CN104650332B - Preparation method of resin intermediate--phthalic acid diethylene glycol polyester - Google Patents
Preparation method of resin intermediate--phthalic acid diethylene glycol polyester Download PDFInfo
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- CN104650332B CN104650332B CN201410748345.5A CN201410748345A CN104650332B CN 104650332 B CN104650332 B CN 104650332B CN 201410748345 A CN201410748345 A CN 201410748345A CN 104650332 B CN104650332 B CN 104650332B
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- phthalic acid
- diethylene glycol
- diglycol
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Abstract
The invention discloses a preparation method of resin intermediate--phthalic acid diethylene glycol polyester. In the preparation method, CTA (Cellulose triacetate) residues mixed with diisooctyl phthalate react with excessive amount of diethylene glycol in presence of a catalyst under a condition of heating to generate mixed phthalic acid diethylene glycol monoester and isooctyl alcohol monomer, after the isooctyl alcohol is discharged, reaction temperature is increased sequentially, and under a negative pressure condition, the excessive amount of diethylene glycol is discharged by polycondensation, and finally, various mixed phthalic acid diethylene glycol polyesters with different polymerization degrees are obtained.
Description
Technical field
The present invention relates to process and the utilization of people's CTA residue, more particularly in PTA production process, CTA residue as resources
The method utilized.
Background technology
Our company application Patent No. ZL201110056079.6 (authorized announcement date: on 04 03rd, 2013), in relate to
And to pure mixed phthalic acid di-isooctyl, be the plasticizer of a kind of function admirable that can directly utilize.But since two thousand eight,
The western countries such as America and Europe assert that the plasticizer containing phthalate limits and use, and therefore such plasticizer does not enters this
The relevant market of a little developed countries, the present invention is that this series products expands new use approach.
Summary of the invention
It is an object of the invention to provide a kind of pure mixed phthalic acid di-isooctyl from CTA residue new make purposes
Footpath.
The technical scheme that the present invention provides: pure mixed phthalic acid di-isooctyl is existed and the condition of heating at catalyst
Under, react with the diglycol of excess, generate pure mixed phthalic acid diglycol monoesters and isooctanol monomer, different pungent
After alcohol is discharged, continuing to rise high reaction temperature and under negative pressure state, the diglycol of excess is discharged by polycondensation, finally
To the pure mixed phthalic acid diethylene glycol polyester of various different polymerization degrees, the present invention is its named PDT.The control of the PDT degree of polymerization
Acid-alcohol ratio needed for producing resin can be determined by system intuitively according to downstream user.
Specifically include following steps:
1, the first step, pure mixed phthalic acid di-isooctyl and excessive diglycol generation ester exchange reaction, by different
Capryl alcohol is discharged, and prepares pure mixed phthalic acid diglycol monoesters.
2, second step, pure mixed phthalic acid diglycol monoesters is under conditions of high temperature, tiny structure, and monoesters contracts
Poly-reaction, diglycol is drained out, and depending on reaction end acid-alcohol ratio needed for the resin of downstream, is discharged by reaction
The quantity of diglycol can accurately judge.
In the preferred embodiment, 1, first step step be: by pure mixed phthalic acid di-isooctyl, catalyst and
Excess diglycol puts in reactor, is warming up to 195 DEG C, and insulation reaction is reacted 5～6 hours, until capryl alcohol quilt completely
Diglycol ester exchange is discharged as terminal；2, second step, is warming up to 240 DEG C, opens vacuum and carries out polycondensation reaction of reducing pressure, a contracting
Diethylene glycol is drained out, and the amount of the diglycol being discharged by metering can accurately determine reaction end.So far, mixed
Close phthalic acid diglycol ester to have prepared.3, the 3rd step, is cooled to less than 40 DEG C, and blowing is packed.
Reaction equation
1, pure mixed phthalic acid di-isooctyl and the ester exchange reaction of diglycol:
nH17C8OOC-R-COOC8H17+2nC4OH8(OH)2
n(HO)H4C4OOC-R-COOC4H4(OH)+2nC8H17OH
In formula: C8H17OH represents two isooctanol
H17C8OOC-R-COOC8H17Represent benzene mixed formic acid two isooctanol
C4OH8(OH)2Represent diglycol
(HO)H4C400C-R-COOC4H4(OH) pure mixed phthalic acid diglycol monoesters is represented
2, the polycondensation reaction of pure mixed phthalic acid diglycol monoesters:
2n(HO)H4C4OOC-R-COOC4H4(OH)
In aforementioned each reaction, the catalyst used is butyl titanate
Seen from the above description, the present invention is by from the pure mixed phthalic acid di-isooctyl of CTA oxidation residua and a contracting two
Ethylene glycol generation ester exchange reaction, generates pure mixed phthalic acid diglycol monoesters, and this monoesters is in high temperature, the condition of vacuum
Under there is again polycondensation reaction, obtain the pure mixed phthalic acid diglycol polyester of the various demand degree of polymerization, replace saturated two
Unit's acid and dihydroxylic alcohols are as the raw material preparing resin.Expand pure mixed phthalic acid di-isooctyl (being only used as conventional plasticizers)
Purposes.
Detailed description of the invention
Embodiment one
1 first step, the preparation of pure mixed phthalic acid diglycol monoesters
Pure mixed phthalic acid di-isooctyl 3.9kg, catalyst and diglycol 2.968kg are put in reactor,
Being warming up to 195 DEG C, insulation reaction, isooctanol is constantly discharged, until the amount measuring the isooctanol discharged is 2.6kg, is considered as
Reaction end.In 6 hours response time, the reactant in reactor is pure mixed phthalic acid diglycol monoesters.
2, second step, the preparation of pure mixed phthalic acid diglycol polyester
Monoesters is continuously heating to 240 DEG C, and vacuum is-0.09Mpa, insulation reaction 4 hours, measures gone out by polycondensation
The amount of diglycol ethylene is 0.212kg.Cooling obtains the pure mixed phthalic acid diglycol polyester that acid-alcohol ratio is 1.3:1
Thing.
Embodiment two:
1 first step, the preparation of pure mixed phthalic acid diglycol monoesters: ibid.
2 second steps, the preparation of pure mixed phthalic acid diglycol polyester
Above monoesters is continuously heating to 240 DEG C, and vacuum is-0.095Mpa, insulation reaction 4 hours, measures by polycondensation
The amount of the diglycol gone out is 0.424kg, and cooling obtains the pure mixed phthalic acid diglycol that acid-alcohol ratio is 1.2:1
Polyester thing.
Embodiment three
1, the first step, the preparation of pure mixed phthalic acid diglycol monoesters: ibid.
2, second step, the preparation of pure mixed phthalic acid diglycol polyester:
Above monoesters is warming up to 250 DEG C, and pressure is-0.09Mpa, insulation reaction 4 hours, measures the contracting two discharged
The amount of ethylene glycol is 0.424kg, and cooling obtains the pure mixed phthalic acid diglycol polyester that acid-alcohol ratio is 1.2:1.
Embodiment four
1, the first step, the preparation of pure mixed phthalic acid diglycol monoesters: ibid.
2, second step, the preparation of pure mixed phthalic acid diglycol polyester
Above monoesters is warming up to 250 DEG C, and pressure is-0.095Mpa, is incubated 4 hours, measures the contracting diethyl discharged
The amount of glycol is 0.636kg, and cooling obtains the pure mixed phthalic acid diglycol polyester kg that acid-alcohol ratio is 1.1:1.
Embodiment five
1, the first step, the preparation of pure mixed phthalic acid diglycol monoesters: ibid.
2, second step, the preparation of pure mixed phthalic acid diglycol polyester
Above monoesters being warming up to 250 DEG C, under conditions of pressure is-0.095Mpa, reacts 5.3 hours, measurement obtains
The amount of diglycol be 0.742kg, cooling obtains pure mixed phthalic acid diglycol polyester thing kg.
Embodiment parameter list is as follows:
Monoesters diglycol all excess 40%
Result:
1, temperature at ambient pressure > 195 DEG C time, pure mixed phthalic acid di-isooctyl can be with diglycol generation ester exchange
Reaction, in about 6 hours response time, reaction i.e. can reach terminal.
2, the pressure that shades (pressure is-0.09Mpa), temperature is between 240 DEG C-260 DEG C, and the response time is the condition of 5 hours
Under, the amount of diglycol can be obtained by polycondensation and judge that gained mixes alkyd in phthalic acid diglycol polyester
Ratio, facilitates calculating and the adjustment of downstream production of resins formula.
Product quality indicator
| Project | PDT product |
| Outward appearance | Faint yellow paste |
| Ester content % | >=99.5% |
Claims (3)
1. a preparation method for phthalic acid diethylene glycol polyester, by the pure mixed phthalic acid di-isooctyl from CTA residue
Exist and under conditions of heating at catalyst, react with the diglycol of excess, generate pure mixed phthalic acid one contracting diethyl
Diol monoester and isooctanol monomer, after isooctanol is discharged, continue to rise high reaction temperature and under negative pressure state, a contracting of excess
Diethylene glycol is discharged by polycondensation, finally obtains the pure mixed phthalic acid diethylene glycol polyester of various different polymerization degree.
The preparation method of a kind of phthalic acid diethylene glycol polyester the most according to claim 1, it is characterised in that the first step
Step is: pure mixed phthalic acid di-isooctyl, catalyst and excess diglycol is put in reactor, is warming up to 195
DEG C, insulation reaction, react 5～6 hours, until isooctanol is discharged as terminal by diglycol ester exchange completely；Second step,
Being warming up to 240 DEG C, open vacuum and carry out polycondensation reaction of reducing pressure, diglycol is drained out, be discharged by metering
The amount of diglycol ethylene can accurately determine reaction end.
The preparation method of a kind of phthalic acid diethylene glycol polyester the most according to claim 1 and 2, it is characterised in that made
Catalyst be butyl titanate.
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| CN107857896B (en) * | 2017-11-16 | 2019-07-09 | 上海炼升化工股份有限公司 | A kind of ester composition and preparation method thereof from PTA substandard goods |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101126005A (en) * | 2007-06-29 | 2008-02-20 | 上海天洋热熔胶有限公司 | Polyester thermosol and preparation method thereof |
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| CN101993548A (en) * | 2010-09-30 | 2011-03-30 | 浙江嘉澳环保科技股份有限公司 | Environment-friendly composite plasticizer and preparation method |
| CN102206156B (en) * | 2011-03-08 | 2013-04-03 | 福建天大化工有限公司 | Method for comprehensive recycling of crude terephthalic acid (CTA) residue |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101126005A (en) * | 2007-06-29 | 2008-02-20 | 上海天洋热熔胶有限公司 | Polyester thermosol and preparation method thereof |
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Effective date of registration: 20200722 Address after: Room 201, building 1, Hengsen factory building, No.2 Xinsheng Road, Xinyang street, Haicang District, Xiamen City, Fujian Province Patentee after: Xiamen biyugu industry and Trade Co., Ltd Address before: Xingtai Industrial Park Economic Development Zone, Changtai County, Fujian city of Zhangzhou province 363000 Patentee before: FUJIAN TIANDA CHEMICAL Co.,Ltd. |
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Address after: 361026 Room 201, building 1, Hengsen plant, No. 2, Xinsheng Road, Xinyang street, Xiamen, Fujian Patentee after: Xiamen Jasper Valley New Material Group Co.,Ltd. Address before: 361022 Room 201, building 1, Hengsen plant, No. 2, Xinsheng Road, Xinyang street, Haicang District, Xiamen City, Fujian Province Patentee before: Xiamen biyugu industry and Trade Co.,Ltd. |
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