CN101787290B - Method for preparing polyimide intercalated grafted magnesium hydroxide flame retardant - Google Patents
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Abstract
The invention relates to a method for preparing polyimide intercalated grafted magnesium hydroxide flame retardant. The method comprises: mixing binary primary amine, amino end-group coupling agent and strong polar non-proton organic solvent; uniformly stirring the mixture at room temperature; adding magnesium hydroxide powder; performing high-speed shearing dispersion for 20 to 30 minutes; adding aromatic dianhydride powder, catalysts and aromatic hydrocarbon solvent; performing water-separating reaction for 6 to 8 hours; and separating out aromatic solvent and part of strong polar non-proton organic solvent to obtain the polyimide intercalated grafted magnesium hydroxide flame retardant. The polyimide intercalated grafted magnesium hydroxide flame retardant has the vertical combustion level at V-0, limiting oxygen index up to 32, tensile strength up to over 13.6 MPa, significant flame retardant effect and good application prospects. In addition, the method has the advantages of simple preparation process, low cost, convenient operation, friendliness to environment, capability of completing preparation in general equipment and help to industrial production.
Description
Technical field
The invention belongs to the halogen-free smoke resistance flame resistance polymeric material field, particularly relate to a kind of preparation method of polyimide intercalated grafted magnesium hydroxide flame retardant.
Background technology
Along with the fast development of plastics industry, electric wire, printed circuit board, automobile, aerospace, textile garment, decorative fabric etc., to the demand of fire retardant, will be more urgent to demand nontoxic, the smoke-inhibiting type inorganic combustion inhibitor particularly.
Because inorganic combustion inhibitor toxicity is low, thereby meet current fire retardant fully to the megatrend of environment-friendly type development.But because inorganic combustion inhibitor (such as aluminium hydroxide, magnesium hydroxide, zinc borate etc.) is packing type, addition is larger in resin, tends to affect to some extent Drawing abillity and mechanical mechanics property.Therefore, traditional inorganic combustion inhibitor is carried out study on the modification and become relatively more popular at present research topic.
The micro encapsulation of inorganic combustion inhibitor, surface modification, few dirt or dustlessization and synergistic effect etc. have become the good plan that addresses this problem.For example, U.S. Suo Laimu company (SolemIndustries) releases a series of through the surface-treated aluminium hydroxides such as silicon-carbon coupling agent, stearic acid, ultrafine aluminium hydroxide and the magnesium hydroxide new variety through improveing, these products can be issued in the situation of few additive preferably flame retardant effect, thereby improve the economic benefit of goods.Therefore in actual applications, be used alone the requirement that inorganic combustion inhibitor usually can't satisfy Flame Retardancy, the normal fire retardant of selecting two or more cooperates or makes composite flame-retardant agent and use.
Magnesium hydroxide is compared with other inorganic combustion inhibitor, making macromolecular material obtain good flame retardant effect simultaneously, can also suppress the generation of the poisonous gass such as smog and hydrogen halide, gives the characteristics such as material non-toxic, non-corrosiveness.Magnesium hydroxide is all unharmful substance dischargings in the process of production, use and generation of waste materials, and environment is not polluted; Decomposition temperature is high, and (its initial decomposition temperature is more much higher than aluminium hydroxide, reach 320 ℃, aluminium hydroxide is 220 ℃), can be composite with Multiple components, and has a resistance to acid, the acidity and the corrosive gases that produce in the energy and in the combustion processes, fire-retardant and the smoke elimination performance is all good, be a kind of eco-friendly Green Flammability agent.
But magnesium hydroxide also has and has following shortcoming: (1) addition is high, and is large on physics-mechanical property and the processing characteristics impact of material.(2) ordinary hydrogen magnesium oxide mostly is hexagonal crystal shape or metamict crystals, and specific surface area is large, and intercrystalline has very strong conglomerate, dispersed very poor in resin, thereby be difficult to plastics compatiblely, and need pass through special processing when the fire retardant, make it to possess special structure.Therefore, according to its characteristics, the compounded technology of studying itself and other fire retardant is very important problem.
Luo Shiping, Li Jinchun, Sun Hui, willow [magnesium hydroxide surface modifying and the application in EVA thereof, the Jiangsu Petrochemical Engineering College journal, 1998,10 (4): 4-7] disclose the preparation method of magnesium hydroxide-EVA flame-retardant system, be primarily characterized in that: adopted anion surfactant sodium oleate, undecylenic acid sodium that magnesium hydroxide is carried out surface modification, investigated concentration, temperature, the pH value, solid-to-liquid ratio is on the impact of adsorptive capacity.Measured the specific surface of modification front and back magnesium hydroxides, wetting angle, IR etc. are filled in the magnesium hydroxide before and after the modification in the EVA resin, measure its tensile strength and oxygen index.Experiment shows: the good dispersity in resin of the magnesium hydroxide after the modification, strengthened and resin between avidity, thereby improved material mechanical property (tensile strength :≤8.28MPa) and flame retardant properties (limiting oxygen index(LOI) :≤28.5).
The shortcoming of the method is: tensile strength and limiting oxygen index(LOI) are on the low side.
Grand people [the stearic acid modified Mg (OH) that waits of the Huanghai Sea
2Mechanism and on the impact of EVA performance, Beijing University of Chemical Technology's journal, 2006,33 (2): 50-54] preparation method of magnesium hydroxide-EVA flame-retardant system is disclosed, be primarily characterized in that: adopt stearic acid first to Mg (OH)
2Carry out surface modification, and then with ethylene-vinyl acetate copolymer (EVA) blend, thereby obtain magnesium hydroxide-EVA flame-retardant system.Its mechanism of action is to rely on the basic group of stearic acidity-COOH and inorganic filler surface to have an effect, and the stearate that reaction generates rests on surface of inorganic particles, plays the effect of surface modification.
The shortcoming of the method is:
(1) tensile strength of magnesium hydroxide-EVA flame-retardant system constantly reduces with the increase of stearic acid (SA) consumption, and elongation at break a rule that grows steadily and increase sharply occurs first along with the increase of stearic acid (SA) consumption; When stearic acid dosage was increased to a certain degree, the elongation at break of magnesium hydroxide-EVA flame-retardant system descended on the contrary to some extent, finally reaches an equilibrium value.Wherein, compare 3%SA modification Mg (OH)
2Infill system is filled 5% stearic acid modified Mg (OH)
2The elongation at break of magnesium hydroxide-EVA flame-retardant system obviously increase, be increased to 528% by 120%.
(2) along with the increase of stearic acid (SA) surface-modifying agent consumption, the flame retardant properties of magnesium hydroxide-EVA flame-retardant system is variation gradually: oxygen index descends; Horizontal firing and vertical combustion variation.When the surface-modifying agent consumption less than 7% the time, the LOI value changes less, still, along with the continuation of SA consumption increases, the LOI of magnesium hydroxide-EVA flame-retardant system obviously drops to 30.5 by 34, nearly 4 numerical value.With regard to horizontal firing, when the SA consumption was excessive, the horizontal firing grade of magnesium hydroxide-EVA flame-retardant system did not reach the FH-1 grade.When utilizing the vertical combustion testing method to weigh the flame retardant properties of magnesium hydroxide-EVA flame-retardant system, find that the vertical combustion grade of magnesium hydroxide-EVA flame-retardant system does not reach the FV-0 grade when surface-modifying agent SA consumption is 2%; When the SA consumption is 3%, the vertical combustion grade of magnesium hydroxide-EVA flame-retardant system even do not reach the FV-1 grade.
Therefore, if use aforesaid method in actual production, the stability of product is relatively relatively poor, is unfavorable for quality control.
The people such as the Ni Zhongbin [application of in-situ polymerization modified magnesium hydroxide in EVA, Chinese Plastics, 2004,18 (4): 47-50] preparation method of magnesium hydroxide-EVA flame-retardant system is disclosed, be primarily characterized in that: adopt styrene monomer to carry out in-situ polymerization on the magnesium hydroxide particle surface, magnesium hydroxide behind the in-situ polymerization and EVA blend make magnesium hydroxide-EVA flame-retardant system, and its mechanical property has larger improvement.The tensile strength 7.8MPa of this magnesium hydroxide-EVA flame-retardant system, limiting oxygen index(LOI) are 29.
The shortcoming of the method is: tensile strength and limiting oxygen index(LOI) are on the low side.
Polyimide (PI) is the loop chain superpolymer that contains imide ring-type structure in the molecular backbone chain, is the heterogeneous ring compound of half ladder structure.PI appears in one piece of patent of nineteen fifty-five Edwardas and Robison the earliest.Because this class superpolymer has outstanding flame retardant resistance, smokeless or few cigarette, thermotolerance, good mechanical property, electric property and anti-solvent stability etc., its each based article such as moulding compound, matrix material, tackiness agent, separatory membrane etc. have been widely used in the numerous areas such as aerospace, electronic industry, light wave communication, bullet resistant material and gas delivery.Chinese scholars has also been done a large amount of research to polyimide.
Polyimide (PI) has good resistance to elevated temperatures and processing characteristics, if can be with magnesium hydroxide and polyimide mortise, the consistency of it and other plastics or matrix resin will be greatly improved so.Polyimide itself has outstanding thermotolerance, can also produce the cooperative flame retardant effect with MH, and it is all better with the consistency of many polymkeric substance.If its molecule itself maybe can insert polyimide molecule by coupling agent and be grafted on magnesium hydroxide internal layer or the surface, be equivalent to form a kind of special organic inorganic hybridization complex body at magnesium hydroxide internal layer or surface, this not only can improve dispersiveness and consistency, can also play the effect of cooperative flame retardant.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of polyimide intercalated grafted magnesium hydroxide flame retardant, and its preparation technology is simple, cost is low, easy to operate, and environmental friendliness is conducive to realize suitability for industrialized production; And the vertical combustion level of polyimide intercalated grafted magnesium hydroxide flame retardant is in the V-0 level, and limiting oxygen index(LOI) is up to 32, and tensile strength is up to more than the 13.6MPa, and flame retardant effect is remarkable, has a good application prospect.
The preparation method of a kind of polyimide intercalated grafted magnesium hydroxide flame retardant of the present invention comprises:
With the aromatic dicarboxylic primary amine, amino end group coupling agent and strong polar non-proton organic solvent mix, stir under the room temperature, add magnesium hydrate powder, adopt high-speed emulsifying machine, disperse 20min-30min in the 6000-10000r/min high speed shear, add aromatic series dianhydride powder, under the room temperature stirring reaction 1-2 hour, add catalyzer and aromatic solvent, the reaction of heat temperature raising reflux water-dividing is after 6-8 hour, tell the amount of aromatic solvent and former strong polar non-proton organic solvent 20%～40%vol., cooling is left standstill, and filters, drying obtains the polyimide intercalated grafted magnesium hydroxide flame retardant powder;
Wherein, the weight ratio of aromatic dicarboxylic primary amine and magnesium hydrate powder is 1: 10-50; The weight ratio of amino end group coupling agent and magnesium hydrate powder is 1: 80-120; The mol ratio of aromatic dicarboxylic primary amine and aromatic series dianhydride is 1.0: 1.0-1.1; The weight ratio of polyimide and magnesium hydroxide is: 1: 3～40.
Described aromatic dicarboxylic primary amine is selected from Ursol D, mphenylenediamine, O-Phenylene Diamine, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenylsulfone(DDS), 4,4 '-benzidine, 4,4 '-diaminodiphenyl sulfide, 3,3 '-dimethyl-4,4 '-benzidine, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl oxide, 3,3 '-diaminodiphenylsulfone(DDS), 3,4 '-diaminodiphenyl oxide, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 4-, 1, two (3-amino-benzene oxygen) benzene of 3-, 1, two (3-amino-benzene oxygen) benzene of 4-, 4,4 '-two (4-amino-benzene oxygen) sulfobenzide, 4,4 '-two (4-amino-benzene oxygen) benzophenone, 4,4 '-two (3-amino-benzene oxygen) sulfobenzide, 4,4 '-two (3-amino-benzene oxygen) benzophenone, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 4,4 '-two (3-amino-benzene oxygen) biphenyl, 4,4 '-two (4-amino-benzene oxygen) diphenyl sulfide, 4,4 '-two (3-amino-benzene oxygen) diphenyl sulfide, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(3-amino-benzene oxygen) phenyl] propane of 2-, two (3-amino-4-hydroxyphenyl) propane of 2,2-, 3,3 '-diamino-4,4 '-dihydroxybiphenyl, 3,3 '-diamino-4,4 '-dihydroxy diphenylsulphone, the mixture of one or more in 3, the 5-diaminobenzoic acid;
Described aromatic series dianhydride is selected from pyromellitic acid anhydride, 3,3 ', 4,4 '-tetracarboxylic acid phenyl ether dianhydride, 3,3 ', 4,4 '-tetracarboxylic acid benzophenone dianhydride, 3,3 ', 4,4 '-the tetracarboxylic acid diphenyl sulfone dianhydride, 3,3 ', 4,4 '-the tetracarboxylic acid biphenyl dianhydride, two [4-(3,4-di carboxyl phenyloxy) phenyl] the propane dianhydrides of 2,2-, 1,4-two (3, the 4-di carboxyl phenyloxy) benzene dianhydride, two (3, the 4-di carboxyl phenyloxy) benzene dianhydrides of 1,3-, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfone dianhydride, 4,4 '-two (3,4-di carboxyl phenyloxy) phenyl ether dianhydride, 4,4 '-one or more mixture in two (3,4-di carboxyl phenyloxy) biphenyl dianhydride;
Described amino end group coupling agent is selected from end aminopropyl trimethoxysilane, end one or both the mixture in the aminopropyl triethoxysilane;
Described strong polar non-proton organic solvent is selected from one or more the mixture in DMF, N,N-dimethylacetamide, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, the dimethyl sulfoxide (DMSO); Wherein, the envelope-bulk to weight ratio of strong polar non-proton organic solvent and magnesium hydroxide is the 10-20 milliliter: 1 gram;
Described catalyzer is selected from one or more the mixture in p-methyl benzenesulfonic acid, methylsulphonic acid, the 3-toluene sulfonic acide; Wherein, the weight ratio of catalyzer and aromatic dicarboxylic primary amine is 0.05-0.10: 1.00;
Described aromatic solvent is selected from one or more the mixture in benzene,toluene,xylene, the ethylbenzene, and wherein, the envelope-bulk to weight ratio of aromatic solvent and aromatic dicarboxylic primary amine is the 10-20 milliliter: 1 gram;
The median size of described aromatic series dianhydride powder is the 1-5 micron;
Described polyimide intercalated grafted magnesium hydroxide flame retardant, wherein the preferred weight ratio of polyimide and magnesium hydroxide is 1: 8-12.
Polyimide intercalated grafted magnesium hydroxide flame retardant of the present invention is applied to the fields such as ethylene-vinyl acetate copolymer, polyethylene, polypropylene, polymeric amide, Resins, epoxy.
With polyimide intercalated grafted magnesium hydroxide flame retardant powder and ethylene-vinyl acetate copolymer EVA by weight 1.4-1.9: 1.0 put into Banbury mixer, under 135 ℃ of-150 ℃ of temperature, banburying mixes, cooling obtains the ethylene-vinyl acetate copolymer (EVA) without halogen smoke suppressing fire-retardant.
Beneficial effect
(1) the vertical combustion level of the fire-retardant ethylene-vinyl acetate copolymer (EVA) of polyimide intercalated grafted magnesium hydroxide of the present invention is in the V-0 level, limiting oxygen index(LOI) is up to 32, tensile strength is up to more than the 13.6MPa, meet or exceed standard value fully, flame retardant effect is remarkable, has a good application prospect;
(2) this preparation technology is simple, cost is low, easy to operate, the three wastes are few, environmental friendliness, the reaction raw materials convenient sources can be finished preparation process in general-purpose equipment, be conducive to realize suitability for industrialized production.
Description of drawings
Fig. 1 is the general structure of polyimide, and wherein ,-Ar-is the residue of divalent of aromatic dicarboxylic primary amine;=Ar '=be the tetravalence residue of aromatic dicarboxylic anhydride;
Fig. 2 is the fourier transform infrared spectrometry figure (FTIR) of polyimide intercalated grafted magnesium hydroxide flame retardant powder;
Fig. 3 is the thermogravimetric curve of the fire-retardant ethylene-vinyl acetate copolymer of polyimide intercalated grafted magnesium hydroxide (EVA).
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
With 2.0 gram (0.01 moles) 4,4 '-diaminodiphenyl oxide aromatic dicarboxylic primary amine, 1.2 gram end aminopropyl trimethoxysilane (KH-550) amino end group coupling agent and 1000 milliliters of N, the strong polar non-proton organic solvent of N-N,N-DIMETHYLACETAMIDE mixes, stir under the room temperature, add 100.0 gram magnesium hydrate powders, adopt high-speed emulsifying machine (6000-10000r/min) high speed shear to disperse 20min-30min, add 2.18 gram (0.01 mole) pyromellitic acid anhydride powder, under the room temperature stirring reaction 1-2 hour, add 0.1 gram toluene sulfonic acide catalyzer and 20 milliliters of toluene aromatic solvents, the reaction of heat temperature raising reflux water-dividing is after 6-8 hour, tell toluene and 20%～40%vol. (volume of relatively former strong polar non-proton organic solvent) N, the N-dimethylacetamide solvent, cooling is left standstill, and filters, drying obtains 102.9 gram polyimide intercalated grafted magnesium hydroxide flame retardant powder.
The fourier transform infrared spectrometry figure (FTIR) of this polyimide intercalated grafted magnesium hydroxide flame retardant powder as shown in Figure 2, wherein upper figure is the FTIR spectrogram of magnesium hydrate powder (unprocessed), figure below is the FTIR spectrogram of polyimide intercalated grafted magnesium hydroxide flame retardant powder, has obvious imines charateristic avsorption band (1719.14cm
-1), phenyl ring charateristic avsorption band (1605.08cm
-1, 1499.90cm
-1) and the charateristic avsorption band (1238.57cm of aryl oxide key
-1).
With polyimide intercalated grafted magnesium hydroxide flame retardant powder taking-up 42.0 grams wherein that obtain, put into Banbury mixer with 30.0 gram ethylene-vinyl acetate copolymer (EVA) pellets, under 135 ℃ of-150 ℃ of temperature, banburying mixes, cooling, obtain the fire-retardant ethylene-vinyl acetate copolymer (EVA) of 72.0 gram polyimide intercalated grafted magnesium hydroxides, be denoted as PIMHEVA-1.
The ethylene-vinyl acetate copolymer (EVA) that above-mentioned PIMHEVA-1 polyimide intercalated grafted magnesium hydroxide is fire-retardant is put into vulcanizing press, in 160 ℃ of-170 ℃ of temperature ranges, be molded into sheet material, recording its tensile strength is 13.6MPa, limiting oxygen index(LOI) is 32, and vertical combustion reaches the V-0 level.
The thermogravimetric curve of the ethylene-vinyl acetate copolymer (EVA) that this polyimide intercalated grafted magnesium hydroxide is fire-retardant as shown in Figure 3.Wherein, curve [1] is pure EVA; Curve [2] is the untreated magnesium hydrate powder of pure EVA+; Curve [3] is pure EVA+ polyimide intercalated grafted magnesium hydroxide powder.
With 21.62 gram (0.1 moles) 3,3 '-diamino-4,4 '-dihydroxybiphenyl aromatic dicarboxylic primary amine, 1.81 the amino end group coupling agent of gram end aminopropyl triethoxysilane and 4300 milliliters of strong polar non-proton organic solvents of METHYLPYRROLIDONE mix, stir under the room temperature, add 216.2 gram magnesium hydrate powders, adopt high-speed emulsifying machine (6000-10000r/min) high speed shear to disperse 20min-30min, add 32.34 gram (0.11 moles) 3,3 ', 4,4 '-tetracarboxylic acid biphenyl dianhydride powder, under the room temperature stirring reaction 1-2 hour, add 2.16 gram toluene sulfonic acide catalyzer and 430 milliliters of dimethylbenzene aromatic solvents, the reaction of heat temperature raising reflux water-dividing is after 6-8 hour, tell the METHYLPYRROLIDONE solvent of dimethylbenzene and 20%～40%vol., cooling is left standstill, and filters, drying obtains 266.2 gram polyimide intercalated grafted magnesium hydroxide flame retardant powder.
With polyimide intercalated grafted magnesium hydroxide flame retardant powder taking-up 57.0 grams wherein that obtain, put into Banbury mixer with 30.0 gram ethylene-vinyl acetate copolymer (EVA) pellets, under 135 ℃ of-150 ℃ of temperature, banburying mixes, cooling, obtain the fire-retardant ethylene-vinyl acetate copolymer (EVA) of 87.0 gram polyimide intercalated grafted magnesium hydroxides, be denoted as PIMHEVA-2.
The ethylene-vinyl acetate copolymer (EVA) that above-mentioned PIMHEVA-2 polyimide intercalated grafted magnesium hydroxide is fire-retardant is put into vulcanizing press, in 160 ℃ of-170 ℃ of temperature ranges, be molded into sheet material, recording its tensile strength is 13.2MPa, limiting oxygen index(LOI) is 31, and vertical combustion reaches the V-0 level.
With 2.0 gram (0.01 moles) 4,4 '-diaminodiphenyl oxide and 2.48 gram (0.01 moles) 4,4 '-the aromatic dicarboxylic primary amine of diaminodiphenylsulfone(DDS), 1.8 gram end aminopropyl trimethoxysilane (KH-550) amino end group coupling agent and 2700 milliliters of N, the strong polar non-proton organic solvent of N-N,N-DIMETHYLACETAMIDE mixes, stir under the room temperature, add 180.0 gram magnesium hydrate powders, adopt high-speed emulsifying machine (6000-10000r/min) high speed shear to disperse 20min-30min, add 2.18 gram (0.01 mole) pyromellitic acid anhydride powder and 2.94 gram (0.01 moles) 3,3 ', 4,4 '-tetracarboxylic acid biphenyl dianhydride powder, under the room temperature stirring reaction 1-2 hour, add 0.31 gram toluene sulfonic acide catalyzer and 20 milliliters of toluene and 50 milliliters of dimethylbenzene aromatic solvents, the reaction of heat temperature raising reflux water-dividing is after 6-8 hour, tell the N of toluene and 20%～40%vol., the N-dimethylacetamide solvent, cooling, leave standstill, filter, drying obtains 188.5 gram polyimide intercalated grafted magnesium hydroxide flame retardant powder.
With polyimide intercalated grafted magnesium hydroxide flame retardant powder taking-up 48.0 grams wherein that obtain, put into Banbury mixer with 30.0 gram ethylene-vinyl acetate copolymer (EVA) pellets, under 135 ℃ of-150 ℃ of temperature, banburying mixes, cooling, obtain the fire-retardant ethylene-vinyl acetate copolymer (EVA) of 78.0 gram polyimide intercalated grafted magnesium hydroxides, be denoted as PIMHEVA-3.
The ethylene-vinyl acetate copolymer (EVA) that above-mentioned PIMHEVA-3 polyimide intercalated grafted magnesium hydroxide is fire-retardant is put into vulcanizing press, in 160 ℃ of-170 ℃ of temperature ranges, be molded into sheet material, recording its tensile strength is 11.7MPa, limiting oxygen index(LOI) is 30, and vertical combustion reaches the V-0 level.
Claims (9)
1. the preparation method of a polyimide intercalated grafted magnesium hydroxide flame retardant comprises:
With the aromatic dicarboxylic primary amine, amino end group coupling agent and strong polar non-proton organic solvent mix, stir under the room temperature, add magnesium hydrate powder, adopt high-speed emulsifying machine, disperse 20min-30min in the 6000-10000r/min high speed shear, add aromatic series dianhydride powder, under the room temperature stirring reaction 1-2 hour, add catalyzer and aromatic solvent, the reaction of heat temperature raising reflux water-dividing is after 6-8 hour, tell the amount of aromatic solvent and former strong polar non-proton organic solvent 20%～40%vol., cooling is left standstill, and filters, drying obtains the polyimide intercalated grafted magnesium hydroxide flame retardant powder;
Wherein, the weight ratio of aromatic dicarboxylic primary amine and magnesium hydrate powder is 1: 10-50; The weight ratio of amino end group coupling agent and magnesium hydrate powder is 1: 80-120; The mol ratio of aromatic dicarboxylic primary amine and aromatic series dianhydride is 1.0: 1.0-1.1; The weight ratio of polyimide and magnesium hydroxide is: 1: 3～40.
2. the preparation method of a kind of polyimide intercalated grafted magnesium hydroxide flame retardant according to claim 1, it is characterized in that: described aromatic dicarboxylic primary amine is selected from Ursol D, mphenylenediamine, O-Phenylene Diamine, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenylsulfone(DDS), 4,4 '-benzidine, 4,4 '-diaminodiphenyl sulfide, 3,3 '-dimethyl-4,4 '-benzidine, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl oxide, 3,3 '-diaminodiphenylsulfone(DDS), 3,4 '-diaminodiphenyl oxide, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 4-, 1, two (3-amino-benzene oxygen) benzene of 3-, 1, two (3-amino-benzene oxygen) benzene of 4-, 4,4 '-two (4-amino-benzene oxygen) sulfobenzide, 4,4 '-two (4-amino-benzene oxygen) benzophenone, 4,4 '-two (3-amino-benzene oxygen) sulfobenzide, 4,4 '-two (3-amino-benzene oxygen) benzophenone, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 4,4 '-two (3-amino-benzene oxygen) biphenyl, 4,4 '-two (4-amino-benzene oxygen) diphenyl sulfide, 4,4 '-two (3-amino-benzene oxygen) diphenyl sulfide, two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, two [4-(3-amino-benzene oxygen) phenyl] propane of 2,2-, 2, two (3-amino-4-hydroxyphenyl) propane of 2-, 3,3 '-diamino-4,4 '-dihydroxybiphenyl, 3,3 '-diamino-4,4 '-dihydroxy diphenylsulphone, the mixture of one or more in 3, the 5-diaminobenzoic acid.
3. the preparation method of a kind of polyimide intercalated grafted magnesium hydroxide flame retardant according to claim 1, it is characterized in that: described aromatic series dianhydride is selected from pyromellitic acid anhydride, 3,3 ', 4,4 '-tetracarboxylic acid phenyl ether dianhydride, 3,3 ', 4,4 '-tetracarboxylic acid benzophenone dianhydride, 3,3 ', 4,4 '-the tetracarboxylic acid diphenyl sulfone dianhydride, 3,3 ', 4,4 '-the tetracarboxylic acid biphenyl dianhydride, 2,2-is two, and [4-(3, the 4-di carboxyl phenyloxy) phenyl] the propane dianhydride, Isosorbide-5-Nitrae-two (3,4-di carboxyl phenyloxy) benzene dianhydride, 1,3-two (3, the 4-di carboxyl phenyloxy) benzene dianhydride, 4,4 '-two (3,4-di carboxyl phenyloxy) diphenyl sulfone dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) phenyl ether dianhydride, 4,4 '-one or more mixture in two (3,4-di carboxyl phenyloxy) biphenyl dianhydride.
4. the preparation method of a kind of polyimide intercalated grafted magnesium hydroxide flame retardant according to claim 1 is characterized in that: described amino end group coupling agent is selected from one or both the mixture in end aminopropyl trimethoxysilane, the end aminopropyl triethoxysilane.
5. the preparation method of a kind of polyimide intercalated grafted magnesium hydroxide flame retardant according to claim 1, it is characterized in that: described strong polar non-proton organic solvent is selected from N, the mixture of one or more in dinethylformamide, N,N-dimethylacetamide, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, the dimethyl sulfoxide (DMSO); Wherein, the envelope-bulk to weight ratio of strong polar non-proton organic solvent and magnesium hydroxide is the 10-20 milliliter: 1 gram.
6. the preparation method of a kind of polyimide intercalated grafted magnesium hydroxide flame retardant according to claim 1 is characterized in that: described catalyzer is selected from one or more the mixture in p-methyl benzenesulfonic acid, methylsulphonic acid, the 3-toluene sulfonic acide; Wherein, the weight ratio of catalyzer and aromatic dicarboxylic primary amine is 0.05-0.10: 1.00.
7. the preparation method of a kind of polyimide intercalated grafted magnesium hydroxide flame retardant according to claim 1, it is characterized in that: the aromatic solvent in described is selected from one or more the mixture in benzene,toluene,xylene, the ethylbenzene, wherein, the envelope-bulk to weight ratio of aromatic solvent and aromatic dicarboxylic primary amine is the 10-20 milliliter: 1 gram.
8. the preparation method of a kind of polyimide intercalated grafted magnesium hydroxide flame retardant according to claim 1, it is characterized in that: the median size of described aromatic series dianhydride powder is the 1-5 micron.
9. the preparation method of 1 described a kind of polyimide intercalated grafted magnesium hydroxide flame retardant as requested, it is characterized in that: described polyimide intercalated grafted magnesium hydroxide flame retardant, wherein the weight ratio of polyimide and magnesium hydroxide is 1: 8-12.
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| CN102010619B (en) * | 2010-11-24 | 2013-01-30 | 沈阳工业大学 | Method for preparing magnesium hydroxide fire retardant and prepared magnesium hydroxide fire retardant |
| CN109503748A (en) * | 2018-08-15 | 2019-03-22 | 青岛神盾防水科技有限公司 | Ethene improved-acetate ethylene copolymer and its manufacturing method |
| CN109667037A (en) * | 2018-12-25 | 2019-04-23 | 象山新光针织印染有限公司 | A kind of durable flame-proof fabric and preparation method thereof |
| CN113045892B (en) * | 2019-12-28 | 2022-06-28 | 合肥杰事杰新材料股份有限公司 | Flame-retardant nylon 66 material and preparation method thereof |
| CN112625526A (en) * | 2020-12-16 | 2021-04-09 | 孙铮 | Gradient heat-insulating fireproof coating and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1927908A (en) * | 2006-09-05 | 2007-03-14 | 东华大学 | Preparation method of phenolic hydroxyl group containing polyimide powder |
| CN101130632A (en) * | 2007-08-08 | 2008-02-27 | 北京航空航天大学 | Polyimide froth in situ filling honeycomb composite material |
| CN101423609A (en) * | 2008-10-21 | 2009-05-06 | 东华大学 | Method for preparing polyimide powder containing active ethylene group |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1927908A (en) * | 2006-09-05 | 2007-03-14 | 东华大学 | Preparation method of phenolic hydroxyl group containing polyimide powder |
| CN101130632A (en) * | 2007-08-08 | 2008-02-27 | 北京航空航天大学 | Polyimide froth in situ filling honeycomb composite material |
| CN101423609A (en) * | 2008-10-21 | 2009-05-06 | 东华大学 | Method for preparing polyimide powder containing active ethylene group |
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