Summary of the invention
The present invention is introduced plant oil and derivative and mineral oil in the system of alkyl-silicone oil, silicon-dioxide, by controlling the average carbon atom number of alkyl-silicone oil thus making itself and mineral oil dissolve each other well, and the ratio control of mineral oil and vegetables oil and derivative thereof is between 1:6 ~ 4:7, finally efficiently solve the problem of film shrinkage cavity, cissing, depression, also improve antifoaming performance and the stability of defoamer simultaneously.
technical scheme
Defoamer of the present invention consists of the following composition:
carrier
Described carrier is made up of mineral oil, vegetables oil and derivative thereof.
Mineral oil is the base oil refined from oil by physics distillating method, work flow is in crude oil extractive process, after fractionating out useful light materials, oil at the bottom of residual tower forms through refining again, and its mineral oil majority is made up of alkane, aromatic hydrocarbons, naphthenic hydrocarbon, some olefin.Kinematic viscosity when described mineral oil is selected from 40 DEG C is 1 ~ 40mm
2the mineral oil of/s, considers and the compatibility of alkyl-silicone oil and antifoaming performance, preferably the kinematic viscosity of 40 DEG C is 2 ~ 10mm
2the mineral oil of/s, is selected from white oil, liquid wax, alkylbenzene.
Described vegetables oil and derivative thereof are all class materials with fat structure, be selected from Viscotrol C, soybean oil, plam oil, rapeseed oil, oleum lini and their derivative, wherein the derivative of vegetables oil comprises the epoxidised compound of vegetables oil, the amidation compound of vegetables oil, and wherein the derivative of vegetables oil can be used alone or used in combination.
The ratio control of described mineral oil and vegetables oil and derivative thereof is between 1:6 ~ 4:7, and carrier consumption is the 80-95% of defoamer total mass.
fatty acid metal soap
Fatty acid metal soap comprise in the magnesium salts of lipid acid, aluminium salt, calcium salt, zinc salt one or more.Preferred fatty acid aluminium can be mono fatty acid aluminium, one or both in bis-fatty acid aluminium mix in any proportion.
Mono fatty acid aluminium comprises butyric acid aluminium, aluminium octoate, tetradecanoic acid aluminium, pentadecylic acid aluminium, aluminum palmitate, margaric acid aluminium, octadecanoic acid aluminium, nondecylic acid aluminium, arachic acid aluminium, docosoic acid aluminium, triacontanoic acid aluminium, tetradecenoic acid aluminium, Decosahedaenoic acid aluminium, linolenic acid aluminium.Preferably octanoic acid aluminium, aluminum palmitate, octadecanoic acid aluminium, docosoic acid aluminium.
Bis-fatty acid aluminium comprises two butyric acid aluminium, two aluminium octoates, two (tetradecanoic acid) aluminium, two (pentadecylic acid) aluminium, two (hexadecanoic acid) aluminium, two (margaric acid) aluminium, two (octadecanoic acid) aluminium, two (nondecylic acid) aluminium, two (arachic acid) aluminium, two (docosoic acid) aluminium, triacontanoic acid aluminium, two (hexadecylenic acid) aluminium, two (octadecenoic acid) aluminium and linolic acid aluminium.Preferably two aluminium octoates, two (hexadecanoic acid) aluminium, two (octadecanoic acid) aluminium, two (docosoic acid) aluminium.
The fatty acid carbon atoms number of mono fatty acid aluminium and bis-fatty acid aluminium is 4-30, and preferred 8-24, is particularly preferably 14-22, can further improve antifoaming performance when carbonatoms is in this scope.Consumption is 2 ~ 8% of defoamer total amount.
alkyl-silicone oil
Alkyl-silicone oil is following structure:
Wherein radicals R is the alkyl being selected from 4-40 carbon atom, wherein the alkyl of preferred 10-30 carbon atom; Subscript m is the integer of 10 ~ 100, and n is the integer of 20 ~ 300, and wherein said alkyl-silicone oil is 100 ~ 3000mPas the kinematic viscosity of 25 DEG C; The carbon atom mean number of described alkyl-silicone oil requires between 1.2 ~ 12.8, can be miscible and have good antifoaming performance with mineral oil.The content of alkyl-silicone oil is the 0.5-10% of defoamer total amount.
antifoam additives
Antifoam additives mainly comprises fatty alcohol, lipid acid, fatty acid ester, fatty wax, modified fat wax, phosphate compounds, and these materials are used alone or used in combination, can help better to improve antifoaming performance.
Lipid acid can use any one in lipid acid and ring type lipid acid, preferred fatty acid, comprises the lipid acid that carbon atom is 2 ~ 30, and preferred carbon atom is the lipid acid of 12 ~ 22.
Fatty alcohol is selected from the fatty alcohol that carbon atom quantity is 2 ~ 30, comprises unitary or polyvalent alcohol, and preferred carbonatoms is the fatty alcohol of 12 ~ 22.
Fatty acid ester is the fatty acid ester by unitary or multi-alcohol and the generation of long-chain fat acid-respons.
Fat wax comprises animal wax, spermaceti, beeswax, river wax, vegetable wax, gama wax, Ka Naba wax, Japan tallow, mineral wax, ore deposit ceresine, ceresine, montanin wax, brown alabaster wax, petroleum wax, paraffin, Microcrystalline Wax, synthetic wax, Fischer-Tropsch wax, polyethylene wax, Poly Propylene Wax, clorafin, emulsifying wax and modifier thereof, preferred paraffin, polyethylene wax and Poly Propylene Wax and derivative thereof.
Total consumption of antifoam additives is 0.1 ~ 5% of defoamer total amount.
water drain silica
Silicon-dioxide is divided into precipitated silica and fumed silica by manufacture method, is divided into hydrophilic silicon dioxide and water drain silica by surfactivity.The specific surface area of the silicon-dioxide that the present invention selects is 20 ~ 500m
2/ g, preferably 50 ~ 200m
2/ g, consumption is 0.1 ~ 5% of defoamer total amount.
emulsifying agent
Emulsifying agent comprises negatively charged ion and nonionic surface active agent, and the two can be used alone or as a mixture.Be used alone, preferred nonionic surfactants, nonionogenic tenside mainly comprises fatty alcohol-polyoxyethylene ether, oleic acid polyoxyethylene, castor oil polyoxyethylene ether, polyoxyethylene fatty amine compound, polyoxyethylene 20 sorbitan monolaurate (Tween-20), polyoxyethylene 20 sorbitan monopalmitate (Tween-40), polyoxyethylene 20 sorbitan monostearate (Tween-60), polyoxyethylene 20 sorbitan monooleate (Tween-80), polyoxyethylene 20 sorbitan trioleate (Tween-85), sorbitan mono-laurate Span-20), sorbitan monopalmitate (Span-40), sorbitan monostearate (Span-60), sorbitan monooleate (Span-80), Witconol AL 69-66 (Span-85), preferred hydrophile-lipophile balance value (HLB) 8 ~ 10.Emulsifier is 1 ~ 15% of defoamer consumption.
A kind of water-borne coatings defoamer, preparation process is as follows:
1, first by alkyl-silicone oil, silicon-dioxide under high speed dispersor with 2000rpm rotating speed high speed dispersion 10min, and be warming up to 100 ~ 160 DEG C, insulation 0.5 ~ 2h obtains mixture A, and kinematic viscosity reaches 3000 ~ 8000 mPas at 25 DEG C.
2, mineral oil and vegetables oil and derivative thereof are joined in container, under constantly stirring, add fatty acid metal soap, antifoam additives and mixture A, and at least stir 10 ~ 30min, system is uniformly dispersed, and then be slowly warming up to again between 140 DEG C ~ 180 DEG C, and be incubated 0.5 ~ 3h; Then start to be cooled between 40 DEG C ~ 80 DEG C, add emulsifying agent, and Keep agitation 60min, obtain mixture B.
3, under room temperature condition, mixture B is disperseed until diameter of particle scope is at 5 ~ 20um through high speed dispersor 3000rpm rotating speed, obtains defoamer of the present invention.
Embodiment
embodiment 1
21g alkyl-silicone oil (average carbon number is 1.3, and the carbonatoms in radicals R is 10) is mixed with 2g precipitated silica, and under 2000rpm rotating speed high speed dispersion 10min, and be warming up to 100 DEG C, insulation 0.5h, obtain mixture A, and kinematic viscosity reaches 3000 mPas at 25 DEG C.
Then in container, add 317g 5# white oil, 577g peanut oil and epoxidized peanut oil, add 9g aluminum palmitate while stirring, 13g bis-aluminium octoate, 23g oxidized polyethlene wax, 25g stearic acid, with said mixture A, then continue to stir 15min.And then after being slowly warming up to 140 DEG C, and be incubated 0.5h, be then cooled between 80 DEG C, then add 18g Witconol AL 69-66 (Span-85), continue to stir 60min, obtain mixture B.
At room temperature, mixture B is disperseed until diameter of particle scope is at 5 ~ 20 μm with 3000rpm rotating speed under high speed dispersor, obtains defoamer I.
embodiment 2
By 96g alkyl-silicone oil, (average carbon number is 2.1, and the carbonatoms in radicals R is 14) mix with 45g precipitated silica, and under 2000rpm rotating speed high speed dispersion 10min, and be warming up to 160 DEG C, insulation 2h obtains mixture A, and kinematic viscosity reaches 4000mPas at 25 DEG C.
Then in container, add 127g7# white oil, 673g soybean oil and amidation soybean oil, add 30g bis-(docosoic acid) aluminium while stirring, 0.5g polyoxypropylene diols, the positive stearyl alcohol of 0.5g, with said mixture A, then continue to stir 10min.And then after being slowly warming up to 180 DEG C, and be incubated 3h, be then cooled to 80 DEG C, then add 28g polyoxyethylene 20 sorbitan trioleate (Tween-85) continuation stirring 60min, obtain mixture B.
At room temperature, mixture B is disperseed until diameter of particle scope is at 5 ~ 20 μm with 3000rpm rotating speed under high speed dispersor, obtains defoamer II.
embodiment 3
By 11g alkyl-silicone oil, (average carbon number is 4.1, and the carbonatoms in radicals R is 18) mix with 4g precipitated silica, and under 2000rpm rotating speed high speed dispersion 10min, and be warming up to 130 DEG C, insulation 1.2h obtains mixture A, and kinematic viscosity reaches 5000mPas at 25 DEG C.
Then in container, add 170 alkylbenzenes, 630g Viscotrol C and epoxidized castor oil, add 20g bis-(octadecanoic acid) aluminium while stirring, 15g phosphoric acid isobutyl ester, 10g stearic acid diethylene glycol dilaurate, with said mixture A, then continue to stir 30min.And then after being slowly warming up to 140 DEG C, and be incubated 3h, be then cooled to 60 DEG C, then add 140g oleic acid polyoxyethylene (6) ether, continue to stir 60min, obtain mixture B.
At room temperature, mixture B is disperseed until diameter of particle scope 5 ~ 20 μm with 3000rpm rotating speed under high speed dispersor, obtains defoamer III.
embodiment 4
By 20g alkyl-silicone oil, (average carbon number is 5.2, and the carbonatoms in radicals R is 22) be incorporated in high speed dispersion 10min under 2000rpm rotating speed with 6g precipitated silica is mixed, and being warming up to 100 DEG C, insulation 1h obtains mixture A, and kinematic viscosity reaches 6500mPas at 25 DEG C.
Then in container, add 216g 300# liquid wax, 584g plam oil and epoxidized palm oil thereof, add 80g aluminium octoate while stirring, 14g polyoxybutylene diols, with said mixture A, then continue to stir 20min.And then after being slowly warming up to 160 DEG C, and be incubated 0.5h, be then cooled to 80 DEG C, then add 80g Soxylat A 25-7 continuation stirring 60min, obtain mixture B.
At room temperature, mixture B is disperseed until diameter of particle scope 5 ~ 20 μm with 3000rpm rotating speed under high speed dispersor, obtains defoamer IV.
embodiment 5
By 10g alkyl-silicone oil, (average carbon number is 8.1, and the carbonatoms in radicals R is 26) be incorporated in high speed dispersion 10min under 2000rpm rotating speed with 1g precipitated silica is mixed, and being warming up to 100 DEG C, insulation 1h obtains mixture A, and kinematic viscosity reaches 7000mPas at 25 DEG C.
Then in container, add 302g alkylbenzene, 628g oleum lini and epoxidized linseed, add 48g bis-aluminium octoate while stirring, 0.5g polyoxybutylene diols, 0.5g stearic acid, with said mixture A, then continue to stir 20min.And then after being slowly warming up to 150 DEG C, and be incubated 0.5h, be then cooled to 70 DEG C, then add 10g fatty alcohol-polyoxyethylene ether continuation stirring 60min, obtain mixture B.
At room temperature, mixture B is disperseed until diameter of particle scope 5 ~ 20 μm with 3000rpm rotating speed under high speed dispersor, obtains defoamer V.
embodiment 6
By 50g alkyl-silicone oil, (average carbon number is 12.1, and the carbonatoms in radicals R is 30) be incorporated in high speed dispersion 10min under 2000rpm rotating speed with 12g precipitated silica is mixed, and being warming up to 100 DEG C, insulation 0.5h obtains mixture A, and kinematic viscosity reaches 8000 mPas at 25 DEG C.
Then in container, add 273g alkylbenzene, 527g rapeseed oil and amidation rapeseed oil, add 60g bis-(hexadecanoic acid) aluminium while stirring, 3g fat wax, with said mixture A, then continue to stir 20min.And then after being slowly warming up to 140 DEG C, and be incubated 3h, be then cooled to 50 DEG C, then add 75g polyoxyethylene 20 sorbitan monostearate (Tween-60) continuation stirring 60min, obtain mixture B.
At room temperature, mixture B is disperseed until diameter of particle scope 5 ~ 20 μm with 3000rpm rotating speed under high speed dispersor, obtains defoamer VI.
comparative example 1
32g dimethyl silicone oil (average carbon number is 1, and the carbonatoms in radicals R is 1) is mixed with 2g precipitated silica, and under 2000rpm rotating speed high speed dispersion 10min, obtain mixture X, and kinematic viscosity reaches 1000mPas at 25 DEG C.
Then in container, add 268g liquid wax, 625g peanut oil and epoxidized peanut oil, add 12g aluminum stearate while stirring, 15g double stearic acid aluminium, 4g oxidized polyethlene wax, 2g stearic acid, with said mixture X, then continue to stir 10min.And then after being slowly warming up to 140 DEG C, and be incubated 0.5h, be then cooled to 80 DEG C, then add 45g Witconol AL 69-66 (Span-85), continue to stir 60min, obtain mixture Y.
At room temperature, mixture Y is disperseed until diameter of particle scope is at 5 ~ 20 μm with 3000rpm rotating speed under high speed dispersor, obtains defoamer C-I.
comparative example 2
By 25g alkyl-silicone oil, (average carbon number is 11.8, and the carbonatoms in radicals R is 30) mix with 3g precipitated silica, and under 2000rpm rotating speed high speed dispersion 10min, and be warming up to 160 DEG C, insulation 2h obtains mixture X, and kinetic viscosity reaches 10000mPas at 25 DEG C.
Then in container, add 300g7# white oil, 590g soybean oil and amidation soybean oil, add 25g bis-(docosoic acid) aluminium while stirring, 11g polyoxypropylene diols, with said mixture X, then continue to stir 10min.And then after being slowly warming up to 180 DEG C, and be incubated 3h, be then cooled to 80 DEG C, then add 51g polyoxyethylene 20 sorbitan trioleate (Tween-85) continuation stirring 60min, obtain mixture Y.
At room temperature, mixture Y is disperseed until diameter of particle scope is at 5 ~ 20 μm with 3000rpm rotating speed under high speed dispersor, obtains defoamer C-II.
comparative example 3
By 20g alkyl-silicone oil, (average carbon number is 13.0, and the carbonatoms in radicals R is 28) mix with 2g precipitated silica, and under 2000rpm rotating speed high speed dispersion 10min, and be warming up to 130 DEG C, insulation 1.2h obtains mixture X, and kinetic viscosity reaches 7000mPas at 25 DEG C.
Then in container, add 200g alkylbenzene, 706g Viscotrol C and epoxidized castor oil, add 30g bis-(octadecanoic acid) aluminium while stirring, 12g phosphoric acid isobutyl ester, 7g stearic acid diethylene glycol dilaurate, with said mixture X, then continue to stir 30min.And then after being slowly warming up to 140 DEG C, and be incubated 3h, be then cooled to 60 DEG C, then add 28g oleic acid polyoxyethylene (6) ether, continue to stir 60min, obtain mixture Y.
At room temperature, mixture Y is disperseed until diameter of particle scope 5 ~ 20 μm with 3000rpm rotating speed under high speed dispersor, obtains defoamer C-III.
comparative example 4
By 44g alkyl-silicone oil, (average carbon number is 6.2, and the carbonatoms in radicals R is 18) be incorporated in high speed dispersion 10min under 2000rpm rotating speed with 3g precipitated silica is mixed, and being warming up to 100 DEG C, insulation 1h obtains mixture X, and kinetic viscosity reaches 9500mPas at 25 DEG C.
Then in container, add 263g 300# liquid wax, 600g plam oil and epoxidized palm oil thereof, add 36g aluminium octoate while stirring, 10g polyoxybutylene diols, with said mixture X, then continue to stir 20min.And then after being slowly warming up to 160 DEG C, and be incubated 0.5h, be then cooled to 80 DEG C, then add 50g Soxylat A 25-7 continuation stirring 60min, obtain mixture Y.
At room temperature, mixture Y is disperseed until diameter of particle scope 5 ~ 20 μm with 3000rpm rotating speed under high speed dispersor, obtains defoamer C-IV.
comparative example 5
By 25g alkyl-silicone oil, (average carbon number is 1.7, and the carbonatoms in radicals R is 42) be incorporated in high speed dispersion 10min under 2000rpm rotating speed with 6g precipitated silica is mixed, and being warming up to 100 DEG C, insulation 0.5h obtains mixture X, and kinematic viscosity reaches 8000mPas at 25 DEG C.
Then in container, add 300g 5# white oil, 580g soybean oil and amidation soybean oil thereof add 40g bis-(hexadecanoic acid) aluminium while stirring, 9g fat wax, with said mixture X, then continue to stir 20min.And then after being slowly warming up to 140 DEG C, and be incubated 3h, be then cooled to 50 DEG C, then add 40g polyoxyethylene 20 sorbitan monostearate (Tween-60) continuation stirring 60min, obtain mixture Y.
At room temperature, mixture Y is disperseed until diameter of particle scope 5 ~ 20 μm with 3000rpm rotating speed under high speed dispersor, obtains defoamer C-VI.
comparative example 6
By 24g alkyl-silicone oil, (average carbon number is 5.2, and the carbonatoms in radicals R is 14) mix with 4g precipitated silica, and under 2000rpm rotating speed high speed dispersion 10min, and be warming up to 160 DEG C, insulation 2h obtains mixture X, and kinematic viscosity reaches 6000mPas at 25 DEG C.
Then in container, add 80g7# white oil, 810g soybean oil and amidation soybean oil, add 25g bis-(docosoic acid) aluminium while stirring, 8g polyoxypropylene diols, the positive stearyl alcohol of 4g, with said mixture X, then continue to stir 10min.And then after being slowly warming up to 180 DEG C, and be incubated 3h, be then cooled to 80 DEG C, then add 50g polyoxyethylene 20 sorbitan trioleate (Tween-85) continuation stirring 60min, obtain mixture Y.
At room temperature, mixture B is disperseed until diameter of particle scope is at 5 ~ 20um with 3000rpm rotating speed under high speed dispersor, obtains defoamer C-VII.
comparative example 7
By 44g alkyl-silicone oil, (average carbon number is 3.8, and the carbonatoms in radicals R is 16) be incorporated in high speed dispersion 10min under 2000rpm rotating speed with 3g precipitated silica is mixed, and being warming up to 100 DEG C, insulation 1h obtains mixture X, and kinetic viscosity reaches 4000mPas at 25 DEG C.
Then in container, add 763g 300# liquid wax, 100g plam oil and epoxidized palm oil thereof, add 36g aluminium octoate while stirring, 10g polyoxybutylene diols, with said mixture X, then continue to stir 20min.And then after being slowly warming up to 160 DEG C, and be incubated 0.5h, be then cooled to 80 DEG C, then add 50g castor oil polyoxyethylene ether continuation stirring 60min, obtain mixture Y.
At room temperature, mixture B is disperseed until diameter of particle scope 5 ~ 20um with 3000rpm rotating speed under high speed dispersor, obtains defoamer C-VIII.
the performance test of defoamer
(1) antifoaming performance test
Testing method: in the stainless cup of 1000ml, add the coating prepared of 135g, then the benzene emulsion of 15g is added, under high speed dispersor, first stir 1min with 600rpm stirring velocity, make coating and benzene emulsion energy Homogeneous phase mixing, then the thickening material of 1% is added, the 2-amino-2-methyl-1-propanol of 0.2%, continue to stir 1min at 600 rpm, finally add the defoamer of 0.3%, 6min is stirred under 600rpm stirring velocity, stop stirring rear record following table and see bubble, then be poured into immediately in the graduated cylinder of 100ml, recording volume V, calculated specific gravity, the antifoaming performance of the explanation defoamer that numerical value is large is good.Test result is as follows:
The suds suppressing properties contrast of table 1 defoamer
Defoamer | Proportion g/ml |
I | 1.4365 |
II | 1.4352 |
III | 1.4377 |
IV | 1.4361 |
V | 1.4329 |
VI | 1.4367 |
C-I | 1.4127 |
C-II | 1.4153 |
C-III | 1.4155 |
C-IV | 1.4210 |
C-V | 1.4165 |
C-VI | 1.4201 |
C-VII | 1.4256 |
By above-mentioned experiment, can find out that defoamer of the present invention has excellent suds suppressing properties.
(2) brushing test
Testing method: after the above-mentioned coating through high speed dispersion is placed 10min, take out and be statically placed in a little on sheet glass, with the wet film preparing device of 75um, coating is at the uniform velocity struck off, observe the state of film, and represent in table 2 by grade
Table 2 coating grade is classified
The coating result contrast of table 3 defoamer
Defoamer | Coating grade |
I | A5 |
II | A5 |
III | A5 |
IV | A5 |
V | A5 |
VI | A5 |
C-I | C2 |
C-II | C3 |
C-III | C3 |
C-IV | C3 |
C-V | C3 |
C-VI | C3 |
C-VII | C3 |
By above-mentioned experiment, can find out do not meet radicals R in alkyl-silicone oil carbonatoms between 4 ~ 40, average carbon number between 1.2 ~ 12.8, the coating of the defoamer of at least one condition of ratio between 1:6 ~ 4:7 in three conditions of mineral oil and vegetables oil will far be worse than defoamer of the present invention.
(3) stability test
Testing method:
1. defoamer is put into the graduated centrifuge tube of band with 3000rpm, high speed centrifugation 15min, after centrifugal end, the stability of the volume larger explanation defoamer of the upper strata oily liquids in centrifuge tube is poorer;
2. defoamer being put into 40 DEG C of baking ovens places after 30 days, and visual observation whether layering, test result is as follows
Table 4 defoamer stability test-dewatering ability
Defoamer | Upper strata oily volume |
I | 0.0 |
II | 0.0 |
III | 0.0 |
IV | 0.0 |
V | 0.0 |
VI | 0.0 |
C-I | 1.0 |
C-II | 1.2 |
C-III | 0.8 |
C-IV | 1.5 |
C-V | 1.1 |
C-VI | 0.7 |
C-VII | 3.0 |
Table 5 defoamer stability test-shelf-stability
Defoamer | Stability |
1 | Not stratified |
II | Not stratified |
III | Not stratified |
IV | Not stratified |
V | Not stratified |
VI | Not stratified |
C-I | Layering |
C-II | Layering |
C-III | Layering |
C-IV | Layering |
C-V | Layering |
C-VI | Layering |
C-VII | Severe delamination |
By above-mentioned experiment, find out that defoamer of the present invention has excellent stability.