CN101463107A - Flame-retardant polymethyl acryloyl imine foam material, as well as preparation method and application thereof - Google Patents
Flame-retardant polymethyl acryloyl imine foam material, as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a flame retardant polymethacrylimide foam material as well as a preparation method and application thereof. The provided flame retardant polymethacrylimide foam material is made from the following main raw materials by weight: 1-100 parts of a propylene monomer containing carboxy or ester groups, 1-100 parts of a propylene monomer containing nitrile groups, 1-100 parts of a Si-P synergistic flame retardant, 0-25 parts of a nucleating agent, 0-25 parts of a foaming agent and 0-25 parts of an initiator. In the method, the Si-P synergistic flame retardant, (methyl) acrylic acid or acrylate monomers and (methyl) acrylonitrile monomers which have specific chemical structures are subject to free radical copolymerization to form a foam precursor copolymer, and flame retardant, high-strength and high-modulus and high-heat resistant polyacrylamide foam materials are formed by a heat foaming procedure; the foam materials can be widely applied to the manufacture of foam sandwich structural members used in space equipment, aircraft equipment, space vehicle and naval vessel, high speed trains and wind power generation equipment.
Description
Technical field
The present invention relates to a kind of flame-retardant polymethyl acryloyl imine foam material and preparation method thereof and application.
Background technology
Polymethacrylimide foam (DE-C2726260) has the incompressible strength and stiffness higher than other polymer foams, more excellent high temperature resistant and wet-hot aging performance, and better high temperature creep-resisting performance and dimensional stability etc., resistance toheat that it is outstanding and high temperature excellent creep-resistant property down make this class A foam A material can bear carbon fiber/epoxy, the high temperature curing process condition of polymer matrix composites such as carbon fiber/span, can realize the disposable co-curing of foam core and prepreg, manufacturing (the DE-C2822885 that is widely used in matrix material foamed sandwich structure spare, DE-A3304882, US Pat.4316934).In addition, because polymethacrylimide foam adopts the manufacturing of solid foamed technology, thus the rate of closed hole height of foam materials, even aperture distribution, unanimity, rate of moisture absorption is low.Above-mentioned performance characteristics makes it be with a wide range of applications in many technical fields such as space flight, aviation, naval vessel, bullet train, wind-power electricity generations.
Polymethacrylimide foam has just been realized commercialization in the sixties in 20th century.In recent years, along with the increase of commercial market demand and the raising of global environmental consciousness, the flame retardant resistance of improving polymethacrylimide foam more and more receives publicity.Making macromolecular material have flame retardancy, self-extinguishing and smoke elimination by adding fire retardant, is the most general method in the present flame-retarded technology.Fire retardant can divide several big classes such as halogen containing flame-retardant, inorganic combustion inhibitor, phosphorus flame retardant, nitrogen flame retardant and silicon-series five-retardant by contained element kind.For a long time, halogen containing flame-retardant is with its flame retarding efficiency height, few, the cheap characteristics of consumption and obtain to use widely.Yet; enhancing along with people's environmental protection consciousness; the secondary pollution that chloride and brominated flame-retardant causes (smog, poison gas distributes and therefore problems such as corrosion thus during burning) problem is subjected to people and pays close attention to greatly, and seeking chloride brominated flame-retardant becomes one and be badly in need of the technical barrier that solves.
Similar to other organic polymer material, polymethacrylimide foam material itself also belongs to inflammable, combustible macromolecular material, heat release rate is big during burning, the calorific value height, flame propagation speed is difficult for extinguishing, and also can produce thick smoke and toxic gas, cause the person and environment damage, had a strong impact on the practical application of polymethacrylimide foam material.Therefore, developing the polymethacrylimide foam material with bromine-free flame-retardant has great importance.German Patent (DE-PS2047096) discloses a kind of preparation method of flame-retardant polymethyl acryloyl imine foam material.To can obviously improve its flame retardant properties in the adding polymethacrylimide foam materials such as phosphoric acid and dibromopropyl phosphoric acid salt.But the wetting ability that the phosphoric acid fire retardant is stronger causes the water-absorbent of foam materials to strengthen, and causes the obvious deterioration of mechanical property of material; In addition, the existence of a large amount of phosphoric acid based flame retardants makes the foam precursor resin board be easy to generate heterogeneous defective in polymerization process.(US Pat.4576971 EP146892) adopts Organophosphonate flame-retardant system and add the fire retardant of metallic salt as polymethacrylimide foam to Baumgartner etc., has good flame-retardant effect.But, therefore the mechanical property of foam materials is brought negative impact because this composite flame-retardant agent needs bigger addition.
In recent years, with 9, the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide compound (DOPO) pays close attention to greatly for the fire retardant of intermediate preparation is subjected to people, and the structural formula of DOPO is shown in formula III.The rigidity biphenyl structural has higher heat resistance in the chemical structure of DOPO, aromatic ring makes phosphoric have stable chemical structure with the covalent linkage effect that contains phosphine groups, conjugative effect between the two can be disperseed the cloud density of phosphorus atom simultaneously, has strengthened the heat-resistant stability and the moisture resistance properties of material; Characteristics such as DOPO and derivative thereof have Halogen, low toxicity, do not move, flame retardant properties is lasting can be used as addition type or reactive flame retardant to be incorporated in the macromolecular material, have good flame retardant effect.In addition, the active phosphine hydrogen bond in the DOPO chemical structure can high conversion passes through addition reaction, produces the phosphonium flame retardant of multiple special chemical structure.
(formula III)
J adds (CN1423678 Dow) such as grace is applied to DOPO and benzoquinone Resins, epoxy/glass cloth laminated board through the product of addition reaction fire retardant, not only make Resins, epoxy have good building-up properties, and making veneer sheet have good flame retardant property, its temperature classification reaches UL94V-0.C.S.Wang etc. (J.Polym.Sci.A Polym.Chem, Vol.37,3903-3909,1999) disclose a kind of preparation method based on the agent of DOPO ethoxyline resin antiflaming.With DOPO and dihydroxyphenyl propane or o-cresol formaldehyde epoxy resin reaction formation phosphorated Resins, epoxy, this resin has the flame retardant rating of UL94V-0 after DDS solidifies.
To the fire-retardant effect of material, can strengthen flame retardant effect when phosphoric and element silicon coexistence, reduce the fire retardant consumption, reduce the negative impact of fire retardant material mechanical performance with cooperative flame retardant.(CN1922252) such as KM armies discloses the preparation method of a kind of silicon-phosphorus synergistic fire retardant.With polysiloxane and phosphate compounds mixture fire retardant, has good flame-retardant effect as Resins, epoxy/glass cloth laminated board.(US20050245670 JP2000327897) discloses the preparation method of a kind of polycarbonate with silicon-phosphorus synergistic fire retardant to SATO ICHIRO etc.With the mixture of polysiloxane and phosphine nitrile or phosphate compounds fire retardant, have good flame retardant property (UL94V-0) and mechanical property as polycarbonate.But, with DOPO and contain silicon derivative and be used for the fire-retardant of polymethacrylimide foam material, do not appear in the newspapers as yet both at home and abroad.Therefore, silicon-phosphorus synergistic fire retardant is used to gather the fire-retardant of (methyl) acrylimide (PMI) foam materials, has important scientific meaning and great application value.
Summary of the invention
The purpose of this invention is to provide a kind of flame-retardant polymethyl acryloyl imine foam material and preparation method thereof and application.
The method for preparing flame-retardant polymethyl acryloyl imine foam material provided by the invention comprises the steps:
1) propylene class monomer, silicon-phosphorus synergistic fire retardant, linking agent, bismaleimide resin toughener, nucleator, whipping agent, releasing agent and the initiator of propylene class monomer, nitrile group-containing that will contain carboxyl or ester group forms homogeneous phase solution in the room temperature mixing;
In the formula I general structure, R
1, R
2, R
3And R
4All be selected from methyl, ethyl, propyl group, methoxyl group, oxyethyl group, propoxy-, phenyl, aminomethyl phenyl, 3,5-dimethylphenyl, trifluoromethyl, two (trifluoromethyl) phenyl, benzyl, benzyl ethyl and the phenoxy group any one or a few;
N=1-10; Preferred n=1-4;
R
5With R
6All be selected from methylene radical, ethylidene, propylidene and the butylidene any one or a few;
R
7-R
14All be selected from hydrogen atom, methyl, ethyl, propyl group, nitro, amino, hydroxyl, carboxyl, methoxyl group, oxyethyl group, propoxy-, phenyl, aminomethyl phenyl, 3,5-dimethylphenyl, trifluoromethyl, two (trifluoromethyl) phenyl, benzyl, benzyl ethyl and the phenoxy group any one or a few;
2) homogeneous phase solution was carried out in 40～150 ℃ polyreaction 12-200 hour, form foam precursor copolymer resin plate;
3) foam precursor copolymer resin plate is foamed, blowing temperature is 180-250 ℃, and foamed time is 1-10 hour, obtains flame-retardant polymethyl acryloyl imine foam material provided by the invention.
In this method, the propylene class monomer that contains carboxyl or ester group be selected from vinylformic acid, methyl acrylate, ethyl propenoate, vinylformic acid n-propyl, vinylformic acid isopropyl ester, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, methacrylic acid, methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, methacrylic acid isopropyl ester, n-BMA, Propenoic acid, 2-methyl, isobutyl ester and the methacrylic tert-butyl acrylate any one or several with arbitrary proportion blended mixture arbitrarily;
The propylene class monomer of nitrile group-containing is vinyl cyanide and/or methacrylonitrile;
Linking agent be in allyl methacrylate, vinylformic acid allyl ester, methacrylic acid alkene 2-methacrylic ester or the vinylformic acid 2-methacrylic ester any one or arbitrarily several with arbitrary proportion blended mixture;
The bismaleimide resin toughener be in the bimaleimide resin shown in the formula II general structure any one or its with arbitrary proportion blended mixture;
(formula II)
In the formula II general structure, R is selected from any one in the following radicals A-group L;
Nucleator is selected from any one or a few mixture with arbitrary proportion in carboxamide, methane amide, Methacrylamide, N-methylformamide or the dinethylformamide;
Whipping agent is selected from any one or a few mixture with arbitrary proportion in ethanol, propyl alcohol, Virahol, water, butanols, the trimethyl carbinol, amylalcohol or the primary isoamyl alcohol;
Releasing agent is selected from any one or a few mixture with arbitrary proportion in methyl-silicone oil, phenyl silicone oil, INT-PS125, INT-1846 or the triphenyl phosphite;
Initiator is selected from any one or a few mixture with arbitrary proportion in dibenzoyl peroxide, di-isopropyl peroxydicarbonate, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), the peroxidation trimethylacetic acid tert-butyl ester, di-tert-butyl peroxide, tert-butyl hydroperoxide 2-ethylhexanoate or the tert butyl peroxy benzoate.
The weight part of above-mentioned each raw material is as follows:
The propylene class monomer 1-100 that contains carboxyl or ester group;
The propylene class monomer 1-100 of nitrile group-containing;
Silicon-phosphorus synergistic fire retardant 1-100;
Nucleator 0-25, but do not comprise 0;
Whipping agent 0-25, but do not comprise 0;
Initiator 0-25, but do not comprise 0;
Linking agent 0-25;
Bismaleimide resin toughener 0-25;
Releasing agent 0-25;
Shown in being preferably as follows of above-mentioned each parts by weight of raw materials:
The propylene class monomer 20-70 that contains carboxyl or ester group, preferred 40-60;
The propylene class monomer 20-70 of nitrile group-containing, preferred 40-60;
Silicon-phosphorus synergistic fire retardant 10-60, preferred 15-50
Linking agent 0.3-15, preferred 3-5;
Bismaleimide resin toughener 0.5-20, preferred 1.5-20;
Nucleator 0.5-15, preferred 1.5-20;
Whipping agent 0.5-15, preferred 3-15;
Releasing agent 0.5-10, preferred 0.5-3.5;
Initiator 0.5-10, preferred 1-10.
In addition, above-mentioned silicon-phosphorus synergistic fire retardant is to be prepared according to the method that following document provides: Ding Jiapei, " design, preparation and the performance of bromine-free flame-retardant epoxy packages material ", Postgraduate School, Chinese Academy of Sciences's doctorate paper, 2008.
Polymethacrylimide foam provided by the invention has the chemical structure shown in the formula V structural formula.
(formula V)
The present invention will have the silicon-phosphorus synergistic fire retardant of particular chemical structure, (methyl) vinylformic acid or esters monomer, (methyl) vinyl cyanide monomer forms foam precursor multipolymer by free radical copolymerization, pass through the flame-retardant polymethyl acryloyl imine foam that the heat foamable process forms then, not only has good incompressible intensity, modulus and resistance toheat, and has an outstanding flame retardant properties, can make up with carbon (glass/quartz or aramid fiber) fiber/Resins, epoxy (cyanate ester resin or bismaleimide resin) prepreg, directly form polymer matrix composites/foam/polymer matrix composites sandwich structure piece through the disposable co-curing of vacuum hotpressing jar.This structural part can be widely used in the manufacturing of the matrix material foamed sandwich structure spare of aircraft, launch vehicle, aviation, naval vessel, bullet train, wind power plant.
Embodiment
The invention will be further described below in conjunction with specific embodiment, but the present invention is not limited to following examples.
Embodiment 1,
With 50 parts of methacrylic acids, 50 parts of methacrylonitriles, 10 parts of Methacrylamides, 10 parts of R
1, R
2, R
3, R
4Base is a methyl, R
5With R
6Be methylene radical, R
7-R
14Be the silicon-phosphorus synergistic fire retardant of hydrogen atom structure, 5 parts of allyl methacrylate(AMA)s, 10 parts of methane amides, 5 parts of dibenzoyl peroxide and 5 parts of peroxidation trimethylacetic acid tert-butyl esters, 15 parts of Virahols, 2.5 parts of INT-PS125; add successively in three mouthfuls of glass flask of 3000mL; under nitrogen protection; stirring at room 2 hours forms homogeneous phase solution.Above-mentioned homogeneous phase solution is transferred in the enclosed system that is formed by 2 sheet glass and seal frame polyreaction under following condition: 50 ℃/24h, 60 ℃～90 ℃/58h, 130 ℃/1h, obtain foam precursor copolymer resin plate.With the above-mentioned foam precursor copolymer resin plate that obtains, under 185 ℃/1h, foam, obtain flame-retardant polymethyl acryloyl imine foam board blank.The above-mentioned flame-retardant polymethyl acryloyl imine foam board blank that obtains through mechanical workout, is obtained the flame retardant type polymethacrylimide foam material, and its density is 90kg/m
3, compressive strength is 1.7MPa, flame retardant properties is by UL94-HB (GB2408-80) test.
Embodiment 2,
With 55 parts of methacrylic acids, 45 parts of methacrylonitriles, 15 parts of R
1, R
2, R
3Base is a methyl, R
4Be phenyl, R
5With R
6Be methylene radical, R
7-R
14For the silicon-phosphorus synergistic fire retardant of hydrogen atom structure, 5 parts-R-base are the bimaleimide resin of C-structure, 1.5 parts of methane amides, 3 parts of peroxidation trimethylacetic acid tert-butyl esters, 2 parts of tert butyl peroxy benzoates, 1 part of tert-butyl hydroperoxide 2-ethylhexanoate, 5 parts of Virahols, 3 parts of INT-PS125; add successively in three mouthfuls of glass flask of 3000mL; under nitrogen protection; stirring at room 2 hours forms homogeneous phase solution.
Above-mentioned homogeneous phase solution is transferred in the enclosed system that is formed by 2 sheet glass and seal frame polyreaction under following condition: 50 ℃/24h, 60 ℃～90 ℃/96h, 100 ℃～120 ℃/3h, obtain flame retardant type foam precursor copolymer resin sheet material.
With the above-mentioned flame retardant type foam precursor copolymer resin sheet material that obtains, under 190 ℃/1h, foam, obtain flame retardant type polymethacrylimide foam sheet material blank.
The above-mentioned flame retardant type polymethacrylimide foam sheet material blank that obtains through mechanical workout, is obtained the flame retardant type polymethacrylimide foam material, and its density is 75kg/m
3, compressive strength is 1.5MPa, tests by UL94-HB (GB2408-80).
The density that this embodiment is prepared is 75kg/m
3, thickness is that flame retardant type KHPM-S foam board and the moulding of C/E covering co-curing of 30mm prepares the KHPM-S foam core filled composite material.Covering is UT500 carbon fiber/601 Resins, epoxy, shop layer angle: C
Cloth/ 0
2/ C
Cloth/ 0
2/ C
Cloth, thickness 1.5mm.The KHPM-S foam board can with the covering co-curing, have good mechanical performance, heat setting type performance and machining property simultaneously.The concora crush intensity of this KHPM-S foam core filled composite material is 1.6MPa, and by UL94-HB (GB2408-80) test, satisfied space flight, aviation, space vehicle and naval vessel, bullet train, wind power plant demand to the foamed sandwich structure material property.
Comparative Examples 1,
With 55 parts of methacrylic acids, 45 parts of methacrylonitriles, 5 parts-R-base is the bimaleimide resin of C-structure, 1.5 parts of methane amides, 3 parts of peroxidation trimethylacetic acid tert-butyl esters, 2 parts of tert butyl peroxy benzoates, 1 part of tert-butyl hydroperoxide 2-ethylhexanoate, 5 parts of Virahols, 3 parts of INT-PS125; add successively in three mouthfuls of glass flask of 3000mL; under nitrogen protection; stirring at room 2 hours forms homogeneous phase solution.
Above-mentioned homogeneous phase solution is transferred in the enclosed system that is formed by 2 sheet glass and seal frame polyreaction under following condition: 50 ℃/24h, 60 ℃～90 ℃/96h, 100 ℃～120 ℃/3h, obtain flame retardant type foam precursor copolymer resin sheet material.
With the above-mentioned flame retardant type foam precursor copolymer resin sheet material that obtains, under 190 ℃/1h, foam, obtain flame retardant type polymethacrylimide foam sheet material blank.
The above-mentioned flame retardant type polymethacrylimide foam sheet material blank that obtains through mechanical workout, is obtained the flame retardant type polymethacrylimide foam material, and its density is 90kg/m
3, compressive strength is 1.7MPa, can not pass through UL94-HB (GB2408-80) test.
Embodiment 3,
With 25 parts of methacrylic acids and 25 parts of vinylformic acid, 30 parts of methacrylonitriles and 20 parts of vinyl cyanide, 20 parts of R
1, R
2, R
3Base is an ethyl, R
4Be phenyl, R
5With R
6Be methylene radical, R
7-R
14For being L and 10 parts-R-base, the silicon-phosphorus synergistic fire retardant of hydrogen atom structure, 10 parts-R-base be the bimaleimide resin of A structure, 5 parts of allyl acrylates, 5 parts of N-methylformamide, 3 parts of Diisopropyl azodicarboxylates and 5 parts of tert butyl peroxy benzoates, 10 parts of trimethyl carbinols, 0.55 portion of triphenyl phosphite and 1.5 parts of INT-PS125; add successively in three mouthfuls of glass flask of 3000mL; under nitrogen protection; stirring at room 2 hours forms homogeneous phase solution.
Above-mentioned homogeneous phase solution is transferred in the enclosed system that is formed by 2 sheet glass and seal frame polyreaction under following condition: 50 ℃/24h, 60 ℃～90 ℃/58h, 100 ℃～120 ℃/10h, obtain flame retardant type foam precursor copolymer resin sheet material.
With the above-mentioned flame retardant type foam precursor copolymer resin sheet material that obtains, under 200 ℃/2h, foam, obtain flame retardant type polymethacrylimide foam sheet material blank.
The above-mentioned flame retardant type polymethacrylimide foam sheet material blank that obtains through mechanical workout, is obtained the flame retardant type polymethacrylimide foam material, and its density is 60kg/m
3, compressive strength is 0.7MPa, tests by UL94-HB (GB2408-80).
Comparative Examples 2,
Being L and 10 parts-R-base with 25 parts of methacrylic acids and 25 parts of vinylformic acid, 30 parts of methacrylonitriles and 20 parts of vinyl cyanide, 5 parts of vinylbenzene, 10 parts-R-base is the bimaleimide resin of A structure, 5 parts of allyl acrylates, 5 parts of N-methylformamide, 3 parts of Diisopropyl azodicarboxylates and 5 parts of tert butyl peroxy benzoates, 10 parts of trimethyl carbinols, 0.55 portion of triphenyl phosphite and 1.5 parts of INT-PS125; add successively in three mouthfuls of glass flask of 3000mL; under nitrogen protection; stirring at room 2 hours forms homogeneous phase solution.
Above-mentioned homogeneous phase solution is transferred in the enclosed system that is formed by 2 sheet glass and seal frame polyreaction under following condition: 50 ℃/24h, 60 ℃～90 ℃/58h, 100 ℃～120 ℃/10h, obtain flame retardant type foam precursor copolymer resin sheet material.
With the above-mentioned flame retardant type foam precursor copolymer resin sheet material that obtains, under 200 ℃/2h, foam, obtain flame retardant type polymethacrylimide foam sheet material blank.
The above-mentioned flame retardant type polymethacrylimide foam sheet material blank that obtains through mechanical workout, is obtained the flame retardant type polymethacrylimide foam material, and its density is 80kg/m
3, compressive strength is 1.5MPa, can not pass through UL94-HB (GB2408-80) test.
Embodiment 2,3 relatively can find with Comparative Examples 1,2: the adding of fire retardant, the density of material have following trend, and compressive strength also descends thereupon to some extent, but flame retardant properties is improved, all can pass through UL94-HB (GB2408-80) test; Comparative Examples 2 is relatively found with embodiment 2, behind the interpolation fire retardant, under the close situation of density, compressive strength does not descend, illustrate to add silicon disclosed by the invention-phosphorus synergistic fire retardant, can under the mechanical situation of mechanics that keeps material, improve the flame retardant properties of material.Advantage of the present invention that Here it is.
Embodiment 4,
With 40 parts of methacrylic acids, 40 parts of methacrylonitriles and 20 parts of vinyl cyanide, 30 parts of R
1, R
3Base is an ethyl, R
2, R
4Be methyl, R
5With R
6Be methylene radical, R
7-R
14For being A and 5 parts-R-base, the silicon-phosphorus synergistic fire retardant of hydrogen atom structure, 5 parts-R-base be the bimaleimide resin of F structure, 3 parts of allyl methacrylate(AMA)s, 5 parts of N-methylformamide, 5 parts of peroxidation trimethylacetic acid tert-butyl esters, 3 parts of tert butyl peroxy benzoates, 2 parts of tert-butyl hydroperoxide 2-ethylhexanoate, 5 parts of trimethyl carbinols and 5 parts of Virahols, 3 parts of INT-1846N and 0.5 part of INT-PS125; in three mouthfuls of glass flask of inferior adding 3000mL; under nitrogen protection; stirring at room 2 hours forms homogeneous phase solution.
Above-mentioned homogeneous phase solution is transferred in the enclosed system that is formed by 2 sheet glass and seal frame polyreaction under following condition: 50 ℃/24h, 60 ℃～90 ℃/58h, 100 ℃/1h, obtain foam precursor copolymer resin sheet material.
With the above-mentioned foam precursor copolymer resin sheet material that obtains, under 200 ℃/1h, foam, obtain flame retardant type polymethacrylimide foam sheet material blank.
The above-mentioned flame retardant type polymethacrylimide foam sheet material blank that obtains through mechanical workout, is obtained the flame retardant type polymethacrylimide foam material, and its density is 60kg/m
3, compressive strength is 0.8MPa, tests by UL94-HB (GB2408-80).
Embodiment 5,
With 60 parts of methacrylic acids, 40 parts of methacrylonitriles, 30 parts of R
1, R
3Base is an ethyl, R
2, R
4Be methyl, R
5With R
6Be methylene radical, R
7-R
14Silicon-phosphorus synergistic fire retardant and 20 parts of R for the hydrogen atom structure
1, R
2, R
3Base is a methyl, R
4Be phenyl, R
5With R
6Be methylene radical, R
7-R
14Use for the silicon of hydrogen atom structure-phosphorus synergistic fire retardant mixes, 5 parts-R-base is the bimaleimide resin of F structure, 3 parts of N-methylformamide, 5 parts of peroxidation trimethylacetic acid tert-butyl esters, 3 parts of tert butyl peroxy benzoates, 1 part of tert-butyl hydroperoxide 2-ethylhexanoate, 3 parts of trimethyl carbinols and 3 parts of Virahols, 0.8 part of INT-PS125 as J and 5 parts-R-base; add successively in three mouthfuls of glass flask of 3000mL; under nitrogen protection; stirring at room 2 hours forms homogeneous phase solution.
Above-mentioned homogeneous phase solution is transferred in the enclosed system that is formed by 2 sheet glass and seal frame polyreaction under following condition: 50 ℃/24h, 60 ℃～90 ℃/72h, 100 ℃～130 ℃/10h, obtain flame retardant type foam precursor copolymer resin sheet material.
With the above-mentioned flame retardant type foam precursor copolymer resin sheet material that obtains, under 205 ℃/1h, foam, obtain flame retardant type polymethacrylimide foam sheet material blank.
The above-mentioned flame retardant type polymethacrylimide foam sheet material blank that obtains through mechanical workout, is obtained the flame retardant type polymethacrylimide foam material, and its density is 40kg/m
3, compressive strength is 0.4MPa, tests by UL94-HB (GB2408-80).
Embodiment 6,
With 45 parts of methacrylic methyl esters, 50 parts of methacrylonitriles, 50 parts of R
1, R
2, R
3, R
4Base is a methyl, R
5With R
6Be methylene radical, R
7-R
14For the silicon-phosphorus synergistic fire retardant of hydrogen atom structure, 0.5 part-R-base add in three mouthfuls of glass flask of 3000mL successively for the bimaleimide resin of D structure, 5 parts of methane amides, 3 parts of peroxidation trimethylacetic acid tert-butyl esters, 6 parts of tert butyl peroxy benzoates, 1 part of tert-butyl hydroperoxide 2-ethylhexanoate, 3 parts of trimethyl carbinols, 3 parts of Virahols, 3 parts of INT-1846N; under nitrogen protection; stirring at room 2 hours forms homogeneous phase solution.
Above-mentioned homogeneous phase solution is transferred in the enclosed system that is formed by 2 sheet glass and seal frame polyreaction under following condition: 50 ℃/24h, 60 ℃～90 ℃/72h, 100 ℃～130 ℃/5h, obtain flame retardant type foam precursor copolymer resin sheet material.
With the above-mentioned flame retardant type foam precursor copolymer resin sheet material that obtains, under 220 ℃/1h, foam, obtain flame retardant type polymethacrylimide foam sheet material blank.
The above-mentioned flame retardant type polymethacrylimide foam sheet material blank that obtains through mechanical workout, is obtained flame retardant type methacrylic acid imide foam material, and its density is 50kg/m
3, compressive strength is 0.5MPa, tests by UL94-HB (GB2408-80).
Claims (9)
1, a kind of flame-retardant polymethyl acryloyl imine foam material is to be made by the raw material of following weight part:
The propylene class monomer 1-100 that contains carboxyl or ester group;
The propylene class monomer 1-100 of nitrile group-containing;
Silicon-phosphorus synergistic fire retardant 1-100;
Nucleator 0-25, but do not comprise 0;
Whipping agent 0-25, but do not comprise 0;
Initiator 0-25, but do not comprise 0;
Linking agent 0-25;
Bismaleimide resin toughener 0-25;
Releasing agent 0-25;
(formula I)
In the described formula I general structure, R
1, R
2, R
3And R
4All be selected from methyl, ethyl, propyl group, methoxyl group, oxyethyl group, propoxy-, phenyl, aminomethyl phenyl, 3,5-dimethylphenyl, trifluoromethyl, two (trifluoromethyl) phenyl, benzyl, benzyl ethyl and the phenoxy group any one or a few;
n＝1-10；
R
5With R
6All be selected from methylene radical, ethylidene, propylidene and the butylidene any one or a few;
R
7-R
14All be selected from hydrogen atom, methyl, ethyl, propyl group, nitro, amino, hydroxyl, carboxyl, methoxyl group, oxyethyl group, propoxy-, phenyl, aminomethyl phenyl, 3,5-dimethylphenyl, trifluoromethyl, two (trifluoromethyl) phenyl, benzyl, benzyl ethyl and the phenoxy group any one or a few.
2, material according to claim 1 is characterized in that: in the described formula I general structure, and n=1-4;
The described propylene class monomer that contains carboxyl or ester group is selected from vinylformic acid, methyl acrylate, ethyl propenoate, the vinylformic acid n-propyl, the vinylformic acid isopropyl ester, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, methacrylic acid, methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, the methacrylic acid isopropyl ester, n-BMA, in Propenoic acid, 2-methyl, isobutyl ester and the methacrylic tert-butyl acrylate any one or several with arbitrary proportion blended mixture arbitrarily;
The propylene class monomer of described nitrile group-containing is vinyl cyanide and/or methacrylonitrile;
Described linking agent be in allyl methacrylate, vinylformic acid allyl ester, methacrylic acid alkene 2-methacrylic ester or the vinylformic acid 2-methacrylic ester any one or arbitrarily several with arbitrary proportion blended mixture;
Described bismaleimide resin toughener be in the bimaleimide resin shown in the formula II general structure any one or its with arbitrary proportion blended mixture;
(formula II)
In the described formula II general structure, R is selected from any one in the following radicals A-group L;
Described nucleator is selected from any one or a few mixture with arbitrary proportion in carboxamide, methane amide, Methacrylamide, N-methylformamide or the dinethylformamide;
Described whipping agent is selected from any one or a few mixture with arbitrary proportion in ethanol, propyl alcohol, Virahol, water, butanols, the trimethyl carbinol, amylalcohol or the primary isoamyl alcohol;
Described releasing agent is selected from any one or a few mixture with arbitrary proportion in methyl-silicone oil, phenyl silicone oil, INT-PS125, INT-1846 or the triphenyl phosphite;
Described initiator is selected from any one or a few mixture with arbitrary proportion in dibenzoyl peroxide, di-isopropyl peroxydicarbonate, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), the peroxidation trimethylacetic acid tert-butyl ester, di-tert-butyl peroxide, tert-butyl hydroperoxide 2-ethylhexanoate or the tert butyl peroxy benzoate.
3, material according to claim 1 is characterized in that: the weight part of described each raw material is as follows:
The propylene class monomer 20-70 that contains carboxyl or ester group, preferred 40-60;
The propylene class monomer 20-70 of nitrile group-containing, preferred 40-60;
Silicon-phosphorus synergistic fire retardant 10-60, preferred 15-50
Linking agent 0.3-15, preferred 3-5;
Bismaleimide resin toughener 0.5-20, preferred 1.5-20;
Nucleator 0.5-15, preferred 1.5-20;
Whipping agent 0.5-15, preferred 3-15;
Releasing agent 0.5-10, preferred 0.5-3.5;
Initiator 0.5-10, preferred 1-10.
4, a kind of method for preparing the described flame-retardant polymethyl acryloyl imine foam material of claim 1 comprises the steps:
1) will contain the propylene class monomer of carboxyl or ester group, propylene class monomer, silicon-phosphorus synergistic fire retardant, linking agent, bismaleimide resin toughener, nucleator, whipping agent, releasing agent and the initiator mixing of nitrile group-containing, form homogeneous phase solution;
Wherein, the general structure of described silicon-phosphorus synergistic fire retardant is suc as formula shown in the I,
In the described formula I general structure, R
1, R
2, R
3And R
4All be selected from methyl, ethyl, propyl group, methoxyl group, oxyethyl group, propoxy-, phenyl, aminomethyl phenyl, 3,5-dimethylphenyl, trifluoromethyl, two (trifluoromethyl) phenyl, benzyl, benzyl ethyl and the phenoxy group any one or a few;
n＝1-10；
R
5With R
6All be selected from methylene radical, ethylidene, propylidene and the butylidene any one or a few;
R
7-R
14All be selected from hydrogen atom, methyl, ethyl, propyl group, nitro, amino, hydroxyl, carboxyl, methoxyl group, oxyethyl group, propoxy-, phenyl, aminomethyl phenyl, 3,5-dimethylphenyl, trifluoromethyl, two (trifluoromethyl) phenyl, benzyl, benzyl ethyl and the phenoxy group any one or a few;
2) described homogeneous phase solution is carried out polyreaction in 40～150 ℃, form foam precursor copolymer resin plate;
3) described foam precursor copolymer resin plate is foamed, obtain described flame-retardant polymethyl acryloyl imine foam material.
5, method according to claim 4 is characterized in that: in the described formula I general structure, and n=1-4;
The described propylene class monomer that contains carboxyl or ester group is selected from vinylformic acid, methyl acrylate, ethyl propenoate, the vinylformic acid n-propyl, the vinylformic acid isopropyl ester, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, methacrylic acid, methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, the methacrylic acid isopropyl ester, n-BMA, in Propenoic acid, 2-methyl, isobutyl ester and the methacrylic tert-butyl acrylate any one or several with arbitrary proportion blended mixture arbitrarily;
The propylene class monomer of described nitrile group-containing is vinyl cyanide and/or methacrylonitrile;
Described linking agent be in allyl methacrylate, vinylformic acid allyl ester, methacrylic acid alkene 2-methacrylic ester or the vinylformic acid 2-methacrylic ester any one or arbitrarily several with arbitrary proportion blended mixture;
Described bismaleimide resin toughener be in the bimaleimide resin shown in the formula II general structure any one or its with arbitrary proportion blended mixture;
(formula II)
In the described formula II general structure, R is selected from any one in the following radicals A-group L;
Described nucleator is selected from any one or a few mixture with arbitrary proportion in carboxamide, methane amide, Methacrylamide, N-methylformamide or the dinethylformamide;
Described whipping agent is selected from any one or a few mixture with arbitrary proportion in ethanol, propyl alcohol, Virahol, water, butanols, the trimethyl carbinol, amylalcohol or the primary isoamyl alcohol;
Described releasing agent is selected from any one or a few mixture with arbitrary proportion in methyl-silicone oil, phenyl silicone oil, INT-PS125, INT-1846 or the triphenyl phosphite;
Described initiator is selected from any one or a few mixture with arbitrary proportion in dibenzoyl peroxide, di-isopropyl peroxydicarbonate, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), the peroxidation trimethylacetic acid tert-butyl ester, di-tert-butyl peroxide, tert-butyl hydroperoxide 2-ethylhexanoate or the tert butyl peroxy benzoate.
6, according to claim 4 or 5 described methods, it is characterized in that: the weight part of described each raw material is as follows:
The propylene class monomer 1-100 that contains carboxyl or ester group;
The propylene class monomer 1-100 of nitrile group-containing;
Silicon-phosphorus synergistic fire retardant 1-100;
Nucleator 0-25, but do not comprise 0;
Whipping agent 0-25, but do not comprise 0;
Initiator 0-25, but do not comprise 0;
Linking agent 0-25;
Bismaleimide resin toughener 0-25;
Releasing agent 0-25;
7, method according to claim 6 is characterized in that: the weight part of described each raw material is as follows:
The propylene class monomer 20-70 that contains carboxyl or ester group, preferred 40-60;
The propylene class monomer 20-70 of nitrile group-containing, preferred 40-60;
Silicon-phosphorus synergistic fire retardant 10-60, preferred 15-50
Linking agent 0.3-15, preferred 3-5;
Bismaleimide resin toughener 0.5-20, preferred 1.5-20;
Nucleator 0.5-15, preferred 1.5-20;
Whipping agent 0.5-15, preferred 3-15;
Releasing agent 0.5-10, preferred 0.5-3.5;
Initiator 0.5-10, preferred 1-10.
8, according to the arbitrary described method of claim 4-7, it is characterized in that: in the described step 1), the mixing temperature is a room temperature;
Described step 2) in, the time of polyreaction is 12-200 hour;
In the described step 3), blowing temperature is 180-250 ℃, and foamed time is 1-10 hour, preferred 1-5 hour.
9, the application of the described flame-retardant polymethyl acryloyl imine foam material of claim 1 in the matrix material foamed sandwich structure spare of preparation aircraft, launch vehicle, aviation, naval vessel, bullet train or wind power plant.
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| CNA2009100771056A CN101463107A (en) | 2009-01-15 | 2009-01-15 | Flame-retardant polymethyl acryloyl imine foam material, as well as preparation method and application thereof |
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|---|---|---|---|
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| CN104017127A (en) * | 2014-06-20 | 2014-09-03 | 江苏兆鋆新材料股份有限公司 | High temperature resistant halogen-free flame retardant adding type AN (acrylic nitrile)/MAA (methyl acrylic acid) copolymer foam and preparation method thereof |
| CN104086695A (en) * | 2014-06-23 | 2014-10-08 | 浙江中科恒泰新材料科技有限公司 | Flame-retardant poly(methyl)acrylimide foamed plastic with high strength and heat resistance |
| JP2015193628A (en) * | 2014-03-28 | 2015-11-05 | 新日鉄住金化学株式会社 | Bismaleimide compound, composition containing the same, and cured product |
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| JP2015193628A (en) * | 2014-03-28 | 2015-11-05 | 新日鉄住金化学株式会社 | Bismaleimide compound, composition containing the same, and cured product |
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| CN104017127B (en) * | 2014-06-20 | 2016-08-17 | 江苏兆鋆新材料股份有限公司 | A kind of high temperature resistant halogen-free flame-retardant resin addition type AN/MAA copolymer foam and preparation method thereof |
| CN104086695A (en) * | 2014-06-23 | 2014-10-08 | 浙江中科恒泰新材料科技有限公司 | Flame-retardant poly(methyl)acrylimide foamed plastic with high strength and heat resistance |
| CN106928457A (en) * | 2017-03-16 | 2017-07-07 | 四川众业长科技有限公司 | A kind of Thermocurable polyimide foam board and preparation method thereof |
| CN112062536A (en) * | 2020-09-04 | 2020-12-11 | 上海晶柏新材料科技有限公司 | Fireproof material for preparing fireproof section and method for preparing fireproof section |
| CN113831442A (en) * | 2021-09-24 | 2021-12-24 | 湖南兆恒材料科技有限公司 | High-cost-performance flame-retardant polymethacrylimide foam and preparation method thereof |
| CN118186782A (en) * | 2024-05-14 | 2024-06-14 | 广州市脉田新材料科技有限公司 | Organic silicon flame-retardant finishing agent and preparation process and application thereof |
| CN118186782B (en) * | 2024-05-14 | 2024-07-23 | 广州市脉田新材料科技有限公司 | Organic silicon flame-retardant finishing agent and preparation process and application thereof |
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