CN104693604A - Halogen-free flame retardant glass-fiber reinforced polypropylene composite material and preparation method thereof - Google Patents
Halogen-free flame retardant glass-fiber reinforced polypropylene composite material and preparation method thereof Download PDFInfo
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- CN104693604A CN104693604A CN201510116367.4A CN201510116367A CN104693604A CN 104693604 A CN104693604 A CN 104693604A CN 201510116367 A CN201510116367 A CN 201510116367A CN 104693604 A CN104693604 A CN 104693604A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 92
- -1 polypropylene Polymers 0.000 title claims abstract description 49
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 48
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 239000003365 glass fiber Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000007822 coupling agent Substances 0.000 claims abstract description 17
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N Melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001376 inorganic hypophosphite Inorganic materials 0.000 claims abstract description 3
- 239000011521 glass Substances 0.000 claims description 25
- 239000002994 raw material Substances 0.000 claims description 23
- FPYJFEHAWHCUMM-UHFFFAOYSA-N Maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 14
- 239000003112 inhibitor Substances 0.000 claims description 13
- 230000002401 inhibitory effect Effects 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 239000000314 lubricant Substances 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 229920001296 polysiloxane Polymers 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 238000005453 pelletization Methods 0.000 claims description 9
- CJZGTCYPCWQAJB-UHFFFAOYSA-L Calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 8
- 230000003078 antioxidant Effects 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 239000008116 calcium stearate Substances 0.000 claims description 8
- 235000013539 calcium stearate Nutrition 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 7
- 239000004925 Acrylic resin Substances 0.000 claims description 6
- 229920000178 Acrylic resin Polymers 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000004698 Polyethylene (PE) Substances 0.000 claims description 3
- 235000019359 magnesium stearate Nutrition 0.000 claims description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 3
- 229920002943 EPDM rubber Polymers 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N Glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- PWZFXELTLAQOKC-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide;tetrahydrate Chemical compound O.O.O.O.[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O PWZFXELTLAQOKC-UHFFFAOYSA-A 0.000 claims description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- CMRVPOBZJFTQHN-UHFFFAOYSA-N octadecylazanide Chemical class CCCCCCCCCCCCCCCCCC[NH-] CMRVPOBZJFTQHN-UHFFFAOYSA-N 0.000 claims description 2
- OGBPILLJZSJJRC-UHFFFAOYSA-N phenoxyphosphonoyloxybenzene Chemical class C=1C=CC=CC=1OP(=O)OC1=CC=CC=C1 OGBPILLJZSJJRC-UHFFFAOYSA-N 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 235000012222 talc Nutrition 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Chemical class [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N Ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 abstract description 9
- 239000004114 Ammonium polyphosphate Substances 0.000 abstract description 9
- 229920001276 Ammonium polyphosphate Polymers 0.000 abstract description 9
- 235000019826 ammonium polyphosphate Nutrition 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 8
- 229920005989 resin Polymers 0.000 abstract description 8
- 239000011347 resin Substances 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 235000010290 biphenyl Nutrition 0.000 abstract 1
- 239000004305 biphenyl Substances 0.000 abstract 1
- 239000003017 thermal stabilizer Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000011152 fibreglass Substances 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 150000004692 metal hydroxides Chemical class 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L Magnesium hydroxide Chemical class [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 159000000013 aluminium salts Chemical class 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 229960001735 pentaerythritol Drugs 0.000 description 2
- 230000000979 retarding Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 206010009866 Cold sweat Diseases 0.000 description 1
- VYRDHRYMAZWQJH-UHFFFAOYSA-N [P].P Chemical compound [P].P VYRDHRYMAZWQJH-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 231100000078 corrosive Toxicity 0.000 description 1
- 231100001010 corrosive Toxicity 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing Effects 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 239000005043 ethylene-methyl acrylate Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 230000003000 nontoxic Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000001473 noxious Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 230000002588 toxic Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- BSUNTQCMCCQSQH-UHFFFAOYSA-N triazine Chemical compound C1=CN=NN=C1.C1=CN=NN=C1 BSUNTQCMCCQSQH-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 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
- 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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention relates to a halogen-free flame retardant glass-fiber reinforced polypropylene composite material, which comprises the following components in weight percentage: 33-59% of polypropylene resin, 15-35% of compound flame retardant, 20-30% of glass fiber, 3-10% of compatibilizing agent, 0.4-2.5% of coupling agent and 1-3% of thermal stabilizer; the compound flame retardant is prepared by mixing and compounding a main flame retardant and an auxiliary flame retardant with a mass ratio of 41-79: 21-59; the main flame retardant is one or a mixture of melamine polyphosphate, melamine phosphate and melamine cyanurate; and the auxiliary flame retardant is one or a mixture of inorganic hypophosphite, diethyl hypophosphite and diphenyl hypophosphite. The polypropylene material is good in fire retardant performance and high in fire retardant efficiency; because ammonium polyphosphate component is excluded, the polypropylene material has the advantages of non-hydroplaning in processing, no release of ammonia gas and less water in bracing.
Description
Technical field
the invention belongs to technical field of polymer materials, be specifically related to a kind of halogen-free flame-retardant glass fiber reinforced polypropylene composite material and preparation method thereof.
Background technology
polypropylene (PP), as one of four large general-purpose plastics, has good mechanical property and the characteristic of chemical-resistant reagent, is easy to machine-shaping and low price, applies comparatively extensive.But when making some engineering part and being applied to high performance material field, polyacrylic mechanical property is difficult to reach requirement, therefore common way adds glass fibre in polypropylene matrix, carries out enhancement process through blending extrusion to it, obtain fiber glass reinforced polypropylene material.In addition, polyacrylic oxygen index (LOI) only has about 17.5, and belong to inflammable material and burning easily drippage, once catch fire, other combustiblematerialss that easily ignite even cause fire, therefore must carry out fire-retardant finish to polypropylene material.
polyacrylic fire-retardant mainly through adding fire retardant blending modification method, the fire retardant itself and the object that serial physical chemical reaction reaches fire-retardant occurs between fire retardant and matrix when burning.Additive flame retardant conventional at present has halogenated flame retardant, but halogenated flame retardant can produce hazardous and noxious substances, the health of serious harm people when burning.The raising be familiar with health along with people and the enhancing of environmental consciousness are clearly promulgated a decree the production and use that limit this based flame retardant and flame retardant products thereof in some countries and regions of representative with European Union.Given this, the exploitation of halogen-free flame retardants is subject to the people's attention and pays close attention to.Common halogen-free flame retardants has expansion type flame retardant, metal hydroxide combustion inhibitor, silicone flame retardant etc.Metal hydroxides is as a kind of inorganic combustion inhibitor, have certain application because it is inexpensive, nontoxic, but there is addition greatly, with resin matrix poor compatibility as fire retardant in metal hydroxides, to shortcomings such as polymer machinery performance compromise are large, application is subject to larger restriction; Silicone flame retardant because of its price, the high and less use of fire retardant material cost.Expansion type flame retardant because addition is relatively less, toxic is little, good with matrix phase capacitive, enjoy market to pay close attention to advantages such as matrix mechanical impact are little.But conventional expanded type fire retardant also existing defects when being used for fiberglass reinforced PP, as not high in flame retarding efficiency and because of containing ammonium polyphosphate (APP), there is very serious neatly problem man-hour extruding to add, during tie rod, water amount is large, make the particle water content of acquisition large, have certain influence to final material property, and this also causes the follow-up drying time of particle long, production cycle is extended, adds tooling cost.In addition, the thermostability of APP is not high enough, adds and has the release of a large amount of ammonia man-hour, affects the health of workshop, facility environment and operator.
Summary of the invention
the present invention is intended to overcome fiberglass reinforced PP Flame Retardancy in prior art can process hydroplaning phenomena problem that is serious, that discharge with a large amount of ammonia by poor, traditional APP type Intumescent Retardant System, provides a kind of halogen-free flame-retardant glass fiber reinforced polypropylene composite material of improvement.
another object of the present invention is to provide the preparation method of above-mentioned halogen-free flame-retardant glass fiber reinforced polypropylene composite material.
for solving above technical problem, the technical scheme that the present invention takes is:
a kind of halogen-free flame-retardant glass fiber reinforced polypropylene composite material, by weight, comprises following component:
acrylic resin 33% ~ 59%
compound flame retardant 15% ~ 35%
glass fibre 20% ~ 30%
compatilizer 3% ~ 10%
coupling agent 0.4% ~ 2.5%
thermo-stabilizer 1% ~ 3%
oxidation inhibitor 0.3% ~ 0.9%
lubricant 0.3% ~ 1%
dispersion agent 0.3% ~ 0.5%
wherein, described compound flame retardant is obtained through mixing composite by quality proportioning 41 ~ 79:21 ~ 59 by main flame retardant and secondary fire retardant, described main flame retardant is the combination of one or more in melamine polyphosphate (MPP), melamine phosphate (MP), melamine cyanurate (MCA), and described secondary fire retardant is the combination of one or more in inorganic hypophosphite, diethyl phosphinates, diphenyl phosphonic acid salt.Described phosphorus (phosphine) hydrochlorate can aluminium salt, magnesium salts, calcium salt, sodium salt, zinc salt and/or protonated ammonia alkali, commonly uses as aluminium salt.
preferably, described glass fibre is alkali-free roving glass fiber.
preferably, the melting index of described acrylic resin is between 20 ~ 40g/10min.
preferably, described compatilizer is the combination of one or more in maleic anhydride inoculated polypropylene, ethylene methyl acrylate copolymer, glycidyl methacrylate, POE grafted maleic anhydride (i.e. ethylene octene copolymer elastomer grafted maleic anhydride), EPDM grafted maleic anhydride (i.e. grafting maleic anhydride with ethylene propylene terpolymer), EVA grafted maleic anhydride (i.e. ethylene-vinyl acetate copolymer elastomer grafted maleic anhydride).
preferably, described coupling agent is silane coupling agent, as KH550, KH560 and KH570 etc.
preferably, described thermo-stabilizer is the combination of one or more in dibutyl tin laurate, three (4-nonyl phenyl) phosphorous acid ester, hydrotalcite, activated magnesia, zinc oxide and talcum powder.
preferably, described oxidation inhibitor is the combination of one or more in irgasfos 168, oxidation inhibitor 628, antioxidant 1010 and oxidation inhibitor 1098.
preferably, described lubricant is the combination of one or more in calcium stearate, Magnesium Stearate, Zinic stearas, polyethylene wax, amide waxe, stearylamide series lubricant agent and pentaerythritol ester series lubricant agent.
preferably, described dispersion agent is silicone powder.
the preparation method of above-mentioned halogen-free flame-retardant glass fiber reinforced polypropylene composite material, comprises the following steps:
(1), by formula rate take main flame retardant and secondary fire retardant, add in high mixer and mix, obtain compound flame retardant;
(2), by formula ratio take acrylic resin, the compound flame retardant of step (1) gained, compatilizer, coupling agent, thermo-stabilizer, oxidation inhibitor, lubricant and dispersion agent, it is even above-mentioned raw materials to be added high-speed mixer and mixing;
(3), the raw material mixed through step (2) is added twin screw extruder from charging opening, the glass of formula ratio is sent into from the glass feed hole of twin screw extruder, through melting mixing, extruding pelletization, obtain described halogen-free flame-retardant glass fiber reinforced polypropylene composite material;
described twin screw extruder is divided between five temperature controlled region from charging opening to head, and fabrication process condition is:
one district's temperature: 170 DEG C ~ 190 DEG C, two district's temperature: 180 DEG C ~ 200 DEG C, three district's temperature: 180 DEG C ~ 200 DEG C, four district's temperature: 170 DEG C ~ 190 DEG C, five district's temperature 170 DEG C ~ 190 DEG C; Head temperature: 180 DEG C ~ 200 DEG C; Screw speed: 220 ~ 260r/min; Melt pressure: 4.75 ~ 6.00MPa; Vacuum tightness :-0.03 ~-0.06MPa.
due to the enforcement of above technical scheme, the present invention compared with prior art tool has the following advantages:
product flame retarding efficiency of the present invention is high and do not comprise ammonium polyphosphate component, has and processes the advantages such as not neatly, water amount be little, and after extruding pelletization, particle can shorten time of drying greatly, reduces energy consumption and cost; And owing to not comprising ammonium polyphosphate component, add and do not have the releasing of corrosive ammonia man-hour in a large number, the permanent placement surface of sample can not be clamminess, and flame retardant resistance can not decline; Testing vertical flammability result shows, can reach 1.6mmV0 rank by this product of UL-94 standard.In addition, the present invention adopts silane coupler modified, makes glass good dispersity, and stronger with basal body binding force, thus product has good mechanical property.
Embodiment
below in conjunction with comparative example and embodiment, the present invention is described in more detail, but is not limited to these embodiments.
comparative example 1
(1) expansion type flame retardant I is prepared: take 50% ammonium polyphosphate, 25% tetramethylolmethane, 25% melamine cyanurate by mass percentage, pour in high-speed mixer and mix, obtain expansion type flame retardant I;
(2) raw material premix: by mass percentage, take 33%PP resin, expansion type flame retardant I, the 7% maleic anhydride graft PP obtained by 25% step (1), 2% zinc oxide, 1.5% coupling agent KH550,0.4% irgasfos 168,0.2% antioxidant 1010,0.6% calcium stearate, 0.3% silicone powder, the above-mentioned each raw material taken fully is mixed in high-speed mixer;
(3) raw material mixed for step (2) is added twin screw extruder from charging opening, glass is sent into from glass feed hole, by arranging engine speed and feeding frequency makes the feeding amount of glass be just in time 30%, melting mixing, extruding pelletization, obtain the polypropylene composite material in this example.Concrete complete processing is:
one district's temperature is: 170 ~ 190 DEG C; Two district's temperature are 180 ~ 200 DEG C; Three district's temperature are 180 ~ 200 DEG C; Four district's temperature are 170 ~ 190 DEG C, and five district's temperature are 170 ~ 190 DEG C; Head temperature is 180 ~ 200 DEG C; Rotating speed 220 ~ 260r/min; Melt pressure 4.75 ~ 6.00MPa; Vacuum tightness-0.03 ~-0.06MPa.
comparative example 2
(1) expansion type flame retardant II is prepared: take 58% ammonium polyphosphate, 31% triazine char-forming agent, 8% melamine cyanurate and 3% synergist by mass percentage, add in high-speed mixer and mix, obtain expansion type flame retardant II; Described synergist organo montmorillonite.
(2) raw material premix: by mass percentage, take 33%PP resin, the expansion type flame retardant II obtained by 25% step (1), 7%POE grafted maleic anhydride, 2% zinc oxide, 1.5% coupling agent KH550,0.4% irgasfos 168,0.2% antioxidant 1010,0.6% calcium stearate, 0.3% silicone powder, the above-mentioned each raw material taken fully is mixed in high-speed mixer;
(3) raw material mixed for step (2) is added twin screw extruder from charging opening, glass is sent into from glass feed hole, by arranging engine speed and feeding frequency makes the feeding amount of glass be just in time 30%, melting mixing, extruding pelletization, obtain the polypropylene composite material in this example.Concrete complete processing is:
one district's temperature is: 170 ~ 190 DEG C; Two district's temperature are 180 ~ 200 DEG C; Three district's temperature are 180 ~ 200 DEG C; Four district's temperature are 170 ~ 190 DEG C, and five district's temperature are 170 ~ 190 DEG C; Head temperature is 180 ~ 200 DEG C; Rotating speed 220 ~ 260r/min; Melt pressure 4.75 ~ 6.00MPa; Vacuum tightness-0.03 ~-0.06MPa.
embodiment 1
(1) compound flame retardant is prepared: take MPP and aluminum diethylphosphinate by quality proportioning 79:21, add in high-speed mixer and mix, obtain compound flame retardant; Also can add a small amount of coupling agent when mixing make both mixed effects better;
(2) raw material premix: by mass percentage, take 33%PP resin, the compound flame retardant obtained by 25% step (1), 7% maleic anhydride graft PP, 2% zinc oxide, 1.5% coupling agent KH550,0.4% irgasfos 168,0.2% antioxidant 1010,0.6% calcium stearate, 0.3% silicone powder, the above-mentioned each raw material taken fully is mixed in high-speed mixer;
(3) raw material mixed for step (2) is added twin screw extruder from charging opening, glass is sent into from glass feed hole, by arranging engine speed and feeding frequency makes the feeding amount of glass be just in time 30%, melting mixing, extruding pelletization, obtain the polypropylene composite material of the present embodiment.Concrete complete processing is:
one district's temperature is: 170 ~ 190 DEG C; Two district's temperature are 180 ~ 200 DEG C; Three district's temperature are 180 ~ 200 DEG C; Four district's temperature are 170 ~ 190 DEG C, and five district's temperature are 170 ~ 190 DEG C; Head temperature is 180 ~ 200 DEG C; Rotating speed 220 ~ 260r/min; Melt pressure 4.75 ~ 6.00MPa; Vacuum tightness-0.03 ~-0.06MPa.
embodiment 2
(1) compound flame retardant is prepared: take MPP, MCA and aluminum diethylphosphinate by quality proportioning 50:10:40, add in high-speed mixer and mix, obtain compound flame retardant; Also can add a small amount of coupling agent when mixing make both mixed effects better;
(2) raw material premix: by mass percentage, take 33%PP resin, the compound flame retardant obtained by 25% step (1), 7% POE grafted maleic anhydride, 2% activated magnesia, 1.5% coupling agent KH550,0.4% oxidation inhibitor 628,0.2% antioxidant 1010,0.3% Magnesium Stearate, 0.3% calcium stearate, 0.3% silicone powder, the above-mentioned each raw material taken fully is mixed in high-speed mixer;
(3) raw material mixed for step (2) is added twin screw extruder from charging opening, glass is sent into from glass feed hole, by arranging engine speed and feeding frequency makes the feeding amount of glass be just in time 30%, melting mixing, extruding pelletization, obtain the polypropylene composite material of the present embodiment.Concrete complete processing is:
one district's temperature is: 170 ~ 190 DEG C; Two district's temperature are 180 ~ 200 DEG C; Three district's temperature are 180 ~ 200 DEG C; Four district's temperature are 170 ~ 190 DEG C, and five district's temperature are 170 ~ 190 DEG C; Head temperature is 180 ~ 200 DEG C; Rotating speed 220 ~ 260r/min; Melt pressure 4.75 ~ 6.00MPa; Vacuum tightness-0.03 ~-0.06MPa.
embodiment 3
(1) compound flame retardant is prepared: take MP and hypo-aluminum orthophosphate by quality proportioning 41:59, add in high-speed mixer and mix, obtain compound flame retardant; Also can add a small amount of coupling agent when mixing make both mixed effects better;
(2) raw material premix: by mass percentage, take 33%PP resin, the compound flame retardant obtained by 25% step (1), 7% ethylene methyl acrylate copolymer, 2% zinc oxide, 1.5% coupling agent KH570,0.4% irgasfos 168,0.2% antioxidant 1010,0.3%PE wax, 0.3% calcium stearate, 0.3% silicone powder, the above-mentioned each raw material taken fully is mixed in high-speed mixer;
(3) raw material mixed for step (2) is added twin screw extruder from charging opening, glass is sent into from glass feed hole, by arranging engine speed and feeding frequency makes the feeding amount of glass be just in time 30%, melting mixing, extruding pelletization, obtain the polypropylene composite material of the present embodiment.Concrete complete processing is:
one district's temperature is: 170 ~ 190 DEG C; Two district's temperature are 180 ~ 200 DEG C; Three district's temperature are 180 ~ 200 DEG C; Four district's temperature are 170 ~ 190 DEG C, and five district's temperature are 170 ~ 190 DEG C; Head temperature is 180 ~ 200 DEG C; Rotating speed 220 ~ 260r/min; Melt pressure 4.75 ~ 6.00MPa; Vacuum tightness-0.03 ~-0.06MPa.
embodiment 4
(1) compound flame retardant is prepared: take MP and hypo-aluminum orthophosphate by quality proportioning 79:21, add in high-speed mixer and mix, obtain compound flame retardant; Also can add a small amount of coupling agent when mixing make both mixed effects better;
(2) raw material premix: by mass percentage, take 43%PP resin, the compound flame retardant obtained by 25% step (1), 7% maleic anhydride graft PP, 3% zinc oxide, 1.5% coupling agent KH550,0.4% irgasfos 168,0.2% antioxidant 1010,0.6% calcium stearate, 0.3% silicone powder, the above-mentioned each raw material taken fully is mixed in high-speed mixer;
(3) raw material mixed for step (2) is added twin screw extruder from charging opening, glass is sent into from glass feed hole, by arranging engine speed and feeding frequency makes the feeding amount of glass be just in time 20%, melting mixing, extruding pelletization, obtain the polypropylene composite material of the present embodiment.Concrete complete processing is:
one district's temperature is: 170 ~ 190 DEG C; Two district's temperature are 180 ~ 200 DEG C; Three district's temperature are 180 ~ 200 DEG C; Four district's temperature are 170 ~ 190 DEG C, and five district's temperature are 170 ~ 190 DEG C; Head temperature is 180 ~ 200 DEG C; Rotating speed 220 ~ 260r/min; Melt pressure 4.75 ~ 6.00MPa; Vacuum tightness-0.03 ~-0.06MPa.
the present invention preferably selects the twin screw extruder being provided with glass feed hole near charging opening, easily causes mixing uneven problem to avoid glass and other raw materials all direct adding from charging opening.
the polypropylene particles of above comparative example and each embodiment granulation gained is made the batten meeting corresponding testing standard, then carries out the test of mechanical property and flame retardant properties, result is see table-1.
table-1
only have 25.5%, UL-94 to test without rank as can be seen from table-1, the polypropylene composite material oxygen index LOI obtained by comparative example 1, flame retardant effect is poor, and adds and have man-hour hydroplaning phenomena, ammonia taste many compared with water amount during dense, tie rod; Polypropylene composite material oxygen index LOI obtained by comparative example 2 can reach 33.5%, UL-94 test can reach V0 rank, illustrates and reaches good flame retardant effect, but add man-hour hydroplaning phenomena still unavoidably, ammonia taste dense, tie rod time water amount many.And from the test result of embodiment 1 ~ embodiment 4, material all can reach higher oxygen index value, UL-94 all can reach V0 rank, illustrate that the halogen-free flame-retardant glass fiber reinforced polypropylene composite material that the present invention obtains has good flame retardant resistance, simultaneously mechanical property is not lost yet, and add effectively can avoid hydroplaning phenomena man-hour, substantially discharge without ammonia, tie rod time water amount few.
above to invention has been detailed description; its object is to allow the personage being familiar with this art can understand content of the present invention and be implemented; can not limit the scope of the invention with this; the equivalence change that all spirit according to the present invention are done or modification, all should be encompassed in protection scope of the present invention.
Claims (10)
1. a halogen-free flame-retardant glass fiber reinforced polypropylene composite material, is characterized in that: by weight, comprises following component:
Acrylic resin 33% ~ 59%
Compound flame retardant 15% ~ 35%
Glass fibre 20% ~ 30%
Compatilizer 3% ~ 10%
Coupling agent 0.4% ~ 2.5%
Thermo-stabilizer 1% ~ 3%
Oxidation inhibitor 0.3% ~ 0.9%
Lubricant 0.3% ~ 1%
Dispersion agent 0.3% ~ 0.5%
Wherein, described compound flame retardant is obtained through mixing composite by quality proportioning 41 ~ 79:21 ~ 59 by main flame retardant and secondary fire retardant, described main flame retardant is the combination of one or more in melamine polyphosphate, melamine phosphate, melamine cyanurate, and described secondary fire retardant is the combination of one or more in inorganic hypophosphite, diethyl phosphinates, diphenyl phosphonic acid salt.
2. halogen-free flame-retardant glass fiber reinforced polypropylene composite material according to claim 1, is characterized in that: described glass fibre is alkali-free roving glass fiber.
3. halogen-free flame-retardant glass fiber reinforced polypropylene composite material according to claim 1, is characterized in that: the melting index of described acrylic resin is between 20 ~ 40g/10min.
4. halogen-free flame-retardant glass fiber reinforced polypropylene composite material according to claim 1, is characterized in that: described compatilizer is the combination of one or more in maleic anhydride inoculated polypropylene, ethylene methyl acrylate copolymer, glycidyl methacrylate, POE grafted maleic anhydride, EPDM grafted maleic anhydride, EVA grafted maleic anhydride.
5. halogen-free flame-retardant glass fiber reinforced polypropylene composite material according to claim 1, is characterized in that: described coupling agent is silane coupling agent.
6. halogen-free flame-retardant glass fiber reinforced polypropylene composite material according to claim 1, is characterized in that: described thermo-stabilizer is the combination of one or more in dibutyl tin laurate, three (4-nonyl phenyl) phosphorous acid ester, hydrotalcite, activated magnesia, zinc oxide and talcum powder.
7. halogen-free flame-retardant glass fiber reinforced polypropylene composite material according to claim 1, is characterized in that: described oxidation inhibitor is the combination of one or more in irgasfos 168, oxidation inhibitor 628, antioxidant 1010 and oxidation inhibitor 1098.
8. halogen-free flame-retardant glass fiber reinforced polypropylene composite material according to claim 1, is characterized in that: described lubricant is the combination of one or more in calcium stearate, Magnesium Stearate, Zinic stearas, polyethylene wax, amide waxe, stearylamide series lubricant agent and pentaerythritol ester series lubricant agent.
9. halogen-free flame-retardant glass fiber reinforced polypropylene composite material according to claim 1, is characterized in that: described dispersion agent is silicone powder.
10. a preparation method for the halogen-free flame-retardant glass fiber reinforced polypropylene composite material according to any one of claim 1 ~ 9, is characterized in that: comprise the following steps:
(1), by formula rate take main flame retardant and secondary fire retardant, add in high mixer and mix, obtain compound flame retardant;
(2), by formula ratio take acrylic resin, the compound flame retardant of step (1) gained, compatilizer, coupling agent, thermo-stabilizer, oxidation inhibitor, lubricant and dispersion agent, it is even above-mentioned raw materials to be added high-speed mixer and mixing;
(3), the raw material mixed through step (2) is added twin screw extruder from charging opening, the glass of formula ratio is sent into from the glass feed hole of twin screw extruder, through melting mixing, extruding pelletization, obtain described halogen-free flame-retardant glass fiber reinforced polypropylene composite material;
Described twin screw extruder is divided between five temperature controlled region from charging opening to head, and fabrication process condition is:
One district's temperature: 170 DEG C ~ 190 DEG C, two district's temperature: 180 DEG C ~ 200 DEG C, three district's temperature: 180 DEG C ~ 200 DEG C, four district's temperature: 170 DEG C ~ 190 DEG C, five district's temperature 170 DEG C ~ 190 DEG C; Head temperature: 180 DEG C ~ 200 DEG C; Screw speed: 220 ~ 260r/min; Melt pressure: 4.75 ~ 6.00MPa; Vacuum tightness :-0.03 ~-0.06MPa.
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