CN105254889B - A kind of linear poly arylidene thio-ester of high-purity and its synthetic method and application - Google Patents
A kind of linear poly arylidene thio-ester of high-purity and its synthetic method and application Download PDFInfo
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Abstract
The invention provides a kind of synthetic method of the linear poly arylidene thio-ester of high-purity, this method comprises the following steps：1）Benzene or benzene series hydroxy derivatives, acid binding agent, metallic catalyst are mixed, dispersed with stirring is uniform at room temperature；2）To step 1）Sulfur dichloride is added dropwise in gains, and process control reaction temperature is added dropwise at 20 40 DEG C, and controlling reaction temperature is reacted 8 15 hours at 20 40 DEG C after completion of dropping；3）By step 2）Gains are added to the ethanol solution of hydrogen chloride that mass fraction is 5%, after filtering, washing, drying, are produced；Wherein, the acid binding agent includes one kind in pyridine, triethylamine, diethylamine；The mol ratio of acid binding agent and sulfur dichloride is 1 1.1:1.Present invention also offers the poly arylidene thio-ester prepared by the above method and its application in terms of electronics, electric equipment products.
Description
Technical field
The invention belongs to poly arylidene thio-ester synthesis field, and in particular to a kind of linear poly arylidene thio-ester of high-purity and its synthetic method
And application.
Background technology
Poly arylidene thio-ester（Polyarylenen sulfide, PAS）It is sulphur and aryl knot to refer to polymer molecule backbone structure
Structure replaces a family macromolecule polymer of connection, and its general molecular formula is：,
The particularity constituted due to this kind of polymer（Contain sulphur atom）And the rigidity of molecular chain structure make it that they are general
All over all have excellent high temperature resistant, it is corrosion-resistant, it is resistance to irradiation, it is fire-retardant, in a balanced way mechanical property and fabulous dimensional stability and
The features such as excellent electrical property, the special engineering plastics of a kind of great development and application prospect are become.Wherein polyphenylene sulfide
Ether（Polypenylene sulfide, PPS）It is wherein most important, is also a most common resin variety.Polyphenylene sulfide by
Phenyl ring and thioether bond are alternately constituted, and make it have excellent heat resistance and chemical-resistant stability.At present, polyphenylene sulfide in the world
The prevailing technology of industrialized production be using paracide and vulcanized sodium or NaHS with NaOH as raw material, it is organic in polarity
Solvent such as 1-METHYLPYRROLIDONE（N-methyl-2-pyrrolidone, NMP）The middle method for carrying out solution polycondensation.This method by
In process route is short, product quality is stable, yield is higher（Typically more than 90%）, thus receive much concern, it is substantial amounts of to study and improve
Expand work around this process route to deploy, by updating and perfect for many years, its industrialization technology level is also obtained
Great raising has been arrived, but refined requirement of this process route to raw material is higher, and due to producing by-product in course of reaction
Thing sodium chloride, thus inorganic salts the ash content of coal is higher in naval stores, so as to cause the correlations such as the moisture-proof of product, electrical property
The decline of energy, and then have impact on application of the product in association area.Simultaneously as reaction needs to enter under conditions of HTHP
OK, solvent is easy to decompose denaturation at high temperature, so that bring manufacturing cost to remain high, and a series of environmental problem.
Fu-gram catalysis route is synthetic linear polyphenylene sulfide the most ancient synthetic method.1897, Genvresse was used
Benzene and sulphur are warm altogether in the presence of Friedel-Crafts catalyst, generate a kind of polymerization of the poor amorphous state of dissolubility
Thing, here it is the polyphenylene sulfide synthesized earliest, the molten point of the polymer is 295 DEG C.Reaction equation is：
,
This kind of reaction belongs to the electrophilic substitution reaction in Veux-psoriasis reaction type on phenyl ring.Would generally using alchlor or
Person's concentrated sulfuric acid etc. is used as catalyst.More accessory substance diphenylene disulfide generation is had in reaction, yield is not high, typically 50 ~
80%, the polymer molecular weight of generation is relatively low, and crosslinking degree and degree of branching are higher.Therefore, it is difficult to be tied by the reaction
The linear polyphenylthioether that structure is single, molecular weight is higher, performance is relatively stable.
1974, G.Montaudo et al. was reported using diphenylsulfide as raw material, in the presence of the catalysis of room temperature iron powder,
Chloroform is solvent, and sulfur dichloride is vulcanizing agent, generates linear polyphenylene sulfide.The polyphenylene sulfide molecular weight arrived of reaction is very
Low, fusing point is only 125 DEG C, and has about 10% or so the compound generation containing cystine linkage in course of reaction.Kenji in 1992
Miyatake et al. is same using diphenylsulfide as raw material, and chloroform, dichloroethanes etc. are solvent, and sulfur dichloride is vulcanizing agent, is examined
The reaction that polyphenylene sulfide is synthesized in the presence of including a series of catalyst such as iron powder, zinc powder, ferric trichloride, alchlor is examined
Process.It is optimal wherein using iron powder as catalyst effect, but obtained molecular weight product is still relatively low, fusing point is in 150-160
℃.Its reaction equation is：
, Massaki in 1987
Wakita etc. reports Diphenyl disulfide ether and depressed in atmosphere at room temperature occurs the fracture of S -- S, generation in the presence of Lewis acid
The polyphenylene sulfide of white powder, the product is dissolved in the 1-METHYLPYRROLIDONE of heat.Then, Rizos etc. has reported out two again
Phenyl disulfide is at VO (acac)2Under catalyst action, in room temperature through O2Oxidation generation PPS.Soon Tsuchida quinones are used as oxygen
Agent has obtained ultrapure PPS, and yield is up to 95%, without crosslinking, branch and cyclic structure in molecule.At the same time, using benzenethiol as
Raw material, can also synthesize the polyphenylene sulfide of outgoing-line type by electrolytic oxidation polymerization in acid condition.Its product is white powder, production
Rate is 77%, and molecular weight can be more than 103, fusing point is between 180-190 °C, and the polyphenylene sulfide fusing point that this method is obtained is relatively low,
Yield is not high.Someone is improved research to Diphenyl disulfide ether oxidative polymerization method again afterwards, its yield accessible 100%, product
Purity is high, and reaction condition is gentle, no coupling product, without expensive organic solvent, and synthesis cycle is short, and obtained polyphenylene sulfide is
Linear structure, is not crosslinked the phenomenon of disproportionation completely.Also exist but the molecular weight of resulting polymers is not also very high, in structure few
The cystine linkage of amount, also has a certain distance from industrialized production.Its reaction equation is：
.However, such is using new
Although the cation electrophilic substitution reaction mechanism of type is gentle come the method reaction condition for preparing linear polyphenylene sulfide, the original of reaction
Material or catalyst are not easy to obtain, or have strong acid medium condition high to consersion unit requirement in course of reaction, obtained product point
The problems such as son amount is universal relatively low.
In summary, prior art not yet find one kind can and meanwhile there is raw material to be easy to get, reaction condition is gentle, yield is high,
Molecular weight is high, inorganic salts content of ashes is low, the high multiple advantage of linearity poly arylidene thio-ester synthetic method.
The content of the invention
For in polyphenylene sulfide synthesis technique to ingredient requirement height, severe reaction conditions, molecular weight is low, yield is low, product
The high shortcoming of middle inorganic salts the ash content of coal, an object of the present invention is that offer one kind can be while have raw material to be easy to get, react
Mild condition, yield are high, molecular weight is high, inorganic salts content of ashes is low, the high multiple advantage of linearity poly arylidene thio-ester synthesis side
Method, this method comprises the following steps：
1）Benzene or benzene series hydroxy derivatives, acid binding agent, metallic catalyst are mixed, dispersed with stirring is uniform at room temperature；
2）To step 1）Sulfur dichloride is added dropwise in gains, and process control reaction temperature is added dropwise after 20-40 DEG C, completion of dropping
Controlling reaction temperature is reacted 8-15 hours at 20-40 DEG C；
3）By step 2）Gains are added to the ethanol solution of hydrogen chloride that mass fraction is 5 %, by filtering, washing, are done
After dry, produce；
Wherein, the acid binding agent includes one kind in pyridine, triethylamine, diethylamine；Mole of acid binding agent and sulfur dichloride
Than for 1-1.1:1.
Due to that can be generated in course of reaction with hydrogen chloride, traditional inorganic acid binding agent, although can also play and tie up acid
Effect, but the inorganic salts material produced after acid is tied up, the decline of poly arylidene thio-ester product purity can be caused again, and then cause its electrical
Can it is low, in the shortcoming for being absorbed in sodium sulfide method technique.
The present inventor gropes to find by prolonged, on the one hand raw after acid binding agent of the present invention is introduced
Into the hydrochloride of acid binding agent can be dissolved in alcohols solvent, can effectively be reclaimed by way of alcohol is washed, the opposing party
Face, because this reaction belongs to the mechanism of electrophilic reaction on phenyl ring, acid binding agent of the present invention such as pyridine etc. is fabulous electrophilic again
Replace solvent, can preferably promote the progress of reaction, it is prior to also have, because acid binding agent is fixed the hydrochloric acid of generation,
Reaction temperature can change in relatively wide scope, without producing the chlorination side reaction on such as methyl, and logical
Cross the molecular weight for improving the poly arylidene thio-ester product that the temperature reacted can further improve generation.Simultaneously as gained polyarylphosphorus
The end group of ether is free of thiophenol sodium or thiophenol, makes it have outstanding heat endurance, and color change is slight in process, do not send out
It is black.As shown in the experimental data in experimental example one of the present invention, the thermal weight loss of present invention gained poly arylidene thio-ester at processing temperatures is small,
Color change is slight.In addition, as shown in the obtained experimental data of experimental example two of the present invention, poly arylidene thio-ester is linear obtained by the present invention
Degree is high.
It is preferred that, the metallic catalyst includes one kind in iron powder, magnesium powder, zinc powder.
It is preferred that, the benzene series hydroxy derivatives include one kind in p-methyl phenol, paraethyl phenol.
It is preferred that, the mol ratio of benzene or the benzene series hydroxy derivatives and sulfur dichloride is 1-1.05:1.Reaction raw materials are matched somebody with somebody
It is more excessive than with benzene or benzene series hydroxy derivatives, blocked as far as possible with benzene or benzene series hydroxy derivatives with the product for ensuring reaction generation,
The correlated performances such as the heat endurance to improve product polyphenylene sulfide.
It is preferred that, the mol ratio of the metallic catalyst and sulfur dichloride is 0.001-0.008:1.
It is preferred that, step 3）Described in mode of washing be：Cyclic washing is carried out using second alcohol and water；The drying mode
For：Under vacuum, dried in 60 DEG C to constant weight.
It is preferred that, the benzene series hydroxy derivatives are that p-methyl phenol, the acid binding agent are triethylamine, the metal catalytic
Agent is zinc powder, and reaction temperature is 30-40 DEG C, and the reaction time is 8-10 hours.
It is a further object to provide the poly arylidene thio-ester prepared by the above method, the poly arylidene thio-ester it is molten
Point is at least more than 210 DEG C, and molecular weight is at least 1.5 × 104More than, the ash content of coal is not more than 0.07 %, Cl-Content is not more than
50 ppm。
Third object of the present invention is the application for providing gained poly arylidene thio-ester in terms of electronics, electric equipment products.Due to
The inorganic salts the ash content of coal of gained poly arylidene thio-ester of the invention is low, and is blocked with benzene and benzene derivative, gained heat endurance is good,
Molecular weight is higher, it is clear that, present invention gained poly arylidene thio-ester is in the application performance including fields such as electronics, electric equipment products
Very prominent.
Beneficial effects of the present invention：
1）The present invention is using benzene or benzene series hydroxy derivatives as raw material, and raw material is cheap and easy to get, and the refinement treatment of raw material is simple；
2）The present invention can avoid the inorganic salts the ash content of coal in the generation of accessory substance, product from being substantially less than prior art, production
The purity of product is high；
3）The reaction condition of the present invention is gentle, without extra high temperature, need to only be reacted under 20-40 DEG C of middle low temperature and is
Can；
4）The present invention ensure raw material be easy to get, high income, reaction condition it is gentle on the premise of, moreover it is possible to so that product have compared with
High molecular weight and heat endurance；
5）The present invention is with low cost without using rare catalyst；The present invention is set without using sour environment to production
It is standby friendly, utilize production.
Brief description of the drawings
The infrared detection collection of illustrative plates for the polyphenylene sulfide that Fig. 1 prepares for the present invention, wherein wavenumber means ripple
Long, transmittance means transmitance.
Embodiment
The present invention is specifically described below by embodiment, it is necessary to it is pointed out here that be following examples be use
It is further detailed in the present invention, it is impossible to be interpreted as limiting the scope of the invention, the field is skilled in technique
Some nonessential modifications and adaptations that personnel are made according to foregoing invention content, still fall within protection scope of the present invention.
Embodiment one
81.9g benzene, 87g pyridines are added band and be stirred at reflux in the four-hole boiling flask of heating and temperature controlling device, then by 0.056g iron
Powder is distributed in above-mentioned system, is sufficiently stirred for being uniformly dispersed；By 102.97g sulfur dichloride（SCl2）Load in constant pressure funnel, control
40 DEG C of temperature in four-hole boiling flask processed, start that sulfur dichloride is added dropwise（SCl2）.Maintenance system temperature is in 40 DEG C of reactions after completion of dropping
8h.Reaction system mixture is poured into 5% ethanol solution of hydrogen chloride by reaction after terminating, and is filtrated to get the polyphenylene sulfide of white
Ether crude product.Polyphenylene sulfide crude product is with after second alcohol and water cyclic washing, and under vacuum, 60 DEG C of dryings produce poly- to constant weight
Diphenyl sulfide, product weight 106g, yield 98.15%, 250 DEG C of fusing point, molecular weight 3.1 × 104, ash 0.052%, Cl-Content≤
50ppm。
Embodiment two
108g p-methyl phenols, 111.3g triethylamines are added band and are stirred at reflux in the four-hole boiling flask of heating and temperature controlling device,
0.52g zinc powders are distributed in above-mentioned system again, are sufficiently stirred for being uniformly dispersed；By 102.97g sulfur dichloride（SCl2）Load permanent
Press in funnel, 20 DEG C of temperature in control four-hole boiling flask starts that sulfur dichloride is added dropwise（SCl2）.40 are to slowly warm up to after completion of dropping
DEG C, and maintenance system temperature reacts 8h at 40 DEG C.Reaction system mixture is poured into 5% ethanolic hydrogen chloride by reaction after terminating
In solution, the poly- of white is filtrated to get（2- methyl -5- hydroxyl -1,4- diphenyl sulfides）Crude product.It is poly-（2- methyl -5- hydroxyls -1,4-
Diphenyl sulfide）Crude product is with after second alcohol and water cyclic washing, and under vacuum, 60 DEG C of dryings produce poly- to constant weight（2- methyl -5-
Hydroxyl -1,4- diphenyl sulfides）, product weight 138g, yield 98.57%, 270 DEG C of fusing point, molecular weight 4 × 104, ash 0.063%, Cl-Contain
Amount≤50ppm.
Embodiment three
78g benzene, 73.14g diethylamine are added band and be stirred at reflux in the four-hole boiling flask of heating and temperature controlling device, then by 0.12g
Magnesium powder is distributed in above-mentioned system, is sufficiently stirred for being uniformly dispersed；By 102.97g sulfur dichloride（SCl2）Load in constant pressure funnel,
20 DEG C of temperature in four-hole boiling flask is controlled, starts that sulfur dichloride is added dropwise（SCl2）.Maintenance system temperature is anti-at 20 DEG C after completion of dropping
Answer 15h.Reaction system mixture is poured into 5% ethanol solution of hydrogen chloride by reaction after terminating, and is filtrated to get the polyphenyl of white
Thioether crude product.Polyphenylene sulfide crude product is with after second alcohol and water cyclic washing, and under vacuum, 60 DEG C of drying to constant weights are produced
Polyphenylene sulfide, product weight 105g, yield 97.22%, 210 DEG C of fusing point, molecular weight 1.5 × 104, ash 0.058%, Cl-Content≤
50ppm。
Example IV
125g paraethyl phenols, 83g pyridines are added band and be stirred at reflux in the four-hole boiling flask of heating and temperature controlling device, then will
0.1g magnesium powders are distributed in above-mentioned system, are sufficiently stirred for being uniformly dispersed；By 102.97g sulfur dichloride（SCl2）Load constant pressure funnel
Interior, 20 DEG C of temperature in control four-hole boiling flask starts that sulfur dichloride is added dropwise（SCl2）.It is to slowly warm up to 30 DEG C after completion of dropping, and
Maintenance system temperature reacts 12h at 30 DEG C.Reaction system mixture is poured into 5% ethanol solution of hydrogen chloride by reaction after terminating
In, it is filtrated to get the poly- of white（2- ethyl -5- hydroxyl -1,4- diphenyl sulfides）Crude product.It is poly-（2- ethyl -5- hydroxyl -1,4- benzene sulphur
Ether）Crude product is with after second alcohol and water cyclic washing, and under vacuum, 60 DEG C of dryings produce poly- to constant weight（2- ethyl -5- hydroxyls
Base -1,4- diphenyl sulfides）, product weight 149g, yield 98.02%, 285 DEG C of fusing point, molecular weight 4.3 × 104, ash 0.07 %, Cl-Contain
Amount≤50ppm.
Comparative example
The hydrated sodium sulfides of 168g five, 300mlN- methyl pyrrolidones, 18.4g sodium acetates are added into band stirring and heating control
In the autoclave of warm device, heating dehydration to water content in system is 18g after putting nitrogen through emptying.It is dehydrated after terminating to dehydration
System add 147g paracide, and add the volume of 1-METHYLPYRROLIDONE in 1-METHYLPYRROLIDONE to system and be
450ml, 220 DEG C of control system reaction temperature is reacted 2 hours, 240 DEG C of reactions 2h, 260 DEG C of reaction 2h.Cooling, filtering, and with steaming
Distilled water cyclic washing filter cake.Under vacuum, 60 DEG C of drying to constant weights produce polyphenylene sulfide to the filter cake that washing is obtained after terminating,
Product weight 100g, yield 92.59%, 285 DEG C of fusing point, molecular weight 4.5 × 104, ash 0.28%, Cl-Content 5000ppm.
Experimental example one
Heat endurance experiment is carried out to embodiment one and comparative example products obtained therefrom, experimental result is as shown in table 1.
Table 1
Experimental example two
Infared spectrum detection is carried out to the products obtained therefrom of embodiment one, accompanying drawing 1 is as a result seen.1571.99cm in spectrogram-1,
1471.69cm-1,1386.82cm-1For the skeletal vibration absworption peak of phenyl ring, moderate strength spike 1095.57cm-1It is on aromatic ring
Ar-S vibrates, 1905 ~ 1700 cm-1Several absworption peaks are C-H out-of-plane vibrations frequency multiplication and sum of fundamental frequencies peak, 813 on Isosorbide-5-Nitrae-disubstituted benzenes ring
cm-1Strong absworption peak is C-H out-of-plane bending vibration absworption peaks on 1,4- disubstituted benzenes rings.Spectrogram is in 860 ~ 880 cm-1Place does not inhale
Peak is received, illustrates that three substitutions/tetra- being not present in resin structure on phenyl ring replace structure.To sum up data analysis, we can be determined that
By polyphenylene sulfide made from method provided by the present invention be comprise only 1,4- bis- replace structure high linearity it is poly-
Diphenyl sulfide resin.
Claims (7)
1. a kind of synthetic method of the linear poly arylidene thio-ester of high-purity, it is characterised in that methods described comprises the following steps：
1) benzene or benzene series hydroxy derivatives, acid binding agent, metallic catalyst are mixed, dispersed with stirring is uniform at room temperature；
2) to step 1) gains dropwise addition sulfur dichloride, process control reaction temperature is added dropwise and is controlled after 20-40 DEG C, completion of dropping
Reaction temperature is reacted 8-15 hours at 20-40 DEG C；
3) by step 2) gains add to mass fraction be 5% ethanol solution of hydrogen chloride, by filtering, washing, dry after,
Produce；
Wherein, the benzene series hydroxy derivatives include one kind in p-methyl phenol, paraethyl phenol；Benzene or the benzene series hydroxyl
The mol ratio of derivative and sulfur dichloride is 1~1.05:1；The acid binding agent includes one kind in pyridine, triethylamine, diethylamine；
The mol ratio of acid binding agent and sulfur dichloride is 1~1.1:1.
2. according to the method described in claim 1, it is characterised in that the metallic catalyst is included in iron powder, magnesium powder, zinc powder
It is a kind of.
3. method according to claim 1 or 2, it is characterised in that the mol ratio of the metallic catalyst and sulfur dichloride
For 0.001~0.008:1.
4. mode of washing is described according to the method described in claim 1, it is characterised in that step 3)：Utilize second alcohol and water
Carry out cyclic washing；The drying mode is：Under vacuum, dried in 60 DEG C to constant weight.
5. method according to claim 3, it is characterised in that the benzene series hydroxy derivatives are p-methyl phenol, described
Acid binding agent is one kind in triethylamine, pyridine, and the metallic catalyst is one kind in zinc powder, iron powder.
6. method according to claim 4, it is characterised in that the benzene series hydroxy derivatives are p-methyl phenol, described
Acid binding agent is one kind in triethylamine, pyridine, and the metallic catalyst is one kind in zinc powder, iron powder.
7. the method according to claim 5 or 6, it is characterised in that the reaction temperature is 30-40 DEG C, the reaction time is
8-10 hours.
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| US5250657A (en) * | 1990-01-29 | 1993-10-05 | Seisan Kaihatsu Kagaku Kenkyusho | Process for preparing polyarylene thioether |
| CN103275320A (en) * | 2013-07-01 | 2013-09-04 | 四川宝利丰科技有限公司 | Method for preparing linear high molecular weight polyphenylene sulfide by utilizing pre-desalting method |
| CN104072772A (en) * | 2014-07-11 | 2014-10-01 | 四川宝利丰科技有限公司 | Treatment method for polyphenylene sulfide resin slurry |
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| JP4844057B2 (en) * | 2005-09-12 | 2011-12-21 | Ｄｉｃ株式会社 | Polyphenylene sulfide and process for producing the same |
| JP2014028917A (en) * | 2012-06-27 | 2014-02-13 | Toray Ind Inc | Process for producing high quality polyarylene sulfide resin |
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| US5250657A (en) * | 1990-01-29 | 1993-10-05 | Seisan Kaihatsu Kagaku Kenkyusho | Process for preparing polyarylene thioether |
| CN103275320A (en) * | 2013-07-01 | 2013-09-04 | 四川宝利丰科技有限公司 | Method for preparing linear high molecular weight polyphenylene sulfide by utilizing pre-desalting method |
| CN104072772A (en) * | 2014-07-11 | 2014-10-01 | 四川宝利丰科技有限公司 | Treatment method for polyphenylene sulfide resin slurry |
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Effective date of registration: 20200108 Address after: 250204 Ji'nan, Zhangqiu, Shandong province Diao Zhen Chemical Industrial Park Patentee after: SHANDONG MINGHUA NEW MATERIAL CO., LTD. Address before: 610000 No. 99 KELONG North Road, Sichuan, Chengdu Patentee before: Chendu Huien Fine Chemical Co., Ltd. |