CN110372504A - A method of polybasic ester is produced using inclined acid anhydride by-product recycling lighter component - Google Patents
A method of polybasic ester is produced using inclined acid anhydride by-product recycling lighter component Download PDFInfo
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- CN110372504A CN110372504A CN201910758566.3A CN201910758566A CN110372504A CN 110372504 A CN110372504 A CN 110372504A CN 201910758566 A CN201910758566 A CN 201910758566A CN 110372504 A CN110372504 A CN 110372504A
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- lighter component
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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
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Abstract
The invention belongs to organic compound preparation technical fields, specifically disclose a kind of method using inclined acid anhydride by-product recycling lighter component production polybasic ester, it is passed through nitrogen in reaction kettle, is mixed using the inclined acid anhydride lighter component residue of crushing and isooctanol as reaction raw materials, while active carbon and soft water is added；Using initial heating, reaction, survey acid, negative pressure dealcoholysis, neutralisation treatment, negative pressure removal of impurities and detection.The synthetic method of polyacid ester plasticizer of the present invention, be esterified, survey sour neutralizations, dealcoholysis, go low-boiling-point substance and etc. it is obtained, acquired plasticizer has the characteristics that lighter color, quality are high, and product acid value is lower and water content is few；Operation technological process is short simple and easy simultaneously, and corrosion-free to equipment, the reaction time is short, and Environmental Safety, easy to industrialized production.
Description
Technical field
It is specifically a kind of to be produced using inclined acid anhydride by-product recycling lighter component the invention belongs to organic compound preparation technical field
The method of polybasic ester is to be related to using the route of multi-anhydride synthesis present in inclined acid anhydride purification residue by inclined acid anhydride rectifying
The preparation method for the mixing polyacid ester plasticizer that tower top light component residue and polyol ester are combined to.
Background technique
Plasticizer is industrial widely used high molecular material additive.Plasticizer is used in plastic processing, it can be with
Play the role of modified to plastics or soften, increases the performances such as its plasticity, flexibility, draftability or dilatancy.Currently, plasticising
Agent industry has evolved into based on petrochemical industry, using phthalic acid ester as the plasticizer of core, is widely used in plastics
In paint industry.However, the plastic products containing phthalate processing, heating, packaging and contain during, meeting
The dissolution of phthalic acid ester is caused, there is certain harm.
Trimellitic acid esters plasticizer has compatibility, electrical property, plasticizing capacity, cryogenic property, resistance to migration, water-fast
Many excellent performances such as extraction, thermal stability, plasticizing efficiency and processing performance are close with phthalic ester plasticizer.Extensively
For 105 DEG C of grades and 125 DEG C of grade heatproof wire CABLE MATERIALSs, automotive interior material and other require heat-resisting and durability plate
The products such as material, sheet material, gasket.
Therefore, the trimellitic acid esters plasticizer more haveing excellent performance is researched and developed, in the following plastics manufacturing
It has a very important significance.
Summary of the invention
The object of the present invention is to provide a kind of method using inclined acid anhydride by-product recycling lighter component production polybasic ester, productions one
The preferable mixed type polyacid ester plasticizers of performance indicators such as kind acid value, heating loss and resistivity, and process flow letter
Single, cost of material is low.
In order to solve the above technical problems, producing polybasic ester using inclined acid anhydride by-product recycling lighter component the present invention provides a kind of
Method, comprising the following steps:
S1, feeding stage: being passed through nitrogen in reaction kettle, using the inclined acid anhydride lighter component residue of crushing and isooctanol as reaction
Raw material mixing, while active carbon and soft water is added；
S2, initial heat-up stage: being warming up to 120-130 DEG C, is stirred at reflux 1.5h, is dissolved completely in multi-anhydride different pungent
In alcohol；
S3, the stage of reaction: in 10~30 minutes, being warming up to 160-180 DEG C, and tetraisopropyl titanate, constant temperature stirring is added
Back flow reaction 1-1.5h, while isolating the water generated in esterification process；
S4, sample detection acidity: it extracts reaction solution and carries out acid esters detection, as acid value < 0.1%, esterification is completed；
S5, negative pressure dealcoholysis: octanol reflux is closed, negative pressure dealcoholysis is carried out, is continuously heating to 210~215 DEG C, keeps temperature not
Become, flow back 1.5~2.5h；
S6, cooling neutralisation treatment stage: after dealcoholysis, being passed through nitrogen, and after being cooled to 90 DEG C under normal pressure, carbonic acid is added
Sodium solution stirs 0.5h；
S7, negative pressure removal of impurities: after neutralization, stop logical nitrogen, vacuumize, be warming up to 150-160 DEG C, negative pressure sloughs reaction
Miscellaneous ester and diformazan acids ester in system, time 1.5h；
S8, sample detection: then stopping vacuumizing, be passed through nitrogen, is restored to normal pressure state to system, stops heating, open
Begin to cool down, sampling, the index of testing product.
Further, active carbon described in S1 accounts for the 0.3%-0.8% of lighter component amount, and the soft water accounts for lighter component amount
0.1%-0.15%.
Specifically, tetraisopropyl titanate described in S3 accounts for the 0.05-0.15% of lighter component amount.
Further, the regurgitant volume of octanol is 8-10m in S33/h。
Further, sodium carbonate liquor accounts for the 0.05-0.1% of lighter component in S6.
Further, the index of product is coloration≤40, acid value (in terms of KOH)/(mg/g)≤0.15, volume resistance in S8
Rate/>=10, moisture≤0.1% (109 Ω .m).
The beneficial effects of the present invention are: the synthetic method of polyacid ester plasticizer of the present invention, be esterified, survey acid neutralization,
Dealcoholysis, go low-boiling-point substance and etc. be made, acquired plasticizer has the characteristics that lighter color, quality are high, and product acid value is lower and contains
Water is few；Operation technological process is short simple and easy simultaneously, and corrosion-free to equipment, the reaction time is short, and Environmental Safety, is easy to work
Industry metaplasia produces.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
In an embodiment of the present invention, it specifically discloses and a kind of utilizes inclined acid anhydride by-product recycling lighter component production polybasic ester
Method, comprising the following steps:
S1, feeding stage: being passed through nitrogen in reaction kettle, using the inclined acid anhydride lighter component residue of crushing and isooctanol as reaction
Raw material mixing, molar ratio 1:3-4.5, while the active carbon for accounting for lighter component amount 0.3%-0.8% is added and accounts for lighter component amount
The soft water of 0.1%-0.15%；
S2, initial heat-up stage: being warming up to 120-130 DEG C, is stirred at reflux 1.5h, is dissolved completely in multi-anhydride different pungent
In alcohol；
S3, the stage of reaction: in 10~30 minutes, it is warming up to 160-180 DEG C, the 0.05- for accounting for lighter component amount is added
0.15% tetraisopropyl titanate controls octanol regurgitant volume 8-10m3/ h, constant temperature is stirred at reflux reaction 1-1.5h, while separating ester output
The water generated during changing；
S4, sample detection acidity: it extracts reaction solution and carries out acid esters detection, as acid value < 0.1%, esterification is completed；
S5, negative pressure dealcoholysis: octanol reflux is closed, negative pressure dealcoholysis is carried out, is continuously heating to 210~215 DEG C, keeps temperature not
Become, flow back 1.5~2.5h；
S6, cooling neutralisation treatment stage: after dealcoholysis, being passed through nitrogen, after being cooled to 90 DEG C under normal pressure, is added
The sodium carbonate liquor of 0.05-0.1%, stirring 0.5h or so；
S7, negative pressure removal of impurities: after neutralization, stop logical nitrogen, vacuumize, be warming up to 150-160 DEG C, negative pressure sloughs reaction
Miscellaneous ester and diformazan acids ester in system, time 1.5h；
S8, sample detection: then stopping vacuumizing, be passed through nitrogen, is restored to normal pressure state to system, stops heating, open
Begin to cool down, sampling, the index of testing product, the index of the index product of product is coloration≤40；Acid value (in terms of KOH)/(mg/
g)≤0.15；Volume resistivity/(109 Ω .m) >=10；Moisture≤0.1%.
Embodiment one
(1) feeding stage: being passed through nitrogen in reaction kettle, using the inclined acid anhydride lighter component residue of crushing and isooctanol as reaction
Raw material is mixed by the molar ratio of 1:3, while the active carbon for accounting for lighter component amount 0.3% is added and accounts for lighter component amount 0.1%
Soft water；
(2) initial heat-up stage: being warming up to 120-130 DEG C, is stirred at reflux 1.5h, is dissolved completely in multi-anhydride different pungent
In alcohol；
(3) stage of reaction: in 10~30 minutes, it is warming up to 160-180 DEG C, the metatitanic acid four for accounting for lighter component 0.05% is added
Isopropyl ester controls octanol regurgitant volume 8-10m3/ h, constant temperature is stirred at reflux reaction 1-1.5h, while isolating in esterification process and generating
Water；
(4) it sample detection acidity: extracts reaction solution and carries out acid esters detection, as acid value < 0.1%, esterification is completed；
(5) negative pressure dealcoholysis: octanol reflux is closed, negative pressure dealcoholysis is carried out, is continuously heating to 210~215 DEG C, keeps temperature not
Become, flow back 1.5~2.5h；
(6) cool down the neutralisation treatment stage: after dealcoholysis, being passed through nitrogen, after being cooled to 90 DEG C under normal pressure, be added 0.05
Sodium carbonate liquor, stirring 0.5h or so；
(7) negative pressure cleans: after neutralization, stopping logical nitrogen, vacuumizes, be warming up to 150-160 DEG C, negative pressure sloughs reaction
Miscellaneous ester and diformazan acids ester in system, time 1.5h；
(8) sample detection: then stopping vacuumizing, be passed through nitrogen, is restored to normal pressure state to system, stops heating, open
Begin to cool down, sampling, the index of testing product, the index of resulting product is coloration 35, acid value 0.08, resistivity 12.4, moisture
0.034%.
Embodiment two
(1) feeding stage: being passed through nitrogen in reaction kettle, using the inclined acid anhydride lighter component residue of crushing and isooctanol as reaction
Raw material is mixed by the molar ratio of 1:4, while the active carbon for accounting for lighter component amount 0.5% is added and accounts for lighter component amount 0.12%
Soft water；
(2) initial heat-up stage: being warming up to 120-130 DEG C, is stirred at reflux 1.5h, is dissolved completely in multi-anhydride different pungent
In alcohol；
(3) stage of reaction: in 10~30 minutes, it is warming up to 160-180 DEG C, the metatitanic acid four for accounting for lighter component 0.1% is added
Isopropyl ester controls octanol regurgitant volume 8-10m3/ h, constant temperature is stirred at reflux reaction 1-1.5h, while isolating in esterification process and generating
Water；
(4) it sample detection acidity: extracts reaction solution and carries out acid esters detection, as acid value < 0.1%, esterification is completed；
(5) negative pressure dealcoholysis: octanol reflux is closed, negative pressure dealcoholysis is carried out, is continuously heating to 210~215 DEG C, keeps temperature not
Become, flow back 1.5~2.5h；
(6) cool down the neutralisation treatment stage: after dealcoholysis, being passed through nitrogen, after being cooled to 90 DEG C under normal pressure, be added
0.08% sodium carbonate liquor, stirring 0.5h or so；
(7) negative pressure cleans: after neutralization, stopping logical nitrogen, vacuumizes, be warming up to 150-160 DEG C, negative pressure sloughs reaction
Miscellaneous ester and diformazan acids ester in system, time 1.5h；
(8) sample detection: then stopping vacuumizing, be passed through nitrogen, is restored to normal pressure state to system, stops heating, open
Begin to cool down, sampling, the index of testing product, the index of resulting product is coloration 30, acid value 0.051, resistivity 14.6, moisture
0.025%.
Embodiment three
(1) feeding stage: being passed through nitrogen in reaction kettle, using the inclined acid anhydride lighter component residue of crushing and isooctanol as reaction
Raw material is mixed by the molar ratio of 1:4.5, while the active carbon for accounting for lighter component amount 0.8% is added and accounts for lighter component amount
0.15% soft water；
(2) initial heat-up stage: being warming up to 120-130 DEG C, is stirred at reflux 1.5h, is dissolved completely in multi-anhydride different pungent
In alcohol；
(3) stage of reaction: in 10~30 minutes, it is warming up to 160-180 DEG C, the metatitanic acid four for accounting for lighter component 0.15% is added
Isopropyl ester controls octanol regurgitant volume 8-10m3/ h, constant temperature is stirred at reflux reaction 1-1.5h, while isolating in esterification process and generating
Water；
(4) it sample detection acidity: extracts reaction solution and carries out acid esters detection, as acid value < 0.1%, esterification is completed；
(5) negative pressure dealcoholysis: octanol reflux is closed, negative pressure dealcoholysis is carried out, is continuously heating to 210~215 DEG C, keeps temperature not
Become, flow back 1.5~2.5h；
(6) cool down the neutralisation treatment stage: after dealcoholysis, being passed through nitrogen, after being cooled to 90 DEG C under normal pressure, be added
0.1% sodium carbonate liquor, stirring 0.5h or so；
(7) negative pressure cleans: after neutralization, stopping logical nitrogen, vacuumizes, be warming up to 150-160 DEG C, negative pressure sloughs reaction
Miscellaneous ester and diformazan acids ester in system, time 1.5h；
(8) sample detection: then stopping vacuumizing, be passed through nitrogen, is restored to normal pressure state to system, stops heating, open
Begin to cool down, sampling, the index of testing product, the index of resulting product is coloration 30, acid value 0.03, resistivity 16.89, moisture
0.02%.
Above disclosed be only a kind of preferred embodiment of the invention, cannot limit the present invention's certainly with this
Interest field, therefore equivalent changes made in accordance with the claims of the present invention, are still within the scope of the present invention.
Claims (6)
1. a kind of method using inclined acid anhydride by-product recycling lighter component production polybasic ester, which comprises the following steps:
S1, feeding stage: being passed through nitrogen in reaction kettle, using the inclined acid anhydride lighter component residue of crushing and isooctanol as reaction raw materials
Mixing, while active carbon and soft water is added；
S2, initial heat-up stage: being warming up to 120-130 DEG C, is stirred at reflux 1.5h, and multi-anhydride is made to be dissolved completely in isooctanol
In；
S3, the stage of reaction: in 10~30 minutes, it is warming up to 160-180 DEG C, tetraisopropyl titanate is added, constant temperature is stirred at reflux
1-1.5h is reacted, while isolating the water generated in esterification process；
S4, sample detection acidity stage: it extracts reaction solution and carries out acid esters detection, as acid value < 0.1%, esterification is completed；
S5, negative pressure dealcoholysis stage: octanol reflux is closed, negative pressure dealcoholysis is carried out, is continuously heating to 210~215 DEG C, keeps temperature not
Become, flow back 1.5~2.5h；
S6, cooling neutralisation treatment stage: after dealcoholysis, being passed through nitrogen, and after being cooled to 90 DEG C under normal pressure, it is molten that sodium carbonate is added
Liquid stirs 0.5h；
S7, negative pressure clean the stage: after neutralization, stopping logical nitrogen, vacuumize, be warming up to 150-160 DEG C, negative pressure sloughs reaction
Miscellaneous ester and diformazan acids ester in system, time 1.5h；
S8, sample detection stage: then stopping vacuumizing, be passed through nitrogen, is restored to normal pressure state to system, stops heating, open
Begin to cool down, sampling, the index of testing product.
2. a kind of method using inclined acid anhydride by-product recycling lighter component production polybasic ester according to claim 1, feature
It is, active carbon described in S1 accounts for the 0.3%-0.8% of lighter component amount, and the soft water accounts for the 0.1%-0.15% of lighter component amount.
3. a kind of method using inclined acid anhydride by-product recycling lighter component production polybasic ester according to claim 1, feature
It is, tetraisopropyl titanate described in S3 accounts for the 0.05-0.15% of lighter component amount.
4. a kind of method using inclined acid anhydride by-product recycling lighter component production polybasic ester according to claim 1, feature
It is, the regurgitant volume of octanol is 8-10m in S33/h。
5. a kind of method using inclined acid anhydride by-product recycling lighter component production polybasic ester according to claim 1, feature
It is, sodium carbonate liquor accounts for the 0.05-0.1% of lighter component in S6.
6. a kind of method using inclined acid anhydride by-product recycling lighter component production polybasic ester according to claim 1, feature
It is, index coloration≤40, acid value≤0.15, volume resistivity >=10, moisture≤0.1% of product in S8.
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| CN110818559A (en) * | 2019-11-26 | 2020-02-21 | 南通百川新材料有限公司 | Method for recycling trimellitic anhydride rectification mother liquor residues |
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