CN100429256C - Biodegradable linear random copolyester and its preparation method and uses - Google Patents
Biodegradable linear random copolyester and its preparation method and uses Download PDFInfo
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- CN100429256C CN100429256C CNB2005101355172A CN200510135517A CN100429256C CN 100429256 C CN100429256 C CN 100429256C CN B2005101355172 A CNB2005101355172 A CN B2005101355172A CN 200510135517 A CN200510135517 A CN 200510135517A CN 100429256 C CN100429256 C CN 100429256C
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Abstract
The present invention discloses biodegradable linear irregular copolyester, a preparation method thereof and an application thereof. The copolyester of the present invention comprises a structural unit (1), wherein m is an integer from 2 to 10; n is an integer from 0 to 8; p is an integer from 2 to 10; m, n and p can be identical or different; x is an integer from 1 to 10; y is an integer from 1 to 10; 100, 000 to 600, 000 g/mol of the weight average molecular weight Mw of the copolyester and 1.2 to 3 of the molecular weight distribution are detected by a GPC method. The copolyester of the present invention has a wide application range in aspects of sectional materials, membranes, fiber and coating layers.
Description
Technical field
The present invention relates to the random fat/aromatic copolyesters of a kind of biodegradable linearity.More specifically, the biodegradable fat/aromatic copolyesters and its production and application that relates to a kind of high molecular, narrow molecular weight distributions.
Background technology
At present, aromatic polyester such 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.But these polymkeric substance can't be degraded in the Nature basically, and can resist the erosion of bacterium, up to the present also there are not tangible bacterium or enzyme can corrode pure aromatic polyester (PET, PBT), these polyester are very insensitive to the water degraded, can reach 16～48 years the work-ing life of PET, and the PET fiber can continue 30 years in human body and animal body.Therefore " white pollution " that brings is the great disaster that the present mankind face, and the research Biodegradable material just seems very urgent.Aliphatic polyester receives publicity day by day because of advantages such as its good biocompatibility, biological degradability, polymkeric substance and degraded product are nontoxic.They have been applied in bio-medical (skeletal fixation and propping material, medicine controlled releasing and slowly-releasing, nerve trachea and artificial blood vessel, operating sutures etc.) and the environment-friendly material (refuse bag, shopping bag, food product pack, tableware, agricultural mulching, daily Bottle ﹠ Can, fishing gear etc.), but 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 excellence use of aromatic polyester and processing characteristics and aliphatic polyester is the focus of current degradable material development.
In recent years, the aliphatic/aromatic copolyesters has been realized commercialization abroad, mainly contain the Ecoflex of German BASF AG, the Eastar Bio of U.S. Eastman company, the Bionelle product of U.S. Showa company (the Showa Highpolymer of Japan and the SK Chemicals Xiang Qi of company of Korea S provide resin), the Sky Green BDP product of SK Chemicals, Biomax of Dupond company or the like.
These copolyesters are difficult to preparation high-molecular weight product because by the condensation polymerization preparation, have the small molecules product to remove, and generally can only prepare several ten thousand product.Because molecular weight is low, the mechanical property of product is difficult to reach the standard of widely used non-degradable material at present, therefore can prepare high-molecular weight copolyesters product so that the mechanics of product and processing characteristics meet the demands, and just seems particularly important.BASF AG is at patent U.S.Pat.No.5, and 817,721,5,889,135,6,018004,6,046,248,6, proposed in 114,042 to adopt 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 (can up to tens0000) 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.Products therefrom is a long-chain cladodification structure, is unfavorable for the processing of material.And add chainextender and directly be connected on the long-chain of polymkeric substance, also make the structure of polymkeric substance become complicated, impure, can't remove.
The polyester of polycondensation preparation, as polyethylene terephtalate, polybutylene terephthalate PBT, Poly(Trimethylene Terephthalate) PPT etc., all through two technological process preparations: the esterification or the transesterify of terephthalic acid or its esterification products and aliphatic dihydroxy alcohol, 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.
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.
It is more sophisticated operational path that condensation polymerization prepares polyester, and heavy metal compounds such as the compound of most at present employing titanium, zinc etc. or lead, tin, antimony, cadmium are as esterification, transesterify and the catalyzer in polycondensation stage.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.
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, EP0626425, CN1446837A etc.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 0626425 usefulness lanthanide series metal composite salt is made Catalyst Production thermoplasticity aryl polycarbonate/aryl polyester components, has 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 halide salts 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.
China is the big country of rare earth element, accounts for about 80% of world saving.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.
At present, condensation polymerization prepares the used polymerisation catalyst system of biodegradable fat/aromatic copolyesters and is titan-alkoxide, tin alkyl, 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
The term " biodegradable " that this paper relates to " be meant that under microbial process organic compound is carbonic acid gas (CO by microbiological degradation
2), water (H
2O) and the mineralising inorganic salt of contained element and new biomass.
The objective of the invention is to obtain a kind of narrow distribution, the biodegradable linear random copolyester of high-molecular weight.
Biodegradable fat/aromatic copolyesters of the present invention is linear random fat/aromatic copolyesters, and it contains following structural unit:
Wherein m is 2～10 integer, and n is 0～8 integer, and p is 2～10 integer, m, and n and p can be identical or different, and x is 1～10 integer, and y is 1～10 integer; Preferred wherein m is 2～4 integer, and n is 2～4 integer, and p is 2～4 integer, and x is that 1～3 integer and/or y are 1～2 integer, and measures its weight-average molecular weight M by the GPC method
wBe 100,000～600,000g/mol, preferred 100,000～300,000g/mol; Molecular weight distribution 1.2～3, preferred 1.5～2.5.
Fat of the present invention/aromatic copolyesters melting range is preferably 20～185 ℃, and second-order transition temperature is preferably-55～-7 ℃.
Another object of the present invention provides a kind of method of synthesizing copolyesters of the present invention in the presence of catalysis of rare-earth compound agent component.
Concrete, the method for synthetic copolyester of the present invention comprises the following steps:
1). will carry out transesterification reaction and/or esterification reaction in following monomer and the nonessential catalyst component Cat1 adding reactor: (a) aromatic acid, its ester, its acid anhydrides or their mixture, (b) aliphatic dihydroxy alcohol, alicyclic dibasic alcohol or their mixture, (c) aliphatic dibasic acid, alicyclic diprotic acid, their ester, their acid anhydrides or their mixture
Wherein said monomer (a) and mol ratio (c) are 5: 95～75: 25;
2). under vacuum condition, with 1) reaction system that obtains carries out pre-polymerization; With
3). to 2) add catalyst component Cat2 in the prepolymer product that obtains, carry out vacuum polycondensation, obtain described polyester;
Wherein, described catalyst component Cat1 is selected from compound of metal titanium, antimony and zinc and composition thereof;
Described catalyst component Cat2 is selected from compound of rare earth metal Ln and composition thereof, and rare earth metal Ln is selected from lanthanon, scandium, yttrium and combination thereof.
When preparation fat/aromatic copolyesters, can be in described step 1) earlier with aromatic monomer (a) and dibasic alcohol monomer (b) reaction, and then add aliphatic monomer (c); Also can earlier aliphatic monomer (c) and dibasic alcohol monomer (b) be reacted, and then add aromatic monomer (a).Preferably, in described step 1),, add reactor and react at first with catalyst component Cat1, monomer (a), monomer (b); And then add monomer (c), react.So more help fully carrying out of transesterify and esterification.
In a specific embodiments, monomer (a) with (b) add earlier reactor with Cat1, preferably carry out esterification or transesterification reaction earlier at 150～230 ℃, small molecules cut to be received reaches 90% when above of theoretical amount, promptly can add reactant (c), carry out second step esterification or the transesterification reaction after reactant (c) adds, preferably carry out at 160～250 ℃, small molecules cut quantities received reaches 90% when above of theoretical amount, the pre-polymerization that enters next step again.
Above-mentioned two step esterifications or transesterification reaction can be carried out under normal pressure, vacuum or pressure state, preferably carry out under normal pressure.
Preferably, described step 2) reaction system is 190～250 ℃ in temperature, and vacuum tightness is 200～600Pa, pre-polymerization under preferred 200～300Pa, prepolymerization reaction 1～3 hour, preferred 1～2 hour; In other words conj.or perhaps in described step 2) the small molecules (comprising unreacted monomer etc.) of reaction system be close to and drain, after the cut temperature remains unchanged, carry out the 3rd) step, add catalyst component Cat2.
In described step 3), the temperature of polycondensation is preferably 200～300 ℃, more preferably 220～280 ℃.Preferably at vacuum tightness≤300Pa, more preferably≤carry out polycondensation under the condition of 200Pa.Preferred polycondensation 3～8 hours.
Pressure involved in the present invention is gauge pressure.
The method for preparing polyester of the present invention can adopt single still operation, promptly described step 1), 2) and 3) in same still, carry out.
In a preferred embodiment of the inventive method, described monomer (a) and mol ratio (c) are 5: 95～65: 35, preferred 35: 65～60: 40; Described monomer (a) is 1 with the ratio of the mole number of (c) mole number sum and monomer (b): (1.0～3.0), preferred 1: (1.0～2.0), more preferably 1: (1.1～1.5), preferred again 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 a preferred embodiment of the inventive method, described monomer (a) is selected from phenyl diprotic acid, its ester or its acid anhydrides, is preferably terephthalic acid or dimethyl terephthalate (DMT); Described monomer (b) is selected from C
2～C
6Aliphatic dihydroxy alcohol, C
5～C
10Alicyclic dibasic alcohol and composition thereof, 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, their acid anhydrides and composition thereof, be preferably hexanodioic acid, sebacic acid or Succinic Acid.
In a preferred embodiment of the inventive method, described monomer (a) is selected from terephthalic acid, its ester, its acid anhydrides or their mixture; Described monomer (b) is selected from C
2～C
6Aliphatic dihydroxy alcohol, C
5～C
10Alicyclic dibasic alcohol or their mixture; With described monomer (c) hexanodioic acid, its ester, its acid anhydrides or their mixture.The mol ratio of wherein said monomer (a) and described monomer (c) is 5: 95～75: 25 and described monomer (a) and the ratio of the mole number of (c) mole number sum and monomer (b) is 1: 1～1: 2.Preferably, the mol ratio of wherein said monomer (a) and described monomer (c) is 25: 75～65: 35 and described monomer (a) and the ratio of the mole number of (c) mole number sum and monomer (b) is 1: 1.2～1: 1.5.
In a preferred embodiment of the inventive method, described catalyst component Cat1 is selected from M (OR
2')
x, M
2O
x, M (R
1' COO)
xAnd composition thereof, be preferably titan-alkoxide Ti (OR
2')
x, zinc acetate, zinc the oxide compound, titanyl compound and composition thereof of oxide compound, antimony, more preferably tetrabutyl titanate, titanium isopropoxide, titanium dioxide, zinc acetate and composition thereof; Described catalyst component Cat2 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, do not comprise the acetylacetonate Sm (a of samarium
ca
c)
3The acetylacetonate Ln (a of rare earth metal
ca
c)
3, their hydrate and above mixture thereof;
The mol ratio of preferred Cat2 and Cat1 is 5: 95～100: 0, more preferably 1: 3～3: 1;
Wherein, preferred described rare earth metal Ln is selected from lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, terbium Td, ytterbium Yb, dysprosium Dy, samarium Sm, scandium Sc and combination thereof, lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, scandium Sc and combination thereof more preferably,
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 2,6-di-t-butyl-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 inventive method, described catalyst component Cat1 is selected from tetrabutyl titanate, titanium isopropoxide, titanium dioxide, zinc acetate and composition thereof; Described catalyst component Cat2 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)
3And composition thereof, and the mol ratio of described Cat2 and Cat1 is 2: 3～3: 2,
Wherein, described rare earth metal Ln is selected from lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, scandium Sc and combination thereof, 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.
The above-mentioned catalyzer that the present invention adopts is 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 particularly useful for making biodegradable fat/aromatic copolyesters.Therefore this catalyst system can be the mixed system of the polycomponent of single component Cat2 or Cat2 and Cat1.
Catalyst component Cat2 rare earth compound described in the 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) is as mentioning in following examples.
The compound of catalyst component Cat1 titanium, antimony and the zinc described in the catalyst system of the present invention can use commercially available product, as mentioning in following examples.
The biodegradable copolyesters of high-molecular weight of the present invention can not add under the condition of components such as chainextender, prepares as catalyzer with by control monomer and the catalyzer when corresponding processing parameter that feeds intake by adding rare earth compound.The products obtained therefrom molecular weight distribution is linear structure less than 3.Multipolymer is formed structure can be by the strict control of feed ratio, the copolyesters product of preparation statistics random distribution.Unless otherwise, all per-cents used herein and ratio are all by weight.
A further object of the present invention provides the purposes of copolyesters of the present invention.
Biodegradable copolyesters of the present invention can be used for preparing section bar, film, fiber or coating.
The publication that this paper quotes is incorporated herein by reference for all purposes.
Biodegradable copolyesters of the present invention has following characteristics:
1) copolyesters of the present invention need not add additives such as chainextender, stablizer, and therefore, product is pure;
2) copolyesters product number average of the present invention and weight-average molecular weight all obviously improve, and molecular weight distribution is less than 3;
3) copolyesters product ratio of component of the present invention can be by monomeric charge than strict control, and the copolymerization ratio of component equals the monomeric charge ratio substantially;
4) copolyesters product of the present invention is the long-chain linear random structure, helps degrading and in conjunction with the excellent properties of two homopolymer;
5) mechanical property of copolyesters product of the present invention meets or exceeds the LDPE product, use temperature a wider range (U.S.Pat.No.5 that is better than BASF AG, the same component product performance described in 889,135), and processing characteristics is good.
Use copolyesters preparation 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 3～8h 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.
4) to be suitable for preparing fat/aromatic series ratio be 35～100: 65～0 polyester to method of the present invention, the gained polyester product can be within eight months complete biodegradable.
Description of drawings
Fig. 1 is the copolyesters product of DMT/ADP=1/1 of the present invention
1The HNMR collection of illustrative plates.
Abcd (a:4.41ppm, b:4.35ppm, c:4.12ppm, d:4.06ppm) in these four peaks, a and d represent the homopolymerization segment respectively, b and c be corresponding cosegment respectively.The mol ratio of two kinds of monomers in polymkeric substance is 50: 50, and the segments that two kinds of monomers directly link to each other have accounted for total polymer segmental 50%, illustrates that copolyesters is the statistics random copolymers.
Fig. 2 is the structural formula of poly adipate succinic acid ester.
Fig. 3 is the structural formula of polybutylene terephthalate.
Fig. 4 is the structural formula of polybutylene terephthalate/hexanodioic acid butyleneglycol copolyesters.
Fig. 5 is the DSC curve of copolyesters product of the present invention.
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.
SCN: Succinic Acid, analytical pure, the sharp chemical in Shenzhen three company limited
Acetic acid: 50%, Beijing chemical reagents corporation
Stearic acid: analytical pure, Beijing chemical reagents corporation
Tetrabutyl titanate: chemical pure, Beijing chemical reagents corporation
Zinc acetate: analytical 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 testing method of relevant data is as follows in the embodiments of the invention:
Polymeric constituent measure by nucleus magnetic resonance (NMR) Bruker Avance DMX500 NMR spectrometer with superconducting magnet (
1HNMR:500MHz) last 25 ℃ of mensuration, CDCl
3Be solvent, TMS is interior mark.
Gel permeation chromatography (GPC) is measured polymericular weight and molecular weight distribution, with tetrahydrofuran (THF) (THF) is solvent, at Waters-208 (band Waters 2410 RI detectors, 1.5ml/min flow velocity, 30 ℃) to measure on the instrument, molecular weight is calibrated with the vinylbenzene standard specimen.
Viscosity number (VN) is in the 0.005g/ml polymers soln of orthodichlorobenzene/phenol weight ratio 50/50, and 25 ℃ of measurements, testing standard is GB/T 17932-1999.
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.
Differential scanning calorimetry (DSC) method is measured the second-order transition temperature (Tg) and the melt temperature (Tm) of polymkeric substance, and on Perkin Elmer Pyris 1 determinator, each sample is heated to 250 ℃ from-100 ℃, adds heat scan through twice, and heating rate is 20 ℃/min.
Tensile mechanical properties carries out according to ASTM D638-03 method.
The biodegradation character of polyester adopts compost to bury the sheet experiment.Polyester sample is cut into the print that surface-area is 2cm * 2cm through hot pressing film forming (10～20 μ m), imbeds in the culture dish that composting soil is housed, and puts into the incubator of fixed temperature and humidity together.Keep humidity about 50%, 58 ± 2 ℃ of temperature.The weightlessness of period sampling measuring sample.
The following example has further described and has proved the preferred embodiment in the scope of the invention.These embodiment that given only are illustrative, and are unintelligible for being limitation of the present invention.
Unless otherwise, below among each embodiment each preparation process of catalyzer and copolyesters all carry out at normal temperatures and pressures.
The preparation of embodiment A 1-6 rare earth catalyst Cat2
The preparation of embodiment A 1 anhydrous lanthanum chloride (LaCl3) (document J Inorg Nucl Chem 1962,34,387)
10g La2O3 is dissolved with excessive hydrochloric acid, heating (temperature 〉=100 ℃) make the NH4C1 that adds metering after the solution concentration (with the La2O3 mol ratio be 3/1,), careful heating (temperature 〉=100 ℃) boils off excessive acid, obtain the solid of LaCl3nH2O+NH4C1, with joining in the quartzy sublimation pipe after the solid grinding, be 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 in the sublimation pipe, take off sublimation pipe, under argon shield, move in the other sealed tube standby.
The preparation of embodiment A 2 acetylacetonate lanthanum La (acac) 3 (document Polymer 2001,42,7511-7516)
In the 250ml three-necked bottle, (3.47g 9.37mmol) is dissolved in the water of 50ml with LaCl37H2O, form solution s1, s1 is dropwise joined methyl ethyl diketone, and (5.63g is among 50ml aqueous solution s2 56.2mmol), stir under the room temperature, adjust pH value to 7 by adding 2NKOH solution.Reaction mixture has the throw out of La (acac) 3, stirs, and filters, and in 60oC vacuum-drying, obtains about 4gLa (acac) 3.
The preparation of embodiment A 3 isopropoxy rare earths (document Inorg Chem 1970,9 (1), 2505-2510)
In the 250ml three-necked bottle, add 0.02mol anhydrous chlorides of rase earth elements 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 rare earth powder.
Embodiment A 4 three (2,6-di-t-butyl-4 methylphenoxy) rare earth synthetic (document Inorg Chim Acta1987,139,183-184)
(0.5～0.8g) to polymerization bottle, operates under argon shield, according to LnCl for the earlier accurate anhydrous LnCl3 of weighing
3Mole number, calculate the weight of required 2,6 di tert butyl 4 methyl phenol by 1: 3 molar ratio.
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.
Synthesizing of embodiment A 5 rare-earth stearates
Take by weighing the Ln of calculated amount with beaker
2O
3, add an amount of distilled water, after add excessive HCl again, heating makes dissolving be clear solution s3; Take by weighing excessive stearic acid with another beaker, add an amount of dehydrated alcohol to be heated into clear solution s4; Get the round-bottomed flask of a 100ml, s4, s3 solution are successively added in the flask, add 10mg phase-transfer catalyst Tetrabutyl amonium bromide again, add magneton.The flask top connects condensate pipe, protects with the nitrogen bag.Oil bath is less than 100 ℃ of heating, and magnetic stirs about 5hr.Take off flask, the separating funnel branch takes off a layer clear liquid, and the clear liquid evaporate to dryness is got final product.
Embodiment A 6 acetic acid rare earths synthetic (document J Inorg Nucl Chem, 1962,24,637-639)
The 10g rare earth oxide is dissolved in 500ml 50% acetum, at the most of solvent of 75 ℃ of evaporates to dryness, with rare-earth salts heating under vacuum to 75～150 ℃ (deciding on different rare earths), is dried to constant weight then.Can make mutually deserved lanthanon acetate.
Comparative example A's 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 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.
The comparative example A 2
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.
The comparative example A 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; 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 A 7
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 is 400Pa, approximately carried out 1 hour, and in system, added methyl ethyl diketone lanthanum 0.073g (0.17mmol), vacuumize and carry out polycondensation, temperature of reaction is at 220～260 ℃, system pressure≤200Pa, vacuum polycondensation 6h.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 A 8
Other condition is with embodiment A 7, and the methyl ethyl diketone lanthanum changes isopropoxy neodymium 0.055g (0.17mmol) into.
Embodiment A 9
Other condition is with embodiment A 7, and the methyl ethyl diketone lanthanum changes three (2,6-di-t-butyl-4-methylphenoxy) lanthanum 0.14g (0.17mmol) into.
The characterization parameter of the copolyesters that comparative example A 1-A3 and embodiment A 7-A9 are obtained is listed in Table A 1.
Table A 1 rare earth compound adds mode to be influenced the copolyesters polymeric
Embodiment B 6-B11
With synthetic fat family/aromatic series mol ratio is that 1/1 copolyesters is an example, and DMT/ADP is 1: 1, and Cat1 uses tetrabutyl titanate or zinc acetate in the catalyst system, and Cat2 uses different rare earth compounds.
In the 500ml three-necked bottle, add 78g (0.4mol) dimethyl terephthalate (DMT) DMT, 86.5g (0.96mol) butyleneglycol BD, catalyst component Cat1 (or not adding); 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.Vacuumize, heating, temperature of reaction is at 220～260 ℃, and system pressure is 400Pa, approximately carries out 1 hour, adds 0.17mmol Cat2 component in system, 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 Cat2 and reaction obtain is listed in table B1.
The performance of the copolyesters of table B1 different catalysts system preparation
Embodiment B 12
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.Vacuumize, heating, temperature of reaction is at 220～260 ℃, and system pressure is 400Pa, approximately carried out 1 hour, and in system, added 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 B 13-B21 is with Cat2 methyl ethyl diketone lanthanum and Cat1 tetrabutyl titanate, and Cat1/Cat2 is catalyst system, the copolyesters of synthetic different aliphatic/aromatic mol ratios at 1: 1.
Embodiment B 13
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 ℃, 0.13g (0.3mmol) methyl ethyl diketone lanthanum, and other condition is with Embodiment B 13.
Embodiment B 19
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 B 13.
Embodiment B 20
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 B 13.
Embodiment B 21
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 B 13.
The copolyesters that Embodiment B 13-21 obtains is analyzed, be the results are shown in table B2.
The preparation and the performance perameter of the copolyesters of table B2 different components ratio
cN.d.:, and do not detect its molecular weight and molecular weight distribution because sample can not be dissolved in tetrahydrofuran solvent fully.
Embodiment C 1
In the 500ml three-necked bottle, add 87.0g (0.45mol) dimethyl terephthalate (DMT), 108g (1.2mol) 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 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.Vacuumize, heating, temperature of reaction is at 220～260 ℃, and system pressure is 400Pa, approximately carried out 1 hour, and in system, added isopropoxy lanthanum 0.10g (0.32mmol), vacuumize heating, temperature of reaction is at 220～260 ℃, system pressure≤200Pa, vacuum polycondensation 7h.
Embodiment C 2
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, 0.11g (0.35mmol) isopropoxy lanthanum, other condition is with Embodiment C 1.
Embodiment C 3
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, 0.10g (0.32mmol) isopropoxy lanthanum, other condition is with Embodiment C 1.
Embodiment C 4
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, 0.09g (0.3mmol) isopropoxy lanthanum, other condition is with Embodiment C 1.
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, isopropoxy lanthanum 0.11g (0.35mmol), other condition is with Embodiment C 1.
Embodiment C 6
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, isopropoxy lanthanum 0.08g (0.26mmol), other condition is with Embodiment C 1.
The copolyesters that Embodiment C 1-C6 obtains is analyzed, be the results are shown in table C1.
a: BT is the aromatic series chain link, and BA is the aliphatics chain link.
bN.d.:, and do not detect its molecular weight and molecular weight distribution because sample can not be dissolved in tetrahydrofuran solvent fully.
Tg represents second-order transition temperature.
Tm represents fusing point.
By adopting
1H NMR method characterizes polymer architecture and finds, with Embodiment C 2 (DMT/ADP=1/1) is example, as shown in Figure 1, has only the characteristics of a melting peak in conjunction with the unimodal characteristic of GPC and DSC, find that copolymer structure is typical random copolymers, the coincidence statistics regularity of distribution.
The preparation and the performance perameter of the copolyesters of table C1 different components ratio
Claims (11)
1, the random fat/aromatic copolyesters of a kind of linearity, it contains following structural unit:
Wherein m is 2～10 integer, and n is 2～8 integer, and p is 2～10 integer, m, and n and p are identical or different, and x is 1～10 integer, and y is 1～10 integer, and
Wherein the weight-average molecular weight Mw of this copolyesters is 100,000～600, and 000g/mol and molecular weight distribution 1.2～3 are measured by the GPC method;
And described copolyesters is prepared by the method that comprises the following steps:
1) will carry out transesterification reaction and/or esterification in following monomer and the catalyst component Cat1 adding reactor: (a) to phenyl diprotic acid, its ester, its acid anhydrides or their mixture, (b) aliphatic dihydroxy alcohol, alicyclic dibasic alcohol or their mixture, and monomer (c) is selected from aliphatic dibasic acid, alicyclic diprotic acid, their ester, their acid anhydrides or the mixture of above compound
Wherein said monomer (a) and mol ratio (c) are 5: 95～75: 25;
2) under vacuum condition, with 1) reaction system that obtains carries out pre-polymerization; With
3) to 2) add catalyst component Cat2 in the prepolymer product that obtains, carry out vacuum polycondensation, obtain described polyester;
Wherein, described catalyst component Cat1 is selected from Ti (OR
2')
x, Ti
2O
x, M (R
1' COO)
xAnd composition thereof and
Described catalyst component Cat2 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, do not comprise the acetylacetonate Sm (a of samarium
ca
c)
3Acetylacetonate Ln (a
ca
c)
3, their hydrate and above mixture,
And the mol ratio of Cat2 and Cat1 is 5: 95～75: 25;
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' identical or inequality,
R
2, R
2' be selected from C
3～C
6Alkyl, R
2, R
2' identical or inequality,
Ar is selected from C
1～C
4The phenyl that replaces of alkyl and
M is metal titanium or zinc, and x is 2,3 or 4;
Rare earth metal Ln is selected from lanthanon, scandium Sc, yttrium Y and combination thereof.
2. copolyesters according to claim 1, wherein m is 2～4 integer; N is 2～4 integer; P is 2～4 integer; X is that 1～3 integer and/or y are 1～2 integer.
3. copolyesters according to claim 1, the weight-average molecular weight M of wherein said copolyesters
wBe 100,000～300,000g/mol and molecular weight distribution are 1.5～2.5.
4. copolyesters according to claim 1, the melting range of wherein said copolyesters are 20 to 185 ℃.
5. copolyesters according to claim 1, the second-order transition temperature of wherein said copolyesters-55 ℃ is to-7 ℃.
6. the method for the described copolyesters of one of synthetic claim 1-5, it comprises the following steps:
1) will carry out transesterification reaction and/or esterification in following monomer and the catalyst component Cat1 adding reactor: (a) to phenyl diprotic acid, its ester, its acid anhydrides or their mixture, (b) aliphatic dihydroxy alcohol, alicyclic dibasic alcohol or their mixture, (c) be selected from aliphatic dibasic acid, alicyclic diprotic acid, their ester, their acid anhydrides or the mixture of above compound
Wherein said monomer (a) and mol ratio (c) are 5: 95～75: 25;
2) under vacuum condition, with 1) reaction system that obtains carries out pre-polymerization; With
3) to 2) add catalyst component Cat2 in the prepolymer product that obtains, carry out vacuum polycondensation, obtain described polyester;
Wherein, described catalyst component Cat1 is selected from Ti (OR
2')
x, Ti
2O
x, M (R
1' COO)
xAnd composition thereof and
Described catalyst component Cat2 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, do not comprise the acetylacetonate Sm (a of samarium
ca
c)
3Acetylacetonate Ln (a
ca
c)
3, their hydrate and above mixture,
And the mol ratio of Cat2 and Cat1 is 5: 95～75: 25;
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' identical or inequality,
R
2, R
2' be selected from C
3～C
6Alkyl, R
2, R
2' identical or inequality,
Ar is selected from C
1～C
4The phenyl that replaces of alkyl and
M is metal titanium or zinc, and x is 2,3 or 4;
Rare earth metal Ln is selected from lanthanon, scandium Sc, yttrium Y and combination thereof.
7. method according to claim 6, wherein said monomer (a) and mol ratio (c) are 35: 65～60: 40, the ratio of the mole number of described monomer (a) and mole number sum (c) and monomer (b) is 1: the mol ratio of (1.0～3.0) and catalyst system and monomer (a) and total amount (c) is 1: (500～10000); Described catalyst system is made up of catalyst component Cat1 and Cat2.
8. method according to claim 6, wherein said monomer (b) is selected from C
2～C
6Aliphatic dihydroxy alcohol, C
5～C
10Alicyclic dibasic alcohol or their mixture and described monomer (c) be selected from C
3～C
10Aliphatic dibasic acid, C
5～C
10Alicyclic diprotic acid, their ester, their acid anhydrides or the mixture of above compound.
9. method according to claim 8, wherein said monomer (a) is terephthalic acid or dimethyl terephthalate (DMT), and described monomer (b) is 1,4-butyleneglycol, 1, ammediol or ethylene glycol and described monomer (c) are hexanodioic acid, sebacic acid or Succinic Acid.
10. method according to claim 6, wherein
Described catalyst component Cat1 is selected from tetrabutyl titanate, titanium isopropoxide, titanium dioxide, zinc acetate and composition thereof,
Described catalyst component Cat2 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)
3And composition thereof,
And the mol ratio of described Cat2 and Cat1 is 2: 3～3: 2,
Wherein, described rare earth metal Ln is selected from lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, scandium Sc and combination thereof, and X is chlorion or bromide anion,
R
1Be ethyl, propyl group, R
2For sec.-propyl, normal-butyl or isopentyl and
Ar is 2,6-di-t-butyl-4-aminomethyl phenyl or 4-butyl phenyl.
11. the application of the described copolyesters of one of claim 1-5 in section bar, film, fiber and coating.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018072748A1 (en) | 2016-10-21 | 2018-04-26 | 中国石油化工股份有限公司 | Polyester composition and preparation method therefor |
| WO2018072746A1 (en) | 2016-10-21 | 2018-04-26 | 中国石油化工股份有限公司 | Polyester composition, preparation method therefor and application thereof |
| US10934391B2 (en) | 2016-10-21 | 2021-03-02 | China Petroleum & Chemical Corporation | Polyester composition and preparation method therefor |
| US11053385B2 (en) | 2016-10-21 | 2021-07-06 | China Petroleum & Chemical Corporation | Polyester composition and preparation method therefor |
| US11466151B2 (en) | 2016-10-21 | 2022-10-11 | China Petroleum & Chemical Corporation | Polyester composition, preparation method therefor and application thereof |
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| CN1807485A (en) | 2006-07-26 |
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