CN107459652B - Heat-resistant silicone resin capable of being cured at room temperature and preparation method thereof - Google Patents
Heat-resistant silicone resin capable of being cured at room temperature and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a heat-resistant silicone resin capable of being cured at room temperature and a preparation method thereof. The invention firstly synthesizes an alkoxy silane compound containing a hexafluoro cyclobutyl aryl ether structure, and then prepares alkoxy-terminated organic silicon resin (R) by copolymerizing the alkoxy silane compound with trifunctional silicon resin prepolymer and hydroxyl silicone oil1SiO1.5)a(R2R3SiO)b(R2R3Si‑R4‑R2R3SiO)cWherein R is1Is aryl, R2、R3Is methyl, aryl or saturated alkyl with 2-10 carbon atoms, R4Is hexafluorocyclobutyl aryl ether group; a + b + c is 1, the value of a is 0-0.5, the value of b is more than 0 and less than 1, the value of c is more than 0 and less than 1, and the mass content of the alkoxy is 0.1-10%. The silicone resin can be cured at room temperature after being mixed with trialkoxysilane and a curing catalyst to obtain the elastic and plastic silicone resin material with the thermal decomposition temperature of more than 450 ℃.
Description
Technical Field
The invention relates to heat-resistant silicone resin capable of being cured at room temperature and a preparation method thereof, belonging to the technical field of organic silicon polymers.
Background
The silicone resin is a crosslinking type semi-inorganic high polymer simultaneously having a Si-O-Si structure and an organic group. The structural particularity of the resin enables the resin to have better heat resistance than common organic resin, and the resin has important application in the fields of aerospace, electronic and electric appliances, military weapons and the like. However, when the temperature reaches 250 ℃ or above, the hydroxyl at the end of the silicone resin generates cyclic oligomer and cage-shaped micromolecule through the back-biting reaction to initiate the trip-type degradation; or Si-R oxidation and thermal decomposition rearrangement of Si-O-Si occur. Therefore, the long-term service temperature of the silicone resin is not more than 250 ℃, and the harsh environmental requirements with higher temperature resistance requirements cannot be met. A bulky chain segment or aromatic ring with higher rigidity is introduced into the Si-O-Si main chain to replace partial oxygen atoms in the main chain, and the inhibition of the cyclic degradation of the main chain at high temperature is an effective method for improving the heat resistance of the silicone resin.
The structure of the hexafluorocyclobutyl aryl ether is prepared by the [2+2] cyclodimerization reaction of trifluorovinyl aryl ether. The polymer containing the hexafluoro cyclobutyl aryl ether structure not only has excellent performances of common fluorine-containing polymers, namely excellent electrical insulation performance, thermal stability and chemical stability, but also has good processability because the structure contains an aromatic ring structure and ether bonds, so that the polymer can be dissolved in various organic solvents. The structure of the hexafluorocyclobutyl aryl ether is introduced into the silicon resin, and the addition of the rigid four-membered ring and the benzene ring structure has a remarkable effect of improving the heat resistance of the silicon resin. Smith et al prepared linear perfluorocyclobutyl aryl ether-dimethylsiloxane alternating copolymers and POSS-perfluorocyclobutyl aryl ether copolymers, respectively, with thermal decomposition temperatures (Td) of the polymers up to 450 ℃ or higher (Macromolecules,1996,29: 852; Polymer,2007,48: 4637). CN104448320 reports a method for preparing a trifluorovinyloxy-phenyl-containing silicone resin, and the 5% thermal weight loss temperature of the fluorine-containing silicone resin obtained after curing can reach 480 ℃. However, in the above reports, a silicone resin prepolymer containing a trifluorovinyl aryl ether structure is prepared, and then the resin is cured by thermal cyclization of trifluorovinyl aryl ether [2+2], wherein the curing temperature is usually above 100 ℃ and even above 200 ℃, which brings great inconvenience to the construction and is accompanied with great energy consumption. Meanwhile, the process often causes incomplete reaction of the trifluorovinyl ether, and the residual trifluorovinyl ether is sensitive to both acid and alkali, which often influences the medium resistance of the material. The fluorine-containing silicone resin reported in CN104448320 is a material with high hardness and high strength, Smith and the like do not study the mechanical properties of the prepared fluorine-containing resin, and the report of room-temperature-curable elastoplastic heat-resistant silicone resin containing a hexafluorocyclobutyl aryl ether structure is not seen at present.
Disclosure of Invention
The invention aims to provide a heat-resistant silicone resin capable of being cured at room temperature and a preparation method thereof. The invention firstly synthesizes an alkoxy silane compound containing a hexafluoro cyclobutyl aryl ether structure, and then prepares alkoxy-terminated silicon resin by copolymerizing the alkoxy silane compound with a trifunctional silicon resin prepolymer and hydroxyl silicone oil. Trialkoxysilane is added into the silicone resin in a certain proportion as a cross-linking agent, and the silicone resin can be cured at room temperature under the action of a catalyst to obtain the elastic and plastic silicone resin material with the thermal decomposition temperature of more than 450 ℃.
The invention is realized by the following technical scheme: a heat-resistant silicone resin capable of being cured at room temperature, which is characterized by comprising the following three components:
(A) the alkoxy-terminated average unit has the formula (R)1SiO1.5)a(R2R3SiO)b(R2R3Si-R4-R2R3SiO)cSilicone resin of
Wherein R is1Is aryl, R2、R3Is methyl, aryl or saturated alkyl with 2-10 carbon atoms, R4Is hexafluorocyclobutyl aryl ether group; a. b and c have the same or different values, a + b + c is 1, a has a value of 0-0.5, b has a value of 0 < b < 1, and c has a value of 0 < c < 1; wherein the end-capped alkoxy is methoxy or saturated alkoxy with 2-10 carbon atoms, preferably methoxy; the mass content of the alkoxy group is 0.1-10%.
Wherein a is preferably more than 0 and less than or equal to 0.5 (i.e. excluding 0), and R is1Preferably phenyl, R2、R3Preferably methyl, R4Preferably, it is
(B) Structural formula is R6Si(OR5)3Wherein R is5Is methyl, ethyl or saturated alkyl with 3-10 carbon atoms, preferably methyl; r6Is methyl, aryl or saturated alkyl with 2-10 carbon atoms, preferably methylEthyl, propyl.
(C) The curing catalyst for promoting the condensation reaction of hydroxyl or alkoxy comprises a basic compound, a metal-containing compound, preferably a titanium-or tin-containing compound, particularly preferably a titanate-based compound or a chelate compound.
The amount of component (B) is: 5 to 10 parts by mass per 100 parts by mass of the silicone resin of component (A).
The amount of component (C) is: 0.001 to 0.01 part by mass per 100 parts by mass of the silicone resin of the component (A).
The construction method comprises the following steps: uniformly mixing (A), (B) and (C) according to the proportion, and adding a small amount of toluene, xylene and the like for dilution if necessary; pouring into a mould, and curing at room temperature. The cured product is a reaction mixture mainly comprising three components and also comprises a part of (A), (B) and (C) components which do not participate in reaction.
The above component (A), i.e., the average unit formula is (R)1SiO1.5)a(R2R3SiO)b(R2R3Si-R4-R2R3SiO)cThe preparation equation of the silicone resin is as follows:
the method comprises the following steps:
(1) mixing water, solvent and acid catalyst, stirring and dropping trialkoxysilane R1Si(OR)3After reflux reaction is carried out for 1-2h, the mixture is cooled to room temperature and then washed by water to be neutral, an organic phase is collected, and hydroxyl and alkoxy end-capped trifunctional silicon resin prepolymer is obtained after drying, filtering and concentrating;
(2) uniformly mixing alkoxy silane containing a trifluorovinyl aryl ether structure with a solvent, reacting at 200-250 ℃ for 0.5-2h in a nitrogen atmosphere, cooling and quenching the reaction, removing the solvent, and carrying out column chromatography separation to obtain a compound 1, wherein the structural formula is shown as above;
(3) preparing the trifunctional silicon resin prepolymer prepared in the step (1), a compound 1 and hydroxy silicone oil HO (R)2R3SiO)nH. Mixing solvent and catalyst, heating and refluxing, removing generated water and methanol, aging for 3-6 hr, cooling to room temperature after reaction, neutralizing, filtering, and evaporating the filtrate under reduced pressure to remove solvent to obtain room temperature curable heat-resistant silicone resin (R)1SiO1.5)a(R2R3SiO)b(R2R3Si-R4-R2R3SiO)c。
The solvent in the step (1) is benzene, toluene or xylene.
The acidic catalyst in the step (1) is a strong acid catalyst, and is selected from one or more of hydrochloric acid, concentrated sulfuric acid, trifluoromethanesulfonic acid, strong acid ion exchange resin and solid acid.
In the step (1), the molar ratio of the trialkoxysilane to the water to the acid catalyst is 1:1.5-3: 0.002-0.01.
Trialkoxysilane R in step (1)1Si(OR)3Preferably phenyltrimethoxysilane.
The solvent in the step (2) is an inert organic solvent with the boiling point higher than 200 ℃, and is preferably diphenyl ether.
The alkoxy silane containing the trifluorovinyl aryl ether structure in the step (2) is preferably trifluorovinyl phenyl ether dimethyl methoxy silane.
The hydroxyl silicone oil HO (R) in the step (3)2R3SiO)nH, wherein R2、R3Is methyl, aryl or saturated alkyl with 2-10 carbon atoms, and n is an integer between 25-1000, preferably an integer between 50-100. Dimethylhydroxy silicone oils are preferred.
And (4) the solvent in the step (3) is benzene, toluene or xylene.
The catalyst in the step (3) is a strong acid catalyst, and is selected from one or more of hydrochloric acid, concentrated sulfuric acid, trifluoromethanesulfonic acid, strong acid ion exchange resin and solid acid.
The trifunctional silicone resin prepolymer in step (3) (with repeating unit R)1SiO1.5Calculated as the repeating unit R), compound 1, hydroxy silicone oil2R3SiO meter) The molar ratio of the catalyst is 1:0.1-1:1-5: 0.0001-0.001.
Compared with the prior art, the invention has the beneficial effects that:
1. the dialkoxysilane compound 1 containing a hexafluoro cyclobutyl aryl ether structure is prepared by [2+2] thermal cyclization reaction of trifluorovinyl aryl ether dimethyl methoxysilane, and then is used for preparing the silicone resin, a rigid four-membered ring and an aromatic ring are introduced into the silicone resin, so that the heat resistance of the silicone resin is remarkably improved, and the thermal decomposition temperature reaches more than 450 ℃, preferably more than 480 ℃. Because a hexafluoro cyclobutyl aryl ether structure is introduced before curing, and a Si-OR dealcoholization curing process is adopted, the high-temperature process required by thermal cyclization curing of the silicone resin prepolymer containing the trifluorovinyl aryl ether structure in the prior art is avoided, trifluorovinyl ether residue is avoided, and the reliability and stability of the material are improved.
2. The invention adopts the mode of firstly preparing the trifunctional silicone resin prepolymer, and then copolymerizing the trifunctional silicone resin prepolymer with the linear hydroxyl silicone oil and the compound 1 to obtain the block silicone resin copolymer, the unique structure of the block silicone resin copolymer endows the block silicone resin copolymer with the advantages of capability of realizing rapid room-temperature curing under the action of a crosslinking agent and a catalyst, surface drying time of less than or equal to 15 minutes, and good elastoplasticity of the obtained silicone resin material.
The performance makes it have wide application in fields such as three proofings (mould proof, moisture proof, salt fog proof), large scale integrated circuit package, aerospace, national defense and the like in the electronic industry.
Drawings
FIG. 1 is a thermogravimetric plot of the silicone resin material obtained from formulation 3 of example 7 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
75.6g of deionized water, 200g of toluene and 2g of hydrochloric acid (concentration: 37%) are placed in a four-neck flask equipped with a thermometer, a stirring paddle and a reflux condenser, and stirred uniformly, and 396g of phenyltrimethoxysilane is added dropwise. After the addition, the mixture was heated to reflux, reacted for 2 hours, and then cooled to room temperature. The reaction solution was washed three times with 400g of deionized water to neutrality. The organic phase was collected and dried overnight with anhydrous calcium chloride. The calcium chloride was filtered, and the filtrate was concentrated to remove toluene, thereby obtaining 240g of a trifunctional silicone resin prepolymer.
Example 2
Vacuumizing the reaction bottle and filling nitrogen twice, adding 262g of trifluorovinyl phenyl ether dimethyl methoxy silane and 500g of diphenyl ether in the nitrogen atmosphere, placing the mixture in an oil bath at 250 ℃ for reaction, taking out the mixture after 1 hour, and quenching the mixture by liquid nitrogen. Column chromatography separation gave 113g of hexafluorocyclobutyl phenyl ether-tetramethyldimethoxydisilane, 43% yield. Hydrogen spectrum characterization (1H NMR，300MHz,CDCl3δ in ppm) 0.33(t,12H),3.55(s,6H),7.15 to 7.18(m,6H),7.3(d, 2H). Characterization of fluorine spectra (19F NMR,282MHz,CDCl3,δin ppm):-127.2～-132.8(m,6F)。
Example 3
20g of the prepolymer prepared in example 1, 5.7g of the compound 1 and 22.9g of dimethylhydroxysiloxane oil (500 mPas) were taken out and put in a reaction flask, and dissolved in 200g of toluene and mixed uniformly, 0.1g of trifluoromethanesulfonic acid was added, heated under reflux, the water and methanol formed were removed, aging was continued for 3 hours, after the reaction was completed, the temperature was lowered to room temperature, and 0.5g of sodium carbonate was added to neutralize the mixture, followed by filtration. The filtrate was concentrated under reduced pressure to remove toluene, to obtain a solution having an average unit formula of (PhSiO)1.5)0.325(Me2SiO)0.65(Me2Si-R4-Me2SiO)0.025Silicone resin (R)4Hexafluorocyclobutyl phenyl ether group, the same applies hereinafter), viscosity (80 ℃,6500mPa · s), methoxy group mass content 2.3%.
Example 4
20g of the prepolymer prepared in example 1, 12.23g of the compound 1 and 22.9g of dimethylhydroxysiloxane oil (100 mPas) were taken out and put in a reaction flask, and dissolved in 200g of toluene and mixed uniformly, 0.12g of trifluoromethanesulfonic acid was added, heated under reflux, the water and methanol formed were removed, aging was continued for 3 hours, after the reaction was completed, the temperature was lowered to room temperature, and 0.6g of sodium carbonate was added to neutralize the mixture, followed by filtration. The filtrate was concentrated under reduced pressure to remove toluene, to obtain a solution having an average unit formula of (PhSiO)1.5)0.317(Me2SiO)0.635(Me2Si-R4-Me2SiO)0.048Of siliconResin, viscosity (80 ℃,5300 mPas) and methoxy group mass content of 2.5%.
Example 5
20g of the prepolymer prepared in example 1, 16.3g of the compound 1 and 20.64g of dimethylhydroxysiloxane oil (500 mPas) were taken out and put in a reaction flask, and dissolved in 200g of toluene and mixed uniformly, 0.1g of trifluoromethanesulfonic acid was added, heated under reflux, the water and methanol formed were removed, aging was continued for 3 hours, after the reaction was completed, the temperature was lowered to room temperature, and 0.5g of sodium carbonate was added to neutralize the mixture, followed by filtration. The filtrate was concentrated under reduced pressure to remove toluene, to obtain a solution having an average unit formula of (PhSiO)1.5)0.33(Me2SiO)0.6(Me2Si-R4-Me2SiO)0.07The silicone resin (2) had a viscosity (80 ℃ C., 7200 mPas) and a methoxy group content of 1.86% by mass.
Example 6
20g of the prepolymer prepared in example 1, 12.23g of the compound 1 and 11.47g of dimethylhydroxysiloxane oil (100 mPas) were taken out and put in a reaction flask, and dissolved in 200g of toluene and mixed uniformly, 0.1g of trifluoromethanesulfonic acid was added, heated under reflux, the water and methanol formed were removed, aging was continued for 3 hours, after the reaction was completed, the temperature was lowered to room temperature, and 0.5g of sodium carbonate was added to neutralize the mixture, followed by filtration. The filtrate was concentrated under reduced pressure to remove toluene, to obtain a solution having an average unit formula of (PhSiO)1.5)0.483(Me2SiO)0.483(Me2Si-R4-Me2SiO)0.034The silicone resin (2) had a viscosity (80 ℃ C., 15000 mPas) and a methoxy group content of 1.05% by mass.
Example 7
The silicone resins prepared in examples 3, 4, 5 and 6 were uniformly mixed with a crosslinking agent methyltrimethoxysilane and a catalyst butyl titanate according to the proportion in table 1, and a small amount of toluene, xylene and the like may be added for dilution if necessary. Pouring the sample into a polytetrafluoroethylene mold, curing at room temperature, and testing the performance after 72 hours. The formulations and results are shown in Table 1. Wherein the thermogravimetric spectrum of the silicone resin material obtained in the formula 3 is shown in figure 1.
TABLE 1 Properties of materials of different formulations
As can be seen from table 1 and fig. 1: the silicone resin material prepared by the invention has the characteristics of room temperature curing, elastoplasticity and high temperature resistance, so that the construction process is simpler and more convenient, the energy is saved, and the silicone resin material is suitable for aerospace high temperature resistant coatings, LED and solar cell panel packaging coatings and other application fields requiring tough, durable and high temperature resistant silicone resin materials.
The above description is for the description of the preferred embodiments of the present invention, but not for the limitation of the scope of the present invention, and various modifications or variations can be made by those skilled in the art without inventive efforts based on the technical solution of the present invention within the scope of the present invention.
Claims (8)
1. A heat-resistant silicone resin capable of being cured at room temperature, which is characterized by comprising the following three components:
(A) a silicone resin;
(B) a crosslinking agent;
(C) a curing catalyst;
the silicone resin (A) has an alkoxy-terminated average unit formula of (R)1SiO1.5)a(R2R3SiO)b(R2R3Si-R4-R2R3SiO)c；
Wherein R is1Is aryl, R2、R3Is methyl, aryl or saturated alkyl with 2-10 carbon atoms, R4Is hexafluorocyclobutyl aryl ether group; a. b and c have the same or different values, a + b + c is 1, a has a value of 0-0.5, b has a value of 0 < b < 1, and c has a value of 0 < c < 1; wherein the end-capped alkoxy is methoxy or saturated alkane oxy with 2-10 carbon atoms; the mass content of the alkoxy is 0.1-10%;
the organic silicon resin (A) is prepared by the following method:
(1) mixing water, solvent and acid catalyst, stirring and dropping trialkoxysilane R1Si(OR)3After reflux reaction is carried out for 1-2h, the mixture is cooled to room temperature and then washed by water to be neutral, an organic phase is collected, and hydroxyl and alkoxy end-capped trifunctional silicon resin prepolymer is obtained after drying, filtering and concentrating;
(2) uniformly mixing alkoxy silane containing a trifluorovinyl aryl ether structure with a solvent, reacting at 200-250 ℃ for 0.5-2h in a nitrogen atmosphere, cooling and quenching the reaction, removing the solvent, and performing column chromatography separation to obtain a compound 1;
(3) preparing the trifunctional silicon resin prepolymer prepared in the step (1), a compound 1 and hydroxy silicone oil HO (R)2R3SiO)nH. Uniformly mixing a solvent and a catalyst, heating and refluxing, removing generated water and methanol, then curing for 3-6 hours, cooling to room temperature after the reaction is finished, neutralizing, filtering, and evaporating the solvent from the filtrate under reduced pressure to obtain organic silicon resin; the catalyst is one or more of hydrochloric acid, concentrated sulfuric acid, trifluoromethanesulfonic acid, strongly acidic ion exchange resin and solid acid; r in trifunctional silicone prepolymer1SiO1.5Compound 1, R in hydroxy silicone oil2R3The mol ratio of SiO to catalyst is 1:0.1-1:1-5: 0.0001-0.001.
2. The room temperature curable heat resistant silicone resin of claim 1, wherein the crosslinking agent (B) is of the formula R6Si(OR5)3Trialkoxysilane of (2), wherein R5Is methyl, ethyl or saturated alkyl with 3-10 carbon atoms; r6Is methyl, aryl or saturated alkyl with 2-10 carbon atoms; the curing catalyst (C) is a curing catalyst which promotes a condensation reaction of a hydroxyl group or an alkoxy group.
3. The room-temperature curable heat-resistant silicone resin according to claim 2, wherein the curing catalyst (C) is a titanium-or tin-containing compound.
4. A room-temperature curable heat-resistant silicone resin as claimed in claim 2 or 3, wherein said component (B) is used in an amount of: 5 to 10 parts by mass per 100 parts by mass of the silicone resin of component (A); the dosage of the component (C) is as follows: 0.001 to 0.01 part by mass per 100 parts by mass of the silicone resin of the component (A).
5. The room-temperature curable heat-resistant silicone resin according to claim 1, wherein the solvent of step (1) is benzene, toluene or xylene; the acidic catalyst is one or more of hydrochloric acid, concentrated sulfuric acid, trifluoromethanesulfonic acid, strongly acidic ion exchange resin and solid acid; the molar ratio of the trialkoxysilane to the water to the acid catalyst is 1:1.5-3: 0.002-0.01; the solvent in the step (2) is an inert organic solvent with the boiling point higher than 200 ℃.
6. The room-temperature curable heat-resistant silicone resin according to claim 1, wherein the hydroxy silicone oil HO (R) in step (3)2R3SiO)nH, wherein R2、R3Is methyl, aryl or saturated alkyl with 2-10 carbon atoms, and the value of n is an integer between 25-1000; the solvent is benzene, toluene or xylene.
7. The method of claim 4, wherein the components (A), (B) and (C) are mixed uniformly in a certain proportion, and the mixture is poured into a mold and cured at room temperature.
8. The method of applying room temperature curable heat resistant silicone resin according to claim 7, wherein the solvent is toluene or xylene for dilution.
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| CN108441115B (en) * | 2018-04-10 | 2020-02-14 | 山东省科学院新材料研究所 | Room-temperature-cured radiation-resistant silicone resin composition and preparation method thereof |
| CN110218521B (en) * | 2019-07-03 | 2021-02-19 | 山东省科学院新材料研究所 | Water-based silicone resin three-proofing coating and preparation method thereof |
| CN110452389B (en) * | 2019-08-23 | 2021-07-23 | 山东省科学院新材料研究所 | Low-temperature-resistant low-permeability silicone resin coating composition and preparation method thereof |
| CN111205462B (en) * | 2020-01-10 | 2021-03-30 | 山东大学 | Preparation method of silicone resin containing perfluor cyclobutyl aryl ether structure |
| CN112194980B (en) * | 2020-09-02 | 2022-03-18 | 广东优贝精细化工有限公司 | Hydrophobic coating agent for automobile windshield and preparation method thereof |
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