CN102617861B - Melamine cyanurate flame retardant agent containing organic silicone and preparation process thereof - Google Patents
Melamine cyanurate flame retardant agent containing organic silicone and preparation process thereof Download PDFInfo
- Publication number
- CN102617861B CN102617861B CN 201210107942 CN201210107942A CN102617861B CN 102617861 B CN102617861 B CN 102617861B CN 201210107942 CN201210107942 CN 201210107942 CN 201210107942 A CN201210107942 A CN 201210107942A CN 102617861 B CN102617861 B CN 102617861B
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- melamine cyanurate
- retardant agent
- phenyl
- mca
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000012757 flame retardant agent Substances 0.000 title abstract 9
- 229920001296 polysiloxane Polymers 0.000 title abstract 3
- 239000003063 flame retardant Substances 0.000 claims abstract description 50
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 7
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000007865 diluting Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 6
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 3
- 241000370738 Chlorion Species 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims 1
- 239000012895 dilution Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- 239000005054 phenyltrichlorosilane Substances 0.000 abstract 1
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 238000001354 calcination Methods 0.000 description 5
- 239000004114 Ammonium polyphosphate Substances 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 4
- 229920001276 ammonium polyphosphate Polymers 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- -1 organosilyl melamine cyanurate Chemical compound 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229940059574 pentaerithrityl Drugs 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241001131796 Botaurus stellaris Species 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000001367 organochlorosilanes Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention belongs to the field of preparing a flame retardant agent and discloses a melamine cyanurate (MCA) flame retardant agent containing organic silicone and a preparation process thereof, wherein the flame retardant agent is prepared by the polycondensation of phenyl trichlorosilane and melamine cyanurate (MCA). The flame retardant agent contains two elements of silicone and nitrogen, which have synergistic flame-retardation effects in the same molecule so that the flame retardant agent has good synergistic flame-retardation effects. According to the flame retardant agent, the MCA is bonded to silicone-contained phenyl so that the hydrophobic performance is good, the compatibility between the flame retardant agent and the polymer matrix is reinforced, the transport phenomenon of the flame retardant agent is difficult to produce, the polymer materials are provided with an enduring flame retardant property, and the mechanical performance and the processing performance of flame retardant polymer materials can be improved.
Description
Technical field
The invention belongs to the preparation field of fire retardant, relate to a kind of environment-friendly type non-bittern combustion inhibitor, be specifically related to a kind of organosilyl melamine cyanurate (MCA) fire retardant, particularly preparation method of this fire retardant of containing.
Background technology
Along with the WEEE of European Union and the enforcement of two instructions of ROHS, the macromolecular material environmental requirement further improves.Have good flame retardant effect and the halogen-free expansion fire retardant of environmental requirement (IFR) develops by leaps and bounds, its Application Areas is more and more extensive.IFR mainly comprises acid source, carbon source and three parts of source of the gas, usually use ammonium polyphosphate (APP) as acid source, trimeric cyanamide (MEL) is as source of the gas, tetramethylolmethane (PER) is made carbon source, be subjected to the high carbonaceous foam layer that can generate even compact when hot, have heat insulation, oxygen barrier, press down cigarette, the effect of anti-molten drop, given play to flame retardant properties preferably.But this fire retardant is rich in hydrophilic radical, mostly is hydrophilic, and is poor with the macromolecule matrix consistency.For reaching fire-retardant requirement, the addition of IFR is larger, generally needs 25～30%, can affect the physicals of flame retarded polymeric material in addition.
Melamine cyanurate (MCA) is a kind of lubricant and the fire retardant that the eighties is invented by Japan and the U.S. in last century, and it is made by trimeric cyanamide and cyanuric acid reaction.MCA is heated highly stable below C at 300 °, begin distillation about 350 ° of C, but do not decompose, and its decomposition temperature is about 440 °～450 ° C.What MCA was most widely used is nylon, because the bond characters of MCA is similar to nylon, therefore nylon fire-retardant had special efficacy.MCA can with the composite use of other fire retardant, have good flame retardant effect.But because the MCA nitrogen content is high, the moisture absorption very easily is to having promoted the use of certain influence.
Organic silicon fibre retardant is a kind of novel halogen-free flame retardants, is also a kind of one-tenth charcoal smoke suppressant, has the advantages such as efficient, smokeless, nontoxic, pollution-free.Except flame retardant properties is arranged preferably, can also improve machinery, the processing characteristics of polymer base material.Because the organic silicon fibre retardant price is more expensive, apply being subject to certain impact.
Summary of the invention
The invention provides a kind of novel halogen-free flame retardants and preparation method.The present invention combines organosilicon and nitrogenated flame retardant, collects silicon, two kinds of elements of nitrogen in a part, and the flame retardant synergistic effect fire retardant more composite than simple physical mixed is better.Because of on the nitrogenated flame retardant first line of a couplet organosilicon, hydrophobic performance is good, strengthened the consistency of this fire retardant and polymer base material, make it with base material better the phase mixed phase hold, be difficult for producing transport phenomena, thereby obtain lasting flame retardant properties, and can also improve mechanical mechanics property and the processing characteristics of flame retarded polymeric material.This fire retardant both can use separately, also can with the composite use of other halogen-free flame retardantss, can be used for the fire-retardant of the macromolecular materials such as PA, PU, rubber, nylon, urethane, polyolefine.
In order to solve the problems of the technologies described above, the present invention is solved by following technical proposals:
Contain organosilyl melamine cyanurate flame retardant, the fire retardant of this fire retardant for being made by phenyl-trichloro-silicane and melamine cyanurate polycondensation.
As preferably, the mol ratio of described phenyl-trichloro-silicane and melamine cyanurate is 0.3-0.66:1.
The present invention utilizes organochlorosilane and contains-NH
2The compound of reactive hydrogen reacts and makes.It is starting raw material that the present invention adopts phenyl-trichloro-silicane and melamine cyanurate (MCA), makes in RSi-Cl in phenyl-trichloro-silicane and MCA-NH
2Polycondensation occuring, emit HCl gas, generates the RSi-N key.Because being associated with three chlorine atoms on same Siliciumatom in phenyl-trichloro-silicane, and remaining two active-NH only on MCA
2, add the impact of steric effect, these two kinds of compounds generate 3 D cross-linked polymkeric substance each intermolecular being cross-linked with each other.Because of MCA-NH
2On the first line of a couplet silyl phenyl, have good hydrophobic performance, eliminated the very easily defective of the moisture absorption of MCA, strengthened the consistency with polymer base material, improved mechanical property and the processing characteristics of flame retarded polymeric material.
The phenyl-trichloro-silicane that the present invention adopts and the chemical structural formula of melamine cyanurate (MCA) are as follows:
Its synthesis preparation method of fire retardant of the present invention comprises the steps and processing condition:
Take a certain amount of melamine cyanurate (MCA) and put into reaction system, add appropriate diluting solvent, the limit is stirred and is added required phenyl-trichloro-silicane, and the mol ratio of MCA and phenyl-trichloro-silicane can be regulated arbitrarily between 1:0.33 to 1:0.66.Heating is controlled temperature of reaction at 50～160 ° of C, and optimal reaction temperature is at 80～130 ° of C.HCl gas with the alkali liquor absorption reaction generates reacted 2～8 hours, until emit without HCl gas.Diluting solvent (recyclable use again) is removed in underpressure distillation, adds appropriate distilled water to be heated to 60～80 ° of C and stirs half an hour, and is cooling, filter, and is washed till without chlorion with distilled water.The white hydrophobic powder that drying obtains is fire retardant of the present invention.
As preferably, described diluting solvent is at least a in benzene,toluene,xylene, hexanaphthene and trichloroethane.
The present invention has significant technique effect owing to having adopted above technical scheme:
Fire retardant of the present invention contains two kinds of elements of silicon, nitrogen that can play the cooperative flame retardant effect in a part, have better cooperative flame retardant effect.Due to this fire retardant on the MCA first line of a couplet silyl phenyl, hydrophobic performance is fine, strengthened the consistency of fire retardant and macromolecule matrix, be difficult for producing the transport phenomena of fire retardant, make macromolecular material have lasting flame retardant properties, also can improve mechanical mechanics property and the processing characteristics of flame retarded polymeric material.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail:
Embodiment 1
Take 38.2g(0.15mol) MCA, be added in many mouthfuls of flasks with agitator, thermometer, prolong (external gas absorbing device), then add 150ml benzene, stir loose back and stir limit dropping 21.2g(0.1mol) phenyl-trichloro-silicane.Heating, 80 ° of C of temperature control make it under refluxad to react, the HCl gas alkali liquor absorption of emitting, stirring reaction 4h emits stopped reaction without HCl gas with the pH detection paper.Benzene (recyclable use again) is removed in underpressure distillation.Add 150ml distilled water after slightly cold, be heated to 70 ° of C and stir half an hour, cooling, filtration.Be washed till in filtrate without chlorion with distilled water, dry to get white loose powder 45.5g, yield 93.1%.300 ° of C calcinations are 30 minutes in retort furnace, and weightless 1.6%.Hydrophobicity is fine, places in water not sink in a week.
Embodiment 2
Other conditions are with embodiment 1, and the phenyl-trichloro-silicane that adds is 10.6g(0.05mol), obtain product 40.2g, yield 92.4%.300 ° of C calcinations are 30 minutes in retort furnace, and weightless 1.2%.Hydrophobicity is still fine, places in water not sink in a week.
Embodiment 3
Other conditions are with embodiment 1, and diluting solvent is used instead and added 150ml toluene, and temperature control detects and emits without HCl gas 100 ° of C back flow reaction 3 hours, and subsequent purification is processed with embodiment 1, gets product 45.3g, yield 92.6%.300 ° of C calcination losses 1.5%.Hydrophobicity is with embodiment 1.
Embodiment 4
Other conditions are with embodiment 1, and diluting solvent is used instead and added 150ml dimethylbenzene, and 120 ° of C stirring reactions of temperature control detect after 2 hours and emit without HCl.The subsequent purification treatment step gets product 45.2g with embodiment 1, yield 92.4%.300 ° of C calcination losses 1.5%, hydrophobicity is with embodiment 1.
Embodiment 5
Take 76.4g(0.3mol) MCA puts into reaction system, adds the 200ml trichloroethane, adds 31.8g(0.15mol while stirring) phenyl-trichloro-silicane, 90 ° of C back flow reaction of temperature control 4 hours detect and emit without HCl gas.The subsequent purification treatment step gets product 85.5g with embodiment 1,92.5%, 300 ° of C calcination loss 1.4% of yield, and hydrophobic performance is with embodiment 1.The fire retardant that this example is made mixes for the ratio of 1:0.8:3 in mass ratio with tetramethylolmethane (PER) and ammonium polyphosphate (APP), obtains halogen-free expansible compound flame retardant A.Compound flame retardant A and polypropylene (PP) dry 3 hours of 120 ° of C, are put into the high-speed mixer mixing for the ratio of 1:3 in mass ratio, and the use torque rheometer is even at 260 ° of C premixs.Then be injection molded into standard test specimen at 280 ° of C, carry out the vertical combustion method by U.S. UL94 standard and measure flame retardant properties, result reaches the V-0 level.Show that fire retardant performance of the present invention is good, can reach the flame-retardant standard requirement of V-0 level under the condition of 25% addition.
In a word, the above is only preferred embodiment of the present invention, and all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to the covering scope of patent of the present invention.
Claims (4)
1. contain organosilyl melamine cyanurate flame retardant, it is characterized in that: the fire retardant of this fire retardant for being made by phenyl-trichloro-silicane and melamine cyanurate polycondensation, the mol ratio of described phenyl-trichloro-silicane and melamine cyanurate is 0.3-0.66:1.
2. the preparation method who contains organosilyl melamine cyanurate flame retardant according to claim 1, is characterized in that, method is as follows:
A, will mix through melamine cyanurate and the phenyl-trichloro-silicane after diluting solvent dilution, controlling temperature of reaction is 50-160 ° of C, and the HCl gas with the alkali liquor absorption reaction generates reacted 2-8 hour, until emit without HCl gas;
Diluting solvent is removed in b, underpressure distillation, adds distilled water to be heated to 60～80 ° of C and stirs 0.5 hour, and cooling, filtration is washed till without chlorion the white hydrophobic powder that obtains after drying with distilled water.
3. the preparation method who contains organosilyl melamine cyanurate flame retardant according to claim 2, it is characterized in that: the temperature of reaction in described step a is 80-130 ° of C.
4. the preparation method who contains organosilyl melamine cyanurate flame retardant according to claim 2 is characterized in that: described diluting solvent is at least a in benzene,toluene,xylene, hexanaphthene and trichloroethane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210107942 CN102617861B (en) | 2012-04-13 | 2012-04-13 | Melamine cyanurate flame retardant agent containing organic silicone and preparation process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210107942 CN102617861B (en) | 2012-04-13 | 2012-04-13 | Melamine cyanurate flame retardant agent containing organic silicone and preparation process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102617861A CN102617861A (en) | 2012-08-01 |
| CN102617861B true CN102617861B (en) | 2013-11-06 |
Family
ID=46558100
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210107942 Active CN102617861B (en) | 2012-04-13 | 2012-04-13 | Melamine cyanurate flame retardant agent containing organic silicone and preparation process thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102617861B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109265689A (en) * | 2018-08-10 | 2019-01-25 | 南京万和新材料有限公司 | A kind of expanding flame-proof material and preparation method thereof of siliceous nitrogen phosphorus |
| CN109735103B (en) * | 2019-01-14 | 2021-12-21 | 浙江新力新材料股份有限公司 | Precipitation-resistant halogen-free flame-retardant polyamide composite material soaked in water and preparation method thereof |
| CN109762013B (en) * | 2019-01-31 | 2021-04-16 | 杭州捷尔思阻燃化工有限公司 | Melamine cyanurate with silane structure, preparation method and application thereof |
| CN114106340B (en) * | 2021-12-28 | 2023-07-21 | 力美达新材料科技研究开发(广东)有限公司 | Organosilicon hybridized melamine cyanurate and preparation method and application thereof |
| CN116425939B (en) * | 2023-06-08 | 2023-09-12 | 广州亚伊汽车零部件有限公司 | Environment-friendly handrail foaming material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1865329A (en) * | 2005-05-20 | 2006-11-22 | 长兴化学工业股份有限公司 | Flame-proof agent and flame-proof resin composition comprising same, and its uses |
| CN101914220A (en) * | 2010-08-27 | 2010-12-15 | 北京工商大学 | Method for preparing nano melamine cyanurate acid (MCA) |
| US7968629B2 (en) * | 2006-03-17 | 2011-06-28 | Mitsubishi Engineering-Plastics Corporation | Flame retardant polyamide resin composition and molded article |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101177289B1 (en) * | 2010-05-07 | 2012-08-27 | 동남이엔씨(주) | Eco-friendly silicon fireproof material for civil structure enabling difficult combustion |
-
2012
- 2012-04-13 CN CN 201210107942 patent/CN102617861B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1865329A (en) * | 2005-05-20 | 2006-11-22 | 长兴化学工业股份有限公司 | Flame-proof agent and flame-proof resin composition comprising same, and its uses |
| US7968629B2 (en) * | 2006-03-17 | 2011-06-28 | Mitsubishi Engineering-Plastics Corporation | Flame retardant polyamide resin composition and molded article |
| CN101914220A (en) * | 2010-08-27 | 2010-12-15 | 北京工商大学 | Method for preparing nano melamine cyanurate acid (MCA) |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102617861A (en) | 2012-08-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102617861B (en) | Melamine cyanurate flame retardant agent containing organic silicone and preparation process thereof | |
| CN105542160B (en) | Bicyclo cage shaped macromolecular expansion type flame retardant of one-component phosphorus nitrogen and its preparation method and application | |
| CN105175777B (en) | It is a kind of for phosphorus nitrogen concerted reaction type fire retardant of polyurethane and its preparation method and application | |
| CN103113619B (en) | Triazine ring containing caged organic phosphate flame retardant and preparation method thereof | |
| CN102146093B (en) | Cage-shaped organic silicon flame retardant charring agent and preparation method thereof | |
| CN102731553B (en) | Tris(dichloropropyl) tribromophenoxy chloropropyl silicate compound and preparation method thereof | |
| CN105348326B (en) | A kind of N P fire proofings and preparation method thereof and the application in textile | |
| CN100462418C (en) | Silicious expanding fire retardant and its prepn process | |
| CN102634017B (en) | Organosilicone-containing nitrogen phosphorus flame retardant and preparation method thereof | |
| CN101935399A (en) | Method for preparing phosphorus-containing organosilicon flame retardant | |
| CN104558684A (en) | DOPO-containing dioxacaprophosphate flame retardant as well as preparation method and application thereof | |
| CN102875816B (en) | Organosilicone modified halogen-free intumescent flame retardant and preparation method thereof | |
| CN105924645A (en) | Halogen-free expanding flame retardant containing polymeric macromolecule triazine rings and preparation method of halogen-free expanding flame retardant | |
| CN103073889B (en) | Flame retardant thermosetting resin and preparation method thereof | |
| CN102617645B (en) | 1-oxo-4-hydroxymethyl-1-phospholane-2, 6, 7-trioxabicyclo [2, 2, 2] octane derivative with flame retardation effect and preparation of derivative | |
| CN104479172B (en) | A kind of preparation method of the APP of Surface coating fluorine containing silicone oil | |
| CN103113409A (en) | Triazine ring structure containing caged organic phosphate and preparation method thereof | |
| CN106928490B (en) | A kind of inorganic-organic hybridization nano compound, preparation method and its flame-proof polylactic acid with the fire-retardant synergistic effect of chain extension- | |
| CN105153468A (en) | Phosphorus-nitrogen-silicon compound loaded montmorillonite flame retardant and preparation method thereof | |
| CN107868255A (en) | The preparation method and applications of POSS DOPO triazine derivative flame retardants with self assembly humidification | |
| CN101891896B (en) | Expansible fire retardant containing fluorine-phosphorus-nitrogen oligomer and preparation method thereof | |
| CN105199146B (en) | A kind of hydrotalcite composite flame-retardant agent and preparation method thereof | |
| CN105968410B (en) | One kind containing polyhydroxy, phosphorus system triazine ring expansion type flame retardant and preparation method | |
| CN102675650B (en) | Organic silicon-modified phosphorus-containing halogen-free expansion flame retardant and preparation method thereof | |
| CN102604655B (en) | Novel nitrogen-containing organic silicon flame retardant and preparation method of the flame retardant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP03 | Change of name, title or address |
Address after: 312300 Zhejiang Province, Shaoxing city Shangyu District Baiguan Street Fortune Plaza No. 3 Building 9 floor Patentee after: ZHEJIANG HUAYI ENGINEERING DESIGN CO.,LTD. Address before: Fortune Plaza Shangyu Baiguan street 312300 city in Zhejiang province Shaoxing city 3 Building 9 floor Patentee before: ZHEJIANG HUAYI ENGINEERING DESIGN Co.,Ltd. |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Melamine cyanurate flame retardant containing organic silicon and its preparation method Effective date of registration: 20211025 Granted publication date: 20131106 Pledgee: Industrial and Commercial Bank of China Limited Shangyu sub branch Pledgor: ZHEJIANG HUAYI ENGINEERING DESIGN CO.,LTD. Registration number: Y2021330002032 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20220707 Granted publication date: 20131106 Pledgee: Industrial and Commercial Bank of China Limited Shangyu sub branch Pledgor: ZHEJIANG HUAYI ENGINEERING DESIGN CO.,LTD. Registration number: Y2021330002032 |