CN104211929B - A kind of organic zinc composition catalyst and method for making thereof and application - Google Patents
A kind of organic zinc composition catalyst and method for making thereof and application Download PDFInfo
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- CN104211929B CN104211929B CN201410384113.6A CN201410384113A CN104211929B CN 104211929 B CN104211929 B CN 104211929B CN 201410384113 A CN201410384113 A CN 201410384113A CN 104211929 B CN104211929 B CN 104211929B
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Abstract
The present invention relates to a kind of organic zinc composition catalyst and method for making thereof and application, the catalyzer solving existing rac-lactide ring-opening polymerization at room temperature or active low and without complete with optionally technical problem.Organic zinc composition catalyst provided by the invention is a kind of assorted scorpion type Zn complex.The type title complex can carry out separately complete in stereoselectivity ring-opening polymerization for catalysis rac-lactide.Present invention also offers method for making and the application of assorted scorpion type Zn complex.The title complex that the method prepares prepares poly(lactic acid) for the ring-opening polymerization of catalysis rac-lactide, and at room temperature have higher entirely with the feature of selectivity and greater activity, the molecular weight distribution of gained poly(lactic acid) is narrower, entirely can reach 85% with content.
Description
Technical field
The present invention relates to organic zinc complex polymerisation field, it is high entirely with the organic zinc composition catalyst of selective polymerisation and method for making thereof and application to be specifically related to catalysis rac-lactide under a kind of room temperature.
Background technology
Along with the shortage of petroleum resources and the day by day serious of environmental pollution, development environment friendly macromolecular material more and more causes the concern of people.Poly(lactic acid) has biodegradability and biocompatibility, and monomer whose derives from renewable farm crop, as corn, potato etc., is the Typical Representative of environmentally friendly macromolecular material.At present, poly(lactic acid) has been widely used in disposable tableware, container, wrapping material, film etc.In addition, owing to having good physiologically acceptable and degradation property, meet the requirement of pharmaceutical macromolecular material, have broad application prospects in fracture patch, operating sutures, tissue engineering bracket and Slow/Controlled Release Drug solid support material etc.
The method of conventional synthesis poly(lactic acid) is polycondensation, and its shortcoming is that energy consumption is high, and resulting polymers molecular weight is low, molecular weight distribution is wider, and may with cyclic side products, and controllability is very poor.In recent years, the rac-Lactide coordination ring-opening polymerization based on metal complexes more and more causes the attention of people.Can obtain highly stereoregulated polymkeric substance by optically pure rac-Lactide (L-rac-Lactide or D-rac-Lactide) ring-opening polymerization, its fusing point can reach 165 ~ 180 DEG C.Rac-lactide, by the effect of different catalysts, can obtain the polymkeric substance of multiple steric configuration, comprises entirely with many blocks, gradient, assorted same and random poly(lactic acid).Wherein complete same structure poly(lactic acid) is crystalline polymer, and fusing point is higher.At present, have Gao Quantong optionally catalyzer mainly concentrate on aluminium system title complex, especially Schiff's base (salen) aluminum complex, but this type title complex does not at room temperature have activity, need to be heated to more than 70 DEG C and could cause ring-opening polymerization, and generally need to add alcohol as coinitiator.
Summary of the invention
The present invention be solve the polymerization of existing catalysis rac-lactide catalyzer at room temperature or active low or without complete with optionally technical problem, provide a kind of and there is higher complete same selectivity, the organic zinc composition catalyst of greater activity and method for making thereof and application.
In order to solve the problems of the technologies described above, technical scheme of the present invention is specific as follows:
A kind of organic zinc composition catalyst, this catalyzer is the assorted scorpion type Zn complex with formula I structure;
Wherein, R
1for hydrogen, methyl, ethyl, sec.-propyl or the tertiary butyl;
R
2for the tertiary butyl, cyclohexyl or phenyl;
Ar is phenyl or the aryl containing C1 ~ C6 straight or branched alkane group;
R is C1 ~ C10 straight or branched alkoxyl group or alkylamino radical.
In technique scheme, described R is methoxyl group, isopropoxy, tert.-butoxy, benzyloxy, two (dimethyl is silica-based) amido or two (trimethyl silicon based) amido.
In technique scheme, described Ar is 2,6-3,5-dimethylphenyl, 2,6-diethyl phenyl or 2,6-diisopropyl phenyl.
In technique scheme, described catalyzer is any one in the assorted scorpion type Zn complex of following 1 ~ 12, wherein:
Assorted scorpion type organic zinc title complex 1:R
1=Me, R
2=Cy, R=N (SiHMe
2)
2;
Assorted scorpion type organic zinc title complex 2:R
1=Me, R
2=Cy, R=N (SiMe
3)
2;
Assorted scorpion type organic zinc title complex 3:R
1=Me, R
2=Cy, R=OCH
2ph;
Assorted scorpion type organic zinc title complex 4:R
1=Me, R
2=Cy, R=OMe;
Assorted scorpion type organic zinc title complex 5:R
1=Me, R
2=Cy, R=O
ipr;
Assorted scorpion type organic zinc title complex 6:R
1=Me, R
2=Cy, R=O
tbu;
Assorted scorpion type organic zinc title complex 7:R
1=Me, R
2=Ph, R=N (SiHMe
2)
2;
Assorted scorpion type organic zinc title complex 8:R
1=Me, R
2=Ph, R=N (SiMe
3)
2;
Assorted scorpion type organic zinc title complex 9:R
1=Me, R
2=Ph, R=OCH
2ph;
Assorted scorpion type organic zinc title complex 10:R
1=Me, R
2=Ph, R=OMe;
Assorted scorpion type organic zinc title complex 11:R
1=Me, R
2=Ph, R=O
ipr;
Assorted scorpion type organic zinc title complex 12:R
1=Me, R
2=Ph, R=O
tbu;
A method for making for organic zinc composition catalyst, this method for making specifically comprises the following steps:
(1) under anhydrous and oxygen-free condition, the assorted scorpion type part with formula (II) structure is dissolved in tetrahydrofuran (THF) and is placed in-80 DEG C ~-30 DEG C, add normal hexane solution, KH or NaH that molar weight is the n-Butyl Lithium of 1 times amount, obtain the first reaction mixture;
(2) above-mentioned first reaction mixture and zinc dichloride are reacted, obtain the second reaction mixture;
(3) in above-mentioned second reaction mixture, add lithium salts containing R base or sylvite reacts, drain solvent, toluene extracts, and under low temperature, recrystallization obtains assorted scorpion type Zn complex;
Wherein, the R described in formula (II)
1for hydrogen, methyl, ethyl, sec.-propyl or the tertiary butyl; R
2for the tertiary butyl, cyclohexyl or phenyl; Ar is phenyl or the aryl containing C1 ~ C6 straight or branched alkane group; Described R is C1 ~ C10 straight or branched alkoxyl group or alkylamino radical.
A method for poly(lactic acid) is prepared in the ring-opening polymerization of organic zinc composition catalyst catalysis rac-lactide, and the method specifically comprises the following steps:
Under the condition of anhydrous and oxygen-free, take rac-lactide and use organic solvent dissolution, then adding organic zinc composition catalyst, carrying out polyreaction at the katalysis racemization rac-Lactide of catalyzer, obtaining higher entirely with the poly(lactic acid) of content; The mol ratio of described rac-lactide and described organic zinc composition catalyst is (100 ~ 1000): 1; The temperature of described polyreaction is 0 DEG C ~ 70 DEG C; The time of described polyreaction is 1.5 ~ 36 hours.
In technique scheme, the zine ion volumetric molar concentration of described organic zinc composition catalyst is 0.001 ~ 0.01mol/L.
In technique scheme, described organic solvent is benzene, toluene or tetrahydrofuran (THF).
The beneficial effect of organic zinc title complex provided by the invention and method for making and application is:
The organic zinc composition catalyst that method of the present invention prepares has high complete in selectivity and highly active feature for catalysis rac-lactide ring-opening polymerization preparation entirely with structure poly(lactic acid), the molecular weight distribution of gained poly(lactic acid) is narrower, entirely can reach 85% with content.And preparation method provided by the invention is simple.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the assorted scorpion type Zn complex 1 that the embodiment of the present invention 1 prepares;
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the assorted scorpion type Zn complex 2 that the embodiment of the present invention 1 prepares;
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of the assorted scorpion type Zn complex 7 that the embodiment of the present invention 3 prepares;
Fig. 4 is the hydrogen nuclear magnetic resonance spectrogram of the assorted scorpion type Zn complex 8 that the embodiment of the present invention 3 prepares;
Fig. 5 is the hydrogen nuclear magnetic resonance spectrogram of the assorted scorpion type Zn complex 9 that the embodiment of the present invention 4 prepares;
Fig. 6 is the same core decoupling resonance hydrogen spectrogram of polymkeric substance prepared by the embodiment of the present invention 17.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in detail.
A kind of organic zinc composition catalyst, this catalyzer is the assorted scorpion type Zn complex with formula I structure;
Wherein, R
1for hydrogen, methyl, ethyl, sec.-propyl or the tertiary butyl, be preferably methyl; R
2for the tertiary butyl, cyclohexyl or phenyl, be preferably cyclohexyl or phenyl; Ar is phenyl or the aryl containing C1 ~ C6 straight or branched alkane group, is preferably phenyl, 2,6-3,5-dimethylphenyls, 2,6-diethyl phenyl or 2,6-diisopropyl phenyl, is more preferably phenyl; R is alkoxyl group or the alkylamino radical of C1 ~ C10 straight or branched, is preferably benzyloxy, two (trimethyl silicon based) amido or two (dimethyl is silica-based) amido.
The above-mentioned assorted scorpion type Zn complex with formula (I) structure provided by the invention, zine ion and assorted scorpion type part (NNN-tridentate ligand) and the coordination of a single anion initiating group.
The present invention to choose and combination is not particularly limited substituent in above-mentioned assorted scorpion type Zn complex, and choose and array mode with well known to those skilled in the art, the present invention preferably has assorted scorpion type Zn complex as described below, wherein,
Assorted scorpion type organic zinc title complex 1:R
1=Me, R
2=Cy, R=N (SiHMe
2)
2;
Assorted scorpion type organic zinc title complex 2:R
1=Me, R
2=Cy, R=N (SiMe
3)
2;
Assorted scorpion type organic zinc title complex 3:R
1=Me, R
2=Cy, R=OCH
2ph;
Assorted scorpion type organic zinc title complex 4:R
1=Me, R
2=Cy, R=OMe;
Assorted scorpion type organic zinc title complex 5:R
1=Me, R
2=Cy, R=O
ipr;
Assorted scorpion type organic zinc title complex 6:R
1=Me, R
2=Cy, R=O
tbu;
Assorted scorpion type organic zinc title complex 7:R
1=Me, R
2=Ph, R=N (SiHMe
2)
2;
Assorted scorpion type organic zinc title complex 8:R
1=Me, R
2=Ph, R=N (SiMe
3)
2;
Assorted scorpion type organic zinc title complex 9:R
1=Me, R
2=Ph, R=OCH
2ph;
Assorted scorpion type organic zinc title complex 10:R
1=Me, R
2=Ph, R=OMe;
Assorted scorpion type organic zinc title complex 11:R
1=Me, R
2=Ph, R=O
ipr;
Assorted scorpion type organic zinc title complex 12:R
1=Me, R
2=Ph, R=O
tbu.
A method for making for organic zinc composition catalyst, this method for making specifically comprises the following steps:
(1) under anhydrous and oxygen-free condition, the assorted scorpion type part with formula (II) structure is dissolved in tetrahydrofuran (THF) and is placed in-80 DEG C ~-30 DEG C, add normal hexane solution, KH or NaH that molar weight is the n-Butyl Lithium of 1 times amount, obtain the first reaction mixture;
(2) above-mentioned first reaction mixture and zinc dichloride are reacted, obtain the second reaction mixture;
(3) in above-mentioned second reaction mixture, add the lithium salts containing R base or sylvite reaction, drain solvent, toluene extracts, and under low temperature, recrystallization obtains assorted scorpion type Zn complex;
Wherein, the R described in formula (II)
1for hydrogen, methyl, ethyl, sec.-propyl or the tertiary butyl; R
2for the tertiary butyl, cyclohexyl or phenyl; Ar is phenyl or the aryl containing C1 ~ C6 straight or branched alkane group; Described R is C1 ~ C10 straight or branched alkoxyl group or alkylamino radical.
A method for poly(lactic acid) is prepared in the ring-opening polymerization of organic zinc composition catalyst catalysis rac-lactide, and the method specifically comprises the following steps:
Under anhydrous and oxygen-free condition, take rac-lactide and be placed in reactor, and add organic solvent dissolution, getting above-mentioned organic zinc composition catalyst adds in reactor, the mol ratio of described rac-lactide and organic zinc composition catalyst is (100 ~ 1000): 1, under the katalysis of above-mentioned organic zinc composition catalyst, rac-lactide generation polymkeric substance, polyreaction carries out 1.5 ~ 36 hours at 0 ~ 70 DEG C, adding volumetric concentration is pour sedimentation in ethanol into after the ethanolic soln termination reaction of the hydrochloric acid of 10%, filter to obtain white solid, within dry 48 hours in 40 DEG C of vacuum drying ovens, obtain poly(lactic acid).
The consumption of the present invention to described organic solvent is not particularly limited, with the consumption of organic solvent in organozinc catalyst catalysis rac-lactide polyreaction well known to those skilled in the art, after preferably described organozinc catalyst being dissolved in organic solvent, zine ion volumetric molar concentration is 0.0001 ~ 0.1mol/L, more preferably zine ion volumetric molar concentration is 0.001 ~ 0.01mol/L, and most preferably zine ion volumetric molar concentration is 0.004mol/L; The present invention is not particularly limited described organic solvent, with the organic solvent preparing organozinc catalyst well known to those skilled in the art, preferably do not cause catalyst deactivation with catalyst reaction, rac-lactide and poly(lactic acid) can be dissolved simultaneously, and fusing point is lower than the organic solvent of minimum temperature required during polymerization, be preferably benzene, toluene or tetrahydrofuran (THF), most preferably be tetrahydrofuran (THF); The condition of the present invention to described anhydrous and oxygen-free is not particularly limited, with the condition of anhydrous and oxygen-free well known to those skilled in the art.
The present invention is not particularly limited vacuum drying pressure, with the pressure of vacuum-drying poly(lactic acid) well known to those skilled in the art; The consumption of the present invention to ethanol is not particularly limited, and for guaranteeing to be precipitated completely by product, is preferably excessive ethanol.The present invention is the content reducing kish and part in resulting polymers, resulting polymers can be dissolved sedimentation again twice again.
In order to understand the present invention further, be described metal complexes provided by the invention and preparation method thereof below in conjunction with embodiment, protection scope of the present invention is not limited by the following examples.
R in following examples
1for methyl, Ar are phenyl, R
2for Cy or Ph, the zinc dichloride in following examples directly buys acquisition.
Embodiment 1
The assorted scorpion type Zn complex 1 ~ 2 of preparation
The process of the assorted scorpion type Zn complex 1 ~ 2 of the present embodiment preparation is as shown in reaction expression (III):
Under anhydrous and oxygen-free condition, the assorted scorpion type part 0.001 mole with formula (II) structure is dissolved in tetrahydrofuran (THF), be cooled to-30 DEG C, and to add concentration be wherein that the hexane solution 1.0mL of the n-Butyl Lithium of 1.0mol/L reacts 30 minutes, gained mixed solution is added dropwise in the tetrahydrofuran (THF) suspension of zinc dichloride, react 3 hours under room temperature, then drip amido potassium [KN (SiXMe wherein
2)
2], react removal of solvent under reduced pressure after 5 hours, add the extraction of 20mL toluene wherein, filter, filtrate is concentrated into 2mL, adds 1mL normal hexane, is put in recrystallization in-30 DEG C of refrigerators, separates out a large amount of white solid after 24 hours.Last separate solid also uses n-hexane twice, and vacuum-drying 2 hours, obtains assorted scorpion type Zn complex.
As X=H, the above-mentioned preparation method of the present embodiment obtains the assorted scorpion type Zn complex 1 with formula III structure, and its molecular formula is C
33h
55n
6pSi
2zn.After testing, productive rate is 74%, and in assorted scorpion type Zn complex 1, element mass percentage content is C:57.58%, H:8.05%, N:12.21%, Zn:9.50%.
As X=Me, the above-mentioned preparation method of the present embodiment obtains the assorted scorpion type Zn complex 2 with formula III structure, and its molecular formula is C
35h
59n
6pSi
2zn.After testing, productive rate is 68%, and in assorted scorpion type Zn complex 2, element mass percentage content is C:58.68%, H:8.30%, N:11.73%, Zn:9.13%.
Proton nmr spectra (C is carried out to the above-mentioned assorted scorpion type Zn complex 1 and 2 with formula (I) structure
6d
6, 400MHz) analyze, as depicted in figs. 1 and 2, Fig. 1 and Fig. 2 illustrates that the present embodiment successfully prepares assorted scorpion type Zn complex 1 and 2 respectively.
Embodiment 2
The assorted scorpion type Zn complex 3 ~ 6 of preparation
The process of the assorted scorpion type Zn complex 3 ~ 6 of the present embodiment preparation is as shown in reaction expression (IV):
Under anhydrous and oxygen-free condition, the assorted scorpion type part 0.001 mole with formula (II) structure is dissolved in tetrahydrofuran (THF), and add the NaH solid reaction 30 minutes of 0.001 mole wherein, gained mixed solution is added dropwise in the tetrahydrofuran (THF) suspension of zinc dichloride, react 5 hours at 50 DEG C, then alkoxyl group sylvite is dripped wherein, react removal of solvent under reduced pressure after 2 hours, add the extraction of 20mL toluene wherein, filter, filtrate is concentrated into 2mL, adds 1mL normal hexane, be put in recrystallization in-30 DEG C of refrigerators, after 24 hours, separate out a large amount of white solid.Last separate solid also uses n-hexane twice, and vacuum-drying 2 hours, obtains assorted scorpion type Zn complex.
Work as R
3=CH
2during Ph, the above-mentioned preparation method of the present embodiment obtains the assorted scorpion type Zn complex 3 with formula IV structure, and its molecular formula is C
36h
48n
5oPZn.After testing, productive rate is 63%, and in assorted scorpion type Zn complex 3, element mass percentage content is C:65.20%, H:7.30%, N:10.56%, Zn:9.86%.
Work as R
3during=Me, the above-mentioned preparation method of the present embodiment obtains the assorted scorpion type Zn complex 4 with formula IV structure, and its molecular formula is C
30h
44n
5oPZn.After testing, productive rate is 65%, and in assorted scorpion type Zn complex 4, element mass percentage content is C:61.38%, H:7.55%, N:11.93%, Zn:11.14%.
Work as R
3=
iduring Pr, the above-mentioned preparation method of the present embodiment obtains the assorted scorpion type Zn complex 5 with formula IV structure, and its molecular formula is C
32h
48n
5oPZn.After testing, productive rate is 55%, and in assorted scorpion type Zn complex 5, element mass percentage content is C:62.48%, H:7.87%, N:11.39%, Zn:10.63%.
Work as R
3=
tduring Bu, the above-mentioned preparation method of the present embodiment obtains the assorted scorpion type Zn complex 6 with formula IV structure, and its molecular formula is C
33h
50n
5oPZn.After testing, productive rate is 68%, and in assorted scorpion type Zn complex 6, element mass percentage content is C:63.00%, H:8.01%, N:11.13%, Zn:10.39%.
Embodiment 3
The assorted scorpion type Zn complex 7 ~ 8 of preparation
The process of the assorted scorpion type Zn complex 7 ~ 8 of the present embodiment preparation is as shown in reaction expression (V):
Under anhydrous and oxygen-free condition, the assorted scorpion type part 0.001 mole with formula (II) structure is dissolved in tetrahydrofuran (THF), be cooled to-30 DEG C, and to add concentration be wherein that the hexane solution 1.0mL of the n-Butyl Lithium of 1.0mol/L reacts 30 minutes, gained mixed solution is added dropwise in the tetrahydrofuran (THF) suspension of zinc dichloride, react 5 hours under room temperature, then drip amido potassium [KN (SiXMe wherein
2)
2], react removal of solvent under reduced pressure after 2 hours, add the extraction of 20mL toluene wherein, filter, filtrate is concentrated into 2mL, adds 1mL normal hexane, is put in recrystallization in-30 DEG C of refrigerators, separates out a large amount of white solid after 24 hours.Last separate solid also uses n-hexane twice, and vacuum-drying 2 hours, obtains assorted scorpion type Zn complex.
As X=H, the above-mentioned preparation method of the present embodiment obtains the assorted scorpion type Zn complex 7 with formula (V) structure, and its molecular formula is C
33h
43n
6pSi
2zn.After testing, productive rate is 77%, and in assorted scorpion type Zn complex 7, element mass percentage content is C:58.61%, H:6.41%, N:12.43%, Zn:9.67%.
As X=Me, the above-mentioned preparation method of the present embodiment obtains the assorted scorpion type Zn complex 8 with formula (V) structure, and its molecular formula is C
35h
47n
6pSi
2zn.After testing, productive rate is 66%, and in assorted scorpion type Zn complex 8, element mass percentage content is C:59.68%, H:6.73%, N:11.93%, Zn:9.28%.
Proton nmr spectra (C is carried out to the above-mentioned assorted scorpion type Zn complex 7 and 8 with formula (I) structure
6d
6, 400MHz) analyze, as shown in Figure 3 and Figure 4, Fig. 3 and Fig. 4 illustrates that the present embodiment successfully prepares assorted scorpion type Zn complex 7 and 8 respectively.
Embodiment 4
The assorted scorpion type Zn complex 9 ~ 12 of preparation
The process of the assorted scorpion type Zn complex 9 ~ 12 of the present embodiment preparation is as shown in reaction expression (VI):
Under anhydrous and oxygen-free condition, the assorted scorpion type part 0.001 mole with formula (II) structure is dissolved in tetrahydrofuran (THF), and add the KH solid reaction 30 minutes of 0.001 mole wherein, gained mixed solution is added dropwise in the tetrahydrofuran (THF) suspension of zinc dichloride, react 5 hours at 50 DEG C, then alkoxyl group sylvite is dripped wherein, react removal of solvent under reduced pressure after 2 hours, add the extraction of 20mL toluene wherein, filter, filtrate is concentrated into 2mL, adds 1mL normal hexane, be put in recrystallization in-30 DEG C of refrigerators, after 24 hours, separate out a large amount of white solid.Last separate solid also uses n-hexane twice, and vacuum-drying 2 hours, obtains assorted scorpion type Zn complex.
Work as R
3=CH
2during Ph, the above-mentioned preparation method of the present embodiment obtains the assorted scorpion type Zn complex 9 with formula VI structure, and its molecular formula is C
36h
36n
5oPZn.After testing, productive rate is 59%, and in assorted scorpion type Zn complex 9, element mass percentage content is C:66.41%, H:5.57%, N:10.76%, Zn:10.04%.
Work as R
3during=Me, the above-mentioned preparation method of the present embodiment obtains the assorted scorpion type Zn complex 10 with formula VI structure, and its molecular formula is C
30h
32n
5oPZn.After testing, productive rate is 67%, and in assorted scorpion type Zn complex 10, element mass percentage content is C:62.67%, H:5.61%, N:12.18%, Zn:11.37%.
Work as R
3=
iduring Pr, the above-mentioned preparation method of the present embodiment obtains the assorted scorpion type Zn complex 11 with formula VI structure, and its molecular formula is C
32h
36n
5oPZn.After testing, productive rate is 58%, and in assorted scorpion type Zn complex 11, element mass percentage content is C:63.74%, H:6.02%, N:11.61%, Zn:10.84%.
Work as R
3=
tduring Bu, the above-mentioned preparation method of the present embodiment obtains the assorted scorpion type Zn complex 12 with formula VI structure, and its molecular formula is C
33h
38n
5oPZn.After testing, productive rate is 67%, and in assorted scorpion type Zn complex 12, element mass percentage content is C:64.23%, H:6.21%, N:11.35%, Zn:10.60%.
Proton nmr spectra (C is carried out to the above-mentioned assorted scorpion type Zn complex 9 with formula (I) structure
6d
6, 400MHz) analyze, as shown in Figure 5, Fig. 5 illustrates that the present embodiment successfully prepares assorted scorpion type Zn complex 9.
In above-described embodiment, only the assorted scorpion type part with formula (II) structure need be replaced with R
1for hydrogen, ethyl, sec.-propyl or the tertiary butyl; R
2for the tertiary butyl; The assorted scorpion type Zn complex that Ar is 2,6-3,5-dimethylphenyl, 2,6-diethyl phenyl or 2,6-diisopropyl phenyl just can prepare corresponding construction, will not enumerate here.
The embodiment of poly(lactic acid) is prepared in the ring-opening polymerization of organic zinc composition catalyst catalysis rac-lactide:
Embodiment 5
In the 25mL polyreaction bottle through anhydrous and oxygen-free process, add 0.576g (4mmol) rac-lactide and 3mL tetrahydrofuran (THF), and polyreaction bottle is placed in 30 DEG C of oil bath pans; Take 13.7mg to mix scorpion type Zn complex 1 (20 μm of ol), dissolve with 2mL tetrahydrofuran (THF), gained solution is added in polyreaction bottle fast, and starts timing.React the ethanol termination reaction adding a little hcl acidifying after 10 hours, then pour reaction solution in ethanol sedimentation, be separated to obtain white polymer, nuclear-magnetism test transformation efficiency is 85%.
To poly(lactic acid) gpc analysis prepared by aforesaid method, its molecular weight M
n=2.17 ten thousand, M
w/ M
n=2.01.
Carrying out same core decoupling hydrogen spectrum analysis to above-mentioned poly(lactic acid), is 68% with content entirely.
Embodiment 6: replaced with title complex 2 by the title complex 1 used in embodiment 5, the reaction times extends to 36 hours, and in addition other conditions are identical, obtains higher isotactic polymer similarly to Example 5.
Embodiment 7: replaced with title complex 3 by the title complex 1 used in embodiment 5, the reaction times becomes 3 hours, and in addition other conditions are identical, obtains higher isotactic polymer similarly to Example 5.
Embodiment 8: replaced with title complex 4 by the title complex 1 used in embodiment 5, the reaction times becomes 3 hours, and in addition other conditions are identical, obtains higher isotactic polymer similarly to Example 5.
Embodiment 9: replaced with title complex 5 by the title complex 1 used in embodiment 5, the reaction times becomes 3 hours, and in addition other conditions are identical, obtains higher isotactic polymer similarly to Example 5.
Embodiment 10: replaced with title complex 6 by the title complex 1 used in embodiment 5, the reaction times becomes 3 hours, and in addition other conditions are identical, obtains higher isotactic polymer similarly to Example 5.
Embodiment 11
In the 25mL polyreaction bottle through anhydrous and oxygen-free process, add 0.576g (4mmol) rac-lactide and 3mL tetrahydrofuran (THF), and polyreaction bottle is placed in 30 DEG C of oil bath pans; Take 13.5mg to mix scorpion type Zn complex 7 (20 μm of ol), dissolve with 2mL tetrahydrofuran (THF), gained solution is added in polyreaction bottle fast, and starts timing.React the ethanol termination reaction adding a little hcl acidifying after 10 hours, then pour reaction solution in ethanol sedimentation, be separated to obtain white polymer, nuclear-magnetism test transformation efficiency is 91%.
To poly(lactic acid) gpc analysis prepared by aforesaid method, its molecular weight M
n=2.56 ten thousand, M
w/ M
n=1.98.
Carrying out same core decoupling hydrogen spectrum analysis to above-mentioned poly(lactic acid), is 74% with content entirely.
Embodiment 12: replaced with title complex 8 by the title complex 7 used in embodiment 11, the reaction times extends to 36 hours, and in addition other conditions are identical, obtains higher isotactic polymer similarly to Example 12.
Embodiment 13: replaced with title complex 9 by the title complex 7 used in embodiment 11, the reaction times becomes 3 hours, and in addition other conditions are identical, obtains higher isotactic polymer similarly to Example 12.
Embodiment 14: replaced with title complex 10 by the title complex 7 used in embodiment 11, the reaction times becomes 3 hours, and in addition other conditions are identical, obtains higher isotactic polymer similarly to Example 12.
Embodiment 15: replaced with title complex 11 by the title complex 7 used in embodiment 11, the reaction times becomes 3 hours, and in addition other conditions are identical, obtains higher isotactic polymer similarly to Example 12.
Embodiment 16: replaced with title complex 12 by the title complex 7 used in embodiment 11, the reaction times becomes 3 hours, and in addition other conditions are identical, obtains higher isotactic polymer similarly to Example 12.
Embodiment 17
In the 25mL polyreaction bottle through anhydrous and oxygen-free process, add 0.576g (4mmol) rac-lactide and 3mL toluene, and polyreaction bottle is placed in 30 DEG C of oil bath pans; Take 13.5mg to mix scorpion type Zn complex 7 (20 μm of ol), dissolve with 2mL toluene, gained solution is added in polyreaction bottle fast, and starts timing.React the ethanol termination reaction adding a little hcl acidifying after 8 hours, then pour reaction solution in ethanol sedimentation, be separated to obtain white polymer, nuclear-magnetism test transformation efficiency is 96%.
To poly(lactic acid) gpc analysis prepared by aforesaid method, its molecular weight M
n=5.10 ten thousand, M
w/ M
n=1.37.
Carry out same core decoupling hydrogen spectrum analysis to above-mentioned poly(lactic acid), as shown in Figure 6, as seen from the figure, the poly(lactic acid) that the embodiment of the present invention 17 prepares is 85% with content entirely.
Embodiment 18: by embodiment 17 use solvent replacement be benzene, the reaction times becomes 4 hours, and in addition other conditions are identical, obtains higher isotactic polymer similarly to Example 17.
Embodiment 19
In the 25mL polyreaction bottle through anhydrous and oxygen-free process, add 0.576g (4mmol) rac-lactide and 3mL tetrahydrofuran (THF), and polyreaction bottle is placed in 70 DEG C of oil bath pans; Take 13.5mg to mix scorpion type Zn complex 7 (20 μm of ol), dissolve with 2mL tetrahydrofuran (THF), gained solution is added in polyreaction bottle fast, and starts timing.React the ethanol termination reaction adding a little hcl acidifying after 1.5 hours, then pour reaction solution in ethanol sedimentation, be separated to obtain white polymer, nuclear-magnetism test transformation efficiency is 90%.
To poly(lactic acid) gpc analysis prepared by aforesaid method, its molecular weight M
n=2.85 ten thousand, M
w/ M
n=1.96.
Carrying out same core decoupling hydrogen spectrum analysis to above-mentioned poly(lactic acid), is 70% with content entirely.
Embodiment 20
In the 25mL polyreaction bottle through anhydrous and oxygen-free process, add 0.576g (4mmol) rac-lactide and 3mL tetrahydrofuran (THF), and polyreaction bottle is placed in 20 DEG C of oil bath pans; Take 13.0mg to mix scorpion type Zn complex 9 (20 μm of ol), dissolve with 2mL tetrahydrofuran (THF), gained solution is added in polyreaction bottle fast, and starts timing.React the ethanol termination reaction adding a little hcl acidifying after 4 hours, then pour reaction solution in ethanol sedimentation, be separated to obtain white polymer, nuclear-magnetism test transformation efficiency is 76%.
To poly(lactic acid) gpc analysis prepared by aforesaid method, its molecular weight M
n=2.42 ten thousand, M
w/ M
n=1.19.
Carrying out same core decoupling hydrogen spectrum analysis to above-mentioned poly(lactic acid), is 77% with content entirely.
Embodiment 21
In the 25mL polyreaction bottle through anhydrous and oxygen-free process, add 0.576g (4mmol) rac-lactide and 3mL tetrahydrofuran (THF), and polyreaction bottle is placed in 0 DEG C of ice-water bath; Take 13.0mg to mix scorpion type Zn complex 9 (20 μm of ol), dissolve with 2mL tetrahydrofuran (THF), gained solution is added in polyreaction bottle fast, and starts timing.React the ethanol termination reaction adding a little hcl acidifying after 15 hours, then pour reaction solution in ethanol sedimentation, be separated to obtain white polymer, nuclear-magnetism test transformation efficiency is 83%.
To poly(lactic acid) gpc analysis prepared by aforesaid method, its molecular weight M
n=2.47 ten thousand, M
w/ M
n=1.21.
Carrying out same core decoupling hydrogen spectrum analysis to above-mentioned poly(lactic acid), is 80% with content entirely.
Embodiment 22
In the 25mL polyreaction bottle through anhydrous and oxygen-free process, add 0.288g (2mmol) rac-lactide and 3mL tetrahydrofuran (THF), and polyreaction bottle is placed in 30 DEG C of oil bath pans; Take 13.0mg to mix scorpion type Zn complex 9 (20 μm of ol), dissolve with 2mL tetrahydrofuran (THF), gained solution is added in polyreaction bottle fast, and starts timing.React the ethanol termination reaction adding a little hcl acidifying after 3 hours, then pour reaction solution in ethanol sedimentation, be separated to obtain white polymer, nuclear-magnetism test transformation efficiency is 85%.
To poly(lactic acid) gpc analysis prepared by aforesaid method, its molecular weight M
n=1.35 ten thousand, M
w/ M
n=1.15.
Carrying out same core decoupling hydrogen spectrum analysis to above-mentioned poly(lactic acid), is 76% with content entirely.
Embodiment 23
In the 25mL polyreaction bottle through anhydrous and oxygen-free process, add 1.44g (10mmol) rac-lactide and 8mL tetrahydrofuran (THF), and polyreaction bottle is placed in 30 DEG C of oil bath pans; Take 13.0mg to mix scorpion type Zn complex 9 (20 μm of ol), dissolve with 2mL tetrahydrofuran (THF), gained solution is added in polyreaction bottle fast, and starts timing.React the ethanol termination reaction adding a little hcl acidifying after 8 hours, then pour reaction solution in ethanol sedimentation, be separated to obtain white polymer, nuclear-magnetism test transformation efficiency is 87%.
To poly(lactic acid) gpc analysis prepared by aforesaid method, its molecular weight M
n=6.41 ten thousand, M
w/ M
n=1.27.
Carrying out same core decoupling hydrogen spectrum analysis to above-mentioned poly(lactic acid), is 75% with content entirely.
Embodiment 24
In the 25mL polyreaction bottle through anhydrous and oxygen-free process, add 2.88g (20mmol) rac-lactide and 13mL tetrahydrofuran (THF), and polyreaction bottle is placed in 30 DEG C of oil bath pans; Take 13.0mg to mix scorpion type Zn complex 9 (20 μm of ol), dissolve with 2mL tetrahydrofuran (THF), gained solution is added in polyreaction bottle fast, and starts timing.React the ethanol termination reaction adding a little hcl acidifying after 10 hours, then pour reaction solution in ethanol sedimentation, be separated to obtain white polymer, nuclear-magnetism test transformation efficiency is 81%.
To poly(lactic acid) gpc analysis prepared by aforesaid method, its molecular weight M
n=12.09 ten thousand, M
w/ M
n=1.35.
Carrying out same core decoupling hydrogen spectrum analysis to above-mentioned poly(lactic acid), is 75% with content entirely.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among the protection domain of the invention.
Claims (8)
1. an organic zinc composition catalyst, is characterized in that, this catalyzer is the assorted scorpion type Zn complex with formula (I) structure;
Wherein, R
1for hydrogen, methyl, ethyl, sec.-propyl or the tertiary butyl;
R
2for the tertiary butyl, cyclohexyl or phenyl;
Ar is phenyl or the aryl containing C1 ~ C6 straight or branched alkane group;
R is C1 ~ C10 straight or branched alkoxyl group, C1 ~ C10 straight or branched alkylamino radical, two (dimethyl is silica-based) amido or two (trimethyl silicon based) amido.
2. organic zinc composition catalyst according to claim 1, is characterized in that, described R is methoxyl group, isopropoxy, tert.-butoxy or benzyloxy.
3. organic zinc composition catalyst according to claim 1, is characterized in that, described Ar is 2,6-3,5-dimethylphenyl, 2,6-diethyl phenyl or 2,6-diisopropyl phenyl.
4. organic zinc composition catalyst according to claim 1, is characterized in that, described catalyzer is any one in the assorted scorpion type Zn complex of following 1 ~ 12, wherein:
Assorted scorpion type organic zinc title complex 1:R
1=Me, R
2=Cy, R=N (SiHMe
2)
2;
Assorted scorpion type organic zinc title complex 2:R
1=Me, R
2=Cy, R=N (SiMe
3)
2;
Assorted scorpion type organic zinc title complex 3:R
1=Me, R
2=Cy, R=OCH
2ph;
Assorted scorpion type organic zinc title complex 4:R
1=Me, R
2=Cy, R=OMe;
Assorted scorpion type organic zinc title complex 5:R
1=Me, R
2=Cy, R=O
ipr;
Assorted scorpion type organic zinc title complex 6:R
1=Me, R
2=Cy, R=O
tbu;
Assorted scorpion type organic zinc title complex 7:R
1=Me, R
2=Ph, R=N (SiHMe
2)
2;
Assorted scorpion type organic zinc title complex 8:R
1=Me, R
2=Ph, R=N (SiMe
3)
2;
Assorted scorpion type organic zinc title complex 9:R
1=Me, R
2=Ph, R=OCH
2ph;
Assorted scorpion type organic zinc title complex 10:R
1=Me, R
2=Ph, R=OMe;
Assorted scorpion type organic zinc title complex 11:R
1=Me, R
2=Ph, R=O
ipr;
Assorted scorpion type organic zinc title complex 12:R
1=Me, R
2=Ph, R=O
tbu.
5. a method for making for organic zinc composition catalyst according to claim 1, is characterized in that, this method for making specifically comprises the following steps:
(1) under anhydrous and oxygen-free condition, the assorted scorpion type part with formula (II) structure is dissolved in tetrahydrofuran (THF) and is placed in-80 DEG C ~-30 DEG C, add normal hexane solution, KH or NaH that molar weight is the n-Butyl Lithium of 1 times amount, obtain the first reaction mixture;
(2) above-mentioned first reaction mixture and zinc dichloride are reacted, obtain the second reaction mixture;
(3) in above-mentioned second reaction mixture, add lithium salts containing R base or sylvite reacts, drain solvent, toluene extracts, and under low temperature, recrystallization obtains assorted scorpion type Zn complex;
Wherein, the R described in formula (II)
1for hydrogen, methyl, ethyl, sec.-propyl or the tertiary butyl; R
2for the tertiary butyl, cyclohexyl or phenyl; Ar is aryl or the aryl containing C1 ~ C6 straight or branched alkane group; Described R is C1 ~ C10 straight or branched alkoxyl group, C1 ~ C10 straight or branched alkylamino radical, two (dimethyl is silica-based) amido or two (trimethyl silicon based) amido.
6. application rights requires that the method for poly(lactic acid) is prepared in the organic zinc composition catalyst catalysis rac-lactide ring-opening polymerization described in 1, and the method specifically comprises the following steps:
Under the condition of anhydrous and oxygen-free, take rac-lactide and use organic solvent dissolution, then adding organic zinc composition catalyst, carrying out polyreaction at the katalysis racemization rac-Lactide of catalyzer, obtaining higher entirely with the poly(lactic acid) of content; The mol ratio of described rac-lactide and described organic zinc composition catalyst is (100 ~ 1000): 1; The temperature of described polyreaction is 0 DEG C ~ 70 DEG C; The time of described polyreaction is 1.5 ~ 36 hours.
7. method according to claim 6, is characterized in that, the zine ion volumetric molar concentration of described organic zinc composition catalyst is 0.001 ~ 0.01mol/L.
8. the method according to claim 6 or 7, is characterized in that, described organic solvent is benzene, toluene or tetrahydrofuran (THF).
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| CN102838734A (en) * | 2012-09-25 | 2012-12-26 | 中国科学院长春应用化学研究所 | Polylactic acid block polymer and preparation method thereof |
| CN103254220A (en) * | 2013-05-31 | 2013-08-21 | 中国科学院长春应用化学研究所 | Chiral zinc compound and preparation method thereof as well as preparation method of polylactic acid |
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| CN102838734A (en) * | 2012-09-25 | 2012-12-26 | 中国科学院长春应用化学研究所 | Polylactic acid block polymer and preparation method thereof |
| CN103254220A (en) * | 2013-05-31 | 2013-08-21 | 中国科学院长春应用化学研究所 | Chiral zinc compound and preparation method thereof as well as preparation method of polylactic acid |
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