CN104311981B - A kind of halogen-free flameproof EVA composite - Google Patents
A kind of halogen-free flameproof EVA composite Download PDFInfo
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- CN104311981B CN104311981B CN201410541370.6A CN201410541370A CN104311981B CN 104311981 B CN104311981 B CN 104311981B CN 201410541370 A CN201410541370 A CN 201410541370A CN 104311981 B CN104311981 B CN 104311981B
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- 239000002131 composite material Substances 0.000 title claims abstract description 92
- -1 phosphate ester Chemical class 0.000 claims abstract description 74
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 72
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 71
- 150000001412 amines Chemical class 0.000 claims abstract description 64
- 239000012757 flame retardant agent Substances 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 238000002360 preparation method Methods 0.000 claims abstract description 35
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 30
- 239000010452 phosphate Substances 0.000 claims abstract description 30
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims description 43
- 239000003063 flame retardant Substances 0.000 claims description 41
- 239000000376 reactant Substances 0.000 claims description 40
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 22
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 claims description 22
- 239000011230 binding agent Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 18
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 16
- 238000003825 pressing Methods 0.000 claims description 16
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 239000011574 phosphorus Substances 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- 238000013517 stratification Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 2
- 239000004254 Ammonium phosphate Substances 0.000 claims 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims 1
- 229920000137 polyphosphoric acid Polymers 0.000 claims 1
- 238000010992 reflux Methods 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 abstract 3
- HWYHDWGGACRVEH-UHFFFAOYSA-N n-methyl-n-(4-pyrrolidin-1-ylbut-2-ynyl)acetamide Chemical compound CC(=O)N(C)CC#CCN1CCCC1 HWYHDWGGACRVEH-UHFFFAOYSA-N 0.000 abstract 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract 3
- 239000000463 material Substances 0.000 description 22
- 239000001257 hydrogen Substances 0.000 description 17
- 229910052739 hydrogen Inorganic materials 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 14
- 239000000523 sample Substances 0.000 description 14
- 238000001228 spectrum Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 238000001914 filtration Methods 0.000 description 13
- 238000007731 hot pressing Methods 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 238000013019 agitation Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 230000005311 nuclear magnetism Effects 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 238000002390 rotary evaporation Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000006837 decompression Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 239000013638 trimer Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000006101 laboratory sample Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 241001597008 Nomeidae Species 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 229920002903 fire-safe polymer Polymers 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- BEOOOFNWPVZYMC-UHFFFAOYSA-N N1=PN=PN=P1.NC1=CC=CC=C1.NC1=CC=CC=C1.NC1=CC=CC=C1.NC1=CC=CC=C1.NC1=CC=CC=C1.NC1=CC=CC=C1 Chemical compound N1=PN=PN=P1.NC1=CC=CC=C1.NC1=CC=CC=C1.NC1=CC=CC=C1.NC1=CC=CC=C1.NC1=CC=CC=C1.NC1=CC=CC=C1 BEOOOFNWPVZYMC-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- BFMKFCLXZSUVPI-UHFFFAOYSA-N ethyl but-3-enoate Chemical compound CCOC(=O)CC=C BFMKFCLXZSUVPI-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
- C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
nullThe invention discloses a kind of halogen-free flameproof EVA composite，Including ethylene vinyl acetate copolymer and composite flame-retardant agent，Described ethylene vinyl acetate copolymer is 32 with the mass ratio of composite flame-retardant agent，Described composite flame-retardant agent is by APP、Three (1 oxo 1 phosphas 2,6,7 trioxa-l-phosphabicyclos [2,2,2] octane 4 methylene) phosphate ester and fatty amine replace phosphazene derivative composition，Described APP and three (1 oxo 1 phosphas 2,6,7 trioxa-l-phosphabicyclos [2,2,2] octane 4 methylene) mass ratio of phosphate ester is 21，Described fatty amine replaces phosphazene derivative and by described APP and three (1 oxo 1 phosphas 2,6,7 trioxa-l-phosphabicyclos [2,2,2] octane 4 methylene) mass ratio of mixture of phosphate ester composition is 1 15 25 39.Composite prepared by the present invention has good comprehensive anti-flammability and mechanical mechanics property, in processing preparation process, and composite flame-retardant agent and the compatibility of EVA and good processability, can be as extensively application such as cable raw materials.
Description
Technical field
The present invention relates to a kind of bittern-free flame-proof material, the halogen-free flameproof EVA of a kind of satisfactory mechanical property is multiple
Condensation material.
Background technology
Ethylene-vinyl acetate copolymer (EVA) itself belongs to and compares combustible polymers material, and its limited oxygen index is only
17.0-19.0%, with vinyl acetate content increase and limited oxygen index increased, but charring rate is low, produces during burning
Molten drop, so being desirable that in a lot of application scenarios and carrying out flame-retardant modified to it.At present, both at home and abroad to ethylene-vinyl acetate altogether
Polymers flame treatment mainly uses additive flame retardant.According to " advanced polymer processing techniques " (Polymers for Advanced
Technologies, 2011,22: 379-394) introduce, use and can be used for the nothing of flame-proof ethylene-vinyl acetate copolymer
In halogen additive flame retardant, hydroxide flame retardant most frequently with, it is inexpensive, nontoxic, presses down cigarette.Hydroxide flame retardant
Mainly by the release steam isolation flame that is heated, dilution oxygen, decompose the metal oxide promoted polymer of generation simultaneously
The condensed ring carbonization when burning, plays solid phase fire retardation.But while interpolation hydroxide flame retardant reaches fire-retardant purpose, hydrogen
Oxide fire retardant can deteriorate the mechanical property of ethylene-vinyl acetate copolymer composite.
Phosphonitrile and derivant thereof are a class Halogen, environmentally friendly nitrogen-phosphorus flame retardant, owing to it has heat stability relatively
High, only containing a series of advantages such as two kinds of ignition-proof elements of P, N, the high and low poison of flame retarding efficiency, studied person expand research widely and
Application.At present, the ring phosphazene flame retardant kind being added on plastic polymer mainly has: 1. hydroxyl ring three phosphonitrile fire retardant, 2.
Amino-contained ring three phosphonitrile fire retardant, the 3. phosphonitrile fire retardant on double bond ring three.Wherein amino-contained ring three phosphonitrile is that one is provided simultaneously with
Synthesis and the phosphazene compound of application performance.At present, in industry, scholar is more for studying in amino-contained ring three phosphonitrile fire retardant
Be aniline basic ring three phosphonitrile, as CN101597308 discloses a kind of hexaaniline cyclotriphosphazene and Halogenless fire retarded epoxy resin
The preparation method of compositions；Its technique is organic solvent, hexachlorocyclotriph,sphazene, aniline, acid binding agent to be added in reaction unit, stirs
Mix, be passed through nitrogen protection, be heated to 50-120 DEG C, in reaction unit, add tetrabutyl ammonium bromide catalyst, react 5-16 h,
Sucking filtration after cooling, carries out decompression distillation, evaporative removal organic solvent, is dried by gained object product, obtains six benzene filtrate
Amino ring three phosphonitrile.This compound is used for preparing EMC Halogen composite, its excellent fireproof performance, charring rate are high, toxicity is little,
Corrosivity is little and preparation method is simple；But, this based flame retardant is inorganic with tradition and organic fire-retardant system is similar, joins
EVA plastic polymer easily deteriorates the mechanical mechanics property of its composite, and its poor compatibility, melting range width, purity are low, molten
Point is high, uses its processing characteristics poor in plastic polymer (such as EVA, PP).At present, for overcoming this problem in industry, past
Toward by reduce the addition of phosphazene flame retardant improve its to the processing of plastic polymer material and mechanical mechanics property, in
This simultaneously, its flame retardant effect will reduce.
Summary of the invention
It is an object of the invention to provide a kind of halogen-free flameproof EVA composite, add EVA to solving existing fire retardant
In plastic matrix, while can reaching flame retardant effect, there is the Mechanics of Machinery of poor processability, easily deterioration composite
The problem of performance.
It is an object of the invention to be achieved through the following technical solutions: a kind of halogen-free flameproof EVA composite, including second
Alkene-vinyl acetate co-polymer (EVA) and composite flame-retardant agent, described ethylene-vinyl acetate copolymer and composite flame-retardant agent
Mass ratio is 32, and described composite flame-retardant agent is by APP (APP), three (1-oxo-1-phospha-2,6,7-trioxa-l-phosphabicyclos
[2,2,2] octane-4-methylene) phosphate ester replaces phosphazene derivative composition, described composite flame-proof with (Trimer) and fatty amine
APP in agent and three (1-oxo-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2] octane-4-methylene) phosphate ester
Mass ratio be 21, described fatty amine replace phosphazene derivative with by described APP and three (1-oxo-1-phospha-2,6,
7-trioxa-l-phosphabicyclo [2,2,2] octane-4-methylene) mass ratio of mixture of phosphate ester composition is 1-15 25-39；Described
Fatty amine replaces the chemical general formula of phosphazene derivative:
The R that described fatty amine replaces in phosphazene derivative chemical general formula is 7 or 11.
Described fatty amine replaces phosphazene derivative and described APP and three (1-oxo-1-phospha-2,6,7-trioxas
Dicyclo [2,2,2] octane-4-methylene) mass ratio preferably 1 3-19 of mixture of phosphate ester composition.
In described halogen-free flameproof EVA composite, the preparation method of fatty amine replacement phosphazene derivative is as follows:
A hexachlorocyclotriph,sphazene and acid binding agent are dissolved in organic solvent by (), be passed through N2Protection, at temperature is 50-80 DEG C
Stir, obtain mixed liquor；Fatty amine is dripped while stirring, at 50-after dropping in 0.5-2h in described mixed liquor
Back flow reaction 9-12h at 80 DEG C, obtains reactant liquor；The mol ratio of described hexachlorocyclotriph,sphazene, acid binding agent and fatty amine is 1 6-
10 6.0-6.6, described fatty amine is the one in 1-Aminooctane or lauryl amine；
B described reactant liquor is cooled down by (), stratification, separates target product and is dried, and obtains fatty amine and replaces phosphonitrile
Derivant.
Described halogen-free flameproof EVA composite, is obtained by following preparation method:
A hexachlorocyclotriph,sphazene and acid binding agent are dissolved in organic solvent by (), be passed through N2Protection, at temperature is 50-80 DEG C
Stirring 5-10 min, obtains uniform mixed liquor；In described mixed liquor, drip fatty amine while stirring, drip complete in 0.5-2h
After at 50-80 DEG C back flow reaction 9-12h, obtain reactant liquor；The mol ratio of described hexachlorocyclotriph,sphazene, acid binding agent and fatty amine
Being 1 6-10 6.0-6.6, described fatty amine is the one in 1-Aminooctane or lauryl amine；
B described reactant liquor is cooled down by (), stratification, separates target product and is dried, and obtains fatty amine and replaces phosphonitrile
Derivant；
C described fatty amine is replaced phosphazene derivative and APP, three (1-oxo-1-phospha-2,6,7-trioxas by ()
Dicyclo [2,2,2] octane-4-methylene) phosphate ester mixing composition composite flame-retardant agent, by described composite flame-retardant agent and ethyl vinyl acetate
Vinyl ester copolymers is 23 mixing in mass ratio, mixing 10-20 min at temperature is 120-130 DEG C, pressing plate or granulation, i.e.
Obtain halogen-free flameproof EVA composite；APP in described composite flame-retardant agent and three (1-oxo-1-phospha-2,6,7-three oxygen
Miscellaneous dicyclo [2,2,2] octane-4-methylene) mass ratio of phosphate ester is 21, described fatty amine replaces phosphazene derivative with described
APP and three (1-oxo-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2] octane-4-methylene) phosphate ester form
The mass ratio of mixture is 1-15 25-39.
The technique of step (a) described in above-mentioned preparation technology can also be: the technique of described step (a) is replaced by: by six
Chlorine ring three phosphonitrile is dissolved in organic solvent, is passed through N2Protection, stirs, at hexachlorocyclotriph,sphazene at temperature is 50-80 DEG C
Solution drips acid binding agent and fatty amine while stirring, drips complete in 0.5-2h, back flow reaction 9-12 at 50-80 DEG C
H, obtains reactant liquor；Described hexachlorocyclotriph,sphazene, acid binding agent are 1 6-10 6.0-6.6 with the mol ratio of fatty amine, described fatty amine
For the one in 1-Aminooctane or lauryl amine.
In above-mentioned preparation technology, described in step (a), acid binding agent is triethylamine.
In above-mentioned preparation technology, organic solvent described in step (a) is any one in dioxane or oxolane.
When in above-mentioned preparation technology, described in step (a), fatty amine is lauryl amine, described hexachlorocyclotriph,sphazene, acid binding agent with
The mol ratio of fatty amine is preferably 1 10 6.0.
When in above-mentioned preparation technology, described in step (a), fatty amine is 1-Aminooctane, described hexachlorocyclotriph,sphazene, acid binding agent with
The mol ratio of fatty amine is preferably 16 6.6.
In above-mentioned preparation technology, hexachlorocyclotriph,sphazene described in step (a) is 1: 8-with the mass volume ratio of organic solvent
50, when dripping fatty amine in described mixed liquor, first described fatty amine is dissolved in appropriate dioxane or oxolane, then carries out
Dropping.
In above-mentioned preparation technology when the fatty amine in step (a) is lauryl amine, described separation target product is also done
Dry technique is: the reactant liquor sucking filtration after standing, and obtains white precipitate, is rinsed with described organic solvent by white precipitate, then use
Deionized water rinsing, the precipitation after rinsing is vacuum dried 12-20 h at being placed in 50-90 DEG C, obtains six-lauryl amine base-ring triphosphine
Nitrile (H-12).
In above-mentioned preparation technology when the fatty amine in step (a) is 1-Aminooctane, described step (b) separates target product
And the technique being dried is: the reactant liquor sucking filtration after standing, filtrate rotary evaporation is obtained dope, described dope is put
At 50-90 DEG C, it is vacuum dried 12-20 h, obtains six-1-Aminooctane base-ring triphosphine nitrile (H-8).
The described granulation of above-mentioned steps (c) is mixing rear material to be joined double screw extruder pelletize, its twin-screw extrusion
Machine from spout, the second bringing-up section, the 3rd bringing-up section, the temperature of the 4th bringing-up section to head be respectively set to 120 DEG C, 130 DEG C,
130 DEG C, 120 DEG C, screw speed is set to 40 r/min.
The described making sheet of above-mentioned steps (c) refers to by the material after mixing on 130-140 DEG C of vulcanizing press, 12-13MPa
Lower hot pressing 10-20min, colds pressing the most again, obtains fire-retardant EVA sheet material.
The present invention have selected the lauryl amine in fatty amine and 1-Aminooctane, have employed specific raw material components ratio and technique
Condition, replaces hexachlorocyclotriph,sphazene under conditions of without catalyst, be prepared for melting range narrow range, purity is high, the compatibility is good and
Six-lauryl amine base of excellent fireproof performance-ring triphosphine nitrile and six-1-Aminooctane base-ring triphosphine nitrile；The present invention is by the both of preparation
Phosphonitrile fire retardant and APP, Trimer are compounding in specific proportions obtains composite flame-retardant agent, then by composite flame-retardant agent by proper proportion
It is added in EVA, then prepares composite by scientific and reasonable method.Being experimentally confirmed, this EVA composite is not
Only there is the vertical combustion performance of higher limited oxygen index and resistance to molten drop, but also composite can be made in the course of processing
The viscosity of middle melt is low, good processability, the good dispersion of component, thus realize comprehensive fire resistance good while, reach
The mechanical mechanics property purpose high to fracture of composite materials percentage elongation, hot strength is big.
The present invention obtains good effect, and the first is the interpolation of freshly prepd two kinds of phosphonitrile fire retardants, described fat
The long fat chain structure of fat amine replacement phosphazene derivative fire retardant can reduce the fusing point of fire retardant, makes fire retardant at macromolecule material
Material EVA processing temperature under in molten condition, and then reduce melt viscosity, promote fire retardant in macromolecule matrix point
Dissipating, thus reach to improve Flame Retardancy energy, physical and mechanical properties and processing characteristics, it two is to be composite flame-proof
The proportioning that in agent, each component is scientific and reasonable, and the conditional parameter of suitable processing technique makes finally to prepare excellent performance
EVA composite.
Simultaneously, in the successful preparation of two kinds of fatty amines replacement phosphazene derivatives of the present invention overcomes industry all the time
The product caused owing to there is embedding problem in the preparation process of fat amido replacement hexachlorocyclotriph,sphazene is impure, productivity is low,
Cannot the problem of popularization and application.
In a word, EVA composite prepared by the present invention not only has good comprehensive anti-flammability and mechanical mechanics property, and
And in processing preparation process, composite flame-retardant agent and the compatibility of EVA and good processability, work can be carried out as cable raw material etc.
Industry metaplasia is produced and extensively applies.
Accompanying drawing explanation
Fig. 1 is the Infrared Characterization figure of the six-lauryl amine base-ring triphosphine nitrile of embodiment 1 preparation；Its 3239cm-1Stretching for N-H
Contracting vibration；2956-2850cm-1Place is C-H stretching vibration；1468cm-1Locate to vibrate for C-H asymmetric bending；1378cm-1Place is
The symmetric curvature vibration of C-H in methyl；1240cm-1Place is the hexa-atomic skeletal vibration of phosphine nitrile；1180、1103cm-1Place stretches for P=N
Contracting vibration；904cm-1Place is P-N stretching vibration；721cm-1Place is-(CH2)n-middle C-H out-of-plane bending vibration；
Fig. 2 is the hydrogen spectrum phenogram of the six-lauryl amine base-ring triphosphine nitrile of embodiment 1 preparation；The reason of four kinds of hydrogen in hydrogen spectrum
Opinion number ratio should be a:b:c:d=1:1:9:1.5；Actual than a:b:c:d=1:0.95:9.21:1.60 and theory ratio basic
Cause, so being regarded as target product；
Fig. 3 is the phosphorus spectrum nuclear-magnetism figure of the six-lauryl amine base-ring triphosphine nitrile of embodiment 1 preparation；Phosphorus spectrum nuclear-magnetism is only 14.09
There is a kind of phosphorus at place, consistent with theory；
Fig. 4 is the Infrared Characterization figure of the six-1-Aminooctane base-ring triphosphine nitrile of embodiment 6 preparation；3242cm-1Stretching for N-H
Vibration；2960-2852cm-1Place is C-H stretching vibration；1466cm-1Locate to vibrate for C-H asymmetric bending；1376cm-1Place is first
The symmetric curvature vibration of C-H in base；1241cm-1Place is the hexa-atomic skeletal vibration of phosphine nitrile；1191、1100cm-1Locate to stretch for P=N
Vibration；930cm-1Place is P-N stretching vibration；721cm-1Place is-(CH2)n-middle C-H out-of-plane bending vibration；
Fig. 5 is the hydrogen spectrum phenogram of the six-1-Aminooctane base-ring triphosphine nitrile of embodiment 6 preparation；The reason of four kinds of hydrogen in hydrogen spectrum
Opinion number ratio should be a:b:c:d=1:1:5:1.5；Actual than a:b:c:d=1:0.95:4.78:1.41 and theory ratio basic
Cause, so being regarded as target product；
Fig. 6 is the phosphorus spectrum nuclear-magnetism figure of the six-1-Aminooctane base-ring triphosphine nitrile of embodiment 6 preparation；Phosphorus spectrum nuclear-magnetism is only 13.77
There is a kind of phosphorus at place, consistent with theory；
Fig. 7 is the SEM figure that embodiment 3 prepares material brittle failure end face in liquid nitrogen, fire retardant being uniformly dispersed in the sample,
Interface between fire retardant and EVA matrix obscures, and the compatibility of illustrative material is improved；
Fig. 8 is the SEM figure that embodiment 9 prepares material brittle failure end face in liquid nitrogen, fire retardant being uniformly dispersed in the sample,
Interface between fire retardant and EVA matrix obscures, and the compatibility of illustrative material is improved；
Fig. 9 is the SEM figure that comparative example 1 prepares material brittle failure end face in liquid nitrogen；
Figure 10 is the SEM figure that comparative example 2 prepares material brittle failure end face in liquid nitrogen, fire retardant APP and Trimer complex
Dispersion in EVA matrix presents certain agglomeration, and the compatibility is poor；
Figure 11 is embodiment 3,4 and comparative example 1,2 prepares sample complex viscosity phenogram at 155 DEG C, aobvious in figure
Show that laboratory sample shows the characteristic of shear shinning, the viscosity of composite disclosed by the invention in whole frequency field along with
The increase of six-lauryl amine base-ring triphosphine nitrile (H-12) addition and reduce；
Figure 12 is embodiment 3,4 and comparative example 1,2 prepares sample storage modulus phenogram at 155 DEG C, from figure
Laboratory sample shows composite flame-retardant agent can be reduced the viscosity of EVA material and improve the mobility of melt, thus improves compound
The anti-flammability of material；
Figure 13 is embodiment 8,9 and comparative example 1,2 prepares sample complex viscosity phenogram at 155 DEG C, aobvious in figure
Show that laboratory sample shows the characteristic of shear shinning, the viscosity of composite disclosed by the invention in whole frequency field along with
The increase of six-1-Aminooctane base-ring triphosphine nitrile (H-8) addition and reduce；
Figure 14 is embodiment 8,9 and comparative example 1,2 prepares sample storage modulus phenogram at 155 DEG C, from figure
Laboratory sample shows composite flame-retardant agent can be reduced the viscosity of EVA material and improve the mobility of melt, thus improves compound
The anti-flammability of material.
Detailed description of the invention
Example below is used for further describing the present invention, but limits the present invention the most in any form.
Embodiment 1
(1) by 3.00g(0.0086 mol) hexachlorocyclotriph,sphazene and 8.73g(0.086mol) triethylamine is dissolved in and filling
In the oblique three neck round bottom flask of 100ml dioxane (with condensing unit), it is passed through N2Protection, puts into 80 DEG C by round-bottomed flask
In oil bath pan, magnetic agitation 10 min makes it dissolve mix homogeneously, obtains uniform mixed liquor；Now, it is added dropwise in mixed liquor
50ml contains 9.546g(0.0516mol) dioxane solution of lauryl amine, drip while stirring, 2h drips off, after dropping
Back flow reaction 12h at 80 DEG C, obtains reactant liquor；
(2) reactant liquor being cooled to room temperature, stand to layering, decompression sucking filtration obtains white precipitate, first rinses with dioxane,
A large amount of deionized water rinsing, the vacuum drying oven that precipitation is finally put into 80 DEG C is used to be dried 12 h, obtain product six-lauryl amine again
Base-ring triphosphine nitrile, productivity is 79.74%, and melting range is 101-104 DEG C, molecular formula: P3N9C72H156(H-12)；Chemical formula is:
(3) by 1g six-lauryl amine base-ring triphosphine nitrile (H-12) and 26 g APPs (APP), 13g tri-(1-oxo-1-
Phospha-2,6,7-trioxa-l-phosphabicyclos [2,2,2] octane-4-methylene) phosphate ester (Trimer) mixing composition composite flame-retardant agent, will
This composite flame-retardant agent mixes with 60g ethylene-vinyl acetate copolymer (EVA), mixing on the duplex roller that temperature is 130 DEG C
20min, on the vulcanizing press of 135 DEG C, hot pressing 10min under 13MPa, colds pressing afterwards, obtains halogen-free flameproof EVA composite wood
Material.
Six-lauryl amine base-Infrared Characterization the figure of ring triphosphine nitrile of preparation, hydrogen spectrum phenogram in above-described embodiment (2nd) step
And phosphorus spectrum nuclear-magnetism figure is as shown in Fig. 1, Fig. 2 and Fig. 3；Nitrogen in its each elemental analysis, carbon, hydrogen content test data are shown in Table
1。
The table 1 six-lauryl amine base-nitrogen of ring triphosphine nitrile, carbon, hydrogen content test data
As shown in table 1: N:C:H theoretical content ratio be 10.16: 69.68: 12.67, the content of actual N:C:H
Ratio is 9.75:66.63:12.38, the most consistent with theoretical value, and illustrating further the compound of preparation in step (2) is mesh
Mark product.
Embodiment 2
(1) by 3.00g(0.0086 mol) hexachlorocyclotriph,sphazene and 8.73g(0.086mol) triethylamine is dissolved in and filling
In the oblique three neck round bottom flask of 100ml dioxane (with condensing unit), it is passed through N2Protection, puts into 50 DEG C by round-bottomed flask
In oil bath pan, magnetic agitation 8 min makes it dissolve mix homogeneously, obtains uniform mixed liquor；Now, it is added dropwise in mixed liquor
50ml contains 9.546g(0.0516mol) dioxane solution of lauryl amine, drip while stirring, 2h drips off, after dropping
Back flow reaction 10h at 80 DEG C, obtains reactant liquor；
(2) reactant liquor being cooled to room temperature, stand to layering, decompression sucking filtration obtains white precipitate, first rinses with dioxane,
A large amount of deionized water rinsing, the vacuum drying oven that precipitation is finally put into 80 DEG C is used to be dried 12 h, obtain product six-lauryl amine again
Base-ring triphosphine nitrile, productivity is 79.54%, and melting range is 101-104 DEG C；
(3) by 2g six-lauryl amine base-ring triphosphine nitrile and 25.33 g APPs, 12.67g tri-(1-oxo-1-phospha-
2,6,7-trioxa-l-phosphabicyclos [2,2,2] octane-4-methylene) phosphate ester mixing composition composite flame-retardant agent, by this composite flame-retardant agent
Mixing with 60g ethylene-vinyl acetate copolymer, mixing 15min on the duplex roller that temperature is 130 DEG C, at the flat board of 130 DEG C
On vulcanizer, hot pressing 15min under 12MPa, colds pressing afterwards, obtains halogen-free flameproof EVA composite.
Embodiment 3
(1) by 3.00g(0.0086 mol) hexachlorocyclotriph,sphazene is dissolved in and fills oblique three mouthfuls of round bottoms of 100ml dioxane and burn
(with condensing unit) in Ping, it is passed through N2Protection, puts in the oil bath pan of 80 DEG C by round-bottomed flask, and magnetic agitation 8 min makes it
Dissolve mix homogeneously, obtain uniform mixed liquor；Now, in mixed liquor, 50ml it is added dropwise over containing 9.546g(0.0516mol) 12
Amine and 8.73g(0.086mol) dioxane solution of triethylamine, drip while stirring, 1h drips off, at 75 DEG C after dropping
Lower back flow reaction 12h, obtains reactant liquor；
(2) reactant liquor being cooled to room temperature, stand to layering, decompression sucking filtration obtains white precipitate, first rinses with dioxane,
A large amount of deionized water rinsing, the vacuum drying oven that precipitation is finally put into 80 DEG C is used to be dried 12 h, obtain product six-lauryl amine again
Base-ring triphosphine nitrile, productivity is 81.24%, and melting range is 101-104 DEG C；
(3) by 5g six-lauryl amine base-ring triphosphine nitrile and 23.33 g APPs, 11.67g tri-(1-oxo-1-phospha-
2,6,7-trioxa-l-phosphabicyclos [2,2,2] octane-4-methylene) phosphate ester mixing composition composite flame-retardant agent, by this composite flame-retardant agent
Mixing with 60g ethylene-vinyl acetate copolymer, mixing 10min on the duplex roller that temperature is 120 DEG C, at the flat board of 135 DEG C
On vulcanizer, hot pressing 20min under 12MPa, colds pressing afterwards, obtains halogen-free flameproof EVA composite.
Embodiment 4
(1) by 3.00g(0.0086 mol) hexachlorocyclotriph,sphazene and 8.73g(0.086mol) triethylamine is dissolved in and filling
In the oblique three neck round bottom flask of 100ml dioxane (with condensing unit), it is passed through N2Protection, puts into 80 DEG C by round-bottomed flask
In oil bath pan, magnetic agitation 10 min makes it dissolve mix homogeneously, obtains uniform mixed liquor；Now, it is added dropwise in mixed liquor
50ml contains 9.546g(0.0516mol) dioxane solution of lauryl amine, drip while stirring, 1 h drips off, after dropping
Back flow reaction 9h at 80 DEG C, obtains reactant liquor；
(2) reactant liquor being cooled to room temperature, stand to layering, decompression sucking filtration obtains white precipitate, first rinses with dioxane,
A large amount of deionized water rinsing, the vacuum drying oven that precipitation is finally put into 80 DEG C is used to be dried 12 h, obtain product six-lauryl amine again
Base-ring triphosphine nitrile；Productivity is 82.55%, and melting range is 100-104 DEG C；
(3) by 10g six-lauryl amine base-ring triphosphine nitrile and 20 g APPs, 10g tri-(1-oxo-1-phospha-2,6,7-
Trioxa-l-phosphabicyclo [2,2,2] octane-4-methylene) phosphate ester mixing composition composite flame-retardant agent, by this composite flame-retardant agent and 60g second
Alkene-vinyl acetate co-polymer mixing, mixing 15min on the duplex roller that temperature is 125 DEG C, at the vulcanizing press of 140 DEG C
On, hot pressing 10min under 13MPa, colds pressing afterwards, obtains halogen-free flameproof EVA composite.
Embodiment 5
(1) by 3.00g(0.0086 mol) hexachlorocyclotriph,sphazene is dissolved in and fills oblique three mouthfuls of round bottoms of 100ml dioxane and burn
(with condensing unit) in Ping, it is passed through N2Protection, puts in the oil bath pan of 65 DEG C by round-bottomed flask, and magnetic agitation 5 min makes it
Dissolve mix homogeneously, obtain uniform mixed liquor；Now, in mixed liquor, 50ml it is added dropwise over containing 9.546g(0.0516mol) 12
Amine and 8.73g(0.086mol) dioxane solution of triethylamine, drip while stirring, 1h drips off, at 50 DEG C after dropping
Lower back flow reaction 12h, obtains reactant liquor；
(2) reactant liquor being cooled to room temperature, stand to layering, decompression sucking filtration obtains white precipitate, first rinses with dioxane,
A large amount of deionized water rinsing, the vacuum drying oven that precipitation is finally put into 60 DEG C is used to be dried 18 h, obtain product six-lauryl amine again
Base-ring triphosphine nitrile；Productivity is 79.88%, and melting range is 100-103 DEG C；
(3) by 15g six-lauryl amine base-ring triphosphine nitrile and 16.67 g APPs, 8.33g tri-(1-oxo-1-phospha-
2,6,7-trioxa-l-phosphabicyclos [2,2,2] octane-4-methylene) phosphate ester mixing composition composite flame-retardant agent, by this composite flame-retardant agent
Mixing with 60g ethylene-vinyl acetate copolymer, mixing 20min on the duplex roller that temperature is 130 DEG C, at the flat board of 135 DEG C
On vulcanizer, hot pressing 10min under 13MPa, colds pressing afterwards, obtains halogen-free flameproof EVA composite.
Embodiment 6
(1) by 5.8g(0.0167 mol) hexachlorocyclotriph,sphazene and 10.1g(0.10mol) triethylamine is dissolved in and fills 50ml tetra-
In the oblique three neck round bottom flask of hydrogen furan (with condensing unit), it is passed through N2Protection, puts into the oil bath pan of 50 DEG C by round-bottomed flask
In, magnetic agitation 10 min makes it dissolve mix homogeneously, obtains uniform mixed liquor；Now, mixed liquor is added dropwise over 14.19g
(0.11mol) 1-Aminooctane, drips while stirring, drips off with 1h, after dropping at 80 DEG C back flow reaction 12h, obtain reactant liquor；
(2) reactant liquor being cooled to room temperature, stand to layering, the reactant liquor sucking filtration after standing, by filtrate rotary evaporation
(utilize U.S. TA company AR-2000EX type rotary evaporation flow graph to test, temperature 50 C, 20 minutes to 40 minutes time,
To evaporating without obvious liquid) dope, described dope is placed at 90 DEG C and is vacuum dried 20 h, obtain six-the most pungent
Amido-ring triphosphine nitrile (H-8)；Productivity is 89.52%, and melting range is 85-92 DEG C, and its chemical formula is:
(3) by 1g six-1-Aminooctane base-ring triphosphine nitrile and 26 g APPs, 13g tri-(1-oxo-1-phospha-2,6,7-
Trioxa-l-phosphabicyclo [2,2,2] octane-4-methylene) phosphate ester mixing composition composite flame-retardant agent, by this composite flame-retardant agent and 60g second
Alkene-vinyl acetate co-polymer mixing, mixing 20min on the duplex roller that temperature is 130 DEG C, at the vulcanizing press of 135 DEG C
On, hot pressing 10min under 13MPa, colds pressing afterwards, obtains halogen-free flameproof EVA composite.
In the present embodiment (2nd) step preparation the six-1-Aminooctane base-Infrared Characterization figure of ring triphosphine nitrile, hydrogen spectrum phenogram with
And phosphorus spectrum nuclear-magnetism figure is as shown in Fig. 1, Fig. 2 and Fig. 3；Nitrogen in its each elemental analysis, carbon, hydrogen content test data are shown in Table 1.
The table 2 six-1-Aminooctane base-nitrogen of ring triphosphine nitrile, carbon, hydrogen content test data
As shown in table 2: N:C:H theoretical content ratio be 13.94: 63.74: 12.04, the content of actual N:C:H
Ratio is 12.28:61.91:11.06, the most consistent with theoretical value, illustrates further the compound of preparation in step (2) and is
Target product.
Embodiment 7
(1) by 5.8g(0.0167 mol) hexachlorocyclotriph,sphazene and 10.1g(0.01mol) triethylamine is dissolved in and fills 50ml bis-
In the oblique three neck round bottom flask of oxygen six ring (with condensing unit), it is passed through N2Protection, puts into the oil bath pan of 80 DEG C by round-bottomed flask
In, magnetic agitation 8 min makes it dissolve mix homogeneously, obtains uniform mixed liquor；Now, mixed liquor is added dropwise over 14.19g
(0.11mol) 1-Aminooctane, drips while stirring, and 1h drips off, after dropping at 80 DEG C back flow reaction 10h, obtain reactant liquor；
(2) reactant liquor being cooled to room temperature, stand to layering, the reactant liquor sucking filtration after standing, by filtrate rotary evaporation
Obtain dope, described dope is placed at 90 DEG C and is vacuum dried 20 h, obtain six-1-Aminooctane base-ring triphosphine nitrile (H-8)；Productivity
Being 89.40%, melting range is 86-91 DEG C；
(3) by 2g six-1-Aminooctane base-ring triphosphine nitrile and 25.33 g APPs, 12.67g tri-(1-oxo-1-phospha-
2,6,7-trioxa-l-phosphabicyclos [2,2,2] octane-4-methylene) phosphate ester mixing composition composite flame-retardant agent, by this composite flame-retardant agent
Mixing with 60g ethylene-vinyl acetate copolymer, mixing 15min on the duplex roller that temperature is 130 DEG C, at the flat board of 135 DEG C
On vulcanizer, hot pressing 10min under 13MPa, colds pressing afterwards, obtains halogen-free flameproof EVA composite.
Embodiment 8
(1) by 5.8g(0.0167 mol) hexachlorocyclotriph,sphazene and 10.1g(0.10mol) triethylamine is dissolved in and fills 50ml tetra-
In the oblique three neck round bottom flask of hydrogen furan (with condensing unit), it is passed through N2Protection, puts into the oil bath pan of 50 DEG C by round-bottomed flask
In, magnetic agitation 10 min makes it dissolve mix homogeneously, obtains uniform mixed liquor；Now, mixed liquor is added dropwise over 14.19g
(0.11mol) 1-Aminooctane, drips while stirring, drips off with 1h, after dropping at 50 DEG C back flow reaction 18h, obtain reactant liquor；
(2) reactant liquor being cooled to room temperature, stand to layering, the reactant liquor sucking filtration after standing, by filtrate rotary evaporation
Obtain dope, described dope is placed at 90 DEG C and is vacuum dried 20 h, obtain six-1-Aminooctane base-ring triphosphine nitrile (H-8)；Productivity
Being 89.50%, melting range is 85-91 DEG C；
(3) by 5g six-1-Aminooctane base-ring triphosphine nitrile and 23.33 g APPs, 11.67g tri-(1-oxo-1-phospha-
2,6,7-trioxa-l-phosphabicyclos [2,2,2] octane-4-methylene) phosphate ester mixing composition composite flame-retardant agent, by this composite flame-retardant agent
Mixing with 60g ethylene-vinyl acetate copolymer, mixing 10min on the duplex roller that temperature is 120 DEG C, at the flat board of 135 DEG C
On vulcanizer, hot pressing 10min under 13MPa, colds pressing afterwards, obtains halogen-free flameproof EVA composite.
Embodiment 9
(1) by 5.8g(0.0167 mol) hexachlorocyclotriph,sphazene and 10.1g(0.10mol) triethylamine is dissolved in and fills 50ml tetra-
In the oblique three neck round bottom flask of hydrogen furan (with condensing unit), it is passed through N2Protection, puts into the oil bath pan of 90 DEG C by round-bottomed flask
In, magnetic agitation 10 min makes it dissolve mix homogeneously, obtains uniform mixed liquor；Now, mixed liquor is added dropwise over 14.19g
(0.11mol) 1-Aminooctane, drips while stirring, drips off with 1h, after dropping at 50 DEG C back flow reaction 18h, obtain reactant liquor；
(2) reactant liquor being cooled to room temperature, stand to layering, the reactant liquor sucking filtration after standing, by filtrate rotary evaporation
Obtain dope, described dope is placed at 90 DEG C and is vacuum dried 20 h, obtain six-1-Aminooctane base-ring triphosphine nitrile (H-8)；Productivity
Being 93.24%, melting range is 85-90 DEG C；
(3) by 10g six-1-Aminooctane base-ring triphosphine nitrile and 20 g APPs, 10g tri-(1-oxo-1-phospha-2,6,7-
Trioxa-l-phosphabicyclo [2,2,2] octane-4-methylene) phosphate ester mixing composition composite flame-retardant agent, by this composite flame-retardant agent and 60g second
Alkene-vinyl acetate co-polymer mixing, mixing 15min on the duplex roller that temperature is 125 DEG C, at the vulcanizing press of 135 DEG C
On, hot pressing 10min under 13MPa, colds pressing afterwards, obtains halogen-free flameproof EVA composite.
Embodiment 10
(1) by 5.8g(0.0167 mol) hexachlorocyclotriph,sphazene and 10.1g(0.10mol) triethylamine is dissolved in and fills 50ml tetra-
In the oblique three neck round bottom flask of hydrogen furan (with condensing unit), it is passed through N2Protection, puts into the oil bath pan of 90 DEG C by round-bottomed flask
In, magnetic agitation 10 min makes it dissolve mix homogeneously, obtains uniform mixed liquor；Now, mixed liquor is added dropwise over 14.19g
(0.11mol) 1-Aminooctane, drips while stirring, drips off with 1h, after dropping at 50 DEG C back flow reaction 18h, obtain reactant liquor；
(2) reactant liquor being cooled to room temperature, stand to layering, the reactant liquor sucking filtration after standing, by filtrate rotary evaporation
Obtain dope, described dope is placed at 90 DEG C and is vacuum dried 20 h, obtain six-1-Aminooctane base-ring triphosphine nitrile (H-8)；
(3) by 15g six-1-Aminooctane base-ring triphosphine nitrile and 16.67 g APPs, 8.33g tri-(1-oxo-1-phospha-
2,6,7-trioxa-l-phosphabicyclos [2,2,2] octane-4-methylene) phosphate ester mixing composition composite flame-retardant agent, by this composite flame-retardant agent
Mixing with 60g ethylene-vinyl acetate copolymer, mixing 20min on the duplex roller that temperature is 130 DEG C, at the flat board of 135 DEG C
On vulcanizer, hot pressing 10min under 13MPa, colds pressing afterwards, obtains halogen-free flameproof EVA composite.
Comparative example 1
Take 100g ethylene-vinyl acetate copolymer, mixing on the duplex roller that temperature is 130 DEG C, then at 135 DEG C
On vulcanizing press, hot pressing under 13MPa, cold pressing the most again and obtain the model that thickness is different, finally sample preparation on universal sampling machine
Obtain EVA test bars.
Comparative example 2
Take 60 g ethylene-vinyl acetate copolymers and 26.67 g APPs and 13.33 g tri-(1-oxo-1-phosphorus
Miscellaneous-2,6,7-trioxa-l-phosphabicyclos [2,2,2] octane-4-methylene) then phosphate ester mix homogeneously is 130 DEG C double in temperature
Refine on roller mixing, on the vulcanizing press of 135 DEG C, hot pressing under 13MPa, cold pressing the most again and obtain model, finally in omnipotent system
On model machine, sample preparation obtains fire-retardant EVA test bars.
Embodiment 11
The properties of the material prepared by the detection present invention and comparative example.
Experimental technique:
(1), according to GB/T1040.3-2006, its elongation at break and hot strength thereof are characterized with electronic tension tester,
Testing result is shown in Table 1.
(2), limited oxygen index (LOI): in nitrogen oxygen mixed gas, maintain the minimum oxygen percentage needed for sample combustion
Number, is used for characterizing the flame retardant effect of sample.By ASTM D2863-2000 standard, use (the Jiangning, Nanjing analysis of HC-2 oxygen index instrument
Instrument plant) measure, specimen size 140mm × 6mm × 3mm, testing result is shown in Table 1.
(3), vertical combustion grade: vertical combustion test uses CZF-3 type horizontal vertical burning analyzer (Jiangning, Nanjing
Analytical tool factory of district), with reference to GB GB/T2408-1996, sample to be tested, sample size is 130 mm × 3, mm × 10
mm.Batten is vertically fixed on specimen holder；Regulation flame height is 20mm, sample applies flame time 10s for the first time, moves back
Fight and record primary flaming combustion time t1；After flaming combustion is extinguished, carry out second time and apply flame time 10s, annealing
And record second time flaming combustion time t2 and glowing time t3, and record and whether have dropping to ignite following defat
Cotton, testing result is shown in Table 1.
(4), EVA composite is observed by Japan's JSM-7500F scanning electron microscope and is analyzed.
(5), infrared analysis be Germany Brooker company tensor 27 type infrared tester on complete, with KBr be
Background, sample and the ratio that mass ratio is 1:100 of KBr are ground, test after tabletting；Hydrogen spectrum and phosphorus spectrum nuclear magnetic data
The ADVANCE III 600 type nuclear-magnetism tester of Brooker company of Germany is tested, carries out with deuterochloroform as solvent
Test；Rheological data utilizes U.S. TA-AR2000EX type rotational rheometer, is measured obtaining at 155 DEG C.
Testing result:
Table 3 product of the present invention is to the fire-retardant of fire-retardant EVA and Effect on Mechanical Properties
As shown in Table 3, the material limits oxygen index (OI) of comparative example 1 preparation only has 19.2%, belongs to inflammable product, and when burning
Easily dripping, ignite absorbent cotton, it is impossible to is tested by UL-94.At the expanding fire retardant APP and the Trimer complex that add 40%
After, it is 26.5% that oxygen index (OI) significantly improves, and can reach the V-0 level of UL-94, but the addition of expanding fire retardant APP Yu Trimer
The hot strength and the elongation at break that make EVA are substantially reduced.When prepared by formula proportion and the preparation method provided according to the present invention
During composite, embodiment 3 and the flame retardant effect of embodiment 9 resulting materials and Mechanics of Machinery combination property are best.
Claims (10)
1. a halogen-free flameproof EVA composite, it is characterised in that include ethylene-vinyl acetate copolymer and composite flame-proof
Agent, described ethylene-vinyl acetate copolymer is 32 with the mass ratio of composite flame-retardant agent, and described composite flame-retardant agent is by polyphosphoric acid
Ammonium, three (1-oxo-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2] octane-4-methylene) phosphate esters and fatty amine replace
Phosphazene derivative forms, the APP in described composite flame-retardant agent and three (1-oxo-1-phospha-2,6,7-trioxa-l-phosphabicyclos
[2,2,2] octane-4-methylene) mass ratio of phosphate ester is 21, described fatty amine replace phosphazene derivative with by described poly-phosphorus
Acid ammonium and the mixing of three (1-oxo-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2] octane-4-methylene) phosphate ester composition
The mass ratio of thing is 1-15 25-39；Described fatty amine replaces the chemical general formula of phosphazene derivative:
R in described chemical general formula is 7 or 11.
Halogen-free flameproof EVA composite the most according to claim 1, it is characterised in that described fatty amine replaces phosphonitrile and spreads out
Biological with by described APP and three (1-oxo-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2] octane-4-methylene)
The mass ratio of the mixture of phosphate ester composition is 1 3-19.
Halogen-free flameproof EVA composite the most according to claim 1, it is characterised in that described fatty amine replaces phosphonitrile and spreads out
Biological preparation method is:
A hexachlorocyclotriph,sphazene and acid binding agent are dissolved in organic solvent by (), be passed through N2Protection, at temperature is 50-80 DEG C, stirring is all
Even, obtain mixed liquor；Fatty amine is dripped while stirring, in 0.5-2h after dropping at 50-80 DEG C in described mixed liquor
Back flow reaction 9-12h, obtains reactant liquor；The mol ratio of described hexachlorocyclotriph,sphazene, acid binding agent and fatty amine is 1 6-10 6.0-
6.6, described fatty amine is the one in 1-Aminooctane or lauryl amine；
B described reactant liquor is cooled down by (), stratification, separates target product and is dried, and obtains fatty amine replacement phosphonitrile and derives
Thing.
Halogen-free flameproof EVA composite the most according to claim 1, it is characterised in that described fatty amine replaces phosphonitrile and spreads out
Biological preparation method is:
A hexachlorocyclotriph,sphazene is dissolved in organic solvent by (), be passed through N2Protection, stirs, six at temperature is 50-80 DEG C
Chlorine ring three phosphonitrile solution drips acid binding agent and fatty amine while stirring, in 0.5-2h after dropping at 50-80 DEG C next time
Stream reaction 9-12h, obtains reactant liquor；Described hexachlorocyclotriph,sphazene, acid binding agent are 1 6-10 6.0-6.6 with the mol ratio of fatty amine,
Described fatty amine is the one in 1-Aminooctane or lauryl amine；
B described reactant liquor is cooled down by (), stratification, separates target product and is dried, and obtains fatty amine replacement phosphonitrile and derives
Thing.
Halogen-free flameproof EVA composite the most according to claim 1, it is characterised in that its preparation method includes following step
Rapid:
A hexachlorocyclotriph,sphazene and acid binding agent are dissolved in organic solvent by (), be passed through N2Protection, stirs 5-at temperature is 50-80 DEG C
10 min, obtain uniform mixed liquor；In described mixed liquor, drip fatty amine while stirring, in 0.5-2h dropping after
Back flow reaction 9-12h at 50-80 DEG C, obtains reactant liquor；The mol ratio of described hexachlorocyclotriph,sphazene, acid binding agent and fatty amine is 1
6-10 6.0-6.6, described fatty amine is the one in 1-Aminooctane or lauryl amine；
B described reactant liquor is cooled down by (), stratification, separates target product and is dried, and obtains fatty amine replacement phosphonitrile and derives
Thing；
C described fatty amine is replaced phosphazene derivative and APP, three (1-oxo-1-phospha-2,6,7-trioxa-l-phosphabicyclos by ()
[2,2,2] octane-4-methylene) phosphate ester mixing composition composite flame-retardant agent, by described composite flame-retardant agent and ethene-vinyl acetate
Ester copolymer is 23 mixing in mass ratio, and at temperature is 120-130 DEG C, mixing 10-20 min, pressing plate or granulation, obtain nothing
Halogen fire-retardant EVA composite；APP in described composite flame-retardant agent and three (1-oxo-1-phospha-2,6,7-trioxas pair
Ring [2,2,2] octane-4-methylene) mass ratio of phosphate ester is 21, described fatty amine replace phosphazene derivative with by described poly-
It is mixed that ammonium phosphate and three (1-oxo-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2] octane-4-methylene) phosphate ester form
The mass ratio of compound is 1-15 25-39.
Halogen-free flameproof EVA composite the most according to claim 1, it is characterised in that its preparation method includes following step
Rapid:
A hexachlorocyclotriph,sphazene is dissolved in organic solvent by (), be passed through N2Protection, stirs, six at temperature is 50-80 DEG C
Chlorine ring three phosphonitrile solution drips acid binding agent and fatty amine while stirring, drips complete in 0.5-2h, reflux at 50-80 DEG C
Reaction 9-12 h, obtains reactant liquor；Described hexachlorocyclotriph,sphazene, acid binding agent are 1 6-10 6.0-6.6 with the mol ratio of fatty amine,
Described fatty amine is the one in 1-Aminooctane or lauryl amine；
B described reactant liquor is cooled down by (), stratification, separates target product and is dried, and obtains fatty amine replacement phosphonitrile and derives
Thing；
C described fatty amine is replaced phosphazene derivative and APP, three (1-oxo-1-phospha-2,6,7-trioxa-l-phosphabicyclos by ()
[2,2,2] octane-4-methylene) phosphate ester mixing composition composite flame-retardant agent, by described composite flame-retardant agent and ethene-vinyl acetate
Ester copolymer is 23 mixing in mass ratio, and at temperature is 120-130 DEG C, mixing 10-20 min, pressing plate or granulation, obtain nothing
Halogen fire-retardant EVA composite；APP in described composite flame-retardant agent and three (1-oxo-1-phospha-2,6,7-trioxas pair
Ring [2,2,2] octane-4-methylene) mass ratio of phosphate ester is 21, described fatty amine replace phosphazene derivative with by described poly-
It is mixed that ammonium phosphate and three (1-oxo-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2] octane-4-methylene) phosphate ester form
The mass ratio of compound is 1-15 25-39.
7. according to the halogen-free flameproof EVA composite described in claim 3,4,5 or 6, it is characterised in that described in step (a)
Acid binding agent is triethylamine.
8. according to the halogen-free flameproof EVA composite described in claim 3,4,5 or 6, it is characterised in that described in step (a)
Organic solvent is any one in dioxane or oxolane.
9. according to the halogen-free flameproof EVA composite described in claim 3,4,5 or 6, it is characterised in that described in step (a)
When fatty amine is lauryl amine, described hexachlorocyclotriph,sphazene, acid binding agent are 1 10 6.0 with the mol ratio of fatty amine.
10. according to the halogen-free flameproof EVA composite described in claim 3,4,5 or 6, it is characterised in that described in step (a)
When fatty amine is 1-Aminooctane, described hexachlorocyclotriph,sphazene, acid binding agent are 16 6.6 with the mol ratio of fatty amine.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0177370A2 (en) * | 1984-10-05 | 1986-04-09 | Ethyl Corporation | Process for phosphazene trimer purification |
| CN1242784A (en) * | 1997-10-15 | 2000-01-26 | 大塚化学株式会社 | Crosslinked phenoxyphosphazene compounds, flame-retardant, flame-retardant resin compositions, and moldings of flame-retardant resins |
| CN102250147A (en) * | 2011-05-17 | 2011-11-23 | 北京理工大学 | Preparation method and application of cyclotriphosphazene containing silicon functional groups |
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| JP2003128909A (en) * | 2001-10-23 | 2003-05-08 | Asahi Kasei Corp | Flame-retardant thermosetting resin composition |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0177370A2 (en) * | 1984-10-05 | 1986-04-09 | Ethyl Corporation | Process for phosphazene trimer purification |
| CN1242784A (en) * | 1997-10-15 | 2000-01-26 | 大塚化学株式会社 | Crosslinked phenoxyphosphazene compounds, flame-retardant, flame-retardant resin compositions, and moldings of flame-retardant resins |
| CN102250147A (en) * | 2011-05-17 | 2011-11-23 | 北京理工大学 | Preparation method and application of cyclotriphosphazene containing silicon functional groups |
Non-Patent Citations (1)
| Title |
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| Synthesis of Polyphosphazenes with Isothiocyanato, Thiourethane, and Thiourea Side Groups;Harry R. Allcock and J. Steven Rutt;《Macromolecules》;19910531;第24卷(第10期);第2852-2857页 * |
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Effective date of registration: 20170717 Address after: LAN Cheng Cun 065000 Langfang city of Hebei province Yongqing Rilan County town (unprocessed Station West) Patentee after: Yongqing Sanli rubber material Co. Ltd. Address before: 071002 East Road, Hebei, Baoding No. 54 Patentee before: Hebei University |