CN101864077B - Polyarylene sulfide ketone and preparation method thereof - Google Patents
Polyarylene sulfide ketone and preparation method thereof Download PDFInfo
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- CN101864077B CN101864077B CN2010102135768A CN201010213576A CN101864077B CN 101864077 B CN101864077 B CN 101864077B CN 2010102135768 A CN2010102135768 A CN 2010102135768A CN 201010213576 A CN201010213576 A CN 201010213576A CN 101864077 B CN101864077 B CN 101864077B
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Abstract
The invention discloses a polyarylene sulfide ketone (PASKA) and a preparation method thereof. The method is characterized in that the method comprises the following steps: respectively adding 13 parts of Na2SxH2O, 0.1-10 parts of alkaline compound and 70-100 parts of organic solvent into a reactor which is provided with a water knockout vessel, a blender, a reflux and a nitrogen inlet, and dehydrating at 150-230 DEG C for 0.5-2h; cooling to 25-120 DEG C, adding 25-35 parts of dihalogen acid benzophenone.schiff base for reaction at 180-200 DEG C for 2-5h, heating to 200-220 DEG C and preserving the temperature for 2-5h, cooling and pouring the reaction liquid into methyl alcohol, precipitating and soaking for 24-48h, and drying and crashing the polymer; extracting with the methyl alcohol or ethanol, deionized water and acetone for 24-48h; drying and then dissolving with tetrahydrofuran, adding inoxidized acid for acidolysis, and filtering to obtain the powdery polymer; and then extracting with the deionized water and acetone for 24-48h, and drying to obtain the PASKA resin.
Description
Technical field
The present invention relates to a kind of polyarylene sulfide ketone and preparation method thereof, belong to the synthetic field of polymer.
Background technology
Polyarylene sulfide ketone (PASK) is after poly arylidene thio-ester, a kind of sulfur-containing aromatic polymers that develops rapidly in recent years.Because PASK has thermostability, electrical insulating property and the isostatic physical strength of higher melt temperature, excellence, is a kind of thermoplastic macromolecule material of excellent combination property therefore.But polyarylene sulfide ketone is insoluble to other any organic solvent at normal temperatures except that the vitriol oil, limited its application.Indian Journal of Chemistry (21,501,1982) and the Japanese Patent JP-A-60-58435 synthetic polyarylene sulfide ketone of employing high pressure sodium sulfide method of having reported for work, the viscosity of resulting polymers all is no more than 0.3dl/gd (H
2SO
4, 0.5g/dl, 28 ℃), and the viscosity of U.S. Pat 005097003A employing high temperature sodium hydrosulfide synthetic polyarylene sulfide ketone (not through Overheating Treatment) is 0.5dl/g (H
2SO
4, 0.5g/dl, 30 ℃).The synthetic polyarylene sulfide ketone of high-pressure process needs conditions such as High Temperature High Pressure, and non-pressure process synthetic polyarylene sulfide ketone molecular weight is generally not high.
Summary of the invention
The objective of the invention is provides a kind of polyarylene sulfide ketone and preparation method thereof at the prior art deficiency.Be characterized under normal pressure, preparing the polyarylene sulfide ketone Schiff's base with sodium sulphite and dihalo-benzophenone Schiff's base, acidolysis then, produce polyarylene sulfide ketone, the polyarylene sulfide ketone that this method obtains has yield height, molecular weight height, easy processing, high temperature resistant, corrosion resistant advantage.
The object of the invention is realized that by following technology wherein said raw material is weight fraction except that specified otherwise.
The chemical equation of this polyarylene sulfide ketone is:
Wherein X=F or Cl, n=10-200, HA are any one in non-oxidizing acid hydrochloric acid, phosphoric acid, the methylsulphonic acid, the dihalo-benzophenone that is adopted is: 4,4 '-dihalo-benzophenone or 2,4 '-dihalo-benzophenone or 3,4 '-dihalo-benzophenone or 3, any one in 3 '-dihalo-benzophenone.
The starting raw material of polyarylene sulfide ketone is composed of the following components:
Na
2SxH
2O Na
260% 13.0 part of S content ≈
Basic cpd 0.1-10 part
Dihalo-benzophenone Schiff's base 25-35 part
Organic solvent 70-100 part
Wherein the molecular formula of dihalo-benzophenone Schiff's base is
, X=F or Cl.
Organic solvent is at least a in N-Methyl pyrrolidone, HMPA, dimethyl sulfoxide (DMSO) and the tetramethylene sulfone.
Basic cpd is any in sodium hydroxide, potassium hydroxide, yellow soda ash or the salt of wormwood.
The preparation method of polyarylene sulfide ketone comprises following steps:
(1) preparation of dihalo-benzophenone Schiff's base
A. the preparation of dihalo-benzophenone Schiff's base
With dihalo-benzophenone 436-500 part, with 279.36 parts of aniline, p-methyl benzenesulfonic acid 0.2-0.5 part, toluene 900-1500 part, add successively and have in the reactor of agitator, thermometer, condenser and water trap, in temperature 113-118 ℃ reflux water-dividing, reaction 48-72h obtains dihalo-benzophenone Schiff's base;
B. the purifying of dihalo-benzophenone Schiff's base
The toluene in the above-mentioned reaction solution is removed in distillation, separate out red solid after the cooling, with 800-1200 part recrystallizing methanol three times of gained solid, the yellow crystals that obtains places temperature 50-80 ℃, the dry 24-48h acquisition of vacuum tightness 0.90-0.95MPa dihalo-benzophenone Schiff's base;
(2) preparation of polyarylene sulfide ketone Schiff's base
A. the preparation of polyarylene sulfide ketone Schiff's base
With Na
2SxH
213 parts of O, 0.1～10 part of basic cpd, solvent is dissolved in the reactor that has agitator, thermometer, reflux and water trap for 70～100 parts, in nitrogen protection, 150～230 ℃ of 0.5～2h that dewater down of temperature.When treating that temperature drops to 25～120 ℃, add dihalo-benzophenone Schiff's base 25-35 part again, react 2～5h down for 180～200 ℃ in temperature, be warmed up to 200-220 ℃ then, reaction 2～5h makes the polyarylene sulfide ketone Schiff's base;
B. the purifying of polyarylene sulfide ketone Schiff's base
Above-mentioned resulting polymers is soaked 24-48h in methyl alcohol, after the pulverizing, respectively with methyl alcohol or ethanol, deionized water and acetone extracting 24-48h, then at temperature 50-80 ℃, the dry 24-48h of vacuum tightness 0.90-0.95MPa;
(3) acidolysis of polyarylene sulfide ketone Schiff's base
A. the acidolysis of polyarylene sulfide ketone Schiff's base
With 3 parts of the above-mentioned polyarylene sulfide ketone Schiff base polymers of handling well, the tetrahydrofuran (THF) of 80-100 part adds and has in the reactor of agitator, thermometer, condenser, dissolve fully until polymkeric substance at temperature 63-68 ℃ of backflow 2-6h, filter then, get filtrate, 10-20 part non-oxidizing acid is added in the filtrate, at temperature 63-68 ℃ of backflow 24-48h, filter, drying obtains polyarylene sulfide ketone;
B. the purifying of polyarylene sulfide ketone
Above-mentioned polyarylene sulfide ketone is used deionized water, acetone extracting 24-48h respectively, and drying obtains resin;
Performance test:
The structure of the polyarylene sulfide ketone Schiff's base of the present invention preparation through infrared spectra and
1H-NMR is confirmed, as Fig. 1～shown in Figure 3.By regulation and control temperature of reaction, material proportion and feed way, the polyarylene sulfide ketone Schiff's base of preparation different viscosity and the polyarylene sulfide ketone after the acidolysis thereof, and be solvent with the tetrahydrofuran (THF) and the vitriol oil respectively, the solution of preparation 0.5g/dl is respectively [η]=0.20～1.0dl/g and [η]=0.30-1.00dl/g at 30.0 ± 0.1 ℃ of following intrinsic viscosities with the determination of ubbelohde viscometer polymkeric substance of temperature.NETZSCH DSC 200PC is adopted in the DSC test, 10 ℃/min of temperature rise rate, and temperature range: 100 ℃～350 ℃, test result is as shown in Figure 4; TA Q600 is adopted in the TG test, 10 ℃/min of temperature rise rate, and temperature range: 100 ℃～800 ℃, test result is as shown in Figure 5.Simultaneously prepared polymkeric substance has been carried out solubility experiment, detailed being shown in Table 1.
The present invention has following advantage:
1. in the dihalo-benzophenone, introduce imines, improved the solvability of polymkeric substance significantly, polymkeric substance can be dissolved in N-Methyl pyrrolidone, HMPA, N-cyclohexyl pyrrolidone and the tetrahydrofuran solvent, for providing favourable condition in the application aspect the film.
2. owing in polymer architecture, introduce imines, make polyreaction by the heterogeneous homogeneous phase that becomes, reaction efficiency improves greatly, and the molecular weight of gained polyarylene sulfide ketone and purity significantly improve after the polymkeric substance acidolysis, also provides convenience indirectly for measuring the polyarylene sulfide ketone molecular weight simultaneously.
3. owing to introduce imines in polymer architecture, make the temperature required polymerization with respect to dihalo-benzophenone and sodium sulphite of polyreaction lower, avoided the waste of high temperature polymerization to the energy, security is good, good stability, the advantage that yield is high.
4. acidolysis gained polyarylene sulfide ketone is used for special engineering plastics and high performance polymer matrix material, and prepares parts and goods heat-resisting, resistance to chemical attack, and the specialty films of making has wide practical use.
Description of drawings:
Fig. 1 is the nuclear magnetic spectrum to two fluoro benzophenone Schiff's base
4,4 '-two fluoro benzophenone Schiff's base
1H-NMR is a solvent with the deuterochloroform, and wherein the ownership at each peak is indicated in Fig. 1 respectively.
Fig. 2 is the nuclear magnetic spectrum of polyarylene sulfide ketone Schiff base polymer
The polyarylene sulfide ketone Schiff base polymer
1H-NMR is solvent with deuterium for tetrahydrofuran (THF), and wherein the ownership at each peak is indicated in Fig. 2 respectively.
Fig. 3 is respectively 4, the infrared spectrum of the polyarylene sulfide ketone after 4 '-two fluoro benzophenone Schiff's base, polyarylene sulfide ketone Schiff base polymer and the acidolysis thereof.
The infrared spectrum of 4,4 '-two fluoro benzophenone Schiff's base: 1616cm
-1Absorption peak absorption peak for-C=N-.
The infrared spectrum of polyarylene sulfide ketone Schiff base polymer: 1610cm
-1For-the C=N-absorption peak, 1551cm
-1, 1484cm
-1, 1396cm
-1Be the skeleton absorption peak of aromatic ring, 1080cm
-1Be the absorption peak of-S-, 838cm
-1Para-orientation absorption peak for aromatic ring.
The infrared spectrum of polyarylene sulfide ketone: 1652cm
-1The absorption peak of-CO-, 1550cm
-1, 1481cm
-1, 1394cm
-1Be the skeleton absorption peak of aromatic ring, 1079cm
-1Be the absorption peak of-S-, 836cm
-1Para-orientation absorption peak for aromatic ring.
Fig. 4 is the DSC curve after polyarylene sulfide ketone Schiff base polymer and the acidolysis thereof.
The DSC curve of polyarylene sulfide ketone Schiff base polymer, the result shows that the second-order transition temperature of polyarylene sulfide ketone Schiff base polymer is 168.5C, has good thermal characteristics.
The DSC curve of polyarylene sulfide ketone Schiff's base acidolysis post polymerization thing, the result shows that the fusing point of polyarylene sulfide ketone for being 347.5 ℃, has good thermal characteristics.
Fig. 5 is the TG curve of the polyarylene sulfide ketone of same viscosity under polyarylene sulfide ketone and the homopolymerization condition after polyarylene sulfide ketone Schiff base polymer and the acidolysis thereof.
Fig. 5 is the TG curve of phase emergencing copolymer, the result shows that the temperature of the decomposition 5% of polyarylene sulfide ketone Schiff base polymer is 470.7 ℃, and the temperature of decomposing the decomposition 5% of back gained polyarylene sulfide ketone is 500.6 ℃, the temperature of the homopolymerization poly arylidene thio-ester ketone decomposition 5% of same viscosity is 509.5 ℃, has similar thermostability.
Embodiment
Below by example the present invention is carried out concrete description, be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified, can not be interpreted as the restriction to the scope of the present invention includes, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Example 1:
(1): the preparation of 4,4 '-two fluoro benzophenone Schiff's base
Will be to 4,4 '-two fluoro benzophenone 436g, with arylamine 279.36g, to methyl aromatic sulfonic acid 0.3g, solvent toluene 1500g, add successively and have in the reactor of agitator, thermometer, condenser, water trap, in 115 ℃ of reflux water-dividings of temperature, behind the reaction 48h, toluene distillation in the solution is removed, then with the solid of separating out recrystallization three times in the 1200g methanol solution, with the gained crystal at the dry 48h of 80 ℃ of temperature, vacuum tightness 0.90MPa, obtain the 410g target product, the nuclear-magnetism of this compound characterizes as Fig. 1, and the result shows that the synthetic product is a target.
(2): the preparation of polyarylene sulfide ketone Schiff base polymer
With 13.0g sodium sulphite, 0.2g sodium hydroxide, the 80ml HMPA, add successively and have agitator, thermometer, condenser, water trap, in the reactor of nitrogen inlet mouth, reflux water-dividing in stream of nitrogen gas is raised to 230 ℃ with temperature, dehydration 1h, become oyster white until solution colour by blueness, be chilled to 60 ℃, 30.179g 4,4 '-two fluoro benzophenone Schiff's base are added in the reactor, be warming up to 180 ℃ and keep 2h, and then be warmed up to 220 ℃, and keep 2h, liquid poured into separate out precipitation in the methanol solution and soak 48h, filter, drying is pulverized, use ethanol more respectively, deionized water, acetone extracting 48h, 80 ℃ of temperature, the dry 48h of vacuum tightness 0.95MPa obtains the polyarylene sulfide ketone Schiff base polymer, and productive rate is 97.5%; It is described that the nuclear-magnetism sign of this polymkeric substance sees Fig. 2 for details, and the result shows that the synthetic product is a subject polymer, and its DSC and TG analyze as Fig. 5 and Fig. 7.
(3): the preparation of polyarylene sulfide ketone
With above-mentioned 3g polyarylene sulfide ketone Schiff base polymer, the 100ml tetrahydrofuran (THF), adding has in the reactor of agitator, reflux condensing tube successively, and 65 ℃ of backflow 5h dissolve fully up to the polyarylene sulfide ketone Schiff base polymer in temperature, in reactor, slowly drip 15ml hydrochloric acid then, at 65 ℃ of following backflow 48h of temperature, filter drying, and use deionized water, acetone extracting 48h respectively, drying obtains the 2.6g product, and productive rate is 86.7%; With the vitriol oil is the solution of 0.5g/dl for the solvent configuration concentration, use Ubbelohde viscometer down for 30.0 ± 0.1 ℃ in temperature, the Infrared Characterization of measuring intrinsic viscosity [η]=this polymkeric substance of 1.0dl/g as described in Figure 4, the result shows that acid hydrolysate is a target product, its dsc analysis such as Fig. 6.
Example 2:
(1): the preparation of 2,4 '-two fluoro benzophenone Schiff's base
Will be to 2,4 '-two fluoro benzophenone 500g are with arylamine 279.36g, to methyl aromatic sulfonic acid 0.5g, solvent toluene 900g, adding has in the reactor of agitator, thermometer, condenser, water trap successively, in 113 ℃ of reflux water-dividings of temperature, behind the reaction 72h, toluene distillation in the solution is removed, with the solid of separating out recrystallization three times in the 800g methanol solution, the gained crystal at 50 ℃ of temperature, the dry 24h of vacuum tightness 0.90MPa, is obtained the 456g target product then.
(2): the preparation of polyarylene sulfide ketone Schiff base polymer
With 13.0g sodium sulphite, 0.1g potassium hydroxide, the 80ml HMPA adds successively and has agitator, thermometer, condenser, in the reactor of water trap, reflux water-dividing in stream of nitrogen gas, temperature is raised to 180 ℃, and dehydration 0.5h becomes oyster white until solution colour by blueness, be chilled to 25 ℃, with 25g 2,4 '-two fluoro benzophenone Schiff's base are added in the reactor, are warming up to 180 ℃ and keep 3 h, and then be warmed up to 210 ℃, and keep 2h, and liquid is poured in the methanol solution, separate out precipitation and soak 24h, filter, drying is pulverized, use ethanol more respectively, deionized water, acetone extracting 24h, then 50 ℃ of temperature, the dry 24h of vacuum tightness 0.90Mpa obtains the polyarylene sulfide ketone Schiff base polymer, and productive rate is 95.8%.
(3): the preparation of polyarylene sulfide ketone
With above-mentioned 3g polyarylene sulfide ketone Schiff base polymer, the 80ml tetrahydrofuran (THF), adding has in the reactor of agitator, reflux condensing tube successively, and 68 ℃ of following backflow 6h dissolve fully up to the polyarylene sulfide ketone Schiff base polymer in temperature, in reactor, slowly drip 10ml phosphoric acid then, at 68 ℃ of following backflow 24h of temperature, filter drying, and use deionized water, acetone extracting 24h respectively, drying obtains the 2.6g product, and productive rate is 86.8%; Is the solution of 0.5g/dl with the vitriol oil for the solvent configuration concentration, uses Ubbelohde viscometer down for 30.0 ± 0.1 ℃ in temperature, measures intrinsic viscosity [η]=0.3dl/g.
Example 3:
(1): the preparation of 3,3 '-two fluoro benzophenone Schiff's base
Will be to 3,3 '-two fluoro benzophenone 448g are with arylamine 279.36g, to methyl aromatic sulfonic acid 0.2g, solvent toluene 1300g, adding has in the reactor of agitator, thermometer, condenser, water trap successively, in 118 ℃ of reflux water-dividings of temperature, behind the reaction 60h, toluene distillation in the solution is removed, with the solid of separating out recrystallization three times in the 1000g methanol solution,, obtain the 400g target product then with 50 ℃ of gained crystalline temps, the dry 24h of vacuum tightness 0.95MPa.
(2): the preparation of polyarylene sulfide ketone Schiff base polymer
With 13.0g sodium sulphite, 2g yellow soda ash, the 70ml HMPA adds successively and has agitator, thermometer, condenser, in the reactor of water trap, reflux water-dividing in nitrogen gas stream, temperature is raised to 200 ℃, and dehydration 2h becomes oyster white until solution colour by blueness, be chilled to 120 ℃, with 35g 3,3 '-two fluoro benzophenone Schiff's base are added in the reactor, are warming up to 180 ℃ and keep 3h, and then be warmed up to 220 ℃, and keep 3h, and pour liquid into methanol solution, separate out 24h in precipitation and the immersion, filter, drying is pulverized, use methyl alcohol more respectively, deionized water, acetone extracting 48h, dry again 24h obtains the polyarylene sulfide ketone Schiff base polymer, and productive rate is 95.6%.
(3): the preparation of polyarylene sulfide ketone
With above-mentioned 3g polyarylene sulfide ketone Schiff base polymer, the 90ml tetrahydrofuran (THF), adding has in the reactor of agitator, reflux condensing tube successively, and 68 ℃ of backflow 2h dissolve the polyarylene sulfide ketone Schiff base polymer fully in temperature, in reactor, slowly drip 20ml hydrochloric acid then, at 68 ℃ of following backflow 40h of temperature, filter drying, and use deionized water, acetone extracting respectively, dry 24h obtains the 2.6g product, and productive rate is 86.2%; Is the solution of 0.5g/dl with the vitriol oil for the solvent configuration concentration, uses Ubbelohde viscometer down for 30.0 ± 0.1 ℃ in temperature, measures intrinsic viscosity [η]=0.48dl/g.
Example 4:
(1): the preparation of 3,4 '-two fluoro benzophenone Schiff's base
Will be to 3,4 '-two fluoro benzophenone 440g are with arylamine 279.36g, to methyl aromatic sulfonic acid 0.4g, solvent toluene 1500g, adding has in the reactor of agitator, thermometer, condenser, water trap successively, in 113 ℃ of reflux water-dividings of temperature, behind the reaction 72h, toluene distillation in the solution is removed, with the solid of separating out recrystallization three times in the 900g methanol solution, the gained crystal at 60 ℃ of temperature, the dry 24h of vacuum tightness 0.93MPa, is obtained the 420g target product then.
(2): the preparation of polyarylene sulfide ketone Schiff base polymer
With 13.0g sodium sulphite, 10g salt of wormwood, the 100mlN-methyl-2-pyrrolidone, add successively and have agitator, thermometer, condenser, in the reactor of water trap, reflux water-dividing in stream of nitrogen gas is raised to 210 ℃ with temperature, dehydration 1h, become oyster white until solution colour by blueness, be chilled to 25 ℃, 30.179g 3,4 '-two fluoro benzophenone Schiff's base are added in the reactor, be warming up to 180 ℃ and keep 5h, and then be warmed up to 200 ℃, and keep 5h, liquid poured into separate out precipitation in the methanol solution and soak 45h, filter, drying is pulverized, use ethanol more respectively, deionized water, acetone extracting 48h, at 70 ℃, the dry 24h of vacuum tightness 0.95MPa obtains the polyarylene sulfide ketone Schiff base polymer, and productive rate is 95.0%.
(3): the preparation of polyarylene sulfide ketone
With above-mentioned 3g polyarylene sulfide ketone Schiff base polymer, the 100ml tetrahydrofuran (THF), adding has in the reactor of agitator, reflux condensing tube successively, and 65 ℃ of backflow 2h directly make the polyarylene sulfide ketone Schiff base polymer dissolve fully in temperature, in reactor, slowly drip the 15ml methylsulphonic acid then, at 65 ℃ of following backflow 45h of temperature, filter drying, and use deionized water, acetone extracting 48h respectively, drying obtains the 2.6g product, and productive rate is 85.7%; Is the solution of 0.5g/dl with the vitriol oil for the solvent configuration concentration, uses Ubbelohde viscometer down for 30.0 ± 0.1 ℃ in temperature, measures intrinsic viscosity [η]=0.3dl/g.
Example 5:
(1): 4, the preparation of 4 '-dichlorobenzene ketone Schiff's base
Will be to 4,4 '-two fluoro benzophenone 436g are with arylamine 279.36g, to methyl aromatic sulfonic acid 0.3g, solvent toluene 1300g, adding has in the reactor of agitator, thermometer, condenser, water trap successively, in 115 ℃ of reflux water-dividings of temperature, behind the reaction 60h, toluene distillation in the solution is removed, with the solid of separating out recrystallization three times in the 1200g methanol solution, the gained crystal at 70 ℃ of temperature, the dry 48h of vacuum tightness 0.95MPa, is obtained the 398g target product then.
(2): the preparation of polyarylene sulfide ketone Schiff base polymer
With 13.0g sodium sulphite, 0.2g sodium hydroxide, the 100ml tetramethylene sulfone, add successively and have agitator, thermometer, condenser, in the reactor of water trap, reflux water-dividing in nitrogen gas stream is raised to 170 ℃ with temperature, dehydration 1h, become oyster white until solution colour by blueness, be chilled to 30 ℃, 32g 4,4 '-dichlorobenzene ketone Schiff's base is added in the reactor, be warming up to 200 ℃ and keep 2h, and then be warmed up to 220 ℃, and keep 3h, liquid poured into separate out precipitation in the methanol solution and soak 40h, filter, drying is pulverized, use methyl alcohol more respectively, deionized water, acetone extracting 48h, again at 60 ℃, the dry 48h of vacuum tightness 0.95MPa obtains the polyarylene sulfide ketone Schiff base polymer, and productive rate is 90%.
(3): the preparation of polyarylene sulfide ketone
With above-mentioned 3g polyarylene sulfide ketone Schiff base polymer, the 100ml tetrahydrofuran (THF), adding has in the reactor of agitator, reflux condensing tube successively, and 64 ℃ of backflow 6h dissolve fully up to the polyarylene sulfide ketone Schiff base polymer in temperature, in reactor, slowly drip 15ml hydrochloric acid then, at 64 ℃ of following backflow 24h of temperature, filter drying, and use deionized water, acetone extracting 44h respectively, drying obtains the 2.6g product, and productive rate is 85.7%; Is the solution of 0.5g/dl with the vitriol oil for the solvent configuration concentration, uses Ubbelohde viscometer down for 30.0 ± 0.1 ℃ in temperature, measures intrinsic viscosity [η]=0.39dl/g.
Example 6:
(1): 2, the preparation of 4 '-dichlorobenzene ketone Schiff's base
Will be to 2,4 '-two fluoro benzophenone 500g are with arylamine 279.36g, to methyl aromatic sulfonic acid 0.3g, solvent toluene 1500g, adding has in the reactor of agitator, thermometer, condenser, water trap successively, in 115 ℃ of reflux water-dividings of temperature, behind the reaction 72h, toluene distillation in the solution is removed, with the solid of separating out recrystallization three times in the 1200g methanol solution, the gained crystal at 80 ℃ of temperature, the dry 48h of vacuum tightness 0.95MPa, is obtained the 450g target product then.
(2): the preparation of polyarylene sulfide ketone Schiff base polymer
With 13.0g sodium sulphite, 1.5g sodium hydroxide, 100ml dimethyl sulfoxide (DMSO) and tetramethylene sulfone (volume 1: 1), add successively and have agitator, thermometer, condenser, in the reactor of water trap, reflux water-dividing in nitrogen gas stream is raised to 150 ℃ with temperature, dehydration 2h, become oyster white until solution colour by blueness, be chilled to room temperature, with 33g 2,4 '-dichlorobenzene ketone Schiff's base is added in the reactor, be warming up to 180 ℃ and keep 5h, and then be warmed up to 200 ℃, and keep 5h, liquid poured into separate out precipitation in the methanol solution and soak 48h, filter, drying is pulverized, use methyl alcohol more respectively, deionized water, acetone extracting 48h, then at 80 ℃, the dry 48h of vacuum tightness 0.95MPa obtains the polyarylene sulfide ketone Schiff base polymer, and productive rate is 94.5%.
(3): the preparation of polyarylene sulfide ketone
With above-mentioned 3g polyarylene sulfide ketone Schiff base polymer, the 90ml tetrahydrofuran (THF), adding has in the reactor of agitator, reflux condensing tube successively, dissolves fully up to the polyarylene sulfide ketone Schiff base polymer in 65 ℃ of backflows of temperature, in reactor, slowly drip 20ml hydrochloric acid then, at 65 ℃ of following backflow 24h of temperature, filter drying, and use deionized water, acetone extracting 48h respectively, drying obtains the 2.6g product, and productive rate is 85.7%; Is the solution of 0.5g/dl with the vitriol oil for the solvent configuration concentration, uses Ubbelohde viscometer down for 30.0 ± 0.1 ℃ in temperature, measures intrinsic viscosity [η]=0.35dl/g.
Example 7:
(1): 3, the preparation of 3 '-dichlorobenzene ketone Schiff's base
Will be to 3,3 '-two fluoro benzophenone 495g are with arylamine 279.36g, to methyl aromatic sulfonic acid 0.45g, solvent toluene 1300g, adding has in the reactor of agitator, thermometer, condenser, water trap successively, in 114 ℃ of reflux water-dividings of temperature, behind the reaction 65h, toluene distillation in the solution is removed, with the solid of separating out recrystallization three times in the 1000g methanol solution,, obtain the 442g target product then with 80 ℃ of gained crystalline temps, the dry 48h of vacuum tightness 0.95MPa.
(2): the preparation of polyarylene sulfide ketone Schiff base polymer
With 13.0g sodium sulphite, 0.8g sodium hydroxide, 100ml dimethyl sulfoxide (DMSO) and tetramethylene sulfone (volume 2: 1), add successively and have agitator, thermometer, condenser, in the reactor of water trap, reflux water-dividing in nitrogen gas stream is raised to 150 ℃ with temperature, dehydration 1h, become oyster white until solution colour by blueness, be chilled to room temperature, with 30g 2,4 '-dichlorobenzene ketone Schiff's base is added in the reactor, be warming up to 180 ℃ and keep 5h, and then be warmed up to 200 ℃, and keep 5h, liquid poured into separate out precipitation in the methanol solution and soak 45h, filter, drying is pulverized, use methyl alcohol more respectively, deionized water, acetone extracting 24h, again at 50 ℃, the dry 48h of vacuum tightness 0.92MPa obtains the polyarylene sulfide ketone Schiff base polymer, and productive rate is 94.5%.
(3): the preparation of polyarylene sulfide ketone
With above-mentioned 3g polyarylene sulfide ketone Schiff base polymer, the 100ml tetrahydrofuran (THF), adding has in the reactor of agitator, reflux condensing tube successively, and 65 ℃ of backflow 5h dissolve the polyarylene sulfide ketone Schiff base polymer fully in temperature, in reactor, slowly drip 17ml hydrochloric acid then, at 65 ℃ of following backflow 24h of temperature, filter drying, and use deionized water, acetone extracting 48h respectively, drying obtains the 2.6g product, and productive rate is 85.7%; Is the solution of 0.5g/dl with the vitriol oil for the solvent configuration concentration, uses Ubbelohde viscometer down for 30.0 ± 0.1 ℃ in temperature, measures intrinsic viscosity [η]=0.5dl/g.
The solvability test of table 1 polyarylene sulfide ketone Schiff's base
In the table+be that room temperature is solvable;-be that room temperature is insoluble;
Claims (1)
1. the preparation method of a polyarylene sulfide ketone is characterized in that the method includes the steps of, is by weight:
(1) preparation of dihalo-benzophenone Schiff's base
A. the preparation of dihalo-benzophenone Schiff's base
With dihalo-benzophenone 436-500 part, with 279.36 parts of aniline, p-methyl benzenesulfonic acid 0.2-0.5 part, toluene 900-1500 part, add successively and have in the reactor of agitator, thermometer, condenser and water trap, in temperature 113-118 ℃ reflux water-dividing, reaction 48-72h obtains dihalo-benzophenone Schiff's base;
B. the purifying of dihalo-benzophenone Schiff's base
The toluene in the above-mentioned reaction solution is removed in distillation, separate out red solid after the cooling, with 800-1200 part recrystallizing methanol three times of gained solid, the yellow crystals that obtains places temperature 50-80 ℃, the dry 24-48h acquisition of vacuum tightness 0.90-0.95MPa dihalo-benzophenone Schiff's base;
(2) preparation of polyarylene sulfide ketone Schiff's base
A. the preparation of polyarylene sulfide ketone Schiff's base
With Na
2SxH
213 parts of O, 0.1～10 part of basic cpd, solvent is dissolved in the reactor that has agitator, thermometer, reflux and water trap for 70～100 parts, in nitrogen protection, and 150～230 ℃ of 0.5～2h that dewater down of temperature, when treating that temperature drops to 25～120 ℃, add dihalo-benzophenone Schiff's base 25-35 part again, react 2～5h down for 180～200 ℃, be warmed up to 200-220 ℃ then in temperature, reaction 2～5h makes the polyarylene sulfide ketone Schiff's base;
B. the purifying of polyarylene sulfide ketone Schiff's base
Above-mentioned resulting polymers is soaked 24-48h in methyl alcohol, after the pulverizing, respectively with methyl alcohol or ethanol, deionized water and acetone extracting 24-48h, then at temperature 50-80 ℃, the dry 24-48h of vacuum tightness 0.90-0.95MPa;
(3) acidolysis of polyarylene sulfide ketone Schiff's base
A. the acidolysis of polyarylene sulfide ketone Schiff's base
With 3 parts of the above-mentioned polyarylene sulfide ketone Schiff base polymers of handling well, the tetrahydrofuran (THF) of 80-100 part adds and has in the reactor of agitator, thermometer, condenser, dissolve fully until polymkeric substance at temperature 63-68 ℃ of backflow 2-6h, filter then, get filtrate, 10-20 part non-oxidizing acid is added in the filtrate, at temperature 63-68 ℃ of backflow 24-48h, filter, drying obtains polyarylene sulfide ketone;
B. the purifying of polyarylene sulfide ketone
Above-mentioned polyarylene sulfide ketone is used deionized water, acetone extracting 24-48h respectively, and drying obtains resin.
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| CN104371104B (en) * | 2014-10-28 | 2016-07-27 | 四川大学 | A kind of method that double solvents method prepares high molecular polyarylene sulfide ketone |
| KR102173641B1 (en) * | 2017-11-24 | 2020-11-03 | 주식회사 엘지화학 | Process for preparing polyarylene sulfide |
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