CN102443156A - Method for preparing polyester - Google Patents
Method for preparing polyester Download PDFInfo
- Publication number
- CN102443156A CN102443156A CN2010105036459A CN201010503645A CN102443156A CN 102443156 A CN102443156 A CN 102443156A CN 2010105036459 A CN2010105036459 A CN 2010105036459A CN 201010503645 A CN201010503645 A CN 201010503645A CN 102443156 A CN102443156 A CN 102443156A
- Authority
- CN
- China
- Prior art keywords
- aerogel
- zro
- catalyst
- polyester
- tio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a method for preparing a polyester, comprising the following step of reacting a reactant in the presence of an aerogel catalyst under the condition of a condensation reaction, wherein the aerogel catalyst is aerogel particles containing TiO2 and ZrO2; diameter of the aerogel particles is 10-200 nm and density is 30-600 mg/cm<3>; the reactant contains an organic ester compound and/or an oligomer of the organic ester compound; the organic ester compound is the compound capable of forming the polyester under the condition of the condensation reaction; and weight-average molecular weight of the oligomer of the organic ester compound is less than 10,000. The method of the invention can effectively alleviate the shortage that the polyester is a little yellow.
Description
Technical field
The present invention relates to a kind of method for preparing polyester.
Background technology
The thermoplasticity aromatic polyester that is widely used at present in industry and the daily life has excellent heat stability ability and mechanical property, is convenient to processing, and is cheap.For example polyethylene terephthalate (PET), and polybutylene terephthalate (PBT) has been widely used in the manufacturing of fiber, film and container.
Catalyzer that can synthesizing polyester has almost related to all the major-minor family elements except that haloid element and lazy element, and still, the compound that more polyester catalyst mainly is antimony, germanium, three series of titanium is used and studied to industrial production at present.Though use the most general antimony-based catalyst catalytic activity high, little to the side reaction promotion, low price, it can be reduced into antimony in reaction, make polyester be the photographic fog look; In addition, antimony-based catalyst also has toxicity, can pollute in process of production, has increased the aftertreatment expense.Germanium series polyester catalyst synthetic PET hue is better, but its catalytic activity is low than antimony, and gained polyester ehter bond is more; Fusing point is lower; And because the germanium resource scarcity of occurring in nature, the germanium series catalysts costs an arm and a leg, and has also limited its widespread use in production of polyester.And for a long time, Titanium series catalyst becomes the maximum kind polyester catalyzer of present research owing to its advantages of high catalytic activity and Safety and Environmental Protection.In polyester synthetic, to compare with antimony-based catalyst, the Titanium series catalyst addition is less, can shorten polycondensation reaction time again; And compare with the germanium series catalysts, the Titanium series catalyst cost is relatively low.Inorganic salt (like potassium fluotitanate, titanium potassium oxalate(T.P.O.) etc.) that the early stage Titanium series catalyst that uses is a titanium or organosilane ester (like tetrabutyl titanate etc.), they exist the shortcoming of poor stability and polyester product yellowing, muddiness always.
In recent years, along with improving constantly of environmental requirement, those skilled in the art have developed many Novel Titanium polyester polycondensation catalysts.For example, CN 1138339A discloses use TiO
2/ SiO
2Coprecipitate or TiO
2/ ZrO
2Coprecipitate as polyester polycondensation catalyst.Though the catalytic activity of the polyester polycondensation catalyst that uses in this patented claim is improved, the form and aspect of polyester product have obtained certain improvement, and the color and luster of polyester product still can turn to be yellow.
Summary of the invention
The objective of the invention is to overcome the above-mentioned defective of the method for existing preparation polyester, a kind of new method for preparing polyester is provided, adopt the polyester of this method preparation to have less form and aspect b
*Value alleviates or has eliminated the polyester product color phenomenon of Huang partially, and this polyester also has higher molecular weight simultaneously.
The invention provides a kind of method for preparing polyester, this method is included under the polycondensation condition, and reactant is reacted in the presence of aerogel catalyst, and this aerogel catalyst is for containing TiO
2And ZrO
2Aerogel particle, the particle diameter of this aerogel particle is the 10-200 nanometer, density is 30-600mg/cm
3This reactant contains the oligopolymer of organic esterified compound and/or organic esterified compound, and said organic esterified compound is for forming the compound of polyester under said polycondensation condition, and the weight-average molecular weight of the oligopolymer of said organic esterified compound is less than 10000.
The polycondensation catalyst that uses according to the method for the invention is aerogel catalyst, not only environmental protection of this aerogel catalyst, nontoxic, and also efficient.
Particularly, compare with the polycondensation catalyst that uses in the existing aliphatic-aromatic preparation process of polyester, said aerogel catalyst can improve condensation polymerization speed, shortens polycondensation reaction time.And; Adopt aerogel catalyst as polycondensation catalyst according to the method for the invention, reduced the side reaction in the polycondensation process, thereby can alleviate or eliminate the phenomenon of final polyester product flavescence; Concrete, the form and aspect b of prepared according to the methods of the invention polyester
*Value is not more than 8, is generally 1-8.
In addition, the middle according to the method for the invention aerogel catalyst that uses is difficult for reuniting, and stable performance is therefore more steady according to the method for the invention, and is easy to control.
Embodiment
The invention provides a kind of method for preparing polyester, this method is included under the polycondensation condition, and reactant is reacted in the presence of aerogel catalyst, and this aerogel catalyst is for containing TiO
2And ZrO
2Aerogel particle, the particle diameter of this aerogel particle is the 10-200 nanometer, is preferably the 20-150 nanometer; Density is 30-600mg/cm
3, be preferably 100-400mg/cm
3, 150-250mg/cm more preferably
3This reactant contains the oligopolymer of organic esterified compound and/or organic esterified compound, and said organic esterified compound is for forming the compound of polyester under said polycondensation condition, and the weight-average molecular weight of the oligopolymer of said organic esterified compound is less than 10000.
According to one embodiment of the present invention, in said aerogel catalyst, TiO
2And ZrO
2Can form through coprecipitation method.In this case, ZrO
2And TiO
2Be distributed in whole aerogel particle equably.In the present invention, said coprecipitation method is meant through in containing two or more cationic homogeneous phase solutions, adding precipitation agent, and through obtaining the sedimentary method of various uniform component after the precipitin reaction.The operating process of said coprecipitation method can be implemented according to the method for routine.
A preferred embodiment of the invention, in said aerogel catalyst, the ZrO in the said aerogel particle of part at least
2Be coated on TiO
2The surface on.In this case; Said aerogel catalyst has the advantage that is difficult for reunion, catalytic activity height and stable performance; Thereby make said polycondensation have higher efficient, and the polyester that adopts this aerogel catalyst to prepare have higher molecular weight and MWD is narrower.Under further preferred situation, in said aerogel catalyst, said ZrO
2Be coated on TiO
2The content of lip-deep aerogel particle be 10-100 weight %, more preferably 50-100 weight %.
According to the present invention, in the said aerogel catalyst, TiO
2With ZrO
2Mol ratio can be 3-20: 1, be preferably 5-15: 1.TiO in said aerogel catalyst
2With ZrO
2Mol ratio in above-mentioned scope the time, can further alleviate the phenomenon of the polyester product flavescence of final preparation.
Based on one embodiment of the present invention, said aerogel catalyst can prepare through following steps:
(1) with the mixing liquid co-precipitation in titanium source and zirconium source, obtains TiO
2-ZrO
2Coprecipitate;
(2) with said TiO
2-ZrO
2Coprecipitate contact with a kind of alcohol, obtain TiO
2-ZrO
2Alcogel;
(3) make said TiO
2-ZrO
2Alcogel in the presence of supercritical medium, carry out supercritical drying;
Said alcohol is the alcohol of C1-C4, and said supercritical medium is carbonic acid gas, methyl alcohol or ethanol.
In the aerogel catalyst according to the above-mentioned steps preparation, ZrO
2With TiO
2Be uniformly distributed in the whole aerogel catalyst.
According to the present invention, in the zr element in titanium elements in the said titanium source and the said zirconium source, the mol ratio in said titanium source and zirconium source can be 3-20: 1, be preferably 5-15: 1.
According to the present invention; The method of said co-precipitation comprises that the mixing solutions with titanium source and zirconium source contacts with alkaline precipitating agent and carries out ageing; The consumption of said alkaline precipitating agent makes that preferably the endpoint pH of reaction system is 8-9; The time that the mixing solutions in said titanium source and zirconium source contacts with alkaline precipitating agent can be 0.5-5 hour, is preferably 1-3 hour.The said aged time can be 10-48 hour, is preferably 15-36 hour.
In the present invention; Said alkaline precipitating agent can be the conventional various alkaline precipitating agent that uses in coprecipitation process; Under the preferable case; Said alkaline precipitating agent is to be selected from least a in sodium hydroxide, Pottasium Hydroxide, yellow soda ash, salt of wormwood, sodium hydrogencarbonate, saleratus, ammoniacal liquor, sodium-acetate and the urea, most preferably is ammoniacal liquor, and the concentration of ammoniacal liquor can be 0.5-6mol/L.
Under preferable case, the method for said co-precipitation also comprises in the mixing solutions in titanium source and zirconium source and adds dispersion agent, reducing the surface tension of this mixing solutions, thereby quickens coprecipitation reaction.Said dispersion agent for example can be in diethylolamine, trolamine, methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, the trimethyl carbinol, acetate, X 2073, sodium lauryl sulphate, StNa, tween, Z 150PH, AEO and the oleic acid at least a.And; Said dispersion agent is selected the different material of solvent types in the mixing solutions with said titanium source and zirconium source for use; For example when the solvent in the mixing solutions in said titanium source and zirconium source is ethanol and/or methyl alcohol, said dispersion agent preferably uses at least a in diethylolamine, trolamine, acetate, X 2073, sodium lauryl sulphate, StNa, tween, Z 150PH, AEO and the oleic acid.The consumption of said dispersion agent can be the 0.1-2 weight % of the weight of the mixing solutions in said titanium source and zirconium source.
According to the present invention, said titanium source and zirconium source can be in the preparation titania aerogel process and the various titaniums source and the zirconium source of conventional use in the preparation ZIRCONIUM DIOXIDE 99.5 gas gel process separately.In a kind of preferred implementation, said titanium source is the titanium alkoxide, and said zirconium source is the zirconium alkoxide.Concrete, said titanium alkoxide is preferably titanium isopropylate and/or tetrabutyl titanate, and said zirconium alkoxide can be four propyl alcohol zirconiums.In another kind of preferred implementation, said titanium source is at least a in titanyl sulfate, titanium sulfate and the titanium tetrachloride, and said zirconium source is at least a in basic zirconium chloride, zirconium chloride, zirconium sulfate and the zirconium nitrate.
According to the present invention, through with said TiO
2-ZrO
2Coprecipitate contact with said alcohol, thereby exchange out said TiO with said alcohol
2-ZrO
2Coprecipitate in solvent (for example, water), to obtain water-free alcogel.In the present invention, said TiO
2-ZrO
2Coprecipitate can comprise with the condition that said alcohol contacts: temperature is 5-45 ℃, is preferably 5-35 ℃; Time is 0.5-3 hour, is preferably 0.5-2 hour.Said alcohol most preferably is ethanol.
Under preferable case, the preparation method of said aerogel catalyst also is included in said TiO
2-ZrO
2Coprecipitate with before said alcohol contacts, to said TiO
2-ZrO
2Coprecipitate wash, with the impurity that adsorbs in this coprecipitate of abundant removal, like fully titanium source, zirconium source, alkaline precipitating agent, dispersion agent and other the ion etc. of reaction.
According to the present invention, said supercritical medium most preferably is ethanol.In this case, said supercritical drying condition is meant the alcoholic acid supercritical state, also is that temperature is 262 ℃, and pressure is 8.5MPa.Under this supercritical drying condition, the time of said supercritical drying can be 30-120 minute, is preferably 30-90 minute.
Based on another embodiment of the invention, said aerogel catalyst can also prepare through following steps:
(1) with ZrO
2Aerogel particle mixes with titanium source solution, and with the mixing liquid co-precipitation that obtains, obtains coating ZrO
2TiO
2-ZrO
2Coprecipitate;
(2) with said TiO
2-ZrO
2Coprecipitate contact with a kind of alcohol, obtain TiO
2-ZrO
2Alcogel;
(3) make said TiO
2-ZrO
2Alcogel in the presence of supercritical medium, carry out supercritical drying;
Said alcohol is the alcohol of C1-C4, and said supercritical medium is carbonic acid gas, methyl alcohol or ethanol.
In the aerogel catalyst according to the above-mentioned steps preparation, ZrO
2Be coated on TiO
2The surface on.
According to aforesaid method, with titanium elements in the said titanium source and said ZrO
2Zr element meter in the aerogel particle, the mol ratio in said titanium source and zirconium source is 3-20: 1, be preferably 5-15: 1.
According to aforesaid method, the method for said co-precipitation comprises titanium source and ZrO
2The mixing liquid of gas gel contacts with alkaline precipitating agent and carries out ageing; The consumption of said alkaline precipitating agent makes that preferably the endpoint pH of reaction system is 8-9; The time that said mixing liquid contacts with alkaline precipitating agent can be 0.5-5 hour, is preferably 1-3 hour.The said aged time can be 10-48 hour, is preferably 15-36 hour.
In the present invention; Said alkaline precipitating agent can be the conventional various alkaline precipitating agent that uses in coprecipitation process; Under the preferable case; Said alkaline precipitating agent is to be selected from least a in sodium hydroxide, Pottasium Hydroxide, yellow soda ash, salt of wormwood, sodium hydrogencarbonate, saleratus, ammoniacal liquor, sodium-acetate and the urea, most preferably is ammoniacal liquor, and the concentration of ammoniacal liquor can be 0.5-6mol/L.
Under preferable case, the method for said co-precipitation also comprises in said mixing liquid and adds dispersion agent, reducing the surface tension of this mixing liquid, thereby quickens coprecipitation reaction.Said dispersion agent for example can be in diethylolamine, trolamine, methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, the trimethyl carbinol, acetate, X 2073, sodium lauryl sulphate, StNa, tween, Z 150PH, AEO and the oleic acid at least a.And; Said dispersion agent select for use with said mixing liquid in the different material of solvent types; For example when the solvent in the said mixing liquid is ethanol and/or methyl alcohol, said dispersion agent preferably uses at least a in diethylolamine, trolamine, acetate, X 2073, sodium lauryl sulphate, StNa, tween, Z 150PH, AEO and the oleic acid.The consumption of said dispersion agent can be the 0.1-2 weight % of the weight of said mixing liquid.
Based on said method, said titanium source can be conventional various titaniums source of using in the preparation titania aerogel process.Under the preferable case, said titanium source is at least a in titanium isopropylate, tetrabutyl titanate, titanyl sulfate, titanium sulfate and the titanium tetrachloride.
According to aforesaid method, said ZrO
2Aerogel particle can be commercially available, and also can adopt conventional method preparation.Said ZrO
2Aerogel particle for example can adopt the combining method of the precipitator method-supercritical drying to prepare, and is concrete, ZrO
2The preparation method of aerogel particle comprises adding acidic precipitation agent in the solution in zirconium source, is adjusted to 5-6 with the endpoint pH with reaction system, ageing 10-48 hour then (being preferably 15-36 hour); Throw out washing with obtaining after the ageing obtains ZrO with alcohol generation solvent exchange afterwards
2Alcogel; Then, make this alcogel in the presence of supercritical medium, carry out supercritical drying.Said zirconium source for example can be basic zirconium chloride, and said acidic precipitation agent for example can be hydrochloric acid, and said alcohol for example can be ethanol.
According to aforesaid method, through with said TiO
2-ZrO
2Coprecipitate contact with said alcohol, thereby exchange out said TiO with said alcohol
2-ZrO
2Coprecipitate in solvent (for example, water), to obtain water-free alcogel.In the present invention, said TiO
2-ZrO
2Coprecipitate can comprise with the condition that said alcohol contacts: temperature is 5-45 ℃, is preferably 5-35 ℃; Time is 0.5-3 hour, is preferably 0.5-2 hour.Said alcohol most preferably is ethanol.
Under preferable case, the preparation method of said aerogel catalyst also is included in said TiO
2-ZrO
2Coprecipitate with before said alcohol contacts, to said TiO
2-ZrO
2Coprecipitate wash, with the impurity that adsorbs in this coprecipitate of abundant removal, like fully titanium source, zirconium source, alkaline precipitating agent, dispersion agent and other the ion etc. of reaction.
According to the present invention, said supercritical medium most preferably is ethanol.In this case, said supercritical drying condition is meant the alcoholic acid supercritical state, also is that temperature is 262 ℃, and pressure is 8.5MPa.Under this supercritical drying condition, the time of said supercritical drying can be 30-120 minute, is preferably 30-90 minute.
According to said method provided by the invention, the consumption of said aerogel catalyst can carry out appropriate selection according to the amount of reactant, is as the criterion so that the polyester that finally obtains satisfies the requirement of expection.Preferably, the weight ratio of the consumption of said aerogel catalyst and said reactant is 1: 1500-100000.When the consumption of said aerogel catalyst is within the above-mentioned scope; Not only can obtain the high-molecular weight polyester product; But also can accelerate the speed of polycondensation, reduce the side reaction in the polycondensation process, thereby reduce or eliminate the flavescence phenomenon of polyester product.More preferably, the weight ratio of the consumption of said aerogel catalyst and said reactant is 1: 3000-40000.
The present invention is through using aerogel catalyst to improve the molecular weight of final copolyesters, and reduces or eliminates the flavescence phenomenon of final polyester product, do not have special qualification for the condition of said polycondensation.Said polycondensation can be carried out well known to a person skilled in the art under the condition.Preferably, said polycondensation condition comprises: temperature is 250-300 ℃, more preferably 270-290 ℃; Pressure is 0-0.08MPa, is preferably 0-0.05MPa; Time is 50-200 minute, is preferably 80-150 minute.Said pressure is meant absolute pressure.
Preparing method according to polyester of the present invention; Said reactant contains the oligopolymer of organic esterified compound and/or this organic esterified compound; Said organic esterified compound is for forming the compound of polyester under said polycondensation condition, the weight-average molecular weight of the oligopolymer of said organic esterified compound is less than 10000.
Preferably, the total content of the oligopolymer of the organic esterified compound in the said reactant and/or this organic esterified compound is more than the 80 weight %.When the total content of the organic esterified compound in said reactant and/or the oligopolymer of this organic esterified compound is in the above-mentioned scope, can further reduce the side reaction in the polycondensation process.
According to the present invention, said organic esterified compound can form the organic ester of polyester through self polycondensation under the polycondensation condition.Preferably, said organic esterified compound is the organic esterified compound with hydroxyl and carboxyl.
More preferably, said organic esterified compound is the compound of structural formula shown in following formula 1:
Formula 1
Wherein, Ar is at least a group that has in phenyl ring, naphthalene nucleus and the anthracene nucleus,, R
1Alkylidene group or C3-C20 cycloalkylidene for C1-C20.
Preferably, in formula 1, Ar is following aryl:
Wherein, R
2, R
3, R
4, R
5, R
6And R
7Be independently of one another hydrogen, C1-C4 alkyl, F, Cl ,-NO
2,-CN or-OR
8, wherein, R
8Alkyl for C1-C4; R
1Alkylidene group for C2-C8.
Most preferably, said organic esterified compound is ethylene glycol terephthalate, mutual-phenenyl two acid bromide two alcohol ester, propylene glycol ester terephthalate, 2,6-(ethylene naphthalate) and 2, at least a in the 6-naphthalic acid butanediol ester.
According to the present invention, the oligopolymer of said organic esterified compound and/or organic esterified compound can be commercially available, and also can adopt the methods known in the art preparation.For example: can be in the presence of esterifying catalyst, di-carboxylic acid is contacted under enzymatic synthesis condition with divalent alcohol and obtains; Perhaps can be in the presence of transesterification catalyst, dibasic acid esters is contacted under transesterification conditions with divalent alcohol and obtains.Can select suitable di-carboxylic acid, divalent alcohol and dibasic acid esters according to the structure of the oligopolymer of organic esterified compound and/or the organic esterified compound of expection.For example, when said organic acid acetic is the oligopolymer of ethylene glycol terephthalate and/or ethylene glycol terephthalate, can be in the presence of transesterification catalyst, DMT. Dimethyl p-benzenedicarboxylate is contacted under transesterification conditions with terepthaloyl moietie and obtains; Also can be in the presence of esterifying catalyst, terephthalic acid is contacted under the esterification condition with terepthaloyl moietie and obtains.
Said transesterification catalyst and esterifying catalyst can be the synthetic field of polyester various catalyzer commonly used; For example: said transesterification catalyst or esterifying catalyst separately can be separated for lime acetate, magnesium acetate, zinc acetate, acetate, in sugar of lead and the cobaltous acetate one or more, and said transesterification catalyst or esterifying catalyst can use with the form that contains crystal water.The consumption of said transesterification catalyst and esterifying catalyst is that the synthetic field of polyester is known, and for example: the mol ratio of said esterifying catalyst or transesterification catalyst and di-carboxylic acid can be 1: 1000-100000 is preferably 1: 1500-10000.
According to the present invention; When preparing the oligopolymer of organic esterified compound and/or organic esterified compound through transesterify or esterification; The existence of said aerogel catalyst can not have a negative impact to esterification or transesterification reaction; Therefore; Said aerogel catalyst can add in the system of esterification or transesterification reaction in the process of the oligopolymer of preparation said organic esterified compound and/or organic esterified compound, and question response carries out polycondensation after generating the oligopolymer of organic esterified compound and/or organic esterified compound again; Also can with the oligopolymer of said organic esterified compound and/or organic esterified compound with carry out polycondensation again after said aerogel catalyst mixes.
Preparing method according to preparation polyester of the present invention; This method can also comprise that the mixture with said reactant and aerogel catalyst mixes with stablizer, and said stablizer is at least a in trimethyl phosphite 99, triphenylphosphate, triphenyl phosphite, the triethyl phosphate.Said stablizer can avoid because the existence of esterifying catalyst or transesterification catalyst and disadvantageous effect that the thermostability of final polyester product is produced.The consumption of said stablizer is well known in the art.Preferably, the weight ratio of said stablizer and said reactant is 1: 6000-35000, more preferably 1: 10000-30000.
Below in conjunction with embodiment the present invention is described in more detail.
In following preparation example, the particle diameter of aerogel particle records according to transmission electron microscope (TEM) observational technique, and the density of aerogel particle records according to the apparent density testing method of Guangzhou Q/HG1-271-86 " AWC WHITE CARBON BLACK ".
Preparation example 1
This preparation example is used for preparing the aerogel catalyst that uses according to the method for the invention.
The titanium isopropylate of 82.7mmol and the four propyl alcohol zirconiums of 9.14mmol are dissolved in the absolute ethyl alcohol of 150mL, obtain solution A 1.Under agitation, under 20 ℃ of room temperatures, be that the ammoniacal liquor of 3mol/L slowly is added dropwise in the solution A 1 with concentration, when the pH of solution value is 9, stop dropping ammonia, continue to stir 2h, ageing 20h then.With the mixture spinning that obtains after the ageing, wash three times, and the coprecipitate that will obtain after will washing mixes with weight ratio with ethanol at 1: 20; Obtain alcogel, this alcogel added in autoclave, with absolute ethyl alcohol as supercritical medium; Under 262 ℃, the condition of 8.5MPa, this alcogel is carried out supercritical drying, the supercritical drying time is 80 minutes; Thereby make particle diameter is the 50-100 nanometer, and density is 190mg/cm
3TiO
2-ZrO
2Aerogel particle S1.
Preparation example 2
This preparation example is used for preparing the aerogel catalyst that uses according to the method for the invention.
The concentration of measuring 18mL is that titanyl sulfate solution and the concentration of 40mL of 4mol/L is that the zirconium nitrate solution of 0.2mol/L mixes, and obtains solution A 2.Under agitation, under 20 ℃ of room temperatures, be that the ammoniacal liquor of 3mol/L slowly is added dropwise in the solution A 2 with concentration, when the pH of solution value is 8, stop dropping ammonia, continue to stir 2h, ageing 36h then.With the mixture spinning that obtains after the ageing, wash three times, and the coprecipitate that will obtain after will washing mixes with weight ratio with ethanol at 1: 20; Obtain alcogel, this alcogel added in autoclave, with absolute ethyl alcohol as supercritical medium; Under 262 ℃, the condition of 8.5MPa, this alcogel is carried out supercritical drying, the supercritical drying time is 60 minutes; Thereby make particle diameter is the 60-120 nanometer, and density is 180mg/cm
3TiO
2-ZrO
2Aerogel particle S2.
Preparation example 3
This preparation example is used for preparing the aerogel catalyst that uses according to the method for the invention.
With the concentration of 12.18mL is the TiCl of 4mol/L
4Solution and the concentration of 27.0mL are that the zirconium oxychloride solution of 0.2mol/L mixes, and obtain solution A 3.Under agitation, be that the 3mol/L sodium hydroxide solution slowly is added dropwise in the solution A 3 with concentration, when the pH of solution value is 8.5, stop dropping sodium solution, continue to stir 1h, ageing 20h then.With the mixture spinning that obtains after the ageing, wash three times, and the coprecipitate that will obtain after will washing mixes with weight ratio with ethanol at 1: 20; Obtain alcogel, this alcogel added in autoclave, with absolute ethyl alcohol as supercritical medium; Under 262 ℃, the condition of 8.5MPa, this alcogel is carried out supercritical drying, the supercritical drying time is 90 minutes; Thereby make particle diameter is the 80-150 nanometer, and density is 175mg/cm
3TiO
2-ZrO
2Aerogel particle S3.
Preparation example 4
This preparation example is used for preparing the aerogel catalyst that uses according to the method for the invention.
(1) preparation ZrO
2Aerogel particle
The concentration of measuring 45mL is the zirconium oxychloride solution of 0.2mol/L, under agitation, under 20 ℃ of room temperatures, is that the ammoniacal liquor of 3mol/L slowly is added dropwise in this solution with concentration; When the pH of this solution value is 9, stop dropping ammonia, and ageing 20h; Wash and spinning with deionized water successively then, the throw out that obtains is mixed with weight ratio with ethanol at 1: 20, obtain alcogel; This alcogel is added in autoclave, with absolute ethyl alcohol as supercritical medium, under 262 ℃, the condition of 8.5MPa; This alcogel is carried out supercritical drying, and be 50 minutes time of drying, thereby make ZrO
2Aerogel particle.
(2) preparation TiO
2-ZrO
2Aerogel particle
The concentration of measuring 12.18ml is the TiCl of 4mol/L
4Solution, and the ZrO that in (1) that wherein adds 5.38mmol, makes
2Aerogel particle under 20 ℃ of room temperatures, stirs 1h and obtains mixing liquid A4.Then, under agitation, be that the ammoniacal liquor of 3mol/L slowly is added dropwise among the mixing liquid A4 with concentration, when the pH of solution value is 9, stop dropping ammonia, continue to stir 1h, ageing 20h then.With the mixture spinning that obtains after the ageing, wash three times, and the coprecipitate that will obtain after will washing mixes with weight ratio with ethanol at 1: 20; Obtain alcogel, this alcogel added in autoclave, with absolute ethyl alcohol as supercritical medium; Under 262 ℃, the condition of 8.5MPa, this alcogel is carried out supercritical drying, the supercritical drying time is 80 minutes; Thereby make particle diameter is the 50-100 nanometer, and density is 195mg/cm
3Coating ZrO
2TiO
2-ZrO
2Aerogel particle S4.
Preparation example 5
This preparation example is used for preparing the aerogel catalyst that uses according to the method for the invention.
(1) preparation ZrO
2Aerogel particle
Method according to embodiment 4 prepares ZrO
2Aerogel particle.
(2) preparation TiO
2-ZrO
2Aerogel particle
The tetrabutyl titanate of 72.0mmol is dissolved in the absolute ethyl alcohol of 80mL, and the ZrO that in (1) that wherein adds 5.38mmol, makes
2Aerogel particle under 20 ℃ of room temperatures, stirs 1h and obtains mixing liquid A5.Then, under agitation, be that the sodium hydroxide solution of 3mol/L slowly is added dropwise among the mixing liquid A4 with concentration, when the pH of solution value is 9, stop dropping sodium solution, continue to stir 1h, ageing 20h then.With the mixture spinning that obtains after the ageing, wash three times, and the coprecipitate that will obtain after will washing mixes with weight ratio with ethanol at 1: 20; Obtain alcogel, this alcogel added in autoclave, with absolute ethyl alcohol as supercritical medium; Under 262 ℃, the condition of 8.5MPa, this alcogel is carried out supercritical drying, be 50 minutes time of drying; Thereby make particle diameter is the 60-110 nanometer, and density is 182mg/cm
3Coating ZrO
2TiO
2-ZrO
2Aerogel particle S5.
Embodiment 1
Present embodiment is used for explaining the method for preparing polyester according to of the present invention.
With the terephthalic acid of 500g, the terepthaloyl moietie of 317g and the Co (CH of 0.02g
3COO)
24H
2The TiO of O and 0.08g
2-ZrO
2Aerogel catalyst S1 adding capacity is in the reaction kettle of 2.5L; With the reaction mass heated to 220 in this reaction kettle ℃; Pressure remains 0.25MPa; And reaction under agitation, after the water that question response generates steamed fully, the oligopolymer ((GPC) records weight-average molecular weight less than 10000 with gel permeation chromatograph) and the ethylene glycol terephthalate total content that obtain ethylene glycol terephthalate were the mixture of 85 weight %; Then, in this mixture, add the trimethyl phosphite 99 of 0.04 gram, and reaction kettle is slowly vacuumized and temperature of reaction is increased to 280 ℃, keep vacuum tightness (also referring to absolute pressure), reacted 90 minutes for not being higher than 50Pa, must polyester P1.
Embodiment 2
Present embodiment is used for explaining the method for preparing polyester according to of the present invention.
With 2 of 500g, the Co (CH of the Ucar 35 of 6-naphthalic acid and 350g and 0.02g
3COO)
24H
2O adding capacity is in the reaction kettle of 2.5L, and with the reaction mass heated to 230 in this reaction kettle ℃, pressure remains 0.25MPa; And reaction under agitation, after the water that question response generates steams fully, obtain 2; The oligopolymer of 6-naphthalic acid propylene glycol ester (recording weight-average molecular weight less than 10000) and 2 with GPC; 6-naphthalic acid propylene glycol ester total content is the mixture of 87 weight %, then, and to the TiO that wherein adds 0.05g
2-ZrO
2Aerogel catalyst S2, and reaction kettle slowly vacuumized and temperature of reaction is increased to 270 ℃, keep vacuum tightness (also referring to absolute pressure) for not being higher than 40Pa, reacted 100 minutes, must polyester P2.
Embodiment 3
Present embodiment is used for explaining the method for preparing polyester according to of the present invention.
With 1 of the terephthalic acid of 500g, 400g, the Co (CH of 4-butyleneglycol and 0.02g
3COO)
24H
2O adding capacity is in the reaction kettle of 2.5L; With the reaction mass heated to 250 in this reaction kettle ℃, pressure remains 0.25MPa, and reaction under agitation; After the water that question response generates steams fully; The oligopolymer (recording weight-average molecular weight less than 10000 with GPC) and the mutual-phenenyl two acid bromide two alcohol ester's total content that obtain the mutual-phenenyl two acid bromide two alcohol ester are the mixture of 86 weight %, then, and to the TiO that wherein adds 0.10g
2-ZrO
2Aerogel catalyst S3, and reaction kettle slowly vacuumized and temperature of reaction is increased to 290 ℃, keep vacuum tightness (also referring to absolute pressure) for not being higher than 50Pa, reacted 120 minutes, must polyester P3.
Embodiment 4 and 5
Embodiment 4 and 5 is used for explaining the method for preparing polyester according to of the present invention.
Method according to embodiment 1 prepares polyester, and different is the TiO for preparing in the preparation example 4 and 5 with identical weight respectively
2-ZrO
2Aerogel catalyst S4 and S5 replace the TiO of preparation in the preparation example 1
2-ZrO
2Aerogel catalyst S1, thus make polyester P4 and P5 respectively.
Embodiment 6
Present embodiment is used for explaining the method for preparing polyester according to of the present invention.
Method according to embodiment 1 prepares polyester, and different is, with the TiO of preparation example 1 preparation of 0.04 gram
2-ZrO
2The TiO of preparation example 5 preparations of aerogel catalyst S1 and 0.04 gram
2-ZrO
2Aerogel catalyst S5 replaces the TiO of preparation in the preparation example 1
2-ZrO
2Aerogel catalyst S1, thus make polyester P6 respectively.
Comparative Examples 1
500g terephthalic acid, 317g terepthaloyl moietie and 0.1g Antimony Trioxide: 99.5Min are added in the 2.5L reaction kettle, and with reaction mass heated to 220 ℃, pressure remains on 0.25MPa; Reaction under agitation, treat that water that esterification generates steams fully after, beginning slowly vacuumizes; Temperature of reaction is raised to 280 ℃; Keep vacuum tightness for not being higher than 50Pa, reacted 90 minutes, make polyester DP1.
Comparative Examples 2
Co (CH with 500g terephthalic acid, 317g terepthaloyl moietie, 0.02g
3COO)
24H
2O and 0.08g antimony acetate add in the 2.5L reaction kettle, and with reaction mass heated to 220 ℃, pressure remains on 0.25MPa; Reaction under agitation, treat that water that esterification generates steams fully after, beginning slowly vacuumizes; Temperature of reaction is raised to 280 ℃; Keep vacuum tightness for not being higher than 50Pa, reacted 90 minutes, obtain polyester DP2.
Comparative Examples 3
Method according to embodiment 1 prepares polyester, and different is, prepares TiO with the method according among the CN1138339A of 0.08 gram
2-ZrO
2Coprecipitate replace the TiO of preparation among the embodiment 1
2-ZrO
2Aerogel catalyst S 1, wherein TiO
2-ZrO
2Coprecipitate in TiO
2With ZrO
2Mol ratio and embodiment 1 in the TiO of preparation
2-ZrO
2Aerogel catalyst S1 is identical, thereby makes polyester DP3.
Test case
Detect polyester P1-P6 and DP1-DP3 intrinsic viscosity with dark type viscometer, said intrinsic viscosity is relevant with the thermal property and the material property of polyester, and intrinsic viscosity is big more, and then the thermal property of polyester is good more;
Detect the form and aspect b of polymerisate P1-P6 and DP1-DP3 according to the method for GB/T14190-93
*Value, form and aspect b
*Be worth more for a short time, then the tone of polymerisate is white more, otherwise then more yellow;
Detect the weight-average molecular weight of polyester P1-P6 and DP1-DP3 with GPC;
Detect the MWD coefficient of polyester P1-P6 and DP1-DP3 with GPC;
Detect the second-order transition temperature of polyester P1-P6 and DP1-DP3 according to DSC (DSC) measuring method;
Its detected result is as shown in table 1 below.
Table 1
In last table 1, through polyester P1 and DP1-DP3 are compared and can find out, polyester P1 has the intrinsic viscosity close with polyester DP1-DP3, but form and aspect b
*Be worth lower.That is, can alleviate the yellow partially defective of polyester color according to the method for the invention effectively.
Claims (14)
1. a method for preparing polyester is characterized in that, this method comprises: under the polycondensation condition, reactant is reacted in the presence of aerogel catalyst, this aerogel catalyst is for containing TiO
2And ZrO
2Aerogel particle, the particle diameter of this aerogel particle is a rice in the 10-200, density is 30-600mg/cm
3This reactant contains the oligopolymer of organic esterified compound and/or organic esterified compound, and said organic esterified compound is for forming the compound of polyester under said polycondensation condition, and the weight-average molecular weight of the oligopolymer of said organic esterified compound is less than 10000.
2. method according to claim 1, wherein, the particle diameter of said aerogel catalyst is a rice in the 20-150, density is 100-400mg/cm
3
3. method according to claim 1 and 2, wherein, the ZrO in the said aerogel catalyst of part at least
2Be coated on TiO
2The surface.
4. method according to claim 1 and 2, wherein, in said aerogel catalyst, TiO
2With ZrO
2Mol ratio be 3-20: 1.
5. method according to claim 4, wherein, in said aerogel catalyst, TiO
2With ZrO
2Mol ratio be 5-15: 1.
6. method according to claim 1, wherein, the weight ratio of the consumption of said aerogel catalyst and said reactant is 1: 1500-100000.
7. method according to claim 6, wherein, the weight ratio of the consumption of said aerogel catalyst and said reactant is 1: 3000-40000.
8. according to claim 1,6 or 7 described methods, wherein, said polycondensation condition comprises: temperature is 250-300 ℃, and pressure is 0-0.08MPa, and the time is 50-200 minute.
9. method according to claim 1, wherein, said organic esterified compound is the organic esterified compound with hydroxyl and carboxyl.
10. method according to claim 9, wherein, said organic esterified compound is the compound of structural formula shown in following formula 1:
Formula 1
Wherein, Ar is at least a group that has in phenyl ring, naphthalene nucleus and the anthracene nucleus, R
1Alkylidene group or C3-C20 cycloalkylidene for C1-C20.
11. method according to claim 10, wherein, in formula 1, Ar is following aryl:
Wherein, R
2, R
3, R
4, R
5, R
6And R
7Be independently of one another hydrogen, C1-C4 alkyl, F, Cl ,-NO
2,-CN or-OR
8, wherein, R
8Alkyl for C1-C4; R
1Alkylidene group for C2-C8.
12. method according to claim 11; Wherein, Said organic esterified compound is ethylene glycol terephthalate, mutual-phenenyl two acid bromide two alcohol ester, propylene glycol ester terephthalate, 2,6-(ethylene naphthalate) and 2, at least a in the 6-naphthalic acid butanediol ester.
13. according to claim 1,9,10,11 or 12 described methods; Wherein, Said method comprises that also the mixture with said reactant and aerogel catalyst mixes with stablizer, and said stablizer is at least a in trimethyl phosphite 99, triphenylphosphate, triphenyl phosphite, the triethyl phosphate.
14. method according to claim 13, wherein, the weight ratio of said stablizer and said reactant is 1: 6000-35000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010503645 CN102443156B (en) | 2010-09-30 | 2010-09-30 | Method for preparing polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010503645 CN102443156B (en) | 2010-09-30 | 2010-09-30 | Method for preparing polyester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102443156A true CN102443156A (en) | 2012-05-09 |
| CN102443156B CN102443156B (en) | 2013-07-03 |
Family
ID=46006121
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010503645 Active CN102443156B (en) | 2010-09-30 | 2010-09-30 | Method for preparing polyester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102443156B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109112697A (en) * | 2018-08-06 | 2019-01-01 | 佛山市南海区佳妍内衣有限公司 | Novel health-care underwear textile fabric |
| CN110041516A (en) * | 2019-05-10 | 2019-07-23 | 淄博成达塑化有限公司 | The preparation method of permanent seal cooling poly butylene succinate |
| WO2019228475A1 (en) * | 2018-06-01 | 2019-12-05 | 弘暖纤科技（北京）有限公司 | Preparation methods for aerogel modified polyester fiber and aerogel modified polyester fabric |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1138339A (en) * | 1994-01-07 | 1996-12-18 | 阿克佐诺贝尔公司 | Process for producing polyesters and copolyesters |
| CN1566180A (en) * | 2003-07-09 | 2005-01-19 | 中国石化上海石油化工股份有限公司 | Process for preparing modified polyester |
| CN101134809A (en) * | 2007-05-21 | 2008-03-05 | 李鹏 | Technical method for preparing aliphatic polyester |
-
2010
- 2010-09-30 CN CN 201010503645 patent/CN102443156B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1138339A (en) * | 1994-01-07 | 1996-12-18 | 阿克佐诺贝尔公司 | Process for producing polyesters and copolyesters |
| CN1566180A (en) * | 2003-07-09 | 2005-01-19 | 中国石化上海石油化工股份有限公司 | Process for preparing modified polyester |
| CN101134809A (en) * | 2007-05-21 | 2008-03-05 | 李鹏 | Technical method for preparing aliphatic polyester |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019228475A1 (en) * | 2018-06-01 | 2019-12-05 | 弘暖纤科技（北京）有限公司 | Preparation methods for aerogel modified polyester fiber and aerogel modified polyester fabric |
| CN109112697A (en) * | 2018-08-06 | 2019-01-01 | 佛山市南海区佳妍内衣有限公司 | Novel health-care underwear textile fabric |
| CN110041516A (en) * | 2019-05-10 | 2019-07-23 | 淄博成达塑化有限公司 | The preparation method of permanent seal cooling poly butylene succinate |
| CN110041516B (en) * | 2019-05-10 | 2019-12-03 | 淄博成达塑化有限公司 | The preparation method of permanent seal cooling poly butylene succinate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102443156B (en) | 2013-07-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103435794B (en) | A kind of preparation method of polycondensation catalyst, catalyzer prepared therefrom and the method with this catalyst preparing PBS and multipolymer thereof | |
| CN103059284B (en) | A kind of Micro/nano-scale sheet type titanium polyester catalyst and application thereof | |
| CN102441370B (en) | Aerogel catalyst and preparation method thereof | |
| CN101314637A (en) | Poly-p-benzene dicarboxylic acid 1,2-propylene glycol ester and copolyester, and preparation thereof | |
| CN101891884A (en) | Polyester polycondensation catalyst and preparation method and application thereof | |
| CN102443158B (en) | Method for preparing polyester | |
| CN102443154B (en) | Aerogel catalyst and preparation method thereof | |
| CN102443156B (en) | Method for preparing polyester | |
| CN103539928B (en) | Titanium series polyester catalyst and the method for producing semi-dull polyester | |
| CN115873223A (en) | Preparation method of poly terephthalic acid-butylene carbonate | |
| CN111378105B (en) | Preparation method of biomass composite catalyst and preparation method of polybutylene terephthalate adipate | |
| CN109081929A (en) | A method of preparing hydrolysis-resistant polyester film | |
| CN113999379B (en) | Titanium composite catalyst for polyester synthesis and preparation and application thereof | |
| CN102443155B (en) | Method for preparing fatty group-aromatic copolyester | |
| CN116874755A (en) | Composite titanium catalyst and preparation method and application thereof | |
| CN115181256B (en) | Cage-shaped polysilsesquioxane titanium catalyst, liquid catalyst, preparation method and application thereof | |
| CN102443157B (en) | Method for preparing aliphatic-aromatic copolyester | |
| CN111944136A (en) | Catalyst for catalyzing esterification reaction and synthesis method thereof | |
| CN111040143A (en) | Preparation method of water-soluble polyester | |
| CN103804665A (en) | Preparation method of polyhydroxyl polyester | |
| CN109575262B (en) | Production method of semi-dull titanium polyester | |
| CN102850534B (en) | Method for preparing high-quality polybutylene terephthalate (PBT) by TiO2/SiO2 composite nano-catalyst | |
| CN109666131B (en) | Preparation method of polybutylene terephthalate resin | |
| CN114621426A (en) | Catalyst for synthesizing degradable polyester and preparation method and application thereof | |
| CN103772682A (en) | Method for preparing polytrimethylene terephthalate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |