CN103289332B - Glass fiber enhanced poly(ethylene terephthalate) nano flame-retardant composite material and preparation method thereof - Google Patents
Glass fiber enhanced poly(ethylene terephthalate) nano flame-retardant composite material and preparation method thereof Download PDFInfo
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- -1 poly(ethylene terephthalate) Polymers 0.000 title claims abstract description 55
- 229920000139 polyethylene terephthalate Polymers 0.000 title claims abstract description 55
- 239000005020 polyethylene terephthalate Substances 0.000 title claims abstract description 55
- 239000003063 flame retardant Substances 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
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003365 glass fiber Substances 0.000 title claims abstract description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000011152 fibreglass Substances 0.000 claims description 28
- 229910052736 halogen Inorganic materials 0.000 claims description 13
- 150000002367 halogens Chemical class 0.000 claims description 13
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical class OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003112 inhibitor Substances 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 229920006351 engineering plastic Polymers 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- 235000013824 polyphenols Nutrition 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims 2
- 125000004402 polyphenol group Chemical group 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 abstract description 10
- 239000001301 oxygen Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 6
- 239000002114 nanocomposite Substances 0.000 abstract description 4
- 239000003963 antioxidant agent Substances 0.000 abstract 1
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 239000002105 nanoparticle Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 9
- 238000002485 combustion reaction Methods 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- 230000000979 retarding effect Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- SZKCCJBKBKSUEH-UHFFFAOYSA-N [Ce].C1(=CC=CC=C1)P(O)(O)=O Chemical compound [Ce].C1(=CC=CC=C1)P(O)(O)=O SZKCCJBKBKSUEH-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 239000012757 flame retardant agent Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910001853 inorganic hydroxide Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- DGZQEAKNZXNTNL-UHFFFAOYSA-N 1-bromo-4-butan-2-ylbenzene Chemical compound CCC(C)C1=CC=C(Br)C=C1 DGZQEAKNZXNTNL-UHFFFAOYSA-N 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000003008 phosphonic acid esters Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses a glass fiber enhanced poly(ethylene terephthalate) nano composite material and a preparation method thereof. The composite material is prepared from the following components in percentage by weight: 80-100% of glass fiber enhanced poly(ethylene terephthalate), 0-10% of phenyl phosphonic acid rare-earth salt, 0-15% of a halogenous flame retardant and 0-3% of an antioxidant, wherein the sum of the weight percentages of the components is 100%. The composite material has the advantages as follows: under the condition that the use amount of the flame retardant is low, the oxygen index is up to 29 and can pass through a V-0 level test of UL94, and nano-particles are well dispersed in poly(ethylene terephthalate). The nano composite material provided by the invention that the preparation method is simple, the use amount of the flame retardant is small and the flame-retardant effect is good. the nano composite material can be widely applied to the fields of mechanical equipment, electrical appliance shells, automotive trims and the like.
Description
Technical field
The present invention relates to blended, the Flame Retardancy energy technical field of measurement and test of organic synthesis, polymer composite, be specifically related to a kind of fiberglass reinforced polyethylene terephthalate nano fire-retarding composite material and preparation method thereof.
Technical background
Polyethylene terephthalate (PET) is one of composite fibre materials be most widely used, be widely used as fiber and thin-film material, and PET is more and more subject to the attention of people as engineering plastics in recent years, particularly fiberglass reinforced PET engineering plastics (Glass-fiber reinforced Poly (ethylene terephthalate), be abbreviated as GF-PET), not only cheap, and there is the advantages such as excellent dimensional stability, high strength and high-modulus, make it have purposes more and more widely in automobile, household electrical appliances, the field such as electric, mechanical.But one of shortcoming that GF-PET is very important is its inflammableness, a large amount of cigarettes produced when the low oxygen index value of 18 ~ 20% and burning, very easily initiation fire cause the fire spreads quickly, this causes very big restriction to the widespread use of PET material.Therefore, the fire-retardant research carrying out PET material especially GF-PET is particularly necessary.
At present, in PET, add effective fire retardant is the most common, effective and one of mode of economy.Wherein can be divided three classes to the effective fire retardant of polyester: (1) halogenated flame retardant, it is comparatively early developed the fire retardant for polyester, and high, the fire-retardant good stability of flame retarding efficiency, wide adaptability, once occupy dominant position, common are decabromodiphynly oxide (DBDPO), TDE (DBDPE), Brominated Polystyrene (BPS), brominated epoxy resin (BER) etc.Owing to there is environmental issue, once some European countries was once limiting the use of some halogenated flame retardant.But the addition of the halogenated flame retardant of synthesizing environment-friendly or reduction halogenated flame retardant is feasible research direction.(2) phosphorus flame retardant, it can be divided into organic and inorganic two kinds, and wherein inorganic phosphorus flame retardant mainly contains red phosphorus, triammonium phosphate, Secondary ammonium phosphate and ammonium polyphosphate etc.; Organic phosphorus flame retardant mainly contains containing halophosphate, non-halophosphate, phosphonic acid ester and phosphine oxide compound etc.Alkyl phosphinic acid salt pair nylon and the linear polyester flame retardant effect of nearest appearance are obvious.Phosphorus flame retardant is subject to increasing research with its flame retardant properties to polyester excellence, environmental protection and excellent over-all properties.(3) inorganic hydroxide fire retardant, the inorganic hydroxides such as magnesium hydroxide are the fire retardants that another kind is applied to PET, have won the favor of insider with environment friendly; But this based flame retardant addition need reach the flame retardant effect that 40wt% ~ 60wt% has just had, this has had a strong impact on the mechanical property of material, therefore, in the process of processing of high molecular material, needs to carry out composite to it, thus improves flame retarding efficiency, improves mechanical property.
In order to improve the flame retarding efficiency of fire retardant, reduce the consumption of fire retardant, a lot of fire retarding synergists is studied and develop.The synergistic effect of metal ion is confirmed widely, and common unit have antimony, zirconium, molybdenum, iron, manganese, zinc etc., generally joins in matrix mainly with the form of metal-salt and plays a role.
Rare earth element (RareEarth) refers to lanthanon in the periodic table of elements---lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), and two elements closely-related with group of the lanthanides---scandium (Sc) and yttrium (Y) totally 17 kinds of elements, be called for short rare earth (Re or R).As a kind of strategic resource, be used for military affairs, metallurgy, petrochemical complex and the novel material such as luminescence, permanent magnetism, have the title of " industrial VITAMIN ", it enriches in china natural resources, great variety of goods.But a kind ofly can reduce halogen consumption as how rare earth is prepared as raw material and fully can improve again the matrix material of flame retardant effect, becoming the technical problem that this area is urgently to be resolved hurrily.
Summary of the invention
The present invention is directed to the above-mentioned deficiency of prior art, provide a kind of halogen consumption fully can improve again the fiberglass reinforced polyethylene terephthalate nano fire-retarding composite material of flame retardant effect less.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: a kind of fiberglass reinforced polyethylene terephthalate nano fire-retarding composite material, is characterized in that, this material is prepared by each component of following weight percent:
(1) fiberglass reinforced polyethylene terephthalate 80 ~ 100%,
(2) phenyl-phosphonic acid rare-earth salts 0 ~ 10%,
(3) halogen containing flame-retardant 0 ~ 15%,
(4) oxidation inhibitor 0 ~ 3%;
Above-mentioned each weight percentages of components sum is 100%.
As preferably, described fiberglass reinforced polyethylene terephthalate nano fire-retarding composite material, is characterized in that: this material is prepared by each component of following weight percent:
(1) fiberglass reinforced polyethylene terephthalate 80 ~ 99.9%,
(2) phenyl-phosphonic acid rare earth 1 ~ 10%,
(3) halogen containing flame-retardant 1 ~ 15%,
(4) oxidation inhibitor 0.05 ~ 3%;
Above-mentioned each weight percentages of components sum is 100%.
Fiberglass reinforced polyethylene terephthalate of the present invention is density 1.39g/cm
3, glass fiber content 15%, trade mark Du Pont 415HP, molecular backbone chain be
the thermoplasticity fiberglass reinforced engineering plastics of chain link.
Halogen containing flame-retardant of the present invention is conventional halogenated flame retardant, as TDE, decabromodiphenyl oxide, brominated Polystyrene etc.
Oxidation inhibitor of the present invention is as being common polyphenol antioxidant 1010.
Phenyl-phosphonic acid rare-earth salts of the present invention is homemade a kind of lamella nano material, and concrete preparation method is: by 5 ~ 10mmol phenyl-phosphonic acid (H
2o
3pC
6h
5) be dissolved in the mixed solvent of 100ml ethanol/water (volume ratio is 1:1) and obtain phenyl-phosphonic acid solution, then gained solution is placed in reaction vessel; By 3 ~ 8mmolReCl
36H
2o is added drop-wise to after being dissolved in 100ml deionized water in the above-mentioned reaction vessel containing phenyl-phosphonic acid solution, stirs, and by the NaOH solution of 0.1mol/L by pH regulator to 1 ~ 9, at 50 ~ 100 DEG C, stirring and refluxing 18 ~ 24 hours, obtains white suspension; The white suspension suction filtration of gained, through deionized water wash, 80 DEG C are dried to the powdery solid granules and phenyl-phosphonic acid rare-earth salts that constant weight obtains.
The present invention also provides a kind of preparation method of above-mentioned fiberglass reinforced polyethylene terephthalate nano fire-retarding composite material, and preparation process comprises:
(1) first by fiberglass reinforced polyethylene terephthalate, halogen containing flame-retardant, phenyl-phosphonic acid rare-earth salts, oxidation inhibitor dry 6 ~ 12h in 100 ~ 150 DEG C of baking ovens respectively;
(2) more dried fiberglass reinforced polyethylene terephthalate, halogen containing flame-retardant, phenyl-phosphonic acid rare-earth salts, oxidation inhibitor are joined in torque rheometer by after formulation ratio premix, at 230 ~ 260 DEG C, melt blending 8 ~ 15min under 40 ~ 80r/min condition, the fiberglass reinforced polyethylene terephthalate nano fire-retarding composite material obtain beige, mixing.
Torque rheometer of the present invention is Thermal-Haake torque rheometer.
Advantage of the present invention and beneficial effect:
(1) the homemade phenyl-phosphonic acid rare-earth salts initial decomposition temperature of the present invention can reach more than 300 DEG C, the requirement of polyethylene terephthalate processing can not only be met, and exceed the processing temperature of other common engineering plastics, therefore it also can be used for the fire-retardant of other common materials, as polyester such as PBT, PA, applied range.
(2) matrix adopts 15% fiberglass reinforced polyethylene terephthalate (being called for short GF-PET) injection grade engineering plastics, after the phenyl-phosphonic acid rare-earth salts of synthesis, halogen containing flame-retardant, oxidation inhibitor and GF-PET matrix premix, obtain PET nano fire-retarding composite material by melt blending, it can reach UL94V-0 rank when little halogenated flame retardant addition, oxygen index reaches 29.This not only reduces the consumption of fire retardant, saves cost, and meets the trend of environmental protection, saving, also can confirm out that nanometer rare earth addition has considerable application prospect in material is fire-retardant to a certain extent.
(3) from the experimental results, there is goodish synergy in the phenyl-phosphonic acid rare-earth salts used by the present invention and halogen containing flame-retardant, this has not only widened the range of application of rare earth on fire-retardant, and provides a kind of route of synthesis of good halogenated flame retardant synergist.
(4) preparation of the present invention, working method are simple, and successful, be applicable to practical situations, have the possibility of the goodish marketization.
Embodiment
Below by specific embodiment, the present invention is described in further detail, but the present invention is not only confined to following examples.Some nonessential improvement that the person skilled in the art in this field makes the present invention according to content of the present invention and adjustment still belong to protection scope of the present invention.
Example formulations is as follows:
The present embodiment is tested for rare-earth element cerium (Ce) synthesis of phenyl phosphonic acids cerium (CeHPP), and namely the synthetic method of phenyl-phosphonic acid cerium adopts the preparation method of above-mentioned phenyl-phosphonic acid rare-earth salts, is specially: by 5 ~ 10mmol phenyl-phosphonic acid (H
2o
3pC
6h
5) be dissolved in the mixed solvent of 100ml ethanol/water (volume ratio 1:1) and obtain phenyl-phosphonic acid solution, then gained solution is placed in flask; 3 ~ 8mmolCeCl
36H
2o is added drop-wise in the flask containing phenyl-phosphonic acid solution after being dissolved in 100ml ionized water, stir, and by the NaOH solution of 0.1mol/L by pH regulator to 1 ~ 9, at 50 ~ 100 DEG C, stirring and refluxing 18 ~ 24h, obtains white suspension; The white suspension suction filtration of gained, through deionized water wash, 80 DEG C are dried to the powdery solid granules and phenyl-phosphonic acid rare-earth salts that constant weight obtains.
Then by preparation phenyl-phosphonic acid cerium and other mixed raw materials for fiberglass reinforced polyethylene terephthalate nano fire-retarding composite material of the present invention, concrete preparation method:
(1) first by fiberglass reinforced PET, decabromodiphenyl oxide (DBDPO), phenyl-phosphonic acid cerium dry 6 ~ 12h in 100 ~ 150 DEG C of baking ovens respectively;
(2) will join in Thermal-Haake torque rheometer after dried fiberglass reinforced PET, decabromodiphenyl oxide, phenyl-phosphonic acid rare-earth salts premix again, at 250 DEG C, melt blending 10min under 70r/min condition, obtains beige, mixed uniformly nano fire-retarding composite material.
Concrete formula is in table 1:
Table 1 embodiment of the present invention formula and sample number into spectrum
Oxidation inhibitor of the present invention is in order to avoid the decomposition of PET in the course of processing.
The formula of the embodiment of the present invention is as shown in table 1.Different numbered samples is prepared burden by the weight percent (wt%) in above table, after melt blending, by prepared matrix material in 240 ~ 280 DEG C of vulcanizing presses after preheating 4 ~ 10min, boost to 10 ~ 20MPa and be incubated 15 ~ 20min, for performance test after pressurize naturally cooling is shaping.
Embodiment flame retardant properties
The test of the present embodiment flame retardant properties is divided into three part of detecting: limiting oxygen index(LOI), vertical combustion and miniature taper calorimetric, and specific implementation process is as follows:
(1) limiting oxygen index(LOI) test (LOI) test is according to GB/T2406-1993 standard, HC-2 type oxygen index instrument is tested, and batten is of a size of 130 × 6 × 3mm3, each sample test 15 battens, then according to the revised law specified in GB, the oxygen index of material is calculated.Test result is as shown in table 2.
(2) vertical combustion test (UL94) is tested according to GB/T2408-1996 standard and is carried out on CZF-3 type horizontal vertical burning determinator, and test sample is of a size of 130 × 13 × 3mm
3, each sample test 5 battens, get average, then according to the regulation in GB, with reference to the incendivity of experimental result evaluation material.Test result is as shown in table 2.
(3) miniature taper calorimetric test (MCC): combustionproperty is carried out on GovmarkMCC-2 micro combustions calorimeter according to ASTMD7309-07 standard.This instrument is a pyrolytic decomposition-combustion flow calorimeter.In experiment; by the powdered sample of 4-6 milligram inert atmosphere (80ml/min) protection under with the speed of 1 DEG C/s from room temperature to 650 DEG C; then the volatile matter decomposed will be mixed into the roasting kiln of 900 DEG C with oxygen (20ml/min), be calculated the enthalpy of combustion of degradation production by record oxygen depletion amount.Test result is as shown in table 3.
Table 2 materials Example limiting oxygen index(LOI) of the present invention and vertical combustion performance
T
1, t
2burning things which may cause a fire disaster is removed, the sustained combustion time after representing sample first time, reignition respectively.
CeHPP and DBDPO adds separately in PET, and the LOI of matrix material improves, but cannot be tested by UL94, all can only reach V-2 rank, two single fire-retardant GF-PET limited efficiency are described.
CeHPP is incorporated into PET/DBDPO flame-retardant system, even a small amount of LOI that adds improves also quite obvious, when CeHPP addition is 2wt%, UL94 test can pass through V-0 level.For PET/DBDPO-Ce (6-3), sample first time light after remove burning things which may cause a fire disaster after, combustion time significantly shortens (t
1=1.3s), second time removes burning things which may cause a fire disaster after lighting namely can self-gravitation, has had significant improvement compared to PET/DBDPO.The flame retardant properties that the composite decabromodiphenyl oxide of CeHPP significantly can improve PET obviously can be obtained from table 2 embodiment.
Table 3 materials Example of the present invention miniature taper calorimetric performance
PHRR: heat release rate peak value; THR: total thermal discharge; T
pHRR: the temperature that heat release rate peak value is corresponding.
In PET/DBDPO flame-retardant system, the CeHPP introducing 1 part can make the flame retardant properties of material slightly reduce, but as interpolation 3 parts of CeHPP, the PHRR value of nano composite material declines obviously, meanwhile, total thermal discharge reduces, and the temperature of maximum heat release place remains unchanged substantially.Above-mentioned data show appropriate CeHPP and DBDPO compositional flame-retardant fiberglass reinforced PET successful and total amount of flame-retardant agent relative to much lower during pure amount of flame-retardant agent.
Flame retardant properties test in above embodiment shows that a small amount of cerium Phenylphosphine hydrochlorate and decabromodiphenyl oxide are used in conjunction, polyethylene terephthalate is strengthened to flame-proof glass fibre there is good effect, and goodish synergy is there is between the two viewed from data, being only 8 parts at total addition level is the V-0 rank that can reach UL94.This not only can reduce amount of flame-retardant agent, cost-saving, and to meeting environmental requirement and keeping PET to have good application prospect as the performance of engineering plastics own.
Claims (3)
1. a fiberglass reinforced polyethylene terephthalate nano fire-retarding composite material, is characterized in that: this material is prepared by each component of following weight percent:
(1) fiberglass reinforced polyethylene terephthalate 80 ~ 99.9%,
(2) phenyl-phosphonic acid rare earth 1 ~ 10%,
(3) halogen containing flame-retardant 1 ~ 15%,
(4) oxidation inhibitor 0.05 ~ 3%;
Above-mentioned each weight percentages of components sum is 100%;
Described fiberglass reinforced polyethylene terephthalate is density 1.39g/cm
3, glass fiber content 15%, trade mark Du Pont 415HP, molecular backbone chain be
the thermoplasticity fiberglass reinforced engineering plastics of chain link;
Described halogen containing flame-retardant is TDE, decabromodiphenyl oxide or brominated Polystyrene;
Described oxidation inhibitor is polyphenol antioxidant 1010;
Described phenyl-phosphonic acid rare-earth salts is the phenyl-phosphonic acid rare-earth salts adopting following preparation method to prepare: 5 ~ 10 mmol phenyl-phosphonic acids being dissolved in volume ratio is obtain phenyl-phosphonic acid solution in the mixed solvent of the 100 ml ethanol/waters of 1:1, then gained solution is placed in reaction vessel; By 3 ~ 8 mmol RECl
36H
2o is added drop-wise to after being dissolved in 100 ml deionized waters in the above-mentioned reaction vessel containing phenyl-phosphonic acid solution, stirs, and by the NaOH solution of 0.1 mol/L by pH regulator to 1 ~ 9, then stirring and refluxing 18 ~ 24 hours at 50 ~ 100 DEG C, obtains white suspension; The white suspension suction filtration of gained, through deionized water wash, 80 DEG C are dried to constant weight and obtain powdery solid granules and phenyl-phosphonic acid rare-earth salts.
2. a preparation method for fiberglass reinforced polyethylene terephthalate nano fire-retarding composite material according to claim 1, is characterized in that: this material preparation process comprises:
(1) first by fiberglass reinforced polyethylene terephthalate, halogen containing flame-retardant, phenyl-phosphonic acid rare-earth salts 100 ~ 150
odry 6 ~ 12h in C baking oven;
(2) will join in torque rheometer, 230 ~ 260 after dried fiberglass reinforced polyethylene terephthalate, halogen containing flame-retardant, phenyl-phosphonic acid rare-earth salts premix again
oc, melt blending 8 ~ 15min under 40 ~ 80 r/min conditions, the fiberglass reinforced polyethylene terephthalate nano fire-retarding composite material obtain beige, mixing.
3. the preparation method of fiberglass reinforced polyethylene terephthalate nano fire-retarding composite material according to claim 2, is characterized in that: described torque rheometer is Thermal-Haake torque rheometer.
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| CN103073856A (en) * | 2012-12-26 | 2013-05-01 | 浙江大学宁波理工学院 | Phenyl phosphonic acid rare-earth salt compounded system flame-retardant glass fiber enhanced PET material and preparation method thereof |
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| CN103073856A (en) * | 2012-12-26 | 2013-05-01 | 浙江大学宁波理工学院 | Phenyl phosphonic acid rare-earth salt compounded system flame-retardant glass fiber enhanced PET material and preparation method thereof |
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