CN107513144A - A kind of boron modified phenolic resin and preparation method thereof - Google Patents
A kind of boron modified phenolic resin and preparation method thereof Download PDFInfo
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- CN107513144A CN107513144A CN201710615123.XA CN201710615123A CN107513144A CN 107513144 A CN107513144 A CN 107513144A CN 201710615123 A CN201710615123 A CN 201710615123A CN 107513144 A CN107513144 A CN 107513144A
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- phenolic resin
- phenol
- boric acid
- paraformaldehyde
- boron
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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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
-
- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of boron modified phenolic resin, its raw material includes phenol, paraformaldehyde and boric acid, and the wherein mol ratio of phenol and paraformaldehyde is 1.0：1.2, and boric acid accounts for the 8% of phenol, paraformaldehyde and boric acid three's component sum.Modified, high temperature resistant phenolic aldehyde/epoxy resin that the present invention synthesizes, the decomposition temperature for inherently improving modified resin reach more than 500 DEG C, ensure that the heat resistance of resin meets expected require.Boron, which changes phenolic resin, has the hot property more excellent than traditional phenolic resin, and the impact flexibility for making to change high-temperature brake friction material, ablation resistant material product that phenolic resin produces as matrix using boron is significantly improved.
Description
Technical field
The present invention relates to naval stores field, specifically a kind of boron modified phenolic resin and preparation method thereof.
Background technology
With the development of aviation, aerospace flight technology and its other field industrial technology, to improving synthetic material temperature classification
It is required that increasingly urgent, in order to seek to improve the heat resistance of phenolic resin, Abroad in Recent Years is inorganic using being introduced in backbone structure
The method of element obtains good effect, is exactly one kind in this kind of high molecular polymer containing boron bakelite resin.
From the point of view of current market demand situation, the product of this class of domestic production is substantially zeroed, enters in such product
In the case that mouthful amount is substantially increased trend in recent years, state that market is in that supply falls short of demand, but imported product prevailing price
Height, the buying haul-cycle time is again long, and domestic correspondent is difficult to receive.On the other hand, modified resin correlation is exported in large quantities in recent years
Product product, with the fast development of domestic market, and the increase that outlet needs.
In general, the synthetic method that boron changes phenolic resin has two kinds：One kind is acid esterification method, by triphenyl borate,
Phenol and formaldehyde carry out copolycondensation, have obtained a kind of higher boron bakelite resin of methylol group content；The boron phenolic tree of this preparation
Fat temperature of initial decomposition is 220 DEG C, and the Residual carbon at 800 DEG C is 71.07%.This method is based on boric acid and phenol
Hydroxyl reaction, the shortcomings of reaction speed is too fast under hydroxyl water suction, discoloration, high pressure is overcome, but process conditions are difficult to control, product
Quality and uniformity it is larger by time effects.Another is the blending method that boron compound adds in reaction original state, should
The advantages of method is that process conditions and product quality are easily controllable.Boron is introduced in the molecular structure, can significantly improve phenolic aldehyde tree
Fat heat resistance and Residual carbon.
The content of the invention
It is an object of the invention to provide a kind of component of phenol, paraformaldehyde and boric acid three ratio（Mole）Reach optimal
The boron modified phenolic resin of value and optimal preparation method.
To achieve the above object, the present invention provides following technical scheme：
A kind of boron modified phenolic resin, its raw material include mole of phenol, paraformaldehyde and boric acid, wherein phenol and paraformaldehyde
Than for 1.0：1.2, and boric acid accounts for the 8% of phenol, paraformaldehyde and boric acid three's component sum.
A kind of preparation method of boron modified phenolic resin, it is comprised the following steps that：
（1）Phenol and dehydrating agent are added to and are provided with the reaction unit of condenser, thermometer, electric agitator and thermocouple；
（2）When temperature in reaction unit is warming up into 90 DEG C, add quantitative boric acid, at the same add NaOH solution adjust pH to
7.5, the solution reacts 2h at a temperature of vacuum decompression dehydration and 90-100 DEG C；
（3）Most backward reaction unit adds paraformaldehyde, is stirred between 100-110 DEG C and reacts 3h under decompression dehydration, cooled down
Produce the resin solid of chartreuse.
As the further scheme of the present invention：The NaOH solution is simultaneously as the catalysis reacted between phenol and boric acid
Agent.
As the further scheme of the present invention：The dehydrating agent is toluene solution.
Boron modified phenolic resin thermal weight loss under the high temperature conditions and Residual carbon are analyzed as follows：When phenol, paraformaldehyde and
The component ratio of boric acid three（Mole）Reach optimum value, i.e.,：For the component ratio of boric acid at 8% or so, analysis modified resin is 500
DEG C and 600 DEG C under the conditions of thermal weight loss show identical trend and be：The boron modified phenolic resin sample of the present invention is at 500 DEG C
Thermal weight loss be 40.46-42.05%, thermal weight loss at 600 DEG C is 47.28-49.72%, far below traditional phenolic resin 500
DEG C when thermal weight loss rate 57.95-59.54%, thermal weight loss at 600 DEG C is 70.33-82.25%；And boron modified phenolic resin exists
Residual carbon at 800 DEG C is 71.07%, far above the Residual carbon 48.48% of traditional phenolic resin.
To sum up, show that boron changes phenolic resin and has the hot property more excellent than traditional phenolic resin, lead over domestic same
The technical merit of industry.Make high-temperature brake friction material, the impact flexibility of ablation resistant material product produced using resin as matrix
It is significantly improved.
The raising of Boron contents is advantageous to the hot property of resin, because general phenolic resin is by C-C key connection benzene
Ring, C-C keys bond energy are 347 kJ/mol；And boron bakelite resin mainly passes through B-O key connection phenyl ring, B-O keys
Bond energy is that 523 kJ/mol. its heat decomposition temperature can reach more than 500 DEG C, hence it is evident that improve phenolic resin heat resistance and
Heat endurance, therefore, boron modified phenolic resin should be high-temperature brake material, friction material, the matrix of ablation resistant material first choice
Resin.
Compared with prior art, the beneficial effects of the invention are as follows：
Brand-new modified, high temperature resistant phenolic aldehyde/epoxy resin is synthesized, the decomposition temperature for inherently improving modified resin reaches 500 DEG C
More than, ensure that the heat resistance of resin meets expected require.
Boron, which changes phenolic resin, has the hot property more excellent than traditional phenolic resin, makes to change phenolic resin as matrix using boron
The high-temperature brake friction material of production, the impact flexibility of ablation resistant material product are significantly improved.
Embodiment
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.Based in the present invention
Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, all
Belong to the scope of protection of the invention.
Embodiment 1
In the embodiment of the present invention, a kind of boron modified phenolic resin, its raw material includes phenol, paraformaldehyde and boric acid, wherein phenol
Mol ratio with paraformaldehyde is 1.0：1.2, and boric acid accounts for the 8% of phenol, paraformaldehyde and boric acid three's component sum.
A kind of preparation method of boron modified phenolic resin, it is comprised the following steps that：
（1）Phenol and dehydrating agent are added to and are provided with the reaction unit of condenser, thermometer, electric agitator and thermocouple；
（2）When temperature in reaction unit is warming up into 90 DEG C, add quantitative boric acid, at the same add NaOH solution adjust pH to
7.5, the solution reacts 2h at a temperature of vacuum decompression dehydration and 90 DEG C；
（3）Most backward reaction unit adds paraformaldehyde, is stirred between 100 DEG C and reacts 3h under decompression dehydration, cooled down and produce
The resin solid of chartreuse.
The NaOH solution is simultaneously as the catalyst reacted between phenol and boric acid.
The dehydrating agent is toluene solution.
Embodiment 2
In the embodiment of the present invention, a kind of boron modified phenolic resin, its raw material includes phenol, paraformaldehyde and boric acid, wherein phenol
Mol ratio with paraformaldehyde is 1.0：1.2, and boric acid accounts for the 8% of phenol, paraformaldehyde and boric acid three's component sum.
A kind of preparation method of boron modified phenolic resin, it is comprised the following steps that：
（1）Phenol and dehydrating agent are added to and are provided with the reaction unit of condenser, thermometer, electric agitator and thermocouple；
（2）When temperature in reaction unit is warming up into 90 DEG C, add quantitative boric acid, at the same add NaOH solution adjust pH to
7.5, the solution reacts 2h at a temperature of vacuum decompression dehydration and 95 DEG C；
（3）Most backward reaction unit adds paraformaldehyde, is stirred between 105 DEG C and reacts 3h under decompression dehydration, cooled down and produce
The resin solid of chartreuse.
The NaOH solution is simultaneously as the catalyst reacted between phenol and boric acid.
The dehydrating agent is toluene solution.
Embodiment 3
In the embodiment of the present invention, a kind of boron modified phenolic resin, its raw material includes phenol, paraformaldehyde and boric acid, wherein phenol
Mol ratio with paraformaldehyde is 1.0：1.2, and boric acid accounts for the 8% of phenol, paraformaldehyde and boric acid three's component sum.
A kind of preparation method of boron modified phenolic resin, it is comprised the following steps that：
（1）Phenol and dehydrating agent are added to and are provided with the reaction unit of condenser, thermometer, electric agitator and thermocouple；
（2）When temperature in reaction unit is warming up into 90 DEG C, add quantitative boric acid, at the same add NaOH solution adjust pH to
7.5, the solution reacts 2h at a temperature of vacuum decompression dehydration and 100 DEG C；
（3）Most backward reaction unit adds paraformaldehyde, is stirred between 110 DEG C and reacts 3h under decompression dehydration, cooled down and produce
The resin solid of chartreuse.
The NaOH solution is simultaneously as the catalyst reacted between phenol and boric acid.
The dehydrating agent is toluene solution.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, Er Qie
In the case of without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, embodiment all should be regarded as exemplary, and be nonrestrictive, the scope of the present invention is by appended power
Profit requires rather than described above limits, it is intended that all in the implication and scope of the equivalency of claim by falling
Change is included in the present invention.
Moreover, it will be appreciated that although the present specification is described in terms of embodiments, not each embodiment is only wrapped
Containing an independent technical scheme, this narrating mode of specification is only that those skilled in the art should for clarity
Using specification as an entirety, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
It is appreciated that other embodiment.
Claims (4)
1. a kind of boron modified phenolic resin, its raw material includes phenol, paraformaldehyde and boric acid, it is characterised in that wherein phenol and
The mol ratio of paraformaldehyde is 1.0：1.2, and boric acid accounts for the 8% of phenol, paraformaldehyde and boric acid three's component sum.
2. a kind of preparation method of boron modified phenolic resin as claimed in claim 1, it is characterised in that its specific steps is such as
Under：
（1）Phenol and dehydrating agent are added to and are provided with the reaction unit of condenser, thermometer, electric agitator and thermocouple；
（2）When temperature in reaction unit is warming up into 90 DEG C, add quantitative boric acid, at the same add NaOH solution adjust pH to
7.5, the solution reacts 2h at a temperature of vacuum decompression dehydration and 90-100 DEG C；
（3）Most backward reaction unit adds paraformaldehyde, is stirred between 100-110 DEG C and reacts 3h under decompression dehydration, cooled down
Produce the resin solid of chartreuse.
3. the preparation method of boron modified phenolic resin according to claim 2, it is characterised in that the NaOH solution is simultaneously
As the catalyst reacted between phenol and boric acid.
4. the preparation method of boron modified phenolic resin according to claim 2, it is characterised in that the dehydrating agent is toluene
Solution.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710615123.XA CN107513144A (en) | 2017-07-26 | 2017-07-26 | A kind of boron modified phenolic resin and preparation method thereof |
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| CN201710615123.XA CN107513144A (en) | 2017-07-26 | 2017-07-26 | A kind of boron modified phenolic resin and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111471149A (en) * | 2020-05-19 | 2020-07-31 | 安徽凯沃科技有限公司 | Silicon modified phenolic resin and preparation method thereof |
| CN111944465A (en) * | 2020-07-29 | 2020-11-17 | 际华集团股份有限公司***工程中心 | Binder for bonding boron carbide ceramic parts, binder adhesive film and bulletproof insert plate |
| CN112759732A (en) * | 2020-12-30 | 2021-05-07 | 上海应用技术大学 | Composite modified water-based phenolic resin and preparation method thereof |
| TWI777567B (en) * | 2021-05-19 | 2022-09-11 | 中國鋼鐵股份有限公司 | Method of preparing boron-containing phenolic resin-salicyl alcohol method |
| CN117362916A (en) * | 2023-11-14 | 2024-01-09 | 山东永创材料科技有限公司 | Modified phenolic resin and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1817928A (en) * | 2006-03-09 | 2006-08-16 | 同济大学 | Production of modified phenolic resin with high boron content |
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2017
- 2017-07-26 CN CN201710615123.XA patent/CN107513144A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1817928A (en) * | 2006-03-09 | 2006-08-16 | 同济大学 | Production of modified phenolic resin with high boron content |
Non-Patent Citations (2)
| Title |
|---|
| 邱军等: "不同硼含量硼改性酚醛树脂的合成及其性能", 《同济大学学报(自然科学版)》 * |
| 邱军等: "硼改性酚醛树脂的合成及其复合材料的性能", 《建筑材料学报》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111471149A (en) * | 2020-05-19 | 2020-07-31 | 安徽凯沃科技有限公司 | Silicon modified phenolic resin and preparation method thereof |
| CN111944465A (en) * | 2020-07-29 | 2020-11-17 | 际华集团股份有限公司***工程中心 | Binder for bonding boron carbide ceramic parts, binder adhesive film and bulletproof insert plate |
| CN111944465B (en) * | 2020-07-29 | 2022-03-04 | 际华集团股份有限公司***工程中心 | Binder for bonding boron carbide ceramic parts, binder adhesive film and bulletproof insert plate |
| CN112759732A (en) * | 2020-12-30 | 2021-05-07 | 上海应用技术大学 | Composite modified water-based phenolic resin and preparation method thereof |
| CN112759732B (en) * | 2020-12-30 | 2022-12-16 | 上海应用技术大学 | Composite modified water-based phenolic resin and preparation method thereof |
| TWI777567B (en) * | 2021-05-19 | 2022-09-11 | 中國鋼鐵股份有限公司 | Method of preparing boron-containing phenolic resin-salicyl alcohol method |
| CN117362916A (en) * | 2023-11-14 | 2024-01-09 | 山东永创材料科技有限公司 | Modified phenolic resin and preparation method thereof |
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Application publication date: 20171226 |
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