CN106496475A - A kind of heat-resistant phenolic resins preparation method for carrying eight amino cage silsesquioxane structures - Google Patents
A kind of heat-resistant phenolic resins preparation method for carrying eight amino cage silsesquioxane structures Download PDFInfo
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- CN106496475A CN106496475A CN201610836207.1A CN201610836207A CN106496475A CN 106496475 A CN106496475 A CN 106496475A CN 201610836207 A CN201610836207 A CN 201610836207A CN 106496475 A CN106496475 A CN 106496475A
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- heat
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- phenolic resins
- cage silsesquioxane
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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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- Organic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
A kind of heat-resistant phenolic resins preparation method for carrying eight amino cage silsesquioxane structures, it is related to a kind of preparation method of phenolic resin, the present invention is being equipped with thermometer, in the there-necked flask of agitator and reflux condenser, add the phenolic compound and base catalyst for melting, it is warming up to 60 65 DEG C, stirring 10min, it is dividedly in some parts in there-necked flask after quantitative aldehyde compound is mixed 5min with modifying agent, it is warmed up to 100 DEG C, 170 DEG C of dehydrations are warming up to after reaction 1.5h with this understanding to vacuumize, cooling adjusts PH to 78, cooling 24 as a child obtained modified target phenolic resin, resin is made up of following part：Phenolic compound, aldehyde compound, modifying agent, catalyst.The features such as there is low, heat-resist thermal conductivity factor, good stability of the dimension and good mechanical performance.Can be applicable to the fields such as building insulation, insulation, fire prevention inside and outside wall board, wind pipe of central air-conditioning insulation material and Aero-Space.
Description
Technical field
The present invention relates to a kind of preparation method of phenolic resin, more particularly to a kind of with eight amino cage-type silsesquioxanes
The heat-resistant phenolic resins preparation method of structure.
Background technology
Phenolic resin is formed by phenol aldehyde or derivatives thereof polycondensation also known as bakelite, the most important characteristic of phenolic resin
Be exactly heat-resisting quantity, though at very high temperatures, also can holding structure globality and dimensional stability, it has also become the present age
Indispensable raw material in industry, have a wide range of applications in electronics, building, printing, field of aerospace.But it is traditional
The heat resistance deficiency of phenolic resin, poor toughness, the hygroscopic defect such as make moist.
The patent of invention of Publication No. CN 104151556A discloses a kind of preparation of polyborosiloxane and to phenolic resin
Heat resistance modified method, obtain resistant to elevated temperatures phenoweld, polycondensation carried out by terminal hydroxy group and phenolic resin
Reaction, improves its heat endurance and adhesion strength, but although the introducing of phenyl ring improves heat resistance, but fragility can be made further to become
Greatly, the use range of phenolic resin is limited.
Content of the invention
It is an object of the invention to provide a kind of heat-resistant phenolic resins system for carrying eight amino cage silsesquioxane structures
Preparation Method, the present invention are introduced with eight amino cage silsesquioxane structures in traditional phenolic resin, are formed after solidification
Cross-linked network, while introducing silica segment in phenolic resin, improves the toughness of phenolic resin, prepared material
Material heat resistance, mechanical property, chemical stability, caking property are good, are a kind of environmentally friendly materials of nontoxic pollution-free.
The purpose of the present invention is achieved through the following technical solutions：
A kind of heat-resistant phenolic resins preparation method for carrying eight amino cage silsesquioxane structures, methods described include following system
Standby process：
In the there-necked flask equipped with thermometer, agitator and reflux condenser, the phenolic compound for melting is added to urge with alkalescence
Agent, is warming up to 60-65 DEG C, stirs 10min, is mixed and stirred for after 5min adding three in batches aldehyde compound and modifying agent
In mouth bottle, lead to N2Then temperature is brought up to 100 DEG C by protection, is warming up to 170 DEG C of dehydrations with this understanding and takes out very after reaction 1.5h
Empty 4-6h, is cooled to 75 DEG C, adjusts PH to 7-8 with PH conditioning agents, and dehydrated cooled 24 as a child obtained modified target phenolic aldehyde tree
Fat.
A kind of described heat-resistant phenolic resins preparation method for carrying eight amino cage silsesquioxane structures, phenols used
Compound is the one kind in phenol, cresols, dimethyl phenol, nonyl phenol, bisphenol-A, resorcinol, propylphenol and ethyl -phenol
Or several, preferably phenol.
A kind of described heat-resistant phenolic resins preparation method for carrying eight amino cage silsesquioxane structures, aldehydes used
Compound is the one kind in formaldehyde, acetaldehyde, butyraldehyde, paraformaldehyde or metaformaldehyde, preferably paraformaldehyde.
A kind of described heat-resistant phenolic resins preparation method for carrying eight amino cage silsesquioxane structures, alkalescence used
Catalyst is the one kind in NaOH, potassium hydroxide or ammoniacal liquor, preferably NaOH.
A kind of described heat-resistant phenolic resins preparation method for carrying eight amino cage silsesquioxane structures, PH used are adjusted
Section agent is acetic acid or the one kind in acetic acid.
A kind of described heat-resistant phenolic resins preparation method for carrying eight amino cage silsesquioxane structures, used changes
Property agent be eight amino cage-type silsesquioxanes.
Advantages of the present invention with effect is：
The flame-retardant phenolic resin with eight amino cage silsesquioxane structures prepared by the present invention, in traditional phenolic resin
In introduce with eight amino cage silsesquioxane structures, define cross-linked network after solidification, while in phenolic resin
In introduce silica segment, improve the toughness of phenolic resin, prepared material has that heat-resist, mechanical property is good, changes
Learn good stability, caking property good, good through testing whole system compatibility, it is easy to industrialize, apply quite varied, whole technique
Process is discharged without toxic solvent, is a kind of environmentally friendly material of nontoxic pollution-free.
Specific embodiment
With reference to embodiment, the present invention is described in detail.
Embodiment 1
The present invention is a kind of flame-retardant phenolic resin for carrying eight amino cage silsesquioxane structures, comprises the following steps：
In the there-necked flask equipped with thermometer, agitator and reflux condenser, the phenol and 1 part of hydrogen-oxygen of 100 parts of thawings are added
Change sodium, be warming up to 65 DEG C, stir 10min, 45 parts of paraformaldehydes are mixed and stirred for 15 part of eight amino cage-type silsesquioxane
Added in there-necked flask in batches after 5min, lead to N2Protection, control were added within half an hour, then with 10 DEG C/min speed by temperature
100 DEG C are brought up to, and 170 DEG C of dehydrations are warming up to after reaction 1.5h with this understanding and are vacuumized 4-6h, are cooled to 75 DEG C, are adjusted with acetic acid
Section PH to 7-8, dehydrated cooled 24 as a child obtained modified target phenolic resin.
Embodiment 2
The present invention is a kind of flame-retardant phenolic resin for carrying eight amino cage silsesquioxane structures, comprises the following steps：
In the there-necked flask equipped with thermometer, agitator and reflux condenser, the phenol and 1 part of hydrogen-oxygen of 100 parts of thawings are added
Change sodium, be warming up to 65 DEG C, stir 10min, 50 parts of paraformaldehydes are mixed and stirred for 20 part of eight amino cage-type silsesquioxane
Added in there-necked flask in batches after 5min, lead to N2Protection, control were added within half an hour, then with 10 DEG C/min speed by temperature
100 DEG C are brought up to, and 170 DEG C of dehydrations are warming up to after reaction 1.5h with this understanding and are vacuumized 4-6h, are cooled to 75 DEG C, are adjusted with acetic acid
Section PH to 7-8, dehydrated cooled 24 as a child obtained modified target phenolic resin.
Embodiment 3
The present invention is a kind of flame-retardant phenolic resin for carrying eight amino cage silsesquioxane structures, comprises the following steps：
In the there-necked flask equipped with thermometer, agitator and reflux condenser, the phenol and 1 part of hydrogen-oxygen of 100 parts of thawings are added
Change sodium, be warming up to 65 DEG C, stir 10min, 55 parts of paraformaldehydes are mixed and stirred for 25 part of eight amino cage-type silsesquioxane
Added in there-necked flask in batches after 5min, lead to N2Protection, control were added within half an hour, and then the speed of 10 DEG C/min is by temperature
100 DEG C are brought up to, and 170 DEG C of dehydrations are warming up to after reaction 1.5h with this understanding and are vacuumized 4-6h, are cooled to 75 DEG C, are adjusted with acetic acid
Section PH to 7-8, dehydrated cooled 24 as a child obtained modified target phenolic resin.
Embodiment 4
The present invention is a kind of flame-retardant phenolic resin for carrying eight amino cage silsesquioxane structures, comprises the following steps：
In the there-necked flask equipped with thermometer, agitator and reflux condenser, the phenol and 1 part of hydrogen-oxygen of 100 parts of thawings are added
Change sodium, be warming up to 60 DEG C, stir 10min, 60 parts of paraformaldehydes are mixed and stirred for 30 part of eight amino cage-type silsesquioxane
Added in there-necked flask in batches after 5min, lead to N2Protection, control were added within half an hour, were then improved temperature with given pace
To 100 DEG C, 170 DEG C of dehydrations are warming up to after reaction 1.5h with this understanding and vacuumize 4-6h, be cooled to 75 DEG C, adjust PH with acetic acid
7-8 is arrived, dehydrated cooled 24 as a child obtained modified target phenolic resin.
Claims (6)
1. a kind of heat-resistant phenolic resins preparation method for carrying eight amino cage silsesquioxane structures, it is characterised in that described
Method includes following preparation process：
In the there-necked flask equipped with thermometer, agitator and reflux condenser, the phenolic compound for melting is added to urge with alkalescence
Agent, is warming up to 60-65 DEG C, stirs 10min, is mixed and stirred for after 5min adding three in batches aldehyde compound and modifying agent
In mouth bottle, lead to N2Then temperature is brought up to 100 DEG C by protection, is warming up to 170 DEG C of dehydrations with this understanding and takes out very after reaction 1.5h
Empty 4-6h, is cooled to 75 DEG C, adjusts PH to 7-8 with PH conditioning agents, and dehydrated cooled 24 as a child obtained modified target phenolic aldehyde tree
Fat.
2. a kind of heat-resistant phenolic resins preparation side for carrying eight amino cage silsesquioxane structures according to claim 1
Method, it is characterised in that phenolic compound used is phenol, cresols, dimethyl phenol, nonyl phenol, bisphenol-A, resorcinol, propyl group
One or more in phenol and ethyl -phenol, preferably phenol.
3. a kind of heat-resistant phenolic resins preparation side for carrying eight amino cage silsesquioxane structures according to claim 1
Method, it is characterised in that aldehyde compound used is the one kind in formaldehyde, acetaldehyde, butyraldehyde, paraformaldehyde or metaformaldehyde, preferably
For paraformaldehyde.
4. a kind of heat-resistant phenolic resins preparation side for carrying eight amino cage silsesquioxane structures according to claim 1
Method, it is characterised in that base catalyst used is the one kind in NaOH, potassium hydroxide or ammoniacal liquor, preferably NaOH.
5. a kind of heat-resistant phenolic resins preparation side for carrying eight amino cage silsesquioxane structures according to claim 1
Method, it is characterised in that PH conditioning agents used are acetic acid or the one kind in acetic acid.
6. a kind of heat-resistant phenolic resins preparation side for carrying eight amino cage silsesquioxane structures according to claim 1
Method, it is characterised in that modifying agent used is eight amino cage-type silsesquioxanes.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610836207.1A CN106496475A (en) | 2016-09-21 | 2016-09-21 | A kind of heat-resistant phenolic resins preparation method for carrying eight amino cage silsesquioxane structures |
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| CN201610836207.1A CN106496475A (en) | 2016-09-21 | 2016-09-21 | A kind of heat-resistant phenolic resins preparation method for carrying eight amino cage silsesquioxane structures |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112708177A (en) * | 2020-12-29 | 2021-04-27 | 江苏宏祺体育用品有限公司 | Elastic rubber ring with high antibacterial property for fitness equipment |
| CN114835903A (en) * | 2022-04-28 | 2022-08-02 | 北京理工大学 | Boron-containing silsesquioxane, preparation method thereof, modified phenolic resin, preparation method and application thereof |
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| US20060058488A1 (en) * | 2002-05-08 | 2006-03-16 | Adolf Kuhnle | Functionalized polyherdral oligomeric silicon-oxygen clusters as cross-linking agents |
| CN1944441A (en) * | 2006-10-30 | 2007-04-11 | 北京化工大学 | Sesqui-siloxane containing benzoxazinyl group and its composition and preparing method |
| CN101319037A (en) * | 2008-07-18 | 2008-12-10 | 黑龙江省科学院石油化学研究院 | Modified phenolic resin and preparation method thereof |
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| CN105254828A (en) * | 2015-10-23 | 2016-01-20 | 航天材料及工艺研究所 | Cage-shaped oligomerization silsesquioxane hybridized phenolic resin with eight phenolic hydroxyl groups and preparation method thereof |
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- 2016-09-21 CN CN201610836207.1A patent/CN106496475A/en active Pending
Patent Citations (5)
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| US20060058488A1 (en) * | 2002-05-08 | 2006-03-16 | Adolf Kuhnle | Functionalized polyherdral oligomeric silicon-oxygen clusters as cross-linking agents |
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| CN101319037A (en) * | 2008-07-18 | 2008-12-10 | 黑龙江省科学院石油化学研究院 | Modified phenolic resin and preparation method thereof |
| CN101503420A (en) * | 2009-03-20 | 2009-08-12 | 北京化工大学 | Octa-epoxy cage type sesquialter siloxane and preparation thereof |
| CN105254828A (en) * | 2015-10-23 | 2016-01-20 | 航天材料及工艺研究所 | Cage-shaped oligomerization silsesquioxane hybridized phenolic resin with eight phenolic hydroxyl groups and preparation method thereof |
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| CHEN QIAO,ET AL: "Polyhedral Oligomeric Silsesquioxane (POSS) Nanoscale Reinforcement of Thermosetting Resin from Benzoxazine and Bisoxazoline", 《MACROMOLECULAR RAPID COMMUNICATIONS》 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112708177A (en) * | 2020-12-29 | 2021-04-27 | 江苏宏祺体育用品有限公司 | Elastic rubber ring with high antibacterial property for fitness equipment |
| CN112708177B (en) * | 2020-12-29 | 2022-11-25 | 江苏宏祺体育用品有限公司 | Elastic rubber ring with high antibacterial property for fitness equipment |
| CN114835903A (en) * | 2022-04-28 | 2022-08-02 | 北京理工大学 | Boron-containing silsesquioxane, preparation method thereof, modified phenolic resin, preparation method and application thereof |
| CN114835903B (en) * | 2022-04-28 | 2023-03-14 | 北京理工大学 | Boron-containing silsesquioxane and preparation method thereof, modified phenolic resin and preparation method and application thereof |
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