CN105949082B - The divalent copper complex of N containing naphthol component, O- coordination, preparation method and applications - Google Patents
The divalent copper complex of N containing naphthol component, O- coordination, preparation method and applications Download PDFInfo
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
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- C08F4/50—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkaline earth metals, zinc, cadmium, mercury, copper or silver
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Abstract
The invention belongs to synthesising chemical technology field, the divalent copper complex of specially a kind of N containing naphthol component, O coordination, preparation method and applications.Schiff base intermediate is obtained by the reaction using 2 hydroxyl, 1 naphthaldehyde as starting material, by itself and a series of aromatic amine compounds in the present invention, then again with hydration copper acetate reaction to get the divalent copper complex being coordinated to corresponding N, O.Synthesis technology of the present invention is simple, has preferable selectivity and yield.The compounds of this invention there is higher catalytic activity, obtained polymer also to have higher molecular weight the polymerization of norbornene.
Description
Technical field
The invention belongs to synthesising chemical technology fields, and in particular to a series of cupric of N containing naphthol component, O- coordination
Complex, preparation method and applications.
Background technology
From late 1860s schiff bases have Schiff find and after gaining the name, it is flexible more because of its substituent group
Become, and the N atoms on hybridized orbit have lone pair electrons, make it have good coordination ability, it can be well with nitrogen, oxygen atom
It is coordinated, forms a series of different metal complex of performance structures with transition metal, these complexs are in three-dimensional
, magnetics, spectroscopy, Coordinative Chemistry, catalysis, analytical chemistry, agricultural and the fields such as photochromic suffer from important role.
The divalent copper complex of wherein N, O- coordination is the more one kind of research, it the advantages of be：(1) synthesis material be easy to get and price just
Preferably, there is good prospects for commercial application；(2) excellent characteristics has been showed in terms of being catalyzed norbornene polymerization,
Catalytic activity is higher than metallocene catalyst, and the molecular weight of obtained polymer and the degree of branching can regulate and control, and performance is stable, is easy to
Prepare etc..Therefore, it explores based on the N that schiff bases is ligand, the divalent copper complex and its synthetic method of O- coordinations are very must
It wants.
Invention content
For overcome the deficiencies in the prior art, it is an object of the invention to propose one kind N containing naphthol component, O- coordination
Divalent copper complex, preparation method and applications.Preparation method of the present invention is simple, and obtained divalent copper complex can be used for being catalyzed
In the polymerisation of norbornene.
The divalent copper complex of N provided by the invention containing naphthol component, O- coordination, has structure as follows：
Wherein：R is selected from H, 4-CN, 4-OMe, 4-iPr、4-CF3、2-CH3, 3-Br or 2,6-iIt is any in Pr.
The present invention also provides the above-mentioned N containing naphthol component, the preparation method of the divalent copper complex of O- coordinations, specific steps
It is as follows：
(1) using 2- hydroxyl-1-naphthalene Formaldehydes and aromatic amine compound as starting material, back flow reaction under the action of catalyst,
After reaction, a large amount of solids have been refrigerated to be precipitated, have been filtered, washing obtains Schiff base intermediate；Wherein：The aromatic amine compound
Structural formula such asIt is shown, wherein：The R is selected from H, 4-CN, 4-OMe, 4-iPr、4-CF3、2-CH3, 3-Br or 2,6-iAny one in Pr；
(2) Schiff base intermediate and copper acetate monohydrate are mixed in alcohols solvent, is stirred at reflux later, freezed
Night, filtering, washing, drying obtain target product.
In above-mentioned steps (1), the catalyst is glacial acetic acid.
In above-mentioned steps (1), the molar ratio of 2- hydroxyl-1-naphthalene Formaldehydes and aromatic amine compound is 2:1~3:1.
In above-mentioned steps (2), alcohols solvent is any one or more in methanol, ethyl alcohol or isopropanol.
In above-mentioned steps (2), the molar ratio of Schiff base intermediate and copper acetate monohydrate is 2:1~3:1.
The present invention also provides a kind of according to the above-mentioned N containing naphthol component, and the divalent copper complex of O- coordinations is dropped in catalysis
Application in the polymerisation of bornylene.During above application, using methylaluminoxane as co-catalyst.Preferably, have
Body application process is as follows：Under the conditions of anhydrous and oxygen-free, the N containing naphthol component is added into norbornene polymerization system, O- coordinations
The cupric of divalent copper complex, the toluene solution of methylaluminoxane, methylaluminoxane and the N containing naphthol component, O- coordination is matched
The molar ratio for closing object is 1000：1~4000：1,0~60 DEG C of reaction temperature, the reaction time is 15~60 minutes, uses volume ratio
The ethanol solution of 10% hydrochloric acid terminates reaction, and products therefrom is filtered, is washed for several times with ethyl alcohol, is dried under vacuum in 60~80 DEG C
Mass conservation.
The beneficial effects of the present invention are the divalent copper complex preparation sides of the N containing naphthol component in the present invention, O- coordination
Method is simple, selectivity and high income, and it has higher urge under mild conditions under the action of co-catalyst MAO
Change activity, obtained addition-type polymers also have higher molecular weight.
Description of the drawings
Fig. 1 is the mono-crystalline structures of compound 1.
Fig. 2 is the mono-crystalline structures of compound 5.
Specific implementation mode
The present invention is further specifically described below by embodiment, the present invention is not limited to the following examples.
In embodiment, the reaction equation of target compound is as follows：
Embodiment 1：The synthesis of the divalent copper complex 1 of N containing naphthol component, O- coordination
At ambient temperature, 2mmol schiff bases L1,1mmol copper acetate monohydrate is dissolved separately in proper amount of methanol, can used
Its ultrasonic-wave assisted dissolving, mixes, and solubilization liquid is to 50ml in there-necked flask.After being stirred at reflux 3h, freeze overnight, filtering are used in combination
A small amount of refrigerated methanol quick wash, drying obtain corresponding dark-brown product.Yield 82%.Fig. 1 is the monocrystalline knot of compound 1
Structure.
Elemental analysis：C34H24O2N2Cu:C 73.43,H 4.35,N 5.04,found:C 73.33,H 4.45,N
5.14.
Embodiment 2：The synthesis of the divalent copper complex 2 of N containing naphthol component, O- coordination
At ambient temperature, 2mmol schiff bases L2,1.5mmol copper acetate monohydrate is dissolved separately in proper amount of methanol, it can
With its ultrasonic-wave assisted dissolving, mixed in there-necked flask, and solubilization liquid is to 55ml.After being stirred at reflux 4h, freeze overnight has solid to go out
Existing, filtering is used in combination a small amount of refrigerated methanol quick wash, drying to obtain corresponding yellow product.Yield 74%.
Elemental analysis：C36H22O2N2F6Cu:C 71.36,H 3.66,N 9.24,found:C 71.28,H 3.53,N
9.44.
Embodiment 3：The synthesis of the divalent copper complex 3 of N containing naphthol component, O- coordination
At ambient temperature, 1mmol schiff bases L3,0.5mmol copper acetate monohydrate is dissolved separately in proper amount of methanol, it can
With its ultrasonic-wave assisted dissolving, mixed in there-necked flask, and solubilization liquid is to 30ml.After being stirred at reflux 3h, freeze overnight, filtering, and
With a small amount of refrigerated methanol quick wash, drying obtains corresponding brown product.Yield 85%.
Elemental analysis：C36H28O4N2Cu:C 70.17,H 4.58,N 4.55,found:C 70.30,H 4.35,N
4.45.
Embodiment 4：The synthesis of the divalent copper complex 4 of N containing naphthol component, O- coordination
At ambient temperature, 2mmol schiff bases L4,1.5mmol copper acetate monohydrate is dissolved separately in proper amount of methanol, it can
With its ultrasonic-wave assisted dissolving, mixed in there-necked flask, and solubilization liquid is to 60ml.After being stirred at reflux 6h, freeze overnight does not occur
Solid, concentrated by rotary evaporation, then a night is freezed, there is solid appearance, filter, a small amount of refrigerated methanol quick wash, drying is used in combination to obtain phase
Answer yellow product.Yield 78%.
Elemental analysis：C37H30N2Cu:C 78.49,H 5.34,N 4.95,found:C 78.53,H 5.45,N 4.87.
Embodiment 5：The synthesis of the divalent copper complex 5 of N containing naphthol component, O- coordination
At ambient temperature, 2mmol schiff bases L5,1mmol copper acetate monohydrate is dissolved separately in proper amount of methanol, can used
Its ultrasonic-wave assisted dissolving, mixes, and solubilization liquid is to 60ml in there-necked flask.After being stirred at reflux 6h, freeze overnight is not consolidated
Body, concentrated by rotary evaporation, then a night is freezed, there is solid appearance, filter, a small amount of refrigerated methanol quick wash, drying is used in combination to obtain corresponding
Yellow product.Yield 79%.Fig. 2 is the mono-crystalline structures of compound 5.
Elemental analysis：C36H22O2N2F6Cu:C 62.47,H 3.20,N 4.05,found:C 62.42,H 3.15,N
4.16.
Embodiment 6：The synthesis of the divalent copper complex 6 of N containing naphthol component, O- coordination
At ambient temperature, 2mmol schiff bases L6,1mmol copper acetate monohydrate is dissolved separately in proper amount of methanol, can used
Its ultrasonic-wave assisted dissolving, mixes, and solubilization liquid is to 60ml in there-necked flask.After being stirred at reflux 6h, freeze overnight is not consolidated
Body, concentrated by rotary evaporation, then a night is freezed, there is solid appearance, filter, a small amount of refrigerated methanol quick wash, drying is used in combination to obtain corresponding
Yellow product.Yield 89%.
Elemental analysis：C35H26N2Cu:C 78.12,H 4.87,N 5.21,found:C 78.24,H 4.69,N 5.29.
Embodiment 7：The synthesis of the divalent copper complex 7 of N containing naphthol component, O- coordination
At ambient temperature, 2mmol schiff bases L7,1.5mmol copper acetate monohydrate is dissolved separately in proper amount of methanol, it can
With its ultrasonic-wave assisted dissolving, mixed in there-necked flask, and solubilization liquid is to 60ml.After being stirred at reflux 6h, freeze overnight does not occur
Solid, concentrated by rotary evaporation, then a night is freezed, there is solid appearance, filter, a small amount of refrigerated methanol quick wash, drying is used in combination to obtain phase
Answer yellow product.Yield 74%.
Elemental analysis：C34H22O2N2Br2Cu:C 57.20,H.3.11,N 3.92,found:C 57.29,H 3.18,N
3.97.
Embodiment 8：The synthesis of the divalent copper complex 8 of N containing naphthol component, O- coordination
At ambient temperature, 6mmol schiff bases L8,4mmol copper acetate monohydrate is dissolved separately in proper amount of methanol, can used
Its ultrasonic-wave assisted dissolving, mixes, and solubilization liquid is to 60ml in there-necked flask.After being stirred at reflux 12h, freeze overnight does not occur
Solid, concentrated by rotary evaporation, then a night is freezed, there is solid appearance, filter, a small amount of refrigerated methanol quick wash, drying is used in combination to obtain phase
Answer khaki product.Yield 69%.
Elemental analysis：C40H36O2N2Cu:C 75.04,H 5.67,N 4.38,found:C 75.14,H 5.59,N
4.43.
Embodiment 9：It is catalyzed norbornene polymerization reaction
Norbornene polymerization reaction is catalyzed using catalyst 1 prepared by embodiment 1, norbornene polymerization is in anhydrous and oxygen-free item
It is carried out under part.Ns of the 5mL containing naphthol component, the chlorobenzene solution of the divalent copper complex 1 of O- coordinations are sequentially added in the reaction system
(1.5 μm of ol), the toluene solution 2.63mL (1300 μm of ol) of MAO, the ratio between 1 and the amount of substance of MAO are 1:867, reaction temperature
35 degree, after reacting 25 minutes, reaction is terminated with containing the ethanol solution that volume ratio is 11% hydrochloric acid, products therefrom is filtered, second is used
Alcohol washs for several times, and mass conservation is dried under vacuum in 60~80 degree.Activity is 2.98 × 106gPNB mol–1Cu h–1, molecular weight is
3.58×106g mol–1, polymerization methods are add-on type polymerization.
Embodiment 10 is catalyzed norbornene polymerization reaction
Norbornene polymerization reaction is catalyzed using catalyst 1 prepared by embodiment 1, norbornene polymerization is in anhydrous and oxygen-free item
It is carried out under part.Ns of the 6mL containing naphthol component, the chlorine of 1 catalyst of divalent copper complex of O- coordinations are sequentially added in the reaction system
Benzole soln (0.6 μm of ol), the toluene solution 1mL (1800 μm of ol) of MAO, the ratio between 1 and the amount of substance of MAO are 1:3000, reaction
30 degree of temperature after reacting 15 minutes, terminates reaction with containing the ethanol solution that volume ratio is 14% hydrochloric acid, products therefrom is filtered,
It is washed for several times with ethyl alcohol, mass conservation is dried under vacuum in 60~80 degree.Activity is 2.61 × 106gPNB mol–1Cu h–1, molecule
Amount is 2.25 × 106g mol–1, polymerization methods are add-on type polymerization.
Embodiment 11：It is catalyzed norbornene polymerization reaction
Norbornene polymerization reaction is catalyzed using catalyst 2 prepared by embodiment 2, norbornene polymerization is in anhydrous and oxygen-free item
It is carried out under part.Ns of the 7mL containing naphthol component, the chlorine of 2 catalyst of divalent copper complex of O- coordinations are sequentially added in the reaction system
Benzole soln (0.7 μm of ol), the toluene solution 1.75mL (2800 μm of ol) of MAO, the ratio between 2 and the amount of substance of MAO are 1:4000, instead
30 degree of temperature is answered, reaction terminates reaction after forty minutes, with containing the ethanol solution that volume ratio is 10% hydrochloric acid, by products therefrom mistake
Filter, is washed for several times with ethyl alcohol, mass conservation is dried under vacuum in 60~80 degree.Activity is 3.54 × 106gPNB mol–1Cu h–1,
Molecular weight is 4.61 × 106g mol–1, polymerization methods are add-on type polymerization.
Embodiment 12：It is catalyzed norbornene polymerization reaction
Norbornene polymerization reaction is catalyzed using catalyst 3 prepared by embodiment 3, norbornene polymerization is in anhydrous and oxygen-free item
It is carried out under part.Ns of the 10mL containing naphthol component is sequentially added in the reaction system, 3 catalyst of divalent copper complex of O- coordinations
Chlorobenzene solution (1.0 μm of ol), the toluene solution 1.88mL (3000 μm of ol) of MAO, the ratio between 3 and the amount of substance of MAO are 1:3000,
30 degree of reaction temperature after reacting 15 minutes, terminates reaction, by products therefrom mistake with containing the ethanol solution that volume ratio is 10% hydrochloric acid
Filter, is washed for several times with ethyl alcohol, mass conservation is dried under vacuum in 60~80 degree.Activity is 1.88 × 106gPNB mol–1Cu h–1,
Molecular weight is 2.79 × 106g mol–1, polymerization methods are add-on type polymerization.
Embodiment 13：It is catalyzed norbornene polymerization reaction
Norbornene polymerization reaction is catalyzed using catalyst 4 prepared by embodiment 4, norbornene polymerization is in anhydrous and oxygen-free item
It is carried out under part.Ns of the 5mL containing naphthol component, the chlorine of 4 catalyst of divalent copper complex of O- coordinations are sequentially added in the reaction system
Benzole soln (0.8 μm of ol), the toluene solution 0.94mL (1500 μm of ol) of MAO, the ratio between 4 and the amount of substance of MAO are 1:3500, instead
10 degree of temperature is answered, after reacting 45 minutes, reaction is terminated with containing the ethanol solution that volume ratio is 10% hydrochloric acid, by products therefrom mistake
Filter, is washed for several times with ethyl alcohol, mass conservation is dried under vacuum in 60~80 degree.Activity is 3.84 × 106gPNB mol–1Cu h–1,
Molecular weight is 2.72 × 106g mol–1, polymerization methods are add-on type polymerization.
Embodiment 14：It is catalyzed norbornene polymerization reaction
Norbornene polymerization reaction is catalyzed using catalyst 5 prepared by embodiment 5, norbornene polymerization is in anhydrous and oxygen-free item
It is carried out under part.Ns of the 3mL containing naphthol component, the chlorine of 5 catalyst of divalent copper complex of O- coordinations are sequentially added in the reaction system
Benzole soln (0.4 μm of ol), the toluene solution 0.94mL (200 μm of ol) of MAO, the ratio between 5 and the amount of substance of MAO are 1:500, reaction
60 degree of temperature after reacting 25 minutes, terminates reaction with containing the ethanol solution that volume ratio is 10% hydrochloric acid, products therefrom is filtered,
It is washed for several times with ethyl alcohol, mass conservation is dried under vacuum in 60~80 degree.Activity is 1.93 × 106gPNB mol–1Cu h–1, molecule
Amount is 2.90 × 106g mol–1, polymerization methods are add-on type polymerization.
Embodiment 15：It is catalyzed norbornene polymerization reaction
Norbornene polymerization reaction is catalyzed using catalyst 6 prepared by embodiment 6, norbornene polymerization is in anhydrous and oxygen-free item
It is carried out under part.Ns of the 5mL containing naphthol component, the chlorine of 6 catalyst of divalent copper complex of O- coordinations are sequentially added in the reaction system
Benzole soln (0.5 μm of ol), the toluene solution 1.32mL (500 μm of ol) of MAO, the ratio between 6 and the amount of substance of MAO are 1:1000, instead
35 degree of temperature is answered, reaction terminates reaction after twenty minutes, with containing the ethanol solution that volume ratio is 10% hydrochloric acid, by products therefrom mistake
Filter, is washed for several times with ethyl alcohol, mass conservation is dried under vacuum in 60~80 degree.Activity is 1.96 × 106gPNB mol–1Cu h–1,
Molecular weight is 2.83 × 106g mol–1, polymerization methods are add-on type polymerization.
Embodiment 16：It is catalyzed norbornene polymerization reaction
Norbornene polymerization reaction is catalyzed using catalyst 7 prepared by embodiment 7, norbornene polymerization is in anhydrous and oxygen-free item
It is carried out under part.Ns of the 4mL containing naphthol component, the chlorine of 7 catalyst of divalent copper complex of O- coordinations are sequentially added in the reaction system
Benzole soln (0.2 μm of ol), the toluene solution 0.63mL (1000 μm of ol) of MAO, the ratio between 7 and the amount of substance of MAO are 1:5000, instead
30 degree of temperature is answered, reaction terminates reaction after twenty minutes, with containing the ethanol solution that volume ratio is 10% hydrochloric acid, by products therefrom mistake
Filter, is washed for several times with ethyl alcohol, mass conservation is dried under vacuum in 60~80 degree.Activity is 2.64 × 106gPNB mol–1Cu h–1,
Molecular weight is 3.53 × 106g mol–1, polymerization methods are add-on type polymerization.
Embodiment 17：It is catalyzed norbornene polymerization reaction
Norbornene polymerization reaction is catalyzed using catalyst 8 prepared by embodiment 8, norbornene polymerization is in anhydrous and oxygen-free item
It is carried out under part.Ns of the 5mL containing naphthol component, the chlorine of 8 catalyst of divalent copper complex of O- coordinations are sequentially added in the reaction system
Benzole soln (0.5 μm of ol), the toluene solution 1mL (1000 μm of ol) of MAO, the ratio between 8 and the amount of substance of MAO are 1:2000, reaction
30 degree of temperature after reacting 25 minutes, terminates reaction with containing the ethanol solution that volume ratio is 10% hydrochloric acid, products therefrom is filtered,
It is washed for several times with ethyl alcohol, mass conservation is dried under vacuum in 60~80 degree.Activity is 2.19 × 106gPNB mol–1Cu h–1, molecule
Amount is 2.10 × 106g mol–1, polymerization methods are add-on type polymerization.
Embodiment 18：It is catalyzed norbornene polymerization reaction
Norbornene polymerization reaction is catalyzed using catalyst 8 prepared by embodiment 8, norbornene polymerization is in anhydrous and oxygen-free item
It is carried out under part.Ns of the 7mL containing naphthol component, the chlorine of 8 catalyst of divalent copper complex of O- coordinations are sequentially added in the reaction system
Benzole soln (0.5 μm of ol), the toluene solution 2mL (2000 μm of ol) of MAO, the ratio between 8 and the amount of substance of MAO are 1:4000, reaction
25 degree of temperature after reacting 25 minutes, terminates reaction with containing the ethanol solution that volume ratio is 10% hydrochloric acid, products therefrom is filtered,
It is washed for several times with ethyl alcohol, mass conservation is dried under vacuum in 60~80 degree.Activity is 3.36 × 106gPNB mol–1Cu h–1, molecule
Amount is 2.77 × 106g mol–1, polymerization methods are add-on type polymerization.
Claims (9)
1. the divalent copper complex of the N containing naphthol component, O- coordination, which is characterized in that the divalent copper complex has following institute
Show structure：
Wherein：R is selected from 4-CN, 4-iPr、4-CF3Or it is any in 3-Br.
2. a kind of preparation method of the divalent copper complex of N according to claim 1 containing naphthol component, O- coordination, tool
Steps are as follows for body：
(1) using 2- hydroxyl-1-naphthalene Formaldehydes and aromatic amine compound as starting material, back flow reaction, reacts under the action of catalyst
After, it has been refrigerated to a large amount of solids and has been precipitated, filtered, washing obtains Schiff base intermediate；Wherein：The knot of the aromatic amine compound
Structure formula is such asIt is shown, wherein：The R is selected from 4-CN, 4-iPr、4-CF3Or it is any in 3-Br.
(2) Schiff base intermediate and copper acetate monohydrate are mixed in alcohols solvent, is stirred at reflux later, freeze overnight, mistake
Filter, washing, drying obtain target product.
3. preparation method according to claim 2, which is characterized in that in step (1), the catalyst is glacial acetic acid.
4. preparation method according to claim 2, which is characterized in that in step (1), 2- hydroxyl-1-naphthalene Formaldehydes and arylamine
The molar ratio of compound is 2:1~3:1.
5. preparation method according to claim 2, which is characterized in that in step (2), alcohols solvent is selected from methanol, ethyl alcohol
Or it is any one or more in isopropanol.
6. preparation method according to claim 2, which is characterized in that in step (2), Schiff base intermediate and a hydration vinegar
The molar ratio of sour copper is 2:1~3:1.
7. the divalent copper complex of a kind of N according to claim 1 containing naphthol component, O- coordination is in catalysis norbornene
Polymerisation in application.
8. the use as claimed in claim 7, which is characterized in that in application process, using methylaluminoxane as co-catalyst.
9. the use as claimed in claim 7, which is characterized in that concrete application method is as follows：Under the conditions of anhydrous and oxygen-free, Xiang Jiangbing
The N containing naphthol component, the divalent copper complex of O- coordinations, the toluene solution of methylaluminoxane, first are added in piece alkene polymerization system
Base aikyiaiurnirsoxan beta and the molar ratio of the divalent copper complex of the N containing naphthol component, O- coordination are 1000：1~4000：1, reaction temperature
0~60 DEG C, the reaction time is 15~60 minutes, reaction is terminated with the ethanol solution of 10% hydrochloric acid of volume ratio, by products therefrom mistake
Filter, is washed for several times with ethyl alcohol, mass conservation is dried under vacuum in 60~80 DEG C.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1388139A (en) * | 2002-07-19 | 2003-01-01 | 中国科学院化学研究所 | Norbornene polymerization catalyst system and its preparing process |
| US20120193570A1 (en) * | 2011-01-31 | 2012-08-02 | Denso Corporation | Heat storage material and heat utilization system using the same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1388139A (en) * | 2002-07-19 | 2003-01-01 | 中国科学院化学研究所 | Norbornene polymerization catalyst system and its preparing process |
| US20120193570A1 (en) * | 2011-01-31 | 2012-08-02 | Denso Corporation | Heat storage material and heat utilization system using the same |
Non-Patent Citations (3)
| Title |
|---|
| 2-羟基-1-萘醛亚胺镍配合物的合成、结构和降冰片烯均聚催化;常飞;《中国优秀硕士论文全文数据库，工程科技I辑》;20041215(第04期);第B014-328页 * |
| Synthesis, structures, spectral and electrochemical properties of copper(II) complexes of sterically hindered Schiff base ligands;Karuppasamy Sundaravel等;《Inorganica Chimica Acta》;20080325;第362卷;第199-207页 * |
| 无;无;《STN REGISTRY数据库》;20110613 * |
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