CN109422875A - A kind of loaded catalyst with surface-active action and its application that polyphenylene oxide is prepared in water-oil phase medium - Google Patents
A kind of loaded catalyst with surface-active action and its application that polyphenylene oxide is prepared in water-oil phase medium Download PDFInfo
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- CN109422875A CN109422875A CN201710762791.5A CN201710762791A CN109422875A CN 109422875 A CN109422875 A CN 109422875A CN 201710762791 A CN201710762791 A CN 201710762791A CN 109422875 A CN109422875 A CN 109422875A
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- active action
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/44—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols by oxidation of phenols
Abstract
The invention discloses a kind of loaded catalysts with surface-active action, for by the complex of the glyoxaline ligand and metal ion that are grafted in the modified nano-silicon dioxide particle in surface；The nano-silicon dioxide particle modified by surface is the nano-silicon dioxide particle that the polyvinyl imidazol class ligand surface by hydrophobic silane coupling agent and one end with silane coupling agent is grafted.Catalyst of the present invention is high-efficient, it is good to the selectivity of product, the oxidative coupling polymerization reaction of catalysis of phenol class monomer in oil water two phase system, after reaction, catalyst and surfactant can be recycled by being centrifuged or being separated by filtration, it is environmentally protective, it is more in line with the requirement of sustainable development.
Description
Technical field
The present invention relates to Catalyst Design technical field more particularly to a kind of supported catalysts with surface-active action
Agent and preparation method thereof, and the loaded catalyst with surface-active action prepare polyphenylene oxide in water-oil phase medium
Using.
Background technique
Poly- 2,6- dimethyl phenylate abbreviation polyphenylene oxide (PPO) is one of five large-engineering plastics, because it is steady with excellent dimensions
Qualitative, heat resistance, acid-alkali-corrosive-resisting, low-k, low dissipation factor etc., and it is widely used in electric, auto industry
And the fields such as machine-building.The public affairs such as United States Patent (USP) US3,306,874, US3,306,875, US3,257,357, US3,257,358
Phenol monomer passes through oxidative coupling polymerization reaction production polyphenyl in organic solvent under cloth monovalence copper complex catalytic action
The homogeneous process of ether.Contain a large amount of copper ions in the crude product of this method production, to influence its electric property, and reaction process
Middle very exothermic needs explosion-proof reactor, in addition, catalyst, which can not recycle, can also improve cost, pollution environment.
The very exothermic of initial reaction stage then can be largely reduced using the polymerization system of water-oil phase, meanwhile,
Using water-soluble catalyst, after reaction, water-soluble catalyst and oil-soluble product can pass through simple liquid separation
Operation separation, to reduce the residual quantity of catalyst in the product.But this kind of method also needs that surfactant is added, and makes body
System becomes increasingly complex, and can not recycling for surfactant can also improve cost and pollute.
The present invention is for the characteristics of the reaction of phenol monomer oxidation coupling polymerization, design is even by silane in water-oil phase solvent
Connection agent and vinyl imidazole are grafted to the surface of nano silica, make it have the effect of solid surfactant, while miaow
Oxazolyl group can be coordinated with copper, manganese divalent ion, be coupled to form metal-amine complex for catalysis of phenol class monomer oxidation
Polymerization reaction prepares PPO.Higher catalytic efficiency and selectivity are realized, after reaction, catalyst can be by simple
Centrifugation or filtering carry out separation and recovery utilization, catalyst less residue in product, and the separation of surfactant is also simple and easy to do.
Summary of the invention
The present invention provides a kind of high catalytic efficiencies, the loaded catalyst with surface-active action being easily recycled.
The present invention also provides a kind of preparation method containing the loaded catalyst with surface-active action, this method behaviour
Make simple, easily controllable, suitable industrialized production.
The present invention also provides a kind of loaded catalysts with surface-active action to prepare in water-oil phase medium
The application method of polyphenylene oxide, the catalyst in this method can be recycled and recycle.
A kind of loaded catalyst with surface-active action, for by the modified nano-silicon dioxide particle in surface
The glyoxaline ligand of grafting and the complex of metal ion:
The nano-silicon dioxide particle modified by surface is to have by hydrophobic silane coupling agent and one end
The nano-silicon dioxide particle of the polyvinyl imidazol class ligand surface grafting of silane coupling agent；
The molar ratio of imidazole group and metal ion is 0.5~100:1, preferably 2~40:1 in the complex；
The metal ion is bivalent cupric ion or divalent manganesetion；
The glyoxaline ligand is the homopolymer of N- vinyl imidazole class monomer；
Wherein, the N- vinyl imidazole class monomer is formula (I) structural formula compound represented；
Formula (I):
In formula (I), R1、R2And R3For hydrogen or C1~C4Alkyl, R1、R2And R3It is identical or different.
The loaded catalyst with surface-active action, which is characterized in that described hydrophobic silane coupled
Agent is methyltrimethoxysilane, methyltriethoxysilane, ethyl trimethoxy silane, ethyl triethoxysilane, propyl
Trimethoxy silane, propyl-triethoxysilicane, butyl trimethoxy silane, butyl triethoxysilane, tert-butyl trimethoxy
One of base silane, t-butyltriethoxysilane are a variety of.
3, as described in claim 1 with the loaded catalyst of surface-active action, which is characterized in that described is poly-
The weight average molecular weight of vinyl imidazole class ligand is 500~10000, preferably 1000~5000.
The loaded catalyst with surface-active action, which is characterized in that the bivalent cupric ion comes from
One of copper chloride, copper bromide, copper sulphate, copper nitrate are a variety of；
Alternatively, the manganese ion comes from manganese chloride, manganous bromide, manganese iodide, manganese carbonate, manganese acetate, manganese nitrate, sulfuric acid
One of manganese, manganese phosphate are a variety of.
The preparation method of the loaded catalyst with surface-active action, comprising the following steps:
(1) equal by free radical initiation N- vinyl imidazole class monomer in the presence of the silane coupling agent with sulfydryl at one end
Poly- method synthesizes the polyvinyl imidazol class ligand that one end has silane coupling agent；
(2) Nano particles of silicon dioxide by surface with hydroxyl and any hydrophobic silane coupling agent in claim 2
And one end obtained is coupled with the polyvinyl imidazol class ligand of silane coupling agent by silane coupling agent in step (1)
Reaction obtains the nano-silicon dioxide particle of hydrophobic grouping and the grafting of polyvinyl imidazol class ligand；
(3) improved silica nanoparticle obtained in step (2) is dispersed in water, it is mixed with aqueous metallic ions
It closes, makes imidazole group and metal ion that complexation reaction occur, the loaded catalyst with surface-active action is made.
The preparation method of the loaded catalyst with surface-active action, which is characterized in that described one end
Silane coupling agent with sulfydryl is 3- mercaptopropyl trimethoxysilane, 3- mercaptopropyltriethoxysilane, 3- mercapto hydroxypropyl methyl
One of dimethoxysilane, 3- mercapto hydroxypropyl methyl diethoxy silane are a variety of.
The loaded catalyst with surface-active action is in catalysis using phenol monomer and oxidant as raw material
The application in the oxidative coupling polymerization reaction of polyphenylene oxide is prepared in water-oil phase medium.
The molar ratio composition of each raw material in the oxidative coupling polymerization reaction are as follows:
Phenol monomer 1；
Metal ion 0.0001~0.1 in loaded catalyst with surface-active action；
Appropriate oxidant.
The phenol monomer is formula (II) structural formula compound represented:
Formula (II)
In formula (II), R4And R5Respectively C1~C4Alkyl, alkylene or phenyl, R4And R5It is identical or different.
A method of it synthesizing polyphenylene oxide in water-oil phase medium, specifically includes following scheme: being mixed in water-oil phase
Phenol monomer and catalyst are added in system, the oxidation Ou Lian polymerization reaction of phenol, institute are carried out in the presence of oxygen-containing gas
The oxygen-containing gas stated is oxidant.
The oxidative coupling polymerization reaction temperature is 10~80 DEG C, and preferably 20~50 DEG C, the reaction time is 1~20 small
When, preferably 4~12 hours, loaded catalyst passed through centrifuge separation after the completion of reaction and recycles.
Commercial product can be used in raw material of the present invention, reagent.
Compared with prior art, the present invention has following marked improvement:
Catalyst of the present invention combines the characteristics of solid surfactant carrier and metal-amine complex: silica is received
Rice corpuscles size is small, has biggish surface area, reaction substrate is come into full contact with catalyst, and its amphipathic property
It can according to need and be adjusted by grafting.After reaction, which can be more simple by being centrifuged filtering etc.
Easy means are recycled.It solves the problems, such as that current water-oil phase synthesis PPO catalyst is difficult to recycle, more meets
The requirement of sustainable development.
Specific embodiment
The preparation of polyvinyl imidazol class ligand of 1 one end of embodiment with silane coupling agent
N- vinyl imidazole 5.44mL (60mmol), 3- mercaptopropyltriethoxysilane 0.6mL (3mmol) are dissolved in
In 60mL methanol, 0.1g azodiisobutyronitrile is added as initiator, under nitrogen protection, 65 DEG C of return stirring 48h.Decompression is steamed
It evaporates, excessive anhydrous ether is added and filters and washs, is dried to obtain the polyvinyl imidazol class ligand that one end has silane coupling agent
Embodiment 2~4
The polyvinyl imidazol class ligand that one end has silane coupling agent is prepared using the method for embodiment 1, unlike
Change the type of the silane coupling agent of one end used when synthesis with sulfydryl and the dosage of VI, be shown in Table 1:
Embodiment 5 has the preparation of the loaded catalyst of surface-active action
The one end being prepared in embodiment 1 is had to the polyvinyl imidazol of silane coupling agent, 30mmol methyl trimethoxy
Oxysilane and 15g Nano particles of silicon dioxide are scattered in toluene, and after 4 hours are heated to reflux in nitrogen, centrifugation is had
There is the particle of surface-active action.Particle obtained above is dispersed in water to and is added 15mmol copper chloride, stirs, be centrifuged
To the loaded catalyst with surface-active action, copper load capacity is 3.1%.
Embodiment 6 and 7
There is the loaded catalyst of surface-active action using the method preparation of embodiment 5, the difference is that changing silane
The type of coupling agent, is shown in Table 2:
Embodiment 8~10
There is the loaded catalyst of surface-active action using the method preparation of embodiment 5, the difference is that changing divalent
The type and dosage of copper compound, are shown in Table 3:
The oxidative coupling polymerization reaction of phenol monomer in 11 oil water two phase system of embodiment
In the jacket reactor with agitating paddle, thermometer and gas inlet and outlet, it is added 2,6- xylenol (DMP)
(2.4432g, 0.02mol) and toluene 25mL, water 50mL are stirring evenly and then adding into the catalyst 0.4129g prepared in embodiment 3
(Cu/DMP=1/100), it is passed through oxygen, under the mixing speed of 1000rotor/min, is reacted 6 hours.Centrifuge separation recycling is urged
Agent, catalyst recovery yield 96.6%.Toluene part is added dropwise in excessive methanol, and centrifugation obtains product, crude product yield
90.8%, wherein by-product DPQ content 0.3%, number-average molecular weight Mn=58000, molecular weight distribution DP=2.0.
Embodiment 12~16
According to the method for embodiment 11 in preparation PPO, the difference is that the catalyst of the preparation of embodiment 6~10 is respectively adopted,
Reaction result is shown in Table 4:
Embodiment 17~19
According to the method for embodiment 11 in preparation PPO, the difference is that change the molar ratio of copper and monomer in catalyst, reaction
It the results are shown in Table 5:
Embodiment 20
According to the method for embodiment 11 in preparation PPO, the difference is that replacing DMP with 2,6- diethyl phenol.Crude product obtains
Rate 90.8%, wherein by-product DPQ content 0.3%, number-average molecular weight Mn=53000, molecular weight distribution DP=2.3, catalyst
The rate of recovery 97.2%.
Embodiment 21
According to embodiment 11 method preparation PPO, unlike by air replace oxygen, crude product yield 91.0%,
Wherein by-product DPQ content 0.4%, number-average molecular weight Mn=45000, molecular weight distribution DP=2.5, catalyst recovery yield
95.8%.
Embodiment 22
According to the method for embodiment 11 in preparation PPO, the difference is that toluene 25mL, water 10mL.Crude product yield 94.3%,
Wherein by-product DPQ content 0.6%, number-average molecular weight Mn=60000, molecular weight distribution DP=2.0, catalyst recovery yield
93.8%.
Embodiment 23
According to the method for embodiment 11 in preparation PPO, the difference is that recycling gained catalyst using embodiment 1.Crude product
Yield 83.9%, wherein by-product DPQ content 0.7%, number-average molecular weight Mn=50000, molecular weight distribution DP=2.1.
Table 1
| Embodiment sequence number | Silane coupling agent | VI dosage (mmol) |
| 2 | 3- mercaptopropyl trimethoxysilane | 40 |
| 3 | 3- mercapto hydroxypropyl methyl dimethoxysilane | 20 |
| 4 | 3- mercapto hydroxypropyl methyl diethoxy silane | 50 |
Table 2
| Embodiment sequence number | Silane coupling agent | Copper load capacity (%) |
| 6 | Methyltriethoxysilane | 2.71 |
| 7 | Ethyl triethoxysilane | 1.78 |
Table 3
| Embodiment sequence number | Copper compound | Copper compound dosage (mmol) | Copper load capacity (%) |
| 8 | Copper nitrate | 10 | 1.71 |
| 9 | Copper sulphate | 8 | 1.23 |
| 10 | Copper bromide | 15 | 3.3 |
Table 4
Table 5
Catalyst of the present invention is high-efficient, good to the selectivity of product, the catalysis of phenol class list in oil water two phase system
The oxidative coupling polymerization of body is reacted, and after reaction, catalyst and surfactant can be by being centrifuged or being separated by filtration circulation benefit
With, it is environmentally protective, it is more in line with the requirement of sustainable development.
Claims (10)
1. a kind of loaded catalyst with surface-active action, which is characterized in that described with surface-active action
Loaded catalyst is matching for glyoxaline ligand by being grafted in the modified nano-silicon dioxide particle in surface and metal ion
Close object:
The nano-silicon dioxide particle modified by surface is by hydrophobic silane coupling agent and one end with silane
The nano-silicon dioxide particle of the polyvinyl imidazol class ligand surface grafting of coupling agent；
The molar ratio of imidazole group and metal ion is 0.5~100:1 in the complex；
The metal ion is bivalent cupric ion or divalent manganesetion；
The glyoxaline ligand is the homopolymer of N- vinyl imidazole class monomer；
Wherein, the N- vinyl imidazole class monomer is formula (I) structural formula compound represented；
Formula (I):
In formula (I), R1、R2And R3For hydrogen or C1~C4Alkyl, R1、R2And R3It is identical or different.
2. as described in claim 1 with the loaded catalyst of surface-active action, which is characterized in that described is hydrophobic
Silane coupling agent is methyltrimethoxysilane, methyltriethoxysilane, ethyl trimethoxy silane, ethyl triethoxy silicane
Alkane, propyl trimethoxy silicane, propyl-triethoxysilicane, butyl trimethoxy silane, butyl triethoxysilane, tert-butyl
One of trimethoxy silane, t-butyltriethoxysilane are a variety of.
3. as described in claim 1 with the loaded catalyst of surface-active action, which is characterized in that the polyethylene
The weight average molecular weight of base glyoxaline ligand is 500~10000.
4. as described in claim 1 with the loaded catalyst of surface-active action, which is characterized in that the cupric
Ion comes from one of copper chloride, copper bromide, copper sulphate, copper nitrate or a variety of；
Alternatively, the manganese ion comes from manganese chloride, manganous bromide, manganese iodide, manganese carbonate, manganese acetate, manganese nitrate, manganese sulfate, phosphorus
One of sour manganese is a variety of.
5. such as the preparation method of the described in any item loaded catalysts with surface-active action of Claims 1 to 4, including
Following steps:
(1) the monomer homopolymerization of N- vinyl imidazole class is caused by free radical in the presence of the silane coupling agent with sulfydryl at one end
Method synthesizes the polyvinyl imidazol class ligand that one end has silane coupling agent；
(2) Nano particles of silicon dioxide by surface with hydroxyl and any hydrophobic silane coupling agent and step in claim 2
Suddenly the polyvinyl imidazol class ligand of one end obtained with silane coupling agent be coupled instead by silane coupling agent in (1)
It answers, obtains the nano-silicon dioxide particle of hydrophobic grouping and the grafting of polyvinyl imidazol class ligand；
(3) improved silica nanoparticle obtained in step (2) is dispersed in water, is mixed with aqueous metallic ions,
Make imidazole group and metal ion that complexation reaction occur, the loaded catalyst with surface-active action is made.
6. the preparation method of the loaded catalyst with surface-active action as claimed in claim 5, which is characterized in that institute
Silane coupling agent of the one end stated with sulfydryl is 3- mercaptopropyl trimethoxysilane, 3- mercaptopropyltriethoxysilane, 3- mercapto
One of hydroxypropyl methyl dimethoxysilane, 3- mercapto hydroxypropyl methyl diethoxy silane are a variety of.
7. the loaded catalyst with surface-active action as described in Claims 1 to 4 catalysis with phenol monomer and
Oxidant prepares the application in the oxidative coupling polymerization reaction of polyphenylene oxide for raw material in water-oil phase medium.
8. the use as claimed in claim 7, which is characterized in that the molar ratio of each raw material in the oxidative coupling polymerization reaction
Composition are as follows:
Phenol monomer 1；
Metal ion 0.0001~0.1 in loaded catalyst with surface-active action；
Appropriate oxidant.
9. the use as claimed in claim 7, which is characterized in that the phenol monomer is to change shown in formula (II) structural formula
Close object:
Formula (II)
In formula (II), R4And R5Respectively C1~C4Alkyl, alkylene or phenyl, R4And R5It is identical or different.
10. the use as claimed in claim 7, which is characterized in that the oxidative coupling polymerization reaction temperature is 10~80 DEG C,
Reaction time is 1~20 hour, and loaded catalyst passes through centrifuge separation after the completion of reaction and recycles.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110280314A (en) * | 2019-07-16 | 2019-09-27 | 中国科学院兰州化学物理研究所 | A method of improving manganese-based low-temperature SCR catalyst water resistant and anti-dust performance |
| CN110804174A (en) * | 2019-12-06 | 2020-02-18 | 中国科学院大连化学物理研究所 | Supported catalyst and application thereof in preparation of low-molecular-weight hydroxyl-terminated polyphenyl ether |
| CN110885441A (en) * | 2019-12-06 | 2020-03-17 | 中国科学院大连化学物理研究所 | Supported catalyst and application thereof in preparation of remote-claw type low molecular weight polyphenylene ether |
| CN111286023A (en) * | 2019-12-06 | 2020-06-16 | 中国科学院大连化学物理研究所 | Supported catalyst and application thereof in preparation of crosslinkable polyphenyl ether |
| CN111286022A (en) * | 2019-12-06 | 2020-06-16 | 中国科学院大连化学物理研究所 | Supported catalyst and application thereof in preparation of low-molecular-weight polyphenylene ether |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110280314A (en) * | 2019-07-16 | 2019-09-27 | 中国科学院兰州化学物理研究所 | A method of improving manganese-based low-temperature SCR catalyst water resistant and anti-dust performance |
| CN110804174A (en) * | 2019-12-06 | 2020-02-18 | 中国科学院大连化学物理研究所 | Supported catalyst and application thereof in preparation of low-molecular-weight hydroxyl-terminated polyphenyl ether |
| CN110885441A (en) * | 2019-12-06 | 2020-03-17 | 中国科学院大连化学物理研究所 | Supported catalyst and application thereof in preparation of remote-claw type low molecular weight polyphenylene ether |
| CN111286023A (en) * | 2019-12-06 | 2020-06-16 | 中国科学院大连化学物理研究所 | Supported catalyst and application thereof in preparation of crosslinkable polyphenyl ether |
| CN111286022A (en) * | 2019-12-06 | 2020-06-16 | 中国科学院大连化学物理研究所 | Supported catalyst and application thereof in preparation of low-molecular-weight polyphenylene ether |
| CN111286022B (en) * | 2019-12-06 | 2022-07-08 | 中国科学院大连化学物理研究所 | Supported catalyst and application thereof in preparation of low-molecular-weight polyphenylene ether |
| CN110804174B (en) * | 2019-12-06 | 2022-07-08 | 中国科学院大连化学物理研究所 | Supported catalyst and application thereof in preparation of low-molecular-weight hydroxyl-terminated polyphenyl ether |
| CN111286023B (en) * | 2019-12-06 | 2022-07-08 | 中国科学院大连化学物理研究所 | Supported catalyst and application thereof in preparation of crosslinkable polyphenyl ether |
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