CN103131115B - A kind of Flame-retardant polyolefin thermoplastic elastomer composition and preparation method thereof - Google Patents
A kind of Flame-retardant polyolefin thermoplastic elastomer composition and preparation method thereof Download PDFInfo
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- CN103131115B CN103131115B CN201310098162.9A CN201310098162A CN103131115B CN 103131115 B CN103131115 B CN 103131115B CN 201310098162 A CN201310098162 A CN 201310098162A CN 103131115 B CN103131115 B CN 103131115B
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Abstract
The invention discloses a kind of flame-retardant thermoplastic elastomer composition and preparation method thereof, particularly disclose a kind of Flame-retardant polyolefin thermoplastic elastomer composition and preparation method thereof.Composition for thermoplastic elastomer prepared by the inventive method uses halogen-free expanded flame-retardant system and inorganic metal compound synergistic flame retardant cooperative flame retardant, the material prepared has excellent flame retardant properties and good mechanical property, fire-retardant rank reaches V-0 level, and oxygen index is greater than 27.
Description
Technical field
The present invention relates to a kind of flame-retardant thermoplastic elastomer composition and preparation method thereof, particularly relate to a kind of halogen-free anti-flaming polyolefin composition for thermoplastic elastomer and preparation method thereof.
Background technology
Thermoplastic elastomer, owing to having had the characteristic of rubber and thermoplastics concurrently, has been developed rapidly since appearance, is widely used at industrial circle.Polyolefins thermoplastic elastomer is the second largest analog thermoplastic elastomer that output is only second to polystyrene-type thermoplastic elastomers, its abundant raw material source, and cost performance is higher, is widely used in the fields such as electric wire, household electrical appliance, automobile industry, medical treatment.Therefore, flame retardant properties also receives much concern as an important indicator of thermoplastic elastomer, and the polyolefins thermoplastic elastomer with excellent fire-retardancy is also widely studied.
Nitrogen phosphorus complex intumescent flame retardant, because of its feature such as environmental friendliness, use safety, becomes the study hotspot in halogen-free flame retardants.Authorize publication number be the Chinese patent of CN 1235965C Tripyrophosphoric acid trimeric cyanamide and char-forming agent tetramethylolmethane Intumscent Flame Retardant System are applied to acrylic plastering fire-retardant in.But above-mentioned Intumscent Flame Retardant System is all only applied to Pp System at present, has no the report be applied in Thermoplastic Elastomer, Olefinic.
In published patent and document, inorganic metal compound is more common as the fire retardant of thermoplastic elastomer, as the Chinese patent that application publication number is CN 102219948A, CN 101747551A, and Authorization Notice No. be CN 1102611C, CN 100556947C, CN 101001909B, CN 101117425B, CN100560646C Chinese patent individually disclose polyolefin elastomer using one or more mixtures in traditional aluminium hydroxide, magnesium hydroxide, zinc borate, red phosphorus etc. as inorganic combustion inhibitor or elastomeric compound.These patents use merely inorganic metal compound that flame retarding efficiency is lower as fire retardant, fire retardant addition accounts for quality of materials per-cent up to 40 ~ 80%, although ensure that the flame retardant properties of material, its higher addition makes the mechanical property of material also greatly reduce.
(the Zhang Long such as Zhang Long, Wang Jianqi, New-type halide-free expansible black lead frie retardant coating, Beijing Institute of Technology's journal, 2001, 21 (5): 649 ~ 652) and (the M Modesti such as M.Modesti, A Lorenzetti, F Simioni, et al.Expandable graphite as an intumescent flame retardant inpolyisocyanurate-polyurethane foams.Polymer Degradation and Stability, 2002, 77 (2), 195 ~ 202) confirm that nickel compound and rare earth oxide have good synergistic effect to chemically expansible flame-retardant system respectively, but these report that the system applied is not thermoplastic elastomer system.
Mandate publication number is that the Chinese patent of CN 101824182B uses coated ammonium polyphosphate Intumescent Retardant System, in conjunction with metallic compound synergistic flame retardant, as zinc borate, titanium oxide, silicon oxide, zinc oxide, magnesium oxide, magnesium hydroxide, brucite, magnesium salt whisker, aluminium hydroxide, aluminum phosphate etc., the blend of fire retardant polyolefin analog thermoplastic elastomer/styrene analog thermoplastic elastomer.Its inorganic metal compound selected does not comprise nickel compound or rare earth oxide, but the lower metallic compound of some flame retarding efficiencies is as magnesium hydroxide, aluminium hydroxide etc., this patent also and the limiting oxygen index(LOI) of unexposed prepared thermoplastic elastic material.
In sum, in current existing technology, also do not report using nickel compound and rare earth oxide as synergist, in conjunction with nitrogen phosphorus expansion type flame retardant be applied to polyolefins thermoplastic elastomer fire-retardant in.
Summary of the invention
Because the above-mentioned defect of prior art, technical problem to be solved by this invention is to provide and a kind of uses nitrogen phosphorus expansion type flame retardant, and has the nickel compound of higher synergistic effect and the fire-retardant halogen-free flame-retardant Thermoplastic Elastomer, Olefinic composition and method of making the same of rare earth oxide synergist.
For achieving the above object, the invention provides a kind of halogen-free flame-retardant Thermoplastic Elastomer, Olefinic composition and method of making the same.Composition for thermoplastic elastomer prepared by the inventive method is the not halogen-containing environment-friendly materials of one, has good flame retardant properties and mechanical property.
On the one hand, the invention discloses a kind of halogen-free flame-retardant Thermoplastic Elastomer, Olefinic composition, the component of this composition for thermoplastic elastomer and mass fraction are:
(a) polyolefins thermoplastic elastomer 60 ~ 80 parts;
(b) melamine phosphate 10 ~ 30 parts;
(c) tetramethylolmethane 10 ~ 20 parts;
(d) metallic compound 0.5 ~ 5 part.
In the present invention, described polyolefins thermoplastic elastomer is preferably ethylene-octene segmented copolymer; Described metallic compound elects nickelous carbonate or lanthanum trioxide as, or the mixture of both arbitrary proportions.
On the other hand, the invention still further relates to a kind of method preparing above-mentioned halogen-free flame-retardant Thermoplastic Elastomer, Olefinic, specifically comprise the following steps:
The first step, carries out drying treatment by polyolefins thermoplastic elastomer, melamine phosphate, tetramethylolmethane, metallic compound, and placement room temperature is stand-by; Then dried polyolefins thermoplastic elastomer, melamine phosphate, metallic compound at room temperature mixed and use mechanical stirring 1-10 minute, obtaining component A;
Second step, carries out combination treatment by component A, obtains halogen-free flame-retardant Thermoplastic Elastomer, Olefinic composition.
In better embodiment of the present invention, described drying treatment refers to: by the vacuum-drying 4 ~ 24 hours at 40 DEG C of polyolefins thermoplastic elastomer, melamine phosphate, tetramethylolmethane, metallic compound;
In another better embodiment of the present invention, described combination treatment refers to: use Banbury mixer at 150 ~ 200 DEG C, after 5 ~ 20 minutes with the rotating speed of 80 ~ 120 revs/min mixing, takes out sample and is cooled to room temperature.
Composition for thermoplastic elastomer prepared by the inventive method uses halogen-free expanded flame-retardant system and inorganic metal compound synergistic flame retardant cooperative flame retardant, the material prepared has good mechanical property and excellent flame retardant properties, fire-retardant rank reaches V-0 level, and oxygen index is greater than 27.And in the prior art, the inorganic metal fire retardant that polyolefins thermoplastic elastomer more employing flame retarding efficiency is lower, addition accounts for quality of materials per-cent up to 40 ~ 80%, although ensure that the flame retardant properties of material, its higher addition makes material mechanical performance greatly reduce.Use metallic compound as in the expandable flame retardant elastomer system of synergist at some, the metallic compound limitednumber selected, the metallic compound of some routines cannot reach good synergistic effect.
Be described further below with reference to the technique effect of accompanying drawing to design of the present invention, concrete structure and generation, to understand object of the present invention, characteristic sum effect fully.
Be described further below with reference to the technique effect of accompanying drawing to design of the present invention, concrete structure and generation, to understand object of the present invention, characteristic sum effect fully.
Accompanying drawing explanation
Fig. 1 is the SEM photo of comparative example 5 combustion residue of the present invention;
Fig. 2 is the SEM photo of embodiments of the invention 2 combustion residue;
Fig. 3 is the SEM photo of embodiments of the invention 5 combustion residue;
Fig. 4 is the SEM photo of embodiments of the invention 7 combustion residue;
Fig. 5 is the SEM photo of embodiments of the invention 8 combustion residue;
Fig. 6 is the SEM photo of embodiments of the invention 10 combustion residue;
Fig. 7 is the SEM photo of embodiments of the invention 12 combustion residue;
Fig. 8 is the SEM photo of embodiments of the invention 13 combustion residue;
Fig. 9 is the SEM photo of embodiments of the invention 14 combustion residue.
Embodiment
Below embodiments of the invention are elaborated.The present embodiment is being implemented premised on technical solution of the present invention, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
The first step, by the vacuum-drying 8 hours at 40 DEG C of POE, melamine phosphate, tetramethylolmethane, metallic compound, it is stand-by to place room temperature; According to the formula of table 1 illustrated embodiment, claim POE 60 mass parts, melamine phosphate 24 mass parts, tetramethylolmethane 16 mass parts, nickelous carbonate 0.5 mass parts, at room temperature mix and use mechanical stirring 5 minutes, obtaining component A.
Second step, uses Banbury mixer at 150 ~ 200 DEG C, with the rotating speed of 80 ~ 120 revs/min, component A mixing, after 5 ~ 20 minutes, is taken out sample and is cooled to room temperature, obtains without halide resistance type combustion Thermoplastic Elastomer, Olefinic composition.
Embodiment 2-16
The implementation step of embodiment 2-16 and comparative example 1-5 is all identical with two steps of above-described embodiment 1, and wherein, the usage quantity reference of POE, melamine phosphate, tetramethylolmethane, nickelous carbonate, lanthanum trioxide is as the raw materials quality number in following table 1.
The raw materials quality number proportioning of table 1: embodiment 1-16 and comparative example 1-5.
The Performance Evaluation that embodiment 1-16 and comparative example 1-5 prepares the composition for thermoplastic elastomer of gained characterizes as follows:
Tensile property: composition for thermoplastic elastomer is cut into dumbbell shape, tests by GB/T528-2009 standard.
Combustionproperty: carry out oxygen index test by GB/T10707-2008 standard, by the inflammableness of UL94-2009 Standards for Testing Materials.
The specific performance assessment of embodiment 1-16 and comparative example 1-5 is as following table 2:
The Performance Evaluation table of table 2: embodiment 1-16 and comparative example 1-5.
As can be seen from the SEM photo of sample combustion residue, in the carbon residue layer formed after not adding the material combustion of nickelous carbonate and lanthanum trioxide, there is obvious hole, can not good covering protection matrix of materials during burning, flame retardant effect is not good.After adding nickelous carbonate and lanthanum trioxide, the hole in layer of charcoal tails off, and carbon layer increases, Char Residues Structure becomes continuous and closely knit, closure and intensity are all fine, the effective and flame of system is isolated, slows down generation and the release of inflammable gas in polymkeric substance thermal degradation process.
More than describe preferred embodiment of the present invention in detail.Should be appreciated that the ordinary skill of this area just design according to the present invention can make many modifications and variations without the need to creative work.Therefore, all technician in the art, all should by the determined protection domain of claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (4)
1. a Flame-retardant polyolefin thermoplastic elastomer composition, is characterized in that, its component and mass fraction are:
Wherein, described metallic compound refers to: nickelous carbonate, or the mixture of nickelous carbonate and lanthanum trioxide arbitrary proportion; Described polyolefins thermoplastic elastomer refers to: ethylene-octene segmented copolymer.
2. prepare a method for Flame-retardant polyolefin thermoplastic elastomer composition as claimed in claim 1, it is characterized in that, comprise the steps:
The first step, carries out drying treatment by polyolefins thermoplastic elastomer, melamine phosphate, tetramethylolmethane, metallic compound, and placement room temperature is stand-by; Then dried polyolefins thermoplastic elastomer, melamine phosphate, tetramethylolmethane, metallic compound at room temperature mixed and use mechanical stirring 1-10 minute, obtaining component A;
Second step, carries out combination treatment by described component A, obtains Flame-retardant polyolefin thermoplastic elastomer composition.
3. preparation method according to claim 2, is characterized in that, described drying treatment refers to: by the vacuum-drying 4 ~ 24 hours at 40 DEG C of described polyolefins thermoplastic elastomer, melamine phosphate, tetramethylolmethane, metallic compound.
4. preparation method according to claim 2, is characterized in that, described combination treatment refers to: use Banbury mixer at 150 ~ 200 DEG C, with the rotating speed of 80 ~ 120 revs/min after blended 5 ~ 20 minutes, takes out sample and is cooled to room temperature.
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| CN103131115B true CN103131115B (en) | 2015-10-14 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103923376A (en) * | 2014-04-24 | 2014-07-16 | 上海交通大学 | Dynamic vulcanized inflaming retarding nylon/ethylene vinyl acetate rubber thermoplastic elastomer and preparation method thereof |
| CN106046422A (en) * | 2016-07-21 | 2016-10-26 | 肖金源 | Incombustible fire-resistant treating agent |
| CN109942946A (en) * | 2019-04-17 | 2019-06-28 | 奥世达弹性体(深圳)有限公司 | A kind of wire and cable thermoplastic elastic material |
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| WO2008079998A1 (en) * | 2006-12-21 | 2008-07-03 | Dow Global Technologies Inc. | Filled tpo compositions, methods of making the same, and articles prepared from the same |
| CN101230276A (en) * | 2007-12-28 | 2008-07-30 | 华东理工大学 | Novel phosphorous-nitrogen system bittern-free flame-proof material |
| CN101469089A (en) * | 2008-06-19 | 2009-07-01 | 上海化工研究院 | Halogen-free polyvinyl composite for manufacturing pipes and manufacturing method thereof |
| CN102477178A (en) * | 2010-11-23 | 2012-05-30 | 上海杰事杰新材料(集团)股份有限公司 | Low-smoke halogen-free flame-retardant antistatic aging-resistant wire and cable material and its preparation method |
| CN102585329A (en) * | 2012-01-16 | 2012-07-18 | 长园集团股份有限公司 | Halogen-free non-red-phosphorus flame-retardant thermal shrinkable tube and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008079998A1 (en) * | 2006-12-21 | 2008-07-03 | Dow Global Technologies Inc. | Filled tpo compositions, methods of making the same, and articles prepared from the same |
| CN101230276A (en) * | 2007-12-28 | 2008-07-30 | 华东理工大学 | Novel phosphorous-nitrogen system bittern-free flame-proof material |
| CN101469089A (en) * | 2008-06-19 | 2009-07-01 | 上海化工研究院 | Halogen-free polyvinyl composite for manufacturing pipes and manufacturing method thereof |
| CN102477178A (en) * | 2010-11-23 | 2012-05-30 | 上海杰事杰新材料(集团)股份有限公司 | Low-smoke halogen-free flame-retardant antistatic aging-resistant wire and cable material and its preparation method |
| CN102585329A (en) * | 2012-01-16 | 2012-07-18 | 长园集团股份有限公司 | Halogen-free non-red-phosphorus flame-retardant thermal shrinkable tube and preparation method thereof |
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