CN103725182A - Preparation method for yellowing resistant aromatic polycarbonate type waterborne polyurethane coating material - Google Patents
Preparation method for yellowing resistant aromatic polycarbonate type waterborne polyurethane coating material Download PDFInfo
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- CN103725182A CN103725182A CN201310676675.3A CN201310676675A CN103725182A CN 103725182 A CN103725182 A CN 103725182A CN 201310676675 A CN201310676675 A CN 201310676675A CN 103725182 A CN103725182 A CN 103725182A
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Abstract
The invention relates to a preparation method for a yellowing resistant aromatic polycarbonate type waterborne polyurethane coating material. The preparation method comprises the following specific steps: through adopting a manner of adding a dispersing agent, dispersing nano TiO2 into DMF well; compounding MDI with IPDI and enabling the mixture to react with polycarbonate diol, so as to reduce the reaction degree of the MDI, and obtain waterborne polyurethane emulsion with higher stability; adding the nano-powder TiO2 into the polyurethane emulsion before emulsification, so as to improve the dispersion stability of the nano-powder TiO2 in polyurethane, and adding an anti-oxidant 1010 and an ultraviolet light absorber UV-327 into the waterborne polyurethane emulsion to achieve a better yellowing resistant effect.
Description
Technical field
The present invention relates to a kind of preparation method of stain resistant aqueous polyurethane coating material, be specifically related to a kind of preparation method of the aromatic copolycarbonate of resistance to xanthochromia type aqueous polyurethane coating material.
Background technology
Designability based on polyurethane molecular and Scalability, polyurethane material is uniquely a kind ofly aspect physicals and chemical property, all to have the polymer materials of the wider scope of application, is therefore widely used in tackiness agent, coating, synthetic leather, material of construction and automatic industrial.Aqueous polyurethane has overcome the with serious pollution shortcoming of solvent borne polyurethane, take water as dispersion medium, has the features such as nontoxic, energy-conservation, safe and reliable, and research be initially widely used in hide finishes.The conjugation group that contains easy color development due to structure though aromatic waterborne polyurethane has good mechanical property when for coating, for white and when leather light color xanthochromia very easily, so limited its application.The anti-yellowing property that how to improve aromatic waterborne polyurethane is attracting the concern of numerous researchers all the time, wherein aspect nano-material modified, has obtained more achievement.Because nano-particles size is little, specific surface area is large, can produce quantum effect and surface effects, make the more conventional matrix material of nano composite material there is more excellent physicals and mechanical property.Adopt suitable method by inorganic nano-particle, carbon nanotube or nano imvite lamella and aqueous polyurethane carry out compound, and the over-all properties of prepared matrix material can be very significantly improved, and has expanded its Application Areas, has improved its result of use.The people such as Chen Jiahua point out that nanometer coating and decorating material can improve resistance to xanthochromia and the ageing-resistant performance of coatings, and wear resistance, water-repellancy, heat-resisting winter hardiness etc. make coating have self-cleaning and sterilizing ability preferably simultaneously, also can improve the opacifying power of coating.
Nano-TiO
2electronic structure, by being full of the valence band of electronics and not having the conduction band structure that the unoccupied orbital of electronics forms to forbid band gap.Work as TiO
2be subject to rayed, be prohibited the large photoabsorption of band gap energy, the electron excitation of valence band is to conduction band.Due to TiO
2the band gap of forbidding be about 2.3eV, be equivalent to the luminous energy of about 410nm wavelength.So TiO
2electrons be subject to wavelength to be less than the ultraviolet excitation of 410nm, thereby form good scattering and absorb the ability of UV-light, join in aqueous polyurethane, can reach fabulous resistance to xanthochromia effect.
In industrial production, conventionally adopt and add the modes such as UV light absorber (benzotriazole category, triazines), hindered amine as light stabilizer and oxidation inhibitor to improve the yellowing resistance of aromatic waterborne polyurethane.But because the compatibility problem of additive and polymkeric substance and the ageing problem of additive etc. is difficult to resistance to xanthochromia effect lastingly.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of the aromatic waterborne polyurethane of resistance to xanthochromia composite coating material, to improve nano-TiO
2dispersiveness in polyaminoester emulsion, reduces the difficulty in aromatic waterborne polyurethane building-up process, is intended to obtain a kind of suitable industrial synthetic method.
Technical scheme of the present invention is as follows:
A preparation method for the aromatic waterborne polyurethane of resistance to xanthochromia coated material, is characterized in that preparation process is as follows:
(1) prepare TiO
2dispersion liquid: accurately take dispersion agent in dry container, add DMF, dispersion agent is dissolved completely, add nano-powder TiO
2, in ultrasonic cell disruptor, under 5400w～600w, ultrasonic 20～40min obtains TiO
2dispersion liquid; Wherein in every 100mlDMF, add 5～10g nano-powder TiO
2, dispersion agent add-on is 1.5～3g;
(2) prepare polycarbonate type aqueous polyurethane dispersing liquid: in a container, add 20～25 weight part polycarbonate dibasic alcohol, the mixture that adds again 0～5 weight part isophorone diisocyanate (IPDI) and 9～15 parts of diphenylmethanediisocyanates (MDI), is placed in the oil bath of 75 ℃～85 ℃ and reacts to NCO and reach theoretical value; Be cooled to 40 ℃～50 ℃, add 1.5～2.5 weight part hydrophilic chain extender dimethylolpropionic acids, reaction 1h～1.5h, be warmed up to 80 ℃, add 0.5～2.5 weight part secondary chain extension agent 1,4-butyleneglycol (BDO), insulation reaction 1h～2h, obtains molecular weight at the base polyurethane prepolymer for use as of 1w～2w left and right; Performed polymer is cooled to 40 ℃～50 ℃, the TiO that adds step (1) to prepare
2dispersion liquid stirs 0.5h～1h in 40 ℃～50 ℃ oil baths, then adds 1.0～2.0 weight part triethylamines (TEA) to neutralize, and reaction 0.5h～1h obtains intermediate; High-speed stirring under the deionized water of 40～70 weight parts is slowly joined in 0.5h～1h in intermediate, simultaneously with 1000r/min～1200r/min high-speed stirring 0.5h～1h, finally obtain polycarbonate type aqueous polyurethane dispersing liquid;
(3) preparation of the aromatic copolycarbonate of resistance to xanthochromia type aqueous polyurethane coating material: the antioxidant 1010 of 0～1.5 weight part and 0～2 weight part UV light absorber UV-327 are joined after compound in the polycarbonate type aqueous polyurethane dispersing liquid that step (2) obtains.
In a preferred embodiment of the invention, in described step (1), described dispersion agent is a kind of in Sodium dodecylbenzene sulfonate, PEG-6000, PEG-4000, Polyethylene glycol-2000, Sodium hexametaphosphate 99.
In a preferred embodiment of the invention, described DMF is DMF, is analytical pure, and content is no less than 99.5%, and acidity is (with H
+meter) be 0.1mmol/100g, moisture content is lower than 1%.
In a preferred embodiment of the invention, described nano-powder TiO
2for rutile-type, purity>=99.9%, particle diameter is 25nm.
In a preferred embodiment of the invention, the alkane glycol with straight chain or side chain and the methyl carbonate copolymerization of described polycarbonate diol cause carbonatoms 4～12 obtain.
In a preferred embodiment of the invention, the average molecular mass Mn of described polycarbonate diol is 1000g/mol～2000g/mol.
In a preferred embodiment of the invention, described antioxidant 1010 is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, white crystalline powder, content >=98%.
In a preferred embodiment of the invention, described UV light absorber UV-327 is 2-(2-hydroxyl-3, the tertiary base phenyl of 5-bis-fourth)-5-chlorinated benzotriazole, faint yellow or white powder, content >=98%.
Positively effect of the present invention is:
The present invention adopts MDI and IPDI is carried out to the composite level of response of reacting to reduce MDI with polycarbonate diol, obtains the aqueous polyurethane emulsion that stability is higher.Adopt the mode of powder synthetic (adding before emulsification) to add TiO
2overcome the mechanical stability that simple mechanical blend causes poor, the problem that inorganic materials and organic phase consistency are poor, in conjunction with the mode that adds antioxidant 1010 and UV light absorber UV-327 composite modifier, obtain the high aromatic copolycarbonate of resistance to xanthochromia type aqueous polyurethane emulsion for coating, for the use field that expands light-coloured coating, played great role.
Accompanying drawing explanation
Fig. 1 is example 1 the first step nano-TiO
2the transmission electron microscope picture of dispersion liquid, 200,000 times of magnifications.
Fig. 2 is the nano-TiO of example 1 preparation
2the transmission electron microscope picture of modified aqueous polyurethane emulsion, 200,000 times of magnifications.
Embodiment
Below in conjunction with specific implementation method, further illustrate the present invention.
Embodiment 1
The first step: nano-TiO
2the preparation of dispersion liquid
Accurately take 0.300g Sodium hexametaphosphate 99 in dry 250ml Erlenmeyer flask, add 30mlDMF, dispersion agent is dissolved completely, add 3.000g nano-powder TiO
2, in ultrasonic cell disruptor, ultrasonic 30min under 540w.Nano-powder TiO wherein
2for rutile-type, purity>=99.9%, particle diameter is 25nm.As can be seen from Figure 1 nano-TiO
2in DMF solution, there is good dispersiveness.
Second step: the preparation of polycarbonate type aqueous polyurethane emulsion.
In the four-hole boiling flask of electric mixer, thermometer, reflux condensing tube, nitrogen tube is housed, add 20.000g PCDL, the mixture that adds again 1.095g isophorone diisocyanate (IPDI) and 9.857g diphenylmethanediisocyanate (MDI), is placed in the oil bath of 75 ℃ and reacts to NCO and reach theoretical value.Be cooled to 40 ℃, add 1.557g hydrophilic chain extender dimethylolpropionic acid (DMBA), reaction 1h.Be warmed up to 80 ℃, add 1.354g secondary chain extension agent BDO (BDO), insulation reaction 1h, obtains having the urethane that molecular weight is 1w～2w.Urethane is lowered the temperature, the nano-TiO of in advance being prepared by step (1)
2dispersion liquid carries out ultrasonic dispersion, takes this nano-TiO of 6.600g
2dispersion liquid joins in polyurethane body, in 40 ℃ of oil baths, stirs 0.5h, then adds 1.010g triethylamine (TEA) to neutralize, and reaction 0.5h obtains intermediate.Under 1200r/min stirs, the deionized water of 41.156g is slowly joined to (about half an hour) in intermediate, under 1200r/min, stir 0.5h simultaneously, finally obtain polycarbonate type aqueous polyurethane emulsion.Nano-TiO as can be seen from Figure 2
2in polyaminoester emulsion, well disperseed.The alkane glycol with straight chain or side chain and the methyl carbonate copolymerization of polycarbonate diol cause carbonatoms 4～12 obtain, and average molecular mass Mn is 1000g/mol～2000g/mol.
The 3rd step: the preparation of the aromatic copolycarbonate of resistance to xanthochromia type aqueous polyurethane coating material: by 0.0306g antioxidant 1010 with 0.0612g UV light absorber UV-327 is compound joins in the polyaminoester emulsion that step (2) obtains.
Embodiment 2
The first step: nano-TiO
2the preparation of dispersion liquid
Accurately take 0.150g Sodium hexametaphosphate 99 in dry 250ml Erlenmeyer flask, add 30mlDMF, dispersion agent is dissolved completely, add 3.000g nano-powder TiO
2, in ultrasonic cell disruptor, ultrasonic 30min under 540w.Described nano-powder TiO
2for rutile-type, purity>=99.9%, particle diameter is 25nm.
Second step: the preparation of polycarbonate type aqueous polyurethane emulsion.
In the four-hole boiling flask of electric mixer, thermometer, reflux condensing tube, nitrogen tube is housed, add 20.000g PCDL, the mixture that adds again 0.690g isophorone diisocyanate (IPDI) and 6.210g diphenylmethanediisocyanate (MDI), is placed in the oil bath of 75 ℃ and reacts to NCO and reach theoretical value.Be cooled to 40 ℃, add 1.883g hydrophilic chain extender dimethylolpropionic acid (DMBA), reaction 1h.Be warmed up to 80 ℃, add 0.154g secondary chain extension agent BDO (BDO), insulation reaction 1h, obtains having the urethane of certain molecular weight.Urethane is lowered the temperature, the nano-TiO of in advance being prepared by step (1)
2dispersion system carries out ultrasonic dispersion, takes this system of 10.912g and joins in polyurethane body, in 40 ℃ of oil baths, stirs 0.5h, then adds 1.350g triethylamine (TEA) to neutralize, and reaction 0.5h obtains intermediate.The deionized water of 53.919g is slowly joined to (about half an hour) in intermediate under high-speed stirring, high-speed stirring 0.5h, finally obtains polycarbonate type aqueous polyurethane emulsion simultaneously.The alkane glycol with straight chain or side chain and the methyl carbonate copolymerization of polycarbonate diol cause carbonatoms 4～12 obtain, and average molecular mass Mn is 1000g/mol～2000g/mol.
The 3rd step: the preparation of the aromatic copolycarbonate of resistance to xanthochromia type aqueous polyurethane coating material: by 0.0101g antioxidant 1010 with 0.0204g UV light absorber UV-327 is compound joins in the polyaminoester emulsion that step (2) obtains.
Embodiment 3
The first step: nano-TiO
2the preparation of dispersion liquid
Accurately take 0.210g Sodium hexametaphosphate 99 in dry 250ml Erlenmeyer flask, add 30mlDMF, dispersion agent is dissolved completely, add 3.000g nano-powder TiO
2, in ultrasonic cell disruptor, ultrasonic 30min under 540w.Described nano-powder TiO
2for rutile-type, purity>=99.9%, particle diameter is 25nm.
Second step: the preparation of polycarbonate type aqueous polyurethane emulsion.
In the four-hole boiling flask of electric mixer, thermometer, reflux condensing tube, nitrogen tube is housed, add 20.000g PCDL, the mixture that adds again 2.903g isophorone diisocyanate (IPDI) and 11.612g diphenylmethanediisocyanate (MDI), is placed in the oil bath of 75 ℃ and reacts to NCO and reach theoretical value.Be cooled to 40 ℃, add 2.071g hydrophilic chain extender dimethylolpropionic acid (DMBA), reaction 1h.Be warmed up to 80 ℃, add 1.672g secondary chain extension agent BDO (BDO), insulation reaction 1h, obtains having the polyurethane dispersions of 1.5w molecular weight.Urethane is lowered the temperature, the nano-TiO of in advance being prepared by step (1)
2dispersion system carries out ultrasonic dispersion, takes this system of 15.927g and joins in polyurethane body, in 40 ℃ of oil baths, stirs 0.5h, then adds 1.485g triethylamine (TEA) to neutralize, and reaction 0.5h obtains intermediate.Under 1200r/min stirs, the deionized water of 129.082g is slowly joined to (about half an hour) in intermediate, 1200r/min stirs 0.5h simultaneously, finally obtains polycarbonate type aqueous polyurethane emulsion.The alkane glycol with straight chain or side chain and the methyl carbonate copolymerization of polycarbonate diol cause carbonatoms 4～12 obtain, and average molecular mass Mn is 1000g/mol～2000g/mol.
The 3rd step: the preparation of the aromatic copolycarbonate of resistance to xanthochromia type aqueous polyurethane coating material: by 0.067g antioxidant 1010 with 0.133g UV light absorber UV-327 is compound joins in the polyaminoester emulsion that step (2) obtains.
Claims (8)
1. a preparation method for the aromatic copolycarbonate of resistance to xanthochromia type aqueous polyurethane coating material, is characterized in that preparation process is as follows:
(1) prepare TiO
2dispersion liquid: accurately take dispersion agent in dry container, add DMF, dispersion agent is dissolved completely, add nano-powder TiO
2, in ultrasonic cell disruptor, under 400w～600w, ultrasonic 20～40min obtains TiO2 dispersion liquid; Wherein in every 100mlDMF, add 5～10g nano-powder TiO
2, dispersion agent add-on is 1.5～3g;
(2) prepare polycarbonate type aqueous polyurethane dispersing liquid: in a container, add 20～25 weight part polycarbonate dibasic alcohol, the mixture that adds again 0～5 weight part isophorone diisocyanate (IPDI) and 9～15 parts of diphenylmethanediisocyanates (MDI), is placed in the oil bath of 75 ℃～85 ℃ and reacts to NCO and reach theoretical value; Be cooled to 40 ℃～50 ℃, add 1.5～2.5 weight part hydrophilic chain extender dimethylolpropionic acids, reaction 1h～1.5h, be warmed up to 80 ℃, add 0.5～2.5 weight part secondary chain extension agent 1,4-butyleneglycol (BDO), insulation reaction 1h～2h, obtains the base polyurethane prepolymer for use as of molecular weight between 1w～2w; Performed polymer is cooled to 40 ℃～50 ℃, the TiO that adds step (1) to prepare
2dispersion liquid stirs 0.5h～1h in 40 ℃～50 ℃ oil baths, then adds 1.0～2.0 weight part triethylamines (TEA) to neutralize, and reaction 0.5h～1h obtains intermediate; Under agitation the deionized water of 40～70 weight parts is slowly joined in 0.5h～1h in intermediate, simultaneously with 1000r/min～1200r/min high-speed stirring 0.5h～1h, finally obtain polycarbonate type aqueous polyurethane dispersing liquid;
(3) preparation of the aromatic copolycarbonate of resistance to xanthochromia type aqueous polyurethane coating material: the antioxidant 1010 of 0～1.5 weight part and 0～2 weight part UV light absorber UV-327 are joined after compound in the polycarbonate type aqueous polyurethane dispersing liquid that step (2) obtains.
2. the preparation method of the aromatic copolycarbonate of resistance to xanthochromia type aqueous polyurethane coating material according to claim 1, is characterized in that: dispersion agent is a kind of in Sodium dodecylbenzene sulfonate, PEG-6000, PEG-4000, Polyethylene glycol-2000, Sodium hexametaphosphate 99.
3. the preparation method of the aromatic copolycarbonate of resistance to xanthochromia type aqueous polyurethane coating material according to claim 1, is characterized in that: DMF is DMF, analytical pure, and content is no less than 99.5%, and acidity is (with H
+meter) be 0.1mmol/100g, moisture content is lower than 1%.
4. the preparation method of the aromatic copolycarbonate of resistance to xanthochromia type aqueous polyurethane coating material according to claim 1, is characterized in that: nano-powder TiO
2for rutile-type, purity>=99.9%, particle diameter is 25nm.
5. the preparation method of the aromatic copolycarbonate of resistance to xanthochromia type aqueous polyurethane coating material according to claim 2, is characterized in that: the alkane glycol with straight chain or side chain and the methyl carbonate copolymerization of described polycarbonate diol cause carbonatoms 4～12 obtain.
6. the preparation method of the aromatic copolycarbonate of resistance to xanthochromia type aqueous polyurethane coating material according to claim 2, is characterized in that: the average molecular mass Mn of described polycarbonate diol is 1000g/mol～2000g/mol.
7. the preparation method of the aromatic copolycarbonate of resistance to xanthochromia type aqueous polyurethane coating material according to claim 3 is characterized in that: antioxidant 1010 is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, white crystalline powder, content >=98%.
8. the preparation method of the aromatic copolycarbonate of resistance to xanthochromia type aqueous polyurethane coating material according to claim 3 is characterized in that: UV light absorber UV-327 is 2-(2-hydroxyl-3, the tertiary base phenyl of 5-bis-fourth)-5-chlorinated benzotriazole, faint yellow or white powder, content >=98%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910348A (en) * | 2015-06-16 | 2015-09-16 | 中国科学院化学研究所 | Polycarbonate polyurethane and green preparation method thereof |
| CN106182280A (en) * | 2016-08-25 | 2016-12-07 | 阜南县永兴工艺品有限公司 | A kind of yellowing-resistant UV resistance straw treatment fluid and preparation method thereof |
| CN106243319A (en) * | 2016-07-28 | 2016-12-21 | 上海维凯光电新材料有限公司 | Aqueous polyurethane emulsion of resistance to bending and preparation method thereof |
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| CN101864242A (en) * | 2010-06-03 | 2010-10-20 | 烟台大学 | Method for preparing yellowing resistant water-borne coating |
| US20120010314A1 (en) * | 2009-01-08 | 2012-01-12 | The University Of Western Ontario | Self-cleaning coatings |
| CN102604039A (en) * | 2012-03-20 | 2012-07-25 | 王全杰 | Preparation method of waterborne polyurethane material with resistance to yellowing |
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2013
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| US20120010314A1 (en) * | 2009-01-08 | 2012-01-12 | The University Of Western Ontario | Self-cleaning coatings |
| CN101747521A (en) * | 2010-01-14 | 2010-06-23 | 同济大学 | Method for preparing self-cleaning coating for TPU conveyor belt |
| CN101864242A (en) * | 2010-06-03 | 2010-10-20 | 烟台大学 | Method for preparing yellowing resistant water-borne coating |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910348A (en) * | 2015-06-16 | 2015-09-16 | 中国科学院化学研究所 | Polycarbonate polyurethane and green preparation method thereof |
| CN106243319A (en) * | 2016-07-28 | 2016-12-21 | 上海维凯光电新材料有限公司 | Aqueous polyurethane emulsion of resistance to bending and preparation method thereof |
| CN106182280A (en) * | 2016-08-25 | 2016-12-07 | 阜南县永兴工艺品有限公司 | A kind of yellowing-resistant UV resistance straw treatment fluid and preparation method thereof |
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Application publication date: 20140416 |