CN114031774B - High-strength super-toughness poly-astragalus-arylene sulfide and preparation method thereof - Google Patents

High-strength super-toughness poly-astragalus-arylene sulfide and preparation method thereof Download PDF

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CN114031774B
CN114031774B CN202111569434.XA CN202111569434A CN114031774B CN 114031774 B CN114031774 B CN 114031774B CN 202111569434 A CN202111569434 A CN 202111569434A CN 114031774 B CN114031774 B CN 114031774B
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stilbene
polyarylene sulfide
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sulfide
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CN114031774A (en
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焦雪菲
邓光进
严永刚
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Zhongding Kairui Technology Chengdu Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/0227—Polyarylenethioethers derived from monomers containing two or more aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/0236—Polyarylenethioethers containing atoms other than carbon or sulfur in a linkage between arylene groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/0236—Polyarylenethioethers containing atoms other than carbon or sulfur in a linkage between arylene groups
    • C08G75/024—Polyarylenethioethers containing atoms other than carbon or sulfur in a linkage between arylene groups containing carbonyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/025—Preparatory processes
    • C08G75/0259—Preparatory processes metal hydrogensulfides

Abstract

The invention relates to high-strength super-toughness poly-astragalus-arylene sulfide and a preparation method thereof, belonging to the field of polymer synthesis. The invention provides a poly-stilbene arylene sulfide, the structural formula of which is shown as a formula I, wherein m is more than or equal to 1 1 ≤99；1≤m 2 ≤99；n＝m 1 +m 2 . According to the invention, the molecular chain structure is changed by designing the molecular chain structure and introducing a unit similar to an ethylene structure, so that the impact strength and the elongation at break of the polyarylene sulfide are greatly increased; obtaining the high-strength super-tough poly-astragalus-arylene sulfide with a new structure.

Description

High-strength super-toughness poly-astragalus-arylene sulfide and preparation method thereof
Technical Field
The invention relates to high-strength super-toughness poly-astragalus-arylene sulfide and a preparation method thereof, belonging to the field of polymer synthesis.
Background
Special engineering plasticThe plastic has become the first large special engineering plastic, and the global production capacity is over 7 ten thousand tons/year. Because of the excellent characteristics of 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 after being modified by various blending filling enhancement, polymer alloy formation and other modification means, the formed composite material is made into structural components required by military equipment, such as an engine radiator, a car body door, an electric pump and the like, a cross-sea land tank turret base, a corrosion-resistant rotary gear, a sealing ring, a piston ring, a sealing gasket, an electric injection engine rotor impeller and the like, so that the weight of a war vehicle can be effectively reduced, and the maneuverability, reliability, damage safety and riding comfort of the war vehicle can be improved; the self-lubricating bearing, sliding gasket and other products made of PPS composite material are very suitable for weapons and armored warcars under various severe natural conditions, and the reliability of equipment and the time of war attendance are improved.
However, because of its rigid structure, it is brittle and has poor toughness, and generally it has an elongation at break of not more than 5% and an impact strength of not more than 30J/m. The defect limits the application of the reinforced polymer in stress elongation, elastic shock absorption and toughness impact resistance environments, so that a great deal of researches on the toughening of polyarylene sulfides such as polyphenylene sulfide and the like are presented, however, the toughness is improved mainly by adding various toughening agents, forming alloys with other polymers and the like, and the effect is not obvious because the molecular chain structure is not changed.
Disclosure of Invention
Aiming at the defects, the invention changes the molecular chain structure of the polyarylene sulfide by designing the molecular chain structure and introducing a unit similar to the ethylene structure, thereby greatly increasing the impact strength and the elongation at break of the polyarylene sulfide; obtaining the high-strength super-tough poly-astragalus-arylene sulfide with a new structure.
The technical scheme of the invention is as follows:
the first technical problem to be solved by the invention is to provide the high-strength super-tough poly-stilbene arylene sulfide, wherein the structural formula of the poly-stilbene arylene sulfide is shown as follows:
in the formula I, the compound (I),
-Ar-＝-S-、
1≤m 1 ≤99；1≤m 2 ≤99；n＝m 1 +m 2 。
further, the melt index of the poly-stilbene arylene sulfide is 5-500 g/10min at 316 ℃ and 5kg pressure.
Further, the weight average molecular weight of the poly-stilbene arylene sulfide is 20000 to 150000; preferably 59000 to 100000.
The second technical problem to be solved by the invention is to provide a preparation method of the poly-stilbene arylene sulfide, which comprises the following steps: taking a sulfur-containing monomer, a dihalogenated monomer and a third monomer as main raw materials, and adopting the existing method for preparing the polyarylene sulfide to prepare the polyarylene sulfide; wherein the third monomer is stilbene compound and hydrogenation product thereof, and the mole ratio of the third monomer to the dihalogenated monomer is as follows: third monomer: dihalo monomer = 0.01-0.99: 0.99 to 0.01; preferably 0.025 to 0.75:0.925 to 0.25.
Further, the third monomer is a substance with the following structure:
wherein X is: F. cl, br or I.
Further, the preparation method of the poly-stilbene arylene sulfide comprises the following steps: firstly, carrying out dehydration reaction on sulfur-containing monomers under the action of alkali and polar aprotic solvent; then adding a third monomer and a dihalogenated monomer to react for 1 to 6 hours at the temperature of between 180 and 280 ℃; then heating to 200-300 ℃ to continue the reaction for 1-6 hours; finally cooling to room temperature, washing, filtering and drying to obtain white product poly-astragalus arylene sulfide; wherein the molar ratio of the sulfur-containing monomer, the dihalogenated monomer and the third monomer is as follows: sulfur-containing monomer: (third monomer+dihalo monomer) =1: 1.05 to 1.15.
Further, the sulfur-containing monomer is selected from: sodium hydrosulfide, sodium sulfide or hydrogen sulfide.
Further, the dihalogenated monomer is shown as a dihaloaromatic compound.
Still further, the dihalogen monomer is selected from the group consisting of: 1, 4-dihalobenzenes2, 4-dihalobenzenes4,4' -dihalobiphenyl->4,4' -dihalodiphenylsulfones4,4' -dihalodiphenylketone +.>Or 4,4' -dihalodiphenyl ether +.>At least one of (a) and (b); wherein x=f, cl, br.
Further, the stilbene compound and its hydrogenation product are selected from: 4, 4-dichloro-trans-stilbene, 4-dibromo-trans-stilbene, 4-diiodo-trans-stilbene or 1, 2-bis (4-halophenyl) ethane.
Further, the polar aprotic solvent is selected from: any of N-methyl-2-pyrrolidone (NMP), N-cyclohexylpyrrolidone (NCHP), 1, 3-dimethyl-2-imidazolidinone (DMI), hexamethylphosphoramide (HMPA), N-dimethylacetamide, N-dimethylamide, N-ethylcaprolactam, N-vinylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone (MI) lactam, tetramethylurea, dimethylsulfoxide or sulfolane.
Further, the base is any one of lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, lithium carbonate, sodium carbonate, potassium acetate, lithium bicarbonate, sodium bicarbonate, and potassium bicarbonate.
Further, the drying means drying at 80-150 ℃ for 6-24 hours.
Further, the preparation method further comprises the following steps: and (3) putting the obtained poly-astragalus arylene sulfide into a polar aprotic solvent, stirring, adding an initiator, and reacting with 60-180 ℃ for 2-6 hours under the protection of inert gas to obtain the poly-astragalus arylene sulfide two-dimensional toughness material.
Further, the polar aprotic solvent is selected from: any of N-methyl-2-pyrrolidone (NMP), N-cyclohexylpyrrolidone (NCHP), 1, 3-dimethyl-2-imidazolidinone (DMI), hexamethylphosphoramide (HMPA), N-dimethylacetamide, N-dimethylamide, N-ethylcaprolactam, N-vinylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone (MI) lactam, tetramethylurea, dimethylsulfoxide or sulfolane.
Further, the initiator is benzoyl peroxide, potassium persulfate or dicumyl peroxide.
The third technical problem to be solved by the invention is to provide a method for improving toughness of polyarylene sulfide, which comprises the following steps: introducing stilbene compounds and hydrogenated products thereof in the preparation process of the polyarylene sulfide; wherein, the stilbene compounds and the hydrogenated products thereof are substances with the following structures:
further, the method for improving toughness of the polyarylene sulfide comprises the following steps: taking a sulfur-containing monomer, a dihalogenated monomer and a third monomer as main raw materials, and adopting the existing method for preparing polyarylene sulfide; wherein the third monomer is stilbene compound and hydrogenation product thereof, and the mole ratio of the third monomer to the dihalogenated monomer is as follows: third monomer: dihalo monomer = 0.01-0.99: 0.99 to 0.01; preferably 0.025 to 0.75:0.925 to 0.25.
Further, the method for improving toughness of the polyarylene sulfide comprises the following steps: firstly, carrying out dehydration reaction on sulfur-containing monomers under the action of alkali and polar aprotic solvent; then adding a third monomer and a dihalogenated monomer to react for 1 to 6 hours at the temperature of between 180 and 280 ℃; then heating to 200-300 ℃ to continue the reaction for 1-6 hours; finally cooling to room temperature, washing, filtering and drying to obtain white product poly-astragalus arylene sulfide; wherein the molar ratio of the sulfur-containing monomer, the dihalogenated monomer and the third monomer is as follows: sulfur-containing monomer: (third monomer+dihalo monomer) =1: 1.05 to 1.15.
The invention has the beneficial effects that:
the weight average molecular weight of the poly-astragalus-arylene sulfide polymer obtained by the invention is 20000-150000, and the melt index is 5-500/10 min; the highest tensile strength can reach 65MPa, the highest elongation at break can reach approximately 300 percent, and the highest impact strength can reach 110J/m, namely the high-strength high-toughness polyarylene sulfide has ultrahigh flexibility which is 50 to 100 times that of the traditional polyarylene sulfide; and the poly (arylene sulfide) has the characteristics of high temperature resistance, corrosion resistance and the like, so that the poly (arylene sulfide) polymer obtained by the invention has wide application.
Detailed Description
The stilbene compound with a specific structure is introduced into the polyarylene sulfide, the stilbene compound can freely rotate according to the phenyl groups of the stilbene and the diphenylethyl and the linked vinyl or ethyl, and simultaneously the vinyl can freely stretch after being converted into the ethyl. Therefore, the obtained molecular chain is rigid and flexible, and the stability of the whole molecular chain is maintained. The polymer of the poly-astragalus arylene sulfide has the high strength and heat resistance of the poly-arylene sulfide, simultaneously endows the poly-arylene sulfide with high elasticity and high toughness, thoroughly changes the original appearance of large brittleness and poor toughness with a new structure, and has excellent performance in extremely cold environment and high impact environment besides meeting the application range of the original poly-phenylene sulfide.
The high-strength super-tough poly-astragalus-arylene sulfide is composed of astragalus-derived sulfide units and aromatic sulfide units; stilbene sulphide units (e.g) With aromatic thioether units (e.gWherein Y= -S-, ->or-O-) by copolymerization to form a high-component linear or two-dimensional planar polymer, as shown in the following structure:
further, the polymerization reaction occurring in the present invention can be represented by the following reaction formula:
1. the third monomer isThe reaction is as follows:
2. the third monomer isThe reaction is as follows:
3. the dihaloaromatic compound is dihalobenzene, and the polymerization is simplified as follows (m1+m2=n):
4. the two-dimensional material has the following reaction formula:
the above-described aspects of the present invention will be described in further detail below by way of specific embodiments of the present invention. It should not be understood that the scope of the above subject matter of the present invention is limited to the following examples only. Various substitutions and alterations are also possible, without departing from the spirit of the invention, and are intended to be within the scope of the invention.
Example 1
2500ml NMP,210gNaOH,400g sodium hydrosulfide (content: 70%) was added to a 10L reactor, heated to 200℃under nitrogen protection, and 790ml of water was distilled out to complete the first stage; then 62.28g of 4,4' -dichloro-trans-stilbene and 698.25g of p-dichlorobenzene are added for reaction for 3 hours at 220 ℃, and the second-stage reaction is completed; the temperature was raised to 260℃for 3 hours to complete the third stage polymerization. Cooling to room temperature, slowly adding deionized water, filtering, washing, and drying at 110 ℃ for 12 hours to obtain 562g of white product namely poly (stilbene phenyl sulfide), and the yield is: 94%, melting point tm=278 ℃, intrinsic viscosity: melt index 0.326: 95g/10min (molecular weight about 61,000).
Extruding the synthesized poly-stilbene phenyl sulfide into granules at 290-310 ℃ by a Hark rheometer or a twin-screw extruder, then preparing a mechanical spline by injection molding, wherein the injection molding temperature is 295-315 ℃, and then testing the tensile strength, the elongation at break and the impact strength, wherein the tensile strength is 55MPa, the elongation at break is 80%, and the impact strength is 60J/m.
200g of synthesized poly-stilbene phenyl sulfide is taken and put into anhydrous NMP to be stirred, 1g of formyl peroxide serving as an initiator is interposed, the mixture reacts with 150-160 ℃ for 4 hours under the protection of nitrogen, the mixture is cooled to room temperature, deionized water is slowly added, the mixture is filtered and washed, and the mixture is dried for 12 hours at 110 ℃ to obtain a white two-dimensional ductile material, wherein the melt index of the white two-dimensional ductile material is: 25g/10min, the melt index is reduced by 2 times compared with that of the poly-stilbene phenyl sulfide; extruding into granules at 290-310 ℃ by a Hark rheometer or a twin-screw extruder, and then preparing the mechanical sample bar by injection molding, wherein the tensile strength is 55Mpa, the elongation at break is 60%, and the impact strength is 70J/m. I.e. its performance is further improved.
Example 2
2500ml NMP,210gNaOH,400g sodium hydrosulfide (content: 70%) was added to a 10L reactor, heated to 200℃under nitrogen protection, and 790ml of water was distilled out to complete the first stage; then 249.15g of 4,4' -dichloro-trans-stilbene and 588.2g of p-dichlorobenzene are added for reaction for 3 hours at 220 ℃, and the second stage reaction is completed; the temperature was raised to 260℃for 3 hours to complete the third stage polymerization. Cooling to room temperature, slowly adding deionized water, filtering, washing, and drying at 110 ℃ for 12 hours to obtain 640g of white product poly (stilbene phenyl sulfide), the yield: 95%, melting point tm=259 ℃, intrinsic viscosity: 0.393, melt index: 60g/10min (molecular weight about 85,000).
The synthesized poly-stilbene phenyl sulfide is extruded into granules at 280-300 ℃ through a Hark rheometer or a twin-screw extruder, then mechanical splines are prepared through injection molding, the injection molding temperature is 280-300 ℃, and then the tensile strength, the elongation at break and the impact strength are tested, wherein the tensile strength is 52MPa, the elongation at break is 200%, and the impact strength is 80J/m.
200g of synthesized poly-stilbene phenyl sulfide is taken and put into anhydrous NMP to be stirred, 1g of formyl peroxide serving as an initiator is interposed, the mixture reacts with 150-160 ℃ for 4 hours under the protection of nitrogen, the mixture is cooled to room temperature, deionized water is slowly added, the mixture is filtered and washed, and the mixture is dried for 12 hours at 110 ℃ to obtain a white two-dimensional ductile material, wherein the melt index of the white two-dimensional ductile material is: 10g/10min, the melt index is reduced by 3 times; extruding into granules at 280-300 ℃ by a Hark rheometer or a twin-screw extruder, and then preparing the mechanical sample bar by injection molding, wherein the tensile strength is 55MPa, the elongation at break is 102%, and the impact strength is 80J/m.
Example 3
2500ml NMP,210gNaOH,400g sodium hydrosulfide (content: 70%) was added to a 10L reactor, heated to 200℃under nitrogen protection, and 790ml of water was distilled out to complete the first stage; then 85.01g of 1, 2-bis (4-bromophenyl) ethane are added698.25g of p-dichlorobenzene is reacted for 3 hours at 220 ℃, and the second-stage reaction is finished; heating to 260 deg.CThe third stage polymerization was completed at 3 hours. Cooling to room temperature, slowly adding deionized water, filtering, washing, and drying at 110 ℃ for 12 hours to obtain 562g of white product namely poly (stilbene phenyl sulfide), and the yield is: 94%, melting point tm=275 ℃, intrinsic viscosity: melt index 0.386: 110g/10min (molecular weight about 59,000).
The synthesized poly-stilbene phenyl sulfide is extruded into granules at 290-310 ℃ through a Hark rheometer or a twin-screw extruder, then mechanical splines are manufactured through injection molding, the injection molding temperature is 295-315 ℃, and then the tensile strength, the elongation at break and the impact strength are tested, wherein the tensile strength is 60MPa, the elongation at break is 120%, and the impact strength is 70J/m.
Example 4
Simultaneous example 3,1, 2-bis (4-bromophenyl) ethane340.1g of paradichlorobenzene 588.2g;1, 2-bis (4-bromophenyl) ethane is greatly increased; 638g of white product poly (stilbene phenyl sulfide) is obtained, and the yield is: 93%, melting point tm=255 ℃, intrinsic viscosity: melt index 0.396: 90g/10min (molecular weight about 60,000).
The synthesized poly-stilbene phenyl sulfide is extruded into granules at 290-310 ℃ through a Hark rheometer or a twin-screw extruder, then mechanical splines are manufactured through injection molding, the injection molding temperature is 295-315 ℃, and then the tensile strength, the elongation at break and the impact strength are tested, wherein the tensile strength is 52MPa, the elongation at break is 220%, and the impact strength is 110J/m.
Example 5
2500ml NMP,210gNaOH,400g sodium hydrosulfide (content: 70%) was added to a 10L reactor, heated to 200℃under nitrogen protection, and 790ml of water was distilled out to complete the first stage; then 62.28g of 4,4' -dichloro-trans-stilbene, 624.75g of p-dichlorobenzene, 4-dichlorodiphenyl sulfone are added143.58g. Reacting for 3 hours at 220 ℃, and completing the second-stage reaction; heating to 260 ℃ for reaction for 3 hours to finish the third-stage polymerizationAnd (3) carrying out a reaction. Cooling to room temperature, slowly adding deionized water, filtering, washing, and drying at 110 ℃ for 12 hours to obtain 593g of white product poly (stilbene phenyl sulfide), the yield: 95%, melting point tm=276 ℃, intrinsic viscosity: melt index 0.358: 92g/10min (molecular weight about 60,000).
The synthesized poly-astragalus arylene sulfide is extruded into granules at 290-310 ℃ through a Hark rheometer or a twin-screw extruder, then mechanical sample bars are prepared through injection molding, the injection molding temperature is 295-315 ℃, and then the tensile strength, the elongation at break and the impact strength are tested, wherein the tensile strength is 50MPa, the elongation at break is 180%, and the impact strength is 70J/m.
200g of synthesized poly-astragalus arylene sulfide is taken to be produced into powder, the powder is put into anhydrous NMP and stirred, 1g of formyl peroxide serving as an initiator is interposed, the mixture reacts with 150-160 ℃ for 4 hours under the protection of nitrogen, the mixture is cooled to room temperature, deionized water is slowly added, the mixture is filtered and washed, and the mixture is dried for 12 hours at 110 ℃ to obtain a white two-dimensional ductile material, wherein the melt index of the white two-dimensional ductile material is: 8g/10min, the melt index is reduced by 4 times; extruding into granules at 290-310 ℃ by a Hark rheometer or a twin-screw extruder, and then preparing the mechanical sample bar by injection molding, wherein the tensile strength is 60MPa, the elongation at break is 150%, and the impact strength is 75J/m.
Example 6
Meanwhile, in example 5, 125.56g of 4, 4-dichloro diphenyl sulfone is replaced by 125.56g of 4, 4-dichloro diphenyl ketone to obtain 625g of white product namely poly (stilbene phenyl sulfide), and the yield is: 92%, melting point tm=258 ℃, intrinsic viscosity: melt index 0.375: 88g/10min (molecular weight about 61,000).
The synthesized poly-stilbene phenyl sulfide is extruded into granules at 290-310 ℃ through a Hark rheometer or a twin-screw extruder, then mechanical splines are manufactured through injection molding, the injection molding temperature is 295-315 ℃, and then the tensile strength, the elongation at break and the impact strength are tested, wherein the tensile strength is 55MPa, the elongation at break is 120%, and the impact strength is 80J/m.
200g of synthesized poly-astragalus arylene sulfide is taken to be produced into powder, the powder is put into anhydrous NMP and stirred, 1g of formyl peroxide serving as an initiator is interposed, the mixture reacts with 150-160 ℃ for 4 hours under the protection of nitrogen, the mixture is cooled to room temperature, deionized water is slowly added, the mixture is filtered and washed, and the mixture is dried for 12 hours at 110 ℃ to obtain a white two-dimensional ductile material, wherein the melt index of the white two-dimensional ductile material is: 5g/10min, the melt index is reduced by 10 times; extruding into granules at 290-310 ℃ by a Hark rheometer or a twin-screw extruder, and then preparing a mechanical spline by injection molding, wherein the tensile strength is 62MPa, the elongation at break is 100%, and the impact strength is 83J/m.
Example 7
2500ml NMP,210gNaOH,400g sodium hydrosulfide (content: 70%) was added to a 10L reactor, heated to 200℃under nitrogen protection, and 790ml of water was distilled out to complete the first stage; then 85.01g of 1, 2-bis (4-bromophenyl) ethane were added624.75g p-dichlorobenzene, 4-dichlorodiphenyl sulfone->143.58g. Reacting for 3 hours at 220 ℃, and completing the second-stage reaction; the temperature was raised to 260℃for 3 hours to complete the third stage polymerization. Cooling to room temperature, slowly adding deionized water, filtering, washing, and drying at 110 ℃ for 12 hours to obtain 562g of white product namely poly (stilbene phenyl sulfide), and the yield is: 94%, melting point tm=272 ℃, intrinsic viscosity: melt index 0.396: 105g/10min (molecular weight about 59,000).
Extruding the synthesized poly-astragalus arylene sulfide into granules at 290-310 ℃ by a Hark rheometer or a twin-screw extruder, then preparing a mechanical spline by injection molding, wherein the injection molding temperature is 295-315 ℃, and then testing the tensile strength, the elongation at break and the impact strength, wherein the tensile strength is 58MPa, the elongation at break is 110%, and the impact strength is 75J/m.
Example 8
Meanwhile, in example 1, 250ml NMP,21gNaOH,40g sodium hydrosulfide (content 70%) is added into a reactor, the mixture is heated to 200 ℃ under the protection of nitrogen, 79ml of water is fractionated, and the first stage is completed; then 62.28g of 4,4' -dichloro-trans-stilbene and 36.75g of p-dichlorobenzene are added for reaction for 3 hours at 220 ℃, and the second stage reaction is completed; the temperature was raised to 260℃for 3 hours to complete the third stage polymerization. Cooling to room temperature, slowly adding deionized water, filtering, washing, and drying at 110 ℃ for 12 hours to obtain 62.2g of white product poly (stilbene phenyl sulfide), yield: 94%, melting point tm=238 ℃, intrinsic viscosity: melt index 0.396: 60g/10min.
The synthesized poly-stilbene phenyl sulfide is extruded into granules at 260-290 ℃ through a Hark rheometer or a twin-screw extruder, then mechanical splines are manufactured through injection molding, the injection molding temperature is 285-295 ℃, and then the tensile strength, the elongation at break and the impact strength are tested, wherein the tensile strength is 45MPa, the elongation at break is 300%, and the impact strength is 90J/m.
Putting the synthesized poly-stilbene phenyl sulfide product into anhydrous NMP, stirring, introducing an initiator benzoyl peroxide, reacting with 150-160 ℃ for 4 hours under the protection of nitrogen, cooling to room temperature, slowly adding deionized water, filtering, washing, and drying at 110 ℃ for 12 hours to obtain a white two-dimensional ductile material, wherein the melt index is: 2g/10min, the melt index is reduced by 30 times; extruding into granules at 285-295 ℃ by a Hark rheometer or a twin-screw extruder, and then preparing the mechanical sample bar by injection molding, wherein the tensile strength is 50MPa, the elongation at break is 200%, and the impact strength is 110J/m.
Comparative example 1
Adding 250ml NMP,20gNaOH,40g sodium hydrosulfide into a 1L reactor, stirring under the protection of nitrogen, heating to 200 ℃, fractionating to obtain 78ml of water, adding 73.5g of paradichlorobenzene, and reacting at 220 ℃ for 3 hours, wherein the first-stage reaction is finished; heating to 260 ℃ for reaction for 3 hours, cooling to 150 ℃, slowly adding deionized water, filtering, washing, drying at 110 ℃ for 24 hours to obtain 53g of white product with the yield: 96%, melting point tm=288 ℃, intrinsic viscosity: melt index 0.214: 600g/10min (molecular weight about 32,600).
Extruding into granules at 290-310 ℃ by a Hark rheometer or a twin-screw extruder, then preparing a mechanical spline by injection molding, wherein the injection molding temperature is 295-315 ℃, and then testing the tensile strength, the elongation at break and the impact strength, wherein the tensile strength is 65MPa, the elongation at break is 5%, and the impact strength is 20J/m.
Comparative example 2
Into a 1L reactor, 250ml NMP,20gNaOH,40g sodium hydrosulfide was charged, the mixture was stirred under nitrogen, heated to 200℃and distilled water was 79ml, and 66.15g of p-dichlorobenzene and 7.18g of 4, 4-dichlorodiphenyl sulfone were addedReacting for 3 hours at 220 ℃, wherein the first-stage reaction is finished; heating to 260 ℃ for reaction for 3 hours, cooling to 150 ℃, slowly adding deionized water, filtering, washing, drying at 110 ℃ for 24 hours to obtain 50g of white product with the yield: 93%, melting point tm=282 ℃, intrinsic viscosity: melt index 0.350: 220g/10min (molecular weight about 50,000).
Extruding into granules at 290-310 ℃ by a Hark rheometer or a twin-screw extruder, then preparing a mechanical spline by injection molding, wherein the injection molding temperature is 295-315 ℃, and then testing the tensile strength, the elongation at break and the impact strength, wherein the tensile strength is 60MPa, the elongation at break is 6%, and the impact strength is 22J/m.
Comparative example 3
As in comparative example 2,7.18g of 4-dichlorodiphenyl sulfoneIs coated with 6.28g of 4, 4-dichloro-benzophenoneReplacement gave 49g of white product, yield: 93%, melting point tm=283 ℃, intrinsic viscosity: melt index 0.350: 210g/10min (molecular weight about 50,000).
Extruding into granules at 290-310 ℃ by a Hark rheometer or a twin-screw extruder, then preparing a mechanical spline by injection molding, wherein the injection molding temperature is 295-315 ℃, and then testing the tensile strength, the elongation at break and the impact strength, wherein the tensile strength is 62MPa, the elongation at break is 5%, and the impact strength is 25J/m.
Comparative example 4
As in comparative example 2, 58.85g of p-dichlorobenzene, 28.72g of 4, 4-dichlorodiphenyl sulfone The content is greatly different from that of comparative example 2, 55g of white product is obtained, yield: 95%, melting point tm=281 ℃, intrinsic viscosity: 0.370 melt index: 190g/10min (molecular weight about 55,000).
Extruding into granules at 290-310 ℃ by a Hark rheometer or a twin-screw extruder, then preparing a mechanical spline by injection molding, wherein the injection molding temperature is 295-315 ℃, and then testing the tensile strength, the elongation at break and the impact strength, wherein the tensile strength is 65MPa, the elongation at break is 65%, and the impact strength is 29J/m.

Claims (13)

1. The structure formula of the poly-stilbene arylene sulfide is shown as formula I:
in the formula I, m is more than or equal to 1 1 ≤99；1≤m 2 ≤99；n＝m 1 +m 2 ；
2. The polyarylene sulfide according to claim 1, wherein the polyarylene sulfide has a melt index of 5 to 500g/10min at 316 ℃ and 5kg pressure.
3. The polyarylene sulfide according to claim 1, wherein the weight average molecular weight of the polyarylene sulfide is 20000 to 150000.
4. The process for preparing a polyarylene sulfide as claimed in claim 1 or 2, wherein the process comprises: the method is characterized in that the poly-stilbene arylene sulfide is prepared by taking a sulfur-containing monomer, a dihalogenated monomer and a third monomer as main raw materials and adopting the following method: firstly, carrying out dehydration reaction on sulfur-containing monomers under the action of alkali and polar aprotic solvent; then adding a third monomer and a dihalogenated monomer to react for 1 to 6 hours at the temperature of between 180 and 280 ℃; then heating to 200-300 ℃ to continue the reaction for 1-6 hours; finally cooling to room temperature, washing, filtering and drying to obtain the poly-stilbene arylene sulfide; wherein the molar ratio of the sulfur-containing monomer, the dihalogenated monomer and the third monomer is: sulfur-containing monomer: (third monomer+dihalo monomer) =1: 1.05 to 1.15;
and the third monomer is stilbene compound or hydrogenation product thereof, and the molar ratio of the third monomer to the dihalogenated monomer is as follows: third monomer: dihalo monomer = 0.01-0.99: 0.99 to 0.01.
5. The method for preparing a polyarylene sulfide as recited in claim 4, wherein the third monomer is a substance having the following structure:
wherein X is: F. cl, br or I.
6. The method for preparing a polyarylene sulfide according to claim 4, wherein the sulfur-containing monomer is selected from the group consisting of: sodium hydrosulfide, sodium sulfide or hydrogen sulfide;
the dihalogenated monomer is a dihalogenated aromatic compound.
7. The process for the preparation of polyarylene sulfide according to claim 6, wherein the dihalogen monomer is selected from the group consisting of:
at least one of (a) and (b); wherein x=f, cl, br.
8. The process for the preparation of polyarylene sulfide as defined in claim 4, wherein the stilbene compound or its hydrogenated product is selected from the group consisting of: 4, 4-dichloro-trans-stilbene, 4-dibromo-trans-stilbene, 4-diiodo-trans-stilbene or 1, 2-bis (4-halophenyl) ethane.
9. The process for the preparation of polyarylene sulfide according to claim 4, wherein the polar aprotic solvent is selected from the group consisting of: any of N-methyl-2-pyrrolidone, N-cyclohexylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, hexamethylphosphoramide, N-dimethylacetamide, N-dimethylamide, N-ethylcaprolactam, N-vinylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone lactam, tetramethylurea, dimethylsulfoxide, or sulfolane;
the alkali is any one of lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, lithium carbonate, sodium carbonate, potassium acetate, lithium bicarbonate, sodium bicarbonate or potassium bicarbonate;
the drying refers to drying for 6-24 hours at 80-150 ℃.
10. The method for preparing a polyarylene sulfide according to claim 4, further comprising: and (3) putting the obtained poly-astragalus-arylene sulfide into a polar aprotic solvent, stirring, adding an initiator, and reacting for 2-6 hours at 60-180 ℃ under the protection of inert gas to obtain the two-dimensional poly-astragalus-arylene sulfide.
11. The process for the preparation of polyarylene sulfide according to claim 10, wherein the polar aprotic solvent is selected from the group consisting of: any of N-methyl-2-pyrrolidone, N-cyclohexylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, hexamethylphosphoramide, N-dimethylacetamide, N-dimethylamide, N-ethylcaprolactam, N-vinylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone lactam, tetramethylurea, dimethylsulfoxide, or sulfolane;
the initiator is benzoyl peroxide, potassium persulfate or dicumyl peroxide.
12. A method for improving toughness of polyarylene sulfide, the method comprising: introducing stilbene compounds or hydrogenated products thereof in the preparation process of polyarylene sulfide; wherein the stilbene compound or the hydrogenated product thereof is a substance with the following structure:
wherein X is: F. cl, br or I.
13. The method for improving toughness of polyarylene sulfide according to claim 12, wherein the method for improving toughness of polyarylene sulfide is: taking a sulfur-containing monomer, a dihalogenated monomer and a third monomer as main raw materials, and firstly, dehydrating the sulfur-containing monomer under the action of alkali and a polar aprotic solvent; then adding a third monomer and a dihalogenated monomer to react for 1 to 6 hours at the temperature of between 180 and 280 ℃; then heating to 200-300 ℃ to continue the reaction for 1-6 hours; finally cooling to room temperature, washing, filtering and drying to obtain the poly-stilbene arylene sulfide; wherein the molar ratio of the sulfur-containing monomer, the dihalogenated monomer and the third monomer is: sulfur-containing monomer: (third monomer+dihalo monomer) =1: 1.05 to 1.15;
and the third monomer is stilbene compound or hydrogenation product thereof, and the molar ratio of the third monomer to the dihalogenated monomer is as follows: third monomer: dihalo monomer = 0.01-0.99: 0.99 to 0.01.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6198526A (en) * 1984-10-19 1986-05-16 Toray Ind Inc Biaxially orientated polyphenylene sulfide film
US5786422A (en) * 1991-02-13 1998-07-28 Tosoh Corporation Polyphenylene sulfide resin composition
CN112029100A (en) * 2020-09-04 2020-12-04 四川大学 Perylene anhydride type polyarylene sulfide with tree structure and preparation method and application thereof
CN113667123A (en) * 2021-09-10 2021-11-19 中鼎凯瑞科技成都有限公司 Polyarylene sulfide compound with ultraviolet fluorescent tracing function and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3747934B1 (en) * 2018-01-31 2024-04-24 Toray Industries, Inc. Polyarylene sulfide copolymer and method for producing same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6198526A (en) * 1984-10-19 1986-05-16 Toray Ind Inc Biaxially orientated polyphenylene sulfide film
US5786422A (en) * 1991-02-13 1998-07-28 Tosoh Corporation Polyphenylene sulfide resin composition
CN112029100A (en) * 2020-09-04 2020-12-04 四川大学 Perylene anhydride type polyarylene sulfide with tree structure and preparation method and application thereof
CN113667123A (en) * 2021-09-10 2021-11-19 中鼎凯瑞科技成都有限公司 Polyarylene sulfide compound with ultraviolet fluorescent tracing function and preparation method thereof

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