CN107880203A - A kind of copolymer rheology modifier and its preparation method and application composition - Google Patents
A kind of copolymer rheology modifier and its preparation method and application composition Download PDFInfo
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- CN107880203A CN107880203A CN201711157685.0A CN201711157685A CN107880203A CN 107880203 A CN107880203 A CN 107880203A CN 201711157685 A CN201711157685 A CN 201711157685A CN 107880203 A CN107880203 A CN 107880203A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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Abstract
The invention provides a kind of preparation method of copolymer rheology modifier：Initiator, dispersant and the crosslinking agent needed for containing at least organic inert solvent of 55wt% varsol, 15wt%~20wt% monomer and reaction are added in reaction vessel；Then it is added to after being mixed containing initiator, dispersant and the crosslinking agent needed at least organic inert solvent of 55wt% esters solvent, remaining monomer and reaction in reaction vessel；Reactant is warming up to 55~75 DEG C and adds initiator after being added dropwise, 1~4h of insulation makes the monomer in reaction system react completely, terminates to react and discharge.It is an object of the invention to provide a kind of copolymer rheology modifier, its be used for formula containing soap base and containing gentle table live be formulated when, the inferior position of formula containing soap base and the work formula containing gentle table can not effectively be thickened by changing traditional acrylic thickener, while can also show excellent suspendability.
Description
Technical field
The present invention relates to high molecular polymer field, especially a kind of copolymer rheology modifier and preparation method thereof and should
Use composition.
Background technology
In thickener field, unsaturated carboxylic acid polymer has good thickening property, improves the thixotropic property of gel rubber system
And stability, it is widely used in the fields such as daily cosmetics, medicine and oil exploitation.Agent for polyacrylic acid thickening typically refer to by
The monomers such as acrylic or methacrylic acid are through appropriately crosslinked obtained polymer.
This kind of polymer such as ZL201510314199.X discloses a kind of fast wetting polymers of carboxylic acid thickener and its preparation
Method, its preparation method be specially added in reaction vessel containing at least organic inert solvent of 55wt% varsol,
Initiator, dispersant and crosslinking agent needed for 15wt%~20wt% monomer and reaction, it is anti-under conditions of 45~55 DEG C
Answer 30~60min；Then at least organic inert solvent of 55wt% esters solvent, remaining monomer and reaction institute will be contained
It was added to after the initiator, dispersant and the crosslinking agent mixing that need in 3~6 hours in reaction vessel, reaction temperature is constant；Reaction
Thing is warming up to 55~75 DEG C and adds initiator after being added dropwise, 1~4h of insulation makes the monomer in reaction system react completely, ties
Shu Fanying simultaneously discharges.Its obtained polymer has the advantages of fast wetting and larger bulk density.
As well known to a person skilled in the art the acrylic resin obtained by precipitation polymerization is applied to gel-type body
In system, if for formula containing soap base and containing gentle table live be formulated when, its thicken and suspension effect it is not ideal.
In order to solve the problem, those skilled in the art by develop the acrylate copolymer of emulsion-type reach thickening and
The effect of suspension, as ZL2007800082086 discloses a kind of liquid soap composition, comprising：(a) about 1-50wt% aliphatic acid
Salt；(b) the swellable acrylic emulsion polymer of the alkali of about 0.1-10wt% crosslinkings；About 0.1-20wt% acidulant (c).
The liquid soap composition shows good stability under elevated storage temperature.
But the problem of can not ignoring is, the acrylate copolymer of emulsion-type has more for temperature, transportation stability
Harsh requirement, easily it is demulsified under high temperature or low temperature condition or in the case of strenuous vibration.
So if a kind of thickening agent of copolymer of powdered acrylic compounds can be developed, with similar to breast
The characteristic of the carbomer thickeners of liquid type, then within the scope of more extensive temperature or severe fortune can passed through
What is showed after defeated link is more excellent.
The content of the invention
The present invention is intended to provide a kind of copolymer rheology modifier and its preparation method and application composition, when the copolymer
When thickener is for formula containing soap base and containing gentle table work formula, changing traditional acrylic thickener can not thicken containing soap
The inferior position of based formulas and formula of being lived containing gentle table, while excellent suspendability can also be showed.
It should be noted that：Wt% refers to mass percent in the present invention.
Technical scheme provided by the invention is：A kind of preparation method of copolymer rheology modifier, comprises the following steps：
Step 1：Added in reaction vessel containing at least organic inert solvent of 55wt% varsols, 15wt%~
Initiator, dispersant and crosslinking agent needed for 20wt% monomer and reaction, react 30 under conditions of 45~55 DEG C~
60min；
Step 2：By containing at least organic inert solvent of 55wt% esters solvents, remaining monomer and reaction needed for
It is added to after initiator, dispersant and crosslinking agent mixing in 3~6h in the reaction vessel of step 1, reaction temperature is constant；
Step 3：After being warming up to 55~75 DEG C, add initiator and being incubated 1~4h makes the monomer in reaction system completely anti-
Should, terminate to react and discharge；Preferably, increasing extent of temperature control is in the range of 5~15 DEG C.
Described monomer is by 85wt%~92.9wt% α, beta-unsaturated carboxylic acid and 7.1wt%~15wt% acrylic acid
C10~C20The C of Arrcostab or methacrylic acid10~C20Arrcostab forms；
Preferably, described monomer is by 85wt%~91.8wt% α, beta-unsaturated carboxylic acid and 8.2wt%~15wt%
Acrylic acid C10~C20The C of Arrcostab or methacrylic acid10~C20Arrcostab forms；
The gross weight of atent solvent in described step 1 and step 2 equivalent to material gross weight 80wt%~
90wt%.
Preferably, atent solvent in step 1 by 55wt%~100wt% varsol and 0wt%~45wt%
Esters solvent forms；
Atent solvent in step 2 is by 0wt%~45wt% varsol and 55wt%~100wt% esters solvent
Composition；
Atent solvent in step 1 accounts for 60wt%~80wt% of the total amount of organic inert solvent.
Preferably, atent solvent in step 1 by 70wt%~100wt% varsol and 0wt%~30wt%
Esters solvent forms；
Atent solvent in step 2 is by 0wt%~45wt% varsol and 55wt%~100wt% esters solvent
Composition；
Atent solvent in step 1 accounts for 60wt%~80wt% of the total amount of organic inert solvent.
It is further preferable that the atent solvent in step 1 accounts for 65wt%~75wt% of the total amount of organic inert solvent.
Preferably, in step 1, the initiator of addition accounts for 10wt%~30wt% of initiator gross weight；Point added
Powder accounts for 20wt%~40wt% of dispersant gross weight, the crosslinking agent of addition account for the 20wt% of crosslinking agent gross weight~
30wt%.
It is further preferable that in step 1, the initiator of addition accounts for 15wt%~25wt% of initiator gross weight；Add
Dispersant account for 25wt%~35wt% of dispersant gross weight, the crosslinking agent of addition account for the 22wt% of crosslinking agent gross weight~
28wt%.
Preferably, the dispersant in step 1 and 2 accounts for 2wt%~5wt% of total reactant, the crosslinking agent in step 1 and 2
Account for 1wt%~3wt% of total reactant, the initiator in step 1 and 2 accounts for 0.2wt%~0.5wt% of total reactant.Need
Illustrate, total reactant of the present invention is monomer, crosslinking agent, dispersant, the summation of initiator.
It is further preferable that the dispersant in step 1 and 2 accounts for 3.1wt%~3.9wt% of total reactant, in step 1 and 2
Crosslinking agent account for 2.1wt%~2.9wt% of total reactant, the initiator in step 1 and 2 account for the 0.2wt% of total reactant~
0.31wt%.
Preferably, in step 2, material is added in reaction vessel in a manner of being added dropwise；
In step 3, the dosage of the initiator in step 3 is no more than the 0.06wt% of total reactant.
It is further preferable that in step 3, the time of insulation is 2~3h；The dosage of initiator in step 3 accounts for total reactant
0.01wt%~0.03wt%.Drying steps in step 3 are specially the heating removing solvent under decompression or vacuum environment, are obtained
To white powder.
Preferably, described α, beta-unsaturated carboxylic acid be acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid,
One or more combinations in itaconic acid.
It is further preferable that described α, beta-unsaturated carboxylic acid be one kind in acrylic acid, methacrylic acid or fumaric acid or
A variety of combinations.
One or more combinations in described varsol n-hexane, isohexane, hexamethylene, benzene, solvent naphtha；It is described
Esters solvent for Ethyl formate, propyl formate, butyl acetate, propyl acetate, ethyl acetate, one kind or group in methyl acetate
Close.
It is further preferable that described varsol is one kind in hexamethylene, n-hexane；
Described esters solvent is one kind in propyl formate, ethyl acetate.
Preferably, described crosslinking agent is pentaerythritol triallyl ether, diethylene glycol (DEG) diallyl ether or sucrose pi-allyl
One or more combinations in ether.
Preferably, described dispersant is the dimerization hydroxy stearic acid ester of polyoxyethylene 30 and/or Span-80.But this hair
It is bright to be not limited only to this, in general it can select as sorbitan fatty ester, polyglyceryl fatty acid ester, sucrose fat
One or more combinations in acid esters, alkylbenzenesulfonate, polyoxyethylene fatty acid ester, polyoxyethylene alkyl ether sulfonate；
It can also select to be poly- containing PEO segment in the block copolymer with hydrophilic radical and with hydrophobic grouping
Compound or maleic anhydride modified polymer.
Preferably, described initiator is acetyl peroxide cyclohexylsulfonyl, peroxidating neodecanoic acid α-isopropyl phenyl ester, peroxide
Change neodecanoic acid -1,1- dimethyl -3- hydroxybutyls ester, dicetyl peroxydicarbonate two (3- methoxybutyls), dicetyl peroxydicarbonate two
Isopropyl ester, dicetyl peroxydicarbonate two (2- ethylhexyls), the new enanthic acid α-isopropyl phenyl ester of peroxidating, peroxy dicarbonate di-n-propyl ester
In one or more combinations, preferably acetyl peroxide cyclohexylsulfonyl.
It is further preferable that described initiator is acetyl peroxide cyclohexylsulfonyl or peroxy dicarbonate di-n-propyl ester.
The present invention also provides a kind of copolymer rheology modifier, and it is prepared by above-mentioned method.
Meanwhile the present invention also provides one kind containing soap-based compositions and containing gentle table work composition.
Specifically, containing the copolymerization being prepared in soap-based compositions containing 0.5wt%~3wt% methods as described above
Rheology modifier, 10wt%~20wt% soap base compositions.Soap base composition include but is not limited to lauric acid/dodecanoic acid, tetradecylic acid, hexadecylic acid,
The salt of stearic acid.
Containing the copolymer rheology being prepared in gentle table work composition containing 0.5wt%~3wt% methods described above
Modifying agent, 10wt%~20wt% amino acid surfactants.Amino acid surfactant includes but is not limited to lauroyl flesh ammonia
Sour sodium, sodium cocoyl glutamate.
Beneficial effects of the present invention
The acrylic copolymer thickener that the present invention is obtained by adjusting the dosage of function monomer to synthesize can be used in containing soap
During based formulas and the work containing gentle table are formulated, lacking for such formula can not effectively be thickened by changing traditional acrylic clear powder thickener
Fall into, and in the case where maintaining formula system viscosity higher, keep excellent suspension effect.
Embodiment
With reference to embodiment, technical scheme is described in further detail, but not formed pair
Any restrictions of the present invention.
Embodiment 1
Step 1：Added into 1000ml reactors 330g hexamethylenes, 15g acrylic acid, 1.1g lauryl methacrylates,
0.5g cane sugar allyl ethers, the dimerization hydroxy stearic acid ester of 0.9g polyoxyethylene 30, are stirred to being uniformly dispersed, so under nitrogen protection
After be warming up to 50 DEG C, once add 0.05g acetyl peroxide cyclohexylsulfonyls.Solution turned cloudy after about 15min, there is white precipitate
Generation.
Step 2：Continue after reacting 30min, with constant speed toward dropwise addition in reactor by 150g ethyl acetate, 72g third
Olefin(e) acid, 7.2g lauryl methacrylates, 1.5g cane sugar allyl ethers, the dimerization hydroxy stearic acid ester of 2g polyoxyethylene 30 and
The mixture of 0.21g acetyl peroxides cyclohexylsulfonyl composition, time for adding 3.5h.
Step 3：0.02g acetyl peroxides cyclohexylsulfonyl is added after being added dropwise and appearance is residued in 15g hexamethylenes handle
Reactant on wall is rinsed in reactor in the lump.60 DEG C of reaction 2h are warming up to after insulation 30min.
Polymer suspension is transferred in single-necked flask, vacuum revolving removes solvent at 90-100 DEG C, obtains exquisiteness
White polymers of carboxylic acid thickener powder.
Embodiment 2
Step 1：330g hexamethylenes, 15g ethyl acetate, 15g acrylic acid, 2.2g methyl-props are added into 1000ml reactors
Olefin(e) acid lauryl, 0.5g cane sugar allyl ethers, the dimerization hydroxy stearic acid ester of 0.9g polyoxyethylene 30, stir under nitrogen protection to
It is uniformly dispersed, then heats to 50 DEG C, once adds 0.05g acetyl peroxide cyclohexylsulfonyls.Solution becomes muddy after about 15min
It is turbid, there is white precipitate generation.
Step 2：Continue after reacting 30min, with constant speed toward dropwise addition in reactor by 135g ethyl acetate, 72g third
Olefin(e) acid, 5.8g lauryl methacrylates, 1.5g cane sugar allyl ethers, the dimerization hydroxy stearic acid ester of 2g polyoxyethylene 30 and
The mixture of 0.21g acetyl peroxides cyclohexylsulfonyl composition, time for adding 3.5h.
Step 3：0.02g acetyl peroxides cyclohexylsulfonyl is added after being added dropwise and appearance is residued in 15g hexamethylenes handle
Reactant on wall is rinsed in reactor in the lump.60 DEG C of reaction 2h are warming up to after insulation 30min.
Polymer suspension is transferred in single-necked flask, vacuum revolving removes solvent at 90-100 DEG C, obtains exquisiteness
White polymers of carboxylic acid thickener powder.
Embodiment 3
Step 1：330g hexamethylenes, 54g ethyl acetate, 15g acrylic acid, 1.35g propylene are added into 1000ml reactors
Sour stearate, 0.5g pentaerythritol triallyl ethers, the dimerization hydroxy stearic acid ester of 0.9g polyoxyethylene 30, under nitrogen protection
Stirring then heats to 50 DEG C to being uniformly dispersed, and once adds 0.04g peroxy dicarbonate di-n-propyl esters.Solution after about 15min
Become cloudy, there is white precipitate generation.
Step 2：Continue after reacting 30min, with constant speed toward dropwise addition in reactor by 96g ethyl acetate, 72g propylene
Acid, 6.5g stearyl acrylates acid esters, 1.5g cane sugar allyl ethers, the dimerization hydroxy stearic acid ester of 2g polyoxyethylene 30 and 0.3g peroxides
Change the mixture of two carbonic acid di-n-propyl esters composition, time for adding 3.5h.
Step 3：0.02g peroxy dicarbonate di-n-propyl esters are added after being added dropwise and appearance is residued in 15g hexamethylenes handle
Reactant on wall is rinsed in reactor in the lump.60 DEG C of reaction 2h are warming up to after insulation 30min.
Polymer suspension is transferred in single-necked flask, vacuum revolving removes solvent at 90-100 DEG C, obtains exquisiteness
White polymers of carboxylic acid thickener powder.
Embodiment 4
Step 1：330g hexamethylenes, 15g ethyl acetate, 15g acrylic acid, 1.5g richness horses are added into 1000ml reactors
Acid, 0.6g lauryl methacrylates, 0.5g pentaerythritol triallyl ethers, 0.9g Span-80s, stir under nitrogen protection to
It is uniformly dispersed, then heats to 50 DEG C, once adds 0.05g acetyl peroxide cyclohexylsulfonyls.Solution becomes muddy after about 15min
It is turbid, there is white precipitate generation.
Step 2：Continue after reacting 30min, with constant speed toward dropwise addition in reactor by 135g ethyl acetate, 72g third
Olefin(e) acid, 7.8g methacrylic acids, 3.3g lauryl methacrylates, 1.5g pentaerythritol triallyl ethers, 2g Span-80s and
The mixture of 0.21g acetyl peroxides cyclohexylsulfonyl composition, time for adding 3.5h.
Step 3：0.02g acetyl peroxides cyclohexylsulfonyl is added after being added dropwise and appearance is residued in 15g hexamethylenes handle
Reactant on wall is rinsed in reactor in the lump.60 DEG C of reaction 2h are warming up to after insulation 30min.
Polymer suspension is transferred in single-necked flask, vacuum revolving removes solvent at 90-100 DEG C, obtains exquisiteness
White polymers of carboxylic acid thickener powder.
Embodiment 5
Step 1：330g hexamethylenes, 15g ethyl acetate, 15g acrylic acid, 1.2g methyl-props are added into 1000ml reactors
Olefin(e) acid lauryl, 0.7g diethylene glycol (DEG)s diallyl ether, the dimerization hydroxy stearic acid ester of 0.9g polyoxyethylene 30, are stirred under nitrogen protection
Mix to being uniformly dispersed, then heat to 50 DEG C, once add 0.05g peroxy dicarbonate di-n-propyl esters.Solution becomes after about 15min
Muddiness, there is white precipitate generation.
Step 2：Continue after reacting 30min, with constant speed toward dropwise addition in reactor by 135g ethyl acetate, 72g third
Olefin(e) acid, 10g lauryl methacrylates, 1.6g diethylene glycol (DEG)s diallyl ether, the dimerization hydroxy stearic acid ester of 2g polyoxyethylene 30 and
The mixture of 0.21g peroxy dicarbonate di-n-propyl esters composition, time for adding 3.5h.
Step 3：0.02g peroxy dicarbonate di-n-propyl esters are added after being added dropwise and appearance is residued in 15g hexamethylenes handle
Reactant on wall is rinsed in reactor in the lump.60 DEG C of reaction 2h are warming up to after insulation 30min.
Polymer suspension is transferred in single-necked flask, vacuum revolving removes solvent at 90-100 DEG C, obtains exquisiteness
White polymers of carboxylic acid thickener powder.
Embodiment 6
Step 1：330g hexamethylenes, 15g ethyl acetate, 15g acrylic acid, 1.2g acrylic acid are added into 1000ml reactors
Stearate, 0.7g pentaerythritol triallyl ethers, the dimerization hydroxy stearic acid ester of 0.9g polyoxyethylene 30, are stirred under nitrogen protection
Mix to being uniformly dispersed, then heat to 50 DEG C, once add 0.05g acetyl peroxide cyclohexylsulfonyls.Solution becomes after about 15min
Muddiness, there is white precipitate generation.
Step 2：Continue after reacting 30min, with constant speed toward dropwise addition in reactor by 135g ethyl acetate, 72g third
Olefin(e) acid, 6.6g stearyl acrylates acid esters, 1.9g pentaerythritol triallyl ethers, the dimerization hydroxy stearic acid ester of 2g polyoxyethylene 30 and
The mixture of 0.21g acetyl peroxides cyclohexylsulfonyl composition, time for adding 3.5h.
Step 3：0.02g acetyl peroxides cyclohexylsulfonyl is added after being added dropwise and appearance is residued in 15g hexamethylenes handle
Reactant on wall is rinsed in reactor in the lump.60 DEG C of reaction 2h are warming up to after insulation 30min.
Polymer suspension is transferred in single-necked flask, vacuum revolving removes solvent at 90-100 DEG C, obtains exquisiteness
White polymers of carboxylic acid thickener powder.
Embodiment 7
Step 1：330g n-hexanes, 15g propyl formates, 13.1g acrylic acid, 1.2g methyl are added into 1000ml reactors
Lauryl acrylate, 0.4g cane sugar allyl ethers, 0.6g Span-80s, stir to being uniformly dispersed, then heat up under nitrogen protection
To 50 DEG C, 0.03g peroxy dicarbonate di-n-propyl esters are once added.Solution turned cloudy after about 15min, there is white precipitate generation.
Step 2：Continue after reacting 30min, with constant speed toward dropwise addition in reactor by 135g propyl formates, 73.9g
Acrylic acid, 6.6g lauryl methacrylates, 1.6g cane sugar allyl ethers, 2.3g Span-80s and 0.23g dicetyl peroxydicarbonates two
The mixture of n-propyl composition, time for adding 3.5h.
Step 3：0.02g peroxy dicarbonate di-n-propyl esters are added after being added dropwise and appearance is residued in 15g hexamethylenes handle
Reactant on wall is rinsed in reactor in the lump.62 DEG C of reaction 2h are warming up to after insulation 30min.
Polymer suspension is transferred in single-necked flask, vacuum revolving removes solvent at 90-100 DEG C, obtains exquisiteness
White polymers of carboxylic acid thickener powder.
Embodiment 8
Step 1：200g hexamethylenes, 88g ethyl acetate, 17.4g acrylic acid, 1.56g third are added into 1000ml reactors
Olefin(e) acid stearate, 0.2g cane sugar allyl ethers, 0.4g diethylene glycol (DEG)s diallyl ether, the dimerization hydroxy stearate of 0.9g polyoxyethylene 30
Acid esters, stir under nitrogen protection to being uniformly dispersed, then heat to 50 DEG C, once add 0.05g acetyl peroxide cyclohexyl
Sulphonyl.Solution turned cloudy after about 10min, there is white precipitate generation.
Step 2：Continue after reacting 30min, with constant speed toward dropwise addition in reactor by 86g hexamethylenes, 106g acetic acid
Ethyl ester, 69.6g acrylic acid, 6.24g stearyl acrylates acid esters, 0.4g cane sugar allyl ethers, 1g diethylene glycol (DEG)s diallyl ether, 2g gather
The mixture of the dimerization hydroxy stearic acid ester of oxygen ethene 30 and 0.21g acetyl peroxides cyclohexylsulfonyl composition, time for adding are
3.5h。
Step 3：0.02g acetyl peroxides cyclohexylsulfonyl is added after being added dropwise and appearance is residued in 15g hexamethylenes handle
Reactant on wall is rinsed in reactor in the lump.70 DEG C of reaction 2h are warming up to after insulation 30min.
Polymer suspension is transferred in single-necked flask, vacuum revolving removes solvent at 90-100 DEG C, obtains exquisiteness
White polymers of carboxylic acid thickener powder.
Embodiment 9
Step 1：230g hexamethylenes, 15g ethyl acetate, 15g acrylic acid, 1g metering systems are added into 1000ml reactors
Sour stearate, 0.3g cane sugar allyl ethers, the dimerization hydroxy stearic acid ester of 1.1g polyoxyethylene 30, stir under nitrogen protection to
It is uniformly dispersed, then heats to 53 DEG C, once adds 0.05g acetyl peroxide cyclohexylsulfonyls.Solution becomes muddy after about 10min
It is turbid, there is white precipitate generation.
Step 2：Continue after reacting 25min, with constant speed toward dropwise addition in reactor by 9g hexamethylenes, 130g acetic acid second
Ester, 72g acrylic acid, 7g stearyl methacrylates, 0.9g cane sugar allyl ethers, the dimerization hydroxy stearate of 2.4g polyoxyethylene 30
The mixture of acid esters and 0.21g acetyl peroxides cyclohexylsulfonyl composition, time for adding 3.5h.
Step 3：0.02g acetyl peroxides cyclohexylsulfonyl is added after being added dropwise and appearance is residued in 15g hexamethylenes handle
Reactant on wall is rinsed in reactor in the lump.58 DEG C of reaction 2h are warming up to after insulation 30min.
Polymer suspension is transferred in single-necked flask, vacuum revolving removes solvent at 90-100 DEG C, obtains exquisiteness
White polymers of carboxylic acid thickener powder.
Embodiment 10
Step 1：Added into 1000ml reactors 574g hexamethylenes, 17.4g acrylic acid, 3g lauryl methacrylates,
0.5g cane sugar allyl ethers, the dimerization hydroxy stearic acid ester of 0.95g polyoxyethylene 30, stir under nitrogen protection to being uniformly dispersed,
47 DEG C are then heated to, once adds 0.04g acetyl peroxide cyclohexylsulfonyls.Solution turned cloudy after about 15min, there is white heavy
Form sediment and generate.
Step 2：Continue after reacting 40min, with constant speed toward dropwise addition in reactor by 211g ethyl acetate, 69.6g
Acrylic acid, 12.35g stearyl acrylates acid esters, 2g cane sugar allyl ethers, the dimerization hydroxy stearic acid ester of 3.6g polyoxyethylene 30 and
The mixture of 0.14g acetyl peroxides cyclohexylsulfonyl composition, time for adding 5h.
Step 3：0.01g acetyl peroxides cyclohexylsulfonyl is added after being added dropwise and appearance is residued in 15g hexamethylenes handle
Reactant on wall is rinsed in reactor in the lump.72 DEG C of reaction 1h are warming up to after insulation 30min.
Polymer suspension is transferred in single-necked flask, vacuum revolving removes solvent at 90-100 DEG C, obtains exquisiteness
White polymers of carboxylic acid thickener powder.
Comparative example 1
Step 1：Added into 1000ml reactors 330g hexamethylenes, 15g acrylic acid, 0.6g lauryl methacrylates,
0.5g cane sugar allyl ethers, the dimerization hydroxy stearic acid ester of 0.9g polyoxyethylene 30, are stirred to being uniformly dispersed, so under nitrogen protection
After be warming up to 50 DEG C, once add 0.05g acetyl peroxide cyclohexylsulfonyls.Solution turned cloudy after about 15min, there is white precipitate
Generation.
Step 2：Continue after reacting 30min, with constant speed toward dropwise addition in reactor by 150g ethyl acetate, 72g third
Olefin(e) acid, 3.3g lauryl methacrylates, 1.5g cane sugar allyl ethers, the dimerization hydroxy stearic acid ester of 2g polyoxyethylene 30 and
The mixture of 0.21g acetyl peroxides cyclohexylsulfonyl composition, time for adding 3.5h.
Step 3：0.02g acetyl peroxides cyclohexylsulfonyl is added after being added dropwise and appearance is residued in 15g hexamethylenes handle
Reactant on wall is rinsed in reactor in the lump.60 DEG C of reaction 2h are warming up to after insulation 30min.
Polymer suspension is transferred in single-necked flask, vacuum revolving removes solvent at 90-100 DEG C, obtains exquisiteness
White polymers of carboxylic acid thickener powder.
Comparative example 2
Commercially available card ripple A.
Method of testing：
1st, 0.5% gel viscosity measuring method：
200g deionized waters are weighed in 500mL beaker, add product 1g, by beaker be placed under electric blender in
1000rpm is stirred until homogeneous；Then 18wt% sodium hydroxide solutions are used while stirring under 300rpm speed, adjust pH value
For：6.8~7.3, stir, centrifugation defoaming, measure viscosity.
2nd, 1% gel viscosity measuring method：
200g deionized waters are weighed in 500mL beaker, add product 2g, by beaker be placed under electric blender in
1000rpm is stirred until homogeneous；Then 18wt% sodium hydroxide solutions are used while stirring under 300rpm speed, adjust pH value
For：6.8~7.3, stir, centrifugation defoaming, measure viscosity.
3rd, it is formulated suspension time measuring method：
150g samples are weighed in 150g sample bottles, 0.2g colored particles is dispersed wherein, it is placed in 45 DEG C of baking ovens,
Observe the suspension situation of particle.Particle does not sink or non-rising, can record 1 day, continues to observe within second day.
Performance test 1
The data that above-mentioned each embodiment and comparative example obtain after being tested according to following method of testings such as following table institute
Show.
The all-round property testing table of table monocarboxylic acid thickening agent of copolymer
| 0.5wt% | 1wt% | |
| Viscosity/mPas | Viscosity/mPas | |
| Embodiment 1 | 40000 | 80000 |
| Embodiment 2 | 42000 | 82000 |
| Embodiment 3 | 33000 | 65000 |
| Embodiment 4 | 42000 | 86000 |
| Embodiment 5 | 34000 | 69000 |
| Embodiment 6 | 37000 | 73000 |
| Embodiment 7 | 28000 | 50000 |
| Embodiment 8 | 31000 | 60000 |
| Embodiment 9 | 36000 | 76000 |
| Embodiment 10 | 28000 | 55000 |
| Comparative example 1 | 52000 | 100000 |
| Comparative example 2 | 45000 | 92000 |
Performance test 2
Table two is the formula table of the formula containing soap base.
The formula table of the formula containing soap base of table two
Table three is the performance test results of the formula containing soap base.
The performance test results of the formula containing soap base of table three
Performance test 3
Table four is the test formulations being formulated of being lived containing gentle table.
The formula table of the work formula containing gentle table of table four
Table five is the performance test results being formulated of being lived containing gentle table.
The test result of the work formula containing gentle table of table five
Above-described is only presently preferred embodiments of the present invention, all timess made in the range of the spirit and principles in the present invention
What modifications, equivalent substitutions and improvements etc., should be included in the scope of the protection.
Claims (12)
1. a kind of preparation method of copolymer rheology modifier, it is characterised in that comprise the following steps：
Step 1：Added in reaction vessel containing at least organic inert solvent of 55wt% varsol, 15wt%~
Initiator, dispersant and crosslinking agent needed for 20wt% monomer and reaction, react 30 under conditions of 45~55 DEG C~
60min；
Step 2：Drawing needed at least organic inert solvent of 55wt% esters solvent, remaining monomer and reaction will be contained
It was added in the reaction vessel of step 1 and reacts in 3~6 hours after hair agent, dispersant and crosslinking agent mixing, reaction temperature is not
Become；
Step 3：After being warming up to 55~75 DEG C, add initiator and being incubated 1~4h makes the monomer in reaction system react completely, tie
Shu Fanying simultaneously discharges, and is dried to obtain white powder；
Described monomer is by 85wt%~92.9wt% α, the C of beta-unsaturated carboxylic acid and 7.1wt%~15wt% acrylic acid10
~C20The C of Arrcostab or methacrylic acid10~C20Arrcostab forms；
80%~90% of the gross weight of organic inert solvent in described step 1 and step 2 equivalent to material gross weight.
2. the preparation method of copolymer rheology modifier according to claim 1, it is characterised in that
Organic inert solvent in step 1 is by 55wt%~100wt% varsol and 0wt%~45wt% esters solvent
Composition；
Organic inert solvent in step 2 is by 0wt%~45wt% varsol and 55wt%~100wt% esters solvent
Composition；
Organic inert solvent in step 1 accounts for 60wt%~80wt% of the total amount of organic inert solvent.
3. the preparation method of copolymer rheology modifier according to claim 1, it is characterised in that
Dispersant accounts for 2wt%~5wt% of total reactant, and crosslinking agent accounts for 1wt%~3wt% of total reactant, and initiator accounts for always
0.2wt%~0.5wt% of reactant.
4. the preparation method of the copolymer rheology modifier according to claim 1 or 3, it is characterised in that
In step 1, the initiator of addition accounts for 10wt%~30wt% of the total amount of initiator；The dispersant of addition accounts for dispersant
Total amount 20wt%~40wt%, the crosslinking agent of addition accounts for 20wt%~30wt% of the total amount of crosslinking agent.
5. the preparation method of copolymer rheology modifier according to claim 1, it is characterised in that
In step 2, material is added in reaction vessel in a manner of being added dropwise；
In step 3, the dosage of initiator is no more than the 0.06wt% of total reactant.
6. the preparation method of copolymer rheology modifier according to claim 1, it is characterised in that described α, β-insatiable hunger
It is one or more combinations in acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid with carboxylic acid
One or more combinations in described varsol n-hexane, isohexane, hexamethylene, benzene, solvent naphtha；Described ester
Class solvent is Ethyl formate, propyl formate, butyl acetate, propyl acetate, ethyl acetate, one kind in methyl acetate or combination.
7. the preparation method of copolymer rheology modifier according to claim 1, it is characterised in that described crosslinking agent is
One or more combinations in pentaerythritol triallyl ether, diethylene glycol (DEG) diallyl ether or cane sugar allyl ether.
8. the preparation method of copolymer rheology modifier according to claim 1, it is characterised in that described dispersant is
The dimerization hydroxy stearic acid ester of polyoxyethylene 30 and/or Span-80.
9. the preparation method of copolymer rheology modifier according to claim 1, it is characterised in that described initiator is
Acetyl peroxide cyclohexylsulfonyl, peroxidating neodecanoic acid α-isopropyl phenyl ester, peroxidating neodecanoic acid -1,1- dimethyl -3- hydroxyl fourths
Base ester, dicetyl peroxydicarbonate two (3- methoxybutyls), di-isopropyl peroxydicarbonate, (the 2- ethyls of dicetyl peroxydicarbonate two
Own ester), the new enanthic acid α-isopropyl phenyl ester of peroxidating, one or more combinations in peroxy dicarbonate di-n-propyl ester.
10. a kind of copolymer rheology modifier, it is characterised in that be prepared into by the method as described in claim 1 to 9 is any
Arrive.
11. one kind contains soap-based compositions, it is characterised in that contains 0.5wt%~3wt% such as claims in described composition
Copolymer rheology modifier, the 10wt%~20wt% soap base compositions that 1 to 9 any described method is prepared.
12. one kind is containing gentle table work composition, it is characterised in that contains 0.5wt%~3wt% such as rights in described composition
It is required that copolymer rheology modifier, the 10wt%~20wt% amino acid surfaces that 1 to 9 any described method is prepared are active
Agent.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3991799A4 (en) * | 2019-06-26 | 2023-07-26 | Sumitomo Seika Chemicals Co., Ltd. | Viscous composition |
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|---|---|---|---|---|
| CN104448107A (en) * | 2014-12-01 | 2015-03-25 | 广州天赐高新材料股份有限公司 | Alkaline-soluble acrylate polymer composition and preparation method thereof |
| CN104861104A (en) * | 2015-06-08 | 2015-08-26 | 广州天赐高新材料股份有限公司 | Quick-wetting carboxylic acid copolymer thickening agent and preparation method thereof |
| CN106632799A (en) * | 2016-11-17 | 2017-05-10 | 广州天赐高新材料股份有限公司 | Acrylic acid type thickener and preparation method thereof |
-
2017
- 2017-11-20 CN CN201711157685.0A patent/CN107880203A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104448107A (en) * | 2014-12-01 | 2015-03-25 | 广州天赐高新材料股份有限公司 | Alkaline-soluble acrylate polymer composition and preparation method thereof |
| CN104861104A (en) * | 2015-06-08 | 2015-08-26 | 广州天赐高新材料股份有限公司 | Quick-wetting carboxylic acid copolymer thickening agent and preparation method thereof |
| CN106632799A (en) * | 2016-11-17 | 2017-05-10 | 广州天赐高新材料股份有限公司 | Acrylic acid type thickener and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP3991799A4 (en) * | 2019-06-26 | 2023-07-26 | Sumitomo Seika Chemicals Co., Ltd. | Viscous composition |
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Application publication date: 20180406 |