CN102108153A - Flame-retarding heat-resistance polypropylene composite containing ceramic fibers and preparation method thereof - Google Patents
Flame-retarding heat-resistance polypropylene composite containing ceramic fibers and preparation method thereof Download PDFInfo
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- CN102108153A CN102108153A CN2009102472326A CN200910247232A CN102108153A CN 102108153 A CN102108153 A CN 102108153A CN 2009102472326 A CN2009102472326 A CN 2009102472326A CN 200910247232 A CN200910247232 A CN 200910247232A CN 102108153 A CN102108153 A CN 102108153A
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Abstract
The invention relates to ceramic fiber-reinforced polypropylene and a composite prepared by flame-retardant modification on polypropylene. The composite is characterized by comprising the following raw materials in part by weight: 55 to 80 parts of polypropylene resin, 10 to 30 parts of ceramic fibers, 1 to 10 parts of flame retardant and 2 to 5 parts of processing assistant. The invention has the advantages that: the ceramic fibers serving as a functional modifying component improve the heat resistance and flame retardance of polypropylene and balance the physical and mechanical properties; and the composite can be used electrical appliance shells, internal structure products, instrument, equipment, automotive parts and the like, which have high flame retardance and heat resistance requirements and high performance requirements. The preparation method of the composite adopts a double-screw extruder, and has the advantages of simple and continuous process flow, high production efficiency and stable product quality.
Description
Technical field
The present invention relates to a kind of ceramic fiber enhanced heat resistant type flame-retardant polypropylene plastics mixture and preparation method thereof.
Background technology
Ceramic fiber is a kind of fibrous light refractory materials that integrates conventional insulation material, refractory materials premium properties, has low heat conductivity, good thermostability, chemical stability, non-corrosiveness.The diameter of ceramic fiber is generally 2 μ m～5 μ m, and length mostly is 30mm～250mm, and it is slick cylindrical that fiber surface is, and cross section is normally circular.Its constructional feature is void content height (generally greater than 90%), and air vent aperture and specific surface area are big.Because the air in the pore has good heat-blocking action, thereby the size of air vent aperture and the character (ventilate or the hole of holding one's breath) of pore have decisive influence to its heat conductivility in the fiber.In fact, the internal organizational structure of ceramic fiber is a kind of mixed structure of being made up of solid-state fiber and air, its microstructure characteristics all are that form with external phase exists in solid phase and gas phase, therefore, in this structure, solid matter exists with filamentous form, and constitutes the external phase skeleton, gas phase then continued presence among the skeleton gap of filamentary material.Have this structure just because of ceramic fiber, make that its void content is higher, air vent aperture and specific surface area be bigger, thereby make ceramic fiber have good heat-proof quality and smaller volume density.Be used for industry insulation, sealing, protective material, electric heating device insulation, lagging material, the insulation of plant and instrument, electrical heating element and heat insulation material, automobile industry lagging material etc. more.
The liquid crystal polyester dipping ceramic fiber of printed circuit board (PCB) and the refinforced cement based composites that is used to build also appear being used in recent years.Do not see that ceramic fiber is used for the report of acrylic plastering modification.
Characteristics such as polypropylene (PP) is inexpensive because of its high comprehensive performance, wide material sources, light weight, easy-formation processing become one of most important general-purpose plastics, also are the fastest plastics varieties of application development in recent years.But polypropylene very easily burns, and its oxygen index is 17.0%-18.0% only, can not put out certainly after catching fire, thereby must carry out flame-retardant modifiedly to it, also needs further to improve the thermotolerance of PP, just can widen its Application Areas.But in existing study on the modification such as heat-resisting, fire-retardant, do not appear in the newspapers and introduce suitable ceramic fiber, improve heat-resisting, the flame retardant properties and the optimization physical and mechanical property of polypropylene composite as function modified component.
Summary of the invention
The present invention seeks to disclose a kind of ceramic fiber reinforced flame retardant heat-resistance polypropylene mixture and preparation method thereof that contains,, satisfy the needs of association area development to overcome the above-mentioned defective that prior art exists.
Ceramic fiber reinforced flame retardant heat-resistance polypropylene mixture of the present invention, its typical weight umber consists of:
55～80 parts of acrylic resins;
10～30 parts of ceramic fibers;
3～10 parts of fire retardants;
Processing aid 2-5 part.
Described acrylic resin is meant homopolymerization PP, comprises common homopolymerization PP (HPP) and high crystallization PP (HJPP), and melting index (MI) is 5-15;
Said ceramic fiber preferably adopts the ceramic fiber of handling through composite coupler.
The composite coupler parts by weight that ceramic fiber is handled consist of:
Phosphate coupling agent 20-40 part, silane coupling agent 35-55 part, Resins, epoxy 5-15 part, glycidyl ester 15-35 part.
Phosphate coupling agent is a chelating type tetra-sodium titanate coupling agent, and can adopt the U.S. Kenrich company trade mark is the product of KR-238S;
The chemical name of silane coupling agent is a vinyltriethoxysilane, and can adopt the domestic Qingdao big chemical industry company limited in the sea trade mark is the product of A-151;
It is the product of R-140 that Resins, epoxy can adopt the Mitsui chemistry trade mark;
Glycidyl ester is isocyanuric acid three-glycidyl ester (TGIC), and domestic a plurality of producers are all on sale.Said composite coupler consumption is for being 0.5～2% based on ceramic fiber weight.
Treatment process is as follows:
Earlier treatment agents such as phosphate coupling agent, silane coupling agent, Resins, epoxy, glycidyl ester are mixed and are positioned in the treatment trough by top proportioning, the ceramic fiber after wire drawing is handled is handled back (flooding 5～10 seconds) by the composite treating agent in the treatment trough and is promptly got the ceramic fiber that required modification is handled.
Preferred Luanping, Hebei Ao Tesiding Industrial Co., Ltd, specification is the ceramic fiber of high temperature (HT) type, 2～4 microns of Fibre diameters.Ceramic fiber after the processing can play good enhancement to material, makes material have high-modulus and rigidity, gives good infiltration, the coating of ceramic fiber and resin, makes that the ceramic fiber height is heat-resisting, fire-resistance property is played a role in resin system.
Said fire retardant is meant eight bromine S ethers, and its chemical name is two (2, the 3-dibromopropyl) ethers of tetrabromo-bisphenol s, and sulfur atom-containing in its molecular structure is good with the PP resin compatible, is difficult for separating out.Add a small amount of synergist simultaneously, generate a large amount of rare gas element secluding airs during burning, and produce fine and closely woven molten drop and take away heat and make fray-out of flame, thereby reach fire-retardant purpose.Eight bromine S ether fusing points are lower, and fusion with the PP blend time can be distributed in the PP resin well, thereby little to the mechanical property influence of material.
Said fire retardant also wraps a kind of or its mixture in stibiated oxide compound, stibnate or the borate, specifically comprises antimonous oxide, antimony peroxide, sodium antimonate or zinc borate etc., and eight bromine S ethers are played good synergistic effect.
Said processing aid is selected from a kind of or its mixture in low molecule ester class, metallic soap class, stearic acid complex ester class, the amides etc., specifically comprise solid paraffin, whiteruss, low molecular polyethylene, CaSt, Zinic stearas, erucicamide, methylene bis stearic amide and N, N-ethylene bis stearic acid amide (EBS) etc., it mainly acts on is to improve the dispersiveness that adds each component in processing and moulding process, reduce harmful friction, thereby improve processing characteristics.
The preparation method who contains ceramic fiber reinforced flame retardant heat-resistance polypropylene mixture of the present invention comprises the steps:
1) with PP resin and fire retardant, processing aid abundant mixing in high speed mixer in advance;
2) above-mentioned miscellany being added length-to-diameter ratio is that 32: 1～40: 1, extrusion temperature are that 180-240 ℃, rotating speed are in the strong shearing twin screw extruder of 350-450rpm, evenly add ceramic fiber by the side direction spout, melt extrude, obtain the finished product after tie rod, cooling, pelletizing, the drying.
Product of the present invention had both had the good flame performance, had characteristics such as height is heat-resisting, high surface hardness, high rigidity simultaneously again.Flame retardant rating can reach UL94 V-0, can satisfy the service requirements of electric appliance casing, inner structural members based article.The flame-proof reinforced polypropylene mixture that contains ceramic fiber of the present invention adopts the twin screw extrusion equipment, have flow process simple, continuously, the advantage of high, the constant product quality of production efficiency.
Embodiment
Embodiment 1～3
Preparation and the physicals that contains ceramic fiber reinforced flame retardant heat-resistance polypropylene mixture of the present invention sees attached list 1, and the testing method standard of employing sees attached list 2:
The PP resin that adopts in the present embodiment is that MI is HPP and the HJPP of 8-12; Ceramic fiber is the ceramic fiber of high temperature (HT) type of Luanping, Hebei Ao Tesiding Industrial Co., Ltd production, 2～4 microns of Fibre diameters; Fire retardant is eight bromine S ether and antimonous oxides; Processing aid is EBS.
The preparation process of material is as described below: PP resin, fire retardant, processing aid EBS etc. are even in high-speed mixer and mixing, feed length-to-diameter ratio again and be 36: 1, extrusion temperature and be 220 ℃, rotating speed and be in the twin screw extruder of strong shear screw element distributed combination of 400rpm, the side direction spout evenly adds ceramic fiber, melt extrude granulation, finally obtain this product.
Table 1
Table 2
| Physicals | Testing standard | Unit |
| Density | ISO1183A | g/cm3 |
| Melting index | ISO1133 | g/10min |
| Tensile strength | ISO527/2-93 | MPa |
| Flexural strength | ISO178-93 | MPa |
| Notched Izod impact strength | ISO180-93 | KJ/m2 |
| Heat-drawn wire | ISO75-1 | ℃ |
| Flame retardant properties | UL94 | Class |
Claims (6)
1. a flame-proof heat-resistant polypropylene composite that contains ceramic fiber is characterized in that, is made up of following weight part raw material:
Acrylic resin 55-80 part,
10 parts-30 parts of ceramic fibers,
1 part-10 parts of fire retardants,
2 parts-5 parts of processing aids.
2. according to the said a kind of flame-proof heat-resistant polypropylene composite that contains ceramic fiber of claim 1, it is characterized in that described ceramic fiber is the ceramic fiber of handling through composite coupler, specification is the ceramic fiber of high temperature (HT) type, 2 ~ 4 microns of Fibre diameters.
3. according to the said a kind of flame-proof heat-resistant polypropylene composite that contains ceramic fiber of claim 1, it is characterized in that described acrylic resin is a homopolymerization PP, comprise common homopolymerization PP (HPP) and high crystallization PP (HJPP), melting index (MI) is 5-15.
4. according to the said a kind of preparation method who contains the flame-proof heat-resistant polypropylene composite of ceramic fiber of claim 1; it is characterized in that; the steps include: that acrylic resin, fire retardant and the processing aid that will measure mix; be sent to twin screw extruder; subsequently ceramic fiber is added forcing machine through the feeder of delicate metering separately; extrude, granulation obtains product.
5. according to the said a kind of flame-proof heat-resistant polypropylene composite that contains ceramic fiber of claim 1, it is characterized in that, said processing aid is a kind of or its mixture in low molecule ester class, metallic soap class, stearic acid complex ester class, the amides etc., specifically comprise solid paraffin, whiteruss, low molecular polyethylene, CaSt, Zinic stearas, erucicamide, methylene bis stearic amide and N, one or more of N-ethylene bis stearic acid amide (EBS) etc.
6. according to the said ceramic fiber of handling through composite coupler of claim 2, it is characterized in that said composite coupler is phosphate coupling agent 20-40 part, silane coupling agent 35-55 part, Resins, epoxy 5-15 part, glycidyl ester 15-35 part.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102472326A CN102108153A (en) | 2009-12-28 | 2009-12-28 | Flame-retarding heat-resistance polypropylene composite containing ceramic fibers and preparation method thereof |
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| CN2009102472326A CN102108153A (en) | 2009-12-28 | 2009-12-28 | Flame-retarding heat-resistance polypropylene composite containing ceramic fibers and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532690A (en) * | 2010-12-28 | 2012-07-04 | 上海金发科技发展有限公司 | Ceramic-fiber-reinforced flame-retardant modified polypropylene complex and preparation method thereof |
| CN112552580A (en) * | 2019-09-26 | 2021-03-26 | 万华化学集团股份有限公司 | Halogen-free flame-retardant scratch-resistant antibacterial polypropylene material and preparation method and application thereof |
| CN113354901A (en) * | 2021-07-19 | 2021-09-07 | 韦小玉 | High-heat-resistance fiber-reinforced polypropylene composite material and preparation method thereof |
-
2009
- 2009-12-28 CN CN2009102472326A patent/CN102108153A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532690A (en) * | 2010-12-28 | 2012-07-04 | 上海金发科技发展有限公司 | Ceramic-fiber-reinforced flame-retardant modified polypropylene complex and preparation method thereof |
| WO2012088743A1 (en) * | 2010-12-28 | 2012-07-05 | 上海金发科技发展有限公司 | Flame retardant modified polypropylene composite improved by ceramic fibre and preparation process thereof |
| CN112552580A (en) * | 2019-09-26 | 2021-03-26 | 万华化学集团股份有限公司 | Halogen-free flame-retardant scratch-resistant antibacterial polypropylene material and preparation method and application thereof |
| CN113354901A (en) * | 2021-07-19 | 2021-09-07 | 韦小玉 | High-heat-resistance fiber-reinforced polypropylene composite material and preparation method thereof |
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Application publication date: 20110629 |