CN102634017B - Organosilicone-containing nitrogen phosphorus flame retardant and preparation method thereof - Google Patents
Organosilicone-containing nitrogen phosphorus flame retardant and preparation method thereof Download PDFInfo
- Publication number
- CN102634017B CN102634017B CN 201210107966 CN201210107966A CN102634017B CN 102634017 B CN102634017 B CN 102634017B CN 201210107966 CN201210107966 CN 201210107966 CN 201210107966 A CN201210107966 A CN 201210107966A CN 102634017 B CN102634017 B CN 102634017B
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- phosphorus
- organosilicone
- preparation
- containing nitrogen
- 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
Landscapes
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the field of synthetic preparation of flame retardants and discloses an organosilicone-containing nitrogen phosphorus flame retardant and a preparation method thereof. The organosilicone-containing nitrogen phosphorus flame retardant is formed by phenyl trichlorosilane, phosphorus oxychloride and melamine cyanuric acid (MCA) through polycondensation. In the organosilicone-containing nitrogen phosphorus flame retardant, three elements, namely, silicon, phosphorus and nitrogen, which can have synergistic flame-retardation effect are contained in the same molecule so that better synergistic flame-retardation effect can be expressed. The organosilicone-containing nitrogen phosphorus flame retardant contains silicon phenyl and has good hydrophobic performance, the compatibility between the organosilicone-containing nitrogen phosphorus flame retardant and a macromolecule matrix is strengthened, the phenomenon of migration precipitation of the flame retardant is not easy to generate, a macromolecule has durable flame retardant property, and the mechanical properties and the processing properties of a macromolecule material can be also improved.
Description
Technical field
The invention belongs to the synthetic preparation field of fire retardant, relate to a kind of novel halogen-free environment-friendly flame-proof agent, be specifically related to a kind of organosilyl phosphorus-nitrogen containing flame retardant that contains, particularly the preparation method of this fire retardant.
Background technology
Current macromolecular material has been widely used in every field, so the fire-retardant research of macromolecular material has become an important research direction in material field.Though traditional halogenated flame retardant flame retardant effect is good, can produce a large amount of smog and toxic gas when meeting fire burns, threaten people's life security.Along with the enhancing of people's environmental protection, awareness of safety, the low cigarette of exploitation, nontoxic halogen-free flame retardants become a focus of current flame retardant area.Halogen-free expansion fire retardant (IFR) has become an important development direction of current fire retardant material because having the high and low cigarette of flame retarding efficiency, characteristics such as nontoxic.IFR is main nucleus with P, N, C, being subjected to highly can to produce P-N cooperative flame retardant effect when hot, generates the carbonaceous foam layer of even compact, has heat insulation, oxygen barrier, presses down the effect of cigarette, anti-molten drop, performance good flame performance.Usually composite as IFR with ammonium polyphosphate (APP), trimeric cyanamide (MEL) and tetramethylolmethane (PER).Owing to be rich in NH among the IFR
4 +,-NH
2,-hydrophilic radicals such as OH, the moisture absorption is poor with the macromolecule matrix consistency easily, and easily migration precipitation is so will carry out surface modification treatment usually.The general consistency that adopts micro encapsulation or coupling agent surface modification can improve IFR and polymer base material.
Melamine cyanurate (MCA) be last century the eighties by the U.S. and day the present invention's a kind of lubricant and fire retardant, nylon fire-retardant had special efficacy.MCA can with the composite use of other fire retardant, have the good flame effect.But because MCA is rich in hydrophilic radical, the moisture absorption very easily.
Organic silicon fibre retardant has efficient, nontoxic, smokeless, no molten drop, advantage such as pollution-free also are a kind of one-tenth charcoal smoke suppressants, with phosphorus, the composite use of nitrogen based flame retardant, can bring into play good cooperative flame retardant effect.In addition, can also improve mechanical property and the processing characteristics of flame retarded polymeric material.But because price is more expensive, it is still not extensive to apply face.
Summary of the invention
The invention provides a kind of organosilyl phosphorus, nitrogen flame retardant and preparation method of containing.The present invention combines organosilicon, P contained compound and nitrogen flame retardant, collects nitrogen, phosphorus, three kinds of elements of silicon in a part, can better bring into play the cooperative flame retardant effect.Owing to introduced organosilicon at the nitrogen flame retardant, has good hydrophobic performance, strengthened the consistency of this fire retardant and polymer base material greatly, make fire retardant be difficult for producing the migration precipitation phenomenon, make macromolecular material obtain lasting flame retardant properties, 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 widely used in the fire-retardant of macromolecular materials such as nylon, rubber, urethane, polyolefine.
In order to solve the problems of the technologies described above, the present invention is solved by following technical proposals:
Contain organosilyl phosphorus-nitrogen containing flame retardant, the fire retardant of this fire retardant for being made by phenyl-trichloro-silicane, phosphorus oxychloride and melamine cyanurate polycondensation.The mol ratio of phenyl-trichloro-silicane, phosphorus oxychloride and melamine cyanurate is 0.1-0.56:0.1-0.56:1.
The present invention utilizes organochlorosilane, phosphorus oxychloride and contains-NH
2The compound of reactive hydrogen reacts and makes.The present invention adopts phenyl-trichloro-silicane, phosphorus oxychloride and melamine cyanurate (MCA) to be prepared from for starting raw material.Three P-Cl keys are arranged in the phosphorus oxychloride, three RSi-Cl keys are arranged in the phenyl-trichloro-silicane, and have two active-NH on the MCA
2Because the influence of steric effect, these three kinds of compounds are difficult to the corresponding compound that generates clear and definite structure one by one, but generate 3 D cross-linked polymkeric substance in each intermolecular polycondensation that is cross-linked with each other.Because having silyl phenyl in this fire retardant, hydrophobic performance is fine, has strengthened the consistency with polymer base material, also can improve machinery, the processing characteristics of flame retarded polymeric material.
The chemical structural formula of phenyl-trichloro-silicane, phosphorus oxychloride and melamine cyanurate (MCA) that the present invention adopts is as follows:
Fire retardant its preparation method of the present invention is as follows:
Take by weighing a certain amount of melamine cyanurate (MCA) and put into reaction system, add an amount of diluting solvent, the limit is stirred and is added required as calculated phenyl-trichloro-silicane and the mixed solution of phosphorus oxychloride.The mol ratio of MCA, phenyl-trichloro-silicane and phosphorus oxychloride can be regulated arbitrarily between 1:0.1～0.56:0.1～0.56.Heating, the control temperature of reaction is at 50～160 ° of C, and optimal reaction temperature is at 80～130 ° of C.HCl gas with the alkali lye absorption reaction generates reacted 2～8 hours, emitted until no HCl gas.Diluting solvent (recyclable use again) is removed in underpressure distillation, adds an amount of distilled water and is heated to 60～80 ° of C and stirs half an hour, cooling, filters, and is washed till no chlorion with distilled water.The white hydrophobic powder that drying obtains is fire retardant of the present invention.
As preferably, described diluting solvent can be one or more the mixed solvent in benzene,toluene,xylene, hexanaphthene, the trichloroethane.
The present invention has significant technique effect owing to adopted above technical scheme:
Fire retardant of the present invention contains the silicon phenyl, hydrophobic performance is fine, has strengthened the consistency of this fire retardant and macromolecule matrix, is difficult for producing the migration precipitation phenomenon of fire retardant, make polymer have lasting flame retardant properties, also can improve mechanical mechanics property and the processing characteristics of flame retarded polymeric material.
Embodiment
Describe in further detail below in conjunction with the present invention of embodiment:
Embodiment 1
Take by weighing 38.2g(0.15mol) MCA, be added in the many mouthfuls of flasks that have agitator, thermometer, prolong (external gas absorbing device), add 150ml benzene again, stirring the back of loosing stirs the limit and drips 10.6g(0.05mol) phenyl-trichloro-silicane and 7.7g(0.05mol) mixed solution of phosphorus oxychloride, drip off post-heating, the control temperature of reaction is that 80 ° of C make it to reflux, the HCl gas of emitting absorbs with alkali lye, stirring reaction 3.5h has not had HCl gas with the pH detection paper and has emitted stopped reaction.Benzene (recyclable use again) is removed in underpressure distillation.Cold slightly back adds 150ml distilled water, is heated to 70 ° of C and stirs half an hour, cooling, filtration.Being washed till with distilled water does not have chlorion in the filtrate, dry white loose powder 42.3g, yield 92.2%.The product hydrophobic performance is fine, places in the water not sink in a week.This product theory contains N 41.1%, contains P 3.4%, contains Si 3.0%.Measured value contains N 41.7%, contains P 3.2%, contains Si 2.9%.300 ° of C calcinations are 30 minutes in retort furnace, and weightless 1.3%.
Embodiment 2
Other conditions are with embodiment 1, and diluting solvent is used instead and added 150ml toluene, 100 ° of C back flow reaction of temperature control 3 hours, and detection has not had HCl gas and has emitted.The subsequent purification treatment step gets product 42.1g with embodiment 1, yield 91.7%, and hydrophobic performance is with embodiment 1.300 ° of C calcination losses 1.2%.
Embodiment 3
Taking by weighing 38.2g(0.15mol) MCA is added in the reaction system with embodiment 1, add 150ml toluene again, stir and to drip 3.2g(0.015mol down) phenyl-trichloro-silicane and 13g(0.085mol) mixed solution of phosphorus oxychloride, 100 ° of C back flow reaction of temperature control 3 hours, detection has not had HCl gas and has emitted.The subsequent purification treatment step gets product 40g with embodiment 1, yield 91.3%.Hydrophobic performance is with 1,300 ° of C calcination loss 1.5% of embodiment.
Embodiment 4
Other conditions are with embodiment 3, drip 18g(0.085mol) phenyl-trichloro-silicane and 2.3g(0.015mol) mixed solution of phosphorus oxychloride, 100 ° of C back flow reaction of temperature control 3 hours.The subsequent purification treatment step gets product 44.2g with embodiment 1, yield 92.3%.Hydrophobic performance is with 1,300 ° of C calcination loss 1.2% of embodiment.
Embodiment 5
Other conditions are with embodiment 1, and diluting solvent is used 150ml dimethylbenzene instead, and 120 ° of C stirring reactions of temperature control detected after 2.5 hours not to have been had HCl and emit.The subsequent purification treatment step gets product 42.1g with embodiment 1, yield 91.7%.Hydrophobic performance is with embodiment 1.300 ° of C calcination losses 1.3%.
Embodiment 6
Taking by weighing 76.4g(0.3mol) MCA puts into the reaction system with embodiment 1, adds the 200ml trichloroethane again, stir to drip 21.2g(0.1mol down) phenyl-trichloro-silicane and 15.3g(0.1mol) mixed solution of phosphorus oxychloride.90 ° of C back flow reaction of temperature control 4 hours.The subsequent purification treatment step gets product 85g with embodiment 1, yield 92.6%, and hydrophobic performance is with embodiment 1.300 ° of C calcination losses 1.4%.The fire retardant that this example is made and tetramethylolmethane (PER) and ammonium polyphosphate (APP) are the mixed of 1:0.8:2.5 by mass ratio, obtain compound flame retardant A.Dry 3 hours of 120 ° of C, be that the ratio of 1:3 put into high-speed mixer mixing in mass ratio with compound flame retardant A and polypropylene (PP), use torque rheometer even at 260 ° of C premixs.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, the result reaches the V-0 level.Show that fire retardant performance of the present invention is good, under the condition of 25% addition, can reach the flame-retardant standard requirement of V-0 level.
In a word, the above only is preferred embodiment of the present invention, and all equalizations of doing according to the present patent application claim change and modify, and all should belong to the covering scope of patent of the present invention.
Claims (4)
1. contain organosilyl phosphorus-nitrogen containing flame retardant, it is characterized in that: the fire retardant of this fire retardant for being made by phenyl-trichloro-silicane, phosphorus oxychloride and melamine cyanurate polycondensation, the mol ratio of described phenyl-trichloro-silicane, phosphorus oxychloride and melamine cyanurate is 0.1-0.56:0.1-0.56:1.
2. the preparation method who contains organosilyl phosphorus-nitrogen containing flame retardant according to claim 1 is characterized in that method is as follows:
A, melamine cyanurate is uniformly dispersed in diluting solvent, adds phenyl-trichloro-silicane and phosphorus oxychloride, the control temperature of reaction is at 50-160 ° of C, and the HCl gas with the alkali lye absorption reaction generates reacted 2-8 hour, emitted until no HCl gas;
Diluting solvent is removed in b, underpressure distillation, adds distilled water and is heated to 60-80 ° of C stirring 0.5 hour, is cooled to room temperature, filters, and is washed till no chlorion with distilled water, the white hydrophobic powder that obtains after the drying.
3. the preparation method who contains organosilyl phosphorus-nitrogen containing flame retardant according to claim 2 is characterized in that: described diluting solvent is one or more the mixed solvent in benzene,toluene,xylene, hexanaphthene, the trichloroethane.
4. the preparation method who contains organosilyl phosphorus-nitrogen containing flame retardant according to claim 2, it is characterized in that: the temperature of reaction of described step a is at 80-130 ° of C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210107966 CN102634017B (en) | 2012-04-13 | 2012-04-13 | Organosilicone-containing nitrogen phosphorus flame retardant and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210107966 CN102634017B (en) | 2012-04-13 | 2012-04-13 | Organosilicone-containing nitrogen phosphorus flame retardant and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102634017A CN102634017A (en) | 2012-08-15 |
| CN102634017B true CN102634017B (en) | 2013-09-25 |
Family
ID=46618601
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210107966 Active CN102634017B (en) | 2012-04-13 | 2012-04-13 | Organosilicone-containing nitrogen phosphorus flame retardant and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102634017B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106349704A (en) * | 2016-08-27 | 2017-01-25 | 曾照韦 | Intumescent flame-retardant fireproof and heatproof material |
| 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 |
| CN109337079A (en) * | 2018-09-11 | 2019-02-15 | 南京理工大学 | Aggretion type phosphorus nitrogen silicon fire retardant, synthetic method and its application |
| CN112538245B (en) * | 2020-12-04 | 2022-11-29 | 广东晨宝复合材料股份有限公司 | Daylighting tile resin and preparation method thereof |
| CN115304636A (en) * | 2022-08-15 | 2022-11-08 | 铨盛聚碳科技股份有限公司 | Organic silicon flame retardant containing phosphorus and nitrogen, and preparation method and application thereof |
| CN115819783B (en) * | 2022-09-26 | 2023-08-22 | 山东天一化学股份有限公司 | Hyperbranched macromolecular flame retardant containing P, N, si and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1847362A (en) * | 2006-05-11 | 2006-10-18 | 华东理工大学 | Expansion type fireproof moisture-resisting phosphorus-nitrogen material and its prepn |
| CN101092503A (en) * | 2007-06-05 | 2007-12-26 | 华东理工大学 | Nano composite material of flame retardant epoxy resin made from salt of phosphate bi melamine |
| CN102070667A (en) * | 2010-12-30 | 2011-05-25 | 上海交通大学 | Organosilicon compound containing phosphorus and nitrogen and preparation method thereof |
| JP5159916B2 (en) * | 2011-04-28 | 2013-03-13 | 株式会社東芝 | host |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05159916A (en) * | 1991-12-04 | 1993-06-25 | Idemitsu Kosan Co Ltd | Magnetic powder composition covered with resin |
| US6495624B1 (en) * | 1997-02-03 | 2002-12-17 | Cytonix Corporation | Hydrophobic coating compositions, articles coated with said compositions, and processes for manufacturing same |
-
2012
- 2012-04-13 CN CN 201210107966 patent/CN102634017B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1847362A (en) * | 2006-05-11 | 2006-10-18 | 华东理工大学 | Expansion type fireproof moisture-resisting phosphorus-nitrogen material and its prepn |
| CN101092503A (en) * | 2007-06-05 | 2007-12-26 | 华东理工大学 | Nano composite material of flame retardant epoxy resin made from salt of phosphate bi melamine |
| CN102070667A (en) * | 2010-12-30 | 2011-05-25 | 上海交通大学 | Organosilicon compound containing phosphorus and nitrogen and preparation method thereof |
| JP5159916B2 (en) * | 2011-04-28 | 2013-03-13 | 株式会社東芝 | host |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102634017A (en) | 2012-08-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102634017B (en) | Organosilicone-containing nitrogen phosphorus flame retardant and preparation method thereof | |
| CN101671568B (en) | Phosphorus-contained organic silicon resin fire retardant and preparation method thereof | |
| CN105175777B (en) | It is a kind of for phosphorus nitrogen concerted reaction type fire retardant of polyurethane and its preparation method and application | |
| CN105348326B (en) | A kind of N P fire proofings and preparation method thereof and the application in textile | |
| CN102146093A (en) | Cage-shaped organic silicon flame retardant charring agent and preparation method thereof | |
| CN105440308A (en) | High phosphorus-nitrogen content flame retardant and preparation method thereof | |
| 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 | |
| CN104497041A (en) | Melamine aminotrimethylene phosphonate and preparation method thereof | |
| CN103113409A (en) | Triazine ring structure containing caged organic phosphate and preparation method thereof | |
| CN108794751A (en) | One kind resin fire retardant of structural silicone containing phosphonitrile and preparation method thereof | |
| CN105175735A (en) | Branched phosphorus-nitrogen type flame retardant and preparation method therefor | |
| CN103289125A (en) | Phosphorus-nitrogen-silicon containing organic and inorganic hybrid fire retardant and preparation method thereof and formed polymer | |
| CN102617861B (en) | Melamine cyanurate flame retardant agent containing organic silicone and preparation process thereof | |
| CN102146092B (en) | Pentaerythritol methylsilicate and preparation method thereof | |
| CN105713042A (en) | Preparation method of bis(PEPA) phenylphosphonate compound | |
| CN102731548B (en) | Triazine chloro-trissilicate compound and preparation method thereof | |
| CN109796496B (en) | Three phosphazene derivative of ring containing alkoxy and its preparation method and application | |
| CN102675650B (en) | Organic silicon-modified phosphorus-containing halogen-free expansion flame retardant and preparation method thereof | |
| CN102604109A (en) | Nitrogen-containing organic silicon flame retardant and preparation method thereof | |
| CN106009039A (en) | Flame-retardant agent containing spirane structure and having antioxidant function and preparation method | |
| CN102604655B (en) | Novel nitrogen-containing organic silicon flame retardant and preparation method of the flame retardant | |
| CN102174057B (en) | Organic silicon flame-retardant carbon-forming agent and preparation method thereof | |
| CN104530478B (en) | A kind of modified melamine cyanurate fire retardant and preparation method thereof |
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 |
Denomination of invention: Phosphorus nitrogen flame retardant containing organic silicon and its preparation method Effective date of registration: 20211025 Granted publication date: 20130925 Pledgee: Industrial and Commercial Bank of China Limited Shangyu sub branch Pledgor: ZHEJIANG HUAYI ENGINEERING DESIGN CO.,LTD. Registration number: Y2021330002032 |
|
| PE01 | Entry into force 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: 20130925 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 |