CN102532476A - Preparation method of low-viscosity polyurethane in electron beam curing - Google Patents
Preparation method of low-viscosity polyurethane in electron beam curing Download PDFInfo
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- CN102532476A CN102532476A CN2011104508160A CN201110450816A CN102532476A CN 102532476 A CN102532476 A CN 102532476A CN 2011104508160 A CN2011104508160 A CN 2011104508160A CN 201110450816 A CN201110450816 A CN 201110450816A CN 102532476 A CN102532476 A CN 102532476A
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Abstract
The invention relates to a preparation method of low-viscosity polyurethane in electron beam curing. The preparation method comprises the following steps of: firstly adopting raw materials such as isocyanate acid ester tripolymer and hydroxyl acrylate to prepare polyurethane semi-additive reactants; and then preparing low-viscosity polyurethane prepolymer by further reaction of the semi-additive reactants with a hydroxyl ion chain extender. The low-viscosity polyurethane prepolymer prepared on the basis of the preparation method is low in viscosity and can reduce the used amount of an active diluent when being used in electron beam curing coating.
Description
Technical field
The present invention relates to a kind of preparation method of urethane, particularly a kind of preparation method of electrocuring low-viscosity polyurethane belongs to technical field of polymer materials.
Background technology
In recent years, the electron beam curable coatings development is rapid, and the industry and the field of application constantly enlarge.Electron beam curable coatings is meant that under the radiation effect of electron beam the liquid-state oligomers in the formulation for coating material system (comprising the reactive thinner monomer molecule) forms the process of solid product fast through crosslinking polymerization.
The electron beam curable coatings formula system generally includes resin prepolymer, reactive thinner monomer molecule and various auxiliary agent.The physical property of the character decision paint solidification caudacoria of resin prepolymer, resin prepolymer commonly used has urethane resin, epoxy resin, vibrin etc.The reactive thinner monomer molecule is low-molecular-weight chemical substance, is mainly used in the viscosity of regulating the high viscosity resins prepolymer, is the indispensable integral part of formulation for coating material system.But mostly the reactive thinner monomer molecule is organic low molecular substance, and their volatilization not only causes the pollution of environment, also skin is had strong impulse property, and this has limited their application.
Summary of the invention
The present invention is intended to address the above problem, and a kind of low viscous urethane resin and preparation method thereof is provided.The curing membrane performance that the urethane resin that is prepared by the present invention forms behind electrocuring is good, has reduced the consumption of reactive thinner monomer molecule.
The present invention provides a kind of preparation method of electrocuring low-viscosity polyurethane, and the characteristic of this method is:
At first in the exsiccant reaction kettle, add 1.0 moles the hexamethylene diisocyanate trimer and the catalyzer and the 0.0050-0.010 mole stopper of 0.0010-0.0015 mole, the stirring at room certain hour makes various raw material thorough mixing.2.0 moles hydroxy acrylates are added in the said mixture, and the control feed rate makes reactor temperature be controlled at 45-50 ℃.Behind reinforced the finishing, reacted 4-5 hour, stopped reaction gets the urethane false add and becomes reactant; In another exsiccant reaction kettle, add 1.0 moles the hydroxyl ion chainextender and the catalyzer and the 0.0050-0.010 mole stopper of 0.0010-0.0015 mole then, the stirring at room certain hour makes various raw material thorough mixing.Become reactant to add in the reaction kettle 1.0 moles urethane false adds, the control feed rate makes reactor temperature be controlled at 45-50 ℃.Behind reinforced the finishing, the rising temperature of reaction kettle reacted 9-10 hour to 50-60 ℃.In reaction kettle, add the propyl carbinol of 0.10-0.15 mole, react after 0.5 hour stopped reaction.Temperature of reaction kettle is reduced to discharging after the room temperature, promptly get the low-viscosity polyurethane prepolymers product.
On the basis of above-mentioned preparation scheme, the present invention can also do following improvement.
Further, the mol ratio=1:2 of described hexamethylene diisocyanate trimer and hydroxy acrylate.
Further, described hydroxy acrylate comprises one or more in Hydroxyethyl acrylate, Rocryl 400, Rocryl 410, vinylformic acid hydroxy butyl ester, the Propylene glycol monoacrylate, preferred Hydroxyethyl acrylate and Rocryl 400.
Further, described hydroxyl ion chainextender is that structural formula is according to disclosed documents and materials self-control:
Further, described urethane false add becomes the mol ratio=1:1 of reactant and hydroxyl ion chainextender.
Further, described urethane false add becomes the mol ratio=1:0.10-0.15 of reactant and propyl carbinol.
Further, described catalyzer comprises one or more in stannous octoate, dibutyl tin laurate, the dibutyl tin dichloride, preferred dibutyl tin laurate.Catalyst consumption is the 0.05%-0.15% of hexamethylene diisocyanate trimer, hydroxy acrylate, hydroxyl ion chainextender gross weight.
Further, described stopper comprises Resorcinol, 4-methoxyl group phenol, 2, one or more in the 6-dinitro-p-cresol, preferred 4-methoxyl group phenol.The consumption of stopper is the 0.05%-0.20% of hexamethylene diisocyanate trimer, hydroxy acrylate, hydroxyl ion chainextender gross weight.
Described hydroxyl ion chainextender is homemade according to the documents and materials of public reported, and the documents and materials of public reported are: in generation, rushed Zhang Shengmao etc.; Preparation of Pd nanoparticle and structural characterization in the hydroxyl functional ionic liquid; Chinese Journal of Inorganic Chemistry, 2007,23 (9): 1653-1656.
Technique effect of the present invention is: the low-viscosity polyurethane prepolymers viscosity of the inventive method preparation is low, is used for electron beam curable coatings, can reduce the consumption of reactive thinner.
Embodiment
Below principle of the present invention and characteristic are described, institute gives an actual example and only is used to explain the present invention, is not to be used to limit scope of the present invention.
Embodiment 1:
In the exsiccant reaction kettle, add 1000.0 gram hexamethylene diisocyanate trimers and 0.5 gram dibutyl tin laurate and 1.25 gram 4-methoxyl group phenol, stirring at room 1 hour makes various raw material thorough mixing.331.8 gram Hydroxyethyl acrylates are added in the said mixture, and the control feed rate makes reactor temperature be controlled at 45-50 ℃.Behind reinforced the finishing, controlled temperature reacts at 45-50 ℃, and through the variation of [NCO] in the examination of infrared spectrum system, as [NCO] when reaching theoretical value, stopped reaction in this about 4-5 consuming time hour step, must become reactant by the urethane false add.
In another exsiccant reaction kettle, add 394.5 gram hydroxyl ion chainextenders and 0.5 gram dibutyl tin laurate and 2.0 gram 4-methoxyl group phenol, stirring at room 1 hour makes various raw material thorough mixing.Become reactant to add in the reaction kettle whole urethane false adds of last step preparation, the control feed rate makes reactor temperature be controlled at 45-50 ℃.Behind reinforced the finishing, the rising temperature of reaction kettle reacts to 50-60 ℃, through the variation of [NCO] in the examination of infrared spectrum system; When [NCO] when reaching theoretical value (this about 9-10 consuming time hour step); In reaction kettle, add 15.5 gram propyl carbinols, react after 0.5 hour stopped reaction.Temperature of reaction kettle is reduced to discharging after the room temperature, promptly get the low-viscosity polyurethane prepolymers product.The product structure formula is:
Embodiment 2:
In the exsiccant reaction kettle, add 1000.0 gram hexamethylene diisocyanate trimers and 0.5 gram dibutyl tin laurate and 1.3 gram 4-methoxyl group phenol, stirring at room 1 hour makes various raw material thorough mixing.371.8 gram Rocryl 400s are added in the said mixture, and the control feed rate makes reactor temperature be controlled at 45-50 ℃.Behind reinforced the finishing, controlled temperature reacts at 45-50 ℃, and through the variation of [NCO] in the examination of infrared spectrum system, as [NCO] when reaching theoretical value, stopped reaction in this about 4-5 consuming time hour step, must become reactant by the urethane false add.
In another exsiccant reaction kettle, add 394.5 gram hydroxyl ion chainextenders and 0.5 gram dibutyl tin laurate and 2.0 gram 4-methoxyl group phenol, stirring at room 1 hour makes various raw material thorough mixing.Become reactant to add in the reaction kettle whole urethane false adds of last step preparation, the control feed rate makes reactor temperature be controlled at 45-50 ℃.Behind reinforced the finishing, the rising temperature of reaction kettle reacts to 50-60 ℃, through the variation of [NCO] in the examination of infrared spectrum system; When [NCO] when reaching theoretical value (this about 9-10 consuming time hour step); In reaction kettle, add 16.0 gram propyl carbinols, react after 0.5 hour stopped reaction.Temperature of reaction kettle is reduced to discharging after the room temperature, promptly get the low-viscosity polyurethane prepolymers product.The product structure formula is:
Performance through following experimental test low-viscosity polyurethane prepolymers of the present invention.
Test example 1:
The low-viscosity polyurethane prepolymers of embodiment 1 preparation is coated on the tinplate tin through line rod spreader, and 30 microns of coating thicknesss use under the electrocuring appearance air atmosphere to be cured, and doses of electron beam radiation is the 110-120 kilogray(kGy).Coating layer solidifies the back places its performance of test after 24 hours, The performance test results such as table 1.
Test example 2:
The low-viscosity polyurethane prepolymers of embodiment 2 preparations is coated on the tinplate tin through line rod spreader, and 30 microns of coating thicknesss use under the electrocuring appearance air atmosphere to be cured, and doses of electron beam radiation is the 110-120 kilogray(kGy).Coating layer solidifies the back places its performance of test after 24 hours, The performance test results such as table 1.
Table 1 solidifies the performance of caudacoria
The above is merely preferred embodiment of the present invention, not in order to restriction the present invention.
Claims (10)
1. the preparation method of an electrocuring low-viscosity polyurethane is characterized in that described preparation method comprises: at first adopt isocyanate trimerization body, hydroxy acrylate feedstock production urethane false add to become reactant; Then through making false add become reactant and hydroxyl ion chainextender further to react, thereby prepare low viscous polyurethane prepolymer.
2. the preparation method of a kind of electrocuring low-viscosity polyurethane according to claim 1 is characterized in that described isocyanate trimerization body is a hexamethylene diisocyanate trimer.
3. the preparation method of a kind of electrocuring low-viscosity polyurethane according to claim 1; It is characterized in that described hydroxy acrylate comprises one or more in Hydroxyethyl acrylate, Rocryl 400, Rocryl 410, vinylformic acid hydroxy butyl ester, the Propylene glycol monoacrylate.
4. the preparation method of a kind of electrocuring low-viscosity polyurethane according to claim 1; It is characterized in that adopting isocyanate trimerization body, hydroxy acrylate feedstock production urethane false add to become reactant; Its preparation process is: in the exsiccant reaction kettle, add 1.0 moles the hexamethylene diisocyanate trimer and the catalyzer and the 0.0050-0.010 mole stopper of 0.0010-0.0015 mole; Stirring at room makes various raw material thorough mixing, and 2.0 moles hydroxy acrylates are added in the said mixture, and the control feed rate makes reactor temperature be controlled at 45-50 ℃; Behind reinforced the finishing; Reacted 4-5 hour, stopped reaction gets the urethane false add and becomes reactant.
5. the preparation method of a kind of electrocuring low-viscosity polyurethane according to claim 4 is characterized in that the mol ratio=1:2 of described hexamethylene diisocyanate trimer and hydroxy acrylate.
6. the preparation method of a kind of electrocuring low-viscosity polyurethane according to claim 1 is characterized in that through making false add become reactant and hydroxyl ion chainextender further to react, thus the preparation low-viscosity polyurethane prepolymers; Its preparation process is: in the exsiccant reaction kettle, add 1.0 moles the hydroxyl ion chainextender and the catalyzer and the 0.0050-0.010 mole stopper of 0.0010-0.0015 mole; Stirring at room makes various raw material thorough mixing, becomes reactant to add in the reaction kettle 1.0 moles urethane false adds, and the control feed rate makes reactor temperature be controlled at 45-50 ℃; Behind reinforced the finishing; The rising temperature of reaction kettle reacted 9-10 hour to 50-60 ℃, in reaction kettle, added the propyl carbinol of 0.10-0.15 mole; React after 0.5 hour; Stopped reaction is reduced to discharging after the room temperature with temperature of reaction kettle, promptly gets the low-viscosity polyurethane prepolymers product.
7. the preparation method of a kind of electrocuring low-viscosity polyurethane according to claim 6 is characterized in that, described urethane false add becomes the mol ratio=1:1 of reactant and hydroxyl ion chainextender.
8. the preparation method of a kind of electrocuring low-viscosity polyurethane according to claim 6 is characterized in that, described urethane false add becomes the mol ratio=1:0.10-0.15 of reactant and propyl carbinol.
9. according to the preparation method of claim 4,6 described a kind of electrocuring low-viscosity polyurethanes, it is characterized in that described catalyzer comprises one or more in stannous octoate, dibutyl tin laurate, the dibutyl tin dichloride.
10. according to the preparation method of claim 4,6 described a kind of electrocuring low-viscosity polyurethanes, it is characterized in that described stopper comprises Resorcinol, 4-methoxyl group phenol, 2, one or more in the 6-dinitro-p-cresol.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558499A (en) * | 2011-12-30 | 2012-07-11 | 南昌航空大学 | Preparation method of electron beam curing high hardness polyurethane |
| CN102952254A (en) * | 2012-10-30 | 2013-03-06 | 张厚远 | Synthetic method of low-viscosity electron beam curing resin |
| CN110028663A (en) * | 2019-04-29 | 2019-07-19 | 韶关方舟长顺有机硅有限公司 | A kind of composite curing polyurethane curing agent and its preparation process |
| CN110831995A (en) * | 2017-07-03 | 2020-02-21 | 喜利得股份公司 | Reactive resin comprising urethane methacrylate compound, reactive resin component and reactive resin system and use thereof |
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| EP0188324A2 (en) * | 1985-01-16 | 1986-07-23 | Morton International, Inc. | Magnetic coating comprising electron beam curable polyurethanes |
| CN1850876A (en) * | 2005-04-22 | 2006-10-25 | 比亚迪股份有限公司 | Method for preparing polyurethane acrylic resin |
| CN1854164A (en) * | 2005-04-29 | 2006-11-01 | 比亚迪股份有限公司 | Production of high-functionality polyurethane acrylic resin |
| EP2130846A1 (en) * | 2008-06-06 | 2009-12-09 | Cytec Surface Specialties, S.A. | Aqueous radiation curable polyurethane compositions |
| CN101792570A (en) * | 2010-02-10 | 2010-08-04 | 汤汉良 | Hydroxyl-containing crylic acid polyurethane aqueous dispersion body and application |
| CN102558499A (en) * | 2011-12-30 | 2012-07-11 | 南昌航空大学 | Preparation method of electron beam curing high hardness polyurethane |
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2011
- 2011-12-30 CN CN 201110450816 patent/CN102532476B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0188324A2 (en) * | 1985-01-16 | 1986-07-23 | Morton International, Inc. | Magnetic coating comprising electron beam curable polyurethanes |
| CN1850876A (en) * | 2005-04-22 | 2006-10-25 | 比亚迪股份有限公司 | Method for preparing polyurethane acrylic resin |
| CN1854164A (en) * | 2005-04-29 | 2006-11-01 | 比亚迪股份有限公司 | Production of high-functionality polyurethane acrylic resin |
| EP2130846A1 (en) * | 2008-06-06 | 2009-12-09 | Cytec Surface Specialties, S.A. | Aqueous radiation curable polyurethane compositions |
| CN101792570A (en) * | 2010-02-10 | 2010-08-04 | 汤汉良 | Hydroxyl-containing crylic acid polyurethane aqueous dispersion body and application |
| CN102558499A (en) * | 2011-12-30 | 2012-07-11 | 南昌航空大学 | Preparation method of electron beam curing high hardness polyurethane |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558499A (en) * | 2011-12-30 | 2012-07-11 | 南昌航空大学 | Preparation method of electron beam curing high hardness polyurethane |
| CN102952254A (en) * | 2012-10-30 | 2013-03-06 | 张厚远 | Synthetic method of low-viscosity electron beam curing resin |
| CN102952254B (en) * | 2012-10-30 | 2014-05-21 | 张厚远 | Synthetic method of low-viscosity electron beam curing resin |
| CN110831995A (en) * | 2017-07-03 | 2020-02-21 | 喜利得股份公司 | Reactive resin comprising urethane methacrylate compound, reactive resin component and reactive resin system and use thereof |
| CN110028663A (en) * | 2019-04-29 | 2019-07-19 | 韶关方舟长顺有机硅有限公司 | A kind of composite curing polyurethane curing agent and its preparation process |
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