CN101165130B - Preparation technique of organic silicon resin for high temperature resisting powder paint - Google Patents
Preparation technique of organic silicon resin for high temperature resisting powder paint Download PDFInfo
- Publication number
- CN101165130B CN101165130B CN2007101320524A CN200710132052A CN101165130B CN 101165130 B CN101165130 B CN 101165130B CN 2007101320524 A CN2007101320524 A CN 2007101320524A CN 200710132052 A CN200710132052 A CN 200710132052A CN 101165130 B CN101165130 B CN 101165130B
- Authority
- CN
- China
- Prior art keywords
- monomer
- powder paint
- high temperature
- organic silicon
- silicon resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The present invention relates to silicone resin preparing process, and is especially process of preparing silicone resin specially for heat resistant powder paint. The silicone resin specially for heat resistant powder paint is prepared through adding the mixture of common silicone monomer and special silicone monomer in water insoluble organic solvent with boiling point lower than 100 deg.c, co-hydrolyzing in water and ketone, ether or ester at temperature lower than 25 deg.c, catalytically polycondensating and regulating activity with regulator, evaporating out solvent, cooling and tabletting. The silicone resin specially is applied for heat resistant powder paint, and has environment friendship and construction safety.
Description
Technical field
The present invention relates to the preparation technology's of silicone resin, particularly a kind of organic silicon resin for high temperature resisting powder paint preparation technology.
Background technology
Silicone resin generally is familiar with by people as high-temperature resistant coating, and traditional preparation method is the toluene solution that is processed into solid content about 50%, with solvent type resin form commodity selling.
The preparation method of solvent type resin as shown in Figure 1, this solvent-type organosilicon resin is applicable to high temperature resistant, the high insulating coating of modulating various uses, and the coating working method as shown in Figure 2, this as can be seen method can produce bigger toxicity, contaminate environment in operating process.And in order to protect environment, reduce and pollute, the development of coatings industry mainly is in the toxicity in reducing construction process, the direction of preventing and remedying pollution develops.Therefore powder coating has become the emphasis that people pay close attention to water soluble paint.
The general non-refractory of traditional powder coating, general heatproof powder coating preferably, its heat resistance only about 180 ℃, reach higher heat resistance, will synthesize the silicone resin that is applicable to powder coating.
General powder coating work flow as shown in Figure 3.
Therefore, requiring special-purpose high-temperature resistant organic silicon resin, must be solid shape, and tack-free under the normal temperature, pulverizing under the temperature＜50 ℃ sticking glutinous, can powdered, about 120 ℃, can soften fusion, at energy curing molding more than 180 ℃.These processing condition requirements, traditional solvent-type organosilicon resin can't adapt at all.
Summary of the invention
The technical problem to be solved in the present invention is: the high-temperature resistant organic silicon resin that solves the method for having now preparation is applied to the big and general problem of hanging down contaminated powders coating non-refractory of coatings industry toxicity, the invention provides a kind of preparation technology of organic silicon resin for high temperature resisting powder paint, with synthetic low the pollution and resistant to elevated temperatures SOLID ORGANIC silicone resin of this method, and can satisfy the processing request of powder coating fully.
The technical solution adopted for the present invention to solve the technical problems is: a kind of preparation technology of organic silicon resin for high temperature resisting powder paint has following processing step:
A. raw material monomer:
Basic organosilane monomer: dimethyldichlorosilane(DMCS), purity 99.9%, it has been the leading skeleton of organosilicon polysiloxane chain; Monomethyl trichlorosilane, purity＞99%, it is the main component of organosilicon racemosus fork structure; Diphenyl dichlorosilane, purity＞99%, it is the main contribution monomer of organosilicon fire-resistant material, is that organosilicon has high temperature resistant and curing performance, has the principal monomer of compatibility performance; One phenyl-trichloro-silicane, purity＞99%, it is the crosslinked principal monomer of the organosilicon material bodily form.Basic organosilane monomer is made up of above-mentioned four kinds of monomers.
Extraordinary organosilane monomer: contain the organosilane monomer of two key groups, as the methyl ethylene dichlorosilane, purity＞99% mainly is to form chemically crosslinked; Contain the reactive hydrogen organosilane monomer, contain silicon hydride chlorid as dimethyl, purity＞99%, main and two key groups are addition-crosslinked; The organosilane monomer that contains specific function, these monomers are called as coupling agent sometimes, purity＞99%, the functional group coupling agent that contains epoxide group, ester group, oh group, acryloyl group, active reactive halogen Cl group commonly used.Extraordinary organosilane monomer is made of in the above-mentioned monomer one or more.
B. above-mentioned each organosilane monomer being added in proportion boiling point behind the thorough mixing is lower than in 100 ℃ the organic solvent that is immiscible in water, wherein the ratio R/Si of organosilicon functional group and Siliciumatom generally is controlled between 1.0～1.6, the phenyl monomer occupy machine silicon monomer total amount 20～60% between, extraordinary organosilane monomer occupies 20～40% of machine silicon monomer total amount, utilize ketone, ethers or esters solvent and water, controlled temperature is being lower than under 25 ℃ the condition, carry out cohydrolysis, wherein water consumption is 1～2 times of an organosilane monomer total mass, ketone, the consumption of ethers or esters solvent is 2～4 times with quality, add catalyzer after the hydrolysis and telomerize polycondensation, add conditioning agent and reduce the gel degree, the conditioning agent consumption is 10% of an organosilane monomer total mass, removes solvent under the negative pressure of vacuum condition, and the cooling compressing tablet makes the solid state finished product.
As preferably, the described monomer that adds in proportion is good between 1.1～1.3 with the ratio R/Si of machine functionalized silicon group and Siliciumatom; What the phenyl monomer occupied machine silicon monomer total mass is good with 20～30%; What extraordinary organosilane monomer occupied machine silicon monomer total mass is good with 25%.
As preferably, described ketone, ethers or esters solvent are a kind of of butanone, methylethylketone, pimelinketone, butyl ether, butyl glycol ether or ethyl acetate.This solvent can make hydrolysis reaction relax, and it is crosslinked too fast undue with crosslinking reaction to prevent, in case form not fusion polymer.
As preferably, the consumption of described ketone, ethers or esters solvent is for being good with 2 times of quality.
As preferably, described cohydrolysis temperature is good with 4～10 ℃.
As preferably, described catalyzer is transition metal salt: PtCl6, cobalt naphthenate or zinc acetate; Select a kind of as catalyzer of above-mentioned substance during application, purpose is promote two keys and hydroxyl crosslinked.
As preferably, described conditioning agent is organosilicon oligopolymer a kind of with hydroxyl, epoxy group(ing) or ester group.Generally be for the active group that prevents to remain in polycondensation process further reacts, finally form gel, can't use.Therefore, conditioning agent generally has the effect of " sealing ".
The invention has the beneficial effects as follows: the present invention is by regulating the prescription of organosilicon basic monomer, wherein high spot reviews methyl group, the effect of phenyl group in the organosilicon polysiloxane structure, various its quantity of group what, residing position is for effect of material performance, designed and had than the spiral helicine structure of polyteny, the macromolecular scaffold that ladder structure is arranged again, make it neither form gel, higher softening temperature is arranged again; Utilization has the specific function group monomer and participates in hydrolysis reaction, is to have many special active groups on the high molecular structure, and they react under the special catalyst condition and form three dimensional structure; Adopt conditioning agent, to reduce the gel degree; Adopt and relax speed of response and the low solvent that is easy to evaporate of boiling point, to guarantee to obtain the silicone resin of solid state body; Select hydrolysis at a lower temperature, reduced speed of response, prevent crosslinkedly too early, and control reaction conditions to guarantee having obtained certain response function, does not produce the SOLID ORGANIC silicone resin of gel again; The appearance of this solid state silicone resin makes powder coating expand to the high-temperature coatings field, has not only expanded the market and the range of application of powder coating greatly, and contributes for coatings industry develops to water-soluble and solid coating direction; In addition,, prevent that the solvent contamination poisoning has positive effect in the construction,, and good social benefit is arranged so this invention not only has good economic benefit for protection environment, guarantee construction safety.
Description of drawings
Fig. 1 is the process flow sheet of preparation solvent type resin.
Fig. 2 is the process flow sheet with high temperature resistant, the high insulating coating of solvent-type organosilicon resin modulation various uses.
Fig. 3 is the process flow sheet of the general powder coating of preparation.
Embodiment
Embodiment one:
A. the composition of raw material proportioning by mass
99.9% 80 parts of dimethyldichlorosilane(DMCS) purity
Monomethyl trichlorosilane purity＞99% 120 part
Diphenyl dichlorosilane purity＞99% 120 part
One phenyl-trichloro-silicane purity＞99% 80 part
Contain ester group organo-silicon coupling agent purity＞99% 120 part
B. above-mentioned each organosilane monomer is added in 600 parts of benzene solvents behind the thorough mixing in proportion, add 1200 parts of butanone and 600 parts of water, controlled temperature is under 5 ℃ condition, carry out cohydrolysis, add 1 part of catalyzer lead naphthenate then and telomerize polycondensation, add the low molecule of 140 parts of conditioning agent epoxy group(ing) organosilicons, reduce the gel degree, remove solvent under the negative pressure of vacuum condition, the cooling compressing tablet obtains the solid state finished product.
It is passable substantially to make the silicone resin performance, and softening temperature, levelling property are better, can ease back after the long period only at room temperature.
Embodiment two:
A. the composition of raw material proportioning by mass
99.9% 60 parts of dimethyldichlorosilane(DMCS) purity
Monomethyl trichlorosilane purity＞99% 110 part
Diphenyl dichlorosilane purity＞99% 110 part
One phenyl-trichloro-silicane purity＞99% 60 part
Methyl ethylene dichlorosilane purity＞99% 65 part
The hydrogeneous dichlorosilane purity of methyl＞99% 60 part
Hydroxyl organo-silicon coupling agent purity＞99% 100 part
B. above-mentioned each organosilane monomer is added in 800 parts of benzene solvents behind the thorough mixing in proportion, add 1800 parts of butyl ether and 900 parts of water, controlled temperature is under 10 ℃ condition, carry out cohydrolysis, add 0.8 portion of catalyzer platinum salt then and telomerize polycondensation, add the low molecule of 180 parts of conditioning agent organic hydroxy silicates, reduce the gel degree, remove solvent under the negative pressure of vacuum condition, the cooling compressing tablet makes the solid state finished product.
It is functional to make silicone resin, but softening temperature is lower slightly, does not influence use, also tack-free under the room temperature, but like flexible.
Embodiment three:
A. the composition of raw material proportioning by mass
99.9% 60 parts of dimethyldichlorosilane(DMCS) purity
Monomethyl trichlorosilane purity＞99% 120 part
Diphenyl dichlorosilane purity＞99% 60 part
One phenyl-trichloro-silicane purity＞99% 110 part
Contain epoxy group(ing) organo-silicon coupling agent purity＞99% 140 part
B. above-mentioned each organosilane monomer is added in 500 parts of benzene solvents behind the thorough mixing in proportion, add 1800 parts of butanone and 1000 parts of water, controlled temperature is being lower than under 10 ℃ the condition, carry out cohydrolysis, add 1 part of catalyzer zinc acetate then and telomerize polycondensation, add the low molecule of 140 parts of conditioning agent organic hydroxy silicates, reduce the gel degree, remove solvent under the negative pressure of vacuum condition, the cooling compressing tablet makes the solid state finished product.
It is functional to make silicone resin, but gel slightly, processing characteristics is better.
Embodiment four:
A. the composition of raw material proportioning by mass
99.9% 80 parts of dimethyldichlorosilane(DMCS) purity
Monomethyl trichlorosilane purity＞99% 120 part
Diphenyl dichlorosilane purity＞99% 60 part
One phenyl-trichloro-silicane purity＞99% 110 part
Contain propenyl organo-silicon coupling agent purity＞99% 120 part
B. above-mentioned each organosilane monomer is added in 600 parts of benzene solvents behind the thorough mixing in proportion, add 1600 parts of ethyl acetate and 800 parts of water, controlled temperature is being lower than under 8 ℃ the condition, carry out cohydrolysis, add 1 part of catalyzer lead naphthenate then and telomerize polycondensation, add the low molecule of 140 parts of conditioning agent ester group organosilicons, reduce the gel degree, remove solvent under the negative pressure of vacuum condition, the cooling compressing tablet makes the solid state finished product.It is functional to make silicone resin, but softening temperature is lower slightly, does not influence use, and processing characteristics is better.
Utilize the key technical indexes of the prepared organic silicon resin for high temperature resisting powder paint of the present invention as follows:
1. outward appearance: Powdered or amorphous sheet.
2. physicals: tack-free under the normal temperature, after tack not below 50 ℃ does not feel like jelly.
3. softening temperature: 120 ± 10 ℃
4. processing characteristics: good consistency is arranged with additive, the filler of powder coating.
5. processability: 180 ℃ of machine-shaping is levelling property preferably again.
6. heat resistance: 〉=300 ℃
7. gloss: 60 °
Utilize the present invention to prepare the high-temperature resistant organic silicon resin of solid shape, can satisfy the processing request of powder coating fully, thereby opened up the high temperature resistant field of powder coating.
Claims (8)
1. the preparation technology of an organic silicon resin for high temperature resisting powder paint is characterized in that having following processing step:
A. raw material monomer:
Basic organosilane monomer: form by dimethyldichlorosilane(DMCS), monomethyl trichlorosilane, diphenyl dichlorosilane and a phenyl-trichloro-silicane;
Extraordinary organosilane monomer: the organosilane monomer by containing two key groups, contain the reactive hydrogen organosilane monomer, contain one or more compositions in the organo-silicon coupling agent of epoxy group(ing), ester group, hydroxyl, acryl or active reactive halogen Cl base;
B. above-mentioned each organosilane monomer being added in proportion boiling point behind the thorough mixing is lower than in 100 ℃ the organic solvent that is immiscible in water, wherein the ratio R/Si of organosilicon functional group and Siliciumatom is controlled between 1.0～1.6, the phenyl monomer occupy machine silicon monomer total amount 20～60% between, extraordinary organosilane monomer occupies 20～40% of machine silicon monomer total mass, utilize ketone, ethers or esters solvent and water, controlled temperature is being lower than under 25 ℃ the condition, carry out cohydrolysis, wherein water consumption is 1～2 times of an organosilane monomer total mass, ketone, the consumption of ethers or esters solvent is 2～4 times with quality, add catalyzer after the hydrolysis and telomerize polycondensation, add conditioning agent and reduce the gel degree, the conditioning agent consumption is 10% of an organosilane monomer total mass, removes solvent under the negative pressure of vacuum condition, and the cooling compressing tablet obtains the solid state finished product.
2. the preparation technology of organic silicon resin for high temperature resisting powder paint according to claim 1, it is characterized in that: the described monomer that adds in proportion is: the ratio R/Si of organosilicon functional group and Siliciumatom is between 1.1～1.3; The phenyl monomer occupies 20～30% of machine silicon monomer total amount; Extraordinary organosilane monomer occupies 25% of machine silicon monomer total amount.
3. the preparation technology of organic silicon resin for high temperature resisting powder paint according to claim 1, it is characterized in that: described ketone, ethers or esters solvent are butanone, methylethylketone, pimelinketone, butyl ether, butyl glycol ether or ethyl acetate.
4. according to the preparation technology of claim 1 or 3 described organic silicon resin for high temperature resisting powder paint, it is characterized in that: the consumption of described ketone, ethers or esters solvent is 2 times with quality.
5. the preparation technology of organic silicon resin for high temperature resisting powder paint according to claim 1, it is characterized in that: described cohydrolysis temperature is 4～10 ℃.
6. the preparation technology of organic silicon resin for high temperature resisting powder paint according to claim 1, it is characterized in that: described catalyzer is a transition metal salt catalyzer.
7. the preparation technology of organic silicon resin for high temperature resisting powder paint according to claim 6, it is characterized in that: described transition metal salt catalyzer is PtCl
6, cobalt naphthenate or zinc acetate.
8. the preparation technology of organic silicon resin for high temperature resisting powder paint according to claim 1, it is characterized in that: described conditioning agent is the organosilicon oligopolymer with hydroxyl, epoxy group(ing) or ester group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101320524A CN101165130B (en) | 2007-09-20 | 2007-09-20 | Preparation technique of organic silicon resin for high temperature resisting powder paint |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101320524A CN101165130B (en) | 2007-09-20 | 2007-09-20 | Preparation technique of organic silicon resin for high temperature resisting powder paint |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101165130A CN101165130A (en) | 2008-04-23 |
| CN101165130B true CN101165130B (en) | 2010-06-09 |
Family
ID=39333990
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101320524A Expired - Fee Related CN101165130B (en) | 2007-09-20 | 2007-09-20 | Preparation technique of organic silicon resin for high temperature resisting powder paint |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101165130B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110734547B (en) * | 2019-10-25 | 2022-04-08 | 常州市嘉诺有机硅有限公司 | Method for preparing organic silicon resin through stepwise hydrolysis |
| CN110818905B (en) * | 2019-11-26 | 2022-04-08 | 常州市嘉诺有机硅有限公司 | Decolorizing and deionizing method of organic silicon resin |
| CN113683941A (en) * | 2021-09-18 | 2021-11-23 | 航佳彩新材料(广东)有限公司 | Open fire-resistant high-temperature powder coating special for fireplace and preparation method thereof |
| CN114054323A (en) * | 2021-10-29 | 2022-02-18 | 安徽兆鑫铝业科技有限公司 | Preparation method of baking-free glazed aluminum alloy curtain wall board |
| CN114133566B (en) * | 2021-12-09 | 2023-02-03 | 常州市嘉诺有机硅有限公司 | Method for preparing organic silicon resin by adopting ethoxy silane |
| CN114456386B (en) * | 2021-12-31 | 2023-05-23 | 杭州吉华高分子材料股份有限公司 | Reactive epoxy modified organic silicon resin and solvent-free high-temperature-resistant coating |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1389491A (en) * | 2002-07-08 | 2003-01-08 | 胡孟进 | Prepn. of environment-protecting silicone resin |
| CN1718656A (en) * | 2005-07-28 | 2006-01-11 | 同济大学 | A kind of ultraviolet-curing paint that contains POSS and preparation method thereof |
| CN1962728A (en) * | 2006-11-01 | 2007-05-16 | 金小凤 | Thermostable organosilicon resin preparation method |
-
2007
- 2007-09-20 CN CN2007101320524A patent/CN101165130B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1389491A (en) * | 2002-07-08 | 2003-01-08 | 胡孟进 | Prepn. of environment-protecting silicone resin |
| CN1718656A (en) * | 2005-07-28 | 2006-01-11 | 同济大学 | A kind of ultraviolet-curing paint that contains POSS and preparation method thereof |
| CN1962728A (en) * | 2006-11-01 | 2007-05-16 | 金小凤 | Thermostable organosilicon resin preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101165130A (en) | 2008-04-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101165130B (en) | Preparation technique of organic silicon resin for high temperature resisting powder paint | |
| CN102977553B (en) | Epoxy/silicone polymer composite material, and preparation method and application thereof | |
| CN105482089B (en) | A kind of water-soluble organic silicon modified polyester resin and the preparation method and application thereof | |
| CN101348611B (en) | Acroleic acid modified polysiloxane resin and coating thereof | |
| CN102731788B (en) | Organosilicone hybrid and organosilicone composite paint and preparations thereof | |
| CN103965822A (en) | Epoxy modified moisture curing polyurethane hot melt adhesive for compounding fabrics | |
| CN103923321A (en) | Polysiloxane with UV (Ultraviolet) and moisture double curing groups and preparation method thereof | |
| CN101885943A (en) | Nano-glass heat insulation paint and preparation method thereof | |
| CN103450797A (en) | Room-temperature cured epoxy polysiloxane resin | |
| CN103589338A (en) | Novel insulating paint for electrical parts and preparation method thereof | |
| CN102816551A (en) | Ultraviolet (UV)-moisture double-curing liquid optical transparent adhesive and preparation method thereof | |
| CN104761872A (en) | Organic silicon modified epoxy resin encapsulating material and preparation method thereof | |
| CN101948561A (en) | Organic/inorganic silicon hybrid resin for coating and preparation method thereof | |
| CN101328380A (en) | Pipeline repaired mouth anti-corrosive primer coating having high adhesive bonding ability with thermal contraction belt | |
| CN102732209A (en) | High-temperature-resistant flexible adhesive cured at normal temperature and preparation method thereof | |
| CN110156997A (en) | It is a kind of can moisture solidification organic silicon block copolymer and preparation method thereof | |
| CN109988538A (en) | The preparation method of no-solvent type polyurethane adhesive | |
| CN103601870B (en) | A kind of low gloss powder coating epoxy resin and its preparation method and application | |
| CN110437711B (en) | Epoxy resin for low-temperature curing type B68 extinction powder and preparation method and application thereof | |
| CN109082184A (en) | A kind of elastic emulsion paint of high adhesion force | |
| CN102268215A (en) | Solvent priming paint special for 3C (China Compulsory Certification) product magnesium-aluminum alloy material and preparation method thereof | |
| CN103666241B (en) | A kind of composite Nano waterborne UV coating and preparation method thereof | |
| CN105273682B (en) | LED glass ball bulb lamps are explosion-proof to use add-on type silica-gel composition | |
| TW200406416A (en) | Solid silane coupling agent composition, method for making the same, and a resin composition containing the same | |
| CN110437424A (en) | Dendroid epoxy resin, preparation method and its application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: CHANGZHOU JIANUO ORGANIC SILICON CO., LTD. Assignor: Hu Mengjin Contract record no.: 2012320000230 Denomination of invention: Preparation technique of organic silicon resin for high temperature resisting powder paint Granted publication date: 20100609 License type: Exclusive License Open date: 20080423 Record date: 20120315 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100609 Termination date: 20150920 |
|
| EXPY | Termination of patent right or utility model |