CN102010536A - Low-smoke halogen-free flame retardant polyolefin composite material and preparation method thereof - Google Patents
Low-smoke halogen-free flame retardant polyolefin composite material and preparation method thereof Download PDFInfo
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- CN102010536A CN102010536A CN 201010590256 CN201010590256A CN102010536A CN 102010536 A CN102010536 A CN 102010536A CN 201010590256 CN201010590256 CN 201010590256 CN 201010590256 A CN201010590256 A CN 201010590256A CN 102010536 A CN102010536 A CN 102010536A
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Abstract
The invention discloses a low-smoke halogen-free flame retardant polyolefin composite material and a preparation method thereof in the technical field of fireproof materials. The material comprises the following components in part by weight: 0 to 100 parts of polyolefin, 0 to 100 parts of ethylene-acrylic acid copolymer and 100 to 160 parts of magnesium hydroxide. The preparation method comprises the following steps of: blending the polyolefin and the ethylene-acrylic acid copolymer, taking the mixture as matrix resin, adding highly filled magnesium hydroxide serving as a flame retardant for mixing, and performing hot pressing to prepare the low-smoke halogen-free flame retardant polyolefin composite material. The oxygen index of the composite material is increased from 28 percent to 39 percent; the breaking elongation is increased from 1.7 percent to 24.4 percent; and the impact strength is increased from 43J/m to 221J/m.
Description
Technical field
What the present invention relates to is material of a kind of fire-retardant material technical field and preparation method thereof, specifically is a kind of halide-free fireproof composite polyolefine material and preparation method thereof.
Background technology
In composite polyolefine material, polyethylene (PE) is one of the world's five big general-purpose plastics, has light weight, nontoxic, and is cheap, resistance to chemical attack, and characteristics such as the convenience of machine-shaping simultaneously are widely used.But poly limiting oxygen index(LOI) only is 18, very easily burns in meeting heat and discharge process and produces a large amount of smog.The drawbacks limit of polyethylene on flame retardant properties its application, therefore need carry out flame-retardant modified to polyethylene.
Before half a century, people have just studied the application of halogenated flame retardant in polyethylene, find the few and good flame retardation effect of addition.But, can cause " secondary pollution " because its amount of being fuming can produce poisonous, corrosive gases greatly and in the combustion processes.And halogen-free flame retardants progressively is used widely with its low-smoke and nontoxicity, and wherein Chang Yong halogen-free flame retardants has magnesium hydroxide and aluminium hydroxide.The addition of oxyhydroxide fire retardant is big, and because polarity is big, bad with the consistency of material, serious to the mechanical property damage of material.
Therefore need to keep the mechanical property of material, simultaneously the LSZH flame retardant resistance of combining hydrogen oxidation thing fire retardant.
Find through retrieval prior art, Liu Ling has reported on " Chinese plastics " 2002 the 16th the 3rd phases of volume and has used LLDPE, ethylene-vinyl acetate copolymer as Halogen cable material main body, and magnesium hydroxide is a main flame retardant development non-halogen flame-retardant cable.When the content of magnesium hydroxide arrived 150 parts, limiting oxygen index(LOI) can reach 30, but tensile strength and shock strength reduce obviously.
Disclose a kind of halogen-free flame-retardant composite material among the United States Patent (USP) GB2190384A, matrix is a kind of polyolefine and a kind of elastomerics, adds ethylene-acrylic acid copolymer simultaneously, is fire retardant with the magnesium hydroxide.Therein ethylene-acrylic copolymer exists with ionomeric form.Can form ionic linkage between report ethylene-acrylic acid copolymer and the Zinic stearas in the patent, in the time of 125 ℃, can effectively reduce the melting index of system, improve limiting oxygen index(LOI) simultaneously, reach 31%.
Chinese patent CN 1796450A discloses a kind of low smoke halogen-free fire retardant polyolefin cable material and preparation method thereof, with ethylene-vinyl acetate copolymer and high density polyethylene(HDPE) as body material, add magnesium hydroxide and two kinds of oxyhydroxide of aluminium hydroxide as fire retardant, add ethene-vinyl acetate grafted maleic anhydride multipolymer simultaneously, with the salt of low-molecular-weight ethylene-acrylic acid copolymer as processing aid, tensile strength reaches 10MPa, elongation at break surpasses 200%, and oxygen index is up to 35%.
Halogen-free flame retardants is under height is filled in the prior art, is difficult to prepare have the intensity height concurrently and the excellent bittern-free flame-proof material of flame retardant properties.
Summary of the invention
The present invention is directed to the prior art above shortcomings, a kind of halide-free fireproof composite polyolefine material and preparation method thereof is provided, on the basis that keeps the original performance of polyolefin resin, have good flame retardancy, make mechanical property and flame retardant properties reach ratio of greater inequality.
The present invention is achieved by the following technical solutions:
The present invention relates to a kind of halide-free fireproof composite polyolefine material, its component and content thereof are: polyolefine 0～100 weight part, ethylene-acrylic acid copolymer 0～100 weight part and magnesium hydroxide 100～160 weight parts.
Described polyolefine is: a kind of or its combination in linear low density polyethylene, high density polyethylene(HDPE), new LDPE (film grade) or the ethylene-octene copolymer, wherein: the density of linear low density polyethylene is 0.91-0.92g/cm
3The density of high density polyethylene(HDPE) is 0.954-0.962g/cm
3The density of new LDPE (film grade) is 0.925g/cm
3The density of ethylene-octene copolymer is 0.863g/cm
3
Acrylic acid content is 8.5-10.5wt% in the described ethylene-acrylic acid copolymer.
The particle diameter of described magnesium hydroxide＜2 μ m and mass percent purity＞90%.
The present invention relates to the preparation method of above-mentioned halide-free fireproof composite polyolefine material, by with after polyolefine and the ethylene-acrylic acid copolymer blend as matrix resin and add high magnesium hydroxide of filling and carry out mixingly as fire retardant, after hot-pressing processing, prepare halide-free fireproof composite polyolefine material then.
The consumption of described magnesium hydroxide is 140 weight parts, and the consumption of matrix resin is 100 weight parts;
The ratio of polyolefine and ethylene-acrylic acid copolymer is 100: 0～0: 100 in the described matrix resin.
Described mixing being meant: adopt Banbury mixer under 130～170 ℃ blending temperature mixing 7～15 minutes, the Banbury mixer rotating speed is 30～80 to change.
Described hot-pressing processing is meant: mixing back matrix material is inserted in the mould, successively in 180 ℃ of following preheatings 10 minutes, hot pressing 5 minutes under 15MPa, the moulding in 5 minutes of colding pressing again.
The oxygen index of the composite polyolefine material that the present invention prepares has brought up to 39% from 28%; Elongation at break brings up to 24.4% from 1.7%; Shock strength is brought up to 221J/m from 43J/m.
Embodiment
Below embodiments of the invention are elaborated, present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Following examples material therefor is as follows: linear low density polyethylene (LLDPE): DFDA-7042, Jilin Petrochemical branch office of China Petro-chemical Co. product, density 0.91-0.92g/cm
3High density polyethylene(HDPE) (HDPE): HD5070EA, Liaoning Hua Jin chemical industry company limited product, density 0.954-0.962g/cm
3New LDPE (film grade) (LDPE): Q281, Shanghai petrochemical industry branch office of China Petro-chemical Co. product, density is 0.925g/cm
3Ethylene-octene copolymer (POE): Engage 8180, the Dow Chemical product, and density is 0.863g/cm
3Ethylene-acrylic acid copolymer (EAA): 1430, Dow Chemical product, acrylic acid content 8.5-10.5wt%; Magnesium hydroxide (Mg (OH)
2): YZ-GX105, Dalian Ya Tai company product, particle diameter＜2um, Mg (OH)
2Content＞94%.
The related testing method of following examples comprises mechanics and combustionproperty test, wherein:
Mechanics Performance Testing: stretch respectively and impact two Mechanics Performance Testings according to GB/T 1040-92 and GB/T 1040-93.
The combustionproperty test: the limiting oxygen index determination standard according to GB/T 2406-1993 is measured.
Specific embodiment component and test data are as follows:
Table 1
| Raw material | Comparative example 1 | Comparative example 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| LLDPE | 100 | 0 | 70 | 60 | 50 | 40 | 30 |
| EAA | 0 | 100 | 30 | 40 | 50 | 60 | 70 |
| Mg(OH) 2 | 140 | 140 | 140 | 140 | 140 | 140 | 140 |
The preparation method of said polyolefins matrix material is:
1. with LLDPE, EAA, Mg (OH)
2Be pre-mixed evenly in table 1 ratio, then melt blending in German Haake RC900 torque rheometer.Blending temperature is 150 ℃, and rotating speed is 60rpm, and the blend time is 10min.
2. the gained sample is placed mould, in 180 ℃ of following preheating 10min, hot pressing 5min under 15MPa then, the sample preparation of GB/T standard is pressed in the 5min moulding of colding pressing again, and material is carried out performance test.
Its Performance Detection such as table 2:
Table 2
By the composite polyolefine material that embodiment 3～7 methods make, tensile strength is better, and shock strength is more excellent, and the matrix material that the while limiting oxygen index(LOI) is compared similar filler addition improves clearly.
In order to further specify the effect that EAA plays in formula system, carry out following comparative example 8～10, embodiment 11～13, prescription (weight part) is as table 3:
Table 3
The preparation method of said polyolefins matrix material is with embodiment 3～7, its Performance Detection such as table 4:
Table 4
Press the composite polyolefine material of embodiment 11～13 preparations, compare with comparative example 8～10, only change the content of EAA, oxygen index is greatly improved.
Claims (9)
1. a halide-free fireproof composite polyolefine material is characterized in that, its component and content thereof are: polyolefine 0～100 weight part, ethylene-acrylic acid copolymer 0～100 weight part and magnesium hydroxide 100～160 weight parts.
2. halide-free fireproof composite polyolefine material according to claim 1, it is characterized in that, described polyolefine is: a kind of or its combination in linear low density polyethylene, high density polyethylene(HDPE), new LDPE (film grade) or the ethylene-octene copolymer, wherein: the density of linear low density polyethylene is 0.91-0.92g/cm
3The density of high density polyethylene(HDPE) is 0.954-0.962g/cm
3The density of new LDPE (film grade) is 0.925g/cm
3The density of ethylene-octene copolymer is 0.863g/cm
3
3. halide-free fireproof composite polyolefine material according to claim 1 is characterized in that, acrylic acid content is 8.5-10.5wt% in the described ethylene-acrylic acid copolymer.
4. halide-free fireproof composite polyolefine material according to claim 1 is characterized in that, the particle diameter of described magnesium hydroxide＜2 μ m and mass percent purity＞90%.
5. preparation method according to the described halide-free fireproof composite polyolefine material of above-mentioned arbitrary claim, it is characterized in that, by with after polyolefine and the ethylene-acrylic acid copolymer blend as matrix resin and add high magnesium hydroxide of filling and carry out mixingly as fire retardant, after hot-pressing processing, prepare halide-free fireproof composite polyolefine material then.
6. the preparation method of halide-free fireproof composite polyolefine material according to claim 5 is characterized in that, the consumption of described magnesium hydroxide is 140 weight parts, and the consumption of matrix resin is 100 weight parts.
7. the preparation method of halide-free fireproof composite polyolefine material according to claim 5 is characterized in that, the ratio of polyolefine and ethylene-acrylic acid copolymer is 100: 0～0: 100 in the described matrix resin.
8. the preparation method of halide-free fireproof composite polyolefine material according to claim 5 is characterized in that, described mixing being meant: adopt Banbury mixer under 130～170 ℃ blending temperature mixing 7～15 minutes, the Banbury mixer rotating speed is 30～80 to change.
9. the preparation method of halide-free fireproof composite polyolefine material according to claim 5, it is characterized in that, described hot-pressing processing is meant: mixing back matrix material is inserted in the mould, successively in 180 ℃ of following preheatings 10 minutes, hot pressing 5 minutes under 15MPa, the moulding in 5 minutes of colding pressing again.
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| CN102532662A (en) * | 2011-12-31 | 2012-07-04 | 潘雪峰 | Preparation method of polyethylene composite material |
| CN111499961A (en) * | 2020-05-25 | 2020-08-07 | 上海方之德新材料有限公司 | High-flame-retardant low-smoke halogen-free flame-retardant polyolefin tight wrapping material |
| CN114456481A (en) * | 2022-03-07 | 2022-05-10 | 金发科技股份有限公司 | Solvent-resistant polyolefin material and preparation method and application thereof |
| CN114736450A (en) * | 2022-03-10 | 2022-07-12 | 金发科技股份有限公司 | High-thermal-shrinkage-resistance and high-toughness thermo-oxidative-aging-resistance polyolefin material and preparation method and application thereof |
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| JP2002170441A (en) * | 2000-12-01 | 2002-06-14 | Sumitomo Wiring Syst Ltd | Insulated wire |
| EP1215237A2 (en) * | 2000-12-12 | 2002-06-19 | Sumitomo Wiring Systems, Ltd. | Electrical wire having a covering of a resin composition |
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| CN102532662A (en) * | 2011-12-31 | 2012-07-04 | 潘雪峰 | Preparation method of polyethylene composite material |
| CN111499961A (en) * | 2020-05-25 | 2020-08-07 | 上海方之德新材料有限公司 | High-flame-retardant low-smoke halogen-free flame-retardant polyolefin tight wrapping material |
| CN114456481A (en) * | 2022-03-07 | 2022-05-10 | 金发科技股份有限公司 | Solvent-resistant polyolefin material and preparation method and application thereof |
| CN114736450A (en) * | 2022-03-10 | 2022-07-12 | 金发科技股份有限公司 | High-thermal-shrinkage-resistance and high-toughness thermo-oxidative-aging-resistance polyolefin material and preparation method and application thereof |
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Application publication date: 20110413 |