CN1962715A - Method for making polyester - Google Patents
Method for making polyester Download PDFInfo
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- CN1962715A CN1962715A CN 200510110291 CN200510110291A CN1962715A CN 1962715 A CN1962715 A CN 1962715A CN 200510110291 CN200510110291 CN 200510110291 CN 200510110291 A CN200510110291 A CN 200510110291A CN 1962715 A CN1962715 A CN 1962715A
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Abstract
The invention discloses a preparing method of polyester catalyst, which is characterized by the following: adopting the reacting product of titanium compound, phosphor compound and polyol as dicarboxylic acids and reacting catalyst of alkylidene glycol; fitting for industrial manufacturing course of polymer.
Description
Technical field
The present invention relates to a kind of preparation method of polyester.
Background technology
Polyethylene terephthalate is a kind of important industrial raw material, can be widely used in materials such as fiber, sheet, film.
The research autopolyester of polyester catalyst had never stopped since coming out, and industrial production and the more polyester catalyst of research mainly are the catalyzer of antimony, germanium and three series of titanium at present, and wherein using most often, antimony-based catalyst (comprises Sb
2O
3, SbAc
3With antimony glycol etc.), 90% polyester is produced by antimony-based catalyst in the world at present.The shortcoming of antimony-based catalyst is: low activity; Heavy metal catalyst pollutes environment; The polymer belt grey.The germanium series catalysts has satisfactory stability, and the side reaction that causes in reaction process is less, and made PET hue is good, but because resource is few, costs an arm and a leg.Titanium series catalyst has high reactivity, but the polyester that Titanium series catalyst makes exists poor stability and goods yellowing, muddy problem, thereby is never used on a large scale.
More and more pay close attention in the whole world under the background of environment for human survival, the production and selling of green textiles will be the trend of following textiles development, can the developed country that with the European Union is representative reach green textile standards more and more as the condition that comes into the market, development through 10 years, European Union's eco-label (Eco-label) is approved by the human consumer of European Union gradually, the pouplarity of sticking on the Ecolabelling commodity also improves gradually, many downstream manufacturers, especially sportwear manufacturer is very interested in not stibiated polyester, and it is not stibiated that this trend makes that production of polyester producer is devoted to exploitation, eco-friendly catalyzer.
Titanium series catalyst is because it is active high, do not contain heavy metal, thereby be subjected to the favor of numerous polyester producers, Titanium series catalyst also is the research focus of polyester catalyst in recent years, company more than ten American-European and Japan has carried out the development of titanium series polyester catalyst, the domestic research work that also has many companies and research institution to carry out this respect of China.Along with the development of molecular designing and catalyst preparation technology, people expectation is carried out modification on traditional titanate catalyst basis, develop environmental protection, highly active and can overcome the Novel Titanium series catalysts of traditional in the past titanium series polyester catalyst shortcoming.Existing many at present companies announce to have succeeded in developing the Novel Titanium series polyester catalyst of excellent property, and commercially produced product can be provided.This Sustainable development to polyester industrial will bring great promoter action.
2-hydroxycarboxylic acid compounds such as lactic acid, citric acid, oxysuccinic acid, tartrate etc. have good stability to hydrolysis with the titanium compound that the titanic acid ester reaction generates, WO02/42537 discloses by 2-hydroxycarboxylic acid compounds such as lactic acid, citric acid, oxysuccinic acid, tartrate etc. and the titanium compound that the titanic acid ester reaction generates and has been used for polyester catalyst, but the PET hue of gained still is not very good.
2-hydroxycarboxylic acid compounds such as lactic acid, citric acid, oxysuccinic acid, tartrate etc. have certain electron donation, and the look that the product that they and titanic acid ester reaction form can present under solar radiation in various degree becomes, by nearly colourless blueness, the reddish-brown of becoming.The light durability of this class titanium compound is bad to be that a kind of changeable valency metal is relevant with titanium, under solar radiation, in the titanium compound with the 2P track of titanium coordinate Sauerstoffatom on an electronics be excited on the 3d unoccupied orbital that transits to titanium atom, variable color is by Ti
4+With Ti
3+Between the valence electron transition absorbed visible light and made it that change in color take place.The bad meeting of this light stability of titanium compound causes it to darken, and when its color and luster that might have influence on its product during as esterification, polycondensation catalyst, produces bad effect.
Summary of the invention
Technical problem to be solved by this invention is the bad problem of light stability of the titanium that exists in the prior art, and a kind of preparation method of new polyester is provided.The catalyzer that this method has a use dissolves in ethylene glycol and becomes homogeneous catalyst, and the polyester that makes of catalyzer has the good characteristics of form and aspect thus.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of polyester, with di-carboxylic acid and aklylene glycol is raw material, in the presence of titanium-containing catalyst, in temperature of reaction is 230～280 ℃, reaction pressure is to carry out esterification under normal pressure～0.5MPa condition, obtain prepolymer, it is 280～320 ℃ in temperature of reaction then, reaction pressure is for to get polyester product less than carrying out polycondensation under the vacuum condition of 150Pa, wherein titanium-containing catalyst comprises (A) titanium compound, (B) organic phospho acid compound and (C) reaction product of phosphorus compound, wherein (A) titanium compound component is the reaction product that is selected from titanic acid ester and 2-hydroxycarboxylic acid compounds; (B) organic phospho acid compound component is selected from 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, Amino Trimethylene Phosphonic Acid, diethylene triamine pentamethylene phosphonic, ethylenediamine tetraacetic fork phosphonic acids or 2-phosphonic acids butane-1,2, at least a in the 4-tricarboxylic acid; (C) phosphorus compound is selected from least a in phosphoric acid, phosphorous acid, Hypophosporous Acid, 50, phosphoric acid ester or the phosphorous acid ester.
In the technique scheme, (A) titanium compound is 2: 1～1: 10 with (B) the mol ratio preferable range of organic phospho acid compound; (A) titanium compound is 2: 1～1: 10 with (C) the mol ratio preferable range of phosphorus compound.The titanic acid ester preferred version is selected from least a in metatitanic acid tetramethyl ester, tetraethyl titanate, metatitanic acid orthocarbonate, titanium isopropylate or the tetrabutyl titanate; 2-hydroxycarboxylic acid compounds preferred version is selected from least a in lactic acid, citric acid, oxysuccinic acid or the tartrate.The mol ratio preferable range of 2-hydroxycarboxylic acid compounds and titanic acid ester is 1～4: 1; 2-hydroxycarboxylic acid compounds preferred version is anhydride or crystalline hydrate.The di-carboxylic acid preferred version is selected from least a in terephthalic acid, phthalic acid, m-phthalic acid, naphthalic acid, biphenyl dicarboxylic acid or the cyclohexane dicarboxylic acid; The aklylene glycol preferred version is selected from ethylene glycol, 1,3 propylene glycol, propylene glycol, 1, at least a in the 4-butyleneglycol.The consumption of titanium-containing catalyst is 1～100PPm in the polyester amount preferable range that generates, and more preferably scope is 1～40PPm.
Phosphorus compound of the present invention is selected from phosphoric acid, phosphorous acid, Hypophosporous Acid, 50, phenyl phosphorous acid, phenyl Hypophosporous Acid, 50, phosphenylic acid alkyl ester, aryl phosphate, alkyl phosphite, aryl phosphite acid trimethyl, triethyl phosphate, tricresyl phosphate propyl ester, tricresyl phosphate isopropyl ester, tributyl phosphate, triphenylphosphate, dimethylphosphite, diethyl phosphite, phosphorous acid dipropyl, diisopropyl phosphite, dibutyl phosphite, phosphorous acid diphenyl ester etc.
The preparation method of polyester is as follows:
Among the preparation method of polyester, raw material uses di-carboxylic acid or its to become ester derivative and dibasic alcohol among the present invention, preferably uses aromatic dicarboxylate or its to become ester derivative and aliphatic dihydroxy alcohol.
Be used for di-carboxylic acid of the present invention and comprise the aromatic dicarboxylate, as terephthalic acid, phthalic acid, m-phthalic acid, naphthalic acid, biphenyl dicarboxylic acid, and alicyclic carboxylic acid such as cyclohexane dicarboxylic acid etc., preferred terephthalic acid.
The example of dibasic alcohol comprises aliphatic dihydroxy alcohol such as ethylene glycol, 1, ammediol, propylene glycol, 1,4-butyleneglycol etc., preferred ethylene glycol.
Preparation process of polyester of the present invention, can adopt known preparation process of polyester, the first step is carried out esterification by terephthalic acid or dimethyl terephthalate (DMT) and ethylene glycol, obtains prepolymer, esterification is carried out at 230～280 ℃, and pressure is normal pressure～0.5MPa.Second step was carried out polycondensation under high vacuum, 280～320 ℃ of temperature of reaction, and pressure is lower than 150Pa.The adding of catalyzer can join in the reaction system simultaneously with phthalic acid or dimethyl terephthalate (DMT) and ethylene glycol, also can join in the reaction system after phthalic acid or dimethyl terephthalate (DMT) and glycol reaction generate prepolymer.
In the present invention, test by the following method such as the limiting viscosity of polyester, end carboxyl, glycol ether and form and aspect:
1) limiting viscosity: the mixed liquid of phenol-tetrachloroethane is made solvent, uses determination of ubbelohde viscometer under 25 ℃ the temperature.
2) end carboxyl: make solvent with ortho-cresol, potassium hydroxide, the titration on potentiometric titrator of ethanol standardized solution.
3) glycol ether: tetraethylene glycol dimethyl ether is interior mark, and sample is through measuring on gas chromatographicanalyzer after the alcoholysis.
4) form and aspect: the pellet sample is measured with the Gardner automatic colour difference meter after 1 hour 135 ℃ of processing.
In present method, owing to use reaction product to be catalyzer by titanium compound, organic phospho acid compound and phosphorus compound, the inventor is surprised to find this catalyzer and can be dissolved in and becomes homogeneous system in the ethylene glycol, can obtain the polyester of good form and aspect with this Preparation of Catalyst polyester, obtain better technical effect.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
The preparation of catalyst A
Agitator is being housed, add monohydrate potassium 154 grams (0.8 mole) and 308 gram Virahols in the reactor of condenser and thermometer, stirring makes the citric acid dissolving, in reactor, slowly splash into titanium isopropylate 114 grams (0.4 mole), 30 ℃ of reflux one hour, vacuumize to steam and remove Virahol, obtain solid matter, adding 200 gram water makes it to dissolve and adds the ammoniacal liquor neutralization again to make the pH value of system be about 7, obtain light yellow transparent liquid, vacuum is steamed and is dewatered, obtaining the citric acid titanium compound powder of white crystals shape, is 8.9 weight % through its titanium content of plasmatron spectrographic analysis.
2.70 gram (0.005 mole) citric acid titanium compounds are dissolved in the 10 gram ethylene glycol, obtain light yellow transparent liquid, the 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid aqueous solution that adds 2.06 gram (0.005 mmoles) 50%, 80 ℃ of reactions add the phosphoric acid of 1.15 gram (0.01 moles) 85% after 1 hour, continue reaction 1 hour, obtain light yellow transparent liquid, be referred to as catalyst A, calculating its titanium content by feeding intake is 1.51 weight %.
The preparation of polyester
500 gram terephthalic acids and 316 gram ethylene glycol and 0.578 are restrained catalyst A (based on the amount of the polyester that generates, the weight of titanium atom is 15PPm), the mixed slurry that is made into, join in the polymeric kettle, carry out esterification, esterification temperature is 230～255 ℃, and pressure is 0.25MPa, discharges the water that reaction generates by rectifier unit.Reduce to normal pressure after esterification finishes, vacuumize and be decompressed to system pressure and be lower than 130Pa, temperature of reaction rises to 280 ℃ gradually simultaneously, when system reaction stopped reaction after reach required viscosity, afterwards reaction product is extruded with bar shaped continuously from the polymeric kettle bottom, cooling, pelletizing are for performance test.
Test result sees Table 1.
[embodiment 2]
Titanium catalyst B preparation
Preparation method with similar catalyst A prepares catalyst B, and the reflux temperature that just prepares titanium compound is 100 ℃, and the time is 4 hours; Temperature of reaction in the step (2) is 25 ℃, and the reaction times is 3 hours, and the temperature of reaction in the step (3) is 30 ℃, and the reaction times is 3 hours, changes 2.06 gram 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid into 5.40 gram (0.01 mole) 2-phosphonic acids butane-1,2,4-tricarboxylic acid.It is 1.25 weight % that catalyst B is calculated its titanium content by feeding intake
The preparation of polyester
Prepare polyester by similarly to Example 1 method, adopt 0.694 gram catalyst B as catalyzer (based on the amount of the polyester that generates, the weight of titanium atom is 15PPm).
Test result sees Table 1.
[embodiment 3]
Catalyzer C preparation
Preparation method with similar catalyst A prepares catalyzer C, and just the phosphoric acid with 1.15 gram (0.01 moles) 85% changes 1.58 gram (0.01 mole) phosphenylic acids into.It is 1.47 weight % that catalyzer C calculates its titanium content by feeding intake.
The preparation of polyester
Prepare polyester by similarly to Example 1 method, adopt 0.590 gram catalyzer C as catalyzer (based on the amount of the polyester that generates, the weight of titanium atom is 15PPm).
Test result sees Table 1.
[embodiment 4]
Catalyzer D preparation
Preparation method with similar catalyst A prepares catalyzer D, and just the weight increase with 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid is 4.12 grams (0.01 mole).It is 1.34 weight % that catalyzer D calculates its titanium content by feeding intake
The preparation of polyester
Prepare polyester by similarly to Example 1 method, adopt 0.647 gram catalyzer D as catalyzer (based on the amount of the polyester that generates, the weight of titanium atom is 15PPm).
Test result sees Table 1.
Table 1
| Catalyzer | Esterification time (min) | Polymerization time (min) | Viscosity (dL/g) | The end carboxyl (mole/t) | Glycol ether (%) | L | a | b | |
| Embodiment 1 | Catalyst A | 80 | 65 | 0.635 | 11.5 | 1.95 | 84.4 | -1.20 | 5.7 |
| Embodiment 2 | Catalyst B | 80 | 63 | 0.639 | 11.4 | 1.88 | 84.5 | -1.25 | 6.7 |
| Embodiment 3 | Catalyzer C | 80 | 64 | 0.641 | 12.4 | 1.86 | 84.3 | -1.28 | 5.8 |
| Embodiment 4 | Catalyzer D | 80 | 64 | 0.645 | 12.7 | 1.80 | 85.3 | -1.26 | 5.5 |
Claims (9)
1, a kind of preparation method of polyester, with di-carboxylic acid and aklylene glycol is raw material, in the presence of titanium-containing catalyst, in temperature of reaction is 230～280 ℃, reaction pressure is to carry out esterification under normal pressure～0.5MPa condition, obtain prepolymer, it is 280～320 ℃ in temperature of reaction then, reaction pressure is for to get polyester product less than carrying out polycondensation under the vacuum condition of 150Pa, it is characterized in that titanium-containing catalyst comprises (A) titanium compound, (B) organic phospho acid compound and (C) reaction product of phosphorus compound, wherein (A) titanium compound component is the reaction product that is selected from titanic acid ester and 2-hydroxycarboxylic acid compounds; (B) organic phospho acid compound component is selected from 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, Amino Trimethylene Phosphonic Acid, diethylene triamine pentamethylene phosphonic, ethylenediamine tetraacetic fork phosphonic acids or 2-phosphonic acids butane-1,2, at least a in the 4-tricarboxylic acid; (C) phosphorus compound is selected from least a in phosphoric acid, phosphorous acid, Hypophosporous Acid, 50, phosphoric acid ester or the phosphorous acid ester.
2,, it is characterized in that (A) titanium compound and (B) mol ratio of organic phospho acid compound are 2: 1～1: 10 according to the preparation method of the described polyester of claim 1; (A) titanium compound is 2: 1～1: 10 with (C) mol ratio of phosphorus compound.
3,, it is characterized in that titanic acid ester is selected from least a in metatitanic acid tetramethyl ester, tetraethyl titanate, metatitanic acid orthocarbonate, titanium isopropylate or the tetrabutyl titanate according to the preparation method of the described polyester of claim 1; 2-hydroxycarboxylic acid compounds is selected from least a in lactic acid, citric acid, oxysuccinic acid or the tartrate.
4, according to the preparation method of the described polyester of claim 1, the mol ratio that it is characterized in that 2-hydroxycarboxylic acid compounds and titanic acid ester is 1～4: 1.
5, according to the preparation method of the described polyester of claim 4, the mol ratio that it is characterized in that 2-hydroxycarboxylic acid compounds and titanic acid ester is 1.5～3.5: 1.
6,, it is characterized in that 2-hydroxycarboxylic acid compounds is anhydride or crystalline hydrate according to the preparation method of the described polyester of claim 3.
7,, it is characterized in that di-carboxylic acid is selected from least a in terephthalic acid, phthalic acid, m-phthalic acid, naphthalic acid, biphenyl dicarboxylic acid or the cyclohexane dicarboxylic acid according to the preparation method of the described polyester of claim 1; Aklylene glycol is selected from ethylene glycol, 1,3 propylene glycol, propylene glycol, 1, at least a in the 4-butyleneglycol.
8,, it is characterized in that the consumption of titanium-containing catalyst is counted 1～100PPm with the polyester amount that generates according to the preparation method of the described polyester of claim 1.
9, the preparation method of described polyester according to Claim 8 is characterized in that the consumption of titanium-containing catalyst is counted 1～40PPm with the polyester amount that generates.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2005101102910A CN1962715B (en) | 2005-11-11 | 2005-11-11 | Method for making polyester |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2005101102910A CN1962715B (en) | 2005-11-11 | 2005-11-11 | Method for making polyester |
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| CN1962715A true CN1962715A (en) | 2007-05-16 |
| CN1962715B CN1962715B (en) | 2010-10-06 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870710A (en) * | 2010-06-17 | 2010-10-27 | 华东理工大学 | Titanate derivative containing secondary amino group and preparation method thereof |
| US20120157619A1 (en) * | 2010-12-20 | 2012-06-21 | Eastman Chemical Company | Color in Titanium Catalyzed Polyesters |
| US8796395B2 (en) | 2010-12-20 | 2014-08-05 | Eastman Chemical Company | Polyesters containing particular phosphorus compounds blended with other polymers |
| CN105161311A (en) * | 2015-08-11 | 2015-12-16 | 上海应用技术学院 | Method for preparing titanium nitride/carbon composite materials |
| CN106117533A (en) * | 2016-07-29 | 2016-11-16 | 中国石化仪征化纤有限责任公司 | A kind of preparation method of PTT |
| CN109232865A (en) * | 2018-08-08 | 2019-01-18 | 济南朝晖科技有限公司 | A kind of titaniferous composition and its preparation method and application |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1139678A (en) * | 1995-07-04 | 1997-01-08 | 天津石油化工公司涤纶厂 | Production method of polyester for high-transparency ultra-thin film |
| US6489433B2 (en) * | 2001-02-23 | 2002-12-03 | E. I. Du Pont De Nemours And Company | Metal-containing composition and process therewith |
-
2005
- 2005-11-11 CN CN2005101102910A patent/CN1962715B/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870710A (en) * | 2010-06-17 | 2010-10-27 | 华东理工大学 | Titanate derivative containing secondary amino group and preparation method thereof |
| US20120157619A1 (en) * | 2010-12-20 | 2012-06-21 | Eastman Chemical Company | Color in Titanium Catalyzed Polyesters |
| US8796395B2 (en) | 2010-12-20 | 2014-08-05 | Eastman Chemical Company | Polyesters containing particular phosphorus compounds blended with other polymers |
| US9156941B2 (en) * | 2010-12-20 | 2015-10-13 | Eastman Chemical Company | Color in titanium catalyzed polyesters |
| CN105161311A (en) * | 2015-08-11 | 2015-12-16 | 上海应用技术学院 | Method for preparing titanium nitride/carbon composite materials |
| CN106117533A (en) * | 2016-07-29 | 2016-11-16 | 中国石化仪征化纤有限责任公司 | A kind of preparation method of PTT |
| CN109232865A (en) * | 2018-08-08 | 2019-01-18 | 济南朝晖科技有限公司 | A kind of titaniferous composition and its preparation method and application |
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| Publication number | Publication date |
|---|---|
| CN1962715B (en) | 2010-10-06 |
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