CN105175670A - Amino resin modified waterborne polyurethane as well as preparation method and application thereof - Google Patents
Amino resin modified waterborne polyurethane as well as preparation method and application thereof Download PDFInfo
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- CN105175670A CN105175670A CN201510633677.3A CN201510633677A CN105175670A CN 105175670 A CN105175670 A CN 105175670A CN 201510633677 A CN201510633677 A CN 201510633677A CN 105175670 A CN105175670 A CN 105175670A
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
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- C08G18/30—Low-molecular-weight compounds
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- C08G18/30—Low-molecular-weight compounds
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6655—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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Abstract
The invention belongs to the technical field of coatings and discloses amino resin modified waterborne polyurethane as well as a preparation method and an application thereof. The amino resin modified waterborne polyurethane is prepared from components in parts by weight as follows: 34.6-39.2 parts of diol, 24.5-29.8 parts of diisocyanate, 0.03-0.09 parts of dibutyltin dilaurate, 1-4 parts of 1,4-butanediol, 2-6 parts of 2,2-dimethylolpropionic acid, 2-8 parts of amino resin, 0.5-1.2 parts of p-toluenesulfonic acid, 2-6 parts of a neutralizer and 1.2-1.9 parts of a small molecular chain extender. A polymerization method is used and an amino resin introduction mode is changed, so that the obtained product has the excellent performance such as good thermal stability, water resistance, solvent resistance, high hardness, low water absorption, excellent mechanical properties and the like, and a paint film prepared from the amino resin modified waterborne polyurethane has low baking temperature and simple process and meets the concept of green and environment-friendly chemical engineering.
Description
Technical field
The invention belongs to technical field of coatings, be specifically related to a kind of aminoresin modified aqueous polyurethane and preparation method thereof and application.
Background technology
Urethane refers to the high molecular polymer containing urethano (-NHCOO-) in molecular chain, and it is made up of soft chain segment and hard segment.Soft chain segment mostly is polyethers, polyester polyol, and give resin flexible soft and toughness, hard segment mostly is the polycondensate of vulcabond and small molecules dibasic alcohol or diamine.The controllable property of soft or hard section due to urethane is strong, and the many merits such as sticking power is good, hardness is high so it has, wear resistance is good, are widely used in multiple fields such as leather, weaving, automobile, building materials, medicine.But, because aqueous polyurethane introduces the deficiency of more hydrophilic radical and degree of crosslinking inherently thereof, cause the hardness of paint film, water tolerance, solvent resistance and thermotolerance good not enough.Therefore, be necessary to carry out cross-linking modified to aqueous polyurethane.
Part methyl-etherified height imino-melamine resin is the aminoresin with methoxymethyl and imino-, simple hard and crisp from the paint film obtained by condensation curing through high temperature by this aminoresin, and poor adhesive force, but with it, modification is carried out to aqueous polyurethane, the degree of crosslinking of system can be improved, thus improve the hardness of paint film, water tolerance, solvent resistance, thermotolerance and reduction water-intake rate etc.General blending and modifying, due to both compatibility problems, effect is not very desirable and package stability is bad, is exactly that baking condition is higher in addition, so will carry out chemical modification to it.
Patent CN104212330A discloses a kind of preparation method of water-polyurethane/amido resin compounded emulsion, homemade aqueous polyurethane and aminoresin are just carried out simple physical mixed by this method, although obtained paint film degree of crosslinking and water-fast erosion resistance all increase, but this composite emulsion needs the solidification value up to 150 DEG C, and blended the describing property of aqueous polyurethane and aminoresin in system that causes of simple physical is not fine, causes emulsion intercalation method bad.
Summary of the invention
In order to solve the shortcoming and defect part of above prior art, primary and foremost purpose of the present invention is to provide a kind of aminoresin modified aqueous polyurethane.
Another object of the present invention is to the preparation method that above-mentioned aminoresin modified aqueous polyurethane is provided.
Another object of the present invention is to provide above-mentioned aminoresin modified aqueous polyurethane joining the application in paint.
The object of the invention is achieved through the following technical solutions:
A kind of aminoresin modified aqueous polyurethane, is prepared from by the component of following mass parts:
One or more in the preferred polycaprolactone glycol of described dibasic alcohol, polypropylene glycol and poly-adipate glycol-BDO esterdiol.
One or more in the preferred tolylene diisocyanate of described vulcabond (TDI), ditan-4,4-vulcabond (MDI), isophorone diisocyanate (IPDI) and hexamethylene diisocyanate (HDI).
Described aminoresin preferably has the part methyl-etherified height imino-melamine resin of molecular structural formula shown in formula (1); Multiple spot is there is with the carboxyl (-COOH) in system and reacts thus reach cross-linking modified effect in the imino-(-NH-) in part methyl-etherified height imino-melamine resin under the effect of an acidic catalyst tosic acid;
Described neutralizing agent be preferably in triethylamine, N, N-dimethylethanolamine and ammoniacal liquor one or more.
Described small molecule chain extender be preferably in diethyl toluene diamine, 3,5-dimethythiotoluene diamines and quadrol one or more.
The preparation method of above-mentioned aminoresin modified aqueous polyurethane, comprises following preparation process:
(1) base polyurethane prepolymer for use as preparation: at 60 ~ 80 DEG C, dibasic alcohol, vulcabond and dibutyl tin laurate are joined in reactor, react 1 ~ 3 hour;
(2) chain extension: at 60 ~ 80 DEG C, is added drop-wise in reactor by the BDO being dissolved in acetone, reacts 30 ~ 60 minutes, then adds 2, the 2-dimethylol propionic acids being dissolved in N-Methyl pyrrolidone, reacts 2 ~ 4 hours;
(3), in and salify: at 50 ~ 60 DEG C, add acetone and reduce viscosity, then add neutralizing agent, stir insulation 10 ~ 30 minutes;
(4) aminoresin modification: at 50 ~ 60 DEG C, joins in reactor by the aminoresin and tosic acid that are dissolved in distilled water, reacts 0.5 ~ 1 hour, obtains the aminoresin modified polyurethane of thick shape;
(5) emulsification and rear chain extension: under agitation, adds deionized water in the aminoresin modified polyurethane of thick shape, disperses 5 ~ 10 minutes, then adds small molecule chain extender, disperses 20 ~ 30 minutes, obtains aminoresin modified aqueous polyurethane.
Preferably, the mass ratio of the N-Methyl pyrrolidone described in step (2) and 2,2-dimethylol propionic acid is (2 ~ 2.5): 1.
Preferably, the aminoresin described in step (4) and tosic acid water-soluble after within 30 minutes, make it be uniformly dispersed by ultrasonic vibration treatment.
Preferably, described in step (5), the stirring velocity of agitation condition is 6000 ~ 7000r/min.
Above-mentioned aminoresin modified aqueous polyurethane is joining the application in paint, described in join the compositions in weight percentage proportioning of paint as follows:
Preferably, described defoamer is preferably the Foamex805 of EVONIK; Described wetting agent is preferably Disperbyk-181.
Preparation method of the present invention and the product tool obtained have the following advantages and beneficial effect:
(1) the present invention uses prepolymerized method, make the imino-in part methyl-etherified height imino-melamine resin and the carboxyl reaction in aqueous polyurethane, successfully part methyl-etherified height imino-melamine resin is linked in aqueous polyurethane, the degree of crosslinking of increase system, resin paint film hardness is improved, water tolerance, solvent resistance, thermotolerance all strengthen, and water-intake rate reduces, and tensile strength and elongation at break increase;
(2) the present invention introduces the method for aminoresin compared to blending method, and the particle diameter of gained resin is more homogeneous, and stability is better, and all comparatively blending method is good in the performances such as thermostability, hardness and sticking power for products therefrom.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) base polyurethane prepolymer for use as preparation: at 75 DEG C, add 39.2g polycaprolactone glycol, 29.8g isophorone diisocyanate (IPDI) and 0.08g dibutyl tin laurate, react 2 hours, adopt Di-n-Butyl Amine-acetone method to carry out titration to NCO residual volume, reach reaction end when NCO residual volume is close or be less than theoretical value;
(2) chain extension: at 75 DEG C, take 2.5g1,4-butanediol is added drop-wise in reactor in 3g acetone, react 30 minutes, take 5.4g dimethylol propionic acid and be dissolved in 7gN-methyl-2-pyrrolidone, join in reactor, react 2 hours, adopt Di-n-Butyl Amine-acetone method to carry out titration to NCO residual volume, reach reaction end when NCO residual volume is close or be less than theoretical value;
(3), in and salify: at being cooled to 50 DEG C ~ 60 DEG C, add 10g acetone and reduce viscosity, then add in 3.8g triethylamine and salify, be incubated 10 minutes, be cooled to room temperature, obtain the urethane of clear viscous shape;
(4) aminoresin modification: at 50 ~ 60 DEG C, 4g part methyl-etherified height imino-melamine resin and 0.6g tosic acid are dissolved in 10g distilled water to be joined in reactor through ultrasonic vibration after 30 minutes, react 30 minutes, obtain the aminoresin modified polyurethane of thick shape;
(5) emulsification and rear chain extension: low whipping speed is under the condition of 7000r/min, 145g deionized water is added to thick aminoresin modified polyurethane, first disperse 5 minutes, add 1.5g again and be dissolved in quadrol in 5g deionized water, disperse 25 minutes, obtain aminoresin modified aqueous polyurethane.
Embodiment 2
(1) base polyurethane prepolymer for use as preparation: at 75 DEG C, add 34.6g polypropylene glycol, 24.5g tolylene diisocyanate (TDI) and 0.08g dibutyl tin laurate, react 2 hours, adopt Di-n-Butyl Amine-acetone method to carry out titration to NCO residual volume, reach reaction end when NCO residual volume is close or be less than theoretical value;
(2) chain extension: at 75 DEG C, take 2.5g1,4-butanediol is added drop-wise in reactor in 4g acetone, react 30 minutes, take 5.8g dimethylol propionic acid and be dissolved in 7gN-methyl-2-pyrrolidone, join in reactor, react 2 hours, adopt Di-n-Butyl Amine-acetone method to carry out titration to NCO residual volume, reach reaction end when NCO residual volume is close or be less than theoretical value;
(3) in and salify: be cooled to less than 50 DEG C, add 10g acetone and reduce viscosity, then add 3.9gN, in N-dimethylethanolamine and salify, be incubated 10 minutes, be cooled to room temperature, obtain thick urethane;
(4) aminoresin modification: at 50 ~ 60 DEG C, 2g part methyl-etherified height imino-melamine resin and 0.25g tosic acid are dissolved in 10g distilled water through ultrasonic vibration after 30 minutes, join in reactor, react 30 minutes, obtain the aminoresin modified polyurethane of thick shape;
(5) emulsification and rear chain extension: low whipping speed is under the condition of 7000r/min, 150g deionized water is added to thick aminoresin modified polyurethane, first disperse 5 minutes, add 1.9g again and be dissolved in diethyl toluene diamine in 5g deionized water, disperse 25 minutes, obtain aminoresin modified aqueous polyurethane.
Embodiment 3
(1) base polyurethane prepolymer for use as preparation: at 75 DEG C, add 37.2g polypropylene glycol, 29g tolylene diisocyanate (TDI) and 0.08g dibutyl tin laurate, react 1.5 hours, adopt Di-n-Butyl Amine-acetone method to carry out titration to NCO residual volume, reach reaction end when NCO residual volume is close or be less than theoretical value;
(2) chain extension: at 75 DEG C, take 1.8g1,4-butanediol is added drop-wise in reactor in 3g acetone, react 30 minutes, take 4.3g dimethylol propionic acid and be dissolved in 6gN-methyl-2-pyrrolidone, join in reactor, react 2 hours, adopt Di-n-Butyl Amine-acetone method to carry out titration to NCO residual volume, reach reaction end when NCO residual volume is close or be less than theoretical value;
(3) in and salify: be cooled to less than 50 DEG C, add 10g acetone and reduce viscosity, then add 2.8gN, in N-dimethylethanolamine and salify, be incubated 10 minutes, be cooled to room temperature, obtain thick urethane;
(4) aminoresin modification: at 50 ~ 60 DEG C, 8g part methyl-etherified height imino-melamine resin and 1.25g tosic acid are dissolved in 20g distilled water through ultrasonic vibration after 30 minutes, join in reactor, react 30 minutes, obtain the aminoresin modified polyurethane of thick shape;
(5) emulsification and rear chain extension: low whipping speed is under the condition of 7000r/min, 153g deionized water is added to thick urethane-part methyl-etherified height imino-melamine resin acid modified alcoholic, first disperse 5 minutes, add 1.8g again and be dissolved in quadrol in 5g deionized water, disperse 25 minutes, obtain aminoresin modified aqueous polyurethane.
Comparative example 1
(1) base polyurethane prepolymer for use as preparation: at 75 DEG C, add 39.2g polycaprolactone glycol, 29.8g isophorone diisocyanate (IPDI) and 0.08g dibutyl tin laurate, react 2 hours, adopt Di-n-Butyl Amine-acetone method to carry out titration to NCO residual volume, reach reaction end when NCO residual volume is close or be less than theoretical value;
(2) chain extension: at 75 DEG C, take 2.5g1,4-butanediol is added drop-wise in reactor in 3g acetone, react 30 minutes, take 5.4g dimethylol propionic acid and be dissolved in 7gN-methyl-2-pyrrolidone, join in reactor, react 2 hours, adopt Di-n-Butyl Amine-acetone method to carry out titration to NCO residual volume, reach reaction end when NCO residual volume is close or be less than theoretical value;
(3), in and salify: at being cooled to 50 DEG C ~ 60 DEG C, add 10g acetone and reduce viscosity, then add in 3.8g triethylamine and salify, be incubated 10 minutes, be cooled to room temperature, obtain the urethane of clear viscous shape;
(4) emulsification and rear chain extension: low whipping speed is under the condition of 7000r/min, add 145g deionized water to thick aminoresin modified polyurethane, first disperse 5 minutes, then add 1.5g and be dissolved in quadrol in 5g deionized water, disperse 25 minutes, obtain aqueous polyurethane.
(5) blending and modifying: directly add 4g part methyl-etherified height imino-melamine resin and 0.6g tosic acid in above-mentioned obtained aqueous polyurethane, and stir with glass stick.
Carried out joining paint by aminoresin modified aqueous polyurethane obtained by example 1 ~ 3 and comparative example 1, the compositions in weight percentage of joining paint is as follows:
Defoamer is the Foamex805 of EVONIK, and wetting agent is Disperbyk-181.
The paint film sample of embodiment 1 ~ 3 was 80 DEG C of bakings 20 minutes, and the paint film sample of comparative example 1 was 130 DEG C of bakings 30 minutes.
Test the performance of emulsion and paint film, result is as shown in table 1.Wherein particle diameter adopts dynamic light scattering laser particle analyzer (DLS, Malvern, ZS-Nano-S) to measure; Water-intake rate is by being cut into the square of 25mmX25mm by glued membrane, weigh (m
1), be at room temperature placed in tap water and soak 24 hours, suck film surface moisture with thieving paper, weigh (m
2), by (m
1-m
2)/m
1x100% formulae discovery; Tensile strength, elongation at break adopt general tension testing machine (InstronCorporation, SeriesIX) to measure; Hardness of paint film is pressed GB/T6739-2006 and is measured; Sticking power is pressed GB/T9286-1998 and is measured; Solvent resistance, by paint film is soaked in 24h in dimethylbenzene, observes paint film change detection.
Table 1 embodiment 1 ~ 3 and comparative example 1 emulsion and paint film property test result
As can be seen from table 1 result, the present invention introduces the method for aminoresin compared to blending method, the properties of gained emulsion and paint film all increases, major embodiment be water-intake rate reduce, draw high intensity increase, elongation at break increase, hardness increases, sticking power improves, solvent resistance strengthens.Along with increasing of aminoresin consumption, system degree of crosslinking increases, and thus paint film shows as performances such as drawing high intensity improves, water-intake rate and elongation at break and declines to some extent.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. an aminoresin modified aqueous polyurethane, is characterized in that, is prepared from by the component of following mass parts:
2. a kind of aminoresin modified aqueous polyurethane according to claim 1, is characterized in that: described dibasic alcohol refer in polycaprolactone glycol, polypropylene glycol and poly-adipate glycol-BDO esterdiol one or more.
3. a kind of aminoresin modified aqueous polyurethane according to claim 1, it is characterized in that: described vulcabond refer in tolylene diisocyanate, ditan-4,4-vulcabond, isophorone diisocyanate and hexamethylene diisocyanate one or more.
4. a kind of aminoresin modified aqueous polyurethane according to claim 1, is characterized in that: described aminoresin for having the part methyl-etherified height imino-melamine resin of molecular structural formula shown in formula (1),
5. a kind of aminoresin modified aqueous polyurethane according to claim 1, is characterized in that: described neutralizing agent is one or more in triethylamine, N, N-dimethylethanolamine and ammoniacal liquor.
6. a kind of aminoresin modified aqueous polyurethane according to claim 1, is characterized in that: described small molecule chain extender is one or more in diethyl toluene diamine, 3,5-dimethythiotoluene diamines and quadrol.
7. the preparation method of the aminoresin modified aqueous polyurethane described in any one of claim 1 ~ 6, is characterized in that, comprises following preparation process:
(1) base polyurethane prepolymer for use as preparation: at 60 ~ 80 DEG C, dibasic alcohol, vulcabond and dibutyl tin laurate are joined in reactor, react 1 ~ 3 hour;
(2) chain extension: at 60 ~ 80 DEG C, is added drop-wise in reactor by the BDO being dissolved in acetone, reacts 30 ~ 60 minutes, then adds 2, the 2-dimethylol propionic acids being dissolved in N-Methyl pyrrolidone, reacts 2 ~ 4 hours;
(3), in and salify: at 50 ~ 60 DEG C, add acetone and reduce viscosity, then add neutralizing agent, stir insulation 10 ~ 30 minutes;
(4) aminoresin modification: at 50 ~ 60 DEG C, joins in reactor by the aminoresin and tosic acid that are dissolved in distilled water, reacts 0.5 ~ 1 hour, obtains the aminoresin modified polyurethane of thick shape;
(5) emulsification and rear chain extension: under agitation, adds deionized water in the aminoresin modified polyurethane of thick shape, disperses 5 ~ 10 minutes, then adds small molecule chain extender, disperses 20 ~ 30 minutes, obtains aminoresin modified aqueous polyurethane.
8. the preparation method of a kind of aminoresin modified aqueous polyurethane according to claim 7, is characterized in that: the mass ratio of the N-Methyl pyrrolidone described in step (2) and 2,2-dimethylol propionic acid is (2 ~ 2.5): 1; Aminoresin described in step (4) and tosic acid water-soluble after within 30 minutes, make it be uniformly dispersed by ultrasonic vibration treatment; Described in step (5), the stirring velocity of agitation condition is 6000 ~ 7000r/min.
9. the aminoresin modified aqueous polyurethane described in any one of claim 1 ~ 6, joining the application in paint, is characterized in that, described in join the compositions in weight percentage proportioning of paint as follows:
10. a kind of aminoresin modified aqueous polyurethane according to claim 9 is joining the application in paint, it is characterized in that, described defoamer is Foamex805; Described wetting agent is Disperbyk-181.
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| CN113831725A (en) * | 2021-11-12 | 2021-12-24 | 成都市红宝丽新材料科技发展有限公司 | Polyurethane-coated flame-retardant sealing rubber strip with high production efficiency and preparation method thereof |
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