CN108892614A - A kind of synthetic method of triisononyl trimellitate plasticizer - Google Patents
A kind of synthetic method of triisononyl trimellitate plasticizer Download PDFInfo
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- CN108892614A CN108892614A CN201811000736.3A CN201811000736A CN108892614A CN 108892614 A CN108892614 A CN 108892614A CN 201811000736 A CN201811000736 A CN 201811000736A CN 108892614 A CN108892614 A CN 108892614A
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- dealcoholysis
- esterification
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- reaction kettle
- triisononyl trimellitate
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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Abstract
The present invention provides a kind of synthetic method of triisononyl trimellitate plasticizer in plasticizer synthesis technical field, specific steps include：Esterification, alkali cleaning washing, removes low-boiling-point substance and adsorption filtration at negative pressure dealcoholysis.Catalyst used in the present invention is composite inorganic acid esters, the transformation efficiency of raw material not only can be improved, but also obtained triisononyl trimellitate product has the characteristics that ester content is high, color is bright and quality is stable.The present invention has the advantages that easy control of process conditions, pollution-free, low energy consumption, easy large-scale production, has good economy and environment feasibility.
Description
Technical field
The present invention relates to a kind of synthetic methods of triisononyl trimellitate plasticizer, belong to plasticizer synthetic technology neck
Domain.
Background technique
Plasticizer, mobility when referring to for reinforced plastics processing and forming make plastic products have flexible one kind
Organic substance has the characteristics that higher boiling, difficult volatilization, does not chemically react with plastics generally.Addition should in plastic processing
Substance can enhance its flexibility, plasticity and dilatancy, improve mobility when plastics processing, to be allowed to be easy to add
Work.The kind of plasticizer is more, at up to thousands of kinds of the kind that its research and development field once occurred, as commodity production
Plasticizer also successively reaches more than 100 kinds.Trimellitic acid esters plasticizer removes extensive adaptability and increasing with universal plasticizer
It moulds outside effect, also has the function of that other are special, meet the requirement of green chemical industry and sustainable development.
With various countries to plasticizer to the harm growing interest of human health, develop the plasticizer of novel non-toxic environmental protection gradually
Emphasis as various countries' research.As a kind of plasticizer of novel non-toxic environmental protection, triisononyl trimellitate, in volatility, resistance to
Water extraction, resistance to migration, low temperature resistant and electrical property etc. performance are all good, especially in compatibility, processability and cryogenic property
Deng but be obviously superior to phthalate.However, phthalic ester plasticizer volatility and migration are extremely strong, containing neighbour
The plastic products of Phthalates will cause the molten of phthalic acid ester during processing, heating, packaging and splendid attire
Out, belong to carcinogen.The developed countries such as North America, West Europe, Japan have promulgated relevant laws and regulations, to phthalate
Strict regulations have been made in the use of plasticizer.Therefore, exploitation novel non-toxic environment-friendly plasticizer substitutes phthalate, at
For the inexorable trend of modern plasticizer industry.
Summary of the invention
The present invention provides a kind of synthetic methods of triisononyl trimellitate plasticizer, make its simple process, produce
Journey safety and environmental protection.
Specific technical solution is as follows：
A kind of synthetic method of triisononyl trimellitate plasticizer, in turn includes the following steps：
S1, esterification：Raw material trimellitic anhydride and isononyl alcohol are put into reaction kettle of the esterification, in nitrogen protection and uniform stirring
Under the conditions of, it is heated to 122~156 DEG C, the molar ratio of the trimellitic anhydride and isononyl alcohol is 1：（3.2~4.0）；Inclined benzene three
After acid anhydrides is dissolved completely in isononyl alcohol, then be warming up to 185 ± 5 DEG C, be added catalyst, the catalyst be metatitanic acid orthocarbonate and
Tetraisopropyl titanate is with 1：（1.2~3.4）Mass ratio is combined, catalyst amount be reaction raw materials gross mass 0.04~
0.12 %；0.5~1 h of insulation reaction, while isolating the water generated in esterification process；218~236 DEG C are continuously heating to, is held
Continuous to carry out constant temperature reflux, ester content is continuously improved in the esterifying liquid in reaction kettle, after reacting a period of time, from esterification bottom
Portion's sampling, surveys acid value；As the 0.07 mg KOH/g of esterifying liquid acid value > of measurement, continue constant temperature reflux；When the esterification of measurement
Liquid acid value≤0.07 mg KOH/g, shows that esterification is completed；Into in next step；
S2, negative pressure dealcoholysis：The bottom esterifying liquid of reaction kettle of the esterification squeezes into dealcoholysis tower and carries out negative pressure dealcoholysis, and dealcoholysis tower vacuum degree is
0.04~0.08Mpa, dealcoholysis time are 1.5~2.5 h, and dealcoholysis temperature is 170~190 DEG C；
S3, alkali cleaning washing：Esterifying liquid after dealcoholysis is passed through nitrogen, beats reflux cycle through heat exchanger under normal pressure, drops reaction system
Temperature is to 75~105 DEG C；Suitable sodium carbonate liquor is put into, neutrality is neutralized to；It adds and is slowly added to distilled water and is washed,
0.4~0.6 h is stood, layering drains lower layer's white flocculate；
S4, low-boiling-point substance is removed：Logical nitrogen, is warming up to 160~190 DEG C, vacuumizes, and vacuum degree is 0.04~0.08Mpa, and negative pressure is de-
Low-boiling-point substance and remaining isononyl alcohol in dereaction system, negative pressure ventilation time are 1.5~2.5 h；Stop taking out after negative pressure ventilation
Vacuum is passed through nitrogen, is restored to normal pressure state to system, stops heating, cooling down；
S5, adsorption filtration：It will be cooled to 70~90 DEG C of esterifying liquid and be transferred to filter, through adsorption bleaching, to get conjunction after filtering
The triisononyl trimellitate of lattice.
It is as a further improvement of the present invention, in step S1, acid anhydride content >=98 % in the raw material trimellitic anhydride；
The purity of the raw material isononyl alcohol >=99 %.
It is as a further improvement of the present invention, in step S5, filtrate is the mixed of active carbon and diatomite in filter
Close object, the active carbon and diatomite mass ratio 1：（0.4~2.0）；The active carbon average particle size is 200 mesh；The diatom
Native average particle size is 300 mesh.
It is as a further improvement of the present invention, the esterification carries out in reaction kettle of the esterification, reaction kettle of the esterification
The gaseous phase outlet at top is connected to the tower top of alcohol-water separation tower after heat exchanger one, and alcohol-water separation tower is connected to ester through return pipe one
Change reaction kettle.
It is as a further improvement of the present invention, the water of the alcohol-water separation tower bottom separation is connected to dealcoholysis tower,
For washing in step S3.
It is as a further improvement of the present invention, goes low-boiling-point substance that can carry out in rectifying column in step S4, it can also be with
It is carried out in dealcoholysis tower.When carrying out in rectifying column, dealcoholysis tower is connected to rectifying column through heat exchanger three, circulating pump, on rectifying column
Return pipe two be connected to dealcoholysis tower, be connected at the top of the rectifying column with vacuum pump.It is carried out in dealcoholysis tower, dealcoholysis tower is through exchanging heat
Device three, circulating pump self-loopa connection, dealcoholysis top of tower are connected with vacuum pump.
Preferably to control temperature when dealcoholysis, in step s 2, the bottom esterifying liquid of reaction kettle of the esterification is through heat exchanger
Dealcoholysis tower is squeezed into again after two heat exchange.By heat exchange, can more easily adjust dealcoholysis temperature is 170~190 DEG C.
The beneficial effects of the present invention are catalyst used is composite inorganic acid esters, and raw material not only can be improved
Transformation efficiency, and obtained triisononyl trimellitate product has the spy that ester content is high, color is bright and quality is stable
Point.The present invention has the advantages that easy control of process conditions, pollution-free, low energy consumption, easy large-scale production, has economical well
And environment feasibility.
Detailed description of the invention
Fig. 1 is a kind of structural schematic diagram of process units of the invention.
Fig. 2 is another structural schematic diagram of process units of the invention.
In figure, 1 reaction kettle of the esterification, 2 return pipes one, 3 heat exchangers one, 4 alcohol-water separation towers, 5 heat exchangers two, 6 dealcoholysis towers, 7
Circulating pump, 8 heat exchangers three, 9 vacuum pumps, 10 rectifying columns, 11 return pipes two, 12 filters, 13 finished pots.
Specific embodiment
Embodiment 1
As shown in Figure 1, for a kind of device for the synthesis of triisononyl trimellitate plasticizer, including reaction kettle of the esterification 1, esterification
The outlet of 1 top gas phase of reaction kettle is connected to 4 top of alcohol-water separation tower through heat exchanger 1, is equipped with return pipe in the middle part of alcohol-water separation tower 4
One 2 are connected to reaction kettle of the esterification 1；1 bottom of reaction kettle of the esterification is connected to dealcoholysis tower 7, and 7 bottom of dealcoholysis tower is connected to through filter 12
Finished pot 13；It is connected with dealcoholysis reflux unit on the dealcoholysis tower 7, which includes rectifying column 10, and dealcoholysis tower 7 passes through
Circulating pump 7, heat exchanger 38 are connected to rectifying column 10, and vacuum pump 9, the return tank of 10 bottom of rectifying column are connected on rectifying column 10
2 11 are connected to dealcoholysis tower 7.Heat exchanger 25 is additionally provided between reaction kettle of the esterification 1 and dealcoholysis tower 7.
The device is synthesized for triisononyl trimellitate plasticizer, in production, is carried out as follows：
S1, esterification：Acid anhydride content >=98 % in raw material trimellitic anhydride；The purity of the raw material isononyl alcohol >=99 %；It will be former
Expect in trimellitic anhydride and isononyl alcohol investment reaction kettle of the esterification 1, under nitrogen protection and stirring well, it is heated to 122~
130 DEG C, the molar ratio of the trimellitic anhydride and isononyl alcohol is 1：3.2；After trimellitic anhydride is dissolved completely in isononyl alcohol, then
185 ± 5 DEG C are warming up to, catalyst is added, the catalyst is metatitanic acid orthocarbonate and tetraisopropyl titanate with 1：1.2 mass ratioes are multiple
It closes, catalyst amount is 0.04 % of reaction raw materials gross mass；Insulation reaction 0.5h, while isolating in esterification process and producing
Raw water；218~225 DEG C are continuously heating to, is exchanged heat by heat exchanger 1, realizes and persistently carries out constant temperature reflux, in reaction kettle
Ester content is continuously improved in esterifying liquid, after reacting a period of time, samples from 1 bottom of reaction kettle of the esterification, surveys acid value；When the ester of measurement
Change 0.07 mg KOH/g of liquid acid value >, continues constant temperature reflux；When esterifying liquid acid value≤0.07 mg KOH/g of measurement, table
Bright esterification is completed；Into in next step；
S2, negative pressure dealcoholysis：The bottom esterifying liquid of reaction kettle of the esterification 1 squeezes into dealcoholysis tower 7 and carries out negative pressure dealcoholysis, can also be through heat exchanger two
Dealcoholysis tower 7 is squeezed into again after 5 heat exchange；7 vacuum degree of dealcoholysis tower is 0.04~0.05Mpa, and the dealcoholysis time is 1.5 h, and dealcoholysis temperature is
170~175 DEG C；
S3, alkali cleaning washing：Esterifying liquid after dealcoholysis is passed through nitrogen, under normal pressure through 38 dozens of reflux cycles of heat exchanger, makes reactant
System is cooled to 75~80 DEG C；Suitable sodium carbonate liquor is put into, neutrality is neutralized to；It adds and is slowly added to distilled water progress water
It washes, stands 0.4 h, layering drains lower layer's white flocculate；The water of 4 bottom of alcohol-water separation tower separation can be connected to dealcoholysis tower 7,
Part water as washing.
S4, low-boiling-point substance is removed：Logical nitrogen, is warming up to 160~165 DEG C, vacuumizes, and vacuum degree is 0.04~0.05Mpa, negative pressure
The low-boiling-point substance and remaining isononyl alcohol in reaction system are sloughed, the negative pressure ventilation time is 1.5h；Stop vacuumizing after negative pressure ventilation,
It is passed through nitrogen, normal pressure state is restored to system, stops heating, cooling down；
S5, adsorption filtration：Will be cooled to 70~90 DEG C of esterifying liquid and be transferred to filter 12, through adsorption bleaching, after filtering to get
Qualified triisononyl trimellitate.Filtrate is the mixture of active carbon and diatomite, the active carbon and silicon in filter 12
Diatomaceous earth mass ratio 1：0.4；The active carbon average particle size is 200 mesh；The diatomite average particle size is 300 mesh.
Embodiment 2
As shown in Fig. 2, for another device for the synthesis of triisononyl trimellitate plasticizer, including reaction kettle of the esterification 1, ester
Change the outlet of 1 top gas phase of reaction kettle and be connected to 4 top of alcohol-water separation tower through heat exchanger 1, is equipped with reflux in the middle part of alcohol-water separation tower 4
Pipe 1 is connected to reaction kettle of the esterification 1；1 bottom of reaction kettle of the esterification is connected to dealcoholysis tower 7, and 7 bottom of dealcoholysis tower is connected through filter 12
To finished pot 13；Be connected with dealcoholysis reflux unit on the dealcoholysis tower 7, the dealcoholysis reflux unit include vacuum pump 9, circulating pump 7,
Heat exchanger 38, dealcoholysis tower 7 are connected through the circulating pump 7,38 self-loopa of heat exchanger, and vacuum pump 9, which is connected at the top of dealcoholysis tower 7, to be connected
It connects.Heat exchanger 25 is additionally provided between reaction kettle of the esterification 1 and dealcoholysis tower 7.
The device is synthesized for triisononyl trimellitate plasticizer, in production, is carried out as follows：
S1, esterification：Acid anhydride content >=98 % in raw material trimellitic anhydride；The purity of the raw material isononyl alcohol >=99 %；It will be former
Expect in trimellitic anhydride and isononyl alcohol investment reaction kettle of the esterification 1, under nitrogen protection and stirring well, it is heated to 150~
156 DEG C, the molar ratio of the trimellitic anhydride and isononyl alcohol is 1：4.0；After trimellitic anhydride is dissolved completely in isononyl alcohol,
It is warming up to 185 ± 5 DEG C again, catalyst is added, the catalyst is metatitanic acid orthocarbonate and tetraisopropyl titanate with 1：3.4 mass ratio
It is combined, catalyst amount is 0.12 % of reaction raw materials gross mass；1 h of insulation reaction, while isolating in esterification process
The water of generation；225~236 DEG C are continuously heating to, is exchanged heat by heat exchanger 1, realizes and persistently carries out constant temperature reflux, in reaction kettle
Esterifying liquid in ester content be continuously improved, react a period of time after, from 1 bottom of reaction kettle of the esterification sample, survey acid value；When measurement
0.07 mg KOH/g of esterifying liquid acid value > continues constant temperature reflux；As esterifying liquid acid value≤0.07 mg KOH/g of measurement,
Show that esterification is completed；Into in next step；
S2, negative pressure dealcoholysis：The bottom esterifying liquid of reaction kettle of the esterification 1 squeezes into dealcoholysis tower 7 and carries out negative pressure dealcoholysis, can also be through heat exchanger two
Dealcoholysis tower 7 is squeezed into again after 5 heat exchange；7 vacuum degree of dealcoholysis tower be 0.08Mpa, the dealcoholysis time be 2.5 h, dealcoholysis temperature be 1780~
190℃；
S3, alkali cleaning washing：Esterifying liquid after dealcoholysis is passed through nitrogen, under normal pressure through 38 dozens of reflux cycles of heat exchanger, makes reactant
System is cooled to 95~105 DEG C；Suitable sodium carbonate liquor is put into, neutrality is neutralized to；It adds and is slowly added to distilled water progress water
It washes, stands 0.6 h, layering drains lower layer's white flocculate；The water of 4 bottom of alcohol-water separation tower separation can be connected to dealcoholysis tower 7,
Part water as washing.
S4, low-boiling-point substance is removed：Logical nitrogen, is warming up to 180~190 DEG C, is vacuumized by vacuum pump 7, vacuum degree is
0.08Mpa, negative pressure slough low-boiling-point substance and remaining isononyl alcohol in reaction system, and the negative pressure ventilation time is 2.5 h；Negative pressure ventilation
Stop vacuumizing afterwards, be passed through nitrogen, is restored to normal pressure state to system, stops heating, cooling down；
S5, adsorption filtration：Will be cooled to 80~90 DEG C of esterifying liquid and be transferred to filter 12, through adsorption bleaching, after filtering to get
Qualified triisononyl trimellitate.Filtrate is the mixture of active carbon and diatomite, the active carbon and silicon in filter 12
Diatomaceous earth mass ratio 1：2.0；The active carbon average particle size is 200 mesh；The diatomite average particle size is 300 mesh.
Embodiment 3
A kind of synthetic method of triisononyl trimellitate plasticizer, in turn includes the following steps：
S1, esterification：Acid anhydride content >=98 % in raw material trimellitic anhydride；The purity of the raw material isononyl alcohol >=99 %；It will be former
Expect in trimellitic anhydride and isononyl alcohol investment reaction kettle of the esterification 1, under nitrogen protection and stirring well, it is heated to 135~
155 DEG C, the molar ratio of the trimellitic anhydride and isononyl alcohol is 1：3.6；After trimellitic anhydride is dissolved completely in isononyl alcohol, then
180 DEG C are warming up to, catalyst is added, the catalyst is metatitanic acid orthocarbonate and tetraisopropyl titanate with 1：2 mass ratioes it is compound and
At catalyst amount is the 0.08% of reaction raw materials gross mass；Insulation reaction 1 h, while isolating and being generated in esterification process
Water；225 DEG C are continuously heating to, is exchanged heat by heat exchanger 1, realizes and persistently carries out constant temperature reflux, in the esterifying liquid in reaction kettle
Ester content is continuously improved, and after reacting a period of time, samples from 1 bottom of reaction kettle of the esterification, surveys acid value；When the esterifying liquid acid value of measurement
0.07 mg KOH/g of > continues constant temperature reflux；As esterifying liquid acid value≤0.07 mg KOH/g of measurement, show that esterification is anti-
It should be completed；Into in next step；
S2, negative pressure dealcoholysis：The bottom esterifying liquid of reaction kettle of the esterification 1 squeezes into dealcoholysis tower 7 and carries out negative pressure dealcoholysis, can also be through heat exchanger two
Dealcoholysis tower 7 is squeezed into again after 5 heat exchange；7 vacuum degree of dealcoholysis tower is 0.06Mpa, and the dealcoholysis time is 2h, and dealcoholysis temperature is 175~185
℃；
S3, alkali cleaning washing：Esterifying liquid after dealcoholysis is passed through nitrogen, under normal pressure through 38 dozens of reflux cycles of heat exchanger, makes reactant
System is cooled to 80~90 DEG C；Suitable sodium carbonate liquor is put into, neutrality is neutralized to；It adds and is slowly added to distilled water progress water
It washes, stands 0.5 h, layering drains lower layer's white flocculate；The water of 4 bottom of alcohol-water separation tower separation can be connected to dealcoholysis tower 7,
Part water as washing.
S4, low-boiling-point substance is removed：Logical nitrogen, is warming up to 170~180 DEG C, vacuumizes, vacuum degree 0.06Mpa, negative pressure is sloughed
Low-boiling-point substance and remaining isononyl alcohol in reaction system, negative pressure ventilation time are 1.8h；Stop vacuumizing after negative pressure ventilation, be passed through
Nitrogen is restored to normal pressure state to system, stops heating, cooling down；
S5, adsorption filtration：It will be cooled to 75~85 DEG C of esterifying liquid and be transferred to filter 12, through adsorption bleaching, to get conjunction after filtering
The triisononyl trimellitate of lattice.Filtrate is the mixture of active carbon and diatomite, the active carbon and diatom in filter 12
Native mass ratio 1：1.0；The active carbon average particle size is 200 mesh；The diatomite average particle size is 300 mesh.
Embodiment 4
A kind of synthetic method of triisononyl trimellitate plasticizer, in turn includes the following steps：
S1, esterification：Acid anhydride content >=98 % in raw material trimellitic anhydride；The purity of the raw material isononyl alcohol >=99 %；It will be former
Expect under nitrogen protection and stirring well, to be heated to 122 in trimellitic anhydride and isononyl alcohol investment reaction kettle of the esterification 1
DEG C, the molar ratio of the trimellitic anhydride and isononyl alcohol is 1：3.8；After trimellitic anhydride is dissolved completely in isononyl alcohol, then rise
Catalyst is added to 190 DEG C in temperature, and the catalyst is metatitanic acid orthocarbonate and tetraisopropyl titanate with 1：2.5 mass ratioes it is compound and
At catalyst amount is 0.12 % of reaction raw materials gross mass；Insulation reaction 0.8h, while isolating and being generated in esterification process
Water；218~236 DEG C are continuously heating to, persistently carries out constant temperature reflux, ester content is continuously improved in the esterifying liquid in reaction kettle, instead
It after answering a period of time, is sampled from 1 bottom of reaction kettle of the esterification, surveys acid value；As the 0.07 mg KOH/g of esterifying liquid acid value > of measurement,
Continue constant temperature reflux；As esterifying liquid acid value≤0.07 mg KOH/g of measurement, show that esterification is completed；Under
One step；
S2, negative pressure dealcoholysis：The bottom esterifying liquid of reaction kettle of the esterification 1 squeezes into dealcoholysis tower 7 and carries out negative pressure dealcoholysis, can also be through heat exchanger two
Dealcoholysis tower 7 is squeezed into again after 5 heat exchange；7 vacuum degree of dealcoholysis tower is 0.08Mpa, and the dealcoholysis time is 1.5~1.8 h, and dealcoholysis temperature is
170℃；
S3, alkali cleaning washing：Esterifying liquid after dealcoholysis is passed through nitrogen, under normal pressure through 38 dozens of reflux cycles of heat exchanger, makes reactant
System is cooled to 75 DEG C；Suitable sodium carbonate liquor is put into, neutrality is neutralized to；It adds and is slowly added to distilled water and is washed, it is quiet
0.6 h is set, is layered, drains lower layer's white flocculate；The water of 4 bottom of alcohol-water separation tower separation can be connected to dealcoholysis tower 7, as water
The part water washed.
S4, low-boiling-point substance is removed：Logical nitrogen, is warming up to 190 DEG C, vacuumizes, vacuum degree 0.08Mpa, negative pressure sloughs reactant
Low-boiling-point substance and remaining isononyl alcohol in system, negative pressure ventilation time are 2.5 h；Stop vacuumizing after negative pressure ventilation, be passed through nitrogen,
It is restored to normal pressure state to system, stops heating, cooling down；
S5, adsorption filtration：It will be cooled to 70~75 DEG C of esterifying liquid and be transferred to filter 12, through adsorption bleaching, to get conjunction after filtering
The triisononyl trimellitate of lattice.Filtrate is the mixture of active carbon and diatomite, the active carbon and diatom in filter 12
Native mass ratio 1：1.6；The active carbon average particle size is 200 mesh；The diatomite average particle size is 300 mesh.
Embodiment 5
A kind of synthetic method of triisononyl trimellitate plasticizer, in turn includes the following steps：
S1, esterification：Acid anhydride content >=98 % in raw material trimellitic anhydride；The purity of the raw material isononyl alcohol >=99 %；It will be former
Expect in trimellitic anhydride and isononyl alcohol investment reaction kettle of the esterification 1, under nitrogen protection and stirring well, it is heated to 122~
156 DEG C, the molar ratio of the trimellitic anhydride and isononyl alcohol is 1：（3.2~4.0）；Trimellitic anhydride is dissolved completely in different nonyl
After in alcohol, then 185 ± 5 DEG C are warming up to, catalyst is added, the catalyst is metatitanic acid orthocarbonate and tetraisopropyl titanate with 1：
（1.2~3.4）Mass ratio is combined, and catalyst amount is 0.04~0.12 % of reaction raw materials gross mass；Insulation reaction 0.5
~1 h, while isolating the water generated in esterification process；218~236 DEG C are continuously heating to, is exchanged heat by heat exchanger 1, it is real
Constant temperature reflux is now persistently carried out, ester content is continuously improved in the esterifying liquid in reaction kettle, after reacting a period of time, from esterification
The sampling of 1 bottom of kettle, surveys acid value；As the 0.07 mg KOH/g of esterifying liquid acid value > of measurement, continue constant temperature reflux；Work as measurement
Esterifying liquid acid value≤0.07 mg KOH/g, show that esterification is completed；Into in next step；
S2, negative pressure dealcoholysis：The bottom esterifying liquid of reaction kettle of the esterification 1 squeezes into dealcoholysis tower 7 and carries out negative pressure dealcoholysis；7 vacuum degree of dealcoholysis tower
For 0.04~0.08Mpa, the dealcoholysis time is 1.5~2.5 h, and dealcoholysis temperature is 170~190 DEG C；
S3, alkali cleaning washing：Esterifying liquid after dealcoholysis is passed through nitrogen, under normal pressure through 38 dozens of reflux cycles of heat exchanger, makes reactant
System is cooled to 75~105 DEG C；Suitable sodium carbonate liquor is put into, neutrality is neutralized to；It adds and is slowly added to distilled water progress water
It washes, stands 0.4~0.6 h, layering drains lower layer's white flocculate；The water of 4 bottom of alcohol-water separation tower separation can be connected to dealcoholysis
Tower 7, the part water as washing.
S4, low-boiling-point substance is removed：Logical nitrogen, is warming up to 160~190 DEG C, vacuumizes, and vacuum degree is 0.04~0.08Mpa, bears
Low-boiling-point substance and remaining isononyl alcohol in pressure-off dereaction system, negative pressure ventilation time are 1.5~2.5 h；Stop after negative pressure ventilation
It only vacuumizes, is passed through nitrogen, be restored to normal pressure state to system, stop heating, cooling down；
S5, adsorption filtration：Will be cooled to 70~90 DEG C of esterifying liquid and be transferred to filter 12, through adsorption bleaching, after filtering to get
Qualified triisononyl trimellitate.Filtrate is the mixture of active carbon and diatomite, the active carbon and silicon in filter 12
Diatomaceous earth mass ratio 1：（0.4~2.0）；The active carbon average particle size is 200 mesh；The diatomite average particle size is 300 mesh.
The yield of above-described embodiment 1-5 is as follows：
High conversion rate of the present invention, byproduct of reaction are easily isolated, so that final product yield is not also higher, production cost is relatively
It is low.
The present invention is not limited to the above embodiments, and the foregoing is only a preferred embodiment of the present invention, and does not have to
In the limitation present invention, although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art
For, it is still possible to modify the technical solutions described in the foregoing embodiments, or to part of technical characteristic
It is equivalently replaced.All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should all wrap
Containing within protection scope of the present invention.
Claims (8)
1. a kind of synthetic method of triisononyl trimellitate plasticizer, which is characterized in that in turn include the following steps：
S1, esterification：Raw material trimellitic anhydride and isononyl alcohol are put into reaction kettle of the esterification, in nitrogen protection and uniform stirring
Under the conditions of, it is heated to 122~156 DEG C, the molar ratio of the trimellitic anhydride and isononyl alcohol is 1：（3.2~4.0）；Inclined benzene three
After acid anhydrides is dissolved completely in isononyl alcohol, then be warming up to 185 ± 5 DEG C, be added catalyst, the catalyst be metatitanic acid orthocarbonate and
Tetraisopropyl titanate is with 1：（1.2~3.4）Mass ratio is combined, catalyst amount be reaction raw materials gross mass 0.04~
0.12 %；0.5~1 h of insulation reaction, while isolating the water generated in esterification process；218~236 DEG C are continuously heating to, is held
Continuous to carry out constant temperature reflux, ester content is continuously improved in the esterifying liquid in reaction kettle, after reacting a period of time, from esterification bottom
Portion's sampling, surveys acid value；As the 0.07 mg KOH/g of esterifying liquid acid value > of measurement, continue constant temperature reflux；When the esterification of measurement
Liquid acid value≤0.07 mg KOH/g, shows that esterification is completed；Into in next step；
S2, negative pressure dealcoholysis：The bottom esterifying liquid of reaction kettle of the esterification squeezes into dealcoholysis tower and carries out negative pressure dealcoholysis, and dealcoholysis tower vacuum degree is
0.04~0.08Mpa, dealcoholysis time are 1.5~2.5 h, and dealcoholysis temperature is 170~190 DEG C；
S3, alkali cleaning washing：Esterifying liquid after dealcoholysis is passed through nitrogen, beats reflux cycle through heat exchanger under normal pressure, drops reaction system
Temperature is to 75~105 DEG C；Suitable sodium carbonate liquor is put into, neutrality is neutralized to；It adds and is slowly added to distilled water and is washed,
0.4~0.6 h is stood, layering drains lower layer's white flocculate；
S4, low-boiling-point substance is removed：Logical nitrogen, is warming up to 160~190 DEG C, vacuumizes, and vacuum degree is 0.04~0.08Mpa, and negative pressure is de-
Low-boiling-point substance and remaining isononyl alcohol in dereaction system, negative pressure ventilation time are 1.5~2.5 h；Stop taking out after negative pressure ventilation
Vacuum is passed through nitrogen, is restored to normal pressure state to system, stops heating, cooling down；
S5, adsorption filtration：It will be cooled to 70~90 DEG C of esterifying liquid and be transferred to filter, through adsorption bleaching, to get conjunction after filtering
The triisononyl trimellitate of lattice.
2. a kind of synthetic method of triisononyl trimellitate plasticizer according to claim 1, which is characterized in that step
In S1, acid anhydride content >=98 % in the raw material trimellitic anhydride；The purity of the raw material isononyl alcohol >=99 %.
3. a kind of synthetic method of triisononyl trimellitate plasticizer according to claim 1, which is characterized in that step
In S5, filtrate is the mixture of active carbon and diatomite, the active carbon and diatomite mass ratio 1 in filter：（0.4~
2.0）；The active carbon average particle size is 200 mesh；The diatomite average particle size is 300 mesh.
4. a kind of synthetic method of triisononyl trimellitate plasticizer according to claim 1, which is characterized in that described
Esterification carries out in reaction kettle of the esterification, and the gaseous phase outlet at the top of reaction kettle of the esterification is connected to alcohol-water separation after heat exchanger one
The tower top of tower, alcohol-water separation tower are connected to reaction kettle of the esterification through return pipe one.
5. a kind of synthetic method of triisononyl trimellitate plasticizer according to claim 4, which is characterized in that described
The water of alcohol-water separation tower bottom separation is connected to dealcoholysis tower, in step s3 for washing.
6. a kind of synthetic method of triisononyl trimellitate plasticizer described in -5 any one according to claim 1, special
Sign is, low-boiling-point substance is gone to carry out in step S4 in rectifying column, and dealcoholysis tower is connected to rectifying column through heat exchanger three, circulating pump, essence
It evaporates the return pipe two on tower and is connected to dealcoholysis tower, be connected at the top of the rectifying column with vacuum pump.
7. a kind of synthetic method of triisononyl trimellitate plasticizer described in -5 any one according to claim 1, special
Sign is, low-boiling-point substance is gone to carry out in step S4 in dealcoholysis tower, and dealcoholysis tower is connected through heat exchanger three, circulating pump self-loopa, dealcoholysis
Top of tower is connected with vacuum pump.
8. a kind of synthetic method of triisononyl trimellitate plasticizer described in -5 any one according to claim 1, special
Sign is, in step S2, the bottom esterifying liquid of reaction kettle of the esterification squeezes into dealcoholysis tower after the heat exchange of heat exchanger two again.
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| CN111574366A (en) * | 2020-06-22 | 2020-08-25 | 南通百川新材料有限公司 | Method for synthesizing triisodecyl trimellitate |
| CN111606803A (en) * | 2020-06-20 | 2020-09-01 | 南通百川新材料有限公司 | Production method of trioctyl trimellitate plasticizer with high volume resistivity |
| CN112387226A (en) * | 2020-11-11 | 2021-02-23 | 润泰化学（泰兴）有限公司 | Dealcoholization tower for producing isobutyl 2,2, 4-trimethyl-3-hydroxypentanoate |
| CN112552170A (en) * | 2020-11-16 | 2021-03-26 | 南通百川新材料有限公司 | Preparation method of low-color tri (C8-10 alcohol) trimellitate |
| CN112619689A (en) * | 2021-01-07 | 2021-04-09 | 江苏正丹化学工业股份有限公司 | Preparation and application method of catalyst for synthesizing triisononyl trimellitate |
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