CN107459652A - A kind of heat resistant silicone of ambient temperature curable and preparation method thereof - Google Patents
A kind of heat resistant silicone of ambient temperature curable and preparation method thereof Download PDFInfo
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- CN107459652A CN107459652A CN201710680478.7A CN201710680478A CN107459652A CN 107459652 A CN107459652 A CN 107459652A CN 201710680478 A CN201710680478 A CN 201710680478A CN 107459652 A CN107459652 A CN 107459652A
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention discloses a kind of heat resistant silicone of ambient temperature curable and preparation method thereof.The present invention has synthesized the alkoxysilane compound containing trialkylsilyl group in molecular structure containing hexafluoro cyclobutyl arylene ether structure first, then by preparing alkoxy end-capped organic siliconresin (R with trifunctional silicones performed polymer, hydroxy silicon oil copolymerization1SiO1.5)a(R2R3SiO)b(R2R3Si‑R4‑R2R3SiO)c, wherein, R1For aryl, R2、R3For the saturated alkane base between methyl, aryl or carbon number 2~10, R4For hexafluoro cyclobutyl arylene ether；A+b+c=1, a numerical value are between 0~0.5, and b numerical value is 0 ＜ b ＜ 1, and c numerical value is 0 ＜ c ＜ 1, and alkoxy mass content is 0.1%~10%.Ambient temperature curable obtains heat decomposition temperature and reaches more than 450 DEG C after the organic siliconresin mixes with trialkoxy silane, curing catalysts, and has plastoelastic silicone material.
Description
Technical field
The present invention relates to a kind of heat resistant silicone of ambient temperature curable and preparation method thereof, belong to organosilicon macromolecule technology
Field.
Background technology
Silicones is the inorganic polymer of cross-linking type half that is a kind of while having Si-O-Si structures and organic group.Its structure
Particularity make it have the heat resistance more excellent than common organic resin, in Aero-Space, electronic apparatus and military weapon etc.
Field has important application.But when temperature reaches 250 DEG C and the above, silicones terminal hydroxy group is generated by " return and sting " reaction
Cyclic oligomer and caged small molecule, trigger the degraded of " tripping " formula；Or Si-R oxidations and Si-O-Si thermal decomposition weight occurs
Row.Therefore, long-term use of temperature of silicones can not meet that heatproof requires higher stringent environmental requirements no more than 250 DEG C.
Rigidity larger large volume segment or aromatic ring are introduced in Si-O-Si main chains, instead of the part oxygen atom in main chain, suppresses main chain
Cyclization degraded is to improve a kind of effective ways of silicones heat resistance at high temperature.
Hexafluoro cyclobutyl arylene ether structure is to be prepared by Trifluorovinyl Aryl Ethers through the reaction of [2+2] Cyclodimerization.
Polymer containing hexafluoro cyclobutyl arylene ether structure not only has excellent properties possessed by general fluoropolymer, i.e., outstanding
Electrical insulation capability, heat endurance and chemical stability, and due to containing aromatic ring structure and ehter bond in its structure so that such
Polymer can be dissolved in a variety of organic solvents, so as to have good processing characteristics.By hexafluoro cyclobutyl arylene ether structure
It is introduced into silicones, the heat resistance of silicones is played due to the addition of rigid four-membered ring and benzene ring structure and is obviously improved work
With.Smith etc. is prepared for linear perfluorocyclobutanearyl aryl-ether-dimethyl siloxane alternate copolymer and POSS- perfluor rings respectively
Butyl aryl ether copolymer, the heat decomposition temperature (Td) of polymer can reach more than 450 DEG C (Macromolecules, 1996,
29:852；Polymer,2007,48:4637).CN104448320 reports a kind of silicones of phenyl containing trifluoro-ethylene
Manufacture method, the thermal weight loss temperature of fluorine-containing silicones 5% obtained after solidification can reach 480 DEG C.But it is first in above-mentioned report
The silicones performed polymer of the structure containing Trifluorovinyl Aryl Ethers is prepared, then passes through Trifluorovinyl Aryl Ethers [2+2] thermal cyclization
Resin solidification is realized, solidification temperature generally wants more than 100 DEG C, even up to more than 200 DEG C, and this brings very big inconvenience to construction,
And along with very big energy resource consumption.Meanwhile this technique often leads to the reaction of trifluoro vinyl ether not exclusively, the three of residual
Fluorovinyl ether can usually influence the resistance to medium of material to the equal sensitivity of bronsted lowry acids and bases bronsted lowry.The fluorine-containing silicones of CN104448320 reports
It is that a kind of material, Smith etc. of high rigidity and high intensity is not studied the mechanical property of the fluorine resin of preparation, at present still
Have not seen the report of the elastoplasticity heat resistant silicone of the ambient temperature curable containing hexafluoro cyclobutyl arylene ether structure.
The content of the invention
It is an object of the invention to provide a kind of heat resistant silicone of ambient temperature curable and preparation method thereof.The present invention closes first
Into the alkoxysilane compound containing trialkylsilyl group in molecular structure containing hexafluoro cyclobutyl arylene ether structure, then by with trifunctional silicones performed polymer,
Hydroxy silicon oil copolymerization prepares alkoxy end-capped silicones.A certain proportion of trialkoxy silane is added in the silicones as friendship
Join agent, cold curing can be achieved under catalyst action and obtain heat decomposition temperature and reach more than 450 DEG C, and there is plastoelastic silicon
Resin material.
The present invention is achieved by the following technical programs：A kind of heat resistant silicone of ambient temperature curable, it is characterized in that, bag
Include following three kinds of components：
(A) alkoxy end-capped averaged unit formula is (R1SiO1.5)a(R2R3SiO)b(R2R3Si-R4-R2R3SiO)cOrganosilicon
Resin
Wherein, R1For aryl, R2、R3For the saturated alkane base between methyl, aryl or carbon number 2~10, R4For hexafluoro
Cyclobutyl arylene ether；A, b, c numerical value are identical or different, a+b+c=1, and a numerical value is between 0~0.5, and b numerical value is 0
＜ b ＜ 1, c numerical value are 0 ＜ c ＜ 1；Saturated alkane of the alkoxy wherein blocked between methoxyl group or carbon number 2~10
Epoxide, preferably methoxyl group；Alkoxy mass content is 0.1~10%.
Wherein, a preferably 0 ＜ a≤0.5 (excluding 0 value), R1Preferably phenyl, R2、R3Preferably methyl, R4Preferably
(B) structural formula is R6Si(OR5)3Trialkoxy silane crosslinking agent, wherein R5For methyl, ethyl or carbon number 3
Saturated alkane base between~10, preferably methyl；R6For the saturated alkane base between methyl, aryl or carbon number 2~10,
It is preferred that methyl, ethyl, propyl group.
(C) hydroxyl or the curing catalysts of alkoxy condensation reaction, including alkali compounds, metal-containing compound are promoted,
It is preferred that titaniferous or tin compound, particularly preferred titanate ester compound or chelate.
The dosage of component (B) is：Organic siliconresin relative to the component (A) of every 100 mass parts is 5~10 mass parts.
The dosage of component (C) is：Organic siliconresin relative to the component (A) of every 100 mass parts is 0.001~0.01 matter
Measure part.
Construction method：(A), (B) and (C) is well mixed with aforementioned proportion, a small amount of toluene, dimethylbenzene can be added if necessary
Etc. being diluted；Pour into mould, cold curing.Solidified after-product main component is the reactant mixture of three kinds of components, is also contained
There are (A), (B), (C) component that part does not participate in reaction.
Said components (A) are that averaged unit formula is (R1SiO1.5)a(R2R3SiO)b(R2R3Si-R4-R2R3SiO)cOrganosilicon
Resin to prepare equation as follows：
Comprise the following steps：
(1) water, solvent and acidic catalyst are well mixed, stir lower dropwise addition trialkoxy silane R1Si(OR)3, add
Back flow reaction 1-2h, neutrality is washed to after being cooled to room temperature, collects organic phase, dried, filter, being concentrated to give hydroxyl and alkoxy envelope
The trifunctional silicones performed polymer at end；
(2) alkoxy silane containing Trifluorovinyl Aryl Ethers structure and solvent are well mixed, under nitrogen atmosphere,
200-250 DEG C of reaction 0.5-2h, cooling are quenched reaction, removing solvent, column chromatography for separation, obtain compound 1, structural formula as above institute
Show；
(3) trifunctional silicones performed polymer, compound 1, the hydroxy silicon oil HO (R prepared step (1)2R3SiO)nH, it is molten
Agent, catalyst are well mixed, and are heated to reflux, and remove water, the methanol of generation, 3-6 hours followed by aging, and reaction is down to room after terminating
Temperature, neutralize, filtering, filtrate decompression is evaporated off solvent, obtains ambient temperature curable heat resistant silicone (R1SiO1.5)a(R2R3SiO)b
(R2R3Si-R4-R2R3SiO)c。
Step (1) described solvent is benzene, toluene or dimethylbenzene.
Step (1) described acidic catalyst is strong acid catalyst, selected from hydrochloric acid, the concentrated sulfuric acid, trifluoromethanesulfonic acid, highly acid from
One or more in sub-exchange resin, solid acid.
Trialkoxy silane, water, the mol ratio of acidic catalyst are 1 in step (1):1.5-3:0.002-0.01.
Trialkoxy silane R in step (1)1Si(OR)3Preferably phenyltrimethoxysila,e.
Step (2) described solvent is the inert organic solvents that boiling point is higher than 200 DEG C, preferably diphenyl ether.
Alkoxy silane containing Trifluorovinyl Aryl Ethers structure described in step (2) is preferably trifluoro vinyl phenyl ether
Base dimethyl methoxy silane.
Step (3) hydroxy silicon oil HO (R2R3SiO)nH, wherein R2、R3For methyl, aryl or carbon number 2~10 it
Between saturated alkane base, n numerical value is the integer between 25~1000, the integer between preferably 50~100.It is preferred that dimethyl hydroxyl
Base silicone oil.
Step (3) described solvent is benzene, toluene or dimethylbenzene.
Step (3) described catalyst is strong acid catalyst, is handed over selected from hydrochloric acid, the concentrated sulfuric acid, trifluoromethanesulfonic acid, strong acidic ion
The one or more changed in resin, solid acid.
Trifunctional silicones performed polymer is (with repeat unit R in step (3)1SiO1.5Meter), compound 1, hydroxy silicon oil (with
Repeat unit R2R3SiO is counted), the mol ratio of catalyst be 1:0.1-1:1-5:0.0001-0.001.
Compared with prior art, the beneficial effects of the invention are as follows：
Contain 1. the present invention is prepared by [2+2] thermal cyclization reaction of Trifluorovinyl Aryl Ethers base dimethyl methoxy silane
Have the dialkoxysilane compounds 1 of hexafluoro cyclobutyl arylene ether structure, be subsequently used for preparing silicones, by rigid four-membered ring and
Aromatic ring introduces silicones, and the effect of being obviously improved is played to the heat resistance of silicones, and heat decomposition temperature reaches more than 450 DEG C,
Preferably more than 480 DEG C.Due to introducing hexafluoro cyclobutyl arylene ether structure before curing, using Si-OR dealcoholysis curing process,
Avoid height required when solidifying in the prior art by the silicones performed polymer thermal cyclization of the structure containing Trifluorovinyl Aryl Ethers
Warm technique, and trifluoro vinyl ether residue is not had, improve the reliability and stability of material.
2. the present invention using trifunctional silicones performed polymer is first prepared, is then copolymerized with linear hydroxy silicon oil, compound 1
Mode synthesizes to obtain block resinous copolymeric siloxane thing, and its unique structure assigns it and can be achieved soon under crosslinking agent and catalyst action
Fast cold curing, surface drying time≤15 minute, while obtained silicone material has preferable elastoplasticity.
Above-mentioned performance make its electronics industry three proofings (mould proof, moisture proof, salt spray proof), lsi package,
The fields such as Aero-Space, national defence have extensive use.
Brief description of the drawings
Fig. 1 is the thermal weight loss spectrogram that the embodiment of the present invention 7 is formulated 3 gained silicone materials.
Embodiment
With reference to embodiment, the present invention is further described.
Embodiment 1
Deionized water 75.6g, toluene are added in the four-hole boiling flask equipped with thermometer, agitating paddle and reflux condensing tube
200g, hydrochloric acid (concentration 37%) 2g, stirs, and phenyltrimethoxysila,e 396g is added dropwise.Add and be warming up to backflow, react
2h, then it is cooled to room temperature.Reaction solution is washed three times to neutral with 400g deionizations.Organic phase is collected, anhydrous calcium chloride is dried
Overnight.Calcium chloride is filtered, filtrate concentration removes toluene and obtains trifunctional silicones performed polymer 240g.
Embodiment 2
Reaction bulb progress vacuum nitrogen gas operation is secondary, trifluoro vinyl phenyl ether two is added under nitrogen atmosphere
Methylmethoxysilane 262g, diphenyl ether 500g, it is placed in 250 DEG C of oil baths and reacts, taken out after 1h, liquid nitrogen is quenched.Column chromatography point
From obtaining hexafluoro cyclobutylphenyl ether tetramethyl xylene epoxide disilane 113g, yield 43%.Hydrogen stave sign (1H NMR,
300MHz,CDCl3,δin ppm):0.33 (t, 12H), 3.55 (s, 6H), 7.15~7.18 (m, 6H), 7.3 (d, 2H).Fluorine is composed
Characterize (19F NMR,282MHz,CDCl3,δin ppm):- 127.2~-132.8 (m, 6F).
Embodiment 3
Performed polymer 20g, the 5.7g compound 1 prepared in Example 1, dimethyl hydroxyl silicon oil (500mPas) 22.9g
Reaction bulb is added, is dissolved and is well mixed with 200g toluene, 0.1g trifluoromethanesulfonic acids is added, is heated to reflux, removes water, the first of generation
Alcohol, continue to cure 3h, room temperature is down in reaction after terminating, added 0.5g sodium carbonate and neutralized, filtering.Filtrate decompression concentration removes first
Benzene, it is (PhSiO to obtain averaged unit formula1.5)0.325(Me2SiO)0.65(Me2Si-R4-Me2SiO)0.025Silicones (R4For six
Fluorine cyclobutylphenyl ether, as follows), viscosity (80 DEG C, 6500mPas), methoxyl group mass content 2.3%.
Embodiment 4
Performed polymer 20g, the 12.23g compound 1 prepared in Example 1, dimethyl hydroxyl silicon oil (100mPas)
22.9g adds reaction bulb, is dissolved and is well mixed with 200g toluene, adds 0.12g trifluoromethanesulfonic acids, is heated to reflux, and removes generation
Water, methanol, continue to cure 3h, reaction is down to room temperature after terminating, and adds 0.6g sodium carbonate and neutralizes, filtering.Filtrate decompression concentrates
Toluene is removed, it is (PhSiO to obtain averaged unit formula1.5)0.317(Me2SiO)0.635(Me2Si-R4-Me2SiO)0.048Silicones,
Viscosity (80 DEG C, 5300mPas), methoxyl group mass content 2.5%.
Embodiment 5
Performed polymer 20g, the 16.3g compound 1 prepared in Example 1, dimethyl hydroxyl silicon oil (500mPas)
20.64g adds reaction bulb, is dissolved and is well mixed with 200g toluene, adds 0.1g trifluoromethanesulfonic acids, is heated to reflux, and removes generation
Water, methanol, continue to cure 3h, reaction is down to room temperature after terminating, and adds 0.5g sodium carbonate and neutralizes, filtering.Filtrate decompression concentrates
Toluene is removed, it is (PhSiO to obtain averaged unit formula1.5)0.33(Me2SiO)0.6(Me2Si-R4-Me2SiO)0.07Silicones, glue
Spend (80 DEG C, 7200mPas), methoxyl group mass content 1.86%.
Embodiment 6
Performed polymer 20g, the 12.23g compound 1 prepared in Example 1, dimethyl hydroxyl silicon oil (100mPas)
11.47g adds reaction bulb, is dissolved and is well mixed with 200g toluene, adds 0.1g trifluoromethanesulfonic acids, is heated to reflux, and removes generation
Water, methanol, continue to cure 3h, reaction is down to room temperature after terminating, and adds 0.5g sodium carbonate and neutralizes, filtering.Filtrate decompression concentrates
Toluene is removed, it is (PhSiO to obtain averaged unit formula1.5)0.483(Me2SiO)0.483(Me2Si-R4-Me2SiO)0.034Silicones,
Viscosity (80 DEG C, 15000mPas), methoxyl group mass content 1.05%.
Embodiment 7
By the silicones prepared in embodiment 3,4,5,6 respectively with crosslinking agent MTMS, catalyst metatitanic acid
Butyl ester is well mixed in the ratio of table 1, can be added a small amount of toluene, dimethylbenzene etc. if necessary and is diluted.Sample pours into polytetrafluoro
In ethene mould, cold curing, its performance is tested after 72h.It is formulated and the results are shown in Table 1.Wherein it is formulated 3 gained silicone materials
Thermal weight loss spectrogram is as shown in Figure 1.
The material performance index of the different formulations of table 1
It can be seen that from table 1 and Fig. 1：Using the silicone material for preparing of the present invention with cold curing, elastoplasticity and
Resistant to elevated temperatures feature so that construction technology is more easy, the energy is saved, suitable for Aero-Space high-temperaure coating, LED and the sun
Energy cell panel encapsulation coating, and other tough and tensile, durable and high-temperature-resistant silicon resin material application fields of needs.
Above-mentioned is the description to the preferred embodiments of the invention, but not limiting the scope of the invention, at this
On the basis of the technical scheme of invention, those skilled in the art need not pay the various modifications that creative work can make or
Deformation is still within protection scope of the present invention.
Claims (10)
1. a kind of organic siliconresin, it is characterized in that, its is alkoxy end-capped, and averaged unit formula is (R1SiO1.5)a(R2R3SiO)b
(R2R3Si-R4-R2R3SiO)c；
Wherein, R1For aryl, R2、R3For the saturated alkane base between methyl, aryl or carbon number 2~10, R4For hexafluoro ring fourth
Base aryl ether；A, b, c numerical value are identical or different, a+b+c=1, and a numerical value is between 0~0.5, and b numerical value is 0 ＜ b ＜
1, c numerical value is 0 ＜ c ＜ 1；Saturated alkane epoxide of the alkoxy wherein blocked between methoxyl group or carbon number 2~10；
Alkoxy mass content is 0.1~10%.
2. a kind of heat resistant silicone of ambient temperature curable, it is characterized in that, including following three kinds of components：
(A) organic siliconresin described in claim 1；
(B) crosslinking agent；
(C) curing catalysts.
3. a kind of heat resistant silicone of ambient temperature curable as claimed in claim 2, it is characterized in that, (B) crosslinking agent is knot
Structure formula is R6Si(OR5)3Trialkoxy silane, wherein R5For the saturated alkane between methyl, ethyl or carbon number 3~10
Base；R6For the saturated alkane base between methyl, aryl or carbon number 2~10；(C) curing catalysts for promote hydroxyl or
The curing catalysts of alkoxy condensation reaction.
4. a kind of heat resistant silicone of ambient temperature curable as claimed in claim 3, it is characterized in that, (C) curing catalysts
For titaniferous or tin compound.
5. a kind of heat resistant silicone of ambient temperature curable as described in claim 3 or 4, it is characterized in that, the component (B)
Dosage is：Organic siliconresin relative to the component (A) of every 100 mass parts is 5~10 mass parts；The dosage of the component (C)
For：Organic siliconresin relative to the component (A) of every 100 mass parts is 0.001~0.01 mass parts.
6. the construction method of the heat resistant silicone of the ambient temperature curable described in claim 5, it is characterized in that, by (A), (B) and (C)
To mix in proportion, pour into mould, cold curing.
7. the construction method of the heat resistant silicone of the ambient temperature curable described in claim 6, it is characterized in that, add solvent toluene or
Dimethylbenzene dilutes.
8. the preparation method of organic siliconresin as claimed in claim 1, it is characterized in that,
(1) water, solvent and acidic catalyst are well mixed, stir lower dropwise addition trialkoxy silane R1Si(OR)3, add backflow
1-2h is reacted, is cooled to after room temperature and is washed to neutrality, collects organic phase, dries, filter, being concentrated to give hydroxyl and alkoxy end-capped
Trifunctional silicones performed polymer；
(2) alkoxy silane containing Trifluorovinyl Aryl Ethers structure and solvent are well mixed, under nitrogen atmosphere, 200-
250 DEG C of reaction 0.5-2h, cooling are quenched reaction, remove solvent, column chromatography for separation, obtain compound 1；
(3) trifunctional silicones performed polymer, compound 1, the hydroxy silicon oil HO (R prepared step (1)2R3SiO)nH, solvent, urge
Agent is well mixed, and is heated to reflux, and removes water, the methanol of generation, 3-6 hours followed by aging, and reaction is down to room temperature after terminating, in
With filtering, filtrate decompression is evaporated off solvent, obtains ambient temperature curable heat resistant silicone.
9. the preparation method of organic siliconresin as claimed in claim 8, it is characterized in that, step (1) solvent is benzene, toluene
Or dimethylbenzene；Acidic catalyst is one kind in hydrochloric acid, the concentrated sulfuric acid, trifluoromethanesulfonic acid, strong-acid ion exchange resin, solid acid
It is or several；Trialkoxy silane, water, the mol ratio of acidic catalyst are 1:1.5-3:0.002-0.01；Step (2) solvent
It is higher than 200 DEG C of inert organic solvents for boiling point.
10. the preparation method of organic siliconresin as claimed in claim 8, it is characterized in that, the step (3) hydroxy silicon oil
HO(R2R3SiO)nThe saturated alkane base of H, wherein R2, R3 between methyl, aryl or carbon number 2~10, n numerical value is 25
Integer between~1000；Solvent is benzene, toluene or dimethylbenzene；Catalyst is hydrochloric acid, the concentrated sulfuric acid, trifluoromethanesulfonic acid, highly acid
One or more in ion exchange resin, solid acid；R in trifunctional silicones performed polymer1SiO1.5, compound 1, hydroxyl silicon
R in oil2R3SiO, the mol ratio of catalyst are 1:0.1-1:1-5:0.0001-0.001.
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| CN108441115A (en) * | 2018-04-10 | 2018-08-24 | 山东省科学院新材料研究所 | A kind of room temperature curing radiation resistance silicon resin composition and preparation method thereof |
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| CN110452389A (en) * | 2019-08-23 | 2019-11-15 | 山东省科学院新材料研究所 | Low temperature resistant low ventilative silicone coatings composition of one kind and preparation method thereof |
| CN111205462A (en) * | 2020-01-10 | 2020-05-29 | 山东大学 | Preparation method of silicone resin containing perfluor cyclobutyl aryl ether structure |
| CN112194980A (en) * | 2020-09-02 | 2021-01-08 | 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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| CN114133574B (en) * | 2021-12-13 | 2023-03-10 | 山东省科学院新材料研究所 | Bridged naphthene toughened silicone resin and preparation method thereof |
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