CN108148161A - The method that flushing-free exempts from addition drop phenol agent synthetic thermoplastic phenolic resin - Google Patents
The method that flushing-free exempts from addition drop phenol agent synthetic thermoplastic phenolic resin Download PDFInfo
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- CN108148161A CN108148161A CN201810069806.4A CN201810069806A CN108148161A CN 108148161 A CN108148161 A CN 108148161A CN 201810069806 A CN201810069806 A CN 201810069806A CN 108148161 A CN108148161 A CN 108148161A
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- phenol
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- flushing
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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
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The present invention relates to a kind of methods that flushing-free exempts from addition drop phenol agent synthetic thermoplastic phenolic resin, belong to thermoplastic phenolic resin preparing technical field.Reaction kettle is set as vacuum negative pressure condition by the present invention, sucks phenol and formalin, and stirring is warming up to 85 88 DEG C, drop evenly oxalic acid, it then heats to 90 92 DEG C of constant temperature 1.5 2.5 hours, then is warming up to 99 101 DEG C, constant temperature 23 hours, dehydration is to 155 DEG C under normal pressure state, 155 ± 1 DEG C of holding constant temperature 12 hours, is warming up to 160 ± 2 DEG C, vacuumizes, detect it is up to standard after, blowing packaging；The molar ratio of the phenol and formaldehyde is 1:0.85‑0.90.The design of the invention is scientific and reasonable, does not generate the dense phenol water of flushing, and energy conservation and environmental protection reduces production link, improves production efficiency, the quality of target product is improved, conducive to industrialized production.
Description
Technical field
The present invention relates to a kind of methods that flushing-free exempts from addition drop phenol agent synthetic thermoplastic phenolic resin, belong to thermoplasticity phenol
Urea formaldehyde preparing technical field.
Background technology
Phenolic resin be it is a kind of with phenolic compound and aldehyde compound through one major class synthetic resin prepared by polycondensation.It is logical
With the thermoplastic phenolic resin in phenolic resin mainly for the manufacture of Moulding powder, founding materials, automotive brake class, adhesive
Deng.In the synthesis of early stage, not using free phenol as important indicator, enough attention are not caused.Attention was improved in recent years
Degree, but because reduce free phenol also there is a series of disadvantage simultaneously.
The technique of existing production thermal plastic phenolic resin generally reduces the trip in resin using the method for steam flush
From phenol content, also there are a small number of proposition addition drop phenol agent such as boric acid, rosin, ferrous sulfate etc. to reduce the method for free phenol content,
But all there are certain drawbacks for both modes.Such as：Steam flush method can generate a large amount of dense phenol water, to business processes this
One block of dense phenol water and increase burden, while be unfavorable for environmental protection；The drop phenol agent such as boric acid, rosin, ferrous sulfate is added, is easily changed
The original purity of changing resin, characteristic etc., can affect to the stability of resin.So it needs to develop a kind of new conjunction
Into the method for thermoplastic phenolic resin.
Invention content
A kind of method for exempting to add drop phenol agent synthetic thermoplastic phenolic resin the purpose of the present invention is to provide flushing-free,
Design is scientific and reasonable, does not generate the dense phenol water of flushing, and energy conservation and environmental protection reduces production link, improves production efficiency, improves
The quality of target product, conducive to industrialized production.
The method that flushing-free of the present invention exempts from addition drop phenol agent synthetic thermoplastic phenolic resin, includes the following steps：
Reaction kettle is set as vacuum negative pressure condition -0.05~-0.07MPa, sucks phenol and formalin, stirring is warming up to 85-88 DEG C,
Oxalic acid is dropped evenly, time control added in 75-90 minutes, then heated to 90-92 DEG C of constant temperature 1.5-2.5 hours, then rose
Temperature is to 99-101 DEG C, and constant temperature 2-3 hours, to 155 DEG C, 155 ± 1 DEG C of holding constant temperature 1-2 hours is warming up to for dehydration under normal pressure state
160 ± 2 DEG C ,≤- 0.07MPa is vacuumized, according to norm controlling vacuum degree, after detection is up to standard, blowing packaging.
The molar ratio of the phenol and formaldehyde is 1:0.85-0.90.The present invention by determine accurately, suitable formaldehyde use
Amount, is allowed to, more fully with phenol reactant, reduce the dewatered residual free phenol amount of normal pressure, improve the pure of target product
Degree.
The dosage of the catalyst oxalic acid is the 0.7-1.0% of phenol amount.The present invention is kept away by adding a small amount of catalyst
Exempt from the resin for synthesizing macromolecule.
Compared with prior art, the present invention it has the advantages that：
The present invention reduces the dewatered residual free phenol amount of normal pressure by controlling the dosage of formaldehyde, and in the prior art
Rinse the 10-14% that the dense phenol water generated accounts for phenol quality；The present invention is by being added dropwise the low temperature of catalyst in condensation course
And substep temperature control, the flexibility of resin is made to be guaranteed；Present invention phase in post synthesis, using 155 ± 1 DEG C of constant temperature 1.5 hours,
Only need very low vacuum that can synthesize the phenolic resin needed currently on the market, conducive to free phenol in resin reduction and
The growth of viscosity.The design of the invention is scientific and reasonable, does not generate the dense phenol water of flushing, energy conservation and environmental protection, while rinse production because avoiding
Raw dense phenol water, production cycle have also obtained very big shortening, eliminate the link for handling dense phenol water, improve production efficiency,
Production cost is reduced, improves the quality of target product, conducive to industrialized production, free phenol contains in the phenolic resin produced
Amount is less than 3%.
Specific embodiment
With reference to embodiment, the present invention is further illustrated, but it is not intended to limit the implementation of the present invention.
Embodiment 1
Produce PF-201：
Reaction kettle is set as vacuum negative pressure condition-(0.06 ± 1) MPa, sucks phenol and formalin, phenol and formaldehyde
Molar ratio is 1:0.88, stirring is warming up to 85-88 DEG C, drops evenly the oxalic acid solution dissolved, 85 minutes used times, is added dropwise
After be warming up to 90-92 DEG C of constant temperature 2 hours, then be warming up to 99-101 DEG C, constant temperature 2.5 hours, under normal pressure state dehydration to 155 DEG C,
155 ± 1 DEG C of holding constant temperature 1.5 hours, is warming up to 160 ± 2 DEG C, is evacuated to -0.060MPa, samples Testing index：Cone-plate
56.5P/150 DEG C, free phenol 2.31%, the requirement of production task list：(52-58P/150 DEG C of cone-plate, free phenol 2.0%-2.8%),
Qualified blowing.It is 3.22% to detect this batch of product alcohol cementing fruit through laboratory, and impurity content meets the requirements, it is desirable that it is≤4.8%,
After being dissolved with alcohol without naked eyes it is observed that impurity.
Embodiment 2
Produce PF-211：
Reaction kettle is set as vacuum negative pressure condition-(0.06 ± 1) MPa, sucks phenol and formalin, phenol and formaldehyde
Molar ratio is 1:0.9, stirring is warming up to 85-88 DEG C, drops evenly the oxalic acid solution dissolved, 90 minutes used times, is added dropwise
After be warming up to 90-92 DEG C of constant temperature 2.5 hours, then be warming up to 99-101 DEG C, constant temperature 3 hours, dehydration is to 120 ± 1 under normal pressure state
DEG C, auxiliary material nitrile rubber is added in, continuing dehydration under normal pressure state, to 155 DEG C, 155 ± 1 DEG C of holding constant temperature 1 hour is warming up to 160
± 2 DEG C, -0.068MPa is evacuated to, samples Testing index：71P/150 DEG C of cone-plate, free phenol 2.1%, production task list will
It asks：(68-73P/150 DEG C of cone-plate, free phenol 1.8%-2.5%), qualified blowing.This batch of product alcohol cementing fruit is detected through laboratory
Be 4.06%, impurity content meets the requirements, it is desirable that for≤4.8%, after being dissolved with alcohol without naked eyes it is observed that impurity.
Embodiment 3
Produce PF-204：
Reaction kettle is set as vacuum negative pressure condition-(0.06 ± 1) MPa, sucks phenol and formalin, phenol and formaldehyde
Molar ratio is 1:0.85, stirring is warming up to 85-88 DEG C, drops evenly the oxalic acid solution dissolved, 75 minutes used times, is added dropwise
After be warming up to 90-92 DEG C of constant temperature 2 hours, then be warming up to 99-101 DEG C, constant temperature 2 hours, under normal pressure state dehydration protected to 155 DEG C
It holds 155 ± 1 DEG C of constant temperature 2 hours, is warming up to 160 ± 2 DEG C, be evacuated to -0.054MPa, sample Testing index：Cone-plate 41P/150
DEG C, free phenol 2.95%, the requirement of production task list：(38-43P/150 DEG C of cone-plate, free phenol 2.5%-3.5%), qualified blowing.
It is 3.68% to detect this batch of product alcohol cementing fruit through laboratory, and impurity content meets the requirements, it is desirable that it is≤4.8%, it is molten with alcohol
Xie Houwu naked eyes it is observed that impurity.
Claims (5)
1. a kind of method that flushing-free exempts from addition drop phenol agent synthetic thermoplastic phenolic resin, it is characterised in that include the following steps：
Reaction kettle is set as vacuum negative pressure condition, sucks phenol and formalin, stirring is warming up to 85-88 DEG C, drops evenly oxalic acid, so
After be warming up to 90-92 DEG C of constant temperature 1.5-2.5 hours, then be warming up to 99-101 DEG C, constant temperature 2-3 hours, be dehydrated under normal pressure state to
155 DEG C, 155 ± 1 DEG C of holding constant temperature 1-2 hours is warming up to 160 ± 2 DEG C, vacuumizes, after detection is up to standard, blowing packaging；
The molar ratio of the phenol and formaldehyde is 1:0.85-0.90.
2. the method that flushing-free according to claim 1 exempts from addition drop phenol agent synthetic thermoplastic phenolic resin, feature exist
In：Phenol is sucked with before formalin, reaction kettle is set as vacuum negative pressure condition -0.05~-0.07MPa.
3. the method that flushing-free according to claim 1 exempts from addition drop phenol agent synthetic thermoplastic phenolic resin, feature exist
In：The dosage of catalyst oxalic acid is the 0.7-1.0% of phenol amount.
4. the method that flushing-free according to claim 1 exempts from addition drop phenol agent synthetic thermoplastic phenolic resin, feature exist
In：When dropping evenly catalyst, time control added in 75-90 minutes.
5. the method that flushing-free according to claim 1 exempts from addition drop phenol agent synthetic thermoplastic phenolic resin, feature exist
In：When being warming up to 160 ± 2 DEG C ,≤- 0.07MPa is vacuumized.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810069806.4A CN108148161A (en) | 2018-01-24 | 2018-01-24 | The method that flushing-free exempts from addition drop phenol agent synthetic thermoplastic phenolic resin |
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| CN201810069806.4A CN108148161A (en) | 2018-01-24 | 2018-01-24 | The method that flushing-free exempts from addition drop phenol agent synthetic thermoplastic phenolic resin |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111349203A (en) * | 2020-03-19 | 2020-06-30 | 山东永汇新材料股份有限公司 | Synthesis process of thermoplastic phenolic resin for friction material |
| CN111909334A (en) * | 2020-07-22 | 2020-11-10 | 山东宇世巨化工有限公司 | Preparation method of low-expansion resin curing agent and low-expansion resin curing agent |
Citations (5)
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| JP2005187649A (en) * | 2003-12-25 | 2005-07-14 | Ube Ind Ltd | Method for producing phenol novolak resin |
| CN101565491A (en) * | 2008-04-25 | 2009-10-28 | 辽阳前进耐火材料有限公司 | Thermoplastic liquid phenolic resin and preparation method thereof |
| CN102993390A (en) * | 2012-10-08 | 2013-03-27 | 山东莱芜润达新材料有限公司 | Continuous production method of thermoplastic phenolic resin |
| CN103613726A (en) * | 2013-11-20 | 2014-03-05 | 江苏九鼎新材料股份有限公司 | Thermoplastic phenolic resin and production method thereof |
| CN104211887A (en) * | 2014-09-23 | 2014-12-17 | 淮南师范学院 | Green and sustainable high-purity thermoplastic phenolic resin preparing system |
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2018
- 2018-01-24 CN CN201810069806.4A patent/CN108148161A/en active Pending
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|---|---|---|---|---|
| JP2005187649A (en) * | 2003-12-25 | 2005-07-14 | Ube Ind Ltd | Method for producing phenol novolak resin |
| CN101565491A (en) * | 2008-04-25 | 2009-10-28 | 辽阳前进耐火材料有限公司 | Thermoplastic liquid phenolic resin and preparation method thereof |
| CN102993390A (en) * | 2012-10-08 | 2013-03-27 | 山东莱芜润达新材料有限公司 | Continuous production method of thermoplastic phenolic resin |
| CN103613726A (en) * | 2013-11-20 | 2014-03-05 | 江苏九鼎新材料股份有限公司 | Thermoplastic phenolic resin and production method thereof |
| CN104211887A (en) * | 2014-09-23 | 2014-12-17 | 淮南师范学院 | Green and sustainable high-purity thermoplastic phenolic resin preparing system |
Non-Patent Citations (3)
| Title |
|---|
| 《工程塑料应用》杂志社: "《2011年中国工程塑料复合材料技术研讨会论文集》", 31 July 2011, 《工程塑料应用》杂志社编辑出版 * |
| 工业分析 编辑部: "《工业分析》", 31 July 1975, 石油化学工业出版社 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111349203A (en) * | 2020-03-19 | 2020-06-30 | 山东永汇新材料股份有限公司 | Synthesis process of thermoplastic phenolic resin for friction material |
| CN111909334A (en) * | 2020-07-22 | 2020-11-10 | 山东宇世巨化工有限公司 | Preparation method of low-expansion resin curing agent and low-expansion resin curing agent |
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Application publication date: 20180612 |
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