CN109423048A - A kind of polyphenyl thioether material and preparation method thereof of organosilicon toughening modifying - Google Patents
A kind of polyphenyl thioether material and preparation method thereof of organosilicon toughening modifying Download PDFInfo
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- CN109423048A CN109423048A CN201710784588.8A CN201710784588A CN109423048A CN 109423048 A CN109423048 A CN 109423048A CN 201710784588 A CN201710784588 A CN 201710784588A CN 109423048 A CN109423048 A CN 109423048A
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- sio
- polyphenylene sulfide
- grafted
- organosilicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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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
- C08G75/0286—Chemical after-treatment
- C08G75/029—Modification with organic compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The present invention relates to a kind of polyphenyl thioether materials and preparation method thereof of organosilicon toughening modifying.The invention material is a kind of SiO after silane coupling agent KH-560 graft modification2The modified material of nano-particles filled fiberglass reinforced organosilicon grafting polyphenylene sulfide system.The novelty for preparing the technical matters of the material is embodied in: first ultrasonic disperse, be stirred to react, KH-560 be grafted on SiO by way of centrifuging treatment2Particle surface prepares the Nano-meter SiO_2 of surface hydrophobicity2Then organic silicon monomer is grafted on polyphenylene sulfide using Suspension Graft and crosslinked with silicane technology, and then the modified polyphenyl thioether material of activeness and quietness is obtained after check rod, cooling, pelletizing by double screw extruder blending extrusion with other auxiliary agent compositing formula systems.While modified material tensile strength with higher, bending strength, impact flexibility with higher greatly improves compared with pure PPS.
Description
Technical field
The present invention relates to polymeric material fields, and in particular to a kind of polyphenyl thioether material of organosilicon toughening modifying and its
Preparation method is widely used in electronic and electrical industry, auto industry, mechanical industry, military project national defence.
Background technique
Polyphenylene sulfide (PPS) is a kind of hemicrystalline thermoplastic special engineering plastic, its molecular backbone be by phenyl ring with
Sulphur atom is alternately arranged, and the regularity of strand is strong, and phenyl ring provides rigidity, and thioether bond provides flexibility, since molecular backbone has
There is hard and soft the characteristics of having both, so polyphenylene sulfide is easy to crystallize, crystallinity reaches as high as 75%.Polyphenylene sulfide it is white or
Near-white is a kind of hard and crisp polymer, and hydroscopicity is very low, only 0.03%.Density is 1.34g/cm3, fusing point is 285 DEG C,
For glass transition temperature at 90 DEG C or so, thermal stability is prominent, just starts to decompose at 430 DEG C~460 DEG C or more in air.In nitrogen
In gas, 500 DEG C or less are heated no apparent mass loss.Flame retardant rating is U-94V-O grades, and 200 DEG C or less insoluble in big absolutely
Most organic solvents, and electrical insulating property is very good.
Due to polyphenylene sulfide excellent combination property, in electronic and electrical industry, auto industry, mechanical industry, military project national defence neck
The application that domain has this important, but its there is also shortcomings, mechanical strength is not high, and tensile strength, bending strength belong to medium
The brittleness of level, especially polyphenylene sulfide is larger, and toughness is poor, this can hinder to a certain extent the polymer in the market
It is widely applied, the brittleness problems for solving polyphenylene sulfide are most important targets in current polyphenylene sulfide study on the modification.With each row
The continuous development of each industry and the continuous developing in high performance material market, can be increasingly to special engineered material requirement
Height, especially some leading-edge fields, defence and military etc..Therefore, the toughness of polyphenylene sulfide is improved for it from now on the market more
Good broadly used has a very important significance.
Summary of the invention
The present invention is prepared for a kind of polyphenyl thioether material of organosilicon toughening modifying, it is therefore an objective in the drawing for improving polyphenylene sulfide
While stretching intensity, bending strength, it may have higher toughness.Silane coupling agent KH-560 is grafted on SiO first2Particle table
Face obtains the Nano-meter SiO_2 of surface hydrophobicity2, then organic silicon monomer is grafted on crosslinked with silicane technology using Suspension Graft poly-
On diphenyl sulfide, and then with other auxiliary agent compositing formula systems by double screw extruder blending extrusion, through check rod, cooling, pelletizing
The modified polyphenyl thioether material of activeness and quietness is obtained afterwards.Method of modifying of the invention slightly has with traditional polyphenylene sulfide method of modifying
Difference is that a kind of novel polyphenyl sulfide material that toughness makes moderate progress has been prepared by the method for chemical structure modification, through silicon
Alkane coupling agent KH-560 is grafted processed SiO2Nanoparticle surface there are Si-O group can with it is organosilicon grafted and modified
The Si-O group on the surface PPS couples, while making modified material tensile strength with higher, the bending strength of preparation,
Impact flexibility with higher.
Technical solution:
Step 1: a certain amount of Nano-meter SiO_2 is weighed2, the toluene of certain volume, room temperature ultrasonic cleaner (300W) ultrasound point is added
30min is dissipated, unit for uniform suspension is obtained, then silane coupling agent KH-560 is added thereto, continues 3~4min of ultrasound, is transferred to dress
There is reflux condensing tube, in reinforcement electric stirring 100mL four-neck flask, is stirred to react in the oil bath temperature set certain
Time.Slurries table-type high-speed refrigerated centrifuge after reaction is centrifugated with the speed room temperature of 12000r/min, is modified
Nano-meter SiO_22.Modified Nano SiO2Ultrasonic disperse, centrifuge separation 6 times.By modified Nano SiO2It is placed in a vacuum drying oven, room temperature
Dry 8h~10h, the modified Nano SiO prepared2White powder.
Step 2: dried PPS powder suspended dispersed is subjected to pre-swollen for a period of time in methylene chloride, in Al2O3
Under the action of, chloroacetic chloride is added, to the end of reacting, reaction solution is moved into cryosel acid and is decomposed, is filtered, first with low concentration
NaOH solution washing, is washed with deionized water and ethyl alcohol, 80~100 DEG C of 20~30h of vacuum drying obtain acetylation repeatedly later
Polyphenylene sulfide.Under nitrogen protection, it disperses acetylation polyphenylene sulfide in dry toluene, is slowly added to silane coupling agent, instead
8~12h is answered, is filtered, washing, and with 20~30h of ethanol solution Soxhlet extraction, it is dried under vacuum to constant weight at 80~100 DEG C, is obtained
Organosilicon grafted and modified polyphenylene sulfide.Crosslinking finally is hydrolyzed in organosilicon grafted and modified polyphenylene sulfide, is filtered, product
It is dried in vacuo at 80~100 DEG C.
Step 3: each component in above-mentioned formula is uniformly mixed in a high speed mixer according to the ratio, by mixed material
It is added in double screw extruder and carries out melting extrusion.
Extrusion temperature range is 285~310 DEG C；Engine speed is 400~600rpm；Feeding revolving speed is 20~30rpm.
The mixture of extrusion is water cooled, be granulated after dry in a vacuum drying oven, then by the blend being baked 290~
Standard sample item is molded at 320 DEG C.
Specific example:
The present invention is described in more detail combined with specific embodiments below, but implements each example the invention is not limited to following:
The present embodiment section of use grand double screw extruder and extra large day injection molding machine again, primary raw material polyphenylene sulfide, technical grade (four
River obtains positive)；GF, technical grade (megalith group)；Silane coupling agent uses KH-560, technical grade (commercially available)；Silica (specific surface
Product 150m2/ g, Guangzhou Ji Bishi S&T tax Co., Ltd)；Toluene (AR, Tianjin great Mao chemical reagent factory)；Antioxidant packages
Include 1010,168(Li Anlong).
One Qu Wendu: 260~275 DEG C of twin-screw extruder barrel temperature, two area's temperature: 280~290 DEG C, three Qu Wendu:
280~290 DEG C；Four Qu Wendu: 280~290 DEG C；Five Qu Wendu: 280~290 DEG C；Six Qu Wendu: 280~290 DEG C, pressure is
10~16MPa, screw slenderness ratio 35~40,400~600r/min of engine speed.The concentration of KH-560 is 0.2%, reaction temperature
It is 90 DEG C, being stirred to react the time is 6h.
Each component is uniformly mixed according to a ratio and is placed in twin-screw extrusion, through melting mixing extruding pelletization.Gained pellet is again
Through 120 DEG C of 8~10h of forced air drying, the performance test batten of standard is molded on injection molding machine.
The corresponding formula of each embodiment of table 1
The corresponding physical property of each embodiment sample of table 2
Claims (3)
1. the formula composition of the polyphenylene sulfide modified material of organosilicon toughening is as follows:
Pre-process PPS 60~70%
GF 30~40%
Nano-meter SiO_22 0.1~0.5%
Auxiliary agent 0.1~3%.
2. the polyphenylene sulfide modified material of organosilicon toughening according to claim 1, it is characterised in that: the SiO2Nanoparticle
Son is stirred to react, centrifuging treatment by ultrasonic disperse, so that KH-560 is grafted on SiO2Particle surface obtains surface and dredges
The Nano-meter SiO_2 of water2, SiO2The concentration that the dosage of nanoparticle is 0.1%~0.5%, KH-560 is 0.1%~3%, and reaction temperature is
60 DEG C~90 DEG C, being stirred to react the time is 6h~10h.
3. the polyphenylene sulfide modified material of organosilicon toughening according to claim 1, it is characterised in that: the pretreatment PPS
Organic silicon monomer (3-aminopropyltriethoxysilane) is grafted on by polyphenylene sulfide using Suspension Graft and crosslinked with silicane technology
Surface and obtain.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710784588.8A CN109423048A (en) | 2017-09-04 | 2017-09-04 | A kind of polyphenyl thioether material and preparation method thereof of organosilicon toughening modifying |
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| CN201710784588.8A CN109423048A (en) | 2017-09-04 | 2017-09-04 | A kind of polyphenyl thioether material and preparation method thereof of organosilicon toughening modifying |
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| CN109423048A true CN109423048A (en) | 2019-03-05 |
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| CN201710784588.8A Pending CN109423048A (en) | 2017-09-04 | 2017-09-04 | A kind of polyphenyl thioether material and preparation method thereof of organosilicon toughening modifying |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110964321A (en) * | 2019-12-11 | 2020-04-07 | 西北师范大学 | Polyphenylene sulfide-silicon dioxide super-hydrophobic composite material and preparation method thereof |
| CN114573984A (en) * | 2022-03-16 | 2022-06-03 | 四川中科兴业高新材料有限公司 | Liquid silicon cement graft modified toughened polyphenylene sulfide and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104629366A (en) * | 2013-11-12 | 2015-05-20 | 黑龙江鑫达企业集团有限公司 | Organic silicon toughened and modified polyphenylene sulfide material and preparation method thereof |
-
2017
- 2017-09-04 CN CN201710784588.8A patent/CN109423048A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104629366A (en) * | 2013-11-12 | 2015-05-20 | 黑龙江鑫达企业集团有限公司 | Organic silicon toughened and modified polyphenylene sulfide material and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110964321A (en) * | 2019-12-11 | 2020-04-07 | 西北师范大学 | Polyphenylene sulfide-silicon dioxide super-hydrophobic composite material and preparation method thereof |
| CN110964321B (en) * | 2019-12-11 | 2022-03-11 | 西北师范大学 | Polyphenylene sulfide-silicon dioxide super-hydrophobic composite material and preparation method thereof |
| CN114573984A (en) * | 2022-03-16 | 2022-06-03 | 四川中科兴业高新材料有限公司 | Liquid silicon cement graft modified toughened polyphenylene sulfide and preparation method thereof |
| CN114573984B (en) * | 2022-03-16 | 2023-11-03 | 四川中科兴业高新材料有限公司 | Liquid silica gel grafted modified toughened polyphenylene sulfide and preparation method thereof |
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Application publication date: 20190305 |