CN101659678B - Organophosphorus based tungsten complex and preparation method and application thereof - Google Patents
Organophosphorus based tungsten complex and preparation method and application thereof Download PDFInfo
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- CN101659678B CN101659678B CN 200910172279 CN200910172279A CN101659678B CN 101659678 B CN101659678 B CN 101659678B CN 200910172279 CN200910172279 CN 200910172279 CN 200910172279 A CN200910172279 A CN 200910172279A CN 101659678 B CN101659678 B CN 101659678B
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Abstract
The invention discloses an organophosphorus based tungsten complex which is bidentate chloride of triphenylphosphine or triphenylphosphine oxide of tungsten. Phenyl in the triphenylphosphine or triphenylphosphine oxide may be alkyl substituted phenyl and the number of the alkyl substituents can be 1-3. The invention also discloses a preparation method of the organophosphorus based tungsten complex and application of the organophosphorus based tungsten complex in synthesizing polydicyclopentadiene. Under the action of organophosphorus ligands, the tungsten complex of the invention has higher catalytic activity in synthesizing polydicyclopentadiene, has high chemical stability and is insensitive to air and water vapors, thus lowering the reaction conditions for synthesizing polydicyclopentadiene. In addition, the raw materials adopted by the organophosphorus based tungsten complex prepared by the invention are low in price and the preparation method is simple; therefore, the tungsten complex is low in preparation cost and has good popularization and application prospect.
Description
Technical field
The present invention relates to a kind of organophosphorus based tungsten complex, also relate to a kind of preparation method of this complex compound, also relate to simultaneously the application of a kind of this complex compound in synthetic polydicyclopentadiene, belong to the macromolecule synthesising technology field.
Background technology
Polydicyclopentadiene (PDCPD) is a kind of engineering plastics that have high impact strength and high modulus in flexure performance concurrently, these plastics also have the characteristics such as good thermotolerance, creep resistance, dimensional stability, erosion resistance simultaneously, can be used for making the large-scale product of the complex-shaped thin-walled of various high-performance, as: the bumper in the transportation, backplate, side plate, engine shield and bodyshell etc.; The housing of the 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 etc. and agricultural machine, civil construction material etc.The states such as the U.S., Japan, Europe have realized the suitability for industrialized production of polydicyclopentadiene, and China does not also have comparatively ripe production technique at present.
External existing PDCPD produces and usually adopts reaction injection moulding (RIM) technique, and this technique has the advantages such as shaping speed is fast, processing temperature is low, injection pressure is low.The present employed catalyzer of RIM technique is mainly the carbone catalyst of aryloxy tungsten complex and ruthenium, osmium, when using, the former need to have aluminum alkyls could effectively make dicyclopentadiene (DCPD) that polymerization occurs as promotor, belong to two-pack complex catalysis system, but it is responsive to air and water to steam ratio, less stable, working conditions are comparatively harsh; The latter's chemical property is more stable, but price is higher, is not suitable for suitability for industrialized production.
Summary of the invention
The purpose of this invention is to provide a kind of stable in properties, lower-cost organophosphorus based tungsten complex.
Another object of the present invention provides a kind of preparation method of organophosphorus based tungsten complex.
Another object of the present invention provides the application of a kind of organophosphorus based tungsten complex in synthetic polydicyclopentadiene.
In order to realize above purpose, the technical scheme that organophosphorus based tungsten complex of the present invention adopts is: a kind of organophosphorus based tungsten complex, and this complex compound has following general formula:
{W[O
zP(PhR
n)
3]
2}Cl
6 (I)
In the formula (I) z be 0 or 1, R be C
1-10The straight or branched alkyl substituent, n is the integer of 0-3.
R is ethyl, propyl group, sec.-propyl or n-nonyl in the formula (I).
Preparation method's step of organophosphorus based tungsten complex of the present invention is as follows: a kind of preparation method of organophosphorus based tungsten complex, and its step is as follows:
(1) under 50-80 ℃ of condition, the saturated aqueous solution of preparation sodium wolframate adds concentrated hydrochloric acid to no longer producing precipitation in the sodium wolframate saturated aqueous solution under continuing stirring, and the continuation reaction is 8-12 hour again; Then filter, filter cake washing, drying obtain wolframic acid;
(2) add concentrated hydrochloric acid in the wolframic acid that obtains to step (1), reflux to solution clarification obtains wolframic acid solution, be cooled to 20-40 ℃ for subsequent use;
(3) get the diethyl ether solution that organic phosphine reagent that wolframic acid mole number 2-5 doubly measures is made into organic phosphine reagent, under continue stirring above-mentioned diethyl ether solution being added and keeping temperature is in 20-40 ℃ the wolframic acid solution, keep temperature-resistant continuing again to stir 6-10 hour, then filter, filter cake is respectively with acetone and ether washing, drying obtains the product organophosphorus based tungsten complex;
Described organic phosphine reagent is triphenylphosphine, triphenylphosphine alkyl-substituted derivative, triphenylphosphine oxide or triphenylphosphine oxide alkyl-substituted derivative.
Described organic phosphine reagent is the compound with following general formula:
O
zP(PhR
n)
3 (II)
In the formula (II) z be 0 or 1, R be C
1-10The straight or branched alkyl substituent, n is the integer of 0-3.
The concentration of the diethyl ether solution that step (3) is made into is 0.1-0.3g/ml.
Temperature dry in step (1) and the step (3) is 50 ℃.
Among formula (I), (II), when z is 0, O
zP (PhR
n)
3Be triphenylphosphine alkyl-substituted derivative P (PhR
n)
3When z is 1, O
zP (PhR
n)
3Be triphenylphosphine oxide alkyl-substituted derivative OP (PhR
n)
3When z is that 0, n is 0 o'clock, O
zP (PhR
n)
3Be triphenylphosphine PPh
3When z is that 1, n is 0 o'clock, O
zP (PhR
n)
3Be triphenylphosphine oxide OPPh
3Ph is phenyl in the formula (I), (II), and R is the straight or branched alkyl substituent that is connected to the carbon atom quantity 1-10 on the phenyl ring, and such as ethyl, propyl group, sec.-propyl, n-nonyl etc., R can be connected on the phenyl ring on any attachable position.
Being applied as of organophosphorus based tungsten complex of the present invention: a kind of machine phosphorus based tungsten complex is as the application of catalyzer in synthetic polydicyclopentadiene.
The method of synthetic polydicyclopentadiene is: it is in 25-80 ℃ the dicyclopentadiene that organophosphorus based tungsten complex is added temperature as catalyzer, the mol ratio of catalyzer and dicyclopentadiene is 1: 1500～2500, then continuing to add alkyl aluminum chloride under the stirring, system is solidified, and obtains polydicyclopentadiene.
Described alkyl aluminum chloride has following general formula:
AlR
x′Cl
3-x (III)
R ' is ethyl, normal-butyl or isobutyl-in the formula (III), and x is 1 or 2.
The mol ratio of described alkyl aluminum chloride and catalyzer is 15-40: 1.
Tungsten complex of the present invention is under the effect of organophosphorus ligand, in synthetic polydicyclopentadiene, has higher catalytic activity, and has very high chemical stability, insensitive to air and steam, therefore reduced the reaction conditions of synthetic polydicyclopentadiene, and the cost of material that the organophosphorus based tungsten complex of the present invention's preparation adopts is lower, and the preparation method is simple, therefore the cost of preparation is lower, has good popularizing application prospect.
Description of drawings
Fig. 1 is the infrared spectrogram of the organophosphorus based tungsten complex of embodiment 2 preparations.
Embodiment
Embodiment 1
The structural formula of the organophosphorus based tungsten complex of present embodiment is as being: [W (OPPh
3)
2] Cl
6
The preparation method of the organophosphorus based tungsten complex of present embodiment is as follows:
1, gets 10g tungstic acid hydrate sodium (Na
2WO
42H
2O) in Erlenmeyer flask, under 50 ℃ of conditions, slowly add distilled water and just constantly be stirred to and dissolve, continuing slowly to add concentrated hydrochloric acid under the stirring until no longer include the yellow mercury oxide generation, add altogether concentrated hydrochloric acid 2ml, and then continue to react 8 hours; Be neutral with a large amount of distilled water repetitive scrubbings to pH value behind the sedimentation and filtration, the gained solid 50 ℃ of vacuum-dryings 4 hours, is obtained yellow wolframic acid (H
2WO
4) pressed powder 6.8g;
2, take by weighing the tungstic acid solid powder that 6g step 1 obtains, under continue stirring, add concentrated hydrochloric acid 150mL, with temperature rise to 90 ℃ be back to be cooled to after the clarification 40 ℃ stand-by, obtain wolframic acid solution, the mass concentration of wolframic acid is 3%;
3, take by weighing triphenylphosphine oxide (OPPh
3) 13.36g, with behind the 45ml ether dissolution, under vigorous stirring, slowly be added drop-wise to maintenance temperature that step 2 obtains and be in 40 ℃ the wolframic acid solution, there is immediately precipitation to generate, keep 40 ℃ of temperature to continue again to stir 6 hours; Use washing with acetone three times behind the precipitation suction filtration, with ether washing three times, then obtained target product 16g in 8 hours in 50 ℃ of vacuum-dryings again.
Embodiment 2
The structural formula of the organophosphorus based tungsten complex of present embodiment is as being: [W (PPh
3)
2] Cl
6
The preparation method of the organophosphorus based tungsten complex of present embodiment is as follows:
1, gets 12g tungstic acid hydrate sodium (Na
2WO
42H
2O) in Erlenmeyer flask, under 60 ℃ of conditions, slowly add distilled water and just constantly be stirred to and dissolve, continuing slowly to add concentrated hydrochloric acid under the stirring until no longer include the yellow mercury oxide generation, add altogether concentrated hydrochloric acid 2ml, and then continue to react 9 hours; Be neutral with distilled water repetitive scrubbing to pH value behind the sedimentation and filtration, the gained solid in 50 ℃ of vacuum-dryings 4 hours, is obtained yellow wolframic acid (H
2WO
4) pressed powder 8.28g.
2, take by weighing the tungstic acid solid powder that 8g step 1 obtains, under continue stirring, add concentrated hydrochloric acid 160mL, with temperature rise to 90 ℃ be back to be cooled to after the clarification 30 ℃ stand-by, the mass concentration of wolframic acid is 4%.
3, take by weighing triphenylphosphine (PPh
3) 26.73g, with behind the 90ml ether dissolution, under vigorous stirring, slowly be added drop-wise in the wolframic acid solution of 30 ℃ of insulations that step 2 obtains, there is immediately precipitation to generate, keep 40 ℃ of temperature to continue again to stir 7 hours; Use washing with acetone three times behind the precipitation suction filtration, with ether washing three times, then obtained target product 21g in 8 hours in 50 ℃ of vacuum-dryings again.The infrared spectra of product is seen Fig. 1.
Embodiment 3
The structural formula of the organophosphorus based tungsten complex of present embodiment is as being: { W[P (PhC
3H
7)
3]
2Cl
6
The preparation method of the organophosphorus based tungsten complex of present embodiment is as follows:
1, gets 15g tungstic acid hydrate sodium (Na
2WO
42H
2O) in Erlenmeyer flask, under 70 ℃ of conditions, slowly add distilled water and just constantly be stirred to and dissolve, continuing slowly to add concentrated hydrochloric acid under the stirring until no longer include the yellow mercury oxide generation, add altogether concentrated hydrochloric acid 2ml, and then continue to react 10 hours; Be neutral with distilled water repetitive scrubbing to pH value behind the sedimentation and filtration, the gained solid is 50 ℃ of vacuum-dryings 4 hours, obtain yellow wolframic acid (H
2WO
4) pressed powder 11g.
2, take by weighing the tungstic acid solid powder that 10g step 1 obtains, under agitation add concentrated hydrochloric acid 158.33mL, with temperature rise to 90 ℃ be back to be cooled to after the clarification 20 ℃ stand-by, the mass concentration of wolframic acid is 6%.
3, take by weighing three (p-isopropyl phenyl) phosphine (P (PhC
3H
7)
3) 55.69g, after dissolving with the 186ml ether, under vigorous stirring, slowly be added drop-wise in the wolframic acid solution of 20 ℃ of insulations that step 2 obtains, there is immediately precipitation to generate, keep 20 ℃ of temperature to continue again to stir 8 hours, use washing with acetone three times behind the precipitation suction filtration, with ether washing three times, then obtained target product 27g in 8 hours in 50 ℃ of vacuum-dryings again.
Embodiment 4
The structural formula of the organophosphorus based tungsten complex of present embodiment is as being: { W[OP (PhC
3H
7)
3]
2Cl
6
The preparation method of the organophosphorus based tungsten complex of present embodiment is as follows:
1, gets 15g tungstic acid hydrate sodium (Na
2WO
42H
2O) in Erlenmeyer flask, under 80 ℃ of conditions, slowly add distilled water and just constantly be stirred to and dissolve, continuing slowly to add concentrated hydrochloric acid under the stirring until no longer include the yellow mercury oxide generation, add altogether concentrated hydrochloric acid 2ml, and then continue to react 11 hours; Be neutral with distilled water repetitive scrubbing to pH value behind the sedimentation and filtration, the gained solid is 50 ℃ of vacuum-dryings 4 hours, obtain yellow wolframic acid (H
2WO
4) pressed powder 11g.
2, take by weighing the tungstic acid solid powder that 10g step 1 obtains, under agitation add concentrated hydrochloric acid 158.33mL, with temperature rise to 90 ℃ be back to be cooled to after the clarification 35 ℃ stand-by, the mass concentration of wolframic acid is 6%.
3, take by weighing three (to the propyl group phenyl) phosphine oxide (OP (PhC
3H
7)
3) 61.23g, after dissolving with the 210ml ether, under vigorous stirring, slowly be added drop-wise in the wolframic acid solution of 35 ℃ of insulations that step 2 obtains, there is immediately precipitation to generate, keep 35 ℃ of temperature to continue again to stir 9 hours, use washing with acetone three times behind the precipitation suction filtration, with ether washing three times, then obtained target product 29.5g in 8 hours in 50 ℃ of vacuum-dryings again.
Embodiment 5
The structural formula of the organophosphorus based tungsten complex of present embodiment is as being: { W[P (PhC
9H
19)
3]
2Cl
6
The preparation method of the organophosphorus based tungsten complex of present embodiment is as follows:
1, gets 15g tungstic acid hydrate sodium (Na
2WO
42H
2O) in Erlenmeyer flask, under 80 ℃ of conditions, slowly add distilled water and just constantly be stirred to and dissolve, continuing slowly to add concentrated hydrochloric acid under the stirring until no longer include the yellow mercury oxide generation, add altogether concentrated hydrochloric acid 2ml, and then continue to react 12 hours; Be neutral with distilled water repetitive scrubbing to pH value behind the sedimentation and filtration, the gained solid is 50 ℃ of vacuum-dryings 4 hours, obtain yellow wolframic acid (H
2WO
4) pressed powder 11g.
2, take by weighing the tungstic acid solid powder that 10g step 1 obtains, under agitation add concentrated hydrochloric acid 158.33mL, with temperature rise to 90 ℃ be back to be cooled to after the clarification 25 ℃ stand-by, the mass concentration of wolframic acid is 6%.
3, take by weighing three (aligning the nonyl phenyl) phosphine (P (PhC
9H
19)
3) 73.51g, after dissolving with the 245ml ether, under vigorous stirring, slowly be added drop-wise in the wolframic acid solution of 25 ℃ of insulations that step 2 obtains, there is immediately precipitation to generate, keep 25 ℃ of temperature to continue again to stir 10 hours; Use washing with acetone three times behind the precipitation suction filtration, with ether washing three times, then obtained target product 36.42g in 8 hours in 50 ℃ of vacuum-dryings again.
Employed concentrated hydrochloric acid is commercially available product among the embodiment 1-5, and concentration is 37%.
Embodiment 6
The present invention adopts tungsten complex as the polydicyclopentadiene synthetic method of catalyzer, and it is synthetic that the tungsten complex that adopts above-described embodiment 1-5 to prepare carries out respectively following polydicyclopentadiene:
In the dry reaction container of 100ml, add DCPD 20ml, by 1: the molar ratio of 1500-2500 adds the catalyzer tungsten complex, reaction vessel carries out being warming up to 25-80 ℃ after the pump drainage displacement with nitrogen, 15-40 according to the catalyzer mole number doubly adds diethyl aluminum chloride, solidified in 10 minutes, and obtained the polymer poly dicyclopentadiene.Concrete reaction conditions and the performance perameter of polymkeric substance see Table 1.
The performance perameter of table 1 polydicyclopentadiene synthesis condition and polymkeric substance
| Embodiment | Catalyzer/DCPD (mol ratio) | Alkyl aluminum chloride/catalyzer (mol ratio) | Temperature of reaction (℃) | Set time (minute) | Polymkeric substance tensile strength (MPa) | Polymkeric substance shock strength (J/M) | Polymkeric substance flexural strength (MPa) |
| 1 | 1∶2500 | 40∶1 | 25 | 10 | 47.24 | 67.56 | 59.20 |
| 2 | 1∶2500 | 40∶1 | 50 | 10 | 47.86 | 68.13 | 59.16 |
| 3 | 1∶2000 | 30∶1 | 80 | 10 | 48.05 | 68.05 | 58.56 |
| 4 | 1∶2000 | 15∶1 | 80 | 10 | 48.14 | 67.68 | 58.71 |
| 5 | 1∶1500 | 30∶1 | 80 | 10 | 48.26 | 68.41 | 59.41 |
Experimental results show that tungsten complex of the present invention has higher activity as catalyzer, activity reaches as high as 2500mol DCPD/mol.
Embodiment 7
Tungsten complex among the embodiment 1 is placed respectively 0 (not ingress of air placement), 0.5,1,2,3 hour in ingress of air, then repeat the synthetic experiment of polydicyclopentadiene of embodiment 6, experiment condition is: the mol ratio of catalyzer and DCPD is 1: 2000, the mol ratio of alkyl aluminum chloride and catalyzer is 20: 1, temperature of reaction is 50 ℃, obtain good circulation ratio, the results are shown in Table 2, therefore tungsten complex of the present invention has preferably stability as catalyzer.
The mechanical property of the aerial stability of table 2 tungsten complex of the present invention and synthetic polymer thereof
| The tungsten complex exposure air time (hour) | 0 | 0.5 | 1 | 2 | 3 |
| Dicyclopentadiene polymerization setting time (minute) | 4.5 | 4.5 | 4.5 | 4.4 | 4.6 |
| Polymkeric substance tensile strength (MPa) | 48.10 | 48.89 | 48.12 | 49.02 | 48.57 |
| Polymkeric substance shock strength (J/M) | 68.69 | 68.49 | 68.71 | 69.01 | 68.53 |
| Polymkeric substance flexural strength (MPa) | 60.01 | 59.65 | 60.45 | 58.97 | 60.23 |
Alkyl aluminum chloride of the present invention can also adopt ethylaluminum dichloride, di-n-butyl aluminum chloride, and diisobutyl aluminum chlorides etc. also can be realized the purpose of synthetic polydicyclopentadiene of the present invention should falling into protection scope of the present invention.
Claims (9)
1. organophosphorus based tungsten complex, it is characterized in that: this complex compound has following general formula:
{W[O
zP(PhR
n)
3]
2}Cl
6 (I)
In the formula (I) z be 0 or 1, R be C
1-10The straight or branched alkyl substituent, n is 0;
Or z=0, and n=1, R=C
3H
7
Or z=1, and n=1, R=C
3H
7
Or z=0, and n=1, R=C
9H
19
2. organophosphorus based tungsten complex according to claim 1 is characterized in that: R is ethyl, propyl group, sec.-propyl or n-nonyl in the formula (I).
3. preparation method of organophosphorus based tungsten complex as claimed in claim 1, it is characterized in that: its step is as follows:
(1) under 50-80 ℃ of condition, the saturated aqueous solution of preparation sodium wolframate adds concentrated hydrochloric acid to no longer producing precipitation in the sodium wolframate saturated aqueous solution under continuing stirring, and the continuation reaction is 8-12 hour again; Then filter, filter cake washing, drying obtain wolframic acid;
(2) add concentrated hydrochloric acid in the wolframic acid that obtains to step (1), reflux to solution clarification obtains wolframic acid solution, be cooled to 20-40 ℃ for subsequent use;
(3) get the diethyl ether solution that organic phosphine reagent that wolframic acid mole number 2-5 doubly measures is made into organic phosphine reagent, under continue stirring above-mentioned diethyl ether solution being added and keeping temperature is in 20-40 ℃ the wolframic acid solution, keep temperature-resistant continuing again to stir 6-10 hour, then filter, filter cake is respectively with acetone and ether washing, drying obtains the product organophosphorus based tungsten complex;
Described organic phosphine reagent is triphenylphosphine, triphenylphosphine alkyl-substituted derivative, triphenylphosphine oxide or triphenylphosphine oxide alkyl-substituted derivative.
4. the preparation method of organophosphorus based tungsten complex according to claim 3, it is characterized in that: the concentration of the diethyl ether solution that step (3) is made into is 0.1-0.3g/ml.
5. the preparation method of organophosphorus based tungsten complex according to claim 3 is characterized in that: temperature dry in step (1) and the step (3) is 50 ℃.
One kind as claimed in claim 1 organophosphorus based tungsten complex as the application of catalyzer in synthetic polydicyclopentadiene.
7. application according to claim 6, it is characterized in that: the method for synthetic polydicyclopentadiene is: it is in 25-80 ℃ the dicyclopentadiene that organophosphorus based tungsten complex is added temperature as catalyzer, the mol ratio of catalyzer and dicyclopentadiene is 1: 1500-2500, then continuing to add alkyl aluminum chloride under the stirring, system is solidified, and obtains polydicyclopentadiene.
8. application according to claim 7 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.
9. application according to claim 7 is characterized in that: the mol ratio of described alkyl aluminum chloride and catalyzer is 15-40: 1.
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| CN101987907B (en) * | 2010-10-18 | 2012-07-04 | 河南科技大学 | Polydicyclopentadiene composite material and preparation method thereof |
| CN102558731B (en) * | 2010-12-15 | 2014-04-23 | 河南科技大学 | Polydicyclopentadiene/polystyrene interpenetrating polymer network and preparation method thereof |
| CN111606955B (en) * | 2020-07-06 | 2023-05-02 | 长春三友智造科技发展有限公司 | Metal organic phosphine complex and preparation method and application thereof |
| CN112250707B (en) * | 2020-10-19 | 2022-10-04 | 河南科技大学 | N-alkyl-P, P-diphenyl hypophosphorous amide and tungsten complex, preparation method and application thereof |
| CN113024614B (en) * | 2021-03-08 | 2021-11-02 | 大成普瑞新材料有限责任公司 | Preparation method of organic tungsten catalyst for injection molding of polydicyclopentadiene composite material |
| CN115028663A (en) * | 2022-05-11 | 2022-09-09 | 常州德能新材料有限公司 | Metal complex of norbornenyl methylene phosphine and derivative 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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| US4729976A (en) * | 1985-10-28 | 1988-03-08 | Shell Oil Company | Polymer of dicyclopentadiene and a process for preparation |
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2009
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|---|---|---|---|---|
| US4729976A (en) * | 1985-10-28 | 1988-03-08 | Shell Oil Company | Polymer of dicyclopentadiene and a process for preparation |
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| Title |
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| Djaber Boutarfa et al.Applications of chloro-aryloxide complexes of tungsten in olefin metathesis: the ring-opening metathesis polymerization of dicyclopentadiene.《Journal of Molecular Catalysis》.1991,第69卷157-169. * |
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Effective date of registration: 20201201 Address after: 124000 Hongqi Street, Shuangtaizi District, Liaoning, Panjin Patentee after: NORTH HUAJIN CHEMICAL INDUSTRIES Group Corp. Address before: 471003 Xiyuan Road, Jianxi District, Henan, No. 48, No. Patentee before: HENAN University OF SCIENCE AND TECHNOLOGY |