CN108117694A - A kind of cold-resistant, rigidity-toughness balanced halogen-free flame retardant polypropylene composite material and preparation method thereof - Google Patents
A kind of cold-resistant, rigidity-toughness balanced halogen-free flame retardant polypropylene composite material and preparation method thereof Download PDFInfo
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- CN108117694A CN108117694A CN201711458474.0A CN201711458474A CN108117694A CN 108117694 A CN108117694 A CN 108117694A CN 201711458474 A CN201711458474 A CN 201711458474A CN 108117694 A CN108117694 A CN 108117694A
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- -1 polypropylene Polymers 0.000 title claims abstract description 64
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 62
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 59
- 239000003063 flame retardant Substances 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 37
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 21
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 239000000945 filler Substances 0.000 claims abstract description 11
- 238000005453 pelletization Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000000314 lubricant Substances 0.000 claims abstract description 8
- 229920000728 polyester Polymers 0.000 claims abstract description 8
- 230000004927 fusion Effects 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract 3
- 239000011574 phosphorus Substances 0.000 claims abstract 3
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 16
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 14
- 229920001903 high density polyethylene Polymers 0.000 claims description 13
- 239000004700 high-density polyethylene Substances 0.000 claims description 13
- 239000007822 coupling agent Substances 0.000 claims description 12
- 238000004381 surface treatment Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000000155 melt Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims description 7
- NOSXUFXBUISMPR-UHFFFAOYSA-N 1-tert-butylperoxyhexane Chemical compound CCCCCCOOC(C)(C)C NOSXUFXBUISMPR-UHFFFAOYSA-N 0.000 claims description 6
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 150000004645 aluminates Chemical class 0.000 claims description 6
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 6
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 235000021355 Stearic acid Nutrition 0.000 claims description 5
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 5
- 230000003750 conditioning effect Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- 239000008117 stearic acid Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000004132 cross linking Methods 0.000 claims description 4
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000012661 block copolymerization Methods 0.000 claims description 3
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 3
- 150000003918 triazines Chemical class 0.000 claims description 3
- 239000010456 wollastonite Substances 0.000 claims description 3
- 229910052882 wollastonite Inorganic materials 0.000 claims description 3
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 4
- 239000012745 toughening agent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004067 bulking agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 229920006213 ethylene-alphaolefin copolymer Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of cold-resistant, rigidity-toughness balanced halogen-free flame retardant polypropylene composite materials and preparation method thereof, which is made of the raw material of following mass parts：Polypropylene：45~68 parts；Nitrogen phosphorus compound flame retardant：22~28 parts；Plasticizing mother particle：8~15 parts；Filler：0~10 part；Antioxidant：0.3~0.5 part；Lubricant：0.4~0.6 part；Multi-level branched polyester：0.4~0.6 part；Active nano-ZnO：0.4~0.6 part；Anti-dripping agent：0.2~0.3 part.Its preparation method is simple, and each material is added in double screw extruder in batches, carries out fusion plastification, tie rod, pelletizing.The halogen-free flame retardant polypropylene composite material cold tolerance and excellent fireproof performance of the present invention, and rigidity-toughness balanced, preparation process is simple, is easy to carry out large-scale industrial production.
Description
Technical field
The present invention relates to a kind of cold-resistant, rigidity-toughness balanced halogen-free flame retardant polypropylene composite materials and preparation method thereof.
Background technology
Polypropylene is a kind of light, nontoxic, acid and alkali-resistance, the plastics of relative low price, be widely used in building, traffic,
Agricultural and industrial circle.However, polyacrylic oxygen index (OI) only has 17.4%, belong to combustible material, it is necessary to carry out fire-retardant change to it
Property could meet the performance requirement under some occasions.In addition, polyacrylic low temperature impact properties are poor, it is impossible to meet low temperature environment
Under requirement, it is also necessary to improve low temperature performance by modified.It is compounded with ammonium polyphosphate (APP) for primary raw material
When obtained halogen-free expanded flame-retardant agent (P-N systems) is used for polypropylene, have it is fire-retardant into carbon effect is good, burning when few cigarette, low toxicity,
No pernicious gas generates, the advantages that molten drop does not occur, meets halogen-free environmental development trend, has obtained being widely recognized as industrial quarters.
Addition toughener carries out polypropylene the method that toughening modifying is the raising polypropylene low temperature performance of current mainstream, but toughening
Agent will necessarily bring rigid loss, and most popular POE, SBS, EPDM class elastomer at present while toughness is made up
Wait toughener that can also have a negative impact to the flame retardant effect of fire retardant.
CN 104262778A disclose a kind of high-impact resistant halogen-free flame-retardant polypropylene composite material and preparation method, will pass through
The inorganic rigid particle attapulgite of surface treatment is introduced into polypropylene halogen-free flame-retardant system, so as to obtain a kind of high-impact
Composite material, but the toughening effect of inorganic rigid particle is extremely limited, and the flame retardant property of the PP composite material is poor.CN
103951876A discloses a kind of environment-friendly type high-ductility, anti-flaming polypropylene material and preparation method thereof, using advance crosslinked ethylene-
Alpha olefin copolymer carries out toughening modifying, and toughening effect is pretty good, and realizes rigidity-toughness balanced to a certain extent, but to fire retardant
Flame retardant effect influence it is big.
Therefore, it is necessary to develop a kind of cold-resistant, halogen-free flame retardant polypropylene composite material of rigidity-toughness balanced.
The content of the invention
It is an object of the invention to provide a kind of cold-resistant, halogen-free flame retardant polypropylene composite material of rigidity-toughness balanced and its preparations
Method.
The technical solution used in the present invention is：
A kind of cold-resistant, halogen-free flame retardant polypropylene composite material of rigidity-toughness balanced, is made of the raw material of following mass parts：
Polypropylene：45~68 parts；
Nitrogen-phosphorus compound flame retardant：22~28 parts；
Plasticizing mother particle：8~15 parts；
Filler：0~10 part；
Antioxidant：0.3~0.5 part；
Lubricant：0.4~0.6 part；
Multi-level branched polyester：0.4~0.6 part；
Active nano-ZnO：0.4~0.6 part；
Anti-dripping agent：0.2~0.3 part.
The polypropylene is at least one of homopolypropylene, atactic copolymerized polypropene, block copolymerization polypropylene, is melted
Melt index as 1~100g/10min, 230 DEG C/2.16kg.
The nitrogen-phosphorus compound flame retardant is the compounding of the ammonium polyphosphate and compound in triazine class that carried out surface treatment
Object, surface conditioning agent used in surface treatment is silane coupling agent, titante coupling agent, aluminate class coupling agent, tristearin
At least one of acid, alkyl phosphate.
The filler be carried out surface treatment 1250~3000 mesh wollastonite, surface used in surface treatment
Inorganic agent is at least one in silane coupling agent, titante coupling agent, aluminate class coupling agent, stearic acid, alkyl phosphate
Kind.
The antioxidant is antioxidant 1010, irgasfos 168, antioxidant 330, antioxidant 1075, antioxidant 1076, anti-
At least one of oxygen agent 245.
The plasticizing mother particle is made of the component of following mass parts：
Propylene-based elastomeric：35~55 parts；
POE：25~40 parts；
HDPE：8~25 parts；
2,5- dimethyl -2,5- two (t-butylperoxy) hexane：0.2~0.4 part；
Antioxidant：0.3~0.5 part.
Melt index≤10g/10min of the propylene-based elastomeric, 190 DEG C/2.16kg；The melting of the POE
Index be 0.5~10g/10min, 190 DEG C/2.16kg；The melt index of the HDPE be 0.5~10g/10min, 190 DEG C/
2.16kg。
The melt index of the plasticizing mother particle be 1~5g/10min, 230 DEG C/2.16kg.
The plasticizing mother particle is prepared by the following method to obtain：By propylene-based elastomeric, POE, HDPE, 2,5- diformazan
(t-butylperoxy) hexane of base -2,5- bis- and antioxidant add in homogenizer and stir evenly, then are transferred to double screw extruder
Melt blending and crosslinking are carried out, squeezes out, pelletizing, obtains plasticizing mother particle.
The preparation method of above-mentioned cold-resistant, rigidity-toughness balanced halogen-free flame retardant polypropylene composite material, comprises the following steps：It will be poly-
Propylene, plasticizing mother particle, filler, antioxidant, lubricant, multi-level branched polyester, active nano-ZnO and anti-dripping agent add in high
Fast mixer is uniformly mixed, then is transferred to double screw extruder from main spout, is carried out fusion plastification, then is added in from side spout
Nitrogen-phosphorus compound flame retardant is uniformly mixed, and tie rod pelletizing is resisted cold, the halogen-free polypropylene flame redardant particle of rigidity-toughness balanced.
The beneficial effects of the invention are as follows：The halogen-free flame retardant polypropylene composite material cold tolerance and flame retardant property of the present invention is excellent
It is different, and rigidity-toughness balanced, preparation process is simple, is easy to carry out large-scale industrial production.
1) present invention is using POE/HDPE as matrix, using propylene-based elastomeric as bulking agent, with 2,5- dimethyl -2,5- bis-
(t-butylperoxy) hexane is crosslinking agent, makes POE, HDPE and propylene-based elastomeric three appropriately crosslinked, obtains toughening effect
Excellent, rigidity-toughness balanced plasticizing mother particle has coordination plasticizing effect to polypropylene；
2) present invention controls the melt index of plasticizing mother particle in certain scope, it can be made to be obtained in polypropylene
Preferably dispersiveness；
3) plasticizing mother particle of the invention has carried out appropriately crosslinked, and toughening while completely will not be to the resistance of P-N intumescent systems
Combustion performance is negatively affected；
4) present invention adds phosphorus-nitrogen combustion inhibitor using side feeding, and not only dispersion performance is more preferable, but also can be utmostly
APP is avoided to degrade in process.
Specific embodiment
A kind of cold-resistant, halogen-free flame retardant polypropylene composite material of rigidity-toughness balanced, is made of the raw material of following mass parts：
Polypropylene：45~68 parts；
Nitrogen-phosphorus compound flame retardant：22~28 parts；
Plasticizing mother particle：8~15 parts；
Filler：0~10 part；
Antioxidant：0.3~0.5 part；
Lubricant：0.4~0.6 part；
Multi-level branched polyester：0.4~0.6 part；
Active nano-ZnO：0.4~0.6 part；
Anti-dripping agent：0.2~0.3 part.
Preferably, the polypropylene be homopolypropylene, atactic copolymerized polypropene, in block copolymerization polypropylene at least
One kind, melt index be 1~100g/10min, 230 DEG C/2.16kg.
Preferably, the nitrogen-phosphorus compound flame retardant is to carry out the ammonium polyphosphate of surface treatment and triazines chemical combination
The compound of object, surface conditioning agent used in surface treatment is silane coupling agent, the coupling of titante coupling agent, aluminate class
At least one of agent, stearic acid, alkyl phosphate.
Preferably, the filler is the wollastonite for 1250~3000 mesh for carrying out surface treatment, and surface treatment is made
Surface conditioning agent is in silane coupling agent, titante coupling agent, aluminate class coupling agent, stearic acid, alkyl phosphate
At least one.
Preferably, the antioxidant is antioxidant 1010, irgasfos 168, antioxidant 330, antioxidant 1075, antioxidant
1076th, at least one of antioxidant 245.
Preferably, the plasticizing mother particle is made of the component of following mass parts：
Propylene-based elastomeric：35~55 parts；
POE：25~40 parts；
HDPE：8~25 parts；
2,5- dimethyl -2,5- two (t-butylperoxy) hexane：0.2~0.4 part；
Antioxidant：0.3~0.5 part.
Preferably, melt index≤10g/10min of the propylene-based elastomeric, 190 DEG C/2.16kg.
Preferably, the melt index of the POE be 0.5~10g/10min, 190 DEG C/2.16kg.
Preferably, the melt index of the HDPE be 0.5~10g/10min, 190 DEG C/2.16kg.
Preferably, the melt index of the plasticizing mother particle be 1~5g/10min, 230 DEG C/2.16kg.
Preferably, the grain size of the plasticizing mother particle is 3~4mm.
Preferably, the plasticizing mother particle is prepared by the following method to obtain：By propylene-based elastomeric, POE, HDPE, 2,
(t-butylperoxy) hexane of 5- dimethyl -2,5- bis- and antioxidant add in homogenizer and stir evenly, then are transferred to twin-screw
Extruder carries out melt blending and crosslinking, squeezes out, pelletizing, obtains plasticizing mother particle.
The preparation method of above-mentioned cold-resistant, rigidity-toughness balanced halogen-free flame retardant polypropylene composite material, comprises the following steps：It will be poly-
Propylene, plasticizing mother particle, filler, antioxidant, lubricant, multi-level branched polyester, active nano-ZnO and anti-dripping agent add in high
Fast mixer is uniformly mixed, then is transferred to double screw extruder from main spout, is carried out fusion plastification, then is added in from side spout
Nitrogen-phosphorus compound flame retardant is uniformly mixed, and tie rod pelletizing is resisted cold, the halogen-free polypropylene flame redardant particle of rigidity-toughness balanced.
The present invention is made further explanation and description with reference to specific embodiment.
Examples 1 to 6：
The cold-resistant of Examples 1 to 6, rigidity-toughness balanced halogen-free polypropylene flame redardant composition of raw materials it is as shown in table 1, preparation side
Method is as follows：By the polypropylene (trade mark：EP300M, CSPC, melt index 9g/10min), plasticizing mother particle, filler, antioxidant,
Lubricant, multi-level branched polyester, active nano-ZnO and anti-dripping agent add in homogenizer and are uniformly mixed, then from main feeding
Mouth is transferred to double screw extruder, carries out fusion plastification, then adds in nitrogen-phosphorus compound flame retardant (trade mark from side spout：EPFR-
100C is surface-treated using preceding with silane coupling agent), it is uniformly mixed, tie rod pelletizing is resisted cold, the nothing of rigidity-toughness balanced
Halogen polypropylene flame redardant particle, is tested for the property, test result is as shown in table 2.
The preparation method for the plasticizing mother particle that Examples 1 to 6 is added is as follows：By 45 parts of propylene-based elastomeric (trades mark：Weida
U.S. 6102, Exxon Mobil, melt index 1.3g/10min), 40 parts of POE (trades mark：8452, DOW Chemical, melt index 3g/
10min), 14.5 parts of HDPE (trades mark：5000S, Daqing Refinery, melt index 1.2g/10min), 0.2 part of 2,5- dimethyl -2,
(t-butylperoxy) hexanes of 5- bis- and 0.3 part of antioxidant 1010 add in homogenizer and stir evenly, then are transferred to twin-screw and squeeze
Go out machine, carry out melt blending and crosslinking, water ring pelletizing at 185 DEG C, obtain the plasticizing mother particle of 3~4mm of grain size.
Comparative example 1~4：
The composition of raw materials of the halogen-free polypropylene flame redardant of comparative example 1~4 is as shown in table 1, preparation process flow and technique ginseng
Number is consistent with Examples 1 to 4, is obtained halogen-free polypropylene flame redardant particle, is tested for the property, test result is as shown in table 2.
The preparation method for the plasticizing mother particle A that comparative example 2 is added is as follows：By 45 parts of propylene-based elastomeric (trades mark：Weida is beautiful
6102, Exxon Mobil, melt index 1.3g/10min), 40 parts of POE (trades mark：8452, DOW Chemical, melt index 3g/
10min), 14.5 parts of HDPE (trades mark：5000S, Daqing Refinery, melt index 1.2g/10min) and 0.3 part of antioxidant 1010 add
Enter homogenizer to stir evenly, then be transferred to double screw extruder, melt blending is carried out at 185 DEG C, water ring pelletizing obtains grain size
The plasticizing mother particle A of 3~4mm.
The raw material composition of the halogen-free polypropylene flame redardant of Examples 1 to 6 and comparative example 1~4 is as follows (with mass fraction
Meter)：
The raw material composition table of the halogen-free polypropylene flame redardant of 1 Examples 1 to 6 of table and comparative example 1~4
Test case：
The halogen-free polypropylene flame redardant prepared to Examples 1 to 6 and comparative example 1~4 is tested for the property, and test result is as follows
Shown in table：
The performance test results of the halogen-free polypropylene flame redardant of 2 Examples 1 to 6 of table and comparative example 1~4
Note：
Bending modulus：It is tested according to ASTM D790 standards；
Notch impact strength：It is tested according to ASTM D256 standards；
Multi-axial Impact performance：Tested according to 6603 standards of ISO, multi-axial Impact sample be disk, a diameter of 60mm,
Thickness is 2mm, a diameter of 20mm of punch used；
Flame retardant property：It is tested according to 94 standards of UL.
As shown in Table 2：Multi-axial Impact of the halogen-free polypropylene flame redardant of Examples 1 to 6 at -30 DEG C is had excellent performance, explanation
Its cold tolerance is excellent, and during the progress multi-axial Impact experiment of the halogen-free polypropylene flame redardant of comparative example 1~4, product has fragmentation to show
As cannot all take into account toughness, rigidity and anti-flammability simultaneously；What is added in the halogen-free polypropylene flame redardant of comparative example 2 is non-crosslinked
The plasticizing mother particle A of processing, toughening effect is poor, and what is added in the halogen-free polypropylene flame redardant of Examples 1 to 6 is to carry out friendship
Join the plasticizing mother particle of processing, can be resisted cold, the halogen-free expanded flame-retardant polypropylene composite material of rigidity-toughness balanced, not only effectively solved
Caused flame retardant property declines (comparative example 3) during traditional POE toughenings of having determined, while also overcomes propylene-based elastomeric toughener
The shortcomings that toughening effect deficiency and modulus are remarkably decreased (comparative example 4).
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention and from above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of cold-resistant, halogen-free flame retardant polypropylene composite material of rigidity-toughness balanced, it is characterised in that：By the raw material of following mass parts
Composition：
Polypropylene：45~68 parts；
Nitrogen-phosphorus compound flame retardant：22~28 parts；
Plasticizing mother particle：8~15 parts；
Filler：0~10 part；
Antioxidant：0.3~0.5 part；
Lubricant：0.4~0.6 part；
Multi-level branched polyester：0.4~0.6 part；
Active nano-ZnO：0.4~0.6 part；
Anti-dripping agent：0.2~0.3 part.
2. the cold-resistant, halogen-free flame retardant polypropylene composite material of rigidity-toughness balanced according to claim 1, it is characterised in that：Institute
The polypropylene stated is homopolypropylene, atactic copolymerized polypropene, at least one of block copolymerization polypropylene, melt index 1
~100g/10min, 230 DEG C/2.16kg.
3. the cold-resistant, halogen-free flame retardant polypropylene composite material of rigidity-toughness balanced according to claim 1, it is characterised in that：Institute
The nitrogen stated-phosphorus compound flame retardant is the compound of the ammonium polyphosphate and compound in triazine class that carried out surface treatment, at surface
Surface conditioning agent used in reason is silane coupling agent, titante coupling agent, aluminate class coupling agent, stearic acid, alkyl phosphorus
At least one of acid esters.
4. the cold-resistant, halogen-free flame retardant polypropylene composite material of rigidity-toughness balanced according to claim 1, it is characterised in that：Institute
The plasticizing mother particle stated is made of the component of following mass parts：
Propylene-based elastomeric：35~55 parts；
POE：25~40 parts；
HDPE：8~25 parts；
2,5- dimethyl -2,5- two (t-butylperoxy) hexane：0.2~0.4 part；
Antioxidant：0.3~0.5 part.
5. the cold-resistant, halogen-free flame retardant polypropylene composite material of rigidity-toughness balanced according to claim 4, it is characterised in that：Institute
Melt index≤the 10g/10min for the propylene-based elastomeric stated, 190 DEG C/2.16kg；The melt index of the POE for 0.5~
10g/10min, 190 DEG C/2.16kg；The melt index of the HDPE be 0.5~10g/10min, 190 DEG C/2.16kg.
6. the cold-resistant, halogen-free flame retardant polypropylene composite material of rigidity-toughness balanced according to claim 4, it is characterised in that：Institute
The melt index for the plasticizing mother particle stated be 1~5g/10min, 230 DEG C/2.16kg.
7. the cold-resistant, halogen-free flame retardant polypropylene composite material of rigidity-toughness balanced according to claim 4, it is characterised in that：Institute
The plasticizing mother particle stated is prepared by the following method to obtain：By propylene-based elastomeric, two (uncles of POE, HDPE, 2,5- dimethyl -2,5-
Butyl peroxy) hexane and antioxidant add in homogenizer and stir evenly, then are transferred to double screw extruder and carry out melt blending
And crosslinking, it squeezes out, pelletizing, obtains plasticizing mother particle.
8. the cold-resistant, halogen-free flame retardant polypropylene composite material of rigidity-toughness balanced according to claim 1, it is characterised in that：Institute
The filler stated is the wollastonite for 1250~3000 mesh for carrying out surface treatment, and surface conditioning agent used in surface treatment is silicon
At least one of alkane coupling agent, titante coupling agent, aluminate class coupling agent, stearic acid, alkyl phosphate.
9. the cold-resistant, halogen-free flame retardant polypropylene composite material of rigidity-toughness balanced according to claim 1, it is characterised in that：Institute
The antioxidant stated is antioxidant 1010, in irgasfos 168, antioxidant 330, antioxidant 1075, antioxidant 1076, antioxidant 245
At least one.
10. the system of cold-resistant, rigidity-toughness balanced the halogen-free flame retardant polypropylene composite material in claim 1~9 described in any one
Preparation Method, it is characterised in that：Comprise the following steps：By polypropylene, plasticizing mother particle, filler, antioxidant, lubricant, multi-level branched
Polyester, active nano-ZnO and anti-dripping agent add in homogenizer and are uniformly mixed, then are transferred to twin-screw from main spout and squeeze
Go out machine, carry out fusion plastification, then nitrogen-phosphorus compound flame retardant is added in from side spout, be uniformly mixed, tie rod pelletizing, resisted cold,
The halogen-free polypropylene flame redardant particle of rigidity-toughness balanced.
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| CN109082010A (en) * | 2018-07-23 | 2018-12-25 | 武汉理工大学 | A kind of halogen-free expanded flame-retardant fibre reinforced acrylic resin composite material and preparation method |
| CN110885498A (en) * | 2019-12-20 | 2020-03-17 | 广东道生科技股份有限公司 | Flame-retardant toughened polypropylene material and preparation method thereof |
| CN113817263A (en) * | 2021-08-17 | 2021-12-21 | 金发科技股份有限公司 | Halogen-free flame-retardant polypropylene composition and preparation method and application thereof |
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| WO2022242297A1 (en) * | 2021-05-18 | 2022-11-24 | 金发科技股份有限公司 | Polypropylene composite material capable of blasting at low temperature, and preparation method therefor and application thereof |
| JP2024516896A (en) * | 2021-05-18 | 2024-04-17 | 金発科技股▲分▼有限公司 | Low temperature burstable polypropylene composite material and its manufacturing method and use |
| JP7668381B2 (en) | 2021-05-18 | 2025-04-24 | 金発科技股▲分▼有限公司 | Low temperature burstable polypropylene composite material and its manufacturing method and use |
| CN113817263A (en) * | 2021-08-17 | 2021-12-21 | 金发科技股份有限公司 | Halogen-free flame-retardant polypropylene composition and preparation method and application thereof |
| WO2023020452A1 (en) * | 2021-08-17 | 2023-02-23 | 金发科技股份有限公司 | Halogen-free flame-retardant polypropylene composition, and preparation method therefor and use thereof |
| CN115160692A (en) * | 2022-07-14 | 2022-10-11 | 江苏金发科技新材料有限公司 | Halogen-free flame-retardant plastic-absorbable polypropylene alloy material and preparation method and application thereof |
| CN115160692B (en) * | 2022-07-14 | 2023-11-17 | 江苏金发科技新材料有限公司 | Halogen-free flame-retardant plastic-sucking polypropylene alloy material and preparation method and application thereof |
| CN119823463A (en) * | 2024-12-13 | 2025-04-15 | 广东聚石化学股份有限公司 | Halogen-free flame-retardant polyolefin material and preparation method and application thereof |
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| CN119978691A (en) * | 2025-04-14 | 2025-05-13 | 广东雄塑科技集团股份有限公司 | A low temperature resistant modified PPR and its preparation process |
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