CN103694890B - A kind of preparation method through epoxy silicones modification laccol photocuring film - Google Patents
A kind of preparation method through epoxy silicones modification laccol photocuring film Download PDFInfo
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- CN103694890B CN103694890B CN201310715388.9A CN201310715388A CN103694890B CN 103694890 B CN103694890 B CN 103694890B CN 201310715388 A CN201310715388 A CN 201310715388A CN 103694890 B CN103694890 B CN 103694890B
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Abstract
The present invention relates to a kind of preparation method through epoxy silicones modification laccol photocuring film, it is characterized in that: laccol and dimethylbenzene are pre-mixed into mixed solution, after dewatering, add epoxy silicones, isothermal reaction, obtains epoxy silicones modification laccol prepolymer mixed solution; The epoxy silicones modification laccol mixed solution of preparation is coated on clean sheet glass or on the tinplate sheet of sand papering, after ultraviolet light irradiation, obtains through epoxy silicones modification laccol photocuring film.The present invention has: 1. laccol is natural reproducible resource, and raw material sources are wide, cheap; 2. can prepare epoxy silicones modification laccol photocuring film fast; 3. adopt the preparation-obtained resistance toheat through epoxy silicones modification laccol photocuring coating with excellent adhesive attraction, flexility, shock resistance, chemical mediator-resitant property and excellence of the technology of the present invention, can be applicable to high-performance coating field.
Description
Technical field
The present invention relates to a kind of preparation method of photocuring film, particularly relate to a kind of preparation method through epoxy silicones modification laccol photocuring film, belong to high-performance chemical industry paint field.
Background technology
Since 21 century, the photocuring industry of China is developed fast, and China develops into gradually after the U.S., Japan, global the third-largest UV solidifying product production area.UV is coating material solidified is a kind of efficient, energy-conservation environment-friendly type coating, high comprehensive performance, has that curing speed is fast, solidification value is low, energy expenditure is low, pollute the advantages such as little, has wide range of applications, and is progressively replacing traditional coating material solidified.And epoxy organosilicon material has excellent chemical stability, bond performance, electrical insulation properties, high and low temperature resistance, mechanical property etc.And China is in the use of natural raw lacquer, have long history, the excellent properties such as its paint film produced has hard, heat-resisting, corrosion-resistant.The main film forming substance of raw lacquer is laccol---be the catechol derivatives with long side carbochain.But through the raw lacquer film of laccase oxypolymerization gained, its set time is long, and by the restriction of temperature, humidity etc. during solidification.Urushiol organic silicon polymkeric substance has concentrated the feature of silicone resin and laccol, has excellent performance.But the current disclosed Urushiol organic silicon polymkeric substance prepared by technology such as transesterifys, although these technology can obtain the Urushiol organic silicon polymkeric substance with excellent properties, its length consuming time, thus its energy consumption will increase, when this just makes to be applicable to suitability for industrialized production, it has high in cost of production shortcoming.
The present invention, under ultraviolet light irradiation, substantially reduces the polymerization time preparing epoxy silicones modification laccol photocuring film, has that solidification rate is fast, an advantage such as environmental protection, energy consumption are low, excellent performance.
Summary of the invention
The object of the invention is to according to the deficiencies in the prior art, provide a kind of and prepare the preparation method through epoxy silicones modification laccol photocuring film that speed is fast, technique simple, production cost is lower.
Object of the present invention can be reached by following measures:
1. dewater
Be equipped with in the there-necked flask of the cleaning of water trap one and add laccol and dimethylbenzene, be pre-mixed into mixed solution, be warming up to 138 DEG C, constant temperature dewaters 30 minutes.Wherein the consumption of laccol and dimethylbenzene by weight, and its ratio is: laccol: dimethylbenzene is 4
:2 ~ 15;
2. prepolymerization
Take off the there-necked flask water trap in step (1), after being cooled to 90 DEG C, in mixed solution, add epoxy silicones, keep temperature 90 ~ 140 DEG C, react 0.5 ~ 3 hour, obtain epoxy silicones modification laccol prepolymer mixed solution.Wherein epoxy silicones is 2 by cycloalkyl groups and the molar weight ratio of laccol
:1 ~ 16;
3. photocuring
The epoxy silicones modification laccol prepolymer mixed solution of preparation is coated on clean sheet glass or on the tinplate sheet of sand papering, irradiation is after 30 ~ 180 seconds under ultraviolet light, obtains epoxy silicones modification laccol photocuring film.Wherein photocuring thickness is 10 ~ 40 μm; Ultraviolet lamp predominant wavelength is 365nm, and light intensity is 103mW/cm
2, radiation length is 10cm.
Described epoxy silicones has the molecular weight of 200 to 2000, can be the mixture of a kind of or above-mentioned epoxy silicones arbitrary proportion in epoxy silane coupling, epoxy silicones oxygen alkane quaternary amine, modifying epoxy resin by organosilicon; Wherein preferred γ-glycidyl ether oxygen propyl trimethoxy silicane (KH560).
Described epoxy silane coupling refers to γ-glycidyl ether oxygen propyl trimethoxy silicane (KH560), γ-glycidyl ether oxygen propyl methyldiethoxysilane (Wetlink78) or β (3,4-epoxycyclohexyl) ethyl triethoxysilane (Wetlink78).
Described epoxy silicones oxygen alkane quaternary amine refers to diethyl-2,3-epoxypropyl-[3-(methyl dimethoxy oxygen base)] silicon propyl ammonium chloride, and it has following structural formula:
Described modifying epoxy resin by organosilicon refers to vinyltriethoxysilane modified epoxy vinylformic acid or vinyltriethoxysilane modified phenolic propylene oxide ester.
The present invention has the following advantages:
1. laccol is natural reproducible resource, and raw material sources are wide, cheap.
2. can prepare epoxy silicones modification laccol photocuring film fast.
3. adopt the preparation-obtained resistance toheat through epoxy silicones modification laccol photocuring coating with excellent adhesive attraction, flexility, shock resistance, chemical mediator-resitant property and excellence of the technology of the present invention.
In the present invention, the Apparatus and method for characterizing epoxy silicones modification laccol photocuring film is as follows:
The preparation of film
By GB/T1727-1992 " the general preparation method of film ", the laccol of preparation/epoxy silicones complex liquid is coated on clean sheet glass or on the tinplate sheet of sand papering, thickness: about 40 μm.Sample is placed in irradiation (GY.UV2KW/ II (s) type ultraviolet light polymerization instrument, Baoding special source electrical apparatus factory) under the high voltage mercury lamp of 365nm and 2kW, light intensity: 103mW/cm
2(UV-A light intensity meter, photoelectric instrument factory of Beijing Normal University).Radiation length: 10cm, experiment is carried out in atmosphere.
Typical physical mechanical property
Be coated on uniformly by the sample of preparation on tinplate sheet, the Typical physical mechanical property of cured film adopts following GB to test respectively.Hardness is pressed GB/T6739-1996 and is adopted pencil method to measure; Sticking power adopts QFZ-I type to smear adherometer test by GB1720-79; Snappiness is pressed GB/T1731-93 and is adopted the pliable and tough tester test of JGI type; Impact resistance is pressed GB/T1732-93 and is adopted the test of QCJ type film knocker.
Solvent resistant performance
Various sample is after ultraviolet radiation certain hour, and difference assay is got film and to be weighed (m
1g), in dehydrated alcohol, sherwood oil, dimethylbenzene, toluene, butylacetate and acetone, soak 48h respectively, weigh after drying (m
2g), with (m
2/ m
1) × 100% weighs the solvent resistant performance of film.
Chemical resistance reagent performance
By various sample respectively at tap water, 10%H
2sO
4, 30%H
2sO
4, soak 7 days in 10%NaOH, 30%NaOH, 10%NaCl.
Thermogravimetric analysis adopts the infrared thermogravimetric combined instrument of METTTLERTGALSDTA851, and nitrogen atmosphere, heat-up rate is 10
oc/min, temperature range: room temperature ~ 600
oc.
Infrared employing NICOLET5700FT-IR spectrophotometer (ATR method).
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of γ-glycidyl ether oxygen propyl trimethoxy silicane modification laccol photocuring film prepared by the present embodiment.
Fig. 2 is the thermogravimetric spectrogram of γ-glycidyl ether oxygen propyl trimethoxy silicane modification laccol photocuring film prepared by the present embodiment.
Embodiment
The present invention is described further below in conjunction with preferred embodiment, but scope of the present invention is not limited to the scope of the present embodiment.
Embodiment 1
In a there-necked flask, add 4.0 grams of laccols and 6.0 grams of dimethylbenzene, be pre-mixed into mixed solution, be warming up to 138 DEG C, constant temperature dewaters 30 minutes.
After mixed solution being cooled to 90 DEG C, add 5.8 grams of γ-glycidyl ether oxygen propyl trimethoxy silicanes (KH560), keep temperature 90 degree, react 3 hours, obtain γ-glycidyl ether oxygen propyl trimethoxy silicane modification laccol prepolymer mixed solution.
γ-glycidyl ether oxygen propyl trimethoxy silicane modification laccol prepolymer mixed solution is coated on clean sheet glass or on the tinplate sheet of sand papering, irradiation is after 30 seconds under ultraviolet light, obtains γ-glycidyl ether oxygen propyl trimethoxy silicane modification laccol photocuring film.
The γ prepared-glycidyl ether oxygen propyl trimethoxy silicane modification laccol photocuring film is carried out examination of infrared spectrum analysis, and its result as shown in Figure 1; Carry out thermogravimetric analysis, its result as shown in Figure 2.
The γ that the present embodiment prepares-glycidyl ether oxygen propyl trimethoxy silicane modification laccol photocuring film properties test result is as follows:
Pencil hardness: 4H
Sticking power: 1 grade
Snappiness: 0.5mm
Shock resistance: 50cm
Solvent resistant performance: pass through
Chemical resistance reagent performance: pass through
Embodiment 2
In a there-necked flask, add 5.8 grams of laccols and 6.0 grams of dimethylbenzene, be pre-mixed into mixed solution, be warming up to 138 DEG C, constant temperature dewaters 30 minutes.
After mixed solution being cooled to 100 DEG C, add 4.1 grams of γ-glycidyl ether oxygen propyl methyldiethoxysilane, keep temperature 100 DEG C degree, react 2 hours, obtain γ-glycidyl ether oxygen propyl methyldiethoxysilane modification laccol prepolymer mixed solution.
γ-glycidyl ether oxygen propyl methyldiethoxysilane modification laccol prepolymer mixed solution is coated on clean sheet glass or on the tinplate sheet of sand papering, irradiation is after 60 seconds under ultraviolet light, obtains γ-glycidyl ether oxygen propyl methyldiethoxysilane modification laccol photocuring film.
The γ that the present embodiment prepares-glycidyl ether oxygen propyl methyldiethoxysilane modification laccol photocuring film properties test result is as follows:
Pencil hardness: 5H
Sticking power: 1 grade
Snappiness: 0.5mm
Shock resistance: 50cm
Solvent resistant performance: pass through
Chemical resistance reagent performance: pass through
Embodiment 3
In a there-necked flask, add 7.4 grams of laccols and 6.0 grams of dimethylbenzene, be pre-mixed into mixed solution, be warming up to 138 DEG C, constant temperature dewaters 30 minutes.
After mixed solution being cooled to 110 DEG C, add 0.9 gram of β (3,4-epoxycyclohexyl) ethyl triethoxysilane, keep temperature 110 degree, react 1.5 hours, obtain β (3,4-epoxycyclohexyl) ethyl triethoxysilane modification laccol prepolymer mixed solution.
By β (3,4-epoxycyclohexyl) ethyl triethoxysilane modification laccol prepolymer mixed solution is coated on clean sheet glass or on the tinplate sheet of sand papering, irradiation is after 90 seconds under ultraviolet light, obtain β (3,4-epoxycyclohexyl) ethyl triethoxysilane modification laccol photocuring film.
β (3,4-epoxycyclohexyl) the ethyl triethoxysilane modification laccol photocuring film properties test result that the present embodiment prepares is as follows:
Pencil hardness: 6H
Sticking power: 1 grade
Snappiness: 0.5mm
Shock resistance: 50cm
Solvent resistant performance: pass through
Chemical resistance reagent performance: pass through
Embodiment 4
In a there-necked flask, add 8.5 grams of laccols and 6.0 grams of dimethylbenzene, be pre-mixed into mixed solution, be warming up to 138 degree, constant temperature dewaters 30 minutes.
After mixed solution being cooled to 120 degree, add 2.5 grams of β (3,4-epoxycyclohexyl) ethyl triethoxysilane and 1.0 grams of diethyl-2,3-epoxypropyl-[3-(methyl dimethoxy oxygen base)] silicon propyl ammonium chloride maintenance temperature 120 degree, react 1 hour, acquisition β (3,4-epoxycyclohexyl) ethyl triethoxysilane-diethyl-2,3-epoxypropyl-[3-(methyl dimethoxy oxygen base)] silicon propyl ammonium chloride modification laccol prepolymer mixed solution.
By β (3,4-epoxycyclohexyl) ethyl triethoxysilane-diethyl-2,3-epoxypropyl-[3-(methyl dimethoxy oxygen base)] silicon propyl ammonium chloride modification laccol prepolymer mixed solution is coated on clean sheet glass or on the tinplate sheet of sand papering, irradiation is after 120 seconds under ultraviolet light, obtain β (3,4-epoxycyclohexyl) ethyl triethoxysilane-diethyl-2,3-epoxypropyl-[3-(methyl dimethoxy oxygen base)] silicon propyl ammonium chloride modification laccol photocuring film.
β (3,4-epoxycyclohexyl) ethyl triethoxysilane-diethyl-2,3-epoxypropyl that the present embodiment prepares-[3-(methyl dimethoxy oxygen base)] silicon propyl ammonium chloride modification laccol photocuring film properties test result is as follows:
Pencil hardness: 6H
Sticking power: 1 grade
Snappiness: 0.5mm
Shock resistance: 50cm
Solvent resistant performance: pass through
Chemical resistance reagent performance: pass through
Embodiment 5
In a there-necked flask, add 9.2 grams of laccols and 6.0 grams of dimethylbenzene, be pre-mixed into mixed solution, be warming up to 138 DEG C, constant temperature dewaters 30 minutes.
0.8 gram of γ-glycidyl ether oxygen propyl trimethoxy silicane (KH560), 1.0 grams of γ-glycidyl ether oxygen propyl methyldiethoxysilane and 0.8 gram of vinyltriethoxysilane modified phenolic propylene oxide ester is added at mixed solution, keep temperature 138 DEG C, react 0.5 hour, obtain three kinds of epoxy silicones common modification laccol prepolymer mixed solutions.
Common modification laccol prepolymer mixed solution is coated on clean sheet glass or on the tinplate sheet of sand papering, irradiation is after 180 seconds under ultraviolet light, obtains modification laccol photocuring film.
The modification laccol photocuring film properties test result that the present embodiment prepares is as follows:
Pencil hardness: 6H
Sticking power: 1 grade
Snappiness: 0.5mm
Shock resistance: 50cm
Solvent resistant performance: pass through
Chemical resistance reagent performance: pass through.
Claims (1)
1. through a preparation method for epoxy silicones modification laccol photocuring film,
1) dewater
Be equipped with in the there-necked flask of the cleaning of water trap one and add laccol and dimethylbenzene, be pre-mixed into mixed solution, be warming up to 138 DEG C, constant temperature dewaters 30 minutes;
2) prepolymerization
Take off the there-necked flask water trap in step 1), after being cooled to 90 DEG C, in mixed solution, add epoxy silicones, keep temperature 90 ~ 140 DEG C, react 0.5 ~ 3 hour, obtain epoxy silicones modification laccol prepolymer mixed solution;
3) photocuring
The epoxy silicones modification laccol prepolymer mixed solution of preparation is coated on clean sheet glass or on the tinplate sheet of sand papering, irradiation is after 30 ~ 180 seconds under ultraviolet light, obtains epoxy silicones modification laccol photocuring film, it is characterized in that:
Described epoxy silicones add-on is that 2 ︰ 1 ~ 16 add by cycloalkyl groups and the molar weight ratio of laccol;
Described epoxy silicones has the molecular weight of 200 to 2000;
Described epoxy silicones specifically refers to the mixture of a kind of or above-mentioned epoxy silicones arbitrary proportion in epoxy silane coupling, epoxy silicones oxygen alkane quaternary amine, modifying epoxy resin by organosilicon;
Described epoxy silane coupling refers to γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-glycidyl ether oxygen propyl methyldiethoxysilane or β (3,4-epoxycyclohexyl) ethyl triethoxysilane;
Described epoxy silicones oxygen alkane quaternary amine refers to diethyl-2,3-epoxypropyl-[3-(methyl dimethoxy oxygen base)] silicon propyl ammonium chloride;
Described modifying epoxy resin by organosilicon refers to vinyltriethoxysilane modified epoxy vinylformic acid or vinyltriethoxysilane modified phenolic propylene oxide ester.
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| CN104761994B (en) * | 2015-04-10 | 2016-11-23 | 南昌航空大学 | A kind of preparation method of photo-curable silicone modified epoxy paint film |
| CN107345087B (en) * | 2016-05-05 | 2019-07-05 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method of laccol propenyl ether photocuring film |
| CN106366921A (en) * | 2016-08-26 | 2017-02-01 | 太仓市美航涂料有限公司 | High-performance ultraviolet curing coating and coating curing process thereof |
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| CN1560155A (en) * | 2004-02-18 | 2005-01-05 | 大庆油田创业金属防腐有限公司 | Nano anticorrosion coat of silicon phenolate paint and preparation process thereof |
| CN1648187A (en) * | 2004-12-31 | 2005-08-03 | 福建师范大学 | Process for preparing urushiol formaldehyde condensation polymer/montmorillonite nano composite paint |
Non-Patent Citations (1)
| Title |
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