CN109517174A - A kind of preparation method of three-dimensional network-like structure polyphenylene sulfide - Google Patents
A kind of preparation method of three-dimensional network-like structure polyphenylene sulfide Download PDFInfo
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- CN109517174A CN109517174A CN201811300164.0A CN201811300164A CN109517174A CN 109517174 A CN109517174 A CN 109517174A CN 201811300164 A CN201811300164 A CN 201811300164A CN 109517174 A CN109517174 A CN 109517174A
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- polyphenylene sulfide
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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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/025—Preparatory processes
- C08G75/0254—Preparatory processes using metal sulfides
Abstract
The present invention provides a kind of preparation methods of three-dimensional network-like structure polyphenylene sulfide, nine water vulcanized sodium are obtained into anhydrous sodium sulfide by the oxygen barrier processing of high temperature first, using potassium carbonate and lithium chloride as combination catalyst, it is mixed with the anhydrous sodium sulfide solution of above-mentioned preparation, with sodium hydroxide tune solution to pH=13 ~ 14,70 ~ 80 DEG C are then heated to, paracide is added, is continually fed into nitrogen under stirring；220 ~ 225 DEG C are then heated to, 2 ~ 2.5 h of isothermal reaction；Washing is filtered, dry, obtains the polyphenylene sulfide of sheet；Laminar structured polyphenylene sulfide is finally subjected to after polymerization by high temperature, obtain the polyphenylene sulfide with three-dimensional network-like structure, this polyphenylene sulfide has bigger specific surface area, therefore various groups (macromolecular/metal oxide or drug etc.) can be easily introduced in gap, for preparing than the polyphenyl thioether composite material by various base group modifications.
Description
Technical field
The present invention relates to a kind of preparation method of polyphenylene sulfide more particularly to a kind of three-dimensional network-like structure polyphenylene sulfides
Preparation method belongs to field of material preparation.
Background technique
Polyphenylene sulfide (Polyphenylene sulfide, abridge PPS) is in molecule containing to phenylene sulfide repetition knot
The polymer of structure unit is a kind of new type functional engineering plastics, has in electronics, automobile, machinery and chemical field and answer extensively
With.Polyphenylene sulfide is that the product obtained after nucleophilic substitution, polyphenylene sulfide occur in organic solvent for vulcanized sodium and paracide
The micromorphology of ether has the structures such as sheet, spherical, flower-shaped, netted, and several microns can be expanded to lateral dimension, can also be longitudinal
Elongation, therefore, the typical size of construct trans general chemistry and material science.Polyphenylene sulfide can be considered a kind of unconventional
New material has many excellent characteristics such as stabilizing mechanical size, high-insulativity, high tenacity, solvent resistant, high temperature resistant.Polyphenyl
Thioether is a kind of two thin property substances, can be seen that its stability very in the alternately arranged structure of its phenyl ring and sulphur atom
By force, substantially insoluble any solvent, to determine its macroscopic property.Therefore, polyphenylene sulfide can be such as catalyst carrier or multiple
Condensation material substrate exists, and activating agent, which is added, can reduce the energy between interface.Therefore, with the polyphenylene sulfide of more multi-pore structure
Can be preferably compound with other materials generation, thus obtain better material.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of tridimensional network polyphenylene sulfide.
The preparation method of tridimensional network polyphenylene sulfide of the present invention, comprises the following steps that:
(1) preparation of anhydrous sodium sulfide solution
It disperses Sodium Sulphate Nine Hydroxide in N- dimethyl pyrrolidone, the oxygen barrier protection of nitrogen is continually fed into, at 150 ~ 160 DEG C
1.5 ~ 2 h are reacted, anhydrous sodium sulfide solution is obtained.
In order to reach better effect, Sodium Sulphate Nine Hydroxide is scattered in N- dimethyl with the mass volume ratio of 10 ~ 13g/mL
In pyrrolidones.The gas velocity for being continually fed into nitrogen is 10 ~ 15 mL/min.
(2) preparation of sheet polyphenylene sulfide
Using potassium carbonate and lithium chloride as combination catalyst, mixed with the anhydrous sodium sulfide solution of above-mentioned preparation, with sodium hydroxide tune
Solution then heats to 70 ~ 80 DEG C, paracide is added, nitrogen is continually fed under stirring, solution is ink at this time to pH=13 ~ 14
Green；220 ~ 225 DEG C are then heated to, 2 ~ 2.5 h of isothermal reaction；Solution is black at this time；Washing is filtered, dry, obtains piece
The polyphenylene sulfide of stratiform.
In combination catalyst, the mass ratio of potassium carbonate and lithium chloride is 1:4 ~ 1:4.4, combination catalyst and anhydrous sodium sulfide
Mass ratio be 1:4 ~ 1:5.In order to be conducive to accelerate catalysis reaction, by combination catalyst with the mass body of 1:10 ~ 1:11 g/mL
Product ratio is scattered in N- dimethyl pyrrolidone.
It is acidulous material that the reason of addition sodium hydroxide is adjusted to solution alkaline in reaction is sulfidion in the solution,
And weak basic condition is easier to react in nucleophilic substitution；Sodium hydroxide and potassium carbonate are also used as reaction promoter simultaneously, promote
Nucleophilic substitution.
The mass ratio of paracide and vulcanized sodium is 1:1.5 ~ 1:2.Vulcanized sodium and paracide mention in reaction for polymer
For raw material, chain propagation reaction is carried out on this basis, generates the polyphenylene sulfide of high polymeric；Deionized water is used in washing process
Heat filtering, ethanol rinse are cleared by impurity such as the oligomer generated in reaction process, inorganic salts.
(3) preparation of three-dimensional network shape polyphenylene sulfide
The sheet polyphenylene sulfide of above-mentioned preparation is distributed in N- dimethyl pyrrolidone, is stirred to react in 270 ~ 275 DEG C
1.5 ~ 2h obtains the substance of white precipitate；Deionized water is added after cooling, filters, the mixed liquor with deionized water and ethyl alcohol is anti-
After backwashing is washed, and is filtered, dry, obtains three-dimensional network shape polyphenylene sulfide.
Pyroreaction is to arrive the higher polyphenylene sulfide of the degree of polymerization；In order to reach better effect, sheet polyphenylene sulfide
Ether is scattered in N- dimethyl pyrrolidone with 1:115 ~ 1:1:120 mg/mL mass volume ratio.
The scanning electron microscope (SEM) photograph of the respectively three-dimensional network shape polyphenylene sulfide prepared by the present invention of Fig. 1,2.It can from Fig. 1
It arrives, polyphenylene sulfide is in three-dimensional network shape, and has large-scale pore structure.Therefore it can easily be introduced in gap each
Kind group (such as metal oxide or drug), so that the polyphenyl thioether composite material by various base group modifications be made.
The present invention has the advantage that compared with the prior art
1, the present invention uses highly polar organic solvent N- dimethyl pyrrolidone, maximum can dissolve this salt of vulcanized sodium, make it
The Na in polymerization process later+Concentration increases, and increases the facilitation to necleophilic reaction.Sulfidion is in high temperature sky simultaneously
It is easy to be oxidized in gas, therefore, also has protection on the surface of aqueous solution in the organic solvent in water smoking, prevent sulphion
It is oxidized；
2, using lithium chloride and potassium carbonate combination catalyst, potassium carbonate is economical and easily available compared to pure lithium chloride, and in the solution
For alkalinity, effect is greatly facilitated to nucleophilic substitution；Secondly, potassium carbonate is readily soluble, it is more simple and convenient to washing step；
3, each step uses same solvent N- dimethyl pyrrolidone, can be recycled to save cost.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph after three-dimensional network shape polyphenylene sulfide prepared by the present invention is dry at 60 DEG C.
Fig. 2 is the scanning electron microscope (SEM) photograph after three-dimensional network shape polyphenylene sulfide prepared by the present invention is dry at 60 DEG C.It is specific real
Apply mode
Below by specific example to works such as the present invention a kind of preparation, the patterns of three-dimensional network-like structure polyphenylene sulfide furtherly
It is bright.
Embodiment 1
(1) preparation of anhydrous sodium sulfide: weighing 79.5 g of Sodium Sulphate Nine Hydroxide, is added to 180mL N- dimethyl pyrrolidone
In, it is continually fed under the oxygen barrier protection (nitrogen flow rate is maintained at 10 mL/min) of nitrogen, 1 h is reacted in 150 ~ 160 DEG C, is obtained
The anhydrous sodium sulfide solution of green, is poured into reaction kettle after cooling；
(2) preparation of combination catalyst: weighing 5.933 g anhydrous lithium chlorides, 1.658 g Anhydrous potassium carbonates, and sealing is mixed, prevented
It is oxidized and deliquesces；
(3) preparation of sheet polyphenylene sulfide: catalyst obtained by step (2) is dissolved in 50 mL N- dimethyl pyrrolidones；It will
Anhydrous sodium sulfide solution obtained by step (1), catalyst solvent are added in high-temperature high-pressure reaction kettle and mix, and (stir in room temperature, stirring
It mixes speed and solution is adjusted to alkaline (pH=13 ~ 14) for sodium hydroxide is added under 40 r/min), be warming up to 70 DEG C, be added with stirring
44.1 g paracide, obtain blackish green solution；After sealing reaction kettle, continue under stirring (mixing speed is 900 r/min)
It is passed through nitrogen (being passed through nitrogen rate is 10 mL/min) and carrys out air in replacement reaction kettle；220 DEG C are then heated to, this temperature is kept
Degree 2.5 h of reaction, solution is black at this time；It is washed repeatedly with deionized water, ethyl alcohol, 60 DEG C of heat filterings, it is dry at 60 DEG C, it obtains
The polyphenylene sulfide of 10.5 g sheets.
(4) preparation of bouquet shape polyphenylene sulfide: by the polyphenylene sulfide of sheet obtained by step (3), it is added to (3) step
In filtered fluid, while 50 mL N- dimethyl pyrrolidones are added, is stirred to react 2h at 270 DEG C, obtains white precipitate substance；
Then 100 DEG C are cooled to, 50 mL deionized waters is added with stirring and is filtered while hot after solution temperature is down to 60 DEG C, spend from
The mixed liquor of sub- water and ethyl alcohol washs repeatedly, and 60 DEG C of dryings obtain the polyphenylene sulfide of bouquet shape.The scanning electron microscope (SEM) photograph of polyphenylene sulfide
As shown in Figure 1, polyphenylene sulfide is in three-dimensional network shape and has large-scale pore structure.Specific surface area is about 171.049
m2/g。
Embodiment 2
(1) preparation of anhydrous sodium sulfide: with embodiment 1；
(2) preparation of catalyst: weighing 8.29 g anhydrous lithium chlorides, 1.658 g Anhydrous potassium carbonates, and sealing mixes (wherein carbonic acid
Potassium and lithium chloride ratio are 1:5)；
(3) preparation of sheet polyphenylene sulfide: with embodiment 1；
(4) preparation of three-dimensional network shape polyphenylene sulfide: by the polyphenylene sulfide of sheet obtained by step (3), it is added to (3) step
In filtered fluid, while 50 mL N- dimethyl pyrrolidones are added, in 270 DEG C, stirring 2 h of lower reaction, obtains having white heavy
The substance in shallow lake；Then 100 DEG C are cooled to, isometric deionized water is added with stirring, after solution temperature is down to 60 DEG C, while hot
Filtering, is washed, 60 DEG C of dryings obtain three-dimensional netted polyphenylene sulfide repeatedly with the mixed liquor of deionized water and ethyl alcohol.Polyphenylene sulfide
The scanning electron microscope (SEM) photograph of ether is as shown in Figure 2.Specific surface area is about 153.473 m2/g.The difference of its pattern and embodiment 1
It is that embodiment 1 has fragmentary netted be scattered.
Claims (8)
1. a kind of preparation method of tridimensional network polyphenylene sulfide, comprises the following steps that:
(1) it the preparation of anhydrous sodium sulfide solution: disperses Sodium Sulphate Nine Hydroxide in N- dimethyl pyrrolidone, is continually fed into nitrogen
The protection of air bound oxygen, 1.5 ~ 2 h are reacted at 150 ~ 160 DEG C, obtain anhydrous sodium sulfide solution；
(2) preparation of sheet polyphenylene sulfide: the anhydrous vulcanization using potassium carbonate and lithium chloride as combination catalyst, with above-mentioned preparation
Sodium solution mixes, and with sodium hydroxide tune solution to pH=13 ~ 14, then heats to 70 ~ 80 DEG C, paracide is added, holds under stirring
Continuous to be passed through nitrogen, solution is blackish green at this time；220 ~ 225 DEG C are then heated to, 2 ~ 2.5 h of isothermal reaction；Solution is black at this time
Color；Washing is filtered, dry, obtains the polyphenylene sulfide of sheet；
(3) the sheet polyphenylene sulfide of above-mentioned preparation the preparation of three-dimensional network shape polyphenylene sulfide: is distributed to N- dimethyl pyrrole
In alkanone, it is stirred to react 1.5 ~ 2h in 270 ~ 275 DEG C, obtains the substance of white precipitate；Deionized water is added after cooling, filters,
It is washed, is filtered repeatedly with the mixed liquor of deionized water and ethyl alcohol, it is dry, obtain three-dimensional network shape polyphenylene sulfide.
2. a kind of preparation method of tridimensional network polyphenylene sulfide as described in claim 1, it is characterised in that: in step (1),
Sodium Sulphate Nine Hydroxide is scattered in N- dimethyl pyrrolidone with the mass volume ratio of 10 ~ 13g/mL.
3. a kind of preparation method of tridimensional network polyphenylene sulfide as described in claim 1, it is characterised in that: step (2)
In combination catalyst, the mass ratio of potassium carbonate and lithium chloride is 1:4 ~ 1:4.4.
4. a kind of preparation method of tridimensional network polyphenylene sulfide as described in claim 1, it is characterised in that: in step (2),
First disperse combination catalyst in N- dimethyl pyrrolidone with the mass volume ratio of 1:10 ~ 1:11 g/mL, then with anhydrous sulphur
Change sodium solution to mix.
5. a kind of preparation method of tridimensional network polyphenylene sulfide as described in claim 1, it is characterised in that: in step (2),
The mass ratio of combination catalyst and anhydrous sodium sulfide is 1:4 ~ 1:5.
6. a kind of preparation method of tridimensional network polyphenylene sulfide as described in claim 1, it is characterised in that: in step (2),
The mass ratio of paracide and vulcanized sodium is 1:1.5 ~ 1:2.
7. a kind of preparation method of tridimensional network polyphenylene sulfide as described in claim 1, it is characterised in that: in step (3),
Sheet polyphenylene sulfide is scattered in N- dimethyl pyrrolidone with 1:115 ~ 1:1:120 mg/mL mass volume ratio.
8. a kind of preparation method of tridimensional network polyphenylene sulfide as described in claim 1, it is characterised in that: in each step,
The gas velocity for being continually fed into nitrogen is 10 ~ 15 mL/min.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110204723A (en) * | 2019-07-02 | 2019-09-06 | 西北师范大学 | A kind of preparation method of heat resistant poly diphenyl sulfide |
| CN110527295A (en) * | 2019-10-11 | 2019-12-03 | 西北师范大学 | A kind of preparation method of polyphenylene sulfide/graphene quantum dot composite flame-retardant agent |
| CN112186208A (en) * | 2020-10-14 | 2021-01-05 | 天津工业大学 | Nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5849718A (en) * | 1981-09-19 | 1983-03-24 | Mitsubishi Electric Corp | Resin material resistant to hot water |
| CN105037728A (en) * | 2015-06-10 | 2015-11-11 | 张家港市新盛新材料有限公司 | Polyphenylene sulfide production method |
| CN106893102A (en) * | 2017-03-10 | 2017-06-27 | 四川中科兴业高新材料有限公司 | A kind of method that synthesis mother liquid prepares polyphenylene sulfide |
-
2018
- 2018-11-02 CN CN201811300164.0A patent/CN109517174A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5849718A (en) * | 1981-09-19 | 1983-03-24 | Mitsubishi Electric Corp | Resin material resistant to hot water |
| CN105037728A (en) * | 2015-06-10 | 2015-11-11 | 张家港市新盛新材料有限公司 | Polyphenylene sulfide production method |
| CN106893102A (en) * | 2017-03-10 | 2017-06-27 | 四川中科兴业高新材料有限公司 | A kind of method that synthesis mother liquid prepares polyphenylene sulfide |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110204723A (en) * | 2019-07-02 | 2019-09-06 | 西北师范大学 | A kind of preparation method of heat resistant poly diphenyl sulfide |
| CN110527295A (en) * | 2019-10-11 | 2019-12-03 | 西北师范大学 | A kind of preparation method of polyphenylene sulfide/graphene quantum dot composite flame-retardant agent |
| CN112186208A (en) * | 2020-10-14 | 2021-01-05 | 天津工业大学 | Nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst and preparation method and application thereof |
| CN112186208B (en) * | 2020-10-14 | 2022-05-27 | 天津工业大学 | Nitrogen and sulfur co-doped carbon-based oxygen reduction catalyst and preparation method and application thereof |
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