CN104017165A - Preparation method of photosensitive polyurethane organic silicon resin - Google Patents
Preparation method of photosensitive polyurethane organic silicon resin Download PDFInfo
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- CN104017165A CN104017165A CN201410149045.5A CN201410149045A CN104017165A CN 104017165 A CN104017165 A CN 104017165A CN 201410149045 A CN201410149045 A CN 201410149045A CN 104017165 A CN104017165 A CN 104017165A
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- preparation
- vulcabond
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- silicone oil
- hydroxyalkyl
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
- C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to the technical field of polyurethane modification and particularly relates to a preparation method of photosensitive polyurethane organic silicon resin. The preparation method disclosed by the invention is simple in process step, low in cost and suitable for industrial production. The photosensitive polyurethane organic silicon resin product prepared by using the preparation method combines the advantages of polyurethane resin and organic silicon resin, overcomes the defect of single polyurethane resin or organic silicon resin, and has favorable wear resistance, water resistance, weather resistance and photosensitiveness; in addition, gel formed after the photosensitive polyurethane organic silicon resin is solidified is high in hardness and good in flexibility.
Description
Technical field
The invention belongs to polyurethane-modified technical field, be specifically related to a kind of preparation method of light sensitive polyurethane silicone resin.
Background technology
Urethane (PU), since occurring the forties in 20th century, has all obtained widespread use at aspects such as coating, elastomerics, porous plastics and tackiness agents, is a kind of multi-functional polymer materials, is also one of macromolecular material with fastest developing speed.Urethane contains feature unit structure amino-formate bond (-NH-CO-), contains soft chain segment and hard segment alternately in chain, and making its aggregated structure is heterogeneous structure, and this has determined the performance such as wear-resisting, pliable and tough that polyurethane coating is good.Yet single polyurethane coating is desirable not enough in the performance of the aspects such as water tolerance, gloss, hardness, by modification, can make it obtain more excellent over-all properties.The modification of urethane has two kinds of modes: a kind of is by simple physical method by two or more mixed with resin with complementary characteristic together; Another kind is to make product have the characteristic of two or more systems by chemical process.
The traditional curing type of polyurethane coating mainly contains moisture-curable, thermohardening type, due to photocuring technology, there is the advantages such as curing speed is fast, the saving energy, saving resource, solvent-free pollution, so photocuring organic silicon polyurethane coating one occurs causing the great interest of people, demonstrates fabulous development prospect.Although the report of more existing light-cured polyurethane silicone resins, organosilicon/acrylate/urethane resin as synthetic in Tao Yonghong, Tang Kai, be made into that ultraviolet light polymerization UV is coating material solidified has more excellent anti-yellowing property, and kept good wear resistance and sticking power.It is raw material that Qi Yusong, Zeng Zhaohua etc. be take hydroxyethyl methylacrylate, isophorone diisocyanate and 21 (γ-tri-ethoxy silylpropyl) amine, synthetic organic silicon modified polyurethane acrylate (Si-PUA) prepolymer, the electrical property of its photocuring film, thermal characteristics are all very good.Zhao Shilin, Chen Guoxin etc. are used the hydrolysis reaction of Silane coupling reagent KH-570 under acidic conditions, and in-situ polymerization becomes alcohol dissolubility silicone resin, simultaneously by nanometer SiO
2disperse wherein, prepared environment-friendly type nano UV shielding clear coating, can be used as the cover of building external paint and woodwork coating, shielding efficiency and the transparency of coating have been improved, and extend work-ing life of coating, but the preparation method of prior art exists synthesis technique complicated, and cost is high, thermotolerance, weathering resistance and the adhesion property of urethane silicone resin product such as also waits to improve at the defect.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art, a kind of preparation method of light sensitive polyurethane silicone resin is provided, step of preparation process is simple, cost is low, make product has good wear resistance, water tolerance, weathering resistance, and the gelinite hardness that forms after photocuring is high and snappiness good.
Above-mentioned purpose of the present invention is achieved by following technical solution:
A preparation method for light sensitive polyurethane silicone resin, comprises the steps:
S1. vulcabond, catalyzer, stopper and solvent are stirred, then add crylic acid hydroxy ester, control temperature of reaction is reacted 5 ~ 8h and is obtained monomer intermediate product at 40 ~ 50 ℃;
S2. hydroxyalkyl silicone oil, catalyzer, stopper and solvent is even, add in the monomer intermediate product that step S1 makes, control temperature of reaction and react 5 ~ 8h at 60 ~ 80 ℃, product washing, dry, except after desolventizing, obtain product;
In step S1, the consumption mol ratio of described vulcabond and crylic acid hydroxy ester is 1:1 ~ 1.2, the consumption of described catalyzer is 0.1 ~ 2% of vulcabond and the total consumption of crylic acid hydroxy ester, and the consumption of described stopper is 0.1 ~ 2% of vulcabond and the total consumption of crylic acid hydroxy ester;
In step S2, the consumption of described hydroxyalkyl silicone oil and step S1 vulcabond consumption mol ratio are 0.4 ~ 0.5, and the consumption of described catalyzer is 0.1 ~ 2% of hydroxyalkyl silicon oil dosage, and the consumption of described stopper is 0.1 ~ 2% of hydroxyalkyl silicon oil dosage.
Vulcabond of the present invention is selected the conventional diisocyanate monomer of polyurethane field, and preferably, described vulcabond is selected from isophorone diisocyanate, Toluene-2,4-diisocyanate, 4-vulcabond, dimethyl diphenyl vulcabond, two pairs of phenyl diisocyanate of methylene radical, PPDI, 1, hexamethylene-diisocyanate, 1,5-naphthalene diisocyanate, 4,4-vulcabond dicyclohexyl methyl hydride, one or more in O-phthalic group diisocyanate are composite.
Crylic acid hydroxy ester of the present invention is selected the conventional diisocyanate monomer of polyurethane field, preferably, described crylic acid hydroxy ester is selected from (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, trimethylolpropane diacrylate, one or more in pentaerythritol triacrylate are composite.
Preferably, in step S1, described crylic acid hydroxy ester adopts the mode dripping to add, temperature of reaction during dropping is controlled at 30 ~ 40 ℃, time for adding is controlled at 25 ~ 35min, the temperature of reaction when mode adopt dripping adds and controls dropping, and object is can not make again reactant velocity too fast when promoting that crylic acid hydroxy ester fully disperses, assurance polyreaction gentleness is steadily carried out, and is beneficial to the control of reaction process.
Hydroxyalkyl silicone oil of the present invention is that wherein one or more are composite for hydroxypropyl silicone oil, methylol silicone oil, hydroxy silicon oil, hydroxyl butyl silicone oil etc.
Preferably, in step S2, described hydroxyalkyl silicone oil adopts the mode dripping to add, temperature of reaction during dropping is controlled at 40 ~ 50 ℃, and time for adding is controlled at 25 ~ 35min, in like manner, adopt the mode dripping to add and control the temperature of reaction while dripping, object is can not make again reactant velocity too fast when promoting that hydroxyalkyl silicone oil fully disperses, and guarantees that polyreaction gentleness steadily carries out, and is beneficial to the control of reaction process.
Solvent of the present invention is the conventional easy volatile solvent in this area, and preferably, described solvent is selected from tetrahydrofuran (THF), hexanaphthene, and toluene, one or more in normal hexane are composite.
It is composite that catalyzer of the present invention can be selected from one or more in dibutyl tin laurate, toxilic acid dibutyl tin, butyl maleate dibutyl tin, stannous octoate.
Stopper of the present invention can be selected from MEHQ, Resorcinol, and one or more in 2,6 ditertbutylparacresols are composite.
The washing of product described in step 2 of the present invention, dry concrete steps are that the sodium hydrogen carbonate solution of product employing 1 ~ 5% washs 2 ~ 4 times, after elimination lower aqueous solution, get upper solution, add Calcium Chloride Powder Anhydrous dry.
Preparation method of the present invention is mainly divided into two steps and carries out, the first step is first to synthesize the monomer intermediate product that contains two keys and isocyanate group, second step is that the monomer intermediate product making is grafted on hydroxyalkyl silicone oil, makes light sensitive polyurethane silicone resin.The present invention successfully combines organosilicon material and the urethane with excellent properties such as high-low temperature resistant, weather-resistant, resistance to ozone, electrical isolation, resistance to combustion, nontoxic, corrosion-free and physiology inertia, make product and retained the performances such as the good wear resistance of urethane, snappiness, given again the product good water tolerance, weathering resistance; In addition, product also has photosensitivity, and after photocuring, the hardness of product and snappiness are better.
Preparation method of the present invention be take pentaerythritol triacrylate as example with isophorone diisocyanate, crylic acid hydroxy ester, and concrete chemical equation is as follows:
The first step is
；
Second step is
。
Compared with prior art, the present invention has following beneficial effect:
(1) preparation method's of the present invention processing step is simple, cost is low, is applicable to suitability for industrialized production.
(2) the light sensitive polyurethane silicone resin product that the present invention makes combines the advantage of urethane resin and silicone resin and overcomes the defect of single urethane resin and silicone resin, there is good wear resistance, water tolerance, weathering resistance, photosensitivity, the gelinite hardness that forms after photocuring is high and snappiness good.
Embodiment
Below in conjunction with specific embodiment, the present invention is further explained, but embodiments of the present invention is not limited in any way.Unless stated otherwise, in embodiment, related reagent, method is the conventional reagent in this area and method.
Embodiment of the present invention vulcabond, crylic acid hydroxy ester, hydroxyalkyl silicone oil, catalyzer, stopper and solvent used is all from buying and obtain on the market.
acetone Di-n-Butyl Amine method
The hydrochloric acid dehydrated alcohol standard titration solution of preparation 0.5mol/L, the Di-n-Butyl Amine acetone soln of 1mol/L, the sample to be tested Mg that takes certain mass is dissolved in the Erlenmeyer flask that 10ml acetone is housed, to the Di-n-Butyl Amine acetone soln concussion that moves 10ml1mol/L in Erlenmeyer flask, solution is fully mixed again, add three tetrabromo-mcresolsulfonphthalein indicator, after placing time of approximately 5 minutes, with the hydrochloric acid dehydrated alcohol standard titration solution of 0.5mol/L, carry out titration, when color becomes grass green and places the unchanged titration end point that is of about 1min color from blueness, consume hydrochloric acid volume and be designated as: V1, do again a blank rating test, consume hydrochloric acid volume and be designated as: V0, the residue percentage composition that concentration of hydrochloric acid note is done C isocyanate groups can be calculated by following formula:
The calculating of level of response: the percentage composition of supposing initial isocyanate groups is N, and level of response R can be expressed as formula:
embodiment 1
The first step is by isophorone diisocyanate 44.71g, catalyzer (dibutyl tin dilaurate) 2.09g, stopper (MEHQ) 1.05g, after solvent (tetrahydrofuran (THF)) mixes, pour into and there is whipping appts, thermometer, prolong, be connected with in the reactor of nitrogen atmosphere, 40 ℃ slowly drip trimethylolpropane diacrylate, note controlling the unlikely temperature generation cataclysm that makes thermometer of rate of addition, make reaction temperature and steadily carry out, the variation of acetone Di-n-Butyl Amine method detection system isocyanate groups for reaction process, determine the process of reaction, when level of response reaches 50%, carry out second step reaction, in reactor, add hydroxypropyl silicone oil 264.73g, catalyzer 5.29g, stopper 2.65g, solvent.At 40 ℃, reaction, detects the wherein variation of isocyanate groups, and after isocyanate groups changes slowly, rising temperature to 60 ℃, until reaction finishes.Alkali cleaning, dry, rotary evaporation, vacuum-drying, obtains pure product.
By infrared nuclear-magnetism, recording contents of ethylene is 4%, and by GPC, recording molecular weight is 4049g/mol, and molecular weight distribution 1.005 meets initial Molecular Structure Design requirement, resin viscosity 6500cps.
embodiment 2
The first step is by Toluene-2,4-diisocyanate, 4-vulcabond 35 g, dibutyl tin dilaurate 2g, MEHQ 1g, after solvent (hexanaphthene) mixes, pour into and there is whipping appts, thermometer, prolong, be connected with in the reactor of nitrogen atmosphere, 40 ℃ slowly drip pentaerythritol triacrylate, note controlling the unlikely temperature generation cataclysm that makes thermometer of rate of addition, make reaction temperature and steadily carry out, the variation of acetone Di-n-Butyl Amine method detection system isocyanate groups for reaction process, determine the process of reaction, when level of response reaches 50%, carry out second step reaction, in reactor, add hydroxypropyl silicone oil 264.73g, catalyzer 5.29g, stopper 2.65g, solvent.At 40 ℃, reaction, detects the wherein variation of isocyanate groups, and after isocyanate groups changes slowly, rising temperature to 60 ℃, until reaction finishes.Alkali cleaning, dry, rotary evaporation, vacuum-drying, obtains pure product.
The viscosity of the present embodiment rosin products is 8000cps, take and 1173 add in the resin of synthesized as photosensitizers 3%, after UV-irradiation, hardness >=H(GB/T 6739-2006), wear resistance RCA 175g >=300 time (GB/T 1730-1993), salt-fog resistant test 168 hours is without noticeable change, acid resistance (5%HCl) 48 hours is unchanged, alkali resistance (5%NaOH) 48 hours is unchanged, shock-resistant >=50cm, snappiness 1mm(GB/T 1731-1993) glossiness >=90(GB/T 1743-1979).
Claims (10)
1. a preparation method for light sensitive polyurethane silicone resin, is characterized in that, comprises the steps:
S1. vulcabond, catalyzer, stopper and solvent are stirred, then add crylic acid hydroxy ester, control temperature of reaction is reacted 5 ~ 8h and is obtained monomer intermediate product at 40 ~ 50 ℃;
S2. hydroxyalkyl silicone oil, catalyzer, stopper and solvent is even, add in the monomer intermediate product that step S1 makes, control temperature of reaction and react 5 ~ 8h at 60 ~ 80 ℃, product washing, dry, except after desolventizing, obtain product;
In step S1, the consumption mol ratio of described vulcabond and crylic acid hydroxy ester is 1:1 ~ 1.2, the consumption of described catalyzer is 0.1 ~ 2% of vulcabond and the total consumption of crylic acid hydroxy ester, and the consumption of described stopper is 0.1 ~ 2% of vulcabond and the total consumption of crylic acid hydroxy ester;
In step S2, the consumption of described hydroxyalkyl silicone oil and step S1 vulcabond consumption mol ratio are 0.4 ~ 0.5, and the consumption of described catalyzer is 0.1 ~ 2% of hydroxyalkyl silicon oil dosage, and the consumption of described stopper is 0.1 ~ 2% of hydroxyalkyl silicon oil dosage.
2. preparation method according to claim 1, is characterized in that, crylic acid hydroxy ester described in step S1 adopts the mode dripping to add, and temperature of reaction during dropping is controlled at 30 ~ 40 ℃, and time for adding is controlled at 25 ~ 35min.
3. preparation method according to claim 1, is characterized in that, the silicone oil of hydroxyalkyl described in step S2 adopts the mode dripping to add, and temperature of reaction during dropping is controlled at 40 ~ 50 ℃, and time for adding is controlled at 25 ~ 35min.
4. according to preparation method described in claim 1 or 2, it is characterized in that, described crylic acid hydroxy ester is selected from (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, trimethylolpropane diacrylate, one or more in pentaerythritol triacrylate are composite.
5. according to preparation method described in claim 1 or 3, it is characterized in that, described hydroxyalkyl silicone oil is that wherein one or more are composite for hydroxypropyl silicone oil, methylol silicone oil, hydroxy silicon oil, hydroxyl butyl silicone oil etc.
6. preparation method according to claim 1, is characterized in that, described vulcabond is selected from isophorone diisocyanate, Toluene-2,4-diisocyanate, 4-vulcabond, dimethyl diphenyl vulcabond, two pairs of phenyl diisocyanate of methylene radical, PPDI, 1, hexamethylene-diisocyanate, 1,5-naphthalene diisocyanate, 4,4-vulcabond dicyclohexyl methyl hydride, one or more in O-phthalic group diisocyanate are composite.
7. preparation method according to claim 1, is characterized in that, described solvent is selected from tetrahydrofuran (THF), hexanaphthene, and toluene, one or more in normal hexane are composite.
8. preparation method according to claim 1, is characterized in that, it is composite that described catalyzer can be selected from one or more in dibutyl tin laurate, toxilic acid dibutyl tin, butyl maleate dibutyl tin, stannous octoate.
9. preparation method according to claim 1, is characterized in that, described stopper can be selected from MEHQ, Resorcinol, and one or more in 2,6 ditertbutylparacresols are composite.
10. preparation method according to claim 1, it is characterized in that, the washing of product described in step 2, dry concrete steps are that the sodium hydrogen carbonate solution of product employing 1 ~ 5% washs 2 ~ 4 times, after elimination lower aqueous solution, get upper solution, add Calcium Chloride Powder Anhydrous dry.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105199077A (en) * | 2015-10-23 | 2015-12-30 | 青岛展辰新材料有限公司 | Preparation method of high-functionality wear-resistant cold light source cured polyurethane acrylate |
| CN106009646A (en) * | 2016-07-12 | 2016-10-12 | 蚌埠高华电子股份有限公司 | Aging-resistant aluminum oxide-nylon heat conducting composite material for LED lamps and preparation method of composite material |
| CN106700025A (en) * | 2016-12-12 | 2017-05-24 | 上海维凯光电新材料有限公司 | Polyurethane-acrylate prepolymer as well as preparation and application of polyurethane-acrylate prepolymer |
| CN110204686A (en) * | 2019-06-13 | 2019-09-06 | 江苏睿浦树脂科技有限公司 | Si modification resistant UV curable urethane acrylate resin and preparation method thereof |
| CN110256959A (en) * | 2019-05-21 | 2019-09-20 | 郝建强 | UV curable silicone release agent |
| CN116751062A (en) * | 2023-06-09 | 2023-09-15 | 辽宁大学 | Method for preparing complex SiC ceramic by DLP printing |
| CN117106268A (en) * | 2023-09-07 | 2023-11-24 | 杭州管康塑业有限公司 | High-impact-resistance high-weather-resistance PVC reinforced pipe and preparation method thereof |
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| CN103396518A (en) * | 2013-08-26 | 2013-11-20 | 张家港康得新光电材料有限公司 | Organic silicon modified water-based acrylate resin and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105199077A (en) * | 2015-10-23 | 2015-12-30 | 青岛展辰新材料有限公司 | Preparation method of high-functionality wear-resistant cold light source cured polyurethane acrylate |
| CN105199077B (en) * | 2015-10-23 | 2017-12-08 | 青岛展辰新材料有限公司 | A kind of high-ranking official it is wear-resisting can cold light source cured polyurethane acrylate preparation method |
| CN106009646A (en) * | 2016-07-12 | 2016-10-12 | 蚌埠高华电子股份有限公司 | Aging-resistant aluminum oxide-nylon heat conducting composite material for LED lamps and preparation method of composite material |
| CN106700025A (en) * | 2016-12-12 | 2017-05-24 | 上海维凯光电新材料有限公司 | Polyurethane-acrylate prepolymer as well as preparation and application of polyurethane-acrylate prepolymer |
| CN110256959A (en) * | 2019-05-21 | 2019-09-20 | 郝建强 | UV curable silicone release agent |
| CN110204686A (en) * | 2019-06-13 | 2019-09-06 | 江苏睿浦树脂科技有限公司 | Si modification resistant UV curable urethane acrylate resin and preparation method thereof |
| CN116751062A (en) * | 2023-06-09 | 2023-09-15 | 辽宁大学 | Method for preparing complex SiC ceramic by DLP printing |
| CN117106268A (en) * | 2023-09-07 | 2023-11-24 | 杭州管康塑业有限公司 | High-impact-resistance high-weather-resistance PVC reinforced pipe and preparation method thereof |
| CN117106268B (en) * | 2023-09-07 | 2024-04-16 | 杭州管康塑业有限公司 | High-impact-resistance high-weather-resistance PVC reinforced pipe and preparation method thereof |
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