CN103570758A - Flame-retardant modified silane coupling agent and preparation method thereof - Google Patents
Flame-retardant modified silane coupling agent and preparation method thereof Download PDFInfo
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- CN103570758A CN103570758A CN201310532280.6A CN201310532280A CN103570758A CN 103570758 A CN103570758 A CN 103570758A CN 201310532280 A CN201310532280 A CN 201310532280A CN 103570758 A CN103570758 A CN 103570758A
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Abstract
The invention discloses a kind of flame-retardant modified silane coupling agents and preparation method thereof, belong to flame retardant area. The molecular structural formula of the silane coupling agent are as follows:
Wherein, R is alkylidene, alkyl arylene or secondary amino group alkylidene, and X is alkoxy. The preparation method, 1) by 2- methyl -2,5- dioxy -1,2- oxygen phospholane and organic solvent are added in reactor, and catalyst is then added, and are stirred evenly, amino silicone is added dropwise to be reacted, the temperature of the reaction is 20~120 DEG C, time of the reaction is 4~for 24 hours, obtain reaction solution; 2) reaction solution obtained in step 1) is separated with separatory funnel, obtains dope, then remove the vacuum drying 3h of the dope, solvent finally obtains the flame-retardant modified silane coupling agent of phosphorus-nitrogen containing. Silane coupling agent of the present invention has better flame retardant effect.
Description
Technical field
The present invention relates to flame retardant area, particularly a kind of flame-retardant modified silane coupling agent and preparation method thereof.
Background technology
Silane coupling agent is by trichlorosilane (HSiCl3) with unsaturated olefin addition under the catalysis of platinum chloric acid of reactive group, then obtains through alcoholysis.Silane coupling agent has combustibility, has great potential safety hazard in application process.Therefore, silane coupling agent being carried out to flame-retardant modified tool is of great significance.
Existing silane coupling agent is being carried out in flame-retardant modified experiment, adopting and in silane coupled agent molecule, introduce phosphoric and nitrogen element.Particularly, take methylene dichloride as solvent, take part polyvalent alcohol or polyphenol as response matrix, drip the phosphorus compound containing active reactive group, filtration obtains filter residue, filter residue be take to tetrahydrofuran (THF) as solvent, triethylamine is attached sour agent, under the protection of rare gas element, dropping is with the siloxane reactions of active function groups, filtration obtains thickness colorless liquid product and is flame-retardant modified silane coupling agent, wherein, the phosphorus compound of active reactive group is phosphorus oxychloride or dichloro-phenyl-phosphate. because phosphoric/nitrogen element has synergistic effect, added in silane coupling agent, can obtain thering is the silane coupling agent compared with high flame retardant effect, the fire-resisting protection of realization to base material, the inflammable problem existing to solve existing silane coupling agent.
In realizing process of the present invention, contriver finds that prior art at least exists following problem:
Existing flame-retardant modified silane coupling agent is in building-up process, the raw material of the active reactive group using is P contained compound, this P contained compound has larger toxicity, in the process of synthetic flame-retardant modified silane coupling agent, P contained compound can endanger the healthy of operator, in addition, the flame-retardant modified synthetic end product of silane coupling agent of existing preparation is mixture, because of its end product not easily separated, the product that wherein has some not clear compositions is residual, thereby affect the use properties of coupling agent, and to the final performance of polymer materials thermostability for example, water-absorbent, mechanical property, antioxidant property causes bad impact.
Summary of the invention
In order to solve the synthesis material of silane coupling agent in prior art, human body is had to the problem of harm, the embodiment of the present invention provides a kind of flame-retardant modified silane coupling agent and preparation method thereof.Described technical scheme is as follows:
On the one hand, the invention provides a kind of flame-retardant modified silane coupling agent, the molecular structural formula of described silane coupling agent is:
Wherein, R is alkylidene group, alkyl arylene or secondary amino group alkylidene group, and X is alkoxyl group.
On the other hand, the invention provides a kind of method of preparing above-mentioned silane coupling agent, described method comprises:
1) by 2-methyl-2, 5-dioxy-1, 2-oxygen phospholane and organic solvent join in reactor according to quality and volume ratio 1g:0.2～4ml, then add catalyzer, described 2-methyl-2, 5-dioxy-1, the quality of 2-oxygen phospholane and described catalyzer and volume ratio are 1g:0.05～0.2ml, stir, dripping aminosiloxane reacts, described 2-methyl-2, 5-dioxy-1, the mol ratio of 2-oxygen phospholane and described aminosiloxane is 1:1～1.1, the temperature of described reaction is 20～120 ℃, the time of described reaction is 4～24h, obtain reaction solution,
2) the described reaction solution obtaining in step 1) is separated with separating funnel, obtain dope, then remove the solvent of described dope, finally obtain described flame-retardant modified silane coupling agent.
Alternatively, described organic solvent is C
5～C
8straight-chain paraffin, hexanaphthene, toluene, acetone, Isosorbide-5-Nitrae-dioxane, DMF and tetrahydrofuran (THF) at least one.
Preferably, described organic solvent is normal heptane.
Further, described catalyzer is tertiary amine compounds.
Preferably, described catalyzer comprises: triethylamine, Tri-n-Propylamine, tri-n-butylamine, N, N-dimethyl butylamine, DIPEA, DMA, N, N-dimethylcyclohexylamine, N, N-diethyl cyclohexylamine or N, N-Diethyl Aniline.Preferably, described catalyzer is triethylamine.
Alternatively, described aminosiloxane is: 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl methyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-aminoethyl)-3-aminopropyl trimethoxysilane, N-(2-aminoethyl)-3-aminopropyl triethoxysilane, m-aminophenyl Trimethoxy silane, p-aminophenyl Trimethoxy silane, 3-aminopropyl three (methoxyl group diethoxy) silane or 3-aminopropyl dimethylethoxysilane.
Preferably, described aminosiloxane is 3-aminopropyl triethoxysilane.
Alternatively, the method except desolventizing described step 2) is vacuum-drying.
The beneficial effect that the technical scheme that the embodiment of the present invention provides is brought is:
1. flame-retardant modified silane coupling agent provided by the invention is mainly used in the interface of the organism/inorganic composite materials of modification, in its molecule, contain carbonamido and hydroxyl activity group, can with resin matrix for example in epoxy resin epoxy group(ing) react, improve the consistency of coupling agent and interlaminar resin, thus less to the detrimentally affect of material mechanical performance.
2. in preparation method provided by the invention, by avirulent 2-methyl-2,5-dioxy-1,2-oxygen phospholane and aminosiloxane react at organic solvent, prepare flame-retardant modified silane coupling agent provided by the invention, thereby in preparation process, avoided the Health hazard to operator of poisonous P contained compound.
3. in preparation method provided by the invention, raw material all can be dissolved in organic solvent provided by the invention completely, and reaction conditions is gentle, temperature of reaction is moderate, there is no the generation of by product, simultaneously, the product generating is insoluble to this organic solvent, can be separated from system at an easy rate, thereby the isolated final product structure of preparation method provided by the invention is clear and definite, composition is single.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, below the accompanying drawing of required use during embodiment is described is briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skills, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the infrared spectra map flow chart of the flame-retardant modified silane coupling agent P-KH550 that provides of the embodiment of the present invention one, and in figure, X-coordinate is wave number, the cm of unit
-1, ordinate zou is transmittance, the % of unit;
Fig. 2 is the EP/SiO that the embodiment of the present invention two provides
2, EP/SiO
2/ KH550 and EP/SiO
2the TG-test result figure of/P-KH550;
Fig. 3 is the EP/SiO that the embodiment of the present invention two provides
2, EP/SiO
2/ KH550 and EP/SiO
2the DTG test result figure of/P-KH550.
Embodiment
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with accompanying drawing, embodiment of the present invention is described further in detail.
On the one hand, the invention provides a kind of flame-retardant modified silane coupling agent, the molecular structural formula of this silane coupling agent is:
Wherein, R is alkylidene group, alkyl arylene or secondary amino group alkylidene group, and X is alkoxyl group.
On the other hand, the invention provides a kind of method of preparing above-mentioned silane coupling agent, the method comprises:
1) by 2-methyl-2,5-dioxy-1,2-oxygen phospholane and organic solvent join in reactor according to quality and volume ratio 1g:0.2～4ml, then add catalyzer, 2-methyl-2,5-dioxy-1, the quality of 2-oxygen phospholane and catalyzer and volume ratio are 1g:0.05～0.2ml, stir, and drip aminosiloxane and react, 2-methyl-2,5-dioxy-1, the mol ratio of 2-oxygen phospholane and aminosiloxane is 1:1～1.1, the temperature of reaction is 20～120 ℃, the time of reaction is 4～24h, obtains reaction solution;
2) the above-mentioned reaction solution obtaining in step 1) is separated with separating funnel, obtain dope, then remove the solvent of dope, finally obtain flame-retardant modified silane coupling agent.
Alternatively, organic solvent is C
5～C
8straight-chain paraffin, hexanaphthene, toluene, acetone, Isosorbide-5-Nitrae-dioxane, DMF and tetrahydrofuran (THF) at least one.Wherein, normal heptane boiling point (98.5 °) temperature is moderate, be easy to remove from product, so normal heptane is preferred organic solvent.
Alternatively, catalyzer is tertiary amine compounds.Comprise: triethylamine, Tri-n-Propylamine, tri-n-butylamine, N, N-dimethyl butylamine, DIPEA, DMA, N, N-dimethylcyclohexylamine, N, N-diethyl cyclohexylamine or N, N-Diethyl Aniline.Wherein triethylamine is moderate, and efficiency is high, is preferred catalyzer,
Alternatively, aminosiloxane is: 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl methyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-aminoethyl)-3-aminopropyl trimethoxysilane, N-(2-aminoethyl)-3-aminopropyl triethoxysilane, m-aminophenyl Trimethoxy silane, p-aminophenyl Trimethoxy silane, 3-aminopropyl three (methoxyl group diethoxy) silane or 3-aminopropyl dimethylethoxysilane.Wherein, 3-aminopropyl triethoxysilane is moderate, and resulting product flame retarding efficiency is high, joins in polymer/inorganic matrix material, the mechanical property of matrix material and thermal characteristics are improved obviously, and be preferred aminosiloxane.
Alternatively, the method except desolventizing step 2) is vacuum-drying.
Embodiment mono-
By 50g2-methyl-2,5-dioxy-1, in the 250ml there-necked flask that 2-oxygen phospholane (OP) and 200ml normal heptane add, on this 250ml there-necked flask, reflux condensing tube, agitator and constant pressure funnel are housed, add again 5ml triethylamine, be warming up to 95 ℃, 80g3-aminopropyl triethoxysilane (KH550) is added to constant pressure funnel and slowly drips, stir reaction 4h simultaneously.Taking-up reaction mixture sat is cooling; with the separated mother liquor of separating funnel; obtain the sticky shape product of lower floor; this product is placed in to the dry about 3h of 100 ℃ of vacuum drying ovens; obtain final product, final product is specially γ-(3-(methyl hydroxy phosphinylidyne base)-propionamido-) propyl-triethoxysilicane, and in this product, R is γ-(3-(methyl hydroxy phosphinylidyne base)-propionamido-) propyl group; be alkylidene group, be called for short P-KH550.
Utilize Attenuated Total Reflectance (Attenuated Total Reflection, ATR) to carry out infrared analysis to the flame-retardant modified silane coupling agent of final product, its gained infrared spectrogram is referring to Fig. 1, known in Fig. 1, and the ownership of each absorption peak is as follows: 3275cm
-1near belong to O-H stretching vibration absorption peak; 2924cm
-1the peak at place belongs to the C-H antisymmetric stretching vibration absorption peak of methylene radical; 1650cm
-1the peak of left and right belongs to the two key stretching vibration absorption peaks of C=O in secondary amide; The peak at 1552cm-1 place belongs to the C-NH flexural vibration absorption peak in secondary amide; 1075cm
-1the peak at place belongs to the antisymmetric stretching vibration absorption peak of Si-O-C; 960cm
-1the peak at place belongs to the stretching vibration absorption peak of C-O key in oxyethyl group; 952cm
-1place belongs to the stretching vibration absorption peak of P-OH.
By infrared analysis result, proved that synthesis technique of the present invention is that reasonably analytical results shows: experimental analysis is consistent with Molecular Structure Design.
Embodiment bis-
Take 100 mass parts silicon-dioxide (purity 99.0%, particle diameter 4.9 μ m), the P-KH550 that the 8 mass parts embodiment of the present invention one provide, join in 500mL ethanol, wherein ethanol is dispersion agent, then adds 2 mass parts Glacial acetic acid, under the Ultrasonic Conditions of 700W, disperses 20min, 80 ℃ of backflow 2h under the condition of strong stirring again, after 2h finishes, suction filtration is also dried, and obtains the SiO of P-KH550 modification
2; P-KH550 is replaced to KH550, repeat above-mentioned experimental procedure, obtain the SiO of KH550 modification
2.
The SiO of any processing will do not passed through
2, KH550 modification SiO
2siO with P-KH550 modification
2with 15 mass parts, add to respectively in the epoxy resin (EP) of three 100 mass parts, and test as follows respectively, 700W ultrasonic wave is after 90 ℃ of dispersing and mixing 30min, adding 25 mass parts diaminodiphenyl-methanes, form curing system, processing condition with 100 ℃/2h+160 ℃/4h are cured system, obtain flame-proof composite material, and composite sample is used EP/SiO successively
2, EP/SiO
2/ KH550, EP/SiO
2/ P-KH550 represents.
Embodiment tri-
By 50g2-methyl-2,5-dioxy-1,2-oxygen phospholane and 120ml hexanaphthene join in 250ml there-necked flask, reflux condensing tube, agitator and constant pressure funnel are housed on flask, add again 10ml Tri-n-Propylamine, be warming up to 20 ℃, 97g N-(2-aminoethyl)-3-aminopropyl triethoxysilane (KH7910) is added to constant pressure funnel and slowly drips, stir reaction 24h simultaneously.Taking-up reaction mixture sat is cooling; with the separated mother liquor of separating funnel; obtain the sticky shape product of lower floor; this product is placed in to the dry about 3h of 100 ℃ of vacuum drying ovens; obtain final product; final product is specially N-(2-aminoethyl)-3-(methyl hydroxy phosphinylidyne base) propionamido-) propyl-triethoxysilicane (in this product, R is N-(2-aminoethyl)-3-(methyl hydroxy phosphinylidyne base) propionamido-) propyl group, R is secondary amino group alkylidene group).Be called for short P-KH791.
Embodiment tetra-
Take 100 mass parts silicon-dioxide (purity 99.0%, particle diameter 4.9 μ m), the P-KH791 that the 8 mass parts embodiment of the present invention three provide, join in 500mL dispersion agent ethanol, add again 2 mass parts Glacial acetic acid, under the Ultrasonic Conditions of 700W, disperse 20min, then under the condition of strong stirring 80 ℃ of backflow 2h, after 2h finishes, suction filtration is also dried, and obtains the SiO of P-KH791 modification
2.
The SiO2 of P-KH791 modification is added to respectively in the epoxy resin (EP) of three 100 mass parts with 15 mass parts, and test as follows respectively, 700W ultrasonic wave is after 90 ℃ of dispersing and mixing 30min, adding 25 mass parts diaminodiphenyl-methanes (DDM), form curing system, processing condition with 100 ℃/2h+160 ℃/4h are cured system, obtain flame-proof composite material EP/SiO2/P-KH791.
Embodiment five
By 50g2-methyl-2,5-dioxy-1, Isosorbide-5-Nitrae-dioxane of 2-oxygen phospholane and 10ml joins in 500ml there-necked flask, and reflux condensing tube, agitator and constant pressure funnel are housed on flask, add again 2.5ml N, accelerine, is warming up to 120 ℃, and the p-aminophenyl Trimethoxy silane of 85g (ATS) is added to constant pressure funnel and slowly drips, stir reaction 10h simultaneously.Taking-up reaction mixture sat is cooling; with the separated mother liquor of separating funnel; obtain the sticky shape product of lower floor; this product is placed in to the dry about 3h of 100 ℃ of vacuum drying ovens; obtain final product; final product is specially p-(3-(methyl hydroxy phosphinylidyne base)-propionamido-) phenylene triethoxyl silane, (in this product, R is p-(3-(methyl hydroxy phosphinylidyne base)-propionamido-) phenylene, and R is alkyl arylene).Be called for short P-ATS.
Embodiment six
Take 100 mass parts silicon-dioxide (purity 99.0%, particle diameter 4.9 μ m), the P-ATS that the 8 mass parts embodiment of the present invention five provide, join in 500mL dispersion agent ethanol, add again 2 mass parts Glacial acetic acid, under the Ultrasonic Conditions of 700W, disperse 20min, then under the condition of strong stirring 80 ℃ of backflow 2h, after 2h finishes, suction filtration is also dried, and obtains the SiO of P-ATS modification
2.
The SiO2 of P-ATS modification is added to respectively in the epoxy resin (EP) of three 100 mass parts with 15 mass parts, and test as follows respectively, 700W ultrasonic wave is after 90 ℃ of dispersing and mixing 30min, adding 25 mass parts diaminodiphenyl-methanes (DDM), form curing system, processing condition with 100 ℃/2h+160 ℃/4h are cured system, obtain flame-proof composite material EP/SiO2/P-ATS.
Adopt oxygen index test and vertical combustion method of testing to test the combustionproperty of above-mentioned three kinds of matrix materials and epoxy resin, adopt Shenzhen to think carefully that universal testing machine tests the mechanical property of matrix material, adopt differential scanning calorimeter (TA-DSC20) the tested glass transition temperature (Tg) of U.S. TA company, adopt German Nai Chi company's thermogravimetric analyzer (TG209F3) test TG-DTG curve, Tg test and TG-DTG(thermogravimetric analysis-derivative thermogravimetric analysis(DTG)) test all at N
2under atmospheric condition, carry out, temperature rise rate is 10 ℃/min, the limiting oxygen index(LOI) of material (LOI), and flexural strength (FS), modulus in flexure (FM), notched Izod impact strength (NIS) and second-order transition temperature (Tg) are as shown in table 1.
Table 1 is matrix material combustionproperty and mechanical performance data
In table: LOI represents limiting oxygen index(LOI); FS represents flexural strength; FM represents modulus in flexure; NIS indication notch shock strength; Tg represents second-order transition temperature.
Table 1 result shows, coupling agent EP/SiO2/P-KH550, the EP/SiO2/P-KH791 of three kinds of modifications that the present invention obtains compares mechanical property, the flame retardant resistance that increases matrix material that all can improve matrix material, improves its second-order transition temperature with all the other matrix materials with EP/SiO2/P-ATS.In addition compare three kinds of fire-retardant coupling agents, wherein P-KH550 adds EP/SiO to
2in after matrix material there is best LOI value and mechanical property.And P-ATS add in EP/SiO2 after composite materials property increase rate relatively little, mechanical property and the second-order transition temperature of the structure influence matrix material of organic group in this explanation coupling agent.
By EP/SiO
2, EP/SiO
2/ KH550 and EP/SiO
2/ P-KH550 carries out TG-DTG test, its result is referring to Fig. 2 and Fig. 3, result shows, the EP/SiO2 matrix material of P-KH550 modification is compared with the EP/SiO2 matrix material of unmodified EP/SiO2 and KH550 modification, there is lower thermolysis speed, higher carbon yield (temperature is greater than 400 ℃ of later carbon yields), and thermostability obviously improves.
Wherein, EP/SiO2/P-KH550 is because P-KH550 phosphorus content in system is high and can effectively improve EP and SiO2 consistency, between each component of material internal, boundary defect is few, thereby makes the limiting oxygen index(LOI) (LOI) of its notched Izod impact strength (NIS), flexural strength (FS) and material higher.
EP/SiO2/P-KH791 contains more amino/amide group in molecule, and energy and EP reaction form more cross-linking set, increase the cross-linking density of resin, thereby make its second-order transition temperature (Tg) higher.
EP/SiO2/P-ATS is the existence due to phenyl ring in ATS, the rigidity of matrix material is increased, thereby make its modulus in flexure (FM) higher.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. a flame-retardant modified silane coupling agent, is characterized in that, the molecular structural formula of described silane coupling agent is:
Wherein, R is alkylidene group, alkyl arylene or secondary amino group alkylidene group, and X is alkoxyl group.
2. a method of preparing silane coupling agent as claimed in claim 1, is characterized in that, described method comprises:
1) by 2-methyl-2, 5-dioxy-1, 2-oxygen phospholane and organic solvent join in reactor according to quality and volume ratio 1g:0.2～4ml, then add catalyzer, described 2-methyl-2, 5-dioxy-1, the quality of 2-oxygen phospholane and described catalyzer and volume ratio are 1g:0.05～0.2ml, stir, dripping aminosiloxane reacts, described 2-methyl-2, 5-dioxy-1, the mol ratio of 2-oxygen phospholane and described aminosiloxane is 1:1～1.1, the temperature of described reaction is 20～120 ℃, the time of described reaction is 4～24h, obtain reaction solution,
2) the described reaction solution obtaining in step 1) is separated with separating funnel, obtain dope, then remove the solvent of described dope, finally obtain described flame-retardant modified silane coupling agent.
3. the method for preparing silane coupling agent according to claim 2, is characterized in that, described organic solvent is C
5～C
8straight-chain paraffin, hexanaphthene, toluene, acetone, Isosorbide-5-Nitrae-dioxane, DMF and tetrahydrofuran (THF) at least one.
4. the method for preparing silane coupling agent according to claim 3, is characterized in that, described organic solvent is normal heptane.
5. the method for preparing silane coupling agent according to claim 1, is characterized in that, described catalyzer is tertiary amine compounds.
6. the method for preparing silane coupling agent according to claim 5, it is characterized in that, described catalyzer comprises: triethylamine, Tri-n-Propylamine, tri-n-butylamine, N, N-dimethyl butylamine, N, N-diisopropylethylamine, DMA, N, N-dimethylcyclohexylamine, N, N-diethyl cyclohexylamine or N, N-Diethyl Aniline.
7. the method for preparing silane coupling agent according to claim 6, is characterized in that, described catalyzer is triethylamine.
8. the method for preparing silane coupling agent according to claim 2, it is characterized in that, described aminosiloxane is: 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl methyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-aminoethyl)-3-aminopropyl trimethoxysilane, N-(2-aminoethyl)-3-aminopropyl triethoxysilane, m-aminophenyl Trimethoxy silane, , p-aminophenyl Trimethoxy silane, 3-aminopropyl three (methoxyl group diethoxy) silane or 3-aminopropyl dimethylethoxysilane.
9. the method for preparing silane coupling agent according to claim 8, is characterized in that, described aminosiloxane is 3-aminopropyl triethoxysilane.
10. the method for preparing silane coupling agent according to claim 2, is characterized in that, described step 2) in except the method for desolventizing be vacuum-drying.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107868254A (en) * | 2017-12-14 | 2018-04-03 | 成都硅宝科技股份有限公司 | A kind of Multifunctional plastic additive and preparation method thereof |
| CN111073348A (en) * | 2019-12-11 | 2020-04-28 | 江苏联瑞新材料股份有限公司 | Preparation method of flame-retardant modified silica micropowder for halogen-free copper-clad plate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000256378A (en) * | 1999-03-08 | 2000-09-19 | Tosoh Corp | Silicon-containing organic phosphoric acid compound, its production, and flame retardant and flame-resistant resin composition containing the same |
| CN101613370A (en) * | 2009-07-22 | 2009-12-30 | 中国科学技术大学 | Flame retardant modified silane coupler of a kind of phosphorous nitrogen and preparation method thereof |
| WO2010062709A2 (en) * | 2008-11-03 | 2010-06-03 | 3M Innovative Properties Company | Phosphorus-containing silsesquioxane derivatives as flame retardants |
| CN102786717A (en) * | 2012-07-19 | 2012-11-21 | 江汉大学 | Acylamino-containing dialkyl phosphinic acid fire retardant and its preparation method |
| CN102816346A (en) * | 2012-07-19 | 2012-12-12 | 江汉大学 | Dialkylphosphinic acid fire retardant containing primary amine groups and preparation method thereof |
-
2013
- 2013-10-31 CN CN201310532280.6A patent/CN103570758A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000256378A (en) * | 1999-03-08 | 2000-09-19 | Tosoh Corp | Silicon-containing organic phosphoric acid compound, its production, and flame retardant and flame-resistant resin composition containing the same |
| WO2010062709A2 (en) * | 2008-11-03 | 2010-06-03 | 3M Innovative Properties Company | Phosphorus-containing silsesquioxane derivatives as flame retardants |
| CN101613370A (en) * | 2009-07-22 | 2009-12-30 | 中国科学技术大学 | Flame retardant modified silane coupler of a kind of phosphorous nitrogen and preparation method thereof |
| CN102786717A (en) * | 2012-07-19 | 2012-11-21 | 江汉大学 | Acylamino-containing dialkyl phosphinic acid fire retardant and its preparation method |
| CN102816346A (en) * | 2012-07-19 | 2012-12-12 | 江汉大学 | Dialkylphosphinic acid fire retardant containing primary amine groups and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| WASSANA YANTASEE等，: "Selective removal of lanthanides from natural waters, acidic streams and dialysate", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107868254A (en) * | 2017-12-14 | 2018-04-03 | 成都硅宝科技股份有限公司 | A kind of Multifunctional plastic additive and preparation method thereof |
| CN111073348A (en) * | 2019-12-11 | 2020-04-28 | 江苏联瑞新材料股份有限公司 | Preparation method of flame-retardant modified silica micropowder for halogen-free copper-clad plate |
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Application publication date: 20140212 |