CN100457800C - Method for synthesizing polyester by using rare earth catalyst - Google Patents
Method for synthesizing polyester by using rare earth catalyst Download PDFInfo
- Publication number
- CN100457800C CN100457800C CNB2004101015477A CN200410101547A CN100457800C CN 100457800 C CN100457800 C CN 100457800C CN B2004101015477 A CNB2004101015477 A CN B2004101015477A CN 200410101547 A CN200410101547 A CN 200410101547A CN 100457800 C CN100457800 C CN 100457800C
- Authority
- CN
- China
- Prior art keywords
- monomer
- acid
- rare earth
- catalyst component
- mol ratio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
This invention publishes a synthesis method for polyesters from rare earth catalysts. In this method, single-kettle operation is adopted. One of the compounds of titanium, stibium and zincum is chosen as the catalyst C1 for transesterification and esterification and is added into the reaction kettle with monomer raw materials before reaction. After a certain period of prepolymerization, a rare earth metal compound as catalyst C2 is added for vacuum condensation polymerization. It is due to the single-kettle operation that this invention has the advantages of simplified technique, accelerated polymerization reaction, promoted product molecular weight, reduced side reactions and significantly improved color of polyester product.
Description
Technical field
The present invention relates to the method for synthesizing polyester, particularly use rare earth compound to do the method for catalyst component synthesizing polyester.
Background technology
Condensation polymerization prepares polyester, as polyethylene terephtalate, polybutylene terephthalate PBT, Poly(Trimethylene Terephthalate) PPT etc., be widely used in the every field of people's daily life as engineering materials, they can make materials such as fiber, beverage bottle, film.The preparation of these polymkeric substance is all through two technological processs: the esterification or the transesterify of terephthalic acid or its esterification products and aliphatic dihydroxy alcohol, and esterification process takes place under condition of high voltage, and the transesterify process is then carried out under normal pressure; The vacuum polycondensation of esterification or ester exchange offspring.These two processes are generally all separately carried out, and need two polymeric kettles.
It is a lot of that condensation polymerization prepares the used catalyst system of polyester, almost related to all major-minor family elements of the periodic table of elements except that haloid element and inert element.But what catalytic effect was best can reduce three major types: titanium system, antimony system and germanium system.When the titanium series elements used as catalyzer, catalytic activity was very high, but the jaundice of gained polyester article poor stability, color and luster; The antimony series elements uses as catalyzer, and polyreaction is very steady, and domestic and international 80% polyester product is antimony-based catalyst at present, but because the toxicity of antimony element is unfavorable for environmental requirement, has limited the Application Areas of polyester article; The germanium series catalysts is one of best polyester catalyst of net effect, but because it costs an arm and a leg, is unfavorable for promoting the use of on a large scale.
The U.S. Pat 5817721 of BASF AG discloses a kind of biodegradable polyester, it is with aromatic acid or ester, aliphatic dihydroxy alcohol, aliphatic dibasic acid or ester are mixed step by step, adopt the catalyzer of compounds such as tin, titanium, react and obtain as esterification, transesterify and polycondensation.
Polyester production process of BASF AG such as US6018004, US6046248, US6114042 are disclosed, and major part all adopts the operation of two stills, carries out in two steps.At first, with hexanodioic acid and 1,4-butyleneglycol (BDO) esterification adopts two stannous octoates to make catalyzer, and the gained esterification products is standby; Then, esterification products and dimethyl terephthalate (DMT) (DMT), BDO, the tetrabutyl titanate (TBOT) of the first step added another reactor simultaneously, DMT and BDO transesterify finish, and system vacuumizes polycondensation.The molecular weight of gained polyester product is not high, and generally about 10,000, weight-average molecular weight is about 30,000 to number-average molecular weight (Mn).If above-mentioned second step add contain a plurality of can with the acid anhydrides of (at least three) functional group of pet reaction, ether, isocyanic ester etc. as chainextender, can obviously increase the weight-average molecular weight of copolyesters, but number-average molecular weight then increases manyly not as weight-average molecular weight, molecular weight of product obviously broaden (3.5～8) that distribute.
Also there is the single still operation carrying out of employing polymeric example in BASF AG, is about to DMT, BDO and adds reactor with TBOT, treats that the approaching adding hexanodioic acid that finishes of transesterify carries out esterification, vacuum polycondensation afterwards.But concrete molecular weight of product does not appear in the newspapers.
At present, condensation polymerization prepares polyester and generally comprises esterification, transesterify and three step of reaction of polycondensation.Normally monomer and esterification or catalyst for ester exchange reaction are added reaction system simultaneously, treat esterification or transesterification reaction finish (looking the small molecules product amount of removing decides), change to another polymeric kettle, add esterification or ester exchange offspring and polycondensation catalyst simultaneously, carry out the vacuum polycondensation.
In recent years, rare earth compound uses the extensive concern that has caused Chinese scholars as catalyzer, utilizes the correlation technique of lanthanide series metal catalyst to synthesize ester also a lot, as CN1112573A, EP626425, CN1446837A etc.Can improve polymerization rate although use rare earth compound to do polyester catalyst, the concrete technology and the apolegamy of catalyzer are still waiting further research.In polyester synthetic technology, also there is the operating procedure complexity, deficiencies such as polymer molecular weight wider distribution.Therefore, need provide a kind of use novel rare-earth catalyst system, simplify existing polyester synthesis technique, reduce the method for the synthesizing polyester of side reaction generation.
Summary of the invention
The purpose of this invention is to provide a kind of in the presence of catalysis of rare-earth compound agent component, the method for synthesizing polyester.
The method of synthesizing polyester of the present invention comprises the following steps:
1) will be selected from least a aromatic acid, its ester derivative or its corresponding acid anhydrides (a), at least a aliphatics or alicyclic dibasic alcohol (b) and at least a aliphatic dibasic acid, alicyclic diprotic acid, their ester derivative or the monomer of their corresponding acid anhydrides (c), and catalyst component C1, add in the reactor and react, wherein said monomer (a) and mol ratio (c) are 0: 100～100: 0;
2) under vacuum condition, with 1) reaction system that obtains carries out pre-polymerization;
3) to 2) add catalyst component C2 in the prepolymer product that obtains, carry out vacuum polycondensation, obtain described polyester;
Wherein, described catalyst component C1 is selected from a kind of in the compound of metal titanium, antimony or zinc;
Described catalyst component C2 is selected from least a in the compound of rare earth metal Ln, and rare earth metal Ln is selected from a kind of in lanthanon, scandium and the yttrium.
The small molecules of reaction system preferred described step 2) is close to be drained, and after the cut temperature remains unchanged, carries out the 3rd) step, add catalyst component C2.
When preparation fat/aromatic copolyesters, can be earlier with aromatic acid or its ester or its corresponding acid anhydrides and diol reaction, and then add aliphatic dibasic acid or its ester or its corresponding acid anhydrides; Also can be earlier with aliphatic dibasic acid or its ester or its corresponding acid anhydrides and diol reaction, and then add aromatic acid or its ester or its corresponding acid anhydrides.Preferably in described step 1),, add reactor and react at first with catalyst component C1, at least a aromatic acid or its ester derivative or its respective acids anhydride monomer (a), at least a aliphatics or alicyclic dibasic alcohol monomer (b); And then add at least a aliphatic dibasic acid, alicyclic diprotic acid or their ester derivative or their respective acids anhydride monomer (c), react.
When preferred method of the present invention is used for synthetic fat family/aromatic series homopolymerization or copolyesters, carrying out transesterification reaction temperature is 150～230 ℃, esterification reaction temperature is 160～250 ℃, and the temperature of polycondensation is 220～280 ℃, polycondensation pressure is general≤and 200Pa.
In a preferred embodiment of the invention, described monomer (a) and mol ratio (c) are 0: 100～65: 35; Described monomer (a) and (c) mole number sum, with the ratio of the mole number of monomer (b) be 1: (1.0～2.0), preferred 1: (1.1～1.5), more preferably 1: (1.2～1.4); The mol ratio of described catalyst system and monomer (a) and total amount (c) is 1: (500～10000), preferred 1: (1000～3000).
In the method for the invention, described monomer (a) is selected from phenyl diprotic acid or ester derivative or corresponding acid anhydrides, is preferably terephthalic acid or dimethyl terephthalate (DMT); Described monomer (b) is selected from C
2～C
6The pure and mild C of binary aliphatic
5～C
10Alicyclic dibasic alcohol at least a, be preferably 1,4-butyleneglycol, 1, ammediol or ethylene glycol; Described monomer (c) is selected from C
3～C
10Aliphatic dibasic acid, C
5～C
10Alicyclic diprotic acid, their ester derivative and their corresponding acid anhydrides at least a, be preferably hexanodioic acid, sebacic acid or Succinic Acid.
In a preferred embodiment of the invention, described catalyst component C1 is selected from M (OR
2')
x, M
2O
xAnd M (R
1' COO)
xIn a kind of, be preferably titan-alkoxide Ti (OR
2')
x, antimony acetate, zinc acetate, the oxide compound of zinc, the oxide compound or the titanyl compound of antimony, more preferably tetrabutyl titanate, titanium isopropoxide, titanium dioxide, antimonous oxide, antimony acetate or zinc acetate;
Described catalyst component C2 is selected from the inorganic halides LnX of rare earth metal
3, carboxylate salt Ln (R
1COO)
3, alkoxide Ln (OR
2)
3, fragrant oxide compound Ln (OAr)
3, and acetylacetonate Ln (a
ca
c)
3And at least a in their hydrate, be preferably selected from the inorganic halides LnX of rare earth metal
3, alkoxide Ln (OR
2)
3, fragrant oxide compound Ln (OAr)
3Acetylacetonate Sm (a that does not comprise samarium
ca
c)
3The acetylacetonate Ln (a of rare earth metal
ca
c)
3In a kind of;
And the mol ratio of C2 and C1 is 5: 95～100: 0, is preferably 1: 3～3: 1, and more preferably 2: 3～3: 2;
Wherein, preferred described rare earth metal Ln is selected from a kind of among lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, terbium Td, ytterbium Yb, dysprosium Dy, samarium Sm and the scandium Sc, more preferably lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd or scandium Sc,
X is a halide-ions, is preferably chlorion or bromide anion, a
ca
cBe the methyl ethyl diketone group,
R
1, R
1' be selected from C
1～C
3Alkyl, R
1, R
1' can be identical or inequality,
R
2, R
2' be selected from C
3～C
6Alkyl, R
2, R
2' can be identical or inequality, preferred R
2Be sec.-propyl, normal-butyl or isopentyl,
Ar is selected from C
1～C
4The phenyl that replaces of alkyl, preferred 2, the 6-dibutyl, 4-aminomethyl phenyl or 4-butyl phenyl,
M is metal titanium, antimony or zinc, and x is 2,3 or 4.
In a preferred embodiment of the invention, described catalyst component C1 is selected from a kind of in tetrabutyl titanate, titanium isopropoxide, titanium dioxide, antimonous oxide, antimony acetate and the zinc acetate,
Described catalyst component C2 is selected from the inorganic halides LnX of rare earth metal
3, carboxylate salt Ln (R
1COO)
3, alkoxide Ln (OR
2)
3, fragrant oxide compound Ln (OAr)
3In a kind of,
And the mol ratio of described C2 and C1 is 2: 3～3: 2,
Wherein, described rare earth metal Ln is selected from a kind of among lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd and the scandium Sc, and X is chlorion or bromide anion,
R
1Be ethyl, propyl group, R
2Be sec.-propyl, normal-butyl or isopentyl,
Ar is 2,6-dibutyl, 4-aminomethyl phenyl or 4-butyl phenyl.
Use method of the present invention, have following effect:
1) method of the present invention adopts single still operation, has simplified operating procedure; Side reaction reduces, and the polyester product color and luster obviously improves;
2) method of the present invention, the catalyst body of use are the catalyst system of efficient, nontoxic or low toxicity, compare with single component titanium compound catalyst system, and polymerization rate obviously increases, and the polycondensation time can reduce to 3～7h from 10h; Can improve the number-average molecular weight of product in the weight-average molecular weight that improves polyester product, molecular weight of product distributes and does not broaden; Reaction process is steady simultaneously, is easy to control;
3) use method of the present invention, can under the situation that does not add chainextender, polymer molecular weight obviously be increased; Therefore polyester product is pure, does not have additives such as chainextender, stablizer.
Embodiment
Raw material used in the embodiments of the invention is as follows:
DMT: dimethyl terephthalate (DMT), chemical pure, Xing Jin chemical plant, Beijing
ADP: hexanodioic acid, analytical pure, Shanghai chemical reagents corporation of Chinese Medicine group
BD: butyleneglycol, analytical pure, Beijing Yili Fine Chemicals Co., Ltd.
Tetrabutyl titanate: chemical pure, Beijing chemical reagents corporation
Rare earth oxide: purity 99.5%, Beijing chemical reagent work of Xinhua
Rare earth chloride hydrate: chemical pure, Beijing chemical reagent work of Xinhua
2,6 di tert butyl 4 methyl phenol: chemical pure, Shanghai chemical reagents corporation of Chinese Medicine group
Virahol: analytical pure, Beijing Chemical Plant
Sodium: Beijing imperial chemical reagent of gold company limited
The preparation of embodiment 1-4 rare earth catalyst C2
Embodiment 1 anhydrous lanthanum chloride (LaCl
3) preparation
With 10g La
2O
3With the excessive hydrochloric acid dissolving, heating concentrates the NH that the back adds metering
4Cl is (with La
2O
3Mol ratio is 3/1), careful heating boils off excessive acid, obtains LaCl
3NH
2O+NH
4The solid of Cl with joining in the quartzy sublimation pipe after the solid grinding, is evacuated to＜5mmHg; In tube furnace, slowly be warmed up to 400 ℃, vacuumize maintenance 1hr; Be cooled to room temperature under the vacuum, charge into argon gas, take off sublimation pipe, under argon shield, move in the pipe standby.
Embodiment 2 acetylacetonate lanthanum La (a
ca
c)
3Preparation
In the 250ml three-necked bottle, with LaCl
37H
2(3.47g 9.37mmol) is dissolved in the water of 50ml O, and (5.63g in 50ml aqueous solution 56.2mmol), stirs under the room temperature, adjusts pH value to 7 by adding 2NKOH solution dropwise to join methyl ethyl diketone.Reaction mixture has La (a
ca
c)
3Throw out, stir, filter, in 60 ℃ of vacuum-dryings, obtain about 4gLa (a
ca
c)
3
The preparation of embodiment 3 isopropoxy neodymiums
In the 250ml three-necked bottle, add 4.87g (0.02mol) anhydrous chlorides of rase neodymium and 80ml Virahol, reflux dissolving postcooling is to room temperature, stir fast down, drip sodium isopropylate solution (the 1.349g sodium Metal 99.5 is dissolved in the mixed solution of 20ml Virahol and 65ml benzene), after dropwising, reflux 4hr, cooling, standing over night.G4 core filter bulb filters, and the filtrate distillation removes desolvates, and after the vacuum-drying, obtains the about 15g of isopropoxy neodymium blue powder.
Synthesizing of embodiment 4 three (2,6-di-t-butyl-4 methylphenoxy) rare earth
The earlier accurate anhydrous LnCl of weighing
3(0.5～0.8g) to polymerization bottle, operates under argon shield, according to LnCl
3Mole number, calculate the weight of required 2,6 di tert butyl 4 methyl phenol by 1: 3 proportional meter.
With quantitative 2; the 6-di-tert-butyl-4-methy phenol adds (Zhi Guanduan leads to argon gas) in the flask of being with arm under argon shield; add the 30ml tetrahydrofuran solvent, be stirred to dissolving, add excessive sodium Metal 99.5; react 2～3hr under the room temperature; do not have bubble to generate to the sodium Metal 99.5 surface, continue to add a little sodium Metal 99.5, judge whether reaction is carried out fully; obtain 2, the tetrahydrofuran solution of 6-di-t-butyl-4 methylphenol sodium.
With load weighted anhydrous LnCl
3Be transferred in the 50ml single port reaction flask, then with 2, the tetrahydrofuran solution of 6-di-t-butyl-4 methylphenol sodium is transferred in the reaction flask sufficient argon gas.Reactant magnetic agitation 2～3 days in 80～90 ℃ of oil baths.Centrifuging, filtrate decompression steams solvent, and vacuum-drying 1hr obtains three (2,6-di-t-butyl-4 methylphenoxy) rare earth catalyst.
Comparative Examples 1 titanium single component catalyst prepares polyester
In the 500ml three-necked bottle, add 136g (0.7mol) dimethyl terephthalate (DMT), 126g (1.4mol) butyleneglycol, 0.20g (0.59mmol) tetrabutyl titanate; the system nitrogen protection; be heated with stirring to backflow; temperature of reaction is controlled at 160～220 ℃; the methyl alcohol that collection steams is collected to methyl alcohol and to be finished.System vacuumizes, heating, and temperature of reaction is at 220～260 ℃, system pressure≤200Pa, vacuum polycondensation 10h.Products therefrom is yellow, and viscosity number VN is 67ml/g (in the 0.005g/ml polymers soln of orthodichlorobenzene/phenol weight ratio 50/50, measuring GB/T 17932-1999 for 25 ℃).
Comparative Examples 2 titanium single component catalysts prepare copolyesters
In the 500ml three-necked bottle, add 78g (0.4mol) dimethyl terephthalate (DMT), 86.5g (0.96mol) butyleneglycol, 0.17g (0.5mmol) tetrabutyl titanate; the system nitrogen protection; be heated with stirring to backflow; temperature of reaction is controlled at 160～220 ℃; the methyl alcohol that collection steams is collected to methyl alcohol and to be finished.Add 58.5g (0.4mol) hexanodioic acid in system, continue to be heated with stirring to backflow, temperature of reaction is controlled at 180～240 ℃, collects the moisture that steams, and collects to moisture to finish.System vacuumizes, heating, and temperature of reaction is at 220～260 ℃, system pressure≤200Pa, vacuum polycondensation 10h.Products therefrom is yellow, and GPC method determining molecular weight Mn is that 2.68 ten thousand, Mw are 5.29 ten thousand, and molecular weight distribution is 1.97.
Comparative Examples 3
In the 500ml three-necked bottle, add 78g (0.4mol) dimethyl terephthalate (DMT), 86.5g (0.96mol) butyleneglycol, 0.11g (0.32mmol) tetrabutyl titanate, methyl ethyl diketone lanthanum 0.073g (0.17mmol); the system nitrogen protection; be heated with stirring to backflow; temperature of reaction is controlled at 160～220 ℃; the methyl alcohol that collection steams is collected to methyl alcohol and to be finished.Add 58.5g (0.4mol) hexanodioic acid in system, continue to be heated with stirring to backflow, temperature of reaction is controlled at 180～240 ℃, collects the moisture that steams, and collects to moisture to finish.System vacuumizes, heating, and temperature of reaction is at 220～260 ℃, system pressure≤200Pa, vacuum polycondensation 7h.Products therefrom is light yellow, and GPC method determining molecular weight Mn is that 3.08 ten thousand, Mw are 6.21 ten thousand, and molecular weight distribution is 2.02.
Comparative Examples 4
In the 500ml three-necked bottle, add 78g (0.4mol) dimethyl terephthalate (DMT), 86.5g (0.96mol) butyleneglycol, 0.11g (0.32mmol) tetrabutyl titanate; the system nitrogen protection; be heated with stirring to backflow; temperature of reaction is controlled at 160～220 ℃; the methyl alcohol that collection steams is collected to methyl alcohol and to be finished.Add 58.5g (0.4mol) hexanodioic acid in system, continue to be heated with stirring to backflow, temperature of reaction is controlled at 180～240 ℃, collects the moisture that steams, and collects to moisture to finish.In system, add methyl ethyl diketone lanthanum 0.073g (0.17mmol), vacuumize, heating, temperature of reaction is at 220～260 ℃, system pressure≤200Pa, vacuum polycondensation 7h.Products therefrom is a white, and GPC method determining molecular weight Mn is that 3.84 ten thousand, Mw are 8.88 ten thousand, and molecular weight distribution is 2.31.
Embodiment 5
In the 500ml three-necked bottle, add 136g (0.7mol) dimethyl terephthalate (DMT), 126g (1.4mol) butyleneglycol, 0.10g (0.29mmol) tetrabutyl titanate; the system nitrogen protection; be heated with stirring to backflow; temperature of reaction is controlled at 160～220 ℃; the methyl alcohol that collection steams is collected to methyl alcohol and to be finished.Vacuumize, heating, temperature of reaction is at 220～260 ℃, and system pressure≤200Pa has steamed to solvent is approaching, and cut is temperature-resistant, adds methyl ethyl diketone lanthanum 0.073g (0.17mmol), vacuum polycondensation 5h in system.Products therefrom is a white, and viscosity number VN is 141ml/g (in the 0.005g/ml polymers soln of orthodichlorobenzene/phenol weight ratio 50/50, measuring GB/T 17932-1999 for 25 ℃).
Embodiment 6
In the 500ml three-necked bottle, add 78g (0.4mol) dimethyl terephthalate (DMT), 86.5g (0.96mol) butyleneglycol, 0.11g (0.32mmol) tetrabutyl titanate; the system nitrogen protection; be heated with stirring to backflow; temperature of reaction is controlled at 160～220 ℃; the methyl alcohol that collection steams is collected to methyl alcohol and to be finished.Add 58.5g (0.4mol) hexanodioic acid in system, continue to be heated with stirring to backflow, temperature of reaction is controlled at 180～240 ℃, collects the moisture that steams, and collects to moisture to finish.Vacuumize, heating, temperature of reaction is at 220～260 ℃, and system pressure≤200Pa has steamed to solvent is approaching, and cut is temperature-resistant, adds methyl ethyl diketone lanthanum 0.073g (0.17mmol), vacuum polycondensation 6h in system.Products therefrom is a white, and GPC method determining molecular weight Mn is that 4.53 ten thousand, Mw are 10.2 ten thousand, and molecular weight distribution is 2.25.
Embodiment 7
Other condition is with embodiment 6, and the methyl ethyl diketone lanthanum changes isopropoxy neodymium 0.055g (0.17mmol) into.
Embodiment 8
Other condition is with embodiment 6, and the methyl ethyl diketone lanthanum changes 2 into, 6-dibutyl-4-methylphenoxy lanthanum 0.14g (0.17mmol).
The characterization parameter of the copolyesters that Comparative Examples 1-4 and embodiment 5-8 are obtained is listed in table 1 and table 2.
Table 1 rare earth compound adds the influence of mode to polyester
| Numbering | Rare earth compound | The polycondensation time (h) | Viscosity number VN (ml/g) | Yellowness index |
| Comparative Examples 1 | Do not add | 10 | 67 | 61.2 |
| Embodiment 5 | Add | 5 | 141 | 41.5 |
Table 2 rare earth compound adds mode to be influenced the copolyesters polymeric
Claims (13)
1, a kind of method of single still operation synthesizing polyester, it comprises the following steps:
1) will be selected from least a aromatic acid, its ester derivative or its acid anhydrides (a), at least a aliphatics or alicyclic dibasic alcohol (b) and at least a aliphatic dibasic acid, alicyclic diprotic acid, their ester derivative or the monomer of their acid anhydrides (c), and catalyst component C1, add in the same reactor and react, wherein said monomer (a) and mol ratio (c) are 0: 100～100: 0;
2) under vacuum condition, with 1) reaction system that obtains carries out pre-polymerization;
3) to 2) add catalyst component C2 in the prepolymer product that obtains, carry out vacuum polycondensation, obtain described polyester;
Wherein,
Described catalyst component C1 is selected from M (OR
2')
x, M
2O
xAnd M (R
1' COO)
xIn a kind of,
Described catalyst component C2 is selected from the inorganic halides LnX of rare earth metal
3, carboxylate salt Ln (R
1COO)
3, alkoxide Ln (OR
2)
3, fragrant oxide compound Ln (OAr)
3, and acetylacetonate Ln (a
ca
c)
3And at least a in their hydrate, rare earth metal Ln is selected from a kind of in lanthanon, scandium and the yttrium;
And the mol ratio of C2 and C1 is 1: 3～3: 1;
Wherein, X is a halide-ions, a
ca
cBe the methyl ethyl diketone group,
R
1, R
1' be selected from C
1～C
3Alkyl, R
1, R
1' can be identical or inequality,
R
2, R
2' be selected from C
3～C
6Alkyl, R
2, R
2' can be identical or inequality,
Ar is selected from C
1～C
4The phenyl that replaces of alkyl,
M is metal titanium, antimony or zinc, and x is 2,3 or 4.
2, method according to claim 1 is characterized in that in described step 2) the cut temperature of reaction system remain unchanged after, add catalyst component C2.
3, method according to claim 1, it is characterized in that in described step 1), at first, add reactor and react catalyst component C1, at least a aromatic acid, its ester derivative monomer or its corresponding acid anhydrides (a), at least a aliphatics or alicyclic dibasic alcohol monomer (b); And then add at least a aliphatic dibasic acid, alicyclic diprotic acid, their ester derivative monomer or their corresponding acid anhydrides (c), react.
4, method according to claim 1, it is characterized in that described monomer (a) and mol ratio (c) are 0: 100～65: 35, described monomer (a) and (c) mole number sum, with the ratio of the mole number of monomer (b) be 1: (1.0～2.0), the mol ratio of catalyst system and monomer (a) and total amount (c) is 1: (500～10000).
5, method according to claim 4, it is characterized in that described monomer (a) and (c) mole number sum, with the mol ratio of monomer (b) be 1: (1.1～1.5), the mol ratio of catalyst system and monomer (a) and total amount (c) is 1: (1000～3000).
6, method according to claim 5, it is characterized in that described monomer (a) and (c) mole number sum, with the mol ratio of monomer (b) be 1: (1.2～1.4).
7, method according to claim 1 is characterized in that described monomer (a) is selected from phenyl diprotic acid, its ester derivative and its acid anhydrides, and described monomer (b) is selected from C
2～C
6The pure and mild C of binary aliphatic
5～C
10Alicyclic dibasic alcohol at least a, described monomer (c) is selected from C
3～C
10Aliphatic dibasic acid, C
5～C
10Alicyclic diprotic acid, their ester derivative and their acid anhydrides at least a.
8, method according to claim 7, it is characterized in that described monomer (a) is terephthalic acid or dimethyl terephthalate (DMT), described monomer (b) is 1,4-butyleneglycol, 1, ammediol or ethylene glycol, described monomer (c) is hexanodioic acid, sebacic acid or Succinic Acid.
9, method according to claim 1 is characterized in that described rare earth metal Ln is selected from a kind of among lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, terbium Td, ytterbium Yb, dysprosium D y, samarium Sm and the scandium Sc.
10, method according to claim 9 is characterized in that described rare earth metal Ln is selected from lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd and scandium Sc.
11, method according to claim 1 is characterized in that
Described catalyst component C1 is titan-alkoxide Ti (OR
2')
x, antimony acetate, zinc acetate, the oxide compound of zinc, the oxide compound or the titanyl compound of antimony;
Described catalyst component C2 is selected from the inorganic halides LnX of rare earth metal
3, alkoxide Ln (OR
2)
3, fragrant oxide compound Ln (OAr)
3Acetylacetonate Sm (a that does not comprise samarium
ca
c)
3The acetylacetonate Ln (a of rare earth metal
ca
c)
3In a kind of,
Wherein, X is chlorion or bromide anion, R
2Be sec.-propyl, normal-butyl or isopentyl.
12, method according to claim 11 is characterized in that described C1 is tetrabutyl titanate, titanium isopropoxide, titanium dioxide, antimonous oxide, antimony acetate or zinc acetate,
And the mol ratio of C2 and C1 is 2: 3～3: 2.
13, method according to claim 1 is characterized in that
Described catalyst component C1 is selected from a kind of in tetrabutyl titanate, titanium isopropoxide, titanium dioxide, antimonous oxide, antimony acetate and the zinc acetate,
Described catalyst component C2 is selected from the inorganic halides LnX of rare earth metal
3, carboxylate salt Ln (R
1COO)
3, alkoxide Ln (OR
2)
3, fragrant oxide compound Ln (OAr)
3In a kind of,
And the mol ratio of described C2 and C1 is 2: 3～3: 2,
Wherein, described rare earth metal Ln is selected from a kind of among lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd and the scandium Sc,
X is chlorion or bromide anion,
R
1Be ethyl or propyl group, R
2Be sec.-propyl, normal-butyl or isopentyl.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004101015477A CN100457800C (en) | 2004-12-23 | 2004-12-23 | Method for synthesizing polyester by using rare earth catalyst |
| US11/312,373 US7332562B2 (en) | 2004-12-23 | 2005-12-21 | Biodegradable linear random copolyester and process for preparing it and use of the same |
| JP2005370374A JP5048245B2 (en) | 2004-12-23 | 2005-12-22 | Biodegradable linear random copolyester and its production and use |
| SG200508323A SG123753A1 (en) | 2004-12-23 | 2005-12-22 | Biodegradable linear random copolyester and process for preparing it and use of the same |
| KR1020050128600A KR101234538B1 (en) | 2004-12-23 | 2005-12-23 | Biodegradable linear random copolyester and process for preparing it and use of the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004101015477A CN100457800C (en) | 2004-12-23 | 2004-12-23 | Method for synthesizing polyester by using rare earth catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1796433A CN1796433A (en) | 2006-07-05 |
| CN100457800C true CN100457800C (en) | 2009-02-04 |
Family
ID=36817759
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004101015477A Active CN100457800C (en) | 2004-12-23 | 2004-12-23 | Method for synthesizing polyester by using rare earth catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100457800C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525429B (en) * | 2009-03-30 | 2013-01-16 | 东华大学 | Binary composite catalyst for preparing biodegradable copolyester |
| CN102453238B (en) * | 2010-10-15 | 2013-06-05 | 中国石油化工股份有限公司 | Preparation method of biodegradable polyester |
| CN102453243B (en) * | 2010-10-15 | 2013-06-05 | 中国石油化工股份有限公司 | Preparation method of polyester and polyester prepared by preparation method |
| CN102453249B (en) * | 2010-10-15 | 2013-06-05 | 中国石油化工股份有限公司 | Catalyst composition |
| CN102453237B (en) * | 2010-10-15 | 2013-03-27 | 中国石油化工股份有限公司 | Preparation method of biodegradable polyester |
| CN113174036B (en) * | 2021-04-28 | 2023-03-28 | 浙江联盛化学股份有限公司 | Rare earth doped molecular sieve catalyst, preparation method and application thereof |
| CN113087884B (en) * | 2021-05-27 | 2021-12-17 | 天津大学 | Method for preparing poly (butylene succinate) |
| CN113336926A (en) * | 2021-06-02 | 2021-09-03 | 安庆和兴化工有限责任公司 | Polyester polycondensation preparation method for producing PPAT \ PBS by rare earth catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1112573A (en) * | 1993-05-24 | 1995-11-29 | 恩尼彻姆公司 | Thermoplastic polyesters possessing high stability in the molten state |
| US5519108A (en) * | 1995-06-07 | 1996-05-21 | Industrial Technology Research Institute | Catalytic compositions containing tetrabutyl titanate and a mixture of cocatalysts for the preparation of poly(butylene terephthalate) |
| CN1446837A (en) * | 2002-03-21 | 2003-10-08 | 中国石油化工股份有限公司 | Catalyst utilized for synthesizing polyester and its usage |
-
2004
- 2004-12-23 CN CNB2004101015477A patent/CN100457800C/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1112573A (en) * | 1993-05-24 | 1995-11-29 | 恩尼彻姆公司 | Thermoplastic polyesters possessing high stability in the molten state |
| US5519108A (en) * | 1995-06-07 | 1996-05-21 | Industrial Technology Research Institute | Catalytic compositions containing tetrabutyl titanate and a mixture of cocatalysts for the preparation of poly(butylene terephthalate) |
| CN1446837A (en) * | 2002-03-21 | 2003-10-08 | 中国石油化工股份有限公司 | Catalyst utilized for synthesizing polyester and its usage |
Non-Patent Citations (2)
| Title |
|---|
| 稀土催化聚酯和共聚酯的合成. 张天骄等.中国稀土学报，第17卷第4期. 1999 |
| 稀土催化聚酯和共聚酯的合成. 张天骄等.中国稀土学报，第17卷第4期. 1999 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1796433A (en) | 2006-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100429256C (en) | Biodegradable linear random copolyester and its preparation method and uses | |
| KR101234538B1 (en) | Biodegradable linear random copolyester and process for preparing it and use of the same | |
| CN100457800C (en) | Method for synthesizing polyester by using rare earth catalyst | |
| CN101704943A (en) | Rare earth catalyst of condensation and polymerization synthesis of polyester and linear functionalization polyester and application thereof | |
| CN115873223A (en) | Preparation method of poly terephthalic acid-butylene carbonate | |
| CN101186692B (en) | Composite catalyst for synthesizing polytrimethylene terephthalate and preparation method thereof | |
| CN102627760B (en) | Catalyst composition and preparation method of polylactic acid | |
| CN100360581C (en) | Catalyst system and application in use for synthesizing degradable polyester | |
| CN102140165B (en) | Biodegradable copolyester and preparation method thereof | |
| CN108774314A (en) | A kind of preparation method of furans biological poly copolyether ester polymer, novel furan biological poly copolyether ester polymer | |
| CN101565499B (en) | Polyester polycondensation catalyst, preparation method and application thereof | |
| CN102453237A (en) | Preparation method of biodegradable polyester | |
| CN102453238A (en) | Preparation method of biodegradable polyester | |
| CN113801311A (en) | Process for preparing polyester | |
| CN114621425B (en) | Titanium composition for synthesizing poly (butylene succinate) -co-terephthalic acid butanediol ester and method for synthesizing PBST (poly (butylene succinate)) by using titanium composition | |
| CN111995633B (en) | Tridentate rare earth metal complex, preparation method and application | |
| CN101302283B (en) | Rare earth compound-containing polylactic acid and preparation thereof | |
| US4153781A (en) | Method of producing polyesters | |
| CN101302281B (en) | Polylactic acid and preparation thereof | |
| CN111269404A (en) | Composite catalyst suitable for synthesizing polytrimethylene terephthalate and preparation method of polytrimethylene terephthalate | |
| CN113429549B (en) | Composite catalyst, preparation method and polycyclohexylene dimethylene terephthalate prepared by using composite catalyst | |
| CN102453249A (en) | Catalyst composition | |
| CN103012766A (en) | Preparation method for synthesizing aluminum series catalyst by utilizing polyester and application thereof | |
| CN1446837A (en) | Catalyst utilized for synthesizing polyester and its usage | |
| CN101328260B (en) | Binary composite catalyst containing lanthanide series bidentate complex, preparation and use thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |