CN102532476B - 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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- CN102532476B CN102532476B CN 201110450816 CN201110450816A CN102532476B CN 102532476 B CN102532476 B CN 102532476B CN 201110450816 CN201110450816 CN 201110450816 CN 201110450816 A CN201110450816 A CN 201110450816A CN 102532476 B CN102532476 B CN 102532476B
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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 low-viscosity polyurethane in electron beam curing, belong to technical field of polymer materials.
Background technology
In recent years, the electron beam curable coatings development is rapid, and industry and the field of application constantly enlarge.Electron beam curable coatings refers under the radiation effect of electron beam, and 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 character of resin prepolymer determines the physical property of paint solidification caudacoria, and 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 regulating the viscosity of high viscosity resins prepolymer, is the indispensable integral part of formulation for coating material system.But the reactive thinner monomer molecule mostly is organic low molecular substance, and their volatilization not only causes the pollution of environment, also skin is had strong impulse, 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 after electrocuring is good, has reduced the consumption of reactive thinner monomer molecule.
The invention provides a kind of preparation method of low-viscosity polyurethane in electron beam curing, the feature of the method is:
At first add the hexamethylene diisocyanate trimer of 1.0 moles and catalyzer and 0.0050-0.010 mole of stopper of 0.0010-0.0015 mole in the reactor of drying, the stirring at room certain hour fully mixes various raw materials.The hydroxy acrylates of 2.0 moles are added in said mixture, control feed rate and make reactor temperature be controlled at 45-50 ℃.After reinforced complete, reacted 4-5 hour, stopped reaction gets urethane half addition reactant; Then add the hydroxyl ion chainextender of 1.0 moles and catalyzer and 0.0050-0.010 mole of stopper of 0.0010-0.0015 mole in the reactor of another drying, the stirring at room certain hour fully mixes various raw materials.The urethane of 1.0 moles half addition reactant is added in reactor, control feed rate and make reactor temperature be controlled at 45-50 ℃.After reinforced complete, the rising temperature of reaction kettle reacted 9-10 hour to 50-60 ℃.The propyl carbinol that adds 0.10-0.15 mole in the reactor reacts after 0.5 hour stopped reaction.Temperature of reaction kettle is down to discharging after room temperature, namely gets 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, hydroxyethyl methylacrylate, Rocryl 410, vinylformic acid hydroxy butyl ester, Propylene glycol monoacrylate, preferred Hydroxyethyl acrylate and hydroxyethyl methylacrylate.
Further, described hydroxyl ion chainextender is that structural formula is according to disclosed documents and materials self-control:
Further, the mol ratio=1:1 of described urethane half addition reactant and hydroxyl ion chainextender.
Further, the mol ratio=1:0.10-0.15 of described urethane half addition reactant and propyl carbinol.
Further, described catalyzer comprises one or more in stannous octoate, dibutyl tin laurate, dibutyl tin dichloride, preferred dibutyl tin laurate.The consumption of catalyzer 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 open report, and the documents and materials of open report are: generation rushes, Zhang Shengmao etc., Pd Nanoparticles in Hydroxyl-functionalized Ionic Liquids preparation and structural characterization, 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 feature are described, example only be used for to be explained the present invention, is not be used to limiting scope of the present invention.
Embodiment 1:
Add 1000.0 gram hexamethylene diisocyanate trimers and 0.5 gram dibutyl tin laurate and 1.25 gram 4-methoxyl group phenol in the reactor of drying, stirring at room 1 hour is fully mixed various raw materials.331.8 gram Hydroxyethyl acrylates are added in said mixture, control feed rate and make reactor temperature be controlled at 45-50 ℃.After reinforced complete, control temperature and react at 45-50 ℃, by the variation of [NCO] in the examination of infrared spectrum system, when reaching theoretical value, stopped reaction in this approximately 4-5 consuming time hour step, gets urethane half addition reactant as [NCO].
Add 394.5 gram hydroxyl ion chainextenders and 0.5 gram dibutyl tin laurate and 2.0 gram 4-methoxyl group phenol in the reactor of another drying, stirring at room 1 hour is fully mixed various raw materials.Whole urethane half addition reactant of previous step preparation is added in reactor, control feed rate and make reactor temperature be controlled at 45-50 ℃.Reinforced complete after, the rising temperature of reaction kettle reacts to 50-60 ℃, by the variation of [NCO] in the examination of infrared spectrum system, as [NCO] when reaching theoretical value (this approximately 9-10 consuming time hour step), add 15.5 gram propyl carbinols in reactor, react after 0.5 hour stopped reaction.Temperature of reaction kettle is down to discharging after room temperature, namely gets the low-viscosity polyurethane prepolymers product.The product structure formula is:
Embodiment 2:
Add 1000.0 gram hexamethylene diisocyanate trimers and 0.5 gram dibutyl tin laurate and 1.3 gram 4-methoxyl group phenol in the reactor of drying, stirring at room 1 hour is fully mixed various raw materials.371.8 gram hydroxyethyl methylacrylates are added in said mixture, control feed rate and make reactor temperature be controlled at 45-50 ℃.After reinforced complete, control temperature and react at 45-50 ℃, by the variation of [NCO] in the examination of infrared spectrum system, when reaching theoretical value, stopped reaction in this approximately 4-5 consuming time hour step, gets urethane half addition reactant as [NCO].
Add 394.5 gram hydroxyl ion chainextenders and 0.5 gram dibutyl tin laurate and 2.0 gram 4-methoxyl group phenol in the reactor of another drying, stirring at room 1 hour is fully mixed various raw materials.Whole urethane half addition reactant of previous step preparation is added in reactor, control feed rate and make reactor temperature be controlled at 45-50 ℃.Reinforced complete after, the rising temperature of reaction kettle reacts to 50-60 ℃, by the variation of [NCO] in the examination of infrared spectrum system, as [NCO] when reaching theoretical value (this approximately 9-10 consuming time hour step), add 16.0 gram propyl carbinols in reactor, react after 0.5 hour stopped reaction.Temperature of reaction kettle is down to discharging after room temperature, namely gets the low-viscosity polyurethane prepolymers product.The product structure formula is:
Performance by following experimental test low-viscosity polyurethane prepolymers of the present invention.
Experimental example 1:
The low-viscosity polyurethane prepolymers of embodiment 1 preparation is coated on tinplate by line rod spreader, and 30 microns of coating thicknesss use under electrocuring instrument air atmosphere to be cured, and doses of electron beam radiation is the 110-120 kilogray (kGy).After solidifying, places coating layer its performance of test after 24 hours, the performance test results such as table 1.
Experimental example 2:
The low-viscosity polyurethane prepolymers of embodiment 2 preparations is coated on tinplate by line rod spreader, and 30 microns of coating thicknesss use under electrocuring instrument air atmosphere to be cured, and doses of electron beam radiation is the 110-120 kilogray (kGy).After solidifying, places coating layer 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 only preferred embodiment of the present invention, not in order to limit the present invention.
Claims (8)
1. the preparation method of a low-viscosity polyurethane in electron beam curing, is characterized in that, described preparation method comprises: at first adopt isocyanate trimerization body, hydroxy acrylate raw material to prepare urethane half addition reactant; Then by making half addition reactant and 1-(N-(1-chloro-2-hydroxypropyl) pyridine)-3-methyl chloride further react for imidazoles hydroxyl ion chainextender, thereby prepare low viscous polyurethane prepolymer.
2. the preparation method of a kind of low-viscosity polyurethane in electron beam curing according to claim 1, is characterized in that, described isocyanate trimerization body is hexamethylene diisocyanate trimer.
3. the preparation method of a kind of low-viscosity polyurethane in electron beam curing according to claim 1, it is characterized in that, described hydroxy acrylate comprises one or more in Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Rocryl 410, vinylformic acid hydroxy butyl ester, Propylene glycol monoacrylate.
4. the preparation method of a kind of low-viscosity polyurethane in electron beam curing according to claim 1, it is characterized in that adopting the isocyanate trimerization body, the hydroxy acrylate raw material prepares urethane half addition reactant, its preparation process is: the hexamethylene diisocyanate trimer and the catalyzer of 0.0010-0.0015 mole and the stopper of 0.0050-0.010 mole that add 1.0 moles in the reactor of drying, stirring at room is fully mixed various raw materials, the hydroxy acrylates of 2.0 moles are added in said mixture, controlling feed rate makes reactor temperature be controlled at 45-50 ℃, after reinforced complete, reacted 4-5 hour, stopped reaction, get urethane half addition reactant,
Wherein, described catalyzer comprises one or more in stannous octoate, dibutyl tin laurate, dibutyl tin dichloride; Described stopper comprises Resorcinol, 4-methoxyl group phenol, 2, one or more in the 6-dinitro-p-cresol.
5. the preparation method of a kind of low-viscosity polyurethane in electron beam curing 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 low-viscosity polyurethane in electron beam curing according to claim 1, it is characterized in that by half addition reactant and 1-(N-(1-chloro-2-hydroxypropyl) pyridine)-3-methyl chloride is further reacted for imidazoles hydroxyl ion chainextender, thereby preparation low-viscosity polyurethane prepolymers, its preparation process is: add the 1-(N-(1-chloro-2-hydroxypropyl) pyridine)-3-methyl chloride of 1.0 moles for imidazoles hydroxyl ion chainextender and the catalyzer of 0.0010-0.0015 mole and the stopper of 0.0050-0.010 mole in the reactor of drying, stirring at room is fully mixed various raw materials, the urethane of 1.0 moles half addition reactant is added in reactor, controlling feed rate makes reactor temperature be controlled at 45-50 ℃, after reinforced complete, the rising temperature of reaction kettle is to 50-60 ℃, reacted 9-10 hour, the propyl carbinol that adds 0.10-0.15 mole in the reactor, react after 0.5 hour, stopped reaction, temperature of reaction kettle is down to discharging after room temperature, namely get the low-viscosity polyurethane prepolymers product,
Wherein, described catalyzer comprises one or more in stannous octoate, dibutyl tin laurate, dibutyl tin dichloride; Described stopper comprises Resorcinol, 4-methoxyl group phenol, 2, one or more in the 6-dinitro-p-cresol.
7. the preparation method of a kind of low-viscosity polyurethane in electron beam curing according to claim 6, it is characterized in that, described urethane half addition reactant and 1-(N-(1-chloro-2-hydroxypropyl) pyridine)-3-methyl chloride is for the mol ratio=1:1 of imidazoles hydroxyl ion chainextender.
8. the preparation method of a kind of low-viscosity polyurethane in electron beam curing according to claim 6, is characterized in that, the mol ratio=1:0.1-0.15 of described urethane half addition reactant and propyl carbinol.
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| CN102558499B (en) * | 2011-12-30 | 2013-10-23 | 南昌航空大学 | Preparation method of electron beam curing high hardness polyurethane |
| CN102952254B (en) * | 2012-10-30 | 2014-05-21 | 张厚远 | Synthetic method of low-viscosity electron beam curing resin |
| EP3424971A1 (en) * | 2017-07-03 | 2019-01-09 | HILTI Aktiengesellschaft | Urethane methacrylate compounds containing reactive resins, and reactive resin systems and their use |
| 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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| US4695604A (en) * | 1985-01-16 | 1987-09-22 | Morton Thiokol, Inc. | Electron beam curable polyuethane polymers for magnetic tape applications |
| CN100487014C (en) * | 2005-04-22 | 2009-05-13 | 比亚迪股份有限公司 | Method for preparing polyurethane acrylic resin |
| CN100532417C (en) * | 2005-04-29 | 2009-08-26 | 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 |
| CN101792570B (en) * | 2010-02-10 | 2011-10-12 | 汤汉良 | Hydroxyl-containing crylic acid polyurethane aqueous dispersion body and application |
| CN102558499B (en) * | 2011-12-30 | 2013-10-23 | 南昌航空大学 | Preparation method of electron beam curing high hardness polyurethane |
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