CN101716524A - High-activity titanium complex catalyst, preparation method and application thereof in copolyester synthesis - Google Patents
High-activity titanium complex catalyst, preparation method and application thereof in copolyester synthesis Download PDFInfo
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Abstract
The invention discloses a high-activity titanium complex catalyst, a preparation method and application thereof in copolyester synthesis. The high-activity titanium complex catalyst comprises a main catalyst, a first cocatalyst and a second cocatalyst, wherein the main catalyst is titanate, the first cocatalyst is nanometer titanium dioxide, and the second cocatalyst is phosphate of IA, IIA or IIIA group metals; and the molar ratio of the nanometer titanium dioxide to the main catalyst is 0-3:1, and the molar ratio of phosphorus atoms in the phosphate to the main catalyst is 0-3:1. The titanium complex catalyst has high activity, and can improve the efficiency of esterification and polycondensation reactions during the catalytic synthesis of polyester; the titanium complex catalyst does not contain heavy metals, and can eliminate the potential hazard of heavy metal catalysts on human health and environmental pollution problem; and the polyester produced by the titanium complex catalyst has better appearance.
Description
Background technology
In the polycondensation process of polyester, have to be to use antimony (Sb) class catalyst more than 90%, by antimony acetate and antimony oxide (Sb
2O
3) wait composition, the about 150-300ppm of the valid density of Sb.Because use simple, low price, catalytic activity height, the almost all available antimony of the polyester of various grades (Sb) catalyst.Although antimony catalyst has excellent performance, recently scientific research is discovered, there is the pollution problem of harm humans health and environment in antimony element, and up-to-date Europe and China's Mainland decree, understand very much restricted antimony content, at textile requirement antimony low content is arranged, and product is with ecological, environmental protective textile and " ECO " label and unofficial " OEKO " label difference identification, particularly to using the gym suit and the underclothes of polyester fiber, the existing sign " no antimony " or the product of " heavy metal free " occur in market.Under this safety and environmental protection trend requires, will force the polyester industrial research to send out the catalyst of developing environmental protection more.
Supreme Being people group exploitation do not contain heavy metal such as antimony fully, the catalyst for polymerization of polyester of the environment that helps preserving our planet, be registered now into
Trade mark, and in group, enter batch process.
This catalyst that does not contain heavy metal has been applied to various fields such as civilian fiber, polyester bottles, polyester film now.Because this product can both be made huge contribution to alleviating the earth environment load in each link that comprises old product processing etc.; the decision of Supreme Being people group enlarges in our company in the Related product production, actively is devoted to this technology transfer is paid attention to the enterprise of environmental protection to other.
Germanium class catalyst is one of kind in the non-antimony catalyst, heat endurance and anti-hydrolysis ability with its synthetic polyester are better, use industrial, but the price comparison of this type of catalyst is expensive, in the process of polycondensation, taken away by vacuum easily, make polycondensation process be difficult to control, so germanium class catalyst also exist certain problem.
Titanate ester has advantages of high catalytic activity and catalytic efficiency, and in addition, the residue of relevant such catalyst is toxicity low in vivo, and therefore, organic titanate is used as environmentally friendly catalyst to be used, as tetrabutyl titanate, tetraisopropoxy titanium.Therefore the class catalyst has good catalytic activity, is widely used in the condensation polymerization reaction of aliphatic polyester and copolyesters.Though the catalytic activity of Titanium series catalyst is higher, but the color of this type of catalyst resulting polyester is relatively poor, limited its further application, therefore must the existing catalyst technology of development, so that between the performance of product and catalytic activity, reach balance preferably.Improve Titanium series catalyst stability and synthetic PET hue by development of technology.
Along with the development of MOLECULE DESIGN and catalyst preparation technology, people's expectation is carried out modification on traditional cruel catalyst basis of the acid of admiring, develop environmental protection, the highly active Novel Titanium series catalysts that can overcome traditional metatitanic acid series polyester catalyst shortcoming again.The Titanium series catalyst of high-efficiency environment friendly replaces the inevitable outcome that traditional antimony-based catalyst will be the polyester industrial development.
Patent 03129983CN discloses a kind of polyester and synthetic titanium series composite catalyst of copolyesters of being used for, it is a kind of titanium series composite catalyst that can be used in polyester and the copolyesters building-up process as polycondensation catalyst, this catalyst by titanium compound and a kind of IVA of being selected from family element compound and one to three kind be selected from IA, IIA, IIIA, IIIB, VIIB, the compound of the metallic element of VIII family basic hydrolysis simultaneously precipitation and preparation, wherein titanium compound is isopropyl titanate, butyl titanate etc.In addition, Titanium series catalyst runs into after the water, and hydrolysis easily reduces its catalytic activity, in order to overcome this type of shortcoming.The method of the open resistance to water Titanium series catalyst of patent CN1403193, the titanium alcoholates is dissolved in organic solvent, the titanium dioxide precipitation that obtains through hydrolysis, through washing and filtering, again precipitation is placed organically-modified solution, perhaps organic modifiers directly joins in the organic solvent in the process of hydrolysis, obtains organically-modified titanium dioxide.Catalyst is used to prepare relative molecular weight less than 10000 saturated polyester resin, and perhaps relative molecular weight is greater than 10000 thermoplastic copolyesters.This organically-modified titanium dioxide has overcome the problem of the manner form and aspect jaundice that obtains in the titanium dioxide precipitation thing catalyzed polymerization process.Though the form and aspect of the catalyst products obtained therefrom in such patent are better, its catalytic activity awaits further to improve.
For a step obtains the color better products, patent 200410101547 discloses a kind of method with catalysis of rare-earth compound agent synthesizing polyester.Employing is selected from a kind of catalytic component C in the compound of Titanium, antimony and zinc
1Be the ester exchange and the catalyst in esterification stage, before reaction, together add in the reactor with raw material monomer; After pre-polymerization after a while, add the catalytic component C that is selected from rare earth compound again
2, carry out the vacuum polycondensation.The method of this invention adopts single still operation, has simplified operating procedure; Accelerate polymerization rate, improved the molecular weight of polymerizate; Side reaction reduces, and has obviously improved the polyester product color and luster.But because the reserves of rare earth material are limited, and the price of rare earth material is higher, makes this type of Application of Catalyst be subjected to bigger restriction.
Along with nearly step of environmental consciousness improves, it has been recognized that non-degradative plastics is more and more higher to the pressure that environment causes, seek novel biodegradable substitution material and be one of problem that current people are most interested in.Aliphatic polyester and aliphatic-aromatic polyester have good biodegradability, by the metabolism of microorganism, finally can be converted into carbon dioxide and water in natural environment.The product to HMW that the Titanium series catalyst of existing synthesis and degradation plastics is difficult to also needs could satisfy instructions for use to the further chain extension of product usually, and the molecular weight distribution of melt chain extension polyester gained is even inadequately, wider distribution.Therefore it is extremely urgent that the catalyst of development of new environmental protection is used for synthetic this type of material.
Patent US005310782 has announced a kind of method of synthetic high polymer amount aliphatic polyester, at first adopting isopropyl titanate is catalyst, the polymer of the synthetic certain molecular weight of melt-polycondensation, the products obtained therefrom color is yellow, and poor heat stability in the process of secondary operations again, it needs to add the color that a certain amount of phosphate is removed product in order to obtain the more product of HMW, and the chain extender that adds isocyanates then improves the molecular weight of polymer.
New catalyst the characteristic that must have:
Catalytic activity height, side reaction be low, be difficult for evaporation, environment-protecting asepsis, price are low.
Though the Titanium series catalyst of existing patented invention has advantages of high catalytic activity, it is in the raising that also needs a nearly step aspect the cost of product heat endurance, product appearance and catalyst itself.
Summary of the invention
The objective of the invention is deficiency and defective, a kind of highly active titanium series composite catalyst that has is provided at the prior art existence.
To achieve these goals, the present invention adopts following technical scheme:
A kind of high-activity titanium series composite catalyst comprises major catalyst, first co-catalyst and second co-catalyst; Described major catalyst is a titanate esters, and described first co-catalyst is a nano titanium oxide, and described second co-catalyst is the phosphate of IA, IIA or IIIA family metal; The mol ratio of nano titanium oxide and major catalyst is 0 ~ 3: 1, and the mol ratio of phosphorus atoms and major catalyst is 0 ~ 3: 1 in the phosphate.
The adding nano titanium oxide has overcome because the hydrolysis of titanate esters forms and loses the oligomer class that is insoluble to dihydroxylic alcohols of catalytic activity, and the problem that causes catalyst performance to descend, nano titanium oxide is a synergistic catalyst in this reaction; Can improve reaction rate and add phosphoric acid salt, shorten the reaction time, improve the form and aspect of polyester.
In above-mentioned high-activity titanium series composite catalyst, described titanate esters is preferably a kind of in tetrabutyl titanate, tetraisopropyl titanate, metatitanic acid tetramethyl ester, tetraethyl titanate, metatitanic acid four monooctyl esters.
In above-mentioned high-activity titanium series composite catalyst, the metallic element in the described phosphate comprises lithium, sodium, potassium, magnesium, calcium, aluminium or zinc.
In above-mentioned high-activity titanium series composite catalyst, the mol ratio of described nano titanium oxide and major catalyst is 0 ~ 3: 1; The mol ratio of phosphorus atoms and major catalyst is 0 ~ 3: 1 in the described phosphate.
Another object of the present invention provides the preparation method of above-mentioned high-activity titanium series composite catalyst, comprise the steps: slowly to join tetraisopropyl titanate or tetrabutyl titanate in the dihydroxylic alcohols, tetraisopropyl titanate or the tetrabutyl titanate molar concentration in mixed solution is for being 1.0 ~ 1.5mol/L, be stirred to and mix, in temperature is to react 8-24 hour under 180 ~ 200 ℃ of conditions, not open closely go into high pure nitrogen, so that remove volatile little molecule, be cooled to room temperature, promptly get the glycol solution of nano titanium oxide; In the glycol solution of nano titanium oxide, add the major catalyst and second co-catalyst, form the high-activity titanium series composite catalyst.
In above-mentioned preparation method, described dihydroxylic alcohols is preferably ethylene glycol, 1,2-propane diols, 1, ammediol, 1,2-butanediol, 1,4-butanediol, 1, the one or more kinds of mixtures in the 5-pentanediol.
Further purpose of the present invention provides the application of above-mentioned high-activity titanium series composite catalyst in fat-aromatic copolyester catalysis is synthetic.
The method of utilizing the high-activity titanium series composite catalyst to be used for catalyzed synthesis of fatty-family's aromatic copolyester is: titanate esters, nano titanium oxide and dihydroxylic alcohols mix, and add with the solution form; Metal phosphate and binary acid mix and join in the reaction system; Aromatic dicarboxylic acid esters or aromatic acid and excess glycol are carried out ester exchange reaction or esterification, and reaction temperature is 190～220 ℃, and the reaction time is 1～2 hour; Add the esterification derivative of aliphatic dibasic acid, cyclisation aliphatic dibasic acid, aliphatic dibasic acid or the esterification derivative of cyclisation aliphatic dibasic acid again and proceed esterification, reaction temperature is 190～210 ℃, and the reaction time is 0.5～1.5 hour; Under the condition that composite catalyst exists, carry out polycondensation reaction then, obtain polymer.
In said method, described aromatic dicarboxylic acid esters or aromatic acid be terephthalic acid (TPA), phthalic acid, M-phthalic acid, to the one or more kinds of mixtures in phenylenediacetic Acid or the phthalic acid; The esterification derivative of described aliphatic dibasic acid, cyclisation aliphatic dibasic acid, aliphatic dibasic acid or the esterification derivative of cyclisation aliphatic dibasic acid are succinic acid, glutaric acid, adipic acid, azelaic acid, decanedioic acid, hendecane dicarboxylic acid, maleic anhydride, 1,1-cyclobutane dicarboxylic acid, 1, the one or more kinds of mixtures in 1-cyclohexanediacetic and the carboxylate thereof.
Compared with prior art, the present invention has following beneficial effect:
Titanium series composite catalyst of the present invention has high activity, in the process of catalysis synthesizing polyester, can improve esterification and polycondensation reaction efficient; Titanium series composite catalyst of the present invention does not contain heavy metal, can eliminate potential hazard and the problem of environmental pollution of heavy metal catalyst to human health; The polyester of titanium series composite catalyst of the present invention production has outward appearance preferably.
The specific embodiment
In the present embodiment, adopt Waters gel chromatography test polymer relative molecular mass, chloroform is the phase that flows, and concentration is 0.3%, rate of outflow 1mL/min, and 40 ℃ of temperature, standard sample is the polystyrene of narrow distribution.
25 ℃ of mensuration, with phenol-o-dichlorohenzene mixed liquor (mass ratio 3: 2) as solvent, the inherent viscosity of working sample, sample concentration is 0.005g/mL.
With orthoresol-chloroform mixed liquor (mass ratio 7: 3) is solvent, adopt Switzerland's ten thousand logical Titrino series automatic potential titrator tests examination content of carboxyl end group, method of testing is referring to standard FZ/T50012-2006 " polyester middle-end carboxyl Content analysis by titration ".
Adopt the melt temperature and the crystallization temperature of Perkin Elmer DSC-6 analyzer specimen, nitrogen atmosphere, flow velocity are 20mL/min.Be heated to 190 ℃ from 20 ℃ with 10 ℃/min during test, stop 3min, be cooled to 20 ℃ with 10 ℃/min again
Embodiment 1
Tetraisopropyl titanate is slowly joined 1, in the 4-butanediol, the molar concentration of tetraisopropyl titanate in mixed solution is for being 1.0mol/L, be stirred to and mix, in temperature is reaction 12 hours under 190 ℃ of conditions, not open closely goes into high pure nitrogen, so that remove volatile little molecule, be cooled to room temperature, promptly get the butanediol solution of titanium dioxide nanoparticle.
Add a certain amount of tetrabutyl titanate (TBOT) and PTPP (PTPP) in the butanediol solution of above-mentioned nano titanium oxide, form tetrabutyl titanate (TBOT), nano titanium oxide (TiO
2), the mixture of PTPP (PTPP), it consists of TBOT/TiO
2/ PTPP=0.2/0.1/0.1, the called after catalyst A.
1,4 butanediol 16.1kg, dimethyl terephthalate (DMT) 10.4kg; trimethylolpropane 85.6g, catalyst A (based on the amount of the polymer that generates, the consumption of titanium is 50ppm) joins in the reactor; under the nitrogen protection, keeping reactor temperature is 180 ℃, reaction 100min.Add the 161kg adipic acid then, react 100min down at 180 ℃.
Then, temperature is warming up to 190 ℃, behind low vacuum (60-70KPa) reaction 30min, beginning slowly is warming up to 235 ℃, progressively increases vacuum simultaneously.When temperature rises to 235 ℃, make the still internal pressure reach 5KPa.Keep temperature-resistant, the still internal pressure is reduced to below the 100Pa, reacted 1.5 hours, promptly get product.
Molecular weight: Mn=32600, Mw=102500, viscosity 1.15dL/g, end carboxyl 15mol/t, 46.0 ℃ of crystallization temperatures, 108.7 ℃ of fusing points.
Embodiment 2
Tetraisopropyl titanate is slowly joined 1, in the 4-butanediol, the molar concentration of metatitanic acid four different esters in mixed solution is 1.0mol/L, be stirred to and mix, in temperature is reaction 8 hours under 200 ℃ of conditions, not open closely goes into high pure nitrogen, so that remove volatile little molecule, be cooled to room temperature, promptly get the butanediol solution of titanium dioxide nanoparticle.
Add a certain amount of tetrabutyl titanate (TBOT) and sodium phosphate trimer (STPP) in the butanediol solution of above-mentioned nano titanium oxide, form tetrabutyl titanate (TBOT), nano titanium oxide (TiO
2), the mixture of sodium phosphate trimer (STPP), it consists of TBOT/TiO
2/ STPP=0.2/0.1/0.1, the called after catalyst B.
1,4 butanediol 60g, dimethyl terephthalate (DMT) 35g joins in the flask, under the nitrogen protection, is warming up to 170 ℃, adds catalyst B (based on the amount of the polymer that generates, the consumption of titanium is 70ppm), reacts 2.5 hours down at 180 ℃.Add the 39g adipic acid then, reacted 2 hours down at 180 ℃.
Then, temperature is warming up to 190 ℃, at low vacuum (60-70KPa) reaction 40min.After temperature to 210 ℃, reacted 30 minutes, begin slowly to be warming up to 235 ℃ then, progressively increase vacuum simultaneously.When temperature rises to 235 ℃, make the flask internal pressure reach 5KPa.Keep temperature-resistant, the still internal pressure is reduced to below the 100Pa, reacted 2 hours, promptly get product.
Molecular weight: Mn=46100, Mw=130100, viscosity 1.19dL/g, end carboxyl 35mol/t, 50.0 ℃ of crystallization temperatures, 101.2 ℃ of fusing points.
Embodiment 3
Tetraisopropyl titanate is slowly joined 1, in the 4-butanediol, the molar concentration of metatitanic acid four different esters in mixed solution is for being 1.5mol/L, be stirred to and mix, in temperature is reaction 10 hours under 190 ℃ of conditions, not open closely goes into high pure nitrogen, so that remove volatile little molecule, be cooled to room temperature, promptly get the butanediol solution of titanium dioxide nanoparticle.
Add a certain amount of tetraisopropyl titanate (TPT) and sodium dihydrogen phosphate (SDP) in the butanediol solution of above-mentioned nano titanium oxide, form tetraisopropyl titanate (TPT), nano titanium oxide (TiO
2), the mixture of sodium dihydrogen phosphate (SDP), it consists of TPT/TiO
2/ SDP=0.2/0.1/0.1, called after catalyst C.
54g 1; 4 butanediols; the 30g dimethyl terephthalate (DMT); the 5g DMIP joins in the flask, under the nitrogen protection, is warming up to 170 ℃; add catalyst C (based on the amount of the polymer that generates; the consumption of titanium is 60ppm), keeping reactor temperature is 180 ℃, reacts 2.5 hours.Add the 32g adipic acid then, reacted 2 hours down at 180 ℃.
Then, temperature is warming up to 190 ℃, at low vacuum (60-70KPa) reaction 40min, after the temperature to 210 ℃, react 30 minutes, begin slowly to be warming up to 235 ℃ then, the while progressively increases vacuum.When temperature rises to 235 ℃, make the flask internal pressure reach 5KPa.Keep temperature-resistant, the flask internal pressure is reduced to below the 100Pa, reacted 2 hours, promptly get product.
Molecular weight: Mn=55000, Mw=110200, viscosity 1.23dL/g, end carboxyl 22mol/t, 53.0 ℃ of crystallization temperatures, 116.5 ℃ of fusing points.
Embodiment 4
Tetraisopropyl titanate is slowly joined 1, in the 4-butanediol, the molar concentration of metatitanic acid four different esters in mixed solution is for being 1.0mol/L, be stirred to and mix, in temperature is reaction 12 hours under 190 ℃ of conditions, not open closely goes into high pure nitrogen, so that remove volatile little molecule, be cooled to room temperature, promptly get the butanediol solution of titanium dioxide nanoparticle.
Add a certain amount of tetraisopropyl titanate (TPT) and PTPP (PTPP) in the butanediol solution of above-mentioned nano titanium oxide, form TPT, TiO
2, PTPP mixture, it consists of TPT/TiO
2/ PTPP=0.2/0.1/0.1, called after catalyst D.
1,4 butanediol 10kg, terephthalic acid (TPA) 9kg, trimethylolpropane 55.8g, catalyst D (based on the amount of the polymer that generates, the consumption of titanium is 80ppm) joins in the reactor, reacts 4 hours down at 210 ℃.Add the 9.4g adipic acid, reacted 3 hours down at 175 ℃.
Then, temperature is warming up to 190 ℃, keeps low vacuum (60-70Kpa), about 40min, add tetrabutyl titanate 30g.After temperature to 210 ℃, reacted 30 minutes, begin slowly to be warming up to 235 ℃ then, progressively increase vacuum simultaneously.When temperature rises to 235 ℃, make the still internal pressure reach 5KPa.Keep temperature-resistant, the still internal pressure is reduced to below the 100Pa, reacted 3 hours, promptly get product.
Molecular weight: Mn=42100, Mw=103500, viscosity 1.24dL/g, end carboxyl 20mol/t, 53.8 ℃ of crystallization temperatures, 120.0 ℃ of fusing points.
Embodiment 5
Tetrabutyl titanate is slowly joined 1, in the 4-butanediol, the molar concentration of tetrabutyl titanate in mixed solution is for being 1.0mol/L, be stirred to and mix, in temperature is reaction 8 hours under 200 ℃ of conditions, not open closely goes into high pure nitrogen, so that remove volatile little molecule, be cooled to room temperature, promptly get the butanediol solution of titanium dioxide nanoparticle.
Add a certain amount of tetrabutyl titanate (TBOT) and sodium dihydrogen phosphate (SDP) in the butanediol solution of above-mentioned nano titanium oxide, form tetrabutyl titanate (TBOT), nano titanium oxide (TiO
2), the mixture of sodium dihydrogen phosphate (SDP), it consists of TBOT/TiO
2/ SDP=0.2/0.1/0.1, called after catalyst E.
54g 1; the 4-butanediol; the 35g dimethyl terephthalate (DMT), the 35g dimethyl adipate, the 0.1g pentaerythrite joins in the flask; under the nitrogen protection; be warming up to 170 ℃, add catalyst E (based on the amount of the polymer that generates, the consumption of titanium is 70ppm); keeping reactor temperature is 180 ℃, reacts 2.5 hours.Then, temperature is warming up to 190 ℃, at low vacuum (60-70KPa) reaction 40min, after the temperature to 210 ℃, react 30 minutes, begin slowly to be warming up to 235 ℃ then, the while progressively increases vacuum.When temperature rises to 235 ℃, make the still internal pressure reach 5KPa.Keep temperature-resistant, the still internal pressure is reduced to below the 100Pa, reacted 2 hours, promptly get product.
Molecular weight: Mn=55300, Mw=120100, viscosity 1.23dL/g, end carboxyl 22mol/t, 43.0 ℃ of crystallization temperatures, 118.5 ℃ of fusing points.
Embodiment 6
Tetrabutyl titanate is slowly joined 1, in the 4-butanediol, the molar concentration of tetrabutyl titanate in mixed solution is for being 1.5mol/L, be stirred to and mix, in temperature is reaction 10 hours under 190 ℃ of conditions, not open closely goes into high pure nitrogen, so that remove volatile little molecule, be cooled to room temperature, promptly get the butanediol solution of titanium dioxide nanoparticle.
Add a certain amount of tetrabutyl titanate (TBOT) and sodium phosphate trimer (STPP) in the butanediol solution of above-mentioned nano titanium oxide, form tetrabutyl titanate (TBOT), nano titanium oxide (TiO
2), the mixture of sodium phosphate trimer (STPP), it consists of TBOT/TiO
2/ STPP=0.2/0.1/0.1, called after catalyst F.
40g 1,4 butanediol, the 28g dimethyl terephthalate (DMT), the 26g dimethyl adipate joins in the flask; under the nitrogen protection, be warming up to 170 ℃, add catalyst F (based on the amount of the polymer that generates; the consumption of titanium is 90ppm), keeping reactor temperature is 180 ℃, reacts 2.5 hours.
Then, temperature is warming up to 190 ℃, behind low vacuum (60-70KPa) reaction 40min.After the temperature to 210 ℃, reacted 30 minutes, begin slowly to be warming up to 235 ℃ then, progressively increase vacuum simultaneously.When temperature rises to 235 ℃, make the flask internal pressure reach 5KPa.Keep temperature-resistant, the flask internal pressure is reduced to below the 100Pa, reacted 2 hours, promptly get product.
Molecular weight: Mn=26200, Mw=82000, viscosity 1.09dL/g, end carboxyl 25mol/t, 45.0 ℃ of crystallization temperatures, 104.5 ℃ of fusing points.
Embodiment 7
Tetrabutyl titanate is slowly joined 1, in the 4-butanediol, the molar concentration of tetrabutyl titanate in mixed solution is for being 1.5mol/L, be stirred to and mix, in temperature is reaction 10 hours under 190 ℃ of conditions, not open closely goes into high pure nitrogen, so that remove volatile little molecule, be cooled to room temperature, promptly get the butanediol solution of titanium dioxide nanoparticle.
Add a certain amount of tetrabutyl titanate (TBOT) and Na in the above-mentioned solution
2HPO
3, make finally to consist of TBOT/TiO
2/ Na
2HPO
3=0.2/0.1/0.1, called after catalyst G.
54g 1,4 butanediol, the 35g dimethyl terephthalate (DMT), catalyst G (based on the amount of the polymer that generates, the consumption of titanium is 70ppm) joins in the flask, under the nitrogen protection, is warming up to 170 ℃, and keeping reactor temperature is 180 ℃, reaction 100min.Add the 32g adipic acid then, react 100min down at 180 ℃.
Then, temperature is warming up to 190 ℃, behind low vacuum (60-70KPa) reaction 40min, after temperature to 210 ℃, react 30 minutes, begin slowly to be warming up to 235 ℃ then, the while progressively increases vacuum.When temperature rises to 235 ℃, make the flask internal pressure reach 5KPa.Keep temperature-resistant, the flask internal pressure is reduced to below the 100Pa, reacted 2 hours, promptly get product.
Molecular weight: Mn=55300, Mw=102200, viscosity 1.10dL/g, end carboxyl 30mol/t, 40.0 ℃ of crystallization temperatures, 99.5 ℃ of fusing points.
Embodiment 8
Tetrabutyl titanate is slowly joined 1, in the 4-butanediol, the molar concentration of tetrabutyl titanate in mixed solution is for being 1.5mol/L, be stirred to and mix, in temperature is reaction 10 hours under 190 ℃ of conditions, not open closely goes into high pure nitrogen, so that remove volatile little molecule, be cooled to room temperature, promptly get the butanediol solution of titanium dioxide nanoparticle.
Add a certain amount of tetrabutyl titanate (TBOT) in the above-mentioned solution, form tetrabutyl titanate (TBOT), nano titanium oxide (TiO
2) mixed solution (TBOT/TiO
2=0.2/0.1), and cooperate potassium dihydrogen phosphate to use called after catalyst H (TBOT/TiO together
2/ K
2HPO
3=0.2/0.1/0.1).
54g 1,4 butanediol, the 35g dimethyl terephthalate (DMT), catalyst H (based on the amount of the polymer that generates, the consumption of titanium is 80ppm) under the nitrogen protection, is warming up to 170 ℃, and keeping reactor temperature is 180 ℃, reaction 100min.Add the 32g succinic acid then, react 100min down at 180 ℃.
Then, temperature is warming up to 190 ℃, behind low vacuum (60-70KPa) reaction 40min, after temperature to 210 ℃, react 30 minutes, begin slowly to be warming up to 235 ℃ then, the while progressively increases vacuum.When temperature rises to 235 ℃, make the flask internal pressure reach 5KPa.Keep temperature-resistant, the flask internal pressure is reduced to below the 100Pa, reacted 2 hours, promptly get product.
Molecular weight: Mn=37200, Mw=1420100, viscosity 1.22dL/g, end carboxyl 21mol/t, 68.0 ℃ of crystallization temperatures, 122.5 ℃ of fusing points.
Embodiment 9
54g 1, the 4-butanediol, the 40g terephthalic acid (TPA), catalyst H (based on the amount of the polymer that generates, the consumption of titanium is 60ppm), under the nitrogen protection, keeping reactor temperature is 220 ℃, reaction 150min.Add the 32g adipic acid then, react 100min down at 180 ℃.
Then, temperature is warming up to 190 ℃, behind low vacuum (60-70KPa) reaction 40min, after temperature to 210 ℃, react 30 minutes, begin slowly to be warming up to 235 ℃ then, the while progressively increases vacuum.When temperature rises to 235 ℃, make the flask internal pressure reach 5KPa.Keep temperature-resistant, the flask internal pressure is reduced to below the 100Pa, reacted 2 hours, promptly get product.
Molecular weight: Mn=42300, Mw=125000, viscosity 1.12dL/g, end carboxyl 19mol/t, 56.0 ℃ of crystallization temperatures, 118.2 ℃ of fusing points.
Embodiment 10
Slowly join butyl titanate in the ethylene glycol, the molar concentration of metatitanic acid four different esters in mixed solution is for being 1.0mol/L, be stirred to and mix, in temperature is to react 8 hours under 180 ℃ of conditions, not open closely go into high pure nitrogen, so that remove volatile little molecule, be cooled to room temperature, promptly get the ethylene glycol solution of titanium dioxide nanoparticle.
Sodium phosphate trimer joins and is heated to 70 ℃ in the ethylene glycol, obtain clear solutions, mix with the ethylene glycol solution of above-mentioned nano titanium oxide, add a certain amount of tetrabutyl titanate (TBOT) and sodium phosphate trimer, form tetrabutyl titanate (TBOT), nano titanium oxide (TiO
2), the mixed solution of sodium phosphate trimer (STPP), catalyst consist of TBOT/TiO
2/ STPP=0.2/0.1/0.1, the called after catalyst I.
30g ethylene glycol, the 35g dimethyl terephthalate (DMT) joins in the flask, under the nitrogen protection, is warming up to 170 ℃, adds catalyst I (based on the amount of the polymer that generates, the consumption of titanium is 60ppm), and keeping reactor temperature is 180 ℃, reacts 2.5 hours.Add the 32g adipic acid then, reacted 2 hours down at 180 ℃.
Then, temperature is warming up to 190 ℃, at low vacuum (60-70KPa) reaction 40min, after the temperature to 210 ℃, react 30 minutes, begin slowly to be warming up to 235 ℃ then, the while progressively increases vacuum.When temperature rises to 245 ℃, make the flask internal pressure reach 5KPa.Keep temperature-resistant, the flask internal pressure is reduced to below the 100Pa, reacted 2 hours, promptly get product.
Molecular weight: Mn=42000, Mw=85200, viscosity 0.82dL/g, end carboxyl 20mol/t, 67.0 ℃ of crystallization temperatures, 136.5 ℃ of fusing points.
Embodiment 11
Tetrabutyl titanate is slowly joined 1, in the ammediol, the molar concentration of tetrabutyl titanate in mixed solution is 1.5mol/L, being stirred to and mixing, is reaction 10 hours under 190 ℃ of conditions in temperature, not open closely goes into high pure nitrogen, so that remove volatile little molecule, be cooled to room temperature, promptly get 1 of titanium dioxide nanoparticle, ammediol solution.
Add a certain amount of tetrabutyl titanate (TBOT) and Na in the above-mentioned solution
2HPO
3, make finally to consist of TBOT/TiO
2/ Na
2HPO
3=0.2/0.1/0.1, called after catalyst J.
47g 1, ammediol, the 35g dimethyl terephthalate (DMT), catalyst J (based on the amount of the polymer that generates, the consumption of titanium is 70ppm) joins in the flask, under the nitrogen protection, is warming up to 170 ℃, and keeping reactor temperature is 180 ℃, reaction 100min.Add the 28g succinic acid then, react 100min down at 180 ℃.
Then, temperature is warming up to 190 ℃, behind low vacuum (60-70KPa) reaction 40min, after temperature to 210 ℃, react 30 minutes, begin slowly to be warming up to 235 ℃ then, the while progressively increases vacuum.When temperature rises to 235 ℃, make the flask internal pressure reach 5KPa.Keep temperature-resistant, the flask internal pressure is reduced to below the 100Pa, reacted 2 hours, promptly get product.
Molecular weight: Mn=51400, Mw=98200, viscosity 1.03dL/g, end carboxyl 31mol/t, 71.0 ℃ of crystallization temperatures, 140.4 ℃ of fusing points.
Embodiment 12
Slowly join butyl titanate in the ethylene glycol, the molar concentration of metatitanic acid four different esters in mixed solution is for being 1.5mol/L, be stirred to and mix, in temperature is to react 10 hours under 170 ℃ of conditions, not open closely go into high pure nitrogen, so that remove volatile little molecule, be cooled to room temperature, promptly get the ethylene glycol solution of titanium dioxide nanoparticle.
Sodium phosphate trimer joins and is heated to 60 ℃ in the ethylene glycol, obtain clear solutions, mix with the ethylene glycol solution of above-mentioned nano titanium oxide, add a certain amount of tetrabutyl titanate (TBOT), form tetrabutyl titanate (TBOT), nano titanium oxide (TiO
2), the mixed solution of sodium phosphate trimer (STPP), catalyst consist of TBOT/TiO
2/ STPP=0.2/0.1/0.1, called after catalyst J.
30g ethylene glycol, 35g dimethyl terephthalate (DMT), 30g dimethyl succinate join in the flask, under the nitrogen protection; be warming up to 170 ℃, add catalyst J (based on the amount of the polymer that generates, the consumption of titanium is 60ppm); keeping reactor temperature is 180 ℃, reacts 2.5 hours.
Then, temperature is warming up to 190 ℃, at low vacuum (60-70KPa) reaction 40min, after the temperature to 210 ℃, reaction 30min begins slowly to be warming up to 235 ℃ then, progressively increases vacuum simultaneously.When temperature rises to 245 ℃, make the flask internal pressure reach 5KPa.Keep temperature-resistant, the flask internal pressure is reduced to below the 100Pa, reacted 2 hours, promptly get product.
Molecular weight: Mn=38000, Mw=75300, viscosity 0.90dL/g, end carboxyl 20mol/t, 75.0 ℃ of crystallization temperatures, 143.5 ℃ of fusing points.
Comparative Examples 1
35.0g dimethyl terephthalate (DMT), tetra-n-butyl titanate 0.1g, 55.0g butanediol are joined in the flask, 180 ℃, reacted 2 hours; Add succinic acid 32.0g then, continue reaction 1 hour under 190 ℃ condition, be warming up to 235 ℃ then, stir fast, be evacuated to 100Pa, about 2 hours of constant temperature promptly gets the light yellow solid product.
Molecular weight: Mn=42500, Mw=113000, viscosity 1.13dL/g, end carboxyl 60mol/t, 55.0 ℃ of crystallization temperatures, 118.2 ℃ of fusing points.
Comparative Examples 2
35.0g dimethyl terephthalate (DMT), nano titanium oxide 0.13g, 55.0g butanediol are joined in the flask, 180 ℃, reacted 2 hours; Add succinic acid 32.0g then, continue reaction 1 hour under 190 ℃ condition, be warming up to 235 ℃ then, stir fast, be evacuated to 100Pa, about 2 hours of constant temperature promptly gets product.
Molecular weight: Mn=22300, Mw=54000, viscosity 0.82dL/g, end carboxyl 70mol/t, 55.0 ℃ of crystallization temperatures, 115.0 ℃ of fusing points
Claims (9)
1. a high-activity titanium series composite catalyst is characterized in that comprising major catalyst, first co-catalyst and second co-catalyst; Described major catalyst is a titanate esters, and described first co-catalyst is a nano titanium oxide, and described second co-catalyst is the phosphate of IA, IIA or IIIA family metal; The mol ratio of nano titanium oxide and major catalyst is 0 ~ 3: 1, and the mol ratio of phosphorus atoms and major catalyst is 0 ~ 3: 1 in the phosphate.
2. high-activity titanium series composite catalyst according to claim 1 is characterized in that described titanate esters is a kind of in tetrabutyl titanate, tetraisopropyl titanate, metatitanic acid tetramethyl ester, tetraethyl titanate, metatitanic acid four monooctyl esters.
3. high-activity titanium series composite catalyst according to claim 1 is characterized in that the metallic element in the described phosphate is lithium, sodium, potassium, magnesium, calcium, aluminium or zinc.
4. high-activity titanium series composite catalyst according to claim 1, the mol ratio that it is characterized in that described nano titanium oxide and major catalyst is 0 ~ 3: 1; The mol ratio of phosphorus atoms and major catalyst is 0 ~ 3: 1 in the described phosphate.
5. the preparation method of the described high-activity titanium series composite catalyst of claim 1, it is characterized in that comprising the steps: slowly joining tetraisopropyl titanate or tetrabutyl titanate in the dihydroxylic alcohols, tetraisopropyl titanate or the tetrabutyl titanate molar concentration in mixed solution is for being 1.0 ~ 1.5mol/L, be stirred to and mix, in temperature is to react 8-24 hour under 180 ~ 200 ℃ of conditions, not open closely go into high pure nitrogen, so that remove volatile little molecule, be cooled to room temperature, promptly get the glycol solution of nano titanium oxide; In the glycol solution of nano titanium oxide, add the major catalyst and second co-catalyst, form the high-activity titanium series composite catalyst.
6. preparation method according to claim 5 is characterized in that described dihydroxylic alcohols is an ethylene glycol, 1,2-propane diols, 1, ammediol, 1,2-butanediol, 1,4-butanediol, 1, the one or more kinds of mixtures in the 5-pentanediol.
8. the application of the described high-activity titanium series composite catalyst of claim 1 in the catalysis of aliphatic-aromatic copolyesters is synthetic.
9. the described high-activity titanium series composite catalyst of claim 1 is used for the method for catalyzed synthesis of fatty-family's aromatic copolyester and is: titanate esters, nano titanium oxide and dihydroxylic alcohols mix, and add with the solution form; Metal phosphate and binary acid mix and join in the reaction system; Aromatic dicarboxylic acid esters or aromatic acid and excess glycol are carried out ester exchange reaction or esterification, and reaction temperature is 190～220 ℃, and the reaction time is 1～2 hour; Add the esterification derivative of aliphatic dibasic acid, cyclisation aliphatic dibasic acid, aliphatic dibasic acid or the esterification derivative of cyclisation aliphatic dibasic acid again and proceed esterification, reaction temperature is 190～210 ℃, and the reaction time is 0.5～1.5 hour; Under the condition that composite catalyst exists, carry out polycondensation reaction then, obtain polymer.
10. method according to claim 9, it is characterized in that described aromatic dicarboxylic acid esters or aromatic acid be terephthalic acid (TPA), phthalic acid, M-phthalic acid, to the one or more kinds of mixtures in phenylenediacetic Acid or the phthalic acid; The esterification derivative of described aliphatic dibasic acid, cyclisation aliphatic dibasic acid, aliphatic dibasic acid or the esterification derivative of cyclisation aliphatic dibasic acid are succinic acid, glutaric acid, adipic acid, azelaic acid, decanedioic acid, hendecane dicarboxylic acid, maleic anhydride, 1,1-cyclobutane dicarboxylic acid, 1, the one or more kinds of mixtures in 1-cyclohexanediacetic and the carboxylate thereof.
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