CN104974324A - Reactive self-delustering waterborne polyurethane resin, and preparation method and application thereof - Google Patents
Reactive self-delustering waterborne polyurethane resin, and preparation method and application thereof Download PDFInfo
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- CN104974324A CN104974324A CN201510386759.2A CN201510386759A CN104974324A CN 104974324 A CN104974324 A CN 104974324A CN 201510386759 A CN201510386759 A CN 201510386759A CN 104974324 A CN104974324 A CN 104974324A
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- 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
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4808—Mixtures of two or more polyetherdiols
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- 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
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates 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
- C08G18/70—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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- 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
- C09D175/06—Polyurethanes from polyesters
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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
- C09D175/08—Polyurethanes from polyethers
Abstract
The invention discloses a reactive self-delustering waterborne polyurethane resin, and a preparation method and application thereof. The reactive self-delustering waterborne polyurethane resin has luster of no more than 20 at 60 DEG C when in a dry state and is prepared through reaction among the following components: 1, at least one aliphatic diisocyanate; 2, at least one carboxylic acid type hydrophilic dihydric alcohol; 3, at least one polymerized dihydric alcohol containing a water-dispersable group; 4, a catalyst used for synthesis of waterborne polyurethane; 5, at least one neutralizer; 6, at least one sulfonic acid type hydrophilic chain extender containing active hydrogen; and 7, at least one small molecule compound containing active hydrogen. The reactive self-delustering waterborne polyurethane resin has solid content of 25 to 40% and an average particle size of 500 to 5000 nm; no delustering agent is needed, and controllable generation of particles in certain particle size distribution can be realized in the process of synthesis; and the particles shrink after drying and dehydration of a film, which leads to increase of microscopic surface roughness and reduction in glossiness.
Description
Technical field
The present invention relates to a kind of novel from Flat paint and preparation method thereof, be specifically related to a kind of reaction from extinction type waterborne polyurethane resin and preparation method thereof and application.
Background technology
Matting resin refers generally to film forming rear surface and is obviously atomized, and the resin of low-luster (dumb light), it is mainly used in coating.Existing matting resin obtains from delustring and outer interpolation matting agent two kinds of modes mainly through reaction.Gloss and surface are more relevant than the ability reflecting more light in the other direction in a certain direction.The major part of their light of directive reflects by high-gloss surface, and low gloss surface is by few part reflection of their light of directive, and internal refraction, absorption mainly occur.Reflect relevant direction to speculum and usually there is the highest reflectivity, be associated to the surface shininess Visual Observations Observations carried out in roughly corresponding angle by the measurement of this testing method.The low gloss coating producing less image deflects usually more makes us feeling joyful aesthetically.
Along with the change of people's aesthetic standards, more and more pursued with the product that delustring (dumb light) is surface decoration, extinction material, also from the high stopping composition of occurring in nature, develops into micro-wax powder, and then be inorganic silicon dioxide flatting silica, and still at the organic quenching resin continuing research.Although this mode by outer interpolation matting agent can reach the object of delustring, its shortcoming is also obvious: a large amount of matting agent cost that uses is higher; Composition condensation causes outward appearance like seediness; Coating fragility increases, and easy fragmentation comes off; The precipitation of matting agent causes the heterogeneity before spreading to mix, thus makes the gloss of whole coating variant; Resistance toly to rub, to bend and rub resistance declines.In order to avoid some defects that outer interpolation matting agent brings, Chinese patent CN104193946A discloses a kind of preparation method from delustring urethane resin, comprise the acrylic acid-grafted class material end-blocking adopting Absorbable rod light, a large amount of use acetone viscosity reduction and later stage adopt distillation process, acetone is difficult to eliminate, and easily has residual.CN103626930A describes a kind of preparation method with Aqueous acrylic urethane's matting resin of phase separation structure, first need to prepare anionic and non-ionic type two kinds of urethane, again acrylate mixture is carried out in two kinds of urethane seeded emulsion polymerization to obtain, and prepare in urethane process need termination process, a large amount of use acetone to make thinner and whole synthesis step loaded down with trivial details time-consuming, being difficult at industrialization production line balance is its weak point.CN104293165A discloses a kind of low chromatic number ultraviolet light polymerization Flat paint for woodenware, adopt and add 2-hydroxybenzene dimethyl sulfide change refraction coefficient to reach the object of delustring, but described system with the addition of poisonous auxiliary agent and the alcohol ether solvents such as many containing benezenes or ketone, large amount of organic is volatile, does not meet the emission standard of the low VOC of the new environmental law of China.
Summary of the invention
In order to overcome the shortcoming of prior art with not enough, primary and foremost purpose of the present invention is to provide a kind of reaction from extinction type waterborne polyurethane resin.This reaction does not use any additional extinction material from extinction type waterborne polyurethane resin, 60 ° of gloss≤20 when drying.
Another object of the present invention is to the preparation method providing above-mentioned reaction from extinction type waterborne polyurethane resin.
Another object of the present invention is the application providing above-mentioned reaction from extinction type waterborne polyurethane resin.
Object of the present invention is achieved through the following technical solutions: a kind of reaction, from extinction type waterborne polyurethane resin, is prepared by following component:
(A) the diisocyanate terminated prepolymer formed by following component
The aliphatic vulcabond of S1, at least one, the mol ratio of described aliphatic vulcabond and polymeric dihydric alcohol is 1.5 ~ 3:1;
S2, the hydrophilic dibasic alcohol of at least one carboxylic acid type, have the molecular weight within the scope of 100 ~ 500g/mol; The mol ratio of the hydrophilic dibasic alcohol of described carboxylic acid type and polymeric dihydric alcohol is 0.3 ~ 0.6:1;
The polymeric dihydric alcohol of the moisture dispersing group of S3, at least one, has the molecular weight within the scope of 500 ~ 2000g/mol;
S4, a kind of synthesis aqueous polyurethane catalyzer, add-on is 0.01 ~ 0.02% of diisocyanate terminated prepolymer quality;
(B) by following component and diisocyanate terminated prepolymer
S5, at least one neutralizing agent (can in and the micromolecular compound of the hydrophilic dibasic alcohol of carboxylic acid type), the mol ratio of described neutralizing agent and the hydrophilic dibasic alcohol of carboxylic acid type is 0.8 ~ 1.0:1;
(C) by following component, chain extension is carried out to the diisocyanate terminated prepolymer after neutralization
S6, at least one are containing the sulfonic acid type hydrophilic chain extender of ripple hydrogen of living, and described is 0.1 ~ 0.2:1 containing the sulfonic acid type hydrophilic chain extender of ripple hydrogen alive and the mol ratio of polymeric dihydric alcohol;
S7, at least one are containing the micromolecular compound of ripple hydrogen of living, and aequum is for making remaining isocyanate reaction complete.
Aliphatic vulcabond described in component S 1, comprise in isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI) and cyclohexanedimethyleterephthalate vulcabond (HXDI) one or more.
The hydrophilic dibasic alcohol of carboxylic acid type described in component S 2 is one or more in dimethylol propionic acid (DMPA), dimethylolpropionic acid (DMBA) and dyhydrobutanedioic acid.
Polymeric dihydric alcohol described in component S 3 is one or more in the polypropylene glycol (PPG) of 500 ~ 2000 molecular weight, PTMG (PTMG), poly-epsilon-caprolactone dibasic alcohol (PCL), PCDL, polyethylene glycol adipate dibasic alcohol and poly-hexanodioic acid-BDO esterdiol (PBA).
Catalyzer described in component S 4 is tertiary butyl tin, dibutyl tin laurate or organic bismuth catalyst etc.
Neutralizing agent described in component S 5 comprise in triethylamine, tripropyl amine, trolamine (TEA), diethylenetriamine (DETA) and dimethylethanolamine one or more.
The sulfonic acid type hydrophilic chain extender containing ripple hydrogen of living described in component S 6 is 2-(2-amino-ethyl) taurine sodium, 2-(2-amino-ethyl) aminopropanesulfonic acid sodium, 1, one or more in 4-butyleneglycol-2-sodium sulfonate and 1,2-dihydroxyl-3-N-morpholinopropanesulfonic acid sodium.
The micromolecular compound containing ripple hydrogen of living described in component S 7 comprises amine, hydrazine class or alcohols small molecule chain extender; Wherein, described amine small molecule chain extender comprises quadrol, thanomin, diethanolamine or trolamine; Described hydrazine class chainextender comprises hydrazine hydrate, carbohydrazide, dimethylhydrazine or adipic acid dihydrazide; Described alcohols small molecule chain extender comprises ethylene glycol, propylene glycol, glycerol or BDO.
Described reaction, from the preparation method of extinction type waterborne polyurethane resin, comprises following steps:
(1) by polymeric dihydric alcohol, the hydrophilic dibasic alcohol heating under vacuum of carboxylic acid type, dewater; Add aliphatic vulcabond and catalyst reaction, generate diisocyanate terminated prepolymer;
(2) add in neutralizing agent and salify in step (1) product, form the diisocyanate terminated prepolymer after neutralization;
(3) in step (2) product, add the aqueous solution of the sulfonic acid type hydrophilic chain extender containing ripple hydrogen of living, carry out first time chain extension, obtain its emulsion;
(4) in step (3) product, drip the aqueous solution of the micromolecular compound containing ripple hydrogen of living, carry out second time chain extension, make remaining isocyanate reaction complete, obtain reaction from extinction type waterborne polyurethane resin.
The temperature of the heating described in step (1) is preferably 105 ~ 120 DEG C; Be more preferably 120 DEG C;
The condition optimization of the reaction described in step (1) is 75 ~ 90 DEG C of reaction 3 ~ 4h; Be more preferably 85 DEG C of reaction 3h;
The condition optimization of the neutralization described in step (2) is in 40 ~ 50 DEG C and 20 ~ 30min;
Diluting water amount in the aqueous solution of the sulfonic acid type hydrophilic chain extender containing ripple hydrogen of living described in step (3) preferably accounts for 60% ~ 95% of the total water requirements of whole reaction in extinction type waterborne polyurethane resin;
Described in step (3) first time chain extension condition optimization be 20 ~ 30 DEG C of chain extension 10 ~ 30min;
The condition optimization of the second time chain extension described in step (4) is 20 ~ 30 DEG C of chain extension 30 ~ 60min.
A kind of reaction, from extinction type waterborne polyurethane resin, is obtained by above-mentioned preparation method; Described reaction from the solid content of extinction type waterborne polyurethane resin preferably 25 ~ 40%, more preferably 30 ~ 35%;
Described reaction from the average particulate size of extinction type waterborne polyurethane resin preferably in 500 ~ 5000nm scope, more preferably in 800 ~ 3500nm scope, and the size of particles most preferably in 1000 ~ 2500nm scope.
Described reaction is from the application of extinction type waterborne polyurethane resin in coatings with low gloss finish.
Described reaction can be used as coatings with low gloss finish from extinction type waterborne polyurethane resin and applies.
The present invention, relative to prior art, has following advantage and effect:
(1) reaction provided by the invention is from extinction type waterborne polyurethane resin, do not need to add any matting agent, the particle of controlled generation certain grain size distribution in the process of synthesis, in dried coating film dehydration post shrinkage, cause surface microroughness to increase, glossiness reduces.
(2) extinction effect of the present invention is produced by resin itself, and this latex particle form identical with paint film body construction, merges completely, and compared with additional matting agent, intensity raising, fragility reduction, resistance toly to rub, to bend and rub resistance significantly improves.
(3) reaction that prepared by the present invention can be used as environment-friendly water-based polyurethane coating from extinction type waterborne polyurethane resin and uses, and do not add any organic solvent, paint film coating uniform, body glossiness is low, and production technique is simple, safety non-toxic.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) by 20g (20mmol) molecular weight be 1000 PTMG, 1g (7.5mmol) DMPA vacuum hydro-extraction at 120 DEG C in a kettle..After stopping vacuum, cool to 60 DEG C, add a small amount of dibutyltin dilaurate catalyst and 11g IPDI (50mmol), be warming up to 80 DEG C, reaction 3h.
(2) be cooled to 50 DEG C, in step (1) product, add 0.7g (7mmol) triethylamine neutralization reaction 30min.
(3) continue to be cooled to less than 30 DEG C, by be dissolved with 0.5g (2.6mmol) 2-(2-amino-ethyl) taurine sodium the aqueous solution (diluting water amount account for whole reaction in extinction type waterborne polyurethane resin total water requirements 80%) join emulsification in reactor, chain extension 10min.
(4) aqueous solution added again containing 0.6g hydrazine hydrate carries out secondary chain extension 1h, is down to room temperature, filters discharging, obtains reaction from extinction type waterborne polyurethane resin.
Reaction prepared by the present embodiment is 2580nm from the average particulate size of extinction type waterborne polyurethane resin.
Embodiment 2
(1) by 20g (20mmol) molecular weight be 1000 PTMG, 1.5g (11mmol) DMPA vacuum hydro-extraction at 105 DEG C in a kettle..After stopping vacuum, cool to 60 DEG C, add a small amount of dibutyltin dilaurate catalyst and 6.67g IPDI (30mmol), be warming up to 85 DEG C, reaction 3h.
(2) be cooled to 50 DEG C, in step (1) product, add 1.5g (10mmol) TEA neutralization reaction 30min.
(3) continue to be cooled to less than 30 DEG C, by be dissolved with 0.5g (2.6mmol) 2-(2-amino-ethyl) taurine sodium the aqueous solution (diluting water amount account for whole reaction in extinction type waterborne polyurethane resin total water requirements 80%) join emulsification in reactor, chain extension 10min.
(4) aqueous solution added again containing 0.7g quadrol carries out secondary chain extension 1h, is down to room temperature, filters discharging, obtains reaction from extinction type waterborne polyurethane resin.
Reaction prepared by the present embodiment is 1895nm from the average particulate size of extinction type waterborne polyurethane resin.
Embodiment 3
(1) by vacuum hydro-extraction at 10g (10mmol) PTMG (molecular weight 1000), 20g (10mmol) PTMG (molecular weight 2000), 1.2g (9mmol) DMPA in a kettle. 120 DEG C.After stopping vacuum, cool to 60 DEG C, add a small amount of organic bismuth catalyst, then add 6g (27mmol) IPDI and 4g (24mmol) HDI, be warming up to 80 DEG C, reaction 4h.
(2) be cooled to 50 DEG C, in step (1) product, add 1.2g (8.4mmol) tripropyl amine neutralization reaction 30min.
(3) continue to be cooled to less than 30 DEG C, by be dissolved with 0.76g (4mmol) 2-(2-amino-ethyl) taurine sodium the aqueous solution (diluting water amount account for whole reaction in extinction type waterborne polyurethane resin total water requirements 90%) join emulsification in reactor, chain extension 10min.
(4) aqueous solution added again containing 0.6g hydrazine hydrate carries out secondary chain extension 1h, is down to room temperature, filters discharging, obtains reaction from extinction type waterborne polyurethane resin.
Reaction prepared by the present embodiment is 3140nm from the average particulate size of extinction type waterborne polyurethane resin.
Embodiment 4
(1) by vacuum hydro-extraction at 10g (10mmol) PTMG (molecular weight 1000), 10g (10mmol) PCL (molecular weight 1000), 0.9g (6mmol) DMBA in a kettle. 110 DEG C.After stopping vacuum, cool to 60 DEG C, add a small amount of dibutyltin dilaurate catalyst and 11g IPDI (50mmol), be warming up to 90 DEG C, reaction 3h.
(2) be cooled to 50 DEG C, in step (1) product, add 0.6g (6mmol) triethylamine neutralization reaction 30min.
(3) continue to be cooled to less than 30 DEG C, by be dissolved with 0.6g (3mmol) 2-(2-amino-ethyl) taurine sodium the aqueous solution (diluting water amount account for whole reaction in extinction type waterborne polyurethane resin total water requirements 60%) join emulsification in reactor, chain extension 10min.
(4) aqueous solution added again containing 1g BDO carries out secondary chain extension 1h, is down to room temperature, filters discharging, obtains reaction from extinction type waterborne polyurethane resin.
Reaction prepared by the present embodiment is 2450nm from the average particulate size of extinction type waterborne polyurethane resin.
Embodiment 5
(1) by vacuum hydro-extraction at 10g (10mmol) PTMG (molecular weight 1000), 10g (10mmol) PCL (molecular weight 1000), 0.9g (6mmol) DMBA in a kettle. 120 DEG C.After stopping vacuum, cool to 60 DEG C, add a small amount of dibutyltin dilaurate catalyst and 11g IPDI (50mmol), be warming up to 80 DEG C, reaction 4h.
(2) be cooled to 50 DEG C, in step (1) product, add 0.5g (5mmol) DETA neutralization reaction 30min.
(3) continue to be cooled to less than 30 DEG C, by be dissolved with 2-(2-amino-ethyl) the aminopropanesulfonic acid sodium of 0.5g (2mmol) the aqueous solution (diluting water amount account for whole reaction in extinction type waterborne polyurethane resin total water requirements 95%) join emulsification in reactor, chain extension 10min.
(4) aqueous solution added again containing 0.6g quadrol carries out secondary chain extension 1h, is down to room temperature, filters discharging, obtains reaction from extinction type waterborne polyurethane resin.
Reaction prepared by the present embodiment is 2670nm from the average particulate size of extinction type waterborne polyurethane resin.
Comparative example 1
(1) by 20g (20mmol) molecular weight be 1000 PTMG and 1g (7.5mmol) DMPA vacuum hydro-extraction at 120 DEG C in a kettle..After stopping vacuum, be cooled to 60 DEG C, in aforesaid reaction vessel, add a small amount of dibutyltin dilaurate catalyst and 8g IPDI (36mmol), be warming up to 80 DEG C, reaction 3h.
(2) be cooled to less than 50 DEG C, add in 0.8g (5.5mmol) tripropyl amine in step (1) product and 30min.
(3) be cooled to less than 30 DEG C, the aqueous solution (diluting water amount calculates by product solid content) being dissolved with 1g hydrazine hydrate joined emulsification in reactor, chain extension 1h, obtains the aqueous polyurethane of blue-tinted transparent.
Reaction prepared by the present embodiment is 280nm from the average particulate size of extinction type waterborne polyurethane resin.
The aqueous polyurethane obtained from extinction type waterborne polyurethane resin and comparative example 1 for the reaction obtained in above-described embodiment 1 ~ 5 below carries out test experiments after drying and forming-film respectively, and acquired results is as shown in the table:
| Numbering | Condition in container | Solid content/wt% | 60 ° of glossiness |
| Embodiment 1 | A small amount of precipitation, redissolves after stirring | 28 | 12 |
| Embodiment 2 | A small amount of precipitation, redissolves after stirring | 28 | 37 |
| Embodiment 3 | Precipitation, redissolves after stirring | 29 | 8 |
| Embodiment 4 | Precipitation, redissolves after stirring | 29 | 20 |
| Embodiment 5 | Precipitation, redissolves after stirring | 27 | 14 |
| Comparative example 1 | Blue-tinted transparent emulsion | 29 | 107 |
From upper table data, the reaction obtained by the present invention from extinction type waterborne polyurethane resin, 60 ° of gloss≤20 when drying; Extinction effect produces by being dispersed in emulsion the resin particle body having certain grain size distribution, and without the need to additional any matting agent, have coating uniform, body glossiness is low, resistance toly to rub, bend and rub resistance good.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. reaction is from an extinction type waterborne polyurethane resin, it is characterized in that: prepared by following component:
(A) the diisocyanate terminated prepolymer formed by following component
The aliphatic vulcabond of S1, at least one, the mol ratio of described aliphatic vulcabond and polymeric dihydric alcohol is 1.5 ~ 3:1;
S2, the hydrophilic dibasic alcohol of at least one carboxylic acid type, have the molecular weight within the scope of 100 ~ 500g/mol; The mol ratio of the hydrophilic dibasic alcohol of described carboxylic acid type and polymeric dihydric alcohol is 0.3 ~ 0.6:1;
The polymeric dihydric alcohol of the moisture dispersing group of S3, at least one, has the molecular weight within the scope of 500 ~ 2000g/mol;
S4, a kind of synthesis aqueous polyurethane catalyzer, add-on is 0.01 ~ 0.02% of diisocyanate terminated prepolymer quality;
(B) by following component and diisocyanate terminated prepolymer
S5, at least one neutralizing agent, the mol ratio of described neutralizing agent and the hydrophilic dibasic alcohol of carboxylic acid type is 0.8 ~ 1.0:1;
(C) by following component, chain extension is carried out to the diisocyanate terminated prepolymer after neutralization
S6, at least one are containing the sulfonic acid type hydrophilic chain extender of ripple hydrogen of living, and described is 0.1 ~ 0.2:1 containing the sulfonic acid type hydrophilic chain extender of ripple hydrogen alive and the mol ratio of polymeric dihydric alcohol;
S7, at least one are containing the micromolecular compound of ripple hydrogen of living, and aequum is for making remaining isocyanate reaction complete.
2. reaction according to claim 1 is from extinction type waterborne polyurethane resin, it is characterized in that:
Aliphatic vulcabond described in component S 1, comprise in isophorone diisocyanate, hexamethylene diisocyanate and cyclohexanedimethyleterephthalate vulcabond one or more.
3. reaction according to claim 1 is from extinction type waterborne polyurethane resin, it is characterized in that:
The hydrophilic dibasic alcohol of carboxylic acid type described in component S 2 is one or more in dimethylol propionic acid, dimethylolpropionic acid and dyhydrobutanedioic acid.
4. reaction according to claim 1 is from extinction type waterborne polyurethane resin, it is characterized in that:
Polymeric dihydric alcohol described in component S 3 is one or more in polypropylene glycol, PTMG, poly-epsilon-caprolactone dibasic alcohol, PCDL, polyethylene glycol adipate dibasic alcohol and poly-hexanodioic acid-BDO esterdiol.
5. reaction according to claim 1 is from extinction type waterborne polyurethane resin, it is characterized in that:
Catalyzer described in component S 4 is tertiary butyl tin, dibutyl tin laurate or organic bismuth catalyst;
Neutralizing agent described in component S 5 comprise in triethylamine, tripropyl amine, trolamine, diethylenetriamine and dimethylethanolamine one or more.
6. reaction according to claim 1 is from extinction type waterborne polyurethane resin, it is characterized in that:
The sulfonic acid type hydrophilic chain extender containing ripple hydrogen of living described in component S 6 is 2-(2-amino-ethyl) taurine sodium, 2-(2-amino-ethyl) aminopropanesulfonic acid sodium, 1, one or more in 4-butyleneglycol-2-sodium sulfonate and 1,2-dihydroxyl-3-N-morpholinopropanesulfonic acid sodium.
7. reaction according to claim 1 is from extinction type waterborne polyurethane resin, it is characterized in that:
The micromolecular compound containing ripple hydrogen of living described in component S 7 comprises amine, hydrazine class or alcohols small molecule chain extender.
8. the reaction described in any one of claim 1 ~ 7, from the preparation method of extinction type waterborne polyurethane resin, is characterized in that comprising following steps:
(1) by polymeric dihydric alcohol, the hydrophilic dibasic alcohol heating under vacuum of carboxylic acid type, dewater; Add aliphatic vulcabond and catalyst reaction, generate diisocyanate terminated prepolymer;
(2) add in neutralizing agent and salify in step (1) product, form the diisocyanate terminated prepolymer after neutralization;
(3) in step (2) product, add the aqueous solution of the sulfonic acid type hydrophilic chain extender containing ripple hydrogen of living, carry out first time chain extension, obtain its emulsion;
(4) in step (3) product, drip the aqueous solution of the micromolecular compound containing ripple hydrogen of living, carry out second time chain extension, make remaining isocyanate reaction complete, obtain reaction from extinction type waterborne polyurethane resin.
9. reaction according to claim 8 is from the preparation method of extinction type waterborne polyurethane resin, it is characterized in that: the condition of the reaction described in step (1) is 75 ~ 90 DEG C of reaction 3 ~ 4h;
The condition of the neutralization described in step (2) is in 40 ~ 50 DEG C and 20 ~ 30min;
Diluting water amount in the aqueous solution of the sulfonic acid type hydrophilic chain extender containing ripple hydrogen of living described in step (3) is account for the total water requirements of whole reaction in extinction type waterborne polyurethane resin 60% ~ 95%;
Described in step (3) first time chain extension condition be 20 ~ 30 DEG C of chain extension 10 ~ 30min;
The condition of the second time chain extension described in step (4) is 20 ~ 30 DEG C of chain extension 30 ~ 60min.
10. the reaction described in any one of claim 1 ~ 7 is from the application of extinction type waterborne polyurethane resin in coatings with low gloss finish.
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Application publication date: 20151014 |