CN107057007A - A kind of bis-phenol ether compound modified pnenolic aldehyde foam material and preparation method thereof - Google Patents
A kind of bis-phenol ether compound modified pnenolic aldehyde foam material and preparation method thereof Download PDFInfo
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- CN107057007A CN107057007A CN201611243078.1A CN201611243078A CN107057007A CN 107057007 A CN107057007 A CN 107057007A CN 201611243078 A CN201611243078 A CN 201611243078A CN 107057007 A CN107057007 A CN 107057007A
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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
- 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
- C08G8/36—Chemically modified polycondensates by etherifying
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08L61/14—Modified phenol-aldehyde condensates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2361/14—Modified phenol-aldehyde condensates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
A kind of bis-phenol ether compound modified pnenolic aldehyde foam material and preparation method thereof, is related to a kind of expanded material and preparation method thereof, first, and the process of producing bisphenol ether compound phenol-formaldehyde resin modified is divided into following two stages of reaction：Stage of reaction I is that with phenol exchange reaction occurs for bis-phenol ether compound, generates the aryl ether compounds of two phenol rings of band；Stage of reaction II is reacted in the basic conditions for the aryl ether compounds generated using stage of reaction I with formaldehyde, generates modified phenolic resin；After bis-phenol ether compound modified phenol, a kind of thermosetting modification phenolic resin is generated with formaldehyde in the basic conditions, then expanded material is prepared by as above proportioning.The present invention generates a kind of new thermosetting modification phenolic resin in the basic conditions, and obtained phenol formaldehyde foam toughness is greatly improved, while improving the combination properties such as the carbon yield and thermal decomposition peak temperature of phenol formaldehyde foam.
Description
Technical field
The present invention relates to a kind of expanded material and preparation method thereof, more particularly to a kind of bis-phenol ether compound modified phenolic
Expanded material and preparation method thereof.
Background technology
The product referred to as phenolic resin that phenolic compound is obtained with aldehyde compound polycondensation reaction, wherein with phenol and formaldehyde
The phenolic resin that copolyreaction is obtained is most important, and its output of industrial product is maximum, and purposes is wide.Phenolic resin have it is cheap,
Mechanical property and the few premium properties of heat-resist, fire-retardant, burning fuming.So in the neck such as national defence, industrial or agricultural, building, traffic
It is used widely in city.
Phenol formaldehyde foam generally by resol, surfactant, foaming agent it is well mixed after add curing agent, stir
Uniform rear foamable is mixed, the phenol formaldehyde foam formed generally has density height, and fragility is big, the defect such as water absorption rate height,
So the phenolic resin that phenolic foam foaming is used needs to use flexible material to be modified, lack the part that solves phenol formaldehyde foam
Fall into.A large amount of study on the modification are carried out to phenolic resin successively both at home and abroad, phenylphenol phenol-formaldehyde resin modified is that wherein performance is more excellent
A different class.By introducing new aromatic yl group on molecular backbone, phenyl ring ratio in structure is greatly improved, so as to improve
System carbon content;Aromatic ring bond energy is higher, and Stability Analysis of Structures is not easy to break during ablation.
Publication number is CN1367187A application for a patent for invention, and it is in the presence of acidic by aralkyl chemical combination
The low molecular weight phenols Novolac of thing and double-core novolaks is reacted, and obtains modified phenol aralkyl resin, and gained is modified tree
The heat resistance and hygroscopicity of fat are preferable.
Publication number is the A of CN 103619793 application for a patent for invention, is closed it discloses a kind of new bis-phenol etherificate
Thing.Bisphenol compound is commonly utilized in polycarbonate synthesis and epoxy resin field at this stage, and in the neck such as polyethers and polyester
Domain is similarly widely used, and they are the important monomers for synthesizing high polymer material.Therefore the present invention selects this new bis-phenol ether
Compound as modified phenolic raw material.
The content of the invention
It is an object of the invention to provide a kind of bis-phenol ether compound modified pnenolic aldehyde foam material and preparation method thereof, this hair
It is bright to generate a kind of new thermosetting modification phenolic resin in the basic conditions, because the bond energy of aromatic ring is higher, Stability Analysis of Structures, and carry
The high phosphorus content of phenolic resin, adds the length of phenolic resin strand, therefore obtained phenol formaldehyde foam toughness is carried significantly
Height, while improving the combination properties such as the carbon yield and thermal decomposition peak temperature of phenol formaldehyde foam.
The purpose of the present invention is achieved through the following technical solutions：
A kind of bis-phenol ether compound modified pnenolic aldehyde foam material, the pnenolic aldehyde foam material is prepared by the raw material of following parts by weight：
100 parts of phenolic resin；
4-6 parts of surfactant；
8-10 parts of foaming agent；
12-14 parts of curing agent.
A kind of described bis-phenol ether compound modified pnenolic aldehyde foam material, the phenol-formaldehyde resin modified, by following parts by weight
Raw material prepare：
65-85 parts of bis-phenol ether compound；
80-100 parts of phenol；
50-60 parts of paraformaldehyde；
1 part of sodium hydroxide；
In bis-phenol ether compound strand-OCH3It is not connected on 2,2 ' on phenyl ring-position.
A kind of described bis-phenol ether compound modified pnenolic aldehyde foam material, surfactant be Tween-80, silicone oil in extremely
Few one kind.
A kind of described bis-phenol ether compound modified pnenolic aldehyde foam material, the foaming agent is dichloromethane, pentane, different
At least one of pentane.
A kind of described bis-phenol ether compound modified pnenolic aldehyde foam material, the curing agent is p-methyl benzenesulfonic acid, diformazan
The one or more in one or more of sulfuric acid in benzene sulfonic acid, phenolsulfonic acid, benzene sulfonic acid.
A kind of bis-phenol ether compound modified pnenolic aldehyde foam material preparation method, methods described includes procedure below：
First, the process of producing bisphenol ether compound phenol-formaldehyde resin modified is divided into following two stages of reaction：Stage of reaction I is double
With phenol exchange reaction occurs for phenol ether compound, generates the aryl ether compounds of two phenol rings of band；Stage of reaction II is using anti-
The aryl ether compounds for answering stage I to be generated react in the basic conditions with formaldehyde, generate modified phenolic resin；
After bis-phenol ether compound modified phenol, a kind of thermosetting modification phenolic resin is generated with formaldehyde in the basic conditions,
Then expanded material is prepared by as above proportioning.
Advantages of the present invention is with effect：
1. generated in the basic conditions the invention provides one kind from being reacted again with formaldehyde after bis-phenol ether compound modified phenol
A kind of preparation method of new thermosetting modification phenolic resin.The bond energy for being primarily due to aromatic ring is higher, Stability Analysis of Structures, and improves
The phosphorus content of phenolic resin, adds the length of phenolic resin strand, therefore obtained phenol formaldehyde foam toughness is greatly improved,
The combination properties such as the carbon yield and thermal decomposition peak temperature of phenol formaldehyde foam are improved simultaneously.
2. the present invention makes aryl ether by introducing aryl on phenol ring, so that modified phenol reacts with formaldehyde,
A large amount of carbon atoms and phenyl ring are introduced in phenolic resin, the structure that interlaminar resin only has methylene connection is changed.Modified foam
Toughness is greatly improved, while the Residual carbon and water absorption rate after burning are also improved.
Embodiment
With reference to embodiment, the present invention is described in detail.
Below by way of the description of embodiment, the invention will be further described, but this is not the limit to the present invention
System, those skilled in the art are according to the basic thought of the present invention, and various modifications may be made or improves, but without departing from this
The basic thought of invention, within the scope of the present invention.
Embodiment 1
By bis-phenol ether compound and phenol according to 65:100 portion rate is added to the 500ml three-necked flasks with reflux condensing tube
In, stirring is warming up to 115 DEG C, continues to react two hours；Room temperature, which is cooled to after 100 DEG C, adds 55 parts of formalins and 1 part of hydrogen-oxygen
Change sodium catalyst, stirring reaction is after 2 hours at 80~100 DEG C, vacuum dehydration；120~175 s are reached when the resin gel time
When stop reaction, you can obtain the sticky solid resin of yellow.Ethanol solution is added after sampling and is stirred dissolving, is modified
Phenol resin solution, by the modified phenolic resin lipoprotein solution of gained and Tween-80, pentane according to 100：4：8 portion rate is carried out
Full and uniform mixing, is stirred 3 minutes, then 12 parts of p-methyl benzenesulfonic acids are added into stirring 15 seconds, then turns the material mixed
Move on in mould, under 70 DEG C of baking ovens react 10 minutes after be stripped, form removal, you can the phenol formaldehyde foam needed.
Embodiment 2
By bis-phenol ether compound and phenol according to 70:95 portion rate is added to the 500ml three-necked flasks with reflux condensing tube
In, stirring is warming up to 115 DEG C, continues to react two hours；Room temperature, which is cooled to after 100 DEG C, adds 55 parts of formalins and 1 part of hydrogen-oxygen
Change sodium catalyst, stirring reaction is after 2 hours at 80~100 DEG C, vacuum dehydration；120~175 s are reached when the resin gel time
When stop reaction, you can obtain the sticky solid resin of yellow.Ethanol solution is added after sampling and is stirred dissolving, is modified
Phenol resin solution, by the modified phenolic resin lipoprotein solution of gained and Tween-80, pentane according to 100：4：8 portion rate is carried out
Full and uniform mixing, is stirred 3 minutes, then 12 parts of p-methyl benzenesulfonic acids are added into stirring 15 seconds, then turns the material mixed
Move on in mould, under 70 DEG C of baking ovens react 10 minutes after be stripped, form removal, you can the phenol formaldehyde foam needed.
Embodiment 3
By bis-phenol ether compound and phenol according to 80:90 portion rate is added to the 500ml three-necked flasks with reflux condensing tube
In, stirring is warming up to 115 DEG C, continues to react two hours；Room temperature, which is cooled to after 100 DEG C, adds 60 parts of formalins and 1 part of hydrogen-oxygen
Change sodium catalyst, stirring reaction is after 2 hours at 80~100 DEG C, vacuum dehydration；120~175 s are reached when the resin gel time
When stop reaction, you can obtain the sticky solid resin of yellow.Ethanol solution is added after sampling and is stirred dissolving, is modified
Phenol resin solution, by the modified phenolic resin lipoprotein solution of gained and Tween-80, pentane according to 100：4：8 portion rate is carried out
Full and uniform mixing, is stirred 3 minutes, then 13 parts of p-methyl benzenesulfonic acids are added into stirring 15 seconds, then turns the material mixed
Move on in mould, under 70 DEG C of baking ovens react 10 minutes after be stripped, form removal, you can the phenol formaldehyde foam needed.
Embodiment 4
By bis-phenol ether compound and phenol according to 85:80 portion rate is added to the 500ml three-necked flasks with reflux condensing tube
In, stirring is warming up to 115 DEG C, continues to react two hours；Room temperature, which is cooled to after 100 DEG C, adds 50 parts of formalins and 1 part of hydrogen-oxygen
Change sodium catalyst, stirring reaction is after 2 hours at 80~100 DEG C, vacuum dehydration；120~175 s are reached when the resin gel time
When stop reaction, you can obtain the sticky solid resin of yellow.Ethanol solution is added after sampling and is stirred dissolving, is modified
Phenol resin solution, by the modified phenolic resin lipoprotein solution of gained and Tween-80, pentane according to 100：4：9 portion rate is carried out
Full and uniform mixing, is stirred 3 minutes, then 13 parts of p-methyl benzenesulfonic acids are added into stirring 15 seconds, then turns the material mixed
Move on in mould, under 70 DEG C of baking ovens react 10 minutes after be stripped, form removal, you can the phenol formaldehyde foam needed.
The performance comparison such as following table of phenol formaldehyde foam and common phenol formaldehyde foam prepared by the embodiment of the present invention 1 to 4：
As seen from the above table, the Bending Deformation for the phenol formaldehyde foam that bis-phenol ether compound is modified improves 4 times than base foam.This be because
To introduce the aryl that structure is relatively stable in phenolic resin, the toughness of material is improved, while adding the length of strand
Degree, adds the steric hindrance of system, reduces the network compactness of phenolic resin, make phenolic resin not easy to break.Phenyl ring
Increase changes the only connected situation of methylene, therefore introducing aryl carrys out modified phenolic in phenolic resin between phenolic resin
Resin can improve that foam matter is crisp, easy efflorescence shortcoming, improve the toughness of material.
The carbon yield results contrast of phenol formaldehyde foam and common phenol formaldehyde foam that bis-phenol ether compound is modified can be seen that, lifted compared with
High carbon content so that modified phenol formaldehyde foam improves about 8~9 percentages than common phenol formaldehyde foam carbon yield
Point.The volatile quantity of phenyl ring class methyl-derivatives, phenols and its methyl-derivatives etc. has all been reduced, and substantially increases the residual of resin
Charcoal rate.Bis-phenol ether compound modified phenolic foam thermal decomposition peak temperature is up to 500.2 DEG C, and more common phenol formaldehyde foam is improved
Nearly 85 DEG C, resistance to stability is significantly improved.
In summary, the phenolic resin that the present invention is generated by bis-phenol ether compound modified phenol and formaldehyde, makes phenol formaldehyde foam
Toughness improves a lot, and carbon yield, thermal decomposition peak temperature have improvement, and the combination property of product is improved.
Claims (6)
1. a kind of bis-phenol ether compound modified pnenolic aldehyde foam material, it is characterised in that the pnenolic aldehyde foam material presses following weight
The raw material of part is prepared：
100 parts of phenolic resin；
4-6 parts of surfactant；
8-10 parts of foaming agent；
12-14 parts of curing agent.
2. a kind of bis-phenol ether compound modified pnenolic aldehyde foam material as claimed in claim 1, it is characterised in that the modified phenol
Urea formaldehyde, is prepared by the raw material of following parts by weight：
65-85 parts of bis-phenol ether compound；
80-100 parts of phenol；
50-60 parts of paraformaldehyde；
1 part of sodium hydroxide；
In bis-phenol ether compound strand-OCH3It is not connected on 2,2 ' on phenyl ring-position.
3. a kind of bis-phenol ether compound modified pnenolic aldehyde foam material as claimed in claim 1, it is characterised in that surfactant
For at least one of Tween-80, silicone oil.
4. a kind of bis-phenol ether compound modified pnenolic aldehyde foam material as claimed in claim 1, it is characterised in that the foaming agent
For at least one of dichloromethane, pentane, isopentane.
5. a kind of bis-phenol ether compound modified pnenolic aldehyde foam material as claimed in claim 1, it is characterised in that the curing agent
For the one or more in one or more of sulfuric acid in p-methyl benzenesulfonic acid, xylene monosulfonic acid, phenolsulfonic acid, benzene sulfonic acid.
6. a kind of bis-phenol ether compound modified pnenolic aldehyde foam material preparation method, it is characterised in that methods described includes procedure below：
First, the process of producing bisphenol ether compound phenol-formaldehyde resin modified is divided into following two stages of reaction：Stage of reaction I is double
With phenol exchange reaction occurs for phenol ether compound, generates the aryl ether compounds of two phenol rings of band；Stage of reaction II is using anti-
The aryl ether compounds for answering stage I to be generated react in the basic conditions with formaldehyde, generate modified phenolic resin；
After bis-phenol ether compound modified phenol, a kind of thermosetting modification phenolic resin is generated with formaldehyde in the basic conditions,
Then expanded material is prepared by as above proportioning.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611243078.1A CN107057007A (en) | 2016-12-29 | 2016-12-29 | A kind of bis-phenol ether compound modified pnenolic aldehyde foam material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611243078.1A CN107057007A (en) | 2016-12-29 | 2016-12-29 | A kind of bis-phenol ether compound modified pnenolic aldehyde foam material and preparation method thereof |
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| CN107057007A true CN107057007A (en) | 2017-08-18 |
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| CN201611243078.1A Withdrawn CN107057007A (en) | 2016-12-29 | 2016-12-29 | A kind of bis-phenol ether compound modified pnenolic aldehyde foam material and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109679041A (en) * | 2018-12-10 | 2019-04-26 | 沈阳化工大学 | A kind of benzidine modified phenolic resin material and preparation method thereof |
| CN109851732A (en) * | 2018-12-10 | 2019-06-07 | 沈阳化工大学 | N- hydroxymethyl acetamide modified pnenolic aldehyde foam material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4178325A (en) * | 1978-01-03 | 1979-12-11 | Desoto, Inc. | High solids coating compositions containing liquid bishydroxy ethyl ether of a bisphenol |
| CN102850715A (en) * | 2012-09-10 | 2013-01-02 | 西安西达地质技术服务有限责任公司 | Modified phenol formaldehyde foam board |
| CN103619793A (en) * | 2011-06-30 | 2014-03-05 | 安格斯化学公司 | Biphenol ether compounds |
| EP3318337A1 (en) * | 2016-11-03 | 2018-05-09 | PPG Industries Ohio, Inc. | A coating composition and coating system |
-
2016
- 2016-12-29 CN CN201611243078.1A patent/CN107057007A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4178325A (en) * | 1978-01-03 | 1979-12-11 | Desoto, Inc. | High solids coating compositions containing liquid bishydroxy ethyl ether of a bisphenol |
| CN103619793A (en) * | 2011-06-30 | 2014-03-05 | 安格斯化学公司 | Biphenol ether compounds |
| CN102850715A (en) * | 2012-09-10 | 2013-01-02 | 西安西达地质技术服务有限责任公司 | Modified phenol formaldehyde foam board |
| EP3318337A1 (en) * | 2016-11-03 | 2018-05-09 | PPG Industries Ohio, Inc. | A coating composition and coating system |
Non-Patent Citations (1)
| Title |
|---|
| 殷荣忠等: "《酚醛树脂及其应用》", 30 June 1990, 化学工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109679041A (en) * | 2018-12-10 | 2019-04-26 | 沈阳化工大学 | A kind of benzidine modified phenolic resin material and preparation method thereof |
| CN109851732A (en) * | 2018-12-10 | 2019-06-07 | 沈阳化工大学 | N- hydroxymethyl acetamide modified pnenolic aldehyde foam material |
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Application publication date: 20170818 |
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