CN107746612A - A kind of preparation method of water-based thickener - Google Patents
A kind of preparation method of water-based thickener Download PDFInfo
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- CN107746612A CN107746612A CN201711047378.7A CN201711047378A CN107746612A CN 107746612 A CN107746612 A CN 107746612A CN 201711047378 A CN201711047378 A CN 201711047378A CN 107746612 A CN107746612 A CN 107746612A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
- C08G18/6755—Unsaturated carboxylic acids
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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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- 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
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
- C08G18/2825—Alkanols, cycloalkanols or arylalkanols including terpenealcohols having at least 6 carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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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
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1803—C3-(meth)acrylate, e.g. (iso)propyl (meth)acrylate
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Abstract
The invention discloses a kind of preparation method of water-based thickener, including：S101. component prepares；S102. the polymerization of polyurethane portion：Polyethylene glycol is added into reaction vessel, under stirring condition, after being warming up to 118 DEG C 122 DEG C, 1 2h of dehydration is vacuumized, then reduces the temperature to 80 DEG C 85 DEG C；Added into reaction vessel and account for the acrylate monomer of acrylate monomer gross mass 10% 40% and stir；Keep reaction temperature to add diisocyanate and catalyst into reaction vessel at 80 DEG C 85 DEG C, react 1.5 2.5h；Continue to keep reaction temperature to add unit alcohol into reaction vessel at 80 DEG C 85 DEG C, react 3 5h, complete the polymerization of polyurethane portion；S103. water-based thickener is obtained.Preparation process of the present invention need not remove the operating procedure of solvent the later stage, be free of organic solvent in the product of preparation, and using effect is good.
Description
Technical field
The present invention relates to thickener field, more particularly, it relates to a kind of its preparation method of water-based thickener.
Background technology
With the appearance of every country environmental regulation and the enhancing of people's environmental consciousness, the coating of Water-borne modification increasingly by
Favor, the research input of each coatings enterprises and research institution to coating Water-borne modification are also more and more more.And water paint, especially
It is often very low, it is necessary to add thickener to adjust its viscosity and rheological property as the coating of film forming matter, its viscosity using emulsion.
In existing thickener products, inorganic thickening agent is because levelability is poor, now less；Cellulose thickener is
Supramolecular water-soluble resin, viscosity is small and influence film richness under high shear, and thixotropy is strong and influences levelability, and easily
It is mouldy, also it has been rarely employed now；The acrylic acid olefin(e) acid ester alkali soluble type thickener that rises is free of solvent, the partially false plastotype of its rheological effect,
It is ineffective in the coating system for needing inclined Newton type fluid；Polyurethane associative thickener can be by rheological effect from vacation
Plastotype is adjusted to newton-type, but generally requires to add organic solvent progress viscosity reduction, end of synthesis in current building-up process
Afterwards, organic solvent is stayed in thickener, adds the VOC content of coating, is had to reduce the pollution to environment, it is necessary to increase and remove
The technique of solvent, both extends technological process, adds process equipment, and solvent is difficult 100% removal.Whether can develop
A kind of using effect is good, and the thickener products without organic solvent, is the technical problem of this area urgent need to resolve.
The content of the invention
For overcome the deficiencies in the prior art, it is an object of the invention to provide a kind of preparation method of water-based thickener,
Preparation process need not remove the operating procedure of solvent the later stage, be free of organic solvent in the product of preparation, and using effect is good.
To solve the above problems, the technical solution adopted in the present invention is as follows：
A kind of preparation method of water-based thickener, including：
S101. component prepares：Prepare polyethylene glycol, acrylate monomer, diisocyanate, catalyst, unit alcohol, initiation
Agent and deionized water；Acrylate monomer is well mixed, and prepares initiator solution, wherein, draw in initiator solution
The mass fraction for sending out agent is 1%；
S102. the polymerization of polyurethane portion：Polyethylene glycol is added into reaction vessel, under stirring condition, be warming up to 118 DEG C-
After 122 DEG C, dehydration 1-2h is vacuumized, then reduces the temperature to 80 DEG C -85 DEG C；Added into reaction vessel and account for acrylate monomer
Gross mass 10%-40% acrylate monomer simultaneously stirs；Reaction temperature is kept at 80 DEG C -85 DEG C, into reaction vessel
Diisocyanate and catalyst are added, reacts 1.5-2.5h；Continue to keep reaction temperature at 80 DEG C -85 DEG C, into reaction vessel
Unit alcohol is added, 3-5h is reacted, completes the polymerization of polyurethane portion；
S103. water-based thickener is obtained：Add deionized water into reaction vessel, it is to be mixed uniformly after, be warming up to 80
DEG C -85 DEG C, the initiator solution for accounting for initiator solution gross mass 10%-40% is added, reacts 0.5-1h；Continue to keep anti-
Temperature is answered at 80 DEG C -85 DEG C, residual acrylic acid ester monomer is added dropwise respectively and remaining initiator solution, the time being added dropwise to complete are
2-2.5h；After being added dropwise to complete, keep reaction temperature to continue to react 1.5-2.5h at 80 DEG C -85 DEG C, produce.
Further, the number-average molecular weight of the polyethylene glycol is 4000-20000.
Further, the acrylate monomer includes methacrylic acid, in addition to methyl methacrylate, metering system
One or more in acetoacetic ester, propyl methacrylate, butyl methacrylate, metering system in the acrylate monomer
The mass fraction of acid is 10%-50%.
Further, the mass ratio for polyurethane portion being obtained in the gross mass of the acrylate monomer and step S102 is
20-40:60-80
Further, the diisocyanate is toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate, oneself two isocyanic acids
Ester, IPDI, trimethyl hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, phenylenedimethylidyne two
One or more in isocyanates, tetramethylxylylene diisocyanate, hexahydrotoluene diisocyanate.
Further, oh group rubs in the molal quantity and polyethylene glycol of isocyanate groups in the diisocyanate
Your ratio of number is 1.5-4:1.
Further, the catalyst is dibutyl tin laurate, dibutyltin diacetate, stannous octoate, maleic
Diacid dibutyl tin, stannous naphthenate, zinc naphthenate, zinc octoate, zinc Isoocatanoate, isooctyl acid bismuth, laurate bismuth, bismuth neodecanoate,
One or more in bismuth naphthenate, bismuth oxide, bismuth nitrate, the addition of the catalyst is polyurethane portion in step S102
Reactant gross mass 0.01%-0.1%.
Further, the unit alcohol is C6-C20Alkylol.
Further, it is surplus that reaction during unit alcohol is not added with the molal quantity and step S102 of the oh group of the unit alcohol
The ratio of the molal quantity of remaining isocyanate groups is 1-1.5:1.
Further, the initiator is the one or more in sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate, described to draw
The addition for sending out agent is the 0.2%-1.0% of acrylate monomer quality.
Compared with prior art, the beneficial effects of the present invention are：The present invention utilizes polyurethane and acrylate interpenetrating networks
Polymerization prepares a kind of water-based thickener, carries out the conjunction of polyurethane as organic solvent using acrylate monomer in synthesis
Into then the polymerisation of progress acrylate, preparation process need not remove the operating procedure of solvent the later stage, and product does not contain
Solvent, the serial thickener prepared with this method, can reach the stream adjusted from false plastotype to newton-type in water paint
Become effect；Water-based thickener prepared by the present invention its can be adjusted to the not cocurrent flow such as newton-type, balanced type and false plastotype as needed
Body type, it is applied widely, have with polyurethane associative thickener identical using effect, and its preparation process is not added with
Solvent, technological process is simpler, and the water-based thickener for producing acquisition is also more environmentally-friendly.
Brief description of the drawings
Fig. 1 is that 1-5 of the embodiment of the present invention water-based thickener prepared and polyurethane association type prepared by comparative example 1-5 thicken
The control of viscosity change curve of the agent under different shear rate.
Embodiment
The present invention is described in further detail with reference to the accompanying drawings and detailed description.
The present invention includes a kind of preparation method of water-based thickener, including：
S101. component prepares：Prepare polyethylene glycol, acrylate monomer, diisocyanate, catalyst, unit alcohol, initiation
Agent and deionized water；Acrylate monomer is well mixed, and prepares initiator solution, wherein, draw in initiator solution
The mass fraction for sending out agent is 1%；
S102. the polymerization of polyurethane portion：Polyethylene glycol is added into reaction vessel, under stirring condition, be warming up to 118 DEG C-
After 122 DEG C, dehydration 1-2h is vacuumized, then reduces the temperature to 80 DEG C -85 DEG C；Added into reaction vessel and account for acrylate monomer
Gross mass 10%-40% acrylate monomer simultaneously stirs；Reaction temperature is kept at 80 DEG C -85 DEG C, into reaction vessel
Diisocyanate and catalyst are added, reacts 1.5-2.5h；Continue to keep reaction temperature at 80 DEG C -85 DEG C, into reaction vessel
Unit alcohol is added, 3-5h is reacted, completes the polymerization of polyurethane portion；
S103. water-based thickener is obtained：Add deionized water into reaction vessel, it is to be mixed uniformly after, be warming up to 80
DEG C -85 DEG C, the initiator solution for accounting for initiator solution gross mass 10%-40% is added, reacts 0.5-1h；Continue to keep anti-
Temperature is answered at 80 DEG C -85 DEG C, residual acrylic acid ester monomer is added dropwise respectively and remaining initiator solution, the time being added dropwise to complete are
2-2.5h；After being added dropwise to complete, keep reaction temperature to continue to react 1.5-2.5h at 80 DEG C -85 DEG C, produce.
Further, the number-average molecular weight of the polyethylene glycol is 4000-20000.The acrylate monomer includes first
In base acrylic acid, in addition to methyl methacrylate, EMA, propyl methacrylate, butyl methacrylate
One or more, the mass fraction of methacrylic acid is 10%-50% in the acrylate monomer.The acrylate list
The mass ratio that polyurethane portion is obtained in the gross mass and step S102 of body is 20-40:60-80, preferably 30:70.Described two is different
Cyanate is toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate, hexamethylene diisocyanate, IPDI, three
Methyl hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, XDI, tetramethylxylene
One or more in diisocyanate, hexahydrotoluene diisocyanate.Isocyanate groups rubs in the diisocyanate
The ratio of the molal quantity of oh group is 1.5-4 in that number and polyethylene glycol:1, preferably 1.8-3:1.The catalyst is February
Dilaurylate, dibutyltin diacetate, stannous octoate, dibutyl tin maleate, stannous naphthenate, zinc naphthenate,
Zinc octoate, zinc Isoocatanoate, isooctyl acid bismuth, laurate bismuth, bismuth neodecanoate, bismuth naphthenate, bismuth oxide, one kind in bismuth nitrate or several
Kind, the addition of the catalyst is the 0.01%-0.1% of the gross mass of the reactant of polyurethane portion in step S102, excellent
Select 0.03%-0.06%.The unit alcohol is C6-C20Alkylol.The molal quantity and step of the oh group of the unit alcohol
The ratio for being not added with reacting the molal quantity of remaining isocyanate groups during unit alcohol in S102 is 1-1.5:1.The initiator
For the one or more in sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate, the addition of the initiator is acrylate monomer matter
The 0.2%-1.0% of amount, preferably 0.4%-0.8%.
With reference to following formula table 1, implement embodiment 1 and comparative example 1 respectively
Formula table 1 (data unit is g in table)
Embodiment 1
S101. component prepares：Each component is weighed, acrylate monomer is well mixed, and prepares initiator solution, its
In, the mass fraction of initiator is 1% in initiator solution；
S102. the polymerization of polyurethane portion：Polyethylene glycol is added with agitator, thermometer, condenser reaction vessel,
Under stirring condition, after being warming up to 120 DEG C, dehydration 1h is vacuumized, then reduces the temperature to 85 DEG C；Added into reaction vessel and account for third
Olefin(e) acid ester monomer gross mass 9.6g acrylate monomer simultaneously stirs；Reaction temperature is kept at 85 DEG C, into reaction vessel
Diisocyanate and catalyst are added, reacts 1.5h；Continue to keep reaction temperature to add unit into reaction vessel at 85 DEG C
Alcohol, 4h is reacted, completes the polymerization of polyurethane portion；
S103. water-based thickener is obtained：Add deionized water into reaction vessel, it is to be mixed uniformly after, be warming up to 85
DEG C, 7.6g initiator solutions are added, react 0.5h；Continue to keep reaction temperature that residual acrylic acid ester is added dropwise respectively at 85 DEG C
Monomer and remaining initiator solution, the time being added dropwise to complete are 2.5h；After being added dropwise to complete, reaction temperature is kept in 85 DEG C of continuation
2h is reacted, produces water-based thickener.
Comparative example 1
1) with agitator, thermometer, condenser reaction vessel in, add polyethylene glycol, under agitation, be warming up to
120 DEG C, dehydration 1h is vacuumized, then reduces the temperature to 85 DEG C；
2) diisocyanate, catalyst and solvent dimethylformamide are added, keeps reaction temperature at 85 DEG C, the reaction time
2h；
3) unit alcohol in upper table is added, continues to keep reaction temperature reaction time 4h, to complete polyurethane portion at 85 DEG C
Polymerization；
4) deionized water is added, stirs, obtains the thickener containing solvent dimethylformamide.
With reference to following formula table 2, implement embodiment 2 and comparative example 2 respectively
Formula table 2 (data unit is g in table)
Embodiment 2
S101. component prepares：Each component is weighed, acrylate monomer is well mixed, and prepares initiator solution, its
In, the mass fraction of initiator is 1% in initiator solution；
S102. the polymerization of polyurethane portion：Polyethylene glycol is added with agitator, thermometer, condenser reaction vessel,
Under stirring condition, after being warming up to 122 DEG C, dehydration 1h is vacuumized, then reduces the temperature to 80 DEG C；Added into reaction vessel and account for third
Olefin(e) acid ester monomer gross mass 8.2g acrylate monomer simultaneously stirs；Reaction temperature is kept at 80 DEG C, into reaction vessel
Diisocyanate and catalyst are added, reacts 2h；Continue to keep reaction temperature to add unit alcohol into reaction vessel at 80 DEG C,
3h is reacted, completes the polymerization of polyurethane portion；
S103. water-based thickener is obtained：Add deionized water into reaction vessel, it is to be mixed uniformly after, be warming up to 80
DEG C, 5.6g initiator solutions are added, react 0.5h；Continue to keep reaction temperature that residual acrylic acid ester is added dropwise respectively at 80 DEG C
Monomer and remaining initiator solution, the time being added dropwise to complete are 2.5h；After being added dropwise to complete, reaction temperature is kept in 80 DEG C of continuation
2.5h is reacted, produces water-based thickener.
Comparative example 2
1) with agitator, thermometer, condenser reaction vessel in, add polyethylene glycol, under agitation, be warming up to
122 DEG C, dehydration 1h is vacuumized, then reduces the temperature to 80 DEG C；
2) diisocyanate, catalyst and solvent dimethylformamide are added, keeps reaction temperature at 80 DEG C, the reaction time
2h；
3) unit alcohol in upper table is added, continues to keep reaction temperature reaction time 4h, to complete polyurethane portion at 80 DEG C
Polymerization；
4) deionized water is added, stirs, obtains the thickener containing solvent dimethylformamide.
With reference to following formula table 3, implement embodiment 3 and comparative example 3 respectively
Formula table 3 (data unit is g in table)
Embodiment 3
S101. component prepares：Each component is weighed, acrylate monomer is well mixed, and prepares initiator solution, its
In, the mass fraction of initiator is 1% in initiator solution；
S102. the polymerization of polyurethane portion：Polyethylene glycol is added with agitator, thermometer, condenser reaction vessel,
Under stirring condition, after being warming up to 118 DEG C, dehydration 1h is vacuumized, then reduces the temperature to 82 DEG C；Added into reaction vessel and account for third
Olefin(e) acid ester monomer gross mass 9.6g acrylate monomer simultaneously stirs；Reaction temperature is kept at 82 DEG C, into reaction vessel
Diisocyanate and catalyst are added, reacts 2.5h；Continue to keep reaction temperature to add unit into reaction vessel at 82 DEG C
Alcohol, 5h is reacted, completes the polymerization of polyurethane portion；
S103. water-based thickener is obtained：Add deionized water into reaction vessel, it is to be mixed uniformly after, be warming up to 82
DEG C, 8.6g initiator solutions are added, react 0.5h；Continue to keep reaction temperature that residual acrylic acid ester is added dropwise respectively at 82 DEG C
Monomer and remaining initiator solution, the time being added dropwise to complete are 2.5h；After being added dropwise to complete, reaction temperature is kept in 82 DEG C of continuation
2.5h is reacted, produces water-based thickener.
Comparative example 3
1) with agitator, thermometer, condenser reaction vessel in, add polyethylene glycol, under agitation, be warming up to
118 DEG C, dehydration 1h is vacuumized, then reduces the temperature to 82 DEG C；
2) diisocyanate, catalyst and solvent dimethylformamide are added, keeps reaction temperature at 82 DEG C, the reaction time
2h；
3) unit alcohol in upper table is added, continues to keep reaction temperature reaction time 4h, to complete polyurethane portion at 82 DEG C
Polymerization；
4) deionized water is added, stirs, obtains the thickener containing solvent dimethylformamide.
With reference to following formula table 4, implement embodiment 4 and comparative example 4 respectively
Formula table 4 (data unit is g in table)
Embodiment 4
S101. component prepares：Each component is weighed, acrylate monomer is well mixed, and prepares initiator solution, its
In, the mass fraction of initiator is 1% in initiator solution；
S102. the polymerization of polyurethane portion：Polyethylene glycol is added with agitator, thermometer, condenser reaction vessel,
Under stirring condition, after being warming up to 118 DEG C, dehydration 1h is vacuumized, then reduces the temperature to 82 DEG C；Added into reaction vessel and account for third
Olefin(e) acid ester monomer gross mass 9.6g acrylate monomer simultaneously stirs；Reaction temperature is kept at 82 DEG C, into reaction vessel
Diisocyanate and catalyst are added, reacts 2h；Continue to keep reaction temperature to add unit alcohol into reaction vessel at 82 DEG C,
4h is reacted, completes the polymerization of polyurethane portion；
S103. water-based thickener is obtained：Add deionized water into reaction vessel, it is to be mixed uniformly after, be warming up to 82
DEG C, 8.6g initiator solutions are added, react 1h；Continue to keep reaction temperature that residual acrylic acid ester list is added dropwise respectively at 82 DEG C
Body and remaining initiator solution, the time being added dropwise to complete are 2.5h；After being added dropwise to complete, reaction temperature is kept to continue at 82 DEG C anti-
2h is answered, produces water-based thickener.
Comparative example 4
1) with agitator, thermometer, condenser reaction vessel in, add polyethylene glycol, under agitation, be warming up to
118 DEG C, dehydration 1h is vacuumized, then reduces the temperature to 82 DEG C；
2) diisocyanate, catalyst and solvent dimethylformamide are added, keeps reaction temperature at 82 DEG C, the reaction time
2h；
3) unit alcohol in upper table is added, continues to keep reaction temperature reaction time 4h, to complete polyurethane portion at 82 DEG C
Polymerization；
4) deionized water is added, stirs, obtains the thickener containing solvent dimethylformamide.
With reference to following formula table 5, implement embodiment 5 and comparative example 5 respectively
Formula table 5 (data unit is g in table)
Embodiment 5
S101. component prepares：Each component is weighed, acrylate monomer is well mixed, and prepares initiator solution, its
In, the mass fraction of initiator is 1% in initiator solution；
S102. the polymerization of polyurethane portion：Polyethylene glycol is added with agitator, thermometer, condenser reaction vessel,
Under stirring condition, after being warming up to 118 DEG C, dehydration 1h is vacuumized, then reduces the temperature to 82 DEG C；Added into reaction vessel and account for third
Olefin(e) acid ester monomer gross mass 9.6g acrylate monomer simultaneously stirs；Reaction temperature is kept at 82 DEG C, into reaction vessel
Diisocyanate and catalyst are added, reacts 2h；Continue to keep reaction temperature to add unit alcohol into reaction vessel at 82 DEG C,
4h is reacted, completes the polymerization of polyurethane portion；
S103. water-based thickener is obtained：Add deionized water into reaction vessel, it is to be mixed uniformly after, be warming up to 82
DEG C, 8.6g initiator solutions are added, react 0.5h；Continue to keep reaction temperature that residual acrylic acid ester is added dropwise respectively at 82 DEG C
Monomer and remaining initiator solution, the time being added dropwise to complete are 2.5h；After being added dropwise to complete, reaction temperature is kept in 82 DEG C of continuation
2h is reacted, produces water-based thickener.
Comparative example 5
1) with agitator, thermometer, condenser reaction vessel in, add polyethylene glycol, under agitation, be warming up to
118 DEG C, dehydration 1h is vacuumized, then reduces the temperature to 82 DEG C；
2) diisocyanate, catalyst and solvent dimethylformamide are added, keeps reaction temperature at 82 DEG C, the reaction time
2h；
3) unit alcohol in upper table is added, continues to keep reaction temperature reaction time 4h, to complete polyurethane portion at 82 DEG C
Polymerization；
4) deionized water is added, stirs, obtains the thickener containing solvent dimethylformamide.
Contrast experiment
The water-based thickener that embodiment 1-5 is obtained should in same formula white paint with the thickener that comparative example 1-5 is obtained
With.By adjustment, the fluid of three kinds of rheological equationms of state is obtained, wherein, embodiment 1 and comparative example 1 are and embodiment 5 and comparative example
5 be Newton type fluid, and embodiment 2 and comparative example 2 are balanced type fluid, embodiment 3 and comparative example 3 and embodiment 4 and contrast
Example 4 is false plastotype fluid.As seen from Figure 1, the rheological curve and pure polyurethane associative thickener that the present embodiment 1-5 is obtained
The rheological curve of (comparative example 1-5) is approximate, has good using effect, and thickener is free of organic solvent in the present invention, more
Add environmental protection, fully meet the performance requirement in market, be with a wide range of applications.
It will be apparent to those skilled in the art that technical scheme that can be as described above and design, make other various
Corresponding change and deformation, and all these changes and deformation should all belong to the protection domain of the claims in the present invention
Within.
Claims (10)
1. a kind of preparation method of water-based thickener, including：
S101. component prepares：Prepare polyethylene glycol, acrylate monomer, diisocyanate, catalyst, unit alcohol, initiator and
Deionized water；Acrylate monomer is well mixed, and prepares initiator solution；
S102. the polymerization of polyurethane portion：Polyethylene glycol is added into reaction vessel, under stirring condition, is warming up to 118 DEG C -122 DEG C
Afterwards, dehydration 1-2h is vacuumized, then reduces the temperature to 80 DEG C -85 DEG C；Added into reaction vessel and account for the total matter of acrylate monomer
Measure 10%-40% acrylate monomer and stir；Reaction temperature is kept to be added at 80 DEG C -85 DEG C into reaction vessel
Diisocyanate and catalyst, react 1.5-2.5h；Continue to keep reaction temperature to add into reaction vessel at 80 DEG C -85 DEG C
Unit alcohol, 3-5h is reacted, completes the polymerization of polyurethane portion；
S103. water-based thickener is obtained：Add deionized water into reaction vessel, it is to be mixed uniformly after, be warming up to 80 DEG C -85
DEG C, the initiator solution for accounting for initiator solution gross mass 10%-40% is added, reacts 0.5-1h；Continue to keep reaction temperature
For degree at 80 DEG C -85 DEG C, it is 2- that residual acrylic acid ester monomer and remaining initiator solution, the time being added dropwise to complete are added dropwise respectively
2.5h；After being added dropwise to complete, keep reaction temperature to continue to react 1.5-2.5h at 80 DEG C -85 DEG C, produce.
2. the preparation method of water-based thickener as claimed in claim 1, it is characterised in that the equal molecule of number of the polyethylene glycol
Measure as 4000-20000.
3. the preparation method of water-based thickener as claimed in claim 1, it is characterised in that the acrylate monomer includes first
In base acrylic acid, in addition to methyl methacrylate, EMA, propyl methacrylate, butyl methacrylate
One or more, the mass fraction of methacrylic acid is 10%-50% in the acrylate monomer.
4. the preparation method of water-based thickener as claimed in claim 3, it is characterised in that total matter of the acrylate monomer
Amount and the mass ratio of acquisition polyurethane portion in step S102 are 20-40:60-80.
5. the preparation method of water-based thickener as claimed in claim 1, it is characterised in that the diisocyanate is toluene two
Oneself two isocyanic acids of isocyanates, '-diphenylmethane diisocyanate, hexamethylene diisocyanate, IPDI, trimethyl
Ester, dicyclohexyl methyl hydride diisocyanate, XDI, tetramethylxylylene diisocyanate, six
One or more in hydrogen toluene di-isocyanate(TDI).
6. the preparation method of water-based thickener as claimed in claim 5, it is characterised in that isocyanic acid in the diisocyanate
The ratio of the molal quantity of oh group is 1.5-4 in the molal quantity and polyethylene glycol of ester group:1.
7. the preparation method of water-based thickener as claimed in claim 1, it is characterised in that the catalyst is tin dilaurate two
Butyl tin, dibutyltin diacetate, stannous octoate, dibutyl tin maleate, stannous naphthenate, zinc naphthenate, zinc octoate,
One or more in zinc Isoocatanoate, isooctyl acid bismuth, laurate bismuth, bismuth neodecanoate, bismuth naphthenate, bismuth oxide, bismuth nitrate, it is described
The addition of catalyst is the 0.01%-0.1% of the gross mass of the reactant of polyurethane portion in step S102.
8. the preparation method of water-based thickener as claimed in claim 1, it is characterised in that the unit alcohol is C6-C20Alkane
Base alcohol.
9. the preparation method of water-based thickener as claimed in claim 8, it is characterised in that the oh group of the unit alcohol
The ratio for being not added with reacting the molal quantity of remaining isocyanate groups during unit alcohol in molal quantity and step S102 is 1-1.5:
1。
10. the preparation method of water-based thickener as claimed in claim 1, it is characterised in that the initiator be sodium peroxydisulfate,
One or more in potassium peroxydisulfate, ammonium persulfate, the addition of the initiator are the 0.2%- of acrylate monomer quality
1.0%, the mass fraction of initiator is 1% in the initiator solution.
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| CN201711047378.7A CN107746612A (en) | 2017-10-31 | 2017-10-31 | A kind of preparation method of water-based thickener |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110128845A (en) * | 2019-04-30 | 2019-08-16 | 江苏彩瑞实业有限公司 | A kind of technical process producing high light-fast fastness, high durable fastness pigment yellow 74 |
| CN111303378A (en) * | 2020-03-06 | 2020-06-19 | 长春工业大学 | TMXDI-based polyurethane anti-sagging resin and preparation method thereof |
| CN117356574A (en) * | 2023-10-16 | 2024-01-09 | 河北鑫淘沅医药科技有限公司 | Dibromohydantoin disinfectant for wastewater treatment and preparation process thereof |
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| CN101328248A (en) * | 2008-07-29 | 2008-12-24 | 温州国仕邦高分子材料有限公司 | Non-solvent preparation of polyurethane-acrylic ester emulsion for leather |
| CN102628228A (en) * | 2012-04-12 | 2012-08-08 | 成都德美精英化工有限公司 | Method for synthesizing coating printing thickening agent |
| CN103396525A (en) * | 2013-07-22 | 2013-11-20 | 南通天和树脂有限公司 | Unsaturated polyester resin for high-impact-resistance car bumper |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101328248A (en) * | 2008-07-29 | 2008-12-24 | 温州国仕邦高分子材料有限公司 | Non-solvent preparation of polyurethane-acrylic ester emulsion for leather |
| CN102628228A (en) * | 2012-04-12 | 2012-08-08 | 成都德美精英化工有限公司 | Method for synthesizing coating printing thickening agent |
| CN103396525A (en) * | 2013-07-22 | 2013-11-20 | 南通天和树脂有限公司 | Unsaturated polyester resin for high-impact-resistance car bumper |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110128845A (en) * | 2019-04-30 | 2019-08-16 | 江苏彩瑞实业有限公司 | A kind of technical process producing high light-fast fastness, high durable fastness pigment yellow 74 |
| CN111303378A (en) * | 2020-03-06 | 2020-06-19 | 长春工业大学 | TMXDI-based polyurethane anti-sagging resin and preparation method thereof |
| CN117356574A (en) * | 2023-10-16 | 2024-01-09 | 河北鑫淘沅医药科技有限公司 | Dibromohydantoin disinfectant for wastewater treatment and preparation process thereof |
| CN117356574B (en) * | 2023-10-16 | 2024-04-19 | 河北鑫淘沅医药科技有限公司 | Dibromohydantoin disinfectant for wastewater treatment and preparation process thereof |
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Application publication date: 20180302 |