CN109364534A - A kind of modified polyether composition - Google Patents
A kind of modified polyether composition Download PDFInfo
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- CN109364534A CN109364534A CN201811171451.6A CN201811171451A CN109364534A CN 109364534 A CN109364534 A CN 109364534A CN 201811171451 A CN201811171451 A CN 201811171451A CN 109364534 A CN109364534 A CN 109364534A
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- polyethers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
- B01D19/0409—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing Si-atoms
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyethers (AREA)
Abstract
The present invention relates to a kind of modified polyether compositions, it includes " H-type " silicon polyethers, line style silicon polyethers, alkynol polyethers and silica composition, it can control foam in acceptable degree, while also have lower surface tension, have good synergism to wetting and levelling.This composition in addition to for water-based ink, coating, industrial wood lacquer etc. foam control and granule surface contral, also can other cannot be in the system of organic silicon defoamer, such as bioanalysis sewage treatment, landfill leachate.
Description
Technical field
The present invention relates to a kind of modified polyether compositions, have foam control function and wetting function, are under the jurisdiction of fining
Work technical field.
Background technique
Under current social environment, environmental protection is impregnated with the various aspects of life it has been mentioned that unprecedented height,
Unquestionably, the safety and environmental protection of residential location is a big problem concerning health of human body.
Water paint is generally by aqueous binder, pigment, filler, dispersing agent, thickener, wetting agent, levelling agent and defoaming
The composition such as agent.Water-based industrial paint is very important a part in water paint large family.Water-based industrial paint mainly with water come
Diluent is made, some solvents of curing agent, solvent or diluent are not needed, is a kind of novel environment friendly antirust, anti-corrosive painting for being different from oiliness industrial paint
Material.The application range of water-based industrial paint is extremely wide, and bridge, steel structure, ship, electromechanics, steel etc. can see its figure everywhere.Cause
Its energy-saving and environmental protection, will not be to human body and environmental pollution and pollution, thus receives praises from customers, and is the following paint industry hair
The direction of exhibition and the substitute products of oil paint.
Wetting agent, levelling agent, dispersing agent in water-based industrial paint belong to surfactant, in filler and pigment grind point
In scattered process, it is easy to blister, cause production efficiency decline even can not normally produce, the dry film formed after construction can also go out
The defects of existing shrinkage cavity, flake, satisfied effect can not be obtained.Therefore, it is necessary to defoaming agent is added to control the generation of foam.
Defoaming agent is broadly divided into organic silicon defoamer and antifoaming agent of non-silicone, specific to applying disappearing in water paint
Infusion, predominantly modified organic silicon defoaming agent and mineral oil antifoam agent two major classes.Mineral oil antifoam agent is more early as a development
Coating defoaming agent, defoaming capacity difference leads to that additive amount is high, mineral oil influences a series of disadvantages such as glossiness and slowly manifests
Come, therefore such product overwhelming majority is served only on engineering coating for internal and external wall.High-grade industrial paint, woodcare paint are come
Say, generally all selection have wetting function Siloxane-Oxyalkylene Copolymers compound product, such as CN101088589 introduce be
The defoaming agent of the block silicon polyethers of ABA type, CN101096417, CN101541858A, US5804099A, US5613988A,
The Siloxane-Oxyalkylene Copolymers for the branched chain type that US20020132860 is introduced substantially are controlled by adjusting the water solubility of silicon polyethers
The performance of foam control processed；US6391831B1 describes the defoaming agent of phenylethene modified polysiloxanes；US201032425A is introduced
The defoaming agent of fluorochemical polyether modified polyorganosiloxane.These products are substantially with offshore company Tego, GOLDSCHMIT institute ridge
It is disconnected.It is said from the angle of technology, the product abridged edition of these companies is mentioned by adjusting the ratio of ethylene oxide and propylene oxide
Rise defoaming and compatibility.The molecule of defoaming agent is relatively simple, and the technical difficulty of production also greatly increases, and solves between batch
Control cost needed for otherness is very high, and the product formed can only contribute defoaming, to wetability almost without contribution, industry
It to be adjusted in the production process of paint or by the way that a large amount of wetting agent is added.
Inventor herein studies through a large number of experiments, discovery " H-type " silicon polyethers, line style silicon polyethers, alkynol polyethers
Foam can be controlled in acceptable degree with the mixture of silica composition, while also there is lower surface tension,
There is good synergism to wetting and levelling.This composition is in addition to for the side such as water-based ink, coating, industrial wood lacquer
The foam in face controls and granule surface contral, also can other cannot in the system with organic silicon defoamer, as bioanalysis sewage treatment,
Landfill leachate.
Summary of the invention
Modified polyether composition of the invention be used in the systems such as coating, ink, aqueous woodware paint have concurrently foam control and
The feature of granule surface contral.
A kind of modified polyether composition of the present invention includes: (A) " H-type " silicon polyethers, (B) line style silicon polyethers and (C)
Alkynol polyethers and (D) silica.
A, " H-type " silicon polyethers
Described " H-type " the silicon polyethers has the following structure general formula:
In formula (I), substituent R and R1It is identical or different, it is selected from:
(1) alkyl that carbon atom number is 1 ~ 30, including it is methyl, ethyl, n-propyl, isopropyl, butyl, amyl, hexyl, pungent
Base, decyl, 12 carbon alkyl, tetradecane base, hexadecane base, octadecyl, icosane base, docosane base,
Tetracosa carbon alkyl, hexacosane base, octacosane base, three decane bases；
(2) aryl, including phenyl,αMethylphenethyl and phenethyl；
SubscriptaIt is 1 or 2；SubscriptbFor 1 ~ 8 integer；Subscriptc、dThe respectively degree of polymerization of EO, PO,cWithdAverage value be 1 ~
15。
From the point of view of being easy to get from raw material, 80% or more substituent R and R1For methyl.
The dosage of described " H-type " the silicon polyethers is the 0.5 ~ 25% of composition gross mass.
B, line style silicon polyethers
The line style silicon polyethers is for improving wetability and spreadability.
The line style silicon polyether structure general formula is as follows:
In formula (II), subscriptgFor the degree of polymerization,gFor 1 ~ 15 integer；eWithfFor the degree of polymerization of EO and PO,eWithfBe averaged
Value is 1 ~ 20；R2It is hydrogen atom or methyl or acetyl group or butyl for end-capping group.
The dosage of the line style silicon polyethers is the 50 ~ 95% of composition gross mass.
C, alkynol polyethers
The alkynol polyether structure general formula is as follows:
In formula (III), subscripthWithiFor the degree of polymerization of EO and PO,hWithiAverage value be 1 ~ 10；R3And R4For substituent group base
Group, the alkyl for being 1 ~ 6 including hydrogen atom and carbon atom.
The dosage of the alkynol polyethers is the 0.5 ~ 20% of composition gross mass.
D, silica
Silica is divided into precipitated silica and two kinds of fumed silica by manufacturing method, by surface nature point
For hydrophilic silicon dioxide and two kinds of hydrophobic silica.The present invention is preferably hydrophobic silica, and specific surface area is 50 ~
300m2/ g, including vapor phase method and precipitation method hydrophobic silica.
Silicic acid anhydride is carried out by using methyl substituted organosilicon material, these organosilicon materials include low viscosity
Dimethyl silicone polymer, the hydroxy silicon oil of low viscosity, hexamethyldisilazane, hexamethyldisiloxane, dimethyl diethoxy
Silane, methyltrimethoxysilane, methyltriethoxysilane.
The technique of hydrophobized silica is usually that catalyst appropriate is added at 80 DEG C or more to be kept for a period of time and made
?.
The dosage of the silica is the 0.5 ~ 10% of composition gross mass.
Modified polyether composition of the invention the preparation method is as follows:
Under room temperature, " H-type " silicon polyethers, line style silicon polyethers, alkynol polyethers are put into container, opens stirring, choosing
It selects under conditions of revolving speed is 300 ~ 10000rpm and silica is slowly added thereto, until the dispersion particle diameter of silica is less than
Until 1 μm；Then reducing revolving speed is 100 ~ 200rpm, and opens vacuum pump, maintains vacuum degree between -0.01 ~ -0.05MPa
Remove gas therein.
In addition to above-mentioned several components, some other components, such as diluent can also further be added into system, no
The essence for changing patent, also belongs to the protection scope of this patent.
Specific embodiment
Embodiment 1:
The example of type " silicon polyethers A:
Embodiment 2
The example of line style silicon polyethers B:
Embodiment 3
The example of alkynol polyethers C:
Embodiment 4
Under room temperature, 1 part of " H-type " silicon polyethers A-1,95 parts of line style silicon polyethers B-5,1 part of alkynol polyethers C-7 are put into
In container, stirring is opened, selects revolving speed for 3 parts of silica R974 are slowly added under conditions of 1000rpm thereto, until two
Until the dispersion particle diameter of silica is less than 1 μm；Then reducing revolving speed is 200rpm, and opens vacuum pump, maintain vacuum degree be-
Gas therein is removed between 0.01MPa, just obtains product of the invention (Polyether Compound-1) PC-1.
Embodiment 5
Under room temperature, by 23 parts of " H-type " silicon polyethers A-6,50 parts of line style silicon polyethers B-2,17 parts of alkynol polyethers C-4 investments
Into container, stirring is opened, selects revolving speed as 10 parts of gas phase hydrophobic titanium dioxides are slowly added under conditions of 10000rpm thereto
Silicon H2000, until the dispersion particle diameter of silica is less than 1 μm；Then reducing revolving speed is 100rpm, and opens vacuum pump,
It maintains vacuum degree to remove gas therein between -0.05MPa, just obtains product PC-2 of the invention.
Embodiment 6
Under room temperature, by 4 parts of " H-type " silicon polyethers A-4,6 parts of " H-type " silicon polyethers A-8,20 parts of line style silicon polyethers B-1,59
Part line style silicon polyethers B-6,7 parts of alkynol polyethers C-2 and 3 parts of alkynol polyethers C-5 are put into container, open stirring, select revolving speed
For 1 part of precipitating hydrophobic silica D10 is slowly added under conditions of 5000rpm thereto, until the dispersion particle diameter of silica
Until 1 μm；Then reducing revolving speed is 200rpm, and opens vacuum pump, and vacuum degree is maintained to remove it between -0.05MPa
In gas, just obtain product PC-3 of the invention.
Embodiment 7
Under room temperature, by 2 parts of " H-type " silicon polyethers A-2,1 part of " H-type " silicon polyethers A-7,80 parts of line style silicon polyethers B-3,10
Part line style silicon polyethers B-4,3 parts of alkynol polyethers C-3 and 1 part of alkynol polyethers C-6 are put into container, open stirring, select revolving speed
For 3 parts of gas phase hydrophobic silica R202 are slowly added under conditions of 400rpm thereto, until the dispersion particle diameter of silica
Until 1 μm；Then reducing revolving speed is 200rpm, and opens vacuum pump, and vacuum degree is maintained to remove it between -0.02MPa
In gas, just obtain product PC-4 of the invention.
Embodiment 8
Under room temperature, 3 parts of " H-type " silicon polyethers A-3,90 parts of line style silicon polyethers B-4,5 parts of alkynol polyethers C-1 are put into
In container, stirring is opened, selects revolving speed as 2 parts of gas phase hydrophobic silicas are slowly added under conditions of 3000rpm thereto
383DS, until the dispersion particle diameter of silica is less than 1 μm；Then reducing revolving speed is 100rpm, and opens vacuum pump, is tieed up
It holds vacuum degree and removes gas therein between -0.03MPa, just obtain product PC-5 of the invention.
Comparative example 1
Under room temperature, 3 parts of " H-type " silicon polyethers A-3,92 parts of line style silicon polyethers B-4,5 parts of alkynol polyethers C-1 are put into
In container, stirring is opened, 10min is mixed, just obtains sample CPC-1.
Comparative example 2
Under room temperature, 93 parts of line style silicon polyethers B-4,5 parts of alkynol polyethers C-1 are put into container, opens stirring, choosing
It selects under conditions of revolving speed is 3000rpm and 2 parts of gas phase hydrophobic silica 383DS is slowly added thereto, until silica
Until dispersion particle diameter is less than 1 μm；Then reducing revolving speed is 100rpm, and opens vacuum pump, maintain vacuum degree be -0.03MPa it
Between remove gas therein, just obtain sample CPC-2.
Comparative example 3
Under room temperature, 90 parts of " H-type " silicon polyethers A-3,8 parts of alkynol polyethers C-1 are put into container, open stirring,
Select revolving speed for 2 parts of gas phase hydrophobic silica 383DS are slowly added under conditions of 3000rpm thereto, until silica
Dispersion particle diameter less than 1 μm until；Then reducing revolving speed is 100rpm, and opens vacuum pump, and maintenance vacuum degree is -0.03MPa
Between remove gas therein, just obtain sample CPC-3.
Comparative example 4
It is CPC-4 according to sample prepared by the example 1 of US20020132860.
Comparative example 5
Sample is prepared according to the example 2 of US639183B1, is CPC-5.
Performance test
1, high speed dispersion method testing and control foaming properties:
The commercially available water-based industrial paint of 250g, 50g deionized water and 0.2g sample to be tested is weighed to be fitted into container, with
The revolving speed of 1500rpm disperses 10min, after part dispersion liquid is poured into graduated cylinder immediately, read the volume V of dispersion liquid, weigh
The weight of the dispersion liquid dosage cylinder is M, then the tamped density ρ of the dispersion liquid is calculated according to following formula:
ρ (g/mL)=M/V × 100%
2, wetability is tested:
A little dispersant liquid drop of the complete tamped density of above-mentioned partial test is taken out on black and white paper, and with 75 μm of wet film makers
It at the uniform velocity strikes off, the state (shrinkage cavity situation) that observation dispersion liquid is presented on black and white paper, with the shrinkage cavity of 1mm on dry film every square centimeter
To indicate.
3, static surface tension is tested:
, air-blowing method testing and control foaming properties:
Weigh the graduated cylinder that the commercially available water-based industrial paint of 200g, 100g deionized water and 0.1g sample to be tested are packed into 1000mL
In, air is blasted into mixture with the flow of 1.5L/min, record foam reaches the time of 1000mL scale, the time more it is long then
Illustrate that suds suppressing properties are better.
From above-mentioned test data it can be seen that
Sample P C-1 ~ the PC-5 and CPC-1 ~ CPC-5 of patented invention will not generate apparent shrinkage cavity in industrial paint.
By the comparison of PC-5 and CPC-1, CPC-2, CPC-3, " H-type " silicon polyethers, line style silicon polyethers, alkynol polyethers are found
There is certain synergistic function between white carbon black these four components, foam control can all be influenced by having lacked any one therein
Performance processed, but the influence to wetability and surface tension is little.
Again from the point of view of PC-1 ~ PC-5 is compared with commercially available W1, no matter high speed dispersion method or air-blowing method can be found out, pass through
The performance for the product that the combination of " H-type " silicon polyethers, line style silicon polyethers, alkynol polyethers and white carbon black obtains, than commercially available single group
The performance of the W1 of part is good.
Claims (8)
1. a kind of modified polyether composition, which is characterized in that the composition includes: (A) " H-type " silicon polyethers, (B) line style silicon
Polyethers and (C) alkynol polyethers and (D) silica；
A, " H-type " silicon polyethers, the dosage of described " H-type " the silicon polyethers are the 0.5 ~ 25% of composition gross mass；
B, line style silicon polyethers, the dosage of the line style silicon polyethers are the 50 ~ 95% of composition gross mass；
C, alkynol polyethers, the dosage of the alkynol polyethers are the 0.5 ~ 20% of composition gross mass；
D, silica, the dosage of the silica are the 0.5 ~ 10% of composition gross mass.
2. a kind of modified polyether composition according to claim 1, which is characterized in that " H-type " silicon polyethers A has
Following general structure:
In formula (I), subscript a is 1 or 2；The integer that subscript b is 1 ~ 8；Subscript c, d is respectively the degree of polymerization of EO and PO, and c and d's is flat
Mean value is 1 ~ 15；
Substituent R and R1It is identical or different, it is selected from:
The alkyl that carbon atom number is 1 ~ 30, including methyl, ethyl, n-propyl, isopropyl, butyl, amyl, hexyl, octyl, the last of the ten Heavenly stems
Base, 12 carbon alkyl, tetradecane base, hexadecane base, octadecyl, icosane base, docosane base, 24
Carbon alkyl, hexacosane base, octacosane base, three decane bases；
Aryl, including phenyl, Alpha-Methyl phenethyl and phenethyl.
3. a kind of modified polyether composition according to claim 2, which is characterized in that " H-type " silicon polyethers A structure
Substituent R and R in formula (I)1In, 80% or more substituent group is methyl.
4. a kind of modified polyether composition according to claim 1, which is characterized in that the line style silicon polyethers B structure
General formula is as follows:
(II) in, subscript g is the degree of polymerization, is 1 ~ 15 integer；E and f is the degree of polymerization of EO and PO, the average value of e and f is 1 ~
20；R2It is hydrogen atom or methyl or acetyl group or butyl for end-capping group.
5. a kind of composition according to claim 1, which is characterized in that the alkynol polyethers C-structure general formula is as follows:
In formula (III), subscript h and i are the degree of polymerization of EO and PO, and the average value of h and i are 1 ~ 10；R3And R4For substituent group group, packet
Include the alkyl that hydrogen atom and carbon atom are 1 ~ 6.
6. a kind of modified polyether composition according to claim 1, which is characterized in that the silica D includes gas
Phase method and precipitation method hydrophobic silica, specific surface area are 50 ~ 300m2/g。
7. a kind of modified polyether composition according to claim 1, which is characterized in that the silica D's is hydrophobic
Material includes the dimethyl silicone polymer of low viscosity, the hydroxy silicon oil of low viscosity, hexamethyldisilazane, two silicon oxygen of hexamethyl
Alkane, dimethyl diethoxysilane, methyltrimethoxysilane, methyltriethoxysilane.
8. a kind of modified polyether composition according to claim 1, which is characterized in that the preparation method of the composition
It is as follows:
Under room temperature, " H-type " silicon polyethers, line style silicon polyethers, alkynol polyethers are put into container, opens stirring, selection turns
Silica is slowly added under conditions of being 300 ~ 10000rpm in speed thereto, until the dispersion particle diameter of silica is less than 1 μm
Until；Then reducing revolving speed is 100 ~ 200rpm, and opens vacuum pump, and vacuum degree is maintained to remove between -0.01 ~ -0.05MPa
Gas therein.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111056765A (en) * | 2019-12-06 | 2020-04-24 | 江苏四新科技应用研究所股份有限公司 | Defoaming agent applied to thin-layer self-leveling mortar and preparation method thereof |
| CN115445250A (en) * | 2022-07-26 | 2022-12-09 | 佛山市南海大田化学有限公司 | Defoaming agent composition and preparation method thereof |
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| CN102307978A (en) * | 2009-02-04 | 2012-01-04 | 陶氏康宁公司 | Foam control composition |
| CN107115694A (en) * | 2016-08-31 | 2017-09-01 | 江苏四新科技应用研究所股份有限公司 | A kind of silicon composition and its preparation, application |
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| CN102307978A (en) * | 2009-02-04 | 2012-01-04 | 陶氏康宁公司 | Foam control composition |
| CN107115694A (en) * | 2016-08-31 | 2017-09-01 | 江苏四新科技应用研究所股份有限公司 | A kind of silicon composition and its preparation, application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111056765A (en) * | 2019-12-06 | 2020-04-24 | 江苏四新科技应用研究所股份有限公司 | Defoaming agent applied to thin-layer self-leveling mortar and preparation method thereof |
| CN111056765B (en) * | 2019-12-06 | 2021-11-19 | 江苏四新科技应用研究所股份有限公司 | Defoaming agent applied to thin-layer self-leveling mortar and preparation method thereof |
| CN115445250A (en) * | 2022-07-26 | 2022-12-09 | 佛山市南海大田化学有限公司 | Defoaming agent composition and preparation method thereof |
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Effective date of registration: 20210914 Address after: 412000 Room 203, Zhongchuang space, innovation and entrepreneurship Park, Xinggong Road, you County, Zhuzhou City, Hunan Province Patentee after: Hunan Zhencheng polymer new material Co.,Ltd. Address before: Room d705, new material science and Technology Park, No.606, ningliu Road, Jiangbei new district, Nanjing City, Jiangsu Province, 210000 Patentee before: NANJING RSI CHEMICAL & TECHNOLOGY Co.,Ltd. |