CN1221756A - Method for preparing organic silicon modified acrylic resin - Google Patents
Method for preparing organic silicon modified acrylic resin Download PDFInfo
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- CN1221756A CN1221756A CN 97126128 CN97126128A CN1221756A CN 1221756 A CN1221756 A CN 1221756A CN 97126128 CN97126128 CN 97126128 CN 97126128 A CN97126128 A CN 97126128A CN 1221756 A CN1221756 A CN 1221756A
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- acid
- acrylic resin
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- estersil
- esterification
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
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- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A process for preparing the organosilicon modified acrylic resin features that the organic silane is chemically introduced to main chain or branch chain of macro moleculae of acrylic resin for using the excellent performance of organosilicon. Said resin is the basis of paint used for preventing corrosion and decorating and gives the paint such properties as higher weatherability and resistance to high temp, brine and salt fog.
Description
The present invention relates to the preparation method of the organic-silicon-modified acrylic resin of a kind of usefulness, particularly a kind of solution-type thermoplastic silicone modified acrylic preparation method of resin.
With the research of organic-silicon-modified acrylic resin, comparatively active in Japan.The organosilane that adopts among the Japanese patent laid-open 6-184248 is:
R in the formula
1And R
3Be hydrogen atom or methyl, R
2Be methyl, ethyl or phenyl.M is 0 or 1, is 0 o'clock at m, and 1 is 0～2 integer; At m is 1 o'clock, and 1 is 2.X is that halogen atom or carbon number are 1～10 alkoxyl group or acetonyl.What other patent was selected for use also is identical substantially organosilane.Silane monomer is generally selected existing Industrial products for use.The monomeric introducing of organosilane has certain improvement to the performance of resin and coating, but improvement effect is not obvious, and the weathering resistance of coating and resin, water tolerance, stain resistance and pencil hardness etc. all have certain defective.
The objective of the invention is to overcome the weak point of above-mentioned organosilicon modified crylic acid resin, a kind of new synthetic monomeric technology of organosilane that contains vinyl group is provided, and, make organosilicon modified crylic acid resin with this organosilane monomer and other vinyl monomer copolymerization.
In order to achieve the above object, our technical scheme of employing is summarized as follows:
(1) hydrolysis reaction, the organosilane that has alkoxy grp under the certain reaction temperature, the water reaction for some time with through measuring, make organic silanol under catalyst action.
(2) esterification, silanol that step (1) is made and methacrylic acid or vinylformic acid are under catalyst action, and at a certain temperature, the insulation reaction certain hour makes methacrylic acid estersil or vinylformic acid estersil.
(3) polyreaction, methacrylic acid estersil that step (2) is made or vinylformic acid estersil and methacrylic acid and ester, vinylformic acid and ester, vinylbenzene etc. make organosilicon modified crylic acid resin through free radical solution polymerization.
Concrete technical scheme is as follows:
(1) hydrolysis reaction, to have the organosilane of alkoxy grp and deionized water by 1: 1～4 moles, preferably 1: 1～3 moles ratio adds in the reactor, the Zeo-karb or other acids that add 0.01～20% (mass percent) are again made catalyzer, with the oil bath heating, at 50～250 ℃, preferably 60～120 ℃ were reacted 0.5～10 hour down, remove by filter catalyzer, filtrate is the organosilicon alcoholic solution.
(2) esterification, with methacrylic acid or vinylformic acid and organic silanol by 1: 1～20 moles, preferably 1: 1～10 moles ratio adds in the reactor, the cation exchange resin as catalyst and a certain amount of band aqua that add 0.01～20% (mass percent) again, at 70～200 ℃, be preferably in 100～140 ℃ and reacted 0.5～5 hour down, make methacrylic acid estersil or vinylformic acid estersil.
(3) polyreaction, with methacrylic acid and ester, vinylformic acid and monomers such as ester, vinylbenzene thereof, by 1～20: 1～5: 1～10 (mol ratio), preferably the ratio of 1～10: 1～3: 0.8～4 (mol ratio) is prepared burden, methacrylic acid estersil that step (2) makes or the dosage of vinylformic acid estersil in polymerization single polymerization monomer account for about 5% of total monomer weight, under action of evocating, under 100～125 ℃, carry out free radical copolymerization, insulation reaction 2～6 hours makes with organic-silicon-modified acrylic resin.
Organosilane used in the present invention is the organosilane that contains alkoxyl group, has following general formula:
Or
R wherein
1Be C
1～C
10Alkyl, R
2O is C
1～C
10Alkoxyl group.
Hydrolysis reaction, the employed catalyzer of esterification are sulfuric acid, hydrochloric acid, tosic acid, Zeo-karb, tin protochloride etc. among the present invention.
Band aqua of the present invention is operable N-BUTYL ACETATE, hexanaphthene, benzene, toluene etc.
The methyl acrylic ester product that the present invention uses is the C of methacrylic acid
1～C
10Alcohol ester, acrylate series products are acrylic acid C
1～C
10Alcohol ester.
Initiator used in the present invention is benzoyl peroxide, azo two isobutyl hydrogen.Outstanding feature of the present invention is:
(1) organosilane is introduced ethylene double bond through hydrolysis and esterification on silane molecule, can guarantee that silane monomer really participates in polyreaction and is grafted on the macromolecular chain.
(2) esterified prod of organosilane and acrylic resin have good consistency, and polymerization product is colourless, transparent.
(3) hydrolysis process, esterification technique reacting balance, stable operation are easy to realize industrial production.
(4) polymerization product has remarkable weather resistance, excellent salt fog resistance, water tolerance, winter hardiness, petrol-resistance, anti-machine oil etc., paint film high comprehensive performance.
In order to illustrate that better the present invention, spy enumerate following embodiment, but the present invention is not limited in following embodiment.
Embodiment:
(1) hydrolysis reaction
Test 1: whipping appts, prolong, dropping funnel, thermometer are installed on the 500ml four-hole boiling flask.Add Union carbide A-162 0.955mol, dimethyldiethoxysilane 0.115mol, sulfuric acid 0.01mol, water 3mol, oil bath is warming up to 75 ℃, and insulation reaction made organic silanol in 5 hours, the method for the organic silanol of test 2～7 preparations with test 1 identically, raw material add-on and reaction conditions, reaction result are listed in the table 1.
Table 1
(2) esterification
Test 8: whipping appts, prolong, dropping funnel, thermometer are installed on the 250ml four-hole boiling flask, get step (1) silanol 0.267mol, vinylformic acid 0.417mol, N-BUTYL ACETATE 0.22mol, 001 * 7 or D001 * 7 type Zeo-karb add-ons account for 8% (m/m) of total charging capacity, progressively heat up, 100～140 ℃ of control reaction material temperature, reacted 3～5 hours, cooling, filtration obtain vinylformic acid estersil product.
The method that test 9～12 prepares methacrylic acid estersil or vinylformic acid estersil is identical with test 8, and raw material add-on and reaction conditions, reaction result are listed in the table 2.
Table 2
(3) polyreaction
Test 13 is equipped with on the 500ml four-hole boiling flask: whipping appts, prolong, dropping funnel, thermometer.In reactor, add N-BUTYL ACETATE 1mol, be warming up to 110～120 ℃, drip the mixing solutions of mix monomer and initiator (mix monomer is accounted for 10% (m/m), the 0.004mol benzoyl peroxide of monomer total amount by 0.7mol methyl methacrylate, 0.37mol butyl acrylate, vinylformic acid estersil add-on), carry out free radicals copolymerization reaction, the control rate of addition, the control dropping time remained on 2～4 hours.After dropwising, insulation reaction 2～4 hours with 0.127mol methyl methacrylate dissolving 0.0015mol benzoyl peroxide, once adds reaction system again, and insulation reaction is 2～4 hours again, is cooled to room temperature, filters discharging.Obtain the rosin products of solid content about 55%.Product yield＞98%.The method that test 14～18 prepares organosilicon modified crylic acid resin is identical with test 13, and raw material add-on and reaction conditions, reaction result are listed in the table 3.
Table 3
Test 13 organosilicon modified crylic acid resins that make are carried out 1000 hours artificial forced agings at synthetic materials research institute of the Ministry of Chemical Industry ageing research tested, carried out the environmental compatibility detection in electronic product environmental compatibility inspection center of Ministry of Machine-Building Industry, detected result sees Table 4.
Table 4
| Test event | Test result | Conclusion |
| Surface drying (min) is done solid work (h) time of drying | ????30 ????4 | |
| Gloss | ????≥90 | |
| Sticking power (level) | ????1 | |
| Pencil hardness | ????2H | |
| Shock strength (Kg.cm) | ????50 | |
| Snappiness (mm) | ????1 | |
| Salt spray resistance (1000h) | Specimen surface do not have foaming, do not have come off, no variable color, outward appearance is good | One-level |
| Winter hardiness (50 ℃, 2h;-20 ℃ 2h.12 circulation) | Specimen surface does not have cracking, nothing comes off | One-level |
| Water tolerance (48h) | Specimen surface do not have foaming, do not have come off, no variable color | One-level |
| Anti-gasoline (4h) | Specimen surface do not have foaming, do not have come off, no variable color | One-level |
| Anti-machine oil (24h) | Specimen surface do not have foaming, do not have come off, no variable color | One-level |
| UV resistant (the artificial forced aging of 1000h, coating loss of gloss rate) | ????12.8％ | Excellent |
Claims (5)
1. preparation method with organic-silicon-modified acrylic resin is characterized in that: 1. hydrolysis reaction, the organosilane that will have an alkoxy grp react with water through metering under catalyst action, make organic silanol; 2. esterification, organic silanol that 1. step is made and methacrylic acid or vinylformic acid are under catalyst action, and insulation reaction is 3～5 hours under 100～140 ℃ temperature, makes methacrylic acid estersil or vinylformic acid estersil; 3. polyreaction, methacrylic acid estersil that 2. step is made or vinylformic acid estersil and methacrylic acid and ester, vinylformic acid and ester, vinylbenzene etc. make organosilicon modified crylic acid resin through free radical solution polymerization.
2. the preparation method of acrylic resin as claimed in claim 1 is characterized in that described hydrolysis reaction, esterification can adopt sulfuric acid, hydrochloric acid, p-methyl benzenesulfonic acid, Zeo-karb, tin protochloride as catalyzer.
3. the preparation method of acrylic resin as claimed in claim 1 is characterized in that the ratio of described methacrylic acid or vinylformic acid and organic silanol is mol ratio 1: 1～20, be preferably 1: 1～and 10.
4. the preparation method of acrylic resin as claimed in claim 1 is characterized in that esterification reaction temperature is controlled in 100～140 ℃ the scope.
5. the preparation method of acrylic resin as claimed in claim 1 is characterized in that reaction time of esterification is 3～5 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97126128A CN1072684C (en) | 1997-12-31 | 1997-12-31 | Method for preparing organic silicon modified acrylic resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97126128A CN1072684C (en) | 1997-12-31 | 1997-12-31 | Method for preparing organic silicon modified acrylic resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1221756A true CN1221756A (en) | 1999-07-07 |
| CN1072684C CN1072684C (en) | 2001-10-10 |
Family
ID=5177556
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97126128A Expired - Fee Related CN1072684C (en) | 1997-12-31 | 1997-12-31 | Method for preparing organic silicon modified acrylic resin |
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|---|---|
| CN (1) | CN1072684C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775101B (en) * | 2010-02-05 | 2011-11-02 | 广东工业大学 | Organic silicon / hydroxyl phosphate composite modified water emulsion acrylic resin and preparation method and application thereof |
| CN104194551A (en) * | 2014-09-28 | 2014-12-10 | 芜湖县双宝建材有限公司 | Impact-resistant flame retardant coating |
| CN107793966A (en) * | 2017-11-09 | 2018-03-13 | 浙江久而久化学有限公司 | A kind of preparation method of mould proof closestool positioning glue |
| CN112851883A (en) * | 2021-01-13 | 2021-05-28 | 山东硅科新材料有限公司 | Synthesis method of self-drying type organic silicon modified acrylic resin |
| CN115417946A (en) * | 2022-09-20 | 2022-12-02 | 黄宇斌 | Preparation method and application of organic silicon acrylate resin monomer composition |
| CN116254023A (en) * | 2023-02-14 | 2023-06-13 | 安庆瑞泰化工有限公司 | Acrylic coating resin for optical algae film and preparation method thereof |
| CN118834337A (en) * | 2024-08-08 | 2024-10-25 | 深圳市康利邦科技有限公司 | Organosilicon modified hydroxy acrylic resin and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3833273A (en) * | 1973-07-30 | 1974-09-03 | Morgan Construction Co | Labyrinth type seal |
| JPS5831805B2 (en) * | 1975-07-25 | 1983-07-08 | 株式会社日立製作所 | Gensuikouzou Seigiyoban |
| JPS6184248A (en) * | 1984-10-02 | 1986-04-28 | Tekunoroole Kk | Inking of offset press |
-
1997
- 1997-12-31 CN CN97126128A patent/CN1072684C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775101B (en) * | 2010-02-05 | 2011-11-02 | 广东工业大学 | Organic silicon / hydroxyl phosphate composite modified water emulsion acrylic resin and preparation method and application thereof |
| CN104194551A (en) * | 2014-09-28 | 2014-12-10 | 芜湖县双宝建材有限公司 | Impact-resistant flame retardant coating |
| CN107793966A (en) * | 2017-11-09 | 2018-03-13 | 浙江久而久化学有限公司 | A kind of preparation method of mould proof closestool positioning glue |
| CN107793966B (en) * | 2017-11-09 | 2019-06-28 | 浙江久而久化学有限公司 | A kind of preparation method of mould proof closestool positioning glue |
| CN112851883A (en) * | 2021-01-13 | 2021-05-28 | 山东硅科新材料有限公司 | Synthesis method of self-drying type organic silicon modified acrylic resin |
| CN112851883B (en) * | 2021-01-13 | 2022-12-06 | 山东硅科新材料有限公司 | Synthesis method of self-drying type organic silicon modified acrylic resin |
| CN115417946A (en) * | 2022-09-20 | 2022-12-02 | 黄宇斌 | Preparation method and application of organic silicon acrylate resin monomer composition |
| CN115417946B (en) * | 2022-09-20 | 2024-07-16 | 黄宇斌 | Preparation method and application of organic silicon acrylic ester resin monomer composition |
| CN116254023A (en) * | 2023-02-14 | 2023-06-13 | 安庆瑞泰化工有限公司 | Acrylic coating resin for optical algae film and preparation method thereof |
| CN118834337A (en) * | 2024-08-08 | 2024-10-25 | 深圳市康利邦科技有限公司 | Organosilicon modified hydroxy acrylic resin and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1072684C (en) | 2001-10-10 |
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