CN102617841A - Catalyst and preparation method thereof, as well as application and application method of catalyst - Google Patents
Catalyst and preparation method thereof, as well as application and application method of catalyst Download PDFInfo
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- CN102617841A CN102617841A CN2012100535407A CN201210053540A CN102617841A CN 102617841 A CN102617841 A CN 102617841A CN 2012100535407 A CN2012100535407 A CN 2012100535407A CN 201210053540 A CN201210053540 A CN 201210053540A CN 102617841 A CN102617841 A CN 102617841A
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- butyrolactone
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- opening polymerization
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Abstract
The invention discloses a catalyst, which is an amino-bridged biaryloxy bis(rare earth metal) aryloxy complex with a general formula of p-C6H4[OLnL(THF)]2, wherein Ln is rare earth metal and is selected from one of scandium, yttrium, lutetium, ytterbium and samarium; and L is Me2NCH2CH2N[CH2-(2-O-C6H2-R<1>-3-R<2>-5)]2, and R is selected from one of hydrogen, methyl and tertiary butyl. The invention also discloses a preparation method of the catalyst as well as application and an application method of the catalyst. The amino-bridged biaryloxy bis(rare earth metal) aryloxy complex is convenient for synthesizing and high in yield; and moreover, the complex can be used as a single-component catalyst to catalyze the polymerization of racemic beta-butyrolactone in milder conditions, the catalytic activity is high, the polymer (Mn>10<4>) with high molecular weight is obtained, the ring-opening polymerization selectivity is good and the obtained polybutyrolactone is mainly syndiotactic.
Description
Technical field
The invention belongs to the field of catalyzer and katalysis, relate in particular to a kind of Catalysts and its preparation method that gathers beta-butyrolactone that is used to prepare.
Background technology
Aliphatic polyester is one type of Biodegradable Polymers, and it promptly can be degraded under physiological condition, and degraded product is nontoxic.Therefore, it is as the compatible material of biological tissue, has obtained application (referring to Hayashi, T.Prog.Polym.Sci., 1994,19,663) clinically.Gathering the complete degraded product of GBL is water and carbonic acid gas, can be absorbed fully by physical environment; Also have good biocompatibility simultaneously, thereby can be used as aspects such as medical material (referring to Sudesh, K.; Abe, H.; Doi, Y.Prog.Polym.Sci., 2000,25,1503).
Ring-opening polymerization is the short-cut method of synthetic fat adoption ester.People have developed the ring-opening polymerization that a lot of catalystsystem are used for cyclic ester, and used catalyzer can be alkoxy compound, alkylate, amino-complex and the hydroborates etc. of main group metal, transition metal and rare earth metal.The catalyzer that wherein is used for the beta-butyrolactone ring-opening polymerization mainly contains following several types:
(1) tin class catalyzer: 1993, human SnBu such as Gross
3OCH
3The ring-opening polymerization of catalysis racemize beta-butyrolactone, polymer yield are between 24%～69%, and normality is between 0.70～0.61 between resulting polymers, and the number-average molecular weight molecular weight is 2500～5300.(referring to: Kemnitzer, J.E.; McCarthy, S.P.; Gross, R.A.Macromolecules, 1993,26,1221-1229).
1997, people such as Eggerstedt were with Bu
2The ring-opening polymerization of SnO catalysis racemize beta-butyrolactone, transformation efficiency is higher, and the polymkeric substance number-average molecular weight is up to 80000, and this type of catalyst selectivity is general, and a normality is about 0.7.(referring to: Kricheldorf, H.R.; Eggerstedt, S.Macromolecules, 1997,30,5693-5697).
(2) aluminium class catalyzer: 1989, Holden seminar water and triethyl aluminum were with the ring-opening polymerization of suitable proportion catalysis racemize beta-butyrolactone, and selectivity is best when both ratios are 1, and polymkeric substance entirely can be up to 0.87 with content.(referring to: Bloembergen, S.; Holden, D.A.Macromolecules 1989,22,1656-1663).
1998; The adducts catalysis racemize beta-butyrolactone ring-opening polymerization of human aluminum alkylss such as Lenz and GBL, polymkeric substance reaches as high as 0.91 with content entirely, and molecular weight is between 1.5～5.3 ten thousand; But MWD broad (Mw/Mn=4.8～8.3) (referring to: Wu, B.; Lenz, R.B.Macromolecules 1998,31,3473-3477).
(3) zinc class catalyzer: 2002; People such as Coates are with the ring-opening polymerization of beta-diimine Zn complex catalysis racemize beta-butyrolactone, and monomer and catalyst ratio reach as high as 2000, and yield is greater than 90%; Molecular weight can reach more than 100,000; But catalyzer does not have selectivity, obtains the random GBL that gathers (referring to Rieth, L.R.; Moore, D.R.; Lobkovsky, E.B.; Coates, G.W.J.Am Chem.Soc.2002,124,15239-15248).
2009, Carpentier was with the beta-ketimine Zn complex and add the ring-opening polymerization of pure system catalysis racemize beta-butyrolactone, obtains the random GBL that gathers.(referring to: 1. Grunova, E.; Roisnel, T.; Carpentier, J-F.Dalton Trans., 2009,9010-9019. is Guillaume 2., C.; Carpentier, J-F.; Guillaume, S.m.Polymer, 2009,50,5909-5917.).
(4) rare earth class catalyzer: Carpentier seminar is with the ring-opening polymerization of a series of amido bridged linkage bis aryloxy catalyzed by rare-earth complex racemize beta-butyrolactone.Choice property is good more more to discover on the part phenyl ring ortho-substituent steric hindrance; Substituting group electronic effect stereo selectivity is also influential on the phenyl ring; It is good in THF to be aggregated in the toluene selectivity ratios; The adding stereo selectivity of Virahol does not have obvious influence.(referring to: 1. Abderramane, A.; Thomas, C.M.; Roisnel, T.; Ilnica, S.; Roisnel, T.; Carpentier, J.-F.Angew.Chem.2006,118,2848-2850. is Ajellal 2., N.; Bouyahyi, M.; Abderramane, A.; Thomas, C.M.; Bondon, A.; Pillin, I.; Grohens, Y.; Carpentier, J.-F.Macromolecules, 2009,42,987-993. is Bouyahyi 3., M.; Ajellal, N.; Kirillov, E.; Thomas, C.M.; Carpentier, J.-F.Chem.Eur.J.2011,17,1872).The activity of pyridine and the ring-opening polymerization of thiophene bridged linkage bis aryloxy rare earth aminate catalysis racemize beta-butyrolactone and stereoselectivity are general (referring to Grunova, E.; Kirillov, E.; Roisnel, T.; Carpentier, J.-F.Dalton Trans.2010,39,6739-6752.) Schiff base rare-earth hydroborate and alkoxide complexes catalysis racemize beta-butyrolactone ring-opening polymerization activity are not high, and do not have stereoselectivity (referring to Mahrova, T.V.; Fukin, G.K.; Cherkasov, A.V.; Trifonov, A.A; Ajellal, N.; Carpentier, J.-F.Inorganic Chemistry, 2009,48,4258-4266.).
People such as Thomas find that the catalytic activity of rare earth hydroborate catalysis racemize beta-butyrolactone ring-opening polymerization of load is general; But obtain the complete partially isostructural GBL that gathers; This is that the first routine rare earth class catalyst racemize beta-butyrolactone ring-opening polymerization of bibliographical information so far obtains complete partially isostructure and gathers GBL (referring to Ajellal, N.; Durieux, G.; Delevoye, L.; Dujardin, C.; Thomas, T.M.; Gauvin, R.2010, Chem.Commun., 46,1032-1034.).
Summary of the invention
To the deficiency of prior art, the technical problem that the present invention solves is to provide a kind of catalyzer, can be as the polymerization of single component catalyst catalysis racemize beta-butyrolactone under relatively mild condition, and catalytic activity is high, and the molecular weight of resulting polymers is high.
For solving the problems of the technologies described above, technical scheme of the present invention is achieved in that
A kind of catalyzer, especially, said catalyzer is the two rare earth metal aryloxy title complexs of amido bridged linkage bis aryloxy, its general formula is expressed as: p-C
6H
4[OLnL (THF)]
2, in the general formula, Ln is a rare earth metal, is selected from a kind of in scandium, yttrium, lutetium, ytterbium or the samarium; L=Me
2NCH
2CH
2N [CH
2-(2-O-C
6H
2-R
1-3-R
2-5)]
2, R is selected from a kind of in hydrogen, methyl or the tertiary butyl, and the chemical structural formula of said catalyzer is:
The invention also discloses a kind of described Preparation of catalysts method, especially, comprise the steps:
(1) under anhydrous and oxygen-free protection of inert gas condition, gets LnCp
3With bridging bis-phenol H
2L, be dissolved in react 0.5～2 hour in aromatic solvent or the ether solvent after, original position adds 1/2 equivalent Resorcinol and continues reaction 10～24 hours again, temperature of reaction is 10～50 ℃, and is no more than the boiling point of solvent,
The chemical structural formula of said bridging bis-phenol is as follows:
(2) reaction solution concentrates, and adds small amount of toluene and regulates solubleness, and clear liquid at room temperature obtains crystal, and this crystal is the two rare earth metal aryloxy title complexs of amido bridged linkage bis aryloxy.
Preferably, in above-mentioned Preparation of catalysts method, in the step (1), said aromatic solvent is benzene or toluene; Said ether solvent is THF, ether or glycol dimethyl ether; LnCp
3With bridging bis-phenol H
2The mol ratio of L is 1: 1.
The invention also discloses the application of said catalyzer in the ring-opening polymerization of racemize beta-butyrolactone.
The invention also discloses the application method of a kind of described catalyzer in the ring-opening polymerization of racemize beta-butyrolactone, especially, may further comprise the steps:
(1) under the inert atmosphere of anhydrous and oxygen-free, the racemize beta-butyrolactone is dissolved in the solvent, stir down, add the solution of catalyzer, carry out ring-opening polymerization;
(2) termination reaction uses precipitation agent to be settled out polymkeric substance, and drying obtains gathering beta-butyrolactone then.
Preferably, in the application method of described catalyzer in the ring-opening polymerization of racemize beta-butyrolactone, in the step (1), the temperature of reaction of ring-opening polymerization is 0 ℃～70 ℃, and is no more than the boiling point of solvent.
Preferably, in the application method of described catalyzer in the ring-opening polymerization of racemize beta-butyrolactone, in the step (1), the temperature of reaction of ring-opening polymerization is 20～30 ℃.
Preferably, in the application method of described catalyzer in the ring-opening polymerization of racemize beta-butyrolactone, in the step (1), the mol ratio of racemize beta-butyrolactone and catalyzer is 200: 1～1000: 1.
Preferably, in the application method of described catalyzer in the ring-opening polymerization of racemize beta-butyrolactone, in the step (1), the reaction times of ring-opening polymerization is 10～300 minutes.
Preferably, in the application method of described catalyzer in the ring-opening polymerization of racemize beta-butyrolactone, in the step (1), said solvent is selected from: a kind of in toluene, benzene, methylene dichloride or the THF.
Because the technique scheme utilization, the present invention compared with prior art has advantage:
1. the two rare earth metal aryloxy title complexs of amido bridged linkage bis aryloxy according to the invention are synthetic convenient, and yield is high.
2. the two rare earth metal aryloxy title complexs of amido bridged linkage bis aryloxy according to the invention can be under relatively mild condition as the polymerization of single component catalyst catalysis racemize beta-butyrolactone; Catalytic activity is high; The molecular weight of resulting polymers is high; The selectivity of catalyst racemize beta-butyrolactone ring-opening polymerization is high simultaneously, and it is main with a rule that gained gathers GBL.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
The embodiment of the invention provides a kind of catalyzer, and said catalyzer is the two rare earth metal aryloxy title complexs of amido bridged linkage bis aryloxy, and its general formula is expressed as: p-C
6H
4[OLnL (THF)]
2, in the general formula, Ln is a rare earth metal, is selected from a kind of in scandium, yttrium, lutetium, ytterbium or the samarium; L=Me
2NCH
2CH
2N [CH
2-(2-O-C
6H
2-R
1-3-R
2-5)]
2, R is selected from a kind of in hydrogen, methyl or the tertiary butyl, and the chemical structural formula of said catalyzer is:
The two rare earth metal aryloxy title complexs of said amido bridged linkage bis aryloxy are synthetic convenient, and yield is high.
Above-mentioned Preparation of catalysts method comprises the steps:
(1) under anhydrous and oxygen-free protection of inert gas condition, gets LnCp
3With bridging bis-phenol H
2L, be dissolved in react 0.5～2 hour in aromatic solvent or the ether solvent after, original position adds 1/2 equivalent Resorcinol and continues reaction 10～24 hours again, temperature of reaction is 10～50 ℃, and is no more than the boiling point of solvent,
The chemical structural formula of said bridging bis-phenol is as follows:
(2) reaction solution concentrates, and adds small amount of toluene and regulates solubleness, and clear liquid at room temperature obtains crystal, and this crystal is the two rare earth metal aryloxy title complexs of amido bridged linkage bis aryloxy.
The two rare earth metal aryloxy title complexs of above-mentioned amido bridged linkage bis aryloxy are active high as the ring-opening polymerization of catalyst racemize beta-butyrolactone; The reaction conditions of ring-opening polymerization is gentle; The selectivity of catalyst racemize beta-butyrolactone ring-opening polymerization is high simultaneously, and it is main with a rule that gained gathers GBL.
LnCp
3But concrete reference: the Birmingham of preparation method, J.M.; Wilkinson, G.J Am Chem Soc 1956,78,42; Bridging bis-phenol H
2But preparing method's reference Tshuva of L, E.Y.; Goldberg, I.; Kol, M.Organometalics, 2001,20,3017.
In above-mentioned Preparation of catalysts method, in the step (1), the factor that choice of Solvent need be considered comprises: solubility property, do not participate in the reaction and boiling point should not be too low.Said aromatic solvent is preferably benzene or toluene; Said ether solvent is preferably THF, ether or glycol dimethyl ether; LnCp
3With bridging bis-phenol H
2The mol ratio of L is preferably 1: 1.
The process of above-mentioned reaction is as follows:
In the technique scheme, the productive rate of the two rare earth metal aryloxy title complexs of amido bridged linkage bis aryloxy is 80%～90%.
The embodiment of the invention also discloses the application of said catalyzer in the ring-opening polymerization of racemize beta-butyrolactone.
The application method of said catalyzer in the ring-opening polymerization of racemize beta-butyrolactone may further comprise the steps:
(1) under the inert atmosphere of anhydrous and oxygen-free, the racemize beta-butyrolactone is dissolved in the solvent, stir down, add the solution of catalyzer, carry out ring-opening polymerization;
(2) termination reaction uses precipitation agent to be settled out polymkeric substance, and drying obtains gathering beta-butyrolactone then.
Preferably, in the application method of described catalyzer in the ring-opening polymerization of racemize beta-butyrolactone, in the step (1), the temperature of reaction of ring-opening polymerization is 0 ℃～70 ℃, and is no more than the boiling point of solvent, and preferred, the temperature of reaction of ring-opening polymerization is 20～30 ℃; The mol ratio of racemize beta-butyrolactone and catalyzer is preferably 200: 1～and 1000: 1; The reaction times of ring-opening polymerization is preferably 10～300 minutes.Solvent is preferably from a kind of in toluene, benzene, methylene dichloride or the THF.
In the technique scheme, catalyzer can directly be added in the polymerization system, but takes more convenient behind the wiring solution-forming.
In the technique scheme, precipitation agent is preferably the methanol solution of hydrochloric acid in the step (2), and its percent by volume is preferably 4～6%.
In order to further specify technical scheme of the present invention; Below in conjunction with embodiment the preferred embodiment of the invention is described; Describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
Embodiment one: preparation p-C
6H
4[OYL (THF)]
2
(1) under 25 ℃ of condition, with 2.0 mmole H
2The tetrahydrofuran solution of L joins and contains YCp
3Tetrahydrofuran solution (2.0 mmole), after reaction half a hour, the tetrahydrofuran solution with 1.0 mmole Resorcinol joins in the above-mentioned reaction solution again, continues stirring reaction 24 hours.
(2) centrifugal reaction solution is removed deposition, and the stillness of night concentrates, and to 20 milliliters, 25 ℃ of condition hold over night are separated out clear crystal 1.23 grams (0.82 mmole), productive rate 82%.Decomposition temperature: 299-301 ℃.Ultimate analysis: C, 66.12; H, 8.84; N, 3.94,
1H NMR (THF-d8,300MHz): δ 7.23 (d, 4H, ArH), 6.96 (d, 4H, ArH), 6.45 (s, 4H, ArH), 4.15 (d, 4H, ArCH
2N), 3.62-3.58 (br, α-CH
2THF), 3.18 (d, 4H, ArCH
2N), 2.62 (s, 4H, NCH
2CH
2N), 2.31 (s, 4H, NCH
2CH
2N), 2.03 (s, 6H, N (CH
3)
2, 1.77-1.73 (br, β-CH
2THF), 1.54 (s, 36, C (CH
3)
3), 1.27 (s, 36, C (CH
3)
3).
13C NMR (C
6D
6, 300MHz): δ 163.69,157.64,137.64,137.51,130.08,127.42,126.66,120.83 (Ar-C), 69.41 (α-CH
2THF), 66.93 (ArCH
2N), 60.86 (N (CH
2)
2), 50.78 (N (CH
2)
2), 47.44 (N (CH
3)
2), 37.08 (C (CH
3)
3), 35.72 (C (CH
3)
3), 33.52 (C (CH
3)
3), 32.03 (C (CH
3)
3), 27.56 (β-CH
2THF), infrared absorption spectrum data: 2830s, 2559m, 2374w, 279w, 2139m, 1953w, 1877w, 1834m, 1767s, 1604s, 1506s, 1113w, 990m, 929w, 736s, 645m, 583m, 530s, 447s, above digital proof compound success.
Embodiment two: preparation p-C
6H
4[OYbL (THF)]
2
(1) under 25 ℃ of condition, with 2.0 mmole H
2The tetrahydrofuran solution of L joins and contains YbCp
3Tetrahydrofuran solution (2.0 mmole), after reaction half a hour, the tetrahydrofuran solution with 1.0 mmole Resorcinol joins in the above-mentioned reaction solution again, continues stirring reaction 24 hours.
(2) centrifugal reaction solution is removed deposition, and the stillness of night concentrates, and to 20 milliliters, 25 ℃ of condition hold over night are separated out clear crystal 1.42 grams (0.85 mmole), productive rate 85%.Decomposition temperature: 282-285 ℃.Ultimate analysis: C, 59.98; H, 7.49; N, 3.08. infrared absorption spectrum data: 2830s, 2569m, 2374w, 282w, 2139m, 1953w, 1875w, 1834m, 1767s, 1604s, 1504s, 1115w, 990m, 929w, 736s, 645m, 583m, 530s, 446s, above digital proof compound success.
Embodiment three: preparation p-C
6H
4[OSmL (THF)]
2
(1) under 25 ℃ of condition, with 2.0 mmole H
2The tetrahydrofuran solution of L joins and contains SmCp
3Tetrahydrofuran solution (2.0 mmole), after reaction half a hour, the tetrahydrofuran solution with 1.0 mmole Resorcinol joins in the above-mentioned reaction solution again, continues stirring reaction 24 hours.
(2) centrifugal reaction solution is removed deposition, and clear liquid concentrates, and to 20 milliliters, 25 ℃ of condition hold over night are separated out clear crystal 1.42 grams (0.87 mmole), productive rate 87%.Decomposition temperature: 275-277 ℃.Ultimate analysis: C, 61.95; H, 8.08; N, 3.52. infrared absorption spectrum data: 2990s, 2552m, 2376w, 2276w, 2116m, 1972w, 1837w; 1766s, 1603s, 2500s, 1170m, 1119m, 991m, 931m; 781m, 737s, 643m, 584m, 530s, 445s, above digital proof compound success.
Embodiment four: p-C
6H
4[OYL (THF)]
2The ring-opening polymerization of catalysis racemize beta-butyrolactone
In the reaction flask of handling through dehydration and deoxidation; Under argon shield, add 0.4 milliliter of beta-butyrolactone of racemize (5 mmole) with syringe; Add 1.67 milliliters of toluene with syringe, after stirring, add 0.83 milliliter of (0.01 mmole milliliter of catalyzer toluene solution with syringe again
-1), polymerization 45 minutes is with the alcohol termination reaction that contains 5% hydrochloric acid;
Polymkeric substance is used industrial alcohol precipitation, must gather GBL 0.31 to constant weight after the vacuum-drying and restrain productive rate 72%.Adopt routine techniques to survey the molecular weight of polymkeric substance, specifically may further comprise the steps: polymkeric substance is made into the tetrahydrofuran solution of desired concn, determining molecular weight and MWD on the PL-50 type gel permeation chromatograph that PL company produces.Test condition: 40 ℃ of temperature, THF is made eluent, and leacheate flow velocity 1.0 ml/min adopt polystyrene standards that molecular weight is proofreaied and correct.The theoretical molecular of polymkeric substance is 3.72 ten thousand [M
n(calcd)=(M
wOf β-BBL) * [β-BBL]/[Cat.] * (polymer yield)=86 * 600 * 72%], GPC actual measurement number-average molecular weight (M
n) be 4.05 ten thousand, MWD (M
w/ M
n) be 1.22.
Embodiment five: p-C
6H
4[OYL (THF)]
2The ring-opening polymerization of catalysis racemize beta-butyrolactone
In the reaction flask of handling through dehydration and deoxidation; Under argon shield, add 0.4 milliliter of beta-butyrolactone of racemize (5 mmole) with syringe; Add 1.88 milliliters of toluene with syringe, after stirring, add 0.63 milliliter of (0.01 mmole milliliter of catalyzer toluene solution with syringe again
-1), polymerization 60 minutes is with the alcohol termination reaction that contains 5% hydrochloric acid;
Polymkeric substance is used industrial alcohol precipitation, must gather GBL 0.26 to constant weight after the vacuum-drying and restrain productive rate 60%.Adopt routine techniques to survey the molecular weight of polymkeric substance, specifically may further comprise the steps: polymkeric substance is made into the tetrahydrofuran solution of desired concn, determining molecular weight and MWD on the PL-50 type gel permeation chromatograph that PL company produces.Test condition: 40 ℃ of temperature, THF is made eluent, and leacheate flow velocity 1.0 ml/min adopt polystyrene standards that molecular weight is proofreaied and correct.The theoretical molecular of polymkeric substance is 4.13 ten thousand [M
n(calcd)=(M
wOf β-BBL) * [β-BBL]/[Cat.] * (polymer yield)=86 * 600 * 72%], GPC actual measurement number-average molecular weight (M
n) be 2.44 ten thousand, MWD (M
w/ M
n) be 1.45.
Embodiment six: p-C
6H
4[OYbL (THF)]
2The ring-opening polymerization of catalysis racemize beta-butyrolactone
In the reaction flask of handling through dehydration and deoxidation, under argon shield, add 0.4 milliliter of beta-butyrolactone of racemize (5 mmole) with syringe, add 2.5 milliliters of (0.01 mmole milliliters of catalyzer toluene solution with syringe
-1), polymerization 10 minutes is with the alcohol termination reaction that contains 5% hydrochloric acid;
Polymkeric substance is used industrial alcohol precipitation, must gather GBL 0.42 to constant weight after the vacuum-drying and restrain productive rate 98%.Adopt routine techniques to survey the molecular weight of polymkeric substance, specifically may further comprise the steps: polymkeric substance is made into the tetrahydrofuran solution of desired concn, determining molecular weight and MWD on the PL-50 type gel permeation chromatograph that PL company produces.Test condition: 40 ℃ of temperature, THF is made eluent, and leacheate flow velocity 1.0 ml/min adopt polystyrene standards that molecular weight is proofreaied and correct.The theoretical molecular of polymkeric substance is 1.69 ten thousand [M
n(calcd)=(M
wOf β-BBL) * [β-BBL]/[Cat.] * (polymer yield)=86 * 600 * 72%], GPC actual measurement number-average molecular weight (M
n) be 2.27 ten thousand, MWD (M
w/ M
n) be 1.47.
Embodiment seven: p-C
6H
4[OYbL (THF)]
2The ring-opening polymerization of catalysis racemize beta-butyrolactone
In the reaction flask of handling through dehydration and deoxidation; Under argon shield, add 0.4 milliliter of beta-butyrolactone of racemize (5 mmole) with syringe; Add 1.25 milliliters of toluene with syringe, after stirring, add 1.25 milliliters of (0.01 mmole milliliters of catalyzer toluene solution with syringe again
-1), polymerization 15 minutes is with the alcohol termination reaction that contains 5% hydrochloric acid;
Polymkeric substance is used industrial alcohol precipitation, must gather GBL 0.41 to constant weight after the vacuum-drying and restrain productive rate 97%.Adopt routine techniques to survey the molecular weight of polymkeric substance, specifically may further comprise the steps: polymkeric substance is made into the tetrahydrofuran solution of desired concn, determining molecular weight and MWD on the PL-50 type gel permeation chromatograph that PL company produces.Test condition: 40 ℃ of temperature, THF is made eluent, and leacheate flow velocity 1.0 ml/min adopt polystyrene standards that molecular weight is proofreaied and correct.The theoretical molecular of polymkeric substance is 3.34 ten thousand [M
n(calcd)=(M
wOf β-BBL) * [β-BBL]/[Cat.] * (polymer yield)=86 * 600 * 72%], GPC actual measurement number-average molecular weight (M
n) be 3.41 ten thousand, MWD (M
w/ M
n) be 1.24.
Embodiment eight: p-C
6H
4[OYbL (THF)]
2The ring-opening polymerization of catalysis racemize beta-butyrolactone
In the reaction flask of handling through dehydration and deoxidation; Under argon shield, add 0.4 milliliter of beta-butyrolactone of racemize (5 mmole) with syringe; Add 1.67 milliliters of toluene with syringe, after stirring, add 0.83 milliliter of (0.01 mmole milliliter of catalyzer toluene solution with syringe again
-1), polymerization 15 minutes is with the alcohol termination reaction that contains 5% hydrochloric acid;
Polymkeric substance is used industrial alcohol precipitation, must gather GBL 0.39 to constant weight after the vacuum-drying and restrain productive rate 90%.Adopt routine techniques to survey the molecular weight of polymkeric substance, specifically may further comprise the steps: polymkeric substance is made into the tetrahydrofuran solution of desired concn, determining molecular weight and MWD on the PL-50 type gel permeation chromatograph that PL company produces.Test condition: 40 ℃ of temperature, THF is made eluent, and leacheate flow velocity 1.0 ml/min adopt polystyrene standards that molecular weight is proofreaied and correct.The theoretical molecular of polymkeric substance is 4.64 ten thousand [M
n(calcd)=(M
wOf β-BBL) * [β-BBL]/[Cat.] * (polymer yield)=86 * 600 * 72%], GPC actual measurement number-average molecular weight (M
n) be 5.57 ten thousand, MWD (M
w/ M
n) be 1.23.
Embodiment nine: p-C
6H
4[OYbL (THF)]
2The ring-opening polymerization of catalysis racemize beta-butyrolactone
In the reaction flask of handling through dehydration and deoxidation; Under argon shield, add 0.4 milliliter of beta-butyrolactone of racemize (5 mmole) with syringe; Add 1.88 milliliters of toluene with syringe, after stirring, add 0.63 milliliter of (0.01 mmole milliliter of catalyzer with syringe again
-1), polymerization 45 minutes is with the alcohol termination reaction that contains 5% hydrochloric acid;
Polymkeric substance is used industrial alcohol precipitation, must gather GBL 0.37 to constant weight after the vacuum-drying and restrain productive rate 87%.Adopt routine techniques to survey the molecular weight of polymkeric substance, specifically may further comprise the steps: polymkeric substance is made into the tetrahydrofuran solution of desired concn, determining molecular weight and MWD on the PL-50 type gel permeation chromatograph that PL company produces.Test condition: 40 ℃ of temperature, THF is made eluent, and leacheate flow velocity 1.0 ml/min adopt polystyrene standards that molecular weight is proofreaied and correct.The theoretical molecular of polymkeric substance is 5.99 ten thousand [M
n(calcd)=(M
wOf β-BBL) * [β-BBL]/[Cat.] * (polymer yield)=86 * 600 * 72%], GPC actual measurement number-average molecular weight (M
n) be 9.75 ten thousand, MWD (M
w/ M
n) be 1.32.
Embodiment ten: p-C
6H
4[OYbL (THF)]
2The ring-opening polymerization of catalysis racemize beta-butyrolactone
In the reaction flask of handling through dehydration and deoxidation, under argon shield, add 0.4 milliliter of beta-butyrolactone of racemize (5 mmole) with syringe, add 2.5 milliliters of (0.01 mmole milliliters of catalyzer tetrahydrofuran solution with syringe again
-1), polyase 13 0 minute is with the alcohol termination reaction that contains 5% hydrochloric acid;
Polymkeric substance is used industrial alcohol precipitation, must gather GBL 0.40 to constant weight after the vacuum-drying and restrain productive rate 92%.Adopt routine techniques to survey the molecular weight of polymkeric substance, specifically may further comprise the steps: polymkeric substance is made into the tetrahydrofuran solution of desired concn, determining molecular weight and MWD on the PL-50 type gel permeation chromatograph that PL company produces.Test condition: 40 ℃ of temperature, THF is made eluent, and leacheate flow velocity 1.0 ml/min adopt polystyrene standards that molecular weight is proofreaied and correct.The theoretical molecular of polymkeric substance is 1.58 ten thousand [M
n(calcd)=(M
wOf β-BBL) * [β-BBL]/[Cat.] * (polymer yield)=86 * 200 * 92%], GPC actual measurement number-average molecular weight (M
n) be 0.96 ten thousand, MWD (M
w/ M
n) be 1.30.
Embodiment 11: p-C
6H
4[OYbL (THF)]
2The ring-opening polymerization of catalysis racemize beta-butyrolactone
In the reaction flask of handling through dehydration and deoxidation, under argon shield, add 0.4 milliliter of beta-butyrolactone of racemize (5 mmole) with syringe, add 5 milliliters of (0.01 mmole milliliters of catalyzer tetrahydrofuran solution with syringe again
-1), polyase 13 0 minute is with the alcohol termination reaction that contains 5% hydrochloric acid;
Polymkeric substance is used industrial alcohol precipitation, must gather GBL 0.31 to constant weight after the vacuum-drying and restrain productive rate 72%.Adopt routine techniques to survey the molecular weight of polymkeric substance, specifically may further comprise the steps: polymkeric substance is made into the tetrahydrofuran solution of desired concn, determining molecular weight and MWD on the PL-50 type gel permeation chromatograph that PL company produces.Test condition: 40 ℃ of temperature, THF is made eluent, and leacheate flow velocity 1.0 ml/min adopt polystyrene standards that molecular weight is proofreaied and correct.The theoretical molecular of polymkeric substance is 1.24 ten thousand [M
n(calcd)=(M
wOf β-BBL) * [β-BBL]/[Cat.] * (polymer yield)=86 * 200 * 72%], GPC actual measurement number-average molecular weight (M
n) be 1.41 ten thousand, MWD (M
w/ M
n) be 1.18.
Embodiment 12: p-C
6H
4[OYbL (THF)]
2The ring-opening polymerization of catalysis racemize beta-butyrolactone
In the reaction flask of handling through dehydration and deoxidation; Under argon shield, add 0.4 milliliter of beta-butyrolactone of racemize (5 mmole) with syringe; Add 1.25 milliliters of THFs with syringe; After stirring, add 1.25 milliliters of (0.01 mmole milliliters of catalyzer tetrahydrofuran solution with syringe again
-1), polyase 13 0 minute is with the alcohol termination reaction that contains 5% hydrochloric acid;
Polymkeric substance is used industrial alcohol precipitation, must gather GBL 0.37 to constant weight after the vacuum-drying and restrain productive rate 85%.Adopt routine techniques to survey the molecular weight of polymkeric substance, specifically may further comprise the steps: polymkeric substance is made into the tetrahydrofuran solution of desired concn, determining molecular weight and MWD on the PL-50 type gel permeation chromatograph that PL company produces.Test condition: 40 ℃ of temperature, THF is made eluent, and leacheate flow velocity 1.0 ml/min adopt polystyrene standards that molecular weight is proofreaied and correct.The theoretical molecular of polymkeric substance is 2.92 ten thousand [M
n(calcd)=(M
wOf β-BBL) * [β-BBL]/[Cat.] * (polymer yield)=86 * 400 * 85%], GPC actual measurement number-average molecular weight (M
n) be 1.87 ten thousand, MWD (M
w/ M
n) be 1.30.
In sum, the invention has the advantages that:
1. the two rare earth metal aryloxy title complexs of amido bridged linkage bis aryloxy according to the invention are synthetic convenient, and yield is high.
2. the two rare earth metal aryloxy title complexs of amido bridged linkage bis aryloxy according to the invention can be under relatively mild condition as the polymerization of single component catalyst catalysis racemize beta-butyrolactone; Catalytic activity is high; The molecular weight of resulting polymers is high; The selectivity of catalyst racemize beta-butyrolactone ring-opening polymerization is high simultaneously, and it is main with a rule that gained gathers GBL.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (10)
1. a catalyzer is characterized in that, said catalyzer is the two rare earth metal aryloxy title complexs of amido bridged linkage bis aryloxy, and its general formula is expressed as: p-C
6H
4[OLnL (THF)]
2, in the general formula, Ln is a rare earth metal, is selected from a kind of in scandium, yttrium, lutetium, ytterbium or the samarium; L=Me
2NCH
2CH
2N [CH
2-(2-O-C
6H
2-R
1-3-R
2-5)]
2, R is selected from a kind of in hydrogen, methyl or the tertiary butyl, and the chemical structural formula of said catalyzer is:
2. the described Preparation of catalysts method of claim 1 is characterized in that, comprises the steps:
(1) under anhydrous and oxygen-free protection of inert gas condition, gets LnCp
3With bridging bis-phenol H
2L, be dissolved in react 0.5～2 hour in aromatic solvent or the ether solvent after, original position adds 1/2 equivalent Resorcinol and continues reaction 10～24 hours again, temperature of reaction is 10～50 ℃, and is no more than the boiling point of solvent,
The chemical structural formula of said bridging bis-phenol is as follows:
(2) reaction solution concentrates, and adds small amount of toluene and regulates solubleness, and clear liquid at room temperature obtains crystal, and this crystal is the two rare earth metal aryloxy title complexs of amido bridged linkage bis aryloxy.
3. Preparation of catalysts method according to claim 2 is characterized in that, in the step (1), said aromatic solvent is benzene or toluene; Said ether solvent is THF, ether or glycol dimethyl ether; LnCp
3With bridging bis-phenol H
2The mol ratio of L is 1: 1.
4. the application of the described catalyzer of claim 1 in the ring-opening polymerization of racemize beta-butyrolactone.
5. the application method of the described catalyzer of claim 1 in the ring-opening polymerization of racemize beta-butyrolactone is characterized in that, may further comprise the steps:
(1) under the inert atmosphere of anhydrous and oxygen-free, the racemize beta-butyrolactone is dissolved in the solvent, stir down, add the solution of catalyzer, carry out ring-opening polymerization;
(2) termination reaction uses precipitation agent to be settled out polymkeric substance, and drying obtains gathering beta-butyrolactone then.
6. the application method of catalyzer according to claim 5 in the ring-opening polymerization of racemize beta-butyrolactone is characterized in that, in the step (1), the temperature of reaction of ring-opening polymerization is 0 ℃～70 ℃, and is no more than the boiling point of solvent.
7. the application method of catalyzer according to claim 6 in the ring-opening polymerization of racemize beta-butyrolactone is characterized in that, in the step (1), the temperature of reaction of ring-opening polymerization is 20～30 ℃.
8. the application method of catalyzer according to claim 5 in the ring-opening polymerization of racemize beta-butyrolactone is characterized in that, in the step (1), the mol ratio of racemize beta-butyrolactone and catalyzer is 200: 1～1000: 1.
9. the application method of catalyzer according to claim 5 in the ring-opening polymerization of racemize beta-butyrolactone is characterized in that, in the step (1), the reaction times of ring-opening polymerization is 10～300 minutes.
10. the application method of catalyzer according to claim 5 in the ring-opening polymerization of racemize beta-butyrolactone is characterized in that, in the step (1), said solvent is selected from: a kind of in toluene, benzene, methylene dichloride or the THF.
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| CN101264456A (en) * | 2008-03-14 | 2008-09-17 | 苏州大学 | High-efficiency catalyst for catalyzing amine and carbodiimide to process addition reaction and application |
| CN101412727A (en) * | 2008-11-06 | 2009-04-22 | 苏州大学 | Imidazolidinyl bridged bis(aryloxide) rare-earth metal aminate and catalysis use thereof |
| CN101503430A (en) * | 2009-03-06 | 2009-08-12 | 苏州大学 | Rare earth-lithium heterobimetallic complex, synthesizing method and use thereof |
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| CN101264456A (en) * | 2008-03-14 | 2008-09-17 | 苏州大学 | High-efficiency catalyst for catalyzing amine and carbodiimide to process addition reaction and application |
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| CN115703720A (en) * | 2021-08-03 | 2023-02-17 | 四川大学 | Spiro Salen ligand, salen catalyst, preparation method and application of spirocyclic Salen ligand and Salen catalyst in ring-opening polymerization |
| CN115703720B (en) * | 2021-08-03 | 2024-01-02 | 四川大学 | Spiro Salen ligand, salen catalyst, preparation method and application thereof in ring-opening polymerization |
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