CN1817934A - Self-crosslinked oxidation and high-efficient dispersion with water polyurethane and production thereof - Google Patents
Self-crosslinked oxidation and high-efficient dispersion with water polyurethane and production thereof Download PDFInfo
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- CN1817934A CN1817934A CN 200610034153 CN200610034153A CN1817934A CN 1817934 A CN1817934 A CN 1817934A CN 200610034153 CN200610034153 CN 200610034153 CN 200610034153 A CN200610034153 A CN 200610034153A CN 1817934 A CN1817934 A CN 1817934A
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Abstract
A high-efficient and oxide self-cross-linking disperser of water-based polyurethane and its production are disclosed. The disperser consists of polyester polybasic alcohol (A) containing at least two hydroxyl groups, drying oil long oil alkyd resin (B) containing at least one hydroxyl group, vulcabond containing at least one aromatic or fatty group and water-based functional monomer. It has better coating comprehensive performance and costs low. It can be used for plastic, wood and metal.
Description
Technical field:
The present invention relates to coating of a kind of self-crosslinked oxidation and high-efficient dispersion with water polyurethane that is used for base materials such as plastics, timber, metal and preparation method thereof.
Background technology:
Urethane has outstanding physico-chemical property, as chemical stability, rub resistance, and toughness, elasticity has been widely used in the covering with paint of base materials such as plastics, timber, metal as coating.Traditional polyurethane coating is solvent type, comprises some organic solvents in the system, and these solvents evaporate in the air at film process, just causes the pollution to environment.Volatile organic solvent is contaminate environment not only, and causes the rising of cost.A kind of feasible method that addresses this problem is to replace the disperse phase of organic solvent as system with water.The method that water-insoluble polymer is scattered in water has the outer emulsion process of pressure and polymkeric substance self-emulsification.Forced emulsification is under the condition that small-molecular emulsifier exists, and shears by high-speed stirring polymer enforced emulsification is distributed to aqueous phase.The shortcoming of forced emulsification be its formation be nonhomogeneous system, the stability of product and the poor water resistance of film.At present general technology is to introduce poly-ethylene oxide block, carboxyl or sulfonic group in molecular chain, and polar group is neutralized into alkali with organic amine or mineral alkali again, make polymkeric substance have in water from dispersion and emulsion.Behind the self-dispersion type polymer film forming, neutralizing agent organic amine wherein can vapor away, and makes the good water tolerance of having filmed.
At present, the solids constituent of the system of aqueous polyurethane is lower, generally at 20%-40%.Non-volatile content content is low, add because aqueous polyurethane is to be dispersion medium with the big water of vaporization heat, the shortcoming that time of drying is long and hardness of paint film is low when having caused aqueous polyurethane as the finishing agent of base materials such as plastics, timber, metal.The method that solves can add the rate of drying that a certain amount of linking agent is filmed with raising in water-based system, but after adding these materials, the package stability of system will be subjected to certain influence.
Summary of the invention:
First purpose of the present invention is the shortcoming at the above aqueous polyurethane, by in the preparation process of system, introducing an oxidable crosslinked segment, rate of drying of filming and the cross-linking density of filming have been improved on the one hand, the problem of avoiding additional crosslink agent to exist on the other hand is improved the performance of aqueous polyurethane dispersion and package stability.
Second purpose of the present invention is less this situation of core material that can be used for preparing aqueous polyurethane dispersion at existing, a series of polyester polyols that are suitable for preparing high-performance water-based polyurethane dispersoid have been designed and synthesized, for the development of China's polyurethane industrial provides service.
Self-crosslinked oxidation and high-efficient dispersion with water polyurethane of the present invention, its synthetic main raw material is:
(a) the minimum polyester polyol (A) that comprises two hydroxyls, its consumption account for 40%～60% of base polyurethane prepolymer for use as quality branch, are preferably 50%-58%;
(b) in the minimum siccative oil that comprises a hydroxyl or long oil alkyd (B), the ratio of its quality and (A) quality 1: 1～1: 3 is preferably in about 1: 2;
(c) in minimum aromatic series or the aliphatic diisocyanate of comprising, polyurethane-reinforcement reaction, the ratio of total isocyanate group and total hydroxyl is between 1.1～3.5 in the system; Optimum value is between 1.2～2.1.
(d) a kind of aqueous functional monomer, its consumption account for 3%～7% of base polyurethane prepolymer for use as quality branch, and being preferably in is 4%～6%.
Polyester polyol of the present invention (A) can adopt the polyester polyol of commercial grade, also can synthesize preparation.The polyester polyol (A) of synthetic preparation is to be made by polyester polyols alcoholization reaction with one or more minimum compounds (D) that comprise two hydroxyls by one or more minimum compounds (C) that comprise two carboxyls.For obtaining (A) that suitable molecular weight and end group are hydroxyl, the mole coefficient of carboxyl functional group and hydroxy functional group should be controlled between 0.60 and 0.85, and hydroxyl value (A) is at 55～250mgKOH/g.Carboxylic compound recited above (C) is to comprise one or more aromatic series that contain minimum 4 carbon atoms or aliphatics is saturated, unsaturated dibasic acid or its acid anhydrides.Suitable diprotic acid is the aliphatic dibasic acid that comprises 4～6 carbon atoms on the per molecule structure among the present invention, as oxalic acid, and Succinic Acid, pentanedioic acid, hexanodioic acid (AA), nonane diacid (AZA), dimeracid, 1,4 cyclohexanedicarboxylic acid (1,4-CHDA); The aliphatics unsaturated dibasic acid has fumaric acid, toxilic acid, methylene-succinic acid or their acid anhydrides.Aromatic acid comprises phthalic anhydride (PA), m-phthalic acid (IPA), terephthalic acid (TPA), tetrahydrophthalic anhydride (THPA), HHPA (HHPA).These diprotic acid and acid anhydride thereof also can mix use.PA mainly acts on and is to reduce cost, and often selects the hydrolytic resistance carboxylic acid for use, as IPA, AA, THPA, HHPA, CHDA etc., and preferred HHPA, CHDA.Wherein the introducing of AA, AZA and dimeracid can improve the snappiness of filming.Oxy-compound recited above (D) comprises following polyvalent alcohol: one or more contain the aliphatic dihydroxy alcohol of minimum two carbon atoms, and one or more contain the aliphatics trivalent alcohol of minimum 3 carbon atoms, and one or more contain the dibasic alcohol of alicyclic structure.Dibasic alcohol suitable among the present invention comprises 2-6 carbon atom in the per molecule structure, polyvalent alcohol can be selected glycerol, tetramethylolmethane, TriMethylolPropane(TMP) (TMP) etc. for use, the dibasic alcohol monomer has ethylene glycol, 1,4-butyleneglycol, 1,2-butyleneglycol, 1, and the 6-hexylene glycol (1,6-HDO), 1,4-cyclohexanedimethanol (1,4-CHDM), 1,5-pentanediol, 1,2-propylene glycol, 2-methyl isophthalic acid, ammediol (MPD), neopentyl glycol (NPG), 2,2,4-trimethylammonium-1,3-pentanediol (TMPD), 2-ethyl-2-butyl-1, ammediol (BEPD), 1, the 2-cyclohexanediol; 1, the 3-cyclohexanediol; 1,4-cyclohexanediol etc.Wherein, TMP is with three primary hydroxyls, and the space steric effect maskable ester group of the ethyl on it improves hydrolytic resistance, is commonly used to introduce branch, and two functionality monomer NPGs similar with it are also often selected; In addition, CHDM, TMPD, BEPD also have hydrolytic resistance preferably, but price is higher.These dibasic alcohol can use separately also can mix use.Monomer is when synthetic (A), and carboxylic compound (C) accounts for 42%～48%, and oxy-compound (D) accounts for 52%～58% of (C), (D) total amount.In (C) class material summation is 100%, and (C) the concrete composition of class material is: the aliphatics that one or more of 50%～100% contain 4 carbon atoms at least is saturated, unsaturated dibasic acid or acid anhydrides; 0%～50% one or more aromatic acids or acid anhydrides.In (D) class material summation is 100%, (D) the concrete composition of class material is: one or more of 50%～85% contain the dibasic alcohol of 2 carbon atoms at least, one or more of 5%～15% contain the trivalent alcohol of 3 carbon atoms at least, the alicyclic dibasic alcohol of one or more of 10%～45%.
(A) be by polyester polyols alcoholization reaction synthetic by (C), (D).Be reflected in the reactor that has thermometer, agitator, water trap, condenser, nitrogen ingress pipe, an electrically heated chuck and carry out.Before dropping into reaction mass, in reactor, lead to nitrogen earlier, add (C), (D) then successively.The reacting by heating system is started stirring to all material dissolutions, reacting balance is carried out, control still temperature is about 160～200 ℃, reacting balance is carried out, keep 3～4 hours after, slowly rise to 220 ℃, be incubated to aquifer yield near theoretical value, be cooled to 180 ℃, vacuumize, vacuum tightness improves gradually, reach 0.05～0.08MPa at last, kept 2 hours.The sampling and measuring acid number makes acid number≤1.0mgKOH/g (resin), is cooled to room temperature, and discharging gets polyester polyol (A).For accelerating reaction process, can in reaction system, add catalyzer.Catalyzer can be selected organotin for use.
Synolac of the present invention (B) in the present invention as modified component, can adopt the Synolac (B) of commercial grade, also can synthesize preparation.The Synolac (B) of synthetic preparation is made by (E), (F) two class substance reactions.Wherein, (E) being carboxylic monomer, (F) is carboxylic monomer.With (E), (F) the component total amount is 100%, (E) accounts for 35%～55%, (F) accounts for 45%～65%.(E) can be following polyvalent alcohol: ethylene glycol (EG), 1,6-hexylene glycol (1,6-HDO), 1, the 4-cyclohexanedimethanol (1,4-CHDM), 1,2-propylene glycol, neopentyl glycol (NPG), 2,2,4-trimethylammonium-1,3-pentanediol (TMPD), the monounsaturated fatty acids ester of the list of TriMethylolPropane(TMP) or dual-allyl ether, glycerol or TriMethylolPropane(TMP) (alcoholysis method by routine is synthetic), glycerol, TriMethylolPropane(TMP), tetramethylolmethane etc.(F) can be aromatic acid, as phthalic anhydride, m-phthalic acid and terephthalic acid.The oil iv of synthetic monounsaturated fatty acids ester should be greater than 100mgKOH/g (oil), as: oleum lini, rape seed oil, oleum gossypii seminis, tung oil, soya-bean oil, synourin oil, Thistle oil, Sunflower Receptacle wet goods.
(B) be at CO
2Under the protection of gas, drying oil fatty acid, polyvalent alcohol, aromatic acid (or acid anhydride), oxidation inhibitor (oxidation inhibitor can adopt triphenyl phosphite) and the adding of backflow dimethylbenzene are had in the reactor of agitator, thermometer, water trap and nitrogen conduit; Be heated to 160 ℃, change down speed and stir, be incubated about 0.5 hour; Be warming up to 180 ℃, be incubated about 1 hour; When water outlet is slack-off, continue to be warming up to 220 ℃, survey acid number after 2 hours; Control acid number≤6.0mgKOH/g (resin), steaming desolventizes, and is cooled to 30 ℃, adds acetone by 80% solid content and stirs, filter Synolac.
(A), (B) two kinds of polymer polyatomic alcohols are as reactive component, to provide the polyurethane-reinforcement reaction required hydroxyl.Suitable number-average molecular weight preferably is controlled between 500～3000 between 300～5000.Self-control synthetic polyester polyol (A) can mix with the polyester polyol of suitable commercial grade or polyethers two or polyvalent alcohol and uses regulating cost and performance, as poly--6-caprolactone dibasic alcohol or polyvalent alcohol, PCDL or polyvalent alcohol, polyoxypropyleneglycol, polyoxytrimethylene triol, polyoxytrimethylene, castor oil polyhydric alcohol, polytetrahydrofuran diol, tetrahydrofuran (THF)-propylene oxide copolymerization glycol.Self-control synthetic Synolac (B) also can with the dryness of suitable commercial grade in or long oil alkyd mix and use.
The synthetic performed polymer of polyurethane-reinforcement reaction is under a kind of protection of inert gas, and small amount of acetone, butanone, N-Methyl pyrrolidone or other solvent carry out under existing.Comprise as the suitable polyisocynate monomer that isocyanate group is provided: tolylene diisocyanate (TDI), ditan-4,4-vulcabond (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), dicyclohexyl methane diisocyanate (HMDI), Methylcyclohexyl diisocyanate (HTDI).In the present invention, preferred isocyanic ester comprises: TDI, MDI, HDI, IPDI or its mixture.In the polyurethane-reinforcement reaction, the ratio of total isocyanate group and total hydroxyl is the leading indicator that will control in the system, and generally between 1.1～3.5, defining this ratio is the R value.Among the present invention, when the R value too greatly or too hour, the isocyanate group ratio in the system is too high or performed polymer viscosity is too big, can make to disperse to encounter difficulties, the suitable R value is between 1.2～2.1.
Among the present invention, a kind ofly minimumly comprise a carboxyl or a sulfonic hydroxy alkyl compound is used as aqueous monomers, can be with this water of realizing prepolymer from dispersed.This suitable compounds comprises: dimethylolpropionic acid (DMBA), dimethylol propionic acid (DMPA), dihydroxymethyl acetate, 2-sodium sulfonate-1,4-butyleneglycol, 2,4-diamino benzene sulfonic acid.Used this material is dihydroxymethyl fourth (third) acid among the present invention, and its consumption accounts for 3%～7% of base polyurethane prepolymer for use as quality branch, is preferably in 4%～6%.
The carboxylic monomer that comprises among the present invention will neutralize with neutralizing agent, to generate hydrophilic anionic polymer.Used this material is alkyl amine and alkyl alcohol amine in invention.This suitable class material comprises triethylamine, tripropylamine, tributylamine, dimethylethyl amine, diethanolamine, trolamine, dimethylethanolamine.Preferred alkyl amine in the present invention is as triethylamine.
In order to improve molecular weight,, can in system, add chainextender at scatter stage and carry out chain extension to improve performances such as the hardness of finally filming, wear-resisting wiping, water tolerance, thermotolerance, solvent resistance.The diamine or the polyamine that contain amido can be selected for use, as quadrol, and isophorone diamine, diethylenetriamine, triethylene tetramine, etc.In the present invention, as the amine of the chainextender mixture of diamine and tertiary amine preferably.Can introduce the above polyamine of more ternary or ternary, to realize bigger cross-linking density.In the present invention, the amount that we control tertiary amine accounts for 0～50% of diamine and tertiary amine mixture, more suitably is 5～20%.Total consumption of diamine and tertiary amine is to be determined with total isocyanic ester base unit weight by the total total amount of hydroxyl groups of reaction system.Simultaneously, diamine is also relevant with chain extension coefficient with total consumption of tertiary amine.In the present invention, chain extension coefficient more suitably is 0.5～0.95 between 0.2～1.Above said chain extension coefficient be meant the total amidine functional group number that chainextender contains and the ratio of total surplus isocyanate group functional group number.
The preparation method of aqueous polyurethane dispersion of the present invention, its technology comprises:
(a) performed polymer is synthetic:
Under nitrogen protection, polyester polyol (A) adding is equipped with in the reactor of agitator, dropping funnel, thermometer, prolong and nitrogen conduit, be warming up to 70 ℃, start stirring, drip vulcabond, added in 1 hour, be incubated 2 hours; The aqueous functional monomer is added reactor after with dissolution with solvents, be incubated 1 hour; Be warming up to 80 ℃ then, be incubated about 3 hours, make NCO content reach theoretical value; Add Synolac (B) modification, be incubated 0.5 hour;
(b) neutralization, emulsification:
Be cooled to 60 ℃, add neutralizing agent; Stir after 15 minutes, adjust viscosity with acetone; Be cooled to below 30 ℃, under stirring fast, drip distilled water, continue to disperse 1 hour; 50 ℃ of decompressions remove acetone, must be with the faint yellow translucent aqueous polyurethane dispersion WPU of blue-fluorescence.
Catalyzer can reduce reaction activity, and the speed of reaction is accelerated, and shortens the reaction times, the control side reaction.Appropriate catalyst comprises organic tertiary amines and organometallic compound class among the present invention.Trimethylamine comprises: N, N-dimethylcyclohexylamine, triethylenediamine, triethylamine, N, N-dimethyl benzylamine, N, N-dimethyl butylamine, N-ethylmorpholine, N-methylmorpholine.Organometallic compound comprises: stannous octoate, dibutyl tin laurate, lead octoate 36, cobalt octoate, iron octoate, naphthenic acid tin, metatitanic acid four isobutyl esters.The most handy organometallic compound class of the present invention catalyzer dibutyl tin laurate.
The present invention, because in the synthesis material of preparation aqueous polyurethane dispersion, Synolac is introduced as oxidation cross-linked unit in innovation ground, the over-all properties of filming after the curing is significantly improved, meet or exceed the performance of oiliness system, have extraordinary market-oriented prospect.The aspect adopts the self-control synthetic to be used to prepare core material---the polyester polyol of high-performance water-based polyurethane dispersoid in addition, guaranteeing both to have grasped the initiative of production under the product quality premise, can reduce production costs again.
Embodiment:
Synthesizing of embodiment 1, polyester polyol resin (A-1).
(1) synthesizing formula:
Material name consumption (weight part):
Hexanodioic acid 260;
HHPA 300;
Neopentyl glycol 360;
Hexylene glycol 120;
Organotin 1.12.
(2) synthesis technique:
Hexanodioic acid, HHPA, neopentyl glycol, hexylene glycol and catalyzer adding are had in the reactor of agitator, thermometer, fractional column and nitrogen conduit; To work as still temperature rise to 160 ℃ with 1.5h, esterification begins, and has water to distillate, and reduces heat-up rate, and reacting balance is carried out, and control still temperature is about 160～200 ℃, and fractional column top temperature is no more than 105 ℃, keeps 3～4 hours.When temperature begins to descend, slowly rise to 220 ℃, be incubated to aquifer yield near theoretical value, be cooled to 180 ℃, vacuumize, vacuum tightness improves gradually, reaches 0.05～0.08MPa at last, keeps 2 hours.The sampling and measuring acid number makes acid number≤1.0mgKOH/g (resin), is cooled to room temperature, and discharging gets A-1.Resin hydroxyl value: 90mgKOH/g (resin).
Synthesizing of embodiment 2, polyester polyol resin (A-2).
(1) synthesizing formula:
Material name consumption (weight part):
Hexanodioic acid 371;
Maleic anhydride 249;
TriMethylolPropane(TMP) 10.6;
Neopentyl glycol 187;
1,4 cyclohexane dimethanol 284;
Butyleneglycol 179;
Organotin 1.6.
(2) synthesis technique is with embodiment 1.Resin hydroxyl value: 78mgKOH/g (resin) is designated as A-2.
Synthesizing of embodiment 3, polyester polyol resin (A-3).
(1) synthesizing formula:
Material name consumption (weight part):
Hexanodioic acid 378;
1,4 cyclohexanedicarboxylic acid 443;
TriMethylolPropane(TMP) 16.5;
Neopentyl glycol 187;
1,2-propylene glycol 150;
2-ethyl-2-butyl-1, ammediol 318;
Organotin 2.2.
(2) synthesis technique is with example 1.Resin hydroxyl value: 50mgKOH/g (resin) is designated as A-3.
Synthesizing of embodiment 4, Synolac (B-1).
(1) synthesizing formula:
Material name consumption (weight part):
Linolenic acid 450;
Phthalic anhydride 200;
M-phthalic acid 50;
TriMethylolPropane(TMP) 232.6;
Neopentyl glycol 150;
Triphenyl phosphite is an amount of.
(2) synthesis technique:
Linolenic acid, phthalic anhydride, m-phthalic acid, TriMethylolPropane(TMP), neopentyl glycol, triphenyl phosphite and the adding of backflow dimethylbenzene are had in the reactor of agitator, thermometer, water trap and nitrogen conduit; Be heated to 160 ℃, change down speed and stir, be incubated about 0.5h; Be warming up to 180 ℃, be incubated about 1h; When water outlet is slack-off, continue to be warming up to 220 ℃, survey acid number behind the 2h; Control acid number≤6.0mgKOH/g (resin), steaming desolventizes, and is cooled to 30 ℃, adds acetone by 80% solid content and stirs, filter Synolac, resin hydroxyl value: 50mgKOH/g (resin) is designated as B-1.
Embodiment 5, Synolac (B-2) synthesize.
(1) synthesizing formula
Material name consumption (weight part):
Ready denier oil acid 400;
HHPA 77;
1,4 cyclohexanedicarboxylic acid 171;
TriMethylolPropane(TMP) 228;
TriMethylolPropane(TMP) mono allyl ether 87;
Triphenyl phosphite is an amount of.
(2) synthesis technique is with embodiment 1.Resin hydroxyl value: 58mgKOH/g (resin) is designated as B-2.
Embodiment 6, aqueous polyurethane (WPU-1) synthesize
(1) synthesizing formula:
Material name consumption (weight part):
A-1 180；
DMBA 16.27；
IPDI 123；
TMP 5；
B-1 135；
Dibutyl tin laurate 0.8;
N-Methyl pyrrolidone 57.2;
Triethylamine 11.65;
Acetone is an amount of;
Quadrol 11.196;
Water 478.5.
(2) synthesis technique:
(a) performed polymer is synthetic:
Under nitrogen protection, (A-1) adding is equipped with in the reactor of agitator, dropping funnel, thermometer, prolong and nitrogen conduit, be warming up to 70 ℃, start stirring, drip IPDI, 1h adds, insulation 2h adds reactor with DMPA after with an amount of solvent heating for dissolving, is incubated 1h; Be warming up to 80 ℃ then, insulation 3h adds TMP, continues insulation, makes NCO content reach theoretical value (5.90% (100% solids constituent)); After performed polymer is synthetic, add
(B-1) modification, insulation 0.5h.
(b) neutralization, emulsification:
Be cooled to 60 ℃, add the triethylamine neutralization; After stirring 15min, adjust viscosity (about 70% solid content) with acetone; Be cooled to below 30 ℃, under stirring fast, drip distilled water, continue to disperse 1h; 50 ℃ of decompressions remove acetone, must be with the faint yellow translucent aqueous polyurethane dispersion WPU-1 of blue-fluorescence.
(2) technical target of the product:
The faint yellow translucent water dispersion of outward appearance;
Solids content 38%;
PH value 8.0;
Viscosity 30mpa.s;
1 grade of sticking power;
Hardness 2H;
Gloss 90;
Water tolerance 96h no change;
Anti-ethanol (50%, V/V) 6h no change.
Synthesizing of embodiment 7, aqueous polyurethane (WPU-2).
(1) synthesizing formula:
Material name consumption (weight part):
A-2 241.3；
DMBA 25.1；
IPDI 123；
1,4 cyclohexane dimethanol 5;
B-2 105；
Dibutyl tin laurate 0.6;
N-Methyl pyrrolidone 69.6;
Triethylamine 18.0;
Acetone is an amount of;
Quadrol 7.89;
Water 568.8.
(2) synthesis technique is with example 6.The NCO theoretical value is 3.50% (100% solids constituent).
(3) technical target of the product:
The faint yellow translucent water dispersion of outward appearance;
Solids content 38%;
PH value 8.0;
Viscosity 50mpa.s;
1 grade of sticking power;
Hardness 1H;
Gloss 90;
Water tolerance 96h no change;
Anti-ethanol (50%, V/V) 6h no change.
Synthesizing of embodiment 8, aqueous polyurethane (WPU-3).
(1) synthesizing formula:
Material name consumption (weight part):
A-3 284；
DMPA 18.65；
IPDI 103.5；
1,4 cyclohexane dimethanol 7;
B-2 156；
Dibutyl tin laurate 0.9;
N-Methyl pyrrolidone 78.0;
Triethylamine 13.36;
Acetone is an amount of;
Quadrol 11.35;
Water 643.5.
(2) synthesis technique is with example 6.The NCO theoretical value is 4.52% (100% solids constituent).
(3) technical target of the product:
The faint yellow translucent water dispersion of outward appearance;
Solids content 38%;
PH value 8.0;
Viscosity 45mpa.s;
1 grade of sticking power;
Hardness 2H;
Gloss 90;
Water tolerance 96h no change;
Anti-ethanol (50%, V/V) 6h no change.
Claims (9)
1, a kind of synthesis material of self-crosslinked oxidation and high-efficient dispersion with water polyurethane comprises:
(a) the minimum polyester polyol (A) that comprises two hydroxyls, its consumption account for 40%～60% of base polyurethane prepolymer for use as quality branch;
(b) in the minimum siccative oil that comprises a hydroxyl or long oil alkyd (B), the ratio of its quality and (A) quality 1: 1～1: 3;
(c) in minimum aromatic series or the aliphatic diisocyanate of comprising, polyurethane-reinforcement reaction, the ratio of total isocyanate group and total hydroxyl is between 1.1～3.5 in the system;
(d) a kind of aqueous functional monomer, its consumption account for 3%～7% of base polyurethane prepolymer for use as quality branch.
2, aqueous polyurethane dispersion according to claim 1 is characterized in that: described polyester polyol (A) by (C) and (D) two class substance reactions make, its resin quality content is 25%～50%:
Described (C) class material is a compound saturated by the aliphatics that comprises 4 carbon atoms in aromatic series or the per molecule structure at least, unsaturated dibasic acid (or its acid anhydride), and its resin quality content is 15%～30%, is 100% in (C) class material, comprises:
(a) one or more aromatic acids of 0%～50%, the perhaps acid anhydride of diprotic acid;
(b) one or more of 50%～100% contain saturated, the unsaturated dibasic acid of aliphatics of at least 4 carbon atoms, or its acid anhydride;
Described (D) class material is the minimum compound that comprises two hydroxyls in the per molecule structure, is 100% in (D) class material, comprises:
(a) one or more of 50%～85% contain the dibasic alcohol of 2 carbon atoms at least;
(b) one or more of 5%～15% contain the trivalent alcohol of 3 carbon atoms at least;
(c) one or more of 10%～45% contain the dibasic alcohol of aliphatics ring texture.
3, aqueous polyurethane dispersion according to claim 1 is characterized in that: described Synolac (B) be by (E) and (F) two class substance reactions make, (E) be carboxylic monomer, its proportioning is: 35%～55%; (F) be carboxylic monomer, its proportioning is: 45%～65%.
4, aqueous polyurethane dispersion according to claim 3, it is characterized in that: described carboxylic monomer (E) is: ethylene glycol, 1,6-hexylene glycol, 1,4-cyclohexanedimethanol, 1,2-propylene glycol, neopentyl glycol, 2,2,4-trimethylammonium-1, the 3-pentanediol, the monounsaturated fatty acids ester of the list of TriMethylolPropane(TMP) or dual-allyl ether, glycerol or TriMethylolPropane(TMP), glycerol, TriMethylolPropane(TMP), tetramethylolmethane.
5, aqueous polyurethane dispersion according to claim 3 is characterized in that: described carboxylic monomer (F) is: aromatic acid, and as phthalic anhydride, m-phthalic acid and terephthalic acid.
6, aqueous polyurethane dispersion according to claim 1, it is characterized by: described aromatic series or aliphatic diisocyanate are: tolylene diisocyanate, ditan-4,4-vulcabond, 1, hexamethylene-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexyl methane diisocyanate, Methylcyclohexyl diisocyanate, be preferably tolylene diisocyanate, ditan-4,4-vulcabond, hexamethylene diisocyanate, isophorone diisocyanate or its mixture.
7, aqueous polyurethane dispersion according to claim 1, it is characterized by: described aqueous functional monomer is: dimethylolpropionic acid, dimethylol propionic acid, dihydroxymethyl acetate, 2-sodium sulfonate-1,4-butyleneglycol, 2, the 4-diamino benzene sulfonic acid is preferably dimethylol propionic acid or dimethylolpropionic acid.
8, aqueous polyurethane dispersion according to claim 1 is characterized in that: the preparation aqueous polyurethane dispersion also comprises chainextender, neutralizing agent, catalyzer, solvent and water.
9, a kind of method for preparing the described aqueous polyurethane dispersion of claim 1, its technology comprises:
(a) performed polymer is synthetic:
Under nitrogen protection, polyester polyol (A) adding is equipped with in the reactor of agitator, dropping funnel, thermometer, prolong and nitrogen conduit, be warming up to 70 ℃, start stirring, drip vulcabond, added in 1 hour, be incubated 2 hours; The aqueous functional monomer is added reactor after with dissolution with solvents, be incubated 1 hour; Be warming up to 80 ℃ then, be incubated about 3 hours, make NCO content reach theoretical value; Add Synolac (B) modification, be incubated 0.5 hour;
(b) neutralization, emulsification
Be cooled to 60 ℃, add neutralizing agent; Stir after 15 minutes, adjust viscosity with acetone; Be cooled to below 30 ℃, under stirring fast, drip distilled water, continue to disperse 1 hour; 50 ℃ of decompressions remove acetone, must be with the faint yellow translucent aqueous polyurethane dispersion WPU of blue-fluorescence.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100341533A CN100475874C (en) | 2006-03-10 | 2006-03-10 | Self-crosslinked oxidation and high-efficient dispersion with water polyurethane and production thereof |
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| CN101914261A (en) * | 2010-08-12 | 2010-12-15 | 河北科技大学 | Polyurethane oil/polyacrylate latex interpenetrating network polymer emulsion material and synthesizing process thereof |
| US8193296B2 (en) | 2010-06-30 | 2012-06-05 | Nike, Inc. | Golf balls including crosslinked thermoplastic polyurethane |
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| GB2285984B (en) * | 1994-01-21 | 1998-01-28 | Ici Plc | Environmentally friendly autoxidisable film-forming alkyd coating compositions |
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| US8979676B2 (en) | 2011-08-23 | 2015-03-17 | Nike, Inc. | Multi-core golf ball having increased initial velocity at high swing speeds relative to low swing speeds |
| US9089739B2 (en) | 2011-08-23 | 2015-07-28 | Nike, Inc. | Multi-core golf ball having increased initial velocity |
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| CN106866931A (en) * | 2015-12-10 | 2017-06-20 | 科思创德国股份有限公司 | The dispersions of polyurethanes of the oxidation drying with special high chemical resistance |
| CN105419622A (en) * | 2015-12-21 | 2016-03-23 | 桂林市和鑫防水装饰材料有限公司 | Compound modified alkyd resin two-component coating and preparation method thereof |
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| CN109810240B (en) * | 2019-01-15 | 2021-06-15 | 陕西科技大学 | Preparation method and application of polyurethane fluorescent whitening emulsion containing piperidine amine |
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Address after: 515500, south side of Huaan Road, Jiedong experimental area, Guangdong, Jieyang (No. 16) Patentee after: Guangdong Tianyin Industrial Co., Ltd. Address before: 515500 south section of Huaan Road, Jiedong Economic Development Zone, Jiedong County, Guangdong Patentee before: Tianyin Chemical Industry Co., Ltd., Guangdong |