CN102660026B - Method for preparing polyphenylene sulfide by taking N-methyl-imidazole derivative as solvent - Google Patents

Method for preparing polyphenylene sulfide by taking N-methyl-imidazole derivative as solvent Download PDF

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CN102660026B
CN102660026B CN201210119374.6A CN201210119374A CN102660026B CN 102660026 B CN102660026 B CN 102660026B CN 201210119374 A CN201210119374 A CN 201210119374A CN 102660026 B CN102660026 B CN 102660026B
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polyphenylene sulfide
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CN102660026A (en
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单玉华
储海霞
常斌斌
毛翠霞
侯蓉
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CHANGZHOU XIAOGUO INFORMATION SERVICES Co.,Ltd.
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Changzhou University
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Abstract

The invention discloses a method for preparing polyphenylene sulfide by taking N-methyl-imidazole derivative as a solvent, and belongs to the field of polymeric chemical industry. The method comprises the following steps: adding industrial sodium sulfide (Na2S.xH2O), a catalyst and the solvent into an autoclave in a certain ratio; dehydrating the mixture at a temperature of not above 190 DEG C; cooling after dehydration; adding p-dichlorobenzene (p-DCB) and an auxiliary agent, and supplementing the solvent; mechanically stirring the mixture, and performing temperature-programmed reaction; after the reaction, cooling and taking material liquid for post-processing; filtering and separating the material liquid; washing a filter cake; and drying the filter cake to obtain PPS (polyphenylene sulfide) resin crude powder. The N-methyl-imidazole compound which is more stable than NMP (N-methyl pyrrolidone) and is high in polarity is taken as the solvent, so that the smooth progression of the reaction is facilitated, the heat resistance of the reaction product PPS is improved, the appearance of the reaction product PPS is better, and the solvent recycling rate is improved.

Description

A kind of is the method that solvent is prepared polyphenylene sulfide by N-Methylimidazole derivative
Technical field
The invention belongs to macromolecule chemical industry field, is the preparation method about polyphenylene sulfide (PPS) material.More specifically saying a kind of is the method that solvent is prepared PPS by N-Methylimidazole derivative.
Background technology
PPS is the sixth-largest engineering plastics, has high temperature resistant, resistance to solvent, the excellent properties such as corrosion-resistant, fire-retardant, is widely used in machinery, electronics, chemical industry, national defence, sophisticated technology field.Worldwide, PPS annual production approaches 20Wan Dun， manufacturer and is mostly distributed in the U.S., Japan, Germany and Belgian.The main method of the suitability for industrialized production of PPS is synthetic PPS, i.e. Phillips route of sodium sulfide method.Its synthetic method is as follows:
This technique is put forward by United States Patent (USP) 3354129.There are many advantages in such technique, raw material is easy to get, and productive rate is more than 90%, good product quality etc., but also there is serious shortcoming in this operational path: 1. solvent N-Methyl pyrrolidone (NMP) is expensive, consumes large; 2. NMP itself has reactive behavior, can form the PPS with pyrrolidone end group, thereby affects the solvent resistance (this is the most important performance of PPS) of PPS; 3. high temperature pressure reaction impels solvent NMP to decompose, and solvent recovering rate is low.
The solvent of the suitability for industrialized production PPS of another less use is HMPA (HMPA), with NMP be solvent phase ratio, HMPA is good reaction solvent, but in HMPA the molecular weight of synthetic PPS low, cost is high.
Generally speaking above-mentioned two kinds of solvent cost of material are expensive, and cost is high, and solvent load is large, and easily divide the recovery of solving problem, and strengthened PPS Technology difficulty.
So United States Patent (USP) 7026439 proposes non-proton polar organic solvent can be for the synthetic PPS of sodium sulfide method, comprising amide compound, lactam compound, urine compounds and organosulfur compound.Amide compound has N, N-dimethylformamide, N,N-dimethylacetamide, N, N-dimethyl benzamide etc.; Lactam compound has N-methyl caprolactam, N-sec.-propyl hexanolactam, N-sec.-propyl-2-Pyrrolidone etc.; Urea compounds has tetramethyl-urea, N, N '-ethylene dimethyl urea, N, N '-dimethyl propylene thiazolinyl urea etc.; Organic sulfide has dimethyl sulfoxide (DMSO), diethyl sulfoxide, diphenyl sulfoxide etc.Synthesized PPS poor product quality in these solvents.
In addition, in Chinese patent CN1869104, disclose with nine water cure sodium (Na 2s9H 2o), santochlor (p-DCB) is raw material, sodium acetate (CH 3cOONa), NaOH is auxiliary agent, 1，2，3-trichlorobenzene is properties-correcting agent, tetramethylene sulfone is the synthetic PPS of solvent.Although the boiling point of tetramethylene sulfone, more than 280 ℃, 220 ℃ of above easily decomposition, produces sulfurous gas and polymkeric substance, suppresses PPS building-up reactions, has a strong impact on quality product.In addition, 27 ~ 28 ℃ of tetramethylene sulfone fusing points, are used inconvenience.So tetramethylene sulfone is solvent, synthetic PPS does not have practical value.
Summary of the invention
For overcoming these shortcomings of prior art, the present invention proposes a kind of N-of take Methylimidazole derivative and prepares the method for PPS as solvent.
technical scheme of the present invention is:
By N-Methylimidazole derivative, be the method that solvent is prepared polyphenylene sulfide, according to following step, carry out:
(1) by a certain proportion of Na 2sxH 2o, catalyzer, solvent join in autoclave, and logical nitrogen replacement air dewaters in not higher than 190 ℃ of situations.
(2) dehydration is cooled to 50 ℃ after finishing, and adds santochlor (p-DCB), promotor, and adds solvent.
(3) mechanical stirring, temperature programming reaction for some time; After reaction finishes, cooling feeding liquid carries out aftertreatment; Feed liquid is separated by filtration, and filter cake makes PPS resinogen powder through washing, oven dry.
Wherein step (1) and (2) solvent for use are N-Methylimidazole derivatives:
Figure 784935DEST_PATH_IMAGE002
,
Wherein: X is Cl, Br, HS; R is the functional group containing carbonyl, hydroxyl or cyano-containing,
As:
Figure 377721DEST_PATH_IMAGE003
Doubly, preferably 4-6 doubly for the 3-8 that wherein the middle solvent for use summation in step (1) and (2) is p-DCB weight.55 ~ 75% of solvent for use, adds in step (1), remaining 25 ~ 45%, in step (2), add.
Step (1) raw material Na wherein 2sxH 2o is nine water cure sodium, or the industrial sodium sulfide of content 60-65%, and the degree of dehydration in step (1) is H 2o and Na 2the mol ratio of S levels off to 1;
Wherein step (2) raw material p-DCB and Na 2sxH 2the mol ratio of O is 1:1.2～1:0.9, preferably 1:1～1:0.95;
Wherein step (1) catalyzer is CH 3cOONa, PhCOONa, Li 3pO 3, LiCl etc., preferably LiCl catalyzer; Catalyst levels account for p-DCB molar weight 5%～15%, preferably 8～10%.
Wherein step (2) promotor is DMA (DMA), 2,5-dichloronitrobenzene (DCNB), 1,2,4-trichlorobenzene (TCB), p-NP (PNP), phenol (PH) etc., preferably DMA; Promotor consumption account for p-DCB molar weight 1%～8%, preferably 3～5%.
Wherein step (3) temperature programming reaction is temperature reaction certain hour stage by stage, and first stage temperature of reaction is 140～210 ℃, and the reaction times is 1h～8h, preferably 170～200 ℃, and 3h～5h preferably; ; Subordinate phase temperature of reaction is 200～260 ℃, and the reaction times is 2h～6h, preferably 220～240 ℃, and 3h～5h preferably.Too high temperature of reaction can cause solvent rotten, and PPS color and luster is dimmed, molecular weight step-down.
effect of the present invention: adopting is solvent compared with NMP N-Methylimidazole more stable, high polarity compounds, promotes carrying out smoothly of reaction, makes that reaction product PPS resistance toheat improves, outward appearance is better, and solvent recovering rate improves.
Embodiment
embodiment 1. in 500mL autoclave, add 34 g Na 2sxH 2o(Containing Sulfur sodium 62%, moisture 36%), 1.9 g LiCl, 120 g 1-methyl-3-(3-carbonyls) butyryl imidazoles sulphur hydrogen salt makes solvent.Enclosed high pressure still, passes into nitrogen, and 7.5g dewaters in not higher than 190 ℃ of situations.After dehydration finishes, be cooled to 50 ℃, add 45 g p-DCB(0.3mol) [p-DCB: Na 2s=1: 0.95(mol ratio)] and 0.95 g DMA, and add solvent 60g.Mechanical stirring, keeps 170 ℃ of reaction 5 h, 240 ℃ of reaction 3 h.After completion of the reaction, cooling feeding liquid carries out aftertreatment.Feed liquid is carried out suction filtration.Filter cake washing, pickling, wash again.Solid materials is dried to constant weight.Reaction result is listed in table 1.
embodiment 2. in 500mL autoclave, add 73 g Na 2s9H 2o(Containing Sulfur sodium 32%, moisture 68%), 1.3 g Li 3pO 3, 100 g 1-methyl-3-(2-cyano group) propyl imidazole Bromide makes solvent.Enclosed high pressure still, passes into nitrogen, and 43.5g dewaters in not higher than 190 ℃ of situations.After dehydration finishes, be cooled to 50 ℃, add 45 g p-DCB(0.3mol) [p-DCB: Na 2s=1: 1(mol ratio)] and 0.8 g PNP, and add solvent 35g.Mechanical stirring, keeps 200 ℃ of reaction 3 h, 220 ℃ of reaction 4 h.After completion of the reaction, cooling feeding liquid carries out aftertreatment.Feed liquid is carried out suction filtration.Filter cake washing, pickling, wash again.Solid materials is dried to constant weight.Reaction result is listed in table 1.
embodiment 3. in 500mL autoclave, add 45.5 g Na 2sxH 2o(Containing Sulfur sodium 62%, moisture 36%), 2.5 g sodium-acetates, 120 g 1-methyl-3-(3-hydroxyls) butyl imidazole chlorate makes solvent.Enclosed high pressure still, passes into nitrogen, and 10g dewaters in not higher than 190 ℃ of situations.After dehydration finishes, be cooled to 50 ℃, add 45 g p-DCB(0.3mol) [p-DCB: Na 2s=1: 1.2(mol ratio)] and 0.8 g PH, and add solvent 60g.Mechanical stirring, keeps 140 ℃ of reaction 8 h, 260 ℃ of reaction 2 h.After completion of the reaction, cooling feeding liquid carries out aftertreatment.Feed liquid is carried out suction filtration.Filter cake washing, pickling, wash again.Solid materials is dried to constant weight.Reaction result is listed in table 1.
embodiment 4. in 500mL autoclave, add 36 g Na 2sxH 2o(Containing Sulfur sodium 62%, moisture 36%), 1.3 g LiCl, 120 g 1-methyl-3-(2,5-dioxo-amyl group-3) imidazoles Bromide makes solvent.Enclosed high pressure still, passes into nitrogen, and 8.0g dewaters in not higher than 190 ℃ of situations.After dehydration finishes, be cooled to 50 ℃, add 45 g p-DCB(0.3mol) [p-DCB: Na 2s=1: 0.95(mol ratio)] and 1.8 g DMA, and add solvent 60g.Mechanical stirring, keeps 190 ℃ of reaction 3 h, 240 ℃ of reaction 3 h.After completion of the reaction, cooling feeding liquid carries out aftertreatment.Feed liquid is carried out suction filtration.Filter cake washing, pickling, wash again.Solid materials is dried to constant weight.Reaction result is listed in table 1.
embodiment 5. at Na 2sxH 2the O water smoking adds solvent 150g, adds solvent 120g after adding p-DCB.All the other are with example 4.Reaction result is listed in table 1.
embodiment 6. at Na 2sxH 2the O water smoking adds solvent 200g, adds solvent 160g after adding p-DCB.Add with 1.65 g TCB and replace 1.8 g DMA in example 4, all the other are with example 4, and reaction result is listed in table 1.
embodiment 7. with 4.4g PhCOONa, replace 1.3 g LiCl, with 1.75g DCNB, replace 1.38 g TCB.All the other are with example 4, and reaction result is listed in table 1.
reference examples: take NMP as solvent, NMP consumption is 180g, and all the other are with example 4, and reaction result is listed in table 1.
products measure explanation:
1. productive rate is to take p-DCB as benchmark, calculates the output of theoretical PPS, actual feed liquid aftertreatment, and the percentage ratio of ratio that is dried to the output of PPS after constant weight and theoretical PPS through washing is its productive rate.
2. fusing point ( tm) by DSC, tested and obtained, the model of DSC is PerkinElmer DSC8500 differential scanning calorimeter;
3. viscosity-average molecular weight (Mw) is calculated and is obtained by Intrinsic Viscosity Method.The α – chloronaphthalene of take is solvent, and concentration is 0.4 g/100mL, and measuring temperature is 208 ℃.Viscosity-average molecular weight is according to formula: ［ η ］=KM w αcalculate, wherein K=8.91 * 10 -5, α=0.747.
The experimental result of table 1 different operating condition
Figure 772930DEST_PATH_IMAGE004

Claims (8)

1. by N-Methylimidazole derivative, be the method that solvent is prepared polyphenylene sulfide, it is characterized in that carrying out according to following step:
(1) by a certain proportion of Na 2sxH 2o, catalyzer, solvent join in autoclave, and logical nitrogen replacement air dewaters in not higher than 190 ℃ of situations;
(2) dehydration is cooled to 50 ℃ after finishing, and adds santochlor, promotor, and adds solvent;
(3) mechanical stirring, temperature programming reaction for some time; After reaction finishes, cooling feeding liquid carries out aftertreatment; Feed liquid is separated by filtration, and filter cake makes PPS resinogen powder through washing, oven dry;
Wherein step (1) and (2) solvent for use are N-Methylimidazole derivatives:
Figure 2012101193746100001DEST_PATH_IMAGE002
, wherein: X is Cl, Br, HS; R is the functional group containing carbonyl, hydroxyl or cyano-containing.
According to claim 1 a kind of by N-Methylimidazole derivative, be the method that solvent is prepared polyphenylene sulfide; it is characterized in that solvent for use summation in wherein step (1) and (2) be p-DCB weight 3-8 doubly; 55 ~ 75% of solvent for use, adds in step (1), remaining 25 ~ 45%, in step (2), add;
Step (1) raw material Na wherein 2sxH 2o is nine water cure sodium, or the industrial sodium sulfide of content 60-65%, and the degree of dehydration in step (1) is H 2o and Na 2the mol ratio of S levels off to 1;
Wherein step (1) catalyzer is CH 3cOONa, PhCOONa, Li 3pO 3, LiCl, catalyst levels account for p-DCB molar weight 5%～15%.
According to claim 1 a kind of by N-Methylimidazole derivative, be the method that solvent is prepared polyphenylene sulfide, it is characterized in that wherein step (2) raw material p-DCB and Na 2sxH 2the mol ratio of O is 1:1.2～1:0.9, and wherein step (2) promotor is DMA DMA, 2,5-dichloronitrobenzene DCNB, 1,2,4-trichlorobenzene TCB, p-NP PNP, phenol PH, promotor consumption account for p-DCB molar weight 1%～8%.
According to claim 1 a kind of by N-Methylimidazole derivative, be the method that solvent is prepared polyphenylene sulfide, it is characterized in that wherein step (3) temperature programming reaction is temperature reaction certain hour stage by stage, first stage temperature of reaction is 140～210 ℃, and the reaction times is 1h～8h; Subordinate phase temperature of reaction is 200～260 ℃, and the reaction times is 2h～6h.
According to claim 2 a kind of by N-Methylimidazole derivative, be the method that solvent is prepared polyphenylene sulfide, it is characterized in that wherein step (1) and (2) solvent for use are:
Figure 2012101193746100001DEST_PATH_IMAGE003
?。
According to claim 3 a kind of by N-Methylimidazole derivative, be the method that solvent is prepared polyphenylene sulfide, it is characterized in that solvent for use summation in wherein step (1) and (2) be p-DCB weight 4-6 doubly;
Wherein step (2) raw material p-DCB and Na 2sxH 2the mol ratio of O is 1:1～1:0.95;
Wherein step (1) catalyzer is LiCl catalyzer; Catalyst levels account for p-DCB molar weight 8～10%.
According to claim 4 a kind of by N-Methylimidazole derivative, be the method that solvent is prepared polyphenylene sulfide, it is characterized in that wherein step (2) promotor is DMA; Promotor consumption account for p-DCB molar weight 3～5%.
According to claim 5 a kind of by N-Methylimidazole derivative, be the method that solvent is prepared polyphenylene sulfide, it is characterized in that wherein step (3) temperature programming reaction is temperature reaction certain hour stage by stage, first stage temperature of reaction is 170～200 ℃, and the reaction times is 3h～5h; Subordinate phase temperature of reaction is 220～240 ℃, and the reaction times is 3h～5h.
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