CN109776790A - A kind of method of oxidative coupling polymerization synthesis polyphenylene oxide - Google Patents
A kind of method of oxidative coupling polymerization synthesis polyphenylene oxide Download PDFInfo
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Abstract
The invention discloses the continuous production methods that a kind of phenol monomer oxidation coupling polymerization prepares polyphenylene oxide, including will be under a certain proportion of phenol monomer, organic solvent and water oxygen-containing gas existence condition, by being equipped with the fixed bed reactors of catalyst, the oxidative coupling polymerization reaction of phenol monomer is carried out；The catalyst is imidazole radicals cross-linked polymer supported copper nano-particle compound.Simple and easy to do, low in cost, the achievable serialization large-scale production of process of the present invention, and this method significantly reduces the residual quantity of catalyst metals in the product, maintain the excellent electric property of polyphenylene oxide, with wide development space and great market application value, more meet the requirement of sustainable development.
Description
Technical field
The present invention relates to phenol monomers in macromolecule chemical industry technical field more particularly to fixed bed reactors in oil/water
The method that oxidative coupling polymerization prepares polyphenylene oxide in two-phase medium.
Background technique
Poly- 2,6- dimethyl phenylate abbreviation polyphenylene oxide (PPE) is one of five large-engineering plastics, has good mechanical property
And electric property, as high glass-transition temperature, good dimensional stability, heat resistance, acid-alkali-corrosive-resisting, low-k,
Low dissipation factor etc. is widely used in the fields such as electric, auto industry and machine-building.United States Patent (USP) US3,306,874,
US3,306,875, US3,257,357, US3,257,358 etc. disclose phenol monomer under monovalence copper complex catalytic action and exist
The homogeneous process of production polyphenylene oxide is reacted in organic solvent by oxidative coupling polymerization.This method produces work using batch tank
Skill, reaction process is highly exothermic, needs explosion-proof reactor, and due to contain in the reason crude product of homogeneous system a large amount of copper from
Son, to influence its electric property, while catalyst and ligand can not recycle can also improve cost, pollution environment.
Reaction process safety and stable product quality can improved using heterogeneous system continuous production polyphenylene oxide
While property, polyphenylene oxide production cost is greatly reduced, while reducing the residual quantity of metal ion in the product, to improve product
Electric property.
The present invention is for the characteristics of the reaction of phenol monomer homogeneous oxidizing coupling polymerization, design is synthesized in water-oil phase medium
The copper nano-particle catalyst of imidazole radicals cross-linked polymer load, is seated in fixed bed, realizes the continuous of polyphenylene oxide
Metaplasia produces, and reacts efficiency and selectivity with higher, stable product quality, catalyst less residue in product.
Summary of the invention
The present invention provides the continuous production methods that a kind of phenol monomer oxidation coupling polymerization prepares polyphenylene oxide.
To achieve the goals above, this method includes depositing phenol monomer, organic solvent and water in molecular oxygen-containing gas
Under conditions, by being equipped with the fixed bed reactors of catalyst, the method for carrying out the oxidative coupling polymerization reaction of phenol monomer；
The catalyst is imidazole radicals cross-linked polymer supported copper nano-particle compound
A kind of method of oxidative coupling polymerization synthesis polyphenylene oxide, which is characterized in that the oxidative coupling polymerization
The mass ratio composition of each raw material in reaction are as follows:
Phenol monomer 1；
Organic solvent 3~40；
Water 0.1~4；
In the presence of molecular oxygen, reaction temperature is 10~60 DEG C, preferably 20~50 DEG C；Reaction pressure be normal pressure~
1.0MPa, preferably normal pressure~0.4MPa, gas space velocity 10mL/min~1L/min, preferably 100mL/min~500mL/
Min, 10~500mL/min of flow rate of liquid, preferably 50~300mL/min.
The phenol monomer is formula (I) structural formula compound represented:
Formula (I)
In formula (I), R1And R2Respectively C1~C4Alkyl, C2~C4Alkylene or phenyl, R1And R2It is identical or different.
The imidazole radicals cross-linked polymer supported copper nano-particle catalyst is imidazole radicals cross-linked polymer and cupric
Through the resulting compound of sodium borohydride reduction after compound solution coordination.
The catalyst is imidazole radicals cross-linked polymer supported copper nano-particle compound.
The phenol monomer is formula (I) structural formula compound represented:
Formula (I)
In formula (I), R1And R2Respectively C1~C4Alkyl, alkylene or phenyl, R1And R2It is identical or different；
The imidazole radicals cross-linked polymer supported copper nano-particle catalyst is imidazole radicals cross-linked polymer and cupric
Through the resulting compound of sodium borohydride reduction after compound solution coordination.
The imidazole radicals cross-linked polymer is divinylbenzene class monomer and vinyl imidazole class monomer and other are a kind of
Or the cross-linked copolymer of a variety of oil-soluble ethylene base monomers；
Divinylbenzene class monomer in the polymer, vinyl imidazole class monomer and other one or more have oil molten
The molar ratio of sex ethylene base monomer is 1~10:1:0.001~1, preferably 1~5:1:0.01~0.3；
Wherein, the divinylbenzene class monomer is formula (II) structural formula compound represented, vinyl imidazole class list
Body is formula (III) structural formula compound represented:
Formula (II)；
In formula (II), R3The alkyl or vinyl for being 1 to 4 for hydrogen, carbon atom number, R4The alkane for being 1 to 4 for hydrogen, carbon atom number
Base or vinyl, R5The alkyl or vinyl for being 1 to 4 for hydrogen, carbon atom number, R6For hydrogen, carbon atom number be 1 to 4 alkyl or second
Alkenyl, R7The alkyl or vinyl for being 1 to 4 for hydrogen, carbon atom number, R3、R4、R5、R6And R7It is identical or different, and at least one
For vinyl；
Formula (III)；
In formula (III), R8The alkyl or vinyl for being 1 to 4 for hydrogen, carbon atom number, R9It is 1 to 4 for hydrogen, carbon atom number
Alkyl or vinyl, R10The alkyl or vinyl for being 1 to 4 for hydrogen, carbon atom number, R11The alkyl for being 1 to 4 for hydrogen, carbon atom number
Or vinyl, R8、R9、R10And R11It is identical or different, and at least one is vinyl；
The oil-soluble ethylene base monomer is styrene monomer, methacrylate monomer or methyl methacrylate list
Body.
The cupric compound solution is that the methanol of at least one of copper chloride, copper bromide, copper nitrate, copper sulphate is molten
Liquid.
The cupric compound and polymer feeds intake mass ratio as 0.5~40:100, preferably 5~20:100；Institute
The molar ratio of the sodium borohydride dosage and cupric compound stated is 0.275~20:1.
The mass ratio of the bivalent compound and imidazole radicals cross-linked polymer contains the immersion of imidazole radicals cross-linked polymer
The methanol solution of cupric compound is simultaneously vigorously stirred 8~24 hours, and the nitrogen in copper ion and imidazole radicals cross-linked polymer occurs
The solid that complexation reaction obtains immerses in the methanol solution by the molar ratio of the cupric compound and sodium borohydride,
It is vigorously stirred 6~24 hours, imidazole radicals cross-linked polymer supported copper nano-particle catalyst is made.
Shared mass fraction is 0.5~20%, preferably 3~12% to the copper nano-particle in the catalyst；Size
Range is 0.5~10nm, preferably 0.5~5nm.
The organic solvent is one of toluene, chloroform, methylene chloride, nitrobenzene.
Commercial product can be used in raw material of the present invention, reagent.
Compared with prior art, the present invention has following marked improvement:
Advantages of the present invention: simple and easy to do, low in cost, the achievable serialization large-scale production of process, and this method pole
The earth reduces the residual quantity of catalyst metals in the product, maintains the excellent electric property of polyphenylene oxide.Catalyst combines
The characteristics of copper nano-particle and imidazole radicals cross-linked polymer；Imidazole radicals cross-linked polymer have space net structure, cupric from
After the sub complexing with nitrogen therein, it can be fixed while being reduced in a network, by adjusting imidazole radicals content, the degree of cross linking
And in the adjustable catalyst of copper dosage copper load capacity；Imidazole radicals is alkali needed for oxidative coupling reaction occurs for phenol monomer
The complexing of property ligand, nitrogen and bivalent cupric ion in preparation process in imidazole radicals makes the copper nano-particle being reduced still
Weaker complexing is maintained with nitrogen therein, while cross-linked polymer is locally increased the concentration of catalyst and ligand, into
And effectively improve oxidizing reaction rate and catalyst efficiency；Synthetic method of the invention is with wide development space and greatly
Market application value more meets the requirement of sustainable development.
Specific embodiment
Embodiment 1 prepares nitrogenous cross-linked polymer supported copper nano-particle catalyst
In three-necked flask, be added divinylbenzene (DVB) (2.0g, 15mmol), vinyl imidazole (VI) (0.483g,
5mmol), methyl methacrylate (0.5g, 5mmol), azodiisobutyronitrile (0.07g) and ethyl acetate (30ml), nitrogen are protected
Shield.It does not stir, for 24 hours, dry out solvent, obtains 2.1g white powder as divinylbenzene and ethylene after reaction for 100 DEG C of reactions
The copolymer (PDVB-MMA-VI) of base imidazoles.
The above-mentioned white powder of 200mg is immersed into CuCl2The methanol solution (10mL) of (10mg), is vigorously stirred 16h, centrifugation,
Methanol washing, is put into the methanol solution (10mL) of sodium borohydride (10mg), is vigorously stirred 16h, is centrifuged, and methanol washing obtains
Nitrogenous cross-linked polymer supported copper nano-particle catalyst, copper mass load capacity 1.34%.
Embodiment 2~7
Nitrogenous cross-linked polymer supported copper nano-particle catalyst is prepared using the method for embodiment 1, the difference is that changing
The dosage of mole when cupric compound of DVB and VI when synthesizing PDVB-MMA-VI, is shown in Table 1:
Embodiment 8~10
Nitrogenous cross-linked polymer supported copper nano-particle catalyst is prepared using the method for embodiment 1, the difference is that changing
The type and dosage of cupric compound, are shown in Table 2:
The oxidative coupling polymerization reaction of phenol monomer in 11 fixed bed of embodiment
1 catalyst 100mg of embodiment is filled in the stainless steel reaction pipe of 13mm diameter, reaction solution 2,6- dimethyl
The mixed solution (wherein DMP: water: toluene mass ratio is 1:1:10) of phenol (DMP), water and toluene, flow 10mL/min, oxygen
Throughput is 100mL/min.After reaction tube is heated to 40 DEG C, start to be passed through reaction solution.With the progress of reaction, DMP conversion ratio
It tends towards stability, solvent portion is added dropwise in excessive methanol, and centrifugation obtains product, and polyphenylene oxide (PPE) yield is about 88.9%, by-product
Object (DPQ) content 0.5%, PPE weight average molecular weight Mn=60000, molecular weight distribution DP=2.2.
Embodiment 12~17
According to the method for embodiment 11 in preparation PPE, the difference is that the catalyst of the preparation of embodiment 2~7 is respectively adopted, instead
3 should be the results are shown in Table:
Embodiment 18~20
According to the method for embodiment 11 in preparation PPE, the difference is that the catalyst of the preparation of embodiment 8~10 is respectively adopted,
Reaction result is shown in Table 4:
Embodiment 21
According to the method selective oxidation alcohol in an aqueous medium of embodiment 11, unlike DMP: water: toluene mass ratio is
2:1:10, DMP conversion ratio tend towards stability about 87.8%, and polyphenylene oxide (PPE) yield is about 85%, by-product (DPQ) content
0.6%, PPE weight average molecular weight Mn=58000, molecular weight distribution DP=2.0.
Table 1
| Embodiment sequence number | Copper chloride dosage (mg) | The molar ratio of DVB and VI in PDVB-VI | Copper load capacity (%) |
| 2 | 20 | 3 | 2.64 |
| 3 | 40 | 3 | 5.01 |
| 4 | 10 | 10 | 1.02 |
| 5 | 20 | 10 | 1.95 |
| 6 | 10 | 1 | 1.57 |
| 7 | 20 | 1 | 3.18 |
Table 2
| Embodiment sequence number | Copper compound | Copper compound dosage (mg) | Copper load capacity (%) |
| 8 | Copper nitrate | 20 | 2.71 |
| 9 | Copper sulphate | 40 | 4.78 |
| 10 | Copper bromide | 30 | 3.11 |
Table 3
| Embodiment sequence number | Catalyst source | Mw | DP | Yield (%) | DPQ (%) |
| 12 | Embodiment 2 | 59000 | 2.3 | 88.1 | 0.8 |
| 13 | Embodiment 3 | 55000 | 1.8 | 91.2 | 0.7 |
| 14 | Embodiment 4 | 64000 | 2.5 | 92.0 | 0.2 |
| 15 | Embodiment 5 | 57000 | 2.3 | 87.9 | 0.5 |
| 16 | Embodiment 6 | 55000 | 1.8 | 89.3 | 0.3 |
| 17 | Embodiment 7 | 58000 | 1.7 | 91.7 | 0.4 |
Table 4
| Embodiment sequence number | Catalyst source | Mw | DP | Yield (%) | DPQ (%) |
| 18 | Embodiment 8 | 57000 | 2.3 | 88.1 | 0.6 |
| 19 | Embodiment 9 | 50000 | 1.8 | 91.2 | 0.5 |
| 20 | Embodiment 10 | 65000 | 2.5 | 92.0 | 0.4 |
Claims (10)
1. a kind of method of oxidative coupling polymerization synthesis polyphenylene oxide, it is characterised in that: phenol monomer, organic solvent and water exist
Under molecular oxygen-containing gas existence condition, by being equipped with the fixed bed reactors of catalyst, the oxidative coupling of phenol monomer is carried out
The method of polymerization reaction；
The catalyst is imidazole radicals cross-linked polymer supported copper nano-particle compound.
2. a kind of method of oxidative coupling polymerization synthesis polyphenylene oxide as described in claim 1, which is characterized in that the oxidation
The mass ratio composition of each raw material in coupling polymerization reaction are as follows:
Phenol monomer 1；
Organic solvent 3~40；
Water 0.1~4；
In the presence of molecular oxygen, reaction temperature is 10~60 DEG C, and reaction pressure is normal pressure~1.0MPa, gas space velocity 10mL/min
~1L/min, 10~500mL/min of flow rate of liquid.
3. a kind of method of oxidative coupling polymerization synthesis polyphenylene oxide as described in claim 1, which is characterized in that the phenol
Class monomer is formula (I) structural formula compound represented:
In formula (I), R1And R2Respectively C1~C4Alkyl, C2~C4Alkylene or phenyl, R1And R2It is identical or different.
4. the method as described in claim 1, which is characterized in that the imidazole radicals cross-linked polymer load copper nano-particle is urged
Agent is after imidazole radicals cross-linked polymer is coordinated with cupric compound solution through the resulting compound of sodium borohydride reduction.
5. the method as described in claim 1, which is characterized in that the imidazole radicals cross-linked polymer is divinylbenzene class list
The cross-linked copolymer of body and vinyl imidazole class monomer and other one or more oil-soluble ethylene base monomers；
Divinylbenzene class monomer in the polymer, vinyl imidazole class monomer and other one or more have oil-soluble second
The molar ratio of alkenyl monomer is 1~10:1:0.001~1；
Wherein, the divinylbenzene class monomer is formula (II) structural formula compound represented, and vinyl imidazole class monomer is
Formula (III) structural formula compound represented:
In formula (II), R3The alkyl or vinyl for being 1 to 4 for hydrogen, carbon atom number, R4For hydrogen, carbon atom number be 1 to 4 alkyl or
Vinyl, R5The alkyl or vinyl for being 1 to 4 for hydrogen, carbon atom number, R6The alkyl or ethylene for being 1 to 4 for hydrogen, carbon atom number
Base, R7The alkyl or vinyl for being 1 to 4 for hydrogen, carbon atom number, R3、R4、R5、R6And R7It is identical or different, and at least one is
Vinyl；
In formula (III), R8The alkyl or vinyl for being 1 to 4 for hydrogen, carbon atom number, R9The alkyl for being 1 to 4 for hydrogen, carbon atom number
Or vinyl, R10The alkyl or vinyl for being 1 to 4 for hydrogen, carbon atom number, R11For hydrogen, carbon atom number be 1 to 4 alkyl or second
Alkenyl, R8、R9、R10And R11It is identical or different, and at least one is vinyl；
The oil-soluble ethylene base monomer is styrene monomer, methacrylate monomer or methyl methacrylate monomer.
6. method as described in claim 1 or 4, which is characterized in that the cupric compound solution is copper chloride, bromination
The methanol solution of at least one of copper, copper nitrate, copper sulphate.
7. method as described in claim 1 or 4, which is characterized in that the cupric compound and polymer feed intake quality
Than for 0.5~40:100；The molar ratio of the sodium borohydride dosage and cupric compound is 0.275~20:1.
8. method as claimed in claim 4, which is characterized in that comprising steps of being handed over by the bivalent compound and imidazole radicals
Imidazole radicals cross-linked polymer is immersed the methanol solution containing cupric compound and is vigorously stirred 8 by the mass ratio of linked polymer
~24 hours, copper ion occurred the solid that complexation reaction obtains with the nitrogen in imidazole radicals cross-linked polymer and immerses by the divalent
It in the methanol solution of the molar ratio of copper compound and sodium borohydride, is vigorously stirred 6~24 hours, it is poly- that imidazole radicals crosslinking is made
Close object supported copper nano-particle catalyst.
9. the method as described in claim 4 or 8, which is characterized in that the copper nano-particle shared quality in the catalyst
Score is 0.5~20%, and size range is 0.5~10nm.
10. the method as described in claim 4 or 8, which is characterized in that the organic solvent be toluene, chloroform, methylene chloride,
One of nitrobenzene.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| US3306874A (en) * | 1962-07-24 | 1967-02-28 | Gen Electric | Oxidation of phenols |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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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