CN107083017A - A kind of normal temperature can send out synthesis and the foaming method of phenolic resin - Google Patents
A kind of normal temperature can send out synthesis and the foaming method of phenolic resin Download PDFInfo
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- CN107083017A CN107083017A CN201710447568.1A CN201710447568A CN107083017A CN 107083017 A CN107083017 A CN 107083017A CN 201710447568 A CN201710447568 A CN 201710447568A CN 107083017 A CN107083017 A CN 107083017A
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- normal temperature
- phenolic resin
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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
- 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
- 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
- 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
-
- 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
Abstract
The present invention relates to synthesis and the foaming method that a kind of normal temperature can send out phenolic resin, part starting phenol is replaced with urea, catalyst and paraformaldehyde is sequentially added, middle temperature hydroxymethylation and high temperature polycondensation is carried out, phenolic resin can be sent out by obtaining a kind of normal temperature；The resin can complete foamed solidification process in 3 ~ 6 minutes under normal temperature environment, and obtained foam dense uniform, intensity is big, good toughness.The inventive method replaces part phenol with urea, reduces cost of material, reacts without vacuum dehydration, reduces assets investment, simplify production process.
Description
Technical field
The present invention relates to the synthesis of high polymer material and the preparation of foamed material, and in particular to a kind of normal temperature can send out phenolic aldehyde tree
The synthesis of fat and foaming method
Background technology
The features such as phenol formaldehyde foam has low thermal conductivity factor, good fire resistance and low smoke and non-toxic, is combination property in insulation material
A kind of preferable material.But phenol formaldehyde foam condition of cure is harsh, typically can only at high temperature under high pressure it be foamed by phenolic resin solid
Change is obtained, and its application is received certain limitation.So synthesis normal temperature can send out phenolic resin and turn into the heat that current people study
Point.Chinese patent 200510030848.X《A kind of low normal temp can send out the synthesis of phenolic resin and prepare the method for phenol formaldehyde foam》With
201210232300.3《The production method of normal-temperature expandable phenolic resin》In improve the synthesis technique of phenolic resin, be made
High activity normal temperature can send out phenolic resin.Or but existing synthesis technique complex manufacturing, production is whard to control；With
Liquid formaldehyde is for raw material, it is necessary to which vacuum dehydration, both adds production cost, and the substantial amounts of phenol wastewater of generation, causes environment dirty again
Dye.
The content of the invention
In order to overcome the shortcomings of the prior art, production is applied to the phenolic resin that normal temperature is poured into a mould, sprayed, the present invention is carried
A kind of normal temperature has been supplied to send out synthesis and the foaming method of phenolic resin.
The technical solution adopted by the present invention is as follows.
A kind of normal temperature can send out the synthesis of phenolic resin, it is characterised in that part starting phenol is replaced with urea, is sequentially added
Catalyst and paraformaldehyde, carry out middle temperature hydroxymethylation and high temperature polycondensation, phenolic resin can be sent out by obtaining a kind of normal temperature.
A kind of normal temperature can send out the synthesis of phenolic resin, calculate by weight, including following raw material：100 parts of phenol, urea
5 ~ 15 parts, 55 ~ 75 parts of paraformaldehyde, 1 ~ 3 part of catalyst.
A kind of normal temperature can send out the synthesis of phenolic resin, comprise the following steps that：
（1）Phenol, urea and catalyst mixing, add paraformaldehyde, at intervals of 20 ~ 40 minutes several times at 50 ~ 70 DEG C；
（2）80 ~ 90 DEG C are warming up to, is reacted 80 ~ 120 minutes；
（3）It is rapid to be cooled to 50 ~ 60 DEG C, pH is adjusted, phenolic resin can be sent out by obtaining normal temperature.
Further, described catalyst is two or more in sodium hydroxide, potassium hydroxide, calcium oxide, barium monoxide.
Further, resulting normal temperature can send out the viscosity of phenolic resin in 3000 ~ 6000 mps.
A kind of above-mentioned normal temperature can send out the foaming method of phenolic resin, it is characterised in that normal temperature can be sent out phenolic aldehyde tree by this method
After the parts by weight of fat 100, the parts by weight of surfactant 2 ~ 5, the parts by weight of foaming agent 4 ~ 9 stir, the weight of curing agent 8 ~ 20 is added
Part stirring half a minute, solidification obtains phenol formaldehyde foam in 3 ~ 6 minutes under normal temperature environment.
Further, described surfactant is one kind in Tween-60, Tween-80, silicone oil H-330.
Further, described foaming agent is one kind in pentane, pentamethylene, petroleum ether.
Further, described curing agent is the one or more in sulfuric acid, phosphoric acid, p-methyl benzenesulfonic acid.
The technology of phenol-formaldehyde resin modified has a lot, but less on the synthesis that normal temperature can send out phenolic resin.The present invention is utilized
Urea replaces part starting phenol, by adding catalyst compounded and adding paraformaldehyde by several times, carries out middle temperature methylolation anti-
Should and high temperature polycondensation, obtain a kind of high active phenolic resin of stabilization.The phenolic resin of the present invention can be 3 under normal temperature environment
Complete foamed solidification process within ~ 6 minutes, obtained foam dense uniform, intensity is big, it is adaptable to normal temperature cast, the life of spray coating foaming
Production. art, has expanded the application of phenol formaldehyde foam significantly.
Beneficial effects of the present invention：
1st, the present invention replaces part phenol with urea, has not only saved cost but also has increased the expandability of resin；
2nd, the present invention replaces liquid formaldehyde with paraformaldehyde, and reaction product is not required to vacuum dehydration, both reduces assets investment, simplifies
Production process, reduce the generation of a large amount of phenol wastewater again, it is to avoid environmental pollution；
3rd, this method has synthesized the phenolic resin poured into a mould, sprayed suitable for normal temperature, and occasion, developing are incubated available for foam-in-place
The application field of phenol formaldehyde foam.
Embodiment
Embodiment 1.
300 g phenol, 25 g urea, 4 g50% sodium hydroxide solution and 3 g oxygen are added in 1000 ml four-hole bottle
Change calcium, in 60 DEG C or so points of 4 195 g paraformaldehydes of addition, every minor tick 30 minutes, paraformaldehyde is incubated 30 after all adding
Minute, it is warming up to 85 DEG C and reacts 100 minutes, 60 DEG C is cooled to rapidly and adjusts pH to obtain phenolic resin to neutrality, viscosity is 4000
mPa·s/25℃。
Take by weight after 100 parts of above-mentioned phenolic resin, 4 parts of Tween-60s, 6 parts of pentanes stir, add 7 parts
Sulfuric acid, 5 parts of phosphoric acid and 3 parts of p-methyl benzenesulfonic acid obtain cured phenolic foam after being stirred at room temperature 30 seconds, 4 minutes.
Embodiment 2.
300 g phenol, 30 g urea, 4 g50% sodium hydroxide solution and 4 g oxygen are added in 1000 ml four-hole bottle
Change barium, in 55 DEG C or so points of 4 200 g paraformaldehydes of addition, every minor tick 30 minutes, paraformaldehyde is incubated 30 after all adding
Minute, it is warming up to 80 DEG C and reacts 90 minutes, 55 DEG C is cooled to rapidly and adjusts pH to obtain phenolic resin to neutrality, viscosity is 3000
mPa·s/25℃。
Take by weight after 100 parts of above-mentioned phenolic resin, 3 parts of Tween-80s, 7 parts of pentanes stir, add 6 parts
Sulfuric acid, 5 parts of phosphoric acid and 4 parts of p-methyl benzenesulfonic acid obtain cured phenolic foam after being stirred at room temperature 30 seconds, 6 minutes.
Embodiment 3.
300 g phenol, 20g urea, 5 g50% potassium hydroxide solution and 3 g oxygen are added in 1000 ml four-hole bottle
Change calcium, in 65 DEG C or so points of 4 195 g paraformaldehydes of addition, every minor tick 30 minutes, paraformaldehyde is incubated 30 after all adding
Minute, it is warming up to 85 DEG C and reacts 110 minutes, 55 DEG C is cooled to rapidly and adjusts pH to obtain phenolic resin to neutrality, viscosity is 3500
mPa·s/25℃。
Take by weight after 100 parts of above-mentioned phenolic resin, 5 parts of Tween-60s, 6 parts of pentanes stir, add 8 parts
Sulfuric acid, 4 parts of phosphoric acid and 3 parts of p-methyl benzenesulfonic acid obtain cured phenolic foam after being stirred at room temperature 30 seconds, 5 minutes.
Embodiment 4.
300 g phenol, 25 g urea, 4 g50% sodium hydroxide solution and 3 g oxygen are added in 1000 ml four-hole bottle
Change calcium, in 60 DEG C or so points of 4 180 g paraformaldehydes of addition, every minor tick 30 minutes, paraformaldehyde is incubated 30 after all adding
Minute, it is warming up to 90 DEG C and reacts 90 minutes, 60 DEG C is cooled to rapidly and adjusts pH to obtain phenolic resin to neutrality, viscosity is 5000
mPa·s/25℃。
Take by weight after 100 parts of above-mentioned phenolic resin, 4 parts of Tween-60s, 7 parts of pentanes stir, add 6 parts
Sulfuric acid, 4 parts of phosphoric acid and 5 parts of p-methyl benzenesulfonic acid obtain cured phenolic foam after being stirred at room temperature 30 seconds, 4 minutes.
Embodiment 5.
300 g phenol, 30 g urea, 4 g50% sodium hydroxide solution and 4 g oxygen are added in 1000 ml four-hole bottle
Change barium, in 60 DEG C or so points of 4 185 g paraformaldehydes of addition, every minor tick 30 minutes, paraformaldehyde is incubated 30 after all adding
Minute, it is warming up to 85 DEG C and reacts 110 minutes, 60 DEG C is cooled to rapidly and adjusts pH to obtain phenolic resin to neutrality, viscosity is 4500
mPa·s/25℃。
Take by weight after 100 parts of above-mentioned phenolic resin, 3 parts of Tween-60s, 7 parts of pentanes stir, add 7 parts
Sulfuric acid, 5 parts of phosphoric acid and 3 parts of p-methyl benzenesulfonic acid obtain cured phenolic foam after being stirred at room temperature 30 seconds, 3 minutes.
Claims (9)
1. a kind of normal temperature can send out the synthesis of phenolic resin, it is characterised in that part starting phenol is replaced with urea, sequentially adds and urges
Agent and paraformaldehyde, carry out middle temperature hydroxymethylation and high temperature polycondensation, phenolic resin can be sent out by obtaining a kind of normal temperature.
2. a kind of normal temperature according to claim 1 can send out the synthesis of phenolic resin, it is characterised in that the raw material of synthetic resin
Component includes as follows by weight：
100 parts of phenol
5 ~ 15 parts of urea
55 ~ 75 parts of paraformaldehyde
1 ~ 3 part of catalyst.
3. a kind of normal temperature according to claim 1 can send out the synthesis of phenolic resin, it is characterised in that including following technique step
Suddenly：
（1）Phenol, urea and catalyst mixing, add paraformaldehyde, at intervals of 20 ~ 40 minutes several times at 50 ~ 70 DEG C；
（2）80 ~ 90 DEG C are warming up to, is reacted 80 ~ 120 minutes；
（3）It is rapid to be cooled to 50 ~ 60 DEG C, pH is adjusted, phenolic resin can be sent out by obtaining normal temperature.
4. a kind of normal temperature according to claim 2 can send out the synthesis of phenolic resin, it is characterised in that described catalyst is
Two or more in sodium hydroxide, potassium hydroxide, calcium oxide, barium monoxide.
5. a kind of normal temperature according to claim 3 can send out the synthesis of phenolic resin, it is characterised in that resulting normal temperature can
The viscosity of phenolic resin is sent out in 3000 ~ 6000 mPas.
6. a kind of obtained normal temperature that synthesized by claim 3 can send out the foaming method of phenolic resin, it is characterised in that this method will
Normal temperature can be sent out after the parts by weight of phenolic resin 100, the parts by weight of surfactant 2 ~ 5, the parts by weight of foaming agent 4 ~ 9 stir, and added
The parts by weight of curing agent 8 ~ 20 stir half a minute, and solidification obtains phenol formaldehyde foam in 3 ~ 6 minutes under normal temperature environment.
7. a kind of normal temperature according to claim 6 can send out the foaming method of phenolic resin, it is characterised in that described surface
Activating agent is one kind in Tween-60, Tween-80, silicone oil H-330.
8. a kind of normal temperature according to claim 6 can send out the foaming method of phenolic resin, it is characterised in that described foaming
Agent is one kind in pentane, pentamethylene, petroleum ether.
9. a kind of normal temperature according to claim 6 can send out the foaming method of phenolic resin, it is characterised in that described solidification
Agent is the one or more in sulfuric acid, phosphoric acid, p-methyl benzenesulfonic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710447568.1A CN107083017A (en) | 2017-06-14 | 2017-06-14 | A kind of normal temperature can send out synthesis and the foaming method of phenolic resin |
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| CN201710447568.1A CN107083017A (en) | 2017-06-14 | 2017-06-14 | A kind of normal temperature can send out synthesis and the foaming method of phenolic resin |
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| CN107083017A true CN107083017A (en) | 2017-08-22 |
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| CN201710447568.1A Pending CN107083017A (en) | 2017-06-14 | 2017-06-14 | A kind of normal temperature can send out synthesis and the foaming method of phenolic resin |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107955117A (en) * | 2017-11-14 | 2018-04-24 | 太尔胶粘剂(广东)有限公司 | A kind of termite-proof, fire resisting phenolic resin preparation method |
| CN110041479A (en) * | 2019-04-08 | 2019-07-23 | 太尔化工（南京）有限公司 | A kind of preparation of novel super absorbent phenolic aldehyde flower mud resin and application method |
| CN111825817A (en) * | 2020-07-22 | 2020-10-27 | 苏州兴业材料科技南通有限公司 | Preparation method of high-activity foaming phenolic resin and neutral phenolic foam |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107955117A (en) * | 2017-11-14 | 2018-04-24 | 太尔胶粘剂(广东)有限公司 | A kind of termite-proof, fire resisting phenolic resin preparation method |
| CN110041479A (en) * | 2019-04-08 | 2019-07-23 | 太尔化工（南京）有限公司 | A kind of preparation of novel super absorbent phenolic aldehyde flower mud resin and application method |
| CN111825817A (en) * | 2020-07-22 | 2020-10-27 | 苏州兴业材料科技南通有限公司 | Preparation method of high-activity foaming phenolic resin and neutral phenolic foam |
| CN111825817B (en) * | 2020-07-22 | 2023-11-03 | 苏州兴业材料科技南通有限公司 | Preparation method of high-activity foaming phenolic resin and neutral phenolic foam |
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| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhou Chunhua Inventor after: Liu Jianguo Inventor after: Kong Xiangkun Inventor before: Liu Jianguo Inventor before: Zhou Chunhua Inventor before: Kong Xiangkun |
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| RJ01 | Rejection of invention patent application after publication | ||
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Application publication date: 20170822 |