CN102206343B - Polyarylenethioethernitrileimide copolymer and preparation method thereof - Google Patents

Abstract

The invention discloses a polyarylene sulfide nitrile imide copolymer, the general structural formula of which is formula I. In formula I, a and b respectively represent the degree of polymerization, and the ratio of a to b is 0.1-99.9:0.1-99.9 ; The thioether bond is at the 3-position or 4-position on the phthalimide structural unit in the polymer, and the 2-position, 3-position, 4-position, 5-position or 6-position on the benzonitrile structural unit ; A is one of a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group. The preparation method comprises: using disubstituted phthalimide and sulfur as raw materials, and carrying out copolymerization reaction with dihalobenzonitrile to prepare polyarylene sulfide nitrile imide copolymer. The copolymer has good and adjustable thermal stability, a wide processing window and good processability.

Description

Polyarylene sulfide nitrile imide copolymer and preparation method thereof

technical field

The invention relates to the field of polymer materials, in particular to a polyarylene sulfide nitrile imide copolymer and a preparation method thereof.

Background technique

Polythioetherimide is a thermoplastic polymer material. Due to the introduction of flexible thioether units into the rigid polyimide main chain, this type of polymer not only has good thermal stability and mechanical properties, but also has Good solubility and melt processability, so there are many reports on the research of polythioetherimide. U.S. Patents US3989712, US4054584, US4092297, US4499285, US4625037, document "The gas permeation properties of homopolymerization and copolyimide synthesized by isomeric thioether dianhydride and oxygen ether diamine" (Journal of Applied Polymer Science 1997, 63, 1821-1826) and "Polyimide Synthesized from Isomerized Diphenyl Sulfide Dianhydride" (Journal of Polymer Science: Part A: Polymer Chemistry, 2006, 44, 959-967) have reported Preparation of polythioetherimides. However, the above-mentioned documents all synthesize thioether dianhydride first, such as the Chinese patent whose publication number is CN1724528A discloses a method for preparing polyimide raw material thioether dianhydride, and then polymerizes with various diamines to prepare polyimide Thietherimide, the reaction steps are more loaded down with trivial details. The Chinese patent application with the publication number CN101531758A discloses an improved method based on the synthesis method of the above-mentioned polythioetherimide, using the method of direct polymerization of disubstituted phthalimide and sulfur to obtain a low-cost And polysulfide imide with excellent comprehensive performance.

Although polythioetherimide has many advantages, its heat resistance and processing performance need to be further improved, and the cost needs to be further reduced. Selecting a suitable comonomer for copolymerization is a method to obtain polymers with tunable properties. European patent EP0292279 and the literature "Polyarylene sulfide with cyano side groups that can be used as high-temperature lamination resins" (Journal of PolymerScience: Polymer Chemistry Edition, 1974, 12, 1301-1311) and "Polyphenylene sulfide Structural Modification" (Polymer Materials Science and Engineering, 1992, 1, 7-15) reported that the heat resistance of polyphenylene sulfide can be improved by introducing cyano side groups in the structure of polyphenylene sulfide, making its glass transition The temperature, melting temperature and decomposition temperature are greatly increased. It can be seen that introducing a highly polar group cyano group into the side chain of the polymer can make the polymer maintain better thermal stability and mechanical properties.

Contents of the invention

The invention provides a polyarylene sulfide nitrile imide copolymer with relatively high molecular weight and good overall performance.

The invention also provides a preparation method of the polyarylene sulfide nitrile imide copolymer.

A kind of polyarylene sulfide nitrile imide copolymer, its general structural formula is such as formula I:

In formula I, a and b represent the degree of polymerization respectively, and the ratio of a to b is 0.1 to 99.9:0.1 to 99.9;

The thioether bond is at the 3-position or 4-position of the phthalimide structural unit in the polymer, and the 2-position, 3-position, 4-position, 5-position or 6-position of the benzonitrile structural unit;

A is one of substituted or unsubstituted aliphatic groups, substituted or unsubstituted aromatic groups;

The aliphatic hydrocarbon group is selected from C ₁ to C ₁₀ aliphatic chain hydrocarbon groups or C ₃ to C ₁₀ alicyclic hydrocarbon groups, or at least two groups formed by connecting with CC bonds;

The aromatic group is selected from C ₆ -C ₃₀ aromatic groups, preferably C ₆ -C ₃₀ benzene-based aromatic groups.

As preferred:

The A is selected from but not limited to

的一种或者是它们中至少两种以C-C键连接而形成的基团。

One or a group formed by connecting at least two of them with a CC bond.

The preparation method of described polyarylene sulfide nitrile imide copolymer comprises steps:

The disubstituted phthalimide of the structure shown in formula II is adopted to carry out copolymerization reaction with sulfur and dihalobenzonitrile in the presence of a reducing agent, a catalyst and a reaction aid to prepare a polyarylene sulfide nitrile imide copolymer;

In formula II, X and X' are the same or different, X and X' are each independently selected from a fluorine atom, a chlorine atom, a bromine atom or a nitro group, and the substitution positions of X and X' are each independently at 3- or 4 bit;

A is one of a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic group, and has the same meaning as A in formula I;

The aliphatic hydrocarbon group is selected from C ₁ to C ₁₀ aliphatic chain hydrocarbon groups or C ₃ to C ₁₀ alicyclic hydrocarbon groups, or at least two groups formed by connecting with CC bonds;

The aromatic group is selected from C ₆ -C ₃₀ aromatic groups.

The preparation method of the disubstituted phthalimide of the structure shown in formula II can refer to the preparation method of the polythioetherimide disclosed in the Chinese patent application with the publication number CN101531758A and the one disclosed in the Chinese patent application with the publication number CN101463132A A preparation method of polythioetherimide.

Its synthesis method includes: using chlorinated phthalic anhydride or nitrophthalic anhydride isomers with the structure shown in formula V as raw materials, and half molar equivalent of organic diamine (H ₂ NA-NH ₂ , since it is the two Each amino group reacts with chlorophthalic anhydride or nitrophthalic anhydride, so the group A in _H2NA - _NH2 has the same meaning as the group A in formula I) reacts to generate the disubstituted phthaloyl of the structure shown in formula II imine.

The reaction can be carried out in an aprotic polar solvent, or in glacial acetic acid, or in a benzene solvent and a polar aprotic mixed solvent, or by heating and melting. The reaction temperature is generally 100°C to 350°C.

In formula V, the R substituent is a chlorine atom or a nitro group, and its substitution position is at the 3- or 4-position.

The organic diamine (H ₂ NA-NH ₂ ) can be selected from 1,6-hexanediamine, 1,2-cyclohexanediamine, p-phenylenediamine, m-phenylenediamine, 4,4′-bis Phenylenediamine, 3,3'-dimethyl-4,4'-biphenylenediamine, 2,2'-dimethyl-4,4'-biphenylenediamine, 4,4'-diaminobis Phenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 3,4 '-Diaminodiphenylsulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylisopropane, 4,4'-diaminodiphenylsulfide, 2,2'-di Chloro-4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 4,4'-diamino-diphenoxy-4", 4"'-biphenyl,4,4'-diamino-diphenoxy-4",4"'-diphenyl ether, 4,4'-diamino-diphenoxy-4", 4"'-bis Phenylsulfone, 4,4'-diamino-diphenoxy-4", 4"'-diphenylisopropane, 2,4-toluenediamine, 5-methyl-4,6-diethyl- 1,3-phenylenediamine, 3,3'-dimethyl-4,4'-diaminodiphenylmethane or 2,2'3,3'-tetramethyl-4,4'-diaminodiphenyl One of methane or a mixture of at least two of them.

As preferred:

The ratio of the amount of dihalobenzonitrile to disubstituted phthalimide is 0.1-99.9:0.1-99.9;

The sulfur is used as a coupling agent, and the ratio of its substance amount to the total substance amount of disubstituted phthalimide and dihalobenzonitrile is 0.90 to 1.30:1, more preferably 0.95 to 1.150:1, the closer the ratio is to At 1:1, it is easier to prepare high molecular weight polymers.

The temperature of the copolymerization reaction is 60°C to 260°C, more preferably 100°C to 190°C.

The structural general formula of described dihalobenzonitrile is as formula III:

In formula III, D and D' are the same or different, D and D' are each independently selected from one of fluorine atoms, chlorine atoms or bromine atoms, and the substitution positions of D and D' are independently at the 2-position, 3- bit, 4-bit, 5-bit or 6-bit.

The dihalobenzonitrile can be selected from but not limited to 2,6-dichlorobenzonitrile, 2,6-difluorobenzonitrile, 2,6-dibromoxynil, 2-chloro-6 bromoxynil, 2 , 4-dichlorobenzonitrile, 3,5-dichlorobenzonitrile, 2,5-difluorobenzonitrile, 2,4-difluorobenzonitrile, 2,4-dibromobenzonitrile, 2-chloro-4- One or more of bromoxynil.

The reducing agent can be selected from but not limited to formate, oxalate, aldehyde (including formaldehyde or acetaldehyde, etc.), hydrazine (including phenylhydrazine or hydrazine hydrate, etc.), hydroxylamine, metal element (including iron powder, aluminum powder or zinc powder, etc.), reducing salts (including ferrous salts, stannous salts and other salts with reducing ability), hydrides (including sodium hydride, calcium hydride, sodium borohydride or lithium aluminum hydride, etc.), ammonia at least one of gas and hydrogen.

The ratio of the amount of reducing agent to the amount of sulfur is preferably 0.2 to 6:1, more preferably 0.4 to 3:1.

Described reaction aid or catalyst can be selected from but not limited to carbonate (comprising lithium carbonate, sodium carbonate or potassium carbonate etc.), bicarbonate (comprising sodium bicarbonate or potassium bicarbonate etc.), phosphate (comprising phosphoric acid sodium hydrogen phosphate or potassium hydrogen phosphate, etc.), hydrogen phosphate (including hydrogen phosphate of disodium hydrogen phosphate or dipotassium hydrogen phosphate), alkali hydroxide (including potassium hydroxide, sodium hydroxide or lithium hydroxide, etc.), halide (including calcium chloride, sodium chloride, potassium chloride, lithium bromide, potassium fluoride or sodium iodide, etc.), phase transfer catalysts (including quaternary ammonium salts, quaternary phosphonium salts or crown ethers, etc.).

The ratio of the amount of reaction aid or the amount of catalyst to the amount of sulfur is preferably 0.02-3:1, more preferably 0.05-1.5:1.

The copolymerization reaction can be carried out in a benzene solvent with good solubility, or in a mixed solvent of a benzene solvent and a polar aprotic solvent, or directly in a polar aprotic solvent with good solubility .

Described polar aprotic solvent is selected from N-methylpyrrolidone (NMP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), dimethylsulfoxide One or more of (DMSO), hexamethylphosphoric triamide (HMPA), diphenyl sulfone, sulfolane or their similar substances.

The benzene solvent is selected from one or more of benzene, toluene, xylene, chlorobenzene or their similar substances.

The copolymerization reaction may be carried out in an atmosphere of an inert gas, which may be selected from but not limited to nitrogen or argon, or may not be carried out in an atmosphere of an inert gas.

The copolymerization reaction can be carried out in the presence of at least one chain-terminating agent, and the degree of polymerization of the reaction and the molecular weight of the final polymer are controlled by the chain-terminating agent. Suitable chain-terminating agents include but are not limited to all those Substances having active substituents suitable for displacement by sulfide ions during polymerization.

The compound of the structure shown in the preferred formula IV of described chain-blocking agent:

B-R-M IV

In formula IV, B can be selected from but not limited to fluorine atom, chlorine atom, bromine atom or nitro group;

R is a substituted or unsubstituted aromatic group or a substituted or unsubstituted alkyl group, the aromatic group may be selected from but not limited to phenyl, biphenylfuryl, pyridyl, naphthyl, quinolinyl or one of their analogous groups, etc.;

M can be selected from but not limited to hydrogen atom, methyl group, acyl group, phenyl acyl group, alkylsulfonyl group, arylsulfonyl group, nitro group, cyano group, azo group, carboxyl group, trifluoromethyl group, imide group or substituted imide groups.

The chain-blocking agent can be further preferably 3-chlorophenyl-tert-butyl ketone, 3-fluorophenyl-tert-butyl ketone, 4-chlorobenzophenone, 3-nitrobenzophenone, 4-nitrobenzophenone phenylmethylsulfone, 4-fluorophenylphenylsulfone, 2-iodonitrobenzene, 4-bromophenylazobenzene, 4-fluoropyridine, 3-chlorobenzoic acid, 1-nitro-4- Trifluoromethylbenzene, 1-chloro-3-trifluoromethylbenzene, N-phenyl-3-chlorophthalimide, N-phenyl-4-fluorophthalimide, N-methyl-3-chlorophthalimide, N-methyl-4-nitrophthalimide, N-butyl-3-chlorophthalimide or N - One or more of cyclohexyl-4-chlorophthalimide and the like.

The ratio of the amount of substance of chain-terminating agent to the amount of substance of sulfur is preferably 0.01-0.30:1.

After the completion of the copolymerization reaction, the polyarylene sulfide nitrile imide copolymer can be separated by conventional methods, and these methods can include but are not limited to one or more steps of precipitation, one or more steps of filtration, one or more steps of water washing or one step Or a combination of one or more of multi-step water boiling, one-step or multi-step Soxhlet extraction, one-step or multi-step drying, etc.

The polyarylene sulfide nitrile imide copolymer of the present invention has an inherent viscosity of about 0.13dL/g to about 3.00dL measured in m-cresol with a concentration of 0.5g/dL by Ubbelohde viscometer at 30°C /g; it has a weight average molecular weight of between about 3,000 and about 140,000 relative to polystyrene standards as determined by gel permeation chromatography, and a polydispersity coefficient of between about 1.8 and about 5.4. The glass transition temperature measured by differential scanning calorimetry (DSC) is about 160 to about 350° C., indicating that the polyarylene sulfide nitrile imide copolymer of the present invention has good heat resistance. The glass transition temperature was measured using a Perkin Elmer Diamond DSC instrument, with a heating rate of 20°C per minute under a nitrogen atmosphere, and the secondary heating data of the program was taken.

The polyarylene sulfide nitrile imide copolymer of the present invention has a tensile strength of about 50 to about 200 MPa measured by an Instron 5567 universal material testing machine at room temperature, a Young's modulus of about 1.0 to about 4.0 GPa, and an elongation at break of about 1.0 to about 4.0 GPa. The elongation ranges from about 1% to about 50%, indicating that the polyarylene sulfide nitrile imide copolymer of the present invention has good mechanical properties. The test sample is a uniform film with a width of 10mm and a thickness of 0.3mm, and the tensile rate is 5mm/min.

The polyarylene sulfide nitrile imide copolymer of the present invention has a viscosity value of about 200 poises to about 100,000 poises measured by a Physica MCR-301 rotational rheometer at 360° C. and 1000 S ⁻¹ . It shows that the polyarylene sulfide nitrile imide copolymer of the present invention has good processability.

Compared with the prior art, the present invention has the advantages of:

1. Using disubstituted phthalimide and dihalobenzonitrile as raw materials and sulfur as coupling agent to prepare polyarylene sulfide nitrile imide, the preparation method is simple, and the obtained product has high molecular weight and good thermal stability and excellent processing performance.

2. A series of polyarylene sulfide nitrile imides with different benzonitrile content can be prepared by adjusting the ratio of disubstituted phthalimide to dihalobenzonitrile, which is a series of copolymerized polyarylene sulfide nitrile imides with continuously adjustable properties. For imines, these continuously adjustable properties include glass transition temperature and processing temperature, so the properties of polymers, especially heat resistance and processing properties, can be adjusted by adjusting the content of dihalobenzonitrile.

3. The price of dihalobenzonitrile is low, which can appropriately reduce the cost of the polymer. The product has a high performance-price ratio, is easy to popularize and use, and has significant economic and social benefits.

Description of drawings

Figure 1 is a schematic diagram of the reaction process of the present invention.

Detailed ways

Below in conjunction with embodiment the present invention is described in further detail.

Example 1

Add 10.953g (0.06mol) 4-chlorophthalic anhydride, 3.651g (0.02mol) 3-chlorophthalic anhydride, 160ml glacial acetic acid into a dry and clean 500ml three-neck flask, stir to dissolve and add 9.053 (0.04mol) 3,3' -Dimethyl-4,4'-diaminodiphenylmethane, heated to 130°C for reflux reaction for 30 hours, cooled to room temperature, poured it into 600ml distilled water and stirred for 3 hours, filtered the obtained filter cake and washed it three times with distilled water , Vacuum drying at 120 ° C to obtain 20.884 g of a crude product of dichlorophthalimide, with a yield of 94%. The crude product was recrystallized from dimethyl sulfoxide and used in the next polymerization reaction. The structural formula of two chlorophthalimides is as follows:

Wherein, the substitution position of the Cl atom is at the 3-position or the 4-position.

Under a nitrogen atmosphere, add 5.5541g (0.010mol) of the above-mentioned dichlorophthalimide monomer, 1.7201g (0.010mol) of 2,6 dichlorobenzonitrile, 0.6602g (0.0206mol) into a dry and clean 500ml three-necked flask Sulfur, 0.9600g (0.04mol) sodium hydride, 2.8471g (0.0206mol) potassium carbonate, 0.2120g (0.005mol) lithium chloride and 100ml N-methylpyrrolidone, stirred and heated to 80°C for 24 hours, then added 0.3092g (0.0012mol) N-phenyl-3-chlorophthalimide was reacted for 4 hours, after cooling to room temperature, the reaction solution was slowly poured into 1L distilled water and stirred for 12 hours, and the filter cake obtained by filtering was washed three times with distilled water , and then extracted with 95% (volume fraction) ethanol for 24 hours, and dried under vacuum at 120° C. to obtain 6.06 g of polymer powder, with a yield of 93%.

The IR (KBr) of the above-mentioned polymer: 3704, 3060, 2924, 2226, 1775, 1709, 1499, 1375, 1114cm ^-1 , is a polyarylene sulfide nitrile imide copolymer, and its structural formula is as follows:

Wherein, the thioether bond is at the 3-position or 4-position of the phthalimide structural unit in the polymer, a and b respectively represent the degree of polymerization, and the ratio of a to b is 0.1-99.9:0.1-99.9.

The inherent viscosity of the above polymer measured in a concentration of 0.5 g/dL m-cresol at 30° C. is 0.76 dL/g. The weight average molecular weight determined by gel permeation chromatography relative to polystyrene standards was 45,000 and the polydispersity index was 3.8. The glass transition temperature determined by differential scanning calorimetry (DSC) was 242°C. The tensile strength measured by an Instron 5567 universal material testing machine at room temperature is 120 MPa, the Young's modulus is 3.0 GPa, and the elongation at break is 7.3%. The viscosity value measured by Physica MCR-301 rotational rheometer at 360° C., 1000 S ⁻¹ is 600 poise.

Example 2

Add 32.86g (0.18mol) 4-chlorophthalic anhydride, 3.65g (0.02mol) 3-chlorophthalic anhydride, 400ml glacial acetic acid into a dry and clean 1L three-neck flask, stir to dissolve and add 19.83 (0.1mol) 4,4' -Diaminodiphenylmethane, heat up to 140°C for reflux reaction for 26 hours, cool to room temperature and filter the obtained filter cake to wash three times with distilled water, and vacuum-dry at 120°C to obtain 48.52g of dichlorophthalimide crude product, yield 92%. The crude product was recrystallized from a mixed solvent of toluene and N,N-dimethylacetamide (4:1, v/v) and used for the next polymerization reaction. The structural formula of two chlorophthalimides is as follows:

Wherein, the substitution position of the Cl atom is at the 3-position or the 4-position.

Under a nitrogen atmosphere, add 3.6917g (0.007mol) of the above-mentioned dichlorophthalimide, 0.5160g (0.003mol) of 2,6 dichlorobenzonitrile, 0.3207g (0.01mol) of sulfur into a 100ml dry and clean three-necked flask, 0.090g (0.001mol) paraformaldehyde, 0.1060g (0.001mol) sodium carbonate, 0.04239 (0.001mol) lithium chloride, 50ml hexamethylphosphoric triamide, stirred and heated to 135°C for 24 hours, cooled to room temperature The reaction solution was slowly poured into 500ml of methanol and stirred for 12 hours, and the filter cake obtained by filtration was washed three times with distilled water, then extracted with 95% (volume fraction) ethanol for 24 hours, and obtained 3.628g of polymer powder after vacuum drying at 120°C. Yield 95%.

The IR (KBr) of the above-mentioned polymer: 3704, 3060, 2924, 2226, 1775, 1709, 1499, 1375, 1114cm ^-1 , is a polyarylene sulfide nitrile imide copolymer, and its structural formula is as follows:

Wherein, the thioether bond is at the 3-position or 4-position of the phthalimide structural unit in the polymer, a and b respectively represent the degree of polymerization, and the ratio of a to b is 0.1-99.9:0.1-99.9.

The inherent viscosity of the above polymer measured in a concentration of 0.5 g/dL m-cresol at 30° C. is 0.63 dL/g. The weight average molecular weight determined by gel permeation chromatography relative to polystyrene standards was 40,000 and the polydispersity index was 3.3. The glass transition temperature measured by differential scanning calorimetry (DSC) is 253°C, the tensile strength measured by Instron 5567 universal material testing machine at room temperature is 113MPa, the Young's modulus is 3.2GPa, and the elongation at break is 8.6%. The viscosity value measured by Physica MCR-301 rotational rheometer at 360° C., 1000 S ⁻¹ is 3000 poise.

Example 3

Add 91.28g (0.50mol) 4-chlorophthalic anhydride, 91.28g (0.50mol) 3-chlorophthalic anhydride, 100.12 (0.50mol) 4,4'-diaminodiphenyl ether in a dry and clean 500ml three-necked flask. Slowly heated to 260°C under vacuum to form a homogeneous melt, stirred for 4 hours, and then cooled to room temperature to obtain 259.38 g of crude bischlorophthalimide, with a yield of 98%. The crude product can be directly used in the next polymerization reaction. The structural formula of two chlorophthalimides is as follows:

Wherein, the substitution position of the Cl atom is at the 3-position or the 4-position.

Under a nitrogen atmosphere, add 31.7598g (0.06mol) of the above-mentioned dichlorophthalimide, 6.8804g (0.04mol) of 2,6 dichlorobenzonitrile, 3.207g (0.1mol) of sulfur into a 1L dry and clean three-neck flask, 3.303g (0.1mol) of hydroxylamine, 6.9105g (0.05mol) of potassium carbonate, 0.1272g (0.003) of lithium chloride, 500ml of dimethyl sulfoxide, stirred and heated to 110°C for 12 hours, the reaction solution was slowly poured into 2L of distilled water, Stir for 12 hours, filter the obtained filter cake and wash it three times with distilled water, then extract it with 95% (volume fraction) ethanol for 24 hours, and obtain 32.67 g of polymer powder after vacuum drying at 120°C, with a yield of 94%.

The IR (KBr) of the above-mentioned polymer: 3704, 2226, 1775, 1709, 1499, 1375, 1241, 1114cm ^-1 , is a polyarylene sulfide nitrile imide copolymer, and its structural formula is as follows:

Wherein, the thioether bond is at the 3-position or 4-position of the phthalimide structural unit in the polymer, a and b respectively represent the degree of polymerization, and the ratio of a to b is 0.1-99.9:0.1-99.9.

The inherent viscosity of the above polymer measured in a concentration of 0.5 d/dL m-cresol at 30° C. is 0.41 dL/g. The weight average molecular weight relative to polystyrene standards determined by gel permeation chromatography was 16,000, and the polydispersity index was 3.0. The glass transition temperature measured by differential scanning calorimetry (DSC) is 238°C, the tensile strength measured by Instron 5567 universal material testing machine at room temperature is 136MPa, the Young's modulus is 2.9GPa, and the elongation at break is 4.5%. The viscosity value measured by a Physica MCR-301 rotational rheometer at 360° C. and 1000 S ⁻¹ is 3300 poise.

Example 4

Add 54.77g (0.30mol) 4-chlorophthalic anhydride, 36.51g (0.20mol) 3-chlorophthalic anhydride, 54.08 (0.25mol) 4,4'-diaminodiphenyl sulfide in a dry and clean 250ml three-necked flask, Slowly heated up to 200° C. to form a homogeneous melt under an argon atmosphere, stirred for 10 hours, and then cooled to room temperature to obtain 129.54 g of a crude product of dichlorophthalimide, with a yield of 95%. The crude product can be directly used in the next polymerization reaction. The structural formula of two chlorophthalimides is as follows:

Wherein the substitution position of the Cl atom is at the 3-position or the 4-position.

Under an argon atmosphere, add 14.7263g (0.027mol) of the above-mentioned dichlorophthalimide, 0.5160g (0.003mol) of 2,6 dichlorobenzonitrile, and 0.9621g (0.03mol) of sulfur into a 500ml dry and clean three-necked flask , 2.4490g (0.035mol) lithium formate, 1.600g (0.040mol) sodium hydroxide, 0.7495g (0.005mol) sodium iodide, 120ml diphenylsulfone and 100ml toluene, stirred and heated to 160°C for 12 hours, and the reaction solution was concentrated After reaching about 150ml, slowly pour it into 1L distilled water, stir for 12 hours, filter the obtained filter cake and wash it three times with distilled water, then extract it with 95% (volume fraction) ethanol for 24 hours, and obtain 12.67g of polymer powder after vacuum drying at 120°C , 90% yield.

The IR (KBr) of the above-mentioned polymer: 3704, 2226, 1775, 1709, 1499, 1375, 1114cm ^-1 , is a polyarylene sulfide nitrile imide copolymer, and its structural formula is as follows:

Wherein, the thioether bond is at the 3-position or 4-position of the phthalimide structural unit in the polymer, a and b respectively represent the degree of polymerization, and the ratio of a to b is 0.1-99.9:0.1-99.9.

The inherent viscosity of the above polymer measured in a concentration of 0.5 g/dL m-cresol at 30° C. is 0.85 dL/g. The weight average molecular weight determined by gel permeation chromatography relative to polystyrene standards was 63,000 and the polydispersity index was 2.9. The glass transition temperature measured by differential scanning calorimetry (DSC) is 260°C, the tensile strength measured by Instron 5567 universal material testing machine at room temperature is 131MPa, the Young's modulus is 3.8GPa, and the elongation at break is 7.8%. The viscosity value measured by a Physica MCR-301 rotational rheometer at 360° C. and 1000 S ⁻¹ is 6000 poise.

Example 5

Add 28.97g (0.15mol) 4-nitrophthalic anhydride, 9.65g (0.05mol) 3-nitrophthalic anhydride, 1500ml xylene into a dry and clean 3L three-necked flask, stir to dissolve and add 19.83 (0.10mol) 4,4' -Diaminodiphenylmethane, heated to 165°C for reflux reaction for 16 hours, cooled to room temperature, filtered the filter cake obtained three times with absolute ethanol, and vacuum-dried at 120°C to obtain 48.82g of dinitrophthalimide crude product, Yield 89%. The crude product was recrystallized from a mixed solvent of toluene and N,N-dimethylacetamide (4:1, v/v) and used for the next polymerization reaction. The structural formula of bisnitrophthalimide is as follows:

Wherein, the substitution position of NO ₂ is at the 3-position or 4-position.

Under a nitrogen atmosphere, add 3.8388g (0.007mol) of the above-mentioned bisnitrophthalimide, 0.4173g (0.003mol) of 2,6 difluorobenzonitrile, 0.3207g (0.01mol) of sulfur into a 100ml dry and clean three-necked flask, 0.027g (0.001mol) of aluminum powder, 0.1060g (0.001mol) of sodium carbonate, 0.04239 (0.001mol) of lithium chloride, 50ml of hexamethylphosphoric triamide, stirred and heated to 135°C for 24 hours, cooled to room temperature The reaction solution was slowly poured into 500ml methanol and stirred for 12 hours, and the filter cake obtained by filtration was washed three times with distilled water, then extracted with 95% (volume fraction) ethanol for 24 hours, and obtained polymer powder 3.63g after vacuum drying at 120°C. The rate is 95%.

The IR (KBr) of the above-mentioned polymer: 3704, 3060, 2960, 2226, 1775, 1709, 1499, 1375, 1114cm ^-1 , is a polyarylene sulfide nitrile imide copolymer, and its structural formula is as follows:

Wherein, the thioether bond is at the 3-position or 4-position of the phthalimide structural unit in the polymer, a and b respectively represent the degree of polymerization, and the ratio of a to b is 0.1-99.9:0.1-99.9.

The inherent viscosity of the above polymer measured in a concentration of 0.5 g/dL m-cresol at 30° C. was 1.21 dL/g. The weight average molecular weight determined by gel permeation chromatography relative to polystyrene standards was 120,000 and the polydispersity index was 3.4. The glass transition temperature measured by differential scanning calorimetry (DSC) is 250°C, the tensile strength measured by Instron 5567 universal material testing machine at room temperature is 150MPa, the Young's modulus is 3.9GPa, and the elongation at break is 5.6%. The viscosity value measured by Physica MCR-301 rotational rheometer at 360° C. and 1000 S ⁻¹ is 80200 poise.

Example 6

Add 289.66g (1.50mol) 4-nitrophthalic anhydride, 96.55g (0.50mol) 3-nitrophthalic anhydride, 200.24g (1.0mol) 4,4'-diaminodiphenyl ether in a dry and clean 2L three-necked flask, Slowly heated up to 320° C. to form a homogeneous melt under vacuum, stirred for 6 hours, and then cooled to room temperature to obtain 528.44 g of crude bisnitrophthalimide, with a yield of 96%. The crude product can be directly used in the next polymerization reaction. The structural formula of bisnitrophthalimide is as follows:

Wherein, the substitution position of NO ₂ is at the 3-position or 4-position.

Under a nitrogen atmosphere, add 33.0276g (0.06mol) of the above-mentioned bisnitrophthalimide, 5.564g (0.04mol) of 2,5-difluorobenzonitrile, and 3.5277g (0.11mol) of sulfur into a 1L dry and clean three-neck flask , 5.473g (0.13mol) calcium hydride, 4.0g (0.1mol) sodium hydroxide, 1.17g (0.02mol) sodium chloride, 500ml dimethyl sulfoxide, stirred and heated to 110°C for 12 hours, the reaction solution was slowly poured into 2L of distilled water, stirred for 12 hours, the filter cake obtained by filtration was washed three times with distilled water, then extracted with 95% (volume fraction) ethanol for 24 hours, and dried under vacuum at 120°C to obtain 31.717g of polymer powder, with a yield of 94%.

The IR (KBr) of the above-mentioned polymer: 3704, 2226, 1775, 1709, 1499, 1375, 1241, 1114cm ^-1 , is a polyarylene sulfide nitrile imide copolymer, and its structural formula is as follows:

Wherein, the thioether bond is at the 3-position or 4-position of the phthalimide structural unit in the polymer, a and b respectively represent the degree of polymerization, and the ratio of a to b is 0.1-99.9:0.1-99.9.

The inherent viscosity of the above polymer measured in a concentration of 0.5 g/dL m-cresol at 30° C. is 0.25 dL/g. The weight average molecular weight relative to polystyrene standards determined by gel permeation chromatography was 8000 and the polydispersity index was 3.2. The glass transition temperature measured by differential scanning calorimetry (DSC) is 232°C, the tensile strength measured by Instron 5567 universal material testing machine at room temperature is 88MPa, the Young's modulus is 2.2GPa, and the elongation at break is 1.5%. The viscosity value measured by Physica MCR-301 rotational rheometer at 360° C., 1000 S ⁻¹ is 800 poise.

Example 7

Add 38.62g (0.20mol) 4-nitrophthalic anhydride, 38.62g (0.02mol) 3-nitrophthalic anhydride, 800ml N,N-dimethylacetamide into a dry and clean 2L three-necked flask, stir to dissolve and add 42.45g (0.20mol) 4,4'-diaminobenzophenone, heated to 150°C for reflux reaction for 17 hours, cooled to room temperature and filtered the filter cake obtained three times with absolute ethanol, and vacuum-dried at 120°C to obtain dinitro The crude product of phthalimide was 106.87g, and the yield was 95%. The crude product was recrystallized from a mixed solvent of toluene and N,N-dimethylformamide (2:1, v/v) for the next step of polymerization. The structural formula of bisnitrophthalimide is as follows:

Wherein, the substitution position of NO ₂ is at the 3-position or 4-position.

Under an argon atmosphere, add 15.1868g (0.027mol) of the above-mentioned bisnitrophthalimide, 0.4667g (0.003mol) of 2chloro-6-fluoro-benzonitrile, 0.9621g (0.03mol) to a 500ml dry and clean three-neck flask ) sulfur, 2.4490g (0.035mol) lithium formate, 1.600g (0.040mol) sodium hydroxide, 0.7495g (0.005mol) sodium iodide, 120ml diphenyl sulfone and 100ml toluene, stirred and heated to 160 ° C for 12 hours, the reaction After the solution was concentrated to about 150ml, it was slowly poured into 1L of distilled water, stirred for 12 hours, and the filter cake obtained by filtration was washed three times with distilled water, then extracted with 95% (volume fraction) ethanol for 24 hours, and dried under vacuum at 120°C to obtain polymer powder. 12.5714g, 90% yield.

The IR (KBr) of the above-mentioned polymer: 3060, 2226, 1784, 1718, 1670, 1600, 1388, 718cm ^-1 , is a polyarylene sulfide nitrile imide copolymer, and its structural formula is as follows:

Wherein, the thioether bond is at the 3-position or 4-position of the phthalimide structural unit in the polymer, a and b respectively represent the degree of polymerization, and the ratio of a to b is 0.1-99.9:0.1-99.9.

The inherent viscosity of the above polymer measured in a concentration of 0.5 g/dL m-cresol at 30° C. is 0.57 dL/g. The weight average molecular weight determined by gel permeation chromatography relative to polystyrene standards was 41,000 and the polydispersity index was 3.7. The glass transition temperature measured by differential scanning calorimetry (DSC) is 253°C, the tensile strength measured by Instron 5567 universal material testing machine at room temperature is 121MPa, the Young's modulus is 3.8GPa, and the elongation at break is 9.2%. The viscosity value measured by a Physica MCR-301 rotational rheometer at 360° C. and 1000 S ⁻¹ is 9000 poise.

Example 8

Add 109.54g (0.60mol) 4-chlorophthalic anhydride, 36.51g (0.20mol) 3-chlorophthalic anhydride, 160ml glacial acetic acid into a dry and clean 3L three-necked flask, stir to dissolve and add 90.53 (0.40mol) 3,3' -Dimethyl-4,4'-diaminodiphenylmethane, heated to 140°C for reflux reaction for 15 hours, cooled to room temperature, filtered the filter cake obtained three times with distilled water, and vacuum-dried at 120°C to obtain dichlorophthalein The imide crude product is 208.84g, and the yield is 94%. The crude product was recrystallized from dimethyl sulfoxide for the next polymerization reaction. The structural formula of bischlorophthalimide is as follows:

Wherein, the substitution position of the Cl atom is at the 3-position or the 4-position.

Under nitrogen atmosphere, add 5.5541g (0.010mol) of the above-mentioned dichlorophthalimide, 1.7201g (0.010mol) of 3,5-dichlorobenzonitrile, 0.6606g (0.0206mol) of sulfur into a dry and clean 500ml three-necked flask , 0.9600g (0.04mol) sodium hydride, 2.8471g (0.0206mol) potassium carbonate, 0.2120g (0.005mol) lithium chloride and 100ml N-methylpyrrolidone, stirred and heated to 80 ℃ for 24 hours, then added 0.3092g ( 0.0012mol) N-phenyl-3-chlorophthalimide was reacted for 4 hours, and after being cooled to room temperature, the reaction solution was slowly poured into 2L distilled water and stirred for 12 hours, and the filter cake obtained by filtering was washed three times with distilled water, Then, it was extracted with 95% (volume fraction) ethanol for 24 hours, and vacuum-dried at 120° C. to obtain 6.06 g of polyarylene sulfide nitrile imide powder, with a yield of 93%.

The IR (KBr) of the above-mentioned polymer: 3704, 3060, 2924, 2226, 1775, 1709, 1499, 1375, 1114cm ^-1 , is a polyarylene sulfide nitrile imide copolymer, and its structural formula is as follows:

Wherein, the thioether bond is at the 3-position or 4-position of the phthalimide structural unit in the polymer, a and b respectively represent the degree of polymerization, and the ratio of a to b is 0.1-99.9:0.1-99.9.

The inherent viscosity of the above polymer measured in a concentration of 0.5 g/dL m-cresol at 30° C. is 0.70 dL/g. The weight average molecular weight determined by gel permeation chromatography relative to polystyrene standards was 53,000 and the polydispersity index was 3.6. The glass transition temperature measured by differential scanning calorimetry (DSC) is 240°C, the tensile strength measured by Instron 5567 universal material testing machine at room temperature is 113MPa, the Young's modulus is 2.9GPa, and the elongation at break is 7.2%. The viscosity value measured by Physica MCR-301 rotational rheometer at 360° C., 1000 S ⁻¹ is 600 poise.

Example 9

Add 10.95g (0.06mol) 4-chlorophthalic anhydride, 7.30g (0.04mol) 3-chlorophthalic anhydride, 500ml xylene into a dry and clean 1L three-necked flask, stir to dissolve and add 5.41g (0.05mol) terephthalic anhydride The amine was heated to 170°C for reflux reaction for 18 hours, cooled to room temperature, and the filter cake obtained by filtration was washed three times with absolute ethanol, and vacuum-dried at 120°C to obtain 25.12 g of crude dichlorophthalimide, with a yield of 87%. The crude product was recrystallized from a mixed solvent of toluene and N,N-dimethylformamide (6:1, v/v) and used for the next polymerization reaction. The structural formula of bischlorophthalimide is as follows:

Wherein, the substitution position of the Cl atom is at the 3-position or the 4-position.

Under an argon atmosphere, add 5.7792g (0.01mol) of the above-mentioned dichlorophthalimide, 0.3207g (0.01mol) of sulfur, 0.24g (0.01mol) of sodium hydride, and 0.8401g to a dry and clean 250ml three-neck flask (0.01mol) sodium bicarbonate, 0.050g (0.000155mol) tetrabutylammonium bromide, 125ml hexamethylphosphoric triamide; add 0.6955g (0.005mol) 2,6 difluoro Benzonitrile, 0.1603g (0.005mol) sulfur, 0.12g (0.005mol) sodium hydride, 0.4200 (0.005mol) sodium bicarbonate, 0.03g (0.000093mol) tetrabutylammonium bromide, 40ml hexamethylphosphoric triamide ;The two reaction flasks were deoxygenated by argon for three times, then heated to 180°C for 8 hours, then mixed the reaction solutions in the two three-necked flasks and then reacted at 180°C for 15 hours, then cooled to room temperature and added N-phenyl-3-chlorophthalimide was then heated to 170° C. for 2 hours, and the reaction solution was cooled to room temperature for post-treatment. Slowly pour the reaction solution into 1L of water and stir for 2 hours, filter and boil with water for 2 hours, filter, wrap the filter cake with filter paper, and extract it in Soxhlet extraction with a mixed solution of ethanol and acetone (volume ratio 1:1). After extraction for 24 hours, the obtained polymer was baked in a vacuum oven at 200° C. for 20 hours to obtain 5.91 g of polymer powder with a yield of 95%.

The IR (KBr) of the above-mentioned polymer: 3708, 2225, 1770, 1712, 1496, 1378, 1119cm ^-1 , is a polyarylene sulfide nitrile imide copolymer, and its structural formula is as follows:

Wherein, the thioether bond is at the 3-position or 4-position of the phthalimide structural unit in the polymer, a and b respectively represent the degree of polymerization, and the ratio of a to b is 0.1-99.9:0.1-99.9.

The intrinsic viscosity of the polymer obtained from the above polymer in m-cresol at 30° C. is 0.41 dL/g, the weight average molecular weight relative to the polystyrene standard measured by gel permeation chromatography is 13000, and the polydispersity coefficient is 3.5. The glass transition temperature measured by differential scanning calorimetry (DSC) is 248°C, the tensile strength measured by Instron 5567 universal material testing machine at room temperature is 109MPa, the Young's modulus is 3.3GPa, and the elongation at break is 8.8%. The viscosity value measured by a PhysicaMCR-301 rotational rheometer at 360° C. and 1000 S ⁻¹ is 7000 poise.

Example 10

Add 10.95g (0.06mol) 4-chlorophthalic anhydride, 3.65g (0.02mol) 3-chlorophthalic anhydride, 160ml glacial acetic acid into a dry and clean 500ml three-neck flask, stir to dissolve and add 9.93 (0.04mol) 4,4' - Diaminodiphenyl sulfone, heated to 130°C for reflux reaction for 30 hours, cooled to room temperature, poured it into 600ml distilled water and stirred for 3 hours, filtered the filter cake obtained by washing three times with distilled water, and dried it under vacuum at 120°C to obtain dichlorodiphenylsulfone Substituted phthalimide crude product 21.71g, yield 94%. The crude product was recrystallized from dimethyl sulfoxide for the next polymerization reaction. The structural formula of two chlorophthalimides is as follows:

Wherein, the substitution position of the Cl atom is at the 3-position or the 4-position.

Under a nitrogen atmosphere, add 1.1548g (0.002mol) of the above-mentioned bischlorophthalimide, 0.1720g (0.001mol) of 3,5-dichlorobenzonitrile, 0.0962g (0.003mol) to a dry and clean 25ml two-necked bottle Sulfur, 0.536g (0.004mol) sodium oxalate, 0.3179g (0.0023mol) potassium carbonate, 0.0525g (0.00035mol) sodium iodide, and 10ml N,N-dimethylformamide, heated to 150°C for 24 hours Finally, after cooling to room temperature, add 3-nitrobenzophenone, then heat to 200 ° C for 1 hour, cool the reaction solution to room temperature, slowly pour it into ethanol and stir for 2 hours, filter and boil with water for 2 hours, filter, The filter cake was wrapped with filter paper, extracted in Soxhlet extraction with a mixed solution of ethanol and acetone (volume ratio 1:1) for 24 hours, and then the obtained polymer was baked in a vacuum oven at 200° C. for 20 hours. 1.1257 g of polymer powder was obtained with a yield of 93%.

The IR (KBr) of the above-mentioned polymer: 3705, 2225, 1773, 1701, 1499, 1377, 1322, 1156, 1114cm ^-1 , is a polyarylene sulfide nitrile imide copolymer, and its structural formula is as follows:

Wherein, the thioether bond is at the 3-position or 4-position of the phthalimide structural unit in the polymer, a and b respectively represent the degree of polymerization, and the ratio of a to b is 0.1-99.9:0.1-99.9.

The intrinsic viscosity of the above polymer in m-cresol at 30° C. is 1.75 dL/g, the weight average molecular weight relative to polystyrene standards measured by gel permeation chromatography is 115,000, and the polydispersity coefficient is 3.9. The glass transition temperature measured by differential scanning calorimetry (DSC) is 260°C, the tensile strength measured by Instron 5567 universal material testing machine at room temperature is 166MPa, the Young's modulus is 3.8GPa, and the elongation at break is 3.8%. The viscosity value measured by Physica MCR-301 rotational rheometer at 360° C. and 1000 S ⁻¹ is 85000 poise.

Example 11

Add 18.26g (0.10mol) 4-chlorophthalic anhydride, 91.28g (0.50mol) 3-chlorophthalic anhydride, 1000ml glacial acetic acid into a dry and clean 2L three-necked flask, stir to dissolve and add 76.31 (0.30mol) 2,2' , 3,3'-tetramethyl-4,4'-diaminodiphenylmethane, heated to 130°C for reflux reaction for 25 hours, cooled to room temperature, poured it into 3L distilled water and stirred for 3 hours, filtered the obtained The cake was washed three times with distilled water, and vacuum-dried at 120° C. to obtain 161.04 g of a crude product of dichlorophthalimide, with a yield of 92%. The crude product was recrystallized from a mixed solvent of toluene and N,N-dimethylacetamide (2:1, v/v) and used for the next polymerization reaction. The structural formula of bischlorophthalimide is as follows:

Wherein, the substitution position of the Cl atom is at the 3-position or the 4-position.

Under a nitrogen atmosphere, add 5.835g (0.01mol) of the above-mentioned dichlorophthalimide, 5.1603g (0.03mol) of 2,4-dichlorobenzonitrile, 1.3469g (0.042mol) to a dry and clean 500ml two-necked bottle Sulfur, 2.40g (0.08mol) paraformaldehyde, 3.20g (0.08mol) sodium hydroxide, 0.20g (0.00062mol) tetrabutylammonium bromide, and 270ml N-methylpyrrolidone, heated to 190°C for 20 reactions After 1 hour, cool to room temperature, add N-cyclohexyl-4-chlorophthalimide, heat to 200°C for 3 hours, cool the reaction solution to room temperature, slowly pour it into deionized water and stir for 2 hours , filtered and boiled with water for 5 hours, filtered, and then the resulting polymer was baked in a vacuum oven at 200°C for 40 hours. 8.59 g of polymer powder was obtained with a yield of 91%.

The IR (KBr) of the above-mentioned polymer: 3701, 3063, 2928, 2224, 1779, 1715, 1499, 1373, 1116cm ^-1 , is a polyarylene sulfide nitrile imide copolymer, and its structural formula is as follows:

Wherein, the thioether bond is at the 3-position or 4-position of the phthalimide structural unit in the polymer, a and b respectively represent the degree of polymerization, and the ratio of a to b is 0.1-99.9:0.1-99.9.

The inherent viscosity of the above polymer measured in a concentration of 0.5 g/dL m-cresol at 30° C. is 0.38 dL/g. The weight average molecular weight determined by gel permeation chromatography relative to polystyrene standards was 10,000 and the polydispersity index was 4.6. The glass transition temperature measured by differential scanning calorimetry (DSC) is 220°C, the tensile strength measured by Instron 5567 universal material testing machine at room temperature is 98MPa, the Young's modulus is 3.1GPa, and the elongation at break is 4.8%. The viscosity value measured by Physica MCR-301 rotational rheometer at 360° C., 1000 S ⁻¹ is 400 poise.

Example 12

Add 91.28g (0.50mol) 4-chlorophthalic anhydride, 91.28g (0.50mol) 3-chlorophthalic anhydride, 100.12g (0.50mol) 4,4'-diaminodiphenyl ether in a dry and clean 500ml three-necked flask, Slowly heated up to 260°C under vacuum to form a homogeneous melt, stirred and reacted for 4 hours, and then cooled to room temperature to obtain 259.38 g of crude bischlorophthalimide, with a yield of 98%. The crude product can be directly used in the next polymerization reaction. The structural formula of two chlorophthalimides is as follows:

Wherein, the substitution position of the Cl atom is at the 3-position or the 4-position.

Under argon atmosphere, add 1.6515g (0.00312mol) of the above-mentioned dichlorophthalimide, 0.3578g (0.00208mol) of 2,6 dichlorobenzonitrile, 0.1668g (0.0052mol) of sulfur into a 100ml dry and clean three-necked flask , 0.5518g (0.0052mol) benzaldehyde, 0.5511g (0.0052mol) sodium carbonate, 1.3318g (0.012mol) calcium chloride, 0.1053g (0.0004mol) 3-nitrodiphenylsulfone, 50mlN-methylpyrrolidone, stirring Heated to 140°C for 10 hours, cooled to room temperature and slowly poured into 500ml distilled water, stirred for 12 hours, filtered the obtained filter cake and washed three times with distilled water, then extracted with 95% (volume fraction) ethanol for 24 hours, vacuumed at 120°C After drying, 1.61 g of polymer powder was obtained, with a yield of 89%.

The IR (KBr) of the above-mentioned polymer: 3704, 2226, 1775, 1709, 1499, 1375, 1241, 1114cm ^-1 , is a polyarylene sulfide nitrile imide copolymer, and its structural formula is as follows:

Wherein, the thioether bond is at the 3-position or 4-position of the phthalimide structural unit in the polymer, a and b respectively represent the degree of polymerization, and the ratio of a to b is 0.1-99.9:0.1-99.9.

The inherent viscosity of the above polymer measured in a concentration of 0.5 g/dL m-cresol at 30° C. is 0.65 dL/g. The weight average molecular weight determined by gel permeation chromatography relative to polystyrene standards was 44,000 and the polydispersity index was 2.3. The glass transition temperature measured by differential scanning calorimetry (DSC) is 245°C, the tensile strength measured by Instron 5567 universal material testing machine at room temperature is 127MPa, the Young's modulus is 2.8GPa, and the elongation at break is 7.3%. The viscosity value measured by a Physica MCR-301 rotational rheometer at 360° C. and 1000 S ⁻¹ is 2000 poise.

Claims (9)

1. poly arylidene thio-ester nitrile imide copolymer, its general structure are suc as formula I:

In the formula I, a and b represent the polymerization degree respectively, and the ratio of a and b is 0.1～99.9: 0.1～99.9;

Thioether bond is 3-position on the phthalimide structural unit or 4-position in polymkeric substance, and the 2-position on the benzene nitrile structural unit, 3-position, 4-position, 5-position or 6-position;

The logarithmic viscosity number of described poly arylidene thio-ester nitrile imide copolymer is that 0.13dL/g is to 3.00dL/g;

Wherein A is selected?

one or at least two of them are connected to CC bond forming groups.

2. the preparation method of poly arylidene thio-ester nitrile imide copolymer according to claim 1 is characterized in that, comprises step:

Two phthalimides and sulphur and two halobenzene nitriles of replacing of structure shown in the employing formula II carry out copolyreaction in the presence of reductive agent, catalyzer and reaction promoter, preparation poly arylidene thio-ester nitrile imide copolymer;

In the formula II, X and X ' are identical or different, and X and X ' independently are selected from a kind of in fluorine atom, chlorine atom, bromine atoms or the nitro separately, and X and X ' the position of substitution are independent of separately 3-or 4-position;

A has identical implication in A and the formula I.

3. preparation method according to claim 2 is characterized in that, described two halobenzene nitriles are 0.1～99.9: 0.1～99.9 with the ratio of the amount of substance of two replacement phthalimides;

The amount of substance of described sulphur is 0.90～1.30: 1 with the ratio of two replacement phthalimides and the total amount of substance of two halobenzene nitriles;

Described copolyreaction temperature is 60 ℃～260 ℃.

4. preparation method according to claim 2 is characterized in that, the general structure of described two halobenzene nitriles is suc as formula III:

In the formula III, D and D ' are identical or different, and D and D ' independently are selected from a kind of in fluorine atom, chlorine atom or the bromine atoms separately, and D and D ' the position of substitution independent separately in the 2-position, 3-position, 4-position, 5-position or 6-position.

5. according to claim 2 or 4 described preparing methods, it is characterized in that described two halobenzene nitriles are selected from 2; 6-dichlorobenzonitrile, 2,6-difluorobenzonilyile, 2,6-dibromobenzene nitrile, 2-chloro-6 bromoxynils, 2; 4-dichlorobenzonitrile, 3,5-dichlorobenzonitrile, 2,5-difluorobenzonilyile, 2; 4-difluorobenzonilyile, 2, one or more in 4-dibromobenzene nitrile, the 2-chloro-4-bromoxynil.

6. preparation method according to claim 2 is characterized in that, described reductive agent is selected from least a in formate, oxalate, aldehyde, hydrazine, azanol, metal simple-substance, reductibility salt, hydrogenate, ammonia, the hydrogen;

Described reaction promoter or catalyzer are selected from least a in carbonate, supercarbonate, phosphoric acid salt, hydrophosphate, alkali hydroxide, halogenide, the phase-transfer catalyst.

7. preparation method according to claim 2 is characterized in that, described copolyreaction is perhaps carried out in the mixed solvent of benzene kind solvent and polar aprotic solvent or in polar aprotic solvent in benzene kind solvent;

Described polar aprotic solvent is selected from N-Methyl pyrrolidone, N, one or more in dinethylformamide, DMAC N,N, DMSO 99.8MIN., HMPA, sulfobenzide or the tetramethylene sulfone;

Described benzene kind solvent is selected from one or more in benzene,toluene,xylene or the chlorobenzene.

8. according to claim 2 or 7 described preparing methods, it is characterized in that described copolyreaction is carried out in inert gas atmosphere.

9. preparation method according to claim 2 is characterized in that described copolyreaction is carried out in the presence of at least a end capping agent;

Described end capping agent is the compound of structure shown in the formula IV:

B-R-M IV

In the formula IV, B is selected from fluorine atom, chlorine atom, bromine atoms or nitro;

R is for replacing or unsubstituted aryl group or replacement or unsubstituted alkyl, and described aromatic group is selected from phenyl, xenyl, furyl, pyridyl, naphthyl or quinolyl;

M is selected from Wasserstoffatoms, methyl, acyl group, phenyl acyl group, alkyl sulphonyl, aryl sulfonyl, nitro, cyanic acid, azo-group, carboxyl, trifluoromethyl, imide or substituted imides base.