CN105418975A - Halogen-free and low-smoke flame retardant for preparing polyethylene material - Google Patents

Halogen-free and low-smoke flame retardant for preparing polyethylene material Download PDF

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Publication number
CN105418975A
CN105418975A CN201510948649.0A CN201510948649A CN105418975A CN 105418975 A CN105418975 A CN 105418975A CN 201510948649 A CN201510948649 A CN 201510948649A CN 105418975 A CN105418975 A CN 105418975A
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Prior art keywords
polyethylene material
parts
halogen
free
low
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Pending
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CN201510948649.0A
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Chinese (zh)
Inventor
雷自强
马德龙
张哲�
赵睿
杨志旺
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Lanzhou Institute of Chemical Physics LICP of CAS
Northwest Normal University
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Northwest Normal University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/01—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating

Abstract

The invention discloses a halogen-free and low-smoke flame retardant for preparing a polyethylene material. The halogen-free and low-smoke flame retardant is prepared by compounding DMMP (Dimethyl Methyl Phosphonate), Mg(OH)2 (available in the market) modified by sodium stearate, 2,3-dimethyl-2,3-diphenylbutane, palygorskite clay and zinc tetraphenylporphyrin. In the polyethylene material prepared by utilizing the halogen-free and low-smoke flame retardant, the oxygen index is not lower than 32, the smoke density under a flameless condition is not higher than 75, the tensile strength is not lower than 12MPa, and the elongation at break is not lower than 180 percent, so that the polyethylene material is a modified halogen-free, low-smoke and anti-flaming polyethylene composite material with a very good performance and can be widely applied to the fields of electric wires and cables, buildings and the like. The flame resistance of the polyethylene material cannot be affected after the polyethylene material is subjected to conventional irradiation cross-linking if cross-linking treatment needs to be carried out on a prepared product, and the mechanical performance of the polyethylene material can be further increased.

Description

A kind of LSOH anti-flaming agent for the preparation of polythene material
Technical field
The present invention relates to a kind of halogen-free smoke inhibition fire retardant, particularly relate to a kind of LSOH anti-flaming agent for the preparation of polythene material, belong to technical field of composite materials.
Background technology
In the last thirty years, Chinese national economy, under the policy of reform and opening-up is guided, achieves and unprecedentedly develop rapidly, but fire hazard degree is but period the most serious since the establishment of the nation.Although the nineties middle and later periods, governments at all levels and various circles of society cause great attention to fire-fighting work, also increase fire-fighting to drop into, but do not check fire ascendant trend, especially the serious fire failure that near one or two years occurs, it is not only warned the dead group of group and hinders fire and present " bounce-back " trend, and reflects that the research and development of current fire retardant material and application seriously lag behind the objective reality of economic construction and social development.
At present, the classification of fire retardant material mainly contains Halogen fire retardant material and the large class of bittern-free flame-proof material two.Halogenated flame retardant is the maximum fire retardant of current consumption, has good flame retardation effect, the advantages such as fire retardant is wide in variety, but due to the chemical property of halogens, halogenated flame retardant also also exists many shortcomings that can not be ignored.First, halogenated flame retardant can release hydrogen halide and with dense smoke under high temperature, fire conditions.Investigation statistics data show, to be burnt produced hydrogen halide and cause human body to suffocate being the most direct factor of injures and deaths in building fire by halogen.Secondly, halogenated flame retardant (particularly many bromobenzenes ether) can decompose generation extractibility organic compound mostly, and this is a kind of environmental persistence organic compound, has the features such as lipophilic is hydrophobic, difficult degradation, by the enrichment in human body of various mode, very big to human health damage.Along with pay close attention to life and health, Sustainable development and environment protection cry more and more higher, since entering 21 century, western countries progressively propose the relevant laws and regulations clause of forbidding many bromobenzenes ether, and forbidding scope also progressively expands.Make to utilize halogen-free flame retardants to substitute halogen containing flame-retardant and become an inevitable trend.
Halogen-free flame retardants mainly contains phosphorus flame retardant, nitrogenated flame retardant, inorganic mineral based flame retardant etc.Halogen-free flame retardants major advantage is that cost is low, non-toxic substance release after burning, but shortcoming to be flame retarding efficiency low, fire retardant addition is large, can reduce the mechanical property of matrix material in most cases, seriously hinder the use range of matrix material.Therefore, the halogen-free flame retardants of exploitation high performance-price ratio is the difficult point that the needs of current flame retardant industry are captured, and is also study hotspot from now on.
Polythene material a kind ofly has excellent resistance to low temperature (minimum use temperature can reach-70 DEG C ~-100 DEG C), electrical insulating property and chemical stability, the erosion (the not resistance to acid with oxidizing property) of the most of soda acid of ability, but heat-resisting, resistance to deterioration is poor, oxygen index is very low.Be insoluble to common solvent under normal temperature, water-absorbent is little, but can be slowly dissolved in some organic solvent, and does not occur swelling.Polyethylene is very sensitive for environmental stress (chemistry and mechanical effect), and its character is different because of kind, depends primarily on molecular structure and density.Due to the performance that polyethylene is good, it all has been widely used in every profession and trade, if but in fields such as building, electric wire, household electrical appliances manufacture, automotive industry, communication space flight, if use polyethylene not have flame retardant resistance, then be very easy to presence of fire, cause various property and human loss.Therefore it is instant for developing a kind of polythene material with LSOH anti-flaming, is also very have market outlook.
Summary of the invention
The object of the invention is for problems of the prior art, a kind of LSOH anti-flaming agent for the preparation of polythene material is provided.
The present invention, for the preparation of the LSOH anti-flaming agent of polythene material, is by dimethyl methyl phosphonate, the Mg (OH) of sodium stearate modification 2, 2,3-dimethyl-2,3-diphenyl butane, palygorskite and Tetraploid rice is composite forms: wherein the weight ratio of each component is as follows:
Dimethyl methyl phosphonate 10 ~ 15 parts, sodium stearate modification Mg (OH) 25 ~ 10 parts, 2,3-dimethyl-2,3-diphenyl butane 0.1 ~ 0.5 part, palygorskite 2 ~ 8 parts, Tetraploid rice 0.3 ~ 1 part.
Optimum ratio: dimethyl methyl phosphonate 12 ~ 13 parts, sodium stearate modification Mg (OH) 27 ~ 9 parts, 2,3-dimethyl-2,3-diphenyl butane 0.3 ~ 0.4 part, palygorskite 4 ~ 6 parts, Tetraploid rice 0.5 ~ 0.8 part.
Optimum proportioning: dimethyl methyl phosphonate 12 parts, sodium stearate modification Mg (OH) 28 parts, 2,3-dimethyl-2,3-diphenyl butane 0.3 part, palygorskite 5 parts, Tetraploid rice 0.6 part.
Below the flame retardant properties of the polythene material utilizing fire retardant of the present invention to prepare and smoke suppressing effect are described.
The preparation of flame-proof polyethylene: get polyethylene 100 parts, compound flame retardant 17.4 ~ 34.5 parts, puts into high-speed mixer and stirs about 30 minutes, add mixing granulator in twin screw extruder and namely obtain fire-retardant polyethylene material.
The performance of flame-proof polyethylene: oxygen index is not less than 32, under nonflame condition, smoke density is not higher than 75, tensile strength is not less than 12MPa, elongation at break is not less than 180%, it is the very good modification LSOH anti-flaming composite polyethylene material of a kind of performance, the fields such as this material can be widely used in electric wire, building.Prepared product if desired crosslinking Treatment, does not affect the flame retardant properties of this material after conventional irradiation is cross-linked, and its mechanical property can improve further.
Embodiment
Below by experiment, the flame retardant properties of the polypropylene material utilizing fire retardant of the present invention to prepare and smoke suppressing effect are described further.
Embodiment 1
Get polyethylene 100 parts, dimethyl methyl phosphonate 12 parts, sodium stearate modification Mg (OH) 28 parts, 2,3-dimethyl-2,3-diphenyl butane 0.3 part, palygorskite 5 parts, Tetraploid rice 0.6 part, puts into high-speed mixer and stirs about 30 minutes, add mixing granulator in twin screw extruder and namely obtain fire-retardant polyethylene material.The oxygen index of fire-retardant polyethylene material is 38, and under nonflame condition, smoke density is 70, and tensile strength is 13.9MPa, and elongation at break is 201%.
Embodiment 2
Get polyethylene 100 parts, dimethyl methyl phosphonate 10 parts, sodium stearate modification Mg (OH) 25 parts, 2,3-dimethyl-2,3-diphenyl butane 0.1 part, palygorskite 2 parts, Tetraploid rice 0.3 part, puts into high-speed mixer and stirs about 30 minutes, add mixing granulator in twin screw extruder and namely obtain fire-retardant polyethylene material.The oxygen index of fire-retardant polyethylene material is 32.5, and under nonflame condition, smoke density is 74.9, and tensile strength is 12.4MPa, and elongation at break is 204%.
Embodiment 3
Get polyethylene 100 parts, dimethyl methyl phosphonate 15 parts, sodium stearate modification Mg (OH) 210 parts, 2,3-dimethyl-2,3-diphenyl butane 0.5 part, palygorskite 8 parts, Tetraploid rice 1 part, puts into high-speed mixer and stirs about 30 minutes, add mixing granulator in twin screw extruder and namely obtain fire-retardant polyethylene material.The oxygen index of fire-retardant polyethylene material is 36, and under nonflame condition, smoke density is 73, and tensile strength is 13.2MPa), elongation at break is 180%.
Embodiment 4
Get polyethylene 100 parts, dimethyl methyl phosphonate 13 parts, sodium stearate modification Mg (OH) 25 parts, 2,3-dimethyl-2,3-diphenyl butane 0.4 part, palygorskite 2 parts, Tetraploid rice 0.7 part, puts into high-speed mixer and stirs about 30 minutes, add mixing granulator in twin screw extruder and namely obtain fire-retardant polyethylene material.The oxygen index of fire-retardant polyethylene material is 35, and under nonflame condition, smoke density is 74, and tensile strength is 12.8MPa, and elongation at break is 187%.
Embodiment 5
Get polyethylene 100 parts, dimethyl methyl phosphonate 15 parts, sodium stearate modification Mg (OH) 28 parts, 2,3-dimethyl-2,3-diphenyl butane 0.44 part, palygorskite 6 parts, Tetraploid rice 0.4 part, puts into high-speed mixer and stirs about 30 minutes, add mixing granulator in twin screw extruder and namely obtain fire-retardant polyethylene material.The oxygen index of fire-retardant polyethylene material is 34.7, and under nonflame condition, smoke density is 73.5, and tensile strength is 12.7MPa, and elongation at break is 195%.

Claims (4)

1., for the preparation of a LSOH anti-flaming agent for polythene material, be by dimethyl methyl phosphonate, the Mg (OH) of sodium stearate modification 2, 2,3-dimethyl-2,3-diphenyl butane, palygorskite and Tetraploid rice is composite forms.
2. as claimed in claim 1 for the preparation of the LSOH anti-flaming agent of polythene material, it is characterized in that: the weight proportion of described each component is as follows:
Dimethyl methyl phosphonate 10 ~ 15 parts, sodium stearate modification Mg (OH) 25 ~ 10 parts, 2,3-dimethyl-2,3-diphenyl butane 0.1 ~ 0.5 part, palygorskite 2 ~ 8 parts, Tetraploid rice 0.3 ~ 1 part.
3. as claimed in claim 1 for the preparation of the LSOH anti-flaming agent of polythene material, it is characterized in that: the weight proportion of described each component is as follows:
Dimethyl methyl phosphonate 12 ~ 13 parts, sodium stearate modification Mg (OH) 27 ~ 9 parts, 2,3-dimethyl-2,3-diphenyl butane 0.3 ~ 0.4 part, palygorskite 4 ~ 6 parts, Tetraploid rice 0.5 ~ 0.8 part.
4. as claimed in claim 1 or 2 for the preparation of the LSOH anti-flaming agent of polythene material, it is characterized in that: the weight proportion of described each component is as follows:
Dimethyl methyl phosphonate 12 parts, sodium stearate modification Mg (OH) 28 parts, 2,3-dimethyl-2,3-diphenyl butane 0.3 part, palygorskite 5 parts, Tetraploid rice 0.6 part.
CN201510948649.0A 2015-12-17 2015-12-17 Halogen-free and low-smoke flame retardant for preparing polyethylene material Pending CN105418975A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106188751A (en) * 2016-07-18 2016-12-07 西北师范大学 The preparation of a kind of halogen-free smoke inhibition fire retardant and the application in preparing cross-link low-density polyethylene
CN108641122A (en) * 2018-04-18 2018-10-12 西北师范大学 A kind of palygorskite Quito functional high molecule material auxiliary agent and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1654529A (en) * 2005-01-18 2005-08-17 西北师范大学 Flame-retardant polypropylene composite materials with palygorskite as flame retardant
CN101284919A (en) * 2008-05-09 2008-10-15 西北师范大学 Paligorskite-butadiene styrene rubber composite fire retardant material
CN102010585A (en) * 2010-11-16 2011-04-13 淮阴师范学院 Preparation method of efficient and environment-friendly composite fire retardant
CN104017264A (en) * 2014-06-20 2014-09-03 西北师范大学 Preparation method of halogen-free low-smoke flame-retardant crosslinked polyethylene composite material

Patent Citations (4)

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CN101284919A (en) * 2008-05-09 2008-10-15 西北师范大学 Paligorskite-butadiene styrene rubber composite fire retardant material
CN102010585A (en) * 2010-11-16 2011-04-13 淮阴师范学院 Preparation method of efficient and environment-friendly composite fire retardant
CN104017264A (en) * 2014-06-20 2014-09-03 西北师范大学 Preparation method of halogen-free low-smoke flame-retardant crosslinked polyethylene composite material

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106188751A (en) * 2016-07-18 2016-12-07 西北师范大学 The preparation of a kind of halogen-free smoke inhibition fire retardant and the application in preparing cross-link low-density polyethylene
CN108641122A (en) * 2018-04-18 2018-10-12 西北师范大学 A kind of palygorskite Quito functional high molecule material auxiliary agent and preparation method thereof
CN108641122B (en) * 2018-04-18 2019-03-29 西北师范大学 A kind of palygorskite Quito functional polymer material auxiliary agent and preparation method thereof

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Inventor after: Lei Ziqiang

Inventor after: Ma Delong

Inventor after: Wang Aiqin

Inventor after: Zhang Zhe

Inventor after: Zhao Rui

Inventor after: Yang Zhiwang

Inventor after: Mou Bin

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Application publication date: 20160323