CN102443155B - Method for preparing fatty group-aromatic copolyester - Google Patents
Method for preparing fatty group-aromatic copolyester Download PDFInfo
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- CN102443155B CN102443155B CN 201010503642 CN201010503642A CN102443155B CN 102443155 B CN102443155 B CN 102443155B CN 201010503642 CN201010503642 CN 201010503642 CN 201010503642 A CN201010503642 A CN 201010503642A CN 102443155 B CN102443155 B CN 102443155B
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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 energy 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 using discarded rear hard degradation, and also not observing so far microorganism has any significantly directly degraded to aromatic polyester such as PET, PBT.For the premium properties in conjunction with aromatic polyester, since the eighties in 20th century, those skilled in the art are devoted to the research of synthetic fat-aromatic copolyester, namely in aliphatic polyester, introduce fragrant segment, both guaranteed that this copolyesters has the premium properties of aromatic polyester, had guaranteed again the biodegradable of this copolyesters.
Catalyzer that can synthesizing polyester has almost related to all the major-minor family elements except haloid element and inert element, and still, the more polyester catalyst of industrial production application and research mainly is the compound of antimony, germanium, three series of titanium at present.Although 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.The PET hue that the germanium series polyester catalyst synthesizes 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 is expensive, has also limited its widespread use in production of polyester.And for a long time, Titanium series catalyst becomes a kind polyester catalyzer of present most study owing to its higher 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.The Titanium series catalyst of early application is the inorganic salt (such as potassium fluotitanate, titanium potassium oxalate(T.P.O.) etc.) of titanium or organosilane ester (such as tetrabutyl titanate etc.), and they exist poor stability and polyester product yellowing, muddy shortcoming 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.Although the catalytic activity of the polyester polycondensation catalyst that uses in this patent application 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 object of the invention is to overcome the existing defects for preparing the method for polyester, a kind of preparation method of aliphatic-aromatic copolyester is provided, adopt the copolyesters of the method preparation to have good biodegradability and higher molecular weight, and alleviate or eliminated the partially yellow phenomenon of polyester product color.
The invention provides a kind of preparation method of aliphatic-aromatic copolyester, the method may further comprise the steps:
(1) in the presence of esterifying catalyst, component a, components b and amount of component b are reacted, described component a is the ester of aromatic acid and/or aromatic acid, described components b is aliphatic dihydroxy alcohol and/or alicyclic dibasic alcohol, and described amount of component b is at least a in the acid anhydrides of the acid anhydrides of ester, aliphatic dibasic acid of aliphatic dibasic acid, alicyclic diprotic acid, the ester of aliphatic dibasic acid, alicyclic diprotic acid and 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 in the method according to this 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, described aerogel catalyst can improve condensation polymerization speed, shortens polycondensation reaction time (polycondensation reaction time can be shortened to 3-7 hour from existing 7-10 hour).And, the method according to this invention adopts aerogel catalyst as polycondensation catalyst, reduce the side reaction in the polycondensation process, thereby can obtain the polyester product of high molecular and narrow molecular weight distribution, can also reduce or eliminate the phenomenon of final polyester product flavescence simultaneously.
Description of drawings
Fig. 1 represents the nmr spectrum of the product of embodiment 1 preparation.
Embodiment
The invention provides a kind of preparation method of aliphatic-aromatic copolyester, the method may further comprise the steps:
(1) in the presence of esterifying catalyst, component a, components b and amount of component b are reacted, described component a is the ester of aromatic acid and/or aromatic acid, described components b is aliphatic dihydroxy alcohol and/or alicyclic dibasic alcohol, and described amount of component b is at least a in the acid anhydrides of the acid anhydrides of ester, aliphatic dibasic acid of aliphatic dibasic acid, alicyclic diprotic acid, the ester of aliphatic dibasic acid, alicyclic diprotic acid and 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
Preparation 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, described component a is the ester of aromatic acid and/or aromatic acid, described components b is aliphatic dihydroxy alcohol and/or alicyclic dibasic alcohol, and described amount of component b is at least a in the acid anhydrides of the acid anhydrides of ester, aliphatic dibasic acid of aliphatic dibasic acid, alicyclic diprotic acid, the ester of aliphatic dibasic acid, alicyclic diprotic acid and alicyclic diprotic acid.
According to the present invention, described component a can synthesize field various aromatic acids commonly used and/or the ester of aromatic acid for polyester.For example, described component a can be m-phthalic acid, terephthalic acid, dimethyl terephthalate (DMT), dimethyl phthalate, NDA, 1,5-naphthalic acid, 2,7-naphthalic acid, 4,4 '-biphenyl dicarboxylic acid, 3, one or more in 4 '-biphenyl dicarboxylic acid.Preferably, described component a is terephthalic acid and/or dimethyl terephthalate (DMT).
According to the present invention, described components b can be the synthetic field of polyester various aliphatic dihydroxy alcohols and/or alicyclic dibasic alcohol commonly used.For example, described components b can be in ethylene glycol, glycol ether, propylene glycol, butyleneglycol, pentanediol, hexylene glycol, cyclohexane diol and the norbornane dimethanol one or more.Described propylene glycol for example can be 1,2-PD and/or 1,3-PD, described butyleneglycol for example can be 1,3-butyleneglycol and/or BDO, described pentanediol for example can be 1,5-pentanediol and/or neopentyl glycol, described hexylene glycol for example can be 1,6-hexylene glycol, and described cyclohexane diol for example can be 1,4-cyclohexane diol and/or 1,3-cyclohexane diol.Preferably, described components b is at least a in propylene glycol, butyleneglycol, pentanediol and the hexylene glycol.
According to the present invention, described amount of component b is at least a in the acid anhydrides of the acid anhydrides of ester, aliphatic dibasic acid of aliphatic dibasic acid, alicyclic diprotic acid, the ester of aliphatic dibasic acid, alicyclic diprotic acid and alicyclic diprotic acid.For example, described 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, in 5-hexanaphthene tetracarboxylic dianhydride, Isosorbide-5-Nitrae-cyclohexane diacid dimethyl ester and the norbornane diacid one or more.Preferably, described 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 described 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 described component a and amount of component b is 1: 0.3-20.When the mol ratio between described 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 characteristics, but also has more excellent biodegradable performance.More preferably, the mol ratio of described component a and amount of component b is 1: 0.5-4.
According to the present invention, the total amount of described component a and amount of component b and the mol ratio of components b can according to the molecular weight of the aliphatic-aromatic copolyester of expecting, adopt the method that well known to a person skilled in the art to determine.Preferably, the mol ratio of the total amount of described component a and amount of component b and components b is 1: 1-2.When the mol ratio of the total amount of described 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 aliphatic-aromatic copolyester of high molecular.More preferably, the mol ratio of the total amount of described component a and amount of component b and components b is 1: 1.15-1.5.
According to the present invention, the method that described component a, components b and amount of component b are reacted is not particularly limited, and can component a, components b and amount of component b be reacted by single stage method, also can component a, components b and amount of component b be reacted by two-step approach.Wherein, described single stage method refers to make component a, components b and amount of component b reaction by single step reaction; Described two-step approach refers to make first component a and components b to react, and 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 by two-step reaction.Namely, 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 the first temperature, and the mixture that will obtain after will reacting and amount of component b react under the second temperature, described the second temperature is than the high 5-30 of the first temperature ℃.
According to the present invention, described the first temperature is for making the temperature of component a and components b generation esterification or transesterification reaction, and preferably, described the first temperature is 150-225 ℃, more preferably 180-210 ℃.The temperature that described the 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, described the second temperature is 160-240 ℃, more preferably 190-230 ℃.The reaction of described component a and components b preferably proceeds to when low-carbon alcohol (such as methyl alcohol, ethanol) that reaction generates and water all steam and stops, and the reaction mixture that described component a and components b reaction obtain and the reaction of amount of component b preferably proceed to when the low-carbon alcohol (such as methyl alcohol, ethanol) of reacting generation and water all steam and stop.
According to the present invention, described esterifying catalyst can be the synthetic field of polyester esterifying catalyst commonly used.Preferably, described esterifying catalyst is at least a in purity titanium tetraethoxide, four titanium propanolates (such as four positive propoxy titanium or tetraisopropoxy titaniums), four titanium butoxide (such as four titanium n-butoxide (being also referred to as tetrabutyl titanate)), four hexyloxy titaniums (such as four positive hexyloxy titaniums), four (2-ethyl hexyl oxy) titanium, four octyloxy titaniums (such as four n-octyloxy titaniums) and the glycolic acid titanium.
According to the present invention, the consumption of described esterifying catalyst can be the conventional amount used of this area.Preferably, the mol ratio of the total amount of described esterifying catalyst and component a and amount of component b is 1: 1000-100000.When the consumption of described 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 described esterifying catalyst and component a and amount of component b is 1: 1500-10000.
Preparation 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 described aerogel catalyst, TiO
2And ZrO
2Can form by coprecipitation method.In this case, ZrO
2And TiO
2Be distributed in equably whole aerogel particle.In the present invention, described coprecipitation method refers to by adding precipitation agent to containing in two or more cationic homogeneous phase solutions, and through obtaining the sedimentary method of various uniform component after the precipitin reaction.The operating process of described coprecipitation method can be implemented according to the method for routine.
A preferred embodiment of the invention, in described aerogel catalyst, the ZrO at least part of described aerogel particle
2Be coated on TiO
2The surface on.In this case, described aerogel catalyst has advantages of the reunion of being difficult for, catalytic activity is high and stable performance, thereby so that described polycondensation has higher efficient, and the copolyesters that adopts this aerogel catalyst to prepare has higher molecular weight and molecular weight distribution is narrower.In further preferred situation, in described aerogel catalyst, described ZrO
2Be coated on TiO
2The content of lip-deep aerogel particle be the 10-100 % by weight, 50-100 % by weight more preferably.
According to the present invention, in the described aerogel catalyst, TiO
2With ZrO
2Mol ratio can be 3-20: 1, be preferably 5-15: 1.TiO in described 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.
According to one embodiment of the present invention, described aerogel catalyst can prepare by following steps:
(1) with the mixing liquid co-precipitation in titanium source and zirconium source, obtains TiO
2-ZrO
2Coprecipitate;
(2) with described TiO
2-ZrO
2Coprecipitate contact with a kind of alcohol, obtain TiO
2-ZrO
2Alcogel;
(3) make described TiO
2-ZrO
2Alcogel in the presence of supercritical medium, carry out supercritical drying;
Described alcohol is the alcohol of C1-C4, and described 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 the titanium elements in the described titanium source and the described zirconium source, the mol ratio in described titanium source and zirconium source can be 3-20: 1, be preferably 5-15: 1.
According to the present invention, the method of described 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 described alkaline precipitating agent is preferred so that the endpoint pH of reaction system is 8-9, the time that the mixing solutions in described titanium source and zirconium source contacts with alkaline precipitating agent can be 0.5-5 hour, is preferably 1-3 hour.The time of described ageing can be 10-48 hour, is preferably 15-36 hour.
In the present invention, described alkaline precipitating agent can be the conventional various alkaline precipitating agent that uses in coprecipitation process, under the preferable case, described alkaline precipitating agent is to be selected from least a in sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus, ammoniacal liquor, sodium-acetate and the urea, most preferably be ammoniacal liquor, the concentration of ammoniacal liquor can be 0.5-6mol/L.
In the present invention, the method for described 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 accelerates coprecipitation reaction.Described dispersion agent for example can be in diethanolamine, trolamine, methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, the trimethyl carbinol, acetic acid, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, sodium stearate, tween, polyvinyl alcohol, fatty alcohol-polyoxyethylene ether and the oleic acid at least a.And, described dispersion agent is selected the diverse material of the solvent in the mixing solutions with described titanium source and zirconium source, for example when the solvent in the mixing solutions in described titanium source and zirconium source is ethanol and/or methyl alcohol, described dispersion agent preferably uses at least a in diethanolamine, trolamine, acetic acid, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, sodium stearate, tween, polyvinyl alcohol, fatty alcohol-polyoxyethylene ether and the oleic acid.The consumption of described dispersion agent can be the 0.1-2 % by weight of the weight of the mixing solutions in described titanium source and zirconium source.
According to the present invention, described titanium source and zirconium source can be in the preparation titania aerogel process and various titaniums source and the zirconium source of conventional use in the preparation ZrO_2 aerogel process separately.In a kind of preferred implementation, described titanium source is the titanium alkoxide, and described zirconium source is the zirconium alkoxide.Concrete, described titanium alkoxide is preferably titanium isopropylate and/or tetrabutyl titanate, and described zirconium alkoxide can be four propyl alcohol zirconiums.In another kind of preferred implementation, described titanium source is at least a in titanyl sulfate, titanium sulfate and the titanium tetrachloride, and described zirconium source is at least a in basic zirconium chloride, zirconium chloride, zirconium sulfate and the zirconium nitrate.
According to the present invention, by with described TiO
2-ZrO
2Coprecipitate contact with described alcohol, thereby be swapped out described TiO with described alcohol
2-ZrO
2Coprecipitate in solvent (for example, water), to obtain water-free alcogel.In the present invention, described TiO
2-ZrO
2Coprecipitate can comprise with the condition that described alcohol contacts: temperature is 5-45 ℃, is preferably 5-35 ℃; Time is 0.5-3 hour, is preferably 0.5-2 hour.Described alcohol most preferably is ethanol.
In the preferred case, the preparation method of described aerogel catalyst also is included in described TiO
2-ZrO
2Coprecipitate with before described alcohol contacts, to described TiO
2-ZrO
2Coprecipitate wash, with the impurity that adsorbs in this coprecipitate of abundant removal, such as fully titanium source, zirconium source, alkaline precipitating agent, dispersion agent and other the ion etc. of reaction.
According to the present invention, described supercritical medium most preferably is ethanol.In this case, described supercritical drying condition refers to the supercritical state of ethanol, also is that temperature is 262 ℃, and pressure is 8.5MPa.Under this supercritical drying condition, the time of described supercritical drying can be 30-120 minute, is preferably 30-90 minute.In the present invention, described pressure refers to absolute pressure.
According to another embodiment of the invention, described aerogel catalyst can also prepare by 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 described TiO
2-ZrO
2Coprecipitate contact with a kind of alcohol, obtain TiO
2-ZrO
2Alcogel;
(3) make described TiO
2-ZrO
2Alcogel in the presence of supercritical medium, carry out supercritical drying;
Described alcohol is the alcohol of C1-C4, and described 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 the titanium elements in the described titanium source and described ZrO
2Zr element meter in the aerogel particle, the mol ratio in described titanium source and zirconium source is 3-20: 1, be preferably 5-15: 1.
According to aforesaid method, the method for described co-precipitation comprises titanium source and ZrO
2The mixing liquid of aerogel contacts with alkaline precipitating agent and carries out ageing, the consumption of described alkaline precipitating agent is preferred so that the endpoint pH of reaction system is 8-9, the time that described mixing liquid contacts with alkaline precipitating agent can be 0.5-5 hour, is preferably 1-3 hour.The time of described ageing can be 10-48 hour, is preferably 15-36 hour.
In the present invention, described alkaline precipitating agent can be the conventional various alkaline precipitating agent that uses in coprecipitation process, under the preferable case, described alkaline precipitating agent is to be selected from least a in sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus, ammoniacal liquor, sodium-acetate and the urea, most preferably be ammoniacal liquor, the concentration of ammoniacal liquor can be 0.5-6mol/L.
In the preferred case, the method for described co-precipitation also comprises in described mixing liquid and adds dispersion agent, reducing the surface tension of this mixing liquid, thereby accelerates coprecipitation reaction.Described dispersion agent for example can be in diethanolamine, trolamine, methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, the trimethyl carbinol, acetic acid, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, sodium stearate, tween, polyvinyl alcohol, fatty alcohol-polyoxyethylene ether and the oleic acid at least a.And, described dispersion agent select with described mixing liquid in the diverse material of solvent, for example when the solvent in the described mixing liquid is ethanol and/or methyl alcohol, described dispersion agent preferably uses at least a in diethanolamine, trolamine, acetic acid, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, sodium stearate, tween, polyvinyl alcohol, fatty alcohol-polyoxyethylene ether and the oleic acid.The consumption of described dispersion agent can be the 0.1-2 % by weight of the weight of described mixing liquid.
According to aforesaid method, described titanium source can be conventional various titaniums source of using in the preparation titania aerogel process.Under the preferable case, described titanium source is at least a in titanium isopropylate, tetrabutyl titanate, titanyl sulfate, titanium sulfate and the titanium tetrachloride.
According to aforesaid method, described ZrO
2Aerogel particle can be commercially available, and also can adopt conventional method preparation.Described 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 and adds the acidic precipitation agent in the solution in zirconium source, is adjusted to 5-6 with the endpoint pH with reaction system, then ageing 10-48 hour (being preferably 15-36 hour); Throw out washing with obtaining after the ageing obtains ZrO with alcohol generation exchange of solvent afterwards
2Alcogel; Then, make this alcogel in the presence of supercritical medium, carry out supercritical drying.Described zirconium source for example can be basic zirconium chloride, and described acidic precipitation agent for example can be hydrochloric acid, and described alcohol for example can be ethanol.
According to aforesaid method, by with described TiO
2-ZrO
2Coprecipitate contact with described alcohol, thereby be swapped out described TiO with described alcohol
2-ZrO
2Coprecipitate in solvent (for example, water), to obtain water-free alcogel.In the present invention, described TiO
2-ZrO
2Coprecipitate can comprise with the condition that described alcohol contacts: temperature is 5-45 ℃, is preferably 5-35 ℃; Time is 0.5-3 hour, is preferably 0.5-2 hour.Described alcohol most preferably is ethanol.
In the preferred case, the preparation method of described aerogel catalyst also is included in described TiO
2-ZrO
2Coprecipitate with before described alcohol contacts, to described TiO
2-ZrO
2Coprecipitate wash, with the impurity that adsorbs in this coprecipitate of abundant removal, such as fully titanium source, zirconium source, alkaline precipitating agent, dispersion agent and other the ion etc. of reaction.
According to the present invention, described supercritical medium most preferably is ethanol.In this case, described supercritical drying condition refers to the supercritical state of ethanol, also is that temperature is 262 ℃, and pressure is 8.5MPa.Under this supercritical drying condition, the time of described supercritical drying can be 30-120 minute, is preferably 30-90 minute.
In the preparation method of described aliphatic-aromatic copolyester provided by the invention, the consumption of described 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 described aerogel catalyst and component a and amount of component b is 1: 1000-100000.When the consumption of described aerogel catalyst is within the above-mentioned scope, not only can obtain the polyester product of high molecular, 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 described aerogel catalyst and the step (1) is 1: 2000-50000.In the present invention, described TiO
2-ZrO
2The molar weight of aerogel catalyst refers to TiO in the described aerogel catalyst
2And ZrO
2The molar weight sum.
The present invention is by the flavescence phenomenon that reduces or eliminates final polyester product with aerogel catalyst and keeps the high molecular of polyester, and there is no particular limitation for the condition of described polycondensation.Described polycondensation can be carried out well known to a person skilled in the art under the condition.Preferably, described polycondensation condition comprises: temperature is 200-300 ℃, more preferably 210-270 ℃, and more preferably 230-260 ℃; Pressure is 0.03-0.08MPa, more preferably 0.04-0.07MPa, more preferably 0.04-0.06MPa; Time is 3-7 hour, more preferably 3-6 hour.Described pressure refers to 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 for the preparation of the aerogel catalyst that uses in the method according to this invention.
The titanium isopropylate of 82.7mmol and the four propyl alcohol zirconiums of 9.14mmol are dissolved in the dehydrated 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 to drip ammoniacal liquor, continue to stir 2h, then ageing 20h.With the mixture centrifugation 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, obtains alcogel, and this alcogel is added in autoclave, with dehydrated 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, be the 50-100 nanometer thereby make particle diameter, density is 190mg/cm
3TiO
2-ZrO
2Aerogel particle S1.
Preparation example 2
This preparation example is for the preparation of the aerogel catalyst that uses in the method according to this invention.
The concentration that measures 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 to drip ammoniacal liquor, continue to stir 2h, then ageing 36h.With the mixture centrifugation 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, obtains alcogel, and this alcogel is added in autoclave, with dehydrated 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, be the 60-120 nanometer thereby make particle diameter, density is 180mg/cm
3TiO
2-ZrO
2Aerogel particle S2.
Preparation example 3
This preparation example is for the preparation of the aerogel catalyst that uses in the method according to this invention.
Be the TiCl of 4mol/L with the concentration of 12.18ml
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 to drip sodium hydroxide solution, continue to stir 1h, then ageing 20h.With the mixture centrifugation 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, obtains alcogel, and this alcogel is added in autoclave, with dehydrated 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, be the 80-150 nanometer thereby make particle diameter, density is 175mg/cm
3TiO
2-ZrO
2Aerogel particle S3.
Preparation example 4
This preparation example is for the preparation of the aerogel catalyst that uses in the method according to this invention.
(1) preparation ZrO
2Aerogel particle
The concentration that measures 45mL is the zirconium oxychloride solution of 0.2mol/L, under agitation, under 20 ℃ of room temperatures, be 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 to drip ammoniacal liquor, and ageing 20h, then wash and centrifugation with deionized water successively, the throw out that obtains is mixed with weight ratio with ethanol at 1: 20, obtain alcogel, this alcogel is added in the autoclave, use dehydrated alcohol as supercritical medium, at 262 ℃, 8.5MPa condition under, 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 that measures 12.18ml is the TiCl of 4mol/L
4Solution, and the ZrO that makes in (1) that wherein adds 5.38mmol
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 to drip ammoniacal liquor, continue to stir 1h, then ageing 20h.With the mixture centrifugation 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, obtains alcogel, and this alcogel is added in autoclave, with dehydrated 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, be the 50-100 nanometer thereby make particle diameter, density is 195mg/cm
3Coating ZrO
2TiO
2-ZrO
2Aerogel particle S4.
Preparation example 5
This preparation example is for the preparation of the aerogel catalyst that uses in the method according to this 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 dehydrated alcohol of 80mL, and the ZrO that makes in (1) that wherein adds 5.38mmol
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 to drip sodium hydroxide solution, continue to stir 1h, then ageing 20h.With the mixture centrifugation 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, obtains alcogel, and this alcogel is added in autoclave, with dehydrated alcohol as supercritical medium, under 262 ℃, the condition of 8.5MPa, this alcogel is carried out supercritical drying, the time is 50 minutes, be the 60-110 nanometer thereby make particle diameter, density is 182mg/cm
3Coating ZrO
2TiO
2-ZrO
2Aerogel particle S5.
Embodiment 1
The present embodiment is used for illustrating the preparation method according to aliphatic-aromatic copolyester of the present invention.
With 0.4 mole dimethyl terephthalate (DMT), 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, reactant in this there-necked flask is heated to 200 ℃, and under agitation reaction, after the methyl alcohol that question response generates steams fully, then the hexanodioic acid that adds 0.4 mole in the reaction product, and temperature of reaction is increased to 220 ℃, after the water that esterification generates steams fully, the TiO of preparation in the embodiment 1 that wherein adds 0.30 mmole
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 nuclear magnetic resonance analyser 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, reactant in this there-necked flask is heated to 200 ℃, and under agitation reaction, after the water that question response generates steams fully, the TiO of preparation in the embodiment 1 that wherein adds 0.30 mmole 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 differential scanning calorimeter (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, reactant in this there-necked flask is heated to 220 ℃, after the water that esterification generates steams fully, the TiO of preparation in the embodiment 1 that wherein adds 0.30 mmole
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 differential scanning calorimeter (DSC) measuring method is-66.5 ℃.
Embodiment 2
The present embodiment is used for illustrating the preparation method according to aliphatic-aromatic copolyester of the present invention.
Be in the there-necked flask of 500mL with 0.26 mole terephthalic acid, 0.96 mole propylene glycol and the purity titanium tetraethoxide adding capacity of 0.44 mmole, reactant in this there-necked flask is heated to 180 ℃, and under agitation reaction, after the methyl alcohol that question response generates steams fully, then the sebacic acid that adds 0.39 mole in the reaction product, and temperature of reaction is increased to 210 ℃, and after the water that esterification generates steams fully, the TiO of preparation in the embodiment 2 that wherein adds 0.26 mmole
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
The present embodiment is used for illustrating 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, reactant in this there-necked flask is heated to 210 ℃, and under agitation reaction, after the methyl alcohol that question response generates steams fully, then the Succinic Acid that adds 0.4 mole in the reaction product, and temperature of reaction is increased to 220 ℃, after the water that esterification generates steams fully, to the TiO of embodiment 3 preparations that wherein add 0.12 mmole
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 illustrating the preparation method according to aliphatic-aromatic copolyester of the present invention.
Method according to embodiment 1 prepares biodegradable copolyesters, and difference is, respectively with the TiO for preparing in the preparation example 4 and 5 of same molar
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
The present embodiment is used for illustrating the preparation method according to aliphatic-aromatic copolyester of the present invention.
Method according to embodiment 1 prepares biodegradable copolyesters, and difference 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 difference is not use the TiO of preparation among the embodiment 1 in reaction process
2-ZrO
2Aerogel catalyst S1, thus make aliphatic-aromatic copolyester DP1.
Comparative Examples 2
Method according to embodiment 1 prepares biodegradable copolyesters, and difference is to replace the TiO of preparation in the preparation example 1 in polycondensation process with four titanium n-butoxide of 0.30 mmole
2-ZrO
2Aerogel catalyst S1, thus make aliphatic-aromatic copolyester DP2.
Comparative Examples 3
Method according to embodiment 1 prepares biodegradable copolyesters, and difference 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 preparation TiO
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) instrument, detect the molecular weight distribution 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 differential scanning calorimeter (DSC) measuring method, detect the yellowness index of aliphatic-aromatic copolyester P1-P5 and DP1-DP3 according to the HG/T3862-2006 method, its detected result is as shown in table 1 below.
Table 1
By the second-order transition temperature of copolyesters P1 and the second-order transition temperature of preparation example 6 and 7 polyester that prepare are compared 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, thus explanation, the prepared according to the methods of the invention copolyesters is aliphatic-aromatic copolyester.
In upper table 1, by 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 molecular weight distribution 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, molecular weight distribution is narrower, and, alleviated the partially yellow defective of biodegradable copolyesters color.
And, by 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 molecular weight distribution coefficient is less, yellowness index is less, this shows, in described 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, molecular weight distribution is narrower, and, further alleviated the partially yellow defective of biodegradable copolyesters color.
Claims (14)
1. the preparation method of an aliphatic-aromatic copolyester is characterized in that, the method may further comprise the steps:
(1) in the presence of esterifying catalyst, component a, components b and amount of component b are reacted, described component a is the ester of aromatic acid and/or aromatic acid, described components b is aliphatic dihydroxy alcohol and/or alicyclic dibasic alcohol, and described amount of component b is at least a in the acid anhydrides of the acid anhydrides of ester, aliphatic dibasic acid of aliphatic dibasic acid, alicyclic diprotic acid, the ester of aliphatic dibasic acid, alicyclic diprotic acid and 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 described aerogel catalyst is the 20-150 nanometer, density is 100-400mg/cm
3
3. method according to claim 1 and 2, wherein, the ZrO at least part of described aerogel catalyst
2Be coated on TiO
2The surface.
4. method according to claim 1 and 2, wherein, in described aerogel catalyst, TiO
2With ZrO
2Mol ratio be 3-20:1.
5. method according to claim 4, wherein, in described 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 described 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 described 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, described polycondensation condition comprises: temperature is 200-300 ℃, vacuum tightness is less than or equal to 500Pa, 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, and the mol ratio of the total amount of the consumption of described 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, and the mol ratio of the total amount of the consumption of described 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 the first temperature, and the mixture that will obtain after will reacting and amount of component b react under the second temperature, and described the second temperature is than the high 5-30 of the first temperature ℃.
12. method according to claim 11, wherein, described the first temperature is 150-225 ℃, and described the second temperature is 160-240 ℃.
13. according to claim 1,9 or 10 described methods, wherein, described 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, described component a is terephthalic acid and/or dimethyl terephthalate (DMT), described components b is at least a in propylene glycol, butyleneglycol, pentanediol and the hexylene glycol, and described amount of component b is at least a in Succinic Acid, hexanodioic acid and the sebacic acid.
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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
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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 |
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