CN103450792A - 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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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 the water-borne coatings field, be specifically related to hyperbranched aqueous polyurethane coating and preparation method thereof.
Technical background
Hyperbranched aqueous polyurethane is due to the environmental protection characteristic with aqueous polyurethane, and has the characteristics such as the solvability of hyperbranched polymer is good, melt viscosity is low and be widely used.Aqueous polyurethane is divided into carboxylic acid type aqueous polyurethane and sulfonic acid type aqueous polyurethane, with the carboxylic acid type aqueous polyurethane, compares, and 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) reported 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, with isophorone diisocyanate and polyether glycol, reacts, and has prepared aqueous polyurethane.The people such as Li Wei (coatings industry, 2011,41(9): 1-4) reported the synthetic of the epoxide modified sulfonate aqueous polyurethane of a kind of high solids content, take isophorone diisocyanate and hexamethylene diisocyanate as vulcabond, poly-hexanodioic acid-1, the 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 water-based solid content and surpasses 50% epoxy modified aqueous urethane.This is because the hydrophilic radical of sulfonate based polyurethane dispersion is strong acid and strong base salt, degree of ionization is higher, improved the zeta-potential of the electrostatic double layer of latex ion, formed stronger electrostatic repulsion between emulsion particle, stoped the emulsion particle cohesion, therefore can make the aqueous polyurethane of high solids content (being greater than 50%).Due to the existence of hydrophilic radical, make water tolerance, solvent resistance and the weathering resistance of aqueous polyurethane all poor, therefore must carry out modification to it.
Summary of the invention
The objective of the invention is in order to solve existing hyperbranched aqueous polyurethane water tolerance, solvent resistance and the poor problem of weathering resistance, and a kind of hyperbranched aqueous polyurethane coating and preparation method thereof is provided.
At first the present invention provides a kind of hyperbranched aqueous polyurethane coating, according to the parts by weight meter, comprises as follows:
Described hyperbranched aqueous polyurethane is with hyper-branched polyester Boltorn
tMh40 is soft section, and the diamino sulfonic acid salt of take prepares as hydrophilic chain extender.
Preferably, the preparation method of described hyperbranched aqueous polyurethane comprises as follows:
Step 1: 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 the modification that step 1 is obtained and di-isocyanate reaction obtain the first intermediate;
Step 3: the first intermediate that step 2 is obtained reacts with small molecule chain extender, obtains the second intermediate;
Step 4: the second intermediate that step 3 is obtained and diamino sulfonic acid reactant salt obtain hyperbranched aqueous polyurethane.
Preferably, the temperature of reaction of described step 1 is 145～160 ℃, and the reaction times is 2～3.5.
Preferably, described vulcabond is selected from a kind of in hexamethylene diisocyanate, isophorone diisocyanate, Methylcyclohexyl diisocyanate or dicyclohexyl methane diisocyanate.
Preferably, described small molecule chain extender is selected from a kind of in BDO or glycol ether.
Preferably, described diamino sulfonic acid salt is selected from a kind of 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, to be selected from model be a kind of in Bayhydur3100, BayhydurXP2655 or BayhydurXP2547 to described solidifying agent.
Preferably, described water-based solubility promoter is selected from a kind of in Virahol, butyl glycol ether or Diethylene Glycol butyl ether.
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 to stirrer for mixing, and then add water-based solubility promoter and solidifying agent to stir, obtain hyperbranched aqueous polyurethane coating.
Beneficial effect of the present invention
At 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, the diamino sulfonic acid salt of take prepares as hydrophilic chain extender, owing to using diamino sulfonic acid salt as hydrophilic chain extender in preparation process, make the hyperbranched aqueous polyurethane obtained there is more excellent stability in storage, with after the centrifugal 30min of 10000 supercentrifuge turned, bottom is without any precipitation.Simultaneously, owing to using hyper-branched polyester Boltorn
tMh40 is soft section, this hyperbranched aqueous polyurethane has higher functionality, there is finer and close network-like structure with the coating obtained after the solidifying agent effect, thereby, improved the mechanical property of the paint film after solidifying, thereby improved widely 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, the 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
At first the present invention provides a kind of hyperbranched aqueous polyurethane coating, according to the parts by weight meter, comprises as follows:
35～68 parts of hyperbranched aqueous polyurethanes, 0.3～0.9 part of aqueous wetting agent, 0.2～0.7 part of water-based flow agent, 0.5～1.1 part of water-based defoamer, 8～12 parts of water-based solubility promoters, 2.5～4.3 parts, solidifying agent; Preferably, 38～60 parts of hyperbranched aqueous polyurethanes, 0.4～0.8 part of aqueous wetting agent, 0.3～0.65 part of water-based flow agent, 0.55～1.0 part of water-based defoamer, 9～11.5 parts of water-based solubility promoters, 3～4 parts, solidifying agent; Described hyperbranched aqueous polyurethane is with hyper-branched polyester Boltorn
tMh40 is soft section, and the diamino sulfonic acid salt of take prepares as hydrophilic chain extender.
The preparation method of hyperbranched aqueous polyurethane of the present invention preferably includes as follows:
Step 1: 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 the modification that step 1 is obtained and di-isocyanate reaction obtain the first intermediate;
Step 3: the first intermediate that step 2 is obtained reacts with small molecule chain extender, obtains the second intermediate;
Step 4: the second intermediate that step 3 is obtained and diamino sulfonic acid reactant salt obtain hyperbranched aqueous polyurethane.
Hyper-branched polyester Boltorn of the present invention
tMh40 refers to the 4th generation hyper-branched polyester Boltorn that Sweden Bai Situo company produces
tMh40, contain 64 hydroxyls on molecule, with the NCO of vulcabond, react, and the polyurethane molecular obtained is too huge, can't be dispersed in water, thereby affect Property of Waterborne Polyurethane.Thereby the present invention is at 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.
Step 1 of the present invention is described by hyper-branched polyester Boltorn
tMbefore H40, Chloride Solid Ascatalyst agent, oxygenant and maleic acid anhydride reactant, first by hyper-branched polyester Boltorn
tMh40 dissolves by stirring solvent, and described solvent is preferably dimethylbenzene, and described whipping temp is preferably 110～135 ℃, and churning time is preferably 20～35min, hyper-branched polyester Boltorn
tMafter H40 dissolves fully, continue again to add Chloride Solid Ascatalyst agent, oxidation inhibitor and MALEIC ANHYDRIDE to be reacted in reaction vessel, described temperature of reaction is preferably 145～160 ℃, reaction times is preferably 2～3.5h, and described oxidation inhibitor is not particularly limited, and is preferably antioxidant 1010, after reaction finishes, under 0.098MPa pressure, except desolventizing, obtain the hyperbranched aqueous polyurethane of modification.Because this structure contains carboxyl, can play self-emulsifying action, make resulting hyperbranched aqueous poly-ammonia there is 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).
Step 2 of the present invention is described by before the hyperbranched aqueous polyurethane and di-isocyanate reaction of modification, preferably, under nitrogen protection, first the hyperbranched aqueous polyurethane of modification is reduced pressure and dewaters, be specially the hyperbranched aqueous polyurethane that first in reaction vessel, adds modification, then temperature of reaction is risen to 100～120 ℃, under 0.098MPa pressure, decompression dewaters 1.5～3 hours, then cooling adds solvent acetone, dripping vulcabond in reaction vessel is reacted, obtain the first intermediate, described temperature of reaction is preferably 70～85 ℃, 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 a kind of in hexamethylene diisocyanate, isophorone diisocyanate, Methylcyclohexyl diisocyanate or dicyclohexyl methane diisocyanate.
After obtaining the first intermediate, in order to reduce system viscosity, add solvent acetone in reaction vessel, then continue to add catalyzer, and drip small molecule chain extender and reacted, obtain the second intermediate; Described catalyzer is preferably a kind of in dibutyl tin laurate or stannous octoate, and small molecule chain extender is preferably a kind of in BDO or glycol ether; Described temperature of reaction is preferably 80-90 ℃, 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 ℃, churning time is preferably 10～15min, then continues to add deionized water and quadrol to stir in reaction vessel, and described churning time is preferably 20～45min, removal of solvent under reduced pressure acetone, obtain hyperbranched aqueous polyurethane.Described diamino sulfonic acid salt is preferably selected from 2, a kind of 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, make the hyperbranched aqueous polyurethane obtained there is 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 model that BYK company produces.
The model that water-based defoamer of the present invention is preferably the production of BYK company is one or more in BYK-019, BYK-020 or BYK-1730.
It is a kind of 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 a kind of in Virahol, butyl glycol ether or Diethylene Glycol butyl ether.
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 to stirrer for mixing, and described churning time is preferably 2h, and stirring velocity is preferably 800rpm-1200rpm, more preferably 900rpm-1100rpm; And then add water-based solubility promoter and solidifying agent to stir, and described churning time is preferably 1.5h, and stirring velocity is preferably 650rpm-800rpm, and more preferably 700rpm-750rpm, obtain hyperbranched aqueous polyurethane coating.
For making those skilled in the art understand better the present invention, below in conjunction with embodiment, further illustrate content of the present invention.In embodiment, mentioned chemical reagent all can obtain by being purchased method.
Embodiment 1
The hyper-branched polyester Boltorn that adds 450g in reaction vessel
tMh40 and 1300g dimethylbenzene, temperature is warmed up to 110 ℃, stirs 20min, after heating is dissolved fully, add the agent of 0.23g Chloride Solid Ascatalyst and 0.01g antioxidant 1010, then, add the 80g MALEIC ANHYDRIDE, be warmed up to 145 ℃, react 2 hours, under 0.098MPa pressure, except removal xylene, obtain the hyperbranched aqueous polyurethane of modification;
Under nitrogen protection, the hyperbranched aqueous polyurethane that adds the 350g modification in reaction vessel, temperature is warmed up to 100 ℃, under 0.098MPa pressure, decompression dewaters 2 hours, temperature drops to 70 ℃, adds 160g acetone, with the speed of 8ml/min, drips 1 of 165g, hexamethylene-diisocyanate, after dropwising, continue reaction 2 hours, obtain the first intermediate;
The acetone that adds 120ml in reaction vessel, reduce system viscosity, then, adds the 0.0015g dibutyltin dilaurate catalyst, temperature is controlled at 80 ℃, 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 ℃, add 2 of 32g in reaction vessel, 4-diamino benzene sulfonic acid sodium, stir 10min, then, adds deionized water 550g and 6g quadrol, continues to stir 20min, and acetone is removed in decompression, obtains hyperbranched aqueous polyurethane.
Embodiment 2
The hyper-branched polyester Boltorn that adds 820g in reaction vessel
tMh40 and 1650g dimethylbenzene, temperature is warmed up to 135 ℃, stirs 35min, after heating is dissolved fully, add the agent of 0.55g Chloride Solid Ascatalyst and 0.03g antioxidant 1010, then, add the 170g MALEIC ANHYDRIDE, be warmed up to 160 ℃, 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 that adds the 672g modification in reaction vessel, temperature is warmed up to 120 ℃, and under 0.098MPa pressure, decompression dewaters 2 hours, temperature drops to 85 ℃, add 240g acetone, with the speed dropping 238g dicyclohexyl methane diisocyanate of 15ml/min, after dropwising, continue reaction 4 hours, obtain the first intermediate;
The acetone that adds 200ml in reaction vessel, reduce system viscosity, then, add the 0.0035g stannous octoate catalyst, temperature is controlled at 90 ℃, 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 ℃, 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, acetone is removed in decompression, obtains hyperbranched aqueous polyurethane.
Embodiment 3
The hyper-branched polyester Boltorn that adds 660g in reaction vessel
tMh40 and 1480g dimethylbenzene, temperature is warmed up to 120 ℃, stirs 30min, and heating adds the agent of 0.45g Chloride Solid Ascatalyst and 0.02g antioxidant 1010 after dissolving fully, then, adds the 120g MALEIC ANHYDRIDE, is warmed up to 150 ℃, reacts 3 hours.Under 0.098MPa pressure, except removal xylene, obtain the hyperbranched aqueous polyurethane of modification;
Under nitrogen protection, the hyperbranched aqueous polyurethane that adds the 450g modification in reaction vessel, temperature is warmed up to 110 ℃, and under 0.098MPa pressure, decompression dewaters 2 hours, temperature drops to 75 ℃, add 180g acetone, with the speed dropping 220g isophorone diisocyanate of 10ml/min, after dropwising, continue reaction 3 hours, obtain the first intermediate;
The acetone that adds 160ml in reaction vessel, reduce system viscosity, then, adds the 0.002g stannous octoate catalyst, temperature is controlled at 85 ℃, 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 ℃, 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, acetone is removed in decompression, obtains hyperbranched aqueous polyurethane.
Embodiment 4
The hyper-branched polyester Boltorn that adds 575g in reaction vessel
tMh40 and 1498g dimethylbenzene, temperature is warmed up to 120 ℃, stirs 20min, after heating is dissolved fully, add the agent of 0.35g Chloride Solid Ascatalyst and 0.025g antioxidant 1010, then, add the 135g MALEIC ANHYDRIDE, be warmed up to 145 ℃, react 3 hours, under 0.098MPa pressure, except removal xylene, obtain the hyperbranched aqueous polyurethane of modification;
Under nitrogen protection, the hyperbranched aqueous polyurethane that adds the 510g modification in reaction vessel, temperature is warmed up to 120 ℃, and under 0.098MPa pressure, decompression dewaters 2 hours, temperature drops to 80 ℃, add 220g acetone, with the speed dropping 204g Methylcyclohexyl diisocyanate of 11ml/min, after dropwising, continue reaction 3.5 hours, obtain the first intermediate;
The acetone that adds 180ml in reaction vessel, reduce system viscosity, then, add the 0.0025g dibutyltin dilaurate catalyst, temperature is controlled at 86 ℃, with the speed dropping 22g glycol ether of 5ml/min, after dropwising, continue reaction 1.5 hours, obtain the second intermediate;
System temperature is dropped to 42 ℃, add 2 of 51g in reaction vessel, 4-diamino benzene sulfonic acid sodium, stir 13min, then, adds deionized water 760g and 14g quadrol, continues to stir 45min, and acetone is removed in decompression, obtains hyperbranched aqueous polyurethane.
Embodiment 5
The hyper-branched polyester Boltorn that adds 766g in reaction vessel
tMh40 and 1580g dimethylbenzene, temperature is warmed up to 130 ℃, stirs 25min, after heating is dissolved fully, add the agent of 0.5g Chloride Solid Ascatalyst and 0.022g antioxidant 1010, then, add the 163g MALEIC ANHYDRIDE, be warmed up to 150 ℃, react 3 hours, under 0.098MPa pressure, except removal xylene, obtain the hyperbranched aqueous polyurethane of modification;
Under nitrogen protection, the hyperbranched aqueous polyurethane that adds the 586g modification in reaction vessel, temperature is warmed up to 100 ℃, and under 0.098MPa pressure, decompression dewaters 2 hours, temperature drops to 75 ℃, add 230g acetone, with the speed dropping 200g isophorone diisocyanate of 10ml/min, after dropwising, continue reaction 3 hours, obtain the first intermediate;
The acetone that adds 175ml in reaction vessel, reduce system viscosity, then, adds the 0.003g dibutyltin dilaurate catalyst, temperature is controlled at 85 ℃, 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 ℃, add 2 of 58g in reaction vessel, 4-diamino benzene sulfonic acid sodium, stir 12min, then, adds deionized water 860g and 13.5g quadrol, continues to stir 35min, and acetone is removed in decompression, obtains hyperbranched aqueous polyurethane.
Embodiment 6
The hyperbranched aqueous polyurethane that 35g embodiment 1 is 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, rotating speed with 800rpm stirs 2h, then add 8g water-based solubility promoter Virahol and 2.5g solidifying agent Bayhydur3100, rotating speed with 650rpm stirs 1.5h, obtains hyperbranched aqueous polyurethane coating.
Embodiment 7
The hyperbranched aqueous polyurethane that 68g embodiment 2 is 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, rotating speed with 1200rpm stirs 2h, then add 12g water-based solubility promoter Virahol and 4.3g solidifying agent BayhydurXP2655, rotating speed with 800rpm stirs 1.5h, obtains hyperbranched aqueous polyurethane coating.
Embodiment 8
The hyperbranched aqueous polyurethane that 47g embodiment 3 is 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, rotating speed with 900rpm stirs 2h, then add 10g water-based solubility promoter butyl glycol ether and 3.1g solidifying agent BayhydurXP2547, rotating speed with 700rpm stirs 1.5h, obtains hyperbranched aqueous polyurethane coating.
Embodiment 9
The hyperbranched aqueous polyurethane that 52g embodiment 4 is 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, rotating speed with 1100rpm stirs 2h, then add 9g water-based solubility promoter butyl glycol ether and 3.8g solidifying agent Bayhydur3100, rotating speed with 750rpm stirs 1.5h, obtains hyperbranched aqueous polyurethane coating.
Embodiment 10
The hyperbranched aqueous polyurethane that 60g embodiment 5 is 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, rotating speed with 900rpm stirs 2h, then add 11g water-based solubility promoter Diethylene Glycol butyl ether and 4g solidifying agent Bayhydur3100, rotating speed with 700rpm stirs 1.5h, obtains hyperbranched aqueous polyurethane coating.
The hyperbranched aqueous polyurethane coating respectively embodiment 6 to embodiment 10 obtained is coated on ABS plastic sheet material, after catching up with the pure qi (oxygen) bubble, at 90 ℃ of baking 2h, the material obtained is tested, test result is 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 is just for helping to understand method of the present invention and core concept thereof.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 improvement and modification also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, make professional and technical personnel in the field can realize or use the present invention.Multiple modification to these embodiment will be apparent for those skilled in the art, and General Principle as defined herein can be in the situation that do not break away from the spirit or scope of the present invention, realization in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (10)
1. hyperbranched aqueous polyurethane coating, is characterized in that, according to the parts by weight meter, comprises as follows:
Described hyperbranched aqueous polyurethane is with hyper-branched polyester Boltorn
tMh40 is soft section, and the diamino sulfonic acid salt of take prepares as hydrophilic chain extender.
2. hyperbranched aqueous polyurethane coating according to claim 1, is characterized in that, the preparation method of described hyperbranched aqueous polyurethane comprises as follows:
Step 1: 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 the modification that step 1 is obtained and di-isocyanate reaction obtain the first intermediate;
Step 3: the first intermediate that step 2 is obtained reacts with small molecule chain extender, obtains the second intermediate;
Step 4: the second intermediate that step 3 is obtained and diamino sulfonic acid reactant salt obtain hyperbranched aqueous polyurethane.
3. hyperbranched aqueous polyurethane coating according to claim 2, is characterized in that, the temperature of reaction of described step 1 is 145～160 ℃, and the reaction times is 2～3.5.
4. hyperbranched aqueous polyurethane coating according to claim 2, it is characterized in that, described vulcabond is selected from a kind of in hexamethylene diisocyanate, isophorone diisocyanate, Methylcyclohexyl diisocyanate or dicyclohexyl methane diisocyanate.
5. hyperbranched aqueous polyurethane coating according to claim 2, is characterized in that, described small molecule chain extender is selected from a kind of in BDO or glycol ether.
6. hyperbranched aqueous polyurethane coating according to claim 2, is characterized in that, described diamino sulfonic acid salt is selected from a kind of in 2,4-diamino benzene sulfonic acid sodium or quadrol base ethyl sulfonic acid sodium.
7. 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.
8. hyperbranched aqueous polyurethane coating according to claim 1, is characterized in that, it is a kind of in Bayhydur3100, BayhydurXP2655 or BayhydurXP2547 that described solidifying agent is selected from model.
9. hyperbranched aqueous polyurethane coating according to claim 1, is characterized in that, described water-based solubility promoter is selected from a kind of in Virahol, butyl glycol ether or Diethylene Glycol butyl ether.
10. according to the preparation method of any one described hyperbranched aqueous polyurethane coating of claim 1-9, comprise as follows:
Hyperbranched aqueous polyurethane, aqueous wetting agent, water-based flow agent and water-based defoamer are joined to stirrer for mixing, and then add water-based solubility promoter and solidifying agent to stir, obtain hyperbranched aqueous polyurethane coating.
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Cited By (13)
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| CN103865252A (en) * | 2014-03-17 | 2014-06-18 | 同济大学 | Preparation method of water-based polyurethane nanosilver composite system with high-concentration nanosilver |
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| CN108752563A (en) * | 2018-05-24 | 2018-11-06 | 哈尔滨工业大学无锡新材料研究院 | Aqueous hyperbranched structurally-modified polyether polyols of one kind and preparation method thereof and selfreparing diffusing reflection coating composition |
| CN108977028A (en) * | 2018-07-10 | 2018-12-11 | 烟台博源科技材料股份有限公司 | A kind of aqueous transfer laser coating and preparation method thereof |
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| CN112646473A (en) * | 2020-12-28 | 2021-04-13 | 安徽匠星联创新材料科技有限公司 | Double-component water-based damping noise-reducing flame-retardant interior and exterior wall thermal insulation coating |
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| CN103865252B (en) * | 2014-03-17 | 2015-12-30 | 同济大学 | A kind of preparation method of aqueous polyurethane nano silver compound system of highly concentrated nano silver |
| CN103865252A (en) * | 2014-03-17 | 2014-06-18 | 同济大学 | Preparation method of water-based polyurethane nanosilver composite system with high-concentration nanosilver |
| CN104693994B (en) * | 2015-03-11 | 2017-08-01 | 江苏兰陵高分子材料有限公司 | A kind of ultraviolet-curing paint containing inorganic color stuffing and preparation method thereof |
| CN104693994A (en) * | 2015-03-11 | 2015-06-10 | 江苏兰陵高分子材料有限公司 | Ultraviolet photocuring coating containing inorganic pigment and filler and preparation method thereof |
| CN105401441A (en) * | 2015-11-27 | 2016-03-16 | 江苏东昉纺织科技有限公司 | Coating agent for down jackets |
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| CN105646816B (en) * | 2016-01-27 | 2018-07-24 | 平顶山正植科技有限公司 | A kind of preparation method for holding viscous aqueous dispersions of polyurethanes |
| CN105837773A (en) * | 2016-04-15 | 2016-08-10 | 武汉赫斯特涂层材料股份有限公司 | Preparation method of double-modified hyperbranched waterborne polyurethane emulsion with silicone and renewable vegetable oil |
| CN108752563A (en) * | 2018-05-24 | 2018-11-06 | 哈尔滨工业大学无锡新材料研究院 | Aqueous hyperbranched structurally-modified polyether polyols of one kind and preparation method thereof and selfreparing diffusing reflection coating composition |
| CN108752563B (en) * | 2018-05-24 | 2020-12-15 | 哈尔滨工业大学无锡新材料研究院 | Waterborne hyperbranched structure modified polyurethane polymer, preparation method thereof and self-repairing diffuse reflection coating composition |
| CN108977028A (en) * | 2018-07-10 | 2018-12-11 | 烟台博源科技材料股份有限公司 | A kind of aqueous transfer laser coating and preparation method thereof |
| CN110306360A (en) * | 2019-07-19 | 2019-10-08 | 浙江海印数码科技有限公司 | A kind of digit printing high stable reactive dye ink and preparation method thereof |
| CN112358803A (en) * | 2020-10-27 | 2021-02-12 | 合肥科天水性科技有限责任公司 | Water-resistant corrosion-resistant water-based conductive coating and preparation method thereof |
| CN112646473A (en) * | 2020-12-28 | 2021-04-13 | 安徽匠星联创新材料科技有限公司 | Double-component water-based damping noise-reducing flame-retardant interior and exterior wall thermal insulation coating |
| CN114769100A (en) * | 2022-04-29 | 2022-07-22 | 江西国天成科技有限公司 | Spraying process and formula of high-flow oxidation-resistant and dirt-resistant coating for reinforcing inner wall of corrugated pipe |
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