CN102964569A - Method for producing terpene-phenolic resins - Google Patents
Method for producing terpene-phenolic resins Download PDFInfo
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- CN102964569A CN102964569A CN2012105242559A CN201210524255A CN102964569A CN 102964569 A CN102964569 A CN 102964569A CN 2012105242559 A CN2012105242559 A CN 2012105242559A CN 201210524255 A CN201210524255 A CN 201210524255A CN 102964569 A CN102964569 A CN 102964569A
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- phenolic resin
- terpene
- terpene phenolic
- phenolic resins
- boron trichloride
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Abstract
The invention provides a method for producing terpene-phenolic resins. The terpene-phenolic resins with high tackifying property are obtained, so that the performance of the terpene-phenolic resins is improved. The method for producing the terpene-phenolic resins comprises the following steps of: A, dipping a-pinene with the purity of not less than 98 percent into a mixed liquid of phenol and methylbenzene under a temperature condition of 30-50 DEG C; adding boron trichloride serving as a catalyst into the mixed liquid to stir at least for one hour; and standing for 3-4 hours under a temperature condition of 40-60 DEG C to obtain a primary reactant; B, putting the primary reactant into hot water with the temperature of 90-100 DEG C to wash away boron trichloride to obtain the resin liquid of the terpene-phenolic resins; and C, clearing the water of the resin liquid of the terpene-phenolic resins; and putting the liquid into a distilled pot to distill and heat to 180 DEG C to obtain methylbenzene serving as a solvent; vacuumizing, distilling and heating methylbenzene; heating methylbenzene to 260 DEG C under a vacuum degree ranging from -0.08Mpa to -0.1Mpa; reducing the temperature to 240 DEG C after the vacuum is destroyed to package so as to obtain the solid terpene-phenolic resins.
Description
Technical field
The invention belongs to the forest chemical technical field, specially refer to a kind of production method of terpene phenolic resin.
Background technology
The terpene phenolic resin (terpene hydrocarbon and phenolic resin) claim again terpene-phenolic resin, a kind of phenol modified resin, be acrylic resin; styrene-butadiene rubber(SBR); the good tackifier of natural rubber and chloroprene rubber etc., be widely used in the industry such as hot melt adhesive sizing agent, pressure-sensitive adhesive agent, coating, printing ink, printed wiring, modifying plastics, rubber item.At present, the terpene phenolic resin is formed through polymerization catalyst by a-firpene and the phenol of light oil or 95%, and resulting terpene phenolic resinous molecular structure is unreasonable, and molecular weight is large, hydroxyl value is large, skewness, and the viscous force of formation is not enough, and intermiscibility is poor.
Summary of the invention
The objective of the invention is to propose a kind of production method of terpene phenolic resin, to obtain the terpene phenolic resin of high tackify, improve the performance of terpene phenolic resin.
The production method of terpene phenolic resin of the present invention comprises the steps:
A: under 30～50 ℃ temperature condition, drip purity in the mixed solution of phenol and toluene and be not less than 98% a-firpene, and add the catalyzer boron trichloride, stirred at least one hour, then under 40～60 ℃ temperature condition, left standstill 3～4 hours, obtain the primary reaction thing;
B: the hot water of the primary reaction thing being put into 90～100 ℃ is washed, and with the flush away boron trichloride, obtains terpene phenolic resin ester liquid;
C: behind terpene phenolic resin ester liquid primary water, put into still pot and distill and be heated to 180 ℃, steam solvent toluene; And then vacuumize distillation heating ,-0.08Mpa～-be heated to 260 ℃ under the vacuum tightness of 0.1Mpa, destroy under the condition that is cooled to 240 ℃ after the vacuum and pack, obtain the terpene phenolic resin of solid.
Specifically, in the described A step, the a-firpene of dropping and the mass ratio of phenol are 1:0.17～0.25.
Specifically, in the described A step, the boron trichloride quality account for phenol, a-firpene and boron trichloride the quality summation 6%.
Specifically, in the described B step, until residue when being yellow fat liquid, just represents flush away boron trichloride.
Specifically, in the described C step, adopt nitrogen to destroy vacuum, stable with the terpene phenolic resin properties that guarantees to obtain.
The present invention directly uses purity to be not less than 98% a-firpene and industrial phenol to come production terpene phenolic resin, and the terpene phenolic molecular resin amount that obtains is evenly distributed, and hydroxyl value is less, has reached the effect of high tackify power.According to test statistics, the molecular-weight average 750g/mol of the terpene phenolic resin that the present invention synthesizes, minimum molecular weight is 600g/mol, and maximum molecular weight is 1000g/mol, even molecular weight distribution, molecular structure is reasonable, hydroxyl value is about 45-60, and better with acrylic acid intermiscibility, Efficient Adhesive Promotion strengthens greatly, stripping strength is large, has reached user's requirement.
Embodiment
Below by the description to embodiment, the effect of the mutual alignment between the shape of the specific embodiment of the present invention such as related each member, structure, the each several part and annexation, each several part and principle of work etc. are described in further detail.
Embodiment 1:
A, industrial phenol 120kg and solvent toluene 550kg are added in the reactor, begin to stir, rotating speed is 400 rev/mins, then add 40kg catalyzer boron trichloride, begin simultaneously to drip purity and be not less than 98% a-firpene, drip speed by 500kg/h and drip 500kg, temperature of reaction is controlled at 30 ℃ in this process, react after 1 hour, temperature is controlled at 40 ℃ of insulations 4 hours, obtain containing the toluene solution of terpene phenolic resin and boron trichloride;
B, above-mentioned toluene solution is put into water washing pan washing, the hot water that adds 90～100 ℃ is washed, and the flush away catalyzer obtains the terpene phenolic resin ester liquid of yellow;
C: behind terpene phenolic resin ester liquid primary water, put into still pot and distill, at first be heated to 180 ℃, steam solvent toluene; And then vacuumize distillation ,-0.08Mpa～-be heated to 260 ℃ under the vacuum tightness of 0.1Mpa, destroy under the condition that is cooled to 240 ℃ after the vacuum with nitrogen and pack, obtain the terpene phenolic resin of solid.
The softening temperature of the terpene phenolic resin that present embodiment obtains is 95 ℃, and molecular-weight average is 750g/mol, and acid number is 0.56mgKOH/g, and the rate of recovery is 86%.
Embodiment 2:
A, industrial phenol 100kg and solvent toluene 550kg are added in the reactor, begin to stir, rotating speed is 400 rev/mins, then add 40kg catalyzer boron trichloride, begin simultaneously to drip purity and be not less than 98% a-firpene, drip speed by 500kg/h and drip 520kg, temperature of reaction is controlled at 30 ℃ in this process, react after 1.1 hours, temperature is controlled at 45 ℃ of insulations 4 hours, obtain containing the toluene solution of terpene phenolic resin and boron trichloride;
B, above-mentioned toluene solution is put into water washing pan washing, the hot water that adds 90～100 ℃ is washed, and the flush away catalyzer obtains the terpene phenolic resin ester liquid of yellow;
C, with behind the terpene phenolic resin ester liquid primary water, put into still pot and distill, at first be heated to 180 ℃, steam solvent toluene; And then vacuumize distillation ,-0.08Mpa～-be heated to 260 ℃ under the vacuum tightness of 0.1Mpa, destroy under the condition that is cooled to 240 ℃ after the vacuum with nitrogen and pack, obtain the terpene phenolic resin of solid.
The softening temperature of the terpene phenolic resin that present embodiment obtains is 100 ℃, and molecular-weight average is 750g/mol, and acid number is 0.6mgKOH/g, and the rate of recovery is 86%.
Claims (5)
1. the production method of a terpene phenolic resin is characterized in that comprising the steps:
A: under 30～50 ℃ temperature condition, drip purity in the mixed solution of phenol and toluene and be not less than 98% a-firpene, and add the catalyzer boron trichloride, stirred at least one hour, then under 40～60 ℃ temperature condition, left standstill 3～4 hours, obtain the primary reaction thing;
B: the hot water of the primary reaction thing being put into 90～100 ℃ is washed, and with the flush away boron trichloride, obtains terpene phenolic resin ester liquid;
C: behind terpene phenolic resin ester liquid primary water, put into still pot and distill and be heated to 180 ℃, steam solvent toluene; And then vacuumize distillation heating ,-0.08Mpa～-be heated to 260 ℃ under the vacuum tightness of 0.1Mpa, destroy under the condition that is cooled to 240 ℃ after the vacuum and pack, obtain the terpene phenolic resin of solid.
2. the production method of terpene phenolic resin according to claim 1 is characterized in that in the described A step, and the a-firpene of dropping and the mass ratio of phenol are 1:0.17～0.25.
3. the production method of terpene phenolic resin according to claim 1 is characterized in that in the described A step, the boron trichloride quality account for phenol, a-firpene and boron trichloride the quality summation 6%.
4. the production method of terpene phenolic resin according to claim 1 is characterized in that in the described B step, until residue when being yellow fat liquid, just represents flush away boron trichloride.
5. the production method of terpene phenolic resin according to claim 1 is characterized in that in the described C step, adopts nitrogen to destroy vacuum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012105242559A CN102964569A (en) | 2012-12-10 | 2012-12-10 | Method for producing terpene-phenolic resins |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012105242559A CN102964569A (en) | 2012-12-10 | 2012-12-10 | Method for producing terpene-phenolic resins |
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| CN102964569A true CN102964569A (en) | 2013-03-13 |
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| CN2012105242559A Pending CN102964569A (en) | 2012-12-10 | 2012-12-10 | Method for producing terpene-phenolic resins |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104788748A (en) * | 2015-04-17 | 2015-07-22 | 广西藤县通轩立信化学有限公司 | Rubber containing modified terpene resin |
| CN104877595A (en) * | 2015-05-19 | 2015-09-02 | 广西众昌树脂有限公司 | Hot-melt adhesive |
| CN110003446A (en) * | 2019-03-20 | 2019-07-12 | 江西金安林产实业有限公司 | A kind of light color and high softening-point terpene phenol resin and the preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4056513A (en) * | 1975-03-11 | 1977-11-01 | Les Derives Resiniques Et Terpeniques | Process for the preparation of terpene-phenol resins by three-stage reaction of phenol with carene using friedel-crafts or lewis acid catalyst |
-
2012
- 2012-12-10 CN CN2012105242559A patent/CN102964569A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4056513A (en) * | 1975-03-11 | 1977-11-01 | Les Derives Resiniques Et Terpeniques | Process for the preparation of terpene-phenol resins by three-stage reaction of phenol with carene using friedel-crafts or lewis acid catalyst |
Non-Patent Citations (3)
| Title |
|---|
| 任东: ""由α-蒎烯生产萜烯酚树脂"", 《合成树脂及塑料》 * |
| 王兴益: ""萜烯酚树脂的研制"", 《兴义民族师范学院学报》 * |
| 袁友珠，程芝: ""萜烯酚树脂的研制"", 《南京林业大学学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104788748A (en) * | 2015-04-17 | 2015-07-22 | 广西藤县通轩立信化学有限公司 | Rubber containing modified terpene resin |
| CN104877595A (en) * | 2015-05-19 | 2015-09-02 | 广西众昌树脂有限公司 | Hot-melt adhesive |
| CN110003446A (en) * | 2019-03-20 | 2019-07-12 | 江西金安林产实业有限公司 | A kind of light color and high softening-point terpene phenol resin and the preparation method and application thereof |
| CN110003446B (en) * | 2019-03-20 | 2021-10-29 | 江西金安林产实业有限公司 | Light-color high-softening-point terpene-phenol resin and preparation method and application thereof |
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Application publication date: 20130313 |