CN110483715A - A kind of preparation method of epoxy-modified silicon phenolic resin adhesive - Google Patents
A kind of preparation method of epoxy-modified silicon phenolic resin adhesive Download PDFInfo
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- CN110483715A CN110483715A CN201910856621.2A CN201910856621A CN110483715A CN 110483715 A CN110483715 A CN 110483715A CN 201910856621 A CN201910856621 A CN 201910856621A CN 110483715 A CN110483715 A CN 110483715A
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- epoxy
- phenolic resin
- modified silicon
- acid
- resin adhesive
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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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C09J161/14—Modified phenol-aldehyde condensates
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
A kind of preparation method of epoxy-modified silicon phenolic resin adhesive is to use epoxy resin modification silicon phenolic resin, modified silicon phenolic resin adhesive is made.The present invention is first by epoxy resin, siloxanyl monomers and phenolic compound three react in acid condition, generate the intermediate containing silicon atom or epoxy group, it is reacted with aldehyde compound again, epoxy-modified silicon phenolic resin adhesive bonding strength with higher under room temperature and hot conditions obtained, due to containing the higher Si-O key of bond energy (460 kJ/mol) in structure, thus the heat resistance of this resin is higher, it is suitable as the matrix resin of instantaneous high-temperature Resistance Adhesives, is a kind of high performance resin for having toughness and heat resistance concurrently.
Description
Technical field
A kind of preparation method of epoxy-modified silicon phenolic resin adhesive, is by epoxy resin, siloxanyl monomers and phenols
Compound three reacts in acid condition, generates the intermediate containing silicon atom or epoxy group, then by itself and aldehyde compound
It is reacted, epoxy-modified silicon phenolic resin adhesive is made, the invention belongs to phenolic resin fields.
Background technique
Phenolic resin (PF) is earliest synthetic resin, and low in raw material price, synthesis technology is easy, and is had excellent
It is the features such as mechanical property, dimensional stability, anti-flammability and electrical insulating property, multiple in chemical industry, building, machinery, aerospace, bonding etc.
Field is applied widely.However, traditional phenolic resin due in molecular structure phenolic hydroxyl group and methylene it is oxidizable, make it
Heat resistance is affected, and 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
Toughness is bad, and industrialized production is still unsatisfactory for, and need to further increase its toughness.
For these reasons, the present invention is specifically proposed.
Summary of the invention
The invention discloses a kind of preparation methods of epoxy-modified silicon phenolic resin adhesive, i.e., first by epoxy resin, silicon
Oxygen alkane monomer and phenolic compound three react in acid condition, generate the intermediate containing silicon atom or epoxy group, then will
It is reacted with aldehyde compound, and epoxy-modified silicon phenolic resin adhesive obtained is due to containing flexible long molecule in structure
Chain and the higher Si-O key (460kJ/mol) of bond energy, thus be a kind of high performance resin adhesive for having toughness and heat resistance concurrently.
Preparation process of the invention includes the following steps:
Epoxy resin, siloxanyl monomers, phenolic compound and acidic catalyst are uniformly mixed, wherein epoxy resin can
To be one of bisphenol A type epoxy resin, bisphenol-s epoxy resin, bisphenol f type epoxy resin, novolac epoxy resin or several
Kind；Siloxanyl monomers can be methyl (or phenyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl,
Undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl) front three
Oxysilane, methyl (or phenyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, ten
Dialkyl group, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl) triethoxysilane, just
Silester, gamma-aminopropyl-triethoxy-silane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-(methacryl
Oxygen) propyl trimethoxy silicane, gamma-mercaptopropyltriethoxysilane, γ-mercaptopropyl trimethoxysilane, N- (β-aminoethyl)-
One or more of γ-aminopropyltriethoxy dimethoxysilane, N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane；Phenol
Class compound can be phenol, methyl (or ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, hendecane
Base, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl) phenol, xylenol,
One or more of naphthols, catechol, anacardol, bisphenol-A, Bisphenol F, bisphenol S；Acidic catalyst can be hydrochloric acid, phosphorus
One of acid, sulfuric acid, oxalic acid, methanesulfonic acid, p-methyl benzenesulfonic acid, dodecyl benzene sulfonic acid, glacial acetic acid, boric acid, formic acid, propionic acid or
It is several, epoxy resin, siloxanyl monomers, four kinds of raw materials of phenolic compound and acidic catalyst mass ratio be 0.05~0.5:
0.1~1.0:1:0.05%~4% reacts 2~8h at 120~180 DEG C, and vacuum distillation removes small molecule, then cooling drop
Temperature, be added aldehyde compound, wherein aldehyde compound can be 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) aldehyde, paraformaldehyde, metaformaldehyde, para-acetaldehyde, chaffs
The molar ratio of one or more of aldehyde, aldehyde compound and phenolic compound is 0.5~1.0:1, is reacted at 60~95 DEG C
0.5~5h, then removed under reduced pressure water and small-molecule substance under 110~140 DEG C, -0.08~-0.09MPa pressure, are made epoxy
Modified silicon phenolic resin adhesive.
By taking bisphenol A type epoxy resin E-20, methyltrimethoxysilane and phenol as an example, in the present invention containing silicon atom or
The reaction occurred in the preparation process of epoxy group intermediate is as follows:
By taking formaldehyde as an example, containing silicon atom or epoxy group intermediate and aldehyde compound in resin preparation process in the present invention
The reaction of middle generation is as follows:
Epoxy-modified silicon phenolic resin adhesive structural formula produced by the present invention is as follows:
The bonding strength with higher under room temperature and hot conditions of modified resin adhesive obtained by this method, due to
Contain the higher Si-O key (460kJ/mol) of bond energy in structure, thus the heat resistance of this resin is higher, is suitable as instantaneous
The matrix resin of high-temperature Resistance Adhesives is a kind of high performance resin for having toughness and heat resistance concurrently.
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: epoxy-modified silicon 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
14.12g bisphenol A type epoxy resin E-20,68.11g methyltrimethoxysilane and 94.11g phenol are added to
It in reaction kettle, is uniformly mixed, 1.88g boric acid is added, stirs evenly heating, 4h is reacted at 160 DEG C, vacuum distillation removes small point
Then son cools, 24.04g paraformaldehyde is added, and is warming up to 90 DEG C, 2h is reacted, then in 120 DEG C, -0.08MPa pressure
The epoxy-modified silicon phenolic resin adhesive is made in lower removed under reduced pressure water and small-molecule substance.
Embodiment 2
9.41g novolac epoxy resin F-51,116.20g methyltrimethoxysilane and 228.29g bisphenol-A are added to instead
It answers in kettle, is uniformly mixed, 3.44g p-methyl benzenesulfonic acid is added, stirs evenly heating, 4.5h is reacted at 175 DEG C, vacuum distillation removes
Go small molecule, then cool, 70.61g formalin is added, is warming up to 95 DEG C, react 1.5h, then 110 DEG C ,-
The epoxy-modified silicon phenolic resin adhesive is made in removed under reduced pressure water and small-molecule substance under 0.09MPa pressure.
Embodiment 3
By N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxy of 18.82g bisphenol A type epoxy resin E-20,41.27g
Base silane and 94.11g phenol are added in reaction kettle, are uniformly mixed, and 1.41g phosphoric acid is added, heating is stirred evenly, at 162 DEG C
Lower reaction 5h, vacuum distillation remove small molecule, then cool, and 26.13g paraformaldehyde is added, and are warming up to 90 DEG C, reaction
2h, then removed under reduced pressure water and small-molecule substance under 115 DEG C, -0.08MPa pressure, are made the epoxy-modified silicon phenolic aldehyde
Resin adhesive.
Claims (7)
1. a kind of preparation method of epoxy-modified silicon phenolic resin adhesive, it is characterised in that by epoxy resin, siloxanyl monomers,
Phenolic compound and acidic catalyst are uniformly mixed, epoxy resin, siloxanyl monomers, phenolic compound and four kinds of acidic catalyst
The mass ratio of raw material be 0.05 ~ 0.5: 0.1 ~ 1.0: 1: 0.05% ~ 4%, at 120 ~ 180 DEG C react 2 ~
8 h, vacuum distillation remove small molecule, then cool, and aldehyde compound is added, and aldehyde compound and phenolic compound rub
You than be 0.5 ~ 1.0: 1, at 60 ~ 95 DEG C react 0.5 ~ 5 h, then 110 ~ 140 DEG C, -0.08 ~ -
Epoxy-modified silicon phenolic resin adhesive is made in removed under reduced pressure water and small-molecule substance under 0.09MPa pressure.
2. a kind of preparation method of epoxy-modified silicon phenolic resin adhesive according to claim 1, it is characterised in that institute
The epoxy resin used can be bisphenol A type epoxy resin, bisphenol-s epoxy resin, bisphenol f type epoxy resin, epoxy novolac
One or more of resin.
3. a kind of preparation method of epoxy-modified silicon phenolic resin adhesive according to claim 1, it is characterised in that institute
The siloxanyl monomers used can be methyl (or phenyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, the last of the ten Heavenly stems
Base, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl) three
Methoxy silane, methyl (or phenyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,
Dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl) triethoxysilane,
Ethyl orthosilicate, gamma-aminopropyl-triethoxy-silane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-(metering system
Acyl-oxygen) propyl trimethoxy silicane, gamma-mercaptopropyltriethoxysilane, γ-mercaptopropyl trimethoxysilane, N- (β-ammonia second
Base)-γ-aminopropyltriethoxy dimethoxysilane, one of N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane or several
Kind.
4. a kind of preparation method of epoxy-modified silicon phenolic resin adhesive according to claim 1, it is characterised in that institute
The phenolic compound used can be phenol, methyl (or ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, the last of the ten Heavenly stems
Base, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl)
One or more of phenol, xylenol, naphthols, catechol, anacardol, bisphenol-A, Bisphenol F, bisphenol S.
5. a kind of preparation method of epoxy-modified silicon phenolic resin adhesive according to claim 1, it is characterised in that institute
The acidic catalyst used can be hydrochloric acid, phosphoric acid, sulfuric acid, oxalic acid, methanesulfonic acid, p-methyl benzenesulfonic acid, dodecyl benzene sulfonic acid, ice
One or more of acetic acid, boric acid, formic acid, propionic acid.
6. a kind of preparation method with ester-interchange method synthesizing organo-silicon phenol-formaldehyde resin modified according to claim 1, special
Sign is that aldehyde compound can be first (or second, third, fourth, penta, oneself, heptan, pungent, nonyl, the last of the ten Heavenly stems, 11,12,13,14, ten
Five, 16,17,18,19,2 0) one or more of aldehyde, paraformaldehyde, metaformaldehyde, para-acetaldehyde, furfurals.
7. a kind of epoxy-modified silicon phenolic resin adhesive, it is characterised in that the epoxy-modified silicon phenolic resin adhesive 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 |
|---|---|---|---|
| CN201910856621.2A CN110483715A (en) | 2019-09-11 | 2019-09-11 | A kind of preparation method of epoxy-modified silicon phenolic resin adhesive |
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| CN201910856621.2A CN110483715A (en) | 2019-09-11 | 2019-09-11 | A kind of preparation method of epoxy-modified silicon phenolic resin adhesive |
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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 |
| CN113264728A (en) * | 2021-05-12 | 2021-08-17 | 烟台蒙特混凝土有限公司 | High-strength high-toughness concrete and preparation method thereof |
-
2019
- 2019-09-11 CN CN201910856621.2A patent/CN110483715A/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 |
| CN113264728A (en) * | 2021-05-12 | 2021-08-17 | 烟台蒙特混凝土有限公司 | High-strength high-toughness concrete and preparation method thereof |
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Application publication date: 20191122 |