CN102286171A - Blow molding type halogen-free flame-retardant polypropylene material - Google Patents
Blow molding type halogen-free flame-retardant polypropylene material Download PDFInfo
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Abstract
The invention provides a blow molding type halogen-free flame-retardant polypropylene material, which comprises the following components in part by weight: 100 parts of polypropylene, 40 to 85 parts of phosphorus-nitrogen series expanded halogen-free composite flame retardant, 3 to 20 parts of resin modifier, 0.05 to 0.5 part of pigment, 0.4 to 2.0 parts of antioxidant, 0.3 to 2.0 parts of ultraviolet absorbent, 0.3 to 2.0 parts of light stabilizer, and 1.0 to 3.0 parts of other processing aids. The material has good tensile strength, high impact strength, good low-temperature performance and excellent flame-retardant performance, and is particularly suitable for hollow blow molding type small and large components of automobiles, furniture and the like.
Description
Technical field
The present invention is relevant with anti-flaming polypropylene material.
Background technology
Chinese patent 101704973A discloses a kind of in light weight, impact-resistant polypropylene flame redardant and preparation method thereof, its components based on weight percentage comprises polypropylene 70%～80%, fire retardant halogen aliphatic phosphate 6%～10%, weisspiessglanz 3%～8%, toughner 5%～8%, nano-kaoline 5%～10%, oxidation inhibitor 0.1%～0.5%, antioxygen assistant agent 0.1%～0.5%, hexenyl bis-stearamides 0.1%～1%.Wherein, the matrix resin of described anti-flaming polypropylene material is exactly traditional common PP resin, after flame-retardant modified, melting index is 8 g/10min, can not satisfy the processing request of hollow blow molding, only be applicable to injection moulding processing, the tensile strength of this anti-flaming polypropylene material is 28.5MPa, and the socle girder notched Izod impact strength is 6.8KJ/M
2, vertical combustion reaches the UL94V0 level, and weak point is that shock strength is lower, and toughness is relatively poor, can not satisfy v-notch shock strengths such as furniture seat greater than 8 KJ/M
2Requirement.What this material fire retardant was selected for use on the other hand is the composite flame-retardant agent of halogen aliphatic phosphate and weisspiessglanz, and still belonging to halogen antimony is fire-retardant category, exists the amount of being fuming big when burning in the scene of a fire, produces defectives such as toxic smog and corrosion processing equipment.
Summary of the invention
The objective of the invention is to overcome above-mentioned shortcoming, provide that a kind of tensile strength is good, impact strength high and low temperature performance is good, flame retardant properties is good, is specially adapted to the blowing type halogen-free anti-flaming polypropylene material of the small-sized and large component of hollow blow molding.
Its set of dispense composition and division in a proportion example of blowing type halogen-free anti-flaming polypropylene material of the present invention is by weight:
Polypropylene 100,
Phosphorus-nitrogen series intumescent Halogenless composite fire retardant 40～85,
Modifier 3～20,
Pigment 0.05～0.5,
Oxidation inhibitor 0.4～2.0,
UV light absorber 0.3～2.0,
Photostabilizer 0.3～2.0,
Other processing aid 1.0～3.0.
Wherein, polypropylene is to melt the acrylic resin A that refers to 0.3～1.0g/10min, melts the acrylic resin B that refers to 1.0～3.0g/10min, melts a kind of or its melt blending body among the acrylic resin C that refers to 0.3～1.5 g/10min; The phosphorus-nitrogen series intumescent Halogenless composite fire retardant is the mixture of basic fire retardant and fire retarding synergist, and its cooperation ratio is basic fire retardant by weight: fire retarding synergist=35～70 ︰ 0.5～15.Wherein, basic fire retardant is coated ammonium polyphosphate, the mixture that becomes charcoal polymkeric substance, trimeric cyanamide and derivative thereof, and the cooperation ratio is to coat poly-phosphorus acid ammonium ︰ to become poly-thing ︰ trimeric cyanamide and derivative=25～60 ︰, 5～25 ︰ 0.5～15 thereof of closing of charcoal by weight.Fire retarding synergist is one or more in whiteness microcapsule red phosphorus fire retardant, molecular sieve, kaolin, clay, vermiculite, the nano imvite that organises, zinc borate, the organic silicon fibre retardant.Wherein, char-forming agent is tetramethylolmethane, Dipentaerythritol, tripentaerythritol, tetramethylolmethane phosphoric acid salt, starch, resol, nylon 6, thermoplastic polyurethane.Trimeric cyanamide and derivative thereof are trimeric cyanamide, melamine cyanurate, melamine phosphate, melamine pyrophosphate, dipentaerythritol triguaiacyl phosphate melamine salt, phosphoric acid bis(pentaerythritolester) melamine salt, dipentaerythritol bis phosphoric acid two hydrogen ester melamine salts; Modifier is one or more in ethylene-vinyl acetate, maleic anhydride inoculated polypropylene, maleic anhydride grafted polyethylene, the maleic anhydride grafted ethene-octene copolymer; Oxidation inhibitor is one or more in four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester, the Tyox B (DLTP); UV light absorber is Octabenzone, 2-(2 ＇-hydroxyl-3 ＇, 5 one di-tert-butyl-phenyls) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-a kind of in the 5-chlorinated benzotriazole; Photostabilizer is oligomeric-[[6-[(1,1,3,3-tetramethyl butyl)-imino-]-1,3,5-triazine-2,4-two bases] [2-(2,2,6, the 6-tetramethyl-piperidyl)-amino]-hexylidene-[4-(2,2,6,6-tetramethyl-piperidyl)-imino-]], poly-(1-hydroxyethyl-2,2,6,6-tetramethyl--4-hydroxy piperidine) succinate, sebacic acid two (2,2,6,6-tetramethyl piperidine) one or more in the ester; Other processing aid is polyethylene wax, Poly Propylene Wax, N, one or more in N '-ethylene bis stearamide, calcium stearate, Zinic stearas, the Magnesium Stearate.
The advantage of blowing type halogen-free anti-flaming polypropylene material of the present invention is, one, matrix resin is a kind of or its melt blending body among acrylic resin A, acrylic resin B and the acrylic resin C, it is poor to preferably resolve traditional anti-flaming polypropylene material melt strength, problem such as difficult forming during aspects such as hollow blow molding tun, furniture, simultaneously, overcome again that traditional anti-flaming polypropylene material poor tensile strength, impact strength are poor, problem such as easy embrittlement under the low temperature.
Two, the phosphorus-nitrogen series intumescent Halogenless composite fire retardant selected for use of the present invention is the composite expansion type halogen-free composite flame-retardant agent that forms of basic fire retardant and fire retarding synergist, this fire retardant integrates multiple fire retardant mechanism, help bringing into play the synergy between fire retardant, both can improve the Flame Retardancy energy, simultaneously can reduce addition again, cause the mechanical property and the combustionproperty of polypropylene flame redardant product further to improve, and satisfied environmental protection, fire-retardant requirement.Three,, make the dispersiveness of fire retardant in polypropylene material obtain remarkable improvement, effectively coordinated halogen-free anti-flaming polypropylene material high strength, high tenacity requirement by adding modifier.Four, blowing type anti-flaming polypropylene material oxygen index of the present invention 〉=32.6%, vertical combustion reach UL94 V0 level, tensile strength 〉=25MPa, elongation at break 〉=150%, flexural strength 〉=35MPa, and unnotched impact strength reaches 〉=100KJ/M
2, v-notch shock strength 〉=11.5 KJ/M
2, smoke density grade (SDR) is 37, has both reached polypropylene flame redardant goods high strength, high tenacity requirement, has satisfied the fire-retardant requirement of material simultaneously again.
Embodiment
Embodiment 1:Set of dispense than by weight is:
Acrylic resin A 100
Phosphorus-nitrogen series intumescent Halogenless composite fire retardant 60.5
Modifier 15
(ethylene-vinyl acetate, maleic anhydride grafted ethene-octene copolymer)
Oxidation inhibitor 0.4
Four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester
UV light absorber 1
(Octabenzone)
Photostabilizer 1
Oligomeric-[[6-[(1,1,3,3-tetramethyl butyl)-imino-]-1,3,5-triazines-2,4-two bases] [2-(2,2,6, the 6-tetramethyl-piperidyl)-amino]-hexylidene-[4-(2,2,6, the 6-tetramethyl-piperidyl)-imino-]]
Pigment 0.3
Processing aid 2
(polyethylene wax, calcium stearate)
Wherein, the proportioning parts by weights meter of composite flame-retardant agent is:
The poly-Lin Suan An ︰ char-forming agent (tetramethylolmethane, starch, tetramethylolmethane phosphoric acid salt) of basic fire retardant 60(: melamine derivative (trimeric cyanamide, melamine phosphate, dipentaerythritol triguaiacyl phosphate melamine salt=35 ︰, 15 ︰ 10)
Combustion synergist (vermiculite) 0.5
Above-mentioned raw materials is mixed through high speed mixer, again through twin screw extruder melt extrude, tie rod, cooling, pelletizing and get.Six sections processing temperatures of twin screw extruder are respectively 155～160 ℃, 160～165 ℃, 170～175 ℃, 175～185 ℃, 175～185 ℃, 155～160 ℃.Experiment shows that the tensile strength of this experiment polypropylene flame redardant material is 26.5MPa, and elongation at break is 218.6%, and unnotched impact strength reaches 〉=114KJ/M
2, v-notch shock strength 〉=13.5 KJ/M
2, flexural strength 〉=36MPa oxygen index is 32.1%, and the horizontal vertical combustion experiment is by UL-94 V0 level, and smoke density grade (SDR) is 35.
Embodiment 2:Component is by weight:
Acrylic resin A 70
Acrylic resin B 30
Composite flame-retardant agent 85
Modifier 20
(maleic anhydride inoculated polypropylene, ethylene-vinyl acetate)
Oxidation inhibitor 1
(four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester,
Tyox B)
UV light absorber 0.3
2-(2 ＇-hydroxyl-3 ＇, 5 one di-tert-butyl-phenyls) benzotriazole
Photostabilizer 2
(poly-(1-hydroxyethyl-2,2,6,6-tetramethyl--4-hydroxy piperidine) succinate, oligomeric-[[6-[(1,1,3, the 3-tetramethyl butyl)-imino-]-1,3,5-triazine-2,4-two bases] [2-(2,2,6, the 6-tetramethyl-piperidyl)-amino]-hexylidene-[4-(2,2,6, the 6-tetramethyl-piperidyl)-imino-]] pigment 0.5
Other processing aid 3
(Poly Propylene Wax, calcium stearate, Zinic stearas)
Wherein, the cooperation parts by weights meter of composite flame-retardant agent is:
Basic fire retardant: 70
(poly-Lin Suan An ︰ char-forming agent (Dipentaerythritol, thermoplastic polyurethane) ︰: melamine derivative (melamine pyrophosphate)=60 ︰ 9.5 ︰ 0.5)
Fire retarding synergist 15
(molecular sieve, whiteness red phosphorus, organic nano imvite, kaolin)
Above-mentioned raw materials taken by weighing by weight after high speed mixer mixes, again through twin screw extruder melt extrude, tie rod, cooling, pelletizing and get.Six sections processing temperatures of twin screw extruder are respectively 155～160 ℃, 160～165 ℃, 170～175 ℃, 175～185 ℃, 175～185 ℃, 155～160 ℃.Experiment shows that the tensile strength of this experiment polypropylene flame redardant reaches 25.2MPA, elongation at break reaches 166.7%, and unnotched impact strength reaches 〉=100KJ/M
2, v-notch shock strength 〉=11.5 KJ/M
2, flexural strength 〉=35MPa oxygen index reaches 34.0%, the horizontal vertical burning reaches UL 94 V0 levels, and smoke density grade (SDR) is 37.。
Embodiment 3:Set of dispense than by weight is:
Acrylic resin A 50
Acrylic resin B 20
Acrylic resin C 30
Composite flame-retardant agent 40
Modifier 3
Maleic anhydride grafted polyethylene
Oxidation inhibitor 2.0
(four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester,
Three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester, Tyox B)
UV light absorber 2
2-(2 ＇-hydroxyl-3 ＇, 5 ＇, one di-tert-butyl-phenyl)-5-chlorinated benzotriazole
Photostabilizer 0.3
Two (2,2,6, the 6-tetramethyl piperidine) esters of sebacic acid
Pigment 0.05
Processing aid 1
(polyethylene wax, N, N '-ethylene bis stearamide, calcium stearate) wherein, composite flame-retardant agent parts by weights meter is:
Basic fire retardant 35
(poly-Lin Suan An ︰ char-forming agent (tripentaerythritol, nylon 6) ︰ melamine derivatives (melamine cyanurate, phosphoric acid bis(pentaerythritolester) melamine salt)=25 ︰, 5 ︰ 5)
Fire retarding synergist 5
(clay, molecular sieve, vermiculite, organosilicon)
Above-mentioned raw materials taken by weighing by weight after high speed mixer mixes, again through twin screw extruder melt extrude, tie rod, cooling, pelletizing and get.Six sections processing temperatures of twin screw extruder are respectively 155～160 ℃, 160～165 ℃, 170～175 ℃, 175～185 ℃, 175～185 ℃, 155～160 ℃.Experiment shows that the tensile strength of this experiment polypropylene flame redardant material is 27.5MPa, and elongation at break is 367.3%, and unnotched impact strength reaches 〉=130KJ/M
2, v-notch shock strength 〉=14.5 KJ/M
2, flexural strength 〉=37.5MPa oxygen index is 30.0%, and the horizontal vertical combustion experiment is by UL-94 V0 level, and smoke density grade (SDR) is 15.。
Embodiment 4:Set of dispense than by weight is:
Acrylic resin B 60
Acrylic resin C 40
Modifier 10
(maleic anhydride grafted polyethylene, maleic anhydride grafted ethene-octene copolymer)
Composite flame-retardant agent 75
Oxidation inhibitor 1.5
(four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester)
UV light absorber 1.5
(Octabenzone, 2-(2 ＇-hydroxyl-3 ＇, 5 one di-tert-butyl-phenyls) benzotriazole)
Photostabilizer 1.5
(two (2,2,6, the 6-tetramethyl piperidine) esters of sebacic acid, oligomeric-[[6-[(1,1,3, the 3-tetramethyl butyl)-imino-]-1,3,5-triazines-2,4-two bases] [2-(2,2,6, the 6-tetramethyl-piperidyl)-amino]-hexylidene-[4-(2,2,6, the 6-tetramethyl-piperidyl)-imino-]]
Pigment 0.15
Other processing aid 2.5
(polyethylene wax, N, N '-ethylene bis stearamide, calcium stearate)
Wherein, composite flame-retardant agent parts by weights meter is:
Basic fire retardant 65
(coating poly-phosphorus acid ammonium ︰ char-forming agent (tetramethylolmethane, resol) ︰ melamine derivative (trimeric cyanamide, dipentaerythritol bis phosphoric acid two hydrogen ester melamine salts)=25 ︰, 25 ︰ 15)
Fire retarding synergist 10
(clay, zinc borate, nano imvite, organosilicon)
Above-mentioned raw materials taken by weighing by weight after high speed mixer mixes, again through twin screw extruder melt extrude, tie rod, cooling, pelletizing and get.Six sections processing temperatures of twin screw extruder are respectively 155～160 ℃, 160～165 ℃, 170～175 ℃, 175～185 ℃, 175～185 ℃, 155～160 ℃.Experiment shows that the tensile strength of this experiment CABLE MATERIALS is 25.8MPa, and elongation at break is 215.2%, and unnotched impact strength reaches 〉=108KJ/M
2, v-notch shock strength 〉=12.5 KJ/M
2, flexural strength 〉=36.2MPa oxygen index is 33.8%, and the horizontal vertical combustion experiment is by UL-94 V0 level, and smoke density grade (SDR) is 32.
Claims (6)
1. blowing type halogen-free anti-flaming polypropylene material is characterized in that component cooperates ratio to be by weight:
Polypropylene 100,
Phosphorus-nitrogen series intumescent Halogenless composite fire retardant 40～85,
Modifier 3～20,
Pigment 0.05～0.5,
Oxidation inhibitor 0.4～2.0,
UV light absorber 0.3～2.0,
Photostabilizer 0.3～2.0,
Other processing aid 1.0～3.0,
Wherein, polypropylene is to melt the acrylic resin A that refers to 0.3～1.0g/10min,, melt the acrylic resin B that refers to 1.0～3.0g/10min, melt a kind of or its melt blending body among the acrylic resin C that refers to 0.3～1.5 g/10min; The phosphorus-nitrogen series intumescent Halogenless composite fire retardant is the mixture of basic fire retardant and fire retarding synergist, its cooperation ratio is basic fire retardant by weight: fire retarding synergist=35～70 ︰ 0.5～15, wherein, basic fire retardant is a coated ammonium polyphosphate, become the charcoal polymkeric substance, the mixture of trimeric cyanamide and derivative thereof, the cooperation ratio is to coat poly-phosphorus acid ammonium ︰ to become poly-thing ︰ trimeric cyanamide and derivative=25～60 ︰, 5～25 ︰ 0.5～15 thereof of closing of charcoal by weight, wherein the polymerization degree of coated ammonium polyphosphate is greater than 1000, and fire retarding synergist is the whiteness microcapsule red phosphorus fire retardant, molecular sieve, kaolin, clay, vermiculite, nano imvite organises, zinc borate, in the organic silicon fibre retardant one or more.
2. blowing type halogen-free anti-flaming polypropylene material as claimed in claim 1 is characterized in that modifier is one or more in ethylene-vinyl acetate, maleic anhydride inoculated polypropylene, maleic anhydride grafted polyethylene, the maleic anhydride grafted ethene-octene copolymer.
3. blowing type halogen-free anti-flaming polypropylene material as claimed in claim 1, it is characterized in that oxidation inhibitor is one or more in four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester, the Tyox B.
4. blowing type halogen-free anti-flaming polypropylene material as claimed in claim 1, it is characterized in that UV light absorber is Octabenzone (UV531), 2-(2 ＇-hydroxyl-3 ＇, 5 one di-tert-butyl-phenyls) benzotriazole (UV328), 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-a kind of in the 5-chlorinated benzotriazole (UV327).
5. blowing type halogen-free anti-flaming polypropylene material as claimed in claim 1, it is characterized in that photostabilizer is oligomeric-[[6-[(1,1,3, the 3-tetramethyl butyl)-and imino-]-1,3,5-triazine-2,4-two bases] [2-(2,2,6, the 6-tetramethyl-piperidyl)-amino]-hexylidene-[4-(2,2,6, the 6-tetramethyl-piperidyl)-imino-]], poly-(1-hydroxyethyl-2,2,6,6-tetramethyl--4-hydroxy piperidine) succinate, sebacic acid two (2,2,6,6-tetramethyl piperidine) one or more in the ester.
6. blowing type halogen-free anti-flaming polypropylene material as claimed in claim 1, it is characterized in that other processing aid is polyethylene wax, Poly Propylene Wax, N, one or more in N '-ethylene bis stearamide, calcium stearate, Zinic stearas, the Magnesium Stearate.
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| 《塑料包装》 20090215 王丽新 "吹塑用聚丙烯的开发及应用" 第4页右栏第3段至第9页右栏第3段 1-6 第19卷, 第1期 * |
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| CN109251408A (en) * | 2018-07-19 | 2019-01-22 | 中国科学院宁波材料技术与工程研究所 | A kind of anti-flaming polypropylene composite of high-efficiency environment friendly |
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| CN109370232A (en) * | 2018-10-08 | 2019-02-22 | 东莞市创之源新材料科技有限公司 | A kind of plastics environmentally friendly composite halogen-free fire retardant and preparation method thereof |
| CN110010288A (en) * | 2019-04-04 | 2019-07-12 | 广州澳通电线电缆有限公司 | Crosslinked polyetylene insulated polyolefin jacket zero-halogen low-smoke flame-retardant B1Grade power cable |
| CN110527206A (en) * | 2019-08-15 | 2019-12-03 | 安徽壹石通材料科技股份有限公司 | A kind of preparation and its application of nitrogen-phosphorus-boron expansion type flame retardant |
| CN111253666A (en) * | 2020-04-10 | 2020-06-09 | 常州市塑料厂有限公司 | Production process of hollow blow molding polyethylene barrel |
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| CN112724580A (en) * | 2020-12-22 | 2021-04-30 | 金发科技股份有限公司 | High-fluidity high-impact halogen-free flame-retardant polypropylene material and preparation method and application thereof |
| CN115850864A (en) * | 2022-12-27 | 2023-03-28 | 广东邦凯塑料科技有限公司 | Formula and preparation method of regenerated fireproof flame-retardant plastic |
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