CN103044650A - Poly (carbonic ester-ether) type waterborne polyurethane, and poly (carbonic ester-ether) type waterborne polyurethane coating material and preparation method thereof - Google Patents
Poly (carbonic ester-ether) type waterborne polyurethane, and poly (carbonic ester-ether) type waterborne polyurethane coating material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a poly (carbonic ester-ether) type waterborne polyurethane, and a poly (carbonic ester-ether) type waterborne polyurethane coating material and a preparation method thereof. According to the method, the technical problem that the existing waterborne polyurethane coating material is produced by depending on petrochemical resources is solved, and the mechanical property and the hydrolysis resistance of the waterborne polyurethane coating material are further improved. The waterborne polyurethane coating material provided by the invention comprises the following components in parts by weight: 65 to 100 parts of the poly (carbonic ester-ether) type waterborne polyurethane, 0.1 to 0.3 part of waterborne flatting agent, 0.2 to 0.6 part of waterborne wetting agent, 0.1 to 0.5 part of waterborne defoaming agent, 5 to 8 parts of waterborne cosolvents and 2.3 to 5.2 parts of waterborne curing agent. The waterborne polyurethane coating material has the advantages that the pollution of carbon dioxide to environment in lowered; the serious dependence of the coating material to the petrochemical resources in the production process is lightened; and a coating film prepared from the coating material has the excellent mechanical property, wherein the elongation at break reaches 570% and the tensile strength reaches 8.1MPa.
Description
Technical field
The present invention relates to a kind of poly-(carbonic ether-ether) type aqueous polyurethane, poly-(carbonic ether-ether) type aqueous polyurethane coating and preparation method thereof, belong to technical field of coatings.
Background technology
Polyurethane coating is the widely used synthetic materials of a class, existing polyurethane coating is mainly solvent-borne type, used solvent such as toluene, benzene, butanone etc. mostly inflammable, explosive, volatile, smell is large, can cause certain atmospheric pollution during use, and human body is caused potential injury.
Aqueous polyurethane is with the polyurethane system of water to replace organic solvent as dispersion medium, also claims water dispersible polyurethane, aqueous polyurethane or waterbased urethane.Aqueous polyurethane is take water as solvent, have pollution-free, safe and reliable, mechanical property is good, consistency good, be easy to the advantages such as modification, is widely used in recent years coating, tackiness agent, fabric coating and finishing composition, hide finishes, sheet surface treating agent and fiber surface treatment agent.
According to the difference of employed polymer diatomic alcohol, aqueous polyurethane mainly is divided into polyester type and polyether-type two large classes.Contain a large amount of ester bonds in the polyester type aqueous polyurethane molecule, the mechanical propertys such as cohesive strength height, scratch resistance are excellent, such as patent CN201110258270.9, CN200910150652.2, yet, polyester type aqueous polyurethane hydrolytic resistance is poor, is mainly used in wood lacquer, indoor paint etc. hydrolysis is required lower place; Polyether type aqueous urethane hydrolytic resistance and lower temperature resistance are good, yet, the bad mechanical properties such as polyether type aqueous polyurethane wear resistant, adhesive property, cause the application of product to be restricted, although adopt polytetrahydrofuran, the own esterdiol of polymerized thylene carbonate can obtain the good aqueous polyurethane coating of cohesive strength height, wear resistance and scraping and wiping resistance performance, but product cost is high, is unfavorable for industrialized scale operation, has limited it and has used and promote.
In addition, the raw materials of polyether-type and polyester type aqueous polyurethane all is the petrochemical industry product, thereby resulting aqueous polyurethane all can't be broken away from the serious dependence to the petrochemical industry resource, has caused resource consumption.
Summary of the invention
For solving in the prior art aqueous polyurethane and aqueous polyurethane coating to the serious dependence of petrochemical industry resource,
Further improve mechanical property and the hydrolytic resistance of aqueous polyurethane coating, the invention provides poly-(carbonic ether-ether) type aqueous polyurethane, poly-(carbonic ether-ether) type aqueous polyurethane coating and preparation method thereof.
The invention provides a kind of poly-(carbonic ether-ether) type aqueous polyurethane, structural formula is formula (I):
Formula (I)
In the formula (I), m, n are integer, 10≤m≤70,10≤n≤70;
The present invention also provides a kind of poly-(carbonic ether-ether) type aqueous polyurethane, and structural formula is formula (II):
Formula (II)
In the formula (II), m, n are integer, 10≤m≤70,10≤n≤70;
The present invention also provides above-mentioned preparation method with poly-(carbonic ether-ether) type aqueous polyurethane of formula (I) structure, may further comprise the steps:
(1) under the inert atmosphere, will gather (carbonic ether-ether) dibasic alcohol and vulcabond and in solvent, react, obtain the first intermediate;
(2) the first intermediate and amine hydrophilic chain extender are reacted in solvent, obtain the second intermediate;
(3) second intermediates and small molecules dibasic alcohol chainextender react in solvent, after the emulsification of adding deionized water, add the protonic acid neutralizing agent, obtain having poly-(carbonic ether-ether) type aqueous polyurethane of formula (I) structure after the reaction.
Preferably, the number-average molecular weight of described poly-(carbonic ether-ether) dibasic alcohol is 1500 ~ 7000 dalton.
Preferably, described vulcabond is 2,4 toluene diisocyanate, dicyclohexyl methane diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate or hexamethylene diisocyanate.
Preferably, described amine hydrophilic chain extender is N methyldiethanol amine, diethanolamine or trolamine.
Preferably, described small molecules dibasic alcohol chainextender is ethylene glycol, butyleneglycol, glycol ether or Triethylene glycol.
Preferably, described protonic acid neutralizing agent is sulfuric acid, oxyacetic acid or trifluoroacetic acid.
The present invention also provides above-mentioned preparation method with poly-(carbonic ether-ether) type aqueous polyurethane of formula (II) structure, may further comprise the steps:
(1) under the inert atmosphere, will gather (carbonic ether-ether) dibasic alcohol and vulcabond and in solvent, react, obtain the first intermediate;
(2) the first intermediate, catalyzer and carboxyl class hydrophilic chain extender are reacted in solvent, obtain in second
Mesosome;
(3) second intermediates and small molecules dibasic alcohol chainextender react in solvent, after the emulsification of adding deionized water, add the amine neutralizing agent, obtain having poly-(carbonic ether-ether) type aqueous polyurethane of formula (II) structure after the reaction.
Preferably, the number-average molecular weight of described poly-(carbonic ether-ether) dibasic alcohol is 1500 ~ 7000 dalton.
Preferably, described vulcabond is 2,4 toluene diisocyanate, dicyclohexyl methane diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate or hexamethylene diisocyanate.
Preferably, described catalyzer is dibutyl tin laurate or stannous octoate.
Preferably, described carboxyl class hydrophilic chain extender is 2,2-dimethylol propionic acid or 2,2-dimethylolpropionic acid.
Preferably, described small molecules dibasic alcohol chainextender is ethylene glycol, butyleneglycol, glycol ether or Triethylene glycol.
Preferably, described amine neutralizing agent is N, N-dimethylethanolamine or triethylamine.
The present invention also provides poly-(carbonic ether-ether) type aqueous polyurethane coating, and its composition and weight part are:
The structural formula of described poly-(carbonic ether-ether) type aqueous polyurethane is formula (I) or formula (II),
Formula (I)
Formula (II)
In formula (I) and the formula (II), m, n are integer, 10≤m≤70,10≤n≤70;
Preferably, composition and the weight part of described poly-(carbonic ether-ether) type aqueous polyurethane coating are:
The present invention also provides the preparation method of above-mentioned poly-(carbonic ether-ether) type aqueous polyurethane coating, may further comprise the steps:
(1) poly-(carbonic ether-ether) type aqueous polyurethane of 65 ~ 100 weight parts, the water-based flow agent of 0.1 ~ 0.3 weight part, the aqueous wetting agent of 0.2 ~ 0.6 weight part and the water-based defoamer of 0.1 ~ 0.5 weight part are added in the whipping appts, stir 1h ~ 3h, obtain mixture;
(2) in described mixture, add the water-based solubility promoter of 5 ~ 8 weight parts and the waterborne curing agent of 2.3 ~ 5.2 weight parts, behind the stirring 15-20min, gathered (carbonic ether-ether) type aqueous polyurethane coating.
Preferably, described water-based flow agent is BYK-380N, BYK-381, BYK-307, BYK-341, BYK-345, BYK-346 or BYK-348.
Preferably, described aqueous wetting agent is BYK-187, BYK-3400 or BYK-3410.
Preferably, described water-based defoamer is BYK-019, BYK-020, BYK-024, BYK-028 or BYK-1730.
Preferably, described water-based solubility promoter is one or more in Virahol, butyl glycol ether, Diethylene Glycol butyl ether, propylene glycol monomethyl ether, propandiol butyl ether and the dipropylene glycol butyl ether.
Preferably, described waterborne curing agent is the water-based polyisocyanates, is more preferably Bayhydur 3100, Bayhydur XP 2487/1, Bayhydur XP 2547 or Bayhydur XP 2451.
Beneficial effect of the present invention:
(1) poly-(carbonic ether-ether) dibasic alcohol is the product that the ring-opening polymerization by carbonic acid gas and propylene oxide obtains, the present invention uses poly-(carbonic ether-ether) dibasic alcohol that contains carbonic ether and ether dual structure unit as the component in the backbone structure of aqueous polyurethane, not only reduce in the environment carbonic acid gas to the pollution of environment, and reduced the production of aqueous polyurethane to the serious dependence of petrochemical industry resource;
(2) it is poor that poly-(carbonic ether-ether) type aqueous polyurethane coating of the present invention preparation has overcome in the prior art polyester type aqueous polyurethane hydrolytic resistance, the bad mechanical properties such as polyether type aqueous polyurethane wear resistant, adhesive property, the defective that causes the application of product to be restricted, test through paint film, the aqueous polyurethane coating of the present invention mechanical excellent performance of filming, elongation at break is up to 570%, and tensile strength is up to 8.1MPa.
Description of drawings
Fig. 1 is the nuclear magnetic spectrogram of poly-(carbonic ether-ether) type aqueous polyurethane of the embodiment of the invention 1;
Fig. 2 is the nuclear magnetic spectrogram of poly-(carbonic ether-ether) type aqueous polyurethane of the embodiment of the invention 4.
Specific implementation method
Poly-(carbonic ether-ether) type aqueous polyurethane, structural formula is formula (I):
Formula (I)
In the formula (I), m, n are integer, 10≤m≤70,10≤n≤70;
Above-mentioned preparation method with poly-(carbonic ether-ether) type aqueous polyurethane of formula (I) structure may further comprise the steps:
(1) under the inert atmosphere, will gather (carbonic ether-ether) dibasic alcohol and vulcabond and in solvent, react, obtain the first intermediate;
(2) the first intermediate and amine hydrophilic chain extender are reacted in solvent, obtain the second intermediate;
(3) second intermediates and small molecules dibasic alcohol chainextender react in solvent, after the emulsification of adding deionized water, add the protonic acid neutralizing agent, obtain having poly-(carbonic ether-ether) type aqueous polyurethane of formula (I) structure after the reaction.
Poly-(carbonic ether-ether) type aqueous polyurethane, structural formula is formula (II):
Formula (II)
In the formula (II), m, n are integer, 10≤m≤70,10≤n≤70;
Above-mentioned preparation method with poly-(carbonic ether-ether) type aqueous polyurethane of formula (II) structure may further comprise the steps:
(1) under the inert atmosphere, will gather (carbonic ether-ether) dibasic alcohol and vulcabond and in solvent, react, obtain the first intermediate;
(2) the first intermediate, catalyzer and carboxyl class hydrophilic chain extender are reacted in solvent, obtain in second
Mesosome;
(3) second intermediates and small molecules dibasic alcohol chainextender react in solvent, after the emulsification of adding deionized water, add the amine neutralizing agent, obtain having poly-(carbonic ether-ether) type aqueous polyurethane of formula (II) structure after the reaction.
Poly-(carbonic ether-ether) dibasic alcohol of the present invention is techniques well known, can be prepared according to techniques well known, sees patent CN102432857 for details; The number-average molecular weight of poly-(carbonic ether-ether) dibasic alcohol is preferably 1500 ~ 7000 dalton, is more preferably 1500-6000 dalton.
Vulcabond of the present invention is preferably 2,4 toluene diisocyanate, dicyclohexyl methane diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate or hexamethylene diisocyanate.
Small molecules dibasic alcohol chainextender of the present invention is preferably ethylene glycol, butyleneglycol, glycol ether or Triethylene glycol.
Solvent of the present invention is this area common solvent, is preferably butanone.
Amine hydrophilic chain extender of the present invention is preferably N methyldiethanol amine, diethanolamine or trolamine.
Protonic acid neutralizing agent of the present invention is preferably sulfuric acid, oxyacetic acid or trifluoroacetic acid.
Carboxyl class hydrophilic chain extender of the present invention is preferably 2,2-dimethylol propionic acid or 2,2-dimethylolpropionic acid.
Amine neutralizing agent of the present invention is preferably N, N-dimethylethanolamine or triethylamine.
Catalyzer of the present invention is dibutyl tin laurate or stannous octoate.
As preferred version, the preparation method with poly-(carbonic ether-ether) type aqueous polyurethane of formula (I) structure is:
(1) under the inert atmosphere, poly-(carbonic ether-ether) dibasic alcohol of 1500 ~ 6000 weight parts is added in the reaction unit, be warmed up to 110 ℃, underpressure distillation 1 ~ 1.5 hour cools to 85 ℃, adds the butanone of 200 ~ 320 weight parts, drip the vulcabond of 526 ~ 768 weight parts with the speed of 8 ~ 12ml/min, after dropwising, reacted 2.5 ~ 4 hours, obtain the first intermediate;
(2) add the butanone of 100 ~ 280 weight parts in the first intermediate, greenhouse cooling to 30 ℃ drips the amine hydrophilic chain extender of 109 ~ 142 weight parts with the rate of addition of 5 ~ 8ml/min, after dropwising, reacts 0.5 ~ 2 hour, obtains the second intermediate;
(3) add the butanone of 150 ~ 380 weight parts in the second intermediate, the small molecules dibasic alcohol chainextender that adds 198 ~ 320 weight parts, be warmed up to 90 ℃, reacted 2 ~ 3 hours, add 1100 ~ 6300 parts by weight of deionized water, add the protonic acid neutralizing agent of 61 ~ 96.9 weight parts, stirred 0.5 ~ 2 hour with the speed of 800 ~ 1200rpm, butanone is removed in underpressure distillation, poly-(carbonic ether-ether) type aqueous polyurethane of (I) structure that obtains having formula.
As preferred version, the preparation method with poly-(carbonic ether-ether) type aqueous polyurethane of formula (II) structure is:
(1) under the inert atmosphere, poly-(carbonic ether-ether) dibasic alcohol of 1750 ~ 5400 weight parts is added in the reaction unit, be warmed up to 110 ℃, underpressure distillation 1 ~ 1.5 hour cools to 85 ℃, adds the butanone of 270 ~ 350 weight parts, drip the vulcabond of 528 ~ 738 weight parts with the rate of addition of 8 ~ 12ml/min, after dropwising, reacted 2 ~ 4 hours, obtain the first intermediate;
(2) add the butanone of 100 ~ 210 weight parts in the first intermediate, greenhouse cooling to 72 ℃ adds 0.001 ~ 0.003 weight part catalyzer, the carboxyl class hydrophilic chain extender that adds in three batches 102 ~ 143 weight parts, add complete after, reacted 0.5 ~ 1.5 hour, obtain the second intermediate;
(3) add the butanone of 180 ~ 290 weight parts in the second intermediate, the small molecules dibasic alcohol chainextender that adds 68 ~ 270 weight parts, be warmed up to 90 ℃, reacted 1.5 ~ 2.5 hours, add 1850 ~ 4800 parts by weight of deionized water, drip the amine neutralizing agent of 85 ~ 115 weight parts with the speed of 15 ~ 22ml/min, stirred 0.5 ~ 2 hour with the speed of 1000 ~ 1300rpm, butanone is removed in underpressure distillation, poly-(carbonic ether-ether) type aqueous polyurethane of (II) structure that obtains having formula.
Preparation has in the preferred version that gathers (carbonic ether-ether) type aqueous polyurethane of formula (II) structure, and in the described step (2), carboxyl class hydrophilic chain extender preferably is divided into three batches of addings.
The present invention also provides poly-(carbonic ether-ether) type aqueous polyurethane coating, and its composition and weight part are:
The structure of described poly-(carbonic ether-ether) type aqueous polyurethane is formula (I) or formula (II).
Among the present invention, described water-based flow agent, aqueous wetting agent, water-based defoamer, water-based solubility promoter and waterborne curing agent all can be bought by company known in this field, and described water-based flow agent is preferably BYK-380N, BYK-381, BYK-307, BYK-341, BYK-345, BYK-346 or the BYK-348 of BYK company;
Described aqueous wetting agent is BYK-187, BYK-3400 or the BYK-3410 of BYK company; Described water-based defoamer is preferably BYK-019, BYK-020, BYK-024, BYK-028 or the BYK-1730 of BYK company; Described waterborne curing agent is preferably the water-based polyisocyanates, is more preferably Bahadur 3100, Bayhydur XP 2487/1, Bayhydur XP 2547 or the Bayhydur XP 2451 of Beyer Co., Ltd; Described water-based solubility promoter is preferably one or more in Virahol, butyl glycol ether, Diethylene Glycol butyl ether, propylene glycol monomethyl ether, propandiol butyl ether and the dipropylene glycol butyl ether.
The preparation method of poly-(carbonic ether-ether) type aqueous polyurethane coating may further comprise the steps:
(1) poly-(carbonic ether-ether) type aqueous polyurethane of 65 ~ 100 weight parts, the water-based flow agent of 0.1 ~ 0.3 weight part, the aqueous wetting agent of 0.2 ~ 0.6 weight part and the water-based defoamer of 0.1 ~ 0.5 weight part are added in the whipping appts, stir 1h ~ 3h, obtain mixture;
(2) in described mixture, add the water-based solubility promoter of 5 ~ 8 weight parts and the waterborne curing agent of 2.3 ~ 5.2 weight parts, behind the stirring 15-20min, gathered (carbonic ether-ether) type aqueous polyurethane coating.
In the preparation method's of poly-(carbonic ether-ether) type aqueous polyurethane coating of the present invention the step (1), the preferred 800 ~ 1000rpm of stirring velocity.
In the preparation method's of poly-(carbonic ether-ether) type aqueous polyurethane coating of the present invention the step (2), the preferred 720 ~ 800rpmrpm of stirring velocity.
Among the preparation method of poly-(carbonic ether-ether) type aqueous polyurethane coating of the present invention, whipping appts is preferably homogenizer.
The performance test of poly-(carbonic ether-ether) type aqueous polyurethane coating that the present invention obtains is adopted: will gather (carbonic ether-ether) type aqueous polyurethane coating and be coated on the tinplate, coating thickness 15 ~ 17 μ m, behind 75 ℃ of lower 30min complete dryinies, filming of obtaining carried out hardness, resistance to impact shock, snappiness and adhesion performance test; To gather (carbonic ether-ether) type aqueous polyurethane coating and be coated on the polytetrafluoroethyldisk disk, coating thickness 15 ~ 17 μ m behind 75 ℃ of lower 30min complete dryinies, will film and take off, carry out the test of elongation at break and tensile strength.
For making those skilled in the art understand better the present invention, further illustrate content of the present invention below in conjunction with embodiment and accompanying drawing.Mentioned chemical reagent all can obtain by being purchased method among the embodiment.
Embodiment 1
In conjunction with Fig. 1 embodiment 1 is described
Preparation with poly-(carbonic ether-ether) type aqueous polyurethane of formula (I) structure:
(1) under the nitrogen protection, with poly-(carbonic ether-ether) dibasic alcohol (number-average molecular weight: 1500 dalton) join in the there-necked flask of 1500g, be warmed up to 110 ℃, underpressure distillation 1 hour cools to 85 ℃, the butanone that adds 200g, drip the 2,4 toluene diisocyanate of 526g with the rate of addition of 8ml/min, after dropwising, reacted 2.5 hours, and obtained the first intermediate;
(2) add the butanone of 100g in the first intermediate, greenhouse cooling to 30 ℃ drips the N methyldiethanol amine of 109g with the 5ml/min rate of addition, after dropwising, reacts 0.5 hour, obtains the second intermediate;
(3) add the butanone of 150g in the second intermediate, add the butyleneglycol of 198g, be warmed up to 90 ℃, reacted 2 hours, then, add the 1100g deionized water, then, the trifluoroacetic acid that adds 96.9g, speed with 1200rpm stirred 0.5 hour, and then, butanone is removed in underpressure distillation, poly-(carbonic ether-ether) aqueous polyurethane (m=10, n=10) of (I) structure that obtains having formula.
Poly-(carbonic ether-ether) type aqueous polyurethane that obtains is carried out nuclear magnetic resonance spectroscopy.
Fig. 1 is the nucleus magnetic hydrogen spectrum (H NMR) of poly-(carbonic ether-ether) type aqueous polyurethane of the embodiment of the invention 1, as can be seen from the figure, has 4.45 ppm, 4.73 ppm, 4.78 ppm, 4.83 ppm, 5.16 ppm, 5.82 ppm, 5.90 ppm, 5.96 ppm, 6.13 ppm, 6.31 ppm, 6.36 ppm, 6.40 ppm, 6.56 ppm, 6.63 ppm, 7.19 ppm, 7.27 ppm, 7.33 ppm, 7.36 ppm, 7.59 ppm, 7.70 ppm, 7.80 ppm, 7.87 ppm, 7.92 ppm, 8.47ppm absorption peak, proved invention has prepared poly-(carbonic ether-ether) type aqueous polyurethane with formula (I) structure really.
Preparation with poly-(carbonic ether-ether) type aqueous polyurethane of formula (I) structure:
(1) under the nitrogen protection, with poly-(carbonic ether-ether) dibasic alcohol of 6000g (number-average molecular weight: 6000 dalton) add in the there-necked flask, be warmed up to 110 ℃, underpressure distillation 1.5 hours cools to 85 ℃, adds the butanone of 320g, drip the dicyclohexyl methane diisocyanate of 768g with the rate of addition of 12ml/min, after dropwising, reacted 4 hours, obtain the first intermediate;
(2) add the butanone of 280g in the first intermediate, greenhouse cooling to 30 ℃ drips the trolamine of 142g, drips with the 8ml/min rate of addition, after dropwising, reacts 2 hours, obtains the second intermediate;
(3) add the butanone of 380g in the second intermediate, add the Triethylene glycol of 320g, be warmed up to 90 ℃, reacted 3 hours, then, add the 6300g deionized water, then, the sulfuric acid that adds 82g, speed with 800rpm stirred 2 hours, and then, butanone is removed in underpressure distillation, poly-(carbonic ether-ether) the type aqueous polyurethane (m=25, n=70) of (I) structure that obtains having formula.
Poly-(carbonic ether-ether) type aqueous polyurethane that obtains is carried out nuclear magnetic resonance spectroscopy, record nucleus magnetic hydrogen spectrum (H NMR): 4.40 ppm, 4.38 ppm, 4.75 ppm, 4.88 ppm, 5.28 ppm, 5.76 ppm, 5.97 ppm, 6.22 ppm, 6.37 ppm, 6.48ppm, 6.61 ppm, 7.21ppm, 7.29 ppm, 7.38 ppm, 7.55 ppm, 7.78ppm, 7.84 ppm, 7.95 ppm, 8.49ppm.
Embodiment 3
Preparation with poly-(carbonic ether-ether) type aqueous polyurethane of formula (I) structure:
(1) under the nitrogen protection, with poly-(carbonic ether-ether) dibasic alcohol of 2000g (number-average molecular weight: 2000 dalton) add in the there-necked flask, be warmed up to 110 ℃, underpressure distillation 1.5 hours cools to 85 ℃, adds the butanone of 260g, drip the isophorone diisocyanate of 662g with the 10ml/min rate of addition, after dropwising, reacted 3 hours, obtain the first intermediate;
(2) add the butanone of 160ml in the first intermediate, greenhouse cooling to 30 ℃ drips the diethanolamine of 102g with the rate of addition of 7ml/min, after dropwising, reacts 1 hour, obtains the second intermediate;
(3) add the butanone of 320g in the second intermediate, add the glycol ether of 242g, be warmed up to 90 ℃, reacted 2.5 hours, then, add the 2350g deionized water, then, the oxyacetic acid that adds 61g, speed with 1000rpm stirred 1.5 hours, and then, butanone is removed in underpressure distillation, poly-(carbonic ether-ether) the type aqueous polyurethane (m=70, n=30) of (I) structure that obtains having formula.
Poly-(carbonic ether-ether) type aqueous polyurethane that obtains is carried out nuclear magnetic resonance spectroscopy, record its nucleus magnetic hydrogen spectrum (H NMR): 4.38ppm, 4.71 ppm, 4.76 ppm, 4.85 ppm, 5.23 ppm, 5.80 ppm, 5.85 ppm, 5.91 ppm, 6.18 ppm, 6.35 ppm, 6.42 ppm, 6.51 ppm, 6.67ppm, 7.08 ppm, 7.21 ppm, 7.38ppm, 7.51 ppm, 7.68 ppm, 7.83 ppm, 7.95 ppm, 8.51ppm.
In conjunction with Fig. 2 embodiment 4 is described
Preparation with poly-(carbonic ether-ether) type aqueous polyurethane of formula (II) structure:
(1) under the nitrogen protection, poly-(carbonic ether-ether) dibasic alcohol (number-average molecular weight: 1750 dalton) add in the there-necked flask with 1750g, be warmed up to 110 ℃, underpressure distillation 1.5 hours cools to 85 ℃, the butanone that adds 280g, drip the hexamethylene diisocyanate of 528g with the rate of addition of 8ml/min, after dropwising, reacted 2 hours, and obtained the first intermediate;
(2) add the butanone of 100g in the first intermediate, greenhouse cooling to 72 ℃ adds the 0.001g dibutyl tin laurate, is divided into three batches of dimethylol propionic acids that add 128g, add complete after, reacted 0.5 hour, obtain the second intermediate;
(3) add the butanone of 180g in the second intermediate, add the butyleneglycol of 68g, be warmed up to 90 ℃, reacted 1.5 hours, and then, added the 1850g deionized water, then, drip the N of 115g with the speed of 15ml/min, the N-dimethylethanolamine stirred 2 hours with the speed of 1000rpm, then, butanone is removed in underpressure distillation, poly-(carbonic ether-ether) the type aqueous polyurethane (m=10, n=10) of (II) structure that obtains having formula.
Poly-(carbonic ether-ether) type aqueous polyurethane that obtains is carried out nuclear magnetic resonance spectroscopy.
Fig. 2 is the nucleus magnetic hydrogen spectrum (H NMR) of poly-(carbonic ether-ether) type aqueous polyurethane of embodiment 4, as can be seen from the figure, has 4.75 ppm, 6.10 ppm, 6.32 ppm, 6.44 ppm, 6.48 ppm, 6.56 ppm, 6.60 ppm, 6.62 ppm, 6.66 ppm, 6.92 ppm, 7.08ppm, 7.26ppm, 7.34 ppm, 7.37 ppm, 7.62 ppm, 7.71 ppm, 7.85 ppm, 7.98 ppm, the 8.48ppm absorption peak, the proved invention has prepared poly-(carbonic ether-ether) type aqueous polyurethane with formula (II) structure really.
Embodiment 5
Preparation with poly-(carbonic ether-ether) type aqueous polyurethane of formula (II) structure:
(1) under the nitrogen protection, poly-(carbonic ether-ether) dibasic alcohol (number-average molecular weight: 5400 dalton) add in the there-necked flask with 5400g, be warmed up to 110 ℃, underpressure distillation 1.5 hours cools to 85 ℃, adds the butanone of 350g, drip the isophorone diisocyanate of 620g with the rate of addition of 12ml/min, after dropwising, reacted 4 hours, obtain the first intermediate;
(2) add the butanone of 150g in the first intermediate, greenhouse cooling to 75 ℃ adds the dibutyl tin laurate of 0.002g, is divided into three batches of dimethylolpropionic acids that add 143g, add complete after, reacted 1.5 hours, obtain the second intermediate;
(3) add the butanone of 260g in the second intermediate, add the glycol ether of 270g, be warmed up to 90 ℃, reacted 2 hours, then, add the 4800g deionized water, then, speed with 22ml/min drips the 87g triethylamine, speed with 1300rpm stirred 2 hours, and then, butanone is removed in underpressure distillation, poly-(carbonic ether-ether) the type aqueous polyurethane (m=25, n=70) of (II) structure that obtains having formula.
Poly-(carbonic ether-ether) type aqueous polyurethane that obtains is carried out nuclear magnetic resonance spectroscopy, record its nucleus magnetic hydrogen spectrum (H NMR): 4.68 ppm, 6.07 ppm, 6.25 ppm, 6.41 ppm, 6.47 ppm, 6.58 ppm, 6.63 ppm, 6.71 ppm, 6.98ppm, 7.09ppm, 7.30ppm, 7.34 ppm, 7.58 ppm, 7.65 ppm, 7.81 ppm, 7.92 ppm, 8.43ppm.
Preparation with poly-(carbonic ether-ether) type aqueous polyurethane of formula (II) structure:
(1) under the nitrogen protection, poly-(carbonic ether-ether) dibasic alcohol (number-average molecular weight: 2300 dalton) add in the there-necked flask with 2300g, be warmed up to 110 ℃, underpressure distillation 1 hour cools to 85 ℃, adds the butanone of 270g, drip the diphenylmethanediisocyanate of 738g with the speed of 11ml/min, after dropwising, reacted 3 hours, obtain the first intermediate;
(2) add the butanone of 210g in the first intermediate, greenhouse cooling to 75 ℃ adds the 0.003g stannous octoate, is divided into three batches of dimethylol propionic acids that add 102g, add complete after, reacted 1.5 hours, obtain the second intermediate;
(3) add the butanone of 290g in the second intermediate, add the butyleneglycol of 76g, be warmed up to 90 ℃, reacted 2.5 hours, then, add the 2600g deionized water, then, drip the triethylamine of 85g with the speed of 20ml/min, speed with 1200rpm stirred 2 hours, and then, butanone is removed in underpressure distillation, poly-(carbonic ether-ether) the type aqueous polyurethane (m=70, n=30) of (II) structure that obtains having formula.
Poly-(carbonic ether-ether) type aqueous polyurethane that obtains is carried out nuclear magnetic resonance spectroscopy, record its nucleus magnetic hydrogen spectrum (H NMR): 4.78 ppm, 6.19 ppm, 6.28 ppm, 6.47 ppm, 6.53 ppm, 6.64 ppm, 6.72 ppm, 6.87 ppm, 7.13ppm, 7.28ppm, 7.39 ppm, 7.60 ppm, 7.78 ppm, 7.89ppm, 7.92 ppm, 8.54ppm.
Embodiment 7
According to the material ratio of table 1, preparation gathers (carbonic ether-ether) type aqueous polyurethane coating in accordance with the following methods:
(1) poly-(carbonic ether-ether) type aqueous polyurethane of 65 ~ 100g, the water-based flow agent of 0.1 ~ 0.3g, the aqueous wetting agent of 0.2 ~ 0.6g and the water-based defoamer of 0.1 ~ 0.5g are added in the homogenizer, rotating speed with 800 ~ 1000rpm stirs 1h ~ 3h, obtains mixture;
(2) in described mixture, add the water-based solubility promoter of 5 ~ 8g and the waterborne curing agent of 2.3 ~ 5.2g, behind rotating speed stirring 15 ~ 20min with 720 ~ 800rpm, gathered (carbonic ether-ether) type aqueous polyurethane coating, be designated as respectively WP1, WP2, WP3, WP4, WP5, WP6, WP7, WP8 and WP9.
To gather respectively (carbonic ether-ether) type aqueous polyurethane coating WP1, WP2, WP3, WP4, WP5, WP6, WP7, WP8 and WP9 are coated on the tinplate, coating thickness 15 ~ 17 μ m, 75 ℃ of lower 30min complete dryinies, filming of obtaining carried out hardness, resistance to impact shock, snappiness and adhesion performance test, to gather (carbonic ether-ether) type aqueous polyurethane coating WP1, WP2, WP3, WP4, WP5, WP6, WP7, WP8 and WP9 are coated on the polytetrafluoroethyldisk disk, coating thickness 15 ~ 17 μ m, 75 ℃ of lower 30min complete dryinies, to film take off after, carry out the test of elongation at break and tensile strength, all test results see Table 2.
The material ratio of poly-(carbonic ether-ether) type aqueous polyurethane coating of table 1 preparation
The film performance test result of poly-(carbonic ether-ether) type aqueous polyurethane coating of table 2
Claims (10)
3. the preparation method of poly-(carbonic ether-ether) type aqueous polyurethane claimed in claim 1 is characterized in that, may further comprise the steps:
(1) under the inert atmosphere, will gather (carbonic ether-ether) dibasic alcohol and vulcabond and in solvent, react, obtain the first intermediate;
(2) the first intermediate and amine hydrophilic chain extender are reacted in solvent, obtain the second intermediate;
(3) second intermediates and small molecules dibasic alcohol chainextender react in solvent, after the emulsification of adding deionized water, add the protonic acid neutralizing agent, are gathered (carbonic ether-ether) type aqueous polyurethane after the reaction.
4. the preparation method of poly-(carbonic ether-ether) type aqueous polyurethane claimed in claim 2 is characterized in that, may further comprise the steps:
(1) under the inert atmosphere, will gather (carbonic ether-ether) dibasic alcohol and vulcabond and in solvent, react, obtain the first intermediate;
(2) the first intermediate, catalyzer and carboxyl class hydrophilic chain extender are reacted in solvent, obtain in second
Mesosome;
(3) second intermediates and small molecules dibasic alcohol chainextender react in solvent, after the emulsification of adding deionized water, add the amine neutralizing agent, are gathered (carbonic ether-ether) type aqueous polyurethane after the reaction.
5. according to claim 3 or the preparation methods of 4 described poly-(carbonic ether-ether) type aqueous polyurethanes, it is characterized in that the number-average molecular weight of described poly-(carbonic ether-ether) dibasic alcohol is 1500 ~ 7000 dalton.
6. according to claim 3 or the preparation methods of 4 described poly-(carbonic ether-ether) type aqueous polyurethanes, it is characterized in that, described vulcabond is 2,4-tolylene diisocyanate, dicyclohexyl methane diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate or hexamethylene diisocyanate.
7. according to claim 3 or the preparation methods of 4 described poly-(carbonic ether-ether) type aqueous polyurethanes, it is characterized in that described small molecules dibasic alcohol chainextender is ethylene glycol, butyleneglycol, glycol ether or Triethylene glycol.
8. gather (carbonic ether-ether) type aqueous polyurethane coating, it is characterized in that its composition and weight part are:
The structural formula of described poly-(carbonic ether-ether) type aqueous polyurethane is formula (I) or formula (II),
Formula (I)
Formula (II)
In formula (I) and the formula (II), m, n are integer, 10≤m≤70,10≤n≤70;
10. the preparation method of poly-(carbonic ether-ether) type aqueous polyurethane coating claimed in claim 8 is characterized in that, may further comprise the steps:
(1) poly-(carbonic ether-ether) type aqueous polyurethane of 65 ~ 100 weight parts, the water-based flow agent of 0.1 ~ 0.3 weight part, the aqueous wetting agent of 0.2 ~ 0.6 weight part and the water-based defoamer of 0.1 ~ 0.5 weight part are added in the whipping appts, stir 1h ~ 3h, obtain mixture;
(2) in described mixture, add the water-based solubility promoter of 5 ~ 8 weight parts and the waterborne curing agent of 2.3 ~ 5.2 weight parts, behind the stirring 15-20min, gathered (carbonic ether-ether) type aqueous polyurethane coating.
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