CN101328260A - Binary composite catalyst containing lanthanide series bidentate complex, preparation and use thereof - Google Patents
Binary composite catalyst containing lanthanide series bidentate complex, preparation and use thereof Download PDFInfo
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- CN101328260A CN101328260A CNA2008100227842A CN200810022784A CN101328260A CN 101328260 A CN101328260 A CN 101328260A CN A2008100227842 A CNA2008100227842 A CN A2008100227842A CN 200810022784 A CN200810022784 A CN 200810022784A CN 101328260 A CN101328260 A CN 101328260A
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- lanthanide series
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- 229910052747 lanthanoid Inorganic materials 0.000 title claims abstract description 26
- 150000002602 lanthanoids Chemical class 0.000 title claims abstract description 26
- 239000003054 catalyst Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000011218 binary composite Substances 0.000 title claims abstract description 8
- -1 poly(butylene terephthalate) Polymers 0.000 claims abstract description 22
- 239000003446 ligand Substances 0.000 claims abstract description 8
- 108010021119 Trichosanthin Proteins 0.000 claims abstract description 7
- 150000002148 esters Chemical class 0.000 claims abstract description 7
- 229920002961 polybutylene succinate Polymers 0.000 claims description 16
- 239000004631 polybutylene succinate Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical group OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 6
- 229920001748 polybutylene Polymers 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- LODHFNUFVRVKTH-ZHACJKMWSA-N 2-hydroxy-n'-[(e)-3-phenylprop-2-enoyl]benzohydrazide Chemical group OC1=CC=CC=C1C(=O)NNC(=O)\C=C\C1=CC=CC=C1 LODHFNUFVRVKTH-ZHACJKMWSA-N 0.000 claims description 3
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Chemical group OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical group OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims description 3
- 229960004889 salicylic acid Drugs 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 241000370738 Chlorion Species 0.000 claims description 2
- 229910052693 Europium Chemical group 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical group [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 125000006606 n-butoxy group Chemical group 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical group [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical group [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical group [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical group [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 1
- 239000002932 luster Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 229920001223 polyethylene glycol Polymers 0.000 abstract 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 abstract 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 150000004696 coordination complex Chemical class 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 229920000728 polyester Polymers 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001012 protector Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 206010023126 Jaundice Diseases 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002290 germanium Chemical class 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a binary composite catalyst containing a lanthanide series bidendate complex and a preparation method thereof and an application in the synthesis of poly(butylenes succinate) (PBS) and poly(butylene terephthalate)-co-poly-(butylene succinate)-b-poly(ethylene glycol). The catalyst is prepared from a lanthanide series metal complex R containing a bidendate ligand and an ester compound Q containing lanthanon which are mixed. The poly(butylenes succinate) (PBS) and the poly(butylene terephthalate)-co-poly-(butylene succinate)-b-poly(ethylene glycol) synthesized by a catalytic system under the molten state have the characteristics of high molecular weight, good color and luster, good mechanical properties and so on.
Description
Technical field:
The present invention relates to a kind of binary composite catalyst and preparation method thereof and the application in polyester is synthetic, relate in particular to a kind of binary composite catalyst that contains lanthanide series bidentate complex and preparation method thereof and the application in poly butylene succinate (PBS), poly butylene succinate-be total to-polybutylene terephthalate (PBST) synthesize.
Background technology:
Plastics have been widely used in the every field of social production in recent years, but because of it is difficult to degraded at occurring in nature, and environment has been produced destruction.In order to solve the problem of environmental pollution that causes because of waste plastic, degradable plastics more and more receives the concern of countries in the world.At present, biodegradable plastic in the world mainly is an aliphatic polyester, and wherein poly butylene succinate (PBS) has favorable biological degradability and controlled degradation speed, but has the lower weakness of fusing point.Aromatic polyester polybutylene terephthalate (PBT) is though be difficult to biological degradation, have but that fusing point height, crystallization velocity are fast, machinery and the good characteristics of processing characteristics, both are in conjunction with obtaining the multipolymer that a series of mechanical properties significantly improved and had degradation property, as a poly-succinic acid-butanediol polybutylene terephthalate (PBST) altogether.
Based on PBS and PBST characteristics separately, need further to reduce their preparation cost, improve its color and luster, and wish to obtain more satisfied high molecular weight polymers.Based on these requirements, the catalyzer of development of new has become and has improved PBS and PBST performance, the feasible path that it is more widely used.
At present, polyester synthetic catalyzer has germanium system, tin system, antimony system, titanium system etc.Good with the polyester color and luster that the germanium series catalysts obtains, thermal characteristics is stable, but costs an arm and a leg, and can not be widely used in suitability for industrialized production; Though tin series catalysts catalytic activity height is unfavorable to processing; And antimony-based catalyst has certain toxicity; Titanium series catalyst gained polyester poor heat stability, and color and luster jaundice.
In recent years, the lanthanide series metal catalyzer more and more receives concern both domestic and external, for the catalyzer of seeking good synthesizing polyester has been opened up new approach.Utilize lanthanide metal salt or double salt to be catalyzer as European patent application EP 626406, prepared the thermoplasticity aromatic polyester; As catalyzer, the intrinsic viscosity of the polyester of production has obtained significant raising to the patent application CN1720216A of the open company limited of Claes Johanson Ma Se with the alkoxide that is selected from the metal in titanium, zirconium, hafnium, aluminium or the lanthanon or condensed alkoxide; The patent application CN1446837A of Sinopec Group as catalyzer, has improved catalytic activity with the mixture of the oxyhydroxide of lanthanide series metal halogeno salt or lanthanide metal-complexed thing and lanthanide series metal, has shortened the reaction times.Yet the patented technology that more than comprises the lanthanide series metal catalyzer is not also seen specifically the application example in PBS and PBST are synthetic, and the performance that these catalyzer of having reported be describeds also is not very desirable, remains further to be studied.
Summary of the invention:
Technical problem to be solved by this invention is good inadequately in order to improve existing polyester synthetic catalyzer thermostability, deficiency such as cost an arm and a leg and proposed a kind of binary composite catalyst that comprises lanthanide series bidentate complex, another object of the present invention provide this Preparation of catalysts method and the application in synthetic poly butylene succinate (PBS), poly butylene succinate-altogether-polybutylene terephthalate (PBST).
Technical scheme of the present invention is: a kind of binary composite catalyst that comprises lanthanide series bidentate complex is characterized in that being mixed by lanthanide metal-complexed thing R that contains bitooth ligand and the ester compound Q that contains rare earth element; Wherein the mol ratio of R and Q is (95～15): (5～75).The mol ratio of preferred R and Q is (75～45): (25～55).
The R structural formula is as follows in the catalyzer of the present invention:
(B)n→M——(X)m
Wherein B is pyridine-2-formic acid, 2-hydroxy benzaldehyde, 2 hydroxybenzoic acid or 2,2-dipyridyl a kind of, and M is any one of lanthanide element, X is any one in the halide-ions, n=1～4, m=0～3.
Wherein B is a kind of in the following structural formula:
Preferred described X is chlorion or bromide anion.Preferred M is lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm) or europium (Eu).
The described ester compound Q that contains rare earth element is N (OBu)
4, N (iOPr)
4, N (OAc)
4Or N (acac)
4In any one, wherein OBu is a n-butoxy, iOPr is an isopropoxy, OAc is an acetate, acac is acetylacetone based; N wherein is any one metal in titanium (Ti), zirconium (Zr) or the hafnium (Hf).
The present invention also provides above-mentioned Preparation of catalysts method, and preparation at first earlier contains the lanthanide metal-complexed thing R of bitooth ligand, and wherein said R is under 20 ℃～60 ℃, by part B and lanthanide metal salt MX
3The aqueous solution, reaction 0.5～10h makes wherein part B and MX
3Mol ratio be 2: 0.1～1; And then the lanthanide metal-complexed thing R that will contain bitooth ligand is (95～15) in molar ratio with the ester compound Q that contains rare earth element: (5～75) mix, and R and Q want thorough mixing even.
The present invention also provides the application in poly butylene succinate (PBS) or poly butylene succinate-altogether-polybutylene terephthalate (PBST) synthetic of above-mentioned catalyzer.
Catalyzer of the present invention is mainly used in synthetic poly butylene succinate (PBS), poly butylene succinate-altogether-polybutylene terephthalate (PBST), in this catalyzer the gross weight of R and Q account for polymerization single polymerization monomer weight 0.01%～0.5%.Processing parameter is as follows: the pre-polymerization temperature is generally: 150 ℃～180 ℃, condensation temperature is generally 220 ℃～240 ℃, and the pressure of polycondensation phase is generally less than 100Pa.To add in the reactor simultaneously with raw material at the catalyzer described in the reaction process.
Beneficial effect:
Advantages such as 1, Catalyst Design of the present invention is ingenious, and technology is simple, ripe, has the molecular weight height with its synthetic PBS, PBST, and good mechanical performance and color and luster are better.
2, bidentate lanthanide complex and rare earth ester compound have played the concerted catalysis effect in the catalyzer of the present invention in polyreaction, have promoted the acceleration of product in pre-polymerization and polycondensation phase, have reduced temperature of reaction, have shortened the reaction times.
Embodiment:
The present invention will be helped further to understand by following embodiment, but content of the present invention can not be limited.
Embodiment 1
With weak ammonia dissolving and be settled to 30mL, following of electronic stirring is dissolved with 0.01molLaCl with 10.0g pyridine-2-formic acid
3Saturated aqueous solution dropwise add, then pH value of solution is transferred to 3～4, mixture filters after down stirring 6h in 30 ℃, uses distilled water then, blots after the cold washing with alcohol, the vacuum-drying solid obtains about 4g solid, represents productive rate about 80% with R1.
Embodiment 2
8.8g 2-hydroxy benzaldehyde with dissolve with ethanol and be settled to 30mL, is transferred to 6 with the 5mol/L sodium hydroxide solution with its pH, and following of magnetic agitation is dissolved with 0.01mol SmCl
3Saturated aqueous solution dropwise add, filter behind the mixture condensing reflux 6h, use cold ethanol then successively, blot behind the distilled water wash, the vacuum-drying solid obtains about 4.7g solid, represents productive rate about 70% with R2.
Embodiment 3
With weak ammonia dissolving and be settled to 30mL, following of electronic stirring is dissolved with 0.01mol PrCl with the 10.1g 2 hydroxybenzoic acid
3Saturated aqueous solution dropwise add, then pH value of solution is transferred to 6, mixture filters after down stirring 7h in 50 ℃, then with blotting behind the distilled water wash, the vacuum-drying solid obtains about 12.2g solid, represents productive rate about 85% with R3.
Embodiment 4
With 12.5g 2, the 2-dipyridyl is with the diluted hydrochloric acid aqueous solution dissolving and be settled to 30mL, and following of electronic stirring is dissolved with 0.01mol EuCl
3Saturated aqueous solution dropwise add, add weak ammonia then with pH value of solution modulation 4～5, mixture filters after stirring 5h down in 45 ℃, then with blotting behind the distilled water wash, the vacuum-drying solid obtains about 5.7g solid, represents productive rate about 90% with R4.
Embodiment 5
With 1 of 1mol Succinic Acid and 1.1mol; the 4-butyleneglycol joins in the reactor that has stirring, heating, N2 protector; add catalyzer of the present invention (catalyst consumption and kind such as table 1) then; the pre-polymerization temperature is: 150 ℃; reaction 2h; condensation temperature is 210 ℃, reaction 2.5h, and the pressure of polycondensation phase is reduced to 100Pa gradually.Under the N2 protection, pour out viscous liquid, be cooled to room temperature, with the chloroform dissolving, be poured in the sherwood oil (60 ℃～90 ℃) then, have milky white precipitate to separate out, filter, use methanol wash twice again,, obtain PBS at 60 ℃ of following vacuum-drying 24h.
Embodiment 6-8 is basic identical with example 5, and catalyzer difference only is as table 1.
Embodiment 9
With 1 of 0.6mol Succinic Acid, 0.4mol terephthalic acid and 1.1mol; the 4-butyleneglycol joins in the reactor that has stirring, heating, N2 protector; add catalyzer of the present invention (catalyst consumption and kind such as table 1) then; pre-polymerization fs temperature is: 160 ℃; pre-polymerization subordinate phase temperature is 220 ℃, reaction 2h, and condensation temperature is generally 240 ℃; reaction 3h, the pressure of polycondensation phase is reduced to 100Pa gradually.Under the N2 protection, pour out viscous liquid, be cooled to room temperature, with the chloroform dissolving, be poured in the sherwood oil (60 ℃～90 ℃) then, have milky white precipitate to separate out, filter, use methanol wash twice again,, obtain PBST at 60 ℃ of following vacuum-drying 24h.
Molecular weight determination: take by weighing an amount of PBST, be dissolved in chloroform, it is formulated as mass concentration is 1% solution.The gel permeation chromatograph temperature is 40 ℃, and flow is 0.2～1ml/min during mensuration.
Mechanics Performance Testing: on the WD4005 material experiment-machine, test mechanical property with reference to GB/T1040-92.Specimen in use makes by mold die, is dumbbell shape.Draw speed is 0.5mm/min during test, and temperature is a room temperature, about 25 ℃.
Embodiment 10-12 is basic identical with example 9, and catalyzer difference only is as table 1.
Table 1
Claims (8)
1. a binary composite catalyst that comprises lanthanide series bidentate complex is characterized in that being mixed by lanthanide metal-complexed thing R that contains bitooth ligand and the ester compound Q that contains rare earth element; Wherein the mol ratio of R and Q is (95～15): (5～75).
2. according to the described catalyzer of claim 1, it is characterized in that the described lanthanide metal-complexed thing R structure that contains bitooth ligand is:
(B)n→M——(X)m
Wherein part B is pyridine-2-formic acid, 2-hydroxy benzaldehyde, 2 hydroxybenzoic acid or 2, and 2-dipyridyl, M are any one of lanthanide element, and X is any one in the halide-ions, n=1～4, m=0～3.
3. according to the described catalyzer of claim 2, it is characterized in that described X is chlorion or bromide anion.
4. according to claims 2 described catalyzer, it is characterized in that described M is lanthanum, cerium, praseodymium, neodymium, samarium or europium.
5. according to claims 1 described catalyzer, it is characterized in that the described ester compound Q that contains rare earth element is N (OBu)
4, N (iOPr)
4, N (OAc)
4Or N (acac)
4In any one, wherein OBu is a n-butoxy, iOPr is an isopropoxy, OAc is an acetate, acac is acetylacetone based; N wherein is any one metal in titanium, zirconium or the hafnium.
6. one kind as claims 1 described Preparation of catalysts method, and its concrete steps are as follows:
A. contain the preparation of the lanthanide metal-complexed thing R of bitooth ligand: under 20 ℃～60 ℃, by part B and lanthanide metal salt MX
3The aqueous solution, reaction 0.5～10h makes wherein part B and MX
3Mol ratio be: 2: 0.1～1;
B. above-mentioned lanthanide metal-complexed thing R that contains bitooth ligand that makes and the ester compound Q that contains rare earth element are (95～15) in molar ratio: (5～75) mix.
7. according to claims 6 described preparation methods, it is characterized in that the mol ratio of described R and Q is (75～45): (25～55).
8. one kind as the application of claims 1 described catalyzer in poly butylene succinate or poly butylene succinate-altogether-polybutylene terephthalate is synthetic.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100227842A CN101328260B (en) | 2008-07-29 | 2008-07-29 | Binary composite catalyst containing lanthanide series bidentate complex, preparation and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100227842A CN101328260B (en) | 2008-07-29 | 2008-07-29 | Binary composite catalyst containing lanthanide series bidentate complex, preparation and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101328260A true CN101328260A (en) | 2008-12-24 |
| CN101328260B CN101328260B (en) | 2011-11-16 |
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| CN2008100227842A Expired - Fee Related CN101328260B (en) | 2008-07-29 | 2008-07-29 | Binary composite catalyst containing lanthanide series bidentate complex, preparation and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106211783A (en) * | 2013-10-04 | 2016-12-07 | 基因组股份公司 | Alcoholdehydrogenase variant |
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| 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 |
| CN100360581C (en) * | 2004-12-23 | 2008-01-09 | 中国石油化工股份有限公司 | Catalyst system and application in use for synthesizing degradable polyester |
| CN1807145A (en) * | 2006-01-26 | 2006-07-26 | 上海瑞华(集团)有限公司 | Hybrid electric Energy carrier drived electric vehicle |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106211783A (en) * | 2013-10-04 | 2016-12-07 | 基因组股份公司 | Alcoholdehydrogenase variant |
| US10563180B2 (en) | 2013-10-04 | 2020-02-18 | Genomatica, Inc. | Alcohol dehydrogenase variants |
| US11384340B2 (en) | 2013-10-04 | 2022-07-12 | Genomatica, Inc. | Alcohol dehydrogenase variants |
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