CN101948581B - Intumescent flame retardant polyethylene containing organosilicon compound - Google Patents
Intumescent flame retardant polyethylene containing organosilicon compound Download PDFInfo
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- CN101948581B CN101948581B CN 201010272219 CN201010272219A CN101948581B CN 101948581 B CN101948581 B CN 101948581B CN 201010272219 CN201010272219 CN 201010272219 CN 201010272219 A CN201010272219 A CN 201010272219A CN 101948581 B CN101948581 B CN 101948581B
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- polyethylene
- expansion type
- synergistic agent
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 60
- -1 polyethylene Polymers 0.000 title claims abstract description 48
- 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 title claims abstract description 41
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 38
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 31
- 150000003961 organosilicon compounds Chemical class 0.000 title abstract 4
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 13
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 229940059574 pentaerithrityl Drugs 0.000 claims description 24
- 239000012747 synergistic agent Substances 0.000 claims description 16
- 239000002131 composite material Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 10
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 10
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 5
- 239000000347 magnesium hydroxide Substances 0.000 claims description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 150000001263 acyl chlorides Chemical class 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- NAPSCFZYZVSQHF-UHFFFAOYSA-N dimantine Chemical compound CCCCCCCCCCCCCCCCCCN(C)C NAPSCFZYZVSQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229950010007 dimantine Drugs 0.000 claims description 3
- 239000011363 dried mixture Substances 0.000 claims description 3
- 239000002608 ionic liquid Substances 0.000 claims description 3
- KFTNEILVDDUXGR-SECBINFHSA-N n-[(1r)-1-(4-bromophenyl)ethyl]-5-fluoro-2-hydroxybenzamide Chemical compound N([C@H](C)C=1C=CC(Br)=CC=1)C(=O)C1=CC(F)=CC=C1O KFTNEILVDDUXGR-SECBINFHSA-N 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 238000005453 pelletization Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 229960004839 potassium iodide Drugs 0.000 claims description 2
- 235000007715 potassium iodide Nutrition 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- GTACSIONMHMRPD-UHFFFAOYSA-N 2-[4-[2-(benzenesulfonamido)ethylsulfanyl]-2,6-difluorophenoxy]acetamide Chemical compound C1=C(F)C(OCC(=O)N)=C(F)C=C1SCCNS(=O)(=O)C1=CC=CC=C1 GTACSIONMHMRPD-UHFFFAOYSA-N 0.000 claims 1
- 101710130081 Aspergillopepsin-1 Proteins 0.000 claims 1
- 102100031007 Cytosolic non-specific dipeptidase Human genes 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 claims 1
- 229920000098 polyolefin Polymers 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000004794 expanded polystyrene Substances 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical class [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 125000001246 bromo group Chemical class Br* 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention belongs to the technical field of polyolefin flame retardant products and particularly relates to intumescent flame retardant polyethylene containing an organosilicon compound, which simultaneously contains intumescent compounded flame retardant and the organosilicon compound and has higher flame retardant efficiency. The intumescent flame retardant polyethylene containing the organosilicon compound also contains a metal oxide hydrate containing an organosilicon flame retardant synergist and comprises the following compositions in percentage by weight: 70-80 percent of polyethylene, 17-29.5 percent of compounded intumescent flame retardant and 0.5-3 percent of the metal oxide hydrate containing the organosilicon flame retardant synergist.
Description
Technical field
The invention belongs to the technical field of polyolefine flame retardant products, specifically, the present invention relates to a kind of higher expansion type retardant polyethylene that contains silicoorganic compound of flame retarding efficiency that contains simultaneously expanded polystyrene veneer compound flame retardant and silicoorganic compound.
Background technology
Polyethylene is with its light weight, low toxicity and good insulativity and limiting performance, although a lot of industries such as the packing of being widely used in, building materials, automobile, electronics/electric, daily necessities, but his is high flammable, and melting drippage after the burning, easily cause new disaster and the problem of loss of life and personal injury, make it comparatively difficult in high flame retardant rank electric and that building trade is required, thereby greatly affected its application in these industries.
Fire retardant is that a class can stop polymer materials to be ignited or suppresses the auxiliary agent of propagation of flame.The fire retardant that is most widely used at present is organic fire-retardant, the Organohalogen compounds of domestic main employing (take ten bromines, hexabromo as representative) and Sb
2O
3Composite use is carried out fire-retardant to PE.This based flame retardant can catch the free radical that the PE DeR generates when combustion decomposition, thereby delays or stop the chain reaction of burning, and discharging simultaneously itself is a kind of gas HX of difficult combustion.This gas density is large, can cover material surface, plays the effect that intercepts surperficial inflammable gas, also can suppress the burning of material.Its weak point: this fire retardant is relatively poor aspect the inhibition drippage, and the amount of being fuming is large when burning, produces macro-corrosion gas and toxic gas, gives and puts out a fire, flees from and resume work and bring very large suffering.
Inorganic combustion inhibitor is a kind of halogen-free flame retardants, have safe, press down cigarette, the advantage such as nontoxic, inexpensive, in fire-retardantization of PE, has critical role, widely used now also is that the type of the halogen-free flame retardants of most study has: metal oxide hydrate (ATH, MAH), Halogen phosphorus flame retardant and expansion type flame retardant.The metal oxide hydrate fire retardant mainly contains Al (OH)
3And Mg (OH)
2, the large calorimetric that the absorbing material burning discharges when decomposing of this fire retardant, thus the material surface temperature is reduced, slow down the degradation speed of superpolymer.Its weak point: their fire retardancy addition not bery strong and that require is large, thereby makes mechanical property and some deterioration in physical properties of material.
The retardant synergist that has now found that has silicoorganic compound, red phosphorus and phosphorus compound, zinc borate, metal oxide etc.Guo Xikun, Yang Jianying have studied red phosphorus, ammonium polyphosphate and Al (OH)
3, Mg (OH)
2Between synergistic effect, find that by differential thermal analysis research the polyphosphoric acid that generates in the fire-retardant process of phosphorus flame retardant, poly-metaphosphoric acid have strong dehydration, thereby can aggravate Al (OH)
3, Mg (OH)
2Thermal endothermic decomposition reaction, play synergism.The people such as Wang Zhengzhou [make Mg (OH) with red phosphorus, expanded graphite respectively
2Retardant synergist, find that micro encapsulation red phosphorus has the addition an of the best, the highest at the limiting oxygen index(LOI) of this point, can also postpone the burning time of material.But, add red phosphorus and can increase the amount of being fuming that material combustion produces.Expanded graphite then comes synergy fire-retardant by generation expanding layer, obstruct thermal feedback in fire-retardant process, so the flame retardant effect of the graphite that rate of expansion is large is better, but graphite itself belongs to combustible matl, so can the premature ignition time.Although the polyethylene of processing with these fire retardants shows low cigarette, nontoxic, characteristics such as good flame retardation effect and certain anti-molten, but still have to some extent some problems: flame retardant effect is desirable not enough, and dripping property of refractory is still waiting to improve etc.
CN1757667A (patent No. 200510022034.1), title " halogen-free expansion type retardant polyethylene that contains organometallic complex ", as base material take polyethylene, wherein contain composite expansion type flame retardant, it is characterized in that also containing organometallic complex, the content of each component is respectively by weight percentage: polyethylene 70～80%, composite expansion type flame retardant 17～29.5%, organometallic complex 0.5～3%.
Summary of the invention
Purpose of design: avoid the weak point in the background technology, design a kind of higher expansion type retardant polyethylene that contains silicoorganic compound of flame retarding efficiency that contains simultaneously expanded polystyrene veneer compound flame retardant and silicoorganic compound.
Design: in order to realize above-mentioned purpose of design.The study on the modification of the application on the basis of the patent No. 200510022034.1, provide a kind of and also have simultaneously the expanded polystyrene veneer compound flame retardant and take organosilicon quaternary ammonium salt or organosilicon ionic liquid as the higher polyethylene of the flame retardant effect of the metal oxide hydrate of retardant synergist, reach and make the flame retardant amount that contains in this polyethylene little, and dripping property of refractory is good.
The expansion type retardant polyethylene that contains the organic silicon flame-retardant synergistic agent provided by the invention, contain composite expansion type flame retardant in this polyethylene, it is characterized in that also containing the metal oxide hydrate of organic silicon flame-retardant synergistic agent, the content of each component is respectively by weight percentage: polyethylene 70～80%, composite expansion type flame retardant 17～29.5% contains the metal oxide hydrate 0.5～3% of organic silicon flame-retardant synergistic agent.
Wherein contained composite expansion type flame retardant is by the pentaerythritol ester with following structure (I), composite the forming of ammonium polyphosphate (II) melamine phosphate (III):
The content of wherein n 〉=20, and its each component is respectively by weight percentage: pentaerythritol ester 6.8～11.8%; Ammonium polyphosphate 4.7～8.2%, preferred 6.4～8.2%; Melamine phosphate 5.5～9.5%, preferred 7.4～9.5%.
Because pentaerythritol ester can not buied on the market, need click the aspect is prepared from: with tetramethylolmethane and 1-oxo-4-methylol-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2] the chloride product of octane (being called for short PEPA) is put into 0.2mol tetramethylolmethane/1000mL dioxane by 1: 3 mol ratio and is dissolved, and adding is made catalyzer by the pyridine of 0.2mol tetramethylolmethane/1.5mL, 90～110 ℃ of back flow reaction 3～6 hours, after the cooling, with acetone, chlorobenzene respectively washed product namely get white solid product 1～2 time.PEPA chloride product can be according to document-" research of Caged bicyclic phosphate derivative-I.1-oxo-4-replaces-2,6,7-trioxa-1-phospha dicyclo [2,2,2] the synthetic and repercussion study of Octane derivatives " (" chemical journal " 1988,46:679) the upper method that discloses is synthetic.
Wherein contained metal oxide hydrate is aluminium hydroxide and magnesium hydroxide.
Contained retardant synergist is organosilicon quaternary ammonium salt or organosilicon ionic liquid, has following structure.
R is the group that can be hydrolyzed in the formula, as-O-COO-Cl and-OC
2H
5Deng; R
1For alkyl, contain oxygen or nitrogen-containing group, such as (CH
2)
3NHCH
2CH
2-,-CH
2COCH
2CH
2-,-CH
2-etc.; R
2Be 1～20 alkyl of carbon atoms; X is Cl, Br, BF
4, PF
6, annotating respectively is synergistic agent 1, synergistic agent 2, synergistic agent 3, synergistic agent 4.
The halogen-free expansion type retardant polyethylene that contains the metal oxide hydrate of organosilicon synergist provided by the invention prepares by following processing step:
(1) the synthesis of pentaerythritol ester after 7-trioxa-l-phosphabicyclo [2,2,2] octanes (PEPA) acyl chlorides product prepares by above disclosed method, uses vacuum drying oven in 70 ℃ of oven dry tetramethylolmethane and 1-oxo-1-methylol-1-phospha-2,6, and is for subsequent use.
(2) the synthesizing organo-silicon quaternary ammonium salt is with γ-chloropropyl trimethoxy silane and N, the Dymanthine reaction is made catalyzer with potassiumiodide, successive reaction 24～36h, synthesized N, N-dimethyl-N-octadecylamine propyl trimethoxy silicane quaternary ammonium salt (BFS).
(3) mechanically mixing joins pentaerythritol ester, melamine phosphate, ammonium polyphosphate, magnesium hydroxide, aluminium hydroxide and BFS in the polyethylene by proportioning, and mixes in high-speed mixer;
(4) mixture after vacuum-drying will mix is put into vacuum drying oven, and is lower dry 8～10 hours at 70 ℃;
(5) melting mixing is put into the twin screw extruder melt blending with dried mixture and is extruded.The temperature in each district of forcing machine is controlled to be respectively 150 ℃, 160 ℃, 170 ℃, 170 ℃, 160 ℃, 150 ℃, and screw speed is controlled to be 25～50 rev/mins;
(6) the cooling and dicing melt blended material is extruded rear naturally cooling pelletizing.
The present invention compared with the prior art, the one, owing to contain autonomous synthetic pentaerythritol ester fire retardant in the composite expansion type flame retardant of the present invention, thereby reduced the addition of ammonium polyphosphate, reduced the ammonium polyphosphate water absorbability to Flame Retardancy can disadvantageous effect; The 2nd, owing to contain autonomous synthetic pentaerythritol ester fire retardant in the composite expansion type flame retardant of the present invention, not only reduced the addition of melamine phosphate, and improved the efficient of fire retardant; The 3rd, added silicoorganic compound in the fire retardant, in fire-retardant process, generate the SiC char layer of ceramic-like, can play heat insulation oxygen barrier effect, and metal oxide hydrate and expansion type flame retardant produce the cooperative flame retardant effect, not only greatly improved the oxygen index flame retardant properties of polythene material, also improved the vertical combustion that embodies dripping property of refractory, solved polythene material and will reach at electric and high flame retardant rank that building trade is required hard problem comparatively.
Embodiment
Below in conjunction with specific embodiment preparation method of the present invention is described further, but protection scope of the present invention is not limited to this.
(1) tetramethylolmethane ester synthesis:
With the 3.00g tetramethylolmethane, 14.03g 1-oxo-1-methylol-1-phospha-2,6, the adding of 7-trioxa-l-phosphabicyclo [2,2,2] octanes (PEPA) acyl chlorides product is placed with in the there-necked flask of 100mL dioxane, stirring and dissolving, and the pyridine of dropping 0.16mL; Be heated to 95～105 ℃ of flow of goods reactions 6 hours; Be cooled to room temperature, then use dioxane, chloroform respectively washed product namely gets white solid product 1～2 time; At last in 70 ℃ of vacuum drying oven dry for standby.The infared spectrum concrete structure of this tetramethylolmethane ester products that obtains is as follows: 3456cm
-1And 1121cm
-1Be O-H; 2924cm
-1Be aliphatic C-H structure; 1736cm
-1And 1234cm
-1Be ester group; 1295cm
-1And 1001cm
-1For phosphate-based; 873cm
-1And 835cm
-1Be cage shape bicyclic phosphate structure.
(2) organosilicon quaternary ammonium salt is synthetic:
The N that in the four-necked bottle that thermometer, agitator, reflux condensing tube are housed, adds successively 62.4g (0.21mol), Dymanthine, 60g solvent Virahol, micro-antioxidant stir and are warming up to the setting temperature of reaction; Drip 39.7g (0.2mol) γ-r-chloropropyl trimethoxyl silane and catalyzer iodate potassium solution, successive reaction 24～36h; Remove by filter insoluble antioxidant residue, decompression and solvent recovery and unreacted reactant; Add again solid acid and remove residual micro-tertiary amine and decolour, get the quaternized silane BFS of light yellow transparent liquid.Productive rate 70.11%, the ζ-potential of specific refractory power 1.4206,2% aqueous solution (20 ℃) is 9.9 * 10
-4V, infrared spectra IR (cm
-1) be 3349 (s, υ
O-H, OH), 2969,2930,2850 (s, υ
C-H,-CH
3,-CH
2), 1630 (w, R
3NH
+Impurity peaks), 1465,1375 (m, δ
C-H, C-CH
2), 1192 (s, δ
s C-H, Si-CH
2), 1075 (s, υ
Si-O), 820 (s, υ
Si-C).
(3) mechanically mixing joins pentaerythritol ester, melamine phosphate, ammonium polyphosphate, magnesium hydroxide, aluminium hydroxide and BFS in the polyethylene by proportioning, and mixes in high-speed mixer;
(4) mixture after vacuum-drying will mix is put into vacuum drying oven, and is lower dry 8～10 hours at 70 ℃;
(5) melting mixing is put into the twin screw extruder melt blending with dried mixture and is extruded.The temperature in each district of forcing machine is controlled to be respectively 150 ℃, 160 ℃, 170 ℃, 170 ℃, 160 ℃, 150 ℃, and screw speed is controlled to be 25～50 rev/mins;
(6) the cooling and dicing melt blended material is extruded rear naturally cooling pelletizing.
Table 1
Annotate: numerical value is weight percentage in the table; Retardant synergist among the embodiment 1～4 is respectively: the X (IV) is respectively Cl, Br, BF
4, PF
6
In order to investigate poly flame retardant properties provided by the invention, the below with the flame-proof polyethylene vacuum-drying of the embodiment of the invention 1～4 happy and harmonious mixing gained after heating platen, after cutting into the standard batten of 130 * 6.5 * 3mm and 130 * 13 * 3mm, and pure polyethylene, the polyethylene that only added halogen-free expansion fire retardant carry out following contrast combustionproperty test:
1. limiting oxygen index determination:
Press the program test of GB2406-93 specified standards with JF-3 type oxygen index instrument.
Table 2
| Description of materials | Oxygen index |
| Pure PE | 17.8 |
| PE/IFR | 26.3 |
| PE/ synergistic agent 1 | 29.2 |
| PE/ synergistic agent 2 | 28.9 |
| PE/ synergistic agent 3 | 29.9 |
| PE/ synergistic agent 4 | 29.6 |
Annotate: PE is polyethylene, and IFR is composite expansion type flame retardant.
It will be appreciated that: although above-described embodiment has been done more detailed text description to mentality of designing of the present invention, but these text descriptions, just the simple text of mentality of designing of the present invention is described, rather than to the restriction of mentality of designing of the present invention, any combination, increase or modification that does not exceed mentality of designing of the present invention all falls within the scope of the present invention.
Claims (2)
1. expansion type retardant polyethylene that contains silicoorganic compound, it is characterized in that: be respectively by weight percentage: polyethylene 70 ~ 80%, composite expansion type flame retardant 17 ~ 29.5% contains aluminium hydroxide and the magnesium hydroxide metal oxide hydrate 0.5 ~ 3% of organic silicon flame-retardant synergistic agent;
Described composite expansion type flame retardant is by the pentaerythritol ester with following structure (I), composite the forming of ammonium polyphosphate (II) melamine phosphate (III):
The content of wherein n 〉=20, and its each component is respectively by weight percentage: pentaerythritol ester 6.8 ~ 11.8%; Ammonium polyphosphate 6.4 ~ 8.2%; Melamine phosphate 7.4 ~ 9.5%;
Described pentaerythritol ester preparation: with tetramethylolmethane and 1-oxo-4-methylol-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2] the chloride product of octane was put into 0.2mol tetramethylolmethane/1000mL dioxane by the mol ratio of 1:3 and is dissolved, and adds and to make catalyzer by the pyridine of 0.2mol tetramethylolmethane/1.5mL, 90 ~ 110 ℃ of back flow reaction 3 ~ 6 hours, after the cooling, namely get white solid product 1 ~ 2 time with acetone, chlorobenzene difference washed product; Contained retardant synergist is organosilicon quaternary ammonium salt or organosilicon ionic liquid, has following structure:
R is the group of hydrolysis in the formula; R
1For alkyl, contain oxygen or nitrogen-containing group; R
2Be 1 ~ 20 alkyl of carbon atoms; X is Cl, Br, BF
4, PF
6, annotating respectively is synergistic agent 1, synergistic agent 2, synergistic agent 3, synergistic agent 4.
2. expansion type retardant polyethylene that contains silicoorganic compound as claimed in claim 1, it is characterized in that: the halogen-free expansion type retardant polyethylene that contains the metal oxide hydrate of organosilicon synergist prepares by following processing step:
(1) synthesis of pentaerythritol ester: with tetramethylolmethane and 1-oxo-1-methylol-1-phospha-2,6, after 7-trioxa-l-phosphabicyclo [2,2,2] octanes (PEPA) acyl chlorides product prepares by above disclosed method, in 70 ℃ of oven dry, for subsequent use with vacuum drying oven;
(2) synthesizing organo-silicon quaternary ammonium salt: with γ-chloropropyl trimethoxy silane and N, the Dymanthine reaction is made catalyzer with potassiumiodide, and successive reaction 24 ~ 36h has synthesized N, N-dimethyl-N-octadecylamine propyl trimethoxy silicane quaternary ammonium salt (BFS);
(3) mechanically mixing: pentaerythritol ester, melamine phosphate, ammonium polyphosphate, magnesium hydroxide, aluminium hydroxide and BFS are joined in the polyethylene by proportioning, and in high-speed mixer, mix;
(4) vacuum-drying: the mixture after will mixing is put into vacuum drying oven, and is lower dry 8 ~ 10 hours at 70 ℃;
(5) melting mixing: dried mixture is put into the twin screw extruder melt blending extrude, the temperature in each district of forcing machine is controlled to be respectively 150 ℃, 160 ℃, 170 ℃, 170 ℃, 160 ℃, 150 ℃, and screw speed is controlled to be 25 ~ 50 rev/mins;
(6) cooling and dicing: melt blended material is extruded rear naturally cooling pelletizing.
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| CN104403169A (en) * | 2014-11-24 | 2015-03-11 | 苏州市贝克生物科技有限公司 | Medical LDPE(low-density polyethylene) antibacterial material and preparation method thereof |
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| CN105273470A (en) * | 2015-11-24 | 2016-01-27 | 宁夏润龙包装新材料股份有限公司 | Halogen-free intumescent flame retardant and preparation method thereof |
| CN106118065B (en) * | 2016-06-23 | 2019-04-30 | 上海工程技术大学 | A kind of expandable flame retardant silicon rubber and preparation method thereof |
| CN109370031A (en) * | 2018-10-04 | 2019-02-22 | 南京万和新材料有限公司 | A kind of rubber-plastic foamed thermal insulation material of damping noise reduction |
| CN111848681B (en) * | 2019-10-28 | 2023-03-28 | 浙江大学宁波理工学院 | Metal coordination intumescent flame retardant and preparation method thereof |
| WO2021193883A1 (en) * | 2020-03-25 | 2021-09-30 | 株式会社Adeka | Flame retardant composition, flame-retardant synthetic-resin composition, and molded object |
| CN112225501A (en) * | 2020-09-21 | 2021-01-15 | 湖州上建华煜混凝土有限公司 | Concrete for preventing microbial corrosion and preparation method thereof |
| CN115260639B (en) * | 2022-09-20 | 2023-01-06 | 河北尚华塑料科技有限公司 | High-flame-retardant insulating material for cable and preparation method thereof |
| CN115521634B (en) * | 2022-10-15 | 2023-06-27 | 温州市和沐环保科技有限公司 | Regenerated flame-retardant plastic particle and processing technology thereof |
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