CN1796434A - Catalyst system and application in use for synthesizing degradable polyester - Google Patents
Catalyst system and application in use for synthesizing degradable polyester Download PDFInfo
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Abstract
This invention publishes a biodegradable polyester catalyst system and its application. Such a catalyst system as a binary system consists of rare earth compound C1 and one of the compounds of titanium, stibium and zincum C2, with a C1/C2 mole ratio of 5:95~100:0. The catalyst is specifically applicable in preparing polyesters with an aliphatic groups/aromatic groups mole ratio of 35/65~100/0 and a weight-average molecular weight of 3000~200000g/mol (identified by GPC). The catalyst system in this invention significantly promotes the condensation polymerization rate and product molecular weight and improves the problem of yellow-color products from single-component titanium catalyst system.
Description
Technical field
The present invention relates to the catalyst system and the application thereof of the synthetic usefulness of polyester, concrete, relate to a kind of be used for degradable homopolymerization and copolyesters synthetic catalyst system and application thereof.
Background technology
At present, it is more sophisticated operational path that condensation polymerization prepares polyester, adopts heavy metal compounds such as the compound of titanium, zinc etc. or lead, tin, antimony, cadmium as esterification, transesterify and the catalyzer in polycondensation stage mostly.The problem that the former exists is that side reaction is serious, gained polyester article poor stability, color and luster jaundice; The latter has certain toxicity, has limited the Application Areas of polyester article.Result of use is the germanium oxide catalyst system preferably, then is difficult to because it costs an arm and a leg promote the use of.Therefore effective, the cheap catalyst system of development of new is the focus of PET industry research.China is the big country of rare earth element, accounts for about 80% of world saving.Rare earth compound uses the extensive concern that has caused Chinese scholars as catalyzer.
In recent years, utilize the correlation technique of lanthanide series metal catalyst to synthesize ester more.The patent application CN1112573A of Italy Enichem S.p.A. discloses with lanthanide metal compound, metal-salt, bimetallic salt complex or to contain salt complex be catalyzer, obtains having under molten state the thermoplasticity aromatic polyester of high anti-degradation property.European patent application EP 626425 usefulness lanthanide series metal composite salt are made Catalyst Production thermoplasticity aryl polycarbonate/aryl polyester components, improved machinery, heat and the electrical property of described thermoplastic component, and advantages of higher stability is arranged.Chinese patent application CN1446837A discloses a kind of lanthanide series metal catalyzer that is used for synthesizing polyester, this catalyst pack contains R1 and R2, wherein R1 is lanthanide series metal halogeno salt and/or lanthanide metal-complexed thing, R2 is a lanthanide series metal oxyhydroxide, more than both mixture can make transesterification reaction fast, carry out stably.
Aromatic polyester such as polyethylene terephtalate, polybutylene terephthalate PBT etc., in the Nature, can't degrade basically, can reach 16～48 years the work-ing life of PET, and there are not tangible bacterium or enzyme can corrode pure aromatic polyester, therefore " white pollution " that brings is the great disaster that the present mankind face, and it is very urgent that the research of Biodegradable material seems.Aliphatic polyester receives publicity day by day because of advantages such as its good biocompatibility, biological degradability, polymkeric substance and degraded product are nontoxic.Compare with the aromatic polyester as engineering materials, aliphatic polyester exists that fusing point is low, poor mechanical property and defective and limited its use as material such as cost an arm and a leg.Therefore fat/the aromatic copolyester that obtains in conjunction with the degradation characteristic of the use of the excellence of aromatic polyester and processing characteristics and aliphatic polyester is the focus of current degradable material development.
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 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.
At present, condensation polymerization prepares the used polymerisation catalyst system of biodegradable fat/aromatic copolyesters and is titan-alkoxide, alkoxyl group tin, germanium oxide etc. in the prior art.As " Nihon Yukagakkaishi " (1999,48 (9), p911-915), European patent EP 1106640A2, the disclosed tetrabutyl titanate of German patent DE 19923053A1 (having another name called the normal-butyl titanium), titanium isopropoxide etc., the disclosed normal-butyl tin of Korean Patent KR9709332B1, the disclosed germanium compound of Japanese Patent JP2004018674A2 etc.The catalyst system that in polyester, generally uses, as described previously, all drawbacks that in polyester is synthetic, occur such as the jaundice of product color and luster, the serious grade of side reaction phenomenon still exists.
In sum, existing polyester catalyst exists polymerization rate slower, and side reaction is many, and is toxic, shortcomings such as product color and luster jaundice.In biodegradable copolyesters synthetic technology, except that above-mentioned shortcoming, also there is the operating procedure complexity, deficiencies such as polymer molecular weight wider distribution.
Summary of the invention
In order to overcome all deficiencies that exist in the catalyzer use in the prior art, the inventor develops a kind of rare earth compound single component or rare earth compound and polynary composite catalyst system of other metallic compound of nontoxic or low toxicity, is applied to prepare degradable fat/fragrant homopolymerization and copolyesters.
An object of the present invention is to provide a kind of catalyst system that is used to prepare biodegradable polyester.
Another object of the present invention provides a kind of method of using catalyst system synthesizing biological degradable polyester of the present invention.
The catalyst system that is used to prepare biodegradable polyester of the present invention, it comprises
C1 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 do not comprise the acetylacetonate Sm (a of samarium
ca
c)
3The acetylacetonate Ln (a of rare earth metal
ca
c)
3And at least a in their hydrate,
And C2, be selected from M (OR
2')
x, M
2O
xAnd M (R
1' COO)
xIn a kind of,
And the mol ratio of C1 and C2 is 5: 95～100: 0, is preferably 1: 3～3: 1, and more preferably 2: 3～3: 2;
Wherein, rare earth metal Ln is selected from a kind of in lanthanon, scandium and the yttrium, preferred a kind of in lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, terbium Td, ytterbium Yb, dysprosium Dy, samarium Sm and scandium Sc, more preferably a kind of in lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd and scandium Sc;
X is a halide-ions, preferred chlorion, bromide anion, more preferably chlorion;
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 Ti, antimony Sb or zinc Zn, and x is 2,3 or 4.
Preferably in catalyst system of the present invention, described C1 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 do not comprise the acetylacetonate Sm (a of samarium
ca
c)
3The acetylacetonate Ln (a of rare earth metal
ca
c)
3In a kind of.
Preferably in catalyst system of the present invention, described C1 is selected from the LnX of rare earth metal
3, alkoxide Ln (OR
2)
3, fragrant oxide compound Ln (OAr)
3In a kind of,
Wherein, X is chlorion or bromide anion; R
2Be sec.-propyl, normal-butyl or isopentyl, preferred R
2Be sec.-propyl; Ar is 2,6-dibutyl, 4-aminomethyl phenyl or 4-butyl phenyl.
Preferably in catalyst system of the present invention, described C2 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; More preferably C2 is tetrabutyl titanate, titanium isopropoxide, titanium dioxide, antimonous oxide, antimony acetate or zinc acetate.
In a preferred embodiment of the invention, catalyst system of the present invention comprises
C1 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 C2, be selected from a kind of in tetrabutyl titanate, titanium isopropoxide, titanium dioxide, antimonous oxide, antimony acetate and the zinc acetate,
And the mol ratio of described C1 and C2 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, propyl group, R
2Be sec.-propyl, normal-butyl or isopentyl,
Ar is 2,6-dibutyl, 4-aminomethyl phenyl or 4-butyl phenyl.
The catalyst system that is used for synthesizing polyester of the present invention can be single component C1 or C1 and the mixed system of C2 polycomponent.
Catalyst system of the present invention can prepare by disclosed method synthetic or the processing rare earth compound in the prior art, as document " J.Inorg.Nucl.Chem. " (1962,34, p387), " Polymer " (2001,42, p7511), " Inorganic Chemistry " (1970,9, p2505), " J.Chem.Soc., Chem.Commun. " (1983, disclosed method such as p1499).
The compound of the titanium described in the catalyst system of the present invention, antimony and zinc can use commercially available product.
Catalyst system of the present invention is used to prepare the method for biodegradable polyester, being included in catalyzer exists down, by being 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), carry out transesterification reaction, esterification and polycondensation, obtain biodegradable polyester, wherein
Described monomer (a) and mol ratio (c) are 0: 100～65: 35, preferred 35: 65～60: 40;
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) are preferably 1: (1000～3000).
In the preferred embodiment of the method for preparing polyester of the present invention, described monomer (a) is selected from benzene diprotic acid or ester 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 or ester derivative, 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.
When catalyst system of the present invention is used to prepare aliphatic/aromatic homopolymerization or copolyesters, carry out general 150～230 ℃ of transesterification reaction temperature, esterification reaction temperature is generally 160～250 ℃, and the temperature of polycondensation is generally 220～280 ℃, and polycondensation pressure is general≤200Pa.
The method for preparing polyester of the present invention adopts single still operation, and described catalyst system can together add in the reactor with raw material monomer before reaction.
Described catalyst system also can add in batches, and promptly C2 is the catalyzer in transesterify and esterification stage, adds reaction system with a kind of diprotic acid (or ester) and dibasic alcohol, treats that the small molecules fraction collection finishes; Add second kind of acid (or ester) monomer again, reaction finishes; Add C1 in polycondensation phase and carry out the vacuum polycondensation.
Beneficial effect of the present invention is as follows:
1) catalyst body of the present invention is the catalyst system of efficient, nontoxic or low toxicity, can accelerate polymerization rate, can improve the number-average molecular weight of product in the weight-average molecular weight that improves polyester product, and reaction process is steady simultaneously, is easy to control;
2) use catalyst system of the present invention, speed of response obviously increases, and compares with single component titanium compound catalyst system, and the polycondensation time can reduce to 3～7h from 10h; Molecular weight of product obviously increases, and compares with the single component titanium compound catalyst, and the Mw of gained polyester product rises to 7～200,000 from 1～50,000; The molecular weight of product narrow distribution, 1.5～2.5;
3) 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;
4) 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;
5) to be particularly suited for preparing fat/aromatic series ratio be 35～100: 65～0 polyester to method of the present invention, gained polyester product fully biodegradable.
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, China Medicine (Group) Shanghai Chemical Reagent Co.,
SCN: Succinic Acid, analytical pure, the sharp chemical in Shenzhen three company limited
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, China Medicine (Group) Shanghai Chemical Reagent Co.,
Virahol: analytical pure, Beijing Chemical Plant
Sodium: Beijing imperial chemical reagent of gold company limited
The preparation of embodiment 1-4 rare earth catalyst C1
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
3NH2O+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 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 220～260 ℃ of temperature of reaction, under the condition of system pressure≤200Pa, vacuum polycondensation 10h.Products therefrom is yellow, and GPC method determining molecular weight, number-average molecular weight Mn are 2.68 ten thousand, and weight-average molecular weight Mw is 5.29 ten thousand, and molecular weight distribution is 1.97.
Comparative Examples 2
Change 58.5g (0.4mol) hexanodioic acid into 47.2 (0.4mol) succsinic acid (Succinic Acid), other condition is with Comparative Examples 1.Products therefrom is yellow, and GPC method determining molecular weight, number-average molecular weight Mn are 2.72 ten thousand, and weight-average molecular weight Mw is 5.79 ten thousand, and molecular weight distribution is 2.13.
Embodiment 5
In the 500ml three-necked bottle; add 78g (0.4mol) dimethyl terephthalate (DMT), 86.5g (0.96mol) butyleneglycol, 0.11g (0.32mmol) tetrabutyl titanate, 0.073g (0.17mmol) methyl ethyl diketone lanthanum; 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.
Embodiment 6-9
With synthetic fat/fragrant mol ratio is that 1/1 copolyesters is an example, and DMT/ADP is 1: 1, and C2 uses tetrabutyl titanate in the catalyst system, and C1 uses different rare earth compounds, and C2/C1 is 2: 1.
In the 500ml three-necked bottle, add 78g (0.4mol) dimethyl terephthalate (DMT) DMT, 86.5g (0.96mol) butyleneglycol BD, 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 ADP 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 the 0.17mmolC1 component, vacuumize, heating, temperature of reaction is at 220～260 ℃, system pressure≤200Pa, vacuum polycondensation 7h.The performance of the polyester product that used catalyst component C1 and reaction obtain is listed in table 1.Yellowness index adopts the full-automatic colour examining colour-difference-metre of TC-PIIG to measure according to the described method of GB 2409-1989.
The performance of the copolyesters of table 1 different catalysts system preparation
| Numbering | Catalyst component C1 | Yellowness index | Molecular weight | ||
| Mn (ten thousand) | Mw (ten thousand) | Mw/Mn | |||
| Embodiment 6 | Methyl ethyl diketone lanthanum 0.073g | 47.9 | 3.84 | 8.88 | 2.31 |
| Embodiment 7 | Lanthanum trichloride hydrate 0.063g | 49.9 | 3.96 | 7.80 | 1.97 |
| Embodiment 8 | Isopropoxy neodymium 0.055g | 36.2 | 6.25 | 10.5 | 1.68 |
| Embodiment 9 | 2,6-dibutyl, 4-methylphenoxy neodymium 0.13g | 41.7 | 7.23 | 12.5 | 1.73 |
Embodiment 10
In the 500ml three-necked bottle, add 78g (0.4mol) dimethyl terephthalate (DMT) DMT, 86.5g (0.96mol) butyleneglycol BD, 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 47.2g (0.4mol) succsinic acid SCN 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 0.055g (0.17mmol) isopropoxy neodymium, 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, number-average molecular weight Mn are 5.41 ten thousand, and weight-average molecular weight Mw is 11.1 ten thousand, and molecular weight distribution is 2.05.
Embodiment 11-21 is with C1 methyl ethyl diketone lanthanum and C2 tetrabutyl titanate, and C2/C1 is catalyst system, the homopolymerization and the copolyesters of synthetic different fat/fragrant mol ratios at 1: 1.
Embodiment 11
In the 500ml three-necked bottle, add 136g (0.7mol) dimethyl terephthalate (DMT), 126g (1.4mol) butyleneglycol, 0.10g (0.3mmol) 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 methyl ethyl diketone lanthanum 0.13g (0.3mmol) in system, system vacuumizes, heating, and temperature of reaction is at 220～260 ℃, system pressure≤200Pa, vacuum polycondensation 4h.
Embodiment 12
In the 500ml three-necked bottle, add 155g (0.8mol) dimethyl terephthalate (DMT), 120g (1.34mol) butyleneglycol, 0.13g (0.37mmol) 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 13.0g (0.089mol) 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 0.16g (0.37mmol), vacuumize, heating, temperature of reaction is at 220～260 ℃, system pressure≤200Pa, vacuum polycondensation 4h.
Embodiment 13
The consumption of monomer and catalyst component is changed into: 117g (0.6mol) dimethyl terephthalate (DMT), 86.5g (0.96mol) butyleneglycol, 0.09g (0.26mmol) tetrabutyl titanate, 29.0g (0.2mol) hexanodioic acid, 0.116g (0.26mmol) methyl ethyl diketone lanthanum, other condition is with embodiment 12.
Embodiment 14
The consumption of monomer and catalyst component is changed into: 87.0g (0.45mol) dimethyl terephthalate (DMT), 108g (1.2mol) butyleneglycol, 0.11g (0.32mmol) tetrabutyl titanate, 44.0g (0.3mol) hexanodioic acid, 0.14g (0.32mmol) methyl ethyl diketone lanthanum, other condition is with embodiment 12.
Embodiment 15
The consumption of monomer and catalyst component is changed into: 78g (0.4mol) dimethyl terephthalate (DMT), 86.5g (0.96mol) butyleneglycol, 0.12g (0.34mmol) tetrabutyl titanate, 58.5g (0.4mol) hexanodioic acid, 0.15g (0.34mmol) methyl ethyl diketone lanthanum, other condition is with embodiment 12.
Embodiment 16
The consumption of monomer and catalyst component is changed into: 58.0g (0.3mol) dimethyl terephthalate (DMT), 81g (0.9mol) butyleneglycol, 0.11g (0.32mmol) tetrabutyl titanate, 66.0g (0.45mol) hexanodioic acid, 0.14g (0.32mmol) methyl ethyl diketone lanthanum, other condition is with embodiment 12.
Embodiment 17
The consumption of monomer and catalyst component is changed into: 58.0g (0.3mol) dimethyl terephthalate (DMT), 108g (1.2mol) butyleneglycol, 0.10g (0.3mmol) tetrabutyl titanate, 88.0g (0.6mol) hexanodioic acid, 0.13g (0.3mmol) methyl ethyl diketone lanthanum, other condition is with embodiment 12.
Embodiment 18
The consumption of monomer and catalyst component is changed into: 58.0g (0.3mol) dimethyl terephthalate (DMT), 122g (1.35mol) butyleneglycol, 0.12g (0.35mmol) tetrabutyl titanate, 110.0g (0.75mol) hexanodioic acid, methyl ethyl diketone lanthanum 0.15g (0.35mmol), other condition is with embodiment 12.
Embodiment 19
The consumption of monomer and catalyst component is changed into: 39.0g (0.2mol) dimethyl terephthalate (DMT), 108g (1.2mol) butyleneglycol, 0.09g (0.26mmol) tetrabutyl titanate, 88.0g (0.6mol) hexanodioic acid, methyl ethyl diketone lanthanum 0.12g (0.26mmol), other condition is with embodiment 12.
Embodiment 20
The consumption of monomer and catalyst component is changed into: 26.1g (0.13mol) dimethyl terephthalate (DMT), 108g (1.2mol) butyleneglycol, 0.11g (0.33mmol) tetrabutyl titanate, 132g (0.9mol) hexanodioic acid, methyl ethyl diketone lanthanum 0.15g (0.33mmol), other condition is with embodiment 12.
Embodiment 21
The consumption of monomer and catalyst component is changed into: 146g (0.75mol) hexanodioic acid, 108g (1.2mol) butyleneglycol, 0.11g (0.33mmol) tetrabutyl titanate, methyl ethyl diketone lanthanum 0.15g (0.33mmol), other condition is with embodiment 12.
The copolyesters that embodiment 11-21 obtains is analyzed, be the results are shown in table 2.
The a polymeric constituent measure by nucleus magnetic resonance (NMR) Bruker Avance DMX500 NMR spectrometer with superconducting magnet (
1H NMR:500MHz) last 25 ℃ of mensuration, CDCl
3Be solvent, TMS is interior mark.
B gel permeation chromatography (GPC) is measured polymericular weight and molecular weight distribution, with tetrahydrofuran (THF) (THF) is solvent, at Waters-208 (band Waters 2410RI detector, 1.5ml/min flow velocity, 30 ℃) to measure on the instrument, molecular weight is calibrated with the vinylbenzene standard specimen.
Cn.d.:, and do not detect its molecular weight and molecular weight distribution because sample can not be dissolved in tetrahydrofuran solvent fully.
The preparation and the performance perameter of the copolyesters of table 2 different components ratio
| Numbering | Monomeric charge mol ratio (DMT/ADP) | The monomer/catalyst mol ratio | Monomer acids/glycol mol ratio (DMT+ADP)/BD | Polymkeric substance aComponent mol ratio (DMT/ADP) | Molecular weight b | ||
| Mn (ten thousand) | Mw (ten thousand) | Mw/Mn | |||||
| Embodiment 11 | 100/0 | 1170 | 1/2 | 100/0 | n.d. c | n.d | n.d. |
| Embodiment 12 | 90/10 | 1200 | 1/1.5 | 90/10 | n.d. | n.d | n.d. |
| Embodiment 13 | 75/25 | 1500 | 1/1.2 | 75/25 | n.d. | n.d | n.d. |
| Embodiment 14 | 60/40 | 1172 | 1/1.2 | 60/40 | n.d. | n.d | n.d. |
| Embodiment 15 | 50/50 | 1172 | 1/1.2 | 50/50 | 2.51 | 5.34 | 2.13 |
| Embodiment 16 | 40/60 | 1172 | 1/1.2 | 40/60 | 2.51 | 5.91 | 2.36 |
| Embodiment 17 | 33/67 | 1500 | 1/1.3 | 35/65 | 2.8 | 6.25 | 2.23 |
| Embodiment 18 | 29/71 | 1500 | 1/1.3 | 30/70 | 2.41 | 5.6 | 2.32 |
| Embodiment 19 | 25/75 | 1540 | 1/1.5 | 25/75 | 2.87 | 5.43 | 1.89 |
| Embodiment 20 | 13/87 | 1560 | 1/1.2 | 13/87 | 2.44 | 5.27 | 2.16 |
| Embodiment 21 | 0/100 | 1140 | 1/1.6 | 0/100 | 3.05 | 5.76 | 1.89 |
Claims (16)
1, a kind of catalyst system that is used to prepare biodegradable polyester, it comprises
C1 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 do not comprise the acetylacetonate Sm (a of samarium
ca
c)
3The acetylacetonate Ln (a of rare earth metal
ca
c)
3And at least a in their hydrate,
And C2, be selected from M (OR
2')
x, M
2O
xAnd M (R
1' COO)
xIn a kind of,
And the mol ratio of C1 and C2 is 5: 95～100: 0;
Wherein, rare earth metal Ln is selected from a kind of in lanthanon, scandium and the yttrium,
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, catalyst system 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 Dy, samarium Sm and the scandium Sc.
3, catalyst system according to claim 2 is characterized in that described rare earth metal Ln is selected from lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd and scandium Sc.
4, catalyst system according to claim 1 is characterized in that described C1 is selected from the inorganic halides LnX of rare earth metal
3, alkoxide Ln (OR
2)
3With fragrant oxide compound Ln (OAr)
3In a kind of,
Wherein, X is chlorion or bromide anion, R
2Be sec.-propyl, normal-butyl or isopentyl, Ar is 2,6-dibutyl, 4-aminomethyl phenyl or 4-butyl phenyl.
5, catalyst system according to claim 1 is characterized in that described C2 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.
6, catalyst system according to claim 5 is characterized in that described C2 is tetrabutyl titanate, titanium isopropoxide, titanium dioxide, antimonous oxide, antimony acetate or zinc acetate.
7, catalyst system according to claim 1, the mol ratio that it is characterized in that described C1 and C2 is 1: 3～3: 1.
8, catalyst system according to claim 7, the mol ratio that it is characterized in that described C1 and C2 is 2: 3～3: 2.
9, a kind of catalyst system that is used to prepare biodegradable polyester, it comprises
C1 is selected from the inorganic halides LnX of rare earth metal
3, carboxylate salt Ln (R
1COO)
3, alkoxide Ln (OR
2)
3With fragrant oxide compound Ln (OAr)
3In a kind of,
And C2, be selected from a kind of in tetrabutyl titanate, titanium isopropoxide, titanium dioxide, antimonous oxide, antimony acetate and the zinc acetate,
And the mol ratio of described C1 and C2 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, propyl group, R
2Be sec.-propyl, normal-butyl or isopentyl,
Ar is 2,6-dibutyl, 4-aminomethyl phenyl or 4-butyl phenyl.
10, a kind of method for preparing biodegradable polyester, being included in the described catalyst system of one of claim 1-9 exists down, by being 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, the monomer of their ester derivative or their corresponding acid anhydrides (c), carry out transesterification reaction, esterification and polycondensation, obtain degradable polyester, wherein
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 described catalyst system and monomer (a) and total amount (c) is 1: (500～10000).
11, method according to claim 10, the mol ratio that it is characterized in that described catalyst system and monomer (a) and total amount (c) is 1: (1000～3000).
12, method according to claim 10, 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).
13, method according to claim 12, 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).
14, method according to claim 10 is characterized in that described monomer (a) and mol ratio (c) are 35: 65～60: 40.
15, method according to claim 10 is characterized in that described monomer (a) is selected from phenyl diprotic acid, the corresponding acid anhydrides with it of its ester derivative, 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 corresponding acid anhydrides at least a.
16, method according to claim 10, 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.
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| CNB2004101015458A CN100360581C (en) | 2004-12-23 | 2004-12-23 | Catalyst system and application in use for synthesizing degradable polyester |
| 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 |
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| CN100360581C CN100360581C (en) | 2008-01-09 |
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| CN101328260B (en) * | 2008-07-29 | 2011-11-16 | 南京工业大学 | Binary composite catalyst containing lanthanide series bidentate complex and preparation method and application thereof |
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Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1264507B1 (en) * | 1993-05-24 | 1996-09-24 | Enichem Spa | THERMOPLASTIC POLYESTERS EQUIPPED WITH HIGH STABILITY IN THE MELTED STATE |
| DE4440850A1 (en) * | 1994-11-15 | 1996-05-23 | Basf Ag | Biodegradable polymers, processes for their production and their use for the production of biodegradable moldings |
| KR100366484B1 (en) * | 1999-12-11 | 2003-01-14 | 주식회사 이래화학 | Copolyester resin composition and a process of preparation thereof |
| CN1233688C (en) * | 2002-03-21 | 2005-12-28 | 中国石油化工股份有限公司 | Catalyst utilized for synthesizing polyester and its usage |
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2004
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| CN101525429B (en) * | 2009-03-30 | 2013-01-16 | 东华大学 | Binary composite catalyst for preparing biodegradable copolyester |
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