CN107629538A - New non-ionic type polyamide rheology modifier for water paint - Google Patents
New non-ionic type polyamide rheology modifier for water paint Download PDFInfo
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- CN107629538A CN107629538A CN201610557145.0A CN201610557145A CN107629538A CN 107629538 A CN107629538 A CN 107629538A CN 201610557145 A CN201610557145 A CN 201610557145A CN 107629538 A CN107629538 A CN 107629538A
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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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block 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
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
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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
- C08G18/60—Polyamides or polyester-amides
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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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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- 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
- 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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- Polymers & Plastics (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
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Abstract
Nonionic rheology modifier is prepared for water paint, the nonionic rheology modifier includes the polyamide prepared by the polymer of acid blocked, the polyamide is by the blocked with polymer comprising non-ionic hydrophilic segment and is then dispersed in water, and the nonionic rheology modifier provides excellent pigment suspension performance and rheological property for water based paint.
Description
Technical field
For the nonionic rheology modifier composition of water paint, it prevents the heavy of pigment and solid particle in coating
Drop.
Background technology
In order to prevent the solid particles sediment of pigment or other fine dispersions during storage in coating, into composition
Add pigment suspension agent or antisettling agent.Antisettling agent can provide excellent pigment suspension performance and stream for water-based paint compositions
Become performance.The settlement issues occurred in coating can be overcome using pigment suspension agent or antisettling agent.In no such antisettling agent
In the case of, pigment and other undissolved materials, once sedimentation, then be likely difficult to be redispersed in coating system.Therefore, originally
Additive (antisettling agent) can be used to control the rheological characteristic of the aqueous fluids system of the solid particle comprising fine dispersion in field
Energy and pigment suspension performance simultaneously make it easier to use.
Because the particle diameter of pigment is big and proportion is also big, therefore aluminium pigment or pearlescent pigment, such as in metallic paint and corrosion resistant
The mica or corrosion-inhibitive pigments used in coating are lost, will cause easily to settle in coating.In solvent based coating, by acid amides
The antisettling agent of wax class or PEO wax class is used to prevent from settling, but these many additives are not suitable for water paint
In.
The material of antisettling agent or pigment suspension agent as organic (or non-aqueous) coating composition is dispersed in organic
Emulsifiable Tissuemat E in solvent.This is disclosed in No. 3,123,488 and No. 3,184,233 United States Patent (USP).3rd,
985, No. 568 United States Patent (USP)s describe butyrous paste, its include be suspended in the castor oil solution of sulphation/sulfonation can breast
The particle of the fine dispersion of the Tissuemat E of change, wherein the castor oil solution is used to change the solid particle for including fine dispersion
Non-aqueous fluid systems rheological property and suspendability.
No. 3,937,678 U.S. Patent Publication will be by making hydrogenated castor oil fatty or comprising hydrogenated castor grease
The mixture for the amide waxe that the organic mixture of fat acid reacts and obtained with amine is applied in non-aqueous fluid systems, can improve bag
The rheological property and suspendability of the non-aqueous fluid systems of solid particle containing fine dispersion.
By the thickener of such as fumed silica or such as, the clay of montmorillonite, hectorite or Attagel is used for water
To adjust pigment sedimentation problem in property coating system.However, these materials, which have, makes the glossiness related to coating material solidified system
The defects of reduction, and adjustment thing is added after being difficult to be used as when coating preparation is completed.In the manufacturing process of coating, these materials
It is difficult to scattered and needs high shear mixing equipment fully dispersed to realize.
No. 4,381,376 U.S. Patent Publication is by ethene and α, β-ethylene linkage insatiable hunger with least one hydroxy-acid group
The low-molecular weight copolymer acid formed with carboxylic acid, the method with forming ionic copolymer salt with 1 to trivalent cation.This
A little materials can be dispersing aid so that the inert material of the fine dispersion of such as pigment is scattered in comprising polypropylene and polyethylene
A variety of non-aqueous polymer compositions.
No. 5,374,687 U.S. Patent Publication is neutralized by alpha-olefin and α, β-ethylene linkage unsaturation carboxylic by using nertralizer
Emulsified copolymer that acid obtains and the material that obtains.Said composition serves as water-based antisettling agent.The additive is liquid, and because
This has operational advantage, but it sinks as the anti-of the pearlescent pigment of the aluminium pigment in waterborne metallic paint or such as mica
It is not sufficiently effective during depressant prescription.
No. 5,994,494 U.S. Patent Publication is used for the antisettling agent of water paint.It is prepared by the following group
Compound：Polyamide, it is by making the primary diamines with 2 to 12 carbon atoms and the dimerization dicarboxyl acid reaction of the amount more than diamine
Obtain, wherein dimerization dicarboxylic acids is by making unrighted acid (common name：Dimeric dibasic acid) or dimeric dibasic acid mixture with addition
Dicarboxylic acids with 3 to 21 carbon atoms and/or the monocarboxylic acid polymerization with 2 to 22 carbon atoms and obtain.With neutralization
In alkali and polyamide, and then neutralized polyamide is scattered in the medium being mainly made up of water.
In recent years, due to environmental problem and ease of use issues, inspection is energetically proposed to water paint.Therefore,
Naturally the antisettling agent for water-based system is sought.Although as described above, so far using a variety of antisettling agents propose as
Water-based antisettling agent, but they have problem, for example, they are not enough to prevent to have big particle diameter and big proportion in effect
The sedimentation of pigment, for example, for the aluminium pigment in waterborne metallic paint and the pearlescent pigment of such as mica, for water-based corrosion-resistant
Corrosion-inhibitive pigments in coating.In addition, gloss and water resistance reduce.
The antisettling agent containing daiamid composition disclosed before this includes aromatic solvent to improve dehydration, and this will cause
The aromatic solvent of residual is stayed in coating, even if applying solvent removal process (the 5th, 994, No. 494 United States Patent (USP)).This
Outside, the antisettling agent for water paint of many early stages needs to use amine neutralizer.As a result, coating property becomes quick to pH
Sense.In some cases, nertralizer will also cause volatility problem.
Excellent pigment suspension performance and rheological property are provided by hydrotropism's coating composition, instant invention overcomes existing
The problem of technology and defect, and without amine neutralizer and consequential pH sensitiveness.
Summary of the invention
In one embodiment, the invention provides the nonionic rheology modifier composition for water paint,
It is obtained by the method having steps of：Make the polyamide of more acid blockeds and the monocyclic oxygen with non-ionic hydrophilic segment
The polymer reaction of end-blocking is to be consequently formed polymer；And the polymer is scattered in the water containing cosolvent to be flowed
Become modifying agent dispersion.
In another embodiment, the invention provides the nonionic rheology modifier composition for water paint,
It including following method by obtaining：The polyamide of more acid blockeds is set to be reacted with alkyl glycidol ether to form intermediate；Make
The polymer reaction that the intermediate blocks with the monoisocyanates with non-ionic hydrophilic segment is polymerize with being consequently formed
Thing；And the polymer is scattered in the water containing cosolvent to obtain rheology modifier dispersion.
In yet another embodiment, the invention provides the nonionic polyamide rheology modifier of formula (1)In formula (1) X be more acid blockeds polyamide, n=2~6, and in formula (1) Y be include it is following
One or more in end group：
Wherein R1 is the terminal aliphatic containing 1 to 22 carbon atom, alicyclic end group or aromatic series end in formula (1)
Base.In one embodiment, R2 is selected from toluene di-isocyanate(TDI), IPDI, six methylenes in formula (1)
Group diisocyanate, diphenyl methane -4,4 '-diisocyanate, dicyclohexyl methyl hydride -4,4 '-di-isocyanate, 1,4- are double
The residue moiety of (2- isocyanic acid -2- bases) benzene, diisocyanate cpd in trimethyl hexamethylene diisocyanate, and
X ' is poly- (C2-4Alkylene oxide).
Preferred embodiment
The purpose of the present invention is by providing antisettling agent or pigment suspension without aromatic and non-volatile method
Agent, compared with the current material with being used for anti-settling and pigment suspension in aqueous coating system, it is more environmentally friendly.
Antisettling agent is easily operated, and is easily incorporated into waterborne compositions.In addition, by using the raw material containing the composition through design
Instead of mixture, when being used for the material of anti-settling in the manufacture present invention can with control process and ratio of components, physical property and
Application performance is also controllable.It is described herein to realize the embodiment of the rheologic additive of this purpose.
One embodiment of present disclosure provides nonionic polyamide rheology modifier, its can by including with
Under method obtain：Make the polyamide of the more acid blockeds polymer epoxy-capped with the list with non-ionic hydrophilic segment anti-
Should.Then, polyamide is scattered in the water containing cosolvent to obtain the rheology modifier of 25% solids content.
In some embodiments, by make at least one dicarboxylic acids with 3 to 54 carbon atoms and/or tricarboxylic acids with
At least one diamine reacts and the polyamide of more acid blockeds is made.In such embodiment, the dicarboxylic acids is selected from：The third two
Acid, butanedioic acid, glutamic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, dodecanedioic acid, M-phthalic acid and two
Polyglycerol fatty acid.In another embodiment, the tricarboxylic acids is selected from：Citric acid, propane -1,2,3- tricarboxylic acids, 1,2,4- butane
Tricarboxylic acids, benzene -1,3,5- tricarboxylic acids, 1,2,4- benzene tricarbonic acids, xenyl -3,4 ', 5- tricarboxylic acids and trimerized fatty acids.Each
In foregoing embodiments, the diamine is selected from：Ethylenediamine, 1,4- diaminobutanes, hexamethylene diamine, the methylenes of 1,10- ten
Base diamines, the methylene diamines of 1,11- 11, the dimethylene diamines of 1,12- ten, dimethylphenylene diamine and 4,4 '-diamino-diphenyl
Methane.
In some embodiments, by reacting epichlorohydrin and monohydroxy non-ionic hydrophilic compound, or pass through
Make the non-ionic hydrophilic compound reaction of single alkyl acid and diglycidyl end-blocking and be made with non-ionic hydrophilic
The epoxy-capped polymer of the list of property segment.In such embodiment, the molecule of monohydroxy non-ionic hydrophilic compound
Measure for 500g/ moles to 3000g/ moles and comprising the terminal aliphatic with 1 to 22 carbon atom, alicyclic end group or fragrance
Poly- (the C of race's end group2-4Alkylene oxide).
In some embodiments, it is anti-in the non-ionic hydrophilic compound of single alkyl acid and diglycidyl end-blocking
In the case of answering, single alkyl acid is selected from：Acetic acid, butyric acid, caproic acid, octanoic acid, capric acid, laurate, myristic acid, palmitic acid, tristearin
Acid, behenic acid, 1,2- hydroxy stearic acids and oleic acid.In such embodiment, the compound of diglycidyl end-blocking
Non-ionic hydrophilic segment molecular weight for 500 to 3000 and including containing 10%-100% ethylene oxide groups gathering
(C2-4Alkylene oxide) segment.
Each foregoing embodiments of the polyamide of more acid blockeds and single epoxy-capped polymer can be combined as non-
The different embodiments of ionic polyamide rheology modifier.
The another embodiment of present disclosure provides nonionic polyamide rheology modifier, its can by comprising with
Under method obtain：The polyamide of more acid blockeds is set to be reacted with alkyl glycidol ether to form intermediate and then make in this
The polymer reaction that mesosome blocks with the monoisocyanates with non-ionic hydrophilic segment.
In one embodiment, by make at least one dicarboxylic acids with 3 to 54 carbon atoms and/or tricarboxylic acids with
The polyamide of more acid blockeds is made at least one diamine reaction.In such embodiment, dicarboxylic acids is selected from：Malonic acid, amber
Amber acid, glutamic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, dodecanedioic acid, M-phthalic acid and two polyesters
Fat acid.In another embodiment, tricarboxylic acids is selected from：Citric acid, propane -1,2,3- tricarboxylic acids, 1,2,4- butane tricarboxylic acids,
Benzene -1,3,5- tricarboxylic acids, 1,2,4- benzene tricarbonic acids, xenyl -3,4 ', 5- tricarboxylic acids and trimerized fatty acids.In each foregoing reality
Apply in scheme, diamine is selected from：Ethylenediamine, 1,4- diaminobutanes, hexamethylene diamine, 1,10- decamethylene diamines, 1,
The methylene diamines of 11- 11, the dimethylene diamines of 1,12- ten, dimethylphenylene diamine and 4,4 '-diaminodiphenyl-methane.
In one embodiment, alkyl glycidol ether is selected from：Alkyl glycidol ether with C2-C16 alkyl, example
Such as：Ethyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, the tert-butyl group shrink
Glycerin ether, octyl glycidyl ether, decyl glycidyl ether, lauryl diglycidyl ether, myristyl
(tetradodecyl) glycidol ether and cetyl glycidyl ether.
In another embodiment, it is made by making diisocyanate be reacted with monohydroxy non-ionic hydrophilic compound
The polymer of monoisocyanates end-blocking with non-ionic hydrophilic segment.In such embodiment, diisocyanate choosing
From：Toluene di-isocyanate(TDI), IPDI, hexamethylene diisocyanate, diphenyl methane -4,4 '-two are different
Cyanate, dicyclohexyl methyl hydride -4,4 '-di-isocyanate, 1,4- double (2- isocyanic acid -2- bases) benzene, tri-methyl hexamethylenes two
Isocyanates, or the mixture of such diisocyanate.In such embodiment, monohydroxy non-ionic hydrophilic chemical combination
The molecular weight M of thing is 500g/ moles to 3000g/ moles and comprising the terminal aliphatic with 1 to 22 carbon atom, alicyclic
Poly- (the C of end group or aromatic series end group2-4Alkylene oxide).
Can by the polyamide of more acid blockeds, alkyl glycidol ether and monoisocyanates block polymer it is each before
State the different embodiments that combination of embodiment is nonionic polyamide rheology modifier.
For each foregoing embodiments of nonionic polyamide rheology modifier, cosolvent is selected from：Ethylene glycol list first
Ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, butyl cellosolve solvent, METHYLPYRROLIDONE, 3- methoxyl group -3- first
Base-n-butyl alcohol, MMB acetic acid esters, methyl -5- (dimethylamino) -2- methyl -5- oxopentanoic acids ester,
N- formyl-morpholines.
The nonionic polyamide rheology modifier of formula (1) is provided in the another embodiment of present disclosure
Wherein X is the polyamide of more acid blockeds and n=2~6.Y is one kind or more in following end group in formula (1)
Kind：
In some embodiments, R1 is the terminal aliphatic containing 1 to 22 carbon atom, alicyclic end group or aromatic series
End group.In some other embodiments, R2 is selected from toluene di-isocyanate(TDI), IPDI, hexa-methylene
Double (the 2- of diisocyanate, diphenyl methane -4,4 '-diisocyanate, dicyclohexyl methyl hydride -4,4 '-di-isocyanate, 1,4-
Isocyanic acid -2- bases) benzene, the residue moiety of diisocyanate cpd in trimethyl hexamethylene diisocyanate,
And X ' is poly- (C2-4Alkylene oxide).
Embodiment
Embodiment A-1：The synthesis of the polyamide of more acid blockeds
0.49 mole of dimeric dibasic acid and 0.11 mole of adipic acid are filled with equipped with agitating device, thermoregulator, water conservancy diversion dress
Put in the 1L four-neck flasks with nitrogen introducing tube, be subsequently agitated for and be heated to 50 DEG C.Gradually add 0.4 moles of ethylene diamine and observe
Heat release situation, stir mixture and be gradually heated to 175 DEG C to carry out dehydration.Palm fibre is obtained by the reaction of two (2) hours
The polyamide A-1 of the more acid blockeds of color, its acid number are 74mg KOH/g.
Embodiment A-2-A-8：The synthetic example of the polyamide of more acid blockeds
According to the synthetic method of embodiment 1, the polyamide synthesis that the composition shown in table 1 carries out other more acid blockeds is real
Example is applied to obtain the polyamide A-2 to A-8 of more acid blockeds.
The composition of the synthetic example of the polyamide of table acid blocked more than 1
Embodiment B1-B2：The synthesis of the epoxy-capped polymer of list with non-ionic hydrophilic segment
MPEG1000 is filled with four necks equipped with agitating device, water-cooled condenser, thermoregulator and nitrogen introducing tube
In round-bottomed flask.The epichlorohydrin of equivalent is added dropwise into flask, reaction is carried out (3) hour at 60 DEG C and further with 5%
The NaOH aqueous solution is extracted through separatory funnel to obtain the epoxy-capped polymer B -1 of the list with non-ionic hydrophilic segment.
It is filled with using diglycidyl PEG1000 and as the triethylamine of catalyst equipped with agitating device, cold water condensation
In four neck round-bottom flasks of device, thermoregulator and nitrogen introducing tube.By the laurate of semi-normal at 70 DEG C in advance fusing and by
Gradually it is added in flask, reaction was carried out for six (6) hours at 85 DEG C to obtain the monocyclic oxygen with non-ionic hydrophilic segment
The polymer B -2 of end-blocking.
Table 2 has the synthetic example of the epoxy-capped polymer of the list of non-ionic hydrophilic segment
Embodiment C1-C2：The synthesis of the polymer of monoisocyanates end-blocking with non-ionic hydrophilic segment
One (1) mole MPEG550 is filled with the necks of 1L tetra- burning equipped with agitating device, thermoregulator and nitrogen introducing tube
In bottle, 70 DEG C are heated to, when MPEG compound melts, one (1) mole IPDI is gradually added into flask, is then cooled to 50
DEG C, add 0.15wt% triethylamine.Obtain monoisocyanates end-blocking polymer synthetic example C-1, wherein NCO% from
10.8% change turns to 5.4%.
The synthetic example C-2 of the polymer of monoisocyanates end-blocking is carried out according to embodiment C-1 synthesis step, and
Title intermediate is obtained, wherein NCO% becomes from 6.9% turns to 3.45%.
Table 3 has the synthetic example of the polymer of the monoisocyanates end-blocking of non-ionic hydrophilic segment
Embodiment 1：The synthesis of nonionic polyamide rheology modifier
By the polyamide A-1 of acid blocked more than one (1) mole and 2 moles of epoxy-capped polymer Bs -1 of list be filled with equipped with
In agitating device, water-cooled condenser, four neck round-bottom flasks of thermoregulator and nitrogen introducing tube.Into flask, addition is used as and urged
The 0.15wt% of agent triethylamine simultaneously makes reaction carry out for six (6) hours at 120 DEG C to obtain nonionic rheology modifier
Embodiment 1.
Embodiment 2-4：The synthetic example of nonionic polyamide rheology modifier
According to the synthetic method of embodiment 1, carry out other nonionic polyamide rheologies with the composition shown in table 4 and change
The synthetic example of property agent is to obtain nonionic polyamide rheology modifier embodiment 2 to 4.
Embodiment 5：The synthesis of nonionic polyamide rheology modifier
The polyamide A-3 of acid blocked more than one (1) mole is filled with equipped with agitating device, water-cooled condenser, temperature adjustment
In four neck round-bottom flasks of device and nitrogen introducing tube, 120 DEG C are heated to fusing, 2 moles of BGE are added in flask, as urging
The 0.15wt% of agent triethylamine, then by making reaction carry out for six (6) hours at 120 DEG C to obtain with acid number<1mg
KOH/g hydroxypolyamide intermediate, is then cooled to 70 DEG C, and monoisocyanates end-blocking in two (2) mole is added into flask
Polymer C-1 simultaneously makes itself and hydroxypolyamide intermediate reaction five (5) hour, while NCO% is less than 0.1%, obtains nonionic
Type polyamide rheology modifier.
Embodiment 6-12：The synthetic example of nonionic polyamide rheology modifier
According to the synthetic method of embodiment 5, it is rheology modified to carry out other nonionic polyamide with the composition shown in table 4
The synthetic example of agent is to obtain the embodiment 6-12 of nonionic polyamide rheology modifier.
The synthetic example of the nonionic polyamide rheology modifier of table 4
Testing example
The water-based styrene acrylic resin coating of the composition of following table 5 gather for the nonionic of water paint
The performance test of acid amides rheology modifier.
The composition of the water-based styrene acrylic resin coating of table 5
The preparation method of water paint：
Under agitation, by DI water, Levelol W-469, DAPRO DF677, AS2610 and Deuadd MA-95 (10%)
Mixing is to obtain the basic coating as part A.BG and DI water is used as cosolvent, under agitation by NUOSPESE FN265 and
AWA40596 (50%) is mixed to obtain the Aluminum Paste as part B.Under agitation, part B is added to part A, then addition
Rheology modifier and thickener Rheolate 150 are to obtain water paint.
The evaluation of the KU viscosity and Brookfield viscosity of water paint：
At 25 DEG C, originated by KU viscosity meters and the KU viscosity of overnight water paint.
At 25 DEG C, water paint is measured with 10rpm to 100rpm with rotor LV3 using DV-II viscosimeters
Brookfield viscosity (cPs), and calculating ratio (viscosity under viscosity/100rpm under 10rpm).
Anti-settling is tested：
The viscosity measured with NK2 flow cups is allowd to be 12 seconds to 15 seconds (25 DEG C) with deionized water dilution coating, will
Diluted coating is transferred in 50-mL teat glasses, and measures the AWA40596 of sedimentation volume and the body of overall coating
Long-pending percentage.
The performance test of the embodiment of table 6 (2% dosage)
The performance test of the embodiment of (connecting table) table 6 (2% dosage)
The performance test results of nonionic polyamide rheology modifier for water paint are shown in table 6.As a result table
Rheology modifier in the bright present invention in thixotropic property, prevent from showing good result in the sedimentations of metallic pigments, and when using
Contribute to the pigment orientation of improvement metallic pigments when in aqueous coating system.
Claims (23)
1. for the nonionic rheology modifier composition of water paint, it including following method by obtaining：
(1) make the polyamide of the more acid blockeds polymer reaction epoxy-capped with the list with non-ionic hydrophilic segment with by
This forms polymer；And
(2) polymer is scattered in the water containing cosolvent to obtain rheology modifier dispersion.
2. nonionic rheology modifier composition as claimed in claim 1, wherein the polyamide of polyacid end-blocking is logical
Cross what is made at least one dicarboxylic acids with 3 to 54 carbon atoms and/or tricarboxylic acids and the reaction of at least one diamine and obtain.
3. nonionic rheology modifier composition as claimed in claim 2, wherein the dicarboxylic acids is selected from malonic acid, amber
Acid, glutamic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, dodecanedioic acid, M-phthalic acid and dimer fatty
Acid.
4. nonionic rheology modifier composition as claimed in claim 2, wherein the tricarboxylic acids is selected from citric acid, third
Alkane -1,2,3- tricarboxylic acids, 1,2,4- butane tricarboxylic acids, benzene -1,3,5- tricarboxylic acids, 1,2,4- benzene tricarbonic acids, xenyl -3,4 ',
5- tricarboxylic acids and trimerized fatty acids.
5. nonionic rheology modifier composition as claimed in claim 2, wherein the diamine be selected from ethylenediamine, Isosorbide-5-Nitrae-
Diaminobutane, hexamethylene diamine, 1,10- decamethylene diamines, the methylene diamines of 1,11- 11, the dimethylenes of 1,12- ten
Diamines, dimethylphenylene diamine and 4,4 '-diaminodiphenyl-methane.
6. nonionic rheology modifier composition as claimed in claim 1, wherein described have non-ionic hydrophilic chain
The polymer that the list of section is epoxy-capped is by following acquisition：
(1) epichlorohydrin is made to be reacted with monohydroxy non-ionic hydrophilic compound, or
(2) react the non-ionic hydrophilic compound of single alkyl acid and diglycidyl end-blocking.
7. nonionic rheology modifier composition as claimed in claim 6, wherein the monohydroxy non-ionic hydrophilic
Compound includes the poly- (C of the terminal aliphatic with 1 to 22 carbon atom, alicyclic end group or aromatic series end group2-4Alkylene
Oxygen), and the molecular weight of wherein described monohydroxy non-ionic hydrophilic compound is 500g/ moles to 3000g/ moles.
8. nonionic rheology modifier composition as claimed in claim 6, wherein single alkyl acid is selected from acetic acid, fourth
Acid, caproic acid, octanoic acid, capric acid, laurate, myristic acid, palmitic acid, stearic acid, behenic acid, 1,2- hydroxy stearic acids and oil
Acid.
9. nonionic rheology modifier composition as claimed in claim 6, wherein diglycidyl end-blocking is non-
The molecular weight of the non-ionic hydrophilic segment of ionic hydrophilic compounds is 500 to 3000 and including containing 10%-100%
Poly- (the C of ethylene oxide group2-4- alkylene oxide) segment.
10. for the nonionic rheology modifier composition of water paint, it including following method by obtaining：
(1) polyamide of more acid blockeds is made to be reacted with alkyl glycidol ether to form intermediate；
(2) polymer reaction that the intermediate blocks with the monoisocyanates with non-ionic hydrophilic segment is made with thus
Form polymer；And
(3) polymer is scattered in the water containing cosolvent to obtain rheology modifier dispersion.
11. nonionic rheology modifier composition as claimed in claim 10, wherein the polyamide of polyacid end-blocking is
By making at least one dicarboxylic acids with 3 to 54 carbon atoms and/or tricarboxylic acids be reacted with least one diamine to obtain
's.
12. nonionic rheology modifier composition as claimed in claim 11, wherein the dicarboxylic acids is selected from malonic acid, amber
Amber acid, glutamic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, dodecanedioic acid, M-phthalic acid and two polyesters
Fat acid.
13. nonionic rheology modifier composition as claimed in claim 11, wherein the tricarboxylic acids is selected from citric acid, third
Alkane -1,2,3- tricarboxylic acids, 1,2,4- butane tricarboxylic acids, benzene -1,3,5- tricarboxylic acids, 1,2,4- benzene tricarbonic acids, xenyl -3,4 ',
5- tricarboxylic acids and trimerized fatty acids.
14. nonionic rheology modifier composition as claimed in claim 11, wherein the diamine is selected from ethylenediamine, 1,
4- diaminobutanes, hexamethylene diamine, 1,10- decamethylene diamines, the methylene diamines of 1,11- 11, the methylenes of 1,12- 12
Base diamines, dimethylphenylene diamine and 4,4 '-diaminodiphenyl-methane.
15. nonionic rheology modifier composition as claimed in claim 10, wherein the alkylene ketal water glycerin ether is selected from
Wherein described hydrocarbyl group has the alkyl glycidol ether of two to ten six carbon atoms, such as ethyl ether, isopropyl
Base glycidol ether, butyl glycidyl ether, isobutyl glycidyl ether, tertiary butyl glycidyl ether, octyl glycidyl ether,
Decyl glycidyl ether, lauryl diglycidyl ether, myristyl glycidol ether and cetyl glycidyl ether.
16. nonionic rheology modifier composition as claimed in claim 10, wherein monoisocyanates end-blocking is poly-
Compound is by making diisocyanate be reacted with monohydroxy non-ionic hydrophilic compound and manufactured.
17. nonionic rheology modifier composition as claimed in claim 11, wherein the diisocyanate is selected from toluene
Diisocyanate, IPDI, hexamethylene diisocyanate, diphenyl methane -4,4 '-diisocyanate,
Dicyclohexyl methyl hydride -4,4 '-di-isocyanate, 1,4- double (2- isocyanic acid -2- bases) benzene, the isocyanic acids of tri-methyl hexamethylene two
Ester, or the mixture of such diisocyanate.
18. nonionic rheology modifier composition as claimed in claim 11, wherein the monohydroxy non-ionic hydrophilic
Property compound includes poly- (C2-4Alkylene oxide)nWith the terminal aliphatic with 1 to 22 carbon atom, alicyclic end group or aromatic series
End group, and the molecular weight of wherein described monohydroxy non-ionic hydrophilic compound is 500g/ moles to 3000g/ moles.
19. the nonionic rheology modifier composition as described in claim 1 or 10, wherein the cosolvent is selected from ethylene glycol
Monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, butyl cellosolve solvent, METHYLPYRROLIDONE, 3- methoxyl groups -3-
Methyl-1-butanol, MMB acetic acid esters, methyl -5- (dimethylamino) -2- methyl -5- oxopentanoic acids
Ester, N- formyl-morpholines.
20. the nonionic polyamide rheology modifier of formula (1)
Wherein X is the polyamide of more acid blockeds,
N=2~6, and Y is the one or more in following end group in formula (1)：
Wherein R1 is the terminal aliphatic with 1 to 22 carbon atom, alicyclic end group or aromatic series end group,
R2 be selected from toluene di-isocyanate(TDI), IPDI, hexamethylene diisocyanate, diphenyl methane-
4,4 '-diisocyanate, dicyclohexyl methyl hydride -4,4 '-di-isocyanate, 1,4- double (2- isocyanic acid -2- bases) benzene, trimethyls
The residue moiety of diisocyanate cpd in hexamethylene diisocyanate,
And X ' is poly- (C2-4Alkylene oxide).
21. composition as claimed in claim 20, wherein Y are：
22. composition as claimed in claim 20, wherein Y are：
23. composition as claimed in claim 20, wherein Y are：
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| CN201610557145.0A CN107629538B (en) | 2016-07-15 | 2016-07-15 | Novel nonionic polyamide rheology modifiers for aqueous coatings |
| PCT/CN2017/092345 WO2018010615A1 (en) | 2016-07-15 | 2017-07-10 | Novel non-ionic polyamide rheology modifier for aqueous coating |
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| JP2018176632A (en) * | 2017-04-19 | 2018-11-15 | 新日鐵住金株式会社 | Coated steel sheet |
| CN113999390A (en) * | 2021-10-29 | 2022-02-01 | 江西省龙海化工有限公司 | Polyurea modified polyamide aqueous rheological additive and preparation method thereof |
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| CN105001417A (en) * | 2015-07-15 | 2015-10-28 | 上海核心新材料科技有限公司 | Modified polyamide structural rheological agent as well as preparation method and application thereof |
| CN105648778A (en) * | 2016-03-02 | 2016-06-08 | 深圳天鼎精细化工制造有限公司 | Preparation method of nonionic hydrophilic fatty acid amide organosilicon copolymer softener |
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| US6448366B1 (en) * | 2000-06-08 | 2002-09-10 | Elementis Specialties, Inc. | Rheological additives and paint and coating compositions containing such additives exhibiting improved intercoat adhesion |
| CN102746501B (en) * | 2012-06-21 | 2014-08-13 | 上海核心新材料科技有限公司 | Manufacturing method of dispersant and dispersant |
| CN104403100B (en) * | 2014-12-16 | 2016-07-06 | 东莞市隆海新材料科技有限公司 | A kind of preparation method of aqueous polyamide thixotroping anti-settling agent |
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| CN105001417A (en) * | 2015-07-15 | 2015-10-28 | 上海核心新材料科技有限公司 | Modified polyamide structural rheological agent as well as preparation method and application thereof |
| CN105648778A (en) * | 2016-03-02 | 2016-06-08 | 深圳天鼎精细化工制造有限公司 | Preparation method of nonionic hydrophilic fatty acid amide organosilicon copolymer softener |
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| JP2018176632A (en) * | 2017-04-19 | 2018-11-15 | 新日鐵住金株式会社 | Coated steel sheet |
| CN113999390A (en) * | 2021-10-29 | 2022-02-01 | 江西省龙海化工有限公司 | Polyurea modified polyamide aqueous rheological additive and preparation method thereof |
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