CN1566174A - Process for preparing polyester for light stabilizer - Google Patents
Process for preparing polyester for light stabilizer Download PDFInfo
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- CN1566174A CN1566174A CN 03129190 CN03129190A CN1566174A CN 1566174 A CN1566174 A CN 1566174A CN 03129190 CN03129190 CN 03129190 CN 03129190 A CN03129190 A CN 03129190A CN 1566174 A CN1566174 A CN 1566174A
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Abstract
The invention discloses a process for preparing polyester for light stabilizer having a composition formula (I), wherein the straight chain hydroxy piperidine alcohol and straight chain binary acidic ester are monomer raw materials, which are subject to polycondensation reaction at the presence of organic acid esters, in the polycondensation reaction system phosphorous acid 3(2, 4-ditertiary butyl phenyl) ester is charged in as anti-oxidant. In formula I, R is ethylene or trimethylene, R1 is C3-C5 straight carbon chain, R2 is methyl or ethyl.
Description
Technical field
The present invention relates to a kind of preparation method who prepares polyester by the polycondensation of the pure and mild straight chain diester of straight chain hydroxy piperidine.
Background technology
The polyester that is obtained by polycondensation by the pure and mild straight chain diester of straight chain hydroxy piperidine is a kind of high molecular hindered amine light stabilizer of excellent property, it is widely used in the various plastics such as polypropylene, polyethylene, polystyrene, ABS resin, polyurethane, polyoxymethylene and polyester elastomer, and the plastics that add this photostabilizer show excellent anti ageing property and sour environment adaptability.Higher during the polycondensation of the pure and mild straight chain diester of straight chain hydroxy piperidine owing to polymeric reaction temperature, reaction system is newly-generated superpolymer thermal destruction and the thermooxidizing that simultaneous is a large amount of in the polycondensation process in the presence of oxygen, thermal destruction not only reduces the molecular weight of resultant, and can make degradation product generation hinge and branching, generate cotton-shaped gel.Thermooxidizing then can destroy the characteristic group of resultant, influences the light stabilising effect of product, and thermooxidizing is that reactant darkens at the shown physical features of resultant.This contain degraded and the photostabilizer of oxidation impurities not only the light stabilising effect descend significantly, but also can respond the appearance luster of plastics, so can not be applied to plastics that transparency is had relatively high expectations.In order to improve the quality of photostabilizer, the normal nitrogen envelope method that adopts is isolated reaction system and oxygen in traditional production technique, introduce as European patent EP 225850 and Japanese Patent J60-36529, the carrying out of thermooxidizing when though this has alleviated polycondensation to a certain extent, but increased the complicacy of polycondensation technology and equipment simultaneously, improved production cost.In addition, because polycondensation process is divided into normal pressure and two stages of decompression usually, adopt nitrogen envelope method to be difficult to avoid fully the generation of thermal destruction and thermooxidizing at decompression phase.
Summary of the invention
The invention provides a kind of method for preparing photostabilizer usefulness polyester by the pure and mild straight chain diester of straight chain hydroxy piperidine by polycondensation, the technical problem that it will solve is to avoid the generation of thermal destruction and thermooxidizing in the polycondensation, and does not increase production cost substantially.
Below be the technical scheme that the present invention solves the problems of the technologies described above:
A kind of preparation method with photostabilizer of structural formula I with polyester, this preparation method is a raw material monomer with the pure and mild straight chain diester with structural formula II I of straight chain hydroxy piperidine with structural formula II, carries out polycondensation in the presence of the catalyzer organic titanate.The monomeric molar ratio of the pure and mild straight chain diester of straight chain hydroxy piperidine is 1: 1～1: 1.3, and catalyst levels is counted 0.1～0.5mol% with straight chain hydroxy piperidine alcohol.Two sections of polycondensation of polycondensation normal pressure and decompression polycondensations, the normal pressure polycondensation time is 1～5 hour, and the decompression polycondensation time is 3～7 hours, and vacuum tightness is that 0.094～0.1Mpa. polymeric reaction temperature is 140～200 ℃.Add oxidation inhibitor tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester in polycondensation reaction system, add-on is 0.1～2.0wt% of reaction raw materials total amount.
Structural formula I, II and III are respectively:
Structural formula I:
Structural formula II:
Structural formula II I:
Wherein R is ethylene or trimethylene, R
1Be C
3～C
5The straight chain carbochain, R
2Be methyl or ethyl, n is 20～50 positive integer.
Oxidation inhibitor tricresyl phosphite in the above-mentioned polycondensation reaction system (2, the 4-di-tert-butyl-phenyl) add-on of ester is preferably 0.2～1.0wt% of reaction raw materials total amount;
Among said structure formula I, II and the III, R is preferably ethylene, R
1Be preferably C
4The straight chain carbochain, R
2Be preferably methyl; And catalyzer is preferably butyl (tetra) titanate or isopropyl titanate.
In the prior art, use oxidation inhibitor suppresses polymkeric substance generation thermal destruction and thermooxidizing is a kind of method relatively more commonly used, but because photostabilizer is the very complicated fine chemical product of a kind of utilisation technology, very small amount of impurity all can influence its result of use.Key of the present invention is to have searched out a kind of suitable oxidation inhibitor, forms combination comparatively closely between its energy and high-polymer molecular, can suppress newly-generated superpolymer effectively and produce thermal destruction and thermooxidizing in polycondensation process.The contriver also finds after by experiment, this oxidation inhibitor is stored in the result of use that not only can not influence photostabilizer as the combination of the superpolymer formation of photostabilizer, and in the following process process, also have the effect that prevents photostabilizer generation thermooxidizing, make photostabilizer become more stable and long-acting.Therefore, advantage compared with prior art of the present invention is the manufacturing cost that does not increase photostabilizer substantially, and during polycondensation owing to there are not side reactions such as thermal destruction and thermooxidizing, the photostabilizer product that obtains has colourless long lasting characteristics, is particularly useful for water white plastics.
Below will the invention will be further described by specific embodiment, because key of the present invention is the use of oxidation inhibitor, other processing condition and the prior art of polycondensation process are basic identical, so the embodiment emphasis is to the description of oxidation inhibitor use.
Embodiment
[embodiment 1～5]
Raw material monomer hydroxyethyl piperidine alcohol (PT) and dimethyl succinate (DME) are pressed molar ratio PT: DME=1: 1.1 drop in the polycondensation vessel, and add oxidation inhibitor tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, and added quantity of antioxidant is in the reaction raw materials total amount.About mixture heating up to 130 ℃, keep half an hour under miscible state, add the catalyst Ti acid butyl ester, the add-on of catalyzer is counted 0.3mol% with hydroxyethyl piperidine alcohol.Reacted 2～5 hours under the condition of normal pressure and 150～170 ℃, system is discharged in by product lower alcohol distillation condensation in the reaction process.When no longer including the lower alcohol outflow in the question response, system is vacuumized, control vacuum tightness is 0.094～0.1MPa, reacts promptly to get the photostabilizer polyester product in 3～6 hours under 140～170 ℃ of temperature temperature, and this polyester has following structural formula:
N is 20～50 positive integer.
[comparative example]
Do not add oxidation inhibitor tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester in the reaction system, all the other together
Embodiment 1～5.
It is 1 listed that the add-on of each embodiment and comparative example oxidation inhibitor, the colourity of the photostabilizer product that obtains see Table.
Table 1.
| Added quantity of antioxidant (wt%) | The colourity of product | |
| Embodiment 1 | ????0.2 | ????1.5 |
| Embodiment 2 | ????0.3 | ????1.0 |
| Embodiment 3 | ????0.5 | ????0.5 |
| Embodiment 4 | ????1.0 | ????0.5 |
| Embodiment 5 | ????1.5 | ????0.5 |
| Comparative example | ????0 | ????18 |
Claims (4)
1, a kind of preparation method with photostabilizer of structural formula I with polyester, this preparation method is a raw material monomer with the pure and mild straight chain diester with structural formula II I of straight chain hydroxy piperidine with structural formula II, in the presence of the catalyzer organic titanate, carry out polycondensation, the monomeric molar ratio of the pure and mild straight chain diester of straight chain hydroxy piperidine is 1: 1～1: 1.3, catalyst levels is counted 0.1～0.5mol% with straight chain hydroxy piperidine alcohol, two sections of polycondensation of polycondensation normal pressure and decompression polycondensations, the normal pressure polycondensation time is 1～5 hour, the decompression polycondensation time is 3～7 hours, vacuum tightness is 0.094～0.1MPa, temperature of reaction is 140～200 ℃, it is characterized in that adding in the polycondensation reaction system oxidation inhibitor tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, its add-on is 0.1～2.0wt% of reaction raw materials total amount, structural formula I, II and III are respectively:
Structural formula I:
Structural formula II:
Structural formula II I:
Wherein R is ethylene or trimethylene, R
1Be C
3～C
5The straight chain carbochain, R
2Be methyl or ethyl, n is 20～50 positive integer.
2, photostabilizer according to claim 1 is characterized in that with the preparation method of polyester the add-on of oxidation inhibitor tricresyl phosphite in the polycondensation reaction system (2, the 4-di-tert-butyl-phenyl) ester is 0.2～1.0wt% of reaction raw materials total amount.
3, photostabilizer according to claim 1 is characterized in that described R is an ethylene, R with the preparation method of polyester
1Be C
4The straight chain carbochain, R
2Be methyl.
4, photostabilizer according to claim 1 is characterized in that with the preparation method of polyester described catalyzer is butyl (tetra) titanate or isopropyl titanate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03129190 CN1282682C (en) | 2003-06-12 | 2003-06-12 | Process for preparing polyester for light stabilizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03129190 CN1282682C (en) | 2003-06-12 | 2003-06-12 | Process for preparing polyester for light stabilizer |
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| Publication Number | Publication Date |
|---|---|
| CN1566174A true CN1566174A (en) | 2005-01-19 |
| CN1282682C CN1282682C (en) | 2006-11-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03129190 Expired - Fee Related CN1282682C (en) | 2003-06-12 | 2003-06-12 | Process for preparing polyester for light stabilizer |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101063030B (en) * | 2006-04-30 | 2010-08-18 | 上海新天和树脂有限公司 | High molecular weight unsaturated polyester binding agent |
| CN101121776B (en) * | 2006-08-08 | 2010-10-06 | 远东新世纪股份有限公司 | Method for preparing polyester using non-antimony catalyst |
| CN104592504A (en) * | 2015-01-21 | 2015-05-06 | 苏州飞翔新材料研究院有限公司 | Method for preparing light stabilizer 622 |
| CN107955144A (en) * | 2017-10-25 | 2018-04-24 | 江汉大学 | A kind of preparation method of condensation polymer type Polymeric hindered amine light stabilizer |
-
2003
- 2003-06-12 CN CN 03129190 patent/CN1282682C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101063030B (en) * | 2006-04-30 | 2010-08-18 | 上海新天和树脂有限公司 | High molecular weight unsaturated polyester binding agent |
| CN101121776B (en) * | 2006-08-08 | 2010-10-06 | 远东新世纪股份有限公司 | Method for preparing polyester using non-antimony catalyst |
| CN104592504A (en) * | 2015-01-21 | 2015-05-06 | 苏州飞翔新材料研究院有限公司 | Method for preparing light stabilizer 622 |
| CN107955144A (en) * | 2017-10-25 | 2018-04-24 | 江汉大学 | A kind of preparation method of condensation polymer type Polymeric hindered amine light stabilizer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1282682C (en) | 2006-11-01 |
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Granted publication date: 20061101 Termination date: 20110612 |