CN100392029C - Pigment wetting dispersing agent for water-base coating - Google Patents
Pigment wetting dispersing agent for water-base coating Download PDFInfo
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- CN100392029C CN100392029C CNB2004100842877A CN200410084287A CN100392029C CN 100392029 C CN100392029 C CN 100392029C CN B2004100842877 A CNB2004100842877 A CN B2004100842877A CN 200410084287 A CN200410084287 A CN 200410084287A CN 100392029 C CN100392029 C CN 100392029C
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- Prior art keywords
- dispersing agent
- wetting dispersing
- water
- pigment
- wetting
- Prior art date
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- 238000009736 wetting Methods 0.000 title claims abstract description 44
- 239000000049 pigment Substances 0.000 title claims abstract description 42
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 34
- 238000000576 coating method Methods 0.000 title description 5
- 239000011248 coating agent Substances 0.000 title description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003973 paint Substances 0.000 claims abstract description 18
- 230000000536 complexating effect Effects 0.000 claims abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- -1 polyoxyethylene glycidyl ether Polymers 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 14
- 238000009413 insulation Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 8
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 150000007514 bases Chemical class 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 4
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical group C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 claims description 3
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 230000003068 static effect Effects 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- PHNCAZJLVQPLRS-UHFFFAOYSA-N C1(=CC=CC=C1)O.C(CCCCCCCC)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)O.C(CCCCCCCC)C1=CC=CC=C1 PHNCAZJLVQPLRS-UHFFFAOYSA-N 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- 125000001033 ether group Chemical group 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 21
- 239000000080 wetting agent Substances 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract 1
- 238000004220 aggregation Methods 0.000 abstract 1
- 150000002170 ethers Chemical class 0.000 abstract 1
- 239000001023 inorganic pigment Substances 0.000 abstract 1
- 239000012860 organic pigment Substances 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 239000002002 slurry Substances 0.000 description 39
- 239000000047 product Substances 0.000 description 24
- 238000012360 testing method Methods 0.000 description 23
- 239000012752 auxiliary agent Substances 0.000 description 14
- 239000002245 particle Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical class COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 5
- 230000000274 adsorptive effect Effects 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229920000151 polyglycol Polymers 0.000 description 5
- 239000010695 polyglycol Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 230000006641 stabilisation Effects 0.000 description 5
- 238000011105 stabilization Methods 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000005352 clarification Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 235000019830 sodium polyphosphate Nutrition 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 description 1
- HLLSOEKIMZEGFV-UHFFFAOYSA-N 4-(dibutylsulfamoyl)benzoic acid Chemical compound CCCCN(CCCC)S(=O)(=O)C1=CC=C(C(O)=O)C=C1 HLLSOEKIMZEGFV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 101710194948 Protein phosphatase PhpP Proteins 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010931 ester hydrolysis Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
Abstract
The present invention relates to a pigment wetting dispersing agent for water-based paint, which is compounded by a wetting agent and a dispersing base group and has double performance of wetting and dispersing. The wetting part is composed of traditional non-ionic surface active agents-polyethenoxy ether type compounds; then, an active base group (shown in the formula I) is introduced on the structure of the wetting part. For further improving the oriented adsorption of the dispersing agent to pigment, a base group containing nitrogen,-CH2CH2OH,-COOR and-COOM (M = MH4<+>, Na<+>, K<+>) or a base group capable of complexing with metal ions is introduced through two active base groups (shown in the formula II). Thus, the obtained dispersing agent is suitable for both organic pigment and inorganic pigment. Obtain color paste after dispersion has the characteristics of low viscosity, high concentration, bright color and high stability. Furthermore, the color paste does not generate the phenomena of aggregation and thickness recovery when diluted to low concentration by water.
Description
Technical field
The present invention relates to be used in a kind of water-based paint pigment wetting dispersive additive, specifically, relate to a kind of pigment wetting dispersing agent that is used for water-based paint.
Background technology
Present water base color stuffing wetting agent, dispersion agent are mainly used in the coating such as emulsion paint, water-based metal finish paint and water dilution alkyd, epoxy, vinylformic acid, are divided into following structured sort substantially:
(1) polycarboxylic acid salt: acrylic copolymer, poly-maleic acid (ester) multipolymer, polyphenyl sulfonic acid cocondensation compound, these belong to anionic dispersing agent.
(2) polyphosphoric acid salt: tripoly phosphate sodium STPP, Sodium hexametaphosphate 99, sodium polyphosphate, alkyl sodium polyphosphate (ammonium, potassium, lithium etc.).
(3) alkyl (alkylaryl) polyglycol ether (being main with the nonyl phenol polyglycol ether wherein) also has its acid product such as urethane and organosilicon etc. to be used as wetting agent in addition.
(4) contain amine-alcohol: as 2-amino-2-methyl-1-propanol, hydramine two phosphinylidyne ethylidene titanic acid ester, alkyl amine group ethanol etc. are as dispersion agent.
(5) cationic surfactant is seldom used in aqueous coating, because it is not suitable for negatively charged ion emulsion paint system.
Point out among the German Patent Ger.Offer.2636946 that the unit alcohol of alkyl (alkylaryl) polyglycol ether or the product that obtains with water-soluble fabulous organic group access all have good wettability and dispersiveness to color stuffing.The common ground of this class dispersion agent is exactly the structure that all contains polyglycol ether, it can effectively improve the wettability and the stability of system, but in dispersion process, be easy to cause foam, make that pigment slurry is loose, volumetric expansion, thereby limited the further dispersion of pigment and the raising of mill base concentration.
German Patent Ger.Offer.2638946 points out to introduce nitrogen-atoms in alkyl (alkylaryl) Soxylat A 25-7, can improve pigment particles and enter ability in the hydrophilic medium.And German Patent Ger.Offer.2807130 points out, polyoxyethylene nonylphenol ether, and n=10 ~ 18 o'clock connect the thanomin acetate, can improve dispersedly, and its structure is as follows:
Though the introducing of nitrogen-atoms and acetate can improve dispersing of pigments to a certain extent, this is for satisfying the demand in the system of high density pigment slurry.Also useful for this reason this quadrat method is improved dispersed, and as pointing out among the Japanese Patent Jpn.Kokai Tokkyo Koho 80,76,810: alkyl (alkylaryl) Soxylat A 25-7 inserts the phosphoric acid group, can improve dispersiveness.Point out again in Jpn.Suzuka Kogyo Koto SemmonGakka Kikyo one literary composition that alkyl polyoxyethylene base ether inserts phosphate group, its wettability with
The n value increase, and dispersedly descend with the increase of n value.The introducing of phosphate group makes the wetting ability of molecular structure increase greatly, so when water dilutes pigment slurry, can produce assembly, return thick phenomenon because of the dispersant-coated particle insufficient strength.
Point out that in United States Patent (USP) U.S.P 6403455 following structure product has wetting action to solid particle surfaces:
Wherein: Z=H, CH
3, C
2H
5, m=1～30, n=0～30;
R
1=H, CH
3, C
2H
5(straight chain C
8～C
12Alkyl); R
2=H, CH
3, C
2H
5Or same R
1
X＝N，O，S，P，Si，PO
3 -，SO
3 -；Y＝H。
The simplest compound is:
This is similar to the compound of organic alcohol amine, and its alkyl has very strong adsorption to color stuffing particle solids, is difficult for peeling off in water; Its polyglycol ether segment has the good hydrophilicity energy, and when it was coated on the solid particle surfaces, surface of pigments was just hydrophilic.When this color stuffing is dipped in the water, such coating layer can effectively be controlled particle and do movement continuously in water, also improved simultaneously interparticle electrostatic force effect (power that particle and dielectric friction produce), thereby reach the purpose of stabilization, but it in the process of water dilution pigment slurry, also easily take place pigment particles assembly, return thick phenomenon.
Summary of the invention
The objective of the invention is to overcome the weak point of water-borne coatings pigment wetting dispersing agent in the above-mentioned background technology, the water-based paint pigment wetting dispersing agent that a kind of widely applicable, moisture dispersibility is strong, the color stuffing dispersion stabilization is high is provided.
The present invention is achieved in that this pigment wetting dispersing agent that is used for water-based paint has as I formula institute
The chemical structural formula that shows, its chemical name are double-active group alkyl polyoxyethylene glycidyl ether,
Wherein: R is C
6～C
18Alkyl or alkylaryl
n
1=4～20 integer; n
2=1～2 integer; n
3=1;
P
1Be halogen X or equal P
3P
2Be OH or O;
P
3Be at following A, choose any one kind of them in B or the C system:
The A system is:
The B system is:
N=2 in the formula, 3
Or 6,
The C system is:
Wherein: R '=-CH
2CH
2COOM ,-CH
2COOM or-CH
2CH
2COOCH
3,
M=Na in the following formula
+, NH
4 +, K
+
Meeting compound in structural formula I among the present invention is:
Or:
Or:
Or:
Or:
Or:
The preparation method who is used for the pigment wetting agent of water and coating of the present invention is: at first synthetic basic compound with chemical structural formula shown in (II), and its chemical name is a double-active group alkyl polyoxyethylene glycidyl ether,
Wherein: R equals C
6～C
18Alkyl or alkylaryl
n
1=4～20 integer, n
2=1～2 integer,
Then, utilize among the said structure II-CH
2Cl and
Two active groups are introduced other and are strengthened the moisture dispersibility group, other strengthen moisture dispersibility group comprise nitrogen-containing group ,-CH
2CH
2OH ,-COOCH
3,-COOM (M=NH
4 +, Na
+, K
+) or can with the group of metal ion generation complexing.
By last structure, the control reaction conditions only makes
Participate in reaction, can introduce various containing-NH
2, the compound of-NH-.General-NH more then
2,-NH-carries out hydrophilic moist curing and promptly inserts hydrophilic dispersion group, example:
In the said structure-NH
2Hydrophilic dispersion treatment as follows:
According in the foundation structure formula-CH
2Cl and
Two active groups, while or priority are carried out hydrophilic wetting and hydrophilic dispersion treatment, can obtain following product:
P in this formula
3Be aforementioned defined group.Can obtain when for example handling with quadrol:
Available on this basis CH
2=CH-COOCH
3, or Cl-CH
2COONa handles, and obtains:
Can there be ligand complex character cooperating of hydroxyl and amido to surfaces such as metal ion and electropositivity pigment and filler crystal angle, crystal edges in this wetting dispersing agent.
The basic compound that concrete synthetic has structure shown in (II) among the present invention is:
Its processing step comprises:
(1) polyoxyethylene nonylphenol ether unit alcohol TX-10 is dropped in the four-hole reaction flask, stir the boron trifluoride ethyl ether complex BF that adds 2.5～3.5% weight down
3OC
2H
5As catalyzer.
(2) be heated to 55～65 ℃ get rid of ether after, splash into epoxy chloropropane, with the water-bath control reaction temperature between 60～75 ℃.After dripping off, insulation reaction 2～3 hours.
(3) slowly be warming up to 80～85 ℃, begin to drip weight again and be 50% the NaOH aqueous solution, separate out solid sodium chloride.Drip off the back this temperature insulation 1 hour, when the pH value near 8.0 the time, with in a small amount of dilute hydrochloric acid and excess NaOH, make pH=6～7.
(4) static back layering removes and desalts and water layer, removes moisture content and unreacted epoxy chloropropane again under reduced pressure, promptly gets product.
The weight percent of above-mentioned steps raw material consists of:
Wetting dispersing agent of the present invention has the advantages that more such other dispersion agents are not had: 1) have the wetting dispersing agent of epoxy group(ing) applicable to containing nitrogen ,-COOH, pigment dyestuffs such as-N=N-; 2) have-NH
2And-wetting dispersing agent of NH-is applicable to containing-SO
3,-COOH ,-NH
2, pigment such as M-OH; 3) have-NH-CH
2CH
2-NH-,-NH-CH
2CH
2The wetting dispersing agent of-COONa can with the pigment generation complexing action of some containing metal atoms; 4) have-CH
2The wetting dispersing agent of Cl all has suitability to organic and mineral dye.Identical but under the diverse prerequisite of dispersion agent, use the pigment slurry viscosity of wetting dispersing agent of the present invention minimum at pigment slurry prescription.This is because it contains group and a plurality of active site that can finely be adsorbed in particle surface, and has the effect that makes the colo(u)rant dispersion stabilization, and this just makes it than the more effective viscosity that reduces mill base of conventional dispersion agent.Therefore in process of production, can obtain higher pigment slurry concentration, improve productivity.Titanium dioxide slurry concentration can reach 69% in this test, carbon black concentration reaches 37%, and bright red slurry concentration can reach 48%, and organic yellow slurry concentration reaches 55%, phthalocyanine blue slurry concentration reaches 46%, and this is that the many in the market dispersion agents of above-mentioned background neutralization institute can not reach.And under the situation of disperseing equal volume pigment, the addition of general dispersion agent wants many than this auxiliary agent.This dispersion agent also has the multiple pigment of adaptation and the wide advantage of pH value scope.Mill base vividness after disperseing in addition is also fine, can more efficient use in actual production.
Embodiment
Now in conjunction with the embodiments content of the present invention is described further, but embodiment is not a limitation of the present invention.
Embodiment 1
The mensuration of the synthetic and moisture dispersibility of double-active group alkyl (alkylaryl) polyoxyethylene glycidyl ether.The basic compound of synthetic following structure:
The raw material of synthetic (III) adopts market TX-10 on sale, and its structural formula is:
Prescription:
Technological process:
Adopt in the experiment that the market polymerization degree on sale is 10, molecular-weight average is 660 tensio-active agent (water-based paint wetting agent) TX-10, its outward appearance is transparent liquid of vicidity.Contain 5～10% moisture content and low-boiling-point substance among the TX-10, must remove (5mmHg is adopted in this experiment) under reduced pressure.
By prescription TX-10 is dropped in the four-hole reaction flask, stir the boron trifluoride ethyl ether complex (BF that adds 3 weight % down
3OC
2H
5) as catalyzer.After being heated to 60 ℃ of eliminating ether, splash into epoxy chloropropane, the reaction process heat release is warmed up to 75 ℃ automatically, and must cool off this moment with water-bath, and control reaction temperature is between 60～75 ℃.After dripping off, insulation reaction 2～3 hours then slowly is warming up to 80～85 ℃, begins the NaOH aqueous solution of Dropwise 5 0% again, and reactant transfers muddiness to from clarification, and separates out solid sodium chloride.Drip off the back this temperature insulation 1 hour, measure the system pH value, when pH value near 8.0 the time, with in a small amount of dilute hydrochloric acid and excess NaOH, make PH=6～7, static back layering removes and desalts and water layer, removes anhydrate part and unreacted epoxy chloropropane under reduced pressure, promptly gets product.
Product specification:
1) outward appearance: orange transparent thick liquid
2) solids content %:100
3) solubility test in the water: 100% is soluble in water
4) calculated value: molecular weight 830 (oxirane value 0.120)
The moisture dispersibility test of double-active group alkyl (alkylaryl) polyoxyethylene glycidyl ether:
Dispersed states of matter index * (following dispersion experiment is all undertaken by this):
The mill base denseness is divided into 1～3 (evaluation method is specifically seen appendix).
Stability (towards rare rank) is divided into one, two, three.If the mill base of secondary or three grades must be joined lacquer experiment (evaluation method is specifically seen appendix) again.
Fineness (evaluation method is specifically seen appendix)
Jitter time in hour.
1. paste formula
(unit: weight part)
2. performance measurement
| The distributed test result | White slurry | Black wash | Red slurry | Yellow slurry | Blue slurry |
| The mill base denseness | 3 | 1 | 3 | 1 | 3 |
| Stability is towards rare rank | Secondary (by) | One-level | One-level | One-level | One-level |
| Fineness | 20 | 16 | 20 | 25 | 30 |
| Jitter time/hour | 2.0 | 2.0 | 2.5 | 3.0 | 2.5 |
This structure has good wetting dissemination to some pigment.This be because some groups (contain carboxyl as carbon black, red contains amido, contains nitrogen-atoms in the phthalocyanine blue) in these pigment can with epoxy group(ing) in the structure or-CH
2Cl has an effect, but titanium dioxide lacks this reactivity.Therefore whether this wetting dispersing agent can be good at dispersed color and also is closely related with the character of pigment self.
Embodiment 2
The wetting dispersing agent of synthetic following structure:
Prescription:
Technological process:
Double-active group alkyl (alkylaryl) polyoxyethylene glycidyl ether (III) is dropped in the reaction flask, be warmed up to 60 ℃ under stirring, splash into Monoethanolamine MEA BASF, temperature of reaction is controlled at 80～90 ℃, insulation reaction 1～2 hour is cooled to 60 ℃ of dischargings again, moves in the separating funnel, remove the sub-cloud by product, obtain the upper strata product.
Product specification:
1) outward appearance: orange transparent viscous fluid
2) solids content %:100
3) solubility test in the water: soluble in water
The wetting distributed test of this auxiliary agent:
1. paste formula
(unit: weight part)
2. performance measurement
| The distributed test result | White slurry | Black wash | Red slurry | Yellow slurry | Blue slurry |
| The mill base denseness | 1 | 1 | 1 | 1 | 1 |
| Stability is towards rare rank | One-level | One-level | One-level | Secondary (by) | One-level |
| Fineness | 30 | 25 | 15 | 25 | 30 |
| Jitter time/hour | 2.0 | 3.0 | 2.0 | 2.5 | 1.5 |
Experimental result:
This product all has bigger adsorptive capacity to all pigment dyestuffs except that less to the titanium dioxide adsorptive capacity, this impels under identical addition, and the mill base concentration of using this auxiliary agent to make is higher.To coat pigment particles comparatively firm because of this auxiliary agent again, thus when the mill base water be difficult for being stripped from when rare and in emulsion paint dispersion stabilization better.
Embodiment 3
The wetting dispersing agent of synthetic following structure:
In the following formula: n=2, then introduce H
2N-CH
2CH
2-NH
2It is quadrol;
N=3 then introduces H
2NCH
2CH
2CH
2NH
2Promptly 1, the 3-propylene diamine;
N=6 then introduces H
2N-(CH
2)
6-NH
2Promptly 1, the 6-hexanediamine.
Quadrol and 1 are got in this experiment, the 6-hexanediamine.
Prescription:
Technological process:
Quadrol is dissolved in 2 times the ethanol, and drops in the reaction flask, be warmed up to 40 ℃ under stirring, splash into double-active group alkyl (alkylaryl) polyoxyethylene glycidyl ether (III), temperature of reaction is controlled at 60～80 ℃, and reaction system becomes muddiness from clarification.After dripping off, insulation reaction 3 hours removes ethanol and unreacted quadrol under reduced pressure, then moves in the separating funnel, removes the sub-cloud by product, collects the upper strata and obtains product.
Product specification:
1) outward appearance: orange transparent viscous fluid
2) solids content %:100
3) solubility test in the water: soluble in water
The wetting distributed test of this auxiliary agent:
1. paste formula
(unit: weight part)
2. performance measurement
| The distributed test result | White slurry | Black wash | Red slurry | Yellow slurry | Blue slurry |
| Defoamer | 0.28 | 0.44 | 0.25 | 0.20 | 0.37 |
| Mould inhibitor | 0.28 | 0.44 | 0.37 | 0.30 | 0.37 |
| The mill base denseness | 1 | 2 | 2 | 1 | 1 |
| Stability is towards rare rank | One-level | One-level | One-level | Secondary (by) | One-level |
| Fineness | 20 | 25 | 30 | 15 | 25 |
| Jitter time/hour | 2.0 | 2.5 | 3.0 | 3.0 | 2.0 |
Experimental result is commented: all pigment are all had moisture dispersibility and dilution stability, but acid pigment is had bigger adsorption relatively.
Embodiment 4
The wetting dispersing agent of synthetic following structure:
Prescription:
Technological process:
Diethylenetriamine is dissolved in 3 times of ethanol, and drop in the reaction flask of reaction unit, be warmed up to 30～40 ℃ under stirring, splash into double-active group alkyl (alkylaryl) polyoxyethylene glycidyl ether (III), temperature of reaction is controlled at 60～85 ℃, after dripping off, insulation reaction 3 hours removes ethanol under reduced pressure, diethylenetriamine, then move in the separating funnel, remove the sub-cloud by product, obtain the upper strata product.
Product specification:
1) outward appearance: orange thick liquid
2) solids content %:100
3) solubility test in the water: 100% is soluble in water
The wetting distributed test of this auxiliary agent:
1. paste formula
(unit: weight part)
2. performance measurement
| The distributed test result | White slurry | Black wash | Red slurry | Yellow slurry | Blue slurry |
| The mill base denseness | 1 | 2 | 2 | 2 | 1 |
| Stability is towards rare rank | One-level | One-level | One-level | One-level | Secondary (by) |
| Fineness | 20 | 25 | 20 | 20 | 30 |
| Jitter time/hour | 2.0 | 2.5 | 3.0 | 2.0 | 2.0 |
Experimental result is commented:
This product all has bigger adsorptive capacity to other pigment dyestuffs except that less to the titanium dioxide adsorptive capacity, this impels the viscosity of mill base to increase.To coat pigment particles comparatively firm because of auxiliary agent again, so be difficult for being stripped from mill base water auxiliary agent when rare, makes mill base that dispersion stabilization preferably be arranged in emulsion paint.
Embodiment 5
The wetting dispersing agent of synthetic following structure:
Prescription:
Technological process:
By proportioning diethylenetriamine is dissolved in 2 times of ethanol, and in the throwing device reaction flask, splash into double-active group alkyl (alkylaryl) polyoxyethylene glycidyl ether (III) under in the time of 40 ℃, stirring, be warming up to 60～85 ℃ of reactions then after 2 hours, steam and remove excessive diethylenetriamine, dropwise addition of acrylic acid methyl esters under this temperature again, temperature of reaction is controlled at 80～90 ℃, and insulation reaction 3 hours gets clear liquid, remove unreacted methyl acrylate under reduced pressure, get product.
Product specification
1) outward appearance: orange transparent thick liquid
2) solids content %:100
3) solubility test in the water: 100% is soluble in water
The wetting distributed test of this auxiliary agent:
1. paste formula
(unit: weight part)
2. performance measurement
| The distributed test result | White slurry | Black wash | Red slurry | Yellow slurry | Blue slurry |
| The mill base denseness | 1 | 2 | 1 | 2 | 1 |
| Stability is towards rare rank | One-level | Secondary (by) | Secondary (by) | One-level | Secondary (by) |
| Fineness | 20 | 25 | 25 | 20 | 30 |
| Jitter time/hour | 2.0 | 3.0 | 2.5 | 2.0 | 3.0 |
Experimental result is commented:
This product has titanium dioxide, the good moisture dispersibility of organic yellow, but to the adsorptive capacity deficiency of phthalocyanine blue, but its mill base can be scattered in the emulsion paint preferably and hiding rare is fine.
Embodiment 6
The wetting dispersing agent of synthetic following structure:
Prescription:
Technological process:
By proportioning hexanediamine is dissolved among the equivalent ethanol, and in the input reaction flask, splash into double-active group alkyl (alkylaryl) polyoxyethylene glycidyl ether (III) under in the time of 40 ℃, stirring, 60～85 ℃ the reaction 2 hours after, dropwise addition of acrylic acid methyl esters, temperature of reaction are controlled at 80～90 ℃, drip the back insulation reaction 3 hours, get clear liquid, then in the time of 80 ℃, drip the 10%NaOH aqueous solution, make the ester hydrolysis go out methyl alcohol and carboxylic acid sodium salt, insulation reaction 2～3 hours, survey pH value, if PH＞7 o'clock,, make PH=6～7 with among the 5%HCl and excessive NaOH, decompression removes moisture content, ethanol, methyl alcohol etc. salt out in the reaction product.After adding an amount of alcohol dilution in the thick product, remove by filter the salt solids, collect the clarification viscous liquid.In the product ethanol can reduce pressure steam or do not steam all available.
Product specification:
1) outward appearance: orange transparent thick liquid
2) solids content %:100
3) solubility test in the water: soluble in water
The wetting distributed test of this auxiliary agent:
1. paste formula
(unit: weight part)
2. performance measurement
| The distributed test result | White slurry | Black wash | Red slurry | Yellow slurry | Blue slurry |
| The mill base denseness | 1 | 1 | 1 | 1 | 1 |
| Stability is towards rare rank | Secondary (by) | Secondary (by) | One-level | One-level | One-level |
| Fineness | 30 | 25 | 25 | 15 | 20 |
| Jitter time/hour | 2.0 | 2.0 | 3.0 | 2.0 | 3.0 |
Experimental result is commented:
This auxiliary agent all is suitable for pigment experiment, usefulness-NH
2The auxiliary agent of end socket is adsorbed in less on the surface of pigments, and this makes the viscosity of mill base descend to some extent, and during the rare mill base of Dang Shuichong, the auxiliary agent layer is just more easily peeled off, when the limit when rare, particle produces assembles, returns thick phenomenon.But in the emulsion paint of non-infinite dilution condition, can disperse finely, the phenomenon that pigment is assembled does not take place.
Embodiment 7
The wetting dispersing agent of synthetic following structure:
Prescription:
Technological process:
By prescription diethylenetriamine is dissolved in 3 times of ethanol, and in the throwing device reaction flask, splash into double-active group alkyl (alkylaryl) polyoxyethylene glycidyl ether (III) under in the time of 40 ℃, stirring, 60 ℃ drip off after again 85 ℃ of down reactions 2 hours, steam to remove excessive diethylenetriamine then, dropwise addition of acrylic acid methyl esters under this temperature again, insulation reaction 3 hours, get clear liquid, remove unreacted methyl acrylate under reduced pressure.Then drip the 10%NaOH aqueous solution in the time of 80 ℃, pH value is surveyed in hydrolysis 2 ~ 3 hours, if PH＞7 o'clock, make PH=6 ~ 7 with the 5%HCl neutralization after, then remove low-boiling-point substances such as water, ethanol under reduced pressure and get product.There is small amounts of salts to separate out in the reaction product, collects the clarification viscous liquid after the filtering, get product.
Product specification
1) outward appearance: orange transparent thick liquid
2) solids content %:100
3) solubility test in the water: soluble in water
The wetting distributed test of this auxiliary agent:
1. paste formula
(unit: weight part)
2. performance measurement
| The distributed test result | White slurry | Black wash | Red slurry | Yellow slurry | Blue slurry |
| The mill base denseness | 1 | 2 | 1 | 2 | 1 |
| Stability is towards rare rank | Secondary (by) | One-level | One-level | One-level | One-level |
| Fineness | 25 | 20 | 20 | 15 | 30 |
| Jitter time/hour | 2.5 | 2.0 | 2..0 | 2.0 | 2.5 |
Experimental result is commented:
Organic and the mineral dye that all quilts are tested all is suitable for.Mill base denseness and water are good towards rare experimental result.
Remarks
* the concrete classification of dispersion experiment performance evaluation:
1, fineness is operated according to GB/T 1724-1989 specific requirement.
2, denseness characterizes
3, stability is towards rare experimental evaluation
Towards rare experimental grade is that two, three grades mill base must be joined the lacquer experiment again, and experimental technique is:
With this mill base and foretell inside door and paint A900-65100 white interiro wall latex paint the mixings stirring test that extra large company limited produces romote antiquity, and brush plate-making, as if no loose colour, grow dim or inconsistent phenomenon and hiding rare well then for passing through, otherwise think defective.
Claims (9)
1. a wetting dispersing agent that is used for water-based paint pigment is characterized in that having the chemical structural formula shown in I, and its chemical name is double-active group alkyl polyoxyethylene glycidyl ether and derivative thereof,
Wherein: R is C
6～C
18Alkyl or alkylaryl
Or
n
1=4～20 integer, n
2=1～2 integer, n
3=1;
P
1Be halogen X or equal P
3, P
2=OH;
P
3Be in following A, B or C system, to choose any one kind of them,
The A system:
The B system:
The C system:
Wherein: R '=-CH
2CH
2COOM ,-CH
2COOM or-CH
2CH
2COOCH
3
In the following formula: M=Na
+, NH
4 +Or K
+
2. wetting dispersing agent according to claim 1 is characterized in that the described compound in structural formula I that meets is:
3. wetting dispersing agent according to claim 1 is characterized in that the described compound in structural formula I that meets is:
Wherein: n=2,3 or 6.
4. wetting dispersing agent according to claim 1 is characterized in that the described compound in structural formula I that meets is:
5. wetting dispersing agent according to claim 1 is characterized in that the described compound in structural formula I that meets is:
6. wetting dispersing agent according to claim 1 is characterized in that the described compound in structural formula I that meets is:
7. wetting dispersing agent according to claim 1 is characterized in that the described compound in structural formula I that meets is:
8. one kind according to the described preparation method who is used for the pigment wetting dispersing agent of water-based paint of claim 1, it is characterized in that: at first synthetic basic compound with structure shown in II:
Wherein: R equals C
6～C
18Alkyl or alkylaryl
Or
n
1=4～20 integer, n
2=1～2 integer,
Then, utilize among the said structure II-CH
2Cl and
Two active groups are introduced other and are strengthened the moisture dispersibility group, other strengthen moisture dispersibility group comprise nitrogen-containing group ,-CH
2CH
2OH,---COOCH
3,-COOM is M=NH wherein
4 +, Na
+, K
+, or can with the group of metal ion generation complexing.
9. the preparation method of wetting dispersing agent according to claim 8, it is characterized in that: at first the synthetic basic compound is:
Its step comprises:
(1) polyoxyethylene nonylphenol ether unit alcohol TX-10 is dropped in the four-hole reaction flask, stir the boron trifluoride ethyl ether complex BF that adds 2.5～3.5 weight % down
3OC
2H
5As catalyzer;
(2) be heated to 55～65 ℃ get rid of ether after, splash into epoxy chloropropane, at 60～75 ℃, after dripping off, be incubated 2～3 hours with the water-bath control reaction temperature;
(3) be warming up to 80～85 ℃, Dropwise 50 weight % aqueous sodium hydroxide solution has solid sodium chloride to separate out.Drip off back insulation 1 hour, when PH equals 8.0, use in the hydrochloric acid and excess NaOH, make pH=6～7;
(4) static back layering removes and desalts and water layer, and moisture content and unreacted epoxy chloropropane are removed in underpressure distillation again, promptly get product;
Raw material weight per-cent in the above-mentioned steps consists of:
Nonylbenzene phenol polyethenoxy ether unit alcohol TX-10 70～83%
Epoxy chloropropane 12～25%
50 weight % aqueous sodium hydroxide solutions 5～6%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100842877A CN100392029C (en) | 2004-11-17 | 2004-11-17 | Pigment wetting dispersing agent for water-base coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100842877A CN100392029C (en) | 2004-11-17 | 2004-11-17 | Pigment wetting dispersing agent for water-base coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1778846A CN1778846A (en) | 2006-05-31 |
| CN100392029C true CN100392029C (en) | 2008-06-04 |
Family
ID=36769306
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100842877A Expired - Fee Related CN100392029C (en) | 2004-11-17 | 2004-11-17 | Pigment wetting dispersing agent for water-base coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100392029C (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4079028A (en) * | 1975-10-03 | 1978-03-14 | Rohm And Haas Company | Polyurethane thickeners in latex compositions |
| US4155892A (en) * | 1975-10-03 | 1979-05-22 | Rohm And Haas Company | Polyurethane thickeners for aqueous compositions |
| US4156616A (en) * | 1976-08-28 | 1979-05-29 | Hoechst Aktiengesellschaft | Pigment dispersion for use in hydrophilic and hydrophobic media |
-
2004
- 2004-11-17 CN CNB2004100842877A patent/CN100392029C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4079028A (en) * | 1975-10-03 | 1978-03-14 | Rohm And Haas Company | Polyurethane thickeners in latex compositions |
| US4155892A (en) * | 1975-10-03 | 1979-05-22 | Rohm And Haas Company | Polyurethane thickeners for aqueous compositions |
| US4079028B1 (en) * | 1975-10-03 | 1990-08-21 | Rohm & Haas | |
| US4156616A (en) * | 1976-08-28 | 1979-05-29 | Hoechst Aktiengesellschaft | Pigment dispersion for use in hydrophilic and hydrophobic media |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1778846A (en) | 2006-05-31 |
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