CN101880420B - Surface precipitation-free flame-retardant polypropylene compound and preparation method thereof - Google Patents

Surface precipitation-free flame-retardant polypropylene compound and preparation method thereof Download PDF

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CN101880420B
CN101880420B CN2010101545873A CN201010154587A CN101880420B CN 101880420 B CN101880420 B CN 101880420B CN 2010101545873 A CN2010101545873 A CN 2010101545873A CN 201010154587 A CN201010154587 A CN 201010154587A CN 101880420 B CN101880420 B CN 101880420B
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antioxidant
peroxide
retardant
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CN101880420A (en
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彭维礼
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HUNAN MEILAIPO SCIENCE AND TECHNOLOGY Co.,Ltd.
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SHANGHAI MEILAIPO CHEMICALS CO Ltd
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Abstract

The invention relates to a surface precipitation-free flame-retardant polypropylene compound and a preparation method thereof. The surface precipitation-free flame-retardant polypropylene compound comprises the following components by weight percent: 70-98.5% of polypropylene resin, 1-15% of melamine hydrobromide, 0.3-7% of phosphinates, 0.2-4% of flame retardant synergist, 0-2% of synergetic flame retardant, 0-1% of antioxidant and 0-1% of processing acid. The preparation method thereof is implemented as follows: weighting the above components based on proportion, evenly mixing, melt-mixing the above mixture, pelletizing and drying to obtain the product in the invention. The surface precipitation-free flame-retardant polypropylene compound has high flame retardant efficiency, good flowability, no precipitation, and high flame retardant rating up to UL94 V-0, and can satisfy the use requirements of flame retardant materials in building materials, electrical appliance casings, sockets, bellows, lighting lamps and the like.

Description

Surface precipitation-free flame-retardant polypropylene compound and preparation method thereof
Technical field
The present invention relates to a kind of surface precipitation-free flame-retardant polypropylene compound and preparation method thereof.
Background technology
Vestolen PP 7052 (PP) becomes one of general-purpose plastics of widespread use because of its excellent comprehensive performance and the good ratio of performance to price, wide in range machine-shaping conditions.But the Vestolen PP 7052 easy firing, its limiting oxygen index(LOI) is 17.0-18.0%, can not extinguish after in air, catching fire, therefore to being used for being prone to produce the facility and the place of fire, Vestolen PP 7052 must carry out flame-retardant modified.
Polyacrylic flame-retardant modified can the realization through the fire retardant that adding have retarded combustion chemistry and a physical reaction process.With regard to prior art, being used for polyacrylic fire retardant has halogen flame and halogen-free flame-retardant, also can be the compound of halogen flame and halogen-free flame-retardant.It influences the raising that requires to environmental protection to Along with people's to promoting material security and minimizing, the efficient low halogenization of fire retardant material, even halogenization is the emphasis direction of Future Development.Vestolen PP 7052 has been obtained certain progress in recent years with halogen-free flame-retardant; But halogen-free flame-retardant systems such as the phosphor-nitrogen expansion type that uses at present, metal hydroxides, red phosphorus, expanded graphite, organosilicon-mineral compound; All exist the fire retardant addition big; To defectives such as material property influence are big, so also there is significant limitation in widespread use, and therefore the polypropylene flame redardant of current high-efficiency environment friendly is main with halogen flame still.
Can be used for polyacrylic halogen flame has chlorine-based flame retardant and bromide fire retardant, because the flame retarding efficiency of chlorine-based flame retardant or thermotolerance not enough (like clorafin) are therefore seldom used in polypropylene flame redardant.The bromide fire retardant that current polypropylene fire retardant uses has decabromodiphynly oxide, TDE, three (2; The 3-dibromopropyl) chlorinated isocyanurates (TBC), 1; Two (tetrabromo phthalimide) ethane (BT93) of 2-, tetrabromo-bisphenol two (2; The 3-dibromopropyl) ether (OBE is called for short eight bromo ether in China), hexabromocyclododecane (HBCD), tetrabromo-bisphenol s two (2, the 3-dibromopropyl) ether (being called for short eight bromine S ethers) etc. in China.Adopt the composite polypropylene fire retardant great majority that are used for of above-mentioned fire retardant and sb oxide to be sophisticated known technology; With polypropylene flame redardants such as decabromodiphynly oxide, TDEs; Because of addition influences material mechanical performance greatly; General and the expensive of TBC and BT93 flame retarding efficiency, flame retarding efficiencies such as OBE are high but be prone to separate out from the polypropylene flame redardant surface.In recent years, the fire retardant of Vestolen PP 7052 use efficiently is eight bromine S ethers both at home and abroad, like Chinese patent 200610029852; USP 6780914 and 7067576 etc. has been reported and has been adopted eight bromine S ethers and Antimony Trioxide: 99.5Min compound system to come polypropylene flame redardant; Though its flame retarding efficiency is higher, the anti-property separated out is good, owing to produce the bisphenol S raw material sources limited (mainly being that production process is seriously polluted) of eight bromine S ethers; Therefore valency is high, and market supply is difficult to ensure.
Summary of the invention
The purpose of this invention is to provide a kind of surface precipitation-free flame-retardant polypropylene compound and preparation method thereof, the component and the weight percentage of surface precipitation-free flame-retardant polypropylene compound of the present invention comprise: acrylic resin 70-98.5%, trimeric cyanamide hydrobromate 1-15%, phosphinates 0.3-7%, retardant synergist 0.2-4%, fire retarding synergist 0-2%, oxidation inhibitor 0-1% and processing aid 0-1%.The preparation method of anti-flaming polypropylene composite of the present invention; Be that acrylic resin, trimeric cyanamide hydrobromate, phosphinates, retardant synergist, fire retarding synergist, oxidation inhibitor and processing aid are mixed after the weighing in proportion; With the said mixture melting mixing, promptly obtain surface precipitation-free flame-retardant polypropylene compound after granulation, the drying then.Anti-flaming polypropylene composite of the present invention, flame retardant rating can reach UL94 V-0, and flame retarding efficiency is high, and good fluidity is not separated out, and can satisfy the request for utilization with fire retardant material such as building materials, electric appliance casing, socket, corrugated tube and light decoration light fitting.
Surface precipitation-free flame-retardant polypropylene compound of the present invention, its component and weight percentage comprise:
Acrylic resin 70-98.5%,
Trimeric cyanamide hydrobromate (MHB) 1-15%,
Phosphinates 0.3-7%,
Retardant synergist 0.2-4%,
Fire retarding synergist 0-2%,
Oxidation inhibitor 0-1%,
Processing aid 0-1%;
Described acrylic resin is meant homopolymerization PP and copolymerization PP;
Described phosphinates refers to have the compound of following structure (I):
Figure GSA00000096378200021
Wherein, R 1=H, C1-12 alkyl or aromatic base, R 2=H, C1-12 alkyl, alkoxyl group, aromatic base or aryloxy; M=K, Na, Li, Mg, Zn, Al, Ca, Ba, Sn, Sb, Bi or aminoguanidine salt or amine ion; Described phosphinates is one or both and the above mixture in the said structure;
Described retardant synergist is meant a kind of or its mixture in compound (III), compound (IV) or the organo-peroxide with following structure;
Figure GSA00000096378200022
Wherein, R 3, R 4, R 5Or R 6All be respectively a kind of in C1-12 alkyl, alkoxyl group, aromatic base or the fragrant oxygen base; X or Y are H, C1-12 alkyl, alkoxyl group, aromatic base, fragrant oxygen base, halogen, nitro, sulfonic group, sulfydryl or polysubstituted aromatic base;
Wherein, R 7Or R 8Be respectively a kind of in C1-12 alkyl or the aromatic base; R 9Be alkyl, alkoxyl group, aromatic base, fragrant oxygen base, halogen, nitro, sulfonic group, sulfydryl or polysubstituted aromatic base; Z is halogen, nitro, sulfonic group or sulfydryl.
As optimized technical scheme:
Aforesaid surface precipitation-free flame-retardant polypropylene compound, wherein, described amine ion is NH 4 +Or organic amine ion; Described organic amine ion is organic primary amine, secondary amine or tertiary amine and from the H of Hypophosporous Acid, 50 +The ion that generates refers in particular to trimeric cyanamide and H from Hypophosporous Acid, 50 +The ion that generates, its structure like (II) does
Figure GSA00000096378200032
Aforesaid surface precipitation-free flame-retardant polypropylene compound, wherein, described organo-peroxide is a kind of or its mixture in hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxy esters or the ketone peroxide; Wherein, described hydroperoxide are tertbutyl peroxide or cumyl hydroperoxide, and described dialkyl peroxide is ditertiary butyl peroxide, dicumyl peroxide, t-butylperoxy isopropyl benzene, two (tert-butyl peroxy base sec.-propyl) benzene, 3,3; 6,6,9-, 9-hexa-methylene-1; 2,4,5-four oxygen cyclononane, 2,5-dimethyl--2; 5-two (t-butylperoxy)-3-acetylene or 2,5-dimethyl--2,5-two (tert-butyl peroxy base) hexane, described diacyl peroxide are Lucidol, peroxo-two (4-chlorobenzoyl) or peroxo-two (2; The 4-dichloro-benzoyl), described peroxy esters is peroxo-tert-butyl acetate or peroxidized t-butyl perbenzoate, 4, two (tert-butyl peroxy base) n-butyl pentanoates of 4-, and described ketone peroxide is 1; The two tert-butyl peroxides-3,3 of 1-, the 5-trimethyl-cyclohexane.
Aforesaid surface precipitation-free flame-retardant polypropylene compound, wherein, described fire retarding synergist is meant a kind of or its mixture in oxide compound, bismuth salt or the borate of oxide compound, stibnate, bismuth of antimony.
Aforesaid surface precipitation-free flame-retardant polypropylene compound, wherein, described oxidation inhibitor is selected from a kind of or its mixture in phenols, phosphorous acid esters, divalent sulfur class or the space suffocated amine antioxidant; Wherein, Described phenolic antioxidant has antioxidant 264, antioxidant 1010, antioxidant 1076, antioxidant SP, antioxidant 2246, antioxidant CA, antioxidant 330, Irganox1890 or antioxidant 3114; Phosphorous acid esters have oxidation inhibitor TNP, oxidation inhibitor ODP, oxidation inhibitor 168, Irganox1093 or Irganox1222; The divalent sulfur kind antioxidant has two LAURIC ACID 99 MIN thiodipropionates (DLTP), distearyl acid thiodipropionate (DSTP), and suffocated amine antioxidant has LS-744, LS-770, GW-540 or Flamstab NOR116.
Aforesaid surface precipitation-free flame-retardant polypropylene compound, wherein, described processing aid is selected from a kind of or its mixture in low molecule lipid, metallic soap class, ester class or the amides processing aid; Wherein, Low molecule lipid is solid paraffin, whiteruss or low molecular weight polycaprolactone alkene wax; The metallic soap class is calcium stearate, Magnesium Stearate, Zinic stearas or barium stearate; The ester class is glycol stearate, stearin or Triple Pressed Stearic Acid pentaerythritol ester, and amides is erucicamide, methylene bis stearic amide or N, the N-ethylene bis stearic acid amide.
The present invention also provides a kind of preparation method of surface precipitation-free flame-retardant polypropylene compound; Acrylic resin, trimeric cyanamide hydrobromate, phosphinates, retardant synergist, fire retarding synergist, oxidation inhibitor and processing aid are mixed after the weighing in proportion; With the said mixture melting mixing, promptly obtain high gloss high transparent surface precipitation-free flame-retardant polypropylene compound after granulation, the drying then;
Perhaps trimeric cyanamide hydrobromate, phosphinates, retardant synergist, fire retarding synergist, oxidation inhibitor and processing aid are mixed after the weighing in proportion and make the fire retardant compound; With fire retardant compound and acrylic resin melting mixing, promptly obtain surface precipitation-free flame-retardant polypropylene compound after granulation, the drying then; In surface precipitation-free flame-retardant polypropylene compound, the weight percentage of each component is:
Acrylic resin 70-98.5%,
Trimeric cyanamide hydrobromate 1-15%,
Phosphinates 0.3-7%,
Retardant synergist 0.2-4%,
Fire retarding synergist 0-2%,
Oxidation inhibitor 0-1%,
Processing aid 0-1%;
Wherein, described acrylic resin is meant the copolymerization PP of homopolymerization PP and propylene and other olefin-copolymerization;
Described phosphinates refers to have the compound of following structure (I):
Figure GSA00000096378200041
Wherein, R 1=H, C1-12 alkyl or aromatic base, R 2=H, C1-12 alkyl, alkoxyl group, aromatic base or aryloxy; M=K, Na, Li, Mg, Zn, Al, Ca, Ba, Sn, Sb, Bi or aminoguanidine salt or amine ion; Described phosphinates is one or both and the above mixture in the said structure;
Described retardant synergist is meant a kind of or its mixture in compound (III), compound (IV) or the organo-peroxide with following structure;
Figure GSA00000096378200051
Wherein, R 3, R 4, R 5Or R 6All be respectively a kind of in C1-12 alkyl, alkoxyl group, aromatic base or the fragrant oxygen base; X or Y are H, C1-12 alkyl, alkoxyl group, aromatic base, fragrant oxygen base, halogen, nitro, sulfonic group, sulfydryl or polysubstituted aromatic base;
Figure GSA00000096378200052
Wherein, R 7Or R 8Be respectively a kind of in C1-12 alkyl or the aromatic base; R 9Be alkyl, alkoxyl group, aromatic base, fragrant oxygen base, halogen, nitro, sulfonic group, sulfydryl or polysubstituted aromatic base; Z is halogen, nitro, sulfonic group or sulfydryl.
Wherein, the preparation method of aforesaid surface precipitation-free flame-retardant polypropylene compound, described amine ion is NH 4 +Or organic amine ion; Described organic amine ion is organic primary amine, secondary amine or tertiary amine and from the H of Hypophosporous Acid, 50 +The ion that generates refers in particular to trimeric cyanamide and H from Hypophosporous Acid, 50 +The ion that generates, its structure like (II) does
Figure GSA00000096378200053
Described organo-peroxide is a kind of or its mixture in hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxy esters or the ketone peroxide; Wherein, described hydroperoxide are tertbutyl peroxide or cumyl hydroperoxide, and described dialkyl peroxide is ditertiary butyl peroxide, dicumyl peroxide, t-butylperoxy isopropyl benzene, two (tert-butyl peroxy base sec.-propyl) benzene, 3,3; 6,6,9-, 9-hexa-methylene-1; 2,4,5-four oxygen cyclononane, 2,5-dimethyl--2; 5-two (t-butylperoxy)-3-acetylene or 2,5-dimethyl--2,5-two (tert-butyl peroxy base) hexane, described diacyl peroxide are Lucidol, peroxo-two (4-chlorobenzoyl) or peroxo-two (2; The 4-dichloro-benzoyl), described peroxy esters is peroxo-tert-butyl acetate or peroxidized t-butyl perbenzoate, 4, two (tert-butyl peroxy base) n-butyl pentanoates of 4-, and described ketone peroxide is 1; The two tert-butyl peroxides-3,3 of 1-, the 5-trimethyl-cyclohexane; Described fire retarding synergist is meant a kind of or its mixture in oxide compound, bismuth salt or the borate of oxide compound, stibnate, bismuth of antimony;
Described oxidation inhibitor is selected from a kind of or its mixture in phenols, phosphorous acid esters, divalent sulfur class or the space suffocated amine antioxidant; Wherein, Described phenolic antioxidant has antioxidant 264, antioxidant 1010, antioxidant 1076, antioxidant SP, antioxidant 2246, antioxidant CA, antioxidant 330, Irganox1890 or antioxidant 3114; Phosphorous acid esters have oxidation inhibitor TNP, oxidation inhibitor ODP, oxidation inhibitor 168, Irganox1093 or Irganox1222; The divalent sulfur kind antioxidant has two LAURIC ACID 99 MIN thiodipropionates (DLTP), distearyl acid thiodipropionate (DSTP), and suffocated amine antioxidant has LS-744, LS-770, GW-540 or Flamstab NOR116;
Described processing aid is selected from a kind of or its mixture in low molecule lipid, metallic soap class, ester class or the amides processing aid; Wherein, Low molecule lipid is solid paraffin, whiteruss or low molecular weight polycaprolactone alkene wax; The metallic soap class is calcium stearate, Magnesium Stearate, Zinic stearas or barium stearate; The ester class is glycol stearate, stearin or Triple Pressed Stearic Acid pentaerythritol ester, and amides is erucicamide, methylene bis stearic amide or N, the N-ethylene bis stearic acid amide.
The present invention provides the preparation method of another kind of surface precipitation-free flame-retardant polypropylene compound again; Trimeric cyanamide hydrobromate, phosphinates, retardant synergist, fire retarding synergist, oxidation inhibitor, processing aid and resin carrier mixed after the weighing in proportion process the fire retardant concentrate feed; Then with fire retardant concentrate feed and acrylic resin melting mixing; The mass ratio of fire retardant concentrate feed and acrylic resin is 1: 1～49, after granulation, drying, promptly obtains surface precipitation-free flame-retardant polypropylene compound; Wherein said resin carrier is Vestolen PP 7052, Vilaterm, PVA or polystyrene support;
In the fire retardant concentrate feed, the weight percentage of each component is:
Resin carrier 4-97%,
Trimeric cyanamide hydrobromate 2-48%,
Phosphinates 0.6-22.4%,
Retardant synergist 0.4-12.8%,
Fire retarding synergist 0-6.4%,
Oxidation inhibitor 0-3.2%,
Processing aid 0-3.2%;
Wherein, described acrylic resin is meant the copolymerization PP of homopolymerization PP and propylene and other olefin-copolymerization;
Described phosphinates refers to have the compound of following structure (I):
Figure GSA00000096378200071
Wherein, R 1=H, C1-12 alkyl or aromatic base, R 2=H, C1-12 alkyl, alkoxyl group, aromatic base or aryloxy; M=K, Na, Li, Mg, Zn, Al, Ca, Ba, Sn, Sb, Bi or aminoguanidine salt or amine ion; Described phosphinates is one or both and the above mixture in the said structure;
Described retardant synergist is meant a kind of or its mixture in compound (III), compound (IV) or the organo-peroxide with following structure;
Wherein, R 3, R 4, R 5Or R 6All be respectively a kind of in C1-12 alkyl, alkoxyl group, aromatic base or the fragrant oxygen base; X or Y are H, C1-12 alkyl, alkoxyl group, aromatic base, fragrant oxygen base, halogen, nitro, sulfonic group, sulfydryl or polysubstituted aromatic base;
Figure GSA00000096378200073
Wherein, R7 or R8 are respectively a kind of in C1-12 alkyl or the aromatic base; R9 is alkyl, alkoxyl group, aromatic base, fragrant oxygen base, halogen, nitro, sulfonic group, sulfydryl or polysubstituted aromatic base; Z is halogen, nitro, sulfonic group or sulfydryl.
The preparation method of aforesaid surface precipitation-free flame-retardant polypropylene compound, described amine ion is NH 4+Or organic amine ion; Described organic amine ion is organic primary amine, secondary amine or tertiary amine and from the H of Hypophosporous Acid, 50 +The ion that generates refers in particular to trimeric cyanamide and H from Hypophosporous Acid, 50 +The ion that generates, its structure like (II) does
Described organo-peroxide is a kind of or its mixture in hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxy esters or the ketone peroxide; Wherein, described hydroperoxide are tertbutyl peroxide or cumyl hydroperoxide, and described dialkyl peroxide is ditertiary butyl peroxide, dicumyl peroxide, t-butylperoxy isopropyl benzene, two (tert-butyl peroxy base sec.-propyl) benzene, 3,3; 6,6,9,9-hexa-methylene-1; 2,4,5-four oxygen cyclononane, 2,5-dimethyl--2; 5-two (t-butylperoxy)-3-acetylene or 2,5-dimethyl--2,5-two (tert-butyl peroxy base) hexane, described diacyl peroxide are Lucidol, peroxo-two (4-chlorobenzoyl) or peroxo-two (2; The 4-dichloro-benzoyl), described peroxy esters is peroxo-tert-butyl acetate or peroxidized t-butyl perbenzoate, 4, two (tert-butyl peroxy base) n-butyl pentanoates of 4-, and described ketone peroxide is 1; The two tert-butyl peroxides-3,3 of 1-, the 5-trimethyl-cyclohexane;
Described fire retarding synergist is meant a kind of or its mixture in oxide compound, bismuth salt or the borate of oxide compound, stibnate, bismuth of antimony;
Described oxidation inhibitor is selected from a kind of or its mixture in phenols, phosphorous acid esters, divalent sulfur class or the space suffocated amine antioxidant; Wherein, Described phenolic antioxidant has antioxidant 264, antioxidant 1010, antioxidant 1076, antioxidant SP, antioxidant 2246, antioxidant CA, antioxidant 330, Irganox1890 or antioxidant 3114; Phosphorous acid esters have oxidation inhibitor TNP, oxidation inhibitor ODP, oxidation inhibitor 168, Irganox1093 or Irganox1222; The divalent sulfur kind antioxidant has two LAURIC ACID 99 MIN thiodipropionates (DLTP), distearyl acid thiodipropionate (DSTP), and suffocated amine antioxidant has LS-744, LS-770, GW-540 or Flamstab NOR116;
Described processing aid is selected from a kind of or its mixture in low molecule lipid, metallic soap class, ester class or the amides processing aid; Wherein, Low molecule lipid is solid paraffin, whiteruss or low molecular weight polycaprolactone alkene wax; The metallic soap class is calcium stearate, Magnesium Stearate, Zinic stearas or barium stearate; The ester class is glycol stearate, stearin or Triple Pressed Stearic Acid pentaerythritol ester, and amides is erucicamide, methylene bis stearic amide or N, the N-ethylene bis stearic acid amide.
The invention has the beneficial effects as follows:
Surface precipitation-free flame-retardant polypropylene compound of the present invention has the flame retarding efficiency height, and good fluidity such as does not separate out at characteristics.Surperficial precipitate-free flame retardant polypropylene composite flame retardant rating of the present invention can reach UL94V-0 (1.6mm), can satisfy the request for utilization with fire retardant material such as building materials, electric appliance casing, socket, corrugated tube and light decoration light fitting.
Embodiment
Below in conjunction with embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
Take by weighing homopolymerization PP resin (melting index 20g/10min) 98KG, 2-carboxyethyl phenyl phosphinic acid aluminium 0.5KG, trimeric cyanamide Hydrogen bromide 1KG, 2-methyl-3-ethyl-2; Dropping into twin screw extruder behind the thorough mixing in 3-phenylbenzene octane 0.3KG, oxidation inhibitor-168 0.1KG, the Magnesium Stearate 0.1KG input mixing tank melt extrudes in 180-200 ℃; Obtain not having the polypropylene flame redardant that separate out on the surface after granulation, the drying; Its fire-retardant rank of the polypropylene flame redardant of gained is UL94 V-2 (1.6mm); Experience 1000 hours down in 80 ℃ of natural air environment, the no fire retardant in surface is separated out.
Embodiment 2-26
Each amount by shown in the table 1 takes by weighing, and drops into then in the mixing tank to drop into twin screw extruder behind the thorough mixing and melt extrude, and obtains not having the polypropylene flame redardant that separate out on the surface after granulation, the drying, tests its fire-retardant and anti-property separated out then, and the result sees table 1.
Table 1
The base butane
4 Homopolymerization PP 80 Ethyl propyl phospho acid barium 6 10 2,3-dimethyl--2-benzyl-3-phenoxy-butane 3 Bismuth carbonate 0.5 Oxidation inhibitor 107 6 0.3 Calcium stearate 0. 2 V-0 Through
5 Homopolymerization PP 80 The butyl phenyl calcium propionate 5 10 2,3-dimethyl--2,3-two (4-chloromethane phenyl) butane 3.5 Bismuthous oxide bismuth trioxide 0.5 Antioxidant SP 0.5 Magnesium Stearate 0. 5 V-1 Through
6 Homopolymerization PP 80 Dodecyl methoxyl group phospho acid tin 5 11 2,3-dimethyl--2-pentyl-3-phenyl 3.5 - 0 Oxidation inhibitor 224 6 0.3 Polyethylene wax 0. 2 V-1 Through
Butane
?7 Copolymerization PP 85 Cyclohexyl phenoxy phospho acid potassium 5 8 2,3-dimethyl--2,3-two (4-nitrophenyl) butane 1 Zinc borate 0.5 Antioxidant CA 0.2 Zinic stearas 0. 3 V-2 Through
?8 Homopolymerization PP 85 Phenyl butoxy phospho acid bismuth 5 7 2,3-dimethyl--2,3-two (4-chloromethane phenyl) butane 2 Antimony peroxide 0.5 Antioxidant 330 0.3 Barium stearate 0. 2 V-2 Through
?9 Homopolymerization PP 85 Diethylammonium phospho acid zinc 5 7 Triphenylmethyl chloride 2 Antimony peroxide, Bismuth carbonate (mass ratio 0.5 Irg ano x18 90 0.3 Glycol stearate 0 2 V-1 Through
2∶1)
1 0 Homopolymerization PP 85 Dimethyl-phospho acid aluminium 5 5.5 2-bromo-2-phenyl butane 4 - 0 Oxidation inhibitor 311 4 0.3 Stearin 02 V-0 Through
1 1 Homopolymerization PP 85 Methylphenoxy phospho acid calcium 7 5 2-sulfydryl-2-naphthyl pentane 2.5 Bismuth carbonate, antimony peroxide (mass ratio 1: 1) 0.4 - 0 The Triple Pressed Stearic Acid pentaerythritol ester 0. 1 V-2 Through
1 2 Homopolymerization PP 90 2-carboxyethyl phenyl phosphinic acid magnesium 3 3 3-nitro-3-(3-fluorophenyl) dodecyl 2 Antimony peroxide, zinc borate (mass ratio 3: 1) 1.5 Oxidation inhibitor OD P 0.3 Erucicamide 0. 2 V-1 Through
1 3 Copolymerization PP 90 The phenyl phosphinic acid melamine salt 4 5 Tertbutyl peroxide 0.4 Bismuth carbonate, Antimony Trioxide: 99.5Min (matter 0.5 Oxidation inhibitor 168 0.1 - 0 V-2 Through
Amount was than 4: 1)
1 4 Homopolymerization PP 90 Methyl dodecyl phospho acid tin 3 6 Cumyl hydroperoxide 0.5 Bismuth carbonate, antimony peroxide (mass ratio 1: 1) 0.3 Irg ano x10 93 0.1 N, the N-ethylene bis stearic acid amide 0. 1 V-2 Through
1 5 Homopolymerization PP 90 Methylcyclohexyl phospho acid bismuth 2 7 Ditertiary butyl peroxide 0.3 Bismuth carbonate, zinc borate (mass ratio 3: 1) 0.5 Irg ano x12 22 0.1 Solid paraffin 0. 1 V-1 Through
1 6 Homopolymerization PP 95 Ethyl (4-chloromethane phenyl) phospho acid aluminium 2 2 Dicumyl peroxide 0.5 Antimony peroxide 0.3 DL TP 0.1 Whiteruss 0. 1 V-2 Through
1 7 Homopolymerization PP 95 Methyl ethoxy 2 2 Lucidol 0.6 Bismuth carbonate 0.2 DS TP 0.1 Calcium stearate 0. 1 V-2 Through
Phosphonic acids barium
1 8 Homopolymerization PP 95 Hydroxymethyl phenyl phospho acid aluminium 1 3.5 The peroxyacetic acid tert-butyl ester 0.3 Antimony Trioxide: 99.5Min 0.2 - 0 - 0 V-2 Through
1 9 Homopolymerization PP 95 One hydrogen perfluorinated butane base phospho acid sodium 1 3 T-butylperoxyl benzoate 0.5 Potassium antimonate 0.2 LS- 770 0.2 Polyethylene wax 0. 1 V-2 Through
2 0 Homopolymerization PP 95 Two (PFO base) phospho acid lithium 1 3 2,5-dimethyl--2,5-two (t-butylperoxy)-3-acetylene 0.7 Zinc antimonates 0.2 G W- 540 0.1 - 0 V-1 Through
2 1 Homopolymerization PP 98 Phenylbenzene 0.6 1 2,3-two 0.4 - 0 - 0 - 0 V-2 Through
Phospho acid aluminium Methyl-2, the 3-diphenyl butane
2 2 Homopolymerization PP 98 Methyl (3-nitrophenyl) phospho acid barium 0.5 1 2,5-dimethyl--2,5-two (tert-butyl peroxy base) hexane 0.3 - 0 Oxidation inhibitor 168 0.2 - 0 V-2 Through
2 3 Homopolymerization PP 98 2-propyloic butyl phospho acid aluminium 0.5 1 4, two (tert-butyl peroxy base) n-butyl pentanoates of 4- 0.3 - Irg ano x10 93 0.1 Stearin 0. 1 V-2 Through
2 4 Homopolymerization PP 98 Dimethyl-time phosphine 0.3 1.2 Peroxo-two (2 0.3 - Antioxidant 330 0.1 The Triple Pressed Stearic Acid pentaerythritol ester 0. 1 V-2 Through
Acid potassium , the 4-dichloro-benzoyl)
2 5 Homopolymerization PP 98.5 2-carboxyethyl phenyl phosphinic acid lithium 0.3 1 1,1-two tert-butyl peroxides-3,3,5-trimethyl-cyclohexane 0.2 - 0 - 0 - 0 V-2 Through
2 6 Homopolymerization PP 98.5 2-carboxyethyl phenyl phosphinic acid ammonium salt 03 1 T-butylperoxy isopropyl benzene and 2,3-dimethyl--2,3-two (4-oil of mirbane 0.2 - 0 - 0 - 0 V-2 Through
Base) mixture of butane, mass ratio 1: 2
Embodiment 27
Take by weighing homopolymerization PP resin (melting index 30g/10min) 95KG, trimeric cyanamide phosphinates 1KG, 2-carboxyethyl phenyl phosphinic acid sodium 1KG, trimeric cyanamide hydrobromate 2KG, 2; 3-diethylammonium-2; Dropping into twin screw extruder behind the thorough mixing in 3-diphenyl butane 0.5KG, the Antimony Trioxide: 99.5Min 0.5KG input mixing tank melt extrudes in 180-200 ℃; Obtain not having the polypropylene flame redardant that separate out on the surface after granulation, the drying; Its fire-retardant rank of the polypropylene flame redardant of gained is UL94V-2 (1.6mm), experiences 1000 hours down in 80 ℃ of natural air environment, and the no fire retardant in surface is separated out.
Embodiment 28
Take by weighing COPP (melting index 2.0g/10min) 90KG, methylethyl phospho acid diethyl amine salt 1KG, trimeric cyanamide hydrobromate 6KG, 2-methyl-3 ethyl-2; 3-diphenyl butane 1KG; Dropping into twin screw extruder behind the thorough mixing in Antimony Trioxide: 99.5Min 1KG, the zinc borate 1KG input mixing tank melt extrudes in 180-200 ℃; Obtain not having the polypropylene flame redardant that separate out on the surface after granulation, the drying; Its fire-retardant rank of the polypropylene flame redardant of gained is UL94 V-2 (1.6mm), experiences 1000 hours down in 80 ℃ of natural air environment, and the no fire retardant in surface is separated out.
Embodiment 29
Take by weighing HOPP (melting index 1.0g/10min) 90KG, 2-carboxyethyl phenyl phosphinic acid melamine salt 2KG, ethylphenyl phospho acid aluminium 1KG, trimeric cyanamide hydrobromate 5KG, 2; 3-dimethyl--2; Dropping into twin screw extruder behind the thorough mixing in 3-dinaphthyl butane 1KG, the antimony peroxide 1KG input mixing tank melt extrudes in 180-200 ℃; Obtain not having the polypropylene flame redardant that separate out on the surface after granulation, the drying; Its fire-retardant rank of the polypropylene flame redardant of gained is UL94V-2 (1.6mm), experiences 1000 hours down in 80 ℃ of natural air environment, and the no fire retardant in surface is separated out.
Embodiment 30
Take by weighing COPP 90KG (melting index 25g/10min), hydroxymethyl phenyl phospho acid ammonium 2KG, diethylammonium phospho acid aluminium 1KG, 2-carboxyethyl phenyl phosphinic acid melamine salt 1KG, trimeric cyanamide hydrobromate 5KG, 2; 3-dimethyl--2; Dropping into twin screw extruder behind the thorough mixing in 3-dinaphthyl butane 0.5KG, the three beneze methane thiol 0.5KG input mixing tank melt extrudes in 180-200 ℃; Obtain not having the polypropylene flame redardant that separate out on the surface after granulation, the drying; Its fire-retardant rank of the polypropylene flame redardant of gained is UL94 V-2 (1.6mm), experiences 1000 hours down in 80 ℃ of natural air environment, and the no fire retardant in surface is separated out.
Embodiment 31
Take by weighing HOPP (melting index 0.8g/10min) 88KG, hydroxymethyl phenyl phospho acid triethylamine salt 5KG, trimeric cyanamide hydrobromate 5KG, 2; 3-dimethyl--2; 3-diphenyl butane 1KG, 2,5-dimethyl--2 drops into twin screw extruder behind the thorough mixing in 5-two (tert-butyl peroxy base) hexane 0.5KG, the bismuthous oxide bismuth trioxide 0.5KG input mixing tank and melt extrudes in 180-200 ℃; Obtain not having the polypropylene flame redardant that separate out on the surface after granulation, the drying; Its fire-retardant rank of the polypropylene flame redardant of gained is UL94 V-0 (1.6mm), experiences 1000 hours down in 80 ℃ of natural air environment, and the no fire retardant in surface is separated out.
Embodiment 32
Take by weighing COPP (melting index 10g/10min) 87KG, aminomethyl phenyl phospho acid aminoguanidine salt 5KG, trimeric cyanamide hydrobromate 6KG, perfluorinated butane base diphenyl-bromomethane 1KG, 2; 5-dimethyl--2; Dropping into twin screw extruder behind the thorough mixing in 5-two (t-butylperoxy)-3-acetylene 0.5KG, Bismuth carbonate 0.3KG, the sodium antimonate 0.22KG input mixing tank melt extrudes in 180-200 ℃; Obtain not having the polypropylene flame redardant that separate out on the surface after granulation, the drying; Its fire-retardant rank of the polypropylene flame redardant of gained is UL94 V-1 (1.6mm), experiences 1000 hours down in 80 ℃ of natural air environment, and the no fire retardant in surface is separated out.
Embodiment 33
Take by weighing HOPP (melting index 20g/10min) 76KG, dimethyl-phospho acid antimony 7KG, trimeric cyanamide hydrobromate 13KG, triphen Toluidrin 2KG, 2; 3-dimethyl--2; Dropping into twin screw extruder behind the thorough mixing in 3-two (4-chloromethane phenyl) butane 2KG, tert-butyl peroxide 0.5KG, the sodium antimonate 1.5KG input mixing tank melt extrudes in 180-200 ℃; Obtain not having the polypropylene flame redardant that separate out on the surface after granulation, the drying; Its fire-retardant rank of the polypropylene flame redardant of gained is UL94 V-0 (1.6mm), experiences 1000 hours down in 80 ℃ of natural air environment, and the no fire retardant in surface is separated out.
Embodiment 34
Take by weighing Vilaterm 50KG, hydroxymethyl phenyl phospho acid zinc 18KG, trimeric cyanamide hydrobromate 25KG, 2; 3-dimethyl--2; 3-two (2; The 4-dibromo phenyl) butane 4KG, triphenylbromomethane 1KG, 2; 5-dimethyl--2,5-two (tert-butyl peroxy base) hexane 0.5KG, Antimony Trioxide: 99.5Min 1KG, oxidation inhibitor 0.3KG, stearic amide 0.2KG drop into and drop into forcing machine in the mixing tank behind the thorough mixing and melt extrude in 140-175 ℃, obtain not having the fire-retardant concentrate feed that separate out on the surface after granulation, the drying; The fire-retardant concentrate feed of gained dropped in the HOPP in 180-200 ℃ by 5% weight percent obtain surface precipitation-free flame-retardant polypropylene compound after in twin screw extruder, melt extruding granulation, drying; Its fire-retardant rank of the polypropylene flame redardant of gained is UL94 V-2 (1.6mm), experiences 1000 hours down in 80 ℃ of natural air environment, and the no fire retardant in surface is separated out.
Embodiment 35
Take by weighing PS 4KG, phospho acid aluminium 10KG, methyl phospho acid zinc 10KG, diethylammonium phospho acid aluminium 25KG, trimeric cyanamide hydrobromate 45KG, 2; 3-dimethyl--2; 3-two (4-nitrophenyl) butane 4KG, 2-bromo-2-phenyl butane 1.5KG, 1; The two tert-butyl peroxides-3 of 1-; 3,5-trimethyl-cyclohexane 0.5KG drops into and to drop into forcing machine in the mixing tank behind the thorough mixing and melt extrude in 180-200 ℃, obtains not having the fire-retardant concentrate feed that separate out on the surface after granulation, the drying; The fire-retardant concentrate feed of gained dropped in the HOPP in 180-200 ℃ by 3% weight percent obtain surface precipitation-free flame-retardant polypropylene compound after in twin screw extruder, melt extruding granulation, drying; Its fire-retardant rank of the polypropylene flame redardant of gained is UL94V-2 (1.6mm), experiences 1000 hours down in 80 ℃ of natural air environment, and the no fire retardant in surface is separated out.
Embodiment 36
Take by weighing PVA 25KG, hydroxymethyl phenyl phospho acid barium 12KG, dibutyl phospho acid aluminium 3KG, trimeric cyanamide hydrobromate 46KG, 2; 3-dimethyl--2; 3-two (2; The 4-dibromo phenyl) butane 10KG, triphenylbromomethane 2KG, 2-sulfydryl-2-phenyl butane 0.5KG, 2,5-dimethyl--2,5-two (tert-butyl peroxy base) hexane 0.3KG, antioxidant 1010 0.6KG, N; Dropping into forcing machine behind the thorough mixing in the two ethylene stearic amide 0.6KG input of the N-mixing tank melt extrudes in 135-160 ℃; Obtain not having the fire-retardant concentrate feed that separate out on the surface after granulation, the drying, the fire-retardant concentrate feed of gained is dropped in the HOPP in 180-200 ℃ by 5% weight percent obtain surface precipitation-free flame-retardant polypropylene compound after in twin screw extruder, melt extruding granulation, drying, its fire-retardant rank of the polypropylene flame redardant of gained is UL94V-2 (1.6mm); Experience 1000 hours down in 80 ℃ of natural air environment, the no fire retardant in surface is separated out.
Embodiment 37
Take by weighing HOPP 97KG, cyclohexyl phenyl phospho acid magnesium 0.6KG, trimeric cyanamide hydrobromate 2KG, 2-methyl-2; 3; Dropping into forcing machine behind the thorough mixing in 3-triphenyl dodecyl 0.2KG, naphthyl phenylbenzene Nitromethane 99Min. 0.1KG, the 2-sulfydryl-2-phenyl butane 0.1KG input mixing tank melt extrudes in 170-190 ℃; Obtain not having the fire-retardant concentrate feed that separate out on the surface after granulation, the drying; The fire-retardant concentrate feed of gained dropped in the HOPP in 180-200 ℃ by 50% weight percent obtain surface precipitation-free flame-retardant polypropylene compound after in twin screw extruder, melt extruding granulation, drying; Its fire-retardant rank of the polypropylene flame redardant of gained is UL94 V-2 (1.6mm), experiences 1000 hours down in 80 ℃ of natural air environment, and the no fire retardant in surface is separated out.
Comparative example 1
With embodiment 1; Take by weighing 2-carboxyethyl phenyl phosphinic acid aluminium 20KG, trimeric cyanamide hydrobromate 65KG (does not add 2-methyl-3-ethyl-2; 3-phenylbenzene octane) dropping into twin screw extruder behind the thorough mixing in the input mixing tank melt extrudes in 180-200 ℃; Obtain polypropylene composite after granulation, the drying, the polypropylene composite of gained does not almost have fire-retardant effect in the air sustained combustion.

Claims (9)

1. surface precipitation-free flame-retardant polypropylene compound is characterized in that:
Component and weight percentage comprise:
Acrylic resin 70-98.5%,
Trimeric cyanamide hydrobromate 1-15%,
Phosphinates 0.3-7%,
Retardant synergist 0.2-4%,
Fire retarding synergist 0-2%,
Oxidation inhibitor 0-1%,
Processing aid 0-1%;
Described acrylic resin is meant homopolymerization PP and copolymerization PP;
Described phosphinates refers to have the compound of following structure (I):
Figure FSB00000699457700011
Wherein, R 1=H, C1-12 alkyl or aromatic base, R 2=H, C1-12 alkyl, alkoxyl group, aromatic base or aryloxy; M=K, Na, Li or aminoguanidine salt or amine ion; Described phosphinates is one or both and the above mixture in the said structure;
Described retardant synergist is meant a kind of or its mixture in compound (III), compound (IV) or the organo-peroxide with following structure;
Figure FSB00000699457700012
Wherein, R 3, R 4, R 5Or R 6All be respectively a kind of in C1-12 alkyl, alkoxyl group, aromatic base or the fragrant oxygen base; X or Y are H, C1-12 alkyl, alkoxyl group, aromatic base, fragrant oxygen base, halogen, nitro, sulfonic group, sulfydryl or polysubstituted aromatic base;
Figure FSB00000699457700013
Wherein, R 7Or R 8Be respectively a kind of in C1-12 alkyl or the aromatic base; R 9Be alkyl, alkoxyl group, aromatic base, fragrant oxygen base, halogen, nitro, sulfonic group, sulfydryl or polysubstituted aromatic base; Z is halogen, nitro, sulfonic group or sulfydryl;
Described fire retarding synergist is meant a kind of or its mixture in oxide compound, bismuth salt or the borate of oxide compound, stibnate, bismuth of antimony.
2. surface precipitation-free flame-retardant polypropylene compound as claimed in claim 1 is characterized in that, described amine ion is NH 4 +Or organic amine ion; Described organic amine ion is organic primary amine, secondary amine or tertiary amine and from the H of Hypophosporous Acid, 50 +The ion that generates; Described primary amine is a trimeric cyanamide, trimeric cyanamide with from the H of Hypophosporous Acid, 50 +The ionic structure that generates like (II) does
Figure FSB00000699457700021
3. surface precipitation-free flame-retardant polypropylene compound as claimed in claim 1 is characterized in that, described organo-peroxide is a kind of or its mixture in hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxy esters or the ketone peroxide; Wherein, described hydroperoxide are tertbutyl peroxide or cumyl hydroperoxide, and described dialkyl peroxide is ditertiary butyl peroxide, dicumyl peroxide, t-butylperoxy isopropyl benzene, two (tert-butyl peroxy base sec.-propyl) benzene, 2; 5-dimethyl--2,5-two (t-butylperoxy)-3-acetylene or 2,5-dimethyl--2; 5-two (tert-butyl peroxy base) hexane, described diacyl peroxide are Lucidol, peroxo-two (4-chlorobenzoyl) or bis(2; Described peroxy esters is peroxo-tert-butyl acetate or peroxidized t-butyl perbenzoate, 4; Two (tert-butyl peroxy base) n-butyl pentanoates of 4-, described ketone peroxide is 1, the two tert-butyl peroxides-3 of 1-; 3, the 5-trimethyl-cyclohexane.
4. surface precipitation-free flame-retardant polypropylene compound as claimed in claim 1 is characterized in that, described oxidation inhibitor is selected from a kind of or its mixture in phenols, phosphorous acid esters, divalent sulfur class or the space suffocated amine antioxidant; Wherein, Described phenolic antioxidant has antioxidant 264, antioxidant 1010, antioxidant 1076, antioxidant SP, antioxidant 2246, antioxidant CA, antioxidant 330, Irganox1890 or antioxidant 3114; Phosphorous acid esters have oxidation inhibitor TNP, oxidation inhibitor ODP, oxidation inhibitor 168, Irganox1093 or Irganox1222; The divalent sulfur kind antioxidant has two LAURIC ACID 99 MIN thiodipropionates, distearyl acid thiodipropionate, and suffocated amine antioxidant has LS-744, LS-770, GW-540 or Flamstab NOR116.
5. surface precipitation-free flame-retardant polypropylene compound as claimed in claim 1 is characterized in that, described processing aid is selected from a kind of or its mixture in low molecule lipid, metallic soap class, ester class or the amides processing aid; Wherein, Low molecule lipid is solid paraffin, whiteruss or low molecular weight polycaprolactone alkene wax; The metallic soap class is calcium stearate, Magnesium Stearate, Zinic stearas or barium stearate; The ester class is glycol stearate, stearin or Triple Pressed Stearic Acid pentaerythritol ester, and amides is erucicamide, methylene bis stearic amide or N, the N-ethylene bis stearic acid amide.
6. the preparation method of a surface precipitation-free flame-retardant polypropylene compound; It is characterized in that: acrylic resin, trimeric cyanamide hydrobromate, phosphinates, retardant synergist, fire retarding synergist, oxidation inhibitor and processing aid are mixed after the weighing in proportion; With the said mixture melting mixing, promptly obtain surface precipitation-free flame-retardant polypropylene compound after granulation, the drying then;
Perhaps trimeric cyanamide hydrobromate, phosphinates, retardant synergist, fire retarding synergist, oxidation inhibitor and processing aid are mixed after the weighing in proportion and make the fire retardant compound; With fire retardant compound and acrylic resin melting mixing, promptly obtain surface precipitation-free flame-retardant polypropylene compound after granulation, the drying then;
In surface precipitation-free flame-retardant polypropylene compound, the weight percentage of each component is:
Acrylic resin 70-98.5%,
Trimeric cyanamide hydrobromate 1-15%,
Phosphinates 0.3-7%,
Retardant synergist 0.2-4%,
Fire retarding synergist 0-2%,
Oxidation inhibitor 0-1%,
Processing aid 0-1%;
Wherein, described acrylic resin is meant the copolymerization PP of homopolymerization PP and propylene and other olefin-copolymerization;
Described phosphinates refers to have the compound of following structure (I):
Figure FSB00000699457700031
Wherein, R 1=H, C1-12 alkyl or aromatic base, R 2=H, C1-12 alkyl, alkoxyl group, aromatic base or aryloxy; M=K, Na, Li or aminoguanidine salt or amine ion; Described phosphinates is one or both and the above mixture in the said structure;
Described retardant synergist is meant a kind of or its mixture in compound (III), compound (IV) or the organo-peroxide with following structure;
Figure FSB00000699457700041
Wherein, R 3, R 4, R 5Or R 6All be respectively a kind of in C1-12 alkyl, alkoxyl group, aromatic base or the fragrant oxygen base; X or Y are H, C1-12 alkyl, alkoxyl group, aromatic base, fragrant oxygen base, halogen, nitro, sulfonic group, sulfydryl or polysubstituted aromatic base;
Figure FSB00000699457700042
Wherein, R 7Or R 8Be respectively a kind of in C1-12 alkyl or the aromatic base; R 9Be alkyl, alkoxyl group, aromatic base, fragrant oxygen base, halogen, nitro, sulfonic group, sulfydryl or polysubstituted aromatic base; Z is halogen, nitro, sulfonic group or sulfydryl;
Described fire retarding synergist is meant a kind of or its mixture in oxide compound, bismuth salt or the borate of oxide compound, stibnate, bismuth of antimony.
7. the preparation method of surface precipitation-free flame-retardant polypropylene compound as claimed in claim 6 is characterized in that, described amine ion is NH 4 +Or organic amine ion; Described organic amine ion is organic primary amine, secondary amine or tertiary amine and from the H of Hypophosporous Acid, 50 +The ion that generates; Described primary amine is a trimeric cyanamide, trimeric cyanamide with from the H of Hypophosporous Acid, 50 +The ionic structure that generates like (II) does
Figure FSB00000699457700043
Described organo-peroxide is a kind of or its mixture in hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxy esters or the ketone peroxide; Wherein, described hydroperoxide are tertbutyl peroxide or cumyl hydroperoxide, and described dialkyl peroxide is ditertiary butyl peroxide, dicumyl peroxide, t-butylperoxy isopropyl benzene, two (tert-butyl peroxy base sec.-propyl) benzene, 2; 5-dimethyl--2,5-two (t-butylperoxy)-3-acetylene or 2,5-dimethyl--2; 5-two (tert-butyl peroxy base) hexane, described diacyl peroxide are Lucidol, peroxo-two (4-chlorobenzoyl) or bis(2; Described peroxy esters is peroxo-tert-butyl acetate or peroxidized t-butyl perbenzoate, 4; Two (tert-butyl peroxy base) n-butyl pentanoates of 4-, described ketone peroxide is 1, the two tert-butyl peroxides-3 of 1-; 3, the 5-trimethyl-cyclohexane;
Described oxidation inhibitor is selected from a kind of or its mixture in phenols, phosphorous acid esters, divalent sulfur class or the space suffocated amine antioxidant; Wherein, Described phenolic antioxidant has antioxidant 264, antioxidant 1010, antioxidant 1076, antioxidant SP, antioxidant 2246, antioxidant CA, antioxidant 330, Irganox1890 or antioxidant 3114; Phosphorous acid esters have oxidation inhibitor TNP, oxidation inhibitor ODP, oxidation inhibitor 168, Irganox1093 or Irganox1222; The divalent sulfur kind antioxidant has two LAURIC ACID 99 MIN thiodipropionates, distearyl acid thiodipropionate, and suffocated amine antioxidant has LS-744, LS-770, GW-540 or Flamstab NOR116;
Described processing aid is selected from a kind of or its mixture in low molecule lipid, metallic soap class, ester class or the amides processing aid; Wherein, Low molecule lipid is solid paraffin, whiteruss or low molecular weight polycaprolactone alkene wax; The metallic soap class is calcium stearate, Magnesium Stearate, Zinic stearas or barium stearate; The ester class is glycol stearate, stearin or Triple Pressed Stearic Acid pentaerythritol ester, and amides is erucicamide, methylene bis stearic amide or N, the N-ethylene bis stearic acid amide.
8. the preparation method of a surface precipitation-free flame-retardant polypropylene compound; It is characterized in that: trimeric cyanamide hydrobromate, phosphinates, retardant synergist, fire retarding synergist, oxidation inhibitor, processing aid and resin carrier are mixed after the weighing in proportion process the fire retardant concentrate feed; Then with fire retardant concentrate feed and acrylic resin melting mixing; The mass ratio of fire retardant concentrate feed and acrylic resin is 1: 1～49, after granulation, drying, promptly obtains high gloss high transparent surface precipitation-free flame-retardant polypropylene compound; Wherein said resin carrier is Vestolen PP 7052, Vilaterm, PVA or polystyrene support;
In the fire retardant concentrate feed, the weight percentage of each component is:
Resin carrier 4-97%,
Trimeric cyanamide hydrobromate 2-48%,
Phosphinates 0.6-22.4%,
Retardant synergist 0.4-12.8%,
Fire retarding synergist 0-6.4%,
Oxidation inhibitor 0-3.2%,
Processing aid 0-3.2%;
Wherein, described acrylic resin is meant the copolymerization PP of homopolymerization PP and propylene and other olefin-copolymerization;
Described phosphinates refers to have the compound of following structure (I):
Figure FSB00000699457700061
Wherein, R 1=H, C1-12 alkyl or aromatic base, R 2=H, C1-12 alkyl, alkoxyl group, aromatic base or aryloxy; M=K, Na, Li or aminoguanidine salt or amine ion; Described phosphinates is one or both and the above mixture in the said structure;
Described retardant synergist is meant a kind of or its mixture in compound (III), compound (IV) or the organo-peroxide with following structure;
Figure FSB00000699457700062
Wherein, R 3, R 4, R 5Or R 6All be respectively a kind of in C1-12 alkyl, alkoxyl group, aromatic base or the fragrant oxygen base; X or Y are H, C1-12 alkyl, alkoxyl group, aromatic base, fragrant oxygen base, halogen, nitro, sulfonic group, sulfydryl or polysubstituted aromatic base;
Wherein, R7 or R8 are respectively a kind of in C1-12 alkyl or the aromatic base; R9 is alkyl, alkoxyl group, aromatic base, fragrant oxygen base, halogen, nitro, sulfonic group, sulfydryl or polysubstituted aromatic base; Z is halogen, nitro, sulfonic group or sulfydryl;
Described fire retarding synergist is meant a kind of or its mixture in oxide compound, bismuth salt or the borate of oxide compound, stibnate, bismuth of antimony.
9. the preparation method of surface precipitation-free flame-retardant polypropylene compound as claimed in claim 8 is characterized in that, described amine ion is NH 4 +Or organic amine ion; Described organic amine ion is organic primary amine, secondary amine or tertiary amine and from the H of Hypophosporous Acid, 50 +The ion that generates; Described primary amine is a trimeric cyanamide, trimeric cyanamide with from the H of Hypophosporous Acid, 50 +The ion that generates, its structure like (II) does
Figure FSB00000699457700071
Described organo-peroxide is a kind of or its mixture in hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxy esters or the ketone peroxide; Wherein, described hydroperoxide are tertbutyl peroxide or cumyl hydroperoxide, and described dialkyl peroxide is ditertiary butyl peroxide, dicumyl peroxide, t-butylperoxy isopropyl benzene, two (tert-butyl peroxy base sec.-propyl) benzene, 3,3; 6,6,9,9-hexa-methylene-1; 2,4,5-four oxygen cyclononane, 2,5-dimethyl--2; 5-two (t-butylperoxy)-3-acetylene or 2,5-dimethyl--2,5-two (tert-butyl peroxy base) hexane, described diacyl peroxide are Lucidol, peroxo-two (4-chlorobenzoyl) or peroxo-two (2; The 4-dichloro-benzoyl), described peroxy esters is peroxo-tert-butyl acetate or peroxidized t-butyl perbenzoate, 4, two (tert-butyl peroxy base) n-butyl pentanoates of 4-, and described ketone peroxide is 1; The two tert-butyl peroxides-3,3 of 1-, the 5-trimethyl-cyclohexane;
Described oxidation inhibitor is selected from a kind of or its mixture in phenols, phosphorous acid esters, divalent sulfur class or the space suffocated amine antioxidant; Wherein, Described phenolic antioxidant has antioxidant 264, antioxidant 1010, antioxidant 1076, antioxidant SP, antioxidant 2246, antioxidant CA, antioxidant 330, Irganox1890 or antioxidant 3114; Phosphorous acid esters have oxidation inhibitor TNP, oxidation inhibitor ODP, oxidation inhibitor 168, Irganox1093 or Irganox1222; The divalent sulfur kind antioxidant has two LAURIC ACID 99 MIN thiodipropionates, distearyl acid thiodipropionate, and suffocated amine antioxidant has LS-744, LS-770, GW-540 or Flamstab NOR116;
Described processing aid is selected from a kind of or its mixture in low molecule lipid, metallic soap class, ester class or the amides processing aid; Wherein, Low molecule lipid is solid paraffin, whiteruss or low molecular weight polycaprolactone alkene wax; The metallic soap class is calcium stearate, Magnesium Stearate, Zinic stearas or barium stearate; The ester class is glycol stearate, stearin or Triple Pressed Stearic Acid pentaerythritol ester, and amides is erucicamide, methylene bis stearic amide or N, the N-ethylene bis stearic acid amide.
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CN114058122A (en) * 2021-12-14 2022-02-18 上海力道新材料科技股份有限公司 Flame-retardant polypropylene resin
CN114059188A (en) * 2021-12-14 2022-02-18 上海力道新材料科技股份有限公司 Flame-retardant polypropylene fiber and preparation method thereof
CN114213758A (en) * 2021-12-30 2022-03-22 苏州禾昌聚合材料股份有限公司 Engineering plastic material with special functional groups and preparation method thereof

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