CN1075529C - Industrial synthetic technology of linear-type high-molecular-weight polyphenyl thio-ether - Google Patents
Industrial synthetic technology of linear-type high-molecular-weight polyphenyl thio-ether Download PDFInfo
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- CN1075529C CN1075529C CN97107357A CN97107357A CN1075529C CN 1075529 C CN1075529 C CN 1075529C CN 97107357 A CN97107357 A CN 97107357A CN 97107357 A CN97107357 A CN 97107357A CN 1075529 C CN1075529 C CN 1075529C
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Abstract
The present invention provides an industrial synthesis technology for synthesizing linear high molecular weight polyphenylene sulfide (PPS) with a sodium sulfide method, which is characterized in that the PPS is synthesized by using anhydrous sodium sulfide and p-dichlorobenzene as raw materials to carry out polycondensation in an HPT solvent at normal pressure without a catalyst. In the production of high molecular weight polyphenylene sulfide in western countries, a third monomer and various catalysts (additive agents) need to be added to synthesize high molecular weight branched chain PPS at applied pressure. The present invention has the advantages of reasonable production technology, good reproducibility of technical conditions and resin quality, and stable operation of all units in the whole technological process. The linear high molecular weight PPS can be obtained through continuous production, and the average product yield is higher than 95%. Compared with a US raw material RyTonV-1, the product of the present invention is superior, and the product of the present invention can be widely used in the industrially technical fields of electronic electric appliances, automobile astronavigation, light industry machinery, petrochemical industry, etc.
Description
The present invention relates to a kind of production technique of high performance engineering plastics, particularly high-molecular linear polyphenyl thioether (english abbreviation: industrial synthetic process PPS).Because the corrosion of the non-oxidizable bronsted lowry acids and bases bronsted lowry of its ability, salt and organic solvent, has good thermostability, self lubricity and flame retardant resistance, radiation hardness, heat-resisting, nontoxic, can be bonding with many metals or non-metallic material, also can with many macromolecular material blend, goods tool isostatic physical and mechanical properties comparatively with its processing, excellent performance such as good electrical properties and dimensional stability, thereby it can be widely used in technical fields such as electronic apparatus, automobile aerospace, light industry and machinery, petrochemical complex and foodstuffs industry.
Show according to pertinent data, synthetic since the 1888 Nian Feishi PPS that begins one's study, had the history of a century so far.The polycondensation method of the PPS of past report, or because of reacting uncontrollable, product does not have circulation ratio, or because of the unit synthetic route is long, the cost costliness is not seen the industrialization report so far.Domesticly also cross high reason because of Technology problem or finished product, all can not suitability for industrialized production high molecular line style PPS resin, the PPS resin raw material of production only can be used by making coatings.The PPS resin of the PPS resin of import or domestic market circulation, many " Rytonv-1 type " [Ryton trade names of producing with U.S. Phillips petrochemical corporation (complex), the patent No.: U.S3.254.129 (1967)] be representative, the low shear viscosity of fusion low (tens pools-hundred pools) is if make engineering plastics with also must hot oxygen crosslinking Treatment, but all can not reel off raw silk from cocoons, film forming, its purposes is restricted.To the production of high molecular weight polyphenylene sulfide, be raw material with sodium sulphite and santochlor abroad, (N-methyl than slightly alkane ketone) NMP makes solvent, adds the 3rd monomer 1,2,4-trichlorobenzene and multiple catalyzer (additive) and depresses synthetic branched polymer amount PPS adding.
The objective of the invention is to overcome above-mentioned the deficiencies in the prior art, the contriver is through the painstaking efforts in surplus ten years, through research trial repeatedly, realized that industrialization synthesizes high-molecular linear polyphenyl thioether (PPS).
The objective of the invention is to realize according to following operational path: with Sodium sulphate anhydrous, 99min and santochlor is main raw material, in solvent hempa (HPT), carry out normal pressure (catalyst-free) polycondensation, synthetic macromolecule amount linear polyphenylthioether resin (HMWPPS, be abbreviated as PPS), the former powder of every production PPS/ton, consumption major ingredient: 2 tons of industrial sodium sulfides, 1.6 tons of santochlor, 0.4 ton of hempa, 0.04 ton of auxiliary material.
Its technical process is feedstock production → polyreaction → purifying, oven dry, packing → former powder finished product.The treated recovery of solvent is used further to feedstock production in purifying, baking operation, so moves in circles.
Its processing step is the above-mentioned technological process of production of contrast, at first industrial sodium sulfide and water are added in the dissolution kettle, heat up and stir, dissolving, after treating that sodium sulphite has dissolved, (the acid of an amount of adding auxiliary material, liming) handle, mixture after will handling then send strainer to filter, filtrate is squeezed into the crystallization kettle crystallisation by cooling, after crystallization is intact, the mixture of mother liquor and crystalline sodium sulfide is delivered to the vacuumfilter suction filtration, mother liquor behind the suction filtration is sent dissolution kettle back to and is made next solvent usefulness, and isolated nine water cure sodium are through the heating of vacuum still, decompression, dehydration, make Sodium sulphate anhydrous, 99min, the sealing of finished product Sodium sulphate anhydrous, 99min, it is standby to keep in Dark Place.
The second, the santochlor elaboration directly uses
Three, industrial hempa uses the back to reclaim after rectification under vacuum, reuses, with Sodium sulphate anhydrous, 99min again, santochlor, auxiliary material, hempa add polymeric kettle, add thermal polycondensation and after reaction in 4--5 hour is finished, reclaim solvent, add water again and stir into uniform sizing material, put into suction filter product is washed, three washing lotions in front and back, discharging after three wastes processing is up to standard, up to standard can directly discharging of posterior segment washing, the product that has washed, after finding time, drying, packing promptly obtains the PPS resin raw material.
Its processing condition comprise the feedstock purification processing, polycondensation and aftertreatment, sodium sulphite-hempa polycondensating process route, the processing condition of polyreaction and the operation control of preparation high molecular line style PPS resin.Feedstock purification is handled: nine water cure sodium (Na
2S.9H
2O), industrial sodium sulfide dissolves in water, 60 ℃ of temperature--and 70 ℃, the every 100kg industrial sodium sulfide of concentration 25---29% drops into auxiliary material 3---10kg, and nine water cure sodium Tcs are 1--2 ℃; Sodium sulphate anhydrous, 99min is made by the dehydration of nine water cure sodium, dehydration vacuum tightness: overbottom pressure≤15mmHg, dehydration temperaturre: normal temperature---170 ℃, dewatering time: 12--15 hour, the industry hempa: directly use, the hempa after the recovery is reused after pure system, and decompression is collected, 140--142 °/40mmHg, 125 ℃/75mmHg, 115 ℃/15mmHg, reflux ratio 1: 3; Polycondensation and aftertreatment: polycondensation batch charging coefficient 60--70%, agitator type and rotating speed: 60--100 rev/min of frame belt, ratio of components (mol): Sodium sulphate anhydrous, 99min: santochlor=1: 1, solvent ratios: 40 milliliters of HPT/ mol Na
2S, polymeric reaction temperature: 185 ℃--230 ℃, polymerization reaction time: 4--5 hour, solvent recuperation adopted the distillation novel process, the water washing number of times: 4--8 time, aftertreatment terminal point: discharge washing water PH--7, use AgNO
3Solvent detects CL
-Sodium sulphite-hempa polycondensating process the route of preparation high molecular line style PPS resin: anhydrous polymerization system, the molecular weight of PPS resin is deferred to monomer ratio " equivalent ratio " rule, because it is the reversible balanced reaction of non-homogeneous solution polycondensation, thereby guarantee that its monomer ratio is its most important condition near the equivalent ratio; Highly active polymerization reaction system, normal pressure synthesis polymerization high-molecular linear polyphenyl thioether, the high reactivity polymerization reaction system that forms based on the polymer solvent of hempa (HMPA), it is the most important condition of normal pressure synthesis high-molecular linear polyphenyl thioether, it had both helped the condensation polymerization reaction between sodium sulphite and santochlor, also promoted the growth of polymeric chain, because above-mentioned factor has determined that Sodium sulphate anhydrous, 99min, santochlor are raw material, hempa is the normal pressure synthesis operational path of solvent; The processing condition of polyreaction and operation Control essentials: heat supply and control, because the polycondensation technological temperature is higher, general industry steam difficulty reaches the heat supply requirement, so adopt oil circulation heat supply, the oil temperature control is at 220 °--and 230 ℃, coking phenomenon can not take place in the PPS resin; Proportioning raw materials sodium sulphite: santochlor=0.99---1.00: 1.00 (mol), HMPA: santochlor=40mL: 1 mol; Polycondensation vessel whipped form and speed for the growth that helps material polymer chain in polycondensation and good heat-conducting effect, prevent sticking still, make material evenly motion in reaction process, adopt the frame ribbon agitator, and stirring velocity is 60--100 rev/min.PPS is synthetic to be that (666 kilocalories/kgPPS) thereby in process of production carry out sectional temperature-controlled: the material temperature rise period, temperature controllable was between 100--200 ℃ for the significant thermopositive reaction of a kind of heat effect, automatically the temperature rise period is the main exothermic phase of polymkeric substance, according to the suitable controlled temperature of practical situation, holding stage one polymer molecular chain build phase, temperature control is about 220 ℃, temperature-fall period adds water and further lowers the temperature after solvent recuperation, and product takes out aftertreatment.
The present invention is because the technological process of production is reasonable, make its technical qualification and resin quality that circulation ratio preferably be arranged, each unit operation of whole process flow is comparatively stable, check through continuous production, all can obtain high-molecular linear PPS, the average yield rate of product is greater than 95%, and the production starting material are easy to get, advantages such as (by existing city price 150,000/tons, the about 6.9 ten thousand/ton of total cost valency) with low cost.
Embodiments of the invention are described in detail in detail below.
Technology of the present invention is produced in the rich and powerful chemical plant of Mianyang City and is implemented designed capacity: 100T/Y, polymeric kettle 1 * 2500 liter, adopt the synthetic line style macromolecular weight poly benzene thioether resin of sodium sulphite, be main raw material promptly with Sodium sulphate anhydrous, 99min and santochlor, in the solvent hempa, carry out normal pressure (catalyst-free) polycondensation, synthetic PPS.Every production PPS raw material/ton, consumption major ingredient: 2 tons of industrial sodium sulfides, 1.6 tons of santochlor, 0.4 ton of hempa, 0.04 ton of consumption auxiliary material (acid, liming).
Its technical process is feedstock production → polyreaction → purifying, oven dry, packing → raw material finished product.The treated recovery of solvent is used further to feedstock production in purifying, baking operation, so moves in circles.
Its processing step is the above-mentioned technological process of production of contrast, at first industrial sodium sulfide and water are added in the dissolution kettle, heat up and stir, dissolving, after treating that sodium sulphite has dissolved, (the acid of an amount of adding auxiliary material, liming) handle, mixture after will handling then send strainer to filter, filtrate is squeezed into the crystallization kettle crystallisation by cooling, after crystallization is intact, the mixture of mother liquor and crystalline sodium sulfide is delivered to the vacuumfilter suction filtration, and the mother liquor behind the suction filtration is sent dissolution kettle back to and is made next solvent usefulness, and isolated nine water cure sodium heat through the vacuum still, decompression, dehydration, make anhydrous (water content＜0.5%) sodium sulphite, the sealing of finished product Sodium sulphate anhydrous, 99min, it is standby to keep in Dark Place.The second, the santochlor elaboration directly uses.The 3rd, industrial hempa is reused after using the back to reclaim rectification under vacuum again, with Sodium sulphate anhydrous, 99min, santochlor, auxiliary material, hempa add polymeric kettle, add thermal polycondensation and reclaim solvent after reaction in 4--5 hour is finished, add water again and stir into uniform sizing material, put into suction filter to the product washing, three washing lotions in front and back, discharging after three wastes processing is up to standard, up to standard can directly discharging of posterior segment washing, the product that has washed, after finding time, drying, packing promptly gets the PPS resin raw material.Its processing condition comprise the feedstock purification processing, polycondensation and aftertreatment, sodium sulphite-hempa operational path, the processing condition of polyreaction and the operation control of preparation high molecular line style PPS resin.Feedstock purification is handled: nine water cure sodium (Na
2SgH
2O), industrial sodium sulfide dissolves in water, 60 ° of temperature--and 70 ℃, the every 100kg industrial sodium sulfide of concentration 25--29% drops into auxiliary material 3--10kg, and nine water cure sodium Tcs are 1--2 ℃; Sodium sulphate anhydrous, 99min is made by nine water cure sodium dehydrations, dehydration vacuum tightness: overbottom pressure≤15mmHg, dehydration temperaturre: normal temperature-170 ℃, dewatering time: 12--15 hour; Santochlor (elaboration) and industrial hempa: directly use.The latter reclaims after pure system back is reused, and decompression is collected: 140--142 ℃/40mmHg, 125 ℃/25mmHg, 115 ℃/15mmHg, and reflux ratio: 1: 3; Polycondensation and aftertreatment: polycondensation batch charging coefficient 60--70%, whipped form and rotating speed: 60--100 rev/min of frame belt, ratio of components (mol): Sodium sulphate anhydrous, 99min: santochlor=1.0: 1.0, solvent ratios: 40 milliliters of HPT/ mol Na
2S, polymeric reaction temperature: 185 ℃--230 ℃, polymerization reaction time: 4--5 hour, solvent recuperation adopted the distillation novel process, the water washing number of times: 4--8 time, aftertreatment terminal point: discharge washing water PH--7, use AgNO
3Solution detects cl-.Sodium sulphite-hempa polycondensating process the route of preparation high molecular line style PPS resin: anhydrous polymerization system, the molecular weight of PPS resin is deferred to monomer ratio " equivalent ratio " rule, because it is the reversible balanced reaction of non-homogeneous solution polycondensation, thereby guarantee that its monomer ratio is its most important condition near the equivalent ratio; Highly active polymerization reaction system, normal pressure synthesis polymerization high-molecular linear polyphenyl thioether, the high reactivity polymerization reaction system that forms based on the polymer solvent of hempa (HMPA), it is the most important condition of normal pressure synthesis high-molecular linear polyphenyl thioether, it had both helped contracting between sodium sulphite and santochlor, polyreaction, also promoted the growth of PPS polymeric chain, because above-mentioned factor has been determined with Sodium sulphate anhydrous, 99min, santochlor is a raw material, and hempa is the normal pressure synthesis operational path of solvent; The processing condition of polyreaction and operation Control essentials: heat supply and control, because the polycondensation technological temperature is higher, general industry steam difficulty reaches the heat supply requirement, so adopt oil circulation heat supply, the oil temperature control is at 220 °--and 230 ℃, coking phenomenon can not take place in the PPS resin; Proportioning raw materials: sodium sulphite: santochlor=0.99--1.00: 1.00 (mol), HMPA: santochlor=40ml: 1 mol; Polycondensation vessel whipped form and speed for the growth that helps material polymer chain in polycondensation and good heat-conducting effect, prevent sticking still, make material evenly motion in reaction process, adopt the frame ribbon agitator, and stirring velocity is 60--100 rev/min.PPS is synthetic be the significant thermopositive reaction of a kind of heat effect (666 kilocalories/kgPPS), thereby carry out sectional temperature-controlled in process of production: material rises and mixes the stage temperature controllable between 100--200 ℃, automatically the temperature rise period is the main exothermic phase of polymkeric substance, according to the suitable controlled temperature of practical situation, holding stage one polymer molecular chain build phase, temperature control is about 220 ℃, and temperature-fall period is after solvent recuperation, add water and further lower the temperature, product takes out aftertreatment.
Production practice show: owing to adopted the Sodium sulphate anhydrous, 99min new process of production to reach the recovery of solvent hempa is reused, the equipment input of making reduces energetically, the rate of recovery improves (average recovery rate＞95%), supplementary material materials consumption, energy consumption all have 0.6 ton of decline by a relatively large margin, one ton of PPS resin consumption of the every production of former old technology hempa, now only consume 0.4 ton, cost greatly descends.Product shows that to low shear melt viscosity test (seeing Appendix 1) viscosity is higher through R﹠D institutions such as Chinese testing research institutes, average viscosity＞2000 pools, infrared spectra (seeing Appendix 2) is consistent with U.S. RyTonV-1 like product infrared spectra, and physicals meets this technical target of the product.
The former powder salient features contrast of product of the present invention and U.S. RyTonV-1PPS is as follows:
The rich and powerful chemical plant of the former powder of project RyTonV-1 former powder appearance white powder white powder fusing point (℃) the low shear viscosity of 275-285 280--297 melting (303 ℃, pool) 50-80＞2000 heat decomposition temperatures, 480 485--520 infrared spectrum infrared spectrograms are identical
Claims (4)
1. industrial synthetic technology of linear-type high-molecular-weight polyphenyl thio-ether, comprise that with sodium sulphite and santochlor be the technology of feedstock production PPS, it is characterized in that: with Sodium sulphate anhydrous, 99min and santochlor is main raw material, in the solvent HMPA, carry out the polycondensation of normal pressure, catalyst-free, synthetic macromolecule amount linear polyphenylthioether resin (PPS), the former powder of every production PPS/ton, 0.04 ton of 2 tons of consumption major ingredient industrial sodium sulfides, 1.6 tons of santochlor, 0.4 ton of HMPA, the auxiliary material formed by acid, liming, its processing step is:
(1) industrial sodium sulfide is made Sodium sulphate anhydrous, 99min through crystallization processes,
(2) the santochlor elaboration directly uses,
(3) industrial HMPA is reused after distil process is handled,
(4) above-mentioned raw materials and auxiliary material are added thermal polycondensation:
The polycondensation batch charging coefficient is 60-70%,
Ratio of components (mol): Sodium sulphate anhydrous, 99min: santochlor=0.99--1.0: 1.0,
Solvent ratios: 40 milliliters of HPT/ mol Na
2S,
Polymeric reaction temperature: 185 ℃--230 ℃
Polymerization reaction time: 4--5 hour,
(5) material after polycondensation is finished adds water and stirs into uniform sizing material, and puts into suction filter to the product washing,
(6) after finding time, drying, packing promptly gets the PPS raw produce.
2. industrial synthetic technology of linear-type high-molecular-weight polyphenyl thio-ether according to claim 1 is characterized in that: polycondensation process adopts oil circulation heat supply, and oily temperature is 220 ℃--and 230 ℃.
3. industrial synthetic technology of linear-type high-molecular-weight polyphenyl thio-ether according to claim 1, it is characterized in that: the polycondensation building-up process adopts sectional temperature-controlled: the material temperature rise period, temperature control was at 100 ℃--between 200 ℃, automatic suitable temperature control of temperature rise period, the holding stage temperature control is about in the of 220 ℃.
4. according to claim 1,2 or 3 described industrial synthetic technology of linear-type high-molecular-weight polyphenyl thio-ether, it is characterized in that: the product P PS of this technology direct production, at the low shear viscosity of 303 ℃ of fusions＞2000 pools.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97107357A CN1075529C (en) | 1997-02-05 | 1997-02-05 | Industrial synthetic technology of linear-type high-molecular-weight polyphenyl thio-ether |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97107357A CN1075529C (en) | 1997-02-05 | 1997-02-05 | Industrial synthetic technology of linear-type high-molecular-weight polyphenyl thio-ether |
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| CN1172823A CN1172823A (en) | 1998-02-11 |
| CN1075529C true CN1075529C (en) | 2001-11-28 |
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| CN97107357A Expired - Fee Related CN1075529C (en) | 1997-02-05 | 1997-02-05 | Industrial synthetic technology of linear-type high-molecular-weight polyphenyl thio-ether |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1095481C (en) * | 2000-12-27 | 2002-12-04 | 古旗高 | Process for preparing high-density high-molecular linear polyphenyl thioether |
| CN100360586C (en) * | 2003-07-24 | 2008-01-09 | 东丽株式会社 | Process for producing polyaryl ylene sulfoether |
| CN1869104B (en) * | 2006-04-24 | 2011-01-12 | 王辛 | Synthesis method of linear high molecular weight poly phenyl thio ether |
| CN103467741A (en) * | 2013-09-22 | 2013-12-25 | 四川大学 | Polyphenylene sulfide and preparation method thereof |
| CN104744698B (en) * | 2015-03-25 | 2017-05-24 | 常州大学 | Method for synthesizing linear high molecular weight polyphenylene sulfide |
| CN107915842B (en) * | 2017-11-29 | 2020-06-16 | 中国石油化工股份有限公司 | Preparation method of low-chlorine polyphenylene sulfide |
| CN109438706B (en) * | 2018-10-25 | 2021-05-04 | 宜宾天原集团股份有限公司 | Precision control method for reaction temperature in polyphenylene sulfide production |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5032781A (en) * | 1973-07-27 | 1975-03-29 | ||
| JPS5331288A (en) * | 1975-11-20 | 1978-03-24 | Worldwide Blast Cleaning Ltd | Surface treating machine |
| US4795799A (en) * | 1987-09-08 | 1989-01-03 | Phillips Petroleum Company | Production of aromatic sulfide/ketone polymers with alkali metal carbonate |
| US5350833A (en) * | 1990-10-08 | 1994-09-27 | Tosoh Corporation | Process for production of polyarylene sulfides |
| JPH0857561A (en) * | 1994-08-24 | 1996-03-05 | Furukawa Electric Co Ltd:The | Method for expanding sheath of duct air cable |
-
1997
- 1997-02-05 CN CN97107357A patent/CN1075529C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5032781A (en) * | 1973-07-27 | 1975-03-29 | ||
| JPS5331288A (en) * | 1975-11-20 | 1978-03-24 | Worldwide Blast Cleaning Ltd | Surface treating machine |
| US4795799A (en) * | 1987-09-08 | 1989-01-03 | Phillips Petroleum Company | Production of aromatic sulfide/ketone polymers with alkali metal carbonate |
| US5350833A (en) * | 1990-10-08 | 1994-09-27 | Tosoh Corporation | Process for production of polyarylene sulfides |
| JPH0857561A (en) * | 1994-08-24 | 1996-03-05 | Furukawa Electric Co Ltd:The | Method for expanding sheath of duct air cable |
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| CN1172823A (en) | 1998-02-11 |
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