CN102649839A - Emulsion type polyester catalyst, and preparation method and application thereof - Google Patents
Emulsion type polyester catalyst, and preparation method and application thereof Download PDFInfo
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- CN102649839A CN102649839A CN2012101213646A CN201210121364A CN102649839A CN 102649839 A CN102649839 A CN 102649839A CN 2012101213646 A CN2012101213646 A CN 2012101213646A CN 201210121364 A CN201210121364 A CN 201210121364A CN 102649839 A CN102649839 A CN 102649839A
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Abstract
The invention discloses an emulsion type polyester catalyst, and a preparation method and an application thereof and belongs to the technical field of a chemical catalyst. The emulsion type polyester catalyst is composed of titanium compound, phosphorus compound, emulsifying agent, acid, water and alcohol. The emulsion type polyester catalyst can be applied to the production of a polyester material. The invention has the advantages that a nanometer emulsion type polyester poly-condensed catalyst with excellent dispersing property is prepared under the high-speed stirring assistance of the emulsifying agent or the ultrasonic action, the technology is simple, the high-temperature treatment is unnecessary, and meanwhile, the defects of the conventional solid catalyst, such as, inferior dissolubility, poor activity caused by uneven dispersing, are overcome.
Description
Technical field
The present invention relates to a kind of polyester polycondensation catalyst, preparation method and application thereof, belong to chemical catalyst area.
Background technology
Polyester is one type of important macromolecular material; Since the thirties in 20th century, synthesized polymer material truly came out; Polyester is one of focus of macromolecular material research always; The important source material used of all trades and professions especially, polyester scientific research and technology progressive each time all made significant contribution for the world industry development of technology.
In the polyester production process, catalyzer is the important factor of decision quality product.At present, the main flow polyester polycondensation catalyst comprises antimony system and titanium system two big classes, also has germanium system, tin system and aluminium system etc. in addition.Antimony is that polycondensation catalyst mainly comprises titanium dioxide three antimony, antimony glycol etc., has advantages of high catalytic activity, polyester product color and luster, better performances.But also there are some significant disadvantages in antimony-based catalyst when being widely used because antimony compounds itself has certain toxicity, occurring in nature again with the arsenic coexistence of severe toxicity, so it is applied in and has received many restrictions to a certain extent.
At present; The application of Titanium series catalyst is more and more wider; Conventional Titanium series catalyst mainly is some organic cpds commonly used, but these catalyzer are because not anti-hydrolysis or activity can not get effective control in whole catalyzed reaction; In reaction, exist poor stability, catalyze side reactions aggravation, problems such as the jaundice of synthetic polyester product, muddiness.For overcoming above shortcoming, the research of Novel Titanium series catalysts in recent years is very active, and multiple follow-on catalyzer is developed.
The C-94 of development is a kind of TiO2/SiO among the Germany Acordis PCT WO of house journal 95/18839
2Composite solid catalyzer, catalytic activity are at least 6-8 times of antimony-based catalyst, and product colourity is good.Yi Shi Man has applied for a Titanium series catalyst patent of invention in 1994, the catalystsystem that adopts alkyl titanate and phosphorus compound, cobalt cpd, toning agent to form, and catalytic activity is 6.6 times of Antimony Trioxide: 99.5Min.The titanium phosphorus complex polyester catalyst (US6593447) of Japan Supreme Being people company development is generated by titanium compound and phosphorus compound reaction, utilizes the strong coordination of phosphorus to improve the stable and active of titanium.Wherein titanium compound can be the product of titan-alkoxide, titan-alkoxide and carboxylic acid or anhydride reaction, and is better with the polyester quality that this catalyzer makes, and solved the problem of polyester granulate flavescence, and simultaneously made fiber dyeability is good, and bright in colour.The active site of the Johnson&Matthey company applied molecular designing technique control titanium of Britain synthesizes two kinds of novel catalyzer, and is active through suitable reduction titanium molecule, improved with Titanium series catalyst synthetic polyester product form and aspect and thermostability.In addition, patent CN101148500A discloses a kind of preparation method of titanium series polyester catalyst, and is main through the preparation liquid-phase catalyst, improve the dispersion effect of catalyzer in polymerization system, but PET hue is still not ideal enough.CN1138339 discloses and has adopted titanic acid ester and silicon ester cohydrolysis to prepare the method for titanium series polyester catalyst, and this method synthetic catalyzer has higher activity, but the dispersion effect in divalent alcohol is relatively poor, is unfavorable for bringing into play higher activity.CN101565499A has announced a kind of based on TiO
2/ SiO
2The high activated catalyst of colloidal sol; Through adding nitrogenous or P contained compound coordinate method, effectively improved the form and aspect of polyester product, but this catalyzer also is a solid; Influenced by the granules of catalyst size bigger for dispersiveness in divalent alcohol, and catalytic activity is wayward with stability.
In a word, the ubiquitous problem of Titanium series catalyst comprises that side reaction is many in (1) polymerization process, hue difference at present.(2) need pyroprocessing in the catalyst preparation process, handle the back and use with the solid particulate state, therefore bad dispersibility in polymerization system influences active and constant product quality property; (3) the catalyzer universality is poor, and when catalytic manufacture of aromatic-aliphatic polyester, temperature of reaction is too high because catalyzer to inconsistent with the aliphatic monomer catalytic activity of aromatic monomer, causes, overlong time, polymer molecular weight are not high.
Summary of the invention
The object of the present invention is to provide a kind of nano emulsion type polyester catalyst, method for preparing catalyst and application thereof, this emulsion catalyst has good dispersiveness and polymerization stability.Catalyzer good dispersiveness in polymerization system, can shorter reaction in the time highly active catalysis polycondensation prepare the high-molecular weight polyester; Side reaction is few in the polymerization process, and the polymerisate form and aspect are good.
A kind of emulsion-type polyester catalyst, said catalyzer is made up of following raw materials by weight percent:
Titanium compound: 1～45%;
Phosphorus compound: 0.5～30%;
Emulsifying agent: 1～15%;
Acid: 0.5～10%;
Water: 20～80%;
Alcohol: 5～70%;
Among the present invention, described titanium compound is one or more in titanium oxide, titanous chloride, titanium tetrachloride, tetra-n-butyl titanate, titanium isopropylate, metatitanic acid tetramethyl ester, the tetraethyl titanate.
Among the present invention, described phosphorus compound is one or more in triphenyl phosphite, dibutyl phosphite, phosphorous acid diisobutyl ester, trimethyl phosphite 99, triphenylphosphate, triethyl phosphate, tricresyl phosphate propyl ester, the tricresyl phosphate isopropyl ester.
Among the present invention, described emulsifying agent is one or more in diethylolamine, lauryl amine, propylene glycol fatty acid ester, glyceryl ester, sorbyl alcohol liver fatty acid ester, oleic acid, the sucrose fatty ester.
Among the present invention, described alcohol is methyl alcohol, ethanol, terepthaloyl moietie, 1,2-Ucar 35,1, one or more in ammediol, the butyleneglycol.
Among the present invention, described acid is a kind of in hydrochloric acid, sulfuric acid, nitric acid, the phosphoric acid.
Further, the preferred concentrated hydrochloric acid of described hydrochloric acid, described vitriolic concentration preferred 5～25%.
Among the present invention; Said Preparation of catalysts method is that titanium compound, phosphorus compound, emulsifying agent, acid, water, alcohol are mixed; Be uniformly dispersed through high-speed stirring or ultrasonic mode; Wherein, said high-speed stirring is under the rotating speed of 5000～15000rpm, to stir 0.5～12h, and said ultrasonic processing is ultrasonic 0.5～3h.
Among the present invention, said catalyzer is used for catalytic manufacture of aromatic adoption ester, aliphatic polyester or fragrant-aliphatic series copolyesters.
Further, said aromatic polyester, aliphatic polyester or fragrant-aliphatic series copolyesters are the copolymerization product of diprotic acid and divalent alcohol.
Advantage of the present invention is the nanoemulsions polyester polycondensation catalyst for preparing good dispersivity through auxiliary high-speed stirring of emulsifying agent or ultrasonication; Technology is simple; Need not pyroprocessing, overcome the shortcomings such as poor activity that common solid catalyst is poorly soluble, disperse inequality to cause simultaneously.
Embodiment
Below in conjunction with embodiment the present invention is further described, but protection scope of the present invention not only is confined to embodiment.
Embodiment 1:
With titanous chloride 5%, water 45%, ethanol 42%; Concentrated hydrochloric acid 0.5%, triphenyl phosphite 2.5%, lauryl amine 5% joins in the reactor drum; High-speed stirring is 6 hours under the rotating speed of 8000rpm, places after 48 hours, continues to stir 2h; Promptly prepared 1# emulsion-type polyester polycondensation catalyst, it is synthetic directly to be used for catalyst, polyester.
Embodiment 2:
With tetra-n-butyl titanate 10%, water 55%, butyleneglycol 25%; Phosphatase 11 %, dibutyl phosphite 2%, diethylolamine 7% joins in the reactor drum; High-speed stirring is 8 hours under the rotating speed of 10000rpm, places after 48 hours, continues to stir 2h; Promptly prepared 2# emulsion-type polyester polycondensation catalyst, it is synthetic directly to be used for catalyst, polyester.
Embodiment 3:
With titanium tetrachloride 8%, water 10%, terepthaloyl moietie 65%; Concentrated hydrochloric acid 2%, phosphorous acid diisobutyl ester 5%, propylene glycol fatty acid ester 10% joins in the reactor drum; High-speed stirring is 5 hours under the rotating speed of 7000rpm, places after 48 hours, continues to stir 2h; Promptly prepared 3# emulsion-type polyester polycondensation catalyst, it is synthetic directly to be used for catalyst, polyester.
Embodiment 4:
With titanium isopropylate 20%, water 49.5%, terepthaloyl moietie 15%; Concentrated hydrochloric acid 0.5%, trimethyl phosphite 99 5%, sucrose fatty ester 10% joins in the reactor drum; High-speed stirring is 5 hours under the rotating speed of 15000rpm, places after 48 hours, continues to stir 2h; Promptly prepared 4# emulsion-type polyester polycondensation catalyst, it is synthetic directly to be used for catalyst, polyester.
Embodiment 5
In the 20L polymerization reaction kettle, add the 4.98Kg terephthalic acid, 2.50Kg terepthaloyl moietie, displacement nitrogen after stirring, is warming up to 210～255 ℃, under 0.3MPa pressure, carries out esterification, reaches theoretical value up to aquifer yield, and esterification finishes.The 1#, 2#, 3# or the 4# catalyzer that add above-mentioned preparation, 255～275 ℃ of reactions down, slowly decompression is lower than 70Pa until pressure, reacts 2 hours, obtains polyester product and is labeled as I, II, III and IV respectively.Analytical results is as shown in table 1.
The contrast of table 1 polymerization results
Embodiment 6
In the 20L polymerization reaction kettle, add to 3.3 1Kg hexanodioic acids, 1.25Kg terephthalic acid, 3.30Kg 1 4-butyleneglycol, displacement nitrogen; After stirring, be warming up to 210～245 ℃, under 0.2MPa pressure, carry out esterification; Reach theoretical value up to aquifer yield, esterification finishes.The 1# and the 2# catalyzer that add above-mentioned preparation, 245～265 ℃ of reactions down, slowly decompression is lower than 70Pa until pressure, reacts 2 hours, obtains polyester product V and VI.
Embodiment 7
In the 20L polymerization reaction kettle, add 2.67Kg Succinic Acid, 1.25Kg terephthalic acid, 2.81Kg 1, the 2-Ucar 35, displacement nitrogen after stirring, is warming up to 210～245 ℃ and carries out esterification, reaches theoretical value up to aquifer yield, and esterification finishes.The 3# and the 4# catalyzer that add above-mentioned preparation, 245～265 ℃ of reactions down, slowly decompression is lower than 70Pa until pressure, reacts 2 hours, obtains polyester product VII and VIII.
Embodiment 8
In the 20L polymerization reaction kettle, add 3.67Kg Succinic Acid, 3.30Kg 1, the 4-butyleneglycol, displacement nitrogen after stirring, is warming up to and carries out esterification under 210 ℃, reaches theoretical value up to aquifer yield, and esterification finishes.The 1# and the 2# catalyzer that add above-mentioned preparation, 235～255 ℃ of reactions down, slowly decompression is lower than 70Pa until pressure, reacts 2 hours, obtains polyester product IX and X.
The contrast of table 2 polymerization results
What should explain at last is: above embodiment only in order to the explanation the present invention and and unrestricted technical scheme described in the invention; Therefore, although this specification sheets has carried out detailed explanation to the present invention with reference to each above-mentioned embodiment,, those of ordinary skill in the art should be appreciated that still and can make amendment or be equal to replacement the present invention; And all do not break away from the technical scheme and the improvement thereof of the spirit and scope of the present invention, and it all should be encompassed in the claim scope of the present invention.
Claims (10)
1. an emulsion-type polyester catalyst is characterized in that, said catalyzer is made up of following raw materials by weight percent:
Titanium compound: 1～45%;
Phosphorus compound: 0.5～30%;
Emulsifying agent: 1～15%;
Acid: 0.5～10%;
Water: 20～80%;
Alcohol: 5～70%.
2. catalyzer according to claim 1 is characterized in that, described titanium compound is one or more in titanium oxide, titanous chloride, titanium tetrachloride, tetra-n-butyl titanate, titanium isopropylate, metatitanic acid tetramethyl ester, the tetraethyl titanate.
3. catalyzer according to claim 1; It is characterized in that described phosphorus compound is one or more in triphenyl phosphite, dibutyl phosphite, phosphorous acid diisobutyl ester, trimethyl phosphite 99, triphenylphosphate, triethyl phosphate, tricresyl phosphate propyl ester, the tricresyl phosphate isopropyl ester.
4. catalyzer according to claim 1 is characterized in that, described emulsifying agent is one or more in diethylolamine, lauryl amine, propylene glycol fatty acid ester, glyceryl ester, sorbyl alcohol liver fatty acid ester, oleic acid, the sucrose fatty ester.
5. catalyzer according to claim 1 is characterized in that, described alcohol is methyl alcohol, ethanol, terepthaloyl moietie, 1,2-Ucar 35,1, one or more in ammediol, the butyleneglycol.
6. catalyzer according to claim 1 is characterized in that, described acid is a kind of in hydrochloric acid, sulfuric acid, nitric acid, the phosphoric acid.
7. catalyzer according to claim 6 is characterized in that, described hydrochloric acid is concentrated hydrochloric acid, and described vitriolic concentration is 5～25%.
8. the preparation method of an emulsion-type polyester catalyst; It is characterized in that; Described preparation method mixes titanium compound, phosphorus compound, emulsifying agent, acid, water, alcohol, and the mode of handling through high-speed stirring or ultrasonic echography is uniformly dispersed, wherein; Described high-speed stirring is under the rotating speed of 5000～15000rpm, to stir 0.5～12h, and described ultrasonic processing is ultrasonic 0.5～3h.
9. the application of an emulsion-type polyester catalyst is characterized in that, described catalyzer is used for catalytic manufacture of aromatic adoption ester, aliphatic polyester or fragrant-aliphatic series copolyesters.
10. Application of Catalyst according to claim 9 is characterized in that, described aromatic polyester, aliphatic polyester or fragrant-aliphatic series copolyesters are the copolymerization product of diprotic acid and divalent alcohol.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103074386A (en) * | 2012-12-28 | 2013-05-01 | 陕西科技大学 | Method for recycling aliphatic polyester in ionic liquid through enzyme catalysis and performing repolymerization |
| JP2015063672A (en) * | 2013-08-29 | 2015-04-09 | 三菱化学株式会社 | Aliphatic polyester resin composition |
| CN113321794A (en) * | 2021-04-16 | 2021-08-31 | 浙江桐昆新材料研究院有限公司 | Preparation method and application of titanium-phosphorus catalyst for polyester synthesis |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1402653A (en) * | 1999-12-02 | 2003-03-12 | 纳幕尔杜邦公司 | Esterification catalyst compositions and use thereof |
| CN1644601A (en) * | 2004-12-29 | 2005-07-27 | 中国石化集团天津石油化工公司 | Preparation of liquid titanium polyester polycondensation catalyst |
| CN1962724A (en) * | 2005-11-11 | 2007-05-16 | 中国石油化工股份有限公司 | Catalyst for preparing polyester |
-
2012
- 2012-04-24 CN CN2012101213646A patent/CN102649839A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1402653A (en) * | 1999-12-02 | 2003-03-12 | 纳幕尔杜邦公司 | Esterification catalyst compositions and use thereof |
| CN1644601A (en) * | 2004-12-29 | 2005-07-27 | 中国石化集团天津石油化工公司 | Preparation of liquid titanium polyester polycondensation catalyst |
| CN1962724A (en) * | 2005-11-11 | 2007-05-16 | 中国石油化工股份有限公司 | Catalyst for preparing polyester |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103074386A (en) * | 2012-12-28 | 2013-05-01 | 陕西科技大学 | Method for recycling aliphatic polyester in ionic liquid through enzyme catalysis and performing repolymerization |
| CN103074386B (en) * | 2012-12-28 | 2015-01-28 | 陕西科技大学 | Method for recycling aliphatic polyester in ionic liquid through enzyme catalysis and performing repolymerization |
| JP2015063672A (en) * | 2013-08-29 | 2015-04-09 | 三菱化学株式会社 | Aliphatic polyester resin composition |
| CN113321794A (en) * | 2021-04-16 | 2021-08-31 | 浙江桐昆新材料研究院有限公司 | Preparation method and application of titanium-phosphorus catalyst for polyester synthesis |
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Application publication date: 20120829 |