CN102492128B - Preparation method and use of low-specific-surface-area titanium polyesterification catalyst - Google Patents
Preparation method and use of low-specific-surface-area titanium polyesterification catalyst Download PDFInfo
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- CN102492128B CN102492128B CN 201110414286 CN201110414286A CN102492128B CN 102492128 B CN102492128 B CN 102492128B CN 201110414286 CN201110414286 CN 201110414286 CN 201110414286 A CN201110414286 A CN 201110414286A CN 102492128 B CN102492128 B CN 102492128B
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Abstract
The invention discloses a preparation method and use of a low-specific-surface-area titanium polyesterification catalyst. According to the method, the low-specific-surface-area titanium polyesterification catalyst is prepared by compounding titanate, phosphate, silicate ester and other metal compounds, a silicate is used to modify the conventional titanium catalyst, and the catalytic activity and side reactions are reduced by reducing the specific surface area, pore area and pore volume, the prepared polyester product has good hue, and other properties of the titanium catalyst are also improved. The catalyst is mainly to solve the technical problem of the conventional polyesterification process and the yellowing problem of polyethylene glycol terephthalate (PET) and improve the quality of the polyester.
Description
Technical field
What the present invention relates to is a kind of preparation method and application thereof of catalyzer, what be particularly related to is a kind of preparation method and application thereof that utilizes tetraethyl orthosilicate and trimethyl phosphate to carry out the low specific surface area titanium series polyester catalyst of modification, belongs to the polyester catalyst field.
Background technology
Polyester is a widely used synthetic materials of class, and wherein polyethylene terephthalate (PET) is owing to having good fibre-forming performance, and noticeable.At present, the catalyzer that uses in polyester industrial production is mainly antimony compounds, as antimonous oxide, antimony acetate, antimony glycol etc.The compound that contains antimony be owing to may work the mischief to environment and human body, and causes people's extensive concern.Many external PET factories are being devoted to development of new non-heavy metal polyester catalyst in the commercial city at present, and wherein Titanium series catalyst is because its higher catalytic activity receives much attention.
In production of polyester, catalyzer is most important, the research of catalyzer is the important topic of PET industry always, the foreign scholar had once carried out extensively and dark people's research production of polyester catalyzer and catalytic mechanism thereof, discovery has the classes of compounds of katalysis various to polycondensation, has almost related to the compound of all major-minors families element except haloid element and inert element.But the more polyester catalyst of industrial production application and research is mainly antimony-based catalyst at present, and its moderate cost is cheap, thereby has obtained general use in polyester industrial.The tradition Titanium series catalyst has satisfactory stability, have high reactivity, but the side reaction that causes in reaction process is more, the poor and goods yellowing of the polyester existence and stability that makes, muddy problem, thereby never used on a large scale.
The form and aspect L value of polyester is relevant with the brightness of polyester, and numerical value is higher for well, and the form and aspect L value of general polyester is in 60 left and right; The form and aspect b value of polyester is anti-yellow relevant with polyester, and numerical value is lower, shows that this polyester more is not easy anti-Huang, greater than 3.0, illustrates that the polyester of producing is yellow all the more serious when form and aspect b value, affects the effect of polyester.
Summary of the invention
Learnt by foregoing: the Titanium series catalyst catalytic is too fast, causes side reaction to increase, and produces many by products, polyester color jaundice then, hue difference.
Come with some shortcomings and defective in order to solve in above-mentioned technology, the present invention is directed to the problems referred to above, a kind of preparation method and application thereof of low specific surface area titanium series polyester catalyst are provided, concrete is a kind ofly prepares this catalyzer by tetraethyl orthosilicate and trimethyl phosphate modification, make it in the process that catalyzes and synthesizes the PET polyester, by specific surface area, hole area and the pore volume that reduces catalyzer, then reduce the catalytic activity of catalyzer, reduce side reaction, the polyester product form and aspect that make are good, can also improve other performances of Titanium series catalyst simultaneously.Simultaneously do not contain poisonous antimony based compound, eliminated the murder by poisoning of antimony based compound to environment and human body.Because the hydrolysis of isopropyl titanate in Trace water generates white titanium dioxide, poorly water-soluble is not given birth to reaction with steeping in water for reconstitution, and character is very stable, therefore this catalyzer has resistance to hydrolysis.
The present invention is achieved through the following technical solutions:
Concrete grammar is as follows: first with constant temperature oil bath, reaction solvent is heated to certain steady temperature, titanic acid ester, phosphoric acid ester, silicon ester and metallic compound are dissolved in organic solvent, stir, constant temperature, drip simultaneously a small amount of water facilitation of hydrolysis, the precipitation washing with acetone that makes is removed residual ethylene glycol.To be deposited at last 70 ℃ of lower vacuum-dryings, namely get the red powder catalyzer.The present invention prepares this catalyzer by organically-modified method, has not only improved the catalytic performance of titanium deoxide catalyst, has also improved the properties of the finished product simultaneously.
Below the present invention is made further description:
1, the metal titanium acid esters is isopropyl titanate, is take propyl carbinol, titanium tetrachloride and ammonia as raw material, makes through esterification in toluene solvant; Phosphoric acid ester is trimethyl phosphate, and silicon ester is tetraethyl orthosilicate, and other metallic compound is aluminum chloride;
2, be that 8 water slowly is added drop-wise in organic solvent with the pH value, make red precipitate, organic solvent is ethylene glycol; The consumption of ethylene glycol is 2500-2600ml/molTi, and the reaction steady temperature is 200 ℃, and the speed of stirring is 2000-3000r/min; The consumption of water is 250-260ml/molTi, and the pH value of water is at 8-8.5, and the time of dropping is in 25-30min;
3, with acetone repetitive scrubbing red precipitate, filter, last vacuum-drying makes the red powder catalyzer;
4, organic modifiers is trimethyl phosphate and tetraethyl orthosilicate, the amount that trimethyl phosphate adds and the mass ratio of titanic acid ester are 9:1, the consumption mol ratio of tetraethyl orthosilicate and titanic acid ester is 1:2, and the consumption mol ratio of aluminum chloride and titanic acid ester is 1:10, the preparation red precipitate;
5, organic modifiers adds in the preparation precipitation process, more is conducive to the modification of catalyzer.
The activity of this catalyzer is more than 20 times of original antimony-based catalyst, and in process of polyester synthesizing, its consumption is 20-30 μ g/g, and the consumption of catalyzer is take the consumption of terephthalic acid as reference.
The form that adds of catalyzer does not affect the activity of catalyzer, determines because the activity of catalyzer is content by Ti, and catalyzer joins reaction system with the form of powder.
The present invention carries out modification and design by introducing organic modifiers tetraethyl orthosilicate and trimethyl phosphate to catalyzer, reduces specific surface area, hole area and the pore volume of catalyzer, then reduces the catalytic activity of catalyzer, reduces side reaction.This catalyzer has substantial characteristics and progress really through verification experimental verification, can effectively overcome the problem of polyester jaundice.
Further verify effect of the present invention below in conjunction with specific embodiment.
Embodiment
Embodiment 1:
The preparation of low specific surface area titanium series polyester catalyst: first with constant temperature oil bath, reaction solvent is heated to certain steady temperature, isopropyl titanate, trimethyl phosphate, tetraethyl orthosilicate and aluminum chloride are dissolved in ethylene glycol, wherein: the amount that trimethyl phosphate adds and the mass ratio of isopropyl titanate are 9:1, the consumption mol ratio of tetraethyl orthosilicate and isopropyl titanate is 1:2, and the consumption mol ratio of aluminum chloride and isopropyl titanate is 1:10; Wherein: the consumption of ethylene glycol is 2500ml/molTi, and the reaction steady temperature is 200 ℃, and the speed of stirring is 2000r/min; Drip simultaneously a small amount of water facilitation of hydrolysis, the consumption of water is 250ml/molTi, and the pH value of water is 8, and the time of dropping is stirred constant temperature in 25min; The precipitation washing with acetone that makes is removed residual ethylene glycol, will be deposited at last 70 ℃ of lower vacuum-dryings, namely gets the red powder catalyzer;
2000g terephthalic acid, 1000g ethylene glycol and this catalyzer 0.04g are carried out pet reaction in the stainless steel cauldron of 5L.This process is in vacuum, carries out under 270 ℃.The PET hue L value that makes is 90.68, and form and aspect b value 1.0, limiting viscosity are 0.722, and carboxyl-content is 13mol/t.
Embodiment 2:
The preparation of low specific surface area titanium series polyester catalyst: first with constant temperature oil bath, reaction solvent is heated to certain steady temperature, isopropyl titanate, trimethyl phosphate, tetraethyl orthosilicate and aluminum chloride are dissolved in ethylene glycol, wherein: the amount that trimethyl phosphate adds and the mass ratio of isopropyl titanate are 9:1, the consumption mol ratio of tetraethyl orthosilicate and isopropyl titanate is 1:2, and the consumption mol ratio of aluminum chloride and isopropyl titanate is 1:10; Wherein: the consumption of ethylene glycol is 2600ml/molTi, and the reaction steady temperature is 200 ℃, and the speed of stirring is 2500r/min; Drip simultaneously a small amount of water facilitation of hydrolysis, the consumption of water is 260ml/molTi, and the pH value of water is 8.5, and the time of dropping is stirred constant temperature in 30min; The precipitation washing with acetone that makes is removed residual ethylene glycol, will be deposited at last 70 ℃ of lower vacuum-dryings, namely gets the red powder catalyzer;
2000g terephthalic acid, 1000g ethylene glycol and this catalyzer 0.05g are carried out pet reaction in the stainless steel cauldron of 5L.This process is in vacuum, carries out under 270 ℃.The PET hue L value that makes is 91.68, and form and aspect b value 1.2, limiting viscosity are 0.712, and carboxyl-content is 12mol/t.
Embodiment 3:
The preparation of low specific surface area titanium series polyester catalyst: first with constant temperature oil bath, reaction solvent is heated to certain steady temperature, isopropyl titanate, trimethyl phosphate, tetraethyl orthosilicate and aluminum chloride are dissolved in ethylene glycol, wherein: the amount that trimethyl phosphate adds and the mass ratio of isopropyl titanate are 9:1, the consumption mol ratio of tetraethyl orthosilicate and isopropyl titanate is 1:2, and the consumption mol ratio of aluminum chloride and isopropyl titanate is 1:10; Wherein: the consumption of ethylene glycol is 2500ml/molTi, and the reaction steady temperature is 200 ℃, and the speed of stirring is 3000r/min; Drip simultaneously a small amount of water facilitation of hydrolysis, the consumption of water is 260ml/molTi, and the pH value of water is 8, and the time of dropping is stirred constant temperature in 30min; The precipitation washing with acetone that makes is removed residual ethylene glycol, will be deposited at last 70 ℃ of lower vacuum-dryings, namely gets the red powder catalyzer;
2000g terephthalic acid, 1000g ethylene glycol and this catalyzer 0.06g are carried out pet reaction in the stainless steel cauldron of 5L.This process is in vacuum, carries out under 270 ℃.The PET hue L value that makes is 87.68, and form and aspect b value 1.5, limiting viscosity are 0.732, and carboxyl-content is 16mol/t.
Embodiment 4:
The preparation of low specific surface area titanium series polyester catalyst: first with constant temperature oil bath, reaction solvent is heated to certain steady temperature, isopropyl titanate, trimethyl phosphate, tetraethyl orthosilicate and aluminum chloride are dissolved in ethylene glycol, wherein: the amount that trimethyl phosphate adds and the mass ratio of isopropyl titanate are 8:1, the consumption mol ratio of tetraethyl orthosilicate and isopropyl titanate is 1:3, and the consumption mol ratio of aluminum chloride and isopropyl titanate is 1:8; Wherein: the consumption of ethylene glycol is 2500ml/molTi, and the reaction steady temperature is 200 ℃, and the speed of stirring is 2000r/min; Drip simultaneously a small amount of water facilitation of hydrolysis, the consumption of water is 250ml/molTi, and the pH value of water is 8, and the time of dropping is stirred constant temperature in 25min; The precipitation washing with acetone that makes is removed residual ethylene glycol, will be deposited at last 70 ℃ of lower vacuum-dryings, namely gets the red powder catalyzer;
2000g terephthalic acid, 1000g ethylene glycol and this catalyzer 0.06g are carried out pet reaction in the stainless steel cauldron of 5L.This process is in vacuum, carries out under 270 ℃.The PET hue L value that makes is 87.68, and form and aspect b value 3.5, limiting viscosity are 0.732, and carboxyl-content is 16mol/t.
Embodiment 5:
The preparation of low specific surface area titanium series polyester catalyst: first with constant temperature oil bath, reaction solvent is heated to certain steady temperature, isopropyl titanate, trimethyl phosphate, tetraethyl orthosilicate and aluminum chloride are dissolved in ethylene glycol, wherein: the amount that trimethyl phosphate adds and the mass ratio of isopropyl titanate are 10:1, the consumption mol ratio of tetraethyl orthosilicate and isopropyl titanate is 1.5:2, and the consumption mol ratio of aluminum chloride and isopropyl titanate is 1:9; Wherein: the consumption of ethylene glycol is 2600ml/molTi, and the reaction steady temperature is 200 ℃, and the speed of stirring is 3000r/min; Drip simultaneously a small amount of water facilitation of hydrolysis, the consumption of water is 260ml/molTi, and the pH value of water is 8.5, and the time of dropping is stirred constant temperature in 30min; The precipitation washing with acetone that makes is removed residual ethylene glycol, will be deposited at last 70 ℃ of lower vacuum-dryings, namely gets the red powder catalyzer;
2000g terephthalic acid, 1000g ethylene glycol and this catalyzer 0.05g are carried out pet reaction in the stainless steel cauldron of 5L.This process is in vacuum, carries out under 270 ℃.The PET hue L value that makes is 87.68, and form and aspect b value 3.5, limiting viscosity are 0.732, and carboxyl-content is 16mol/t.
Embodiment 6:
The preparation of low specific surface area titanium series polyester catalyst: first with constant temperature oil bath, reaction solvent is heated to certain steady temperature, isopropyl titanate, trimethyl phosphate, tetraethyl orthosilicate and aluminum chloride are dissolved in ethylene glycol, wherein: the amount that trimethyl phosphate adds and the mass ratio of titanic acid ester are 9:2, the consumption mol ratio of tetraethyl orthosilicate and titanic acid ester is 1:2.5, and the consumption mol ratio of aluminum chloride and titanic acid ester is 1.5:10; Wherein: the consumption of ethylene glycol is 2500ml/molTi, and the reaction steady temperature is 200 ℃, and the speed of stirring is 3000r/min; Drip simultaneously a small amount of water facilitation of hydrolysis, the consumption of water is 260ml/molTi, and the pH value of water is 8, and the time of dropping is stirred constant temperature in 25min; The precipitation washing with acetone that makes is removed residual ethylene glycol, will be deposited at last 70 ℃ of lower vacuum-dryings, namely gets the red powder catalyzer;
2000g terephthalic acid, 1000g ethylene glycol and this catalyzer 0.04g are carried out pet reaction in the stainless steel cauldron of 5L.This process is in vacuum, carries out under 270 ℃.The PET hue L value that makes is 87.68, and form and aspect b value 3.5, limiting viscosity are 0.732, and carboxyl-content is 16mol/t.
Conclusion: can show by above embodiment data, the PET hue L value that embodiment 1 makes is 90.68, form and aspect b value 1.0, and the higher while b of its L value value is also lower, is preferred plan of the present invention; The major influence factors that affects PET hue L value and form and aspect b value is the consumption mol ratio of consumption mol ratio, aluminum chloride and titanic acid ester of mass ratio, tetraethyl orthosilicate and the titanic acid ester of amount that in the preparation process of low specific surface area titanium series polyester catalyst, trimethyl phosphate adds and titanic acid ester, other factors do not affect the activity of catalyzer, thereby affect PET hue L value and form and aspect b value.
Claims (4)
1. the preparation method of a low specific surface area titanium series polyester catalyst: first with constant temperature oil bath, reaction solvent is heated to certain steady temperature, titanic acid ester, phosphoric acid ester, silicon ester and metallic compound are dissolved in organic solvent, stir, constant temperature, drip simultaneously a small amount of water facilitation of hydrolysis, the precipitation washing with acetone that makes is removed residual ethylene glycol; To be deposited at last 70 ℃ of lower vacuum-dryings, namely get the red powder catalyzer, it is characterized in that:
(1), titanic acid ester is isopropyl titanate, is take propyl carbinol, titanium tetrachloride and ammonia as raw material, make through esterification in toluene solvant; Phosphoric acid ester is trimethyl phosphate, and silicon ester is tetraethyl orthosilicate, and metallic compound is aluminum chloride;
(2), be that 8 water slowly is added drop-wise in organic solvent with the pH value, make red precipitate, organic solvent is ethylene glycol; The consumption of ethylene glycol is 2500-2600ml/molTi, and the reaction steady temperature is 200 ℃, and the speed of stirring is 2000-3000r/min; The consumption of water is 250-260ml/molTi, and the pH value of water is 8, and the time of dropping is in 25-30min;
(3), with acetone repetitive scrubbing red precipitate, filter, last vacuum-drying makes the red powder catalyzer;
(4), organic modifiers is trimethyl phosphate and tetraethyl orthosilicate, the amount that trimethyl phosphate adds and the mass ratio of titanic acid ester are 9:1, the consumption mol ratio of tetraethyl orthosilicate and titanic acid ester is 1:2, and the consumption mol ratio of aluminum chloride and titanic acid ester is 1:10, the preparation red precipitate;
(5), organic modifiers adds in precipitation process in preparation, more is conducive to the modification of catalyzer.
2. the preparation method of a kind of low specific surface area titanium series polyester catalyst according to claim 1, it is characterized in that: the activity of this catalyzer is more than 20 times of original antimony-based catalyst.
3. the application of a kind of low specific surface area titanium series polyester catalyst according to claim 1, it is characterized in that: for catalyzing and synthesizing the PET polyester of form and aspect b value lower than 2, in process of polyester synthesizing, its consumption is 20-30 μ g/g, and the consumption of catalyzer is take the consumption of terephthalic acid as reference.
4. the application of a kind of low specific surface area titanium series polyester catalyst according to claim 3, it is characterized in that: the form that adds of catalyzer does not affect the activity of catalyzer, because the activity of catalyzer is to be determined by the content of Ti, catalyzer joins reaction system with the form of powder.
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Citations (4)
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| US6316584B1 (en) * | 1997-06-10 | 2001-11-13 | Akzo Nobel Nv | Method for producing polyesters and copolyesters |
| 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 |
| CN101121777A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Titanium series polyester catalyst |
| CN102250330A (en) * | 2011-05-05 | 2011-11-23 | 常州大学 | Highly transparent copolyester synthesized by biomass-resource-derived monomers and preparation method for highly transparent copolyester |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6316584B1 (en) * | 1997-06-10 | 2001-11-13 | Akzo Nobel Nv | Method for producing polyesters and copolyesters |
| 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 |
| CN101121777A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Titanium series polyester catalyst |
| CN102250330A (en) * | 2011-05-05 | 2011-11-23 | 常州大学 | Highly transparent copolyester synthesized by biomass-resource-derived monomers and preparation method for highly transparent copolyester |
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