CN114146455A - Defoaming compositions - Google Patents
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- CN114146455A CN114146455A CN202111095860.4A CN202111095860A CN114146455A CN 114146455 A CN114146455 A CN 114146455A CN 202111095860 A CN202111095860 A CN 202111095860A CN 114146455 A CN114146455 A CN 114146455A
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- 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
Abstract
The invention introduces a defoaming composition taking an acrylate polymer as an active matter, and the defoaming composition has excellent defoaming and foam inhibiting performance and good compatibility in a foaming system; the defoaming composition is synthesized by a solution polymerization method, and the specific preparation method comprises the following steps: 1) preparing a polymer X by using a methyl/alkyl acrylate (alkyl number is 1-8) monomer A and/or a methyl/hydroxyalkyl acrylate B, an organic solvent S and an initiator I according to a solution polymerization method known in the industry; 2) preparing a polymer Y by using a methyl/alkyl acrylate (alkyl number is 9-18) monomer D and/or an olefin monomer O, an organic solvent S and an initiator I according to a solution polymerization method known in the industry; 3) preparing a polymer Z by all monomers used by a polymer X and a polymer Y, a cross-linking agent monomer C, hydrophobic particles K, an organic solvent S and an initiator I according to a solution polymerization method known in the industry; 4) the polymer X, Y, Z was mixed well by a shearing device to give a defoaming composition.
Description
Technical Field
The invention belongs to the technical field of fine chemical preparations, relates to a fine chemical preparation, and particularly relates to a defoaming composition, in particular to a defoaming composition taking an acrylate polymer as a main active substance, and application thereof in systems rich in anionic surfactants, such as papermaking, water treatment, textile and other industries.
Background
Defoamers are compositions used in industrial processes to control foam in various processes. In industrial production, especially in the industries of paper making, water treatment, textile and the like, various chemical auxiliaries are added into a water system due to specific requirements, and the foaming is easily caused along with large mechanical energy, such as stirring, washing, thickening processes and the like. Liquid media (e.g., water), chemical aids (e.g., surfactants), air sources, and mechanical energy are the primary reasons for foam generation in industrial processes.
The defoaming agent was developed to eliminate unnecessary foaming generated in industrial production. The defoaming agents are classified into two categories, namely non-silicon defoaming agents and organic silicon defoaming agents according to active ingredients, wherein the common non-silicon defoaming agents take mineral oil, polyether, amide or fatty alcohol as an active substance, and the organic silicon defoaming agents take polysiloxane as an active substance.
The defoaming agent introduced in patent CN102120106A consists of mineral oil, polyol stearate, white carbon black and an emulsifier, and has good defoaming performance in the industries of papermaking and water-based paint. The defoaming agent introduced in patent CN104069653A is composed of mineral oil, fatty acid/fatty acid metal soap, fatty acid amide, tributyl citrate, octanol, triethanolamine and emulsifier, and is widely used in the fields of ink production, paint production, sewage treatment and latex production. The defoaming agents referred to in the above patents belong to the group of mineral oil defoaming agents, i.e., defoaming agents using mineral oil as a carrier, hydrocarbon oil substances such as mineral oil can generate tetrachlorodibenzo-p-dioxin (TCDD) harmful substances when subjected to high temperature, causing damage to the environment and human health, and are deficient in the ability to suppress foam in a system rich in anionic surfactants.
As the main active substance of mineral oil defoamers, the use of EBS is common, other diamides or mixtures of diamides can also be used in such defoamers. Patent application CN101362063A describes a defoamer consisting of vegetable oils, EBS and other types of amides, mainly used in the textile printing industry. The patent CN102976429B discloses a defoaming agent for water treatment, which mainly comprises EBS, liquid paraffin, engine oil, kerosene, dimethyl silicone oil and white carbon black. In the using process, EBS in the mineral oil defoaming agent is easy to deposit due to strong hydrophobicity, so that the production efficiency and the product quality are influenced.
Patent CN102343165A uses silicone grease mixture as active substance to mix polyether silicone oil emulsifier to improve defoaming and foam inhibition performance, dispersibility and compatibility. Patent CN107638718A improves the high temperature stability of the emulsion by polysiloxane silicone grease and ethyoxyl alkynol emulsifier, the polysiloxane silicone grease improves the compatibility of the product, and the emulsifier with a gemini structure improves the compatibility of the emulsifier and the water phase. The defoaming agents described in the above patents all adopt silicone grease as a defoaming active substance, but due to the characteristics of silicone grease, silicone grease gradually precipitates in the use process of the defoaming agent, and when the defoaming agent is accumulated for a long time, silicone grease also precipitates in a large amount, which affects the product quality on one hand, and deposits on equipment are difficult to clean and even cause equipment blockage. Therefore, although silicone grease is generally considered to have the characteristics of rapid defoaming and long-lasting foam inhibition, many industrial processes avoid the use of silicone grease-containing defoamer products.
Therefore, there is an increasing demand for an antifoaming agent that does not contain hydrocarbon oil, EBS, or silicone grease. Patent 101045880 discloses a defoaming agent compounded by high molecular block polyether, fatty alcohol and solvent, wherein the high molecular block polyether is polyethylene glycol with molecular weight of 10000-20000 and is a block copolymer of ethylene oxide and propylene oxide as initiator, the fatty alcohol is isooctanol, and the solvent is ethanol and water. The defoaming agent does not contain any silicon element, does not affect the downstream hydrogenation process and the quality of the final light oil product, but has the defects of insufficient active components, slow permeation and diffusion in a tower, large addition amount, higher cost than that of an organic silicon defoaming agent, poor high-temperature resistance and low defoaming efficiency at high temperature. . Patent CN102126763A describes an antifoaming agent consisting of polyether and low carbon alcohol, mainly used for garbage leachate treatment. The above patent does not use mineral oil, and avoids the harm of mineral oil to the environment, but the defoaming and foam inhibiting performance of the non-silicon defoaming agent using polyether or fatty alcohol as main active matter in a system rich in anionic surfactant is not satisfactory, and the capability of inhibiting foam cannot meet the industrial production requirement. Therefore, researchers have developed a new type of defoaming agent to solve the above problems, and have developed a new type of defoaming agent to solve the above problems.
Patent US5152925A describes a defoaming agent with acrylic resin as the main defoaming active substance, wherein the acrylic ester polymer mainly uses acrylic resin prepared by hydroxyl-containing acrylic monomer in organic diluent diisodecyl phthalate (DIDP) as the main active substance, and is applied to the washing of coarse pulp and other paper making processes. Patent CN102428142B also mentions that acrylic ester polymer is used as a main active substance to prepare a defoaming agent, wherein the acrylic ester polymer is prepared from monomers such as isooctyl acrylate, hydroxyalkyl acrylate and acrylic acid in organic diluent diisooctyl adipate (DIOA), and the prepared acrylic ester polymer is used as a main active ingredient of the defoaming agent and is compounded with defoaming aids such as white carbon black and alkyl silicone oil, and is applied to industries such as petroleum industry, water treatment, pigment and coating, food and beverage processing, mining industry, textile industry, agriculture and paper making. The defoaming agent can solve the problems of environmental damage and silicon precipitation residue, but the defoaming and foam inhibiting performance of the defoaming agent prepared by the prior art still has a great space for improvement. Therefore, the improvement of the defoaming and foam inhibiting performance of the acrylate polymer defoaming agent is of great significance.
Disclosure of Invention
The invention discloses a defoaming composition taking an acrylate polymer as a main active matter, which has excellent defoaming and foam inhibiting performance in a foaming system and good compatibility. The defoaming composition is synthesized by a solution polymerization method, and the specific preparation method comprises the following steps: 1) preparing a polymer X by using a methyl/alkyl acrylate (alkyl number is 1-8) monomer A and/or a methyl/hydroxyalkyl acrylate B, an organic solvent S and an initiator I according to a solution polymerization method known in the industry; 2) preparing a polymer Y by using a methyl/alkyl acrylate (alkyl number is 9-18) monomer D and/or an olefin monomer O, an organic solvent S and an initiator I according to a solution polymerization method known in the industry; 3) preparing a polymer Z by all monomers used by a polymer X and a polymer Y, a cross-linking agent monomer C, hydrophobic particles K, an organic solvent S and an initiator I according to a solution polymerization method known in the industry; 4) the polymer X, Y, Z was mixed well by a shearing device to give polymeric defoamer composition P. The polymer X obtained by independent self-polymerization or mixed copolymerization by taking the methyl/alkyl acrylate A and the methyl/hydroxyalkyl acrylate B as monomers has lower glass transition temperature and lower molecular weight and mainly plays the roles of quick spreading and quick dispersion; the polymer Y obtained by independent self-polymerization or mixed copolymerization by taking methyl/alkyl acrylate D and olefin O as monomers has proper molecular weight and mainly plays a role in inhibiting bubbles; the polymer Z obtained by mixing and copolymerizing all the monomers used by the polymer X and the polymer Y and the crosslinking monomer C can fully mix the polymer X and the polymer Y on one hand because the polymer Z simultaneously contains the structures of the polymer X and the polymer Y to play a role of a solvent, and on the other hand, can play a role of inhibiting bubbles because of the network structure of macromolecules thereof.
The purpose of the invention is realized by the following technical scheme:
a defoaming composition comprises a methyl/alkyl acrylate (alkyl number is 1-8) monomer A, a methyl/hydroxyalkyl acrylate monomer B, a methyl/alkyl acrylate (alkyl number is 9-18) monomer D, an olefin monomer O, a cross-linking agent monomer C, an organic solvent S, hydrophobic particles K and an initiator I; the amount of the methyl/alkyl acrylate (alkyl number is 1-8) monomer A accounts for 10-25% of the total mass of the defoaming agent composition, the amount of the methyl/hydroxyalkyl acrylate monomer B accounts for 5-15% of the total mass of the defoaming agent composition, the amount of the methyl/alkyl acrylate (alkyl number is 9-18) monomer D accounts for 10-25% of the total mass of the defoaming agent composition, the amount of the olefin monomer O accounts for 0.5-5% of the total mass of the defoaming agent composition, the amount of the cross-linking agent monomer C accounts for 0.5-5% of the total mass of the defoaming agent composition, the amount of the organic solvent S accounts for 30-60% of the total mass of the defoaming agent composition, the amount of the hydrophobic particles K accounts for 1-8% of the total mass of the defoaming agent composition, and the amount of the initiator I accounts for 0.1-1% of the total mass of the defoaming agent composition.
Preferably, the amount of the methyl/alkyl acrylate (alkyl number 1-8) monomer A is 15-20% of the total mass of the defoaming agent composition, the dosage of the methyl/acrylic acid hydroxyalkyl ester monomer B accounts for 8-12% of the total mass of the defoaming agent composition, the amount of the methyl/alkyl acrylate (alkyl number 9-18) monomer D accounts for 15-20% of the total mass of the defoaming agent composition, the dosage of the olefin monomer O accounts for 2-4% of the total mass of the defoaming agent composition, the dosage of the cross-linking agent monomer C accounts for 2-4% of the total mass of the defoaming agent composition, the amount of the organic solvent S accounts for 40-50% of the total mass of the defoaming agent composition, the amount of the hydrophobic particles K accounts for 3-6% of the total mass of the defoaming agent composition, and the amount of the initiator I accounts for 0.4-0.8% of the total mass of the defoaming agent composition.
The preparation method of the defoaming composition comprises the following steps:
1) preparing a polymer X by using a methyl/alkyl acrylate (alkyl number is 1-8) monomer A and/or a methyl/hydroxyalkyl acrylate B, an organic solvent S and an initiator I according to a solution polymerization method known in the industry;
2) preparing a polymer Y by using a methyl/alkyl acrylate (alkyl number is 9-18) monomer D and/or an olefin monomer O, an organic solvent S and an initiator I according to a solution polymerization method known in the industry;
3) preparing a polymer Z by all monomers used by a polymer X and a polymer Y, a cross-linking agent monomer C, hydrophobic particles K, an organic solvent S and an initiator I according to a solution polymerization method known in the industry;
4) the polymer X, Y, Z is mixed evenly by a shearing device to obtain the defoaming composition P
A. Methyl/alkyl acrylate (alkyl number 1-8) monomer
The methyl/alkyl acrylate (alkyl number is 1-8) monomer can be used singly or in combination; selected from the group consisting of acrylates and methacrylates, and specifically but not exclusively methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isooctyl methacrylate.
Preferably, the methyl/alkyl acrylate (alkyl number is 1-8) monomer is butyl acrylate, isooctyl acrylate or isooctyl methacrylate.
B. Hydroxyalkyl methyl/acrylate monomers
The above-mentioned hydroxyalkyl methyl/acrylate monomer may be used singly or in combination; selected from hydroxyalkyl acrylate and hydroxyalkyl methacrylate, and is particularly, but not limited to, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate.
Preferably, the methyl/hydroxyalkyl acrylate monomer is hydroxyethyl acrylate or hydroxypropyl acrylate.
D. Methyl/alkyl acrylate (alkyl number 9-18) monomer
The methyl/alkyl acrylate (the number of alkyl groups is 9-18) monomers can be used singly or in a mixture; selected from alkyl acrylate and alkyl methacrylate, and concretely, but not limited to lauryl acrylate, stearyl acrylate, lauryl methacrylate and stearyl methacrylate.
Preferably, the methyl/alkyl acrylate (alkyl number 9-18) monomer is lauryl methacrylate or stearyl methacrylate.
Olefin monomer
The olefin monomer is any one or a mixture of more of linear alpha-olefin, alpha-aromatic olefin or branched alpha-olefin, and comprises alpha-octene, alpha-decene, alpha-dodecene, alpha-tetradecene, alpha-hexadecene, alpha-octadecene, alpha-eicosene, C20-C24 linear alpha-olefin mixture, C24-C28 linear alpha-olefin mixture, alpha-triacontene, alpha-methylstyrene and alpha-styrene, and can be used alone or mixed in any proportion.
Preferably, the olefin monomer is alpha-dodecene, alpha-tetradecene, alpha-hexadecene, alpha-octadecene, alpha-methylstyrene and alpha-styrene.
C. Crosslinker monomers
The cross-linking agent monomer is a monomer which at least contains two or more vinyl groups in one molecule and can form a polymer soluble in an organic solvent; selected from allyl methacrylate, methacrylic acid polyol esters (ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1, 3-butylene glycol dimethacrylate), divinyl benzene, double-end vinyl-terminated polysiloxane, tetravinyl tetramethylcyclotetrasiloxane and vinyl MQ silicone resin, and can be used alone or mixed in any proportion.
Preferably, the crosslinker monomer is allyl methacrylate, ethylene glycol dimethacrylate, double-end vinyl terminated polysiloxane, vinyl MQ silicone resin.
I. Initiator
Examples of free radical generating initiators useful in the present invention are selected from, but not limited to, 2 ' -azobis (2-methylpropanenitrile), 2 ' -azobis (2, 4-dimethylvaleronitrile), 2 ' -azobis (2-methylbutyronitrile), benzoyl peroxide; preferably, the initiator is benzoyl peroxide.
S. organic solvent
Examples of suitable organic solvents for use in the present invention may be selected from, but are not limited to, diisodecyl phthalate, diisooctyl adipate, diisooctyl phthalate, dioctyl adipate, 2-ethyl-1-hexanol, isooctanol, polyethylene glycol, polypropylene glycol, polybutylene glycol, liquid polybutene, liquid polyisobutylene, fatty alcohol polyoxyethylene ether, polyether ester, polyether amine, alone or in combination; preferably, the organic solvent is polypropylene glycol or fatty alcohol-polyoxyethylene ether.
K. Hydrophobic particles
The hydrophobic particles are inorganic hydrophobic particles, and specific examples include, but are not limited to, magnesium salts of fatty acids, calcium salts of fatty acids, aluminum salts of fatty acids, zinc salts of fatty acids, granular polyisobutylene, granular polymethacrylic acid resin, granular polyacrylic acid resin, granular silicone resin and white carbon black, which can be used alone or in combination; preferably, the hydrophobic particles are granular polyisobutylene, granular polymethacrylic resin, granular polyacrylic resin, granular organic silicon resin and white carbon black.
The defoaming agent composition disclosed by the invention is applied to defoaming and foam inhibiting in a system rich in anionic surfactant, such as defoaming and foam inhibiting in the industries of papermaking, water treatment, textile and the like.
Detailed Description
Example 1
1) Taking 5g of butyl acrylate, 15g of polypropylene glycol and 0.03g of benzoyl peroxide, and preparing a polymer X according to a solution polymerization method known in the industry;
2) taking 12g of lauryl acrylate, stearyl acrylate, 20g of polypropylene glycol and 0.03g of benzoyl peroxide, and preparing a polymer Y according to a solution polymerization method known in the industry;
3) taking 5g of butyl acrylate, 12g of dodecyl acrylate and octadecyl acrylate, 5g of double-end vinyl-terminated polysiloxane, 6.9g of granular polyisobutylene, 19g of polypropylene glycol and 0.04g of benzoyl peroxide, and preparing a polymer Z according to a solution polymerization method known in the industry;
4) the polymer X, Y, Z is evenly mixed by a shearing device to obtain a polymer defoamer composition P
Example 2
1) Taking 12.5g of isooctyl acrylate, 16g of isooctanol and 0.33g of 2, 2' -azobis (2-methylbutyronitrile), and preparing a polymer X according to a solution polymerization method known in the industry;
2) preparing polymer Y by taking 9g of octadecyl acrylate, 16g of isooctanol and 0.33g of 2, 2' -azobis (2-methylbutyronitrile) according to a solution polymerization method known in the industry;
3) taking 12.5g of isooctyl acrylate, 9g of octadecyl acrylate, 3g of diethylene glycol dimethacrylate, 5g of granular polymethacrylic resin, 16g of isooctyl alcohol and 0.34g of 2, 2' -azobis (2-methylbutyronitrile), and preparing a polymer Z according to a solution polymerization method known in the industry;
4) the polymer X, Y, Z is evenly mixed by a shearing device to obtain a polymer defoamer composition P
Example 3
1) Taking 12.5g of isooctyl methacrylate, 15g of polyethylene glycol and 0.33g of 2, 2' -azobis (2-methyl propionitrile), and preparing a polymer X according to a solution polymerization method known in the industry;
2) preparing polymer Y by taking 2.5g of alpha-dodecene, 25g of polyethylene glycol and 0.33g of 2, 2' -azobis (2-methyl propionitrile) according to a solution polymerization method known in the industry;
3) taking 12.5g of isooctyl methacrylate, 2.5g of alpha-dodecene, 4.9g of divinyl benzene, 4.1g of granular polymethacrylic resin, 20g of polyethylene glycol and 0.34g of 2, 2' -azobis (2-methylpropanenitrile), and preparing a polymer Z according to a solution polymerization method known in the industry;
4) the polymer X, Y, Z is evenly mixed by a shearing device to obtain a polymer defoamer composition P
Example 4
1) Taking 10.5g of methyl acrylate, 20g of polytetramethylene glycol and 0.33g of 2, 2' -azobis (2, 4-dimethylvaleronitrile), and preparing a polymer X according to a solution polymerization method known in the industry;
2) taking 2.5g of alpha-tetradecene, 20g of polytetramethylene glycol and 0.33g of 2, 2' -azobis (2, 4-dimethylvaleronitrile), and preparing a polymer Y according to a solution polymerization method known in the industry;
3) taking 10.5g of methyl acrylate, 2.5g of alpha-tetradecene, 5g of 1, 3-butanediol dimethacrylate, 8g of granular polyacrylic resin, 20g of polytetramethylene glycol and 0.34g of 2, 2' -azobis (2, 4-dimethylvaleronitrile), and preparing a polymer Z according to a solution polymerization method known in the industry;
4) the polymer X, Y, Z is evenly mixed by a shearing device to obtain a polymer defoamer composition P
Example 5
1) Taking 2.5g of hydroxyethyl acrylate, 19g of 2-ethyl-1-hexanol, 0.26g of 2,2 '-azobis (2-methylpropionitrile) and 2, 2' -azobis (2-methylbutyronitrile), and preparing a polymer X according to a solution polymerization method known in the industry;
2) taking 12.5g of octadecyl acrylate and octadecyl methacrylate, 19.6g of polypropylene glycol and 0.26g of 2, 2' -azobis (2-methylpropanenitrile), and preparing a polymer Y according to a solution polymerization method known in the industry;
3) preparing polymer Z by taking 2.5g of hydroxyethyl acrylate, 12.5g of stearyl acrylate and stearyl methacrylate, 3.6g of vinyl MQ silicon resin, 8g of granular polyacrylic resin, 19g of polypropylene glycol and 0.28g of 2, 2' -azobis (2-methylbutyronitrile) according to a solution polymerization method known in the industry;
4) the polymer X, Y, Z is evenly mixed by a shearing device to obtain a polymer defoamer composition P
Example 6
1) Taking 7.5g of hydroxypropyl acrylate, 19.4g of fatty alcohol-polyoxyethylene ether and 0.3g of benzoyl peroxide, and preparing a polymer X according to a solution polymerization method known in the industry;
2) taking 7.8g of lauryl methacrylate, 2.5g of alpha-hexadecene, 15.4g of fatty alcohol-polyoxyethylene ether and 0.3g of 2, 2' -azobis (2, 4-dimethylvaleronitrile), and preparing a polymer Y according to a solution polymerization method known in the industry;
3) preparing polymer Z by taking 7.5g of hydroxypropyl acrylate, 7.8g of lauryl methacrylate, 2.5g of alpha-hexadecene, 3.3g of ethylene glycol dimethacrylate, 8g of white carbon black, 17.4g of fatty alcohol-polyoxyethylene ether and 0.3g of benzoyl peroxide according to a solution polymerization method known in the industry;
4) the polymer X, Y, Z is evenly mixed by a shearing device to obtain a polymer defoamer composition P
Example 7
1) Taking 7.5g of butyl methacrylate, 4g of hydroxypropyl acrylate, 19g of diisodecyl phthalate and 0.2g of 2, 2' -azobis (2-methylpropanenitrile), and preparing a polymer X according to a solution polymerization method known in the industry;
2) taking 2.3g of alpha-styrene, 10g of octadecyl methacrylate, 16g of diisodecyl phthalate and 0.2g of 2, 2' -azobis (2-methylpropanenitrile), and preparing a polymer Y according to a solution polymerization method known in the industry;
3) taking 7.5g of butyl methacrylate, 4g of hydroxypropyl acrylate, 2.3g of alpha-styrene, 5g of octadecyl methacrylate, 1.8g of allyl methacrylate, 3g of granular polyacrylic resin and white carbon black, 17g of diisodecyl phthalate and 0.2g of 2, 2' -azobis (2-methylpropionitrile), and preparing a polymer Z according to a solution polymerization method known in the industry;
4) the polymer X, Y, Z is evenly mixed by a shearing device to obtain a polymer defoamer composition P
Example 8
1) Preparing polymer X by taking 9g of butyl acrylate, 6g of hydroxyethyl methacrylate and hydroxypropyl methacrylate, 17.7 g of diisooctyl adipate and 0.3g of 2, 2' -azobis (2, 4-dimethylvaleronitrile) according to a solution polymerization method known in the industry;
2) taking 2.6g of alpha-octene, 17.7 g of diisooctyl adipate and 0.3g of 2, 2' -azobis (2, 4-dimethylvaleronitrile), and preparing a polymer Y according to a solution polymerization method known in the industry;
3) preparing polymer Z by taking 9g of butyl acrylate, 6g of hydroxyethyl methacrylate and hydroxypropyl methacrylate, 2.6g of alpha-octene, 4.8g of tetravinyl tetramethylcyclotetrasiloxane, 6g of granular polyacrylic resin and white carbon black, 17.7 g of diisooctyl adipate and 0.3g of 2, 2' -azo-bis (2, 4-dimethyl valeronitrile) according to a solution polymerization method known in the industry;
4) the polymer X, Y, Z is evenly mixed by a shearing device to obtain a polymer defoamer composition P
Example 9
1) Taking 12.5g of isooctyl acrylate and isooctyl methacrylate, 4g of hydroxyethyl acrylate, 8g of diisooctyl phthalate, 0.2g of 2,2 '-azobis (2-methylpropionitrile) and 2, 2' -azobis (2-methylbutyronitrile), and preparing a polymer X according to a solution polymerization method known in the industry;
2) taking 12.5g of octadecyl acrylate and dodecyl methacrylate, 12g of diisooctyl phthalate, 0.2g of 2,2 '-azobis (2-methylpropanenitrile) and 2, 2' -azobis (2-methylbutyronitrile), and preparing a polymer Y according to a solution polymerization method known in the industry;
3) taking 12.5g of isooctyl acrylate and isooctyl methacrylate, 4g of hydroxyethyl acrylate, 12.5g of octadecyl acrylate and dodecyl methacrylate, 4.4g of a mixture of allyl methacrylate and ethylene glycol dimethacrylate, 7g of magnesium fatty acid, 10g of diisooctyl phthalate, 0.2g of 2,2 '-azobis (2-methylpropionitrile) and 2, 2' -azobis (2-methylbutyronitrile), preparing a polymer Z according to a solution polymerization method known in the industry;
4) the polymer X, Y, Z is evenly mixed by a shearing device to obtain a polymer defoamer composition P
Example 10
1) Taking 5.2g of ethyl methacrylate, 18g of dioctyl adipate, 0.05g of 2, 2' -azobis (2, 4-dimethylvaleronitrile) and benzoyl peroxide, and preparing a polymer X according to a solution polymerization method known in the industry;
2) taking 10g of octadecyl methacrylate, 2.5g of alpha-eicosene, 22g of dioctyl adipate, 0.05g of 2, 2' -azobis (2, 4-dimethylvaleronitrile) and benzoyl peroxide, and preparing a polymer Y according to a solution polymerization method known in the industry;
3) taking 5.2g of ethyl methacrylate, 9.95g of stearyl methacrylate, 2.5g of alpha-eicosene, 3.5g of divinyl benzene and divinyl-terminated polysiloxane, 1.00g of aluminum fatty acid and granular polyisobutylene, 20g of dioctyl adipate, 0.05g of 2, 2' -azobis (2, 4-dimethylvaleronitrile) and benzoyl peroxide, preparing the polymer Z according to a solution polymerization method known in the industry;
4) the polymer X, Y, Z is evenly mixed by a shearing device to obtain a polymer defoamer composition P
Example 11
1) Taking 7.5g of ethyl acrylate and methyl methacrylate, 7.5g of hydroxypropyl acrylate, 20g of liquid polybutene and 0.22g of benzoyl peroxide, and preparing a polymer X according to a solution polymerization method known in the industry;
2) taking 1.17g C20-alpha olefin, 24g of liquid polybutene and 0.22g of benzoyl peroxide, and preparing a polymer Y according to a solution polymerization method known in the industry;
3) taking 7.5g of ethyl acrylate and methyl methacrylate, 7.5g of hydroxypropyl acrylate, 1.17g C20-alpha olefin, 4.6g of a mixture of diethylene glycol dimethacrylate and vinyl MQ silicon resin, 2.4g of granular polyacrylic resin and white carbon black, 16g of liquid polybutene and 0.22g of benzoyl peroxide, and preparing the polymer Z according to a solution polymerization method known in the industry;
4) the polymer X, Y, Z is evenly mixed by a shearing device to obtain a polymer defoamer composition P
Example 12
1) Taking 12.5g of ethyl methacrylate, 5.5g of hydroxyethyl methacrylate, 16.6g of liquid polyisobutene and 0.3g of 2, 2' -azobis (2-methylbutyronitrile), and preparing a polymer X according to a solution polymerization method known in the industry;
2) taking 2.4g of alpha-dodecene and alpha-octadecene, 16.8g of liquid polyisobutene and 0.3g of 2, 2' -azobis (2-methylbutyronitrile), and preparing a polymer Y according to a solution polymerization method known in the industry;
3) taking 12.5g of ethyl methacrylate, 5.5g of hydroxyethyl methacrylate, 2.4g of alpha-dodecene and alpha-octadecene, 4.5g of double-end vinyl terminated polysiloxane, 3.8g of fatty acid calcium and fatty acid zinc, 16.6g of liquid polyisobutene and 0.3g of 2, 2' -azobis (2-methylbutyronitrile), and preparing the polymer Z according to a solution polymerization method known in the industry;
4) the polymer X, Y, Z is evenly mixed by a shearing device to obtain a polymer defoamer composition P
Example 13
1) Taking 11.5g of butyl acrylate and butyl methacrylate, 19g of polypropylene glycol and fatty alcohol-polyoxyethylene ether and 0.15g of 2, 2' -azobis (2-methyl propionitrile), and preparing a polymer X according to a solution polymerization method known in the industry;
2) taking 5g of stearyl methacrylate, 0.25g of alpha-decene, 19g of polypropylene glycol, fatty alcohol-polyoxyethylene ether and 0.15g of 2, 2' -azobis (2-methylpropanenitrile), and preparing a polymer Y according to a solution polymerization method known in the industry;
3) taking 11.5g of butyl acrylate and butyl methacrylate, 5g of stearyl methacrylate, 0.25g of alpha-decene, 3.2g of vinyl MQ silicon resin, 5.85g of white carbon black, 19g of polypropylene glycol and fatty alcohol polyoxyethylene ether and 0.15g of 2, 2' -azobis (2-methylpropanenitrile), and preparing a polymer Z according to a solution polymerization method known in the industry;
4) the polymer X, Y, Z is evenly mixed by a shearing device to obtain a polymer defoamer composition P
Example 14
1) 4g of hydroxypropyl acrylate, 19g of fatty alcohol-polyoxyethylene ether and 0.18g of 2, 2' -azobis (2-methyl propionitrile) are taken to prepare a polymer X according to a solution polymerization method known in the industry;
2) taking 12.5g of lauryl acrylate, 2.5g of alpha-octadecene, 19g of fatty alcohol-polyoxyethylene ether and 0.18g of 2, 2' -azobis (2-methyl propionitrile), and preparing a polymer Y according to a solution polymerization method known in the industry;
3) 4g of hydroxypropyl acrylate and hydroxybutyl acrylate, 12.5g of dodecyl acrylate, 2.5g of alpha-octadecene, 0.5g of ethylene glycol dimethacrylate, 3.96g of fatty acid zinc, 19g of fatty alcohol polyoxyethylene ether and 0.18g of 2, 2' -azobis (2-methylpropanenitrile) are taken, and the polymer Z is prepared according to a solution polymerization method known in the industry;
4) the polymer X, Y, Z is evenly mixed by a shearing device to obtain a polymer defoamer composition P
Example 15
1) Taking 12g of butyl acrylate, 4.7g of hydroxyethyl acrylate, 14.12g of diisooctyl adipate, polypropylene glycol and 0.08g of 2, 2' -azobis (2, 4-dimethylvaleronitrile), and preparing a polymer X according to a solution polymerization method known in the industry;
2) taking 7.5g of lauryl methacrylate, 1g of alpha-methylstyrene, 14.12g of diisooctyl adipate, polypropylene glycol and 0.08g of 2, 2' -azobis (2, 4-dimethylvaleronitrile), and preparing a polymer Y according to a solution polymerization method known in the industry;
3) taking 12g of butyl acrylate, 4.7g of hydroxyethyl acrylate, 7.5g of lauryl methacrylate, 1g of alpha-methylstyrene, 5g of allyl methacrylate, 2g of aluminum fatty acid, 14.12g of diisooctyl adipate, polypropylene glycol and 0.08g of 2, 2' -azobis (2, 4-dimethylvaleronitrile), and preparing a polymer Z according to a solution polymerization method known in the industry;
4) the polymer X, Y, Z is evenly mixed by a shearing device to obtain a polymer defoamer composition P
Example 16
1) Taking 10g of isooctyl acrylate, 6.41g of hydroxypropyl methacrylate, 13.3g of dioctyl adipate, 0.13g of 2,2 '-azobis (2-methylpropanenitrile) and 2, 2' -azobis (2-methylbutyronitrile), and preparing a polymer X according to a solution polymerization method known in the industry;
2) taking 10g of octadecyl acrylate, 2g of alpha-dodecene, 13.3g of isooctanol, 0.13g of 2,2 '-azobis (2-methylpropanenitrile) and 2, 2' -azobis (2-methylbutyronitrile), and preparing a polymer Y according to a solution polymerization method known in the industry;
3) taking 10g of isooctyl acrylate, 6.3g of hydroxypropyl methacrylate, 10g of octadecyl acrylate, 2g of alpha-dodecene, 2g of allyl methacrylate and ethylene glycol dimethacrylate, 1g of calcium fatty acid, 13.3g of dioctyl adipate and isooctyl alcohol, 0.13g of 2,2 '-azobis (2-methylpropanenitrile) and 2, 2' -azobis (2-methylbutyronitrile), and preparing the polymer Z according to a solution polymerization method known in the industry;
4) the polymer X, Y, Z is evenly mixed by a shearing device to obtain a polymer defoamer composition P
Example 17
1) Taking 7.5g of hydroxyethyl acrylate, hydroxypropyl acrylate, 19.2g of polyether ester, 0.3g of 2, 2' -azobis (2, 4-dimethylvaleronitrile) and benzoyl peroxide, and preparing a polymer X according to a solution polymerization method known in the industry;
2) taking 8g of octadecyl acrylate, 2.5g of alpha-triacontene and alpha-tetradecene, 18g of polyether amine, 0.3g of 2, 2' -azobis (2, 4-dimethylvaleronitrile) and benzoyl peroxide, and preparing a polymer Y according to a solution polymerization method known in the industry;
3) taking 7.5g of hydroxyethyl acrylate and hydroxypropyl acrylate, 8g of octadecyl acrylate, 2.5g of alpha-triacontene and alpha-tetradecene, 4g of divinyl benzene and vinyl-terminated polysiloxane, 3.9g of fatty acid aluminum and granular silicone resin, 18g of polyether ester, 0.3g of 2, 2' -azobis (2, 4-dimethylvaleronitrile) and benzoyl peroxide, and preparing the polymer Z according to a solution polymerization method known in the industry;
4) the polymer X, Y, Z is evenly mixed by a shearing device to obtain a polymer defoamer composition P
Comparative example 1
A mineral oil defoamer prepared according to patent CN102120106A, example 1.
Comparative example 2
Silicone defoamer prepared according to example 1 of patent CN 102343165A.
Comparative example 3
Polyether defoamer prepared according to example 1 of patent CN 102126763A.
Comparative example 4
EBS defoamer prepared according to example 1 of patent CN 101362063A.
Comparative example 5
1) Taking 21g of ethyl methacrylate, 10.6g of hydroxyethyl methacrylate, 29g of liquid polyisobutene and 1.9g of 2, 2' -azobis (2-methylbutyronitrile), and preparing a polymer X by a solution polymerization method known in the industry;
2) taking 6.6g of alpha-dodecene and alpha-octadecene, 29g of liquid polyisobutene and 1.9g of 2, 2' -azobis (2-methylbutyronitrile), and preparing a polymer Y according to a solution polymerization method known in the industry;
3) the polymer X, Y is evenly mixed by a shearing device to obtain a polymer defoamer composition P
Comparative example 6
1) Taking 16.1g of butyl methacrylate, 4g of hydroxypropyl acrylate, 26g of diisodecyl phthalate and 1.5g of 2, 2' -azobis (2-methylpropanenitrile), and preparing a polymer X according to a solution polymerization method known in the industry;
2) taking 16.1g of butyl methacrylate, 4g of hydroxypropyl acrylate, 1.8g of allyl methacrylate, 3g of granular polyacrylic resin and white carbon black, 26g of diisodecyl phthalate and 1.5g of 2, 2' -azobis (2-methylpropanenitrile), and preparing a polymer Z according to a solution polymerization method known in the industry;
3) the polymer X, Z is evenly mixed by a shearing device to obtain a polymer defoamer composition P
Comparative example 7
1) Taking 9g of alpha-tetradecene, 29g of polytetramethylene glycol and 1.5g of 2, 2' -azobis (2, 4-dimethylvaleronitrile), and preparing a polymer Y according to a solution polymerization method known in the industry;
2) taking 13g of alpha-tetradecene, 9g of double-end vinyl-terminated polysiloxane, 8g of granular polyacrylic resin, 29g of polytetramethylene glycol and 1.5g of 2, 2' -azobis (2, 4-dimethylvaleronitrile), and preparing a polymer Z according to a solution polymerization method known in the industry;
3) the polymer Y, Z is evenly mixed by a shearing device to obtain a polymer defoamer composition P
Comparative example 8
1) Taking 15g of hydroxyethyl acrylate, 18.4g of hydroxypropyl acrylate, 0.3g of 2, 2' -azobis (2, 4-dimethylvaleronitrile) and benzoyl peroxide, and preparing a polymer X according to a solution polymerization method known in the industry;
2) taking 8g of octadecyl acrylate, 2.5g of alpha-triacontene and alpha-tetradecene, 18.4g of polyether ester, 0.3g of 2, 2' -azobis (2, 4-dimethylvaleronitrile) and benzoyl peroxide, and preparing a polymer Y according to a solution polymerization method known in the industry;
3) taking 8g of octadecyl acrylate, 2.5g of alpha-triacontene and alpha-tetradecene, 4g of divinyl benzene and divinyl terminated polysiloxane, 3.9g of fatty acid aluminum and granular polyisobutylene, 18.4g of polyether ester, 0.3g of 2, 2' -azobis (2, 4-dimethylvaleronitrile) and benzoyl peroxide, and preparing the polymer Z according to a solution polymerization method known in the industry;
4) the polymer X, Y, Z is evenly mixed by a shearing device to obtain a polymer defoamer composition P
Comparative example 9
1) Taking 12g of butyl acrylate, 4.7g of hydroxyethyl acrylate, 14.12g of diisooctyl adipate, polypropylene glycol and 0.08g of 2, 2' -azobis (2, 4-dimethylvaleronitrile), and preparing a polymer X according to a solution polymerization method known in the industry;
2) taking 11.5g of lauryl methacrylate, 5.5g of alpha-methylstyrene, 14.12g of diisooctyl adipate, polypropylene glycol and 0.08g of 2, 2' -azobis (2, 4-dimethylvaleronitrile), and preparing a polymer Y according to a solution polymerization method known in the industry;
3) taking 12g of butyl acrylate, 4.7g of hydroxyethyl acrylate, 5g of allyl methacrylate, 2g of aluminum fatty acid, 14.12g of diisooctyl adipate, polypropylene glycol and 0.08g of 2, 2' -azobis (2, 4-dimethylvaleronitrile), and preparing a polymer Z according to a solution polymerization method known in the industry;
4) the polymer X, Y, Z is evenly mixed by a shearing device to obtain a polymer defoamer composition P
Comparative example 10
1) Taking 10.2g of ethyl methacrylate, 20g of dioctyl adipate, 0.05g of 2, 2' -azobis (2, 4-dimethylvaleronitrile) and benzoyl peroxide, and preparing a polymer X according to a solution polymerization method known in the industry;
2) taking 15.7g of octadecyl methacrylate, 9.5g of alpha-eicosene, 20g of dioctyl adipate, 0.05g of 2, 2' -azobis (2, 4-dimethylvaleronitrile) and benzoyl peroxide, and preparing a polymer Y according to a solution polymerization method known in the industry;
3) 3.5g of bisvinylbenzene and a bisvinyl-terminated polysiloxane, 0.95g of aluminum fatty acid and granular polyisobutylene, 20g of dioctyl adipate, 0.05g of 2, 2' -azobis (2, 4-dimethylvaleronitrile) and benzoyl peroxide were taken to prepare a polymer Z according to a solution polymerization method well known in the industry;
4) the polymer X, Y, Z is evenly mixed by a shearing device to obtain a polymer defoamer composition P
Defoaming and foam suppressing performance test
Method for testing papermaking black liquor system
Adding 600mL of papermaking pulping black liquor into a circulating bubbler with a glass tube with scales of 0-500 mL and an inner diameter of 5cm, enabling the liquid level of the papermaking pulping black liquor to reach the position of '0 mL' of the lowest scale, then setting the temperature to be 80 ℃, the flow to be 6L/min and the voltage to be 220V, then opening a temperature control switch, heating the papermaking pulping black liquor to the set temperature, starting a circulating pump to start impact foaming, adding 0.2mL of defoaming agent when foam rises to the position of 350mL, and recording the change of the foam height along with the time. The shorter the time for the foam to reach the lowest scale is, and the lower the scale reached is, the better the instant defoaming performance of the defoaming agent is; the longer the time elapsed at which the foam regained 350mL, indicates the better foam suppression performance of the defoamer
Claims (10)
1. The defoaming composition is characterized by comprising the following components:
a: methyl/alkyl acrylate monomer
The alkyl number of the methyl/alkyl acrylate monomer is 1-8, the methyl/alkyl acrylate monomer is one or a mixture of acrylic ester and methacrylic ester, and the methyl/alkyl acrylate monomer is specifically selected from methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and isooctyl methacrylate, and the using amount of the methyl/alkyl acrylate monomer accounts for 10-25% of the total mass of the defoaming composition;
b: hydroxyalkyl methyl/acrylate monomers
The methyl/hydroxyalkyl acrylate monomer is one or a mixture of hydroxyalkyl acrylate and hydroxyalkyl methacrylate, is specifically selected from hydroxyalkyl acrylate and hydroxyalkyl methacrylate, is specifically but not limited to hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate, and accounts for 5-15% of the total mass of the defoaming composition;
c: crosslinker monomers
The cross-linking agent monomer is a monomer which at least contains two or more vinyl groups in one molecule and can form a polymer soluble in an organic solvent; selected from allyl methacrylate, methacrylic acid polyol esters (ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1, 3-butylene glycol dimethacrylate), divinyl benzene, double-end vinyl-terminated polysiloxane, tetravinyl tetramethylcyclotetrasiloxane and vinyl MQ silicon resin, can be used independently or mixed at any proportion, and the using amount accounts for 0.5-5% of the total mass of the defoaming composition;
d: methyl/alkyl acrylate monomer
The alkyl number of the methyl/alkyl acrylate is 9-18, the methyl/alkyl acrylate is one or more of alkyl acrylate and alkyl methacrylate, and is specifically selected from one or more of lauryl acrylate, stearyl acrylate, lauryl methacrylate and stearyl methacrylate, and the dosage of the methyl/alkyl acrylate accounts for 10-25% of the total mass of the defoaming composition;
o: olefin monomer
The olefin monomer is any one or more of linear alpha-olefin, alpha-aromatic olefin or branched alpha-olefin, and is specifically selected from one or more of alpha-octene, alpha-decene, alpha-dodecene, alpha-tetradecene, alpha-hexadecene, alpha-octadecene, alpha-eicosene, C20-C24 linear alpha-olefin mixtures, C24-C28 linear alpha-olefin mixtures, alpha-triacontene, alpha-methylstyrene and alpha-styrene; the using amount accounts for 0.5-5% of the total mass of the defoaming composition;
i: initiator
The initiator is selected from 2,2 ' -azobis (2-methylpropionitrile), 2 ' -azobis (2, 4-dimethylvaleronitrile), 2 ' -azobis (2-methylbutyronitrile) and benzoyl peroxide; the using amount accounts for 0.1-1% of the total mass of the defoaming composition;
s: organic solvent
The organic solvent is selected from diisodecyl phthalate, diisooctyl adipate, diisooctyl phthalate, dioctyl adipate, 2-ethyl-1-hexanol, isooctyl alcohol, polyethylene glycol, polypropylene glycol, polybutylene glycol, liquid polybutylene, liquid polyisobutylene, fatty alcohol-polyoxyethylene ether, polyether ester and polyether amine, and can be used alone or mixed; the using amount accounts for 30-60% of the total mass of the defoaming composition;
k: hydrophobic particles
The hydrophobic particles are inorganic hydrophobic particles, are selected from fatty acid magnesium salt, fatty acid calcium salt, fatty acid aluminum salt, fatty acid zinc salt, particle polyisobutylene, particle polymethacrylic resin, particle polyacrylic resin, particle organic silicon resin and white carbon black, and can be used singly or in a mixed way; the amount of the defoaming composition is 1-8% of the total mass of the defoaming composition.
2. The defoaming composition of claim 1 wherein the amount of the methyl/alkyl acrylate (alkyl 1-8) monomer A is 15-20% by weight of the total defoaming composition, the dosage of the methyl/acrylic acid hydroxyalkyl ester monomer B accounts for 8-12% of the total mass of the defoaming composition, the amount of the methyl/alkyl acrylate (alkyl number 9-18) monomer D accounts for 15-20% of the total mass of the defoaming composition, the dosage of the olefin monomer O accounts for 2-4% of the total mass of the defoaming composition, the dosage of the cross-linking agent monomer C accounts for 2-4% of the total mass of the defoaming composition, the amount of the organic solvent S accounts for 40-50% of the total mass of the defoaming composition, the amount of the hydrophobic particles K accounts for 3-6% of the total mass of the defoaming composition, and the amount of the initiator I accounts for 0.4-0.8% of the total mass of the defoaming composition.
3. The defoaming composition of claim 1 wherein said methyl/alkyl acrylate monomer a is selected from the group consisting of
Butyl acrylate, isooctyl methacrylate.
4. The defoamer composition of claim 1, wherein said methyl/alkyl acrylate monomer B is selected from the group consisting of hydroxyethyl acrylate and hydroxypropyl acrylate.
5. The defoaming composition of claim 1 wherein said olefinic monomer O is selected from the group consisting of α -dodecene, α -tetradecene, α -hexadecene, α -octadecene, α -methylstyrene, and α -styrene.
6. The defoamer composition of claim 1, wherein said crosslinker monomer C is selected from the group consisting of allyl methacrylate, ethylene glycol dimethacrylate, double-ended vinyl terminated polysiloxane, vinyl MQ silicone.
7. The defoaming composition of claim 1 wherein said initiator I is benzoyl peroxide.
8. The defoaming composition of claim 1 wherein the organic solvent S is selected from the group consisting of polypropylene glycol and fatty alcohol polyoxyethylene ether.
9. The defoaming composition of claim 1 wherein said hydrophobic particles K are particulate polyisobutylene, particulate polymethacrylic resin, particulate polyacrylic resin, particulate silicone resin, white carbon black.
10. The defoaming composition of claim 1 prepared by the following method:
1) preparing a polymer X by using a methyl/alkyl acrylate (alkyl number is 1-8) monomer A and/or a methyl/hydroxyalkyl acrylate B, an organic solvent S and an initiator I according to a solution polymerization method known in the industry;
2) preparing a polymer Y by using a methyl/alkyl acrylate (alkyl number is 9-18) monomer D and/or an olefin monomer O, an organic solvent S and an initiator I according to a solution polymerization method known in the industry;
3) preparing a polymer Z by all monomers used by a polymer X and a polymer Y, a cross-linking agent monomer C, hydrophobic particles K, an organic solvent S and an initiator I according to a solution polymerization method known in the industry;
4) the polymer X, Y, Z was mixed well by a shearing device to give a defoamer composition.
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| PCT/CN2021/132745 WO2023040045A1 (en) | 2021-09-18 | 2021-11-24 | Defoaming composition |
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| CN115317963A (en) * | 2022-10-17 | 2022-11-11 | 烟台恒鑫化工科技有限公司 | Organic silicon defoaming agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103641195A (en) * | 2013-12-13 | 2014-03-19 | 深圳市安品有机硅材料有限公司 | Organic silicon defoamer and preparation method thereof |
| CN108786188A (en) * | 2017-05-05 | 2018-11-13 | 江苏四新科技应用研究所股份有限公司 | A kind of non-silicon defoaming agent |
| CN111013201A (en) * | 2019-12-03 | 2020-04-17 | 江苏四新科技应用研究所股份有限公司 | Defoaming agent composition |
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| CN103272411B (en) * | 2013-06-07 | 2015-03-18 | 南京四新科技应用研究所有限公司 | Foam inhibitor and preparation method thereof |
| WO2019000339A1 (en) * | 2017-06-29 | 2019-01-03 | Kemira Oyj | Aqueous emulsion and use thereof |
| CN110201427A (en) * | 2019-05-09 | 2019-09-06 | 江苏四新科技应用研究所股份有限公司 | A kind of polymer defoaming agent and preparation method thereof |
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| CN103641195A (en) * | 2013-12-13 | 2014-03-19 | 深圳市安品有机硅材料有限公司 | Organic silicon defoamer and preparation method thereof |
| CN108786188A (en) * | 2017-05-05 | 2018-11-13 | 江苏四新科技应用研究所股份有限公司 | A kind of non-silicon defoaming agent |
| CN111013201A (en) * | 2019-12-03 | 2020-04-17 | 江苏四新科技应用研究所股份有限公司 | Defoaming agent composition |
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| CN115317963A (en) * | 2022-10-17 | 2022-11-11 | 烟台恒鑫化工科技有限公司 | Organic silicon defoaming agent and preparation method thereof |
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