CN102702678B - Halogen-free flame retardant toughened epoxy resin based composite material and preparation method thereof - Google Patents
Halogen-free flame retardant toughened epoxy resin based composite material and preparation method thereof Download PDFInfo
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- CN102702678B CN102702678B CN201210167655.9A CN201210167655A CN102702678B CN 102702678 B CN102702678 B CN 102702678B CN 201210167655 A CN201210167655 A CN 201210167655A CN 102702678 B CN102702678 B CN 102702678B
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Abstract
The invention provides a halogen-free flame retardant toughened epoxy resin based composite material and a preparation method thereof, and relates to a composite material with a flame retardant. The compositions of the composite materia include epoxy resin, a curing agent 4,4 '- diamino diphenyl methane and a nitrogen-phosphorous-boron-carbon chain quaternity flame retardant. The mass ratio of the epoxy resin, the curing agent and the flame retardant is 1:0.218:(0.015-0.1). Phosphoric acid and boric acid are added into a container. Organic protonic solvent or a mixture of organic protonic solvent and water is added. And then a fatty long-chain amine is added to obtain a mixed liquor. The mixed liquor is transferred to a reaction vessel after ultrasonic processing, and then placed in a constant temperature drying oven to obtain a reaction product. The reaction product is washed with industrial alcohol and dried to obtain a nitrogen-phosphorous-boron-carbon chain quaternity flame retardant; and the nitrogenphosphorusboroncarbon chain quaternity flame retardant and the epoxy resin are mixed and subjected to ultrasonic dispersion to obtain a mixture. The mixture is added with curing agent for solidifying to obtain the halogen-free flame retardant toughened epoxy resin based composite material.
Description
Technical field
The present invention relates to a kind of matrix material with fire retardant, especially relate to a kind of preparation method of halogen-free flame-proof toughening epoxy resin-base composite material.
Background technology
Epoxy resin cured product belongs to thermosetting resin, has many good physical and chemical performances, as excellent specific tenacity, to the adhesive property of metal or non-metallic material, good dielectric properties, low cure shrinkage, resistance to chemical attack, heat-resisting etc.Epoxy resin is widely used in the industries such as building, electric, aviation, wind-power electricity generation as coating, tackiness agent, perfusion packaged material, matrices of composite material etc.2009,115.8 ten thousand tons of China's content of epoxy resin, 23.5 ten thousand tons of import volumes.Relying on the epoxy resin of import is mainly special epoxy resin, as fire retarding epoxide resin.The oxygen index of not fire-retardant epoxy resin is 19.8, belongs to inflammable material.Therefore, all the time, the fire-retardant research of epoxy resin receives much concern.
According to ignition-proof element, be present in the fire retardant of interpolation or be present in the epoxy monomer of modification, flame-retardant epoxide resin material can be divided into additive flame retardant epoxy resin and reaction-type flame-retarding epoxy resin.Wherein, additive flame retardant epoxide resin material has application widely because simple to operate, cost is low industrial.The additive flame retardant adopting in flame-retardant epoxide resin material mainly contains halogen flame retardant, phosphorus flame retardant, nitrogenated flame retardant etc.Halogen flame retardant flame retardant effect is better, is widely used in the fire-retardant of epoxy resin in electric device.But during polybromodiphenyl ether pyrolytic decomposition, produce hypertoxic dibenzodioxin English and tribromide diphenylene-oxide, 2006, WEEE instruction and RoHs instruction clearly stipulate can not contain Polybrominated biphenyl and Poly Brominated Diphenyl Ethers in electronic and electrical equipment, and the halogen-free flameproof of environment-friendly type becomes the development trend of fire retardant in flame-retardant epoxide resin material.Phosphorus flame retardant can catalysis carbon-forming in condensed phase, discharges that PO free radical can catch H and HO stops combustion chain reaction in gas phase, when few additive, can reach good flame retardant effect.Thereby nitrogenated flame retardant easily decomposes generation oxygen barrier performance as heat insulation in non-combustible gas such as nitrogen fire retardation when being heated, and toxicity is little and flame retarding efficiency is high.Nitrogen and phosphorus have good synergy.Chinese patent CN201010142916.2 discloses with Ureaphil mother liquor and uric acid and on strict reaction pressure, temperature rise rate and the insulation temperature rank controlled, has synthesized a kind of phosphor nitrogen combustion inhibitor by certain mass ratio; Chinese patent CN201010176891.8 first generates intermediate by phosphorus oxychloride and tetramethylolmethane reaction, then uses concentrated nitric acid oxidation, and then reacts with sulfur oxychloride, finally reacts with trimeric cyanamide and makes a kind of phosphor nitrogen combustion inhibitor; Chinese patent CN200910273169.3 is paraformaldehyde depolymerization neutralization, then with trimeric cyanamide polycondensation, hexamethylolmelamine and phosphorus oxychloride esterification, then react with trimeric cyanamide and obtain a kind of phosphor nitrogen combustion inhibitor; Chinese patent CN201110178279.9 is first by hexamethylolmelamine and Phosphorates phosphorus Halides esterification, after hydrolysis, removes organic phase, then reacts with trimeric cyanamide and obtain a kind of phosphorus nitrogen carbon trinity fire retardant.Phosphor nitrogen combustion inhibitor of a great variety, but preparation were established need to a minute multistep complete, and working method is more loaded down with trivial details.Because melting under higher temperature action, the boron in boron flame retardant forms hard glass state tectum, thereby the transmission path of isolated inflammable gas, therefore, the technology of the cooperative flame retardant epoxy resin of nitrogen, phosphorus and three kinds of ignition-proof elements of boron has very large development prospect.
In addition, because will reaching desirable flame retardant effect, general additive flame retardant need addition larger, and worsen with the poor mechanical property of material that causes of the consistency of matrix, therefore seek a kind ofly not only to have reached fire-retardant object but also given the fire retardant of material excellent toughness and apply this fire retardant that to prepare fire-retardant toughened epoxy resin-base composite material be a very significant job.
Summary of the invention
The object of the present invention is to provide a kind of halogen-free flame-proof toughening epoxy resin-base composite material and preparation method thereof.
Technical scheme of the present invention is the fire retardant with the synthetic a kind of nitrogen-phosphorus-boron-carbochain quaternity of single stage method, this fire retardant is applied in epoxy resin, make this fire retardant when few additive, not only can reach the flame retardant effect good to epoxy resin base material, and can improve the toughness of epoxy resin base material.
The composition of described halogen-free flame-proof toughening epoxy resin-base composite material comprises epoxy resin, solidifying agent 4, the fire retardant of 4 '-diaminodiphenylmethane and nitrogen-phosphorus-boron-carbochain quaternity, described epoxy resin, solidifying agent 4, the mass ratio of the fire retardant of 4 '-diaminodiphenylmethane and nitrogen-phosphorus-boron-carbochain quaternity is 1: 0.218: (0.008～0.1).
Described epoxy resin, solidifying agent 4, the mass ratio of the fire retardant of 4 '-diaminodiphenylmethane and nitrogen-phosphorus-boron-carbochain quaternity can be 1: 0.218: (0.02～0.05).
The preparation method of described halogen-free flame-proof toughening epoxy resin-base composite material comprises the following steps:
1) phosphoric acid and boric acid are placed in to container, add organic protonic solvent, or the mixture of organic protonic solvent and water, add while stirring aliphatic long-chain amine, obtain mixed solution;
2) after the mixed solution of step 1) gained is ultrasonic, be transferred in reaction vessel, be placed in thermostatic drying chamber and react, obtain reaction product;
3) by step 2) reaction product of gained is with dry after industrial spirit washing, obtains the fire retardant of nitrogen-phosphorus-boron-carbochain quaternity;
4) fire retardant of step 3) gained nitrogen-phosphorus-boron-carbochain quaternity and epoxy resin are mixed and ultrasonic dispersion, obtain mixture;
5) mixture of step 4) gained added to solidifying agent and is cured, obtaining halogen-free flame-proof toughening epoxy resin-base composite material.
In step 1), in mass ratio, the proportioning of phosphoric acid, boric acid and aliphatic long-chain amine can be 1: (0.5～4): (1～4), is preferably 1: (1～2): (1～2), is preferably 1: 1: 1; Described aliphatic long-chain amine can be bought from the market, can be selected from a kind of in amino dodecane, tetradecy lamine, cetylamine, stearylamine etc.
In step 2) in, the described ultrasonic time can be 20～40min, is preferably 25～35min, is preferably 30min; The temperature of described reaction can be 303～423K, the time of described reaction can be 1～4 day, and the temperature of described reaction is preferably 343～383K, and the time of described reaction is preferably 1～3 day, the temperature of described reaction is preferably 363K, and the time of described reaction is preferably 2 days.
In step 3), described dry, can in thermostatic drying chamber, be dried, dry temperature can be 343 ~ 383K, and the dry time can be 1 ~ 3h; Dry temperature is preferably 353 ~ 373K, and the dry time is preferably 1.5 ~ 2.5h; Dry temperature is preferably 363K, the dry time be preferably 2h.
In step 4), the add-on of the fire retardant of described nitrogen-phosphorus-boron-carbochain quaternity can be 0.8%～20% of epoxy resin quality, is preferably 1.5% ~ 10%, is preferably 5%.
In step 5), described solidifying agent can be selected from 4,4 '-diaminodiphenylmethane etc.; Described solidifying agent and epoxy resin can be 1 in mass ratio: (1 ~ 7), and optimum value is 1: 5; Described curing mode can be after 90 ℃ of curing 2h, is warming up to 120 ℃ of curing 2h; The bubble that can ultrasonic dispersion final vacuum before described solidify degass, the time of described dispersion can be 15min.
The present invention only reacts aliphatic long-chain amine, phosphoric acid, boric acid and water to the fire retardant that has synthesized nitrogen-phosphorus-boron-carbochain quaternity by single stage method, easy and simple to handle, with this fire retardant and epoxy resin, the matrix material after compound and curing has the resistance to impact shock that good flame retardant properties has also improved epoxy base material simultaneously.
After adopting the fire retardant of nitrogen-phosphorus-boron of the present invention-carbochain quaternity and epoxy resin compound, add epoxy hardener 4,4 '-diaminodiphenylmethane is solidified, and the flame retardant properties of gained matrix material and shock resistance are tested according to GB/T 2406.1-2008 and GB/T 1043-93 testing method respectively.When fire retardant addition is 1.5% time, limiting oxygen index(LOI) can reach 28.Resistance to impact shock increases with the increase of fireproof powder weight percentage ratio.Therefore, can be used as the contour performance fire retardant material of body material of coating, electronic package material, veneer sheet, matrix material.
Accompanying drawing explanation
Fig. 1 is the Small angle XRD figure spectrum of the fire retardant of prepared nitrogen-phosphorus-boron-carbochain quaternity in embodiment 1 ~ 4.In Fig. 1, X-coordinate be diffraction angle 2 θ (°), ordinate zou is relative diffracted intensity; Curve a is C
12aBP, curve b is C
14aBP, curve c is C
16aBP, curve d is C
18aBP.
Fig. 2 is the collection of illustrative plates that the shock strength of prepared halogen-free flame-proof toughening epoxy resin-base composite material in embodiment 5 ~ 8 changes with fire retardant addition.In Fig. 2, X-coordinate is amino dodecane borophosphate (C
12aBP) mass percent in epoxy resin-matrix (%), ordinate zou is resistance to impact shock (kJ/m
2).
Embodiment
Following examples are to further illustrate of the present invention, but the invention is not restricted to following embodiment.
Aliphatic long-chain amine, 4 in following examples, 4 '-diaminodiphenylmethane is bought from Shanghai Aladdin reagent company, and boric acid and phosphoric acid are bought from Xiamen grass Bo Yi company limited, and epoxy resin is three wooden institutional purchase from Jiangsu.
Embodiment 1
1.8g boric acid and 4.0g phosphoric acid are added in reaction vessel, add 3mL water and 3mL ethanol, stir, add while stirring 3.6g amino dodecane, reaction vessel is placed in to the ultrasonic 20min of ultrasonic apparatus, reaction vessel is placed in to 393K reaction 2 days, reaction product is with after industrial washing with alcohol, at 363K vacuum drying oven, dry, the fire retardant that obtains nitrogen-phosphorus-boron-carbochain quaternity (is called for short: C
12aPB).
Embodiment 2
1.8g boric acid and 4.0g phosphoric acid are added in reaction vessel, add 3mL water and 3mL ethanol, stir, add while stirring 4.2g tetradecy lamine, reaction vessel is placed in to the ultrasonic 20min of ultrasonic apparatus, reaction vessel is placed in to 393K reaction 2 days, reaction product is with after industrial washing with alcohol, at 363K vacuum drying oven, dry, the fire retardant that obtains nitrogen-phosphorus-boron-carbochain quaternity (is called for short: C
14aPB).
Embodiment 3
1.8g boric acid and 4.0g phosphoric acid are added in reaction vessel, add 3mL water and 3mL ethanol, stir, add while stirring 4.8g cetylamine, reaction vessel is placed in to the ultrasonic 20min of ultrasonic apparatus, reaction vessel is placed in to 393K reaction 2 days, reaction product is with after industrial washing with alcohol, at 363K vacuum drying oven, dry, the fire retardant that obtains nitrogen-phosphorus-boron-carbochain quaternity (is called for short: C
16aPB).
Embodiment 4
1.8g boric acid and 4.0g phosphoric acid are added in reaction vessel, add 3mL water and 3mL ethanol, stir, add while stirring 5.3g stearylamine, reaction vessel is placed in to the ultrasonic 20min of ultrasonic apparatus, reaction vessel is placed in to 393K reaction 2 days, reaction product is with after industrial washing with alcohol, at 363K vacuum drying oven, dry, the fire retardant that obtains nitrogen-phosphorus-boron-carbochain quaternity (is called for short: C
18aPB).
In embodiment 1 ~ 4, the Small angle XRD figure of the fire retardant of prepared nitrogen-phosphorus-boron-carbochain quaternity spectrum is referring to Fig. 1.
Embodiment 5
Extracting epoxy resin 30g and 6.54g4,4 '-diaminodiphenylmethane 6.54g evenly mixes, vacuumize removal bubble, 90 ℃ of curing 2h, then be warming up to 120 ℃ of after fixing 2h, according to GB/T 2406.1-2008 testing method, record this cured article oxygen index: LOI=25.0, according to GB/T 1043-93 testing method, record simply supported beam unnotched impact strength 4.11kJ/m
2.
Embodiment 6
Get the fire retardant 0.6g described in embodiment 1, epoxy resin 30g and 6.54g4, the even 6.54g of 4 '-diaminodiphenylmethane mixes, vacuumize removal bubble, 90 ℃ of curing 2h, then be warming up to 120 ℃ of after fixing 2h, according to GB/T 2406.1-2008 testing method, record the oxygen index of this matrix material: LOI=27.5, according to GB/T 1043-93 testing method, record simply supported beam unnotched impact strength 5.44kJ/m
2.
Embodiment 7
Get the fire retardant 0.9g described in embodiment 1, epoxy resin 30g and 6.54g4, the even 6.54g of 4 '-diaminodiphenylmethane mixes, vacuumize removal bubble, 90 ℃ of curing 2h, then be warming up to 120 ℃ of after fixing 2h, according to GB/T 2406.1-2008 testing method, record the oxygen index of this matrix material: LOI=27.0, according to GB/T 1043-93 testing method, record simply supported beam unnotched impact strength 5.93kJ/m
2.
Embodiment 8
Get the fire retardant 1.5g described in embodiment 1, epoxy resin 30g and 6.54g4, the even 6.54g of 4 '-diaminodiphenylmethane mixes, vacuumize removal bubble, 90 ℃ of curing 2h, then be warming up to 120 ℃ of after fixing 2h, record the oxygen index of this matrix material: LOI=27.0 according to GB/T 2406.1-2008 testing method, according to GB/T 1043-93 testing method, recording simply supported beam unnotched impact strength is 6.47kJ/m
2.
The collection of illustrative plates that in embodiment 5 ~ 8, the shock strength of prepared halogen-free flame-proof toughening epoxy resin-base composite material changes with fire retardant addition is referring to Fig. 2.
Embodiment 9
Similar to Example 8, get the fire retardant 3g described in embodiment 1, epoxy resin 30g and 6.54g4, the even 6.54g of 4 '-diaminodiphenylmethane mixes, vacuumize removal bubble, 90 ℃ of curing 2h, are then warming up to 120 ℃ of after fixing 2h, according to GB/T2406.1-2008 testing method, record the oxygen index of this matrix material: LOI=26.0, according to GB/T 1043-93 testing method, recording simply supported beam unnotched impact strength is 5.46kJ/m
2.
Embodiment 10
Similar to Example 6, get the fire retardant 0.24g described in embodiment 1, epoxy resin 30g and 6.54g4, the even 6.54g of 4 '-diaminodiphenylmethane mixes, vacuumize removal bubble, 90 ℃ of curing 2h, are then warming up to 120 ℃ of after fixing 2h, according to GB/T 2406.1-2008 testing method, record the oxygen index of this matrix material: LOI=26.5, according to GB/T 1043-93 testing method, record simply supported beam unnotched impact strength 4.87kJ/m
2.
Claims (16)
1. a halogen-free flame-proof toughening epoxy resin-base composite material, it is characterized in that its composition comprises epoxy resin, solidifying agent 4, the fire retardant of 4 '-diaminodiphenylmethane and nitrogen-phosphorus-boron-carbochain quaternity, described epoxy resin, solidifying agent 4, the mass ratio of the fire retardant of 4 '-diaminodiphenylmethane and nitrogen-phosphorus-boron-carbochain quaternity is 1: 0.218: (0.015～0.1);
Described halogen-free flame-proof toughening epoxy resin-base composite material is prepared by following methods:
1) phosphoric acid and boric acid are placed in to container, add organic protonic solvent, or the mixture of organic protonic solvent and water, add while stirring aliphatic long-chain amine, obtain mixed solution; In mass ratio, the proportioning of phosphoric acid, boric acid and aliphatic long-chain amine is 1: (0.5～4): (1～4), and described aliphatic long-chain amine is selected from a kind of in amino dodecane, tetradecy lamine, cetylamine, stearylamine;
2) by step 1) after the mixed solution of gained is ultrasonic, be transferred in reaction vessel, be placed in thermostatic drying chamber and react, obtain reaction product;
3) by step 2) reaction product of gained is with dry after industrial spirit washing, obtains the fire retardant of nitrogen-phosphorus-boron-carbochain quaternity;
4) by step 3) fire retardant of gained nitrogen-phosphorus-boron-carbochain quaternity and epoxy resin mixes and ultrasonic dispersion, obtains mixture;
5) by step 4) mixture of gained adds solidifying agent and is cured, and obtains halogen-free flame-proof toughening epoxy resin-base composite material.
2. a kind of halogen-free flame-proof toughening epoxy resin-base composite material as claimed in claim 1, it is characterized in that described epoxy resin, solidifying agent 4, the mass ratio of the fire retardant of 4 '-diaminodiphenylmethane and nitrogen-phosphorus-boron-carbochain quaternity is 1: 0.218: (0.02～0.05).
3. a preparation method for halogen-free flame-proof toughening epoxy resin-base composite material, is characterized in that comprising the following steps:
1) phosphoric acid and boric acid are placed in to container, add organic protonic solvent, or the mixture of organic protonic solvent and water, add while stirring aliphatic long-chain amine, obtain mixed solution; In mass ratio, the proportioning of phosphoric acid, boric acid and aliphatic long-chain amine is 1: (0.5～4): (1～4), and described aliphatic long-chain amine is selected from a kind of in amino dodecane, tetradecy lamine, cetylamine, stearylamine;
2) by step 1) after the mixed solution of gained is ultrasonic, be transferred in reaction vessel, be placed in thermostatic drying chamber and react, obtain reaction product;
3) by step 2) reaction product of gained is with dry after industrial spirit washing, obtains the fire retardant of nitrogen-phosphorus-boron-carbochain quaternity;
4) by step 3) fire retardant of gained nitrogen-phosphorus-boron-carbochain quaternity and epoxy resin mixes and ultrasonic dispersion, obtains mixture; The add-on of the fire retardant of described nitrogen-phosphorus-boron-carbochain quaternity is 0.8%～20% of epoxy resin quality;
5) by step 4) mixture of gained adds solidifying agent and is cured, and obtains halogen-free flame-proof toughening epoxy resin-base composite material; Described solidifying agent is selected from 4,4 '-diaminodiphenylmethane; Described solidifying agent and epoxy resin are 1 in mass ratio: (1～7).
4. the preparation method of a kind of halogen-free flame-proof toughening epoxy resin-base composite material as claimed in claim 3, is characterized in that in mass ratio, and the proportioning of phosphoric acid, boric acid and aliphatic long-chain amine is 1: (1～2): (1～2).
5. the preparation method of a kind of halogen-free flame-proof toughening epoxy resin-base composite material as claimed in claim 4, is characterized in that in step 1) in mass ratio, the proportioning of phosphoric acid, boric acid and aliphatic long-chain amine is 1: 1: 1.
6. the preparation method of a kind of halogen-free flame-proof toughening epoxy resin-base composite material as claimed in claim 3, it is characterized in that in step 2) in, the described ultrasonic time is 20～40min, and the temperature of described reaction is 303～423K, and the time of described reaction is 1～4 day.
7. the preparation method of a kind of halogen-free flame-proof toughening epoxy resin-base composite material as claimed in claim 6, the temperature that it is characterized in that described reaction is 343～383K, the time of described reaction is 1～3 day.
8. the preparation method of a kind of halogen-free flame-proof toughening epoxy resin-base composite material as claimed in claim 7, the temperature that it is characterized in that described reaction is 363K, the time of described reaction is 2 days.
9. the preparation method of a kind of halogen-free flame-proof toughening epoxy resin-base composite material as claimed in claim 3, is characterized in that in step 3) in, described dry, be dry in thermostatic drying chamber, dry temperature is 343～383K, the dry time is 1～3h.
10. the preparation method of a kind of halogen-free flame-proof toughening epoxy resin-base composite material as claimed in claim 9, is characterized in that described dry temperature is 353～373K, and the dry time is 1.5～2.5h.
The preparation method of 11. a kind of halogen-free flame-proof toughening epoxy resin-base composite materials as claimed in claim 10, is characterized in that described dry temperature is 363K, and the dry time is 2h.
The preparation method of 12. a kind of halogen-free flame-proof toughening epoxy resin-base composite materials as claimed in claim 3, the add-on that it is characterized in that the fire retardant of described nitrogen-phosphorus-boron-carbochain quaternity is 1.5%～10% of epoxy resin quality.
The preparation method of 13. a kind of halogen-free flame-proof toughening epoxy resin-base composite materials as claimed in claim 12, the add-on that it is characterized in that the fire retardant of described nitrogen-phosphorus-boron-carbochain quaternity is 5% of epoxy resin quality.
The preparation method of 14. a kind of halogen-free flame-proof toughening epoxy resin-base composite materials as claimed in claim 3, is characterized in that described solidifying agent and epoxy resin are 1: 5 in mass ratio.
The preparation method of 15. a kind of halogen-free flame-proof toughening epoxy resin-base composite materials as claimed in claim 3, is characterized in that in step 5) in, after described curing mode is 90 ℃ of curing 2h, be warming up to 120 ℃ of curing 2h.
The preparation method of 16. a kind of halogen-free flame-proof toughening epoxy resin-base composite materials as claimed in claim 3, is characterized in that in step 5) in, the ultrasonic dispersion final vacuum bubble that degass before described solidify, the time of described dispersion is 15min.
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| CN105585735B (en) * | 2016-03-08 | 2018-04-06 | 西北师范大学 | A kind of palygorskite surface modifying method |
| CN110183619A (en) * | 2019-04-30 | 2019-08-30 | 广州今朝环保材料有限公司 | A kind of fire-retardant epoxy resin solidfied material and its preparation method and application of phosphorus nitrogen one |
| CN112442895B (en) * | 2019-09-03 | 2024-01-12 | 天津工业大学 | Chelate coordination type phosphorus-boron-nitrogen synergistic flame retardant and preparation method thereof |
| CN113956533A (en) * | 2021-11-10 | 2022-01-21 | 安徽江淮汽车集团股份有限公司 | Polyolefin flame-retardant filler, preparation method and application |
| CN116120562A (en) * | 2022-12-09 | 2023-05-16 | 江苏宝源高新电工有限公司 | Halogen-free flame retardant, and preparation method and application thereof |
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| CN101050288A (en) * | 2007-05-22 | 2007-10-10 | 大庆石油管理局 | Method for preparing fire retardant modified plastics without halogen in use for producing plastic laminated tube with steel skeleton |
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| CN101050288A (en) * | 2007-05-22 | 2007-10-10 | 大庆石油管理局 | Method for preparing fire retardant modified plastics without halogen in use for producing plastic laminated tube with steel skeleton |
Non-Patent Citations (3)
| Title |
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| JP特开2003-226818A 2003.08.15 |
| 磷酸三聚氰胺硼酸盐阻燃剂的合成;赵爱明等;《山东化工》;20091231;第38卷(第12期);第2页右栏第2段到第5页左栏表3 * |
| 赵爱明等.磷酸三聚氰胺硼酸盐阻燃剂的合成.《山东化工》.2009,第38卷(第12期),第2页右栏第2段到第5页左栏表3. |
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