CN1174018C - Method for preparing polyester and copolyester - Google Patents
Method for preparing polyester and copolyester Download PDFInfo
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- CN1174018C CN1174018C CNB021452636A CN02145263A CN1174018C CN 1174018 C CN1174018 C CN 1174018C CN B021452636 A CNB021452636 A CN B021452636A CN 02145263 A CN02145263 A CN 02145263A CN 1174018 C CN1174018 C CN 1174018C
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- acid
- polycondensation
- polyester
- ester
- catalyst
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Abstract
The present invention discloses a method for preparing polyester and copolyester. The present invention comprises the polyester pre-polycondensation product step that dicarboxylic acid ester carries out ester exchange reaction, or dicarboxylic acid directly reacts with excessive glycol in order to obtain the mixture of ester and oligo-ester, and comprises the polycondensation reaction step that pre-polycondensation products carry out polycondensation reaction in the existence of a polycondensation catalyst. The polycondensation catalyst is a mixed oxide of titanium and silicon. The method for preparing the polycondensation catalyst comprises steps that (1) prepared metal alkoxide is dissolved in an organic solvent; (2) acid or alkali water solution is added to the organic solvent containing the metal alkoxide in step (1), and precipitates are collected in order to obtain the catalyst of the present invention, namely the coprecipitate of TiO2 and SiO2. The catalyst prepared by the method is adopted in the preparation of polyester and copolyester. The present invention can conveniently regulate the catalytic activity and the selectivity of the catalyst by changing the pH value of the reaction system. Besides, the color shade of products can be obviously improved. The value of b<*> is from 1 to 10.
Description
Technical field
The present invention relates to the preparation method of polyester and copolyesters, particularly the Preparation of catalysts method that is adopted in the polycondensation process.
Background technology
Polyester and copolyesters are a kind of macromolecular compound, have in fields such as light industry, machinery, electronics, packings very to use widely.Polyester and the copolyesters that reaches of the present invention is the macromolecular compound with following structure fragment: (is example with the polyester)
M=2,3 or 4, n is the polymerization degree, common n 〉=50, its molecular weight is greater than 1000.The component that be used to improve polyester performance of copolyesters in the polyester building-up process, adding, as m benzene dicarboxylic acid and derivative thereof, polyoxyethylene glycol, polytetramethylene glycol etc.
The preparation process of said polyester and copolyesters is divided into two stages usually.Fs is that dicarboxylic ester is carried out transesterification reaction or dicarboxylic acid is directly reacted the polyester precondensation product that obtains ester and low polyester mixture with excess diol.Subordinate phase is that the precondensation product that the fs obtains is carried out polycondensation, thereby obtains high-molecular weight polyester and copolyesters.In the subordinate phase reaction process,, generally need to add specific polycondensation catalyst and quicken polycondensation in order to improve the molecular weight of polyester and copolyesters.
What adopt in the polyester production device in the whole world about 90% at present is antimony class catalyzer, as Sb
2O
3And antimony acetate, its advantage is that side reaction is few, low price; But shortcoming also is conspicuous, and antimony class catalyst activity is low, can partial reduction become antimony in reaction process, produces ash content, and can separate out in the last handling process of polyester, causes environmental pollution.Along with the enhancing of people's environmental consciousness, the use of antimony class catalyzer is subjected to increasing restriction, and people wish to develop a kind of new catalyst that can substitute antimony class catalyzer.For output and the quality that improves polyester and copolyesters, reduce of the pollution of antimony class catalyzer to environment, people have developed many polycondensation catalysts that are used to accelerate polycondensation of polyester.Catalyzer newly developed is difficult to be promoted the use of owing to come with some shortcomings but up to the present.
Titanium series catalyst is because the catalytic activity height is subjected to people's favor.Titanium series catalyst commonly used is the titan-alkoxide acid esters, as tetrabutyl titanate and titanium isopropylate.Yet easy catalyst, polyester of titanic acid ester and copolyester degradation side reaction, simultaneously unreacted titanic acid ester can with the acetaldehyde reaction that forms in the polycondensation process, make the polymkeric substance flavescence.In order to change the shortcoming of Titanium series catalyst, people improve Titanium series catalyst, as add P contained compound, amine and co-catalyst (US Patent 6,066,714), co-catalyst (US Patent 6 such as phosphite and ester class thereof (US Patent 5,922,828) or adding cobalt, aluminium, antimony, 255,441).
Except titanic acid ester, (USPatent 6,034 as polyester polycondensation catalyst also can to use titanyl compound, 203), or the mol ratio of titania/silica is that 90: 10 coprecipitated product is as polyester polycondensation catalyst (US Patent 5,789,528).Though this class catalyzer activity is improved, the still yellowing of the form and aspect of product has limited its application in industrial production.
Summary of the invention
The technical issues that need to address of the present invention are the preparation methods that disclose a kind of polyester and copolyesters, to overcome the above-mentioned defective that prior art exists.
Technical conceive of the present invention is such:
The present invention utilizes the method for hydrolysis of alkoxide to prepare the titanium titanium-silicon mixed oxide as polyester polycondensation catalyst, wherein used alkoxide is titanium alkoxide and silicon alkoxide, the present invention adds different acid in reaction process or alkali changes the speed of the hydrolysis and the condensation reaction of alkoxide, thereby changes the catalytic activity and the selectivity of catalyzer.By changing the Preparation of catalysts processing condition, regulate and control the catalytic activity of catalyzer in the polycondensation of polyester process, and, the form and aspect of polyester product are significantly increased suitably reducing under the prerequisite of catalytic activity.
Technical scheme of the present invention:
The preparation method of said polyester of the present invention and copolyesters comprises dicarboxylic ester is carried out transesterification reaction or dicarboxylic acid is directly reacted the polyester precondensation product step that obtains ester and low polyester mixture with excess diol, and with the polycondensation steps of precondensation product in the presence of polycondensation catalyst, the polycondensation temperature is 270 ℃～280 ℃, be reflected under the high vacuum state and carry out, pressure is 20～60Pa, and said polycondensation catalyst is a kind of titanium titanium-silicon mixed oxide.
Catalyzer of the present invention can adopt conventional alkoxide hydrolysis to be prepared, and concrete preparation method comprises the steps:
(1) metal alkoxide is dissolved in organic solvent;
The chemical structure of general formula of the metal alkoxide of being addressed is: M (OR)
m, wherein M is Ti and Si, m=4, R are C
nH
2n-1, n=1～6.
(2) aqueous solution adding step (1) with acid or alkali contains in the organic solvent of metal alkoxide, and the collecting precipitation thing obtains catalyzer of the present invention, i.e. TiO
2/ SiO
2Coprecipitate.
TiO
2/ SiO
2The mol ratio of coprecipitate is:
TiO
2: SiO
2=90: 10～20: 80, be preferably 90: 10～50: 50.
Selected alkoxide kind is to have the monohydroxy-alcohol of 1～6 carbon atom or the metal alcoholate of polyvalent alcohol, also can use the mixture of above-mentioned alkoxide kind;
Used organic solvent preferably has the monohydroxy-alcohol and/or the polyvalent alcohol of 1～6 carbon atom.
In the process of hydrolysis, add the hydrolysis rate that an amount of acid or alkali are regulated and control metal alkoxide.Acids commonly used is various mineral acids and/or organic acid, and preferred mineral acid is a hydrochloric acid, nitric acid, and sulfuric acid, phosphoric acid, preferred organic acid is an acetic acid, oxalic acid.Bases commonly used is NaOH, KOH, and ammoniacal liquor, preferred bases is an ammoniacal liquor.Bronsted lowry acids and bases bronsted lowry can add in the different steps of reaction, also can add bronsted lowry acids and bases bronsted lowry respectively in the different steps of same reaction.
The add-on of acid or alkali is: 0.0001～1mol/L is preferably 0.001～0.1mol/L
Utilize the prepared TiO of the present invention
2/ SiO
2Co-precipitation can be used as polyester polycondensation catalyst, and consumption is that benchmark is about 5-500ppm in ester or the oligomer ester for the treatment of polycondensation, is preferably 20-200ppm, the b of gained polyester product
*Value is 1-10.
B wherein
*Representing the champac balance, is the leading indicator of estimating PET hue, b
*Low more, the form and aspect of product are good more.
Under the popular response condition, the used coprecipitate of the present invention can also be used with one or more other polycondensation catalysts under the suitable situation as the polycondensation catalyst of various polyester and copolyesters in principle.
The reaction formula of this reaction process is:
Alkoxide forms the hydrous oxide network by condensation reaction in the process of hydrolysis.Titanium alkoxide and silicon alkoxide except self condensation reaction takes place, form the hydrous oxide precipitation in hydrolytic process, also condensation reaction can take place between titanium alkoxide and the silicon alkoxide, produce the mixed oxide that contains the Ti-O-Si key.Because the existence of surface charge, these particles are mutually exclusive, can not reunite, and its main particle size is less than 1 μ m.Advantage that it is generally acknowledged alkoxide hydrolysis is that can to obtain purity higher, the ultrafine powder of even particle distribution.
Although the titanium titanium-silicon mixed oxide can be used as polyester polycondensation catalyst, because the hydrolysis and the condensation reaction speed of titanium alkoxide and silicon alkoxide have evident difference, the hydrolysis rate of titanium alkoxide causes hydrolysate TiO far faster than silicon alkoxide
2And SiO
2Skewness inside and outside granules of catalyst has influenced activity of such catalysts and selectivity.The present invention is by adding various acid or alkali in the hydrolysis of alkoxide process, can change the hydrolysis and the condensation reaction speed of titanium alkoxide and silicon alkoxide, help the different condensation reaction between titanium alkoxide and the silicon alkoxide simultaneously, form the Ti-O-Si key, thereby change the co-ordination state of Ti, change its catalytic activity and selectivity.
In the preparation of polyester and copolyesters, adopt the catalyzer of method for preparing, can pass through to change the pH value of reaction system easily, and the catalytic activity and the selectivity of regulating catalyzer, the form and aspect of product also can significantly be taken on a new look in addition, b
*Value 1-10.
Embodiment
The present invention is carried out more detailed by the following example to describing.The polyester quality is carried out with reference to GB/T 14190-93 fiber polyester chip analytical procedure analyzing.Described relative solution viscosity is measured in 25 ℃ of phenol-tetrachloroethane mixed solution (mass ratio is 1: 1).The form and aspect of polyester adopt L
*a
*b
*Colour system is as the assessment benchmark.This system is owing to be higher than the recommendation that was subjected to CIE (International Commission on Illumination) in 1976 in the accuracy aspect the description aberration.In this system, L
*Be the luminance brightness factor, a
*And b
*Be the color measuring number.b
*Expression champac balance has very important significance b to the polyester color
*Be worth lowly more, the form and aspect of polyester are good more, especially thread-forming polyester cut into slices.It is not very important in polyester product for those color being required, and higher numerical value also is acceptable.
A, preparation TiO
2/ SiO
2Co-precipitation
Embodiment 1
50g titanium isopropylate and 4g tetraethoxy are dissolved in (solution A) in the 150mL dehydrated alcohol.1gNaOH is dissolved in (solution B) in the 30g deionized water.Under situation about stirring, B is added dropwise to A, produce white precipitate mixture was stirred 3 hours, centrifugation, throw out washing three times 70 ℃ of following vacuum-dryings, obtains TiO at last
2/ SiO
2Co-precipitation.
Embodiment 2
50g titanium isopropylate and 4g tetraethoxy are dissolved in (solution A) in the 150mL dehydrated alcohol.30g deionized water and 4mL ammoniacal liquor (15mol/L) are dissolved in (solution B) in the 150mL dehydrated alcohol.Under situation about stirring, B is added dropwise to A, produce white precipitate, mixture was stirred 3 hours, centrifugation, throw out washing three times 70 ℃ of following vacuum-dryings, obtains TiO at last
2/ SiO
2Co-precipitation.
Embodiment 3
40g tetrabutyl titanate and 3.5g tetraethoxy are dissolved in 100mL ethanol (solution A), 14g deionized water and 1mL phosphoric acid (15mol/L) are dissolved in (solution B) in the 100mL dehydrated alcohol.Under situation about stirring, solution A is added dropwise to solution B, produce white precipitate, mixture stirred after 1 hour, centrifugation, throw out washing three times 70 ℃ of following vacuum-dryings, obtains TiO at last
2/ SiO
2Co-precipitation.
Embodiment 4
40g tetrabutyl titanate and 3.5g tetraethoxy are dissolved in 100mL ethanol (solution A), 14g deionized water and 1mL hydrochloric acid (12mol/L) are dissolved in (solution B) in the 100mL dehydrated alcohol.Under situation about stirring, solution B is added dropwise to solution A, produce white precipitate, mixture stirred after 1 hour, centrifugation, throw out washing three times 180 ℃ of following vacuum-dryings, obtains TiO at last
2/ SiO
2Co-precipitation.
Embodiment 5
20g tetrabutyl titanate and 2g tetraethoxy are dissolved in (solution A) in the 300mL ethylene glycol, 20g deionized water and 1mL sulfuric acid (18mol/L) are dissolved in (solution B) in the 200mL dehydrated alcohol.Under situation about stirring, solution B is added dropwise to solution A, produce white precipitate.Drip 1mL ammoniacal liquor (15mol/L) solution again, then mixture was stirred 1 hour, centrifugation, throw out washing three times 180 ℃ of following vacuum-dryings, obtains TiO at last
2/ SiO
2Co-precipitation.
Embodiment 6
50g titanium isopropylate and 3g methyl silicate are dissolved in (solution A) in the 150mL dehydrated alcohol.30g deionized water and 4mL ammoniacal liquor (15mol/L) are dissolved in (solution B) in the 150mL dehydrated alcohol.Under situation about stirring, B is added dropwise to A, produce white precipitate, mixture was stirred 3 hours, centrifugation, throw out washing three times 70 ℃ of following vacuum-dryings, obtains TiO at last
2/ SiO
2Co-precipitation.
B, polycondensation embodiment
Embodiment 7
Be equipped with polyethylene terephthalate according to the PTA legal system.6mol terephthalic acid (PTA) and 8mol ethylene glycol (EG) are mixed, add Co (Ac)
24H
2O 40ppm is according to the TiO of embodiment 2 preparations
2/ SiO
2Precipitation 100ppm (is benchmark with PTA).At 230～260 ℃, pressure is to carry out esterification under the 0.25MPa.After esterification finishes, add trimethyl phosphite 99 40ppm as thermo-stabilizer.Polycondensation is at 280 ℃, and pressure is to carry out under the 50Pa.After 75 minute reaction times, obtaining relative viscosity is 0.716,258.3 ℃ of fusing points, b
*Value is 9.8 polymkeric substance.
Embodiment 8
Be equipped with polyethylene terephthalate according to the PTA legal system.6mol terephthalic acid (PTA) and 8mol ethylene glycol (EG) are mixed, add Co (Ac)
24H
2O 40ppm is according to the TiO of embodiment 4 preparations
2/ SiO
2Precipitation 100ppm (is benchmark with PTA).At 230～260 ℃, pressure is to carry out esterification under the 0.25MPa.After esterification finishes, add trimethyl phosphite 99 40ppm as thermo-stabilizer.Polycondensation is at 276 ℃, and pressure is to carry out under the 42Pa.After 180 minute reaction times, obtaining relative viscosity is 0.719,256.9 ℃ of fusing points, b
*Value is 1.7 polymkeric substance.
Embodiment 9
Be equipped with polyethylene terephthalate according to the PTA legal system.6mol terephthalic acid (PTA) and 8mol ethylene glycol (EG) are mixed, add Co (Ac)
24H
2O 40ppm is according to the TiO of embodiment 5 preparations
2/ SiO
2Precipitation 100ppm (is benchmark with PTA).At 230～260 ℃, pressure is to carry out esterification under the 0.25MPa.After esterification finishes, add trimethyl phosphite 99 40ppm as thermo-stabilizer.Polycondensation is at 285 ℃, and pressure is to carry out under the 30Pa.After 107 minute reaction times, obtaining relative viscosity is 0.755,252.1 ℃ of fusing points, b
*Value is 3 polymkeric substance.
Embodiment 10
Be equipped with polyethylene terephthalate according to the PTA legal system.6mol terephthalic acid (PTA) and 8mol ethylene glycol (EG) are mixed, add Co (Ac)
24H
2O 40ppm is according to the TiO of embodiment 3 preparations
2/ SiO
2Precipitation 100ppm (is benchmark with PTA).At 230～260 ℃, pressure is to carry out esterification under the 0.25MPa.After esterification finishes, add trimethyl phosphite 99 40ppm as thermo-stabilizer.Polycondensation is at 280 ℃, and pressure is to carry out under the 35Pa.After 120 minute reaction times, obtaining relative viscosity is 0.712,250.9 ℃ of fusing points, b
*Value is 3.0 polymkeric substance.
Claims (12)
1. the preparation method of polyester and copolyesters, comprise dicarboxylic ester is carried out transesterification reaction or dicarboxylic acid is directly reacted the polyester precondensation product step that obtains ester and low polyester mixture with excess diol, and with the polycondensation steps of precondensation product in the presence of polycondensation catalyst, said polycondensation catalyst is a kind of titanium titanium-silicon mixed oxide, it is characterized in that the Preparation of catalysts method of being addressed comprises the steps:
(1) the preparation metal alkoxide is dissolved in organic solvent;
The chemical structure of general formula of the metal alkoxide of being addressed is: M (OR)
m, wherein M is Ti or Si, m=4, R are C
nH
2n-1, n=1～6;
(2) aqueous solution adding step (1) with acid or alkali contains in the organic solvent of metal alkoxide, and the collecting precipitation thing obtains catalyzer of the present invention, i.e. TiO
2/ SiO
2Coprecipitate.
2. method according to claim 1 is characterized in that TiO
2/ SiO
2The mol ratio of coprecipitate is: TiO
2: SiO
2=90: 10～20: 80.
3. method according to claim 2 is characterized in that TiO
2/ SiO
2The mol ratio of coprecipitate is: 90: 10～50: 50.
4. method according to claim 1 is characterized in that, selected alkoxide is the monohydroxy-alcohol with 1～6 carbon atom.
5. method according to claim 1 is characterized in that, used organic solvent is selected monohydroxy-alcohol or the polyvalent alcohol with 1～6 carbon atom for use.
6. method according to claim 1 is characterized in that, said acid is mineral acid or organic acid.
7. method according to claim 6 is characterized in that, mineral acid is a kind of in hydrochloric acid, nitric acid, sulfuric acid or the phosphoric acid.
8. method according to claim 7 is characterized in that, organic acid is acetic acid or oxalic acid.
9. method according to claim 1 is characterized in that, said alkali is a kind of in NaOH, KOH or the ammoniacal liquor.
10. method according to claim 1 is characterized in that the add-on of acid or alkali is counted with the volume of organic solvent that contains metal alkoxide: 0.0001～1mol/L.
11., it is characterized in that TiO according to each described method of claim 1～10
2/ SiO
2The consumption of coprecipitate is that benchmark is counted 5-500ppm with ester or the oligomer ester for the treatment of polycondensation.
12. method according to claim 11 is characterized in that TiO
2/ SiO
2The consumption of coprecipitate is that benchmark is counted 20-200ppm with ester or the oligomer ester for the treatment of polycondensation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021452636A CN1174018C (en) | 2002-11-12 | 2002-11-12 | Method for preparing polyester and copolyester |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021452636A CN1174018C (en) | 2002-11-12 | 2002-11-12 | Method for preparing polyester and copolyester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1415643A CN1415643A (en) | 2003-05-07 |
| CN1174018C true CN1174018C (en) | 2004-11-03 |
Family
ID=4750815
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021452636A Expired - Fee Related CN1174018C (en) | 2002-11-12 | 2002-11-12 | Method for preparing polyester and copolyester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1174018C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294176C (en) * | 2003-07-09 | 2007-01-10 | 中国石化上海石油化工股份有限公司 | Composite catalyst for preparing modified polyester |
| CN101270185B (en) * | 2007-03-20 | 2010-11-10 | 上海华明高技术（集团）有限公司 | Process for preparing liquid condition titanium catalyst for preparing polyester and copolyester |
| CN101367919B (en) * | 2007-08-16 | 2011-07-20 | 广州金发科技股份有限公司 | Titanium-silicon catalyst, preparation method and uses thereof |
| CN101367917B (en) * | 2007-08-16 | 2011-10-05 | 金发科技股份有限公司 | Solid phase catalyst, preparation method and uses thereof |
| CN101671435B (en) * | 2008-09-08 | 2011-12-28 | 上海华明高技术（集团）有限公司 | Catalyst for preparing polybutylene succinate and copolyesters thereof and preparation method thereof |
-
2002
- 2002-11-12 CN CNB021452636A patent/CN1174018C/en not_active Expired - Fee Related
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|---|---|
| CN1415643A (en) | 2003-05-07 |
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