CN110483714A - A kind of preparation method of resistance to medium temperature phenolic resin adhesive - Google Patents
A kind of preparation method of resistance to medium temperature phenolic resin adhesive Download PDFInfo
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- CN110483714A CN110483714A CN201910839297.3A CN201910839297A CN110483714A CN 110483714 A CN110483714 A CN 110483714A CN 201910839297 A CN201910839297 A CN 201910839297A CN 110483714 A CN110483714 A CN 110483714A
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- phenolic resin
- resistance
- medium temperature
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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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- 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
The invention discloses a kind of preparation methods of phenolic resin adhesive of resistance to medium temperature, belong to adhesive preparation technical field.The present invention generates alkyl phenoxy silane intermediate first under acidic catalyst effect, through siloxanyl monomers and phenolic compound reaction；It is further reacted with acrylic acid, aldehyde compound later, a kind of phenolic resin adhesive of resistance to medium temperature is made.It increases in modified phenolic resin structure due to introducing higher bond energy Si-O key (460 kJ/mol), the more unmodified phenolic resin of heat resistance compared with C-O key (326 kJ/mol)；And the addition of acrylic acid, the brittleness of phenolic resin is improved, its toughness is improved, heat resistance is moderately declined, and requirement of medium temperature (360 ~ 420 DEG C) environment to resin property is still met.
Description
Technical field
The invention belongs to adhesive preparation technical fields, and in particular to a kind of preparation side for the phenolic resin adhesive of resistance to medium temperature
Method.
Background technique
Phenolic resin is with glass transition temperature height, the advantages such as good stability of the dimension, linear expansion coefficient is small, water absorption rate is low
And it is widely used in the fields such as automobile, building, machinery, aerospace, bonding.However, traditional phenolic resin is due to molecular structure
In phenolic hydroxyl group and methylene it is oxidizable, so that its heat resistance is affected, limit it in certain fields especially high-temperature field
In application.
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 performed poor, and industrialized production is still unsatisfactory for, and need to carry out toughening modifying to it.
For these reasons, the present invention is specifically proposed.
Summary of the invention
The problems of in view of the above technology, the present invention provides a kind of preparation sides of phenolic resin adhesive of resistance to medium temperature
Method.
A kind of phenolic resin adhesive of resistance to medium temperature of the present invention, it is specific the preparation method is as follows:
Siloxanyl monomers, phenolic compound and acidic catalyst are added in reaction kettle, are uniformly mixed, temperature programming,
Alkyl phenoxy silane intermediate is generated in 110~200 DEG C of reactions；It cools later, a certain amount of acrylic acid and aldehydes is added
A kind of phenol of resistance to medium temperature is made by further reacting at a temperature of 70~95 DEG C with alkyl phenoxy silane intermediate in compound
Urea formaldehyde adhesive.
A kind of preparation method of resistance to medium temperature phenolic resin adhesive, raw materials: siloxanyl monomers, phenolic compound,
The mass ratio of four kinds of raw materials of acidic catalyst and acrylic acid is 0.1~1.0:1:0.05%~4%:0.05~0.60；Aldehydes
The dosage for closing object and phenolic compound is 0.5~1.0:1 of molar ratio.
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 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, boric acid, formic acid, propionic acid.
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.
Using the method for the invention, the beneficial effect reached is: due to introducing in modified phenolic resin structure
The higher bond energy Si-O key (460kJ/mol) compared with C-O key (326kJ/mol), the more unmodified phenolic resin of heat resistance is
It improves；And the addition of acrylic acid, the brittleness of phenolic resin is improved, its toughness is improved, heat resistance is moderately declined, still full
Sufficient requirement of medium temperature (360~420 DEG C) environment to resin property.
By taking phenol and methyltrimethoxysilane as an example, in the present invention in the preparation process of alkyl phenoxy silane intermediate
The reaction of generation is as follows:
By taking formaldehyde as an example, alkyl phenoxy silane intermediate and aldehyde compound are sent out in resin preparation process in the present invention
Raw reaction is as follows:
The phenolic resin adhesive of resistance to medium temperature 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: the phenolic resin of resistance to medium temperature of the present invention is with conventional thermoplastic's phenolic resin using identical
Solidfied material sample, the program curing of sample is prepared in condition of cure 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
68.11g methyltrimethoxysilane, 94.11g phenol and 1.88g methanesulfonic acid are added in reaction kettle, mixing is equal
Even, temperature programming generates alkyl phenoxy silane intermediate in 150 DEG C of reactions；It cools later, 29.28g acrylic acid is added
It is made a kind of resistance to by further reacting at a temperature of 85 DEG C with alkyl phenoxy silane intermediate with 24.04g paraformaldehyde
Medium temperature phenolic resin adhesive.
Embodiment 2
By N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, 94.11g phenol and the 1.41g phosphorus of 41.27g
Acid is added in reaction kettle, is uniformly mixed, temperature programming, generates alkyl phenoxy silane intermediate in 160 DEG C of reactions；It is cold later
But cool down, 24.87g acrylic acid and 26.13g paraformaldehyde be added, by with alkyl phenoxy silane intermediate in 85 DEG C of temperature
Lower further reaction, is made a kind of phenolic resin adhesive of resistance to medium temperature.
Embodiment 3
116.20g methyltrimethoxysilane, 228.29g bisphenol-A and 3.44g p-methyl benzenesulfonic acid are added to reaction kettle
In, it is uniformly mixed, temperature programming, generates alkyl phenoxy silane intermediate in 175 DEG C of reactions；It cools, is added later
60.57g acrylic acid and 70.61g formalin, by further anti-at a temperature of 90 DEG C with alkyl phenoxy silane intermediate
It answers, a kind of phenolic resin adhesive of resistance to medium temperature is made.
Claims (7)
1. a kind of preparation method for the phenolic resin adhesive of resistance to medium temperature, which is characterized in that the preparation method is as follows: by siloxanes list
Body, phenolic compound and acidic catalyst are added in reaction kettle, are uniformly mixed, temperature programming, are reacted in 110 ~ 200 DEG C
Generate alkyl phenoxy silane intermediate；Cool later, a certain amount of acrylic acid and aldehyde compound be added, by with alkyl
Phenoxy group silane intermediate further reacts at a temperature of 70 ~ 95 DEG C, and a kind of phenolic resin adhesive of resistance to medium temperature is made.
2. a kind of preparation method of phenolic resin adhesive of resistance to medium temperature according to claim 1, which is characterized in that silicon oxygen
Alkane monomer, phenolic compound, four kinds of raw materials of acidic catalyst and acrylic acid mass ratio be 0.1 ~ 1.0: 1: 0.05% ~
4% : 0.05 ~ 0.60；The dosage of aldehyde compound and phenolic compound is molar ratio 0.5 ~ 1.0: 1.
3. a kind of preparation method of phenolic resin adhesive of resistance to medium temperature according to claim 1, which is characterized in that described
Siloxanyl monomers are methyl (or phenyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, hendecane
Base, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl) trimethoxy silicon
Alkane, methyl (or phenyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecane
Base, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl) triethoxysilane, positive silicic acid
Ethyl ester, gamma-aminopropyl-triethoxy-silane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-(methacryloxypropyl)
Propyl trimethoxy silicane, gamma-mercaptopropyltriethoxysilane, γ-mercaptopropyl trimethoxysilane, N- (β-aminoethyl)-γ-
One or more of aminopropyltriethoxy dimethoxysilane, N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane.
4. a kind of preparation method of phenolic resin adhesive of resistance to medium temperature according to claim 1, which is characterized in that described
Phenolic compound is 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.
5. a kind of preparation method of phenolic resin adhesive of resistance to medium temperature according to claim 1, which is characterized in that described
Acidic catalyst be hydrochloric acid, phosphoric acid, sulfuric acid, oxalic acid, methanesulfonic acid, p-methyl benzenesulfonic acid, dodecyl benzene sulfonic acid, glacial acetic acid, boric acid,
One or more of formic acid, propionic acid.
6. a kind of preparation method of phenolic resin adhesive of resistance to medium temperature according to claim 1, which is characterized in that described
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, ten
Seven, 18,19,2 0) one or more of aldehyde, paraformaldehyde, metaformaldehyde, para-acetaldehyde, furfurals.
7. a kind of preparation method for the phenolic resin adhesive of resistance to medium temperature, it is characterised in that the phenol-formaldehyde resin modified is using power
Benefit requires the preparation method of 1-6 any one to be made.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201910839297.3A CN110483714A (en) | 2019-09-05 | 2019-09-05 | A kind of preparation method of resistance to medium temperature phenolic resin adhesive |
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| CN201910839297.3A CN110483714A (en) | 2019-09-05 | 2019-09-05 | A kind of preparation method of resistance to medium temperature phenolic resin adhesive |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114514300A (en) * | 2019-11-29 | 2022-05-17 | 东洋纺株式会社 | Adhesive composition, adhesive sheet, laminate, and printed wiring board |
-
2019
- 2019-09-05 CN CN201910839297.3A patent/CN110483714A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114514300A (en) * | 2019-11-29 | 2022-05-17 | 东洋纺株式会社 | Adhesive composition, adhesive sheet, laminate, and printed wiring board |
| CN114514300B (en) * | 2019-11-29 | 2023-11-14 | 东洋纺Mc株式会社 | Adhesive composition, adhesive sheet, laminate, and printed wiring board |
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Application publication date: 20191122 |