.Such as carry out emulsification with other aqueous polymer resin through physical blending, or carrying out emulsification through water-base resin monomer emulsion polymerization through physical blending, or on nitrocellulose cellulose molecular chain, carry out hydrophilic polymer segment grafting modification carry out emulsification.Wherein, the aqueous nitrocellulose element emulsion that physical method obtains is a kind of mixed emulsion of multicomponent polymeric resin, and the wetting ability of soluble cotton itself is not strong.The graft modification soluble cotton that chemical process obtains, its graft reaction complex process, product is not easily separated, long reaction time, and product performance are wayward.
Carboxymethyl cellulose nitrate (CMCN) is a kind of novel amphiphilic cellulose ether esters, and its synthetic method is shown in that Beijing Institute of Technology's application number is the Patent Application Publication of 201010000551.X.
A kind of preparation method of carboxymethyl cellulose nitrate comprises two parts: the preparation of carboxymethyl cellulose and the nitric acid esterification of carboxymethyl cellulose.
One) preparation of carboxymethyl cellulose.Be divided into cellulosic alkalization, carboxymethylation and aftertreatment three phases:
Cellulosic alkalization: mixed with aqueous sodium hydroxide solution with sodium hydroxide or organic medium by organic medium, with fibrin reaction at 5-35 DEG C, obtains soda cellulose.Wherein Mierocrystalline cellulose and organic medium weight ratio are 1:2-15, and the mass concentration of organic medium is not less than 85%; The weight ratio of Mierocrystalline cellulose and sodium hydroxide is 1:0.2-0.7; Reaction times is 0.5-3h.
Carboxymethylation reaction: add etherifying agent-organic medium solution after quaternization terminates, temperature of reaction is 45 ~ 80 DEG C, and the reaction times is 30 ~ 180min.Wherein etherifying agent used is Mono Chloro Acetic Acid or sodium chloroacetate or chloracetate, etherifying agent-organic medium concentration of polymer solution 40 ~ 60%; The weight ratio of Mierocrystalline cellulose and etherifying agent is 1:0.2-1.37.
Aftertreatment: after carboxymethylation reaction terminates, adds neutralization reagent and neutralizes, then carry out washing, centrifugal, dry, pulverize after stand-by.The neutralization reagent used is hydrochloric acid/organic medium or Glacial acetic acid/organic medium mixed system.
Cellulosic degree of polymerization is at 800-1300.
Organic medium comprises the one in Virahol, ethanol, Virahol/ethanol, acetone, toluene, ethanol/toluene, iso-propanol/toluene, isopropylcarbinol.
Two) the nitric acid esterification of carboxymethyl cellulose
Carboxymethyl cellulose is dispersed in carry out in nitrification liquid nitrated.Temperature controls at 20-40 DEG C, and carboxymethyl cellulose and nitrification liquid weight ratio are 1:30-50, and the reaction times is 30-60min.Reaction terminate after, first by reaction solution through suction filtration, carboxymethyl cellulose nitrate and nitrification liquid are stripped out, obtain white or faint yellow filter cake.
Filter cake is put into large water gaging and is washed, and namely obtains carboxymethyl cellulose nitrate after dispelling remaining nitrification liquid and impurity.
Nitrification liquid is nitrated-methylene dichloride mixed solution or nitric acid-sulfuric acid mixed solution.Nitric acid and methylene dichloride weight ratio are 30 ~ 70:30 ~ 70, nitric acid: sulfuric acid: the mass ratio of water is 20 ~ 32:59 ~ 69:6 ~ 16.
The preparation method of this patent relative in prior art, chemical preparation process technique simplifies greatly, and product performance are easy to control, and industrialization is produced and is easy to realize.The carboxymethyl cellulose nitrate resin aqueous dispersion that carboxymethyl cellulose nitrate of the present invention will be used this patented method and prepares.
Carboxymethyl cellulose nitrate had both had the excellent mechanical properties of the good film-forming properties of cellulose nitrate and film, can disperse again in water, and during for water-borne coatings, when can reduce paint spay-coating, organic solvent is consumption, reduces toxicity and the pollution to environment.
Natural cellulose aboundresources, carboxymethyl cellulose (CMC) and nitro-cotton (NC) suitability for industrialized production all possess deep rich experience, and thus carboxymethyl cellulose nitrate (CMCN) industrialization is produced strong.Modified alkyd resin is also ripe Industrial products, added in carboxymethyl cellulose nitrate (CMCN) aqueous dispersion, the mechanical property of film can be improved greatly, especially can improve film low temperature brittleness, spray stream levelling significantly, also can improve the solid content of coating.The carboxymethyl cellulose nitrate resin aqueous dispersion of preparation is uniformly dispersed, and stability in storage is good, good film-forming property, and solid content is high, and application prospect is boundless.
Summary of the invention
The object of the invention is to be provided as the traditional nitro-lacquer organic solvent of solution, especially benzene kind solvent consumption is too much, to environment and problem human health being had to larger pollution and injury, do not need additional aqueous polymer resin can obtain stable emulsion yet.
The present invention is achieved by the following technical solution:
A kind of carboxymethyl cellulose nitrate resin aqueous dispersion comprises following weight percent composition:
Further, described resin is modified alkyd resin.Modified alkyd resin namely in Synolac except lipid acid, polyvalent alcohol, phthalate anhydride (or m-phthalic acid), add other compositions again, the new Synolac that after chemical reaction is formed, as rosin modified alkyd resin, styrene alkyd resin, benzoic acid modified Synolac etc.
Preferred further, described modified alkyd resin is one or more cooperations in coconut alkyd resin, soya-bean oil modified alkyd resin, castor oil modified Synolac.
Further, the solubleness of described modified alkyd resin in butyl glycol ether is not less than 20g/100g.
Further, described modified alkyd resin is not when adding other auxiliary agents, also can add deionized water wherein and be no less than the every 120g modified alkyd resin of 20g, and the mixing solutions that with the addition of ionized water formation is Clear colourless or limpid opalescent, its viscosity is not higher than 100mPas.That is, Synolac through modification dissolves at least 20g in 100g butyl glycol ether, when not adding other auxiliary agents, deionized water can also be added in 120g modified alkyd resin/butyl glycol ether saturated solution and be no less than 20g, and ensure that solution does not have solute to separate out, the viscosity of gained solution not higher than 100mPas, preferably not higher than 50mPas.
Adding of described modified resin, the solid content of water-borne coatings can be improved on the one hand, the ratio of water in water-borne coatings can be improved on the one hand, prior, resin has plastification, can preferably and CMCN merge and keep the stability of water-borne coatings, improve the toughness of coating, when coating is dry, not easily cause be full of cracks.In fact, when not adding modified resin, when simple nitro-cotton (NC) operates according to embodiment, easily there is layering and coagulation in the emulsion obtained, and film there will be full of cracks and can not form the film of flat transparent when drying at room temperature.
Preferred further, on each glucose unit ring of described carboxymethyl cellulose nitrate, the average substitution degree of carboxymethyl is 0.2 ~ 0.6, and the average substitution degree of itrate group is 2.1 ~ 2.8.
Further, described cellosolve is one or more cooperations in acetone, butanone, pimelinketone, ethanol, propyl alcohol, propyl carbinol, ethylene glycol, ethyl acetate, butylacetate, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, butyl glycol ether, propylene glycol monomethyl ether, propylene glycol propyl ether, propandiol butyl ether, diethylene glycol dimethyl ether, dipropylene glycol methyl ether, dipropylene.
Further preferred, described emulsifying agent is one in alkylphenol polyoxyethylene, nonionic emulsifier, alkyl benzene sulfonate anionic emulsifier or any two kinds of cooperations.
Preferred further, described softening agent is the cooperation of one or more in dibutyl phthalate, dioctyl phthalate (DOP), diisononyl phthalate.
Preferred further, described carboxymethyl cellulose nitrate resin aqueous dispersion also comprises pH adjusting agent, and its weight percent composition is:
Described pH adjusting agent to be massfraction be 25% ammoniacal liquor, N, N-dimethylethanolamine, triethylamine, diethanolamine, the cooperation of one or more in trolamine.
The present invention has following beneficial effect:
1, the carboxymethyl cellulose nitrate resin aqueous dispersion prepared of the present invention, technique is simple, emulsion dispersion is even, stability in storage is good, good film-forming property, replaces part organic solvent with water, fundamentally solves organic solvent accounting in traditional nitro paint too large, break off the use of benzene kind solvent, the pollution of environment and human health and injury have been declined greatly.Instead of urethane, the polyvalent alcohol of polyacrylic acid Lipase absobed, polynary ether resin with natural modified soluble cotton, reduce environmental pollution, saved fossil energy simultaneously.
2, it is even that the carboxymethyl cellulose nitrate resin aqueous dispersion that the present invention obtains not only has emulsion dispersion, and the advantages such as stability in storage is good, and film forming properties is good, have very high industrialization throughput, application prospect is boundless simultaneously.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described.Described embodiment is only the preferred embodiments of the present invention, is not limited to the present invention, and for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Listed by table 1 is the preparation formulation Example of carboxymethyl cellulose nitrate resin aqueous dispersion, and table 2 is performance index of all carboxymethyl cellulose nitrate resin aqueous dispersion of corresponding table 1.
In table 1, the preparation method of listed carboxymethyl cellulose nitrate resin aqueous dispersion is:
1) add a certain proportion of cellosolve in a reservoir, under stirring at 25 ~ 35 DEG C, slowly add carboxymethyl cellulose nitrate powder, fully stir and ensure that powder all dissolves, obtain transparent in particle solution;
2) add resin, continue to be stirred to evenly at 25 ~ 35 DEG C, form transparent mixed solution;
3) add partial emulsifier, continue to be stirred to evenly at 45 ~ 60 DEG C, form transparent grey cyan mixed solution i;
4) by the emulsifying agent of remainder and deionized water Homogeneous phase mixing, mixed solution ii is made;
5) under 50 ~ 80 DEG C of agitation conditions, mixed solution ii is joined in mixed solution i according to the speed of 0.4ml/min, adopt phase conversion emulsifying, obtain O/W type emulsion, obtained carboxymethyl cellulose nitrate resin aqueous dispersion.
When needs add pH adjusting agent, can by step 4) change into, by qs pH adjuster, remaining emulsifying agent and deionized water Homogeneous phase mixing, make mixed solution ii.
The preparation formulation Example of table 1 carboxymethyl cellulose nitrate water-borne dispersion
The performance index of table 2 carboxymethyl cellulose nitrate water-borne dispersion
| Test event | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Mobility | Thickness | Thickness | Thickness | Thickness |
| PH value | 5.2 | 7.4 | 7.2 | 7.0 |
| Stability | 3 months | 3 months | 3 months | 3 months |
| Film clarity | Transparent | Transparent | Transparent | Transparent |
Explanation about film clarity test:
1, the dispersion prepared in embodiment is creamy white or white or pale-yellow emulsion shape at first, and high speed centrifugation can not disperse, and after film, coating is variable transparency after 1 day;
2, dry painting is placed in pure water soaks under room temperature, and after 7 days, only observing coatingsurface has and turn white slightly, with bamboo toothpick scratching coatingsurface, does not have cut, and water body is mutually in as clear as crystal, and not observing coating has and come off or dissolution phenomena.
In table 2 performance index of carboxymethyl cellulose nitrate dispersion test in pH value recorded by plum Teller-Tuo benefit S210 type pH potentiometer.
Stability test step in table 2 is: by preparation be creamy white or yellowish carboxymethyl cellulose nitrate water-borne dispersion leaves standstill for some time under airtight, room temperature condition, there is not the emulsion such as demulsification, breakdown of emulsion, layering, flocculation, coagulation unstable situation; Further, the dispersion after leaving standstill is applied film forming again, still can form the film of transparent and homogeneous.The stability being considered as water-borne coatings during this period of time left standstill.
Can find out, carboxymethyl cellulose nitrate water-borne dispersion prepared by the present embodiment possesses higher solid content and moisture content simultaneously, effectively can reduce the use of organic solvent, reduce costs Environmental Safety simultaneously, belong to green water-based pyroxylin(e)finish coating, for traditional nitro paint equal solvent type coating provides an outlet.
Claims (10)
1. a carboxymethyl cellulose nitrate resin aqueous dispersion, is characterized in that: comprise following weight percent composition:
2. carboxymethyl cellulose nitrate resin aqueous dispersion according to claim 1, is characterized in that: described resin is modified alkyd resin.
3. carboxymethyl cellulose nitrate resin aqueous dispersion according to claim 2, is characterized in that: described modified alkyd resin is one or more cooperations in coconut alkyd resin, soya-bean oil modified alkyd resin, castor oil modified Synolac.
4. carboxymethyl cellulose nitrate resin aqueous dispersion according to claim 3, is characterized in that: the solubleness of described modified alkyd resin in butyl glycol ether is not less than 20g/100g.
5. according to claim 3 or 4 carboxymethyl cellulose nitrate resin aqueous dispersion, it is characterized in that: described modified alkyd resin is not when adding other auxiliary agents, also can add deionized water wherein and be no less than the every 120g modified alkyd resin of 20g, and the mixing solutions that with the addition of ionized water formation is Clear colourless or limpid opalescent, its viscosity is not higher than 100mPas.
6. carboxymethyl cellulose nitrate resin aqueous dispersion as claimed in any of claims 1 to 4, it is characterized in that: on each glucose unit ring of described carboxymethyl cellulose nitrate, the average substitution degree of carboxymethyl is 0.2 ~ 0.6, the average substitution degree of itrate group is 2.1 ~ 2.8.
7. carboxymethyl cellulose nitrate resin aqueous dispersion as claimed in any of claims 1 to 4, is characterized in that: described cellosolve is one or more cooperations in acetone, butanone, pimelinketone, ethanol, propyl alcohol, propyl carbinol, ethylene glycol, ethyl acetate, butylacetate, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, butyl glycol ether, propylene glycol monomethyl ether, propylene glycol propyl ether, propandiol butyl ether, diethylene glycol dimethyl ether, dipropylene glycol methyl ether, dipropylene.
8. carboxymethyl cellulose nitrate resin aqueous dispersion as claimed in any of claims 1 to 4, is characterized in that: described emulsifying agent is one in alkylphenol polyoxyethylene, nonionic emulsifier, alkyl benzene sulfonate anionic emulsifier or any two kinds of cooperations.
9. carboxymethyl cellulose nitrate resin aqueous dispersion as claimed in any of claims 1 to 4, is characterized in that: described softening agent is the cooperation of one or more in dibutyl phthalate, dioctyl phthalate (DOP), diisononyl phthalate.
10. carboxymethyl cellulose nitrate resin aqueous dispersion as claimed in any of claims 1 to 4, is characterized in that: described carboxymethyl cellulose nitrate resin aqueous dispersion also comprises pH adjusting agent, and its weight percent composition is:
Described pH adjusting agent to be massfraction be 25% ammoniacal liquor, N, N-dimethylethanolamine, triethylamine, diethanolamine, the cooperation of one or more in trolamine.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110283525A (en) * | 2019-07-26 | 2019-09-27 | 长沙秋点兵信息科技有限公司 | A kind of flame-retardant and anti-static waterborne two-component polyurethane coating and preparation method thereof |
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| CN101735324A (en) * | 2010-01-13 | 2010-06-16 | 北京理工大学 | Carboxymethyl cellulose nitrate and preparation method thereof |
| CN101942113A (en) * | 2010-08-18 | 2011-01-12 | 北京理工大学 | Carboxymethyl cellulose nitrate water-borne dispersion and preparation method thereof |
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| CN101735324A (en) * | 2010-01-13 | 2010-06-16 | 北京理工大学 | Carboxymethyl cellulose nitrate and preparation method thereof |
| CN101942113A (en) * | 2010-08-18 | 2011-01-12 | 北京理工大学 | Carboxymethyl cellulose nitrate water-borne dispersion and preparation method thereof |
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| CN110283525A (en) * | 2019-07-26 | 2019-09-27 | 长沙秋点兵信息科技有限公司 | A kind of flame-retardant and anti-static waterborne two-component polyurethane coating and preparation method thereof |
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Effective date of registration: 20160726 Address after: 100081 No. 5, Zhongguancun South Street, Haidian District, Beijing Applicant after: BEIJING INSTITUTE OF TECHNOLOGY Applicant after: JIANGSU TAILIDA NEW MATERIAL Co.,Ltd. Applicant after: Beijing Beifang Shiji Cellulose Techn Development Co., Ltd. Address before: 100081 No. 5, Zhongguancun South Street, Haidian District, Beijing Applicant before: BEIJING INSTITUTE OF TECHNOLOGY Applicant before: Nantong Tailida Chemical Co., Ltd. Applicant before: Beijing Beifang Shiji Cellulose Techn Development Co., Ltd. |
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