CN109438229A - A kind of phthalic acid two (1- Zhong Xin, 2- is tertiary pungent) ester new plasticizer and preparation method thereof - Google Patents
A kind of phthalic acid two (1- Zhong Xin, 2- is tertiary pungent) ester new plasticizer and preparation method thereof Download PDFInfo
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- CN109438229A CN109438229A CN201811372241.3A CN201811372241A CN109438229A CN 109438229 A CN109438229 A CN 109438229A CN 201811372241 A CN201811372241 A CN 201811372241A CN 109438229 A CN109438229 A CN 109438229A
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- phthalic acid
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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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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Abstract
The invention patent relates to plasticizer production technical field, a kind of phthalic acid two (1- Zhong Xin, 2- is tertiary pungent) ester new plasticizer and preparation method thereof is disclosed.(1- Zhong Xin, 2- the is tertiary pungent) ester plasticiser of phthalic acid two occurs level-one esterification with phthalic acid after first refining sec-octyl alcohol and DCP monoesters mixed liquor is made using sec-octyl alcohol, phthalic acid and industrial octanol as raw material；Purification DCP monoesters is made using stripping dealcoholation treatment later；Then purification DCP monoesters and industrial octanol are put into second order reaction kettle, catalyst is added, constant temperature esterification reacts to obtain DCOP dibasic acid esters mixed liquor；Phthalic acid two (1- Zhong Xin, 2- is tertiary pungent) ester new plasticizer finally is made in the alkali cleaning of DCOP dibasic acid esters mixed liquor, stripping dealcoholysis, active carbon decolorization.The preparation method simple process, low in cost, yield is high, easily controllable and be mass produced, while phthalic acid obtained two (1- Zhong Xin, 2- is tertiary pungent) ester plasticiser plasticization effect is good, and stability is strong.
Description
Technical field
The invention patent relates to plasticizer production technical field, especially a kind of phthalic acid two (1- Zhong Xin, uncle 2-
It is pungent) ester new plasticizer and preparation method thereof.
Background technique
Plasticizer weakens secondary valence between polymer molecule and is good for, is i.e. model as a kind of high molecular material auxiliary agent due to having
De Huali increases the mobility of polymer molecular chain and the plasticity of polymer, reduces the crystallinity and polymerization of polymer molecular chain
Hardness, modulus, softening temperature and the brittle temperature of object, improve the characteristics such as elongation, flexibility and the flexibility of polymer, by
It is widely applied to the every field such as engineering plastics, rubber coating, binder and sealing material.
Currently, common plasticizer is mainly phthalic ester plasticizer on the market, such as dioctyl phthalate
(DOP), di-sec-octyl phthalate (DCP) etc., wherein dioctyl phthalate (DOP) although have preferable oil resistant and
Fuel-proof extractable and plasticizing efficiency, but often there is the defects of fast light and against weather is poor, and phthalic acid two
Secondary monooctyl ester (DCP) has preferable fast light and weather-resistant property, but in oil resistant and fuel-proof extractable and plasticizing efficiency
Aspect is often not satisfactory.This not only strongly limits the application range of traditional phthalic ester plasticizer, but also with
The fast development of modern industry, plasticizer demand it is growing day by day, traditional phthalic ester plasticizer is increasingly
It is not able to satisfy industrial demand.Therefore the more excellent and stable plasticizer of exploitation performance has highly important reality meaning
Justice.
Summary of the invention
For the problems of the prior art, the invention aims to provide a kind of low in cost, superior performance, stability
Good phthalic acid two (1- Zhong Xin, 2- are tertiary pungent) ester (DCOP) new plasticizer and preparation method thereof.
In order to achieve the above object, the technical scheme is that
A kind of preparation method of phthalic acid two (1- Zhong Xin, 2- is tertiary pungent) ester (DCOP) new plasticizer, including it is following
Step:
(1) sec-octyl alcohol refines
Outsourcing sec-octyl alcohol is subjected to the denier phenol and organic acid in alkali cleaning processing removing material, then refined filtration processing removing
Trace metal ion is finally dehydrated to obtain purification sec-octyl alcohol；
(2) it feeds intake and alcoholysis
Phthalic acid and purification sec-octyl alcohol obtained above is taken to put into first order reaction kettle, stirring rises after mixing
Temperature, then isothermal reaction is complete to alcoholysis, obtains DCP monoesters mixed liquor；
(3) dealcoholysis is stripped
DCP monoesters mixed liquor obtained above stripping dealcoholation treatment must be refined into DCP monoesters；
(4) it is esterified
It takes purification DCP monoesters obtained above and industrial octanol to put into second order reaction kettle, catalyst is added, mixing is equal
Stirring heating after even, then constant temperature esterification reacts to obtain DCOP dibasic acid esters mixed liquor；
(5) product purification
O-phthalic is made through alkali cleaning, stripping dealcoholysis, active carbon decolorization in DCOP dibasic acid esters mixed liquor obtained above
Sour two (1- Zhong Xin, 2- is tertiary pungent) ester (DCOP) new plasticizers.
Specifically, in the step (1) outsourcing sec-octyl alcohol content >=99.8%.
Specifically, mixing speed is 45~55r/min, the throwing of phthalic acid and purification sec-octyl alcohol in the step (2)
Entering molar ratio is 1:1.15, and warming temperature is 75~85 DEG C, 3~5h of reaction time.
Specifically, the pressure of saturated steam is 0.4~0.5MPa when stripping dealcoholysis in the step (3).
Specifically, the investment molar ratio of purification DCP monoesters and industrial octanol is 1:1.25, catalyst in the step (4)
For tetraisopropyl titanate, catalyst charge is refine DCP monoesters and industrial octanol total amount 0.01~0.02%, warming temperature
It is 175~185 DEG C.
Specifically, novel using (1- Zhong Xin, 2- the is tertiary pungent) ester of phthalic acid two made from any of the above method (DCOP)
Plasticizer.
Compared with prior art, the invention has the advantages that
1. phthalic acid two (1- Zhong Xin, 2- is tertiary pungent) ester new plasticizer provided by the invention and preparation method thereof technique
Simply, low in cost, yield is high, easily controllable and be mass produced, while phthalic acid obtained two (1- Zhong Xin, uncle 2-
It is pungent) ester new plasticizer plasticization effect is good, and stability is strong.
2. relative to traditional dioctyl phthalate (DOP) and di-sec-octyl phthalate (DCP) plasticizer, this
Phthalic acid two (1- Zhong Xin, 2- is tertiary pungent) ester (DCOP) new plasticizer that invention provides has both the Optimality of DOP and DCP
Can, there is higher oil resistant, fuel-proof extractable, plasticizing efficiency, fast light and effect of weather, be greatly broadened plasticizer
Application space has very vast market prospect.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described.
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
Embodiment 1
A kind of preparation method of phthalic acid two (1- Zhong Xin, 2- is tertiary pungent) ester (DCOP) new plasticizer, including it is following
Step:
(1) sec-octyl alcohol refines
By the denier phenol and organic acid of content >=99.8% carried out in alkali cleaning processing removing material, then refined filtration is handled
Trace metal ion is removed, purification sec-octyl alcohol is finally dehydrated to obtain；
(2) it feeds intake and alcoholysis
Phthalic acid and purification sec-octyl alcohol obtained above is taken to put into first order reaction kettle by the molar ratio of 1:1.15,
75 DEG C are warming up to the mixing speed of 45r/min after mixing, then isothermal reaction 5h is complete to alcoholysis, obtains DCP monoesters
Mixed liquor；
(3) dealcoholysis is stripped
Be passed through into DCP monoesters mixed liquor obtained above 0.4MPa saturated steam carry out stripping dealcoholation treatment obtain it is smart
DCP monoesters processed；
(4) it is esterified
Purification DCP monoesters obtained above and industrial octanol is taken to put into second order reaction kettle by the molar ratio of 1:1.25,
The tetraisopropyl titanate catalyst for accounting for purification DCP monoesters and industrial octanol total amount 0.01%, after mixing stirring heating is added
To 175 DEG C, then constant temperature esterification reacts to obtain DCOP dibasic acid esters mixed liquor；
(5) product purification
O-phthalic is made through alkali cleaning, stripping dealcoholysis, active carbon decolorization in DCOP dibasic acid esters mixed liquor obtained above
Sour two (1- Zhong Xin, 2- is tertiary pungent) ester (DCOP) new plasticizers.
Embodiment 2
A kind of preparation method of phthalic acid two (1- Zhong Xin, 2- is tertiary pungent) ester (DCOP) new plasticizer, including it is following
Step:
(1) sec-octyl alcohol refines
By the denier phenol and organic acid of content >=99.8% carried out in alkali cleaning processing removing material, then refined filtration is handled
Trace metal ion is removed, purification sec-octyl alcohol is finally dehydrated to obtain；
(2) it feeds intake and alcoholysis
Phthalic acid and purification sec-octyl alcohol obtained above is taken to put into first order reaction kettle by the molar ratio of 1:1.15,
80 DEG C are warming up to the mixing speed of 50r/min after mixing, then isothermal reaction 4h is complete to alcoholysis, obtains DCP monoesters
Mixed liquor；
(3) dealcoholysis is stripped
The saturated steam that 0.45MPa is passed through into DCP monoesters mixed liquor obtained above carries out stripping dealcoholation treatment and obtains
Refine DCP monoesters；
(4) it is esterified
Purification DCP monoesters obtained above and industrial octanol is taken to put into second order reaction kettle by the molar ratio of 1:1.25,
The tetraisopropyl titanate catalyst for accounting for purification DCP monoesters and industrial octanol total amount 0.015%, after mixing stirring heating is added
To 180 DEG C, then constant temperature esterification reacts to obtain DCOP dibasic acid esters mixed liquor；
(5) product purification
O-phthalic is made through alkali cleaning, stripping dealcoholysis, active carbon decolorization in DCOP dibasic acid esters mixed liquor obtained above
Sour two (1- Zhong Xin, 2- is tertiary pungent) ester (DCOP) new plasticizers.
Embodiment 3
A kind of preparation method of phthalic acid two (1- Zhong Xin, 2- is tertiary pungent) ester (DCOP) new plasticizer, including it is following
Step:
(1) sec-octyl alcohol refines
By the denier phenol and organic acid of content >=99.8% carried out in alkali cleaning processing removing material, then refined filtration is handled
Trace metal ion is removed, purification sec-octyl alcohol is finally dehydrated to obtain；
(2) it feeds intake and alcoholysis
Phthalic acid and purification sec-octyl alcohol obtained above is taken to put into first order reaction kettle by the molar ratio of 1:1.15,
85 DEG C are warming up to the mixing speed of 55r/min after mixing, then isothermal reaction 3h is complete to alcoholysis, obtains DCP monoesters
Mixed liquor；
(3) dealcoholysis is stripped
Be passed through into DCP monoesters mixed liquor obtained above 0.5MPa saturated steam carry out stripping dealcoholation treatment obtain it is smart
DCP monoesters processed；
(4) it is esterified
Purification DCP monoesters obtained above and industrial octanol is taken to put into second order reaction kettle by the molar ratio of 1:1.25,
The tetraisopropyl titanate catalyst for accounting for purification DCP monoesters and industrial octanol total amount 0.02%, after mixing stirring heating is added
To 185 DEG C, then constant temperature esterification reacts to obtain DCOP dibasic acid esters mixed liquor；
(5) product purification
O-phthalic is made through alkali cleaning, stripping dealcoholysis, active carbon decolorization in DCOP dibasic acid esters mixed liquor obtained above
Sour two (1- Zhong Xin, 2- is tertiary pungent) ester (DCOP) new plasticizers.
Field technical staff can be realized or using the present invention.Various modifications to these embodiments are to those skilled in the art
It will be apparent for member, the general principles defined herein can be in the feelings for not departing from the spirit or scope of the present invention
Under condition, realize in other embodiments.Therefore, the present invention will not be limited to the embodiments shown herein, but wants
Meet the widest scope consistent with the principles and novel features disclosed herein.
Claims (6)
1. a kind of preparation method of phthalic acid two (1- Zhong Xin, 2- is tertiary pungent) ester (DCOP) new plasticizer, which is characterized in that
The following steps are included:
(1) sec-octyl alcohol refines
Outsourcing sec-octyl alcohol is subjected to the denier phenol and organic acid in alkali cleaning processing removing material, then refined filtration processing removing is micro
Metal ion is finally dehydrated to obtain purification sec-octyl alcohol；
(2) it feeds intake and alcoholysis
Phthalic acid and purification sec-octyl alcohol obtained above is taken to put into first order reaction kettle, after mixing stirring heating,
Then isothermal reaction is complete to alcoholysis, obtains DCP monoesters mixed liquor；
(3) dealcoholysis is stripped
DCP monoesters mixed liquor obtained above stripping dealcoholation treatment must be refined into DCP monoesters；
(4) it is esterified
It takes purification DCP monoesters obtained above and industrial octanol to put into second order reaction kettle, catalyst is added, after mixing
Stirring heating, then constant temperature esterification reacts to obtain DCOP dibasic acid esters mixed liquor；
(5) product purification
Phthalic acid two is made through alkali cleaning, stripping dealcoholysis, active carbon decolorization in DCOP dibasic acid esters mixed liquor obtained above
(1- Zhong Xin, 2- is tertiary pungent) ester (DCOP) new plasticizer.
2. the preparation method of phthalic acid two (1- Zhong Xin, 2- is tertiary pungent) ester new plasticizer as described in claim 1, special
Sign is: content >=99.8% of outsourcing sec-octyl alcohol in the step (1).
3. the preparation method of phthalic acid two (1- Zhong Xin, 2- is tertiary pungent) ester new plasticizer as described in claim 1, special
Sign is: mixing speed is 45~55r/min, the investment molar ratio of phthalic acid and purification sec-octyl alcohol in the step (2)
For 1:1.15, warming temperature is 75~85 DEG C, 3~5h of reaction time.
4. the preparation method of phthalic acid two (1- Zhong Xin, 2- is tertiary pungent) ester new plasticizer as described in claim 1, special
Sign is: the pressure of saturated steam is 0.4~0.5MPa when stripping dealcoholysis in the step (3).
5. the preparation method of phthalic acid two (1- Zhong Xin, 2- is tertiary pungent) ester new plasticizer as described in claim 1, special
Sign is: the investment molar ratio of purification DCP monoesters and industrial octanol is 1:1.25 in the step (4), and catalyst is metatitanic acid four
Isopropyl ester, catalyst charge are refine DCP monoesters and industrial octanol total amount 0.01~0.02%, warming temperature is 175~
185℃。
6. the novel plasticising of (1- Zhong Xin, 2- the is tertiary pungent) ester of phthalic acid two made from either method as claimed in claims 1-5
Agent.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811372241.3A CN109438229A (en) | 2018-11-16 | 2018-11-16 | A kind of phthalic acid two (1- Zhong Xin, 2- is tertiary pungent) ester new plasticizer and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811372241.3A CN109438229A (en) | 2018-11-16 | 2018-11-16 | A kind of phthalic acid two (1- Zhong Xin, 2- is tertiary pungent) ester new plasticizer and preparation method thereof |
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| CN109438229A true CN109438229A (en) | 2019-03-08 |
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| CN201811372241.3A Pending CN109438229A (en) | 2018-11-16 | 2018-11-16 | A kind of phthalic acid two (1- Zhong Xin, 2- is tertiary pungent) ester new plasticizer and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113735152A (en) * | 2020-05-29 | 2021-12-03 | 中国石油化工股份有限公司 | Method for removing alcohol entrained in aluminum hydroxide slurry |
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|---|---|---|---|---|
| US2820771A (en) * | 1954-06-09 | 1958-01-21 | Consortium De Prod Chim Et De | Secondary-2-n-octyl primary-n-heptyl phthalate and synthetic plastics containing same |
| US2975210A (en) * | 1958-03-14 | 1961-03-14 | Monsanto Chemicals | Esterification process comprising reacting a mono olefin with an acid ester |
| GB904340A (en) * | 1958-03-14 | 1962-08-29 | Monsanto Chemicals | Improvements in or relating to an esterification process |
| CN1733695A (en) * | 2005-09-05 | 2006-02-15 | 吉化集团公司 | Diisodecyl phthalate preparation method |
| CN101891620A (en) * | 2010-07-03 | 2010-11-24 | 潍坊市元利化工有限公司 | Continuous esterification production method of di-sec-octyl phthalate |
-
2018
- 2018-11-16 CN CN201811372241.3A patent/CN109438229A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2820771A (en) * | 1954-06-09 | 1958-01-21 | Consortium De Prod Chim Et De | Secondary-2-n-octyl primary-n-heptyl phthalate and synthetic plastics containing same |
| US2975210A (en) * | 1958-03-14 | 1961-03-14 | Monsanto Chemicals | Esterification process comprising reacting a mono olefin with an acid ester |
| GB904340A (en) * | 1958-03-14 | 1962-08-29 | Monsanto Chemicals | Improvements in or relating to an esterification process |
| CN1733695A (en) * | 2005-09-05 | 2006-02-15 | 吉化集团公司 | Diisodecyl phthalate preparation method |
| CN101891620A (en) * | 2010-07-03 | 2010-11-24 | 潍坊市元利化工有限公司 | Continuous esterification production method of di-sec-octyl phthalate |
Non-Patent Citations (1)
| Title |
|---|
| 中国标准出版社编: "《化学工业标准汇编 有机化工 1996（下）》", 31 January 1997, 中国标准出版社出版 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113735152A (en) * | 2020-05-29 | 2021-12-03 | 中国石油化工股份有限公司 | Method for removing alcohol entrained in aluminum hydroxide slurry |
| CN113735152B (en) * | 2020-05-29 | 2023-09-05 | 中国石油化工股份有限公司 | Method for removing entrained alcohol in aluminum hydroxide slurry |
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