CN104726019A - Isocyanate modified organic silicon resin composition and preparation method and application thereof - Google Patents
Isocyanate modified organic silicon resin composition and preparation method and application thereof Download PDFInfo
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- CN104726019A CN104726019A CN201510164274.9A CN201510164274A CN104726019A CN 104726019 A CN104726019 A CN 104726019A CN 201510164274 A CN201510164274 A CN 201510164274A CN 104726019 A CN104726019 A CN 104726019A
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- polyisocyanates
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- isocyanate
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Abstract
The invention discloses isocyanate modified organic silicon resin composition and a preparation method and application thereof. The obtained isocyanate modified organic silicon resin composition contains more than 60% of solids and is used for hardening and resisting scratches of the surface of optical plastics, and surface hardness and scratch resistance of the optical plastics are improved.
Description
Technical field
The invention belongs to field of material preparation, be specifically related to a kind of isocyanate-modified organosilicon resin composition and its preparation method and application.
Background technology
Optical plastics have density little, be easy to the advantages such as forming process, but hardness is low, easily scratches, and be greatly limit use range.In optical plastics surface-coated one deck stiffened scratch resistance coating, can effectively address this problem.Between 20-40%, there is a large amount of solvents in the general solid content of current use stiffened scratch resistance silicone resin coating material, gives transport and use to bring very large inconvenience, and in use, also bring the pollution of safety factor and VOC.
Summary of the invention
The object of the present invention is to provide a kind of isocyanate-modified organosilicon resin composition and its preparation method and application, the solid content of obtained isocyanate-modified organosilicon resin composition is more than 60%, for the stiffened scratch resistance process on optical plastics surface, surface hardness and the adhesion strength of optical plastics significantly can be improved.
For achieving the above object, the present invention adopts following technical scheme:
A kind of solid content of isocyanate-modified organosilicon resin composition is more than 60%.
Preparation method comprises the following steps:
(1) polyisocyanates, monohydroxy polyprotonic acid, the material being used for blocked isocyanate functional group, toluene and catalysts are mixed, react more than 5 hours at 100-110 DEG C, detect without NCO absorption peak to infrared spectrum;
(2) 25-30 DEG C is cooled to, add siloxanyl monomers, phase-transfer catalyst and deionized water, 2-36 hour is reacted at 5-50 DEG C, underpressure distillation at 55-60 DEG C, sampling is when to test solid content at 180 DEG C be more than 60%, stop underpressure distillation, add urethane cures catalyzer and flow agent, stirring and evenly mixing.
Monohydroxy polyprotonic acid, be 40-55:50-65:100 for the material of blocked isocyanate functional group and the mol ratio of NCO functional group, the weight ratio of toluene, catalysts and polyisocyanates is 10-20:0.001-0.01:1; The weight ratio of siloxanyl monomers, phase-transfer catalyst and polyisocyanates is 1:0.005-0.05:0.125-0.25, the mol ratio of siloxanyl monomers and deionized water is 1:3-8, and the weight ratio of urethane cures catalyzer, flow agent and polyisocyanates is 0.01-5:0.1-1:100.
Described polyisocyanates is vulcabond or triisocyanate, or by polyisocyanates that the isocyanate groups of vulcabond, triisocyanate itself is obtained by reacting; Described monohydroxy polyprotonic acid is the organism containing at least 2 hydroxy-acid groups and an oh group in molecular formula, and total carbon number that contains is less than 10.
The described material for blocked isocyanate functional group, for can react with NCO, makes it at room temperature not have reactive behavior, when being heated to 70-150 DEG C, reversible reaction occurring, makes NCO again have the material of reactive behavior.
Described catalysts is zinc class, tin class or bismuth class catalyzer.
The molecular formula of described siloxanyl monomers is (R
0)
x-Si (OR
1)
(4-X), X=0,1,2,3, R
0for methyl, ethyl, containing epoxy group(ing), containing thiazolinyl, containing acryloxy, containing the one in sulfydryl, amido, R
1for methyl, ethyl or propyl group.
Described phase-transfer catalyst is the one in benzyltriethylammoinium chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride.
Described urethane cures catalyzer is the one in triethylene diamine, N, N-dimethylcyclohexylamine, dimethyl benzylamine, N, N'-lupetazin, open-chain crown ether, 2,4,6-tri-(dimethylamino methyl) phenol; Described flow agent is silicone based or acrylic acid or the like flow agent.
Described isocyanate-modified organosilicon resin composition is used for the stiffened scratch resistance process on optical plastics surface.
Remarkable advantage of the present invention is: the solid content of obtained isocyanate-modified organosilicon resin composition, more than 60%, for the stiffened scratch resistance process on optical plastics surface, significantly can improve surface hardness and the adhesion strength of optical plastics.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of embodiment 1.
Embodiment
A kind of solid content of isocyanate-modified organosilicon resin composition is more than 60%.
Preparation method comprises the following steps:
(1) polyisocyanates, monohydroxy polyprotonic acid, the material being used for blocked isocyanate functional group, toluene and catalysts are mixed, react more than 5 hours at 100-110 DEG C, detect without NCO absorption peak to infrared spectrum;
(2) 25-30 DEG C is cooled to, add siloxanyl monomers, phase-transfer catalyst and deionized water, 2-36 hour is reacted at 5-50 DEG C, underpressure distillation at 55-60 DEG C, sampling is when to test solid content at 180 DEG C be more than 60%, stop underpressure distillation, add urethane cures catalyzer and flow agent, stirring and evenly mixing.
Monohydroxy polyprotonic acid, be 40-55:50-65:100 for the material of blocked isocyanate functional group and the mol ratio of NCO functional group, the weight ratio of toluene, catalysts and polyisocyanates is 10-20:0.001-0.01:1; The weight ratio of siloxanyl monomers, phase-transfer catalyst and polyisocyanates is 1:0.005-0.05:0.125-0.25, the mol ratio of siloxanyl monomers and deionized water is 1:3-8, and the weight ratio of urethane cures catalyzer, flow agent and polyisocyanates is 0.01-5:0.1-1:100.
Described polyisocyanates is vulcabond or triisocyanate, as butane diisocyanate, pentane diisocyanate, hexane diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethanediisocyanate, triphenylmethane triisocyanate etc., or pass through vulcabond, the polyisocyanates that the isocyanate groups of triisocyanate itself is obtained by reacting, as carbodiimide compound, isocyanurate compound etc., common commercial goods is as Bayer Bitterfeld GmbH Desmodur N75, N3390, Mitsui chemical curing agent M-432T, D-208T, the trimer curing agent HXR of NPU company of Japan.
Described monohydroxy polyprotonic acid is the organism containing at least 2 hydroxy-acid groups and an oh group in molecular formula, and total carbon number that contains is less than 10, as tartronic acid, hydroxy-butanedioic acid, hydroxyl pentanedioic acid, Hydroxy M Phthalic Acid, citric acid etc.
The described material for blocked isocyanate functional group is for can react with NCO, it is made at room temperature not have reactive behavior, when being heated to 70-150 DEG C, there is reversible reaction, make NCO again have the material of reactive behavior, comprise phenols, lactams, oximes, beta-dicarbonyl compound, imidazoles, pyrazoles etc., as Resorcinol, ε-caprolactam, Diacetylmonoxime, diethyl malonate, 1,2,4-triazole, 3，5-dimethylpyrazole etc.
Described catalysts is zinc class, tin class or bismuth class catalyzer, as zinc acetylacetonate, tetramethyl-pimelic acid zinc, zinc salicylate, dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, 2 ethyl hexanoic acid bismuth, bismuth acetate etc., preferred bismuth class and zinc class catalyzer.
The molecular formula of described siloxanyl monomers is (R
0)
x-Si (OR
1)
(4-X), X=0,1,2,3, R
0for methyl, ethyl, containing epoxy group(ing), containing thiazolinyl, containing acryloxy, containing the one in sulfydryl, amido, R
1for methyl, ethyl or propyl group.
Described phase-transfer catalyst is the one in benzyltriethylammoinium chloride (TEBA), Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate (TBAB), tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride.
Described urethane cures catalyzer is the one in triethylene diamine, N, N-dimethylcyclohexylamine, dimethyl benzylamine, N, N'-lupetazin, open-chain crown ether, 2,4,6-tri-(dimethylamino methyl) phenol.
Described flow agent is silicone based or acrylic acid or the like flow agent, as German Bi Ke chemistry BYK 330, BYK358, and enlightening height glide 450, glide 410 etc.
Described isocyanate-modified organosilicon resin composition is used for the stiffened scratch resistance process on optical plastics surface.
Embodiment 1:
Get the Bayer Bitterfeld GmbH N3390(NCO% ≈ 19.6% of 100g) polyisocyanates, the oxysuccinic acid (hydroxy-butanedioic acid) of 25g, the Diacetylmonoxime of 24.5g, 1500g toluene and 0.2g bismuth acetate, after stirring, start to be heated to 105 DEG C, continue reaction 5 hours, infrared spectrum detection is carried out in sampling, as found out at 2270cm in Fig. 1, figure
-1neighbouring NCO absorption peak disappears.When being cooled to 25 DEG C, add Union carbide A-162 500g, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane 50g, 4-butyl ammonium hydrogen sulfate 5g and deionized water 300g, stir lower maintenance liquid temperature to react 24 hours at 25 DEG C, underpressure distillation afterwards, liquid temperature remains on 50 DEG C, and in still, absolute pressure is 100kPa.After 8 hours, sample thief dries 1 hour in 180 DEG C of baking ovens, and test solid content, as table 1, solid content is 66%.Stop underpressure distillation, add 1g open-chain crown ether and 0.5g BYK358 flow agent, continue stirring 20 minutes, be designated as A liquid.
In envrionment temperature 20 DEG C, humidity 55% time, on polycarbonate (PC) sheet material, apply prepared A liquid, after top coat levelling, put into baking box, toast 3 hours at 120 DEG C.Carry out Performance Detection after taking out cooling, as shown in table 2 contrasts, the obtained isocyanate-modified organosilicon resin composition of high solids content significantly improves surface hardness and the adhesion strength of PC.
Table 1 solid content test result
PC performance comparison before and after table 2 stiffened
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (10)
1. an isocyanate-modified organosilicon resin composition, is characterized in that: solid content is more than 60%.
2. prepare a method for isocyanate-modified organosilicon resin composition as claimed in claim 1, it is characterized in that: comprise the following steps:
Polyisocyanates, monohydroxy polyprotonic acid, the material being used for blocked isocyanate functional group, toluene and catalysts are mixed, reacts more than 5 hours at 100-110 DEG C, detect without NCO absorption peak to infrared spectrum;
Be cooled to 25-30 DEG C, add siloxanyl monomers, phase-transfer catalyst and deionized water, 2-36 hour is reacted at 5-50 DEG C, underpressure distillation at 55-60 DEG C, sampling is when to test solid content at 180 DEG C be more than 60%, stop underpressure distillation, add urethane cures catalyzer and flow agent, stirring and evenly mixing.
3. method according to claim 2, it is characterized in that: monohydroxy polyprotonic acid, be 40-55:50-65:100 for the material of blocked isocyanate functional group and the mol ratio of NCO functional group, the weight ratio of toluene, catalysts and polyisocyanates is 10-20:0.001-0.01:1; The weight ratio of siloxanyl monomers, phase-transfer catalyst and polyisocyanates is 1:0.005-0.05:0.125-0.25, the mol ratio of siloxanyl monomers and deionized water is 1:3-8, and the weight ratio of urethane cures catalyzer, flow agent and polyisocyanates is 0.01-5:0.1-1:100.
4. method according to claim 2, is characterized in that: described polyisocyanates is vulcabond or triisocyanate, or by polyisocyanates that the isocyanate groups of vulcabond, triisocyanate itself is obtained by reacting; Described monohydroxy polyprotonic acid is the organism containing at least 2 hydroxy-acid groups and an oh group in molecular formula, and total carbon number that contains is less than 10.
5. method according to claim 2, it is characterized in that: the described material for blocked isocyanate functional group, for can react with NCO, makes it at room temperature not have reactive behavior, when being heated to 70-150 DEG C, there is reversible reaction, make NCO again have the material of reactive behavior.
6. method according to claim 2, is characterized in that: described catalysts is zinc class, tin class or bismuth class catalyzer.
7. method according to claim 2, is characterized in that: the molecular formula of described siloxanyl monomers is (R
0)
x-Si (OR
1)
(4-X), X=0,1,2,3, R
0for methyl, ethyl, containing epoxy group(ing), containing thiazolinyl, containing acryloxy, containing the one in sulfydryl, amido, R
1for methyl, ethyl or propyl group.
8. method according to claim 2, is characterized in that: described phase-transfer catalyst is the one in benzyltriethylammoinium chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride.
9. method according to claim 2, it is characterized in that: described urethane cures catalyzer is triethylene diamine, N, N-dimethylcyclohexylamine, dimethyl benzylamine, N, N'-lupetazin, open-chain crown ether, 2, one in 4,6-tri-(dimethylamino methyl) phenol; Described flow agent is silicone based or acrylic acid or the like flow agent.
10. an application for isocyanate-modified organosilicon resin composition as claimed in claim 1, is characterized in that: described isocyanate-modified organosilicon resin composition is used for the stiffened scratch resistance process on optical plastics surface.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6610777B1 (en) * | 1999-07-30 | 2003-08-26 | Ppg Industries Ohio, Inc. | Flexible coating compositions having improved scratch resistance, coated substrates and methods related thereto |
| CN101679598A (en) * | 2007-04-27 | 2010-03-24 | 纳米X有限公司 | Method for the production of a coating material |
| CN102070987A (en) * | 2009-11-23 | 2011-05-25 | 比亚迪股份有限公司 | Coating and optical element |
| CN104231914A (en) * | 2014-09-16 | 2014-12-24 | 上海应用技术学院 | Optical plastic protection coating and preparation method thereof |
-
2015
- 2015-04-09 CN CN201510164274.9A patent/CN104726019B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6610777B1 (en) * | 1999-07-30 | 2003-08-26 | Ppg Industries Ohio, Inc. | Flexible coating compositions having improved scratch resistance, coated substrates and methods related thereto |
| CN101679598A (en) * | 2007-04-27 | 2010-03-24 | 纳米X有限公司 | Method for the production of a coating material |
| CN102070987A (en) * | 2009-11-23 | 2011-05-25 | 比亚迪股份有限公司 | Coating and optical element |
| CN104231914A (en) * | 2014-09-16 | 2014-12-24 | 上海应用技术学院 | Optical plastic protection coating and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| WANG HUEI-HSIUNG ET AL: "Silicon-containing anionic water-borne polyurethane with covalently bonded reactive dye", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
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Effective date of registration: 20180628 Address after: 361023 Room 102, Zhang Zhuang village, Ding Xu village, Jimei District, Xiamen, Fujian, China. 27 Patentee after: Xiamen Zhuo Yao Technology Co. Ltd. Address before: 361023 251 fish Fu Club, Li Lin village, Jimei District, Xiamen City, Fujian Province Patentee before: Chen Weidu |