CN102146596A - Preparation method for halogen-free flame-retardant polypropylene fibers - Google Patents
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Abstract
The invention discloses a preparation method for halogen-free flame-retardant polypropylene fibers. The preparation method is characterized by comprising the following steps of: melting, mixing, extruding and granulating 30 to 60 weight parts of polypropylene slices, 30 to 68.5 weight parts of intumescent flame retardant and 1.5 to 10 weight parts of additives in a twin-screw extruder at the temperature of 210 to 230 DEG C to obtain intumescent flame-retardant master batches; after mixing 10 to 25 weight parts of the flame-retardant master batches and 75 to 90 weight parts of the polypropylene slices, spinning by using a melt-spinning machine; after beaming the prepared halogen-free flame-retardant polypropylene protofilaments, feeding the beamed halogen-free flame-retardant polypropylene protofilaments into electronic irradiation equipment for performing irradiation cross-linking treatment, wherein the thickness of tow is made below 2 mm by using shaping equipment and the irradiation measurement is 50 to 400 kGy when irradiating; and obtaining the finished halogen-free flame-retardant polypropylene protofilaments by winding the irradiated fibers, wherein the finished fibers have the fineness of 0.5 to 100 dtex, the strength of 2 to 9 cN/dtex, and the breaking elongation of 5 to 18 percent, and the limiting oxygen index of the fibers is 28 to 34.
Description
Technical field
The present invention relates to a kind of halogen-free polypropylene flame redardant (PP) fiber preparation method.The preparation field that belongs to the halogen-free flameproof fiber.
Background technology
Polypropylene fibre formally begins suitability for industrialized production in nineteen fifty-seven, is the up-and-coming youngster in the synthetic fiber.Because it is simple that polypropylene fibre has production technology, relative density little (0.91g/ml), raw material and production cost are low, characteristics such as fibre strength height, and therefore development is very fast, and polypropylene fibre has been the fourth-largest kind of synthetic fiber at present.The deficiency of polypropylene fibre maximum is its inflammability, and polypropylene is the polymeric material of carbon containing protium only, its oxygen index (OI) low (only about 18), and very easily burning, and caloric value is big during burning, produces a large amount of molten drops, very easily propagating flame.Therefore the inflammable characteristic of polypropylene fibre has limited its application to a great extent, and it is significant for enlarging range of application to give its fire resistance.
Halogenated flame retardant is traditional flame-retardant additive of flame-retardant polypropylene.Disclose among the Chinese patent CN101713105A and a kind ofly be mixed with wig by bromide fire retardant and antimony class synergist etc. with polypropylene, with the method for low-temperature flame retardant polypropylene fibers, the anti-flammability of the polypropylene fibre that makes reaches the V-0 level.A kind of method of the flame-retardant polypropylene that is made by the fire-retardant master granule and the polypropene blended spinning of preparations such as TDE and antimonous oxide is disclosed among the Chinese patent CN 101476171A.Adopt halogenated flame retardant can obtain to have the flame retardant polypropylene fibers of good flame-retardance energy.But halogenated flame retardant was because of producing macro-corrosion gas (as HCI, HBr etc.) and noxious material just by progressively restriction use in burning.Therefore halogen-free flameproof is the main developing direction of flame-retardant polypropylene.In for polyacrylic all kinds of halogen-free flameproof methods, adding expansion type flame retardant is have big potentiality a kind of.Expansion type flame retardant (IFR) has characteristics such as the high and low cigarette of efficient, nontoxic, no etchant gas release.IFR generally is made up of three function ingredients, acid source: the salt such as phosphoric acid, sulfuric acid, boric acid and the phosphate etc. that generate acid when referring generally to the inorganic acid burning; Carbon source: the polyol compound such as pentaerythrite, ethylene glycol and the phenolic resins etc. that generally refer to carbon containing more; Source of the gas: be generally nitrogenous many carbon compounds such as urea, dicyandiamide, polyamide, Lauxite etc.The fire retardant mechanism of expansion type flame retardant is to promote polymer to become charcoal, forms the homogeneous charcoal layer of one deck expansion porous at material surface, plays heat insulation, oxygen barrier, presses down cigarette, prevents the effect of molten drop, reaches fire-retardant purpose.Also have the expanding fire retardant of molecule type in the expansion type flame retardant, promptly include acid source, carbon source and source of the gas in this based flame retardant molecular structure, as pentaerythrite spiro-phosphate double density amine salt etc.In polypropylene flame redardant, often adopt APP, pentaerythrite, melamine composite expansion flame-retardant system, or adopt the molecule-type expanding fire retardant to carry out fire-retardant.As disclosing the method that a kind of fire retardant systems of being made up of melamine cyanurate salt, melamine phosphamide, pentaerythrite and hydroxide prepares flame-retardant polypropylene composite material among the Chinese patent CN 101693835A; Disclose among the Chinese patent CN 101831109A and a kind ofly be tied to form carbon-blowing agent, APP and ethylene-acrylate-expandable flame retardant system that maleic anhydride terpolymer intercalation organo montmorillonite is formed by triazine and prepare the method for halogen-free polypropylene flame redardant film.Though the expandable flame retardant system has good fire retardation to polypropylene, just can obtain flame retardant effect preferably when needing big addition.The addition of expansion type flame retardant is generally all more than 15wt% in the polypropylene flame redardant.High flame retardant agent addition is bigger for the mechanical property influence of polypropylene fibre, and has promoted material cost greatly.Under the situation that the expansion type flame-retarding agent content is lower in the polypropylene fibre, the foaming carbon-coating thinner thickness that forms during burning, polypropylene when burning melted by heating, thin foaming carbon-coating is in the bath surface instability, is easy to landing or breaks and influence fire resistance.Therefore the flame retardant effect that improves polypropylene fibre under than the situation of low bulk flame retardant agent content is significant.
The electronic irradiation modified technology of polymeric material is a kind of faster of development in recent years.Polymer behind the employing electron beam irradiation can take place partial cross-linked, and the heat resistance of polymer is improved, and mechanical property also certain change will take place simultaneously.As disclosing a kind of preparation method of electron beam irradiation modified high molecular weight polyethylene board material among the Chinese patent CN 101716809A, the physical property by sheet material behind the irradiation all increases.Irradiation technique can combine with flame-retarded technology simultaneously, preparation has good flame-retardance, stable on heating fire proofing, these class methods have obtained extensive use in cable industry, all disclose the crosslinked method for preparing fire-resistant cable material of electron irradiation among Chinese patent CN1137495C, CN1237770A, CN100555476C, CN101286377A, the CN101914236A.
The present inventor finds, the electron irradiation crosslinking technological is applied to the addition that halogen-free expanded flame-retardant polypropylene can reduce expanding fire retardant greatly, and obtains to have the polypropylene product of good flame-retardance energy.Electron irradiation can make polypropylene generation cross-linking reaction, thereby polyacrylic heat decomposition temperature is improved, and is beneficial to the carbon that is foamed into of expanding fire retardant, and the carbon-coating that forms during burning is more stable, and the anti-flammability of fiber is improved.
Summary of the invention
The objective of the invention is provides a kind of halogen-free polypropylene flame redardant fiber preparation method at the deficiencies in the prior art.Be characterized in preparing the polypropylene flame redardant precursor, more fire-retardant precursor carried out electron irradiation and handle, obtain the halogen-free polypropylene flame redardant fibrous finished product by adding expanding halide-free fire-retardant.
Purpose of the present invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
The halogen-free polypropylene flame redardant fiber preparation method may further comprise the steps:
(1) preparation of halogen-free expansion type flame-proof master batch
With polypropylene chip 30～60 weight portions, expansion type flame retardant 30～68.5 weight portions and additive 1.5～10 weight portions in double screw extruder, in 210～230 ℃ of melting mixing extruding pelletizations of temperature, obtain the expansion type flame-retarding master batch together;
(2) preparation of halogen-free polypropylene flame redardant precursor
With the above-mentioned fire-retardant master granule that makes 10～25 weight portions with after polypropylene chip 75～90 weight portions mix, carry out spinning by melt spinning machine, spinning technique is identical with conventional production of polypropylene fibers technology, according to application requirements, the former silk size of polypropylene that spinning is made is controlled at 0.5～100dtex, the intensity of precursor is at 5～10cN/dtex, and the extension at break of precursor is 10%～20%, and the limited oxygen index of precursor is 22～26;
(3) the electron irradiation crosslinking Treatment of halogen-free polypropylene flame redardant precursor
The above-mentioned halogen-free polypropylene flame redardant precursor that makes is carried out sending into behind the boundling electron irradiation equipment to carry out cross-linking radiation and handles, need during irradiation to make tow thickness less than 2mm by shaping device, the irradiation metering is at 50～400kGy, fiber is reeled behind irradiation, obtain the halogen-free polypropylene flame redardant fibrous finished product, the fiber number of gained finished fiber is 0.5～100dtex, and intensity is 2～9cN/dtex; Extension at break is 5～18%; The limited oxygen index of fiber is 28～34;
Expansion type flame retardant is the expanding fire retardant of Compositional type or the expanding fire retardant of molecule-type, and the expanding fire retardant of Compositional type is formed by acid source, carbon source, source of the gas three configuration; Wherein acid source is phosphate or phosphate, is preferably APP, polyphosphoric acid melamine or triphenyl phosphate; Carbon source is pentaerythrite, neopentyl glycol or ethylene glycol; Be preferably pentaerythrite; Source of the gas is melamine, urea, dicyandiamide or cyanuric acid; Be preferably melamine; Three's ratio is 4～8 parts of acid sources, 0.5～2 part of carbon source, 2～4 parts of sources of the gas; The expanding fire retardant of molecule-type is the phosphate molecule-type expanding fire retardant that contains circulus; Preferred molecular structure is as follows:
Molecule-type expanding fire retardant I or
Molecule-type expanding fire retardant II or
Among the molecule-type expanding fire retardant III any.
Additive is dispersant, antioxidant and ultra-violet absorber;
Dispersant is ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-vinyl acetate copolymer (EVA), at least a in polyethylene (PE) wax and polypropylene (PP) wax.；
Antioxidant is at least a in antioxidant 1010, composite antioxidant 215 and the composite antioxidant 225;
Ultra-violet absorber is the hydroxy-phenyl benzotriazole class;
Electron irradiation equipment is continous mode electron irradiation process units or low energy electron beam irradiation device.
Performance test:
The tensile property of fiber adopts single fiber electronics tensometer to test, and the combustibility of fiber adopts the limited oxygen index instrument to test, and the oxygen index (OI) method of testing is carried out with reference to GB/T 2406-93 standard.Test result shows that the intensity of the polypropylene fibre precursor that the adding halogen-free expansion fire retardant makes is at 5～10cN/dtex, and extension at break is 10%～20%, and limited oxygen index is 22～26.Intensity and extension at break through the crosslinked back of electron irradiation expandable flame retardant polypropylene fibre descend to some extent, but limited oxygen index increases substantially, and fibre strength is 2～9cN/dtex; Extension at break is 5～18%; The limited oxygen index of fiber is 28～34.
The present invention has following advantage:
1. the expansion type flame retardant addition is significantly less than the needed amount of the conventional fire-retardant PP fiber of spinning, has reduced the preparation cost of fiber.And lower fire retardant addition is less to spinning process influence, fracture of wire and fire retardant seldom occur and situation such as separates out.
2. the fire-retardant PP fiber that makes has the characteristic of halogen-free flameproof, and good flame resistance.Smokeless substantially during product contact flame combustion, the limited oxygen index of fiber can reach more than 30.
3. fibre strength is higher, can reach more than the 7cN/dtex, is higher than the fire-retardant PP fiber of the equal oxygen index (OI) of conventional method gained, applied range.
The specific embodiment
Below by example the present invention is specifically described; be necessary to be pointed out that at this following examples only are used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can content make some nonessential improvement and adjustment to the present invention according to the present invention.
Embodiment 1
With 55 kilograms of PP sections, 35 kilograms of Compositional type expanding fire retardant (APP: pentaerythrite: melamine=6: 1: 3), 8.5 kilogram EVA, 1.48 kilogram antioxidant 1010,0.02 kilogram hydroxy-phenyl benzotriazole class ultra-violet absorber mixes the back and carries out mixing granulation by double screw extruder for 210～230 ℃ in temperature, obtains PP expandable flame retardant master batch.With 100kg fire-retardant master granule and 700kgPP section carrying out co-blended spinning, extruder temperature is controlled at 195～230 ℃, measuring pump specification 0.6ml/r, measuring pump revolution 10r/min, spinneret orifice diameter 0.6mm, hole count 16, spray silk speed 133m/min, winding speed 300m/min, the back tow of reeling carries out 4 times of hot drawing-offs, obtains fire-retardant PP precursor.With being shaped to the tow sheet that thickness is 1mm behind the precursor boundling, send into low energy electron beam irradiation equipment continuously and carry out continuous irradiation, irradiation metering 150kGy rolls up on the tow behind the irradiation and obtains finished product halogen-free flameproof polypropylene fibre.This fibre number 2.5dtex, intensity 5cN/dtex, extension at break 12.5%, limited oxygen index 29.
Embodiment 2
With 60 kilograms of PP sections, 33 kilograms of Compositional type expanding fire retardant (triphenyl phosphates: neopentyl glycol: melamine=8: 0.5: 1.5), 6 kilograms of PP waxes, 0.98 kilogram composite antioxidant 215,0.02 kilogram hydroxy-phenyl benzotriazole class ultra-violet absorber mixes the back and carries out mixing granulation by double screw extruder for 210～230 ℃ in temperature, obtains PP expandable flame retardant master batch.With 100kg fire-retardant master granule and 300kgPP section carrying out co-blended spinning, extruder temperature is controlled at 195～230 ℃, measuring pump specification 0.6ml/r, measuring pump revolution 10r/min, spinneret orifice diameter 0.6mm, hole count 16, spray silk speed 133m/min, winding speed 300m/min, the back tow of reeling carries out 4 times of hot drawing-offs, obtains fire-retardant PP precursor.With being shaped to the tow sheet that thickness is 1mm behind the precursor boundling, send into low energy electron beam irradiation equipment continuously and carry out continuous irradiation, irradiation metering 50kGy rolls up on the tow behind the irradiation and obtains finished product halogen-free flameproof polypropylene fibre.This fibre number 2.4dtex, intensity 2.5cN/dtex, extension at break 13.5%, limited oxygen index 28.
Embodiment 3
With 50 kilograms of PP sections, 40 kilograms of Compositional type expanding fire retardant (polyphosphoric acid melamines: pentaerythrite: melamine=7: 1: 2), 8.6 kilogram PP wax, 1.38 kilogram composite antioxidant 225,0.02 kilogram hydroxy-phenyl benzotriazole class ultra-violet absorber mixes the back and carries out mixing granulation by double screw extruder for 210～230 ℃ in temperature, obtains PP expandable flame retardant master batch.With 100kg fire-retardant master granule and 800kgPP section carrying out co-blended spinning, extruder temperature is controlled at 195～230 ℃, measuring pump specification 0.6ml/r, measuring pump revolution 10r/min, spinneret orifice diameter 0.8mm, hole count 8, spray silk speed 149m/min, winding speed 400m/min, the back tow of reeling carries out 3 times of hot drawing-offs, obtains fire-retardant PP precursor.With being shaped to the tow sheet that thickness is 1mm behind the precursor boundling, send into low energy electron beam irradiation equipment continuously and carry out continuous irradiation, irradiation metering 400kGy rolls up on the tow behind the irradiation and obtains finished product halogen-free flameproof polypropylene fibre.This fibre number 5dtex, intensity 2.7cN/dtex, extension at break 11.6%, limited oxygen index 33.
Embodiment 4
With 30 kilograms of PP sections, 68.5 kilogram molecule-type expanding fire retardant I, 1.48 215,0.02 kilograms of hydroxy-phenyl benzotriazole classes of kilogram composite antioxidant ultra-violet absorber mixes the back and carries out mixing granulation by double screw extruder for 210～230 ℃ in temperature, obtains PP expandable flame retardant master batch.With 100kg fire-retardant master granule and 900kgPP section carrying out co-blended spinning, extruder temperature is controlled at 195～230 ℃, measuring pump specification 0.6ml/r, measuring pump revolution 10r/min, spinneret orifice diameter 0.4mm, hole count 36, spray silk speed 133m/min, winding speed 400m/min, the back tow of reeling carries out 2 times of hot drawing-offs, obtains fire-retardant PP precursor.With being shaped to the tow sheet that thickness is 1mm behind the precursor boundling, send into low energy electron beam irradiation equipment continuously and carry out continuous irradiation, irradiation metering 200kGy rolls up on the tow behind the irradiation and obtains finished product halogen-free flameproof polypropylene fibre.This fibre number 1.6dtex, intensity 7.2cN/dtex, extension at break 9.5%, limited oxygen index 32.
Embodiment 5
With 30 kilograms of PP sections, 68.5 kilogram molecule-type expanding fire retardant II, 1.48 225,0.02 kilograms of hydroxy-phenyl benzotriazole classes of kilogram composite antioxidant ultra-violet absorber mixes the back and carries out mixing granulation by double screw extruder for 210～230 ℃ in temperature, obtains PP expandable flame retardant master batch.With 100kg fire-retardant master granule and 800kgPP section carrying out co-blended spinning, extruder temperature is controlled at 195～230 ℃, measuring pump specification 0.6ml/r, measuring pump revolution 10r/min, spinneret orifice diameter 0.6mm, hole count 8, spray silk speed 265m/min, winding speed 400m/min, the back tow of reeling carries out 2 times of hot drawing-offs, obtains fire-retardant PP precursor.With being shaped to the tow sheet that thickness is 1mm behind the precursor boundling, send into low energy electron beam irradiation equipment continuously and carry out continuous irradiation, irradiation metering 300kGy rolls up on the tow behind the irradiation and obtains finished product halogen-free flameproof polypropylene fibre.This fibre number 7.5dtex, intensity 2.8cN/dtex, extension at break 12.3%, limited oxygen index 34.
Embodiment 6
With 30 kilograms of PP sections, 68.5 kilogram molecule-type expanding fire retardant III, 1.48 1010,0.02 kilograms of hydroxy-phenyl benzotriazole classes of kilogram composite antioxidant ultra-violet absorber mixes the back and carries out mixing granulation by double screw extruder for 210～230 ℃ in temperature, obtains PP expandable flame retardant master batch.With 100kg fire-retardant master granule and 700kgPP section carrying out co-blended spinning, extruder temperature is controlled at 195～230 ℃, measuring pump specification 0.6ml/r, measuring pump revolution 10r/min, spinneret orifice diameter 0.4mm, hole count 36, spray silk speed 133m/min, winding speed 400m/min, the back tow of reeling carries out 2 times of hot drawing-offs, obtains fire-retardant PP precursor.With being shaped to the tow sheet that thickness is 1mm behind the precursor boundling, send into low energy electron beam irradiation equipment continuously and carry out continuous irradiation, irradiation metering 150kGy rolls up on the tow behind the irradiation and obtains finished product halogen-free flameproof polypropylene fibre.This fibre number 1.6dtex, intensity 5.4cN/dtex, extension at break 10.3%, limited oxygen index 32.5.
Claims (7)
1. halogen-free polypropylene flame redardant fiber preparation method is characterized in that this method may further comprise the steps:
(1) preparation of halogen-free expansion type flame-proof master batch
With polypropylene chip 30～60 weight portions, expansion type flame retardant 30～68.5 weight portions and additive 1.5～10 weight portions in double screw extruder, in 210～230 ℃ of melting mixing extruding pelletizations of temperature, obtain the expansion type flame-retarding master batch together;
(2) preparation of halogen-free polypropylene flame redardant precursor
With the above-mentioned fire-retardant master granule that makes 10～25 weight portions with after polypropylene chip 75～90 weight portions mix, carry out spinning by melt spinning machine, spinning technique is identical with conventional production of polypropylene fibers technology, according to application requirements, the fiber number that spinning is made the polypropylene precursor is controlled at 0.5～100dtex, the intensity of precursor is at 5～10cN/dtex, and the extension at break of precursor is 10%～20%, and the limited oxygen index of precursor is 22～26;
(3) the electron irradiation crosslinking Treatment of halogen-free polypropylene flame redardant precursor
The above-mentioned halogen-free polypropylene flame redardant precursor that makes is carried out sending into behind the boundling electron irradiation equipment to carry out cross-linking radiation and handles, need during irradiation to make tow thickness less than 2mm by shaping device, the irradiation metering is at 50～400kGy, fiber is reeled and is obtained finished product halogen-free polypropylene flame redardant precursor behind irradiation, the fiber number of gained finished fiber is 0.5～100dtex, and intensity is 2～9cN/dtex; Extension at break is 5～18%; The limited oxygen index of fiber is 28～34.
2. halogen-free polypropylene flame redardant fiber preparation method according to claim 1 is characterized in that expansion type flame retardant is the expanding fire retardant of Compositional type or the expanding fire retardant of molecule-type, and the expanding fire retardant of Compositional type is formed by acid source, carbon source, source of the gas three configuration; Wherein acid source is APP, polyphosphoric acid melamine or triphenyl phosphate; Carbon source is pentaerythrite, neopentyl glycol or ethylene glycol; Source of the gas is melamine, urea, dicyandiamide or cyanuric acid; The expanding fire retardant of molecule-type is:
Molecule-type expanding fire retardant I or
Molecule-type expanding fire retardant II or
Among the molecule-type expanding fire retardant III any.
3. halogen-free polypropylene flame redardant fiber preparation method according to claim 1 is characterized in that additive is dispersant, antioxidant and ultra-violet absorber.
4. as halogen-free polypropylene flame redardant fiber preparation method as described in the claim 3, it is characterized in that dispersant is ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-vinyl acetate copolymer, at least a in PE wax and the PP wax.
5. as halogen-free polypropylene flame redardant fiber preparation method as described in the claim 3, it is characterized in that antioxidant is at least a in antioxidant 1010, composite antioxidant 215 and the composite antioxidant 225.
6. as halogen-free polypropylene flame redardant fiber preparation method as described in the claim 3, it is characterized in that ultra-violet absorber is the hydroxy-phenyl benzotriazole class.
7. halogen-free polypropylene flame redardant fiber preparation method according to claim 1 is characterized in that electron irradiation equipment is continous mode electron irradiation process units or low energy electron beam irradiation device.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336970A (en) * | 2011-09-30 | 2012-02-01 | 中山市纳普工程塑料有限公司 | Polypropylene composite material incombustible for 850 DEG C glowing filament and production method thereof |
| CN102560747A (en) * | 2011-12-11 | 2012-07-11 | 武汉纺织大学 | Preparation method of durable low-smoke halogen-free flame-retardant polyacrylonitrile fiber |
| CN102732985A (en) * | 2012-06-26 | 2012-10-17 | 常州灵达特种纤维有限公司 | Preparation method of halogen free flame retardation polypropylene bulked filament |
| CN103173884A (en) * | 2011-12-21 | 2013-06-26 | 上海杰事杰新材料(集团)股份有限公司 | Halogen-free flame-retardant polypropylene fiber and preparation method thereof |
| CN103289178A (en) * | 2011-12-29 | 2013-09-11 | 青岛科技大学 | Halogen-free flame retardant ethylene and vinyl acetate composite material and preparation method thereof |
| CN103724786A (en) * | 2013-12-12 | 2014-04-16 | 扬州大学 | Halogen-free intumescent flame retardant EVA special material and preparation method thereof |
| CN105507012A (en) * | 2016-01-27 | 2016-04-20 | 佛山佛塑科技集团股份有限公司 | Method for manufacturing thickened, reinforced, flame-retardant and durable polyethylene woven cloth and corresponding product |
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| CN114457455A (en) * | 2022-03-25 | 2022-05-10 | 广州俊麒无纺布企业有限公司 | Heat-resistant flame-retardant non-woven fabric and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101418099A (en) * | 2008-12-02 | 2009-04-29 | 上海金发科技发展有限公司 | Natural fiber reinforcement halogen-free flame retardant polypropylene composite material and preparation method thereof |
| KR100997052B1 (en) * | 2010-03-08 | 2010-11-29 | (주)폴리원테크놀로지 | Master batch composite for polypropylene flame retardant corrugated pipe |
| CN102002770A (en) * | 2010-09-20 | 2011-04-06 | 四川大学 | Preparation method of halogen-free flame retardant high-intensity polyvinyl alcohol fibers |
-
2011
- 2011-05-11 CN CN 201110120927 patent/CN102146596B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101418099A (en) * | 2008-12-02 | 2009-04-29 | 上海金发科技发展有限公司 | Natural fiber reinforcement halogen-free flame retardant polypropylene composite material and preparation method thereof |
| KR100997052B1 (en) * | 2010-03-08 | 2010-11-29 | (주)폴리원테크놀로지 | Master batch composite for polypropylene flame retardant corrugated pipe |
| CN102002770A (en) * | 2010-09-20 | 2011-04-06 | 四川大学 | Preparation method of halogen-free flame retardant high-intensity polyvinyl alcohol fibers |
Non-Patent Citations (5)
| Title |
|---|
| 《中国优秀硕士学位论文全文数据库》 20080915 何庆东 《膨胀型阻燃聚丙烯及其母粒的性能研究》 正文56-59页 1-7 , 2 * |
| 《中国优秀硕士学位论文全文数据库》 20091115 李艳涛 《高效膨胀型阻燃聚丙烯材料的制备与性能研究》 正文第6页第二段-第8页 1-7 , 2 * |
| 《中国核科学技术进展报告第一卷》 20091130 刘伟等 《辐照接枝阻燃涤纶纤维的开发》 正文第1-4页 1-7 , 2 * |
| 《塑料助剂》 20081020 王丽红等 《蓄电池专用耐候环保阻燃ABS母粒的研制 》 正文第2页-第3页 1-7 , 2 * |
| 《广西化纤通讯》 19970630 王冼燕等 《阻燃聚丙烯长丝的试制》 正文第1页-第4页 1-7 , 2 * |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336970A (en) * | 2011-09-30 | 2012-02-01 | 中山市纳普工程塑料有限公司 | Polypropylene composite material incombustible for 850 DEG C glowing filament and production method thereof |
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| CN103289178A (en) * | 2011-12-29 | 2013-09-11 | 青岛科技大学 | Halogen-free flame retardant ethylene and vinyl acetate composite material and preparation method thereof |
| CN102732985A (en) * | 2012-06-26 | 2012-10-17 | 常州灵达特种纤维有限公司 | Preparation method of halogen free flame retardation polypropylene bulked filament |
| CN103724786A (en) * | 2013-12-12 | 2014-04-16 | 扬州大学 | Halogen-free intumescent flame retardant EVA special material and preparation method thereof |
| CN105507012A (en) * | 2016-01-27 | 2016-04-20 | 佛山佛塑科技集团股份有限公司 | Method for manufacturing thickened, reinforced, flame-retardant and durable polyethylene woven cloth and corresponding product |
| CN106498542A (en) * | 2016-11-22 | 2017-03-15 | 浙江金霞新材料科技有限公司 | One kind is without dye environmental protection flame retardant fiber and preparation method thereof |
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| CN112813521B (en) * | 2019-10-23 | 2022-03-29 | 广东柏奴斯股份有限公司 | Flame-retardant antistatic fabric for coal mine industry |
| CN112831861B (en) * | 2019-10-23 | 2022-05-17 | 东营红星劳保用品有限责任公司 | Flame-retardant antistatic fabric for coal mine industry |
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| CN114457455A (en) * | 2022-03-25 | 2022-05-10 | 广州俊麒无纺布企业有限公司 | Heat-resistant flame-retardant non-woven fabric and preparation method thereof |
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