CN103304414A - Preparation method of isobornyl acrylate matters - Google Patents
Preparation method of isobornyl acrylate matters Download PDFInfo
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- CN103304414A CN103304414A CN2013102243696A CN201310224369A CN103304414A CN 103304414 A CN103304414 A CN 103304414A CN 2013102243696 A CN2013102243696 A CN 2013102243696A CN 201310224369 A CN201310224369 A CN 201310224369A CN 103304414 A CN103304414 A CN 103304414A
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Abstract
The invention discloses a preparation method of isobornyl acrylate matters, and the preparation method comprises the following steps of: reacting acrylates matters, and camphene or a mixture of camphene and tricyclene used as raw materials in the presence of Amberlyst15 strong acidic resin used as a catalyst, and a polymerization inhibitor by controlling the reaction temperature, thereby synthetizing isobornyl acrylate matters. The temperature control on a resin tube is performed through the heat exchange of a jacket, a fast reaction temperature can be kept in the resin tube, a low temperature can be kept in a mixing kettle, so that a situation that double-bond olefins are heated and then subjected to a side reaction is prevented, and the problem that in low-temperature seasons such as autumn and winter, the resin tube can not carry out reaction at an ideal temperature due to the heat dissipation of a circulation loop also can be solved.
Description
Technical field
The present invention relates to a kind of preparation method of isobornyl acrylate class thing, be specifically related to that a kind of UV is coating material solidified, sizing agent and printing ink is with the preparation method of isobornyl acrylate or isobornyl methacrylate.
Background technology
Entered since 21 century, the coating material solidified industry of the UV of China obtains fast development, and is annual with the speed increment more than 25% in recent years, now developed into after the U.S., Japan, the whole world three big UV solidifying products are produced and are used the area, and China UV solidifying product industrial market was about 10,000,000,000 yuan in 2007.Reactive thinner (reactive diluent) accounts for 30%～50% as the important component part of UV solidify material in UV solidifying product recipe ingredient.The technical development of reactive thinner directly has influence on the performance of UV solidifying product, and its market demand increases fast with the continuous expansion of UV solidifying product application.
CN1133281A and US Patent No. 5672733 propose to use the Amberlyst15 strong resin to make catalyzer respectively, and catalyst A mberlyst15 is seated in the not interior preparation technology of resin cartridge of strap clamp cover, as shown in Figure 1.
US Patent No. 3087962 and US6329543B1 propose respectively by the acrylic or methacrylic acid of carrying out under the strong acid catalyst such as sulfuric acid or the acid of the Lewis such as boron trifluoride the existence and the method for camphene prepared in reaction isobornyl acrylate class thing, and US Patent No. 5399744 has proposed to make of molybdenum heteropolyacid the method for Preparation of Catalyst isobornyl acrylate class thing in addition.
Catalyst A mberlyst15 is seated in the not resin cartridge interior (Fig. 1) of strap clamp cover; because this technology; when (methyl) vinylformic acid and amphene and catalyzer contact reacts; reaction heat can not in time be got rid of; temperature of reaction is too high; be easy to generate heavy byproduct (oligopolymer class), even make under the extreme case that polymerization ofathe reactants, productive rate are low not to be suitable for large-scale production.
Do the corrosion that Preparation of Catalyst isobornyl acrylate class thing easily causes conversion unit with sulfuric acid or boron trifluoride, so this method can not be used with technical scale.Make catalyzer with molybdenum heteropolyacid, catalytic activity is low, the polymerization of the higher thing that easily induces reaction of temperature of reaction, in addition, needs to add earlier in the product aftertreatment in the alkali with after the molybdenum heteropolyacid filtration and carries out underpressure distillation again, the complicated value that does not have popularization of aftertreatment technology.
Summary of the invention
Technical problem to be solved by this invention is: the preparation method that a kind of isobornyl acrylate class thing is provided.
For solving the problems of the technologies described above, technical scheme of the present invention is: the preparation method of (methyl) isobornyl acrylate, the steps include: that with acrylic acid or the like material, amphene or amphene and tricyclene mixture be raw material, with Amberlyst15 strong resin (available from RhomHaas(U.S. Rhom and Hass)) be catalyzer, in the presence of stopper, by the control temperature of reaction, the synthetic isobornyl acrylate class thing that obtains;
Described acrylic acid or the like material is acrylic or methacrylic acid;
The structural formula of described isobornyl acrylate class thing is:
Wherein, R=H or CH
3
Described stopper is selected from one or more in the following substances: Resorcinol (HQ), hydroquinone monomethyl ether (MQ), thiodiphenylamine (PZ), piperidines free radical type stopper (ZJ-701), copper dibutyldithiocarbamate (AI-61R).
The consumption of described catalyst A mberlyst15 strong resin accounts for 6～12% of material total mass.
The mol ratio of described amphene and acrylic acid or the like thing material is 1.2 ± 0.1.
In the described acrylic acid synthesizing isobornyl thiocyanoacetate class thing process, temperature of reaction is 30～45 ℃.
Described isobornyl acrylate class thing building-up reactions is carried out in the resin column of catalyst filling Amberlyst15 strong resin, described resin column strap clamp cover heat-exchanger rig.
Described isobornyl acrylate class thing building-up reactions is: reaction raw materials is finished reaction by resin column continuously, and reaction raw materials flow in resin column is 1L/h～6.7L/h.
In the described acrylic acid synthesizing isobornyl thiocyanoacetate class thing process, feeding mode is acrylic acid or the like thing material and amphene is disposable feeds intake, or acrylic acid or the like thing material enrichment feeds intake.
Described catalyst A mberlyst15 strong resin recycled.
Described catalyst A mberlyst15 strong resin recycled pre-treating process: described catalyst A mberlyst15 strong resin recycled pre-treating process: catalyzer is taken out and suction filtration from reactor, and place 50 ± 5 ℃ of vacuum drying ovens, vacuum tightness 0.096 ± 0.004MPa, dry 12～22h(purpose is to remove the moisture that catalyst activity is reduced); Or catalyzer taken out and suction filtration, the dilute sulphuric acid soaking flushing 4 ± 1h with 5 ± 1%, 40 ± 5 ℃ of temperature, suction filtration and wash repeatedly with deionized water then, flush away sulfuric acid, 50 ± 5 ℃ of vacuum-dryings, pressure-0.1 ± 0.05MPa, time of drying 17 ± 5h.
Beneficial effect of the present invention:
1) by the chuck heat exchange resin cartridge is carried out temperature control as Fig. 2, the temperature that can keep faster reaction in resin cartridge, and keep lesser temps at mixing kettle, to prevent that two key alkene are subjected to pyrogenetic side reaction, also can solve simultaneously at the autumn and winter low temperature season because the heat radiation of circulation loop 2 causes the resin cartridge can't be in the problem of desirable thermotonus.
2) light constituent can recycled after the thick product underpressure distillation of isobornyl acrylate class thing, has improved utilization ratio of raw materials, has reduced production cost.
3) introducing of the introducing by moisture in the minimizing system and metal ion prolongs the work-ing life of catalyzer.
4) catalyzer is repeatedly using the back by acid soak and vacuum drying mode, and catalyst activity can restore.
Figure of description
Fig. 1 is the process route chart that the resin cartridge of not strap clamp cover prepares isobornyl acrylate class thing.
Fig. 2 carries out the process route chart of temperature control preparation isobornyl acrylate class thing to the catalyst resin tube for the chuck heat exchange.
Fig. 3 is amphene: the vinylformic acid mol ratio is 1.2,30 ℃ of temperature of reaction, and flow 1L/h in the resin column, above-mentioned condition is all constant, and catalyst levels is respectively the yield of 12%, 10%, 8%, 6% isobornyl acrylate of amphene and vinylformic acid total amount.
Fig. 4 is amphene: the vinylformic acid mol ratio is 1.2,30 ℃ of temperature of reaction, and flow 1L/h in the resin column, above-mentioned condition is all constant, catalyst levels and the relation in yield GC% and reaction times
Fig. 5 is amphene: the vinylformic acid mol ratio is 1.2,30 ℃ of temperature of reaction, and flow 1L/h in the resin column, above-mentioned condition is all constant, the different catalysts consumption, the variation tendency of resin column temperature out,
Fig. 6 is 8% of amphene and vinylformic acid total mass for catalyst levels, amphene and vinylformic acid mol ratio 1.2, and the reactor flow is 3L/h, above-mentioned condition remains unchanged, the yield GC% of differential responses temperature, differential responses time isobornyl acrylate.
Among Fig. 1,1, the mixing kettle of strap clamp cover, 2, circulation loop, 3, resin cartridge, 4, the crude product still, 5, built-in coil pipe, 6, cooling tube, 7, screen, 8, valve, 9, raw material adds pipeline.
Among Fig. 2,1, the reaction mixing kettle, 2, circulation loop, 3, resin cartridge, 4, the crude product still, 5, built-in coil pipe, 6, water cooler, 7 screens, 8, valve, 9, raw material adds pipeline, 10, the resin cartridge heat exchange jacket, 11, the jacket water (J.W.) terminal valve.
Embodiment
With vinylformic acid, the mixture of amphene or amphene and tricyclene and thiodiphenylamine add pipeline 9 by raw material and join in the reaction mixing kettle 1, flow with regulation makes it through circulation loop 2, screen 7 is by being equipped with (Amberlyst-15 account for total material 10%) resin cartridge 3 of Amberlyst-15, get back in the reaction mixing kettle in 1 through valve 8, mixed solution in the reaction mixing kettle 1 is through circulation loop 2, resin cartridge 3, continue in reaction mixing kettle 1 and resin cartridge 3 circulations, test by GC, after productive rate reaches requirement, close and lead to the valve 8 that reacts mixing kettle 1 and open the valve that leads to crude product still 4 simultaneously, crude product will be stored in the crude product still 4.
Mixture in the crude product still 4 gets product and gets isobornyl acrylate after underpressure distillation.
Embodiment 1
Experimental program: amphene: the vinylformic acid mol ratio is 1.2, reaction times is 6h, 30 ℃ of temperature, flow 1L/h in the resin column, above-mentioned condition is all constant, catalyst A mberlyst15 strong resin consumption accounts for 12%, 10%, 8% of amphene and the total charging capacity of vinylformic acid respectively, 6%, at the 3h of each reaction, 4.5h, 6h get a sample respectively and survey GC.Catalyst levels and yield GC% graphic representation are seen Fig. 3; Catalyst levels and yield GC% and reaction times are seen Fig. 4.
Experimental data such as following table 1:
Different Ca t. consumption, the variation tendency of resin column temperature out sees Table 2 and Fig. 5.
Table 2
By table 2 and Fig. 5 as can be known, a temperature runaway process is arranged during reactor catalysis, the Cat. consumption is more big, and catalysis speed is more fast, and liberated heat is more big in the identical time, and temperature is more high.This reaction is to temperature sensitive, and temperature runaway may cause more side reaction, even causes polymerization.Such as, Cat. is 12% reaction, and temperature runaway is up to 65 ℃, after crude product is placed a night, becomes muddy yellow-white liquid by faint yellow transparent clear liquor, and viscosity obviously increases, and doubts to be polymerization.So, adopt relatively large Cat. to be easy to generate temperature runaway in the short period of time, so preferred Cat. consumption is 8% in synthesis technique, on the other hand, the height of reactor temperature runaway degree is relevant with mass flow in the reactor, flow is more big, along with material flows out fast, can take heat out of reaction system faster.This serial experiment, the flow of employing is 1L/h, and flow is less and cross-sectional area reactor is relatively large, and flow state is laminar flow substantially in the observed reactor, and flow velocity is slow.
Catalyst levels is 8% of amphene and vinylformic acid total mass, amphene and vinylformic acid mol ratio 1.2, and the reactor flow is 3L/h, above-mentioned condition remains unchanged, respectively 30 ℃ of temperature of reactor, 35 ℃, 40 ℃, test under 45 ℃, test respectively at 2h at every turn, 3h, 4h, 5h, 6h, 6.5h GC is surveyed in sampling, observes the GC variation tendency, data such as table 3.
Table 3
In the reaction process product yield GC% in time variation tendency see Fig. 6.
Other conditionally completes are identical, and the feeding mode difference is to the influence of IBOA building-up reactions, and a kind of is disposable feeding intake, and another kind of for the vinylformic acid enrichment feeds intake, influence comprises two aspects: heat release situation and the yield of reaction process.
Experimental program:
Experiment one: amphene and vinylformic acid mol ratio are 1.2, Cat. the quality percentage composition is 10% of amphene and the total charging capacity of vinylformic acid, 30 ℃ of temperature, the mass fraction of thiodiphenylamine is 0.2 ‰ of amphene and the total charging capacity of vinylformic acid, amphene and vinylformic acid, the disposable input mixing kettle of thiodiphenylamine, recycle pump 1L/h, reaction 6h, observing response device temperature out and yield change.
Experiment two: condition is identical with experiment one, and amphene drops into mixing kettle, and vinylformic acid slowly drips from separating funnel, and observing response device temperature out and yield change.
Experimental data:
Table 4
During the vinylformic acid enrichment fed intake and tests, before dropwise addition of acrylic acid, temperature of reactor changed very little, and after beginning to drip, reactor begins to be warming up to 36 ℃, and temperature slowly descends subsequently, is tending towards about 30 ℃.
As seen from the above table, two kinds of feeding modes yield that can reach is very approaching.
Amphene and vinylformic acid mol ratio are that 1.2, Cat. quality percentage composition is 8% of amphene and the total charging capacity of vinylformic acid, 35 ℃ of temperature, amphene 153g, vinylformic acid 97g, the mass fraction of thiodiphenylamine are amphene and acrylic acid charging capacity 0.2 ‰, pumping capacity 2.5L/h, reaction times 7h.Catalyzer 20g, repeatedly recycled is taken a sample when the 7h that at every turn applies mechanically and is surveyed GC, and experimental data sees Table 5.
Table 5
That investigates catalyzer 8% repeats to apply mechanically number of times, catalyzer work-ing life, attempts the renovation process of catalyzer.Amphene and vinylformic acid mol ratio are that the quality percentage composition of 1.2, Cat. is 8% of amphene and the total charging capacity of vinylformic acid, and temperature is 35 ℃, amphene 153g, vinylformic acid 97g, the mass fraction of thiodiphenylamine are 0.2 ‰ of amphene and the total charging capacity of vinylformic acid, pumping capacity 6.7L/h, reaction times 7h.Catalyzer 20g, repeatedly recycled is taken a sample when the 7h that at every turn applies mechanically and is surveyed GC, and experimental data sees Table 6.
Table 6
Amphene and vinylformic acid mol ratio are 1.2, Cat. quality percentage composition is 8% of amphene and the total charging capacity of vinylformic acid, temperature is 35 ℃, 113g vinylformic acid, 137g amphene and 0.05g thiodiphenylamine (accounting for the 0.2%o of total material), catalyzer 20g, pumping capacity 6.7L/h, reaction times 7h, reaction yield are 85%.
Get the 635.25g reaction solution, the 0.13g thiodiphenylamine carries out rectification under vacuum in there-necked flask.Overhead fraction is collected situation such as table 7:
Table 7
The light constituent vinylformic acid that rectification under vacuum is collected, amphene are 1.2 to add recycled behind vinylformic acid and the amphene according to amphene and vinylformic acid mol ratio, Cat. quality percentage composition is 8% of amphene and the total charging capacity of vinylformic acid, 35 ℃ of temperature, the mass fraction of thiodiphenylamine is 0.2 ‰ of amphene and the total charging capacity of vinylformic acid, pumping capacity 6.7L/h, reaction times 7h is by GC test, IBOA productive rate: 80.9%.
Claims (10)
1. the preparation method of an isobornyl acrylate class thing, the steps include: that the mixture with acrylic acid or the like material, amphene or amphene and tricyclene is raw material, is catalyzer with the strong resin, in the presence of stopper, by the control temperature of reaction, the synthetic isobornyl acrylate class thing that obtains;
Described acrylic acid or the like material is acrylic or methacrylic acid;
The structural formula of described isobornyl acrylate class thing is:
Wherein, R=H or CH
3
2. the preparation method of a kind of isobornyl acrylate class thing according to claim 1, it is characterized in that: described strong resin is the Amberlyst15 strong resin; The consumption of described catalyst A mberlyst15 strong resin accounts for 6～12% of material total mass.
3. the preparation method of a kind of isobornyl acrylate class thing according to claim 1, it is characterized in that: described stopper is selected from one or more in the following substances: Resorcinol, hydroquinone monomethyl ether, thiodiphenylamine, piperidines free radical type stopper, copper dibutyldithiocarbamate.
4. the preparation method of a kind of isobornyl acrylate class thing according to claim 1, it is characterized in that: the mol ratio of the mixture of described pure amphene or amphene and tricyclene and acrylic acid or the like thing material is 1.2 ± 0.1.
5. the preparation method of a kind of isobornyl acrylate class thing according to claim 1, it is characterized in that: in the described acrylic acid synthesizing isobornyl thiocyanoacetate class thing process, temperature of reaction is 30～45 ℃.
6. the preparation method of a kind of isobornyl acrylate class thing according to claim 1, it is characterized in that: described isobornyl acrylate class thing building-up reactions, in the resin column of catalyst filling Amberlyst15 strong resin, carry out described resin column strap clamp cover heat-exchanger rig.
7. the preparation method of a kind of isobornyl acrylate class thing according to claim 6, it is characterized in that: described isobornyl acrylate class thing building-up reactions is: reaction raw materials is finished reaction by resin column continuously, and reaction raw materials flow in resin column is 1L/h～6.7L/h.
8. the preparation method of a kind of isobornyl acrylate class thing according to claim 1, it is characterized in that: in the described acrylic acid synthesizing isobornyl thiocyanoacetate class thing process, feeding mode is acrylic acid or the like material and amphene is disposable feeds intake, or acrylic acid or the like material enrichment feeds intake.
9. the preparation method of a kind of isobornyl acrylate class thing according to claim 1 is characterized in that: described catalyst A mberlyst15 strong resin recycled.
10. the preparation method of a kind of isobornyl acrylate class thing according to claim 1, it is characterized in that: described catalyst A mberlyst15 strong resin recycled pre-treating process: catalyzer is taken out and suction filtration from reactor, and place 50 ± 5 ℃ of vacuum drying ovens, vacuum tightness 0.096 ± 0.004MPa, dry 12～22h; Or catalyzer taken out and suction filtration, the dilute sulphuric acid soaking flushing 4 ± 1h with 5 ± 1%, 40 ± 5 ℃ of temperature, suction filtration and wash repeatedly with deionized water then, flush away sulfuric acid, 50 ± 5 ℃ of vacuum-dryings, pressure-0.1 ± 0.05MPa, time of drying 17 ± 5h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104815667A (en) * | 2015-04-02 | 2015-08-05 | 陕西延长石油（集团）有限责任公司炼化公司 | Use of solid acid catalyst in synthesis of isobornyl acrylate |
| CN108531125A (en) * | 2018-03-29 | 2018-09-14 | 佛山市高明绿色德化工有限公司 | A kind of Environment-friendlyglue glue and preparation method thereof |
| CN112142593A (en) * | 2020-08-28 | 2020-12-29 | 华南农业大学 | Preparation method of isobornyl (meth) acrylate of biological origin |
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| CN1133281A (en) * | 1994-12-22 | 1996-10-16 | 埃勒夫阿托化学有限公司 | Method for preparation of (methyl) propenoic acid isoborneol ester |
| CN101863763A (en) * | 2010-06-04 | 2010-10-20 | 南京林业大学 | Method for catalytically synthesizing isobornyl methacrylate by activated carbon supported stannic chloride |
| CN102276453A (en) * | 2011-06-30 | 2011-12-14 | 福州大学 | Method for preparing isobomyl acetate through camphene esterification |
| CN102417474A (en) * | 2011-09-26 | 2012-04-18 | 深圳翰宇药业股份有限公司 | New method for preparing D-iso-glutamoyl-D-tryptophan |
-
2013
- 2013-06-07 CN CN2013102243696A patent/CN103304414A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1133281A (en) * | 1994-12-22 | 1996-10-16 | 埃勒夫阿托化学有限公司 | Method for preparation of (methyl) propenoic acid isoborneol ester |
| CN101863763A (en) * | 2010-06-04 | 2010-10-20 | 南京林业大学 | Method for catalytically synthesizing isobornyl methacrylate by activated carbon supported stannic chloride |
| CN102276453A (en) * | 2011-06-30 | 2011-12-14 | 福州大学 | Method for preparing isobomyl acetate through camphene esterification |
| CN102417474A (en) * | 2011-09-26 | 2012-04-18 | 深圳翰宇药业股份有限公司 | New method for preparing D-iso-glutamoyl-D-tryptophan |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104815667A (en) * | 2015-04-02 | 2015-08-05 | 陕西延长石油（集团）有限责任公司炼化公司 | Use of solid acid catalyst in synthesis of isobornyl acrylate |
| CN108531125A (en) * | 2018-03-29 | 2018-09-14 | 佛山市高明绿色德化工有限公司 | A kind of Environment-friendlyglue glue and preparation method thereof |
| CN112142593A (en) * | 2020-08-28 | 2020-12-29 | 华南农业大学 | Preparation method of isobornyl (meth) acrylate of biological origin |
| CN112142593B (en) * | 2020-08-28 | 2021-07-06 | 华南农业大学 | Preparation method of isobornyl (meth) acrylate of biological origin |
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Application publication date: 20130918 |