CN108250445A - A kind of phenol aldehyde modified silicones of high temperature resistant environment-protective and preparation method thereof - Google Patents
A kind of phenol aldehyde modified silicones of high temperature resistant environment-protective and preparation method thereof Download PDFInfo
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- CN108250445A CN108250445A CN201711471614.8A CN201711471614A CN108250445A CN 108250445 A CN108250445 A CN 108250445A CN 201711471614 A CN201711471614 A CN 201711471614A CN 108250445 A CN108250445 A CN 108250445A
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- high temperature
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- aldehyde modified
- temperature resistant
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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
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- Phenolic Resins Or Amino Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention proposes phenol aldehyde modified silicones of a kind of high temperature resistant environment-protective and preparation method thereof, using Effect of Organosilicon-modified Phenol-formaldehyde Resin, its embrittlement and use reliability can be improved, it is good with its manufactured composite material temperature tolerance, instantaneous heat-resisting material can be used as, as ablators such as rocket, guided missiles；Optimize silicone content, increase with the content of Si O Si chains in phenolic resin, improve phenolic resin heat resistance cause its 200 DEG C toast 12h under the conditions of color it is unchanged, without loss of gloss, adhesive force, flexibility, impact resistance can be greatly improved.
Description
Technical field
The present invention relates to phenolic resins field more particularly to a kind of phenol aldehyde modified silicones of high temperature resistant environment-protective and its systems
Preparation Method.
Background technology
Phenolic resin has good heat resistance, rigidity, dimensional stability, dielectric mechanical property, adhesive strength, high carbon residue
Rate etc., and it is at low cost, but brittleness is big, particularly easily cracks under high temperature, using by larger limitation.
Automobile, space flight and the rapid development of mechanical processing industry propose higher requirement to the heat resistance of adhesive, such as
Launching pad seat arrangement, guided missile and rocket high-temperature systems material, rocket and supersonic plane head, impact type jet are started
Machine combustion chamber, high temperature radar cover material, atomic pile are required to the operating temperature of high-temperature resistance adhesive higher than 500 DEG C, and
Still there is higher adhesive strength under conditions of 800 DEG C, and this performance can be kept before the deadline.It is existing through inorganic
The operating temperature of the thermostable phenolic resin adhesive of filler hybrid modification is less than 500 DEG C, is used in 500 DEG C or more long term times
Can substantially reduce the adhesive strength of adhesive；500 DEG C are although resistant to using ceramic modified thermostable phenolic resin adhesive
More than high temperature, but curing process is harsh, needs to be post-processed under high temperature and high vacuum condition higher than 500 DEG C, complex process,
And glue brittleness is larger.
Invention content
In view of this, it is phenol aldehyde modified to propose the good high temperature resistant environment-protective of a kind of adhesive force, flexibility, impact resistance by the present invention
Silicones and preparation method thereof.
The technical proposal of the invention is realized in this way：On the one hand, the present invention provides a kind of high temperature resistant environment-protective phenolic aldehyde to change
Property silicones includes the component of following mass fraction,
300-370 parts of phenol；
Mass concentration is 400-600 parts of the formalin of 36-37%；
Mass concentration is the Na of 5-15%2CO310-40 parts of aqueous solution；
100-250 parts of tetraethoxysilane.
Second aspect of the present invention provides the preparation method of the phenol aldehyde modified silicones of high temperature resistant environment-protective described in first aspect,
Including step S1, by phenol, formalin, Na2CO3Aqueous solution is added in reactor, and 20-40min is stirred at 40-75 DEG C,
Then start gradually to heat up, start timing when occurring phegma in condenser, condensation reaction 1-3 hours at 80-120 DEG C,
The sampling analysis degree of polymerization.
On the basis of above technical scheme, it is preferred that further include step S2, be cooled to 50-90 DEG C, add acid for adjusting pH extremely
Neutrality, washing, stratification separate upper water, and lower-layer resin is dehydrated under 0.08-0.09MPa vacuum degrees, and it is saturating can to obtain bronzing
Bright phenolic resin.Specifically, the acid is HCl solution.
It is further preferred that further including step S3, synthetic phenolic resin is taken to be slowly added under stirring in reactor
Tetraethoxysilane is warming up to 50-70 DEG C and reacts 0.5-1.5 hours, it is small to then heat to 80-110 DEG C of back flow reaction 0.5-1.5
When, vacuum extraction solvent stops during temperature rise vacuumizing, adds in ethyl alcohol cooling, obtain phenol aldehyde modified organic siliconresin.
Phenol aldehyde modified silicones of high temperature resistant environment-protective of the present invention and preparation method thereof has relative to the prior art with following
Beneficial effect：
(1) using Effect of Organosilicon-modified Phenol-formaldehyde Resin, its embrittlement and use reliability can be improved, with its manufactured composite wood
Expect temperature tolerance it is good, can at 200-260 DEG C job applications for quite a long time, and can be used as instantaneous heat-resisting material, as rocket,
The ablators such as guided missile；
(2) silicone content is optimized, increases with the content of Si-O-Si chains in phenolic resin, improves phenolic resin
Heat resistance cause its 200 DEG C toast 12h under the conditions of color it is unchanged, without loss of gloss, adhesive force, flexibility, impact resistance
It can be greatly improved.
Specific embodiment
Below in conjunction with embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only the embodiment of a part of embodiment of the present invention rather than whole.Based in the present invention
Embodiment, the every other embodiment party that those of ordinary skill in the art are obtained without making creative work
Formula shall fall within the protection scope of the present invention.
Embodiment 1
The phenol aldehyde modified silicones of high temperature resistant environment-protective of the present embodiment, composition of raw materials are as follows：
Phenol 300kg；
Mass concentration is 36 formalin 400kg；
Mass concentration is 5% Na2CO3Aqueous solution 10kg；
Tetraethoxysilane 100kg.
Preparation process is as follows：
S1, by phenol, formalin, Na2CO3Aqueous solution is added in reactor, and 20min, Ran Houkai are stirred at 40 DEG C
Beginning gradually heats up, and starts timing when occurring phegma in condenser, condensation reaction 1 hour at 80 DEG C, sampling analysis polymerization
Degree；
S2 is cooled to 40 DEG C, adds in HCl solution under stiring and adjusts pH to neutrality, washes, stratification separates upper strata
Water, lower-layer resin are dehydrated under 0.08MPa vacuum degrees, and resin temperature stops vacuum when rising, and stop heating, it is transparent can to obtain bronzing
Phenolic resin；
S3 takes synthetic phenolic resin to be slowly added to tetraethoxysilane in reactor under stirring, be warming up to 50 DEG C
Reaction 0.5 hour, then heats to 80 DEG C of back flow reactions 0.5 hour, vacuum extraction solvent, and when temperature rise stops vacuumizing,
Ethyl alcohol cooling is added in, obtains phenol aldehyde modified organic siliconresin.
The phenol aldehyde modified organic siliconresin that the present embodiment is prepared color under the conditions of 200 DEG C of baking 12h is unchanged, nothing
Loss of gloss, adhesive force grade reach 1 grade, flexibility 2mm, impact resistance 45kg.cm.
Embodiment 2
The phenol aldehyde modified silicones of high temperature resistant environment-protective of the present embodiment, composition of raw materials are as follows：
Phenol 340kg；
Mass concentration is 36% formalin 500kg；
Mass concentration is 10% Na2CO3Aqueous solution 25kg；
Tetraethoxysilane 120kg.
Preparation process is as follows：
S1, by phenol, formalin, Na2CO3Aqueous solution is added in reactor, and 30min, Ran Houkai are stirred at 60 DEG C
Beginning gradually heats up, and starts timing when occurring phegma in condenser, condensation reaction 2 hours at 100 DEG C, sampling analysis polymerization
Degree；
S2 is cooled to 70 DEG C, adds in HCl solution under stiring and adjusts pH to neutrality, washes, stratification separates upper strata
Water, lower-layer resin are dehydrated under 0.09MPa vacuum degrees, and resin temperature stops vacuum when rising, and stop heating, it is transparent can to obtain bronzing
Phenolic resin；
S3 takes synthetic phenolic resin to be slowly added to tetraethoxysilane in reactor under stirring, be warming up to 60 DEG C
Reaction 1 hour, then heats to 90 DEG C of back flow reactions 1 hour, vacuum extraction solvent, and when temperature rise stops vacuumizing, and adds in
Ethyl alcohol cools down, and obtains phenol aldehyde modified organic siliconresin.
The phenol aldehyde modified organic siliconresin that the present embodiment is prepared color under the conditions of 200 DEG C of baking 12h is unchanged, nothing
Loss of gloss, adhesive force grade reach 2 grades, and flexibility reaches 2mm, and impact resistance reaches 50kg.cm.
Embodiment 3
The phenol aldehyde modified silicones of high temperature resistant environment-protective of the present embodiment, composition of raw materials are as follows：
Phenol 370kg；
Mass concentration is 37% formalin 600kg；
Mass concentration is 15% Na2CO3Aqueous solution 40kg；
Tetraethoxysilane 250kg.
Preparation process is as follows：
S1, by phenol, formalin, Na2CO3Aqueous solution is added in reactor, and 40min, Ran Houkai are stirred at 75 DEG C
Beginning gradually heats up, and starts timing when occurring phegma in condenser, condensation reaction 3 hours at 120 DEG C, sampling analysis polymerization
Degree；
S2 is cooled to 90 DEG C, adds in HCl solution under stiring and adjusts pH to neutrality, washes, stratification separates upper strata
Water, lower-layer resin are dehydrated under 0.09MPa vacuum degrees, and resin temperature stops vacuum when rising, and stop heating, it is transparent can to obtain bronzing
Phenolic resin；
S3 takes synthetic phenolic resin to be slowly added to tetraethoxysilane in reactor under stirring, be warming up to 70 DEG C
Reaction 1.5 hours, then heats to 110 DEG C of back flow reactions 1.5 hours, vacuum extraction solvent, and when temperature rise stops vacuumizing,
Ethyl alcohol cooling is added in, obtains phenol aldehyde modified organic siliconresin.
The phenol aldehyde modified organic siliconresin that the present embodiment is prepared color under the conditions of 200 DEG C of baking 12h is unchanged, nothing
Loss of gloss, adhesive force grade reach 1 grade, and flexibility reaches 2mm, and impact resistance reaches 55kg.cm.
The foregoing is merely the better embodiments of the present invention, are not intended to limit the invention, all the present invention's
Within spirit and principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (5)
1. a kind of phenol aldehyde modified silicones of high temperature resistant environment-protective, it is characterised in that：It includes the component of following mass fraction,
300-370 parts of phenol；
Mass concentration is 400-600 parts of the formalin of 36-37%；
Mass concentration is the Na of 5-15%2CO310-40 parts of aqueous solution；
100-250 parts of tetraethoxysilane.
2. the preparation of the phenol aldehyde modified silicones of the phenol aldehyde modified silicones of high temperature resistant environment-protective high temperature resistant environment-protective as described in claim 1
Method, it is characterised in that：It includes step S1, by phenol, formalin, Na2CO3Aqueous solution is added in reactor, in 40-
20-40min is stirred at 75 DEG C, then starts gradually to heat up, starts timing when occurring phegma in condenser, at 80-120 DEG C
Lower condensation reaction 1-3 hours, the sampling analysis degree of polymerization.
3. the preparation method of the phenol aldehyde modified silicones of high temperature resistant environment-protective as claimed in claim 2, it is characterised in that：Further include step
Rapid S2, is cooled to 50-90 DEG C, and acid for adjusting pH is added to be washed, stratification separates upper water, and lower-layer resin is in 0.08- to neutrality
It is dehydrated under 0.09MPa vacuum degrees, bronzing transparent phenol resin can be obtained.
4. the preparation method of the phenol aldehyde modified silicones of high temperature resistant environment-protective as claimed in claim 3, it is characterised in that：The acid is
HCl solution.
5. the preparation method of the phenol aldehyde modified silicones of high temperature resistant environment-protective as claimed in claim 3, it is characterised in that：Further include step
Rapid S3 takes synthetic phenolic resin to be slowly added to tetraethoxysilane under stirring in reactor, is warming up to 50-70 DEG C instead
It answers 0.5-1.5 hours, then heats to 80-110 DEG C of back flow reaction 0.5-1.5 hours, vacuum extraction solvent, when temperature rise stops
It only vacuumizes, adds in ethyl alcohol cooling, obtain phenol aldehyde modified organic siliconresin.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711471614.8A CN108250445A (en) | 2017-12-29 | 2017-12-29 | A kind of phenol aldehyde modified silicones of high temperature resistant environment-protective and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711471614.8A CN108250445A (en) | 2017-12-29 | 2017-12-29 | A kind of phenol aldehyde modified silicones of high temperature resistant environment-protective and preparation method thereof |
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| CN108250445A true CN108250445A (en) | 2018-07-06 |
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| CN201711471614.8A Pending CN108250445A (en) | 2017-12-29 | 2017-12-29 | A kind of phenol aldehyde modified silicones of high temperature resistant environment-protective and preparation method thereof |
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| CN (1) | CN108250445A (en) |
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2017
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