CN103450792B - Hyperbranched water-based polyurethane coating and preparation method thereof - Google Patents
Hyperbranched water-based polyurethane coating and preparation method thereof Download PDFInfo
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- CN103450792B CN103450792B CN201310358774.7A CN201310358774A CN103450792B CN 103450792 B CN103450792 B CN 103450792B CN 201310358774 A CN201310358774 A CN 201310358774A CN 103450792 B CN103450792 B CN 103450792B
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Abstract
The invention provides a hyperbranched water-based polyurethane coating and a preparation method thereof, belongs to the field of water-based coating, and is used for solving the problem that the existing hyperbranched water-based polyurethane is poor in waterproofness, solvent resistance and weather fastness. The coating comprises 35-68 parts of hyperbranched water-based polyurethane, 0.3-0.9 part of water-based wetting agent, 0.2-0.7 part of water-based flatting agent, 0.5-1.1 parts of water-based deformaer, 8-12 parts of water-based cosolvent and 2.5-4.3 parts of curing agent. The hyperbranched water-based polyurethane is prepared with hyperbranched polyester BoltornTMH40 as a soft segment and diaminosulfonate as a hydrophilic chain extender. A film formed by the cured hyperbranched water-based polyurethane coating provided by the invention has no phenomena of blushing, bubbling and falling even after being soaked in normal-temperature water for 60 hours, and also has no phenomena of blushing, facing and dulling even after being wiped 200 times by using ethanol and acetone.
Description
Technical field
The invention belongs to water-borne coatings field, be specifically related to hyperbranched aqueous polyurethane coating and preparation method thereof.
Technical background
Hyperbranched aqueous polyurethane is owing to having the environmental protection characteristic of aqueous polyurethane, and the feature such as the solvability with hyperbranched polymer is good, melt viscosity is low and being widely used.Aqueous polyurethane is divided into carboxylic acid type aqueous polyurethane and sulfonic acid type aqueous polyurethane, and compared with carboxylic acid type aqueous polyurethane, the good stability of sulfonic acid type aqueous polyurethane, solid content is high.The people such as Jiang Li (polyurethane industrial, 2012,27(4): 39-42) report the aqueous polyurethane that a kind of solid content is 50%, its core technology is with 1,2-dihydroxyl-3-N-morpholinopropanesulfonic acid sodium is hydrophilic chain extender, reacts, prepared aqueous polyurethane with isophorone diisocyanate and polyether glycol.The people such as Li Wei (coatings industry, 2011,41(9): 1-4) report the synthesis of the epoxide modified sulfonate aqueous polyurethane of a kind of high solids content, with isophorone diisocyanate and hexamethylene diisocyanate for vulcabond, poly-hexanodioic acid-1,4-butanediol ester is soft section, BDO is small molecule chain extender, and quadrol base ethyl sulfonic acid sodium is hydrophilic chain extender, epoxy resin E-51 is properties-correcting agent, obtains the epoxy modified aqueous urethane of water-based solid content more than 50%.This is because the hydrophilic radical of sulfonic acid salt polyurethane dispersions is strong acid and strong base salt, degree of ionization is higher, improve the zeta-potential of the electrostatic double layer of latex ion, stronger electrostatic repulsion is defined between emulsion particle, prevent emulsion particle to condense, therefore the aqueous polyurethane of high solids content (being greater than 50%) can be obtained.Due to the existence of hydrophilic radical, make the water tolerance of aqueous polyurethane, solvent resistance and weathering resistance all poor, therefore modification must be carried out to it.
Summary of the invention
The object of the invention is the problem in order to solve existing hyperbranched aqueous polyurethane water tolerance, solvent resistance and weathering resistance difference, and a kind of hyperbranched aqueous polyurethane coating and preparation method thereof is provided.
First the present invention provides a kind of hyperbranched aqueous polyurethane coating, comprises as follows according to weight parts:
Described hyperbranched aqueous polyurethane is with hyper-branched polyester Boltorn
tMh40 is soft section, with diamino sulfonic acid salt for hydrophilic chain extender prepares.
Preferably, the preparation method of described hyperbranched aqueous polyurethane, comprises as follows:
Step one: by hyper-branched polyester Boltorn
tMh40, Chloride Solid Ascatalyst agent, oxidation inhibitor and maleic acid anhydride reactant, obtain the hyperbranched aqueous polyurethane of modification;
Step 2: the hyperbranched aqueous polyurethane of modification step one obtained and di-isocyanate reaction, obtains the first intermediate;
Step 3: the first intermediate step 2 obtained and small molecule chain extender react, and obtain the second intermediate;
Step 4: the second intermediate step 3 obtained and diamino sulfonic acid reactant salt, obtain hyperbranched aqueous polyurethane.
Preferably, the temperature of reaction of described step one is 145 ~ 160 DEG C, and the reaction times is 2 ~ 3.5.
Preferably, described vulcabond is selected from the one in hexamethylene diisocyanate, isophorone diisocyanate, Methylcyclohexyl diisocyanate or dicyclohexyl methane diisocyanate.
Preferably, described small molecule chain extender is selected from the one in BDO or glycol ether.
Preferably, described diamino sulfonic acid salt is selected from the one in 2,4-diamino benzene sulfonic acid sodium or quadrol base ethyl sulfonic acid sodium.
Preferably, described aqueous wetting agent is selected from one or more in BYK-307, BYK-333 or BYK-377.
Preferably, it is one in Bayhydur3100, BayhydurXP2655 or BayhydurXP2547 that described solidifying agent is selected from model.
Preferably, described water-based solubility promoter is selected from the one in Virahol, butyl glycol ether or butyl.
The invention provides a kind of preparation method of hyperbranched aqueous polyurethane coating, comprise as follows:
Hyperbranched aqueous polyurethane, aqueous wetting agent, water-based flow agent and water-based defoamer are joined stirrer for mixing, and then adds water-based solubility promoter and solidifying agent stirring, namely obtain hyperbranched aqueous polyurethane coating.
Beneficial effect of the present invention
First the present invention provides a kind of hyperbranched aqueous polyurethane coating, and this coating main component is hyperbranched aqueous polyurethane, and described hyperbranched aqueous polyurethane is with hyper-branched polyester Boltorn
tMh40 is soft section, with diamino sulfonic acid salt for hydrophilic chain extender prepares, owing to using diamino sulfonic acid salt as hydrophilic chain extender in preparation process, the hyperbranched aqueous polyurethane obtained is made to have more excellent stability in storage, after the centrifugal 30min of the supercentrifuges of 10000 turns, bottom is without any precipitation.Meanwhile, owing to using hyper-branched polyester Boltorn
tMh40 is soft section, this hyperbranched aqueous polyurethane has higher functionality, with the coating obtained after solidifying agent effect, there is finer and close network-like structure, thus, improve the mechanical property of the paint film after solidification, thus greatly increase the water tolerance of paint film, solvent resistance and weathering resistance, experimental result shows: the paint film obtained after hyperbranched aqueous polyurethane paint solidification of the present invention soaks 60 hours in room temperature water, turning white does not appear in paint film, bubble, the phenomenon come off, through ethanol, acetone wiping 200 times, turning white does not appear in paint film, fade, loss of gloss phenomenon.
The present invention also provides a kind of preparation method of hyperbranched aqueous polyurethane coating, and this preparation method's technique is simple, with low cost, and the hyperbranched aqueous polyurethane coating prepared has excellent water tolerance, solvent resistance and weathering resistance.
Embodiment
First the present invention provides a kind of hyperbranched aqueous polyurethane coating, comprises as follows according to weight parts:
Hyperbranched aqueous polyurethane 35 ~ 68 parts, aqueous wetting agent 0.3 ~ 0.9 part, water-based flow agent 0.2 ~ 0.7 part, water-based defoamer 0.5 ~ 1.1 part, water-based solubility promoter 8 ~ 12 parts, 2.5 ~ 4.3 parts, solidifying agent; Preferably, hyperbranched aqueous polyurethane 38 ~ 60 parts, aqueous wetting agent 0.4 ~ 0.8 part, water-based flow agent 0.3 ~ 0.65 part, water-based defoamer 0.55 ~ 1.0 part, water-based solubility promoter 9 ~ 11.5 parts, 3 ~ 4 parts, solidifying agent; Described hyperbranched aqueous polyurethane is with hyper-branched polyester Boltorn
tMh40 is soft section, with diamino sulfonic acid salt for hydrophilic chain extender prepares.
The preparation method of hyperbranched aqueous polyurethane of the present invention, preferably includes as follows:
Step one: by hyper-branched polyester Boltorn
tMh40, Chloride Solid Ascatalyst agent, oxidation inhibitor and maleic acid anhydride reactant, obtain the hyperbranched aqueous polyurethane of modification;
Step 2: the hyperbranched aqueous polyurethane of modification step one obtained and di-isocyanate reaction, obtains the first intermediate;
Step 3: the first intermediate step 2 obtained and small molecule chain extender react, and obtain the second intermediate;
Step 4: the second intermediate step 3 obtained and diamino sulfonic acid reactant salt, obtain hyperbranched aqueous polyurethane.
Hyper-branched polyester Boltorn of the present invention
tMh40 refers to the forth generation hyper-branched polyester Boltorn that Bai Situo company of Sweden produces
tMh40, containing 64 hydroxyls on molecule, react with the NCO of vulcabond, then the polyurethane molecular obtained is too huge, cannot be dispersed in water, thus affect Property of Waterborne Polyurethane.Thus, the present invention is first by hyper-branched polyester Boltorn
tMh40 and maleic acid anhydride reactant, after consuming some hydroxyls, less hydroxyl reacts with NCO again, and the urethane obtained can be dispersed in water well, just can obtain the aqueous polyurethane of stable performance.
Described in step one of the present invention by hyper-branched polyester Boltorn
tMbefore H40, Chloride Solid Ascatalyst agent, oxygenant and maleic acid anhydride reactant, first by hyper-branched polyester Boltorn
tMh40 stirring solvent is dissolved, and described solvent is preferably dimethylbenzene, and described whipping temp is preferably 110 ~ 135 DEG C, and churning time is preferably 20 ~ 35min, hyper-branched polyester Boltorn
tMafter H40 dissolves completely, continue in reaction vessel, add Chloride Solid Ascatalyst agent, oxidation inhibitor and MALEIC ANHYDRIDE again to react, described temperature of reaction is preferably 145 ~ 160 DEG C, reaction times is preferably 2 ~ 3.5h, and described oxidation inhibitor is not particularly limited, and is preferably antioxidant 1010, after reaction terminates, under 0.098MPa pressure, except desolventizing, obtain the hyperbranched aqueous polyurethane of modification.Because this structure contains carboxyl, can self-emulsifying action be played, make obtained hyperbranched aqueous poly-ammonia have excellent stability.Described hyper-branched polyester Boltorn
tMthe mass ratio of H40, Chloride Solid Ascatalyst agent, oxidation inhibitor and MALEIC ANHYDRIDE is: (450 ~ 820): (0.23 ~ 0.55): (0.01 ~ 0.03): (80 ~ 170).
Described in step 2 of the present invention by before the hyperbranched aqueous polyurethane of modification and di-isocyanate reaction, preferably, under nitrogen protection, first carry out decompression to the hyperbranched aqueous polyurethane of modification to dewater, be specially the hyperbranched aqueous polyurethane first adding modification in reaction vessel, then temperature of reaction is risen to 100 ~ 120 DEG C, under 0.098MPa pressure, decompression dewaters 1.5 ~ 3 hours, then cooling adds solvent acetone, in reaction vessel, drip vulcabond react, namely the first intermediate is obtained, described temperature of reaction is preferably 70 ~ 85 DEG C, reaction times is preferably 2 ~ 4h, the rate of addition of vulcabond is preferably 8 ~ 15ml/min, the hyperbranched aqueous polyurethane of described modification and the mass ratio of vulcabond are: (350 ~ 672): (165 ~ 238).Described vulcabond is preferably selected from the one in hexamethylene diisocyanate, isophorone diisocyanate, Methylcyclohexyl diisocyanate or dicyclohexyl methane diisocyanate.
After obtaining the first intermediate, in order to reduce system viscosity, in reaction vessel, add solvent acetone, then continue to add catalyzer, and drip small molecule chain extender and react, namely obtain the second intermediate; Described catalyzer is preferably the one in dibutyl tin laurate or stannous octoate, and small molecule chain extender is preferably the one in BDO or glycol ether; Described temperature of reaction is preferably 80-90 DEG C, reaction times is preferably 1-2h, the rate of addition of small molecule chain extender is preferably 3-8ml/min, and the mass ratio of the hyperbranched aqueous polyurethane of described modification, catalyzer and small molecule chain extender is: (350 ~ 672): (0.0015 ~ 0.0035): (18 ~ 26).
After obtaining the second intermediate, temperature in reaction vessel is reduced, continue again to add diamino sulfonic acid salt stirring reaction, described temperature of reaction is preferably 35 ~ 45 DEG C, churning time is preferably 10 ~ 15min, then continues in reaction vessel, add deionized water and quadrol stirring, and described churning time is preferably 20 ~ 45min, removal of solvent under reduced pressure acetone, namely obtains hyperbranched aqueous polyurethane.Described diamino sulfonic acid salt is preferably selected from 2, one in 4-diamino benzene sulfonic acid sodium or quadrol base ethyl sulfonic acid sodium, owing to using diamino sulfonic acid salt as hydrophilic chain extender in preparation process, the hyperbranched aqueous polyurethane obtained is made to have more excellent stability in storage.The mass ratio of the hyperbranched aqueous polyurethane of described modification, diamino sulfonic acid salt, deionized water and quadrol is: (350 ~ 672): (32 ~ 65): (550 ~ 980): (6 ~ 15).
Aqueous wetting agent of the present invention is that to be preferably the model that BYK company produces be one or more in BYK-307, BYK-333 or BYK-377.
It is one or both in BYK-381 or BYK-345 that water-based flow agent of the present invention is preferably the model that BYK company produces.
It is one or more in BYK-019, BYK-020 or BYK-1730 that water-based defoamer of the present invention is preferably the model that BYK company produces.
It is one in Bayhydur3100, BayhydurXP2655 or BayhydurXP2547 that solidifying agent of the present invention is preferably selected from model.
Water-based solubility promoter of the present invention is preferably the one in Virahol, butyl glycol ether or butyl.
The invention provides a kind of preparation method of hyperbranched aqueous polyurethane coating, comprise as follows:
Hyperbranched aqueous polyurethane, aqueous wetting agent, water-based flow agent and water-based defoamer are joined stirrer for mixing, and described churning time is preferably 2h, and stirring velocity is preferably 800rpm-1200rpm, is more preferably 900rpm-1100rpm; And then adding water-based solubility promoter and solidifying agent stirring, described churning time is preferably 1.5h, and stirring velocity is preferably 650rpm-800rpm, is more preferably 700rpm-750rpm, namely obtains hyperbranched aqueous polyurethane coating.
For making those skilled in the art understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment.In embodiment, mentioned chemical reagent all obtains by being purchased method.
Embodiment 1
The hyper-branched polyester Boltorn of 450g is added in reaction vessel
tMh40 and 1300g dimethylbenzene, temperature, to 110 DEG C, stirs 20min, after heating is dissolved completely, add the agent of 0.23g Chloride Solid Ascatalyst and 0.01g antioxidant 1010, then, add 80g MALEIC ANHYDRIDE, be warmed up to 145 DEG C, react 2 hours, under 0.098MPa pressure, except removal xylene, obtain the hyperbranched aqueous polyurethane of modification;
Under nitrogen protection, in reaction vessel, add the hyperbranched aqueous polyurethane of 350g modification, temperature to 100 DEG C, under 0.098MPa pressure, decompression dewaters 2 hours, temperature drops to 70 DEG C, adds 160g acetone, drips 1 of 165g with the speed of 8ml/min, hexamethylene-diisocyanate, after dropwising, continue reaction 2 hours, obtain the first intermediate;
In reaction vessel, add the acetone of 120ml, reduce system viscosity, then, add 0.0015g dibutyltin dilaurate catalyst, temperature controls at 80 DEG C, drips the BDO of 18g with the speed of 3ml/min, after dropwising, continue reaction 1 hour, obtain the second intermediate;
System temperature is dropped to 35 DEG C, add 2, the 4-diamino benzene sulfonic acid sodium of 32g in reaction vessel, stir 10min, then, add deionized water 550g and 6g quadrol, continue to stir 20min, decompression removing acetone, obtains hyperbranched aqueous polyurethane.
Embodiment 2
The hyper-branched polyester Boltorn of 820g is added in reaction vessel
tMh40 and 1650g dimethylbenzene, temperature, to 135 DEG C, stirs 35min, after heating is dissolved completely, add the agent of 0.55g Chloride Solid Ascatalyst and 0.03g antioxidant 1010, then, add 170g MALEIC ANHYDRIDE, be warmed up to 160 DEG C, react 3.5 hours, under 0.098MPa pressure, except removal xylene, obtain the hyperbranched aqueous polyurethane of modification;
Under nitrogen protection, the hyperbranched aqueous polyurethane of 672g modification is added in reaction vessel, temperature is to 120 DEG C, and under 0.098MPa pressure, decompression dewaters 2 hours, temperature drops to 85 DEG C, add 240g acetone, drip 238g dicyclohexyl methane diisocyanate, after dropwising with the speed of 15ml/min, continue reaction 4 hours, obtain the first intermediate;
In reaction vessel, add the acetone of 200ml, reduce system viscosity, then, add 0.0035g stannous octoate catalyst, temperature controls at 90 DEG C, drips the glycol ether of 26g with the speed of 8ml/min, after dropwising, continue reaction 2 hours, obtain the second intermediate;
System temperature is dropped to 45 DEG C, add 65g quadrol base ethyl sulfonic acid sodium in reaction vessel, stir 15min, then, add deionized water 980g and 15g quadrol, continue to stir 45min, decompression removing acetone, obtains hyperbranched aqueous polyurethane.
Embodiment 3
The hyper-branched polyester Boltorn of 660g is added in reaction vessel
tMh40 and 1480g dimethylbenzene, temperature, to 120 DEG C, stirs 30min, and heating adds the agent of 0.45g Chloride Solid Ascatalyst and 0.02g antioxidant 1010, then, adds 120g MALEIC ANHYDRIDE, be warmed up to 150 DEG C, react 3 hours after dissolving completely.Under 0.098MPa pressure, except removal xylene, obtain the hyperbranched aqueous polyurethane of modification;
Under nitrogen protection, the hyperbranched aqueous polyurethane of 450g modification is added in reaction vessel, temperature is to 110 DEG C, and under 0.098MPa pressure, decompression dewaters 2 hours, temperature drops to 75 DEG C, add 180g acetone, drip 220g isophorone diisocyanate, after dropwising with the speed of 10ml/min, continue reaction 3 hours, obtain the first intermediate;
In reaction vessel, add the acetone of 160ml, reduce system viscosity, then, add 0.002g stannous octoate catalyst, temperature controls at 85 DEG C, drips the BDO of 20g with the speed of 5ml/min, after dropwising, continue reaction 1.5 hours, obtain the second intermediate;
System temperature is dropped to 40 DEG C, add 40g quadrol base ethyl sulfonic acid sodium in reaction vessel, stir 12min, then, add deionized water 620g and 9g quadrol, continue to stir 30min, decompression removing acetone, obtains hyperbranched aqueous polyurethane.
Embodiment 4
The hyper-branched polyester Boltorn of 575g is added in reaction vessel
tMh40 and 1498g dimethylbenzene, temperature, to 120 DEG C, stirs 20min, after heating is dissolved completely, add the agent of 0.35g Chloride Solid Ascatalyst and 0.025g antioxidant 1010, then, add 135g MALEIC ANHYDRIDE, be warmed up to 145 DEG C, react 3 hours, under 0.098MPa pressure, except removal xylene, obtain the hyperbranched aqueous polyurethane of modification;
Under nitrogen protection, the hyperbranched aqueous polyurethane of 510g modification is added in reaction vessel, temperature is to 120 DEG C, and under 0.098MPa pressure, decompression dewaters 2 hours, temperature drops to 80 DEG C, add 220g acetone, drip 204g Methylcyclohexyl diisocyanate, after dropwising with the speed of 11ml/min, continue reaction 3.5 hours, obtain the first intermediate;
In reaction vessel, add the acetone of 180ml, reduce system viscosity, then, add 0.0025g dibutyltin dilaurate catalyst, temperature controls at 86 DEG C, drips 22g glycol ether with the speed of 5ml/min, after dropwising, continue reaction 1.5 hours, obtain the second intermediate;
System temperature is dropped to 42 DEG C, add 2, the 4-diamino benzene sulfonic acid sodium of 51g in reaction vessel, stir 13min, then, add deionized water 760g and 14g quadrol, continue to stir 45min, decompression removing acetone, obtains hyperbranched aqueous polyurethane.
Embodiment 5
The hyper-branched polyester Boltorn of 766g is added in reaction vessel
tMh40 and 1580g dimethylbenzene, temperature, to 130 DEG C, stirs 25min, after heating is dissolved completely, add the agent of 0.5g Chloride Solid Ascatalyst and 0.022g antioxidant 1010, then, add 163g MALEIC ANHYDRIDE, be warmed up to 150 DEG C, react 3 hours, under 0.098MPa pressure, except removal xylene, obtain the hyperbranched aqueous polyurethane of modification;
Under nitrogen protection, the hyperbranched aqueous polyurethane of 586g modification is added in reaction vessel, temperature is to 100 DEG C, and under 0.098MPa pressure, decompression dewaters 2 hours, temperature drops to 75 DEG C, add 230g acetone, drip 200g isophorone diisocyanate, after dropwising with the speed of 10ml/min, continue reaction 3 hours, obtain the first intermediate;
In reaction vessel, add the acetone of 175ml, reduce system viscosity, then, add 0.003g dibutyltin dilaurate catalyst, temperature controls at 85 DEG C, drips the BDO of 25g with the speed of 6ml/min, after dropwising, continue reaction 1 hour, obtain the second intermediate;
System temperature is dropped to 45 DEG C, add 2, the 4-diamino benzene sulfonic acid sodium of 58g in reaction vessel, stir 12min, then, add deionized water 860g and 13.5g quadrol, continue to stir 35min, decompression removing acetone, obtains hyperbranched aqueous polyurethane.
Embodiment 6
Hyperbranched aqueous polyurethane 35g embodiment 1 obtained, 0.3g aqueous wetting agent BYK-307,0.2g water-based flow agent BYK-381,0.5g water-based defoamer BYK-019 join in homogenizer, 2h is stirred with the rotating speed of 800rpm, then 8g water-based solubility promoter Virahol and 2.5g solidifying agent Bayhydur3100 is added, stir 1.5h with the rotating speed of 650rpm, obtain hyperbranched aqueous polyurethane coating.
Embodiment 7
Hyperbranched aqueous polyurethane 68g embodiment 2 obtained, 0.9g aqueous wetting agent BYK-307,0.7g water-based flow agent BYK-381,1.1g water-based defoamer BYK-019 join in homogenizer, 2h is stirred with the rotating speed of 1200rpm, then 12g water-based solubility promoter Virahol and 4.3g solidifying agent BayhydurXP2655 is added, stir 1.5h with the rotating speed of 800rpm, obtain hyperbranched aqueous polyurethane coating.
Embodiment 8
Hyperbranched aqueous polyurethane 47g embodiment 3 obtained, 0.4g aqueous wetting agent BYK-307,0.1g aqueous wetting agent BYK-333,0.4g water-based flow agent BYK-381,0.1g water-based flow agent BYK-345,0.9g water-based defoamer BYK-020 join in homogenizer, 2h is stirred with the rotating speed of 900rpm, then 10g water-based solubility promoter butyl glycol ether and 3.1g solidifying agent BayhydurXP2547 is added, stir 1.5h with the rotating speed of 700rpm, obtain hyperbranched aqueous polyurethane coating.
Embodiment 9
Hyperbranched aqueous polyurethane 52g embodiment 4 obtained, 0.7g aqueous wetting agent BYK-333,0.3g water-based flow agent BYK-345,0.6g water-based defoamer BYK-1730 join in homogenizer, 2h is stirred with the rotating speed of 1100rpm, then 9g water-based solubility promoter butyl glycol ether and 3.8g solidifying agent Bayhydur3100 is added, stir 1.5h with the rotating speed of 750rpm, obtain hyperbranched aqueous polyurethane coating.
Embodiment 10
Hyperbranched aqueous polyurethane 60g embodiment 5 obtained, 0.1g aqueous wetting agent BYK-307,0.8g aqueous wetting agent BYK-377,0.6g water-based flow agent BYK-381,0.1g water-based defoamer BYK-019,0.6g water-based defoamer BYK-1730 join in homogenizer, 2h is stirred with the rotating speed of 900rpm, then 11g water-based solubility promoter butyl and 4g solidifying agent Bayhydur3100 is added, stir 1.5h with the rotating speed of 700rpm, obtain hyperbranched aqueous polyurethane coating.
Hyperbranched aqueous polyurethane paint embodiment 6 to embodiment 10 obtained respectively is on ABS plastic sheet material, after catching up with pure qi (oxygen) to steep, at 90 DEG C of baking 2h, the material obtained is tested, test result in table 1, the performance test results of paint film after the hyperbranched aqueous polyurethane paint solidification that table 1 provides for the embodiment of the present invention.
Table 1
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (9)
1. hyperbranched aqueous polyurethane coating, is characterized in that, comprises as follows according to weight parts:
Described hyperbranched aqueous polyurethane is with hyper-branched polyester Boltorn
tMh40 is soft section, with diamino sulfonic acid salt for hydrophilic chain extender prepares;
The preparation method of described hyperbranched aqueous polyurethane, comprises as follows:
Step one: by hyper-branched polyester Boltorn
tMh40, Chloride Solid Ascatalyst agent, oxidation inhibitor and maleic acid anhydride reactant, obtain the hyperbranched aqueous polyurethane of modification;
Step 2: the hyperbranched aqueous polyurethane of modification step one obtained and di-isocyanate reaction, obtains the first intermediate;
Step 3: the first intermediate step 2 obtained and small molecule chain extender react, and obtain the second intermediate;
Step 4: the second intermediate step 3 obtained and diamino sulfonic acid reactant salt, obtain hyperbranched aqueous polyurethane.
2. hyperbranched aqueous polyurethane coating according to claim 1, is characterized in that, the temperature of reaction of described step one is 145 ~ 160 DEG C, and the reaction times is 2 ~ 3.5h.
3. hyperbranched aqueous polyurethane coating according to claim 1, it is characterized in that, described vulcabond is selected from the one in hexamethylene diisocyanate, isophorone diisocyanate, Methylcyclohexyl diisocyanate or dicyclohexyl methane diisocyanate.
4. hyperbranched aqueous polyurethane coating according to claim 1, is characterized in that, described small molecule chain extender is selected from the one in BDO or glycol ether.
5. hyperbranched aqueous polyurethane coating according to claim 1, is characterized in that, described diamino sulfonic acid salt is selected from the one in 2,4-diamino benzene sulfonic acid sodium or quadrol base ethyl sulfonic acid sodium.
6. hyperbranched aqueous polyurethane coating according to claim 1, is characterized in that, described aqueous wetting agent is selected from one or more in BYK-307, BYK-333 or BYK-377.
7. hyperbranched aqueous polyurethane coating according to claim 1, is characterized in that, it is one in Bayhydur3100, BayhydurXP2655 or BayhydurXP2547 that described solidifying agent is selected from model.
8. hyperbranched aqueous polyurethane coating according to claim 1, is characterized in that, described water-based solubility promoter is selected from the one in Virahol, butyl glycol ether or butyl.
9., according to the preparation method of the hyperbranched aqueous polyurethane coating of claim 1-8 described in any one, comprise as follows:
Hyperbranched aqueous polyurethane, aqueous wetting agent, water-based flow agent and water-based defoamer are joined stirrer for mixing, and then adds water-based solubility promoter and solidifying agent stirring, namely obtain hyperbranched aqueous polyurethane coating.
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| CN102352011B (en) * | 2011-08-12 | 2013-03-13 | 安徽大学 | Preparation method of aqueous hyperbranched polyurethane |
| CN102851987B (en) * | 2012-10-11 | 2015-01-07 | 北京理工大学 | Hyperbranched waterborne polyurethane coating agent |
| CN103030765B (en) * | 2012-12-10 | 2017-12-12 | 中国科学院福建物质结构研究所 | Hold sulfonate type hyperbranched aqueous polyurethane emulsion and preparation method thereof |
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