CN103304883A - Composition of halogen-free flame-retardant ethylene/vinyl acetate copolymer of phosphorus-containing heterocyclic compound - Google Patents
Composition of halogen-free flame-retardant ethylene/vinyl acetate copolymer of phosphorus-containing heterocyclic compound Download PDFInfo
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Abstract
The invention belongs to the field of halogen-free flame-retardant ethylene/vinyl acetate copolymers, relates to a composition of the halogen-free flame-retardant ethylene/vinyl acetate copolymer of a phosphorus-containing heterocyclic compound, and in particular relates to a composition of the halogen-free flame-retardant ethylene/vinyl acetate copolymer, and the composition is prevented from being flamed under the synergistic action of a metal hydroxide and an organophosphorus heterocyclic compound. The composition contains the following components by weight percent: 30% to 50% of the ethylene/vinyl acetate copolymer, 40% to 60% of the metal hydroxide and 0.1% to 10% of the organophosphorus heterocyclic compound. The composition is prepared conveniently, which is beneficial to the industrial production. The composition has the excellent flame-retardant property and also has the mechanical property and heat stability of materials. In addition, the composition is good in rheological property and can be processed simply. As a result, the composition provided by the invention can be applied to the fields of electric wires and cables, and the like.
Description
Technical field
The invention belongs to non-halogen flame-proof ethylene-acetate ethylene copolymer field, specially refer to the composition of the ethylene-vinyl acetate copolymer of a kind of metal hydroxides and organophosphorus heterogeneous ring compound cooperative flame retardant.
Background technology
Ethylene-vinyl acetate copolymer (EVA) is the macromolecular material that is formed by ethene and vinyl acetate copolymerization by a certain percentage, and general vinyl acetate content is at 5wt%～40wt%.Compare with polyethylene, because ethylene-vinyl acetate copolymer has been introduced the Vinyl Acetate Monomer of polarity in molecular chain, thereby reduced high-crystallinity, snappiness, shock resistance, filler consistency and heat seal performance have been improved, fields such as the footwear material that is widely used in foaming, functional canopy film, packing film, hot melt adhesive, electric wire and toy.
Along with the increase of vinyl acetate content in the ethylene-vinyl acetate copolymer, its flame retardant properties improves, but still can not satisfy some special service requirementss.And the EVA burning time can produce the black smoke that has poisonous gas in a large number, limited its application at aspects such as household electrical appliances, building, building materials and electric wires, so the fire-retardant attention that more and more causes people of ethylene-vinyl acetate copolymer.
The fire retardant that contains halogen because of its flame retarding efficiency height, consumption is few, price is low once was favourably welcome.But halogen containing flame-retardant also can discharge poisonous and hazardous gas, contaminate environment, harm humans health when burning.European Union at first releases " instruction of waste electronic electrical equipment " and reaches " in the electronic and electrical equipment forbidding objectionable impurities instruction " afterwards from February, 2003, a lot of countries and regions have also begun the action of discarded halogen containing flame-retardant, make the use of halogen containing flame-retardant be subjected to very big impact.Phosphonium flame retardant then becomes the focus of people's research and concern as a kind of effective surrogate of halogen containing flame-retardant.
9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound (DOPO), it is a kind of phosphorous luxuriant and rich with fragrance heterogeneous ring compound, have characteristics (Vlad-Bubulac T such as exclusive phosphorous, the non-coplanarity of phospho hetero phenanthrene group, the interaction with intramolecularly or intermolecular group, massive structure, molecular polarity, Hamciuc C.Polymer, 2009,50:2220～2227; Qian LJ, Zhi JG, Tong B, Shi JB, Yang F, Dong YP.Polymer, 2009,50:4813～4820).P-H group property in the DOPO molecule is active, is easy to break to form H, DOPO free radical, can (dredge and draw Wei Ping, Min Feng, Wang Chen, Liu Qing with other unsaturated compound generation free radical addition reaction.Polymer material science and engineering, 2009,25 (5): 122～128; Wang CS, Hsuan LC.Polymer, 1999,40:747～757), also can with alcohol take place dehydration reaction or with ester generation transesterification reaction (Schartel B, Braun U, Balabanovich AI, Artner J, Ciesielski M,
M, Perez RM, Sandler JK W,
V.Eur.Polym.J, 2008,44:704～715), perhaps wait other chemical reaction by the free radical replacement, form the novel cpd with property.As a class new phosphorus-containing flame retardant, DOPO and derivative Halogen thereof, smokeless, nontoxic, do not move, flame retardant properties is lasting, can be used for the fire-retardant of multiple polymers such as linear polyester, polymeric amide, Resins, epoxy, urethane, be widely used in and press layer, circuit card, semiconductor packages, photosensitive and luminous field in synthon, electronics, the brass.
Magnesium hydroxide and aluminium hydroxide belong to metal hydroxides, are the main fire retardants of fire-retardant EVA, and they have simultaneously fills and fire-retardant effect, do not produce poisonous or corrosive gas during burning, and the source is sufficient, cheap, is the fire retardant of the economic environmental protection of a class.But the metal hydroxides surface polarity is strong, the particle aggregation sexual orientation is big, poor with the consistency of EVA, and want the fire-retardant rank that reaches higher, the addition of metal hydroxides need reach about 60wt% usually, this makes the mechanical property of material and processing characteristics all reduce greatly, is difficult to reach industrial requirements.For addressing these problems, metallic hydrogen magnesium oxide is carried out surface modification, improve the consistency of itself and ethylene-vinyl acetate copolymer, be present a kind of important method.Halogen-free phosphorus-free modified magnesium hydroxide flame retardant ethylene alkene-acetate ethylene copolymer and preparation method thereof) and people's (preparation and application of magnesium hydroxide microcapsule such as Chen Xu people such as Yu Xinhai (Chinese patent 201010272389.7:, insulating material, 2009,42 (5): 14-16) disclose respectively with containing amino silane coupling agent and the magnesium hydroxide of melamine resin prepolymer Q3 and carry out surface treatment, and then obtained magnesium hydroxide-ethylene-vinyl acetate copolymer flame-retardant system with the ethylene-vinyl acetate copolymer blend.Experiment shows: the dispersiveness of the magnesium hydroxide after the modification in resin improves, and improved the flame retardant properties of material.But all there is a shortcoming in the two: the elongation at break of material is lower, and the former is no more than 60%, and the latter then only reaches 18.9%.In addition, with metal hydroxides and other material (as silicon-containing compound) collaborative composite also be a kind of important method of improving flame-proof ethylene-acetate ethylene copolymer.People such as Fu (Mouzheng Fu, Baojun Qu.Polymer Degradation and Stability, 2004,85:633～639) find that magnesium hydroxide and silicon-dioxide have good synergy when flame-proof ethylene-acetate ethylene copolymer.When the addition of magnesium hydroxide be 47wt%, when the silicon-dioxide addition is 8wt%, identical flame retardant effect in the time of can reaching with independent interpolation 60wt% magnesium hydroxide.Find at present when flame-proof ethylene-acetate ethylene copolymer, with metal hydroxides synergistic have silicon-dioxide, carbon nanotube, silicon rubber, siloxanes etc. are arranged, then do not appear in the newspapers about the document of metal hydroxides and organophosphorus heterogeneous ring compound cooperative flame retardant ethylene-vinyl acetate copolymer.
Summary of the invention
The object of the present invention is to provide a kind of non-halogen flame-proof ethylene-acetate ethylene copolymer of phosphorus hetercyclic compound, specifically is the composition of a kind of metal hydroxides and organophosphorus heterogeneous ring compound cooperative flame retardant ethylene-vinyl acetate copolymer.The preparation of compositions of this ethylene-vinyl acetate copolymer is convenient, is conducive to suitability for industrialized production; The flame retardant properties excellence has been taken into account mechanical property and the thermostability of material, and good rheological property, and complete processing is simple, can be used for fields such as electric wire.
The composition of the non-halogen flame-proof ethylene-acetate ethylene copolymer of phosphorus hetercyclic compound of the present invention comprises following component:
Ethylene-vinyl acetate copolymer 30～50wt%
Organophosphorus heterogeneous ring compound 0.1～10wt%.
The part of the described ethylene-vinyl acetate copolymer (EVA) in the composition of the non-halogen flame-proof ethylene-acetate ethylene copolymer of described phosphorus hetercyclic compound can be substituted by polyethylene (PE), make in the composition of non-halogen flame-proof ethylene-acetate ethylene copolymer of described phosphorus hetercyclic compound and also contain polyethylene (PE), described poly content is a part that has taken the content of described ethylene-vinyl acetate copolymer, and described poly consumption is 1%～40wt% of described ethylene-vinyl acetate copolymer and described polyethylene gross weight.PE has good chemical stability, at room temperature is dissolved in any solvent hardly, the corrosion of energy acid-and base-resisting, salt etc., and temperature limit of brittleness is low, has good low-temperature flexibility and high-frequency electrical insulativity, and good processability, and light weight is inexpensive.Substitute the EVA of part with PE after, the tensile strength of the composition of the non-halogen flame-proof ethylene-acetate ethylene copolymer of the phosphorus hetercyclic compound that provides among the present invention, low-temperature impact and thermostability etc. can obtain improvement to a certain degree.
Described metal hydroxides is magnesium hydroxide (Mg (OH)
2, the abbreviation MDH), aluminium hydroxide (Al (OH)
3Or make Al
2O
33H
2O, abbreviation ATH) or their mixture of arbitrary proportion.
Described organophosphorus heterogeneous ring compound is phospho hetero phenanthrene class material, specifically be 9-oxa--10-phospho hetero phenanthrene-10-oxide compound and derivative thereof (abbreviate " 9-oxa--10-phospho hetero phenanthrene-10-oxide derivative " as, its structure is suc as formula shown in the I:
Formula I
Among the formula I, R
1-R
8Be independently selected from hydrogen atom, C
1-C
5Alkyl, nitro, C
1-C
5Alkoxyl group, aryl, aryloxy in a kind of.R
9Be selected from hydrogen atom, C
1-C
10Alkyl, aryl, C
1-C
10Thiazolinyl, ketone group, phenolic group, pyridyl, itrile group, sulfenyl, carboxylic acid group, anhydride group, ester group, siliceous organic group in a kind of.
Among the formula I of the present invention, R
1-R
8In described C
1-C
5Alkyl can specifically be selected from a kind of in methyl, ethyl, propyl group, butyl, the amyl group independently; Described C
1-C
5Alkoxyl group can specifically be selected from a kind of in methoxyl group, oxyethyl group, propoxy-, the butoxy independently; Described aryl can specifically be selected from a kind of in phenyl, aminomethyl phenyl, 3,5-dimethylphenyl, benzyl, the benzyl ethyl independently; Described aryloxy can be phenoxy group.
Among the formula I of the present invention, R
9In described C
1-C
10Alkyl can specifically preferably be selected from a kind of in methyl, ethyl, the propyl group.Described aryl can specifically preferably be selected from a kind of in phenyl, tolyl, ethylbenzene base, benzyl, p-methoxy-phenyl, the ethoxyl phenenyl.Described C
1-C
10Thiazolinyl can specifically preferably be selected from allyl group.Described ketone group can specifically preferably be selected from a kind of in hexamethylene ketone group, the β-butanone base.Described phenolic group can specifically preferably be selected from phenylol, a kind of in the hexichol phenolic group.Described pyridyl can be the pyridyl ethyl.Described itrile group can specifically preferably be selected from a kind of in propionitrile base, the acetonitrile-base phenyl.Described sulfenyl can specifically preferably be selected from a kind of in benzyl sulfenyl, the cyclohexyl sulfenyl.Described carboxylic acid group can specifically preferably be selected from a kind of in propionyloxy, Succinic Acid base, pyrovinic acid base, the Beta-methyl propionyloxy.Described anhydride group can specifically preferably be selected from a kind of in Succinic anhydried base, the pyrovinic acid acid anhydride base.Described ester group can specifically preferably be selected from a kind of in methyl propionate base, ethyl propionate base, dimethyl succinate base, diethyl succinate base, pyrovinic acid diformazan ester group, pyrovinic acid diethyl-ester group, Beta-methyl methyl propionate base, the Beta-methyl ethyl propionate base.
According to above description, the simplest 9-oxa--10-phospho hetero phenanthrene-10-oxide compound is 9, and the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound (being abbreviated as DOPO), the R among the corresponding I
1-R
9Group all is hydrogen atom, and its structure is suc as formula shown in the II:
Formula II
Among the present invention, the radicals R on the phosphorus atom (P) in the formula I phospho hetero phenanthrene class material
9It can be siliceous organic group.As previously mentioned, some silicon-containing compounds have the synergy anti-flaming function.For making silicon-containing compound good distribution in the EVA matrix, the retention homogeneity can be connected to siliceous organic group on the phospho hetero phenanthrene quasi-molecule, makes the organic polymer of itself and EVA and so on have consistency preferably.Utilize the activity of P-H key, with R
9Be 9 of hydrogen atom (H), the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide derivative (being called for short " DOPO derivative ", structure such as formula III) and reactive reactive organic silicon compound, can obtain R
9DOPO derivative for siliceous organic group.
Formula III
R in the formula
1-R
8Definition described with claim 5.
At least contain a reactable group in the described reactive silicoorganic compound, described reactable group is selected from a kind of in vinyl, ethynyl, isocyanate group, epoxy group(ing), the halogen atom.Reactive silicoorganic compound with these groups comprise vinyltriethoxysilane, vinyltrimethoxy silane, the methyl ethylene diethoxy silane, allyltrimethoxysilanis, methacryloxypropyl trimethoxy silane, the ethynyl trimethyl silane, 3-isocyanate group propyl trimethoxy silicane, 3-isocyanate group propyl-triethoxysilicane, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, γ-(2,3-epoxy third oxygen) propyl group methyl dimethoxysilane, γ-chloropropyl triethoxysilane, γ-r-chloropropyl trimethoxyl silane, trimethylchlorosilane, chlorotriethyl silane, hexamethyldisilazane, etc.These reactive silicoorganic compound can with the DOPO derivative on the P-H key react and obtain the DOPO derivative that R9 contains element silicon, concrete grammar can be with reference to the reference of mentioning in aforementioned " background technology ".For example, shown in the formula IV is by 9, the 10-dihydro-9-oxy is assorted-and the P-H key of 10-phospho hetero phenanthrene-10-oxide compound and the two keys of the C=C of vinyltriethoxysilane carry out the triethoxy silica ethyl DOPO derivative that contains organosilicon radical of addition reaction (preparation method can referring to Chinese patent application 201010128439.4) generation, corresponding I, R
1-R
8Complete is hydrogen atom, R
9Be the triethoxy silica ethyl.
Formula IV
The composition of the non-halogen flame-proof ethylene-acetate ethylene copolymer of phosphorus hetercyclic compound of the present invention, can adopt the conventional compound method of compounding of polymer composites to be prepared, namely (general temperature is 90～220 ℃) uses twin screw extruder, three-screw extruder blend extruding pelletization under the EVA molten state, perhaps uses mill, mixer mixing and granulation.When feeding in raw material blend, can be in advance that all components pre-mixing is even, join in the blending equipment mixing even then in the lump; Also can be earlier join ethylene-vinyl acetate copolymer or ethylene-vinyl acetate copolymer and poly compound in the blending equipment earlier, after treating its melt blending certain hour, add components such as metal hydroxides and organophosphorus heterogeneous ring compound again and continue mixing even.The composition of the non-halogen flame-proof ethylene-acetate ethylene copolymer that can obtain phosphorus hetercyclic compound is finished in blend.
The composition of the non-halogen flame-proof ethylene-acetate ethylene copolymer of phosphorus hetercyclic compound of the present invention in its actual production process, can comprise an amount of oxidation inhibitor and/or tinting material.Oxidation inhibitor is a base polymer functional agent, for example antioxidant 1010, oxidation inhibitor 168, antioxidant 264 and antioxidant 1076 etc., can independent or composite use, its effect is to suppress the oxidative degradation that polymkeric substance or its composition Yin Gaowen or other factors in processing and use cause, thereby keep material property, prolong product life, consumption is generally 0.1%～0.6% of described composition total weight.Tinting material comprises pigment and/or dyestuff, and effect is the color that changes polymkeric substance or its composition material, to satisfy the requirement of this material in application.The use in the polymer materials field of oxidation inhibitor and/or tinting material is well-known, at the composition of the non-halogen flame-proof ethylene-acetate ethylene copolymer of phosphorus hetercyclic compound of the present invention, only need to select to be fit to the corresponding commodity of EVA and use according to its application note and customer need to get final product.It is pointed out that the use of oxidation inhibitor and/or tinting material, do not limit protection scope of the present invention.
The preparation of compositions of the non-halogen flame-proof ethylene-acetate ethylene copolymer of phosphorus hetercyclic compound of the present invention is convenient, is conducive to suitability for industrialized production; The flame retardant properties excellence has been taken into account mechanical property and the thermostability of material, and good rheological property, and complete processing is simple, can be used for fields such as electric wire.
Description of drawings:
Fig. 1. the infrared spectrum of the compound shown in the structural formula IV.
Fig. 2. the nucleus magnetic hydrogen spectrum spectrogram of the compound shown in the structural formula IV.
Fig. 3. the phospho hetero phenanthrene cyclic cpds is to the particle diameter of magnesium hydroxide and the dispersed comparison diagram that influences.Wherein:
A: the stereoscan photograph of the composition of the ethylene-vinyl acetate copolymer/magnesium hydroxide of Comparative Examples 2 of the present invention (mass ratio of ethylene-vinyl acetate copolymer and magnesium hydroxide is 1: 1, i.e. EVA 50%, MDH 50%), magnification is 10000 times.
B: the stereoscan photograph of the composition of the ethylene-vinyl acetate copolymer/magnesium hydroxide of the embodiment of the invention 3/phospho hetero phenanthrene cyclic cpds, magnification are 10000 times.
Fig. 4. the thermogravimetric curve of three different samples in air atmosphere.Wherein:
A: ethylene-vinyl acetate copolymer raw material;
B: the composition of the ethylene-vinyl acetate copolymer/magnesium hydroxide of Comparative Examples 2 of the present invention (mass ratio of ethylene-vinyl acetate copolymer and magnesium hydroxide is 1: 1, i.e. EVA 50%, MDH 50%);
C: the composition of the ethylene-vinyl acetate copolymer/magnesium hydroxide of the embodiment of the invention 3/phospho hetero phenanthrene cyclic cpds.
Embodiment
Further set forth the present invention below in conjunction with embodiment.Should be understood that following examples only are used for the present invention being described and being not used in restriction protection scope of the present invention.In addition, it should be understood that after having read content disclosed by the invention those skilled in the art can make various changes or modification to the present invention, these equivalent form of values fall within claims of the present invention institute restricted portion equally.
When the balancing torque of the composition that relates among Comparative Examples of the present invention and the embodiment refers to that each component of described composition is mixing in Banbury mixer, the numerical value when its torque value tends to balance in mixing time.The Haake torque rheometer Rheomix OS that used banburying instrument is Thermo Fisher Scientific Inc..
The selected instrument of the limiting oxygen index(LOI) of the test composition that relates among Comparative Examples of the present invention and the embodiment is the JF-3 limiting oxygen index(LOI) instrument of Nanjing Jiangning District analytical instrument factory.Its test condition is carried out according to the GB/T2406-93 standard.
The selected instrument of the tensile strength of the test composition that relates among Comparative Examples of the present invention and the embodiment and elongation at break is 3365 tensile testing machines of Instron (Instron) company.Its test condition is carried out according to ISO 527-1 standard.
Comparative Examples 1
The composition of composition and weight percent are:
Ethylene-vinyl acetate copolymer 48wt%
Magnesium hydroxide 52wt%
Take by weighing the ethylene-vinyl acetate copolymer of 28.8g and the magnesium hydroxide of 31.2g, be pre-mixed said components evenly after, under 135 ℃, in Banbury mixer mixing 10 minutes, obtain ethylene-vinyl acetate copolymer/magnesium hydroxide composition.The mixing balancing torque of said composition is 12.6Nm, limiting oxygen index(LOI) 26%, tensile strength 14.9MPa, elongation at break 125%.
Comparative Examples 2
The composition of composition and weight percent are:
Ethylene-vinyl acetate copolymer 50wt%
Magnesium hydroxide 50wt%
Take by weighing the ethylene-vinyl acetate copolymer of 30.0g and the magnesium hydroxide of 30.0g, be pre-mixed said components evenly after, under 135 ℃, in Banbury mixer mixing 10 minutes, obtain ethylene-vinyl acetate copolymer/magnesium hydroxide composition.The mixing balancing torque of said composition is 12.0Nm, limiting oxygen index(LOI) 24%, tensile strength 14.6MPa, elongation at break 135%.
Comparative Examples 3
The composition of composition and weight percent are:
Ethylene-vinyl acetate copolymer 52wt%
Magnesium hydroxide 48wt%
Take by weighing the ethylene-vinyl acetate copolymer of 31.2g and the magnesium hydroxide of 28.8g, be pre-mixed said components evenly after, under 135 ℃, in Banbury mixer mixing 10 minutes, obtain ethylene-vinyl acetate copolymer/magnesium hydroxide composition.The mixing balancing torque of said composition is 11.6Nm, limiting oxygen index(LOI) 23%, tensile strength 14.0MPa, elongation at break 138%.
Embodiment 1
The composition of composition and weight percent are:
Ethylene-vinyl acetate copolymer 44wt%
Magnesium hydroxide 48wt%
DOPO 8wt％
Take by weighing 9 of the magnesium hydroxide of ethylene-vinyl acetate copolymer, 28.8g of 26.4g and 4.8g, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound (being abbreviated as DOPO), after being pre-mixed said components evenly, under 135 ℃, in Banbury mixer mixing 10 minutes, obtain the EVA/MDH/DOPO composition.The mixing balancing torque of said composition is 9.0Nm, limiting oxygen index(LOI) 37%, tensile strength 11.7MPa, elongation at break 158%.
The composition of composition and weight percent are:
Ethylene-vinyl acetate copolymer 42wt%
Aluminium hydroxide 53wt%
DOPO 5wt％
Take by weighing the ethylene-vinyl acetate copolymer of 25.2g, the aluminium hydroxide of 31.8g and the DOPO of 3.0g, be pre-mixed said components evenly after, under 150 ℃, in Banbury mixer mixing 13 minutes, obtain the EVA/ATH/DOPO composition of halogen-free flameproof.The mixing balancing torque of said composition is 9.6Nm, limiting oxygen index(LOI) 41%, tensile strength 12.5MPa, elongation at break 122%.
Embodiment 3
The composition of composition and weight percent are:
Ethylene-vinyl acetate copolymer 45wt%
Magnesium hydroxide 50wt%
Compound 5wt% shown in the structural formula IV
The ethylene-vinyl acetate copolymer that takes by weighing 27.0g earlier joins in the Banbury mixer, after treating its fusion, compound shown in the magnesium hydroxide of adding 30.0g and the structural formula IV of 3.0g, under 135 ℃, in Banbury mixer mixing 10 minutes, the mixing balancing torque of resulting composition was 8.8Nm, limiting oxygen index(LOI) 39%, tensile strength 11.6MPa, elongation at break 167%.
Embodiment 4
The composition of composition and weight percent are:
Ethylene-vinyl acetate copolymer 50wt%
Magnesium hydroxide 47wt%
DOPO-BQ 3wt％
Take by weighing the ethylene-vinyl acetate copolymer of 30.0g, the magnesium hydroxide of 28.2g and the 10-(2 of 1.8g, the 5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound (compound shown in the structural formula V, be abbreviated as DOPO-BQ), after being pre-mixed said components evenly, under 140 ℃, in Banbury mixer mixing 12 minutes, obtain the EVA/MDH/DOPO-BQ composition of halogen-free flameproof.The mixing balancing torque of said composition is 9.1Nm, and limiting oxygen index(LOI) reaches 36%, tensile strength 12.7MPa, elongation at break 137%.
Formula V
Embodiment 5
The composition of composition and weight percent are:
Ethylene-vinyl acetate copolymer 48wt%
Magnesium hydroxide 50wt%
DOPO-BQ 2wt％
Take by weighing the ethylene-vinyl acetate copolymer of 288g, the magnesium hydroxide of 300g and the DOPO-BQ of 12g, in high mixer, be pre-mixed evenly, in 110 ℃～170 ℃ temperature range, blend extruding pelletization in Φ 30 twin screw extruders obtains the EVA/MDH/DOPO-BQ composition of halogen-free flameproof.The said composition limiting oxygen index(LOI) reaches 40%, tensile strength 12.9MPa, elongation at break 134%.
The composition of composition and weight percent are:
Ethylene-vinyl acetate copolymer 46wt%
Aluminium hydroxide 50wt%
DOPO-BDA 4wt％
The mixture of antioxidant 1010 and oxidation inhibitor 168 is with respect to the 0.3wt% of above component total amount
Taking by weighing the ethylene-vinyl acetate copolymer of 27.6g and the mixture of 0.180g antioxidant 1010 and oxidation inhibitor 168 (weight ratio of antioxidant 1010 and oxidation inhibitor 168 is 1: 2) earlier adds in the Banbury mixer, after treating its fusion, compound (being abbreviated as DOPO-BDA) shown in the aluminium hydroxide of adding 30.0g and the structural formula VI of 2.4g, under 135 ℃, in Banbury mixer mixing 8 minutes, obtain the EVA/ATH/DOPO-BDA composition.The mixing balancing torque of said composition is 9.1Nm, and limiting oxygen index(LOI) reaches 40%, tensile strength 13.5MPa, elongation at break 126%.
Formula VI
Embodiment 7
The composition of composition and weight percent are:
The mixture of antioxidant 1010 and oxidation inhibitor 168, consumption is with respect to the 0.3wt% of above component total amount
Taking by weighing the ethylene-vinyl acetate copolymer of 27.6g and the mixture of 0.180g antioxidant 1010 and oxidation inhibitor 168 (weight ratio of antioxidant 1010 and oxidation inhibitor 168 is 1: 2) earlier adds in the Banbury mixer, after treating its fusion, the aluminium hydroxide, the magnesium hydroxide of 21.0g and the DOPO-BDA of 2.4g that add 9.0g, under 145 ℃, in Banbury mixer mixing 11 minutes, obtain the EVA/ATH/MDH/DOPO-BDA composition.The mixing balancing torque of said composition is 9.0Nm, and limiting oxygen index(LOI) reaches 43%, tensile strength 13.8MPa, elongation at break 123%.
Embodiment 8
The composition of composition and weight percent are:
Ethylene-vinyl acetate copolymer 50wt%
Magnesium hydroxide 48wt%
Compound 2wt% shown in the structural formula VII
Take by weighing the ethylene-vinyl acetate copolymer of 30.0g, 28.8g magnesium hydroxide and 1.2g (9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound)-(its structure is the compound shown in the formula VII to Succinic anhydried, with reference to US Patent No. 4127590, with 9, the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide compound and Succinic anhydried (mol ratio 1: 1) make under condition of heating and stirring), after being pre-mixed said components evenly, under 135 ℃, in Banbury mixer mixing 10 minutes, obtain polyethylene/vinyl-acetate ethylene copolymer/magnesium hydroxide/(9,10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound)-Succinic anhydried composition.The mixing balancing torque of said composition is 8.9Nm, and limiting oxygen index(LOI) reaches 38%, tensile strength 13.1MPa, elongation at break 121%.
Formula VII
Embodiment 9
The composition of composition and weight percent are:
Ethylene-vinyl acetate copolymer 50wt%
Magnesium hydroxide 40wt%
Compound 10wt% shown in the structural formula VII
Take by weighing (9 of the magnesium hydroxide of ethylene-vinyl acetate copolymer, 24.0g of 30.0g and 6.0g, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound)-Succinic anhydried (compound shown in the structural formula VII), after being pre-mixed said components evenly, under 135 ℃, in Banbury mixer mixing 10 minutes, obtain polyethylene/vinyl-acetate ethylene copolymer/magnesium hydroxide/(9,10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound)-Succinic anhydried composition.The mixing balancing torque of said composition is 8.5Nm, and limiting oxygen index(LOI) reaches 35%, tensile strength 12.2MPa, elongation at break 137%.
The composition of composition and weight percent are:
The mixture of antioxidant 1010 and oxidation inhibitor 168, consumption is with respect to the 0.3wt% of above component total amount
Take by weighing the polyethylene of 60g, the ethylene-vinyl acetate copolymer of 216g, the magnesium hydroxide of 300g, DOPO and the antioxidant 1010 of 1.8g and the mixture (weight ratio of antioxidant 1010 and oxidation inhibitor 168 is 1: 2) of oxidation inhibitor 168 of 24g, after in high mixer, being pre-mixed evenly, under 110 ℃～170 ℃, blend extruding pelletization in Φ 30 twin screw extruders obtains the EVA/PE/MDH/DOPO composition of halogen-free flameproof.The said composition limiting oxygen index(LOI) reaches 39%, tensile strength 14.9MPa, elongation at break 107%.
Embodiment 11
The composition of composition and weight percent are:
Ethylene-vinyl acetate copolymer 30wt%
Magnesium hydroxide 60wt%
DOPO 10wt％
Take by weighing the ethylene-vinyl acetate copolymer of 18.0g, the magnesium hydroxide of 36.0g, the DOPO of 6.0g, be pre-mixed said components evenly after, under 150 ℃, in Banbury mixer mixing 15 minutes, obtain the EVA/MDH/DOPO composition.The mixing balancing torque of said composition is 11.3Nm, and limiting oxygen index(LOI) reaches 52%, tensile strength 15.6MPa, elongation at break 101%.
Embodiment 12
The composition of composition and weight percent are:
Ethylene-vinyl acetate copolymer 50wt%
Magnesium hydroxide 49.9wt%
DOPO 0.1wt％
Take by weighing the ethylene-vinyl acetate copolymer of 30.0g, the magnesium hydroxide of 29.94g, the DOPO of 0.06g, be pre-mixed said components evenly after, under 140 ℃, in Banbury mixer mixing 12 minutes, obtain the EVA/MDH/DOPO composition.The mixing balancing torque of said composition is 10.8Nm, and limiting oxygen index(LOI) reaches 31%, tensile strength 14.2MPa, elongation at break 123%.
Embodiment 13
The composition of composition and weight percent are:
Take by weighing the ethylene-vinyl acetate copolymer of 26.73g, the polyethylene of 0.27g, the magnesium hydroxide of 31.20g, the DOPO of 1.80g.After being pre-mixed said components evenly, under 150 ℃, in Banbury mixer mixing 11 minutes, obtain the EVA/PE/MDH/DOPO composition.The mixing balancing torque of said composition is 11.3Nm, and limiting oxygen index(LOI) reaches 41%, tensile strength 14.3MPa, elongation at break 120%.
Embodiment 14
The composition of composition and weight percent are:
The mixture of antioxidant 1010 and oxidation inhibitor 168, consumption is with respect to the 0.3wt% of above component total amount
Take by weighing the ethylene-vinyl acetate copolymer of 180g, the polyethylene of 120g, the magnesium hydroxide of 294g, DOPO and the antioxidant 1010 of 1.8g and the mixture (weight ratio of antioxidant 1010 and oxidation inhibitor 168 is 1: 2) of oxidation inhibitor 168 of 6g, after in high mixer, being pre-mixed evenly, under 120 ℃～175 ℃, blend extruding pelletization in Φ 30 twin screw extruders obtains the EVA/PE/MDH/DOPO composition of halogen-free flameproof.The said composition limiting oxygen index(LOI) reaches 35%, tensile strength 15.8MPa, elongation at break 102%.
Claims (10)
1. the composition of the non-halogen flame-proof ethylene-acetate ethylene copolymer of a phosphorus hetercyclic compound is characterized in that, said composition comprises following component:
Ethylene-vinyl acetate copolymer 30～50wt%
Metal hydroxides 40～60wt%
Organophosphorus heterogeneous ring compound 0.1～10wt%.
2. the composition of the non-halogen flame-proof ethylene-acetate ethylene copolymer of phosphorus hetercyclic compound according to claim 1, it is characterized in that: the part of the described ethylene-vinyl acetate copolymer in the composition of the non-halogen flame-proof ethylene-acetate ethylene copolymer of described phosphorus hetercyclic compound is substituted by polyethylene, and described poly consumption is 1%～40wt% of described ethylene-vinyl acetate copolymer and described polyethylene gross weight.
3. the composition of the non-halogen flame-proof ethylene-acetate ethylene copolymer of phosphorus hetercyclic compound according to claim 1, it is characterized in that: described metal hydroxides is magnesium hydroxide, aluminium hydroxide or their mixture.
4. the composition of the non-halogen flame-proof ethylene-acetate ethylene copolymer of phosphorus hetercyclic compound according to claim 1, it is characterized in that: described organophosphorus heterogeneous ring compound is 9-oxa--10-phospho hetero phenanthrene-10-oxide compound and derivative thereof, has the structure shown in the formula I:
Formula I
Among the formula I:
R
1-R
8Be independently selected from hydrogen atom, C
1-C
5Alkyl, nitro, C
1-C
5Alkoxyl group, aryl, aryloxy in a kind of;
R
9Be selected from hydrogen atom, C
1-C
10Alkyl, aryl, C
1-C
10Thiazolinyl, ketone group, phenolic group, pyridyl, itrile group, sulfenyl, carboxylic acid group, anhydride group, ester group, siliceous organic group in a kind of.
5. the composition of the non-halogen flame-proof ethylene-acetate ethylene copolymer of phosphorus hetercyclic compound according to claim 4 is characterized in that: R
1-R
8In described C
1-C
5Alkyl be independently selected from a kind of in methyl, ethyl, propyl group, butyl, the amyl group; Described C
1-C
5Alkoxyl group be independently selected from a kind of in methoxyl group, oxyethyl group, propoxy-, the butoxy; Described aryl is independently selected from a kind of in phenyl, aminomethyl phenyl, 3,5-dimethylphenyl, benzyl, the benzyl ethyl; Described aryloxy is phenoxy group.
6. the composition of the non-halogen flame-proof ethylene-acetate ethylene copolymer of phosphorus hetercyclic compound according to claim 4 is characterized in that: R
9In described C
1-C
10Alkyl be selected from a kind of in methyl, ethyl, the propyl group; Described aryl is selected from a kind of in phenyl, tolyl, ethylbenzene base, benzyl, p-methoxy-phenyl, the ethoxyl phenenyl; Described C
1-C
10Thiazolinyl be selected from allyl group; Described ketone group is selected from a kind of in hexamethylene ketone group, the β-butanone base; Described phenolic group is selected from phenylol, a kind of in the hexichol phenolic group; Described pyridyl is the pyridyl ethyl; Described itrile group is selected from a kind of in propionitrile base, the acetonitrile-base phenyl; Described sulfenyl is selected from a kind of in benzyl sulfenyl, the cyclohexyl sulfenyl; Described carboxylic acid group is selected from a kind of in propionyloxy, Succinic Acid base, pyrovinic acid base, the Beta-methyl propionyloxy; Described anhydride group is selected from a kind of in Succinic anhydried base, the pyrovinic acid acid anhydride base; Described ester group is selected from a kind of in methyl propionate base, ethyl propionate base, dimethyl succinate base, diethyl succinate base, pyrovinic acid diformazan ester group, pyrovinic acid diethyl-ester group, Beta-methyl methyl propionate base, the Beta-methyl ethyl propionate base.
7. the composition of the non-halogen flame-proof ethylene-acetate ethylene copolymer of phosphorus hetercyclic compound according to claim 4, it is characterized in that: 9-oxa--10-phospho hetero phenanthrene-10-oxide compound and the derivative thereof with structure shown in the formula I, be to have 9 of formula III structure, the 10-dihydro-9-oxy is assorted-and R9 that 10-phospho hetero phenanthrene-10-oxide derivative and reactive reactive organic silicon compound obtain is the 9-oxa--10-phospho hetero phenanthrene-10-oxide derivative of siliceous organic group;
Formula III
R in the formula
1-R
8Definition described with claim 4.
8. the composition of the non-halogen flame-proof ethylene-acetate ethylene copolymer of phosphorus hetercyclic compound according to claim 7 is characterized in that: the R in the formula III
1-R
8Definition described with claim 5.
9. the composition of the non-halogen flame-proof ethylene-acetate ethylene copolymer of phosphorus hetercyclic compound according to claim 7, it is characterized in that: contain a reactable group in the described reactive silicoorganic compound at least, described reactable group is selected from a kind of in vinyl, ethynyl, isocyanate group, epoxy group(ing), the halogen atom.
10. according to the composition of the non-halogen flame-proof ethylene-acetate ethylene copolymer of claim 7 or 9 described phosphorus hetercyclic compounds, it is characterized in that: described reactive silicoorganic compound are selected from vinyltriethoxysilane, vinyltrimethoxy silane, the methyl ethylene diethoxy silane, allyltrimethoxysilanis, methacryloxypropyl trimethoxy silane, the ethynyl trimethyl silane, 3-isocyanate group propyl trimethoxy silicane, 3-isocyanate group propyl-triethoxysilicane, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, γ-(2,3-epoxy, third oxygen) propyl group methyl dimethoxysilane, γ-chloropropyl triethoxysilane, γ-r-chloropropyl trimethoxyl silane, trimethylchlorosilane, chlorotriethyl silane, a kind of in the hexamethyldisilazane.
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