CN110452342A - A kind of preparation method of boron-and-silicon-containing phenolic resin - Google Patents
A kind of preparation method of boron-and-silicon-containing phenolic resin Download PDFInfo
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- CN110452342A CN110452342A CN201910856630.1A CN201910856630A CN110452342A CN 110452342 A CN110452342 A CN 110452342A CN 201910856630 A CN201910856630 A CN 201910856630A CN 110452342 A CN110452342 A CN 110452342A
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- silicon
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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
- C08G8/28—Chemically modified polycondensates
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Abstract
The invention belongs to phenolic resin fields, more particularly to a kind of boron-and-silicon-containing phenolic resin, the boron-and-silicon-containing phenolic resin is prepared according to the following steps to obtain: in the presence of acidic, boric acid, siloxanyl monomers and phenolic compound are reacted, the intermediate containing boron atom or silicon atom is obtained, then it is reacted with aldehyde compound, boron-and-silicon-containing phenolic resin is made.The present invention is modified phenolic resin by using specific silicone-modified dose and boric acid, so that the phenolic resin obtained is had excellent performance, its toughness of resin and the more traditional phenolic resin of heat resistance after solidification significantly improve.
Description
Technical field
The invention belongs to phenolic resin field more particularly to a kind of boron-and-silicon-containing phenolic resins.
Background technique
Phenolic resin is that artificial synthesized earliest and industrialized production a kind of synthetic resin, raw material are easy to get in the world, raw
Production. art is simple, and high comprehensive performance is widely used, such as the national economy such as automobile, aviation, machinery, refractory material, bonding are each
A field.However, traditional phenolic resin due in molecular structure phenolic hydroxyl group and methylene it is oxidizable, make its heat resistance by shadow
It rings, limits its application in the especially high-temperature field of certain fields.
For the thermal stability for improving phenolic resin, silicon atom is introduced into enfeoffment in the middle part of phenolic resin macromolecular structure and locks phenol
Hydroxyl is formed simultaneously the Si-O key (460kJ/mol) for having higher bond energy compared with C-O key (326kJ/mol), is to improve phenolic resin
The effective way of heat resistance.But traditional silicon phenolic resin preparation process is complicated, there are hydrolysis autohemagglutination, the phenol of organic silicon monomer
Aldehyde autohemagglutination, the copolymerization of monomer and phenolic aldehyde etc. reacts, and reactive polymeric degree is uncontrollable.
The present inventor has been synthetically prepared out novel silicon phenolic resin (SPF) by ester-interchange method in early-stage study, solution
Reaction process is difficult to control problem during prepared by the above silicon phenolic resin of having determined；However, the novel silicon phenolic resin prepared
Heat resistance is bad, and industrialized production is still unsatisfactory for, and need to further increase its heat resistance.
For these reasons, the present invention is specifically proposed.
Summary of the invention
In consideration of it, using this hair the purpose of the present invention is to provide a kind of preparation method of boron-and-silicon-containing phenolic resin
The heat resistance of the phenol-formaldehyde resin modified of bright preparation, cured product significantly improves more before modified.
The present invention provides a kind of boron-and-silicon-containing phenolic resin, is prepared according to the following steps to obtain: depositing in acidic catalyst
Under, boric acid, siloxanyl monomers and phenolic compound are reacted, wherein acidic catalyst, boric acid, siloxanyl monomers and phenol
The mass ratio of four kinds of raw materials of class compound is 0.05%~4%:0.06~0.40:0.1~1.0:1, obtain containing boron atom or
The intermediate of silicon atom；It is reacted with aldehyde compound again, the molar ratio of aldehyde compound and phenolic compound is 0.5
~1.0:1；Product is dried in vacuum desiccator, boron-and-silicon-containing phenolic resin is made.Wherein, it is deposited in acidic catalyst
Under, boric acid, siloxanyl monomers and phenolic compound are reacted at 110~200 DEG C, are obtained containing boron atom or silicon atom
Intermediate；It carries out being reacted at 70~95 DEG C containing boron atom or silicon atom intermediate and aldehyde compound, borosilicate is made
Double-modification phenolic resin.
The acidic catalyst is hydrochloric acid, phosphoric acid, sulfuric acid, oxalic acid, methanesulfonic acid, p-methyl benzenesulfonic acid, detergent alkylate sulphur
One or more of acid, glacial acetic acid, formic acid, propionic acid.
The siloxanyl monomers are methyl (or phenyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl
Base, decyl, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecane
Base) trimethoxy silane, methyl (or phenyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, 11
Alkyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl) triethoxy
Silane, ethyl orthosilicate, gamma-aminopropyl-triethoxy-silane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-(first
Base acryloyl-oxy) propyl trimethoxy silicane, gamma-mercaptopropyltriethoxysilane, γ-mercaptopropyl trimethoxysilane, N- (β-
Aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, one of N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane
Or it is several.
The phenolic compound is phenol, methyl (or ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl
Base, decyl, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecane
Base) phenol, xylenol, naphthols, catechol, anacardol, bisphenol-A, Bisphenol F, one or more of bisphenol S.
The aldehyde compound is first (or second, third, fourth, penta, oneself, heptan, pungent, nonyl, the last of the ten Heavenly stems, 11,12,13, ten
Four, 15,16,17,18,19,2 0) one of aldehyde, paraformaldehyde, metaformaldehyde, para-acetaldehyde, furfural or
It is several.
By adopting the above technical scheme, the present invention has the advantage that:
(1) in provided ratio range internal modulation raw material different ratio and its preparation process condition is controlled, boron obtained
Silicon double-modification phenolic resin can reach following index: moisture content≤2.0%, free phenol≤1.5%, 30~60mm of fluidity, Gu
140~160 DEG C of temperature, solidification rate (150 DEG C) 60~85s of change, fugitive constituent≤5%, 90~105 DEG C of softening point, partial size 200
Now at least 95%；
(2) the solidfied material heat resistance of boron-and-silicon-containing phenolic resin prepared by the present invention is significantly improved；
(3) solidfied material of boron-and-silicon-containing phenolic resin prepared by the present invention has excellent mechanical property；
(4) the preparation method step of boron-and-silicon-containing phenolic resin of the invention is simple, low in cost, process control, fits
In popularization.
With boric acid, for methyltrimethoxysilane and phenol, the system containing boron atom or silicon atom intermediate in the present invention
The reaction occurred during standby is as follows:
By taking formaldehyde as an example, the intermediate containing boron atom or silicon atom and aldehyde compound were prepared in resin in the present invention
The reaction occurred in journey is as follows:
Boron-and-silicon-containing phenolic resin structural formula produced by the present invention is as follows:
Specific implementation method
Embodiment in following embodiments can be further combined or replace, and embodiment is only to of the invention
Preferred embodiment is described, and it is not intended to limit the concept and scope of the present invention, is not departing from design philosophy of the present invention
Under the premise of, the various changes and modifications that professional and technical personnel in the art make technical solution of the present invention belong to this hair
Bright protection scope.
Solidfied material condition of cure: boron-and-silicon-containing phenolic resin and conventional thermoplastic's phenolic resin use identical solidified bars
Solidfied material sample, the program curing of sample is prepared in part are as follows: 1~10 DEG C/min heating, 80 DEG C, 100 DEG C, 120 DEG C, 140 DEG C,
160 DEG C keep the temperature 2h respectively, are warming up to 180 DEG C of heat preservation 4h, Temperature fall.
Embodiment 1
By 1.41g phosphoric acid, 31.06g boric acid, N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane of 41.27g
It is added in reaction kettle, stirs evenly with 94.11g phenol, gradient increased temperature is reacted at 160 DEG C, obtained containing boron atom
Or the intermediate of silicon atom；Then it cools, 26.13g paraformaldehyde is added, is reacted to terminal at 85 DEG C；It will produce
Object is dried in vacuum desiccator, and boron-and-silicon-containing phenolic resin is made.
Embodiment 2
By 1.88g methanesulfonic acid, 32.94g boric acid, 68.11g methyltrimethoxysilane and 94.11g phenol are added to reaction
It in kettle, stirs evenly, gradient increased temperature, is reacted at 150 DEG C, obtain the intermediate containing boron atom or silicon atom；Then
It cools, 24.04g paraformaldehyde is added, is reacted to terminal at 85 DEG C；Product is done in vacuum desiccator
It is dry, boron-and-silicon-containing phenolic resin is made.
Embodiment 3
By 3.44g p-methyl benzenesulfonic acid, 57.07g boric acid, 116.20g methyltrimethoxysilane and 228.29g bisphenol-A add
Enter into reaction kettle, stir evenly, gradient increased temperature is reacted at 175 DEG C, obtains the centre containing boron atom or silicon atom
Body；Then it cools, 70.61g formalin is added, is reacted to terminal at 90 DEG C；By product in vacuum drying
Device is dried, and boron-and-silicon-containing phenolic resin is made.
Claims (7)
1. a kind of boron-and-silicon-containing phenolic resin is prepared according to the following steps to obtain: in the presence of acidic, boric acid, silicon
Oxygen alkane monomer and phenolic compound are reacted, wherein acidic catalyst, boric acid, siloxanyl monomers and four kinds of phenolic compound
The mass ratio of raw material is 0.05% ~ 4%: 0.06 ~ 0.40: 0.1 ~ 1.0: 1, is obtained containing boron atom or silicon atom
Intermediate；It is reacted with aldehyde compound again, the molar ratio of aldehyde compound and phenolic compound is 0.5 ~ 1.0:
1；Product is dried in vacuum desiccator, boron-and-silicon-containing phenolic resin is made.
2. a kind of boron-and-silicon-containing phenolic resin according to claim 1, which is characterized in that the acidic catalyst is
One of hydrochloric acid, phosphoric acid, sulfuric acid, oxalic acid, methanesulfonic acid, p-methyl benzenesulfonic acid, dodecyl benzene sulfonic acid, glacial acetic acid, formic acid, propionic acid
Or it is several.
3. a kind of boron-and-silicon-containing phenolic resin according to claim 1, which is characterized in that the siloxanyl monomers are
Methyl (or phenyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, ten
Trialkyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl) trimethoxy silane, methyl (or phenyl,
Ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, 14
Alkyl, pentadecyl, cetyl, heptadecyl, octadecyl) triethoxysilane, ethyl orthosilicate, γ-aminopropyl three
Ethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane,
Gamma-mercaptopropyltriethoxysilane, γ-mercaptopropyl trimethoxysilane, N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxy
One or more of base silane, N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane.
4. a kind of boron-and-silicon-containing phenolic resin according to claim 1, which is characterized in that the phenolic compound is
Phenol, methyl (or ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, ten
Trialkyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl) phenol, xylenol, naphthols, catechol,
One or more of anacardol, bisphenol-A, Bisphenol F, bisphenol S.
5. a kind of boron-and-silicon-containing phenolic resin according to claim 1, which is characterized in that the aldehyde compound is
First (or second, third, fourth, penta, oneself, heptan, pungent, nonyl, the last of the ten Heavenly stems, 11,12,13,14,15,16,17,18,19,
2 0) one or more of aldehyde, paraformaldehyde, metaformaldehyde, para-acetaldehyde, furfurals.
6. a kind of boron-and-silicon-containing phenolic resin according to claim 1, which is characterized in that the step is specifically wrapped
It includes:
(a) in the presence of acidic, boric acid, siloxanyl monomers and phenolic compound carry out instead at 110 ~ 200 DEG C
It answers, obtains the intermediate containing boron atom or silicon atom；
(b) it is reacted at 70 ~ 95 DEG C containing boron atom or silicon atom intermediate and aldehyde compound, borosilicate pair is made and changes
Property phenolic resin.
7. a kind of preparation method of boron-and-silicon-containing phenolic resin, it is characterised in that the boron-and-silicon-containing phenolic resin is adopted
It is made with the preparation method of claim 1-6 any one.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910856630.1A CN110452342A (en) | 2019-09-11 | 2019-09-11 | A kind of preparation method of boron-and-silicon-containing phenolic resin |
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| CN201910856630.1A CN110452342A (en) | 2019-09-11 | 2019-09-11 | A kind of preparation method of boron-and-silicon-containing phenolic resin |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110484176A (en) * | 2019-09-30 | 2019-11-22 | 河南工业大学 | A kind of preparation method of modified silicon phenolic resin adhesive |
| CN111423549A (en) * | 2020-05-22 | 2020-07-17 | 安徽凯沃科技有限公司 | Boron phenolic resin compositely modified by cashew nut shell oil and organic silicon and preparation method thereof |
-
2019
- 2019-09-11 CN CN201910856630.1A patent/CN110452342A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110484176A (en) * | 2019-09-30 | 2019-11-22 | 河南工业大学 | A kind of preparation method of modified silicon phenolic resin adhesive |
| CN110484176B (en) * | 2019-09-30 | 2021-09-03 | 河南工业大学 | Preparation method of modified silicon phenolic resin adhesive |
| CN111423549A (en) * | 2020-05-22 | 2020-07-17 | 安徽凯沃科技有限公司 | Boron phenolic resin compositely modified by cashew nut shell oil and organic silicon and preparation method thereof |
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