CN102993390A - Continuous production method of thermoplastic phenolic resin - Google Patents
Continuous production method of thermoplastic phenolic resin Download PDFInfo
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- CN102993390A CN102993390A CN2012103771276A CN201210377127A CN102993390A CN 102993390 A CN102993390 A CN 102993390A CN 2012103771276 A CN2012103771276 A CN 2012103771276A CN 201210377127 A CN201210377127 A CN 201210377127A CN 102993390 A CN102993390 A CN 102993390A
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Abstract
The invention discloses a continuous production method of a thermoplastic phenolic resin. The continuous production method of the thermoplastic phenolic resin is characterized by comprising the following steps of: calculating the material flow of the following components in parts by weight of 100 parts of phenol, 30-80 parts of aldehyde and 0.5-5 parts of acid catalyst; respectively metering and feeding the components into a static pipeline mixer by a material pump, and then feeding into a pipeline reactor; and conveying to a film evaporator after reaction is finished, ejecting moisture and free phenol, and pelletizing to obtain the thermoplastic phenolic resin after the free phenol is smaller than 1% and the softening point achieves 60-130 DEG C. According to the method, a tubular reactor is adopted to change the traditional intermittent reaction into a continuous process, so as to achieve the effects of feeding the materials from one end and discharging products from the other end. The heat exchange area is greatly increased, and reaction heat release can be stably controlled, so that the reaction speed is set according to the set changing curve completely; the consistency of a reaction endpoint and time is guaranteed; achievement of full-automatic control of the production process is facilitated; and the stability of the product is also guaranteed.
Description
Technical field
The present invention relates to a kind of production method of resol, a kind of continuous production method of novolac resin specifically, this novolac resin is applicable to the binding agent of the industries such as copper-clad plate, capsulation material, phenol aldehyde type epoxy resin, electric molding composite, phenolic fibre, friction materials, refractory materials, grinding tool abrasive material.
Background technology
Resol has heat resistanceheat resistant, insulation, high temperature resistant, anti-corrosion and good machining property, can be applicable to make moulding compound, stratified plastics, porous plastics, cellularpiston etc., also can be used as paint raw materials, tackiness agent, protection against corrosion with clay and the ion exchange resin take resol as the basis etc., also can be used as the tackiness agent of emery wheel, brake facing metal casting model, in national defense industry, resol also is widely used.
At present, main production method domestic or international novolac resin is under the catalysis of organic acid or mineral acid, to adopt batch production technique, mainly be divided into reaction, dehydration, three production phases of granulation, the first two stage all is to carry out in reactor, because equipment is single, step of reaction mostly is and is the normal pressure stage, water smoking then is divided into normal pressure and two stages of vacuum, so that deviate from unreacting phenol, improve the purity of resol, to adapt to the requirement of different application industry.Dewater complete after, then in reactor or dehydrating kettle, wait for finishing of granulating working procedure quietly, whole technological process belongs to batch production.Because the technological problemses such as temperature control, can't guarantee the stability of various processing condition, can't guarantee to make every batch of product gelation time index basically identical, finally cause the molecular weight of product and molecular weight distribution all will rise and fall, can't guarantee the stability of resin quality fully; Simultaneously, because the unstable variation that also can cause the process time of each operation stage processing condition, to such an extent as to always exist the part producing plant factor to descend, turnout is affected.
Summary of the invention
The object of the present invention is to provide simple, the easily control of a kind of technique, improve product stability, the continuous production method of the novolac resin that can uninterruptedly produce continuously, the method can be produced the stable resol of industries such as being suitable for precoated sand, copper-clad plate, capsulation material, phenol aldehyde type epoxy resin, electric molding composite, phenolic fibre, friction materials, refractory materials, grinding tool abrasive material.
In order to reach above purpose, the technical solution adopted in the present invention is: a kind of continuous production method of novolac resin is characterized in that: may further comprise the steps and finish:
(1), by weight the calculation mass flow, 0.5-5 parts of 100 parts in phenol, 30-80 parts in aldehyde and acid catalysts;
(2), the phenol with measuring, aldehyde and acid catalyst be respectively with the product pump metering and send into static line mixer, is delivered to pipeline reactor by static line mixer again;
(3), material reaction times in pipeline reactor is 2-5 hours, temperature of reaction is 40-98 ℃;
(4), the reaction complete after, material directly is delivered to thin-film evaporator, 80-180 ℃ of temperature, pressure is deviate from moisture and free phenol for carrying out thin film evaporation under the-0.08MPa vacuum, when free phenol less than 1%, after softening temperature reached 60-130 ℃, granulation got novolac resin.
The present invention also implements by following measure:
Described pipeline reactor, its temperature of reaction is the control of staged temperature of reaction, be the water-bath temperature control from 40 ℃ to 98 ℃, be divided into 12 temperature sections, can be according to required control accuracy and volume and the temperature in operational path setting each temperature of reaction stage of pipeline reactor, the bath temperature section that present method is set is divided into: 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃ and 95 ℃, can accurately control the tube side of institute's controlling temperature.
Described acid catalyst is any or two kinds the mixture wherein in sulfuric acid, oxalic acid and the hydrochloric acid.
Described phenol is phenol or ortho-cresol.
Described aldehyde is the common formalin of 32-50%.
The mol ratio of described phenol and aldehyde is 1.0:(0.1-1).
Beneficial effect of the present invention is: the production technique that the present invention adopts is with the tubular reactor reaction process; thin film evaporation technique; granulation process is that Main Means makes whole production process serialization; adopt tubular reactor; traditional intermittent reaction is become continuous process; whole reaction process is carried out in tubular reactor; pipeline reactor directly is connected with thin-film evaporator; thin-film evaporator then directly is connected with tablets press; the accurate calculation input speed; speed of response; thin film evaporation speed; granulation speed; make input speed and speed of response; thin film evaporation speed; granulation speed is in full accord; reach production line one end and advance raw material; one brings out the effect of finished product, thereby realizes the real continuous operation that resol is produced.Because heat interchanging area increases considerably, and can stablize the control exothermic heat of reaction, and speed of response is carried out according to the change curve that sets fully, has guaranteed the consistence of reaction end and time, is conducive to realize the Automatic Control of production process.What the increase of stable process conditions also brought thereupon is the lifting of product stability, the Application Areas of particularly using after with the novolac resin dissolution with solvents, the viscosity that can guarantee resin solution can be stabilized in the narrower domain of walker, thereby has guaranteed the stability of product application.
Embodiment
Embodiment 1:
A kind of continuous production method of novolac resin is characterized in that: may further comprise the steps and finish:
(1), by weight the calculation mass flow, 30 parts of the common formalins of 100 parts of phenol, 32-50% and acid catalyst are with 0.5 part of 25% sulphuric acid soln;
(2), the phenol with measuring, aldehyde and acid catalyst be respectively with the product pump metering and send into static line mixer, is delivered to pipeline reactor by static line mixer again;
(3), material reaction times in pipeline reactor is 2 hours, temperature of reaction is 40-98 ℃; Described pipeline reactor, its temperature of reaction is the control of staged temperature of reaction, from 40 ℃ to 98 ℃ for the water-bath temperature control, be divided into 12 temperature sections, be respectively: 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃ and 95 ℃;
(4), reaction complete after, material directly is delivered to thin-film evaporator, 80 ℃ of temperature, pressure is deviate from moisture and free phenol for carrying out thin film evaporation under the-0.08MPa vacuum, when free phenol less than 1%, after softening temperature reached 60 ℃, granulation got novolac resin.
After testing, the detection index of this high-purity thermoplastic phenolic resin is: free phenol concentration≤1%, the light yellow transparent inclusion-free particle of outward appearance.
Embodiment 2:
A kind of continuous production method of novolac resin is characterized in that: may further comprise the steps and finish:
(1), by weight the calculation mass flow, 50 parts of the common formalins of 100 parts of phenol, 32-50% and acid catalyst are with 5 parts of 35% oxalic acid solutions;
(2), the phenol with measuring, aldehyde and acid catalyst be respectively with the product pump metering and send into static line mixer, is delivered to pipeline reactor by static line mixer again;
(3), material reaction times in pipeline reactor is 4 hours, temperature of reaction is 40-98 ℃; Described pipeline reactor, its temperature of reaction is the control of staged temperature of reaction, from 40 ℃ to 98 ℃ for the water-bath temperature control, be divided into 12 temperature sections, be respectively: 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃ and 95 ℃;
(4), reaction complete after, material directly is delivered to thin-film evaporator, 180 ℃ of temperature, pressure is deviate from moisture and free phenol for carrying out thin film evaporation under the-0.08MPa vacuum, when free phenol less than 1%, after softening temperature reached 110 ℃, granulation got novolac resin.
After testing, the detection index of this high-purity thermoplastic phenolic resin is: free phenol concentration≤1%, the light yellow transparent inclusion-free particle of outward appearance.
Embodiment 3:
A kind of continuous production method of novolac resin is characterized in that: may further comprise the steps and finish:
(1), by weight the calculation mass flow, 80 parts of the common formalins of 100 parts of phenol, 32-50% and acid catalyst are with 2 parts of 10% hydrochloric acid solns;
(2), the phenol with measuring, aldehyde and acid catalyst be respectively with the product pump metering and send into static line mixer, is delivered to pipeline reactor by static line mixer again;
(3), material reaction times in pipeline reactor is 3 hours, temperature of reaction is 40-98 ℃; Described pipeline reactor, its temperature of reaction is the control of staged temperature of reaction, from 40 ℃ to 98 ℃ for the water-bath temperature control, be divided into 12 temperature sections, be respectively: 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃ and 95 ℃;
(4), reaction complete after, material directly is delivered to thin-film evaporator, 120 ℃ of temperature, pressure is deviate from moisture and free phenol for carrying out thin film evaporation under the-0.08MPa vacuum, when free phenol less than 1%, after softening temperature reached 130 ℃, granulation got novolac resin.
After testing, the detection index of this high-purity thermoplastic phenolic resin is: free phenol concentration≤1%, the light yellow transparent inclusion-free particle of outward appearance.
Embodiment 4:
A kind of continuous production method of novolac resin is characterized in that: may further comprise the steps and finish:
(1), by weight calculation mass flow, 2 parts of 40 parts of the common formalins of 100 parts of ortho-cresols, 32-50% and acid catalyst; Described acid catalyst is the weight ratio 1:1 mixing solutions of 35% oxalic acid and 10% hydrochloric acid;
(2), the phenol with measuring, aldehyde and acid catalyst be respectively with the product pump metering and send into static line mixer, is delivered to pipeline reactor by static line mixer again;
(3), material reaction times in pipeline reactor is 3 hours, temperature of reaction is 40-98 ℃; Described pipeline reactor, its temperature of reaction is the control of staged temperature of reaction, from 40 ℃ to 98 ℃ for the water-bath temperature control, be divided into 12 temperature sections, be respectively: 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃ and 95 ℃;
(4), reaction complete after, material directly is delivered to thin-film evaporator, 160 ℃ of temperature, pressure is deviate from moisture and free phenol for carrying out thin film evaporation under the-0.08MPa vacuum, when free phenol less than 1%, after softening temperature reached 95 ℃, granulation got novolac resin.
After testing, the detection index of this high-purity thermoplastic phenolic resin is: free phenol concentration≤1%, the light yellow transparent inclusion-free particle of outward appearance.
Claims (6)
1. the continuous production method of a novolac resin is characterized in that: may further comprise the steps and finish:
(1), by weight the calculation mass flow, 0.5-5 parts of 100 parts in phenol, 30-80 parts in aldehyde and acid catalysts;
(2), the phenol with measuring, aldehyde and acid catalyst be respectively with the product pump metering and send into static line mixer, is delivered to pipeline reactor by static line mixer again;
(3), material reaction times in pipeline reactor is 2-5 hours, temperature of reaction is 40-98 ℃;
(4), the reaction complete after, material directly is delivered to thin-film evaporator, 80-180 ℃ of temperature, pressure is deviate from moisture and free phenol for carrying out thin film evaporation under the-0.08MPa vacuum, when free phenol less than 1%, after softening temperature reached 60-130 ℃, granulation got novolac resin.
2. the continuous production method of a kind of novolac resin according to claim 1, it is characterized in that: described pipeline reactor, its temperature of reaction is the control of staged temperature of reaction, be the water-bath temperature control from 40 ℃ to 98 ℃, be divided into 12 temperature sections, be respectively: 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃ and 95 ℃.
3. the continuous production method of a kind of novolac resin according to claim 1 is characterized in that: described acid catalyst is any or two kinds the mixture wherein in sulfuric acid, oxalic acid and the hydrochloric acid.
4. the continuous production method of a kind of novolac resin according to claim 1, it is characterized in that: described phenol is phenol or ortho-cresol.
5. the continuous production method of a kind of novolac resin according to claim 1, it is characterized in that: described aldehyde is the common formalin of 32-50%.
6. the continuous production method of a kind of novolac resin according to claim 1, it is characterized in that: the mol ratio of described phenol and aldehyde is 1.0:(0.1-1).
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107383294A (en) * | 2017-09-04 | 2017-11-24 | 江苏三吉利化工股份有限公司 | A kind of preparation method of the two acid catalyzed light o-cresol-formaldehyde resin of synthesis |
| CN107674218A (en) * | 2017-11-10 | 2018-02-09 | 中国科学院山西煤炭化学研究所 | It is a kind of continuously to prepare high-purity method for spinning phenolic resin particle |
| CN107955328A (en) * | 2017-12-27 | 2018-04-24 | 珠海邦瑞合成材料有限公司 | A kind of low-temperature fast-curing thermoplasticity powder phenolic resin for color resin grinding tool and preparation method thereof |
| CN108148161A (en) * | 2018-01-24 | 2018-06-12 | 山东永汇新材料股份有限公司 | The method that flushing-free exempts from addition drop phenol agent synthetic thermoplastic phenolic resin |
| CN110527041A (en) * | 2019-10-12 | 2019-12-03 | 山东阳谷华泰化工股份有限公司 | A kind of synthetic method of phenolic resin |
| CN112142934A (en) * | 2020-10-27 | 2020-12-29 | 江苏准信自动化科技股份有限公司 | Phenolic resin for paper-based copper-clad plate and preparation method thereof |
| CN112321780A (en) * | 2021-01-04 | 2021-02-05 | 山东友泉新材料有限公司 | Continuous production method of thermosetting phenolic resin |
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| CN102002138A (en) * | 2010-10-14 | 2011-04-06 | 山东莱芜润达化工有限公司 | Method for producing high-purity thermoplastic phenolic resin |
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| CN102002138A (en) * | 2010-10-14 | 2011-04-06 | 山东莱芜润达化工有限公司 | Method for producing high-purity thermoplastic phenolic resin |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107383294A (en) * | 2017-09-04 | 2017-11-24 | 江苏三吉利化工股份有限公司 | A kind of preparation method of the two acid catalyzed light o-cresol-formaldehyde resin of synthesis |
| CN107383294B (en) * | 2017-09-04 | 2019-05-07 | 江苏三吉利化工股份有限公司 | A kind of two acid catalyzed preparation method for synthesizing light o-cresol-formaldehyde resin |
| CN107674218A (en) * | 2017-11-10 | 2018-02-09 | 中国科学院山西煤炭化学研究所 | It is a kind of continuously to prepare high-purity method for spinning phenolic resin particle |
| CN107955328A (en) * | 2017-12-27 | 2018-04-24 | 珠海邦瑞合成材料有限公司 | A kind of low-temperature fast-curing thermoplasticity powder phenolic resin for color resin grinding tool and preparation method thereof |
| CN108148161A (en) * | 2018-01-24 | 2018-06-12 | 山东永汇新材料股份有限公司 | The method that flushing-free exempts from addition drop phenol agent synthetic thermoplastic phenolic resin |
| CN110527041A (en) * | 2019-10-12 | 2019-12-03 | 山东阳谷华泰化工股份有限公司 | A kind of synthetic method of phenolic resin |
| CN112142934A (en) * | 2020-10-27 | 2020-12-29 | 江苏准信自动化科技股份有限公司 | Phenolic resin for paper-based copper-clad plate and preparation method thereof |
| CN112321780A (en) * | 2021-01-04 | 2021-02-05 | 山东友泉新材料有限公司 | Continuous production method of thermosetting phenolic resin |
| CN112321780B (en) * | 2021-01-04 | 2021-04-09 | 山东友泉新材料有限公司 | Continuous production method of thermosetting phenolic resin |
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Application publication date: 20130327 |