CN104592030B - Method for synthesizing phthalate compounds - Google Patents
Method for synthesizing phthalate compounds Download PDFInfo
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- CN104592030B CN104592030B CN201410784037.8A CN201410784037A CN104592030B CN 104592030 B CN104592030 B CN 104592030B CN 201410784037 A CN201410784037 A CN 201410784037A CN 104592030 B CN104592030 B CN 104592030B
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- phthalic anhydride
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Abstract
The invention provides a method for synthesizing phthalate compounds. By taking a weak acid as a main catalyst assisted by a composite catalyst formed by other co-catalysts, the phthalate compounds are synthesized. The method specifically comprises the following steps: adding phthalic anhydride, alcohol and the composite catalyst into a reactor, wherein the molar ratio of phthalic anhydride and alcohol is 1: (2.1-5.0) and the addition of the composite catalyst is 0.2-10wt% of phthalic anhydride; and sealing the reactor, raising the temperature till boiling, reacting for 0.5-2 hours and rectifying to obtain a product. The method not only can realize a catalytic effect of concentrated sulfuric acid, but also overcome the defects. Moreover, the used catalyst can be separated and reused by using a conventional method, so that the separating flow is greatly simplified and continuous production is facilitated.
Description
Technical field
Invention belongs to chemosynthesis technical field, is related to a kind of synthesis side of phthalate compound
Method.
Background technology
Phthalic acid ester, also known as phthalate ester, abridge pae, is the general designation of the ester that phthalic anhydride is formed.O-phthalic
Acid esters has excellent comprehensive process performance, and plasticizing efficiency is high, and volatility is little, and cold resistance, pliability, electrical property etc. are good.
Phthalate compound, uses mainly as plasticizer (plasticiser), is added to elastic, transparent to strengthen in plastics
Degree, durability and service life, and be widely used in multiple product, the casing of such as pill and nutritional supplement, viscosity agent, glue
Solidifying agent, help film, stabilizer, dispersant, lubricant, binding agent, emulsifying agent and suspending agent etc..
Phthalate compound when being used as plastic plasticizer, generally referred to as phthalic acid with containing 1～
The ester that the alcohol of 15 carbon is formed, its reaction is mainly existed in acid catalyst (as the concentrated sulfuric acid) with corresponding alcohol by phthalic anhydride
Lower esterification forms, and its technological process and working condition depend primarily on catalyst.Earliest catalyst is made using the concentrated sulfuric acid, because dense
Sulfuric acid has acidity by force, thus its catalysis activity is higher, and desired reaction temperature is relatively low, generally 140～160 DEG C of reaction temperature,
But there is serious corrosivity in it, post processing is complicated, produce the defects such as waste residue.Chinese scholars constantly research and develop new catalytic body
System.For now, multiple catalyst system and catalyzings have been have developed, liquid acid in addition to the concentrated sulfuric acid, salt, heteropoly acid and its immobilized, solid
Body (superpower) acid etc., but these catalyst generally there are catalysis activity relatively low (reaction temperature is typically at 200 DEG C or more), stablize
Property not so good (as the solid acid of various support types, salt etc.) etc. clearly disadvantageous it is difficult to realize industrialization.Industrial use at present
Catalyst be mainly the concentrated sulfuric acid, titanate esters etc..Therefore, research and develop a kind of catalytic effect that can either reach the concentrated sulfuric acid can overcome again
The catalyst system and catalyzing of its shortcoming is current urgent problem.
Content of the invention
Goal of the invention: for the concentrated sulfuric acid in prior art make catalyst presence corrosivity is too strong, reaction terminate after need
With and make production technology elongated and produce useless solid a kind of not enough, present invention catalytic effect that can reach the concentrated sulfuric acid of offer is provided,
The synthetic method of its not enough phthalate compound can be overcome again.And the catalyst being used can be using routine
Method separating and recovering, enormously simplify separation process, is easy to continuous prodution.
Technical scheme: synthetic method of the present invention, a kind of new catalyst system and catalyzing is provided: with weak acid as major catalyst,
It is aided with composite catalyst synthesis phthalate compound (predominantly butyl ester and monooctyl ester) of other co-catalysts composition.Tool
Body, the present invention is to add in reactor by phthalic anhydride, alcohol and composite catalyst, phthalic anhydride and alcohol mole
For 1:2.1～5.0, the addition of composite catalyst is the 0.2%～10% of the weight of phthalic anhydride to ratio.Ensure reactor
Sealing, is warming up to boiling, after reacting 0.5～2 hour, rectifying, and obtain product.
Described alcohol is butanol, isooctanol.
Described composite catalyst includes major catalyst and co-catalyst, and major catalyst with the mass ratio of co-catalyst is
10:0.1～1.
Major catalyst is weak acid or salt.Described weak acid is sulfamic acid, p-methyl benzenesulfonic acid or oxalic acid；Described salt is sulfuric acid
Hydrogen sodium, potassium acid sulfate, iron chloride, stannic chloride, aluminium chloride.
Co-catalyst is nitrogen group element compound or polyethylene glycol.Described nitrogen group element compound is quaternary salt, arsenic
Crown ether, quaternary ammonium salt, Tetrabutylammonium bromide or methyl tricapryl ammonium chloride.
Composite catalyst can be separated with product after terminating by reaction by distillation, and the composite catalyst of recovery is capable of circulation to be made
With.
Further, nitrogen group element compound and polyethylene glycol are combined and use as co-catalyst by the present invention, permissible
Improve further reaction conversion ratio, improve product yield.Wherein nitrogen group element compound and the mass ratio of polyethylene glycol are
10:1～25.
Beneficial effect: due to present invention employs such scheme, compared with prior art, there is following good effect:
(1) this programme employs new composite catalyst and carries out this reaction, and its catalytic effect meets or exceeds the concentrated sulfuric acid
Catalytic effect, reaction is temperature required relatively low, has not only saved the energy, and side reaction is few；
(2) this programme employs new composite catalyst and carries out this reaction, with raw catelyst reacted material color relatively
Light, it is to avoid the problem more than side reaction that sulphuric acid catalysis exist；
(3) this programme employs new composite catalyst and carries out this reaction, can be by distillation by catalyst and product after reaction
Thing separates, and reacted catalyst can be recycled；
(4) this programme employs new composite catalyst and carries out this reaction, and after reaction, product separates simply with catalyst, no
Only simplify using sulphuric acid catalysis method separation process longer wait not enough, it is to avoid need after reaction with alkali and wait operation, making this
The production procedure of product greatly shortens, and will not produce useless solid, and waste liquid amount also can greatly reduce, thus production cost can be more
Low, and more environmentally-friendly.
Specific embodiment:
Phthalic anhydride and corresponding alcohols (as butanol, isooctanol etc.) are in conventional tank reactor in composite catalyst
Phthalate compound is obtained through esterification, the mol ratio of phthalic anhydride and corresponding alcohols is 1:2.1 under effect
～5.0, catalyst charge is 0.2%～10% (thinking phthalic anhydride benchmark).Its course of reaction is as follows:
(1) to add in stirring, the reactor of water knockout drum and reflux condensing tube or rectifying separator phthalic anhydride,
N-butanol, composite catalyst, the air-tightness of check device, carry out the operation of (2) step after qualified；
(2) it is warming up to boiling reaction 0.5～2h；
(3) reactor is lowered the temperature, be down to its related content of less than 70 DEG C sample analysis, calculate the performance of this catalyst；
(4) product phthalate compound can pass through the operation such as rectifying and realize it to separate with catalyst, separates
Catalyst after process can be continuing with lower batch reaction, and its catalytic performance can continue to keep.
Below by way of specific embodiment, the present invention is further described:
Embodiment 1
To with stirring, water knockout drum and reflux condensing tube 250 milliliters of there-necked flasks in add 50 grams of phthalic anhydride,
N-butanol addition is 2.4 times of phthalic anhydride molal quantity, 0.25 gram of catalyst (by weight percentage, niter cake:
Tetrabutylammonium bromide: polyethylene glycol=10:1.0:0.1), after being warming up to boiling reaction 1h, chromatograph obtains this catalyst
Catalytic performance: phthalic anhydride conversion ratio be 99.1%, dibutyl phthalate yield be 98.0%.
Embodiment 2
To with stirring, water knockout drum and reflux condensing tube 250 milliliters of there-necked flasks in add 50 grams of phthalic anhydride,
N-butanol addition is 4.0 times of phthalic anhydride molal quantity, 2.0 grams of catalyst (by weight percentage, potassium acid sulfate:
Polyethylene glycol=10:0.1), after being warming up to boiling reaction 2h, chromatograph obtains the catalytic performance of this catalyst: adjacent benzene two
Formic anhydride conversion ratio is 93.5%, and dibutyl phthalate yield is 93.2%.
Embodiment 3
To with stirring, water knockout drum and reflux condensing tube 250 milliliters of there-necked flasks in add 50 grams of phthalic anhydride,
N-butanol addition is 2.4 times of phthalic anhydride molal quantity, 2.5 grams of catalyst (by weight percentage, niter cake:
Tetrabutylammonium bromide=10:0.8), after being warming up to boiling reaction 0.5h, chromatograph obtains the catalytic performance of this catalyst:
Phthalic anhydride conversion ratio is 94.6%, and dibutyl phthalate yield is 94.2%.
Embodiment 4
To with stirring, water knockout drum and reflux condensing tube 250 milliliters of there-necked flasks in add 50 grams of phthalic anhydride,
By weight percentage, n-butanol addition is 2.4 times of phthalic anhydride molal quantity, and 1.0 grams of catalyst is (to toluene sulphur
Acid: Tetrabutylammonium bromide: polyethylene glycol=10:0.2:0.5), after being warming up to boiling reaction 1h, chromatograph obtains this catalysis
The catalytic performance of agent: phthalic anhydride conversion ratio is 97.6%, dibutyl phthalate yield is 95.8%.
Embodiment 5
To with stirring, water knockout drum and reflux condensing tube 250 milliliters of there-necked flasks in add 50 grams of phthalic anhydride,
N-butanol addition is 2.2 times of phthalic anhydride molal quantity, 2.0 grams of catalyst (by weight percentage, potassium acid sulfate:
Tetrabutylammonium bromide: polyethylene glycol=10:0.5:0.1), after being warming up to boiling reaction 1h, chromatograph obtains this catalyst
Catalytic performance: phthalic anhydride conversion ratio be 96.4%, dibutyl phthalate yield be 95.0%.
Embodiment 6
To with stirring, water knockout drum and reflux condensing tube 250 milliliters of there-necked flasks in add 50 grams of phthalic anhydride,
Isooctanol addition is 2.4 times of phthalic anhydride molal quantity, 2.0 grams of catalyst (by weight percentage, potassium acid sulfate:
Tetrabutylammonium bromide: polyethylene glycol=10:0.5:0.1), after being warming up to boiling reaction 1h, chromatograph obtains this catalyst
Catalytic performance: phthalic anhydride conversion ratio be 99.1%, dioctyl phthalate yield be 97.8%.
Embodiment 7
To with stirring, simple rectification device and reflux condensing tube 5000 milliliters of tank reactors in add adjacent benzene two
1000 grams of formic anhydride, n-butanol addition is 2.4 times of phthalic anhydride molal quantity, and 20.0 grams of catalyst is (with weight percent
Ratio meter, potassium acid sulfate: Tetrabutylammonium bromide: polyethylene glycol=10:0.5:0.1), after being warming up to boiling reaction 1h, divided with chromatogram
Analysis obtains the catalytic performance of this catalyst: phthalic anhydride conversion ratio is 98.6%, and dibutyl phthalate yield is
98.3%.
Embodiment 8 (catalyst performance after recovery)
(1) catalyst reclaims
By reacted for embodiment 2 product through atmospheric distillation, temperature is less than 120 DEG C of dehydrations and n-butanol, collects 200
DEG C～300 DEG C of cut (mixture such as unreacted phthalic anhydride and co-catalyst), collect 330～345 DEG C of product neighbours
Dibatyl phithalate cut, remaining component is merged the catalyst ii after being recycled with cut i.
(2) catalytic reaction
To with stirring, water knockout drum and reflux condensing tube 250 milliliters of there-necked flasks in add 50 grams of phthalic anhydride,
N-butanol addition is 2.4 times of phthalic anhydride molal quantity, adds the catalyst ii after the recovery in (1), is warming up to boiling
After rising reaction 2h, chromatograph obtains the catalytic performance of this catalyst: phthalic anhydride conversion ratio is 93.4%, adjacent benzene two
Formic acid dibutyl ester yield is 93.2%.
Reference Example 1 (sulphuric acid catalysis)
To with stirring, water knockout drum and reflux condensing tube 250 milliliters of there-necked flasks in add 50 grams of phthalic anhydride,
N-butanol addition is 2.4 times of phthalic anhydride molal quantity, and 2.0 grams of the concentrated sulfuric acid, after being warming up to boiling reaction 1h, uses chromatogram
Analysis obtains the catalytic performance of this catalyst: phthalic anhydride conversion ratio is 98.5%, and dibutyl phthalate yield is
92.5%.
Reference Example 2 (Sold Stannous Chloride Catalyzes)
To with stirring, water knockout drum and reflux condensing tube 250 milliliters of there-necked flasks in add 50 grams of phthalic anhydride,
N-butanol addition is 2.4 times of phthalic anhydride molal quantity, and 2.0 grams of stannous chloride, after being warming up to boiling reaction 2h, uses color
Analysis of spectrum obtains the catalytic performance of this catalyst: phthalic anhydride conversion ratio is 70.5%, dibutyl phthalate yield
For 67.2%.
Reference Example 3 (sulphuric acid catalysis)
To with stirring, simple rectification device and reflux condensing tube 5000 milliliters of tank reactors in add adjacent benzene two
1000 grams of formic anhydride, n-butanol addition is 2.4 times of phthalic anhydride molal quantity, and 20.0 grams of the concentrated sulfuric acid is warming up to boiling
After reaction 1h, chromatograph obtains the catalytic performance of this catalyst: phthalic anhydride conversion ratio is 98.3%, O-phthalic
Dibutyl phthalate yield is 93.2%.
Each embodiment obtained experimental result is shown in Table 1.
Table 1
Composite catalyst provided by the present invention (embodiment 1～7) is adopted to synthesize phthalic acid as can be seen from Table 1
Dibutyl ester, compared with prior art (Reference Example 1～3), dibutyl phthalate is selectively superior to Reference Example 1～3, in phase
Under similar reaction condition, embodiment catalyst activity (conversion ratio of phthalic anhydride) makees catalyst better than stannous chloride,
It is not less than the catalytic performance of the concentrated sulfuric acid, and do not have concentrated sulfuric acid corrosivity by force etc. not enough.
Embodiment 8 be produced using embodiment 2 terminate after the composite catalyst that reclaims, its yield is same as Example 2, can
See, composite catalyst provided by the present invention can be recycled, and catalytic effect does not reduce.
Can be seen that nitrogen group element compound from result compared with other embodiment for the embodiment 2,3 and polyethylene glycol is multiple
Close and use, the yield of its reaction conversion ratio and product is better than being used alone.
Claims (4)
1. a kind of method of synthesis phthalate compound, with phthalic anhydride and alcohol as raw material, through esterification
Obtain phthalate compound it is characterised in that adding in reactor phthalic anhydride, alcohol, composite catalyst, close
Envelope, is warming up to boiling, after reacting 0.5～2 hour, rectifying, and obtain product；
The addition of composite catalyst is the 0.2%～10% of the weight of phthalic anhydride；Described composite catalyst includes leading
Catalyst and co-catalyst, major catalyst is weak acid or salt；
In described composite catalyst, major catalyst and the mass ratio of co-catalyst are 10:0.1～1；
Described co-catalyst is nitrogen group element compound and/or polyethylene glycol；
Described nitrogen group element compound is Tetrabutylammonium bromide；
Described weak acid is p-methyl benzenesulfonic acid；Described salt is niter cake, potassium acid sulfate；
Described alcohol is butanol or isooctanol.
2. the method for synthesis phthalate compound as claimed in claim 1 is it is characterised in that described co-catalysis
Agent is nitrogen group element compound and polyethylene glycol, and wherein nitrogen group element and the mass ratio of polyethylene glycol are 10:1～25.
3. the method for synthesis phthalate compound as claimed in claim 1 is it is characterised in that described adjacent benzene two
Formic anhydride is 1:2.1～5.0 with the mol ratio of alcohol.
4. the method for synthesis phthalate compound as claimed in claim 1 is it is characterised in that pass through after reaction to steam
Evaporate and composite catalyst is separated with product, the composite catalyst of recovery recycles.
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| CN105037161B (en) * | 2015-07-08 | 2017-04-12 | 中山联成化学工业有限公司 | Continuous synthesis method of cyclohexane polyacid ester |
| CN108993509B (en) * | 2018-08-14 | 2020-05-15 | 宿州青果知识产权服务有限公司 | Catalyst for improving synthesis conversion rate of dioctyl phthalate plasticizer |
| CN111468032B (en) * | 2020-05-28 | 2021-03-26 | 江南大学 | Easily soluble/cleavable/self-thickening surfactant and preparation method thereof |
| CN112812008A (en) * | 2021-01-11 | 2021-05-18 | 大连理工大学 | Method for preparing diacid diester compound under catalysis of deep eutectic solvent |
| CN115368242A (en) * | 2021-05-20 | 2022-11-22 | 浙江建业化工股份有限公司 | Preparation method of diisobutyl phthalate |
| CN113477087B (en) * | 2021-06-28 | 2022-11-29 | 浙江工业大学 | Polyester modified polysulfone ultrafiltration membrane and preparation method thereof |
| CN114588935A (en) * | 2022-03-04 | 2022-06-07 | 浙江大学 | Preparation of sulfonic acid type supported catalyst for phthalic anhydride esterification |
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