CN104497684B - A kind of polyurea type anti-settling agent - Google Patents
A kind of polyurea type anti-settling agent Download PDFInfo
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- CN104497684B CN104497684B CN201410783600.XA CN201410783600A CN104497684B CN 104497684 B CN104497684 B CN 104497684B CN 201410783600 A CN201410783600 A CN 201410783600A CN 104497684 B CN104497684 B CN 104497684B
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
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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
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6523—Compounds of group C08G18/3225 or C08G18/3271 or polyamines of C08G18/38
- C08G18/6529—Compounds of group C08G18/3225 or polyamines of C08G18/38
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/45—Anti-settling agents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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Abstract
The present invention relates to a kind of polyurea type anti-settling agent, it is Hydroxylated acrylic resin and diisocyanate compound solution, at 40～60 DEG C, reaction 1～3h, then 0～40 DEG C it is cooled to, again with aminated compounds solution reaction 1～2h, the acrylic resin of the polyureas grafting that cooling discharge prepares, solids content is 45～55wt%, urea bond content is 3.0～4.5wt%, its polyurea structure is grafted on the side chain of Hydroxylated acrylic resin molecule, above-mentioned each raw material dosage is as follows: Hydroxylated acrylic resin 70～90wt%, diisocyanate compound solution 5～15wt%, aminated compounds solution 5～15wt%.This anti-settling agent is transparency liquid, has thixotropic behavior, and result of prevention is good, and charging is convenient, may be used for, in one-component high-temperature baking coating, double-component polyurethane coating, one-component thermoplastic coating, not affecting gloss and the clarity of coating.
Description
Technical field
The present invention relates to a kind of polyurea type anti-settling agent, be particularly suitable for double-component polyurethane coating, the baking of one-component high temperature
Roasting coating and one-component thermoplastic coating.
Background technology
Coating material production and use during through being commonly encountered sedimentation phenomenon, therefore, in dope preparing process sometimes for
Add anti-settling agent, in coating, i.e. introduce loose webs thixotropy structure, pigment, filler particles can be made to suspend and not lump, anti-
Only pigment sedimentation, improves coating property, keeps excellent levelability.Conventional anti-settling agent has multiple, but all deposits during using
In some defects, such as: organobentonite, its chemical resistance is undesirable and affects gloss, it is impossible to for topcoating；BYK410
Etc thixotropic agent, diphenyl diimide, easy xanthochromia can be formed under illumination effect, weatherability is poor；Polyamide wax is easily formed azo compounds
Thing, easy xanthochromia, and affect gloss, it is impossible to for topcoating；Tissuemat E class affects gloss, and addition is big, and thixotropic effects is also paid no attention to
Think, it is impossible to for topcoating；Nonaqueous dispersion resin thixotropic effects does not highlight, and its basic function is not intended to thixotroping, but increases
Macromolecule improves coating physical mechanical and chemical resistance performance；Aerosil affects gloss, cannot be used for topcoating；Typically
Rheology modified resin microemulsion, be only used in amino-stoving varnish, because its particulate polyurea at high temperature reacts with amino, can be formed
Transparent paint film, and when polyurethane system or air-drying property thermoplastic propene's acid system, owing to particulate polyurea can not participate in reaction,
The paint film microemulsion formed, affects its gloss and clarity.
Summary of the invention
It is an object of the invention to: providing a kind of polyurea type anti-settling agent, this anti-settling agent is transparency liquid, have the most anti-
Heavy, thixotropic effects.Can be used for double-component polyurethane coating, one-component high-temperature baking coating and one-component thermoplastic coating, and not
Affect gloss and the clarity of coating.
The technical scheme realizing the object of the invention is: a kind of polyurea type anti-settling agent, it is characterised in that it is hydroxy acrylic acid
Resin and diisocyanate compound solution, at 40～60 DEG C, react 1～3h, be then cooled to 0～40 DEG C, then with amine
Compounds solution reaction 1～2h, cooling discharge prepare polyureas grafting acrylic resin, its solids content be 45～
55wt%, urea bond content is 3.0～4.5wt%, and polyurea structure is grafted on the side chain of Hydroxylated acrylic resin molecule, above-mentioned respectively
Raw material dosage is as follows: Hydroxylated acrylic resin 70～90wt%, diisocyanate compound solution 5～15wt%, amine
Polymer solution 5～15wt%, above each raw material dosage sum is 100wt%, and wherein, Hydroxylated acrylic resin is to use hydroxy
Acid ester monomer is i.e.: in 2-(Acryloyloxy)ethanol, Hydroxypropyl acrylate, hydroxyethyl methylacrylate, Hydroxypropyl methacrylate
Plant or several and acrylic acid, butyl acrylate, ethyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, methacrylic acid
Butyl ester, isobutyl methacrylate, styrene, tertiary ethylene carbonate, glycidyl acrylate, tertiary carbonic acid glycidyl ester,
One or more in isobornyl acrylate, isobornyl methacrylate monomer, add in the presence of peroxide initiator
Heat carries out polymerisation in solution acquisition, each raw material dosage by weight percentage: monomer total amount is 45%～80%, wherein, hydroxyl
Acrylate monomer accounts for the 1.0～4.0wt% of monomer total amount, solvent 20～50%, and peroxide initiator 1～10% is above
Each component sum is 100%, and the solids content of this Hydroxylated acrylic resin is 50～80wt%, Mn number-average molecular weight be 2000～
5000, molecular weight distribution is 1.8～2.2, and hydroxy radical content 0.17～0.42wt%, containing hydroxyl value≤1 in per molecule on average
Individual.
In above-mentioned polyurea type anti-settling agent, the concrete preparation method of its described Hydroxylated acrylic resin is as follows: first added by solvent
Entering in reaction bulb, be warming up to 100～170 DEG C, at the uniform velocity dropping monomer and the mixture of initiator, time for adding is 3～6h, dropping
Terminating insulation 2～3h, cooling discharge can be prepared by.
Above-mentioned polyurea type anti-settling agent is transparency liquid, has thixotropic behavior: under the low-shearing force effect of rotating speed 2r/min,
Viscosity is 60000～300000mPa.s, and under the high shear rotating 60r/min, viscosity is 2000～8000mPa.s,
The time used by the high viscosity of low-shearing force that returns to from the low viscosity of high shear force is 10～20s, and described viscosity is to use
BROOKFIELD DV-III Ultra flow graph, at 25 DEG C, records with No. 4 rotors.
In above-mentioned polyurea type anti-settling agent, its described diisocyanate compound solution is aromatic diisocyanate, fat
One or more in fat (cyclo) aliphatic diisocyanates, alicyclic diisocyanate and varsol, ketones solvent, esters solvent, ether
A kind of solution being mixed to form in kind solvent, solvent of ether ester type, the mass ratio of the two mixing is 1:0.5～4.5.
In above-mentioned polyurea type anti-settling agent, its described aminated compounds solution is aliphatic amine, aromatic amine, hydramine
Class, ether amines apoplexy due to endogenous wind one or more with varsol, ketones solvent, esters solvent, ether solvent, solvent of ether ester type in one
Planting the solution being mixed to form, mass ratio of the two mixing is 1:1～13.5.
The solution have the advantages that: the polyurea type anti-settling agent of technical solution of the present invention is the acrylic acid tree of polyureas grafting
Fat, by homemade Hydroxylated acrylic resin and diisocyanate compound solution reaction, remaining diisocyanate again with
Aminated compounds solution reaction, is grafted to polyurea structure on the side chain of Hydroxylated acrylic resin molecule, creates and well touches
Degeneration and result of prevention, it and traditional anti-settling agent such as organobentonite, aerosil, polyamide wax, Tissuemat E, stream
Become and control resin-phase ratio, have the advantage that 1. owing to urea bond is on the side chain of Hydroxylated acrylic resin molecular resin, anti-settling agent
The compatibility with resin is more preferable, therefore anti-settling agent is transparent, can be not only used in one-component high-temperature baking coating, it is also possible to use
At double-component polyurethane coating, one-component thermoplastic coating, do not affect gloss and the clarity of coating, simultaneously as improve
The compatibility of resin, the anti-settling agent of the present invention has with acrylic resin, polyester resin, synthctic fat acid resin, epoxy resin etc.
There is the good compatibility good, can add to and multiple coating system does not affect gloss of film, can be used in finish paint and varnish；②
By graft modification, in anti-settling agent, polyurea structure is greatly improved, and anti-settling, thixotropic effects becomes apparent from, and can significantly improve coating
Rheological property, under low-shearing force effect, viscosity is big, and viscosity is little under high shear, extensive from the low viscosity of high shear
The high viscosity time arriving low sheraing again is short, therefore is used in coating and can play the most anti-settling and resist sagging performance；3. prevent due to this
Heavy agent is transparency liquid, and charging is convenient, it is not necessary to ripening, it is not necessary to grind, and stirring 10～20min under high speed dispersion just can be very
Good is dispersed in coating；4. the polyurea type anti-settling agent of the present invention is the acrylic resin structure of polyureas grafting, good weatherability, no
Xanthochromia, is particularly suitable in automobile finish and coating varnish.Concrete detection data are shown in Table 2.
Accompanying drawing explanation
Fig. 1 is viscosity and the shearing force graph of a relation of polyurea type anti-settling agent of the present invention.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further, but is not limited to this.
Embodiment raw materials is unless otherwise indicated commercially available industrial goods, can be buied by commercial channel.
(1) Hydroxylated acrylic resin is prepared
Hydroxylated acrylic resin of the present invention is with hydroxy-acrylate monomer i.e.: 2-(Acryloyloxy)ethanol, Hydroxypropyl acrylate,
One or more in hydroxyethyl methylacrylate, Hydroxypropyl methacrylate and acrylic acid, butyl acrylate, acrylic acid second
Ester, Isooctyl acrylate monomer, methyl methacrylate, butyl methacrylate, isobutyl methacrylate, styrene, versatic acid
Vinyl acetate, glycidyl acrylate, tertiary carbonic acid glycidyl ester, isobornyl acrylate, isobornyl methacrylate list
One or more in body, in the presence of peroxide initiator, heating carries out polymerisation in solution acquisition, and each raw material dosage is by weight
Amount percentages: monomer total amount is 45%～80%, wherein, hydroxy-acrylate monomer accounts for 1.0～4.0wt%, solvent 20～
50%, peroxide initiator 1～10%, above each component sum is 100%, and concrete preparation method is as follows: first added by solvent
Entering in reaction bulb, be warming up to 100～170 DEG C, at the uniform velocity dropping monomer and the mixture of initiator, time for adding is 3～6h, dropping
Terminating insulation 2～3h, cooling discharge can be prepared by.
The number-average molecular weight (Mn) of following Hydroxylated acrylic resin uses gel permeation chrommatograph to record.
Embodiment 1 prepares the Hydroxylated acrylic resin of Mn2000
In four mouthfuls of reaction bulbs of the 500ml equipped with agitator, thermometer, Dropping funnel and condenser, add S100# molten
Agent 200g (is equivalent to 40wt%), under nitrogen protection, starts stirring, is warming up to reflux (about 165 DEG C), starts at the uniform velocity to drip list
Body and the mixed liquor 300g (including monomer and initiator) of peroxide initiator, wherein, monomer is hydroxyethyl methylacrylate
9.5g and methyl methacrylate 100g, butyl methacrylate 60g, butyl acrylate 40g, styrene 30g and versatic acid second
Alkene ester 40g amount to 279.5g (be equivalent to monomer total amount 55.9wt%, wherein, hydroxy-acrylate monomer i.e.: hydroxyethyl methacrylate
Ethyl ester accounts for the 3.4wt% of monomer total amount, concrete calculating 9.5 ÷ 279.5=3.4wt%)；Initiator is two tertiary amyl peroxide
20.5g (is equivalent to 4.1wt%), carries out polymerisation in solution at 160～170 DEG C, and about 6h drips complete, then is incubated 3 hours, fall
Temperature, discharging, prepare solvent-borne type Hydroxylated acrylic resin 500g；Gained resin solid content is 60wt%, and hydroxy radical content is
0.42wt%, Mn are about 2000, and molecular weight distribution is 1.8～1.9, containing hydroxyl value≤1 in per molecule on average, preserve
Standby.
Embodiment 2 prepares the Hydroxylated acrylic resin of Mn3000
In four mouthfuls of reaction bulbs of the 500ml equipped with agitator, thermometer, Dropping funnel and condenser, add dimethylbenzene
Solvent 200g (is equivalent to 40wt%), under nitrogen protection, starts stirring, is warming up to reflux (about 138 DEG C), starts at the uniform velocity to drip
Monomer and the mixed liquor 300g (including monomer and initiator) of peroxide initiator, wherein, monomer is 2-(Acryloyloxy)ethanol
5.5g and methyl methacrylate 100g, butyl methacrylate 80g, butyl acrylate 58g and styrene 40g amount to 283.5g
(be equivalent to monomer total amount 56.7wt%, wherein, hydroxy-acrylate monomer i.e.: 2-(Acryloyloxy)ethanol accounts for monomer total amount
1.94wt%)；Initiator is that peroxidized t-butyl perbenzoate 16.5g (being equivalent to 3.3wt%) carries out solution at 135～140 DEG C
Polymerization, about 6h drips complete, then is incubated 3 hours, cooling, discharging, prepares solvent-borne type Hydroxylated acrylic resin 500g；Gained tree
Fat solids content is 60wt%, hydroxy radical content be 0.28wt%, Mn be about 3000, molecular weight distribution is 1.9～2.0, averagely
Containing hydroxyl value≤1 in each molecule, save backup.
Embodiment 3 prepares the Hydroxylated acrylic resin of Mn4000
In four mouthfuls of reaction bulbs of the 500ml equipped with agitator, thermometer, Dropping funnel and condenser, add acetic acid fourth
Ester solvent 225g (is equivalent to 45wt%), under nitrogen protection, starts stirring, is warming up to reflux (about 128 DEG C), starts at the uniform velocity to drip
Adding the mixed liquor 275g (including monomer and initiator) of monomer and peroxide initiator, wherein, monomer is Hydroxypropyl acrylate
4.5g and methyl methacrylate 80g, butyl methacrylate 80g, butyl acrylate 65g and styrene 30g amount to 259.5g
(be equivalent to monomer total amount 51.9wt%, wherein, hydroxy-acrylate monomer i.e.: Hydroxypropyl acrylate accounts for monomer total amount
1.73wt%)；Initiator is peroxidized t-butyl perbenzoate 15.5g (being equivalent to 3.1wt%), carries out solution at 125～130 DEG C
Polymerization, about 5h drips complete, then is incubated 3 hours, cooling, discharging, prepares solvent-borne type Hydroxylated acrylic resin 500g；Gained tree
Fat solids content is 55wt%, hydroxy radical content be 0.21wt%, Mn be about 4000, molecular weight distribution is 2.0～2.1, averagely
Containing hydroxyl value≤1 in each molecule, save backup.
Embodiment 4 prepares the Hydroxylated acrylic resin of Mn5000
In four mouthfuls of reaction bulbs of the 500ml equipped with agitator, thermometer, Dropping funnel and condenser, add toluene molten
Agent 250g (is equivalent to 50.0wt%), under nitrogen protection, starts stirring, is warming up to reflux (about 110 DEG C), starts at the uniform velocity to drip
Monomer and the mixed liquor 250g (including monomer and initiator) of peroxide initiator, wherein, monomer is methacrylic acid hydroxypropyl
Ester 3.5g and methyl methacrylate 75g, butyl methacrylate 75g, butyl acrylate 60g and styrene 25g amount to
238.5g (be equivalent to monomer total amount 47.7wt%, wherein, hydroxy-acrylate monomer i.e.: Hydroxypropyl methacrylate accounts for monomer
The 1.46wt% of total amount)；Initiator is benzoyl peroxide 11.5g (being equivalent to 2.3wt%), carries out solution at 105～115 DEG C
Polymerization, about 5h drips complete, then is incubated 3 hours, cooling, discharging, prepares solvent-borne type Hydroxylated acrylic resin 500g；Gained tree
Fat solids content is 50wt%, hydroxy radical content be 0.17wt%, Mn be about 5000, molecular weight distribution is 2.1～2.2, averagely
Containing hydroxyl value≤1 in each molecule, save backup.
(2) polyurea type anti-settling agent is prepared
The polyurea type anti-settling agent of the present invention is Hydroxylated acrylic resin and diisocyanate compound solution, 40～60
At DEG C, react 1～3h, be then cooled to 0～40 DEG C, then with aminated compounds solution reaction 1～2h, it is poly-that cooling discharge prepares
The acrylic resin of urea grafting, its solids content is 45～55wt%, and urea bond content is 3.0～4.5wt%, and its polyurea structure connects
Branch is on the side chain of Hydroxylated acrylic resin molecule, and above-mentioned each raw material dosage is as follows: Hydroxylated acrylic resin 70～90wt%, and two
Isocyanate ester compound solution 5～15wt%, aminated compounds solution 5～15wt%, above each raw material dosage sum is
100wt%.
Polyurea type anti-settling agent structural formula of the present invention is as follows:
In above formula:
Representation hydroxy acrylate main chain
R1、R2For aromatic hydrocarbons group or aliphatic hydrocarbon group；
N=0～4.
Embodiment 5
In the beaker of 1000ml, the Hydroxylated acrylic resin 400g of the Mn2000 adding embodiment 1 preparation (is equivalent to
80wt%), it is placed under high speed dispersor, starts stirring 1000～1200r/min, and be heated to 60 DEG C with water-bath, add pre-
Diisocyanate compound solution (hexamethylene diisocyanate 9.96g mixes with the dimethylbenzene 40.04g) 50g first prepared
(being equivalent to 10wt%), reacts 2h, is cooled to 20 DEG C, adds aminated compounds solution (the ethylenediamine 3.56g and two prepared in advance
Toluene 46.44g mixes) 50g (being equivalent to 10wt%), react 2h, discharging, obtaining clear viscous liquids, to be polyurea type anti-settling
Agent, its solids content is 50.7wt%, and urea bond content is 2.70wt%.
Embodiment 6
In the beaker of 1000ml, add the solvent-borne type Hydroxylated acrylic resin 400g (phase of the Mn3000 of embodiment 2 preparation
When in 80wt%), it is placed under high speed dispersor, starts stirring 1000～1200r/min, and be heated to 60 DEG C with water-bath, add
Enter the diisocyanate compound solution (hexamethylene diisocyanate 9.96g mixes) prepared in advance with dimethylbenzene 40.04g
50g (is equivalent to 10wt%), reacts 2h, is cooled to less than 20 DEG C, adds the aminated compounds solution (isophorone prepared in advance
Diamidogen 10.10g mixes with dimethylbenzene 39.90g) 50g (being equivalent to 10wt%), reacts 2h, discharging, obtains clear viscous liquids i.e.
For polyurea type anti-settling agent, its solids content is 52wt%, and urea bond content is 4.01wt%.
Embodiment 7
In the beaker of 1000ml, add the solvent-borne type Hydroxylated acrylic resin 420g (phase of the Mn4000 of embodiment 3 preparation
When in 84wt%), it is placed under high speed dispersor, starts stirring 1000～1200r/min, and be heated to 60 DEG C with water-bath, add
(isophorone diisocyanate 12.67g and dimethylbenzene 27.33g mix to enter the diisocyanate compound solution for preparing in advance
Close) 40g (being equivalent to 8wt%), reacts 2h, is cooled to less than 20 DEG C, add the aminated compounds solution (diformazan prepared in advance
Phenylenediamine 7.76g mixes with dimethylbenzene 32.24g) 40g (being equivalent to 8wt%), reacts 2h, discharging, obtains clear viscous liquids i.e.
For polyurea type anti-settling agent, its solids content is 50.3wt%, and urea bond content is 4.07wt%.
Embodiment 8
In the beaker of 1000ml, add the solvent-borne type Hydroxylated acrylic resin 450g (phase of the Mn5000 of embodiment 4 preparation
When in 90wt%), it is placed under high speed dispersor, starts stirring 1000～1200r/min, and be heated to 40 DEG C with water-bath, add
(toluene di-isocyanate(TDI) 15.66g mixes with dimethylbenzene 9.34g, 25g to enter the diisocyanate compound solution for preparing in advance
(being equivalent to 5wt%), reacts 2h, is cooled to 20 DEG C, adds the aminated compounds solution (m-xylene diamine prepared in advance
12.24g mixes with dimethylbenzene 12.76g) 25g (being equivalent to 5wt%), reacts 2h, discharging, obtains clear viscous liquids and be poly-
Urea type anti-settling agent, its solids content is 40.6wt%, and urea bond content is 5.58wt%.
The viscosity of polyurea type anti-settling agent that above-described embodiment 5～8 prepares is shown in accompanying drawing 1 with the relation of shearing force.
Accompanying drawing 1 is with BROOKFIELD DV-III Ultra flow graph, at 25 DEG C, uses No. 4 rotors, measures difference and turns
The viscosity number of the lower polyurea type anti-settling agent of speed, with viscosity (mPa.s) as ordinate, the rotating speed (r/min) of rotor is that abscissa makes
's.
The detection of embodiment 5～8 polyurea type anti-settling agent thixotropic behavior
(1) detection method
1. viscosity measurement
With BROOKFIELD DV-III Ultra flow graph, at 25 DEG C, using No. 4 rotors, rotating speed is transferred to 2r/min and is rotated
After 2min until viscosity basicly stable constant time, the viscosity writing down anti-settling agent transparency liquid is the viscosity under low-shearing force effect；
At 25 DEG C, use No. 4 rotors, rotating speed be transferred to 60r/min rotate after 2min until viscosity basicly stable constant time, write down
The viscosity of anti-settling agent transparency liquid is the viscosity under high shear；
2. the assay method of the high viscosity required time of low sheraing is returned to by the low viscosity of high shear
With BROOKFIELD DV-III Ultra flow graph, at 25 DEG C, use No. 4 rotors, the rotating speed of rotor is transferred to
60r/min, after rotation 2min when viscosity is basicly stable, record viscosity value (being the viscosity under high shear), will
The adjustment of rotational speed of rotor is allowed to rotate to 2r/min again, starts timing with stopwatch simultaneously, until viscosity basicly stable constant time (low
Viscosity under shear action), the record time used is exactly the high viscosity being returned to low-shearing force by the low viscosity of high shear force
Required time.
(2) testing result is shown in Table 1.
Table 1
Detect the polyurea type anti-settling agent of the present invention application effect in dual-component polyurethane finishing varnish
(1) dual-component polyurethane finishing varnish is used in detection
1. the formula of varnish is shown in Table 2.
Table 2
2. the preparation of varnish
In the beaker of 250ml, add each material of table 2 formula ratio, be placed under high speed dispersor, start stirring, with
600～800r/min rotating speed stirring 20min, are uniformly dispersed and can prepare varnish 1～6 respectively.
3. the preparation of dual-component polyurethane finishing varnish
Respectively by N-3390 firming agent and the dimethylbenzene of prepared varnish 1～6 and Beyer Co., Ltd, by varnish: N-3390 is solid
Agent: dimethylbenzene=3.5:1:2 mix homogeneously can be prepared by dual-component polyurethane finishing varnish 1～6.
(2) preparation of paint film
It is typically prepared law regulation method by GB/T 1727-1992 paint film, makes with dual-component polyurethane finishing varnish 1～6 respectively
Standby paint film, preserves for detection.
(3) detection method
Concrete assay method is as follows:
1. coating appearance and appearance of film
Detect by an unaided eye；
2. the thixotropic index of coating
With BROOKFIELD DV-III Ultra flow graph, No. 4 rotors, when 25 DEG C, rotating speed is transferred to 6r/min, rotates
After 2min when viscosity is basicly stable, write down viscosity during 6r/min rotating speed, then adjustment of rotational speed to 60r/min, rotate 2min
After when viscosity is basicly stable, write down viscosity during 60r/min rotating speed, the ratio of the numerical value of twice measurement be exactly this varnish touch
Varying index；
3. gloss of film
By GB/T9754-2007 paint and varnish without 20 ° of colored paint paint film of metallic pigments, 60 ° and 85 ° of bright lusters
Assay method regulation detection.
4. paint film aberration
Measuring method Part II by GB/T11186.2-1989 film color: the assay method inspection that color measuring specifies
Survey；
5. QUV is aging
It is exposed to fluorescent UV and water regulation by the artificial weathering aging of GB/T 23987-2009 paint and varnish coating
Assay method detection, fluorescent tube used is I type, exposes employing method A-containing the exposure of condensation.
(4) testing result is shown in Table 4.
Table 4
Dual-component polyurethane finishing varnish 1 every using polyurea type anti-settling agent of the present invention is can be seen that by table 4 testing result
Detection data prove that polyurea type anti-settling agent of the present invention can be applied in dual-component polyurethane finishing varnish and apply effect to surpass comprehensively
Cross existing tradition anti-settling agent.
Claims (4)
1. a polyurea type anti-settling agent, it is characterised in that it is Hydroxylated acrylic resin and diisocyanate compound solution,
At 40～60 DEG C, react 1～3h, be then cooled to 0～40 DEG C, then with aminated compounds solution reaction 1～2h, cooling discharge
The acrylic resin of the polyureas grafting prepared, its solids content is 45～55wt%, and urea bond content is 3.0～4.5wt%, polyureas
Structure is grafted on the side chain of Hydroxylated acrylic resin molecule, and above-mentioned each raw material dosage is as follows: Hydroxylated acrylic resin 70～
90wt%, diisocyanate compound solution 5～15wt%, aminated compounds solution 5～15wt%, above each raw material dosage
Sum is 100wt%, and wherein, Hydroxylated acrylic resin is with hydroxy-acrylate monomer i.e.: 2-(Acryloyloxy)ethanol, acrylic acid hydroxyl
One or more in propyl ester, hydroxyethyl methylacrylate, Hydroxypropyl methacrylate and acrylic acid, butyl acrylate, propylene
Acetoacetic ester, Isooctyl acrylate monomer, methyl methacrylate, butyl methacrylate, isobutyl methacrylate, styrene, uncle
Ethylene carbonate, glycidyl acrylate, tertiary carbonic acid glycidyl ester, isobornyl acrylate, methacrylic acid isoborneol
One or more in ester monomer, in the presence of peroxide initiator, heating carries out polymerisation in solution acquisition, each raw material dosage
By weight percentage: monomer total amount is 45%～80%, wherein, hydroxy-acrylate monomer account for monomer total amount 1.0～
4.0wt%, solvent 20～50%, peroxide initiator 1～10%, above each component sum is 100%, this hydroxy acrylic acid
The solids content of resin is 50～80wt%, and Mn number-average molecular weight is 2000～5000, molecular weight distribution 1.8～2.2, hydroxyl
Content 0.17～0.42wt%, containing hydroxyl value≤1 in per molecule on average；This anti-settling agent is transparency liquid, has thixotroping
Characteristic: under the low-shearing force effect of rotating speed 2r/min, viscosity is 60000～300000mPa.s, at the height rotating 60r/min
Under shear action, viscosity is 2000～8000mPa.s, returns to the high viscosity institute of low-shearing force from the low viscosity of high shear force
Being 10～20s with the time, described viscosity is to use BROOKFIELD DV-III Ultra flow graph, at 25 DEG C, with No. 4 rotors
Record.
Polyurea type anti-settling agent the most according to claim 1, it is characterised in that the concrete preparation of described Hydroxylated acrylic resin
Method is as follows: first add in reaction bulb by solvent, is warming up to 100～170 DEG C, at the uniform velocity dropping monomer and the mixture of initiator,
Time for adding is 3～6h, and completion of dropwise addition insulation 2～3h, cooling discharge can be prepared by.
Polyurea type anti-settling agent the most according to claim 1, it is characterised in that described diisocyanate compound solution is
One or more in aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate and varsol, ketone
A kind of solution being mixed to form in kind solvent, esters solvent, ether solvent, solvent of ether ester type, the mass ratio of the two mixing is
1:0.5～4.5.
Polyurea type anti-settling agent the most according to claim 1, it is characterised in that described aminated compounds solution is aliphatic amine
Class, aromatic amine, alcamines, ether amines apoplexy due to endogenous wind one or more with varsol, ketones solvent, esters solvent, ethers molten
A kind of solution being mixed to form in agent, solvent of ether ester type, the mass ratio of the two mixing is 1:1～13.5.
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| CN107849209B (en) * | 2015-07-27 | 2020-12-15 | 毕克化学有限公司 | Urea urethanes for rheology control |
| CN106147603A (en) * | 2016-06-22 | 2016-11-23 | 安徽汇利涂料科技有限公司 | A kind of corrosion resistant water super-thin steel structure fire-proof paint |
| CN106047088A (en) * | 2016-06-22 | 2016-10-26 | 安徽汇利涂料科技有限公司 | Gas cabinet anti-corrosion paint and preparation method thereof |
| CN105907255A (en) * | 2016-06-22 | 2016-08-31 | 安徽汇利涂料科技有限公司 | Solvent-free static conducting coating and preparation method thereof |
| CN106186848A (en) * | 2016-06-28 | 2016-12-07 | 王青 | A kind of coating material of anti-concrete carbonization |
| CN109554093B (en) * | 2018-11-25 | 2020-12-11 | 中国海洋石油集团有限公司 | Two-component waterborne polyurethane floating coating composition with anti-sagging characteristic and preparation method thereof |
| CN109554048B (en) * | 2018-11-25 | 2021-01-19 | 中国海洋石油集团有限公司 | Baking type water-based acrylic acid middle coating composition with anti-sagging characteristic and preparation method thereof |
| CN110003419B (en) * | 2019-03-08 | 2021-10-08 | 黎明化工研究设计院有限责任公司 | Pre-gel and preparation method and application thereof |
| CN111763296B (en) * | 2020-06-17 | 2022-04-05 | 广东柯力森树脂有限公司 | Modified acrylic resin and preparation method thereof |
| CN113248180A (en) * | 2021-04-12 | 2021-08-13 | 广西军泰建材有限公司 | Aggregate regulator for concrete and preparation method thereof |
| CN114369219B (en) * | 2021-12-20 | 2023-11-10 | 上海金仕迈树脂有限公司 | Polyurea particle modified thixotropic resin and preparation method thereof |
| CN116478069A (en) * | 2023-03-03 | 2023-07-25 | 天津大学 | Diurea anti-sagging agent and synthesis method thereof |
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