CN102443155A - Method for preparing fatty group-aromatic copolyester - Google Patents
Method for preparing fatty group-aromatic copolyester Download PDFInfo
- Publication number
- CN102443155A CN102443155A CN2010105036425A CN201010503642A CN102443155A CN 102443155 A CN102443155 A CN 102443155A CN 2010105036425 A CN2010105036425 A CN 2010105036425A CN 201010503642 A CN201010503642 A CN 201010503642A CN 102443155 A CN102443155 A CN 102443155A
- Authority
- CN
- China
- Prior art keywords
- component
- acid
- amount
- aerogel
- catalyst
- 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
Images
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a method for preparing fatty group-aromatic copolyester, which comprises the following steps: 1) under the existence of an esterification catalyst, an ingredient a is reacted with an ingredient b and an ingredient c, wherein the ingredient a is aromatic diacid and/or ester of aromatic diacid, the b is fatty group dihydric alcohol and/or alicyclic dihydric alcohol, the ingredient c is at least one of aliphatic dibasic acid, alicyclic diacid, ester of aliphatic dibasic acid, ester of alicyclic diacid, anhydride of aliphatic dibasic acid and anhydride of alicyclic diacid. 2) under the condensation polymerization condition, the reaction product obtained in step 1) is reacted under the existence of an aerogel catalyst, the aerogel catalyst is aerogel particles containing TiO2 and ZrO2, the particle diameter of the aerogel particle is 10-200 nanometers, and the density is 30-600mg/cm<3>. The prepared copolyester has the characteristics of high polymerization degree and narrower molecular weight distribution, and is capable of mitigating the color of the biodegradable copolyester from becoming yellow.
Description
Technical field
The present invention relates to a kind of preparation method of aliphatic-aromatic copolyester.
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.Yet these aromatic polyesters are difficult to degraded after discarded using, and also not observing mikrobe so far has any significantly directly degraded to aromatic polyester such as PET, PBT.In order to combine the premium properties of aromatic polyester; Since the eighties in 20th century; Those skilled in the art are devoted to the research of synthetic fat-aromatic copolyester; Promptly in aliphatic polyester, introduce fragrant segment, both guaranteed that this copolyesters has the premium properties of aromatic polyester, had guaranteed the biodegradable of this copolyesters again.
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.Therefore, the method that needs a kind of new biodegradable copolyesters of preparation of exploitation.
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 preparation method of aliphatic-aromatic copolyester is provided; Adopt the copolyesters of this method preparation to have good biodegradability and higher molecular weight, and alleviate or eliminated the polyester product color phenomenon of Huang partially.
The invention provides a kind of preparation method of aliphatic-aromatic copolyester, this method may further comprise the steps:
(1) in the presence of esterifying catalyst; Component a, components b and amount of component b are reacted; Said component a is the ester of aromatic acid and/or aromatic acid; Said components b is aliphatic dihydroxy alcohol and/or alicyclic divalent alcohol, and said amount of component b is at least a in the acid anhydrides of acid anhydrides and alicyclic diprotic acid of ester, aliphatic dibasic acid of aliphatic dibasic acid, alicyclic diprotic acid, the ester of aliphatic dibasic acid, alicyclic diprotic acid;
(2) under the polycondensation condition, the reaction product that obtains in (1) 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 the 10-200 nanometer, density is 30-600mg/cm
3
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 (can polycondensation reaction time be shortened to 3-7 hour from existing 7-10 hour).And; Adopt aerogel catalyst as polycondensation catalyst according to the method for the invention; Reduce the side reaction in the polycondensation process, thereby can obtain the polyester product of HMW and narrow molecular weight distribution, can also reduce or eliminate the phenomenon of final polyester product flavescence simultaneously.
Description of drawings
Fig. 1 representes the nmr spectrum of the product of embodiment 1 preparation.
Embodiment
The invention provides a kind of preparation method of aliphatic-aromatic copolyester, this method may further comprise the steps:
(1) in the presence of esterifying catalyst; Component a, components b and amount of component b are reacted; Said component a is the ester of aromatic acid and/or aromatic acid; Said components b is aliphatic dihydroxy alcohol and/or alicyclic divalent alcohol, and said amount of component b is at least a in the acid anhydrides of acid anhydrides and alicyclic diprotic acid of ester, aliphatic dibasic acid of aliphatic dibasic acid, alicyclic diprotic acid, the ester of aliphatic dibasic acid, alicyclic diprotic acid;
(2) under the polycondensation condition, the reaction product that obtains in (1) 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 the 10-200 nanometer, density is 30-600mg/cm
3
Preparing method according to the aliphatic-aromatic copolyester of inventing is included under the existence of esterifying catalyst; Component a, components b and amount of component b are reacted; Wherein, Said component a is the ester of aromatic acid and/or aromatic acid; Said components b is aliphatic dihydroxy alcohol and/or alicyclic divalent alcohol, and said amount of component b is at least a in the acid anhydrides of acid anhydrides and alicyclic diprotic acid of ester, aliphatic dibasic acid of aliphatic dibasic acid, alicyclic diprotic acid, the ester of aliphatic dibasic acid, alicyclic diprotic acid.
According to the present invention, said component a can synthesize the field various aromatic acids commonly used and/or the ester of aromatic acid for polyester.For example, said component a can be m-phthalic acid, terephthalic acid, DMT. Dimethyl p-benzenedicarboxylate, dimethyl phthalate, 2,6-naphthalic acid, 1; 5-naphthalic acid, 2; 7-naphthalic acid, 4,4 '-biphenyl dicarboxylic acid, 3, one or more in 4 '-biphenyl dicarboxylic acid.Preferably, said component a is terephthalic acid and/or DMT. Dimethyl p-benzenedicarboxylate.
According to the present invention, said components b can be the synthetic field of polyester various aliphatic dihydroxy alcohols and/or alicyclic divalent alcohol commonly used.For example, said components b can be in terepthaloyl moietie, glycol ether, Ucar 35, butyleneglycol, pentanediol, pinakon, cyclohexane diol and the norbornane dimethanol one or more.Said Ucar 35 for example can be 1,2-Ucar 35 and/or 1, and ammediol, said butyleneglycol for example can be 1; 3-butyleneglycol and/or 1,4-butyleneglycol, said pentanediol for example can be 1; 5-pentanediol and/or NSC 6366, said pinakon for example can be 1, the 6-pinakon; Said cyclohexane diol for example can be 1,4-cyclohexane diol and/or 1,3-cyclohexane diol.Preferably, said components b is at least a in Ucar 35, butyleneglycol, pentanediol and the pinakon.
According to the present invention, said amount of component b is at least a in the acid anhydrides of acid anhydrides and alicyclic diprotic acid of ester, aliphatic dibasic acid of aliphatic dibasic acid, alicyclic diprotic acid, the ester of aliphatic dibasic acid, alicyclic diprotic acid.For example; Said amount of component b can be Succinic Acid, Succinic anhydried, dimethyl adipate, hexanodioic acid, adipic anhydride, nonane diacid, sebacic acid, dodecanedioic acid, 1; 4-cyclohexane diacid, 1,2,4; 5-hexanaphthene tetracarboxylic dianhydride, 1, one or more in 4-cyclohexane diacid dimethyl ester and the norbornane diacid.Preferably, said amount of component b is at least a in Succinic Acid, hexanodioic acid and the sebacic acid.
According to the present invention, the mol ratio between said component a and the amount of component b can be carried out appropriate selection according to the use occasion of the aliphatic-aromatic copolyester that finally obtains.Preferably, the mol ratio of said component a and amount of component b is 1: 0.3-20.When the mol ratio between said component a and amount of component b was within the above-mentioned scope, the aliphatic-aromatic copolyester that obtains not only had excellent mechanical property and thermal property, but also has more excellent biodegradable performance.More preferably, the mol ratio of said component a and amount of component b is 1: 0.5-4.
According to the present invention, the total amount of said component a and amount of component b and the mol ratio of components b can adopt the method that well known to a person skilled in the art to confirm according to the molecular weight of the aliphatic-aromatic copolyester of expecting.Preferably, the mol ratio of the total amount of said component a and amount of component b and components b is 1: 1-2.When the mol ratio of the total amount of said component a and amount of component b and components b is within the above-mentioned scope, adopt method provided by the invention can obtain the high-molecular weight aliphatic-aromatic copolyester.More preferably, the mol ratio of the total amount of said component a and amount of component b and components b is 1: 1.15-1.5.
According to the present invention, the method that said component a, components b and amount of component b are reacted is not special to be limited, and can component a, components b and amount of component b reacted through single stage method, also can component a, components b and amount of component b reacted through two-step approach.Wherein, said single stage method is meant through single step reaction and makes component a, components b and amount of component b reaction; Said two-step approach is meant component a and components b is reacted, and the reaction product and the amount of component b of component a and components b is reacted again.
The present invention preferably reacts component a, components b and amount of component b through two-step reaction.Promptly; In step (1); The method that component a, components b and amount of component b are reacted comprises: component a and components b are reacted under first temperature, and the mixture that will obtain after will reacting and amount of component b react under second temperature, said second temperature is than the high 5-30 of first temperature ℃.
According to the present invention, said first temperature is for making the temperature of component a and components b generation esterification or transesterification reaction, and preferably, said first temperature is 150-225 ℃, more preferably 180-210 ℃.The temperature that said second temperature is reacted for the reaction mixture that can make the reaction of component a and components b and obtain and amount of component b.Preferably, said second temperature is 160-240 ℃, more preferably 190-230 ℃.The reaction of said component a and components b preferably proceeds to when low-carbon alcohol (like methyl alcohol, ethanol) that reaction generates all steams with water and stops, and the reaction of said component a reaction mixture that reaction obtains with components b and amount of component b preferably proceeds to when the low-carbon alcohol (like methyl alcohol, ethanol) of reacting generation and water all steam and stops.
Based on the present invention, said esterification catalyst can be the synthetic field of polyester esterification catalyst commonly used.Preferably, said esterifying catalyst is at least a in purity titanium tetraethoxide, four titanium propanolates (like four positive propoxy titanium or tetraisopropoxy titaniums), four titanium butoxide (like four titanium n-butoxide (being also referred to as tetrabutyl titanate)), four hexyloxy titaniums (like four positive hexyloxy titaniums), four (2-ethyl hexyl oxy) titanium, four octyloxy titaniums (like four n-octyloxy titaniums) and the glycolic acid titanium.
According to the present invention, the consumption of said esterifying catalyst can be the conventional amount used of this area.Preferably, the mol ratio of the total amount of said esterifying catalyst and component a and amount of component b is 1: 1000-100000.When the consumption of said catalyzing esterification is within the above-mentioned scope, not only can obtains gratifying esterification speed, and can the thermostability of final aliphatic-aromatic copolyester not had a negative impact.More preferably, the mol ratio of the total amount of said esterifying catalyst and component a and amount of component b is 1: 1500-10000.
Preparing method according to aliphatic-aromatic copolyester of the present invention also is included under the polycondensation condition, and the reaction product that obtains in (1) 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
3
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 copolyesters 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 copolyesters 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.
In the present invention, the method for said co-precipitation can also comprise in the mixing solutions in titanium source and zirconium source and add 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.In the present invention, said pressure is meant absolute pressure.
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.
In the preparation method of said aliphatic-aromatic copolyester provided by the invention; The consumption of said aerogel catalyst can carry out appropriate selection according to the amount of the reaction product that obtains in the step (1), is as the criterion so that the aliphatic-aromatic copolyester that finally obtains satisfies the requirement of expection.Preferably, the mol ratio of the total amount of the consumption of said aerogel catalyst and component a and amount of component b is 1: 1000-100000.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, in step (2), the weight ratio of the reaction product that obtains in the consumption of said aerogel catalyst and the step (1) is 1: 2000-50000.In the present invention, said TiO
2-ZrO
2The molar weight of aerogel catalyst is meant TiO in the said aerogel catalyst
2And ZrO
2The molar weight sum.
The present invention is through using aerogel catalyst to reduce or eliminate the flavescence phenomenon of final polyester product and keep the high-molecular weight of polyester, does 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 200-300 ℃, more preferably 210-270 ℃, further is preferably 230-260 ℃; Pressure is 0.03-0.08MPa, and more preferably 0.04-0.07MPa further is preferably 0.04-0.06MPa; Time is 3-7 hour, more preferably 3-6 hour.Said pressure is meant absolute pressure.
Below in conjunction with embodiment the present invention is explained 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, under 20 ℃ of room temperatures, 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 50 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 the time is 50 minutes, thereby makes 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, the time is 50 minutes; 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 preparation method according to aliphatic-aromatic copolyester of the present invention.
With 0.4 mole DMT. Dimethyl p-benzenedicarboxylate, 0.96 mole 1; Four titanium n-butoxide adding capacity of 4-butyleneglycol and 0.26 mmole are in the there-necked flask of 500mL; With the reaction mass heated to 200 in this there-necked flask ℃, and reaction under agitation, after the methyl alcohol that question response generates steams fully; The hexanodioic acid that in reaction product, adds 0.4 mole then; And temperature of reaction is increased to 220 ℃, treat that water that esterification generates steams fully after, the TiO of preparation in the embodiment that wherein adds 0.30 mmole 1
2-ZrO
2Aerogel catalyst S1, and begin slowly to vacuumize, temperature of reaction is increased to 250 ℃, keep the vacuum tightness of reaction system to be≤500Pa, and carry out polycondensation 6h, obtain aliphatic-aromatic copolyester P1.With AVANCE 300 NMRs of Switzerland Bruker company, adopt deuterochloroform as solvent, this copolyesters is carried out nuclear magnetic resonance experiment, obtain nmr spectrum as shown in Figure 1.
Preparation example 6
With 0.4 mole terephthalic acid, 0.96 mole 1; Four titanium n-butoxide adding capacity of 4-butyleneglycol and 0.26 mmole are in the there-necked flask of 500mL; With the reaction mass heated to 200 in this there-necked flask ℃; And reaction under agitation, after the water that question response generates steams fully, the TiO that in the embodiment that wherein adds 0.30 mmole 1, prepares then
2-ZrO
2Aerogel catalyst S1, and begin slowly to vacuumize, temperature of reaction is increased to 250 ℃, keep the vacuum tightness of reaction system to be≤500Pa, and carry out polycondensation 6h, obtain polyester product.The second-order transition temperature that records this polyester according to DSC (DSC) measuring method is 62.0 ℃.
Preparation example 7
With 0.4 mole hexanodioic acid, 0.96 mole 1; Four titanium n-butoxide adding capacity of 4-butyleneglycol and 0.26 mmole are in the there-necked flask of 500mL; With the reaction mass heated to 220 in this there-necked flask ℃; After treating that water that esterification generates steams fully, the TiO of preparation in the embodiment that wherein adds 0.30 mmole 1
2-ZrO
2Aerogel catalyst S1, and begin slowly to vacuumize, temperature of reaction is increased to 230 ℃, keep the vacuum tightness of reaction system to be≤500Pa, and carry out polycondensation 6h, obtain polyester product.The second-order transition temperature that records this polyester according to DSC (DSC) measuring method is-66.5 ℃.
Embodiment 2
Present embodiment is used for explaining the preparation method according to aliphatic-aromatic copolyester of the present invention.
With 0.26 mole terephthalic acid, 0.96 mole Ucar 35 and the purity titanium tetraethoxide adding capacity of 0.44 mmole is in the there-necked flask of 500mL; With the reaction mass heated to 180 in this there-necked flask ℃, and reaction under agitation, after the methyl alcohol that question response generates steams fully; The sebacic acid that in reaction product, adds 0.39 mole then; And temperature of reaction is increased to 210 ℃, treat that water that esterification generates steams fully after, the TiO of preparation in the embodiment that wherein adds 0.26 mmole 2
2-ZrO
2Aerogel catalyst S2, and begin slowly to vacuumize, temperature of reaction is increased to 190 ℃, keep the vacuum tightness of reaction system to be≤600Pa, and carry out polycondensation 5h, obtain aliphatic-aromatic copolyester P2.
Embodiment 3
Present embodiment is used for explaining the preparation method according to aliphatic-aromatic copolyester of the present invention.
With 0.4 mole 2, the 6-naphthalic acid, 1.18 moles 1, the tetraisopropoxy titanium adding capacity of 5-pentanediol and 0.29 mmole is in the there-necked flask of 500mL; With the reaction mass heated to 210 in this there-necked flask ℃, and reaction under agitation, after the methyl alcohol that question response generates steams fully; The Succinic Acid that in reaction product, adds 0.4 mole then; And temperature of reaction is increased to 220 ℃, treat that water that esterification generates steams fully after, to the TiO of the embodiment that wherein adds 0.12 mmole 3 preparations
2-ZrO
2Aerogel catalyst S3, and begin slowly to vacuumize, temperature of reaction is increased to 230 ℃, keep the vacuum tightness of reaction system to be≤400Pa, and carry out polycondensation 4h, obtain aliphatic-aromatic copolyester P3.
Embodiment 4 and 5
Embodiment 4 and 5 is used for explaining the preparation method according to aliphatic-aromatic copolyester of the present invention.
Method according to embodiment 1 prepares biodegradable copolyesters, and different is the TiO for preparing in the preparation example 4 and 5 with same molar 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 aliphatic-aromatic copolyester P4 and P5.
Embodiment 6
Present embodiment is used for explaining the preparation method according to aliphatic-aromatic copolyester of the present invention.
Method according to embodiment 1 prepares biodegradable copolyesters, and different is, with the TiO of preparation example 1 preparation of 0.15 mmole amount
2-ZrO
2The TiO of preparation example 5 preparations of aerogel catalyst S1 and 0.15 mmole
2-ZrO
2Aerogel catalyst S5 replaces the TiO of preparation in the preparation example 1
2-ZrO
2Aerogel catalyst S1, thus make aliphatic-aromatic copolyester P6.
Comparative Examples 1
Method according to embodiment 1 prepares biodegradable copolyesters, and different is in reaction process, not use the TiO of preparation among the embodiment 1
2-ZrO
2Aerogel catalyst S1, thus make aliphatic-aromatic copolyester DP1.
Comparative Examples 2
Method according to embodiment 1 prepares biodegradable copolyesters, and different is that four titanium n-butoxide with 0.30 mmole in polycondensation process replace preparing the TiO for preparing in the example 1
2-ZrO
2Aerogel catalyst S1, thus make aliphatic-aromatic copolyester DP2.
Comparative Examples 3
Method according to embodiment 1 prepares biodegradable copolyesters, and different is that the method according among the CN 1138339A with 0.30 mmole in polycondensation process prepares TiO
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 aliphatic-aromatic copolyester DP3.
Test case
Detect the weight-average molecular weight of aliphatic-aromatic copolyester P1-P6 and DP1-DP3 with gel permeation chromatography (GPC) appearance; Detect the MWD coefficient of aliphatic-aromatic copolyester P1-P6 and DP1-DP3 according to the gel permeation chromatography method; Detect the second-order transition temperature of aliphatic-aromatic copolyester P1-P6 and DP1-DP3 according to DSC (DSC) measuring method; According to the yellowness index of HG/T3862-2006 method detection aliphatic-aromatic copolyester P1-P5 and DP1-DP3, its detected result is as shown in table 1 below.
Table 1
Second-order transition temperature through polyester that the second-order transition temperature of copolyesters P1 and preparation example 6 and 7 are prepared compares and can find out; The second-order transition temperature of prepared according to the methods of the invention polyester is between aliphatic polyester and aromatic polyester; Explanation thus, the prepared according to the methods of the invention copolyesters is an aliphatic-aromatic copolyester.
In last table 1; Through aliphatic-aromatic copolyester P1 and DP1-DP3 are compared and can find out, the weight-average molecular weight of aliphatic-aromatic copolyester P1 is higher, the MWD coefficient is less, yellowness index is less, this shows; Adopt the biodegradable copolyesters of aerogel catalyst preparation provided by the invention to have the higher polymerization degree; MWD is narrower, and, alleviated the yellow partially defective of biodegradable copolyesters color.
And; Through aliphatic-aromatic copolyester P4, P5 and P6 and P1-P3 are compared and can find out; The weight-average molecular weight of aliphatic-aromatic copolyester P4, P5 and P6 is higher, the MWD coefficient is less, yellowness index is less; This shows, in said aerogel catalyst, contain coating ZrO
2TiO
2-ZrO
2During aerogel catalyst, adopt the biodegradable copolyesters of method preparation of the present invention to have the higher polymerization degree, MWD is narrower, and, further alleviated the yellow partially defective of biodegradable copolyesters color.
Claims (14)
1. the preparation method of an aliphatic-aromatic copolyester is characterized in that, this method may further comprise the steps:
(1) in the presence of esterifying catalyst; Component a, components b and amount of component b are reacted; Said component a is the ester of aromatic acid and/or aromatic acid; Said components b is aliphatic dihydroxy alcohol and/or alicyclic divalent alcohol, and said amount of component b is at least a in the acid anhydrides of acid anhydrides and alicyclic diprotic acid of ester, aliphatic dibasic acid of aliphatic dibasic acid, alicyclic diprotic acid, the ester of aliphatic dibasic acid, alicyclic diprotic acid;
(2) under the polycondensation condition, the reaction product that obtains in (1) 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 the 10-200 nanometer, density is 30-600mg/cm
3
2. method according to claim 1, wherein, the particle diameter of said aerogel catalyst is the 20-150 nanometer, 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, in step (2), the mol ratio of the total amount of the consumption of said aerogel catalyst and component a and amount of component b is 1: 1000-100000.
7. method according to claim 6, wherein, in step (2), the mol ratio of the total amount of the consumption of said aerogel catalyst and component a and amount of component b is 1: 2000-50000.
8. according to claim 1,6 or 7 described methods, wherein, said polycondensation condition comprises: temperature is 200-300 ℃, and pressure is 0.03-0.08MPa, and the time is 3-7 hour.
9. method according to claim 1; Wherein, In step (1); The mol ratio of component a and amount of component b is 1: 0.3-20, the total amount of component a and amount of component b and the mol ratio of components b are 1: 1-2, the mol ratio of the total amount of the consumption of said esterifying catalyst and component a and amount of component b is 1: 1000-100000.
10. method according to claim 9; Wherein, In step (1); The mol ratio of component a and amount of component b is 1: 0.5-4, the total amount of component a and amount of component b and the mol ratio of components b are 1: 1.15-1.5, the mol ratio of the total amount of the consumption of said esterifying catalyst and component a and amount of component b is 1: 1500-10000.
11. according to claim 1,9 or 10 described methods; Wherein, In step (1); The method that component a, components b and amount of component b are reacted comprises: component a and components b are reacted under first temperature, and the mixture that will obtain after will reacting and amount of component b react under second temperature, said second temperature is than the high 5-30 of first temperature ℃.
12. method according to claim 11, wherein, said first temperature is 150-225 ℃, and said second temperature is 160-240 ℃.
13. according to claim 1,9 or 10 described methods, wherein, said esterifying catalyst is at least a in purity titanium tetraethoxide, four titanium propanolates, four titanium butoxide, four hexyloxy titaniums, four (2-ethyl hexyl oxy) titanium, four octyloxy titaniums and the glycolic acid titanium.
14. according to claim 1,9 or 10 described methods; Wherein, Said component a is terephthalic acid and/or DMT. Dimethyl p-benzenedicarboxylate; Said components b is at least a in Ucar 35, butyleneglycol, pentanediol and the pinakon, and said amount of component b is at least a in Succinic Acid, hexanodioic acid and the sebacic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010503642 CN102443155B (en) | 2010-09-30 | 2010-09-30 | Method for preparing fatty group-aromatic copolyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010503642 CN102443155B (en) | 2010-09-30 | 2010-09-30 | Method for preparing fatty group-aromatic copolyester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102443155A true CN102443155A (en) | 2012-05-09 |
| CN102443155B CN102443155B (en) | 2013-03-27 |
Family
ID=46006120
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010503642 Active CN102443155B (en) | 2010-09-30 | 2010-09-30 | Method for preparing fatty group-aromatic copolyester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102443155B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103665777A (en) * | 2013-11-21 | 2014-03-26 | 金发科技股份有限公司 | Biodegradable aliphatic-aromatic copolyester and preparation method thereof |
| CN108715632A (en) * | 2018-06-01 | 2018-10-30 | 弘暖纤科技（北京）有限公司 | The preparation method of aeroge modified polyester fiber and aeroge modified poly ester fabric |
| CN112920388A (en) * | 2021-01-27 | 2021-06-08 | 唐山睿安科技有限公司 | Biodegradable aliphatic-aromatic copolyester and preparation method thereof |
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 201010503642 patent/CN102443155B/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 (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103665777A (en) * | 2013-11-21 | 2014-03-26 | 金发科技股份有限公司 | Biodegradable aliphatic-aromatic copolyester and preparation method thereof |
| CN103665777B (en) * | 2013-11-21 | 2015-11-18 | 金发科技股份有限公司 | A kind of Biodegradable aliphatic-aromatic copolyester and preparation method thereof |
| CN108715632A (en) * | 2018-06-01 | 2018-10-30 | 弘暖纤科技（北京）有限公司 | The preparation method of aeroge modified polyester fiber and aeroge modified poly ester fabric |
| 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 |
| CN112920388A (en) * | 2021-01-27 | 2021-06-08 | 唐山睿安科技有限公司 | Biodegradable aliphatic-aromatic copolyester and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102443155B (en) | 2013-03-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5656716A (en) | Titanium-containing catalyst and process for the production of polyester | |
| CN103059284B (en) | A kind of Micro/nano-scale sheet type titanium polyester catalyst and application thereof | |
| US9074047B2 (en) | Polycondensation catalyst for producing polyester and method for producing the same and method for producing polyester | |
| CN102441370B (en) | Aerogel catalyst and preparation method thereof | |
| CN101891884A (en) | Polyester polycondensation catalyst and preparation method and application thereof | |
| CN112048059A (en) | Method for catalytically synthesizing polyester by using titanium catalyst | |
| CN105273176A (en) | Catalyst used for preparation of polyester, preparation method and application thereof | |
| CN103539928B (en) | Titanium series polyester catalyst and the method for producing semi-dull polyester | |
| CN102443154B (en) | Aerogel catalyst and preparation method thereof | |
| WO2023202449A1 (en) | Solid bimetallic titanium-based polyester catalyst, preparation method therefor, and use thereof | |
| CN102443155B (en) | Method for preparing fatty group-aromatic copolyester | |
| CN109081929A (en) | A method of preparing hydrolysis-resistant polyester film | |
| CN110204700A (en) | A method of efficiently preparation polypropylene terephthalate (PTT) | |
| CN102443157B (en) | Method for preparing aliphatic-aromatic copolyester | |
| TW388765B (en) | Process for the preparation of polyesters and copolyesters | |
| CN102443158B (en) | Method for preparing polyester | |
| CN102443156B (en) | Method for preparing polyester | |
| CN116874755A (en) | Composite titanium catalyst and preparation method and application thereof | |
| JP5658678B2 (en) | Hybrid type polyester resin, film-forming resin composition, polyester film, fiber, and method for producing hybrid type polyester resin | |
| US20140349842A1 (en) | Preparation method of polyester synthesis composite catalyst | |
| CN111944136A (en) | Catalyst for catalyzing esterification reaction and synthesis method thereof | |
| CN114790282B (en) | Preparation method and application of nano-microparticle in-situ polymerization catalyst | |
| CN103469355B (en) | A kind of preparation method of fluorine-containing PET-PET blended fiber | |
| CN114920917A (en) | Low-melting-index high-crystallization-temperature branched poly (butylene terephthalate-adipate) and preparation method thereof | |
| TWI626256B (en) | Catalyst composition and preparation method for synthesizing an amorphous copolyester |
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 |