CN105925971B - Environment-friendly type film agent - Google Patents
Environment-friendly type film agent Download PDFInfo
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- CN105925971B CN105925971B CN201610421283.6A CN201610421283A CN105925971B CN 105925971 B CN105925971 B CN 105925971B CN 201610421283 A CN201610421283 A CN 201610421283A CN 105925971 B CN105925971 B CN 105925971B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
Abstract
Environment-friendly type film agent, in parts by weight, it at least contains：100 parts of water, 58 parts of succinic acid, 12 parts of indolebutyric acid sodium, 0.5 2 parts of Glycolic acid, 0.1 2 parts of sodium nitrate, 6.3 8.7 parts of quaternized organosilan, 0.05 0.1 parts of surfactant；The quaternized organosilan is prepared by the raw material comprising organosilan and N alkyl morpholines, and the surfactant is anion surfactant or nonionic surfactant.
Description
Technical field
The present invention relates to Coating Pretreatment field, and in particular to a kind of environment-friendly type film agent.
Background technology
With the development of China's metal Surface Treatment Technique, walked with world's pace after particularly joining WTO, people are to metallic article table
The decoration technique in face requires more and more higher, and coated metal pre-treatment is also increasingly taken seriously.Coated metal pre-treatment is not only
Workpiece surface application is enable by appropriate processing, the performance of coating is also greatly influenceed, such as strengthens the adhesive force of coating, carry
The corrosion resistance of high coating.
Film agent is a kind of metal conditioner, can produce reaction with metal, while metal surface corrosion is removed,
It is not soluble in water to form one kind, and there is chemical inertness, the diaphragm of metal surface can be attached to, this diaphragm is advantageous to prevent
Only metal is oxidized, and is also beneficial in follow-up metal surface spraying process, makes the attachment of the paint film of spraying, molding powder and metal
Power strengthens, thus is widely used in coated metal pre-treatment field.
Usual film agent is rich in phosphate, and phosphate is primary pollution source of the water body by eutrophication pollution.Advising
The film agent processing method commonly used in modelling industrial production is required for heating, and equipment investment and maintenance cost are big, and high energy consumption is unfavorable
In energy-saving and emission-reduction.In addition, phosphatization slag is easily produced in film agent processing procedure, the nozzle not being merely blocked by spraying production line, and
And phosphatization slag belongs to the row of National Hazard solid waste register, processing is more difficult.
Chinese patent CN101660154B discloses a kind of non-phosphate film agent；Chinese patent CN103938199B discloses nothing
Chromium film agent and preparation method thereof；Chinese patent CN104233252A discloses a kind of novel normal-temperature non-phosphate film agent；It is Chinese special
Sharp CN104894550A disclose a kind of without phosphorus made of Biological inositol, floride-free, heavy metal free novel environment friendly film agent, its
Preparation method and applications.
The present inventor has found under study for action, without phosphorus, Chrome-free film agent will in a short time smooth film forming, it is necessary to certain journey
The heating of degree, and thermal dimensional stability is bad after application, and easily being ftractureed in temperature change comes off.
The content of the invention
In order to solve prior art problem, one aspect of the present invention provides a kind of environment-friendly type film agent, in parts by weight,
It at least contains：
The quaternized organosilan is prepared by the raw material comprising organosilan and N- alkyl morpholines,
The surfactant is anion surfactant or nonionic surfactant.
In some embodiments, in parts by weight, it at least contains：
In some embodiments, the organosilan is epoxy radicals silicone hydride or halocarbon base silane.
In some embodiments, the N- alkyl morpholine be selected from N-methylmorpholine, N-ethylmorpholine, N- propylmorpholins,
One kind in N- butyl morpholines.
In some embodiments, the quaternized organosilan is by including γ-r-chloropropyl trimethoxyl silane and N- second
The raw material of base morpholine is prepared.
In some embodiments, also containing citric acid-modified chitosan 1-2 parts.
In some embodiments, the citric acid-modified chitosan is by including citric acid, chitosan, 1- (3- diformazan ammonia
Base propyl group) -3- ethyl-carbodiimide hydrochlorides, the raw material of n-hydroxysuccinimide be prepared.
In some embodiments, the preparation method of the citric acid-modified chitosan is：
(1) chitosan and ethanol are added in container A, stirring, chitosan is uniformly dispersed；
(2) citric acid and ethanol are added in container B, adds 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides
Hydrochloride, n-hydroxysuccinimide is added after stirring 30-45min, 45-60min is stirred at 0-5 DEG C；
(3) solution in container B is added drop-wise in container A, 15-30min is stirred at 0-5 DEG C, returns to room temperature afterwards,
Continue to stir 5-10h；
(4) centrifuge, wash precipitation 3-4 times with ethanol, dry, produce.
In some embodiments, the mol ratio of the citric acid and chitosan is 3.5-4.5.
The second aspect of the invention provides above-mentioned environment-friendly type film agent in automobile, ship, machine-building and aviation
Application in aerospace industry.
Embodiment
Unless otherwise defined, all technologies used herein and scientific terminology have and the common skill of art of the present invention
The identical implication that art personnel are generally understood that.When contradiction be present, the definition in this specification is defined.
" quality, concentration, temperature, time or other values or parameter are preferred with scope, preferred scope or a series of upper limits
During the Range Representation that value and lower preferable values limit, this, which is appreciated that, specifically discloses by any range limit or preferred value
All scopes that any pairing with any range lower limit or preferred value is formed, regardless of whether the scope separately discloses.
For example, 1-50 scope is understood to include selected from 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,
19、20、21、22、23、24、25、26、27、28、29、30、31、32、33、34、35、36、37、38、39、40、41、42、43、
44th, 45,46,47,48,49 or 50 any numeral, number combinatorics on words or subrange and all between above-mentioned integer
Fractional value, for example, 1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8 and 1.9.It is specific to consider from scope on subrange
Interior any end points starts " the nested subrange " of extension.For example, exemplary range 1-50 nested subrange can include
1-10,1-20,1-30 and 1-40 on one direction, or 50-40,50-30,50-20 and 50-10 on other direction.”
One aspect of the present invention provides a kind of environment-friendly type film agent, and in parts by weight, it at least contains：
Water uses as solvent in the present invention, and in parts by weight, the content for the water that the present invention uses is 100 parts.
In some embodiments, the electrical conductivity of used water is less than 300 μ s/cm2。
Succinic acid
Succinic acid, also known as butanedioic acid, molecular weight 118.09, colourless crystallization body is sour, flammable.There are two kinds of crystalline forms, relatively
Density 1.572 (25/4 DEG C).No. CAS is 110-15-6,188 DEG C of fusing point, is decomposed at 235 DEG C.Industrially, the preparation method of succinic acid
It is more, mainly have following several：
1. oxidizing process, paraffin generates the mixture of various carboxylic acids through deep oxidation, then by steam distillation and crystallization etc.
Succinic acid can be obtained after separating step.
2. hydrogenation method, maleic anhydride or the fumaric acid hydrogenation reaction under catalyst action, succinic acid is generated, so
By isolated finished product.Catalyst is nickel or noble metal, and reaction temperature is about 130-140 DEG C.
3. acrylic acid oxo synthesis, acrylic acid and carbon monoxide under catalyst action, generate succinic acid.It is not yet industrial
Change.
4. electrolytic oxidation, phthalic anhydride presses 1 with sulfuric acid and water：0.5：4 ratios, it is electrolysed in ceramic electrolytic cell, fourth two can be obtained
Acid.The raw material of electrolysis synthesis is maleic acid or cis-butenedioic anhydride, cathode and anode liquid dilute sulfuric acid, is separated by cationic membrane, yin, yang
Stereotype is generally used in pole, is generally synthesized with plate and frame electrolytic cell.
5. acetylene method, acetylene is with carbon monoxide and water in [Co (CO)4] in the presence of catalyst, reaction can in acid medium
Obtain succinic acid, 80-250 DEG C of reaction temperature, pressure 2.94-49.03MPa.
6. emerging fermentation method.Compared with traditional chemical routes, Production by Microorganism Fermentation succinic acid has many advantages, such as：
Production cost has competitiveness；Include carbon dioxide as raw material by the use of reproducible agricultural resource, avoid to petrochemical material
Dependence；Reduce pollution of the chemical synthesis process to environment.
Counted by 100 parts by weight of water, the content of succinic acid used in the present invention is 5-8 parts, preferably 6.5 parts.
Indolebutyric acid sodium
The molecular formula of indolebutyric acid sodium is C12H12NO2Na, No. CAS is 10265-70-0.Inventor has found under study for action, Yin
Diindyl sodium butyrate can improve the film forming speed of film agent, the particularly film forming speed at lower temperature (such as 10 DEG C or so).But
For heteroauxin sodium but without this effect, inventor's supposition is probably that the relative position between the nitrogen-atoms on indoles and butyric acid root has
Close, also can quickly remove the free ion in metal surface at a lower temperature.
Counted by 100 parts by weight of water, the content of indolebutyric acid sodium used in the present invention is 1-2 parts, preferably 1.5 parts.
Glycolic acid
Glycolic acid is also referred to as glycolic or hydroxyacetic acid, is colourless deliquescent crystal.Molecular weight is 76.05, and No. CAS is
79-14-1.Because existing hydroxyl has carboxyl in molecule again, the duality of alcohol and acid is had concurrently.It is heated and is decomposed into when being heated to 100 DEG C
Formaldehyde, carbon monoxide and water, formaldehyde can further form paraformaldehyde or formic acid.Glycolic acid can be with calcium hydroxide reaction shape
Precipitated into Calcium Glycolate white solid.
The effect of Glycolic acid and purposes include：
1st, Chemical cleaning：The solution of Glycolic acid 70% is mainly used as cleaning agent, 2% Glycolic acid and 1% formic acid mixed acid
It is the low cleaning agent of a kind of efficiency high, cost, may be used as air-conditioning, boiler, power plant's conveyance conduit, condenser, heat exchanger etc.
Main wash raw material.
2nd, biodegradation material：It is widely used in and prepares internal heeling-in type slow release medicine system, heeling-in type repair the device, biology
Surgical sutures, artificial skeleton and organ material etc. are absorbed, very with DEVELOPMENT PROSPECT.PLA and polyglycolic acid have turned into new
The developing focus of Material Field.
3rd, bactericide：Because Glycolic acid contains the special construction of hydroxyl and carboxyl, coordinate bond can be passed through with metal cation
Hydrophilic chelate thing is formed, therefore the growth to iron-oxidizing bacterium has obvious inhibitory action, can be used as bactericide, is also used in
Make inhibitor in a variety of ore floatations.
4th, daily chemicals：99% hydroxyacetic acid is that curative effect preferably removes dead skin and fine hair medicament, can synthesize anti-skin
Aging, skin-lightening cosmetic raw material tartaric acid, moisturizing, Glycerin can be reached, promote the effect of epidermal renewal.The molecule of glycolic
Amount is very small, it can effectively skin permeation pore, solve skin aging in a short time, wrinkle, blackspot, dark sore etc. asks
Topic, therefore unanimously praised highly by medical cosmetology circle.
5th, plate surface is handled：Glycolic can be additionally used in electroplating industry, and glycolic sodium salt, sylvite can be used as plating addition
Agent, it can also make to electroplate the green chemical industry raw material of grinding, pickling of metal, leather coloring and tanning agent.Glycolic is also chemical nickel plating
Complexing agent, have the advantages that corrosion-resistant, reaction is fast, finish is good, be the best ingredients raw material for improving chemical nickel plating quality.
In addition, Glycolic acid can be used for dyeing and finishing wool fiber and cellulose fabric crosslinking couplant or containing carboxylic in textile industry
The crosslinking catalyst of base fabric；Dispensing and the synthesis for also acting as bonding agent, petroleum demulsifier, welding compound and coating are a variety of
Medicine, agricultural chemicals and chemical assistant etc..
In the present invention, Glycolic acid and succinic acid realize film forming function together, realize and phosphorus is entirely free of in film agent.
Counted by 100 parts by weight of water, the content of Glycolic acid used in the present invention is 0.5-2 parts, preferably 1.2 parts.
Sodium nitrate
Sodium nitrate, fusing point are 306.8 DEG C, and density is 2.257 grams/cc (at 20 DEG C), for water white transparency or white micro-
Band yellow rhomboidan.Its bitter is salty, soluble in water and liquefied ammonia, is slightly soluble in glycerine and ethanol, easy deliquescence, is especially containing pole
During a small amount of sodium chloride as impurity, sodium nitrate hygroscopy just greatly increases.Its solution temperature reduces when dissolved in water, during solution is in
Property.In heating, sodium nitrate easily resolves into natrium nitrosum and oxygen.
Sodium nitrate is used as fluxing agent, oxidant and the raw material for preparing enamel frit in porcelain enamel industry.In glass industry
In be used as the decolorising agents of various glass and product, defoamer, fining agent and oxidation fluxing agent.It is used as melting in inorganic industrial to burn
The decolorising agent of alkali and for manufacturing other Nitrateses.It is used as the colour former of meat packing in the food industry, meat can be prevented
It is rotten, and seasoning can be played.It is used as the quick-acting fertilizer for being applicable acid soil in chemical fertilizer industry, particularly suitable root crop,
Such as beet, radish.It is used as the raw material for producing bitter taste acid and direct dyes in dye industry.It is used as steel-making in metallurgical industry, aluminium closes
The heat treatment agent of gold.It is used as metal cleaner in mechanical industry and prepares ferrous metal blueing agent.It is used as in medical industry
The culture medium of penicillin.It is used as the combustion adjuvant of tobacco in cigarette industry.It is used as chemical reagent in analytical chemistry.In addition,
For producing explosive etc..Sodium nitrate is also used in the oxidation solution of low chromic acid passivation and magnesium alloy of zinc coat.
In environment-friendly type film agent provided by the invention, sodium nitrate has oxidisability, it is possible to increase the film forming speed of film agent
Degree, especially improve the film-formation result to aluminum component product.
Counted by 100 parts by weight of water, the content of sodium nitrate used in the present invention is 0.1-2 parts, preferably 0.8 part.
Quaternized organosilan
Quaternized organosilan used in the present invention is by being prepared comprising the raw material of organosilan and N- alkyl morpholines
Obtain.
The synthetic method of quaternized organosilan has many kinds, and concrete mode can include, such as：Epoxy silane and uncle
The addition reaction of amine, the substitution reaction of halocarbon base silane and tertiary amine, the quaterisation of amino silane, amino silane and epoxidation
The ring-opening reaction of compound.
As the example of epoxy silane, can include, such as：Glycidoxypropyl MTMS, shrink
Glycerine epoxide MTES, glycidoxypropyl methyl tripropoxy silane, α-glycidoxypropyl ethyl front three
TMOS, α-glycidoxypropyl ethyl triethoxysilane, β-glycidoxypropyl ethyl trimethoxy silane, β-shrink
Glycerine epoxide ethyl triethoxysilane, β-glycidoxypropyl ethyl tripropoxy silane, α-glycidoxypropyl three
Methoxy silane, α-glycidoxypropyl triethoxysilane, α-glycidoxypropyl tripropoxy silane, β-contracting
Water glycerine epoxide propyl trimethoxy silicane, β-glycidoxypropyl triethoxysilane, β-glycidoxypropyl
Tripropoxy silane, γ-glycidoxypropyltrimewasxysilane, γ-glycidoxypropyl triethoxysilane,
γ-glycidoxypropyl tripropoxy silane, 2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane, 2- (3,4- rings
Oxygen cyclohexyl) ethyl triethoxysilane, γ-glycidoxypropyl-metil-dimethoxysilane, γ-glycidol oxygen
Double (trimethylsiloxy) methyl-monosilanes of base propyl group, γ-glycidoxypropyl-methyl-diethoxy silane, γ-
Glycidoxypropyl-methyl-diisopropyl alkenyloxy group silane and γ-glycidoxypropyl ethoxycarbonyl propyl-methyl-two
Methoxy silane, 2- [[3- (methoxyl group dimethylsilyl) propoxyl group] methyl]-oxirane, 2- (3,4- 7-oxa-bicyclo[4.1.0s
Base) ethyl triethoxysilane, (2- tert-butyl group oxirane -2- bases)-trimethyl silane, trimethyl-(3- trimethylsilyls
Oxirane -2- bases) silane, fert-butyidimethylsilyl (((S)-Oxyranyle) methoxyl group) silane, (R)-fert-butyidimethylsilyl
(Oxiranylmethoxy) silane, the fluoro- 2- Oxyranyles -3,4- dihydros of 4- tert-butyl dimethylsilyl epoxide -6- -
2H-1- chromenes, 1- [(2S, 3S) -3- (trimethylsilyl) -2- Oxyranyles] ethyl ketone, 1,3,5,7,9,11,13,
15- eight ({ dimethyl [(3- propyl group -2- Oxyranyles) methoxyl group] silylation } epoxide) five rings [7.7.1.13,7.15,13.111 ,15] eight siloxanes, (2S, 3S) -3- (trimethylsilyl) -2- oxirane formaldehyde, (2R, 3R) -3- (trimethylsilyl) -
2- oxirane formaldehyde, trimethyl (oxirane -2- bases) silane, 2- [[3- (ethyoxyl dimethylsilyl) propoxyl group] first
Base]-oxirane, 1,4- phenylenes two { dimethyl [3- (2- Oxiranylmethoxies) propyl group] silane }, 3- (2,3- epoxies
Third oxygen) propyl trimethoxy silicane, trimethoxy-[3- (oxirane -2- ylmethoxies) propyl group] silane, 2- (3,4- epoxies
Hexamethylene) ethyl trimethoxy silane, (3- isopropyl -2- Oxyranyles) (trimethyl) silane, trimethyl (2- oxirane
Ethyl-acetylene base) silane, trimethyl [(2R) -2- Oxyranyles acetenyl] silane, 3- (oxygen of (2,3)-epoxy third) hydroxypropyl methyl
Dimethoxysilane, 3- chloropropyls-dimethoxy-[3- (2- Oxiranylmethoxies) propyl group] silane, 5,6- epoxyhexyls
Triethoxysilane, ((2R, 3R) -3- [2- (t-butyl-dimethyI-sila base epoxide)-ethyl]-Oxyranyle)-methanol,
Trimethoxy [3- (2- Oxiranylmethoxies) propyl group] silane, (3- (2,3- glycidoxies) propyl group) (2- methoxyl group second
Epoxide) dimethylsilane, trimethyl [2- (2- methyl-2-propyls) -2- Oxyranyles] silane.
As the example of halocarbon base silane, can include, such as：(chloromethyl) silane, ethyoxyl dimethyl chloride methyl
Silane, (dichloromethyl) (dimethyl) (2- methyl-2-propyls) silane, 1- (chloromethyl)-N- [(chloromethyl) dimethylsilanes
Base] -1,1- dimethyl-silanes amine, chloromethyl triethoxysilane, dichloromethyl trichlorosilane, (chloromethyl) trichlorosilane,
(dichloromethyl) dimethyl dichlorosilane (DMCS), (chloromethyl) dimethyl dichlorosilane (DMCS), vinyl (chloromethyl) dimethylsilane, dichloromethyl
[3- (1,1,2,2- tetrafluoros ethyoxyl) propyl group] silane, CMDMCS chloromethyl dimethyl chlorosilane, trichloromethyl trichlorosilane, 3,5- bis-
(chloromethyl) -1,1,1,7,7,7- hexamethyls -3,5- two [(trimethylsilyl) epoxide] tetrasiloxane, [1,4- phenylenes two
(epoxide)] two [(chloromethyl) (dimethyl) silane], dichloro [two (chloromethyl)] silane, chloromethyl (dimethyl) methoxyl group silicon
Alkane, the isopropoxy silane of chloromethyl three, chloromethyl dimethyl isopropoxy silane, two (chloromethyl) methylchlorosilanes, (dichloromethane
Base) dimethylchlorosilane, (chloromethyl) (dichloromethyl) dimethylsilane, [[(chloromethyl) dimethylsilyl] methyl] front three
Base-silane, dimethyl chloride aminomethyl phenyl silane, dichloromethyl triethoxysilane, [1,3- phenylenes two (epoxide)] two [(chlorine
Methyl) (dimethyl) silane], (chloromethyl) (4- chlorophenoxies) dimethylsilane, (dichloromethyl) (dimethyl) propyl silane,
(chloromethyl) methyl diisopropoxy silane, (chloromethyl) methyldiethoxysilane, chloromethyl-methyl-dimethylsilane, chlorine
Methyltrimethylsilane, 4- (chloromethyl) phenyltrimethoxysila,e, 1- [(dichloromethyl) dimethylsilyl] -1- hexins -
3- alcohol, two chloro- two (trichloromethyl) silane, two (chloromethyl) dimethylsilanes, chloromethyl dimethyl n butylsilane, (chloromethane
Base) dimethyl ethyl silane, chloromethyl (dimethyl) silane, pi-allyl (chloromethyl) dimethylsilane, 3- (dichloro methyl silanes
Base) -2 Methylpropionic acid methyl esters, chloromethyl three (trimethylsiloxy group) silane, 11- (dichloro methyl silane base) hendecanoic acid first
Ester, 2- (dichloro methyl silane base) ethylhexoate, (chloromethyl) (isobutoxy) dimethylsilane, dichloromethyl myristyl
Silane, chloromethyl trimethoxy silane, (dichloromethyl) trimethyl silane, (trichloromethyl) trimethyl silane, dichloromethyl [3-
(2,2,2- trifluoro ethoxies) propyl group] silane, chloromethyl-decyl-dimethylsilane, (chloromethyl) dodecyl dimethyl-silicon
Alkane, (chloromethyl) dimethyl -1- acrylsilanes, (chloromethyl) (4- chlorphenyls) dimethylsilane, 3- (dichloro methyl silanes
Base) propyl group laurate, (chloromethyl) (dimethyl) silylation butyrate.
As the example of amino silane, can include, such as：Aminopropyltriethoxysilane, aminopropyl three
Methoxy methyl silane, amino propyl methyl diethoxy monosilane, amino propyl methyl dimethoxy monosilane, amino-ethyl ammonia
Base hydroxypropyl methyl dimethoxysilane, diethylidene triamido propyl-triethoxysilicane, diethylidene triamido propyl group front three
TMOS, diethylidene triamido hydroxypropyl methyl diethoxy silane, phenvlaminomethvl trimethoxy silane, diethylidene
Triamido hydroxypropyl methyl dimethoxysilane, Cyclohexylamino propyl trimethoxy silicane, phenvlaminomethvl triethoxysilicane
Alkane, Cyclohexylamino propyl-triethoxysilicane, diethylamino methyltriethoxy silane alkane, (diethylamino ethyl) methyl
Diethoxy silane, dimethylaminopropyl trimethoxy silane, HMDS, amino-ethyl triethoxysilane, γ-
Aminopropyltriethoxywerene werene, gamma-amino hydroxypropyl methyl diethoxy silane, gamma-amino ethyl diethoxy silane,
Gamma-amino propyl group phenyl diethoxy silane, gamma-amino propyl trimethoxy silicane, δ-ammobutyltriethoxysilane, δ-
Aminobutyl ethyl diethoxy silane, (2- amino ethoxies) (tert-butyl group) dimethylsilane, 2- [(diethylaminos) (two
Methyl) silylation] propionitrile, 2- (diethylamino-dimethylsilyl) propionitrile, 2- (butylthio) -3- ((1E) -2- (4- ((2-
(((tert-butyl group) dimethylsilyl) epoxide) ethyl) ethylamino) phenyl) vinyl) -5,5- dimethyl -2- cyclohexene -1-
Ketone, (2E) -2- (2- (butylthio) -3- ((1E) -2- (4- ((2- (((tert-butyl group) dimethylsilyl) epoxide) ethyl) ethyls
Amino) phenyl) vinyl) -5,5- dimethyl -2- cyclohexene -1- subunits)-acetonitrile, (2E) -2- (2- (butylthio) -3-
((1E) -2- (4- ((2- (((tert-butyl group) dimethylsilyl) epoxide) ethyl) ethylamino) phenyl) vinyl) -5,5- two
Methyl -2- cyclohexene -1- subunits)-acetaldehyde, (diethylamino methyl) trimethyl silane, 4- ((dimethylamino) dimethyl-silicons
Alkyl) butyronitrile, [3- (amino epoxide) propoxyl group] (dimethyl) (2- methyl-2-propyls) silane, 2- [(diethylamino) first
Base] -4- { [dimethyl (2- methyl-2-propyls) silylation] epoxide } -2- cyclopentene-1-ones, double (4- amino-benzene oxygens) diformazans
Base silane, 2- hydroxyls -3- { [3- (triethoxysilicane alkyl) propyl group] amino } propyl acrylate, trimethylsilyl 1- amino
Cyclopentane-carboxylic acid ester, trimethylsilyl 1- amino -2,2- dimethyl cyclopropane carboxylic acids ester, three (dimethylamino) chlorosilanes,
Two (dimethylamino) ethylene methacrylic base silanes, N- (6- Aminohexyls) amino methyl triethoxysilane, three (dimethylaminos
Base) silane, dimethyl-two-(N- phenyl aminos phenoxy group) silane, methyl 1- [(trimethylsilyl) amino] cyclopropane-carboxylic acid
Ester, (4- amino -3,3- dimethylbutyls) (methyl) dimethoxysilane, 4- amino -3,3- dimethylbutyl trimethoxy silicon
Alkane, 2- (2- amino ethoxies-dimethyl-silane base) epoxide ethamine, 1- dimethylamino -4- trimethylsilyls benzene, 4-
[(dimethylamino) (diisopropyl) silylation] butyronitrile, two [2- (diethylamino) ethyoxyl] dimethylsilanes, three (2- ammonia
Base oxethyl) phenyl silane, three [2- (diethylamino) ethyoxyl] (methyl) silane, three [2- (diethylamino) ethyoxyls]
Ethylsilane, three [2- (diethylamino) ethyoxyl] phenyl silanes, N- [3- [[3- (2- aminoethylaminos) propyl group-diformazan
Base silane base] epoxide-dimethylsilyl] propyl group] ethane -1,2- diamines, (3- aminopropyls) ethyoxyl dimethylsilane, four
[2- (diethylamino) ethyoxyl] silane, 1,4- bis- (3- aminopropyldimethylsilanes base) benzene, 1,2- (three (dimethylaminos
Base) silylation) ethane, N, N- dimethyl trimethyl silicanes amine, N- (2-N- benzyls aminoethyl) -3- aminopropyl trimethoxy silicon
Alkane, double (diethylamino) silane, 2,2'- [[[3- (2- amino ethoxies) propyl group] methyl-monosilane base alkene] two (epoxides)] two
(ethamine), three (dimethylamino) ethylsilanes, N- methyl -3- aminopropyl trimethoxysilanes, (3- aminopropyls) dimethyl
Methoxy silane, 3- (N- allyl aminos) propyl trimethoxy silicane, (aminoethylamino) -3- isobutyl group dimethyl methoxies
Base silane, N- (hydroxyethyl)-N- dimethylaminopropyls trimethoxy silane, two (dimethylamino) diethylsilanes, two (two
Methylamino) aminomethyl phenyl silane, (N, N- dimethyl -3- aminopropyls) trimethoxy silane, (N, N- dimethylamino) three
Ethylsilane, 4- aminobutyls dimethyl methoxy silane, (2- amino isopropyl) triethoxysilane, three (dimethylaminos)
Methyl-monosilane, double (dimethylamino) dimethylsilanes, N- dimethylaminopropyls three (trimethylsiloxy group) silane, (((2- ammonia
Base ethyl) amino) methyl) triethoxysilane, 3- aminopropyls two (trimethylsiloxy group) methyl-monosilane, two (diethyl aminos
Base) dimethylsilane, three (dimethylamino) phenyl silanes, (the butylamino) -2,2- of 1,1,1,2- tetra- dimethyldisilanes, two
Amino two (1,1- dimethylethyloxies) silane, (butylamino methyl) triethoxysilane, 3- (3- amino-benzene oxygens) propyl group
Trimethoxy silane, 1,1'- [[3- (triethoxysilicane alkyl) propyl group] imino group] two [3- chlorine propan-2-ols], 1- dimethylaminos
Base -3- (trimethylsilyl) -2- propine, chlorine (diethylamino) dimethylsilane, two (isopropylamino) dimethylsilanes,
Two (single-N- butylaminos) dimethylsilanes, N- (2- amino-ethyls)-N- (3- (dimethoxymethylsilane base) propyl group) -1,
2- ethylenediamines, two (ethylamino) dimethylsilanes, 3- dimethylaminopropyls (dimethoxy) methyl-monosilane, 3- aminophenyls
Trimethoxy silane, (aminoethylaminomethyl) phenethyl trimethoxy silane, the second of two (2- hydroxyethyls) aminopropyl three
TMOS, octadecyldimethyl (dimethylamino) silane, 3- aminopropyls three (methoxyethoxyethoxy) silane,
1,1- dimethyl-N, N'- di-secondary fourth amino silane, (3- (butylamino) propyl group) triethoxysilane, N- (2- amino-ethyls)-
N'- (3- (dimethoxymethylsilane base) propyl group) -1,2- ethylenediamines.
In some embodiments, the organosilan is epoxy radicals silicone hydride or halocarbon base silane.
In some embodiments, the N- alkyl morpholine be selected from N-methylmorpholine, N-ethylmorpholine, N- propylmorpholins,
One kind in N- butyl morpholines.
In some embodiments, the quaternized organosilan is by including γ-r-chloropropyl trimethoxyl silane and N- second
The raw material of base morpholine is prepared.
In some embodiments, the preparation method of the quaternized organosilan is：
Equipped with condenser pipe, thermometer, constant pressure funnel three-necked bottle in add 0.11mol N-ethylmorpholines and
40mL ethanol, it is uniform with magnetic stirrer, nitrogen 30min is passed through into system, drains the air in reaction unit, is heated
0.1mol γ-r-chloropropyl trimethoxyl silane is added dropwise to 90 DEG C, then with constant pressure funnel, adds 0.1mmol KIs, holds
Continue stirring 15h, filtering after having reacted, boil off solvent using Rotary Evaporators, add 2g sodium carbonate, stir 30min, filter,
Produce.
Inventor has found under study for action, and quaternized organosilan can improve the strong of epithelium after low temperature (10 DEG C or so) film forming
Degree, paint adhesion can be improved after introducing morpholine group, when particularly temperature quickly changes, also will not because of expanding with heat and contract with cold and
It is deformed, is cracked, wrinkle.Silane can form covalent bond with the hydroxyl reaction of metal surface, and silane quaternary can improve skin
Engaging force between film and coating, particularly morpholine group can increase the thermal dimensional stability of epithelium.
Counted by 100 parts by weight of water, the content of quaternized organosilan used in the present invention is 6.3-8.7 parts, preferably
For 7.2 parts.
Surfactant
Surfactant for the present invention is anion surfactant or nonionic surfactant.
Anion surfactant is divided into higher fatty acid salt, sulfonate, sulfuric acid, fatty acyl-peptide institute compound.
The chemical formula of higher fatty acid salt is RCOOM, and R is alkyl here, and its carbon number is between 8-22, M Na, K,
Generally Na.Soap is to have been heated with the aqueous solution of natural animal and plant grease and alkali made from saponification.Alkali used in saponification
Can be sodium hydroxide, potassium hydroxide.
The chemical formula of sulfonate is R-SO3Na, the carbon number in carbochain is between 8-20.This kind of surfactant is readily soluble
Yu Shui, there is good foaming effect.Sulfonate does not hydrolyze in an acidic solution.
Alkylbenzenesulfonate is not formed with calcium, magnesium ion in hard water and precipitated, and resistance to bronsted lowry acids and bases bronsted lowry.Manufacture alkylbenzenesulfonate
Raw material mainly obtained by oil industry.Sulfonating reaction is carried out to alkylbenzene with sulfuric acid or oleum to be easy to that benzene sulfonamide is made
Hydrochlorate.Actually obtained surfactant is various isomer mixtures, collectively referred to as alkylbenzenesulfonate.Most common of which
It is neopelex.Industrially it is using propylene as raw material, aggregates into laurylene, then is reacted with benzene, is made 12
The mixture of alkylbenzene, it is then sulfonated again, and neutralized with alkali, that is, neopelex is made.
The detergency of alkylsulfonate is similar to linear alkylbenzene sulfonate (LAS), but to the stability and biological degradability of hard water
Can be better.Primarily now it is made using sulfoxidation method.Normal alkane is under ultraviolet irradiation, same to SO2And O2Reaction, but
While forming sodium alkyl sulfonate, SO2And O2With H2O reaction generation sulfuric acid, is then neutralized, the product of gained is cream with NaOH again
Shape thing.This law is not required to use chlorine, and accessory substance is few, can simplify purifying process, reduce cost.
The structural formula of Disodium sulfosuccinate isCarbon number 4-8 in R bases, dioctyl amber
Amber acid esters sodium sulfonate is White waxy plasticity thing, and soluble in water and ethanol is stable in hard water.
Alpha-olefin and SO3React the mixture that obtained product is alkenyl alkyl sulfonate and hydroxyl alkyl sulfonate.By epoxy second
Alkyl ethoxy sulfonate can be made in alkane and sodium hydrogensulfite reaction.
Petroleum sulfonate is the mixture of various sulfonate, and main component is complicated alkylbenzenesulfonate and alkylnaphthalene sulphur
Hydrochlorate, secondly it is then the sulfonate of aliphatic hydrocarbon and the sulfonate and its oxide of cyclic hydrocarbon.
The chemical general formula of sulfuric acid is ROSO3M, M Na, K, N (CH2CH2OH)3, the carbon number in alkyl is 8-18.
Analiphatic sulphur acid esters salt is then to use alkali through sulfating reaction with fatty alcohol, fatty alcohol ether or glycerine monofatty ester
Neutralize and be made.Lauryl sulfate base sodium or the main representative that lauryl sodium sulfate is this kind of surfactant, for white
Powder, there is special odor, it is soluble in water.
Polyoxyethylene straight chain alcohol sulfuric acid, such as polyoxyethylene lauryl alcohol sodium sulfovinate, its water solubility is better than sulfuric acid 12
Sodium alkyl, there are preferable lime soap dispersing power and saline-alkaline tolerance.
Lauric monoglyceride sodium sulphate is to be heated with laurate and glycerine under base catalysis, generates monoglyceride, so
Afterwards with sulfuric acid treatment, then neutralize and be made through alkali.This surfactant is soluble in water, stable to hard water, has good hair
Bubble, emulsification and washability.
Containing hydroxyl and the aliphatic acid of unsaturated double-bond or its esters after sulphation, sulfuric acid equally can be made.This
Kind of sulfuric acid is very different with fatty alcohol sulfate salt, because its hydrophilic sulfate is among molecule, therefore
Its washability is poor, is used in fiber industry.
In addition also can be that raw material carries out sulphation to prepare sulfuric acid with alkene.Alkene is made by Pintsch process paraffin
, C12-18 alkene is chosen, through sulphation, the sulfuric ester salt form surfactant with superperformance is made.
The chemical general formula of fatty acyl-peptide institute compound is R1CONHR2COOH, R1Carbon number be 8-18, R2For amino
Aliphatic group, formed by fatty acid chloride and protein hydrolysate polycondensation, stable under weak acid, its salt is steady to hard water
It is fixed, there is good washability.Wherein representative substances have, sodium lauroyl sarcosine, by lauric acyl chlorides and methyl amimoacetic acid
Sodium condensation is made.
Nonionic surfactant does not dissociate when being dissolved in water, lipophilic group and ionic surfactant in its molecule
Agent it is roughly the same, its hydrophilic radical mainly by with a number of oxy radical (such as hydroxyl and polyoxyethylene chain) structure
Into.
Nonionic surfactant, so its stability is high, is not easy in the solution due to being existed with ionic condition
Influenceed, can be used in mixed way with other types surfactant, compatibility is good, has in various solvents good by acid, alkali
Dissolubility, strong adsorption does not occur on a solid surface.
Nonionic surfactant is mostly liquid and pulpous state state, its solubility with temperature rise in water and reduce.
Nonionic surfactant, which has, good to be washed, disperses, emulsifying, foaming, soaking, be solubilized, be antistatic, level dyeing, anticorrosion, killing
The multiple performance such as bacterium and protecting colloid, is widely used for weaving, papermaking, food, plastics, leather, fur, glass, oil, change
Fibre, medicine, agricultural chemicals, coating, dyestuff, chemical fertilizer, film, photograph, intermetallic composite coating, ore dressing, building materials, environmental protection, cosmetics, fire-fighting and agriculture
Industry etc..
Nonionic surfactant is classified by hydrophilic group, there is polyethylene glycol type and the class of polyol type two.
Polyethylene glycol type nonionic surfactant is to use the hydrophobicity raw material with reactive hydrogen atom to enter with oxirane
Made from row addition reaction.So-called reactive hydrogen atom refers to-OH ,-COOH ,-NH2With-CONH2Deng the hydrogen atom in group.These
Hydrogen atom chemism in group is big, is easily reacted with oxireme, and generates polyethylene glycol type non-ionic surface active
Agent.
Long-chain fatty alcohol APEO.Long-chain fatty alcohol APEO is carried out with long-chain fatty alcohol and oxirane
Made from addition reaction.This kind of surfactant stability is higher, and biological degradability and water solubility are preferable, and have good
Wettability.Manufacturing the long-chain fatty alcohol of such product has coconut oil also carbinol, laruyl alcohol, hexadecanol, oleyl alcohol and cetanol.
APES.Phenol used in synthesis of alkyl phenol polyethenoxy ether can be phenol, cresols, naphthols
Deng.Although alkyl phenol differs greatly with fatty alcohol in chemistry, both property is similar.It is this when being synthesized from nonyl phenol
During nonionic surfactant, water can not be dissolved in the product of four molecule ethyleneoxide additions；Add with six, seven molecule oxirane
Into product, at room temperature can be completely soluble；There is good profit with the product of eight to 12 molecule ethyleneoxide additions
Wet, infiltration and washability, emulsifying capacity is also preferable, therefore is widely used, and can be used as detergent and bleeding agent；With more than 15 points
The product of the ethyleneoxide addition of son does not permeate and washability, can be used as special emulsifying dispersant.
The chemical stability of APES is high, even if being not easy to break ring by strong acid, highly basic at high temperature, therefore
Can be additionally used in metal pickle liquor and strong basicity detergent in.For APES is compared with AEO,
Compared with difficult for biological degradation.
Polyoxyethylene carboxylate.Aliphatic acid plays addition reaction, generation fat with oxirane in the presence of a catalyst
Sour polyoxyethylene ester.Another preparation method is to carry out esterification with polyethylene glycol with aliphatic acid to be made.This surfactant with
AEO and APES compare, and infiltration and washability are all poor, are mainly used as emulsifying agent, divide
Powder, fibre finishing and dyeing assistant etc..This product is easily hydrolyzed by acid, aqueous slkali and forms former aliphatic acid and polyethylene glycol, institute
With in strong acid solution washability disappear.
Ester exchange reaction is carried out under base catalysis with olive oil and polyethylene glycol, can obtain polyethylene glycol (PEG) oleate and oleic acid
The mixture of monoglyceride.This mixture is the oil soluble emulsifying agent for having property, has extensive use.
Polyoxyethylene alkyl amine.Oxirane and alkylamine play addition reaction, can generate 2 kinds of reaction products.It is this kind of it is non-from
Sub- surfactant is not soluble in water when the number of oxygen ethene is few and be dissolved in oil as other nonionic surfactants, but
Because it has the structure of organic amine, therefore dissolve in acidic aqueous solution.So polyoxyethylene alkyl amine simultaneously have nonionic and
Some characteristics of cationic surfactant, it is such as acidproof not alkaline-resisting, there is bactericidal property.When the number of oxygen ethene is more, its
Nonionic can increase, and not separated out in alkaline solution, i.e., good activity is also shown in alkaline solution.Due to nonionic
Increase, cationic properties are relatively reduced, show the compatibility with anion surfactant.This kind of surfactant is due to tool
There is the property of both nonionic and cation, therefore be commonly used for dyeing assistant, be also commonly used in rayon production fine to strengthen regeneration
The intensity of silk is tieed up, the plot of spinneret orifice can be also kept, prevent dirt deposition.
Polyxyethylated alkylolamides.Oxirane generates polyxyethylated alkylolamides with alkylolamides reaction.It is this kind of
There is nonionic surfactant stronger foaming and foam stabilizing to act on, therefore be commonly used for foam booster and foam stabiliser, wherein
Some has preferable washability and solubilising, thickening power.
Lauroyl diethanolamine is this kind of product more early occurred, and it is stirred under nitrogen flowing by laurate and diethanol amine
Heating is mixed to carry out made from condensation reaction.This material itself is not soluble in water, is combined into when again with a molecule ethylene glycol amine compound
Thing, at this moment just there is good water solubility and washability, can be used as the foam stabilizer in detergent, it is also possible to make emulsifying agent and prevent
Rust agent.The stability and hydrolytic resistance of this kind of nonionic surfactant are better than polyoxyethylene carboxylate.
Polyol-based non-ionic surfactant.Polyol-based non-ionic surfactant refers to by containing multiple hydroxyls
The esters that polyalcohol is esterified and generated with aliphatic acid.Additionally include by with NH2Or the amino alcohol and band of NH bases
There are the carbohydrate of-CHO bases and fatty acid or ester to carry out reacting obtained nonionic surfactant.Due to their very phases in nature
Seemingly, therefore it is referred to as polyol-based non-ionic surfactant.
Fatty acid glyceride and pentaerythritol fatty ester.The following method system of this kind of surfactant generally use
It is standby：1mol glycerine or pentaerythrite and 1mol aliphatic acid (such as laurate or palmitic acid).In the presence of having alkali, heating is allowed to anti-
Should, it is esterified and generates nonionic surfactant.Industrially the method frequently with grease and glycerine progress ester exchange is prepared this kind of
Material, condition are that temperature is slightly higher (200-240 DEG C).
Ester exchange is carried out using pentaerythrite and grease, must in addition to pentaerythrite stearate monoesters main component is obtained
To glyceryl monostearate accessory substance.
This kind of surfactant is at normal temperatures missible oil color waxy solid, in water-bath after heating and melting, adds water to emulsify,
Ethanol can be dissolved in.
Span and sorbitan fatty acid ester.The fatty-acid monoester of sorbierite and anhydrous sorbitol is to adopt
Prepared by esterification being carried out with alcohol with acid, such as 1mol sorbierites and 1mol laurate are taken, add 2gNaOH, protected in nitrogen stream
Under shield, heating stirring, the lauric acid monoester of dehydration generation sorbierite and the mixture of dibasic acid esters are carried out at 190 DEG C or so.When
When reaction temperature rises to 230-250 DEG C, while esterification, sorbierite occurs dehydration and forms anhydrous sorbitol, can then make
Obtain anhydrous sorbitol lauric acid monoester.There is the anhydrous sorbitol lauric acid monoester of part two in product, also there is part dibasic acid esters.
Arlacels is not soluble in water, is dissolved in organic solvent, therefore be seldom used alone.It is if it is water-soluble with other
Property surfactant it is compound, such as to it carry out it is polyoxyethylated, then obtain nonionic surfactant of good performance.
Sucrose fatty ester.1mol fatty acid methyl esters are dissolved in dimethylformamide in stirring and 90-100 with 3mol sucrose
Ester exchange is carried out under the conditions of DEG C, you can obtain sucrose fatty ester.Sucrose fatty ester is nontoxic, odorless, tasteless, soluble in water to be in
Clear solution, it can be used as the emulsifying agent of low foam detergent and food and medicine.
Alkylolamides.Alkylolamides is it and polyol fatty acid ester with made from aliphatic acid and alkyl alcoholamine
Difference is that ester bond is substituted by amido link, therefore has good anti-hydrolytic performance, and it also has foaming, foam stabilizing, solubilising, increasing in addition
Many performances such as thick.Representative in this kind of surfactant is lauroyl diethanolamine and lauroyl Propanolamine.
From the aspect of the ability of deoiling and promotion film forming, surfactant used in the present invention is preferably dodecyl sulphur
Sour sodium.
Counted by 100 parts by weight of water, the content of surfactant used in the present invention is 0.05-0.1 parts, is preferably
0.08 part.
In some embodiments, environment-friendly type film agent provided by the invention also contains citric acid-modified chitosan.
Citric acid-modified chitosan
Citric acid is also known as Chinese holly edge acid, chemical name 2- hydroxy propanes -1,2,3- tricarboxylic acids.According to the difference of its water content,
It is divided into Citric Acid Mono and anhydrous citric acid.
At room temperature, citric acid is semi-transparent clear crystal or white particle or white crystalline powder, odorless, taste pole
Acid, it is micro- in malaria to have hygroscopy.It can exist in the form of without hydrate or monohydrate：Citric acid is from warm
When being crystallized in water, no hydrate is generated；Crystallized in cold water, generate monohydrate.Monohydrate can decompose when being heated to 78 DEG C
Obtain no hydrate.At 15 DEG C, citric acid can also dissolve in absolute ethyl alcohol.Citric acid crystal habit is different because of crystallization condition
And it is different, there is anhydrous citric acid C6H8O7Also there is the citric acid 2C containing the crystallization water6H8O7H2O、C6H8O7H2O or C6H8O7 2H2O。
Citric acid is a kind of tricarboxylic acid compounds, and therefore has similar physics and chemical property to other carboxylic acids.
When being heated to 175 DEG C, it, which can be decomposed, produces carbon dioxide and water, some remaining white crystals.Citric acid is that a kind of stronger have
Machine acid, there is 3 H+It can ionize；Heating can resolve into multi-products, be reacted with acid, alkali, glycerine etc..
Citric acid be mainly used as acid, solubilizer, buffer, antioxidant, except raw meat deodorant, flavor promoting agent, glue
Solidifying agent, toner etc..Suppress bacterium, color protection in addition, citric acid also has, improve flavor, promote the effect such as sucrose inversion.Citric acid
Also there is chelation, some poisonous metals can be removed.Citric acid can prevent the oxygen caused by enzymatic and metal catalytic
Change acts on, so as to prevent quick-frozen fresh fruits discoloration spoiled.
Citric acid can be used for food industry.Because citric acid has the tart flavour of gentle frankness, various beverages, vapour are commonly used to
The manufacture of the food such as water, grape wine, candy, dessert, biscuit, canned fruit juice, dairy products.In the market of all organic acids, lemon
Lemon acid occupation rate of market more than 70%, flavor enhancement, it is also possible to make the antioxidant of edible oil.Improve the aesthetic of food simultaneously
Shape, whet the appetite and promote internal calcium, phosphorus substance to digest and assimilate.Anhydrous citric acid is largely used to solid beverage.Citric acid
Salt such as calcium citrate and ironic citrate are the hardening agents for needing to add calcium ion and iron ion in some food.The ester of citric acid
Class such as triethyl citrate can make nontoxic plasticizer, manufacture food packaging plastic sheeting, be the tart flavour of drink and food industry
Agent, preservative.
Citric acid can be used for chemical industry and textile industry.Citric acid can make chemical analysis reagent on chemical technology, with putting into effect
Test reagent, chromatography reagent and biochemical reagents；As complexing agent, screening agent；To prepare cushioning liquid.Using citric acid or
Citric acid salt makees builder, can improve the performance of cleaning product, can rapid precipitate metal ion, prevent that pollutant is again attached
On fabric, keep washing necessary alkalescence；Dirt and ash is set to disperse and suspend；The performance of surfactant is improved, is one
The excellent intercalating agent of kind；It can be used as the acid proof reagent of test architecture ceramic tile.The formaldehyde pollution of clothes has been very sensitive
The problem of, citric acid and Modified Citric Acid can be made into a kind of formaldehyde-free crease-proofing finishing agent, the wrinkle proofing for pure cotton fabric.No
Only wrinkle-proof effect is good, and cost is low.
Citric acid can be used for environmental protection.Citric acid-sodium citrate buffer solution is used for flue gas desulfurization.Coal resources in China enriches,
It is the major part for forming the energy, but lacks effective flue gas desulfurization technique always, causes air SO2It is seriously polluted.Research
Effective sulfur removal technology, the actually task of top priority.Citric acid-sodium citrate buffer is because its steam forces down, nontoxic, chemically
Matter is stablized, to SO2The reasons such as absorptivity height, it is the desulfurization absorbent of great Development volue.
Citric acid produces available for poultry.Citric acid is added in pig starter feed, can ahead of time wean, improve feed conversion
Rate 5%~10%, increase sows farrowing amount.1%~2% citric acid is added in growing-finishing pigs diets, daily gain can be improved,
Feedstuff-meat ratio is reduced, improves protein digestibility, reduces back fat thickness, improves meat and Carcass Characteristics.Lemon acid rare earth is a kind of
New and effective feed addictive, suitable for the various animals such as pig, chicken, fish, shrimp, ox, sheep, rabbit, silkworm, have and promote growth of animal,
Improve product quality, improve resistance against diseases and survival rate, improve food conversion ratio, the features such as shortening feeding cycle.
Citric acid can be used for cosmetics.Citric acid belongs to one kind of tartaric acid, and main function is to speed up cutin renewal, is usually used in
Emulsion, creams, shampoo, whitening articles for use, anti-aging articles for use, Acne etc..The renewal of cutin contributes to black in skin
The peeling of pigment, the receipts of pore are thin, dissolving of blackhead etc..
Citric acid can be used for sterilizing.Citric acid and 80 DEG C of temperature synergy have the function that well to kill bacterial spore,
And it can effectively kill the bacterial spore polluted in haemodialysis control unit pipeline.The lemon of " king of western-style food " good reputation is enjoyed with very strong
Bactericidal action, very good to food hygiene, along with the faint scent of lemon, people always like making cold dish with it, no
It is only delicious tasty and refreshing, it can also improve a poor appetite.
Citric acid can be used for medicine.In the formation of thrombokinase and later coagulation process, it is necessary to have calcium from
Son is participated in.Citric acid radical ion can form a kind of soluble complexes for being difficult to dissociate with calcium ion, thus reduce calcium in blood
Ion concentration, blood clotting is set to be obstructed.The product are in blood transfusion or laboratory blood sample anti-freezing, as external anticoagulation.
Chitosan (chitosan) is also known as chitosan, is chitin (chitin) warp being widely present by nature
Cross what deacetylation obtained, chemical name is Chitosan (1-4) -2- amino-B-D glucose.From 1859, Frenchman
After Rouget obtains chitosan first, the biological functionality and compatibility of this natural polymer, blood compatibility, security,
The premium properties such as microbic resolvability are by all trades and professions extensive concern, in medicine, food, chemical industry, cosmetics, water process, metal
The application study of the numerous areas such as extraction and recovery, biochemical and biomedical engineering achieves major progress.For patient, shell gathers
Sugared reducing blood lipid, the existing research report of hypoglycemic effect.Meanwhile chitosan is included in state food as thickener, fruit glaze agent
Additive uses standard GB-2760.
Chitosan is the product that chitin takes off N- acetyl group, it is however generally that, N- acetyl group, which sloughs more than 55%, to be claimed
Be chitosan, in other words, 1% chitosan, this deacetylated crust can be dissolved in 1% acetic acid or 1% hydrochloric acid
Element is referred to as chitosan.In fact, N- deacetylations are more than 55% chitin, can just be dissolved in this diluted acid.Make
For the chitosan of industrial goods, N- deacetylations are more than 70%.N- deacetylations are low deacetylation shells 55%~70%
Glycan, 70%~85% is middle deacetylation chitosan, and 85%~95% is chitosan with high deacetylation degree, 95%~
100% is chitosan with ultrahigh deacetylation degree.The extremely difficult preparation of chitosan of N- deacetylations 100%.Each glycosyl of chitin
On, perhaps there is N- acetyl group, perhaps differ and established a capital N- acetyl group, every N- acetyl degree is all referred to as below 50%
For chitin, because its diluted acid insoluble in above-mentioned concentration certainly.
Under given conditions, chitosan can hydrolyze, be alkylated, being acylated, carboxy methylation, sulfonation, nitrification, halogen
Change, oxidation, reduction, condensation and complexing etc. chemically react, and the various chitosan derivatives with different performance can be generated, so as to expand
The big application of chitosan.
There are active hydroxyl and amino in chitosan macromolecular, they have stronger chemical reaction ability.In alkaline bar
Hydroxyl under part on C-6 can occur to react as follows：Hydroxyethylation-chitosan is reacted with oxirane, can obtain ethoxy
The derivative of change.Carboxy methylation-chitosan and chloroacetate reaction just carboxymethylated derivative.Sulfonic acid esterification-chitin and
Chitosan generates sulphonic acid ester as cellulose, with that can be reacted after alkali process with carbon disulfide.Cyanoethylation-acrylonitrile and shell gather
Addition reaction can occur for sugar, generate the derivative of cyanoethylation.
In some embodiments, the citric acid-modified chitosan is by including citric acid, chitosan, 1- (3- diformazan ammonia
Base propyl group) -3- ethyl-carbodiimide hydrochlorides, the raw material of n-hydroxysuccinimide be prepared.
In some embodiments, the preparation method of the citric acid-modified chitosan is：
(1) chitosan and ethanol are added in container A, stirring, chitosan is uniformly dispersed；
(2) citric acid and ethanol are added in container B, adds 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides
Hydrochloride, n-hydroxysuccinimide is added after stirring 30-45min, 45-60min is stirred at 0-5 DEG C；
(3) solution in container B is added drop-wise in container A, 15-30min is stirred at 0-5 DEG C, returns to room temperature afterwards,
Continue to stir 5-10h；
(4) centrifuge, wash precipitation 3-4 times with ethanol, dry, produce.
In some embodiments, the mol ratio of the citric acid and chitosan is 3.5-4.5.
In some embodiments, the preparation method of the citric acid-modified chitosan is：
(1) 0.1mol chitosans and 50mL ethanol are added in container A, stirring, chitosan is uniformly dispersed；
(2) 0.35mol citric acids and 30mL ethanol are added in container B, adds 0.35mol 1- (3- dimethylaminos third
Base) -3- ethyl-carbodiimide hydrochlorides, 0.35mol n-hydroxysuccinimides are added after stirring 40min, are stirred at 0-5 DEG C
Mix 50min；
(3) solution in container B is added drop-wise in container A, 20min is stirred at 0-5 DEG C, returns to room temperature afterwards, after
Continuous stirring 8h；
(4) centrifuge, wash precipitation 3-4 times with ethanol, dry, produce.
Counted by 100 parts by weight of water, the content of citric acid-modified chitosan used in the present invention is 1-2 parts, is preferably
1.5 part.
The present inventor has found that citric acid-modified chitosan of the present invention can not only during the present invention is completed
The intensity after film agent film forming is improved, can also improve the consistency of epithelium, is not in pin hole and crackle after fast filming,
Self-healing property is preferable.It is probably because citric acid-modified chitosan can closely arrange when can be with quaternized organosilan film forming, mutually
Between effect epithelium can be made finer and close.
The second aspect of the invention provides above-mentioned environment-friendly type film agent in automobile, ship, machine-building and aviation
Application in aerospace industry.
Embodiment
A deionized waters, electrical conductivity are 250 μ s/cm2
B succinic acid
C1 indolebutyric acid sodium
C2 heteroauxin sodium
C3 sodium molybdates
D Glycolic acids
E sodium nitrate
The quaternized organosilans of F1
It is prepared by the raw material comprising γ-r-chloropropyl trimethoxyl silane and N-ethylmorpholine.
Preparation method is：Equipped with condenser pipe, thermometer, constant pressure funnel three-necked bottle in add 0.11mol N- second
Base morpholine and 40mL ethanol, it is uniform with magnetic stirrer, nitrogen 30min is passed through into system, is drained in reaction unit
Air, 90 DEG C are heated to, then 0.1mol γ-r-chloropropyl trimethoxyl silane is added dropwise with constant pressure funnel, add 0.1mmol
KI, 15h is persistently stirred, filtering after having reacted, boil off solvent using Rotary Evaporators, add 2g sodium carbonate, stir
30min, filtering, is produced.
F2 3- aminopropyl triethoxysilanes
F3 γ-glycidyl ether oxygen propyl trimethoxy silicane
G dodecyl sodium sulfates
H1 citric acid-modified chitosans
Preparation method is：(1) 0.1mol chitosans and 50mL ethanol are added in container A, stirring, makes chitosan scattered equal
It is even；(2) 0.35mol citric acids and 30mL ethanol are added in container B, add 0.35mol 1- (3- dimethylamino-propyls)-
3- ethyl-carbodiimide hydrochlorides, 0.35mol n-hydroxysuccinimides are added after stirring 40min, are stirred at 0-5 DEG C
50min；(3) solution in container B is added drop-wise in container A, 20min is stirred at 0-5 DEG C, return to room temperature afterwards, continued
Stir 8h；(4) centrifuge, wash precipitation 3-4 times with ethanol, dry, produce.
H2 chitosans
H3 citric acids
The embodiment 1-6 of table 1 and comparative example 1-9 formula
| A | B | C1 | C2 | C3 | D | E | F1 | F2 | F3 | G | H1 | H2 | H3 | |
| Example 1 | 100 | 6.5 | 1.5 | 1.2 | 0.8 | 7.2 | 0.08 | |||||||
| Example 2 | 100 | 5 | 1 | 0.5 | 0.1 | 6.3 | 0.05 | |||||||
| Example 3 | 100 | 8 | 2 | 2 | 2 | 8.7 | 0.1 | |||||||
| To 1 | 100 | 6.5 | 1.5 | 1.2 | 0.8 | 7.2 | 0.08 | |||||||
| To 2 | 100 | 6.5 | 1.5 | 1.2 | 0.8 | 7.2 | 0.08 | |||||||
| To 3 | 100 | 6.5 | 1.5 | 1.2 | 0.8 | 7.2 | 0.08 | |||||||
| To 4 | 100 | 6.5 | 1.5 | 1.2 | 0.8 | 7.2 | 0.08 | |||||||
| To 5 | 100 | 6.5 | 1.5 | 1.2 | 0.8 | 0.08 | ||||||||
| To 6 | 100 | 6.5 | 1.2 | 0.8 | 7.2 | 0.08 | ||||||||
| To 7 | 100 | 6.5 | 1.2 | 0.8 | 0.08 | |||||||||
| Example 4 | 100 | 6.5 | 1.5 | 1.2 | 0.8 | 7.2 | 0.08 | 1.5 | ||||||
| Example 5 | 100 | 5 | 1 | 0.5 | 0.1 | 6.3 | 0.05 | 1 | ||||||
| Example 6 | 100 | 8 | 2 | 2 | 2 | 8.7 | 0.1 | 2 | ||||||
| To 8 | 100 | 6.5 | 1.5 | 1.2 | 0.8 | 7.2 | 0.08 | 1.5 | ||||||
| To 9 | 100 | 6.5 | 1.5 | 1.2 | 0.8 | 7.2 | 0.08 | 1.5 |
Method of testing
1. preparation of specimen
The processing model of embodiment 1, embodiment 4 and comparative example 1-9 is cold-reduced sheet, using spray process, epitheliumization processing
Step is：To carrying out epitheliums at 10 DEG C or so after workpiece progress oil removing, then dried at 70 DEG C.After percutaneous membranization processing
Cold rolling plate surface with cross-cut tester draw 100 specifications be 5mm × 5mm grid, obtain model, it is stand-by.Wherein, during epithelium
Between include 30s, 1min, 2min, 4min.
2. the apparent test of epithelium
The outward appearance of model is observed, record has the lattice number of pin hole or crackle, and the results are shown in Table 2.
Table 2
| The epithelium time | Embodiment 1 | Embodiment 4 | Comparative example 8 | Comparative example 9 |
| 30s | 3 | 0 | 8 | 11 |
| 1min | 1 | 0 | 4 | 5 |
| 2min | 0 | 0 | 1 | 2 |
| 4min | 0 | 0 | 0 | 0 |
3. adhesive force is tested
The finish paint of about 70 μm of thickness is coated on model.With 3M610 tape-strippings on finish paint, quick pull-up adhesive tape, remember
The lattice number of paint is fallen in record, and the results are shown in Table 3.
Table 3
| The epithelium time | 30s | 1min | 2min | 4min |
| Embodiment 1 | 5 | 2 | 0 | 0 |
| Embodiment 4 | 0 | 0 | 0 | 0 |
| Comparative example 1 | 20 | 14 | 9 | 6 |
| Comparative example 2 | 15 | 9 | 5 | 2 |
| Comparative example 3 | 25 | 19 | 15 | 10 |
| Comparative example 4 | 26 | 20 | 14 | 12 |
| Comparative example 5 | 44 | 40 | 38 | 35 |
| Comparative example 6 | 48 | 45 | 40 | 36 |
| Comparative example 7 | 49 | 44 | 42 | 39 |
4. thermal dimensional stability is tested
Model is put into LP/KWB-100 temperature quickly to change in chamber, design temperature change program is with 10 DEG C/min
Heating rate be warming up to 45 DEG C, keep 10min, then -10 DEG C are cooled to 10 DEG C/min rate of temperature fall, keep 10min, instead
Multiple heating cools 5 times, takes out record cracking, cracking, the grid number of wrinkle after model, is as a result reported in Table 4 below.
From test result as can be seen that environment-friendly type film agent provided by the invention can have fast filming at 10 DEG C
Effect, and the adhesive force of epithelium is strong, and good thermal dimensional stability can be kept after application, is not in cracking, cracking, wrinkle etc.
Phenomenon.
Claims (6)
1. environment-friendly type film agent, it is characterised in that in parts by weight, it at least contains：
The quaternized organosilan is prepared by the raw material comprising organosilan and N- alkyl morpholines,
The surfactant is anion surfactant or nonionic surfactant；
Also contain citric acid-modified chitosan 1-2 parts；
The citric acid-modified chitosan is by including citric acid, chitosan, 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides
Hydrochloride, the raw material of n-hydroxysuccinimide are prepared；
The preparation method of the citric acid-modified chitosan is：
(1) chitosan and ethanol are added in container A, stirring, chitosan is uniformly dispersed；
(2) citric acid and ethanol are added in container B, adds 1- (3- dimethylamino-propyls) -3- ethyl carbodiimide hydrochlorides
Salt, n-hydroxysuccinimide is added after stirring 30-45min, 45-60min is stirred at 0-5 DEG C；
(3) solution in container B is added drop-wise in container A, 15-30min is stirred at 0-5 DEG C, return to room temperature afterwards, continued
Stir 5-10h；
(4) centrifuge, wash precipitation 3-4 times with ethanol, dry, produce；
The mol ratio of the citric acid and chitosan is 3.5-4.5.
2. environment-friendly type film agent as claimed in claim 1, it is characterised in that in parts by weight, it at least contains：
3. environment-friendly type film agent as claimed in claim 1, it is characterised in that the organosilan is epoxy radicals silicone hydride or halocarbon
Base silane.
4. environment-friendly type film agent as claimed in claim 1, it is characterised in that the N- alkyl morpholine be selected from N-methylmorpholine,
One kind in N-ethylmorpholine, N- propylmorpholins, N- butyl morpholines.
5. environment-friendly type film agent as claimed in claim 1, it is characterised in that the quaternized organosilan is by including γ-chlorine
The raw material of propyl trimethoxy silicane and N-ethylmorpholine is prepared.
6. the environment-friendly type film agent as described in any one of claim 1-5 claim is in automobile, ship and Aero-Space
Application in industry.
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| CN106435545A (en) * | 2016-10-16 | 2017-02-22 | 合肥太通制冷科技有限公司 | Aluminum tube online anticorrosion reagent |
| CN110832115A (en) * | 2017-07-04 | 2020-02-21 | 深圳市长宏泰科技有限公司 | Washing-free zinc-calcium phosphating agent, metal part and surface phosphating method thereof |
| CN108385099A (en) * | 2018-05-24 | 2018-08-10 | 江蔓青 | A kind of passivating treating agent for environment-friendly galvanized steel sheets |
| CN112095109A (en) * | 2020-08-11 | 2020-12-18 | 湖北工程学院 | Electrolytic copper foil antioxidant |
| CN112877705A (en) * | 2021-01-08 | 2021-06-01 | 璞奔(常州)新材料科技有限公司 | Processing technology for magnesium alloy finish turning bright surface |
| CN114182244A (en) * | 2021-12-17 | 2022-03-15 | 惠州市四维化工有限公司 | Environment-friendly nanometer multifunctional coating agent |
| CN116926528B (en) * | 2023-07-07 | 2024-03-22 | 苏州家益厨具科技有限公司 | Passivation method and process for preparing anti-yellowing pot by using same |
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