CN1733830A - Preparation of polyphenylene sulfide/polypropylene in situ microfiber blender - Google Patents
Preparation of polyphenylene sulfide/polypropylene in situ microfiber blender Download PDFInfo
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- CN1733830A CN1733830A CN 200410040339 CN200410040339A CN1733830A CN 1733830 A CN1733830 A CN 1733830A CN 200410040339 CN200410040339 CN 200410040339 CN 200410040339 A CN200410040339 A CN 200410040339A CN 1733830 A CN1733830 A CN 1733830A
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- polyphenylene sulfide
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Abstract
The invention discloses a preparation method for PPS/PP micro fibrillated polyblend. Wherein, mixing PPS and PP with given proportion for fusion extruding-hot tension-quenching process; finally, one obtains the product with fibrous PPS and higher tensile strength and modulus. This invention also fits for recovery of PPS and PP.
Description
One, technical field
The invention belongs to the novel high polymer material technical field, is to be the method for a kind of novel in-situ micro-fibril intermingling material of feedstock production with special engineering plastics polyphenylene sulfide (PPS) and general-purpose plastics polypropylene (PP).
Two, background technology
" original position is compound " is meant two kinds of limited polymkeric substance of consistency in the melt blending process, makes disperse phase because of being subjected to shearing, the distortion of stretching action streamwise, orientation, and (In-situ) forms fiber on the spot in matrix.Broad research is thermoplastic polymer (TP)/thermoplastic polymer (TP) in-situ composite at present, it is compared with TP/ macroscopic fiber (as glass, carbon fibre etc.) matrix material and TP/ TLCP (TLCP) type in-situ composite, have starting material wide material sources, moderate cost, processing forming good, to advantages such as equipment attrition are little, thereby be subjected to people's attention (Z M Li, et al.Polym-Plast Tech Eng.2002,41 (1): 19; Li Zhongming etc., Chinese patent, ZL01128896.5).
The TP/TP in-situ composite is made up of two kinds of TP with obvious processing temperature difference, and the component that wherein has high processing temperature forms fiber in the course of processing.At present, roughly adopted following two kinds of methods to prepare this in-situ composite:
(1) solid phase stretching (solid state drawing) will be carried out after two kinds of TP blend, between two component fusing points, anneal then, make low-melting component molecular chain disorientation as matrix, maintenance is as orientation phase structure (the M Evstatiev of the high melting point component of disperse phase, et al.Polymer.1992,33:877; S Fakirov, et al.Macromolecules.1993,26:5219), this can be described as " melt extruding-solid phase stretching-anneal " method.
(2) when blend is extruded, take advantage of and melt is carried out thermal stretch (hot stretching) before uncured, make the high melting point component of disperse phase form fiber, and quenching keep fiber get off (Z M Li, et al.J Mater TechEng.2002,18:419; M F Boyaud, et al.Polymer.2001,42:6515), this can be described as " melt extruding-thermal stretch-quenching " method.
The research of fibrillation blend is to realizing general-purpose plastics high performance (M Evstatiev, et al.J ApplPolym Sci.1998,67:723; Yu Feng etc., the polymer circular, 2001,4:31) with technics of reclaim of plastic waste significant (S Falirov, et al.Polymer Blends, Volumn 2:Performance.D R Paul, etal. (eds); Li Zhongming etc., Chinese patent, No:03135186.7,2003).(I Pesneau such as Pesneau, etal.Polym Eng Sci.2002,42:1990) studied the mechanical property of polyamide (PA)/polypropylene (PP) in-situ micro-fibril blend, found to compare with pure PP, the Young's modulus and the tensile strength of in-situ micro-fibril matrix material are higher.(M Evstatiev such as Evstatiev, et al.J Appl Polym Sci.1998,67:723) studied polyethylene terephthalate (PET)/nylon-6 (PA-6), nylon-66 (PA-66)/PA-6 and PET/PA-6/PA-66 in-situ micro-fibril matrix material, the Young's modulus of three kinds of materials and tensile strength all exceed 2-4 and 2-2.5 respectively doubly than pure PA-6.They (A M Cunha, et al.Structure Development DuringPolymer Processing.p311) also studied PET/PP in-situ micro-fibril matrix material, and its tensile strength and Young's modulus are respectively 8 and 4 times of pure PP.Gachter and Muller (R Gachter, et al. (eds.), CarlHanser Verlag, Munchen, Wien.Plastics Additives Handbook.1985) PET/PP in-situ micro-fibril matrix material and short glass fiber strengthen the PP matrix material, find that the tensile strength of the former (50/50 weight ratio) exceeds 4 times than latter's (the glass weight content is 30%), and Young's modulus exceeds 20%, the former is about 80% by breaking strain, and the latter only is 3-5%.(Li Xuedong etc., polymer material science and journey, 1999,15 (6): 120) discover that PA-6 becomes fibre that PP is played very big toughening effect in the PA-6/PP in-situ fibrillation compound system such as Li Xuedong.Feng gives magnitude, and (Feng gives magnitude, the matrix material journal, 2001,18 (2): 4) studied terpolymer EP rubber/nylon (EPDM/PA) in-situ micro-fibril matrix material, the EPDM fento plays good reinforcing effect, compare before with reinforcement, the high temperature tear strength of material, normal temperature tear strength and tensile strength are improved largely in the time of 121 ℃.(Z M Li, et al.Mater Lett.2002 56:756) find that also the tensile strength of PET/ polyethylene (PE) in-situ micro-fibril blend and the common PET/PE blend of modular ratio are significantly improved in our research.The in-situ micro-fibril matrix material is used for plastics recovery and has great application prospect.All available this recovery of waste or used plastics of most kinds; Recovery technology is simple, and not high to equipment requirements, technology is controlled easily, the level of automation height; Raw material sources extensively, be easy to get, production cost is low, promotes the use of easily; Production process does not produce three waste prodss to environment and human body harmful; The The comprehensive performance height, the field is widely used.
At present, also fewer to the research report of in-situ micro-fibril blend.Research is system, not deeply not very also, does not more form a more complete theoretical system.(what 6:395) studied mainly is the PET/PA system for SFakirov, et al.Adv Mater.1994 to be engaged in the Evatatiev etc. of this area research the earliest, the method that adopts is " melt extruding-solid phase stretching-anneal ", the process complexity, efficient is low, only can do theoretical investigation.If " melt extruding-thermal stretch-quenching " method of employing prepares the in-situ micro-fibril blend, do not need reheat to carry out solid phase and stretch and aftertreatment, technology is continuous, is easy to control and simple relatively, and the production efficiency height obtains practical application easily.But the research of relevant this method is reported seldom, and research range is narrow, and the material property that obtains is not good enough, and performance characterization is also insufficient.In research before, we have prepared PET/PE, PET/PP, PC/PE, PC/PP, PA-6/PE, PA-6/PP in-situ micro-fibril system and PET/ carbon black (CB)/network combined material of PE original position conduction fento, and its form and performance are discussed.
Three, summary of the invention
One of purpose of the present invention is the deficiency at domestic and international research, promptly both at home and abroad seldom and the deficiency of aspect such as scope is narrow for the research of in-situ micro-fibril blend, a kind of preparation method of novel in-situ micro-fibril blend is provided, promptly prepare PPS/PP in-situ micro-fibril blend, the PPS fento has enhancement to this blend.
Two of purpose of the present invention is the problems at domestic and international technics of reclaim of plastic waste, be that domestic and international existing technics of reclaim of plastic waste method exists a lot of problems, incinerating method as extensive employing is a kind of waste to resource, and this method facility investment is big, can only be confined to some inflammable plastics; Some chemical recovery method process complexity, the expense height, productive rate is low; Directly the method by pulverizing, screening, utilize although process is simpler, reclaims product and can only make low value-added product; Some recovery methods can cause environmental pollution etc., and a kind of novel waste and old plastics recovery method is provided, and make that removal process cleans, greenization, make to reclaim product and have more high added value and can use in the requirements at the higher level field.
The used starting material of the present invention are PPS and PP.PPS can be commercially available any.Polypropylene adopts the polypropylene of modest viscosity, as melt flow index at 0.3～5.0g/10min.
The method for preparing PPS/PP in-situ micro-fibril blend provided by the invention is with the PP of 70～100 parts of the PPS of 0～30 part of weight part and weight parts, is prepared by following processing step and condition:
(1) dry with above-mentioned PPS resin in 100～140 ℃ baking oven dry 8～24 hours, control water ratio＜0.01%.
(2) mixing is just stirred the cooled PPS of drying at normal temperatures by proportioning and is mixed.
(3) melting mixing is extruded and first blended material is placed the forcing machine melting mixing and is extruded, and extrusion temperature is 150～295 ℃, 220～295 ℃ of die temperatures, 10～200 rev/mins of extruder screw rotating speeds.The big I of forcing machine determines that according to turnout basic demand is: length-to-diameter ratio is 20～40; Not additional hybrid element.The principal character of mouth mould is that the bevel angle of inlet is 45 degree.To the circular port mould, length-to-diameter ratio is 5～10, and diameter is 1.0～2.0cm.To narrow rectangular channel mouth mould, narrow slit thickness is 1.0～2.0mm, and width is 5～10 with the thickness ratio.
(4) the material bar that will extrude of thermal stretch carries out thermal stretch under normal temperature air, and hot-draw ratio is controlled to be 2～20.The towing mechanism adjustable speed is to obtain different hot-draw ratio (stretch ratio is defined as the ratio of the material bar sectional area behind mouthful mode cross section area and the drawn).
(5) to force cooling that the material bar behind the drawn is immersed water temperature be to force cooling in 0～25 ℃ the cooling trough, then granulation.
The present invention processes high melt point thermoplastic plastics PPS and low melting point thermoplastics PP according to a certain ratio by " melt blending is extruded-thermal stretch-quenching " provided by the invention method, in the course of processing, PPS original position under shearing and drawing force field action forms the fiber of micron or submicron order, and by quick cooling fento is preserved, after granulation, obtain the finished product of the present invention---PPS/PP in-situ micro-fibril blend.This blend can extruded, in the reprocessing process such as injection moulding, mold pressing, keep its microfibrillar structure, thereby played the enhanced effect for material.
Working method provided by the invention can adopt general device of plastic processing to implement, and employed major equipment is single screw extrusion machine or twin screw extruder, flat and mouth mould and towing mechanism that runner seamlessly transits.
The present invention has the following advantages:
(1) raw material that adopts method of the present invention to prepare PPS/PP in-situ micro-fibril blend can utilize waste and old PPS and PP plastics, and cost is lower, is easy to apply.
(2) adopt method of the present invention to prepare PPS/PP in-situ micro-fibril blend, its technology is simple, is easy to control, less demanding to equipment, and employed equipment is general device of plastic processing, reduced investment.
(3) adopt method of the present invention to prepare PPS/PP in-situ micro-fibril blend, its mechanical property is compared with common PPS/PP blend, and tensile strength is well improved, and engineering plastics such as alternative ABS use.
Four, description of drawings
Fig. 1 is the common blend brittle failure of the PPS/PP of embodiment 2 a profile scanning electron micrograph.
Fig. 2 removes the electron scanning micrograph of the PPS/PP in-situ micro-fibril blend of gained behind the PP matrix of top layer for embodiment 3 is molten.
Fig. 3 is the common blend brittle failure of the PPS/PP of embodiment 4 a profile scanning electron micrograph.
Fig. 4 removes the electron scanning micrograph of the PPS/PP in-situ micro-fibril blend of gained behind the PP matrix of top layer for embodiment 5 is molten.
Fig. 5 removes the electron scanning micrograph of the PPS/PP in-situ micro-fibril blend of gained behind the PP matrix of top layer for embodiment 7 is molten.
Fig. 6 removes the electron scanning micrograph of the PPS/PP in-situ micro-fibril blend of gained behind the PP matrix of top layer for embodiment 9 is molten.
Fig. 7 is the common blend brittle failure of the PPS/PP of embodiment 10 a profile scanning electron micrograph.
Fig. 8 removes the electron scanning micrograph of the PPS/PP in-situ micro-fibril blend of gained behind the PP matrix of top layer for embodiment 11 is molten.
Fig. 9 is the brittle failure profile scanning electron micrograph of PPS/PP in-situ micro-fibril blend after mold pressing reprocessing of embodiment 7.
Five, embodiment
Embodiment given below is to specific descriptions of the present invention; be necessary to be pointed out that at this following examples only are used for that the present invention is described further; can not be interpreted as limiting the scope of the invention; this art skilled person makes some nonessential improvement and adjustment according to the invention described above content to the present invention, still belongs to protection scope of the present invention.
Embodiment 1～11:
(1) dry with the PPS resin 100～140 ℃ dry 8～24 hours down, control water ratio＜0.01% (exsiccant actual temp and time are looked the situation of raw material own, as long as water ratio in specialized range just can);
(2) mixing just mixes cooled PPS of drying and PP stirring at normal temperatures according to a certain ratio.
(3) melting mixing is extruded and first blended material is placed the forcing machine melting mixing and is extruded, extrusion temperature is 150～295 ℃, 220～295 ℃ of die temperatures (a mouthful mould has two kinds of flat narrow slot mould and circular port moulds), 10～200 rev/mins of extruder screw rotating speeds;
(4) the material bar that will extrude that stretches carries out thermal stretch under normal temperature air, and hot-draw ratio is controlled to be 2～20;
(5) to force cooling that the material bar behind the drawn is immersed water temperature be to force cooling in 0～25 ℃ the cooling trough, then granulation.
The prescription of table one embodiment 1～9
| Embodiment | The PPS resin | The PP resin | Hot-draw ratio | Mouth mould type | |
| Umber (weight part) | Umber (weight part) | Melt flow index (g/10min) | |||
| 1 | 0 | 100 | 2.0 | 8.9 | Flat |
| 2 | 5 | 95 | 2.0 | 1 | The circular port mould |
| 3 | 5 | 95 | 2.0 | 8.9 | Flat narrow slot mould |
| 4 | 15 | 85 | 2.0 | 1 | The |
| 5 | 15 | 85 | 2.0 | 6.4 | Flat |
| 6 | 15 | 85 | 0.3 | 8.9 | Flat |
| 7 | 15 | 85 | 2.0 | 8.9 | Flat |
| 8 | 15 | 85 | 4.8 | 8.9 | Flat |
| 9 | 15 | 85 | 2.O | 12.5 | Flat narrow slot mould |
| 10 | 30 | 70 | 2.0 | 1 | The circular port mould |
| 11 | 30 | 70 | 2.0 | 8.9 | Flat narrow slot mould |
Annotate: circular port mould herein, length-to-diameter ratio is 8, diameter is 1.5cm; Narrow rectangular channel mouth mould, narrow slit thickness are 1.5mm, and width is 10 with the thickness ratio.
For the physical and mechanical properties of the in-situ micro-fibril blend of investigating the present invention preparation, the matrix material of gained is placed press, pressing process condition routinely is pressed into sheet material, and is cut into test sample.
The tensile property test: rate of extension is 50 millimeters/minute, 25 ± 2 ℃ of temperature.See attached list two.
The tensile strength of table two PPS/PP in-situ micro-fibril matrix material
| Material category | Tensile strength (MPa) | Tensile modulus (GPa) |
| Embodiment 1 | 32.53 | 1.146 |
| | 31.34 | 1.042 |
| Embodiment 3 | 32.06 | 1.047 |
| Embodiment 4 | 25.22 | 0.832 |
| Embodiment 5 | 27.80 | 1.028 |
| Embodiment 6 | 31.48 | 1.209 |
| Embodiment 7 | 31.69 | 1.218 |
| Embodiment 8 | 31.74 | 1.220 |
| | 33.08 | 1.020 |
| Embodiment 10 | 21.70 | 1.013 |
| Embodiment 11 | 30.61 | 1.447 |
Morphologic observation: the sample that is used for morphologic observation divides two kinds, and a kind of is to adopt hot dimethylbenzene (120 ℃) dissolving 1～2 hour, and the surface that makes after washing with pure dimethylbenzene; Another kind is to use cooled with liquid nitrogen 0.5～1 hour, the section that impact fracture obtains.Adopt sem observation sample form, acceleration voltage 20KV.See accompanying drawing 1～9.
Claims (7)
1. the method for preparing polyphenylene sulfide (PPS)/polypropylene (PP) in-situ micro-fibril blend provided by the invention is characterized in that preparing polyphenylene sulfide fento content by following processing step and condition is polyphenylene sulfide/polypropylene in-situ micro-fibril blend of 0～30%:
(1) drying is descended above-mentioned PPS resin dry 8～24 hours at 100～140 ℃, control water ratio＜0.01%;
(2) just mix the cooled PPS of drying and PP stirred at normal temperatures by proportioning and mix.
(3) melting mixing is extruded and first blended material is placed the forcing machine melting mixing and is extruded, and extrusion temperature is 150～295 ℃, 220～295 ℃ of die temperatures, 10～200 rev/mins of extruder screw rotating speeds;
(4) the material bar that will extrude that stretches carries out thermal stretch under normal temperature air, and hot-draw ratio is controlled to be 2～20;
(5) to force cooling that the material bar behind the drawn is immersed water temperature be to force cooling in 0～25 ℃ the cooling trough, then granulation.
2. the preparation method of polyphenylene sulfide according to claim 1/polypropylene in-situ micro-fibril blend is characterized in that polypropylene selects the homopolymerization isotactic polyprophlene of melt flow index at 0.3～5.0g/10min for use.
3. the preparation method of polyphenylene sulfide according to claim 1/polypropylene in-situ micro-fibril blend is characterized in that polyphenylene sulfide selects for use commercially available any.
4. a device for preparing polyphenylene sulfide/polypropylene in-situ micro-fibril blend comprises forcing machine, cooling trough, and the length-to-diameter ratio that it is characterized in that forcing machine is 20～40, and the bevel angle of mouthful mould inlet is 45 degree.To the circular port mould, length-to-diameter ratio is 5～10, and diameter is 1.0～2.0cm.To narrow rectangular channel mouth mould, narrow slit thickness is 1.0～2.0mm, and width is 5～10 with the thickness ratio.
5. the device of preparation polyphenylene sulfide according to claim 4/polypropylene in-situ micro-fibril blend is characterized in that also comprising the haulage gear of an adjustable speed.
6. according to the preparation method of claim 1 or 2 or 3 described polyphenylene sulfides/polypropylene in-situ micro-fibril blend, it is characterized in that polyphenylene sulfide/polypropylene in-situ micro-fibril blend can be through reprocessing processes such as mold pressings.
7. according to claim 1 or 2 or 3 or 6 described methods, polyphenylene sulfide/polypropylene in-situ micro-fibril the blend of preparation is characterized in that the tensile strength of prepared blend and the tensile strength and the modulus of the common blend of the corresponding polyphenylene sulfide/polypropylene of modular ratio have improvement.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102162153A (en) * | 2011-03-15 | 2011-08-24 | 浙江理工大学 | Method for preparing hollow three-dimensional crimped polyphenylene sulfide staple fibers |
| CN103774277A (en) * | 2014-01-15 | 2014-05-07 | 北京服装学院 | Polyphenylene sulfide superfine fiber and preparation method thereof |
| CN103804793A (en) * | 2014-01-22 | 2014-05-21 | 常州大学 | Blending material capable of improving flowability and solvent resistance of polypropylene and preparation method of blending material |
| CN103965631A (en) * | 2014-04-23 | 2014-08-06 | 安徽依采妮纤维材料科技有限公司 | Polyropylene fiber modified polyphenyl thioether material for automobile plastic part |
| CN106800778A (en) * | 2017-01-19 | 2017-06-06 | 广州市聚赛龙工程塑料股份有限公司 | A kind of preparation method and applications of environmental friendly regenerated enhancing PEEK/PPS composites |
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2004
- 2004-08-02 CN CN 200410040339 patent/CN1733830A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102162153A (en) * | 2011-03-15 | 2011-08-24 | 浙江理工大学 | Method for preparing hollow three-dimensional crimped polyphenylene sulfide staple fibers |
| CN102162153B (en) * | 2011-03-15 | 2012-12-26 | 浙江理工大学 | Method for preparing hollow three-dimensional crimped polyphenylene sulfide staple fibers |
| CN103774277A (en) * | 2014-01-15 | 2014-05-07 | 北京服装学院 | Polyphenylene sulfide superfine fiber and preparation method thereof |
| CN103774277B (en) * | 2014-01-15 | 2016-03-30 | 北京服装学院 | A kind of polyphenylene sulfide superfine fiber and preparation method thereof |
| CN103804793A (en) * | 2014-01-22 | 2014-05-21 | 常州大学 | Blending material capable of improving flowability and solvent resistance of polypropylene and preparation method of blending material |
| CN103965631A (en) * | 2014-04-23 | 2014-08-06 | 安徽依采妮纤维材料科技有限公司 | Polyropylene fiber modified polyphenyl thioether material for automobile plastic part |
| CN106800778A (en) * | 2017-01-19 | 2017-06-06 | 广州市聚赛龙工程塑料股份有限公司 | A kind of preparation method and applications of environmental friendly regenerated enhancing PEEK/PPS composites |
| CN106800778B (en) * | 2017-01-19 | 2019-04-19 | 广州市聚赛龙工程塑料股份有限公司 | A kind of preparation method and applications of environmental friendly regenerated enhancing PEEK/PPS composite material |
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