阅读说明：本技术 具有紫外荧光示踪功能的聚芳硫醚化合物及制备方法 (Polyarylene sulfide compound with ultraviolet fluorescent tracing function and preparation method thereof ) 是由 严永刚 邓光进 焦雪菲 严大卫 任浩浩 李鹏程 于 2021-09-10 设计创作，主要内容包括：本发明涉及一种具有超强紫外-荧光示踪功能的高性能聚芳硫醚及制备方法,属于聚苯硫醚材料领域。本发明提供一种具有紫外荧光示踪功能的聚芳硫醚化合物的制备方法,所述制备方法为：将第一组分、第二组分和含硫物质在极性非质子溶剂和催化剂的作用下,于180～300℃反应得到具有紫外荧光示踪功能的聚芳硫醚类化合物；其中,所述第一组分为不含极性官能团的卤代芘或卤代苝,第二组分为二卤代芳烃化合物。本发明所得的新型聚芳硫醚保持了聚苯硫醚的完全结构并获得在450-550nm波段的超强紫外-荧光效应(最高强度可达55000),成为一类新型的具有超强紫外-荧光示踪功能的高性能聚芳硫醚。(The invention relates to high-performance polyarylene sulfide with an ultra-strong ultraviolet-fluorescent tracing function and a preparation method thereof, belonging to the field of polyphenylene sulfide materials. The invention provides a preparation method of a polyarylene sulfide compound with an ultraviolet fluorescent tracing function, which comprises the following steps: reacting the first component, the second component and a sulfur-containing substance at 180-300 ℃ under the action of a polar aprotic solvent and a catalyst to obtain a polyarylene sulfide compound with an ultraviolet fluorescent tracing function; wherein the first component is halogenated pyrene or halogenated perylene without polar functional groups, and the second component is a dihalogenated aromatic compound. The novel polyarylene sulfide obtained by the invention maintains the complete structure of polyphenylene sulfide and obtains the ultra-strong ultraviolet-fluorescence effect (the highest intensity can reach 55000) at the wave band of 450-550nm, thereby becoming a novel high-performance polyarylene sulfide with the ultra-strong ultraviolet-fluorescence tracing function.)

1. A preparation method of polyarylene sulfide compound with ultraviolet fluorescence tracing function is characterized by comprising the following steps: reacting the first component, the second component and a sulfur-containing substance at 180-300 ℃ under the action of a polar aprotic solvent and a catalyst to obtain a polyarylene sulfide compound with an ultraviolet fluorescent tracing function; wherein the first component is halogenated pyrene or halogenated perylene without polar functional groups, and the second component is a dihalogenated aromatic compound.

2. The method for preparing polyarylene sulfide compound with ultraviolet fluorescent tracing function as recited in claim 1, wherein the ratio of the first component, the second component and the polar aprotic solvent is: (first component + second component): 0.5-4 mol:1L of polar aprotic solvent;

further, the molar ratio of the first component to the second component to the sulfur-containing species is: (first component + second component): 0.9-1.1% of sulfur in the sulfur-containing substance: 1.

3. the method for preparing polyarylene sulfide compound with ultraviolet fluorescent tracing function according to claim 1 or 2, wherein the molar ratio of the first component to the second component is 0.1-20%; further, the pH value of the reaction system is controlled to be 8-12.

4. The method for preparing the polyarylene sulfide compound with the ultraviolet fluorescent tracing function according to any one of claims 1 to 3, wherein the first component is a dihalo-substituted pyrene compound, a tetrahalo-substituted pyrene compound, a dihalo-substituted perylene compound or a tetrahalo-substituted perylene compound.

5. The method for preparing a polyarylene sulfide compound with an ultraviolet fluorescent tracing function as claimed in claim 4, wherein the dihalogen-substituted or tetrahalo-substituted pyrene compound is selected from one of the following compounds:

6. the method for producing a polyarylene sulfide compound having an ultraviolet fluorescent tracing function as recited in any one of claims 1 to 5, wherein the dihalogenated aromatic compound is a p-dihalogenated or m-dihalogenated aromatic compound;

further, the dihalo-aromatic compound is selected from one of the following compounds: x is halogen.

7. The method for preparing polyarylene sulfide compound with ultraviolet fluorescent tracing function according to any one of claims 1 to 6, wherein the sulfur-containing substance is at least one selected from sodium sulfide, sodium hydrosulfide or sulfur; and/or:

the polar aprotic solvent is: one of amines, lactams, sulfones or sulfones; preferably, the polar aprotic solvent is selected from: n-methyl-2-pyrrolidone, N-cyclohexylpyrrolidone, 1, 3-dimethyl-2-imidazolone, hexamethylphosphoramide, N-dimethylacetamide, N-dimethylamide, N-ethylcaprolactam, N-vinylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone lactam, tetramethylurea, dimethylsulfoxide, or sulfolane; and/or:

the catalyst is selected from amino or amino carboxylate, hydroxycarboxylate and organic phosphate compounds; the dosage of the catalyst is 0.2 to 25 weight percent of the mass of the polar aprotic solvent;

further, the amino or amino carboxylate compound is selected from: sodium aminotriacetate, edetate or diethylenetriamine pentacarboxylate; preferably trisodium (or tetrasodium) ethylenediaminetetraacetate, as in ethylenediaminetetraacetate; the hydroxycarboxylic acid salt compound is selected from: tartaric acid, heptonate, sodium gluconate, sodium alginate; preferably sodium alginate; the organic phosphonate compound is selected from: ethylene diamine tetra methylene sodium phosphate, diethylene triamine penta methylene phosphonate, amine trimethophor phosphate; preferably sodium ethylene diamine tetra methylene phosphate.

8. A polyarylene sulfide compound with an ultraviolet fluorescent tracing function, which is prepared by the method of any one of claims 1 to 7.

9. The polyarylene sulfide compound with ultraviolet fluorescence tracing function according to claim 8, wherein the polyarylene sulfide compound has a structure represented by formula I or formula II:

wherein the value ranges of m1, m2, m3 and m4 are as follows: 80-99.9%; n is more than or equal to 1 and less than or equal to 200.

10. The polyarylene sulfide compound with an ultraviolet fluorescent tracing function according to claim 9, wherein the weight average molecular weight of the polyarylene sulfide compound with an ultraviolet fluorescent tracing function is 30000-200000, the melt index is 10-500 g/10min, and the melting point is 230-370 ℃;

further, the polyarylene sulfide compound with the ultraviolet fluorescent tracing function is one of the following compounds:

Technical Field

The invention relates to high-performance polyarylene sulfide with an ultra-strong ultraviolet-fluorescent tracing function and a preparation method thereof, belonging to the field of polyphenylene sulfide materials.

Background

The special engineering plastic PPS is the first special engineering plastic at present, and the annual demand in China reaches 10 ten thousand tons per year. Due to the characteristics of excellent corrosion resistance, high temperature resistance, good rigidity, high strength, small specific gravity and the like, the composite material can be used for replacing metal materials, and can be prepared into structural components required by military equipment after modification by various modification means such as blending, filling, reinforcing, forming polymer alloy and the like, wherein the modification means comprises the following steps: the electric tank is characterized by comprising an engine radiator, a vehicle body door, an electric pump and the like, wherein a sea-crossing amphibious tank turret base, a corrosion-resistant rotating gear, a sealing ring, a piston ring, a sealing gasket, an electric injection engine rotor impeller and the like can effectively reduce the weight of the chariot, and improve the maneuverability, reliability, damage safety and riding comfort; the products such as the self-lubricating bearing, the sliding gasket and the like made of the PPS composite material are very suitable for weapons and armored combat vehicles to be used under various severe natural conditions, and the reliability and the wartime attendance rate of the equipment are improved. However, the modification mainly aims at improving the toughness and the strength of the PPS and has some performances of other materials, the PPS is not functionalized from a main chain structure and endowed with new special functions, and the inherent potential that special engineering plastic molecules can be endowed with new functions is not fully exerted.

The applicant of the present invention has long devoted to the study of the functionalization of polyarylene sulfide and developed modified polyphenylene sulfide with various functions, such as: bonded polyarylene sulfide metal composite material with nuclear radiation protection function and preparation thereof (CN 110564154B), boron-containing two-dimensional polyarylene sulfide material with neutron absorption function and preparation method thereof (CN 110724263B), high boronization activity polyarylene sulfide composite material with nuclear radiation protection function and preparation thereof (110698858B), linear polyarylene sulfide (201510325423.5) with active reaction side group-ionic reaction side group, color-changeable polyarylene sulfide compound and preparation method thereof (CN 102702529B), functional boron-containing polyarylene sulfide copolymer and preparation method thereof (202010950439.6), perylene anhydride type polyarylene sulfide with tree structure and preparation method and application thereof (202010918954.6) and the like, in particular to the color-changeable polyarylene sulfide compound and preparation method thereof (CN 102702529B) which endow PPS with multicolor effect, and the obtained product has rich color in the visible light range, the color of the PPS near-white resin cannot be reserved and cannot be processed into a target color, the introduced monomers all contain polar functional groups, so that the polarity and dipole moment of a molecular chain are changed, and the ultraviolet-fluorescence effect is very weak (the fluorescence intensity of the obtained color-changeable polyarylene sulfide compound is less than 3000).

However, in many cases, the material is used under extreme physical conditions such as high speed, high stress, high humidity, high heat, radiation and the like, the fatigue, injury and the like of the material need to be tracked, tested or checked in the using process, and various complex detection devices such as X-ray detection, a sound wave instrument and the like need to be used, but the polymer has high X transmittance, the change of the material is difficult to find, and the sound wave instrument is difficult to detect signals and find specific points with problems, so that the tracking and the detection of the high-performance polymerization are particularly important.

No related report of polyarylene sulfide with super-strong ultraviolet-fluorescence effect exists in the prior art.

Disclosure of Invention

Aiming at the defects, the invention provides the high-performance polyarylene sulfide with the ultra-strong ultraviolet-fluorescence tracing function, the obtained modified polyarylene sulfide has the ultra-strong ultraviolet-fluorescence effect (the fluorescence intensity is more than 10000, the highest intensity can reach 55000) in the wave band of 550nm of 450-.

The technical scheme of the invention is as follows:

the first technical problem to be solved by the invention is to provideA preparation method of polyarylene sulfide compound with ultraviolet fluorescence tracing function comprises the following steps: reacting the first component, the second component and a sulfur-containing substance at 180-300 ℃ under the action of a polar aprotic solvent and a catalyst to obtain a polyarylene sulfide compound with an ultraviolet fluorescent tracing function; wherein the first component is halogenated pyrene or halogenated perylene without polar functional group, and the second component is dihalogenated aromatic compound (ArX)₂)。

Further, the ratio of the first component, the second component and the polar aprotic solvent is: (first component + second component): 0.5-4 mol of polar aprotic solvent: 1L; preferably 1 to 3 mol:1L of the compound.

Further, the molar ratio of the first component to the second component to the sulfur-containing species is: (first component + second component): 0.9-1.1% of sulfur in the sulfur-containing substance: 1; preferably 0.95-1.05: 1.

further, the molar ratio of the first component to the second component is 0.1-20%.

Further, the pH value of the reaction system is controlled to be 8-12.

Further, the first component is a dihalo-substituted pyrene compound, a tetrahalo-substituted pyrene compound, a dihalo-substituted perylene compound or a tetrahalo-substituted perylene compound.

Further, the dihalo-substituted or tetrahalo-substituted pyrene compound is selected from one of the following compounds:

(Ar₁-1)1, 6-dibromopyrene:(Ar₁-2)1, 8-dichloropyrene:(Ar₁-3)1,3,6, 8-tetrabromopyrene:(Ar₁-4)3, 9-dibromoperylene,(Ar₁-5)3, 10-dibromoperyleneEtc.; polycyclic is a compound with a di-or tetra-substituted pyrene or perylene.

Further, the dihalo-aromatic compound (ArX)₂) Is a para-dihalogenated or meta-dihalogenated aromatic compound, and is selected from one of the following compounds: (Ar)₂-1)1, 4-dihalobenzenes(Ar₂-2)2, 4-dihalobenzenes(Ar₂-3)4, 4' -dihalobiphenyl(Ar₂-4)4, 4' -dihalodiphenylsulfone(Ar₂-5)4, 4' -dihalobenzophenones(Ar₂-6)4, 4' -dihalodiphenyl etherAnd X is halogen.

Further, the sulfur-containing substance is at least one selected from sodium sulfide, sodium hydrosulfide or sulfur.

Further, the polar aprotic solvent is: one of amines, lactams, sulfones or sulfones; preferably the polar aprotic solvent is selected from: n-methyl-2-pyrrolidone (NMP), N-cyclohexylpyrrolidone (NCHP), 1, 3-dimethyl-2-imidazolone (DMI), Hexamethylphosphoramide (HMPA), N-dimethylacetamide, N-dimethylamide, N-ethylcaprolactam, N-vinylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone (MI) lactam, tetramethylurea, dimethyl sulfoxide, sulfolane, or the like.

Further, the catalyst is selected from compounds such as amino or amino carboxylate, hydroxycarboxylate and organic phosphate; the amount of catalyst used is generally between 0.2% and 25% by weight, preferably between 0.5% and 10% by weight, based on the mass of polar aprotic solvent.

Further, among the above-mentioned amine-or aminocarboxylate-based compounds, preferred are sodium aminotriacetate (NTA), ethylenediaminetetraacetate (EDTA salt), Diethylenetriaminepentacarboxylate (DTPA), and the like; more preferably trisodium (or tetrasodium) ethylenediaminetetraacetate, among ethylenediaminetetraacetate salts; among the hydroxycarboxylic acid salt compounds, tartaric acid, heptonate, sodium gluconate, sodium alginate, etc. are preferable; more preferably sodium alginate; among the organic phosphonate compounds, preferred are ethylene diamine tetra methylene sodium phosphate (EDTMPS), diethylenetriamine penta methylene phosphonate (DETPMS), amine trimetaphosphate, and the like; more preferably sodium Ethylene Diamine Tetra Methylene Phosphate (EDTMPS).

The second technical problem to be solved by the invention is to provide a polyarylene sulfide compound with an ultraviolet fluorescent tracing function, which is prepared by adopting the method.

Further, the structure of the polyarylene sulfide compound is shown as a formula I or a formula II:

in the formula, m1, m2, m3 and m4 refer to molar percentage content, and the value ranges are as follows: 80-99.9%; n is more than or equal to 1 and less than or equal to 200.

Further, the weight average molecular weight of the polyarylene sulfide compound with the ultraviolet fluorescent tracing function is 30000-200000, the melt index is 10-500 g/10min, the melting point is 230-370 ℃, and the preferable range is 250-300 ℃.

Further, the polyarylene sulfide compound is one of the following compounds:

the invention has the beneficial effects that:

(1) the fluorescent-ultraviolet polycyclic system selected by the invention does not contain functional groups causing polarity change at all, and the benzene ring has no other functional groups which can react or cause polarity change except halogen atoms used for reacting with sulfur, and belongs to an inert structure.

(2) The selected halogenated pyrene or halogenated perylene can enter a molecular chain in a linear structure or form a radial two-dimensional structure, has the same chemical linkage with pure PPS, does not change the chemical bond structure, and therefore, the thermal property and other properties of the polyphenylene sulfide can be completely maintained.

(3) The novel polyarylene sulfide obtained by the invention is high-performance polyarylene sulfide with a super-strong ultraviolet-fluorescence tracing function, has the weight average molecular weight of 30000-200000 and the melt index of 1-500 g/10min, has the super-strong ultraviolet-fluorescence tracing function, maintains the complete structure of polyphenylene sulfide, obtains the super-strong ultraviolet-fluorescence effect (the highest intensity can reach 55000) in a wave band of 450-550nm, and becomes a novel high-performance polyarylene sulfide with the super-strong ultraviolet-fluorescence tracing function.

Description of the drawings:

FIG. 1a is a graph showing the super-strong ultraviolet-fluorescence effect of the products obtained in examples 1 to 5 and comparative example 1 at a wavelength of 450 to 550nm, and FIG. 1b is a graph showing the super-strong ultraviolet-fluorescence effect of the products obtained in examples 6 to 10 at a wavelength of 450 to 550 nm.

FIG. 2a is a fluorescence emission spectrum of examples 1 to 5; FIG. 2b is the fluorescence emission spectrum of comparative example 3.

Detailed Description

The invention provides a high-performance polyarylene sulfide with a superstrong ultraviolet-fluorescence tracing function and a preparation method thereof, wherein the high-performance polyarylene sulfide with the superstrong ultraviolet-fluorescence tracing function has a structure shown as a formula I or a formula II, a polycyclic unit without any polarity is introduced while the structure of the polyarylene sulfide is maintained, and the molecular polarity and the structure are not changed except for increasing the ultraviolet-fluorescence function of the polyarylene sulfide; wherein the content of the polycyclic structure is 0.1 to 20 percent (mol percentage); the obtained high-performance polyarylene sulfide has the weight average molecular weight of 30000-200000, the melt index of 1-500 g/10min, and the ultra-strong ultraviolet-fluorescence tracing function, maintains the complete structure of polyphenylene sulfide, obtains the ultra-strong ultraviolet-fluorescence effect (the highest intensity can reach 55000) in the wave band of 450-550nm, has the ultra-strong ultraviolet-fluorescence tracing function, has the thermal stability consistent with PPS and the mechanical property higher than PPS, is the high-performance polyarylene sulfide with the ultra-strong ultraviolet-fluorescence tracing function, and has wide application prospect.

The reaction process of the polyarylene sulfide compound with the ultraviolet-fluorescent tracing function is as follows:

more specific reaction process is as follows:

z is sulfoneKetonesEthers (-O-), amines (-NH-), biphenyls (-NH-), and the like.

The above-mentioned contents of the present invention will be further described in detail by the following specific embodiments of examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. Various substitutions and alterations according to the general knowledge and conventional practice in the art are intended to be included within the scope of the present invention without departing from the technical spirit of the present invention as described above.

Example 1

Into a 1000ml reactor were charged 500ml of N-methyl-2-pyrrolidone (NMP),130g of sodium sulfide (60%, 1mol of Na)₂S), heating to 195 deg.C, fractionating to obtain total 80ml of water and NMPA first stage; then 146.6g (0.9975mol) of dichlorobenzene and 0.9g of 1, 6-dibromopyrene (0.0025mol) are added to react for 3 hours at 220 ℃, and the second stage reaction is finished; then the temperature is increased to 260 ℃, the reaction is carried out for 3 hours, and the third stage is finished; finally, the mixture is cooled to 120 ℃, deionized water is slowly added, and the mixture is filtered, washed and dried for 18 hours at 110 ℃ to obtain a milky white product of 105.5 g.

The test shows that the yield of the obtained product is as follows: 96.1%, melting point Tm: 283 ℃, thermal decomposition temperature Td: 485 ℃, tensile strength: 71.5MP, modulus of elasticity: 2.85GPa, melt index: 180g/10min, intrinsic viscosity eta_sp: 0.316, molecular weight: 6,7000, respectively; the ultra-strong UV-fluorescence effect at the wavelength of 450-550nm is shown in FIG. 1.

Example 2

Into a 1000ml reactor were charged 500ml of N-methyl-2-pyrrolidone (NMP),130g of sodium sulfide (60%, 1mol of Na)₂S), heating to 195 ℃, and fractionating to obtain 80ml of water and NMP to finish the first stage; then 146.2g (0.995mol) of dichlorobenzene and 1.29g of 1,3,6, 8-tetrabromopyrene (0.0025mol) are added for reaction at 225 ℃ for 3 hours, and the second stage reaction is finished; then the temperature is increased to 255 ℃, the reaction is carried out for 3 hours, and the third stage is finished; finally, the mixture is cooled to 110 ℃, deionized water is slowly added, and the mixture is filtered, washed and dried for 18 hours at 100 ℃ to obtain 105.6g of milky white product.

The test shows that the yield of the obtained product is as follows: 96.2%, melting point Tm: 281 ℃, thermal decomposition temperature Td: 490 ℃, tensile strength: 70.2MPa, modulus of elasticity: 3.15GPa, melt index: 120g/10min, intrinsic viscosity eta_sp: 0.332, molecular weight: 7,0000, respectively; has super-strong ultraviolet-fluorescence effect in the 450-550nm wave band, as shown in figure 1.

Examples 3 to 10

The specific preparation method is the same as that of example 1, the tensile strength of the obtained product is greater than 60.0MPa, and the raw material ratio, the melting point, the melt index and the ultraviolet fluorescence effect result of each example are shown in Table 1.

Table 1 Material proportioning, thermal Properties and Strong UV fluorescence Effect results for the examples

Comparative example 1

150ml of NMP, 0.6g of NaOH (0.015mol) and 39g of sodium sulfide (0.3mol) were placed in a 500ml reactor, heated to 180 ℃ and fractionated to give 15.6ml (0.87mol) of water, completing the first stage; adding 44.1g (0.3mol) of p-dichlorobenzene, and reacting at 220 ℃ for 3 hours to finish the second-stage reaction; heating to 260 ℃, and reacting for 3 hours to complete the third-stage reaction; cooling to 150 ℃, slowly adding deionized water, filtering, washing, and drying at 110 ℃ for 18 hours to obtain 30.1g of white product, yield: 92.9 percent, namely obtaining the traditional polyphenylene sulfide product; melting point Tm: 286 ℃, thermal decomposition temperature Td: 481 ℃, tensile strength: 67.9MP, modulus of elasticity: 3.11GPa, melt index: 120g/10min, intrinsic viscosity eta_sp: 0.359, molecular weight: 67,000. The product has no color function conversion. Example 1 has significant uv absorption compared to comparative example 1.

Comparative example 2

Adding 2500ml of NMP, 21g of NaOH, 650g of sodium sulfide and 50g of trisodium EDTA into a 5L reactor, heating to 200 ℃ under the protection of nitrogen, fractionating to obtain 790ml of water, adding 661.5 g of p-dichlorobenzene and 73.5g of m-dichlorobenzene, and reacting for 3 hours at 220 ℃ to complete the first-stage reaction; heating to 260 ℃ for reaction for 3 hours, cooling to 150 ℃, slowly adding deionized water, filtering, washing, and drying at 110 ℃ for 24 hours to obtain 510g of white product, wherein the yield is as follows: 94%, melting point Tm 280 ℃, intrinsic viscosity: 0.38, melt index: 135g/10min (molecular weight about 65,000). The product obtained, which is pure PPS, has no color function conversion nor UV fluorescence effect.

Comparative example 3

150ml of N-methyl-2-pyrrolidone (NMP), 0.6g of NaOH (0.015mol) and 39g of sodium sulfide (0.3mol) were charged into a 500ml reactor, heated to 180 ℃ and fractionated to give 15.6ml (0.87mol) of water, thereby completing the first stage; 43.69g (0.297mol) of p-dichlorobenzene and reduced golden yellow RK [ i.e. (Ar) ]were added₁-4)Br₂]1.47g (0.003mol), and the reaction is finished in the second stage at 220 ℃ for 3 hours; then heating to 260 ℃, adding 1.3g (0.03mol) of lithium chloride to react for 3 hours, and finishing the third stage; is cooled toDeionized water was slowly added at 150 ℃, filtered, washed, and dried at 110 ℃ for 18 hours to give 31.2g of a yellow product, yield: 94.1%, melting point Tm: 286 ℃, thermal decomposition temperature Td: 480 ℃, tensile strength: 71.5MP, modulus of elasticity: 2.85GPa, melt index: 308g/10min, intrinsic viscosity eta_sp: 0.274, molecular weight: 46,700, green and light green in 98% and 80% concentrated sulfuric acid, respectively. Function conversion: yellow-green-pale green; the obtained product has no strong ultraviolet-fluorescence effect.

Comparative example 4

150ml of N-methyl-2-pyrrolidone (NMP), 0.6g of NaOH (0.015mol) and 39g of sodium sulfide (0.3mol) were charged into a 500ml reactor, heated to 180 ℃ and fractionated to give 15.6ml (0.87mol) of water, thereby completing the first stage; 85.24g (0.297mol) of 4, 4' -dichlorodiphenyl sulfone and reduced golden RK [ i.e. (Ar) ]were added₁-4)Br₂]1.47g (0.003mol), and the reaction is finished in the second stage at 220 ℃ for 3 hours; heating to 240 ℃, adding 1.3g (0.03mol) of lithium chloride to react for 3 hours, and finishing the third stage; after cooling to 150 ℃, deionized water was slowly added, filtered, washed, and dried at 110 ℃ for 18 hours to obtain 71.1g of a yellow product, yield: 95%, melting temperature Tm: 280 ℃, thermal decomposition temperature Td: 490 ℃, tensile strength: 65.5MP, elastic modulus: 3.2GPa, melt index: 420g/10min, and respectively showing green and light green in 98% and 80% concentrated sulfuric acid. The product belongs to the modified polyphenylene sulfide sulfone class, is an amorphous product, but has high glass transition temperature, is not the same series as examples 1-10, and still has the natural color function and the color change function in solution. Function conversion: yellow-green-pale green; the obtained product has no strong ultraviolet-fluorescence effect.

Comparative example 5

150ml of N-methyl-2-pyrrolidone (NMP), 0.6g of NaOH (0.015mol) and 39g of sodium sulfide (0.3mol) were charged into a 500ml reactor, heated to 180 ℃ and fractionated to give 15.6ml (0.87mol) of water, thereby completing the first stage; 74.55.24g (0.297mol) of 4, 4' -dichlorobenzophenone and reduced golden RK [ i.e. (Ar) ]were added₁-4)Br₂]1.47g (0.003mol), and the reaction is finished in the second stage at 220 ℃ for 3 hours; the temperature is raised to 260 ℃ and 1.3g (0.03 mo) of lithium chloride is addedl) reacting for 3 hours, and finishing the third stage; cooling to 150 ℃, slowly adding deionized water, filtering, washing, drying at 110 ℃ for 18 hours to obtain a dark yellow brown product 60.2g, yield: 94%, melting temperature Tm: 320 ℃, thermal decomposition temperature Td: 520 ℃, tensile strength: 62.5MP, modulus of elasticity: 3.05GPa, melt index: 570g/10min, respectively showing green and light green in 98% and 80% concentrated sulfuric acid; the obtained product has no strong ultraviolet-fluorescence effect.