CN110452646A - A kind of dicyandiamide modified silicon phenolic resin adhesive and preparation method thereof - Google Patents
A kind of dicyandiamide modified silicon phenolic resin adhesive and preparation method thereof Download PDFInfo
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- CN110452646A CN110452646A CN201910820056.4A CN201910820056A CN110452646A CN 110452646 A CN110452646 A CN 110452646A CN 201910820056 A CN201910820056 A CN 201910820056A CN 110452646 A CN110452646 A CN 110452646A
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- dicyandiamide
- resin adhesive
- phenolic resin
- modified 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
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/12—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
- C09J161/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C09J161/04, C09J161/18 and C09J161/20
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- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a kind of dicyandiamide modified silicon phenolic resin adhesives and preparation method thereof, are technically characterized in that, in terms of mass parts, it is made of following raw material: 10~100 parts of siloxanyl monomers, 0.05~4 part of acidic catalyst, 100 parts of phenolic compound, 10~50 parts of dicyandiamide；In addition, the dosage of aldehyde compound and phenolic compound is 0.5~1.0:1 of molar ratio.The present invention passes through siloxanyl monomers first and phenolic compound uniformly mixes, and under acidic catalyst catalytic action, heat temperature raising, reaction generates alkyl phenoxy silane intermediate；It cools later, a certain amount of dicyandiamide and aldehyde compound is added, reacted at a certain temperature to terminal with alkyl phenoxy silane intermediate, a kind of dicyandiamide modified silicon phenolic resin adhesive is made in vacuum distillation after vacuum drying.The Resin adhesive shows as higher heat resistance and flexibility due to introducing flexible long chain and highly polar heat-resisting group-C ≡ N.
Description
Technical field
The present invention relates to adhesive technology field, specifically a kind of dicyandiamide modified silicon phenolic resin adhesive and its
Preparation method.
Background technique
Phenolic resin adhesive adhesive strength is high, and there are raw materials for production to be easy to get, resin after synthesis technology simplicity and solidification
The features such as mechanical strength is high is applied in the every field closely bound up with national economy.However, traditional phenolic resin glue
Glutinous agent due in molecular structure phenolic hydroxyl group and methylene it is oxidizable, so that its heat resistance is affected, limit it in certain necks
Application in the especially high-temperature field of domain.
For the thermal stability for improving phenolic resin adhesive, silicon atom is introduced into part in phenolic resin macromolecular structure
Phenolic hydroxyl group is blocked, the Si-O key (460kJ/mol) that there is higher bond energy compared with C-O key (326kJ/mol) is formed simultaneously, is to improve phenol
The effective way of urea formaldehyde heat resistance.But traditional silicon phenolic resin adhesive preparation process is complicated, there are organic silicon monomers
Hydrolysis autohemagglutination, phenolic 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 adhesive by ester-interchange method in early-stage study
(SPF), solve the problems, such as that reaction process is difficult to control in the above silicon phenolic resin adhesive preparation process；However, prepare
The tough sex expression of novel silicon phenolic resin adhesive is insufficient, 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
To solve the above problems, the object of the present invention is to provide a kind of dicyandiamide modified silicon phenolic resin adhesive and its systems
Preparation Method.
The present invention to achieve the above object, is achieved through the following technical solutions:
A kind of dicyandiamide modified silicon phenolic resin adhesive is made of following raw material in terms of mass parts: siloxanyl monomers 10
~100 parts, 0.05~4 part of acidic catalyst, 100 parts of phenolic compound, 10~50 parts of dicyandiamide；In addition, aldehyde compound with
The dosage of phenolic compound is 0.5~1.0:1 of molar ratio.
A kind of dicyandiamide modified silicon phenolic resin adhesive is prepared according to the following steps to obtain:
Siloxanyl monomers and phenolic compound are uniformly mixed first, under acidic catalyst catalytic action, heat temperature raising
110~200 DEG C, reaction generates alkyl phenoxy silane intermediate；It cools later, a certain amount of dicyandiamide and aldehydes is added
Compound is reacted to terminal for 70~95 DEG C, vacuum distillation, vacuum at a certain temperature with alkyl phenoxy silane intermediate
A kind of dicyandiamide modified silicon phenolic resin adhesive is made after drying.
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 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 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.
The present invention provides a kind of dicyandiamide modified silicon phenolic resin adhesives and preparation method thereof, and the present invention passes through first
Siloxanyl monomers and phenolic compound uniformly mix, under acidic catalyst catalytic action, 110~200 DEG C of heat temperature raising, and reaction
Generate alkyl phenoxy silane intermediate；It cools later, a certain amount of dicyandiamide and aldehyde compound is added, with alkylbenzene
Oxysilane intermediate is reacted to terminal for 70~95 DEG C at a certain temperature, and one kind is made in vacuum distillation after vacuum drying
Dicyandiamide modified silicon phenolic resin adhesive.The Resin adhesive is due to introducing flexible long chain and highly polar resistance to hot radical
Group-C ≡ N, and show as higher heat resistance and flexibility.
By taking methyltrimethoxysilane, phenol, dicyandiamide and formaldehyde as an example, dicyandiamide modified silicon phenolic resin in the present invention
The reaction occurred in the preparation process of adhesive is as follows:
Dicyandiamide modified silicon phenolic resin adhesive 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: dicyandiamide modified silicon phenolic resin adhesive is adopted with conventional thermoplastic's phenolic resin adhesive
Solidfied material sample, the program curing of sample is prepared with identical 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, be warming up to 180 DEG C of heat preservation 4h, Temperature fall.
Embodiment 1
116.20g methyltrimethoxysilane and 228.29g bisphenol-A are uniformly mixed, in 3.44g Catalyzed by p-Toluenesulfonic Acid
Under effect, 175 DEG C ± 5 DEG C of heat temperature raising, reaction generates alkyl phenoxy silane intermediate；It cools, is added later
60.34g dicyandiamide and 70.61g formalin are reacted at 90 DEG C of temperature to end with alkyl phenoxy silane intermediate
Point, vacuum distillation, is made a kind of dicyandiamide modified silicon phenolic resin adhesive after vacuum drying.
Embodiment 2
68.11g methyltrimethoxysilane and 94.11g phenol are uniformly mixed, under the effect of 1.88g methanesulfonic acid catalyzed,
150 DEG C ± 5 DEG C of heat temperature raising, reaction generates alkyl phenoxy silane intermediate；It cools later, 39.82g dicyandiamide is added
It with 24.04g paraformaldehyde, is reacted at 85 DEG C of temperature with alkyl phenoxy silane intermediate to terminal, vacuum distillation, very
A kind of dicyandiamide modified silicon phenolic resin adhesive is made after sky is dry.
Embodiment 3
N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane and 94.11g phenol of 41.27g are uniformly mixed,
Under the effect of 1.41g phosphoric acid catalyzed, 160 DEG C ± 5 DEG C of heat temperature raising, reaction generates alkyl phenoxy silane intermediate；It is cold later
But cool down, 27.26g dicyandiamide and 26.13g paraformaldehyde be added, with alkyl phenoxy silane intermediate at 85 DEG C of temperature into
To terminal, a kind of dicyandiamide modified silicon phenolic resin adhesive is made in vacuum distillation after vacuum drying for row reaction.
Claims (6)
1. a kind of dicyandiamide modified silicon phenolic resin adhesive and preparation method thereof, it is characterised in that: in terms of mass parts, by following
Raw material composition: 10 ~ 100 parts of siloxanyl monomers, 0.05 ~ 4 part of acidic catalyst, 100 parts of phenolic compound, dicyandiamide 10 ~
50 parts；In addition, the dosage of aldehyde compound and phenolic compound is molar ratio 0.5 ~ 1.0: 1；A kind of dicyandiamide changes
Property silicon phenolic resin adhesive is prepared according to the following steps to obtain: siloxanyl monomers and phenolic compound uniformly mixed first,
Under acidic catalyst catalytic action, 110 ~ 200 DEG C of heat temperature raising, reaction generates alkyl phenoxy silane intermediate；Later
It cools, a certain amount of dicyandiamide and aldehyde compound is added, with alkyl phenoxy silane intermediate at a certain temperature 70
~ 95 DEG C are reacted to terminal, and a kind of dicyandiamide modified silicon phenolic resin adhesive is made in vacuum distillation after vacuum drying.
2. a kind of dicyandiamide modified silicon phenolic resin adhesive according to claim 1 and preparation method thereof, feature exists
In: siloxanyl monomers 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.
3. a kind of dicyandiamide modified silicon phenolic resin adhesive according to claim 1 and preparation method thereof, feature exists
In: the acidic catalyst is 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.
4. a kind of dicyandiamide modified silicon phenolic resin adhesive according to claim 1 and preparation method thereof, feature exists
In: the phenolic compound 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 dicyandiamide modified silicon phenolic resin adhesive according to claim 1 and preparation method thereof, feature exists
In: the aldehyde compound 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.
6. a kind of dicyandiamide modified silicon phenolic resin adhesive and preparation method thereof, it is characterised in that the modified silicon phenolic aldehyde tree
Rouge adhesive is made using the preparation method of claim 1-5 any one.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114536905A (en) * | 2022-02-21 | 2022-05-27 | 江苏耀鸿电子有限公司 | Epoxy glass cloth-based copper-clad plate and preparation method thereof |
-
2019
- 2019-08-31 CN CN201910820056.4A patent/CN110452646A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114536905A (en) * | 2022-02-21 | 2022-05-27 | 江苏耀鸿电子有限公司 | Epoxy glass cloth-based copper-clad plate and preparation method thereof |
| CN114536905B (en) * | 2022-02-21 | 2023-08-08 | 江苏耀鸿电子有限公司 | Epoxy glass cloth-based copper-clad plate and preparation method thereof |
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Application publication date: 20191115 |
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