CN1301155C - Prepn and application of solid catalyst for synthesizing tetroisooctyl pyromellitate - Google Patents

Prepn and application of solid catalyst for synthesizing tetroisooctyl pyromellitate Download PDF

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CN1301155C
CN1301155C CNB2004100646941A CN200410064694A CN1301155C CN 1301155 C CN1301155 C CN 1301155C CN B2004100646941 A CNB2004100646941 A CN B2004100646941A CN 200410064694 A CN200410064694 A CN 200410064694A CN 1301155 C CN1301155 C CN 1301155C
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preparation
solid super
catalyst
super acid
acid catalyst
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CN1608731A (en
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管国锋
谭强
万辉
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Nanjing Tech University
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Nanjing Tech University
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Abstract

The present invention relates to a preparation method and applications of a catalyst used for synthesizing tetraoctyl pyromelliate (TOPM for short). Titanium sulfate, aluminum nitrate and sulfuric acid are used as raw materials and are synthesized into a novel solid super acid of SO4<2->/TiO2-Al2O3; the composition of the solid super acid is that tetracarboxylic dianhydride and isooctanol are used as raw materials and are synthesized into tetraoctyl pyromelliate in a reflux reaction device. The yield and the selectivity of the TOPM respectively reach more than 98% and more than 99%. The catalyst of the present invention has the advantages of simple preparation, high activity, high selectively, low reaction temperature, light color of esterification reaction products, long service life and good industrialization prospects.

Description

A kind of solid acid catalyst preparation and application of synthetic Pyromellitic Acid four different monooctyl esters
Technical field
The present invention relates to a kind of preparation method of solid super acid catalyst, relate in particular to a kind of production high-performance plasticizer---the preparation method of the solid super acid catalyst of Pyromellitic Acid four different monooctyl esters (TOPM).
Background technology
It is super hear resistance (super F level) plasticizer that Pyromellitic Acid four different monooctyl esters (Tetra-2-Ethyl Promellitate) are abbreviated as (TOPM), is the heat-resisting plasticizer of polyvinyl chloride.
(1) has excellent electric insulation performance and heat aging performance and low performance property, cold resistance and machinability, be the heat-resisting of PVC and durability plasticizer, it and PVC have compatibility preferably, are mainly used in the high temperature resistant PVC electric wire, produce 102～120 ℃ of heat proof cables and produce the polrvinyl chloride product that special durable heat resistant plastice aspect is used.
(2) because plasticizer volatile, extract out, migration, harm environment, the toxicity problem of Here it is plasticizer.Therefore the low toxicity plasticizer becomes the target of research and development.The neighbour dioctyl phthalate (DOP) of the toxicity of Pyromellitic Acid four monooctyl esters (TOPM) is much lower, and all lower with plasticizer than current general industry, it has multiple premium properties in addition, can deserve to be called the fine quality of nontoxic plasticizer.TOPM succeeds in developing, and is a breakthrough that reduces plasticizer toxicity, makes medical plastic ware find the minimum plasticizer of toxicity up to now.The application of TOPM in medical plastic ware constantly widened; Particularly the application development of TOPM is rapid, has promoted the development of medical plastic ware.
The synthetic TOPM reaction of traditional esterification all adopts sulfuric acid to make catalyst, and it is cheap, and therefore the catalytic activity height is widely adopted industrial.But, use the drawback of sulfuric acid catalyst more and more very important: it is serious to equipment corrosion, three wastes discharge amount is big, the post processing complexity, simultaneously, sulfuric acid catalyst uses the back accessory substance many, and reaction selectivity is poor, organic matter carbonizing during high temperature, make product painted simultaneously, so its limitation is remarkable day by day.Since Hino in 1979 and the synthetic for the first time SO of Arata 4 2-/ ZrO 2Since [M.Hino, K.Arata, J.Am.Chem.Soc., 101 (21), 6439 (1979)], SO 4 2-/ M xO yThe research of type solid super-strong acid is very active, and its application is more and more wider, has been applied to by everybody at present in the organic synthesis such as esterification, and has demonstrated very high catalytic activity.Therefore people wish by the research and development of this novel solid super-strong acid catalyst being gone out to substitute the catalyst that industrial application value is arranged of sulfuric acid.
In old, people such as Ding Laixin [Ding Laixin, in old, Wei Yanli. Speciality Petrochemicals, 1997 (3): 26～28] synthesize Pyromellitic Acid four (the 2-ethyl is own) ester with butyl titanate catalysis, research through experiment, drawing with the butyl titanate is catalyst, and the optimum reaction condition of synthetic Pyromellitic Acid four (2 ethyls are own) ester is: acid anhydride: alcohol is 1: 8 (mol ratio), and catalyst amount is 5%～6% (accounting for the consumption of acid anhydride), 200～205 ℃ of reaction temperatures, the reaction time is 2h.Under this condition, the product yield can reach 97.4%, and product color is yellowish, and sulfuric acid do catalyst not only product color be pale brown look, and side reaction is also many, has influenced the quality of product.They used rare earth compound solid-acid SO afterwards 4 2-/ TiO 2-La 2O 3Synthetic Pyromellitic Acid four (the 2-ethyl is own) ester [in old, Ding Laixin, Cui Liyan. Institutes Of Technology Of Nanjing's journal, 1996 (6): 501～504], result of study shows that this reaction temperature is lower than 190 ℃, with respect to butyl titanate, reaction temperature has reduced, and the reaction yield is also more than 98%.Yet rare earth compound solid-acid cost is higher, and consumption illustrates that up to 7% (with respect to equal acid anhydride) activity of such catalysts awaits further to improve.
Summary of the invention:
The objective of the invention is that the activity that exists at existing catalyst is not high, large usage quantity, cost be than problems such as height, provide that a kind of to be used for Pyromellitic Acid four different monooctyl esters novel, active high, selectivity is good, with low cost, the life-span is long solid super acid catalyst SO 4 2-/ TiO 2-Al 2O 3The preparation method, and by the application of catalyst in Pyromellitic Acid four different monooctyl esters are synthetic of this method preparation, to replace this traditional catalyst of sulfuric acid.
Technical scheme of the present invention is: a kind of solid super acid catalyst that is used for synthetic Pyromellitic Acid four different monooctyl esters (being called for short TOPM) is SO 4 2-/ TiO 2-Al 2O 3The preparation method, step comprises
A. the preparation molar content that contains Ti is 50.0～90.9%, the Al molar content is 9.1～50.0% Ti (SO 4) 2And Al (NO 3) 39H 2O mixing salt solution a;
B. use NH 3H 2PH value to 6～10 that O regulates mixing salt solution a obtain containing the mixture of white precipitate, and after ageing after 6～24 hours, suction filtration, washing, oven dry grinds extremely≤200 orders then, obtains white powder b;
C. use 0.1～1molL -1H 2SO 4Solution is by 10～30mlg -1Ratio stirs dipping white powder b down, and suction filtration is gone out unnecessary H then 2SO 4, drying grinds then to≤200 orders, obtains white powder, obtains solid super acid catalyst after the activation of 523～973K roasting temperature in air atmosphere.
The present invention is with Ti (SO 4) 2And Al (NO 3) 39H 2O is a raw material, and suitable titanium, aluminium molar content are respectively:, mol (Ti) %=50.0～83.3%, mol (Al) %=16.7～50.0%.
The precipitation pH value that the present invention suits is 7～9.
The sulfuric acid impregnation concentration that the present invention suits is 0.3～1.0molL -1
The sintering temperature that the present invention suits is 673～923K.
The synthetic TOPM of the catalysis of catalyst is active to be investigated as following: take by weighing 0.1g (account for equal acid anhydride 1.8%) catalyst, take by weighing the 5.5g pyromellitic acid anhydride, measure the 27ml isooctanol and join in the there-necked flask.Plug thermometer, reflux condensing tube, separator on the there-necked flask, pick up counting when beginning to reflux, after reaction a period of time, leach catalyst, excessive isooctanol is isolated in decompression distillation, obtains thick ester product.The analytical method of being narrated in the mensuration according to GB GB/T 1668-95 plasticizer acid number and acidity is carried out the acid number analysis to product, and calculates equal acid anhydride conversion ratio.Catalyst provided by the invention is as the solid super acid catalyst of the synthetic TOPM of catalysis, and at 160～182 ℃ down behind the reaction 2h, yield is the highest can reach more than 99.4% in reaction, and reaction 3h just can reach 99.6%.Have very high activity and selectivity, and the product lighter color; Method for preparing catalyst is simple, and cost is lower, and the life-span is longer.
Beneficial effect:
Catalyst S O provided herein 4 2-/ TiO 2-Al 2O 3When consumption is 1.8% (accounting for the consumption of equal acid anhydride), reaction temperature is between 162～184 ℃, reaction 2h yield is the highest can be reached more than 99.4%, filter out catalyst after the reaction and directly apply to down secondary response without any processing, repeated use is reacted yield and still can be reached more than 98% more than 13 times, and the product color that obtains is yellowish, the product quality height.Compare with the catalyst of forefathers' research, catalyst activity is higher, and production cost is lower.To compare advantage as shown in table 1 with forefathers' result of study.
The catalytic activity of table 1 different catalysts
Catalyst type Catalyst amount (relatively with equal acid anhydride) Reaction temperature Reaction 2h
Product color The product yield
98% concentrated sulfuric acid butyl titanate SO 4 2-/ Ti-La super acids SO 4 2-/TiO 2-Al 2O 3Super acids 32.7％ 5％～6％ 7％ 1.8％ 126℃～160℃ 200℃ 190℃ 160℃～182℃ Light brown is transparent light yellow transparent light yellow transparent light yellow transparent 91.9％ 97.4％ 98.2％ 99.4％
Embodiment:
Embodiment one:
Preparation of catalysts
At room temperature be 50.0% Al (NO with the molar content of Al 3) 39H 2O and Ti (SO 4) 2Two kinds of salting liquids stir and mix evenly, use NH 3H 2The pH value of O regulator solution is 10, and ageing 8h after suction filtration, the washing, with the down dry 15～24h of 383K, grinds to≤200 orders and uses 1molL -1H 2SO 4Solution is according to 15mlg -1Ratio dipping 15min, with dry 1h under the 393K, grind to≤200 orders, in air atmosphere, be placed in the drier and preserve in 653K roasting temperature 5h.
TOPM is synthesized in catalysis
Take by weighing the catalyst of 0.1g (account for equal acid anhydride weight 1.8%), take by weighing the 5.5g pyromellitic dianhydride, measure the 27ml isooctanol and join in the there-necked flask.Plug thermometer, reflux condensing tube, separator on the there-necked flask, pick up counting when beginning to reflux, reaction temperature is 167～183 ℃, behind the reaction 2h, leaches catalyst, and excessive isooctanol is isolated in decompression distillation, obtains thick ester product.The analytical method of being narrated in the mensuration according to GB GB/T 1668-95 plasticizer acid number and acidity is carried out the acid number analysis to product, and calculate the reaction yield be 98.0%.
Embodiment two:
Preparation of catalysts
At room temperature be 16.7% Al (NO with the molar content of Al 3) 39H 2O and Ti (SO 4) 2Two kinds of salting liquids stir and mix evenly, use NH 3H 2The pH value of O regulator solution is 6, and ageing 8h after suction filtration, the washing, with dry 24h under the 393K, grinds to≤200 orders and uses 0.5molL -1H 2SO 4Solution is according to 10mlg -1Ratio dipping 20min, with dry 2h under the 393K, grind to≤200 orders, in air atmosphere, be placed in the drier and preserve in 773K roasting temperature 5h.
TOPM is synthesized in catalysis
Esterification is carried out according to the method for example 1, and reaction temperature is 168～183 ℃, and the reaction yield is 98.1%.
Embodiment three
At room temperature be 23.1% Al (NO with the molar content of Al 3) 39H 2O and Ti (SO 4) 2Two kinds of salting liquids stir and mix evenly, use NH 3H 2The pH value of O regulator solution is 8, and ageing 6h after suction filtration, the washing, with dry 24h under the 383K, grinds to≤200 orders the H with 0.1molL 2SO 4Solution, grinds to≤200 orders with dry 1h under the 393K according to the ratio of 10mlg dipping 25min, is placed in the drier in 873K roasting temperature 5h in air atmosphere and preserves.
TOPM is synthesized in catalysis
Esterification is carried out according to the method for example 1, and reaction temperature is 168～182 ℃, and the reaction yield is 98.5%
Embodiment four
Preparation of catalysts
At room temperature be 23.1% Al (NO with the molar content of Al 3) 39H 2O and Ti (SO 4) 2Two kinds of salting liquids stir and mix evenly, use NH 3H 2The pH. value of O regulator solution is 9, and ageing 8h after suction filtration, the washing, with dry 24h under the 383K, grinds to≤200 orders and uses 0.4molL -1H 2SO 4Solution is according to 10mlg -1Ratio dipping 30min, with dry 3h under the 393K, grind to≤200 orders, in air atmosphere, be placed in the drier and preserve in 623K roasting temperature 3h.
TOPM is synthesized in catalysis
Esterification is carried out according to the method for example 1, and reaction temperature is 164～182 ℃, and the reaction yield is 98.5%.
Embodiment five
Preparation of catalysts
At room temperature be 33.3% Al (NO with the molar content of Al 3) 39H 2O and Ti (SO 4) 2Two kinds of salting liquids stir and mix evenly, use NH 3H 2The pH value of O regulator solution is 8, and ageing 24h after suction filtration, the washing, with dry 24h under the 383K, grinds to≤200 orders and uses 0.5molL -1H 2SO 4Solution is according to 15mlg -1Ratio dipping 15min, with dry 3h under the 393K, grind to≤200 orders, in air atmosphere, be placed in the drier and preserve in 673K roasting temperature 3h.
TOPM is synthesized in catalysis
Esterification is carried out according to the method for example 1, and reaction temperature is 160～182 ℃, and the reaction yield is 99.4%.
Embodiment six
Preparation of catalysts
At room temperature be 23.1% Al (NO with the molar content of Al 3) 39H 2O and Ti (SO 4) 2Two kinds of salting liquids stir and mix evenly, use NH 3H 2The pH value of O regulator solution is 7, and ageing 24h after suction filtration, the washing, with dry 24h under the 383K, grinds to≤200 orders and uses 0.5molL -1H 2SO 4Solution is according to 30mlg -1Ratio dipping 5min, with dry 2h under the 393K, grind to≤200 orders, in air atmosphere, be placed in the drier and preserve in 923K roasting temperature 5h.
TOPM is synthesized in catalysis
Esterification is carried out according to the method for example 1, and reaction temperature is 160～182 ℃, and the reaction yield is 98.7%.
Embodiment seven
Preparation of catalysts
At room temperature be 23.1% Al (NO with the molar content of Al 3) 39H 2O and Ti (SO 4) 2Two kinds of salting liquids stir and mix evenly, use NH 3H 2The pH value of O regulator solution is 9, and ageing 24h after suction filtration, the washing, with dry 24h under the 383K, grinds to≤200 orders and uses 0.6molL -1H 2SO 4Solution is according to 15mlg -1Ratio dipping 15min, with dry 2h under the 393K, grind to≤200 orders, in air atmosphere, be placed in the drier and preserve in 673K roasting temperature 5h.
TOPM is synthesized in catalysis
Esterification is carried out according to the method for example 1, and reaction temperature is 160～180 ℃, and the reaction yield is 99.4%, and the reaction time extends to 3h, and the reaction yield is 99.6%.

Claims (5)

1. preparation method who is used for the solid super acid catalyst of synthetic Pyromellitic Acid four different monooctyl esters, its preparation process comprises:
A. the preparation molar content that contains Ti is 50.0～90.9%, the Al molar content is 9.1～50.0% Ti (SO 4) 2And Al (NO 3) 39H 2O mixing salt solution a;
B. use NH 3H 2PH value to 6～10 that O regulates mixing salt solution a obtain containing the mixture of white precipitate, and after ageing after 6～24 hours, suction filtration, washing, oven dry grinds extremely≤200 orders then, obtains white powder b;
C. use 0.1～1molL -1H 2SO 4Solution is by 10～30mlg -1Ratio stirs dipping white powder b down, and suction filtration is removed unnecessary H then 2SO 4, drying grinds then to≤200 orders, obtains white powder, obtains solid super acid catalyst after the activation of 523～973K roasting temperature in air atmosphere.
2. according to the preparation method of solid super acid catalyst described in the claim 1, it is characterized in that titanium in the catalyst, aluminium molar content are respectively: mol (Al) %=16.7～50.0%, mol (Ti) %=50.0～83.3%.
3. according to the preparation method of solid super acid catalyst described in the claim 1, it is characterized in that using NH 3H 2O regulates Ti (SO 4) 2And Al (NO 3) 39H 2The pH value of O mixing salt solution is 7～9.
4. according to the preparation method of solid super acid catalyst described in the claim 1, the temperature that it is characterized in that roasting in the air atmosphere is 673K～923K.
5. according to the preparation method of solid super acid catalyst described in the claim 1, it is characterized in that H 2SO 4Impregnation concentration is 0.3～1.0molL -1
CNB2004100646941A 2004-09-20 2004-09-20 Prepn and application of solid catalyst for synthesizing tetroisooctyl pyromellitate Expired - Fee Related CN1301155C (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015149195A1 (en) * 2014-04-02 2015-10-08 East China University Of Science And Technology Methods and materials for hydrolyzing polyesters
CN105562038B (en) * 2015-12-25 2017-12-29 江西西林科股份有限公司 A kind of method that solid super acid catalyst for the esterification of acid type antiwear additive prepares fatty acid ester antiwear additive
CN115385790B (en) * 2022-09-08 2023-11-24 江苏正丹化学工业股份有限公司 Synthesis method of tetraoctyl pyromellitate

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3296298A (en) * 1958-07-17 1967-01-03 Rohm & Haas Tetra (2-ethylhexyl) pyromellitate
JPS5867660A (en) * 1981-10-16 1983-04-22 Asahi Chem Ind Co Ltd Condensing method of n-phenylcarbamic ester
JPH06321878A (en) * 1993-05-17 1994-11-22 Inoue Koryo Seizosho:Kk Production of ester
JPH11152249A (en) * 1997-11-21 1999-06-08 Mitsubishi Chemical Corp Production of unsaturated carboxylic acid ester
JPH11228494A (en) * 1998-02-12 1999-08-24 Toagosei Co Ltd Production of fatty acid ester

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3296298A (en) * 1958-07-17 1967-01-03 Rohm & Haas Tetra (2-ethylhexyl) pyromellitate
JPS5867660A (en) * 1981-10-16 1983-04-22 Asahi Chem Ind Co Ltd Condensing method of n-phenylcarbamic ester
JPH06321878A (en) * 1993-05-17 1994-11-22 Inoue Koryo Seizosho:Kk Production of ester
JPH11152249A (en) * 1997-11-21 1999-06-08 Mitsubishi Chemical Corp Production of unsaturated carboxylic acid ester
JPH11228494A (en) * 1998-02-12 1999-08-24 Toagosei Co Ltd Production of fatty acid ester

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