CN103965475A - High-toughness polyphenylene sulfide and preparation method thereof - Google Patents
High-toughness polyphenylene sulfide and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-toughness polyphenylene sulfide and a preparation method thereof. The high-toughness polyphenylene sulfide comprises the following ingredients by weight: 10 mol of dichlorobenzene, 10-15 mol of Na2S9H2O10, 10-30 g of micro butadiene styrene rubber, 0.02-0.5 mol of prepolymerization catalysts, 0.01-0.03 mol of branching catalysts, 0.3-0.8 mol of copolymerization catalysts, 1-3 mol of branching agents, 0.2-0.8 mol of thickening agents, and 500-1,000 ml of solvents. The polyphenylene sulfide is toughened by adopting micron-sized butadiene styrene rubber particles as a toughening agent, the branching agents are added during the polymerization process, the prepared high-toughness polyphenylene sulfide has relatively high toughness, the flowing property of the high-toughness polyphenylene sulfide is improved greatly, and the requirements of the spinning process of the polyphenylene sulfide can be met.
Description
Technical field
The invention belongs to synthesis of polymer material field, be specifically related to a kind of high toughness polyphenyl thioether and preparation method thereof.
Background technology
Polyphenylene sulfide is a kind of hemicrystalline engineering plastics, because polyphenylene sulfide has that mechanical property is high, high temperature resistant, a series of advantage such as radiation hardness, chemical-resistant reagent, corrosion-resistant, antifatigue, is widely used in the fields such as automobile, machinery, chemical industry.Manufacture field at fiber, polyphenylene sulfide also possesses good performance simultaneously.
But due to the existence of polyphenylene sulfide middle-high density phenyl ring, make its material more crisp, toughness is poor, not polyphenylene sulfide toughness reinforcing not difficult.But in spinning process, because the performance requriements to raw material is higher, common toughness reinforcing means cannot meet the requirement of spinning technique.Because the fusing point of polyphenylene sulfide is high, flowing property is poor simultaneously, and frictional coefficient is high, and low viscous polyphenylene sulfide also can cause spinning easily to rupture in spinning process, therefore in the spinning of common polyphenylene sulfide, also has certain difficulty.Chinese patent CN101903576A discloses a kind of polyphenylene sulfide spunbond fiber, adopts the method for blend to make polyphenylene sulfide polymer in the time of 300 DEG C, have the approximately zero-shear viscosity of 21500 ~ 28000PaS.Although the method adopts blending technology to have certain effect, the dispersiveness of polyphenylene sulfide and can anti-performance cannot being further enhanced.
If in improving the impact resistance of polyphenylene sulfide, improve polyphenylene sulfide can anti-performance, make it to be applied to preferably in spinning technique, will have good market potential.
Summary of the invention
For solving the above-mentioned defect existing in prior art, the object of this invention is to provide a kind of high toughness polyphenyl thioether and preparation method thereof.The high toughness polyphenyl thioether making has good toughness, and flowing property excellence can meet the harsh requirement of tech. polyphenyl thioether spinning to raw material flowing property preferably.
Technical scheme of the present invention is as follows:
A kind of high toughness polyphenyl thioether, made by the component that comprises following weight part:
P-dichlorobenzene 10mol,
Na
2S·9H
2O 10~15mol，
Micron styrene-butadiene rubber(SBR) 10 ~ 30g,
Prepolymerization catalyst 0.02 ~ 0.5mol,
Branching catalyzer 0.01 ~ 0.03mol,
Catalyst for copolymerization 0.3 ~ 0.8mol,
Branching agent 1 ~ 3mol,
Thickening material 0.2 ~ 0.8mol,
Solvent 500 ~ 1000ml.
Preferably, the particle diameter of described micron styrene-butadiene rubber(SBR) is 5 ~ 100um.
Preferably, described prepolymerization catalyst is that Sodium Benzoate and nitro p-dichlorobenzene are the mixture of 3:1 in molar ratio.
Preferably, described branching catalyzer is selected from one or more in Sodium Benzoate, salt of wormwood, sodium carbonate.
Preferably, described catalyst for copolymerization is selected from one or more in lithium chloride, sodium hydroxide, potassium hydroxide, sodium-acetate, sodium phosphate.
Preferably, described branching agent is selected from 1，2，3-trichlorobenzene, 1,2, one or more in 4-trichlorobenzene or 1,3,5-trichlorobenzene, and preferred, described branching agent is 1,2,4-trichlorobenzene.
Preferably, described thickening material is ethylenediamine tetraacetic sodium oxalate and ethylene glycol 200, ethylene glycol 400, ethylene glycol 1000 or ethylene glycol 4000 1:(1 ~ 3 in molar ratio) mixture.
In polymerization process, use the mixture of ethylenediamine tetraacetic sodium oxalate and ethylene glycol as thickening material, can improve the flowing property of polyphenylene sulfide in spinning process, can meet the demand that spinning is produced.
Preferably, the solvent of stating is selected from one or more in N-Methyl pyrrolidone, HMPA, dimethyl formamide, chloroform, tetrahydrofuran (THF), N,N-dimethylacetamide; Preferably, described solvent is HMPA and the dimethyl formamide mixture of 2:1 by volume.
A preparation method for above-mentioned high toughness polyphenyl thioether, comprises the following steps:
(1) styrene-butadiene rubber(SBR) is ground into micron-sized styrene-butadiene rubber(SBR) particle by pulverize at low temperature method, micron styrene-butadiene rubber(SBR) particle is added in solvent, microwave disperses 0.5 ~ 2 hour, is uniformly dispersed;
(2) by Na
2s9H
2o carries out processed, then adds autoclave, then adds santochlor, solvent and prepolymerization catalyst, is warming up to 180 ~ 200 DEG C, and prepolymerization 1 ~ 2 hour, obtains prepolymer;
(3) prepolymer obtaining in step (2) mesohigh still is poured out to 60% ~ 80% parts by volume for subsequent use, then the solvent that contains styrene-butadiene rubber(SBR) in step (1) is added in the autoclave of step (2), add branching agent and branching catalyzer simultaneously, under nitrogen atmosphere, stir, be warming up to 220 ~ 240 DEG C, control reaction pressure is 0.5 ~ 1.0MPa, reacts 2 ~ 3 hours;
(4) prepolymer of 60% ~ 80% parts by volume of pouring out is added in the autoclave in step (3), add catalyst for copolymerization and thickening material, under nitrogen atmosphere, stir, be warming up to 240 ~ 260 DEG C, control reaction pressure is 0.5 ~ 1.5MPa, reacts 4 ~ 8 hours; Then after product in autoclave being poured into precipitation in hot water, filtration, washing, extracting makes described high toughness polyphenyl thioether.
Preferably, described micron styrene-butadiene rubber(SBR), is made by styrene-butadiene rubber(SBR) at-20 DEG C after grinding and high-speed impact.
Preferably, in described step (4), first adopt water to carry out extracting, then adopt acetone to carry out extracting.
Compared to the prior art, beneficial effect of the present invention is:
(1) the present invention is prepared in the process of high toughness polyphenyl thioether, adopt micron-sized styrene-butadiene rubber(SBR) particle to carry out toughness reinforcing as toughner p-poly-phenyl thioether, in reaction process, first prepare polyphenylene sulfide prepolymer, then a small amount of prepolymer and micron order styrene-butadiene rubber(SBR) particle are carried out to in-situ polymerization, in polymerization process, add branching agent, in polymerization process, polyphenylene sulfide molecular chain can combine preferably with styrene-butadiene rubber(SBR) particle, the existence of branching agent simultaneously makes the polyphenylene sulfide molecular chain of combination on styrene-butadiene rubber(SBR) particle have multiple reactive groups, in follow-up reaction, can form the multi-arm structure taking styrene-butadiene rubber(SBR) particle as core, thereby significantly promote the toughness of the polyphenylene sulfide obtaining.
(2) because polyphenylene sulfide polymerization technique requires stricter to reaction, different addition step, catalyzer, reaction times, reaction pressures all can cause obvious impact to the product finally making, the present invention is by the optimization to preparation technology, add different auxiliary agents in different steps, make the high toughness polyphenyl thioether making on microcosmic, there is the nucleocapsid structure taking styrene-butadiene rubber(SBR) particle as core, significantly increased impact resistance and the flowing property of high toughness polyphenyl thioether.
(3) the present invention adds thickening material in polyreaction, makes the high toughness polyphenyl thioether making can be good at meeting the needs of spinning technique.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
A kind of high toughness polyphenyl thioether, makes in accordance with the following methods:
(1) by styrene-butadiene rubber(SBR) at-20 DEG C, through grinding and high-speed impact is ground into the micron-sized styrene-butadiene rubber(SBR) particle of 50um, get 20g micron styrene-butadiene rubber(SBR) particle and add in 150ml solvent, microwave dispersion 1 hour, is uniformly dispersed;
(2) by the Na of 12mol
2s9H
2o carries out processed, then adds autoclave, then adds 10mol santochlor, 600ml solvent and 0.2mol prepolymerization catalyst, is warming up to 180 DEG C, and prepolymerization 1.5 hours, obtains prepolymer;
(3) prepolymer obtaining in step (2) mesohigh still is poured out to 70% parts by volume for subsequent use, then the solvent that contains styrene-butadiene rubber(SBR) in step (1) is added in the autoclave of step (2), add 2mol branching agent and 0.02mol branching catalyzer simultaneously, under nitrogen atmosphere, stir, be warming up to 230 DEG C, control reaction pressure is 1.0MPa, reacts 3 hours;
(4) prepolymer of 70% parts by volume of pouring out is added in the autoclave in step (3), add 0.5mol catalyst for copolymerization and 0.6mol thickening material, under nitrogen atmosphere, stir, be warming up to 250 DEG C, control reaction pressure is 1.5MPa, reacts 6 hours; Then product in autoclave poured in hot water into precipitation, filtered, successively water and acetone carry out extracting and make described high toughness polyphenyl thioether after washing.
Wherein, described prepolymerization catalyst is that Sodium Benzoate and nitro p-dichlorobenzene are the mixture of 3:1 in molar ratio; Described branching catalyzer is Sodium Benzoate; Described catalyst for copolymerization is lithium chloride; Described branching agent is 1,3,5-trichlorobenzene; Described thickening material is ethylenediamine tetraacetic sodium oxalate and ethylene glycol 4000 mixture of 1:2 in molar ratio; Described solvent is HMPA.
The high toughness polyphenyl thioether making is carried out to performance test, and the fusing point that records this high toughness polyphenyl thioether is 284 DEG C, and shock strength is 38J/M, is 32000PaS at the zero-shear viscosities of 300 DEG C.
Embodiment 2
A kind of high toughness polyphenyl thioether, makes in accordance with the following methods:
(1) by styrene-butadiene rubber(SBR) at-20 DEG C, through grinding and high-speed impact is ground into the micron-sized styrene-butadiene rubber(SBR) particle of 20um, get 18g micron styrene-butadiene rubber(SBR) particle and add in 200ml solvent, microwave dispersion 2 hours, is uniformly dispersed;
(2) by the Na of 10mol
2s9H
2o carries out processed, then adds autoclave, then adds 10mol santochlor, 500ml solvent and 0.3mol prepolymerization catalyst, is warming up to 200 DEG C, and prepolymerization 1 hour, obtains prepolymer;
(3) prepolymer obtaining in step (2) mesohigh still is poured out to 80% parts by volume for subsequent use, then the solvent that contains styrene-butadiene rubber(SBR) in step (1) is added in the autoclave of step (2), add 2mol branching agent and 0.02mol branching catalyzer simultaneously, under nitrogen atmosphere, stir, be warming up to 220 DEG C, control reaction pressure is 0.5MPa, reacts 3 hours;
(4) prepolymer of 80% parts by volume of pouring out is added in the autoclave in step (3), add 0.8mol catalyst for copolymerization and 0.5mol thickening material, under nitrogen atmosphere, stir, be warming up to 240 DEG C, control reaction pressure is 1.5MPa, reacts 8 hours; Then product in autoclave poured in hot water into precipitation, filtered, successively water and acetone carry out extracting and make described high toughness polyphenyl thioether after washing.
Wherein, described prepolymerization catalyst is that Sodium Benzoate and nitro p-dichlorobenzene are the mixture of 3:1 in molar ratio; Described branching catalyzer is sodium carbonate; Described catalyst for copolymerization is lithium chloride; Described branching agent is 1,3,5-trichlorobenzene; Described thickening material is ethylenediamine tetraacetic sodium oxalate and ethylene glycol 4000 mixture of 1:1 in molar ratio; Described solvent is N,N-dimethylacetamide.
The high toughness polyphenyl thioether making is carried out to performance test, and the fusing point that records this high toughness polyphenyl thioether is 283 DEG C, and shock strength is 36J/M, is 31000PaS at the zero-shear viscosities of 300 DEG C.
Embodiment 3
A kind of high toughness polyphenyl thioether, makes in accordance with the following methods:
(1) by styrene-butadiene rubber(SBR) at-20 DEG C, through grinding and high-speed impact is ground into the micron-sized styrene-butadiene rubber(SBR) particle of 17um, get 20g micron styrene-butadiene rubber(SBR) particle and add in 150ml solvent, microwave dispersion 2 hours, is uniformly dispersed;
(2) by the Na of 12mol
2s9H
2o carries out processed, then adds autoclave, then adds 10mol santochlor, 600ml solvent and 0.4mol prepolymerization catalyst, is warming up to 180 DEG C, and prepolymerization 2 hours, obtains prepolymer;
(3) prepolymer obtaining in step (2) mesohigh still is poured out to 70% parts by volume for subsequent use, then the solvent that contains styrene-butadiene rubber(SBR) in step (1) is added in the autoclave of step (2), add 2mol branching agent and 0.02mol branching catalyzer simultaneously, under nitrogen atmosphere, stir, be warming up to 230 DEG C, control reaction pressure is 1.0MPa, reacts 3 hours;
(4) prepolymer of 70% parts by volume of pouring out is added in the autoclave in step (3), add 0.5mol catalyst for copolymerization and 0.6mol thickening material, under nitrogen atmosphere, stir, be warming up to 250 DEG C, control reaction pressure is 1.2MPa, reacts 6 hours; Then product in autoclave poured in hot water into precipitation, filtered, successively water and acetone carry out extracting and make described high toughness polyphenyl thioether after washing.
Wherein, described prepolymerization catalyst is that Sodium Benzoate and nitro p-dichlorobenzene are the mixture of 3:1 in molar ratio; Described branching catalyzer is sodium carbonate; Described catalyst for copolymerization is lithium chloride; Described branching agent is 1,2,4-trichlorobenzene; Described thickening material is ethylenediamine tetraacetic sodium oxalate and ethylene glycol 4000 mixture of 1:2.5 in molar ratio; Described solvent is HMPA and the dimethyl formamide mixture of 2:1 by volume.
The high toughness polyphenyl thioether making is carried out to performance test, and the fusing point that records this high toughness polyphenyl thioether is 284 DEG C, and shock strength is 38J/M, is 31000PaS at the zero-shear viscosities of 300 DEG C.
Embodiment 4
A kind of high toughness polyphenyl thioether, makes in accordance with the following methods:
(1) by styrene-butadiene rubber(SBR) at-20 DEG C, through grinding and high-speed impact is ground into the micron-sized styrene-butadiene rubber(SBR) particle of 5um, get 10g micron styrene-butadiene rubber(SBR) particle and add in 100ml solvent, microwave dispersion 0.5 hour, is uniformly dispersed;
(2) by the Na of 10mol
2s9H
2o carries out processed, then adds autoclave, then adds 10mol santochlor, 400ml solvent and 0.02mol prepolymerization catalyst, is warming up to 180 DEG C, and prepolymerization 1 hour, obtains prepolymer;
(3) prepolymer obtaining in step (2) mesohigh still is poured out to 80% parts by volume for subsequent use, then the solvent that contains styrene-butadiene rubber(SBR) in step (1) is added in the autoclave of step (2), add 1mol branching agent and 0.01mol branching catalyzer simultaneously, under nitrogen atmosphere, stir, be warming up to 220 DEG C, control reaction pressure is 0.5MPa, reacts 2 hours;
(4) prepolymer of 80% parts by volume of pouring out is added in the autoclave in step (3), add 0.3mol catalyst for copolymerization and 0.2mol thickening material, under nitrogen atmosphere, stir, be warming up to 240 DEG C, control reaction pressure is 0.5MPa, reacts 4 hours; Then product in autoclave poured in hot water into precipitation, filtered, successively water and acetone carry out extracting and make described high toughness polyphenyl thioether after washing.
Wherein, described prepolymerization catalyst is that Sodium Benzoate and nitro p-dichlorobenzene are the mixture of 3:1 in molar ratio; Described branching catalyzer is Sodium Benzoate; Described catalyst for copolymerization is lithium chloride; Described branching agent is 1,2,4-trichlorobenzene; Described thickening material is ethylenediamine tetraacetic sodium oxalate and ethylene glycol 200 mixture of 1:1 in molar ratio; Described solvent is HMPA and the dimethyl formamide mixture of 2:1 by volume.
The high toughness polyphenyl thioether making is carried out to performance test, and the fusing point that records this high toughness polyphenyl thioether is 283 DEG C, and shock strength is 32J/M, is 29000PaS at the zero-shear viscosities of 300 DEG C.
Embodiment 5
A kind of high toughness polyphenyl thioether, makes in accordance with the following methods:
(1) by styrene-butadiene rubber(SBR) at-20 DEG C, through grinding and high-speed impact is ground into the micron-sized styrene-butadiene rubber(SBR) particle of 100um, get 30g micron styrene-butadiene rubber(SBR) particle and add in 200ml solvent, microwave dispersion 2 hours, is uniformly dispersed;
(2) by the Na of 15mol
2s9H
2o carries out processed, then adds autoclave, then adds 10mol santochlor, 800ml solvent and 0.5mol prepolymerization catalyst, is warming up to 200 DEG C, and prepolymerization 2 hours, obtains prepolymer;
(3) prepolymer obtaining in step (2) mesohigh still is poured out to 60% parts by volume for subsequent use, then the solvent that contains styrene-butadiene rubber(SBR) in step (1) is added in the autoclave of step (2), add 3mol branching agent and 0.03mol branching catalyzer simultaneously, under nitrogen atmosphere, stir, be warming up to 240 DEG C, control reaction pressure is 1.0MPa, reacts 3 hours;
(4) prepolymer of 60% parts by volume of pouring out is added in the autoclave in step (3), add 0.8mol catalyst for copolymerization and 0.8mol thickening material, under nitrogen atmosphere, stir, be warming up to 260 DEG C, control reaction pressure is 1.5MPa, reacts 8 hours; Then product in autoclave poured in hot water into precipitation, filtered, successively water and acetone carry out extracting and make described high toughness polyphenyl thioether after washing.
Wherein, described prepolymerization catalyst is that Sodium Benzoate and nitro p-dichlorobenzene are the mixture of 3:1 in molar ratio; Described branching catalyzer is salt of wormwood; Described catalyst for copolymerization is lithium chloride and the sodium hydroxide mixture of 1:1 in molar ratio; Described branching agent is 1，2，3-trichlorobenzene; Described thickening material is ethylenediamine tetraacetic sodium oxalate and ethylene glycol 400 mixture of 1:3 in molar ratio; Described solvent is HMPA and the dimethyl formamide mixture of 2:1 by volume.
The high toughness polyphenyl thioether making is carried out to performance test, and the fusing point that records this high toughness polyphenyl thioether is 285 DEG C, and shock strength is 42J/M, is 34000PaS at the zero-shear viscosities of 300 DEG C.
Embodiment 6
A kind of high toughness polyphenyl thioether, makes in accordance with the following methods:
(1) by styrene-butadiene rubber(SBR) at-20 DEG C, through grinding and high-speed impact is ground into the micron-sized styrene-butadiene rubber(SBR) particle of 10um, get 25g micron styrene-butadiene rubber(SBR) particle and add in 150ml solvent, microwave dispersion 1.5 hours, is uniformly dispersed;
(2) by the Na of 10mol
2s9H
2o carries out processed, then adds autoclave, then adds 10mol santochlor, 600ml solvent and 0.3mol prepolymerization catalyst, is warming up to 180 DEG C, and prepolymerization 1.5 hours, obtains prepolymer;
(3) prepolymer obtaining in step (2) mesohigh still is poured out to 70% parts by volume for subsequent use, then the solvent that contains styrene-butadiene rubber(SBR) in step (1) is added in the autoclave of step (2), add 2.5mol branching agent and 0.03mol branching catalyzer simultaneously, under nitrogen atmosphere, stir, be warming up to 230 DEG C, control reaction pressure is 1.0MPa, reacts 3 hours;
(4) prepolymer of 70% parts by volume of pouring out is added in the autoclave in step (3), add 0.5mol catalyst for copolymerization and 0.6mol thickening material, under nitrogen atmosphere, stir, be warming up to 250 DEG C, control reaction pressure is 1.0MPa, reacts 8 hours; Then product in autoclave poured in hot water into precipitation, filtered, successively water and acetone carry out extracting and make described high toughness polyphenyl thioether after washing.
Wherein, described prepolymerization catalyst is that Sodium Benzoate and nitro p-dichlorobenzene are the mixture of 3:1 in molar ratio; Described branching catalyzer is sodium carbonate; Described catalyst for copolymerization is lithium chloride; Described branching agent is 1,2,4-trichlorobenzene; Described thickening material is ethylenediamine tetraacetic sodium oxalate and ethylene glycol 4000 mixture of 1:2.5 in molar ratio; Described solvent is N-Methyl pyrrolidone.
The high toughness polyphenyl thioether making is carried out to performance test, and the fusing point that records this high toughness polyphenyl thioether is 285 DEG C, and shock strength is 40J/M, is 33000PaS at the zero-shear viscosities of 300 DEG C.
The above embodiment is preferred embodiments of the present invention, is not to limit the scope of the present invention, and the equivalence of doing according to structure, feature and principle described in the present patent application the scope of the claims therefore all changes or modifies, and all should comprise in patent claim of the present invention.
Claims (10)
1. a high toughness polyphenyl thioether, its characteristic is: be made up of the component that comprises following weight part:
P-dichlorobenzene 10mol,
Na
2S·9H
2O 10~15mol，
Micron styrene-butadiene rubber(SBR) 10 ~ 30g,
Prepolymerization catalyst 0.02 ~ 0.5mol,
Branching catalyzer 0.01 ~ 0.03mol,
Catalyst for copolymerization 0.3 ~ 0.8mol,
Branching agent 1 ~ 3mol,
Thickening material 0.2 ~ 0.8mol,
Solvent 500 ~ 1000ml.
2. a kind of high toughness polyphenyl thioether according to claim 1, is characterized in that: the particle diameter of described micron styrene-butadiene rubber(SBR) is 5 ~ 100um.
3. a kind of high toughness polyphenyl thioether according to claim 1, is characterized in that: described prepolymerization catalyst is that Sodium Benzoate and nitro p-dichlorobenzene are the mixture of 3:1 in molar ratio.
4. a kind of high toughness polyphenyl thioether according to claim 1, is characterized in that: described branching catalyzer is selected from one or more in Sodium Benzoate, salt of wormwood, sodium carbonate.
5. a kind of high toughness polyphenyl thioether according to claim 1, is characterized in that: described catalyst for copolymerization is selected from one or more in lithium chloride, sodium hydroxide, potassium hydroxide, sodium-acetate, sodium phosphate.
6. a kind of high toughness polyphenyl thioether according to claim 1, is characterized in that: described branching agent is selected from 1，2，3-trichlorobenzene, 1,2, one or more in 4-trichlorobenzene or 1,3,5-trichlorobenzene, and preferred, described branching agent is 1,2,4-trichlorobenzene.
7. a kind of high toughness polyphenyl thioether according to claim 1, is characterized in that: described thickening material is ethylenediamine tetraacetic sodium oxalate and ethylene glycol 200, ethylene glycol 400, ethylene glycol 1000 or ethylene glycol 4000 1:(1 ~ 3 in molar ratio) mixture.
8. a kind of high toughness polyphenyl thioether according to claim 1, it is characterized in that: described solvent is selected from one or more in N-Methyl pyrrolidone, HMPA, dimethyl formamide, chloroform, tetrahydrofuran (THF), N,N-dimethylacetamide; Preferably, described solvent is HMPA and the dimethyl formamide mixture of 2:1 by volume.
9. as a preparation method for the high toughness polyphenyl thioether as described in arbitrary in claim 1 ~ 8, it is characterized in that, comprise the following steps:
(1) styrene-butadiene rubber(SBR) is ground into micron-sized styrene-butadiene rubber(SBR) particle by pulverize at low temperature method, micron styrene-butadiene rubber(SBR) particle is added in solvent, microwave disperses 0.5 ~ 2 hour, is uniformly dispersed;
(2) by Na
2s9H
2o carries out processed, then adds autoclave, then adds santochlor, solvent and prepolymerization catalyst, is warming up to 180 ~ 200 DEG C, and prepolymerization 1 ~ 2 hour, obtains prepolymer;
(3) prepolymer obtaining in step (2) mesohigh still is poured out to 60% ~ 80% parts by volume for subsequent use, then the solvent that contains styrene-butadiene rubber(SBR) in step (1) is added in the autoclave of step (2), add branching agent and branching catalyzer simultaneously, under nitrogen atmosphere, stir, be warming up to 220 ~ 240 DEG C, control reaction pressure is 0.5 ~ 1.0MPa, reacts 2 ~ 3 hours;
(4) prepolymer of 60% ~ 80% parts by volume of pouring out is added in the autoclave in step (3), add catalyst for copolymerization and thickening material, under nitrogen atmosphere, stir, be warming up to 240 ~ 260 DEG C, control reaction pressure is 0.5 ~ 1.5MPa, reacts 4 ~ 8 hours; Then after product in autoclave being poured into precipitation in hot water, filtration, washing, extracting makes described high toughness polyphenyl thioether.
10. the preparation method of high toughness polyphenyl thioether according to claim 9, is characterized in that, described micron styrene-butadiene rubber(SBR), is made by styrene-butadiene rubber(SBR) at-20 DEG C after grinding and high-speed impact.
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| CN104744697A (en) * | 2015-03-04 | 2015-07-01 | 常州大学 | Polyphenylene sulfide copolymer containing p-phenyl dibenzyl structural unit and preparation method for polyphenylene sulfide copolymer |
| CN104817697A (en) * | 2015-03-04 | 2015-08-05 | 常州大学 | Branched polyphenylene sulfide copolymer containing polycyclic aromatic hydrocarbon, and preparation method thereof |
| CN106750346A (en) * | 2017-01-20 | 2017-05-31 | 广州市鹏云工程塑料有限公司 | XNBR is grafted polyphenylene sulfide and its synthetic method |
| CN108752586A (en) * | 2018-07-04 | 2018-11-06 | 西北师范大学 | A kind of preparation method of colored fascicular texture polyphenylene sulfide |
| CN110256686A (en) * | 2019-06-10 | 2019-09-20 | 宜宾天原集团股份有限公司 | A kind of preparation method of hyperbranched polyphenylene sulfide |
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| CN104744697A (en) * | 2015-03-04 | 2015-07-01 | 常州大学 | Polyphenylene sulfide copolymer containing p-phenyl dibenzyl structural unit and preparation method for polyphenylene sulfide copolymer |
| CN104817697A (en) * | 2015-03-04 | 2015-08-05 | 常州大学 | Branched polyphenylene sulfide copolymer containing polycyclic aromatic hydrocarbon, and preparation method thereof |
| CN106750346A (en) * | 2017-01-20 | 2017-05-31 | 广州市鹏云工程塑料有限公司 | XNBR is grafted polyphenylene sulfide and its synthetic method |
| WO2018133471A1 (en) * | 2017-01-20 | 2018-07-26 | 广州市鹏云工程塑料有限公司 | Carboxylated nitrile butadiene rubber grafted polyphenylene sulfide resin and synthetic method therefor |
| CN108752586A (en) * | 2018-07-04 | 2018-11-06 | 西北师范大学 | A kind of preparation method of colored fascicular texture polyphenylene sulfide |
| CN110256686A (en) * | 2019-06-10 | 2019-09-20 | 宜宾天原集团股份有限公司 | A kind of preparation method of hyperbranched polyphenylene sulfide |
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