CN104448535A - Modified polypropylene material - Google Patents
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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Abstract
The invention discloses a modified polypropylene material which is characterized by comprising, by weight, 85-90% of polypropylene, 1.0-1.5% of a main fire retardant such as hexabromocyclododecane, 0.2-0.4% of a synergistic fire retardant such as decabromodiphenyl ether, 1.5-2.0% of carbon black, 5-10% of hormite clay such as sepiolite powder, 0.5-2% of an electrostatic agent such as ethylene oxide, 2-5% of shell powder, 0.2-0.5% of a chain scission agent such as a CC initiator of 2,3-dimethyl-2,3-diphenylbutane, 0.2-0.5% of an foaming agent such as 5-phenyl tetrazolium, 0.3-0.5% of a surfactant such as a sodium stearate anionic surfactant, 0.3-0.5% of a coupling agent such as an aluminic acid ester coupling agent, 0.2-0.5% of an anti-oxidant such as 2,6-di-tert-butyl phenol, and 0.1-0.3% of a heat stabilizer such as DSTP. According to the invention, the polypropylene material has excellent weatherability, flame resistance achieving the UL 94V-0 level, good temperature resistance and low temperature impact resistance, good antistatic property and high impact strength.
Description
Technical field
The present invention relates to technical field of composite materials, particularly relate to a kind of modified polypropylene material.
Background technology
Polypropylene good mechanical performance, thermotolerance are good, chemical stability is high, electrical insulating property is excellent, and have good workability, are a kind of general-purpose plastics of excellent combination property.But due to the existence of its saturated hydrocarbon structure and tertiary carbon atom, polypropylene very easily burns and weathering resistance is not good.And toughness and this major defect of shock resistance difference limit its Application Areas as engineering plastics greatly.Traditional toughening modifying method is undertaken blended by PP and rubber, thermoplastics, thermosetting resin etc., but intensity, the rigidity of their often loss material preciousnesses, reduce the dimensional stability of material, thermotolerance and processability.
Halogenated flame retardant addition is few, flame retarding efficiency is high, affect minimum on polymer performance, for the most effective flame-retardant additive of polyolefine material, conventional kind mainly contains ten bromines, TDE, hexabromocyclododecane, eight bromo ether, eight bromine S ethers, three (2,3-dibromopropyl) isocyanic ester (TBC), three (2,2-bis-brooethyl-3-bromopropyl) phosphonates (TTBNP) etc.Carbon black is then a kind of efficiency light stablizer of polyolefine material, high temperature resistant, non-volatile, persistence is strong.But because carbon black and halogenated flame retardant exist certain antagonistic effect, when content of carbon black is higher (>1wt%), obviously can weaken the anti-flaming function of halogenated flame retardant.Thus, for halogen system polypropylene flame redardant, at present mainly on the basis of not adding or adding minute quantity carbon black (<0.5 wt %), by add appropriate UV light absorber, UV quenchers, hindered amine as light stabilizer method improve its weathering resistance.
Disclosed halogen system flame-proof weather-resisting technology at present, its weather-proof technology all have employed UV light absorber and/or hindered amine as light stabilizer, not yet solve only use carbon black as weather-proof properties-correcting agent time, namely, when high carbon black content (>1wt%), the polyacrylic problem of flame-proof weather-resisting how is prepared; And there is following common deficiency, have impact on its use in every field:
1. UV light absorber and hindered amine as light stabilizer are polar organic small molecules, there is saturated, volatilization problems with non-polar polypropylene resin, and under long term ultraviolet effect, the also side reaction such as existence degraded and even day by day Problem of Failure.
2. conventional hindered amine as light stabilizer reacts with bromide fire retardant due to the higher meeting of alkalescence, there is the antagonism problem of weather resisting agent and fire retardant.
3. compared with carbon black, UV light absorber and hindered amine as light stabilizer more expensive.
Shell is a kind of natural biological nano matrix material cheap and easy to get.But the poor compatibility of sea shell micropowder and macromolecular material, not easily disperses.Therefore need with surface-modifying agent process sea shell micropowder, sea shell micropowder is made to be dispersed in polypropylene, increase polyacrylic toughness polypropylene good mechanical performance, thermotolerance is good, chemical stability is high, electrical insulating property is excellent, and there is good workability, be a kind of general-purpose plastics of excellent combination property.
At some chemical enterprise, polypropylene film becomes the wrapping material generally used.At some chemical enterprises, the article deposited also need anti-electrostatic, to avoid fire.Though find have through retrieval ... polypropylene material high temperature resistant, anti-skidding a bit, but lack anlistatig function, actual safe handling can not be met, cause potential accident potential.
The polypropylene material how producing a kind of excellent weather-resistance flame-retardant performance, resistance to voltage, warm erosion-resisting characteristics and mechanical property becomes the technical problem to be solved in the present invention.
Summary of the invention
For solving deficiency of the prior art, the object of the invention is to provide a kind of modified polypropylene material, it is characterized in that, raw material composition according to weight percent is:
Polypropylene 85-90%;
Main flame retardant: hexabromocyclododecane 1.0-1.5%;
Synergistic flame retardant: decabromodiphynly oxide 0.2-0.4%;
Carbon black: 1.5-2.0 %;
Fiber rod stone kind clay: sepiolite powder 5-10%;
Electrostatic agent: oxyethane 0.5-2%;
Oyster shell whiting: 2-5%;
Chain-cutting agent: CC initiator 2,3-dimethyl-2,3-diphenyl butane 0.2-0.5%;
Whipping agent: 5-phenyltetrazole 0.2-0.5%;
Tensio-active agent: sodium stearate anion surfactant 0.3-0.5%;
Coupling agent: aluminate coupling agent 0.3-0.5%;
Oxidation inhibitor: 2,6-di-tert-butylphenol 0.2-0.5%;
Thermo-stabilizer: DSTP 0.1-0.3%.
Above-mentioned a kind of modified polypropylene material, is characterized in that, described polypropylene is homo-polypropylene, and ethylene content is lower than 1%, and melt flow rate (MFR) is 60-90g/10min.
Above-mentioned a kind of modified polypropylene material, is characterized in that, described main flame retardant is one or more in hexabromocyclododecane, TBC, the two tetrabromo phthalimide of ethylene.
Above-mentioned a kind of modified polypropylene material, is characterized in that, described carbon black is thermally oxidized black, and particle diameter is 10-15nm.
Above-mentioned a kind of modified polypropylene material, is characterized in that, described chain-cutting agent is high-temperature initiator, when 235 DEG C, decomposes hardly, when 25 DEG C, and transformation period >6min.
Above-mentioned a kind of modified polypropylene material, is characterized in that, described whipping agent is high-temperature foaming agent, aerial temperature of initial decomposition >235 DEG C, gas production rate >180ml/g.
Above-mentioned a kind of modified polypropylene material, is characterized in that, described tensio-active agent can be zinc octadecanate anion surfactant.
Beneficial effect of the present invention:
By selecting carbon black to be weather-proof properties-correcting agent, select brominated flame-retardant, synergistic flame retardant and high temperature chain-cutting agent and high-temperature foaming agent and use, the Weather-resistant flame-retardant polypropylene composite material that melt blending obtains, weather resistance excellence, flame retardant properties reaches UL94 V-0 level.Polypropylene material is made to have good heat resistance and low-temperature impact performance by adding sepiolite powder.Formula of the present invention with the addition of the polypropylene material that static inhibitor is produced, and has very strong static resistance, can the electrostatic built up of elimination in time, safely has market application foreground widely.Obtain the polypropylene composite material with high-impact by adding oyster shell whiting, it, under the prerequisite of tensile strength of not losing polypropylene matrix, improves polyacrylic resistance to impact shock.Polypropylene prepared by the present invention is a kind of novel material modified, and production process is simple, and production efficiency is high and cost is lower.
Embodiment
Ethylene content is lower than 1%, and melt flow rate (MFR) is the polypropylene 80-90% of 60-90g/10min; Main flame retardant: hexabromocyclododecane 1.0-1.5%; Synergistic flame retardant: decabromodiphynly oxide 0.2-0.4%; Particle diameter is the thermally oxidized black of 10-15nm: 1.5-2.0 %; Fiber rod stone kind clay: sepiolite powder 5-10%; Electrostatic agent: oxyethane 0.5-2%; Oyster shell whiting: 2-5%; When 235 DEG C, decompose hardly, when 25 DEG C, the chain-cutting agent of transformation period >6min: CC initiator 2,3-dimethyl-2,3-diphenyl butane 0.2-0.5%; The whipping agent of aerial temperature of initial decomposition >235 DEG C, gas production rate >180ml/g: 5-phenyltetrazole 0.2-0.5%; Tensio-active agent: sodium stearate anion surfactant 0.3-0.5%; Coupling agent: aluminate coupling agent 0.3-0.5%; Oxidation inhibitor: 2,6-di-tert-butylphenol 0.2-0.5%; Thermo-stabilizer: DSTP 0.1-0.3%.
The component concentration of the formula of embodiment 1-9 and two comparative example of this modified polypropylene composite material is as table one.
The component concentration table of the formula of table one, embodiment 1-9 and two comparative example
Preparation method above-mentioned materials being prepared Weather-resistant flame-retardant polypropylene composite material is as follows:
(1) each component is taken by the weight proportion of formula;
(2) by ethylene content lower than 1%, melt flow rate (MFR) is the polypropylene of 60-90g/10min, hexabromocyclododecane, synergistic flame retardant, particle diameter are 10-15nm thermally oxidized black, fiber rod stone kind clay, electrostatic agent and oyster shell whiting join in high speed mixer successively, mix 5 ~ 20 minutes; Rotating speed 800rpm.
(3) by step (2) gained compound, join in twin screw extruder by main spout, and when adding 235 DEG C by side feeding manner according to formula rate, decompose hardly, when 25 DEG C, the chain-cutting agent of transformation period >6min, aerial temperature of initial decomposition >235 DEG C, the whipping agent of gas production rate >180ml/g, the uniform mixture of tensio-active agent, coupling agent, oxidation inhibitor and thermo-stabilizer, through melt extruding, cooling, dry, pelletizing, obtain granulated product.Screw zones temperature is 140 ~ 220 DEG C, and screw speed is 200 ~ 450rpm.
The preparation method of the comparative example 1 in above-mentioned table is as follows:
(1) each component is taken by the weight proportion of formula;
(2) by ethylene content lower than 1%, the thermally oxidized black that melt flow rate (MFR) is the polypropylene of 60-90g/10min, particle diameter is 10-15nm joins in high speed mixer successively, mixes 5 ~ 20 minutes; Rotating speed 800rpm.
(3) by step (2) gained compound, joined in twin screw extruder by main spout, and when adding 235 DEG C by side feeding manner according to formula rate, decompose hardly, when 25 DEG C, the chain-cutting agent of transformation period >6min, the whipping agent of aerial temperature of initial decomposition >235 DEG C, gas production rate >180ml/g, the uniform mixture of oxidation inhibitor, through melt extruding, cooling, dry, pelletizing, obtain granulated product.Screw zones temperature is 140 ~ 220 DEG C, and screw speed is 200 ~ 450rpm.
The embodiment 1 ~ 9 of Weather-resistant flame-retardant polypropylene composite material of the present invention and the performance test of comparative example 1 ~ 2 as follows:
Performance evaluation mode and the standard of implementation:
The plastic grain prepared by aforesaid method is placed in the air dry oven of 60 ~ 80 DEG C after dry 2 ~ 3 hours, joins in injection moulding machine, and the obtained standard test specimen of injection, injection temperature is 140 ~ 220 DEG C.
According to the flame retardant resistance of U.S. UL94 standard testing sample; According to the melt mass flow rate of GB test sample, stretching yield stress, tensile strain at yield, elongation at break, Izod notched impact strength and artificial accelerated aging performance (fluorescent ultraviolet lamp, II type, exposure chamber 1, total open-assembly time 1000hrs)
Through above-mentioned test, result is as table two.
Table two, test result contrast table
As can be seen here, the polypropylene material weather resistance that the present invention obtains is excellent, and flame retardant properties reaches UL94 V-0 level, has good heat resistance and low-temperature impact performance, and has very strong static resistance and resistance to impact shock.
Claims (7)
1. a modified polypropylene material, is characterized in that, raw material composition according to weight percent is:
Polypropylene 85-90%;
Main flame retardant: hexabromocyclododecane 1.0-1.5%;
Synergistic flame retardant: decabromodiphynly oxide 0.2-0.4%;
Carbon black: 1.5-2.0 %;
Fiber rod stone kind clay: sepiolite powder 5-10%;
Electrostatic agent: oxyethane 0.5-2%;
Oyster shell whiting: 2-5%;
Chain-cutting agent: CC initiator 2,3-dimethyl-2,3-diphenyl butane 0.2-0.5%;
Whipping agent: 5-phenyltetrazole 0.2-0.5%;
Tensio-active agent: sodium stearate anion surfactant 0.3-0.5%;
Coupling agent: aluminate coupling agent 0.3-0.5%;
Oxidation inhibitor: 2,6-di-tert-butylphenol 0.2-0.5%;
Thermo-stabilizer: DSTP 0.1-0.3%.
2. a kind of modified polypropylene material according to claim 1, is characterized in that, described polypropylene is homo-polypropylene, and ethylene content is lower than 1%, and melt flow rate (MFR) is 60-90g/10min.
3. a kind of modified polypropylene material according to claim 1, is characterized in that, described main flame retardant is one or more in hexabromocyclododecane, TBC, the two tetrabromo phthalimide of ethylene.
4. a kind of modified polypropylene material according to claim 1, is characterized in that, described carbon black is thermally oxidized black, and particle diameter is 10-15nm.
5. a kind of modified polypropylene material according to claim 1, is characterized in that, described chain-cutting agent is high-temperature initiator, when 235 DEG C, decomposes hardly, when 25 DEG C, and transformation period >6min.
6. a kind of modified polypropylene material according to claim 1, is characterized in that, described whipping agent is high-temperature foaming agent, aerial temperature of initial decomposition >235 DEG C, gas production rate >180ml/g.
7. a kind of modified polypropylene material according to claim 1, is characterized in that, described tensio-active agent can be zinc octadecanate anion surfactant.
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| CN201310428090.XA CN104448535A (en) | 2013-09-21 | 2013-09-21 | Modified polypropylene material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107674316A (en) * | 2017-11-14 | 2018-02-09 | 东莞市鑫益电子科技有限公司 | A kind of preparation method of modified polypropene |
| CN112409684A (en) * | 2020-11-03 | 2021-02-26 | 临沂利方塑胶制品有限公司 | Processing method of high-strength toy plastic |
-
2013
- 2013-09-21 CN CN201310428090.XA patent/CN104448535A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107674316A (en) * | 2017-11-14 | 2018-02-09 | 东莞市鑫益电子科技有限公司 | A kind of preparation method of modified polypropene |
| CN112409684A (en) * | 2020-11-03 | 2021-02-26 | 临沂利方塑胶制品有限公司 | Processing method of high-strength toy plastic |
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Application publication date: 20150325 |