CN101659679B - Organic molybdenum complex compound and application thereof - Google Patents
Organic molybdenum complex compound and application thereof Download PDFInfo
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- CN101659679B CN101659679B CN2009103080721A CN200910308072A CN101659679B CN 101659679 B CN101659679 B CN 101659679B CN 2009103080721 A CN2009103080721 A CN 2009103080721A CN 200910308072 A CN200910308072 A CN 200910308072A CN 101659679 B CN101659679 B CN 101659679B
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Abstract
The invention discloses an organic molybdenum complex compound; organic ligand containing nitrogen group elements can be adopted to be matched with molybdenum to form metal organic compound, wherein the organic ligand includes triphenyl phosphine or alkyl-substituted derivative of the triphenyl phosphine, triphenyl phosphine oxide or alkyl-substituted derivative of the triphenyl phosphine oxide, triphenyl amine or alkyl-substituted derivative of the triphenyl amine, triphenyl amine oxide or alkyl-substituted derivative of the triphenyl amine oxide, triphenyl arsine or alkyl-substituted derivative of the triphenyl arsine, and triphenyl arsine oxide or alkyl-substituted derivative of the triphenyl arsine oxide. Meanwhile, the invention further discloses a preparation method of the organic molybdenum complex compound and the application of taking the organic molybdenum complex compound as catalyst in synthesizing poly-dicyclo-pentadiene. The organic molybdenum complex compound has higher chemical stability, is not sensitive for air and water vapor, can be taken as the catalyst to be applied in synthesizing the poly-dicyclo-pentadiene with higher catalytic activity, reduces the reaction conditions required by synthesizing the poly-dicyclo-pentadiene due to the chemical stability, and has good popularization and application prospects.
Description
Technical field
The present invention relates to a kind of organometallics, particularly a kind of organic molybdenum complex compound relates to a kind of preparation method of this organic molybdenum complex compound simultaneously, also relates to the application of a kind of this organic molybdenum complex compound in synthetic polydicyclopentadiene.
Background technology
Dicyclopentadiene (DCPD) can obtain a kind of cross-linked thermal set polydicyclopentadiene (PDCPD) plastics by ring opening metathesis polymerization.These plastics have characteristics such as good thermotolerance, creep resistance, dimensional stability, erosion resistance.Reaction injection moulding (RIM) technology is adopted in the production of PDCPD, this technology has superior characteristics such as shaping speed is fast, processing temperature is low, injection pressure is low, can be used for making the large-scale product of thin-walled of various high-performance complicated shapes, as the bumper in the transportation, backplate, side plate, engine shield and bodyshell etc.; The housing of large electric equipment such as the electric motor in the electric installation, air conditioning machinery; The member of the snowmobile in the sports equipment, surfboard, golf cart and agricultural machine, civil construction material etc., so polydicyclopentadiene is a kind of high performance material of widespread use.
Catalyzer is the key of producing dicyclopentadiene material, uses catalyzer to have the carbone catalyst of aryloxy tungsten complex or ruthenium and osmium to be Primary Catalysts at present.The former prepares easily, and cost is low, is promotor with aluminum alkyls when using, but responsive to air and water to steam ratio, makes that the synthesis condition of polydicyclopentadiene is comparatively harsh; The latter is more stable, but price is higher, is difficult to apply.
Summary of the invention
The organic molybdenum complex compound that the purpose of this invention is to provide a kind of stable in properties.
Another object of the present invention provides a kind of preparation method of organic molybdenum complex compound.
Another object of the present invention provides a kind of organic molybdenum complex compound as the application of catalyzer in synthetic polydicyclopentadiene.
In order to realize above purpose, the technical scheme that organic molybdenum complex compound of the present invention adopted is: a kind of organic molybdenum complex compound has following general formula:
MoO
2[O
yL(PhR
n)
3]
2Cl
2 (I)
In the formula (I):
L is selected from N, P or As;
R is ortho position or a para-orienting group on the phenyl, is selected from hydrogen atom or C
1-10The straight or branched alkyl substituent;
Y is 0 or 1;
N is 1 or 2;
Described R is selected from ethyl, propyl group, butyl, sec.-propyl, isobutyl-, the tertiary butyl, isopentyl, amyl group, octyl group or decyl.
The preparation method of organic molybdenum complex compound of the present invention is: comprise the steps:
1) with adding concentrated hydrochloric acid to dissolving fully under molybdic acid and 40-80 ℃ of condition, obtains the hydrochloric acid soln of molybdic acid;
2) doubly measure part adding organic solvent according to step 1) molybdic acid mole number 2-5 and be made into ligand solution, under agitation in the hydrochloric acid soln of the molybdic acid that this ligand solution adding step 1) is obtained, produce precipitation, continued again stirring reaction 2-6 hour, filter, filter cake with acetone and ether washing, obtains organic molybdenum complex compound respectively after the drying;
Step 2) described part is triphenylphosphine or its alkyl-substituted derivative, triphenylphosphine oxide or its alkyl-substituted derivative, triphenylamine or its alkyl-substituted derivative, triphenyl amine oxide or its alkyl-substituted derivative, triphenylarsine or its alkyl-substituted derivative or triphenyl arsenoxide or its alkyl-substituted derivative.
Step 2) described part has following general formula:
O
yL(PhR
n)
3 (II)
In the formula (II):
L is selected from N, P or As;
R is ortho position or a para-orienting group on the phenyl, is selected from hydrogen atom or C
1-10The straight or branched alkyl substituent;
Y is 0 or 1;
N is 1 or 2.
Step 2) described organic solvent is ethanol, ether or acetone.
Step 2) concentration of described ligand solution is 0.1-0.3g/ml.
Step 2) described drying temperature is 50-80 ℃.
O among formula (I), (II)
yL (PhR
n)
3For containing the organic ligand of nitrogen group element, with the center molybdenum ion coordination of complex compound, wherein L represents nitrogen group element, is selected from N, P or As, and when y is 0, when R was hydrogen atom, organic ligand was triphenylphosphine, triphenylamine, triphenylarsine; When y is 1, when R was hydrogen atom, organic ligand was triphenylphosphine oxide, triphenyl amine oxide, triphenyl arsenoxide; R can also be for being connected the C on the phenyl
1-10The straight or branched alkyl substituent, this alkyl substituent is connected the ortho position or the contraposition of phenyl, make organic ligand become corresponding alkyl-substituted derivative, R is selected from ethyl, propyl group, sec.-propyl, normal-butyl, sec.-propyl, the tertiary butyl, amyl group, isopentyl, n-octyl or decyl; N is the number of alkyl substituent.
Being applied as of organic molybdenum complex compound of the present invention: a kind of organic molybdenum complex compound is as the application of catalyzer in synthetic polydicyclopentadiene.
The method of the synthetic polydicyclopentadiene of organic molybdenum complex compound catalysis is: it is in 50-80 ℃ the dicyclopentadiene that organic molybdenum complex compound is added temperature as catalyzer, the mol ratio of catalyzer and dicyclopentadiene is 1: 1000-3000, under agitation add alkyl aluminum chloride then, system curing obtains polydicyclopentadiene, and the mol ratio of described catalyzer and alkyl aluminum chloride is 1: 15-40.
Described alkyl aluminum chloride has following general formula:
AlR′
xCl
3-x (III)
R ' is ethyl, normal-butyl or isobutyl-in the formula (III), and x is 1 or 2.
Organic molybdenum complex compound of the present invention is under the effect of nitrogen group element organic ligand, has higher chemical stability, insensitive to air and steam, and in synthetic polydicyclopentadiene, has advantages of high catalytic activity as catalyzer, its chemical stability that has has reduced the reaction conditions of synthetic polydicyclopentadiene simultaneously, and it is lower to prepare the cost of material that organic molybdenum complex compound of the present invention adopts, the preparation method is simple, therefore the cost of preparation is lower, has good popularizing application prospect.
Embodiment
Embodiment 1
The organic molybdenum complex compound of present embodiment is [MoO
2(NPh
3)
2] Cl
2
The preparation method of the organic molybdenum complex compound of present embodiment is as follows:
Take by weighing the molybdic acid (H of 6g
2MoO
4), under constantly stirring, adding concentrated hydrochloric acid 21ml in 50 ℃, elevated temperature is cooled to 40 ℃ after being back to clarification, obtains the hydrochloric acid soln of molybdic acid;
Take by weighing triphenylamine 18.15g, after adding 181ml ethanol stirring and dissolving, under vigorous stirring, slowly be added drop-wise in the hydrochloric acid soln of above-mentioned 40 ℃ molybdic acid, there is precipitation to generate, continue then to stir 6 hours, filter cake washing with acetone three times behind the precipitation suction filtration with ether washing three times, obtained organic molybdenum complex compound 17.4g with the filter cake after the washing in 8 hours in 50 ℃ of vacuum-dryings again.
Embodiment 2
The organic molybdenum complex compound of present embodiment is { MoO
2[N (PhC
4H
9)
3]
2Cl
2
The preparation method of the organic molybdenum complex compound of present embodiment is as follows:
Take by weighing the molybdic acid (H of 6g
2MoO
4), under constantly stirring, adding concentrated hydrochloric acid 21ml in 40 ℃, elevated temperature is cooled to 40 ℃ after being back to clarification, obtains the hydrochloric acid soln of molybdic acid;
Take by weighing three (4-n-butylphenyl) amine 24.6g, after adding 126ml ethanol stirring and dissolving, under vigorous stirring, slowly be added drop-wise in the hydrochloric acid soln of above-mentioned 40 ℃ molybdic acid, there is precipitation to generate, continue then to stir 6 hours, filter cake washing with acetone three times behind the precipitation suction filtration with ether washing three times, obtained organic molybdenum complex compound 23.3g with the filter cake after the washing in 8 hours in 60 ℃ of vacuum-dryings again.
Embodiment 3
The organic molybdenum complex compound of present embodiment is [MoO
2(PPh
3)
2] Cl
2
The preparation method of the organic molybdenum complex compound of present embodiment is as follows:
Take by weighing the molybdic acid (H of 6g
2MoO
4), under constantly stirring, adding concentrated hydrochloric acid 21ml in 80 ℃, elevated temperature is cooled to 40 ℃ after being back to clarification, obtains the hydrochloric acid soln of molybdic acid;
Take by weighing triphenylphosphine 19.43g, after adding 65ml ethanol stirring and dissolving, under vigorous stirring, slowly be added drop-wise in the hydrochloric acid soln of above-mentioned 40 ℃ molybdic acid, there is precipitation to generate, continue then to stir 5 hours, filter cake washing with acetone three times behind the precipitation suction filtration with ether washing three times, obtained organic molybdenum complex compound 22.1g with the filter cake after the washing in 8 hours in 80 ℃ of vacuum-dryings again.
Embodiment 4
The organic molybdenum complex compound of present embodiment is { MoO
2[P (PhC
2H
5)
3]
2Cl
2
The preparation method of the organic molybdenum complex compound of present embodiment is as follows:
Take by weighing the molybdic acid (H of 10g
2MoO
4), under constantly stirring, adding concentrated hydrochloric acid 36ml in 40 ℃, elevated temperature is cooled to 40 ℃ after being back to clarification, obtains the hydrochloric acid soln of molybdic acid;
Take by weighing three (2-ethylphenyl) phosphine 64.71g, after adding 216ml ethanol stirring and dissolving, under vigorous stirring, slowly be added drop-wise in the hydrochloric acid soln of above-mentioned 40 ℃ molybdic acid, there is precipitation to generate, continue then to stir 2 hours, filter cake washing with acetone three times behind the precipitation suction filtration with ether washing three times, obtained organic molybdenum complex compound 59.21g with the filter cake after the washing in 8 hours in 50 ℃ of vacuum-dryings again.
Embodiment 5
The organic molybdenum complex compound of present embodiment is [MoO
2(OPPh
3)
2] Cl
2
The preparation method of the organic molybdenum complex compound of present embodiment is as follows:
Take by weighing the molybdic acid (H of 15g
2MoO
4), under constantly stirring, adding concentrated hydrochloric acid 54ml in 50 ℃, elevated temperature is cooled to 40 ℃ after being back to clarification, obtains the hydrochloric acid soln of molybdic acid;
Take by weighing triphenylphosphine oxide 128.88g, after adding 430ml ethanol stirring and dissolving, under vigorous stirring, slowly be added drop-wise in the hydrochloric acid soln of above-mentioned 40 ℃ molybdic acid, there is precipitation to generate, continue then to stir 4 hours, filter cake washing with acetone three times behind the precipitation suction filtration with ether washing three times, obtained organic molybdenum complex compound 98.5g with the filter cake after the washing in 8 hours in 80 ℃ of vacuum-dryings again.
Embodiment 6
The organic molybdenum complex compound of present embodiment is { MoO
2{ OP[Ph (C
2H
5)
2]
3}
2Cl
2
The preparation method of the organic molybdenum complex compound of present embodiment is as follows:
Take by weighing the molybdic acid (H of 15g
2MoO
4), under constantly stirring, adding concentrated hydrochloric acid 54ml in 60 ℃, elevated temperature is cooled to 40 ℃ after being back to clarification, obtains the hydrochloric acid soln of molybdic acid;
(2,4-diethyl phenyl) the phosphine oxide 101.5g that takes by weighing three, after adding 338ml ethanol stirring and dissolving, under vigorous stirring, slowly be added drop-wise in the hydrochloric acid soln of above-mentioned 40 ℃ molybdic acid, there is precipitation to generate, continue then to stir 6 hours, filter cake washing with acetone three times behind the precipitation suction filtration with ether washing three times, obtained organic molybdenum complex compound 98.5g with the filter cake after the washing in 8 hours in 70 ℃ of vacuum-dryings again.
Embodiment 7
The organic molybdenum complex compound of present embodiment is [MoO
2(AsPh
3)
2] Cl
2
The preparation method of the organic molybdenum complex compound of present embodiment is as follows:
Take by weighing the molybdic acid (H of 6g
2MoO
4), under constantly stirring, adding concentrated hydrochloric acid 21ml in 70 ℃, elevated temperature is cooled to 40 ℃ after being back to clarification, obtains the hydrochloric acid soln of molybdic acid;
Take by weighing triphenylarsine 22.67g, after adding 76ml ethanol stirring and dissolving, under vigorous stirring, slowly be added drop-wise in the hydrochloric acid soln of above-mentioned 40 ℃ molybdic acid, there is precipitation to generate, continue then to stir 3 hours, filter cake washing with acetone three times behind the precipitation suction filtration with ether washing three times, obtained organic molybdenum complex compound 18.13g with the filter cake after the washing in 8 hours in 50 ℃ of vacuum-dryings again.
Embodiment 8
The organic molybdenum complex compound of present embodiment is { MoO
2[OAs (PhC
2H
5)
3]
2Cl
2
The preparation method of the organic molybdenum complex compound of present embodiment is as follows:
Take by weighing the molybdic acid (H of 6g
2MoO
4), under constantly stirring, adding concentrated hydrochloric acid 21ml in 50 ℃, elevated temperature is cooled to 40 ℃ after being back to clarification, obtains the hydrochloric acid soln of molybdic acid;
Take by weighing three (4-ethylphenyl) arsenoxide 29.12g, after adding 97ml ethanol stirring and dissolving, under vigorous stirring, slowly be added drop-wise in the hydrochloric acid soln of above-mentioned 40 ℃ molybdic acid, there is precipitation to generate, continue then to stir 6 hours, filter cake washing with acetone three times behind the precipitation suction filtration with ether washing three times, obtained organic molybdenum complex compound 24.75g with the filter cake after the washing in 8 hours in 60 ℃ of vacuum-dryings again.
Embodiment 9
Present embodiment as catalyzer, carries out the compound experiment of polydicyclopentadiene with the foregoing description 1-8 prepared organic molybdenum complex, and its synthetic method is as follows:
In the dry reaction container of 100ml, add dicyclopentadiene (DCPD) 20ml, add catalyzer according to catalyzer and dicyclopentadiene mol ratio 1/1000-3000, reaction vessel carries out being warming up to 50-80 ℃ after the pump drainage displacement with nitrogen, 15-40 according to the catalyzer mole number extraordinarily goes into diethyl aluminum chloride, solidified in 3-12 minute, and obtained the polymer poly dicyclopentadiene.The concrete synthesis condition that adopts sees Table 1.
The synthesis condition of table 1 polydicyclopentadiene and polymer properties parameter
| Embodiment | DCPD/ catalyzer (mol ratio) | Catalyzer/alkyl aluminum chloride (mol ratio) | Temperature of reaction (℃) | Set time (minute) | Polymkeric substance tensile strength (MPa) | Polymkeric substance shock strength (J/m) |
| 1 | 1∶2000 | 1∶40 | 50 | 10 | 48.04 | 65.37 |
| 2 | 1∶1500 | 1∶15 | 60 | 8 | 49.34 | 54.13 |
| 3 | 1∶1000 | 1∶20 | 80 | 6 | 50.26 | 68.41 |
| 4 | 1∶2000 | 1∶40 | 80 | 3 | 49.54 | 68.47 |
| 5 | 1∶2500 | 1∶30 | 80 | 8 | 49.15 | 67.41 |
| 6 | 1∶3000 | 1∶20 | 50 | 12 | 49.14 | 66.97 |
| 7 | 1∶3000 | 1∶30 | 70 | 8 | 50.10 | 73.24 |
| 8 | 1∶1500 | 1∶40 | 60 | 5 | 49.87 | 51.08 |
Present embodiment proves the catalyzer of organic molybdenum complex compound of the present invention as synthetic polydicyclopentadiene, has advantages of high catalytic activity, and is active in 3000mol DCPD/mol catalyzer.
Embodiment 10
Present embodiment experimentizes to the stability of organic molybdenum complex compound as synthetic polydicyclopentadiene catalyzer, and concrete experimentation and result are as follows:
Organic molybdenum complex compound among the embodiment 1,4,7 was placed respectively in ingress of air 3 and 6 hours, repeat the compound experiment of polydicyclopentadiene among the embodiment 9 then, synthesis condition is: the mol ratio of catalyzer and DCPD is 1/2000, the mol ratio of catalyzer and alkyl aluminum chloride is 1: 30,70 ℃ of temperature of reaction, the polymer properties parameter sees Table 2.The result as seen, in the time range of experiment, catalyzer aerial exposure duration, organic molybdenum complex compound therefore of the present invention had stable preferably as the catalyzer of synthetic polydicyclopentadiene to polymerization activity and not influence of polymer performance.
The aerial stability of organic molybdenum complex compound among table 2 embodiment 1,4,7 and the performance of synthetic polymer thereof
Embodiments of the invention are the non-limiting technical scheme of the present invention in order to explanation only, and wherein alkyl aluminum chloride can also adopt ethylaluminum dichloride, di-n-butyl aluminum chloride, diisobutyl aluminum chloride or normal-butyl al dichloride; The solvent that wherein dissolves organic ligand and adopted can also adopt ether or acetone, also can realize the purpose of synthetic polydicyclopentadiene of the present invention, should fall into protection scope of the present invention.
Claims (5)
1. organic molybdenum complex compound is characterized in that: have following general formula:
{MoO
2[L(PhR
n)
3]
2}Cl
2
In the formula:
L is selected from N, P or As;
R is ortho position or a para-orienting group on the phenyl, is selected from hydrogen atom or C
1-10The straight or branched alkyl substituent;
N is 1 or 2.
2. organic molybdenum complex compound according to claim 1 is characterized in that: described R is selected from ethyl, propyl group, butyl, sec.-propyl, isobutyl-, the tertiary butyl, isopentyl, octyl group or decyl.
3. an organic molybdenum complex compound is as the application of catalyzer in synthetic polydicyclopentadiene, and described organic molybdenum complex compound has following general formula:
{MoO
2[O
yL(PhR
n)
3]
2}Cl
2 （I）
In the formula (I):
L is selected from N, P or As;
R is ortho position or a para-orienting group on the phenyl, is selected from hydrogen atom or C
1-10The straight or branched alkyl substituent;
Y is 0 or 1;
N is 1 or 2.
4. application according to claim 3, it is characterized in that: the method for the synthetic polydicyclopentadiene of organic molybdenum complex compound catalysis is: it is in 50-80 ℃ the dicyclopentadiene that organic molybdenum complex compound is added temperature as catalyzer, the mol ratio of catalyzer and dicyclopentadiene is 1:1000-3000, under agitation add alkyl aluminum chloride then, system curing obtains polydicyclopentadiene, and the mol ratio of described catalyzer and alkyl aluminum chloride is 1:15-40.
5. application according to claim 4 is characterized in that: described alkyl aluminum chloride has following general formula:
AlR′
xCl
3-x （Ⅲ）
R ' is ethyl, normal-butyl or isobutyl-in the formula III, and x is 1 or 2.
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| CN102558731B (en) * | 2010-12-15 | 2014-04-23 | 河南科技大学 | Polydicyclopentadiene/polystyrene interpenetrating polymer network and preparation method thereof |
| CN105061513B (en) * | 2015-08-14 | 2017-08-04 | 张玉清 | A kind of organic phosphine molybdenum match, preparation method and application |
| CN108203477A (en) * | 2016-12-20 | 2018-06-26 | 中国石油天然气股份有限公司 | Preparation method of chromium-molybdenum-containing polyethylene catalyst |
| CN108203479A (en) * | 2016-12-20 | 2018-06-26 | 中国石油天然气股份有限公司 | Preparation method of supported polyethylene catalyst |
| CN108203476A (en) * | 2016-12-20 | 2018-06-26 | 中国石油天然气股份有限公司 | Supported polyethylene catalyst and preparation method thereof |
| CN112175011B (en) * | 2019-07-05 | 2022-09-27 | 中国石油化工股份有限公司 | Continuous preparation method of homogeneous organic molybdenum compound |
| CN115028663B (en) * | 2022-05-11 | 2024-08-02 | 常州德能新材料有限公司 | Metal complex of norbornenyl methylene phosphine and derivative thereof |
| CN114835905B (en) * | 2022-06-01 | 2023-03-31 | 常州巨德新材料有限公司 | Polyphosphazene amide metal complex catalyst for catalytic polymerization and preparation method thereof |
| CN115677777A (en) * | 2022-11-02 | 2023-02-03 | 北方华锦化学工业股份有限公司 | Diphenyl hypophosphite-tungsten complex, preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1696061A (en) * | 2004-05-14 | 2005-11-16 | 王戈 | Complexes of molybdenum base in high valency, preparation method and application |
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|---|---|---|---|---|
| CN1696061A (en) * | 2004-05-14 | 2005-11-16 | 王戈 | Complexes of molybdenum base in high valency, preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| S. M. HORNER et al..The Reactions of Some Oxygen Donors with Molybdenum Pentachloride: Coordination Compounds of Molybdenum(V) Oxotrichloride and Molybdenum(VI) Dioxodichloride.《Inorganic chemistry》.1962,第1卷(第1期),第122-127页. * |
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