CN101613449A - Waterborne polyurethane resin of ultraviolet light polymerization and preparation method thereof - Google Patents
Waterborne polyurethane resin of ultraviolet light polymerization and preparation method thereof Download PDFInfo
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- CN101613449A CN101613449A CN200910017333A CN200910017333A CN101613449A CN 101613449 A CN101613449 A CN 101613449A CN 200910017333 A CN200910017333 A CN 200910017333A CN 200910017333 A CN200910017333 A CN 200910017333A CN 101613449 A CN101613449 A CN 101613449A
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- ultraviolet light
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Abstract
The invention discloses a kind of waterborne polyurethane resin of ultraviolet light polymerization, its general structure is right formula, the waterborne polyurethane resin of this kind ultraviolet light polymerization is introduced polyether glycol in the polyurethane backbone, and can introduce more two key in the such polyurethane chain of monomer end-blocking with the monohydroxy esters of acrylic acid and carry out crosslinking polymerization, improved the crosslinked and relative molecular weight of filming, effectively improve the chemical resistance of UV curable water-borne system, can take into account hardness and snappiness two sides performance simultaneously.
Description
Technical field
The present invention relates to a kind of urethane resin, particularly waterborne polyurethane resin of a kind of ultraviolet light polymerization and preparation method thereof belongs to technical field of polymer materials.
Background technology
The waterborne polyurethane resin of ultraviolet light polymerization is with the new polyurethane system of water to replace organic solvent as dispersion medium, because of it is pollution-free, safe and reliable, mechanical property is good, consistency is good, be easy to advantages such as modification, have a wide range of applications at coating and adhesive area.
At present, the waterborne polyurethane resin of ultraviolet light polymerization that many bibliographical informations arranged, as: periodical name " coating technology and digest " disclosed " the synthetic and performance study of water-based UV curing urethane dispersion ", Chinese University of Science and Technology's polymer science and engineering department, Hefei 230026, author: Li Weihu etc.2003 30 volume 4 phases disclosed " research of aqueous polyurethane acrylate prepolymer UV solidified film performance " of periodical name " Hunan University's newspaper ", author: Zhao Xu etc.2004 27 volumes of periodical name " China Synthetic Rubber Industry ", 3 phases disclosed " ultraviolet light solidfication water polyurethane acrylate " author: Wang Dening etc.
The degree of crosslinking that the technology of above-mentioned bibliographical information, curing urethane are filmed is not high, and relative molecular weight is less, and chemical resistance is relatively poor, can not can take into account hardness and flexible requirement simultaneously.
Summary of the invention
The objective of the invention is to overcome the prior art deficiency, and a kind of waterborne polyurethane resin of ultraviolet light polymerization is provided.
Another object of the present invention provides the preparation method of the waterborne polyurethane resin of kind of ultraviolet light polymerization.
The present invention's technical scheme of taking of dealing with problems is:
The waterborne polyurethane resin of ultraviolet light polymerization is characterized in that, its general structure is:
The preparation method of the waterborne polyurethane resin of described ultraviolet light polymerization comprises the steps:
1) polyether glycol of 50～80 weight parts and the polyisocyanates of 30～50 weight parts are added in the reactor, react 1.5～2.5h down at 60～80 ℃;
2) in reactor, add the dimethylol propionic acid of 6～10 weight parts, at 60～80 ℃ of reaction 1.5～2.5h down;
3) to step 2) add the acetone of 20～30 weight parts in the reacted product, under nitrogen protection, add 2 of the dibutyl tin laurate of monohydroxy acrylate, 0.1～1 weight part of 10～20 weight parts and 0.5～1.5 weight part then, 6 ditertbutylparacresols are 80～90 ℃ of reaction 2.5～3.5h down in temperature;
4) adding the pentaerythritol diacrylate of 15～30 weight parts in the reacted product of step 3), is 50～70 ℃ of reaction 2.5～3.5h down in temperature, adds the triethylamine neutralization of 0.5～3 weight part then;
5) water that adds 100～200 weight parts in the reacted product of step 4) mixes, and vacuum sloughs acetone, promptly gets product.
The preparation method of the waterborne polyurethane resin of described ultraviolet light polymerization, wherein the molecular weight of the polyether glycol described in the step 1) is 1000～3000, and described polyisocyanates is any one in tolylene diisocyanate, isophorone diisocyanate, the diphenylmethanediisocyanate.
The preparation method of the waterborne polyurethane resin of described ultraviolet light polymerization, wherein the molecular weight of the polyether glycol described in the step 1) is preferably 1000, the preferred tolylene diisocyanate of described polyisocyanates.
The preparation method of the waterborne polyurethane resin of described ultraviolet light polymerization, wherein the monohydroxy acrylate described in the step 3) is any one in Hydroxyethyl acrylate, Propylene glycol monoacrylate, the pentaerythritol triacrylate.
The preparation method of the waterborne polyurethane resin of described ultraviolet light polymerization, wherein the monohydroxy acrylate preferred acrylate hydroxypropyl acrylate described in the step 3).
The preparation process of the waterborne polyurethane resin of described ultraviolet light polymerization is as follows:
The invention has the beneficial effects as follows:
Polyether glycol is introduced in the polyurethane backbone, and can introduce more two key in the such polyurethane chain of monomer end-blocking with the monohydroxy esters of acrylic acid and carry out crosslinking polymerization, improved the crosslinked and relative molecular weight of filming, effectively improve the chemical resistance of UV curable water-borne system, can take into account hardness and snappiness two sides performance simultaneously.Product has good hardness of film and snappiness, environment-protecting asepsis, and production cost is low.Waterborne polyurethane resin with solid part 10%～50%.Acrylate thinner with 5%～10%, the light trigger with 0.1%～10%, the auxiliary agent with 0.1%～1% has been made photo curable water-borne coatings.
Its performance such as table 1:
Table 1
| Test event | Solidification rate/s | Pendulum-rocker hardness | Snappiness | Sticking power |
| Test result | ??50 | ??0.66 | ??≤1mm | ??100/100 |
Embodiment
The used polyether glycol of the embodiment of the invention is the N210 product of Plant of Tianjin Petrochemical Company, polyisocyanates is the product of Bayer A.G, the monohydroxy acrylate is the product of Shanghai Gaoqiao petro-chemical corporation, dimethylol propionic acid is the product of Sweden Perstor company, and pentaerythritol diacrylate is the product of Changxing, Taiwan chemical company.
Embodiment 1
The preparation of the waterborne polyurethane resin of ultraviolet light polymerization:
1) be that 1000 the polyether glycol and the tolylene diisocyanate of 30 weight parts add in the reactor with the molecular weight of 55 weight parts, at 80 ℃ of reaction 2h down;
2) dimethylol propionic acid of adding 9 weight parts in reactor reacts 2h down at 70 ℃;
3) to step 2) add the acetone of 25 weight parts in the reacted product, under nitrogen protection, add 2 of the dibutyl tin laurate of 18 parts by weight of acrylic hydroxypropyl acrylates, 0.5 weight part and 0.8 weight part then, 6 ditertbutylparacresols are 90 ℃ of reaction 3h down in temperature;
4) pentaerythritol diacrylate of adding 25 weight parts in the reacted product of step 3) is 60 ℃ of reaction 3h down in temperature, adds the triethylamine neutralization of 0.6 weight part then;
5) water that adds 170 weight parts in the reacted product of step 4) mixes, and vacuum sloughs acetone, promptly gets product.
Embodiment 2
The preparation of the waterborne polyurethane resin of ultraviolet light polymerization:
1) be that 1000 the polyether glycol and the isophorone diisocyanate of 35 weight parts add in the reactor with the molecular weight of 50 weight parts, at 70 ℃ of reaction 2.5h down;
2) dimethylol propionic acid of adding 8 weight parts in reactor reacts 2.5h down at 70 ℃;
3) to step 2) add the acetone of 30 weight parts in the reacted product, under nitrogen protection, add 2 of the dibutyl tin laurate of 15 parts by weight of acrylic hydroxypropyl acrylates, 0.5 weight part and 0.8 weight part then, 6 ditertbutylparacresols are 80 ℃ of reaction 3h down in temperature;
4) pentaerythritol diacrylate of adding 20 weight parts in the reacted product of step 3) is 60 ℃ of reaction 3h down in temperature, adds the triethylamine neutralization of 0.6 weight part then;
5) water that adds 160 weight parts in the reacted product of step 4) mixes, and vacuum sloughs acetone, promptly gets product.
Embodiment 3
The preparation of the waterborne polyurethane resin of ultraviolet light polymerization:
1) with the molecular weight of 50 weight parts be 1000 polyether glycol, the tolylene diisocyanate of 40 weight parts adds in the reactor at 70 ℃ of reaction 2.5h.
2) dimethylol propionic acid of adding 8 weight parts in reactor reacts 2.5h. down at 70 ℃
3) to step 2) add the acetone of 30 weight parts in the reacted product, under nitrogen protection, add 2 of the dibutyl tin laurate of 15 parts by weight of acrylic hydroxyl ethyl esters, 0.5 weight part and 0.8 weight part then, 6 ditertbutylparacresols are 80 ℃ of reaction 3h down in temperature;
4) pentaerythritol diacrylate of adding 20 weight parts in the reacted product of step 3) is 60 ℃ of reaction 3h down in temperature, adds the triethylamine neutralization of 0.6 weight part then;
5) water that adds 160 weight parts in the reacted product of step 4) mixes, and vacuum sloughs acetone, promptly gets product.
Embodiment 4
The performance measurement of the waterborne polyurethane resin of the ultraviolet light polymerization of preparation:
1) solid content:
Method is measured solids content by weight.Place weighing bottle after weighing on the analytical balance, to put into case small amount of sample and dry by the fire 1 hour to constant weight at 120 ℃.
2) mensuration of total volatile organic compound (TVOC): TVOC adopts stepped approach to carry out: (1) measures total volatile content in water-borne coatings or the resin; (2) use potentiometric titration is measured water with KarlFischer reagent content (or adopting vapor-phase chromatography); (3) density of mensuration water-borne coatings or resin; (4) with the content of the inspection-free solvent of gas chromatography determination (not requiring in China's relevant criterion at present); (5) calculate TVOC content.
3) viscosity: use rotational viscosimeter, select suitable rotor and rotating speed according to odometer, coefficient is determined.The particular factor that the reading of indicating on the pointer scale dish during mensuration must be multiplied by coefficient table just is the absolute viscosity (Mpa.s) that records.Rotating speed is 60rpm, selects rotor for use No. 2,25 ℃ of temperature.
4) pendulum-rocker hardness of filming: adopt the method test of GB/T1730-1993.
The The performance test results such as the table 2 of the product that each embodiment makes:
Table 2
| Test item | Embodiment 1 makes product | Embodiment 2 makes product | Embodiment 3 makes product |
| Outward appearance | Milky white liquid | Milky white liquid | Milky white liquid |
| Solid content | ??42％ | ??42％ | ??40％ |
| ??TVOC | ≤ 150g/L (actual measurement 50) | ≤ 150g/L (actual measurement 50) | ≤ 150g/L (actual measurement 50) |
| PH value | ??7 | ??7 | ??6 |
| Viscosity | ??30mPa.s | ??30mPa.s | ??40mPa.s |
| The pendulum-rocker hardness of filming | ??0.65 | ??0.65 | ??0.66 |
Claims (6)
1, the waterborne polyurethane resin of ultraviolet light polymerization is characterized in that, its general structure is:
2, according to the preparation method of the waterborne polyurethane resin of the described ultraviolet light polymerization of claim 1, it is characterized in that, comprise the steps:
1) polyether glycol of 50～80 weight parts and the polyisocyanates of 30～50 weight parts are added in the reactor, react 1.5～2.5h down at 60～80 ℃;
2) in reactor, add the dimethylol propionic acid of 6～10 weight parts, at 60～80 ℃ of reaction 1.5～2.5h down;
3) to step 2) add the acetone of 20～30 weight parts in the reacted product, under nitrogen protection, add 2 of the dibutyl tin laurate of monohydroxy acrylate, 0.1～1 weight part of 10～20 weight parts and 0.5～1.5 weight part then, 6 ditertbutylparacresols are 80～90 ℃ of reaction 2.5～3.5h down in temperature;
4) adding the pentaerythritol diacrylate of 15～30 weight parts in the reacted product of step 3), is 50～70 ℃ of reaction 2.5～3.5h down in temperature, adds the triethylamine neutralization of 0.5～3 weight part then;
5) water that adds 100～200 weight parts in the reacted product of step 4) mixes, and vacuum sloughs acetone, promptly gets product.
3, according to the preparation method of the waterborne polyurethane resin of the described ultraviolet light polymerization of claim 2, it is characterized in that, the molecular weight of the polyether glycol described in the step 1) is 1000～3000, and described polyisocyanates is any one in tolylene diisocyanate, isophorone diisocyanate, the diphenylmethanediisocyanate.
4, according to the preparation method of the waterborne polyurethane resin of the described ultraviolet light polymerization of claim 3, it is characterized in that the molecular weight of the polyether glycol described in the step 1) is 1000, described polyisocyanates is a tolylene diisocyanate.
5, according to the preparation method of the waterborne polyurethane resin of the described ultraviolet light polymerization of claim 2, it is characterized in that the monohydroxy acrylate described in the step 3) is any one in Hydroxyethyl acrylate, Propylene glycol monoacrylate, the pentaerythritol triacrylate.
6, according to the preparation method of the waterborne polyurethane resin of the described ultraviolet light polymerization of claim 5, it is characterized in that the monohydroxy acrylate described in the step 3) is the acrylate hydroxypropyl acrylate.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993655A (en) * | 2010-10-28 | 2011-03-30 | 华南理工大学 | Ultraviolet cured waterborne wood lacquer and preparation method thereof |
| CN102190803A (en) * | 2011-03-22 | 2011-09-21 | 北京市射线应用研究中心 | Internal-crosslinking aqueous polyurethane emulsion and preparation method thereof |
| CN102504527A (en) * | 2011-11-15 | 2012-06-20 | 华东理工大学 | Ultraviolet curing cationic aqueous polyurethane dispersion liquid with ion-containing soft segment, and preparation method thereof |
| CN102516864A (en) * | 2011-12-07 | 2012-06-27 | 华南理工大学 | Composite aqueous UV coating |
| CN103214652A (en) * | 2013-04-25 | 2013-07-24 | 广东工业大学 | Ultraviolet cured waterborne polyurethane acrylate vacuum coating base-coating resin |
| CN103627313A (en) * | 2013-11-29 | 2014-03-12 | 广州机械科学研究院有限公司 | Ultraviolet-cured stripping protective material and preparation method and application thereof |
| CN104312422A (en) * | 2014-10-28 | 2015-01-28 | 成都纳硕科技有限公司 | Ultraviolet-curable water-based paint for plastic surface |
| CN105051112A (en) * | 2013-03-29 | 2015-11-11 | Dic株式会社 | Urethane resin composition, coating agent, and article |
| CN105199593A (en) * | 2015-11-02 | 2015-12-30 | 淄博夸克医药技术有限公司 | Modified polyurethane fireproof coating with wear resistance |
| JP2016074751A (en) * | 2014-10-02 | 2016-05-12 | Dic株式会社 | Aqueous resin composition, coating agent and article |
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2009
- 2009-07-27 CN CN200910017333A patent/CN101613449A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993655A (en) * | 2010-10-28 | 2011-03-30 | 华南理工大学 | Ultraviolet cured waterborne wood lacquer and preparation method thereof |
| CN102190803A (en) * | 2011-03-22 | 2011-09-21 | 北京市射线应用研究中心 | Internal-crosslinking aqueous polyurethane emulsion and preparation method thereof |
| CN102504527A (en) * | 2011-11-15 | 2012-06-20 | 华东理工大学 | Ultraviolet curing cationic aqueous polyurethane dispersion liquid with ion-containing soft segment, and preparation method thereof |
| CN102516864A (en) * | 2011-12-07 | 2012-06-27 | 华南理工大学 | Composite aqueous UV coating |
| TWI616486B (en) * | 2013-03-29 | 2018-03-01 | Dainippon Ink & Chemicals | Urethane resin composition, coating agent and article |
| CN105051112A (en) * | 2013-03-29 | 2015-11-11 | Dic株式会社 | Urethane resin composition, coating agent, and article |
| CN105051112B (en) * | 2013-03-29 | 2017-10-10 | Dic株式会社 | Urethane resin compositions, smears and article |
| CN103214652A (en) * | 2013-04-25 | 2013-07-24 | 广东工业大学 | Ultraviolet cured waterborne polyurethane acrylate vacuum coating base-coating resin |
| CN103627313B (en) * | 2013-11-29 | 2016-08-17 | 广州机械科学研究院有限公司 | A kind of peelable protection material of ultraviolet light polymerization and its preparation method and application |
| CN103627313A (en) * | 2013-11-29 | 2014-03-12 | 广州机械科学研究院有限公司 | Ultraviolet-cured stripping protective material and preparation method and application thereof |
| JP2016074751A (en) * | 2014-10-02 | 2016-05-12 | Dic株式会社 | Aqueous resin composition, coating agent and article |
| CN104312422A (en) * | 2014-10-28 | 2015-01-28 | 成都纳硕科技有限公司 | Ultraviolet-curable water-based paint for plastic surface |
| CN105199593A (en) * | 2015-11-02 | 2015-12-30 | 淄博夸克医药技术有限公司 | Modified polyurethane fireproof coating with wear resistance |
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Open date: 20091230 |