CN105694103A - DOPO/MMT nano-composite flame retardant and preparation method thereof - Google Patents

DOPO/MMT nano-composite flame retardant and preparation method thereof Download PDF

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Publication number
CN105694103A
CN105694103A CN201610115310.7A CN201610115310A CN105694103A CN 105694103 A CN105694103 A CN 105694103A CN 201610115310 A CN201610115310 A CN 201610115310A CN 105694103 A CN105694103 A CN 105694103A
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dopo
montmorillonite
fire retardant
temperature
preparation
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CN105694103B (en
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张文超
何向东
杨荣杰
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Beijing Institute of Technology BIT
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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
    • 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
    • C08K3/34—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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Fireproofing Substances (AREA)

Abstract

The invention relates to a DOPO/MMT nano-composite flame retardant and a preparation method thereof and belongs to the technical field of flame retardance. The preparation method comprises the specific steps that according to the parts by weight, a phosphorus containing micromolecule fire retardant DOPO monomer is added into a reactor with a temperature control device, a stirring device and an ultrasound device, montmorillonoid with a small amount of organic solvent is added as needed, the materials are mechanically stirred at a high speed on the ultrasound condition and then stored at a constant temperature in a drying oven, then the mixture is taken out, naturally cooled, smashed and screened, and montmorillonoid powder modified through the phosphorus containing micromolecule fire retardant is obtained. The structural formula of the phosphorus containing micromolecule fire retardant is shown in the description. According to the montmorillonoid material prepared through the method, due to the fact that the phosphorus containing micromolecule fire retardant DOPO enters the laminate layer of montmorillonoid under the effect of the solvent and the high temperature, the layer distance is obviously increased, the dispersing performance of the micromolecule in the polymer is improved, and the fire retardance of the polymer is improved.

Description

A kind of DOPO/MMT composite nanometer flame retardant and preparation method thereof
Technical field
The present invention relates toA kind of DOPO/MMT composite nanometer flame retardant and preparation method thereof, belong to field of fire-proof technology。
Background technology
Montmorillonite (MMT) is the most attractive nano inorganic material, because its reserves are big, possess nano-meter characteristic and be widely studied, can as fire retardant for flame retardant area, nano composite polymer-montmorillonoid material is provided with the feature of high-molecular organic material and inorganic material, montmorillonite can improve the mechanical performance of polymer, fire resistance and gas barrier property, and the performance of these excellences is often from the dispersion of montmorillonite nano-scale in the polymer。And due to the problem of the compatibility, general montmorillonite is difficult to fully dispersed in the polymer so that its performance is had a greatly reduced quality, therefore need before use to carry out organically-modified process。Although and composite nano polymer/clay material can increase heat stability, neat coal amout and the HRR peak value substantially reduced, but need nonetheless remain for additionally adding fire retardant will pass through fire performance test。
9,10-dihydro-9-oxy assorted-10-phospho hetero phenanthrene-10-oxide (DOPO) is a kind of halogen-free flame retardants being widely used, but itself decomposition temperature is relatively low, to polymer when although addition is 5%～10%, such as epoxy resin etc., there is good fire retardation, but can be very big to mechanical performance infringement when individually adding。
Simple interpolation montmorillonite can improve the mechanical performance of polymer, but the fire resistance of polymer is affected less, and depend entirely on the dispersibility of montmorillonite nano-scale in polymeric matrix, and DOPO can improve the fire resistance of polymer but bring negative impact to the mechanical property of polymer。Therefore montmorillonite is combined in some way with DOPO and can play the advantage of the two, make up the two respective shortcoming。
Summary of the invention
The present invention, for the purpose of flame-proofed polymer material, adds the dispersion problem in polymer to for solving montmorillonite, it is proposed toA kind of DOPO/MMT composite nanometer flame retardant and preparation method thereof。
It is an object of the invention to be achieved through the following technical solutions。
The present invention is a kind of DOPO/MMT composite nanometer flame retardant, utilizes phosphorous little molecule fire retardant DOPO to enter in the lamella of montmorillonite and the interlamellar spacing of montmorillonite is increased, thus be more prone to dispersion when flame-retardant polymer。The gross mass of the composite nanometer flame retardant to prepare, wherein the percentage composition of each component is:
Phosphorous little molecule fire retardant DOPO70%～90%
Montmorillonite 10%～30%
The structural formula of the phosphorous little molecule fire retardant DOPO used asUnder。
The present invention'sA kind of DOPO/MMT composite nanometer flame retardant and preparation method thereof, its concrete preparation process is:
Phosphorous little molecule fire retardant DOPO monomer is joined in the reactor with temperature regulating device, agitating device and Vltrasonic device, the temperature controlling reactor is 120-160 DEG C, the ratio of 1 adds the montmorillonite containing a small amount of organic solvent on request again, after under ultrasound condition, high speed machine stirs 1～5 hour, mixed system is transferred in container, and constant temperature preserves 0.5-2 hour in the baking oven of 100-170 DEG C。Then take out and make its Temperature fall to room temperature condition。Light yellow solid is obtained after having lowered the temperature。This solid obtains the powder of DOPO/MMT composite nanometer flame retardant after process such as pulverizing, sieve。
In above-mentioned steps, organic solvent is: C1～C3Alcohol, acetone, acetonitrile, dichloromethane, chloroform, benzene,toluene,xylene, dioxane, oxolane or its mixture, solvent is preferably C1～C3Alcohol；The ratio of montmorillonite and solvent is: 1g:10～30ml；
In above-mentioned steps, montmorillonite is: calcium-base montmorillonite, sodium-based montmorillonite, organic modification montmonrillonite。
Above-mentioned steps is connected on reactor condensate recycling device, can collect and be recovered in the process of high-temperature machinery stirring the organic solvent being evaporated。
Beneficial effect
Compared with prior art, the present invention adopts phosphorous little molecule fire retardant DOPO to process montmorillonite, montmorillonite layer spacing is made to be increased to more than 3.60nm by about 1.47nm, simultaneously because phosphorous little molecule fire retardant DOPO has reactivity, can react with polymeric matrix, thus the segment contributing to polymer enters when reacting with fire retardant in the lamella of montmorillonite, thus contributing to montmorillonite dispersion in the polymeric material, improve the flame retardant effect of polymer。The present invention uses phosphorous little molecule fire retardant DOPO directly montmorillonite to be carried out intercalation processing, and the response time is short, and product can be directly appended in polymer, is the montmorillonite intercalation method of modifying of a kind of green high-efficient。Process of preparing of the present invention is simple, it is easy to operation, is especially suitable for industrialized production。
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described, but present invention scope required for protection is not limited to the scope involved by embodiment。
Embodiment 1
By 5 part 9,10-dihydro-9-oxy assorted-10-phospho hetero phenanthrene-10-oxide (DOPO) joins in the reactor with temperature regulating device, agitating device and Vltrasonic device, the temperature controlling reactor is 130 DEG C, add 1 part of calcium-base montmorillonite containing a small amount of dehydrated alcohol, after under ultrasound condition, high speed machine stirs 5 hours, mixed system is poured out to container, and constant temperature preserves 2 hours in the baking oven of 120 DEG C。Then take out and make its Temperature fall to room temperature condition。Light yellow solid is obtained after having lowered the temperature。This solid obtains the powder of DOPO/MMT composite nanometer flame retardant after process such as pulverizing, sieve。The interlamellar spacing d=3.60nm of the montmorillonite in XRD test analysis, this DOPO/MMT composite nanometer flame retardant。
Embodiment 2
By 5 part 9,10-dihydro-9-oxy assorted-10-phospho hetero phenanthrene-10-oxide (DOPO) joins in the reactor with temperature regulating device, agitating device and Vltrasonic device, the temperature controlling reactor is 140 DEG C, add 1 part of sodium-based montmorillonite containing a small amount of oxolane, after under ultrasound condition, high speed machine stirs 4 hours, mixed system is poured out to container, and constant temperature preserves 1.5 hours in the baking oven of 140 DEG C。Then take out and make its Temperature fall to room temperature condition。Light yellow solid is obtained after having lowered the temperature。This solid obtains the powder of DOPO/MMT composite nanometer flame retardant after process such as pulverizing, sieve。The interlamellar spacing d=3.62nm of the montmorillonite in XRD test analysis, this DOPO/MMT composite nanometer flame retardant。
Embodiment 3
By 5 part 9,10-dihydro-9-oxy assorted-10-phospho hetero phenanthrene-10-oxide (DOPO) joins in the reactor with temperature regulating device, agitating device and Vltrasonic device, the temperature controlling reactor is 150 DEG C, add 1 part of calcium-base montmorillonite containing a small amount of toluene, after under ultrasound condition, high speed machine stirs 3 hours, mixed system is poured out to container, and constant temperature preserves 1 hour in the baking oven of 150 DEG C。Then take out and make its Temperature fall to room temperature condition。Light yellow solid is obtained after having lowered the temperature。This solid obtains the powder of DOPO/MMT composite nanometer flame retardant after process such as pulverizing, sieve。The interlamellar spacing d=3.64nm of the montmorillonite in XRD test analysis, this DOPO/MMT composite nanometer flame retardant。
Embodiment 4
By 5 part 9,10-dihydro-9-oxy assorted-10-phospho hetero phenanthrene-10-oxide (DOPO) joins in the reactor with temperature regulating device, agitating device and Vltrasonic device, the temperature controlling reactor is 160 DEG C, add 1 part of calcium-base montmorillonite containing a small amount of dehydrated alcohol, after under ultrasound condition, high speed machine stirs 2 hours, mixed system is poured out to container, and constant temperature preserves 0.5 hour in the baking oven of 160 DEG C。Then take out and make its Temperature fall to room temperature condition。Light yellow solid is obtained after having lowered the temperature。This solid obtains the powder of DOPO/MMT composite nanometer flame retardant after process such as pulverizing, sieve。The interlamellar spacing d=3.62nm of the montmorillonite in XRD test analysis, this DOPO/MMT composite nanometer flame retardant。

Claims (2)

1. DOPO/MMT composite nanometer flame retardant and preparation method thereof, it is characterised in that phosphorous little molecule fire retardant DOPO enters in the lamella of montmorillonite and the interlamellar spacing of montmorillonite is increased, thus being more prone to dispersion when flame-retardant polymer。Wherein phosphorous little molecule fire retardant DOPO with the percentage composition of montmorillonite is:
Phosphorous little molecule fire retardant DOPO70%～90%
Montmorillonite 10%～30%
The structural formula of phosphorous little molecule fire retardant DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) used is as follows:
2. DOPO/MMT composite nanometer flame retardant and preparation method thereof, it is characterised in that its concrete preparation process is:
Phosphorous little molecule fire retardant DOPO monomer is joined in the reactor with temperature regulating device, agitating device and Vltrasonic device, the temperature controlling reactor is 120-160 DEG C, the ratio of 1 adds the montmorillonite containing a small amount of organic solvent on request again, after under ultrasound condition, high speed machine stirs 1～5 hour, mixed system is transferred in container, and constant temperature preserves 0.5-2 hour in the baking oven of 100-170 DEG C。Then take out and make its Temperature fall to room temperature condition。Light yellow solid is obtained after having lowered the temperature。This solid obtains the powder of DOPO/MMT composite nanometer flame retardant after process such as pulverizing, sieve。
In above-mentioned steps, organic solvent is: C1～C3Alcohol, acetone, acetonitrile, dichloromethane, chloroform, benzene,toluene,xylene, dioxane, oxolane or its mixture, solvent is preferably C1～C3Alcohol；The ratio of montmorillonite and solvent is: 1g:10～30ml；
In above-mentioned steps, montmorillonite is: calcium-base montmorillonite, sodium-based montmorillonite, organic modification montmonrillonite。
Above-mentioned steps is connected on reactor condensate recycling device, can collect and be recovered in the process of high speed machine stirring the organic solvent being evaporated。
CN201610115310.7A 2016-03-01 2016-03-01 A kind of DOPO/MMT composite nanometer flame retardants and preparation method thereof Active CN105694103B (en)

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
CN108102362A (en) * 2017-12-20 2018-06-01 贵州省材料产业技术研究院 A kind of halogen-free flame-retarded heat-conducting plastic alloy and preparation method thereof
CN110128703A (en) * 2019-04-29 2019-08-16 北京理工大学 A kind of tricresyl phosphate (2- chloropropyl) ester and montmorillonite nano composite flame-proof agent and preparation method thereof
CN113416365A (en) * 2021-07-12 2021-09-21 安徽瑞联节能科技股份有限公司 Preparation method of composite thermal insulation material added with graphene
CN113621177A (en) * 2021-07-20 2021-11-09 山东科技大学 Preparation method of DOPO/ZIF 67/polyaniline nano-composite flame retardant
CN115073888A (en) * 2022-06-24 2022-09-20 沈阳工业大学 Method for preparing transparent flame-retardant epoxy resin by using compound flame retardant

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JP2003268155A (en) * 2002-03-13 2003-09-25 Showa Denko Kk Filler coated with phosphorus compound, and polymeric composite material made by using it
CN103788408A (en) * 2014-01-22 2014-05-14 广州辰东化工科技有限公司 DOPO modified inorganic fire retardant and preparation method thereof
CN104774344A (en) * 2015-04-09 2015-07-15 上海工程技术大学 Preparation method of phosphorus-nitrogen-silicon synergistic phyllosilicate flame retardant

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JP2003268155A (en) * 2002-03-13 2003-09-25 Showa Denko Kk Filler coated with phosphorus compound, and polymeric composite material made by using it
CN103788408A (en) * 2014-01-22 2014-05-14 广州辰东化工科技有限公司 DOPO modified inorganic fire retardant and preparation method thereof
CN104774344A (en) * 2015-04-09 2015-07-15 上海工程技术大学 Preparation method of phosphorus-nitrogen-silicon synergistic phyllosilicate flame retardant

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108102362A (en) * 2017-12-20 2018-06-01 贵州省材料产业技术研究院 A kind of halogen-free flame-retarded heat-conducting plastic alloy and preparation method thereof
CN108102362B (en) * 2017-12-20 2020-09-22 贵州省材料产业技术研究院 Halogen-free flame-retardant heat-conducting plastic alloy and preparation method thereof
CN110128703A (en) * 2019-04-29 2019-08-16 北京理工大学 A kind of tricresyl phosphate (2- chloropropyl) ester and montmorillonite nano composite flame-proof agent and preparation method thereof
CN113416365A (en) * 2021-07-12 2021-09-21 安徽瑞联节能科技股份有限公司 Preparation method of composite thermal insulation material added with graphene
CN113621177A (en) * 2021-07-20 2021-11-09 山东科技大学 Preparation method of DOPO/ZIF 67/polyaniline nano-composite flame retardant
CN113621177B (en) * 2021-07-20 2022-06-28 山东科技大学 Preparation method of DOPO/ZIF 67/polyaniline nano-composite flame retardant
CN115073888A (en) * 2022-06-24 2022-09-20 沈阳工业大学 Method for preparing transparent flame-retardant epoxy resin by using compound flame retardant
CN115073888B (en) * 2022-06-24 2024-04-16 沈阳工业大学 Method for preparing transparent flame-retardant epoxy resin by using compound flame retardant

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