CN102604221A - Halogen-free flame-retardant polypropylene composite for auto fuse holder, preparation method and application - Google Patents

Halogen-free flame-retardant polypropylene composite for auto fuse holder, preparation method and application Download PDF

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Publication number
CN102604221A
CN102604221A CN201210065891XA CN201210065891A CN102604221A CN 102604221 A CN102604221 A CN 102604221A CN 201210065891X A CN201210065891X A CN 201210065891XA CN 201210065891 A CN201210065891 A CN 201210065891A CN 102604221 A CN102604221 A CN 102604221A
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CN
China
Prior art keywords
halogen
mixture
fuse box
free
automobile fuse
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201210065891XA
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Chinese (zh)
Inventor
陈瑶
宁凯军
刘奇祥
李永华
罗忠富
杨波
王灿耀
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
MIANYANG DONGFANG SPECIAL ENGINEERING PLASTIC Co Ltd
Kingfa Science and Technology Co Ltd
Shanghai Kingfa Science and Technology Co Ltd
Original Assignee
MIANYANG DONGFANG SPECIAL ENGINEERING PLASTIC Co Ltd
Kingfa Science and Technology Co Ltd
Shanghai Kingfa Science and Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by MIANYANG DONGFANG SPECIAL ENGINEERING PLASTIC Co Ltd, Kingfa Science and Technology Co Ltd, Shanghai Kingfa Science and Technology Co Ltd filed Critical MIANYANG DONGFANG SPECIAL ENGINEERING PLASTIC Co Ltd
Priority to CN201210065891XA priority Critical patent/CN102604221A/en
Publication of CN102604221A publication Critical patent/CN102604221A/en
Pending legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders

Abstract

The invention discloses a halogen-free flame-retardant polypropylene composite for an auto fuse holder, a preparation method and application. The polypropylene composite is prepared by 32-83% of polypropylene, 0-1% of heat stabilizer, 0-1% of processing agent, 10-30% of halogen-free intumescent flame retardant, 2-6% of compatilizer and 5-30% of reinforcing filler, wherein the halogen-free intumescent flame retardant refers to phosphorus-nitrogen halogen-free intumescent flame retardant. The halogen-free flame-retardant polypropylene composite for the auto fuse holder has excellent flame-retardant effect, high CTI (comparative tracking index) value, good comprehensive mechanical property, excellent folding resistance and high heat distortion temperature, the flame retardant property can reach 1.6mm V0, tensile strength is larger than or equal to 30MPa, bending modulus is larger than or equal to 2000MPa, CTI is larger than or equal to 500V, hinge folding times are larger than or equal to 106, notch impact strength is larger than or equal to 3.5KJ/m2, and heat distortion temperature (0.45MPa) is larger than or equal to 120 DEG C.

Description

Automobile fuse box is with halogen-free polypropylene flame redardant mixture and preparation method and application
Technical field
The invention belongs to the modified plastics field; Be specifically related to a kind of automobile fuse box with halogen-free polypropylene flame redardant mixture and preparation method thereof and application, this polypropylene composite has that high flame retardant, high CTI value, folding are folded, high heat resistance and good comprehensive mechanical property.
Background technology
Automobile fuse box is main at present to adopt the talc powder filled polypropylene injection moulding, but the flame retardant rating of this material can only reach the requirement of UL94 HB level.
Along with developing of automobile industry, the flame retardant rating of automobile fuse box material can further improve, and CTI value and non-halogen requirement are also progressively improved, and therefore, it is imperative that exploitation has other automobile fuse box material of UL94 V-0 flame retardant grade.
Summary of the invention
For the shortcoming and deficiency that overcomes prior art; Primary and foremost purpose of the present invention is to provide a kind of automobile fuse box to use the halogen-free polypropylene flame redardant mixture, and this polypropylene composite has that high flame retardant, high CTI value, folding are folded, high heat resistance and good comprehensive mechanical property.
Another object of the present invention is to provide the preparation method of above-mentioned automobile fuse box with the halogen-free polypropylene flame redardant mixture.
A purpose more of the present invention is to provide the purposes of above-mentioned automobile fuse box with the halogen-free polypropylene flame redardant mixture.
The object of the invention is realized through following technical proposals:
A kind of automobile fuse box is used the halogen-free polypropylene flame redardant mixture, is prepared by the composition of following mass percent:
Vestolen PP 7052: 32-83%
Thermo-stabilizer: 0-1%
Processing aid: 0-1%
Halogen-free expansion fire retardant: 10-30%
Compatilizer: 2-6%
Reinforcing filler: 5-30%.
Preferably, above-mentioned automobile fuse box prepares with the composition of halogen-free polypropylene flame redardant mixture by following mass percent:
Vestolen PP 7052: 42-82.5%
Thermo-stabilizer: 0.3-1%
Processing aid: 0.2-1%
Halogen-free expansion fire retardant: 10-30%
Compatilizer: 2-6%
Reinforcing filler: 5-20%.
Described Vestolen PP 7052 is more than one in HOPP, COPP or the atactic copolymerized polypropene; Said polyacrylic melt flow rate(MFR) is 0.01-100g/10min.
Described thermo-stabilizer is the mixture type thermal stabilizing agent of phenols thermo-stabilizer, amine thermo-stabilizer, phosphorous acid ester type thermal stabilizing agent, half Hinered phenols thermo-stabilizer, acryl functional group and monothioester or in the calixarene thermo-stabilizer more than one, and the main effect of thermo-stabilizer is to suppress polyacrylic degraded in the preparation process.
Described processing aid is more than one in low molecule ester class, metallic soap class, Triple Pressed Stearic Acid complex ester class or the amides, and the main effect of processing aid is the processing characteristics that improves polypropylene composite.
Described halogen-free expansion fire retardant is the P-N type halogen-free expansion fire retardant.
Described compatilizer is the polar monomer graftomer, and the main effect of compatilizer is the consistency that increases spun glass and polymeric matrix (being Vestolen PP 7052);
Polymkeric substance in the said polar monomer graftomer is more than one in Vilaterm, Vestolen PP 7052, ethene-α-ethylene-octene copolymer, styrene-butadiene copolymer, polyethylene-polystyrene-polypropylene terpolymer, ethylene-propylene-butadiene terpolymer, ethylene-acrylate copolymer or the ethylene-acrylate-glycidyl methacrylate copolymer;
Polar monomer in the said polar monomer graftomer is maleic anhydride and analogue and/or vinylformic acid and ester derivative thereof;
Described maleic anhydride and analogue thereof comprise maleic anhydride, fumaric acid, methylene-succinic acid, citraconic acid, citraconic anhydride, vinyl Succinic anhydried;
Described vinylformic acid and ester derivative thereof comprise vinylformic acid, methylacrylic acid, methyl acrylate, ethyl propenoate, TEB 3K, GMA.
Described reinforcing filler is more than one in talcum powder, lime carbonate, mica, wollastonite, kaolin, glass microballon or the permanent white.
Above-mentioned automobile fuse box may further comprise the steps with the preparation method of halogen-free polypropylene flame redardant mixture:
Vestolen PP 7052, thermo-stabilizer, processing aid, compatilizer and reinforcing filler are joined melting mixing dispersion in the twin screw extruder, and halogen-free expansion fire retardant adds from the side spout, and extruding pelletization obtains automobile fuse box and uses the halogen-free polypropylene flame redardant mixture;
The length-to-diameter ratio of said twin screw extruder is 40: 1;
The said temperature of extruding is 170-240 ℃.
Above-mentioned halogen-free polypropylene flame redardant mixture can be applied in the automobile fuse box.
The present invention has following advantage and effect with respect to prior art:
Automobile fuse box of the present invention has excellent fire retardant effect, high CTI value, good comprehensive mechanical properties with the halogen-free polypropylene flame redardant mixture; Excellent folding resistance ability and higher heat-drawn wire, its flame retardant properties can reach 1.6mm V0, tensile strength>=30MPa; Modulus in flexure>=2000MPa; CTI>=500V, hinge folding times>=106 time, notched Izod impact strength>=3.5KJ/m 2, heat-drawn wire (0.45Mpa)>=120 ℃.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail, but embodiment of the present invention is not limited thereto.
Embodiment 1
A kind of automobile fuse box may further comprise the steps with the preparation method of halogen-free polypropylene flame redardant mixture:
With 40 kilograms of Vestolen PP 7052 PP S700; 42.5 5 kilograms of kilogram Vestolen PP 7052 PP SM256,0.3 kilogram of phenols thermo-stabilizer Irganox 1010 (CIBA company), 0.2 kilogram of processing aid EBS, 2 kilograms of GMAs (GMA) graft polypropylene, 10 kilograms of expanding fire retardant FP-2200, talcum powder are that melting mixing is disperseed in 1: 40 the twin screw extruder in length-to-diameter ratio; Fire retardant adds from the side feeding; Extrusion temperature is 200 ℃; Extruding pelletization obtains automobile fuse box and uses the halogen-free polypropylene flame redardant mixture.
The performance of products obtained therefrom is following:
Performance Unit Testing standard Test result
Flame retardant resistance -- UL94 1.6V-0
CTI V ASTM?D-3638 600
HDT(0.45MPa) ℃ ISO75/1-93 123
Tensile strength MPa ISO527/2-93 32
Modulus in flexure MPa ISO178-93 2200
Notched Izod impact strength KJ/m 2 ISO180-93 4.0
Folding times -- 0.5mm 10 7
Embodiment 2
A kind of automobile fuse box may further comprise the steps with the preparation method of halogen-free polypropylene flame redardant mixture:
With 50 kilograms of Vestolen PP 7052 PP BX3800; 10 kilograms of 21 kilograms of Vestolen PP 7052 PP SM198,0.5 kilogram of phenols thermo-stabilizer Irganox 1010 (CIBA company), 0.5 kilogram of processing aid EBS, 3 kilograms of maleic anhydrides (MAH) graft polypropylene, 15 kilograms of expanding fire retardant FP-2200, wollastonites are that melting mixing is disperseed in 1: 40 the twin screw extruder in length-to-diameter ratio; Fire retardant adds from the side feeding; Extrusion temperature is 200 ℃; Extruding pelletization obtains automobile fuse box and uses the halogen-free polypropylene flame redardant mixture.
The performance of products obtained therefrom is following:
Performance Unit Testing standard Test result
Flame retardant resistance -- UL94 1.6V-0
CTI V ASTM?D-3638 600
HDT(0.45MPa) ℃ ISO75/1-93 125
Tensile strength MPa ISO527/2-93 34
Modulus in flexure MPa ISO178-93 2500
Notched Izod impact strength KJ/m 2 ISO180-93 4.5
Folding times -- 0.5mm 10 7
Embodiment 3
A kind of automobile fuse box may further comprise the steps with the preparation method of halogen-free polypropylene flame redardant mixture:
Is that melting mixing is disperseed in 1: 40 the twin screw extruder with 15 kilograms of 60 kilograms of Vestolen PP 7052 PP RP346R, 0.5 kilogram of phenols thermo-stabilizer Irganox 1010 (CIBA company), 0.5 kilogram of processing aid calcium stearate, 4 kilograms of maleic anhydrides (MAH) graft polypropylene, 20 kilograms of expanding fire retardant FP-2200, kaolin in length-to-diameter ratio; Fire retardant adds from the side feeding; Extrusion temperature is 200 ℃; Extruding pelletization obtains automobile fuse box and uses the halogen-free polypropylene flame redardant mixture.
The performance of products obtained therefrom is following:
Performance Unit Testing standard Test result
Flame retardant resistance -- UL94 1.6V-0
CTI V ASTM?D-3638 600
HDT(0.45MPa) ℃ ISO75/1-93 121
Tensile strength MPa ISO527/2-93 33
Modulus in flexure MPa ISO178-93 2400
Notched Izod impact strength KJ/m 2 ISO180-93 4.7
Folding times -- 0.5mm 10 7
Embodiment 4
A kind of automobile fuse box may further comprise the steps with the preparation method of halogen-free polypropylene flame redardant mixture:
With 28 kilograms of Vestolen PP 7052 PP SM198,20 kilograms of Vestolen PP 7052 PP AP3N, 1 kilogram of phenols thermo-stabilizer Irganox 1010 (CIBA company), 1 kilogram of processing aid calcium stearate, 5 kilograms of maleic anhydrides (MAH) graft polypropylene, 25 kilograms of expanding fire retardant JLS-PNPID (Hangzhou Jie Ersi; Down with), 20 kilograms in lime carbonate is that melting mixing is disperseed in 1: 40 the twin screw extruder in length-to-diameter ratio, fire retardant adds from the side feeding, extrusion temperature is 200 ℃, extruding pelletization obtains automobile fuse box and uses the halogen-free polypropylene flame redardant mixture.
The performance of products obtained therefrom is following:
Performance Unit Testing standard Test result
Flame retardant resistance -- UL94 1.6V-0
CTI V ASTM?D-3638 600
HDT(0.45MPa) ℃ ISO75/1-93 123
Tensile strength MPa ISO527/2-93 31
Modulus in flexure MPa ISO178-93 2100
Notched Izod impact strength KJ/m 2 ISO180-93 5.0
Folding times -- 0.5mm 10 7
Embodiment 5
A kind of automobile fuse box may further comprise the steps with the preparation method of halogen-free polypropylene flame redardant mixture:
Is that melting mixing is disperseed in 1: 40 the twin screw extruder with 20 kilograms on 42 kilograms of Vestolen PP 7052 PP SM198,1 kilogram of phenols thermo-stabilizer Irganox 1010 (CIBA company), 1 kilogram of processing aid Zinic stearas, 6 kilograms of GMAs (GMA) graft polypropylene, 30 kilograms of expanding fire retardant JLS-PNPID, mica in length-to-diameter ratio; Fire retardant adds from the side feeding; Extrusion temperature is 200 ℃; Extruding pelletization obtains automobile fuse box and uses the halogen-free polypropylene flame redardant mixture.
The performance of products obtained therefrom is following:
Performance Unit Testing standard Test result
Flame retardant resistance -- UL94 1.6V-0
CTI V ASTM?D-3638 600
HDT(0.45MPa) ℃ ISO75/1-93 121
Tensile strength MPa ISO527/2-93 38
Modulus in flexure MPa ISO178-93 2700
Notched Izod impact strength KJ/m 2 ISO180-93 4.2
Folding times -- 0.5mm 10 7
The foregoing description is a preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.

Claims (10)

1. an automobile fuse box is used the halogen-free polypropylene flame redardant mixture, it is characterized in that it being that composition by following mass percent prepares:
Vestolen PP 7052: 32-83%
Thermo-stabilizer: 0-1%
Processing aid: 0-1%
Halogen-free expansion fire retardant: 10-30%
Compatilizer: 2-6%
Reinforcing filler: 5-30%;
Described halogen-free expansion fire retardant is the P-N type halogen-free expansion fire retardant.
2. automobile fuse box according to claim 1 is used the halogen-free polypropylene flame redardant mixture, it is characterized in that: described automobile fuse box prepares with the composition of halogen-free polypropylene flame redardant mixture by following mass percent:
Vestolen PP 7052: 42-82.5%
Thermo-stabilizer: 0.3-1%
Processing aid: 0.2-1%
Halogen-free expansion fire retardant: 10-30%
Compatilizer: 2-6%
Reinforcing filler: 5-20%.
3. automobile fuse box according to claim 1 is used the halogen-free polypropylene flame redardant mixture, it is characterized in that: described Vestolen PP 7052 is more than one in HOPP, COPP or the atactic copolymerized polypropene; Said polyacrylic melt flow rate(MFR) is 0.01-100g/10min.
4. automobile fuse box according to claim 1 is used the halogen-free polypropylene flame redardant mixture, it is characterized in that: described thermo-stabilizer is the mixture type thermal stabilizing agent of phenols thermo-stabilizer, amine thermo-stabilizer, phosphorous acid ester type thermal stabilizing agent, half Hinered phenols thermo-stabilizer, acryl functional group and monothioester or in the calixarene thermo-stabilizer more than one.
5. automobile fuse box according to claim 1 is used the halogen-free polypropylene flame redardant mixture, it is characterized in that: described processing aid is more than one in low molecule ester class, metallic soap class, Triple Pressed Stearic Acid complex ester class or the amides.
6. automobile fuse box according to claim 1 is used the halogen-free polypropylene flame redardant mixture, it is characterized in that:
Described compatilizer is the polar monomer graftomer;
Polymkeric substance in the said polar monomer graftomer is more than one in Vilaterm, Vestolen PP 7052, ethene-α-ethylene-octene copolymer, styrene-butadiene copolymer, polyethylene-polystyrene-polypropylene terpolymer, ethylene-propylene-butadiene terpolymer, ethylene-acrylate copolymer or the ethylene-acrylate-glycidyl methacrylate copolymer;
Polar monomer in the said polar monomer graftomer is maleic anhydride and analogue and/or vinylformic acid and ester derivative thereof;
Described maleic anhydride and analogue thereof are maleic anhydride, fumaric acid, methylene-succinic acid, citraconic acid, citraconic anhydride, vinyl Succinic anhydried;
Described vinylformic acid and ester derivative thereof are vinylformic acid, methylacrylic acid, methyl acrylate, ethyl propenoate, TEB 3K, GMA.
7. automobile fuse box according to claim 1 is used the halogen-free polypropylene flame redardant mixture, it is characterized in that: described reinforcing filler is more than one in talcum powder, lime carbonate, mica, wollastonite, kaolin, glass microballon or the permanent white.
8. each described automobile fuse box of claim 1-7 is characterized in that may further comprise the steps with the preparation method of halogen-free polypropylene flame redardant mixture:
Vestolen PP 7052, thermo-stabilizer, processing aid, compatilizer and reinforcing filler are joined melting mixing dispersion in the twin screw extruder, and halogen-free expansion fire retardant adds from the side spout, and extruding pelletization obtains automobile fuse box and uses the halogen-free polypropylene flame redardant mixture.
9. automobile fuse box according to claim 8 is characterized in that with the preparation method of halogen-free polypropylene flame redardant mixture:
The length-to-diameter ratio of said twin screw extruder is 40: 1;
The said temperature of extruding is 170-240 ℃.
10. each described automobile fuse box of claim 1-7 is with the application of halogen-free polypropylene flame redardant mixture in automobile fuse box.
CN201210065891XA 2012-03-13 2012-03-13 Halogen-free flame-retardant polypropylene composite for auto fuse holder, preparation method and application Pending CN102604221A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210065891XA CN102604221A (en) 2012-03-13 2012-03-13 Halogen-free flame-retardant polypropylene composite for auto fuse holder, preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210065891XA CN102604221A (en) 2012-03-13 2012-03-13 Halogen-free flame-retardant polypropylene composite for auto fuse holder, preparation method and application

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CN102604221A true CN102604221A (en) 2012-07-25

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103102593A (en) * 2013-02-20 2013-05-15 四川大学 Supported metal oxide catalytic synergistic inorganic flame retardant polypropylene composite material and preparation method thereof
CN105348636A (en) * 2015-11-06 2016-02-24 中国人民武装警察部队学院 Expansion flame-retardant toughening polypropylene blend composite material and preparation method therefor

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101020774A (en) * 2006-12-11 2007-08-22 杭州鸿雁电器有限公司 Environment friendly fireproof composite polypropylene material and its prepn process
CN101412830A (en) * 2008-12-02 2009-04-22 上海金发科技发展有限公司 Non-halogen flame-retardant polypropylene composite material and preparation thereof
CN101747547A (en) * 2008-12-04 2010-06-23 上海杰事杰新材料股份有限公司 Non halogen flame retardant polyolefin/montmorillonite composite and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101020774A (en) * 2006-12-11 2007-08-22 杭州鸿雁电器有限公司 Environment friendly fireproof composite polypropylene material and its prepn process
CN101412830A (en) * 2008-12-02 2009-04-22 上海金发科技发展有限公司 Non-halogen flame-retardant polypropylene composite material and preparation thereof
CN101747547A (en) * 2008-12-04 2010-06-23 上海杰事杰新材料股份有限公司 Non halogen flame retardant polyolefin/montmorillonite composite and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103102593A (en) * 2013-02-20 2013-05-15 四川大学 Supported metal oxide catalytic synergistic inorganic flame retardant polypropylene composite material and preparation method thereof
CN105348636A (en) * 2015-11-06 2016-02-24 中国人民武装警察部队学院 Expansion flame-retardant toughening polypropylene blend composite material and preparation method therefor

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Application publication date: 20120725