CN110407689A - A kind of preparation method of low molecular weight polytetrahydrofuran dibenzoate plasticiser - Google Patents
A kind of preparation method of low molecular weight polytetrahydrofuran dibenzoate plasticiser Download PDFInfo
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- CN110407689A CN110407689A CN201910600029.6A CN201910600029A CN110407689A CN 110407689 A CN110407689 A CN 110407689A CN 201910600029 A CN201910600029 A CN 201910600029A CN 110407689 A CN110407689 A CN 110407689A
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- molecular weight
- polytetrahydrofuran
- low molecular
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
Abstract
A kind of preparation method of low molecular weight polytetrahydrofuran dibenzoate plasticiser, the invention belongs to plastic additive preparation technical fields, and in particular to a kind of preparation of low molecular weight polytetrahydrofuran dibenzoate plasticiser.It using low molecular weight polytetrahydrofuran and benzoic acid as raw material, places it in flask, catalyst needed for being stirring evenly and then adding into esterification and water entrainer, back flow reaction 3-7h at a temperature of 180-210 DEG C；Catalyst is filtered out after reaction, then is neutralized through sodium bicarbonate, washing, be evaporated under reduced pressure, obtain colourless or yellowish transparent polytetrahydrofuran dibenzoate after decoloration.The present invention can be used as the plasticizer of the various kinds of resin such as PVC, PVA.
Description
Technical field
The invention belongs to plastic additive preparation fields, and in particular to a kind of low molecular weight polytetrahydrofuran dibenzoate increasing
Mould the preparation method of agent.
Background technique
According to State Statistics Bureau's data statistics: China plastic article yield in 2017 is accumulative up to 7515.5 ten thousand tons, increases by a year-on-year basis
3.4%, plasticizer is production capacity and the maximum kind of consumption figure in plastic additive, and it is total that tradition neighbour's benzene class plasticizer consumption accounts for plasticizer
80% or more of yield, since adjacent benzene class plasticizer has carcinogenic, teratogenesis, can put aside in human body and biological degradability difference etc. lacks
Point, various countries are also limited or even are forbidden to phthalic ester plasticizer in succession, and the nontoxic green of R and D as early as possible is needed
Plasticizer product.
Polytetrahydrofuran (PTMEG) is a kind of high molecular material haveing excellent performance, wherein being greater than the PTMEG of 1000 molecular weight
It is mainly used for synthesizing spandex and fiber, the PTMEG excess capacity and Downstream Products of low molecular weight is less.Low molecular weight poly- four
Hydrogen furans dibenzoate has the characteristics that small toxicity, dissolubility are strong, compatibility is good, thermal stability is good, resistant to extraction, performance with
DOP is suitable, is the accessible biggish plasticizer of packaging material for food safety, can be used as the plasticising of the various kinds of resin such as PVC, PVA
Agent prepares material.
Summary of the invention
The purpose of the present invention is to provide low molecular weight polytetrahydrofuran dibenzoates that is a kind of nontoxic and haveing excellent performance
Plasticizer preparation method.
Realize that the technical solution of the object of the invention is such that a kind of low molecular weight polytetrahydrofuran dibenzoate plasticising
The preparation method of agent is placed it in flask, is stirring evenly and then adding into using low molecular weight polytetrahydrofuran and benzoic acid as raw material
Catalyst needed for esterification and water entrainer, back flow reaction 3-7h at a temperature of 180-210 DEG C；It filters out and urges after reaction
Agent, then colourless or yellowish transparent polytetrahydrofuran two is obtained after sodium bicarbonate neutralization, washing, vacuum distillation, decoloration
Benzoic ether.
The low molecular weight polytetrahydrofuran dibenzoate average molecular weight prepared by adopting the above technical scheme is 440-520
G/mol, specific structure is as follows, n=3~4:
Plasticizer preparation method described above, specific steps are as follows:
By feed ratio be n (PTMEG): n (benzoic acid)=1:1.9~2.3 low molecular weight polytetrahydrofuran and benzoic acid in
In flask, it is stirring evenly and then adding into the Titanium Sieve Molecular Sieve of alkyd gross mass 0.05%-2% or any one in titanium zirconium molecular sieve is urged
Agent, methylbenzene water-taking agent, back flow reaction 3-7h at a temperature of 180-210 DEG C；Catalyst is filtered out after reaction, then through carbonic acid
Hydrogen sodium neutralizes, obtains colourless or yellowish transparent polytetrahydrofuran hexichol after washing, vacuum distillation, recessed soil or active carbon decoloring
Formic acid esters.
Detailed description of the invention
Fig. 1 is the infrared spectroscopy of polytetrahydrofuran of the present invention (PTMEG) and polytetrahydrofuran dibenzoate (PTMGDB)
Figure.
In figure: Absorbance is absorbance；Wavenumbers is wave number；PTMEG is polytetramethylene ether diol；
PTMGDB is polytetrahydrofuran dibenzoate.
Specific embodiment
A specific embodiment of the invention is further described by following embodiment and attached drawing:
Embodiment 1:
The polytetrahydrofuran of 234 g/mol molecular weight and benzoic acid are put into flask by acid-alcohol ratio for 1:1.9 and stirred evenly, is added
Enter the n (TiO of the 0.05% of alkyd gross mass2) : n(SiO2)=90:10 catalyst and q. s. toluene further add mixture
Heat maintains 3h to 180 DEG C；Then catalyst filtration is measured into the 440g/mol molecular weight that esterification yield is 86.3% with Buchner funnel
Polytetrahydrofuran dibenzoate crude product, then in the sodium bicarbonate aqueous solution of 2 wt.% and washing after, vacuum pump pressure
Remaining water and water entrainer equal solvent are distilled out, finally obtains polytetrahydrofuran dibenzoate with activity carbon decoloring.
Embodiment 2:
The polytetrahydrofuran of 306 g/mol molecular weight and dibenzoate is equal for stirring in 1:2.3 investment flask by acid-alcohol ratio
It is even, 2% n (TiO of alkyd gross mass is added2) : n(ZrO2)=90:10 catalyst and q. s. toluene, mixture is further
210 DEG C are heated to, 7h is maintained；Then catalyst filtration is measured into 520 g/mol points that esterification yield is 99.6% with Buchner funnel
Son amount polytetrahydrofuran dibenzoate crude product, then in the sodium bicarbonate aqueous solution of 0.5 wt.% and wash after, vacuum pump
It is evaporated under reduced pressure out remaining water and water entrainer equal solvent, finally obtains polytetrahydrofuran dibenzoate with recessed soil decoloration.
As shown in Figure 1, the infrared spectrum analysis carried out to low molecular weight polytetrahydrofuran dibenzoic acid ester structure:
3416cm-1The broad peak of left and right is the OH absorption peak to form hydrogen bond association state, 1106cm-1It is absorbed for the stretching vibration of C-O-C
Peak, in PTMGDB, 1711 cm-1For the stretching vibration absworption peak of ester carbonyl group, and in 1272 cm-1There is the asymmetry of C-O-C to stretch
Contracting vibration strong absworption peak and 1175 cm-1The symmetrical stretching vibration at place illustrates there is the generation of esters structural material, in 707 cm-1It is left
The right side is the monosubstituted absorption peak of phenyl ring, illustrates that polytetrahydrofuran dibenzoate is successfully prepared.
Embodiment described above, preferable specific embodiment only of the invention, the scope of protection of the present invention is not limited to this,
Anyone skilled in the art can obviously obtain in the technical foundation that the claims in the present invention disclose
The simple change or equivalent replacement of technical solution of the present invention are fallen within the protection scope of the present invention.
Claims (3)
1. a kind of preparation method of low molecular weight polytetrahydrofuran dibenzoate plasticiser, it is characterised in that: with low molecular weight
Polytetrahydrofuran and benzoic acid are raw material, are placed it in flask, catalyst needed for being stirring evenly and then adding into esterification and
Water entrainer, back flow reaction 3-7h at a temperature of 180-210 DEG C；Catalyst is filtered out after reaction, then neutralized through sodium bicarbonate,
Colourless or yellowish transparent polytetrahydrofuran dibenzoate is obtained after washing, vacuum distillation, decoloration.
2. the preparation method of plasticizer according to claim 1, which is characterized in that low molecular weight polytetrahydrofuran dibenzoic acid
Ester average molecular weight is 440-520 g/mol, and low molecular weight polytetrahydrofuran dibenzoate specific structure is as follows, n=3~4:
。
3. the preparation method of plasticizer according to claim 1, it is characterised in that: low molecular weight polytetrahydrofuran (PTMEG)
Molar ratio with benzoic acid is 1:1.9-2.3；The catalyst for esterification reaction is in Titanium Sieve Molecular Sieve or titanium zirconium molecular sieve
Any one, dosage is the 0.05%-2% of alkyd gross mass；Esterification water entrainer is toluene, and decolorising agent is recessed soil or activity
Any one in charcoal.
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| CN201910600029.6A CN110407689A (en) | 2019-07-04 | 2019-07-04 | A kind of preparation method of low molecular weight polytetrahydrofuran dibenzoate plasticiser |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007118826A1 (en) * | 2006-04-18 | 2007-10-25 | Basf Se | Thermoplastic plastic materials, particularly polyurethane, containing polytetrahydrofuran-ester as a softening agent |
| JP2010285474A (en) * | 2009-06-09 | 2010-12-24 | Sanyo Chem Ind Ltd | Thermoplastic polyurethane resin powder molding material and molded product |
| CN103012127A (en) * | 2011-09-28 | 2013-04-03 | 中国石油化工股份有限公司 | Method for subjecting phenol and dimethyl ester to transesterification |
| CN103086891A (en) * | 2013-02-22 | 2013-05-08 | 厦门大学 | Preparation method of plasticizer diethylene glycol dibenzoate |
| CN107778475A (en) * | 2017-10-20 | 2018-03-09 | 天津普莱化工技术有限公司 | Nontoxic plasticiser of PTMEG classes and preparation method thereof |
| CN108752803A (en) * | 2018-06-21 | 2018-11-06 | 江南大学 | A kind of preparation method and application for the environmentally friendly polyester plasticizer of adipic acid series that molecular weight is different and controllable |
-
2019
- 2019-07-04 CN CN201910600029.6A patent/CN110407689A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007118826A1 (en) * | 2006-04-18 | 2007-10-25 | Basf Se | Thermoplastic plastic materials, particularly polyurethane, containing polytetrahydrofuran-ester as a softening agent |
| JP2010285474A (en) * | 2009-06-09 | 2010-12-24 | Sanyo Chem Ind Ltd | Thermoplastic polyurethane resin powder molding material and molded product |
| CN103012127A (en) * | 2011-09-28 | 2013-04-03 | 中国石油化工股份有限公司 | Method for subjecting phenol and dimethyl ester to transesterification |
| CN103086891A (en) * | 2013-02-22 | 2013-05-08 | 厦门大学 | Preparation method of plasticizer diethylene glycol dibenzoate |
| CN107778475A (en) * | 2017-10-20 | 2018-03-09 | 天津普莱化工技术有限公司 | Nontoxic plasticiser of PTMEG classes and preparation method thereof |
| CN108752803A (en) * | 2018-06-21 | 2018-11-06 | 江南大学 | A kind of preparation method and application for the environmentally friendly polyester plasticizer of adipic acid series that molecular weight is different and controllable |
Non-Patent Citations (2)
| Title |
|---|
| 蒋平平主编: "《环保增塑剂》", 31 October 2009, 国防工业出版社 * |
| 陆敏山: "钛硅分子筛催化制备聚丁二酸丁二醇酯的研究", 《天津化工》 * |
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Application publication date: 20191105 |