CN100374495C - Fire retardant composite material of nano-aluminium hydroxide, clay and ethylene-vinyl acetate copolymer - Google Patents
Fire retardant composite material of nano-aluminium hydroxide, clay and ethylene-vinyl acetate copolymer Download PDFInfo
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- CN100374495C CN100374495C CNB2004100779708A CN200410077970A CN100374495C CN 100374495 C CN100374495 C CN 100374495C CN B2004100779708 A CNB2004100779708 A CN B2004100779708A CN 200410077970 A CN200410077970 A CN 200410077970A CN 100374495 C CN100374495 C CN 100374495C
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Abstract
The present invention relates to a fire-retardant composite material of nanometer aluminium hydroxide, clay and an ethylene acetate copolymer which is composed of the following main constituents by weight percentages: the surface modified nanometer aluminium hydroxide with the particle diameter of 80 to 150 nanometers and 40% to 50% of a surface modifying agent-a titanate coupling agent, 4% to 10% of the nanometer organic montmorillonite clay, 0% to 3% of zinc borate, 25% to 45% of the ethylene acetate copolymer and 5% to 15% of a maleic anhydride grafted ethylene acetate copolymer. The present invention is a white fire-retardant composite material of ethylene acetate copolymers, which has fine performance of fire retardance, fine mechanical properties and fine processing performance even through using less aluminium hydroxide as a fire retardant.
Description
Technical field
The present invention relates to a kind of flame-proof composite material that contains inorganic combustion inhibitor, particularly is matrix resin with the ethylene-vinyl acetate copolymer, and nano-aluminum hydroxide, clay are the flame-proof composite material of main fire retardant.
Background technology
Ethylene-vinyl acetate copolymer is a kind of matrix resin of fire retardant material.It is a kind of Halogen material, decomposites water and carbonic acid gas when burning, does not produce tangible smog and obnoxious flavour, and itself is not fire-retardant, needs to add halogen-free flame retardants, just can become practical halogen-free flame-retardant composite material as inorganic filled-type fire retardant.
Introduced aluminium hydroxide fire retardant at " application of aluminium hydroxide fire retardant in macromolecular material " (" Chinese plastics " 1999 the 6th phase the 80th～85 page), it have fire-retardant, eliminate smoke and fill three functions, do not produce secondary pollution, can produce synergistic effect with multiple fire retardant again, when aluminium hydroxide uses separately, addition must just have flame retardant effect preferably more than 60%, but high filler loading capacity can influence processing of plastic and mechanical property.The superfine aluminium hydroxide that is adopted is micron order aluminium hydroxide just.
" exploitation of halogen-free flame-retardant cable material " (" insulating material communication " 1994 the 2nd phase the 15th～16 page) reported in polyolefin copolymer, be added into aluminium hydroxide to Flame Retardancy can influence, in 100 parts of polyolefin copolymers, the add-on of aluminium hydroxide is in the time of 150 parts, and material just can reach cable material must reach oxygen index in the requirement more than 27.When aluminium hydroxide was 150 parts, the tensile strength of material only was 8.0Mpa.Aluminium hydroxide is as flame retardant filler, and very inequality on physical aspect and chemical structure with macromolecular material, both affinities are very poor.Therefore, add a large amount of aluminium hydroxide after, the mechanical property of material is obviously descended.In order to change the surfactivity of aluminium hydroxide, can in material, add coupling agent, improve the mechanical property of material.In 100 parts of polyolefin copolymers, add 2.4 parts of organo-peroxides, 1 part of stearic acid, 150 parts in aluminium hydroxide, 1 part of metal ester coupling agent, the oxygen index 33.0% of flame-proof composite material, tensile strength 4.9Mpa, elongation 445%.The tensile strength of matrix material does not still reach the performance requriements of flame-proof cable material.Aluminium hydroxide usually be with multiple retardant synergist together, make their produce cooperative flame retardant effect.In order to reduce the addition of flame retardant filler, except adding phosphorus flame retardant, can also add zinc borate.Red phosphorus is the most obvious to the synergistic effect of aluminium hydroxide in the phosphorus flame retardant, with the composite use of red phosphorus, the consumption of aluminium hydroxide is reduced, and the flame retardant properties and the mechanical property of material are better.But the red phosphorus raw material is a kind of hazardous substance, and its color and water-intake rate influence its application.Zinc borate is a kind of retardant synergist commonly used.
(Montmorillonite MMT) is a kind of of layered silicate, and it is the natural clay that belongs to wilkinite one class in polynite.Polynite is the bigger natural clay mineral of China's output.Therefore easily its structure lamella is a nanoscale, and lamella has negative charge, carries out ion exchange reaction generation organic montmorillonoid (OMMT) with alkyl quaternary ammonium salts or other organic cation.Organic montmorillonoid can be further used for preparing composite nano polymer/clay material.
The decomposition of polynite occurs in 270 ℃ to 420 ℃, but because its caloric receptivity is very little, uses flame retardant effect to be not so good as aluminium hydroxide separately.
People such as M.Cross are at " Effects of tin additives on the flammability andsmoke emission characteristics of hal.ogen-free ethylene-vinyl acetatecopolymer " ([J] .Polymer Degradation and Stability, 2003 (79): 311) reported that nanoscale organized clay and zinc are used as retardant synergist and aluminium hydroxide, the particle diameter of aluminium hydroxide is 2 microns.Add 81 parts of aluminium hydroxides, 9 parts of zinc and 10 parts of organic claies in 100 parts of ethylene-vinyl acetate copolymers after, oxygen index is 27.6 only, not have the data of report about burn grade and mechanical property in this article.The zinc of using costs an arm and a leg, toxic.
Summary of the invention
The objective of the invention is to propose a kind of under the few condition of aluminium hydroxide fire retardant consumption all good ethylene-vinyl acetate copolymer flame-proof composite material of flame retardant resistance, mechanical property.
The technical characterictic of nano-aluminum hydroxide of the present invention, clay and ethylene-vinyl acetate copolymer composite flame-proof material is: aluminium hydroxide is the nano-aluminum hydroxide with the titanate coupling agent modification, also has clay in the retardant synergist: nano organic montmorillonite, added maleic anhydride grafted ethene-acetate ethylene copolymer, the mass percent content of composite flame-proof material main ingredient is as follows:
(1) surface-modified nano aluminium hydroxide: the particle diameter of aluminium hydroxide is 80～150 nanometers, and surface-modifying agent is a titanate coupling agent, and consumption is 40～50%;
(2) nano organic montmorillonite, consumption are 4～10%;
(3) the zinc borate consumption is 0～3%;
(4) the ethylene-vinyl acetate copolymer consumption is 25～45%;
(5) maleic anhydride grafted ethene-acetate ethylene copolymer, consumption are 5～15%.
Composite flame-proof material of the present invention, vinyl acetate between to for plastic mass percent content is 10～20% in the ethylene-vinyl acetate copolymer that is adopted, melting index is 2～10g/10min.
Composite flame-proof material of the present invention, the mass ratio of titanate coupling agent and nano-aluminum hydroxide is 0.5～1.5% in the surface-modified nano aluminium hydroxide that is adopted, and the mass ratio of titanate coupling agent and nano-aluminum hydroxide is 0.5% in the preferred surface modified Nano aluminium hydroxide.
The present invention adopts known dry method modification method, with titanate coupling agent nano-aluminum hydroxide is carried out surface modification.Promptly the titanate coupling agent dilution is sprayed at the nano-aluminum hydroxide surface, stirs the surface-modified nano aluminium hydroxide that obtains with whiteruss.The flame-proof composite material that adopts nanometer that does not add surface modification and the nano-aluminum hydroxide that passes through surface modification to obtain, more as can be known, the dispersion state of nano-aluminum hydroxide in matrix resin of process surface modification has clear improvement by transmission electron microscope photo.The present invention is 0.5% pair of better effects if that nano-aluminum hydroxide carries out modification through the mass ratio of experiment screening titanate coupling agent consumption and nano-aluminum hydroxide.So selecting the titanate coupling agent consumption in an embodiment for use is 0.5% to further specify for example.
The nano organic montmorillonite that the present invention is used, for commercially available commodity are called " nano organic montmorillonite " (OMMT), detection is dispersed into the synusia shape in polymeric matrix through electron microscope, the thickness of synusia is 5～20 nanometers, length is 50～200 nanometers, so be called " nano organic montmorillonite ".The effect of nano organic montmorillonite is fire-resistant synergistic and improves tensile property.If do not add nano organic montmorillonite, oxygen index only is 24.0, and vertical combustion is not for putting out certainly, and tensile strength is 9.2MPa, can not satisfy the demand.
Zinc borate effect of the present invention is a fire-resistant synergistic, can make vertical combustion bring up to 0 grade.
The present invention adopts the maleic anhydride grafted ethene-vinyl acetate between to for plastic (MEVA) of commercially available maleic anhydride content 2%, and its effect is to improve tensile property and fire-resistant synergistic.At the nano-aluminum hydroxide consumption is the maleic anhydride grafted ethene-vinyl acetate between to for plastic of interpolation 10% in 50% o'clock, can make the tensile strength of flame-proof composite material reach 11.0MPa, improves 37% than the Comparative Examples of not adding maleic anhydride grafted ethene-vinyl acetate between to for plastic.Vertical combustion is then brought up to 0 grade by 1 grade.
Ethylene-vinyl acetate copolymer is commercially available, is polyolefine fire retardant material matrix polymer commonly used.Vinyl acetate between to for plastic (VA) mass percent content is 10～20% in the ethylene-vinyl acetate copolymer (EVA), and melting index is 2～10g/10min.The content of vinyl acetate between to for plastic is low excessively, with the adhesivity deficiency of inorganic filler, the too high levels of vinyl acetate between to for plastic, the corresponding decline of the mechanical property of material.Melting index is low excessively, and the melt fluidity of material is poor, and melting index is too high, the corresponding decline of the mechanical property of material.
Behind the raw material premix with flame-proof composite material of the present invention,, obtain the flame-proof composite material (pellet) of white, can be further used for making fire-retardant product through the twin screw extruder granulation.
The flame-proof composite material of the present invention's preparation adopts ISO527/2-1993 (E) test tensile strength, elongation at break, presses the oxygen index of GB2406-93 method test material, presses ANSI/UL94 method test vertical combustion grade.
Because it is composite that the present invention adopts with the nano level aluminium hydroxide and the retardant synergist of titanate coupling agent modification; Added maleic anhydride grafted ethene-acetate ethylene copolymer in flame-proof composite material, the consistency of improving ethylene-vinyl acetate copolymer and aluminium hydroxide is guaranteed the flame retardant properties of flame-proof composite material and mechanical property simultaneously.Make the consumption of nano-aluminum hydroxide be no more than 50%, add that retardant synergist fire retardant total amount also is no more than 60%; Even the consumption of nano-aluminum hydroxide only is 40% both to be to add that retardant synergist fire retardant total amount also is no more than 50%, just can make composite flame-proof material have the ideal flame retardant properties.Under the prerequisite that can guarantee the fire-retardant performance of matrix material, reduce the mechanical property that the aluminium hydroxide consumption more helps improving matrix material.Flame-proof composite material of the present invention is not owing to use halogen fire retardant and red phosphorus, the defective that does not yet cause thus.
The flame-proof composite material that the present invention makes is when the aluminium hydroxide consumption is 40%; Maleic anhydride grafted ethene-acetate ethylene copolymer consumption is 10%; The ethylene-vinyl acetate copolymer consumption is 40%; Nano organic montmorillonite 8～10%; The zinc borate consumption is 0～2% o'clock, and the performance of flame-proof composite material can reach oxygen index 〉=32%; 1 grade or 0 grade of vertical combustion (UL94); Tensile strength 〉=10Mpa; Elongation at break 〉=150% can satisfy the requirement that fire-resistant cable material uses.
As everyone knows, the consumption that reduces mineral filler can improve the flowability of matrix material, helps improving the processing flowability of polymer composites.Learnt that by experimental result when EVA is 100%, modified Nano aluminium hydroxide is 0, melt flow rate (MFR) (being melting index) is 1.68g/10min; When EVA is 60%, modified Nano aluminium hydroxide is 40%, and melt flow rate (MFR) is 1.41g/10min; When EVA is 40%, modified Nano aluminium hydroxide is 60%, and melt flow rate (MFR) is 0.53g/10min.When modified Nano aluminium hydroxide consumption was 40%, the melt flow rate (MFR) of mixture was only a little less than pure EVA, but modified Nano aluminium hydroxide consumption is 60% o'clock, and melt flow rate (MFR) just has been significantly less than pure EVA.As seen, reducing modified Nano aluminium hydroxide consumption plays an important role to the melt fluidity of improving material.
The present invention adopts the nano level aluminium hydroxide of surface modification to make fire retardant, and the flame retardant effect of matrix material and mechanical property are increased.To the composite suitable retardant synergist of nano-aluminum hydroxide, adopting montmorillonite, zinc borate can obtain all good ethylene-vinyl acetate copolymer flame-proof composite material of flame retardant properties, mechanical property as retardant synergist under the few condition of aluminium hydroxide fire retardant consumption.Can be used for making flame retardant cable or other fire-retardant product.This flame-proof composite material is white, good flowing properties, and purposes is wide.
Embodiment
The flame-proof composite material prescription of embodiments of the invention 1～9 and Comparative Examples 1, Comparative Examples 2 sees Table 1, and the unit in the table is a mass percent.The particle size range of nano-aluminum hydroxide is in 80～150 nanometers, and the titanate coupling agent consumption is 0.5% pair of nano-aluminum hydroxide surface modification.
The performance of the flame-proof composite material of embodiments of the invention 1～6 and Comparative Examples 1 and Comparative Examples 2 sees Table 2.
By in table 1 and the table 2 embodiment 5 and Comparative Examples 1 composition and performance more as can be known, do not add maleic anhydride grafted ethene-acetate ethylene copolymer (maleic anhydride graft EVA) in the Comparative Examples 1, ethylene-vinyl acetate copolymer (EVA) is 44%, embodiment 5 maleic anhydride graft EVA are 10%, EVA is 34%, and all the other components are identical.After adding maleic anhydride graft EVA, the tensile strength and the elongation at break of flame-proof composite material all significantly improve.
By the composition and performance of the Comparative Examples in table 1 and the table 22 and embodiment 1 and embodiment 2 more as can be known, in their component, surface-modified nano aluminium hydroxide is identical with the content of maleic anhydride graft EVA, Comparative Examples 2 does not contain nano organic montmorillonite, and the nano organic montmorillonite content of embodiment 1 and embodiment 2 is different.After adding nano organic montmorillonite, oxygen index, tensile strength, elongation at break all significantly improve, and the vertical combustion performance is also brought up to 1 grade by not putting out certainly.
Table 1
| Example | Surface-modified nano aluminium hydroxide | Nano organic montmorillonite | Maleic anhydride graft EVA | Zinc borate | EVA |
| Embodiment 1 | 40 | 8 | 10 | 0 | 42 |
| Embodiment 2 | 40 | 10 | 10 | 0 | 40 |
| Embodiment 3 | 40 | 8 | 10 | 2 | 40 |
| Embodiment 4 | 50 | 4 | 10 | 0 | 36 |
| Embodiment 5 | 50 | 6 | 10 | 0 | 34 |
| Embodiment 6 | 50 | 6 | 10 | 2 | 32 |
| Embodiment 7 | 50 | 8 | 15 | 2 | 25 |
| Embodiment 8 | 40 | 8 | 10 | 3 | 39 |
| Embodiment 9 | 40 | 8 | 5 | 2 | 45 |
| Comparative Examples 1 | 50 | 6 | 0 | 0 | 44 |
| Comparative Examples 2 | 40 | 0 | 10 | 0 | 50 |
Table 2
| Example | Oxygen index % | Vertical combustion | Tensile strength MPa | Elongation at break % |
| Embodiment 1 | 31.6 | 1 grade | 11.4 | 340 |
| Embodiment 2 | 32.0 | 1 grade | 12.4 | 270 |
| Embodiment 3 | 33.8 | 0 grade | 11.0 | 311 |
| Embodiment 4 | 35.6 | 1 grade | 12.0 | 301 |
| Embodiment 5 | 36.2 | 0 grade | 11.0 | 262 |
| Embodiment 6 | 36.6 | 0 grade | 10.1 | 231 |
| Comparative Examples 1 | 35.2 | 1 grade | 8.0 | 85 |
| Comparative Examples 2 | 24.0 | Can not put out certainly | 9.2 | 661 |
Claims (4)
1. a nano-aluminum hydroxide, polynite and ethylene-vinyl acetate copolymer composite flame-proof material, with the ethylene-vinyl acetate copolymer is matrix resin, comprise aluminium hydroxide and retardant synergist zinc borate in the fire retardant, it is characterized in that: aluminium hydroxide is the nano-aluminum hydroxide with the titanate coupling agent modification, added maleic anhydride grafted ethene-acetate ethylene copolymer, also have nano organic montmorillonite in the retardant synergist, the mass percent content of each component of composite flame-proof material is as follows:
(1) surface-modified nano aluminium hydroxide: the particle diameter of aluminium hydroxide is 80～150 nanometers, and surface-modifying agent is a titanate coupling agent, and consumption is 40～50%;
(2) nano organic montmorillonite, consumption are 4～10%;
(3) the zinc borate consumption is 0～3%;
(4) the ethylene-vinyl acetate copolymer consumption is 25～45%;
(5) maleic anhydride grafted ethene-acetate ethylene copolymer, consumption are 5～15%.
2. composite flame-proof material according to claim 1 is characterized in that: vinyl acetate between to for plastic mass percent content is 10～20% in the ethylene-vinyl acetate copolymer, and melting index is 2～10g/10min.
3. composite flame-proof material according to claim 1 is characterized in that: the mass ratio of titanate coupling agent and nano-aluminum hydroxide is 0.5～1.5% in the surface-modified nano aluminium hydroxide.
4. composite flame-proof material according to claim 3 is characterized in that: the mass ratio of titanate coupling agent and nano-aluminum hydroxide is 0.5% in the surface-modified nano aluminium hydroxide.
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| CN100445329C (en) * | 2006-05-19 | 2008-12-24 | 宁波一舟塑胶有限公司 | Nano kaoline fire-resistant synergistic halogen-free non-phosphor cable sheath material |
| CN100391846C (en) * | 2006-08-29 | 2008-06-04 | 惠州学院 | Method for prepring and modifying high heat-resistant aluminium hydroxide |
| CN101724415B (en) * | 2009-12-18 | 2013-04-24 | 暨南大学 | Non-halogen flame retardant containing phosphonium actericide modified montmorillonite, preparation method and application thereof |
| CN101851348B (en) * | 2010-07-08 | 2012-05-30 | 山东川君化工股份有限公司 | Boron type composite fire retardant |
| CN102568670A (en) * | 2011-12-09 | 2012-07-11 | 上海摩恩电气股份有限公司 | Flexible spraying-resisting shock resistance nanometer intervention type medium voltage fire-resisting cable |
| CN103205053B (en) * | 2013-04-12 | 2014-12-10 | 江苏领瑞新材料科技有限公司 | Nano-modified low-shrinkage low-smoke halogen-free and flame-retardant polyolefin cable material and preparation thereof |
| CN103724788B (en) * | 2013-12-18 | 2016-01-06 | 福建福硕线缆有限公司 | A kind of cable sheath and preparation method thereof |
| ES2944608T3 (en) | 2017-12-12 | 2023-06-22 | Borealis Ag | Flame retardant and fire resistant polyolefin composition |
| EP3499516A1 (en) | 2017-12-12 | 2019-06-19 | Borealis AG | Flame retardant and fire resistant polyolefin composition |
| CN109473236B (en) * | 2018-10-25 | 2020-05-29 | 江苏亨通电力电缆有限公司 | Manufacturing process of B1-grade green environment-friendly medium-voltage power cable for super high-rise building |
| CN109734990A (en) * | 2018-12-28 | 2019-05-10 | 北京理工大学 | Two-dimensional material nano modification flame-proof ethylene-vinyl acetate copolymer method |
| CN109880160B (en) * | 2019-03-04 | 2020-04-24 | 北京理工大学 | Aluminum hydroxide and montmorillonite nano composite flame retardant and preparation method thereof |
| CN112466536B (en) * | 2020-12-01 | 2022-07-15 | 无锡市明珠电缆有限公司 | Jet flame and hydrocarbon flame resistant medium-voltage cable for offshore oil platform and manufacturing method thereof |
| CN113072763A (en) * | 2021-04-23 | 2021-07-06 | 江西恒东管业有限公司 | Spiral winding Krah pipe and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000069961A1 (en) * | 1999-05-17 | 2000-11-23 | Du Pont-Mitsui Polychemicals Co., Ltd | Flame retardant resin composition |
| CN1401691A (en) * | 2002-09-24 | 2003-03-12 | 张万喜 | Nanopowder composite polymer memory material |
| CN1401704A (en) * | 2002-09-24 | 2003-03-12 | 吉林大学 | Method for mfg. low pressure heat-shrinkable material using waste plastics |
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2004
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000069961A1 (en) * | 1999-05-17 | 2000-11-23 | Du Pont-Mitsui Polychemicals Co., Ltd | Flame retardant resin composition |
| CN1401691A (en) * | 2002-09-24 | 2003-03-12 | 张万喜 | Nanopowder composite polymer memory material |
| CN1401704A (en) * | 2002-09-24 | 2003-03-12 | 吉林大学 | Method for mfg. low pressure heat-shrinkable material using waste plastics |
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