CN102321369A - Low-density polyarylene sulfide composite material and preparation method thereof - Google Patents
Low-density polyarylene sulfide composite material and preparation method thereof Download PDFInfo
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- CN102321369A CN102321369A CN201110231162A CN201110231162A CN102321369A CN 102321369 A CN102321369 A CN 102321369A CN 201110231162 A CN201110231162 A CN 201110231162A CN 201110231162 A CN201110231162 A CN 201110231162A CN 102321369 A CN102321369 A CN 102321369A
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Abstract
The invention discloses a low-density polyarylene sulfide composite material and a preparation method thereof, and belongs to the technical field of high-molecular material. The low-density polyarylene sulfide composite material provided by the invention has decreased density as well as remained mechanical properties that can satisfy usage requirements. The low density polyarylene sulfide composite material comprises raw materials of, by weight, 100 parts of polyarylene sulfide and 5-60 parts of low-density filling, wherein the low-density filling has a compressive strength no less than 60 MPa, a grain size of 40-60 um and a true density of 0.5-0.8g/cm<3>, and comprises at least one selected from hollow glass microsphere (HGM) and hollow ceramic microballoon. According to the technical scheme of the invention, the low-density polyarylene sulfide material has substantially reduced density (maximum 30% reduction); and the addition of an interface modifier endows the polyarylene sulfide material a better mechanical strength and flame resistance.
Description
Technical field
The present invention relates to matrix material of a kind of thermoplastic polymer and preparation method thereof, belong to technical field of polymer materials.
Background technology
Low density is value and high-strength materials has a wide range of applications in fields such as aerospace, automobile, steamers.
Poly arylidene thio-ester is the polymkeric substance that the molecule main chain is made up of aryl and thioether bond, comprising the multipolymer of polyphenylene sulfide (PPS), polyaryl thioether sulfone (PASS), polyarylene sulfide ketone (PASK), aromatic polythioether amide (PASA), polyarylene imide sulfide (PASI), poly arylidene thio-ester nitrile (PASN) and above-mentioned polymkeric substance.Poly arylidene thio-ester is one type of special engineering plastics with very good mechanical properties, resistance toheat, excellent properties such as corrosion-resistant, fire-retardant, is the preferred material of heat resistant structure parts in the fields such as electronic apparatus, automobile, aerospace.But the density of poly arylidene thio-ester is all at 1.4g/cm
3About, this has limited its some application in fields such as aviation, navigation, high-speed railway.In some particular application; Hope polyarylene sulfide resin when keeping original excellent properties, also have the low density of trying one's best (as for the aircraft stock material, according to estimates; Density reduces by 1/3, wants aspect the structural weight effect of specific tenacity or rigidity raising 50% also big alleviating).
Generally speaking, the density that reduces a kind of polymkeric substance used the preparation foam materials to realize often.Its method generally be through chemicalfoaming or physical foaming method with gas dispersion in polymeric matrix.Yet for polyarylphosphorus ethers material; Its processing temperature generally higher (processing temperature like polyphenylene sulfide is about 300 ℃); Be difficult to find suitable chemical foaming agent, adopt the physical blowing method to be difficult to solve the mechanical resistance to air loss problem in the high temperature process process again simultaneously.Therefore at present domestic production application research at poly arylidene thio-ester resinoid foam materials does not also appear in the newspapers.Contriver of the present invention has carried out a large amount of research to the poly arylidene thio-ester material.
Summary of the invention
The present invention is directed to above-mentioned defective, a kind of low density polyaryl thioether composite material is provided, keep mechanical property can satisfy request for utilization when it reduces than the poly arylidene thio-ester density of material.
Technical scheme of the present invention is:
The low density polyaryl thioether composite material contains poly arylidene thio-ester, low density filler in its raw material, its weight proportion is: 100 parts of poly arylidene thio-esters, 5～60 parts of low density fillers; Wherein, low density filler ultimate compression strength >=50Mpa, the density of low density filler is lower than the density of poly arylidene thio-ester material.
Said low density filler true density≤1g/cm
3, preferred 0.5-0.8g/cm
3Said poly arylidene thio-ester is at least a in polyphenylene sulfide (PPS), polyaryl thioether sulfone (PASS), polyarylene sulfide ketone (PASK), aromatic polythioether amide (PASA), polyarylene imide sulfide (PASI) or the poly arylidene thio-ester nitrile (PASN).
Preferably, above-mentioned low density filler is selected from least a in hollow glass micropearl (HGM), the hollow ceramic microballoon.Hollow glass micropearl more preferably.
Preferably, above-mentioned low density filler ultimate compression strength >=60Mpa.
Preferably, above-mentioned low density filler particle diameter is 40-60um.
Preferred, the particle diameter of above-mentioned low density filler is 50um.
Hollow glass micropearl be by coal through 1500 ℃ of high-temp combustion fusions after rapidly cooling and the hollow glass spheroid that forms, its chemical ingredients is mainly SiO
2, Al
2O
3, Fe
2O
3Deng.General granularity is 10-250 micron, true density 0.1-0.8g/cm
3, wall thickness is the 1-2 micron.The hollow ceramic microballoon is a kind of HS, inertia, hard, meticulous spherical particle, and its staple is oxidation sial or alkaline oxygenated sial pottery, and general granularity is the 10-200 micron, true density 0.6-2.5g/cm
3Above-mentioned true density refers to the actual volume of solid matter in the volume of material under absolute dense state, does not comprise internal voids; Breakdown point when ultimate compression strength refers to that external force is pressure.
Further, above-mentioned low density polyaryl thioether composite material also contains interface modifier in its raw material, and the addition of interface modifier is 1～8 part; Wherein, interface modifier is selected from least a in silane coupling agent, the titanate coupling agent.
Further, above-mentioned low density polyaryl thioether composite material also contains toughness reinforcing filler in its raw material, and the addition of toughness reinforcing filler is 2～30 parts; Wherein, toughness reinforcing filler is selected from least a in Injecatable EVA Copolymer (EVA), terpolymer EP rubber (EPDM), methyl-silicone oil, the vinyl silicone oil.
Further, above-mentioned low density polyaryl thioether composite material also contains reinforcing filler in its raw material, and the addition of reinforcing filler is 5～50 parts; Wherein, reinforcing filler is selected from least a in thomel, aramid fiber, the spun glass.
The present invention also provides the preparation method of above-mentioned low density polyaryl thioether composite material, is specially: with above-mentioned poly arylidene thio-ester and low density filler; Or poly arylidene thio-ester, low density filler and interface modifier; Or poly arylidene thio-ester, low density filler, interface modifier and toughness reinforcing filler; Or poly arylidene thio-ester, low density filler, interface modifier, toughness reinforcing filler and reinforcing filler are carried out mechanical blending according to aforementioned proportion and are promptly made the low density polyaryl thioether composite material more than the fusing point of poly arylidene thio-ester.
Preferably, among the preparation method of above-mentioned low density polyaryl thioether composite material, adopt prepared in twin-screw extruder, be about to above-mentioned raw materials in proportion through the twin screw extruder fusion, mixing, extrude, cool off, dry, pelletizing and packing.
Preferred, among the preparation method of above-mentioned low density polyaryl thioether composite material, the poly arylidene thio-ester in the above-mentioned raw materials, interface modifier, toughner, toughener are added from the loading hopper of twin screw extruder in proportion; The downstream of low density filler in the raw material from twin screw extruder directly are added to the melt, extrude then, cool off, dry, pelletizing and packing.
To make material property get the increasing degree degree little owing to hollow glass micropearl very easily breaks in the course of processing, can't reach due effect; Therefore among the above-mentioned low density polyaryl thioether composite material preparation method, should control low density filler and add opportunity, to avoid or to reduce the breakage of low density filler (tiny balloon filler).
Beneficial effect of the present invention:
1, low density filler reduction poly arylidene thio-ester material result is obvious, and its density is the highest to be reduced about 30%; And the adding of coupling agent etc. makes that the performances such as mechanical strength, flame retardant resistance of poly arylidene thio-ester material are excellent more, reaches the actual demand in fields such as aviation, navigation, high-speed railway.
2, the method for low density poly arylidene thio-ester material matrix material provided by the invention is simple to operate, efficient is high, be easy to industriallization, and product performance height, steady quality, cost are low.
Description of drawings
Fig. 1 is the electronic scanning Electronic Speculum figure (SEM) of the PPS/HGM composite structure among the embodiment 1, can be found out by figure, adopts preparation method HGM of the present invention not have fragmentation, thereby guarantees that it plays corresponding effect.
Embodiment
In order to understand the present invention better, invent furtherly below in conjunction with embodiment.Present embodiment only is used for the present invention is further specified, and can not be interpreted as the restriction to protection domain of the present invention, and the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Contriver of the present invention has done the experiment that low density fillers such as a large amount of employings such as hollow glass micropearl reduce the poly arylidene thio-ester material; Find that hollow glass micropearl very easily breaks in the course of processing; Thereby make improper the reduction on the contrary of the density of gained polyaryl thioether composite material increase, explore and obtain stable low density poly arylidene thio-ester material and guarantee its mechanical property as far as possible so done a large amount of research.
Embodiment
Adopt raw material and the proportioning shown in the embodiment 1-6 shown in the table 1; Utilize twin screw extruder to extrude the preparation polyaryl thioether composite material: polyarylene sulfide resin is added at forcing machine master feeding place, and low density filler adds from the side spout in forcing machine stage casing, controls the proportion of composing of matrix material through the feed rate of controlling main feeding and side feeding; Under the screw speed of 100rpm with they melt kneading; Double-screw extruding machine barrel respectively distinguish TR different and different according to polyarylene sulfide resin (wherein, PPS:260-310 ℃, PASS:200-330 ℃; PASK:270-370 ℃, PASA:270-330 ℃); The melt composition that flows out die head adopts water cooling, 120 ℃ of dry down polyaryl thioether composite material pellets that get of hot blast.Wherein, the index of correlation of employed low density filler is as shown in table 2.The sem photograph of the PPS/HGM matrix material that the embodiment of the invention 1 makes is as shown in Figure 1; Can find out by figure; Adopt preparation method HGM of the present invention not have fragmentation, thereby guarantee that it plays corresponding effect (reducing the density of poly arylidene thio-ester), this possibly be because selected HGM ultimate compression strength is higher; In addition, the present invention side spout place of being employed in the forcing machine stage casing adds the fragmentation that HGM has also been avoided in low density filler.
Mechanical property when Comparative Examples 1 is not added any additives for PPS.In addition; Because the character of low density filler self is influential to the present invention; The present invention also uses preparation matrix materials (Comparative Examples 2-6) such as other hollow glass micropearls (HGM6) and poly arylidene thio-ester, and the proportioning raw materials of Comparative Examples is as shown in table 1, wherein; The index of correlation of employed low density filler is as shown in table 2 in the Comparative Examples, and preparation technology is identical with the preparation method of the foregoing description.
After the above-mentioned extrudate thorough drying that makes, be injection molded into the testing standard batten with injection moulding machine by standard size, the test mechanical performance.Mechanical property is tested by national standard respectively: density is pressed GB/T 208-94; Tensile strength is pressed GB/T 1040-92 standard, and compressive strength is tested by the UL94 standard by GB/T 1843-1996 standard, flame retardant rating by GB/T 9341-2000 standard, unnotched impact strength by GB/T 1041-2008 standard, flexural strength.The index of the mechanical property of gained low density polyaryl thioether composite material is as shown in table 3.
Table 1 proportioning raw materials
The physicals of table 2 low density filler
The performance of table 3 polyaryl thioether composite material
Can know by last table, add the density that polyaryl thioether composite material that low density filler, toughener, toughner and interface modifier obtain has not only reduced poly arylidene thio-ester in the poly arylidene thio-ester, and its mechanical property be excellent more, makes it can be applied to aviation field.In PPS, add low density filler among the embodiment 1 separately, though its mechanical property has reduction slightly than PPS, it still can satisfy request for utilization.
Comparative Examples 2-6 prepares polyphenyl thioether composite material; Maybe be because the ultimate compression strength of HGM be lower; HGM is easy to fragmentation when using twin screw to shear; The adding of HGM is equivalent to add glass in fact so, and the density of glass is higher, thereby makes the density of gained polyphenyl thioether composite material not only not reduce rising on the contrary.
Claims (10)
1. the low density polyaryl thioether composite material is characterized in that, contains poly arylidene thio-ester, low density filler in its raw material, and its weight proportion is: 100 parts of poly arylidene thio-esters, 5～60 parts of low density fillers; Wherein, low density filler ultimate compression strength >=50Mpa, the density of low density filler is lower than the density of poly arylidene thio-ester material.
2. low density polyaryl thioether composite material according to claim 1 is characterized in that, above-mentioned low density filler is selected from least a in hollow glass micropearl, the hollow ceramic microballoon; Preferred hollow glass micropearl.
3. low density polyaryl thioether composite material according to claim 1 and 2 is characterized in that, above-mentioned low density filler ultimate compression strength >=60Mpa.
4. according to each described low density polyaryl thioether composite material of claim 1-3, it is characterized in that above-mentioned low density filler particle diameter is 40-60um, preferred 50um.
5. according to each described low density polyaryl thioether composite material of claim 1-4, it is characterized in that also contain interface modifier in its raw material, the addition of interface modifier is 1～8 part; Wherein, interface modifier is selected from least a in silane coupling agent, the titanate coupling agent.
6. according to each described low density polyaryl thioether composite material of claim 1-5, it is characterized in that also contain toughness reinforcing filler in its raw material, the addition of toughness reinforcing filler is 2～30 parts; Wherein, toughness reinforcing filler is selected from least a in Injecatable EVA Copolymer, terpolymer EP rubber, methyl-silicone oil, the vinyl silicone oil.
7. according to each described low density polyaryl thioether composite material of claim 1-6, it is characterized in that also contain reinforcing filler in its raw material, the addition of reinforcing filler is 5～50 parts; Wherein, reinforcing filler is selected from least a in thomel, aramid fiber, the spun glass.
8. the preparation method of each described low density polyaryl thioether composite material of claim 1-7 is specially:
With above-mentioned poly arylidene thio-ester and low density filler; Or
Poly arylidene thio-ester, low density filler and interface modifier; Or
Poly arylidene thio-ester, low density filler, interface modifier and toughness reinforcing filler; Or
Poly arylidene thio-ester, low density filler, interface modifier, toughness reinforcing filler and reinforcing filler are carried out mechanical blending according to aforementioned proportion and are promptly made the low density polyaryl thioether composite material more than the fusing point of poly arylidene thio-ester.
9. the preparation method of low density polyaryl thioether composite material according to claim 8; It is characterized in that; Adopt prepared in twin-screw extruder, be about to above-mentioned raw materials in proportion through the twin screw extruder fusion, mixing, extrude, cool off, dry, pelletizing and packing.
10. the preparation method of low density polyaryl thioether composite material according to claim 9 is characterized in that, the poly arylidene thio-ester in the above-mentioned raw materials, interface modifier, toughner, toughener are added from the loading hopper of twin screw extruder in proportion; The downstream of low density filler in the raw material from twin screw extruder directly are added to the melt, extrude then, cool off, dry, pelletizing and packing.
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Cited By (5)
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| CN103450620A (en) * | 2012-06-04 | 2013-12-18 | 上海斯瑞聚合体科技有限公司 | Glass microsphere cable filling material and preparation method thereof |
| CN103756312A (en) * | 2013-12-19 | 2014-04-30 | 成都德美精英化工有限公司 | Low-density high temperature resistant cyano resin composite material and preparation method thereof |
| CN109852056A (en) * | 2018-12-28 | 2019-06-07 | 上海锦湖日丽塑料有限公司 | A kind of carbon fiber enhancing polyphenylene sulfide composition of abrasion resistant fire blocking and preparation method thereof |
| CN110031301A (en) * | 2019-04-18 | 2019-07-19 | 北京师范大学 | The intensity characterizing method of ceramic hollow ball particle |
| CN110877427A (en) * | 2018-09-06 | 2020-03-13 | 西安交通大学 | Composite material containing hollow ceramic balls and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103450620A (en) * | 2012-06-04 | 2013-12-18 | 上海斯瑞聚合体科技有限公司 | Glass microsphere cable filling material and preparation method thereof |
| CN103756312A (en) * | 2013-12-19 | 2014-04-30 | 成都德美精英化工有限公司 | Low-density high temperature resistant cyano resin composite material and preparation method thereof |
| CN103756312B (en) * | 2013-12-19 | 2017-02-01 | 成都德美精英化工有限公司 | Low-density high temperature resistant cyano resin composite material and preparation method thereof |
| CN110877427A (en) * | 2018-09-06 | 2020-03-13 | 西安交通大学 | Composite material containing hollow ceramic balls and preparation method thereof |
| CN110877427B (en) * | 2018-09-06 | 2021-07-06 | 西安交通大学 | Composite material containing hollow ceramic balls and preparation method thereof |
| CN109852056A (en) * | 2018-12-28 | 2019-06-07 | 上海锦湖日丽塑料有限公司 | A kind of carbon fiber enhancing polyphenylene sulfide composition of abrasion resistant fire blocking and preparation method thereof |
| CN109852056B (en) * | 2018-12-28 | 2021-09-07 | 上海锦湖日丽塑料有限公司 | Wear-resistant flame-retardant carbon fiber reinforced polyphenylene sulfide composition and preparation method thereof |
| CN110031301A (en) * | 2019-04-18 | 2019-07-19 | 北京师范大学 | The intensity characterizing method of ceramic hollow ball particle |
| CN110031301B (en) * | 2019-04-18 | 2021-02-26 | 北京师范大学 | Method for characterizing strength of ceramic hollow sphere particles |
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