CN104017163A - Applications of cyclic phosphorus-nitrogen synergic halogen-free flame retardant - Google Patents

Applications of cyclic phosphorus-nitrogen synergic halogen-free flame retardant Download PDF

Info

Publication number
CN104017163A
CN104017163A CN201410286827.3A CN201410286827A CN104017163A CN 104017163 A CN104017163 A CN 104017163A CN 201410286827 A CN201410286827 A CN 201410286827A CN 104017163 A CN104017163 A CN 104017163A
Authority
CN
China
Prior art keywords
halogen
free flame
add
ring
flame retardants
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.)
Granted
Application number
CN201410286827.3A
Other languages
Chinese (zh)
Other versions
CN104017163B (en
Inventor
罗运军
顾丽敏
李�杰
葛震
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing Institute of Technology BIT
Original Assignee
Beijing Institute of Technology BIT
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Beijing Institute of Technology BIT filed Critical Beijing Institute of Technology BIT
Priority to CN201410286827.3A priority Critical patent/CN104017163B/en
Publication of CN104017163A publication Critical patent/CN104017163A/en
Application granted granted Critical
Publication of CN104017163B publication Critical patent/CN104017163B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fireproofing Substances (AREA)

Abstract

The invention relates to applications of cyclic phosphorus-nitrogen synergic halogen-free flame retardant, and particularly relates to applications of 2,7-bis(N,N-dimethylamine)-1,6,3,8,2,7-octahydrodioxadiazole diphosphinic acid, belonging to the field of synthesizing a novel halogen-free high polymer material. As a hard segment chain extender, 2,7-bis(N,N-dimethylamine)-1,6,3,8,2,7-octahydrodioxadiazole diphosphinic acid is applied to halogen-free flame-retardant modification of water-based polyurethane emulsion. Cyclic phosphamide flame retardant 2,7-bis(N,N-dimethylamine)-1,6,3,8,2,7-octahydrodioxadiazole diphosphinic acid as the hard segment chain extender is embedded into a water-based polyurethane macromolecular chain; the research shows that due to the addition of the flame retardant, the limit oxygen index of a polyurethane membrane can be improved to a greater extent, the thermal stability of the polyurethane membrane is enhanced, the carbon residue rate of the material after which is decomposed at high temperature is increased, and the usage amount of the flame retardant is reduced.

Description

A kind of application of ring-type phosphorus nitrogen synergistic halogen-free flame retardants
Technical field
The present invention relates to a kind of application of ring-type phosphorus nitrogen synergistic halogen-free flame retardants, be specifically related to a kind of 2,7-bis-(N, N dimethylamine base)-1,6,3,8, the application of 2,7-octahydro dioxadiazole diphosphinic acid, belongs to novel halogen-free flame-retardant synthesis of polymer material field.
Background technology
Along with the development of Macromolecular materials industry, the synthetic materialss such as plastics, rubber, fiber, more and more widely for fields such as weaving, building, chemical industry, military affairs and traffic.Meanwhile, due to the inflammableness of macromolecular material, make flame-retarded technology receive global concern.
At present, according to fire retardant and by the relation of ignition resistant substrate, fire retardant can be divided into addition type and the large class of response type two.The high polymer processing technique fire-retardant with additive flame retardant is simple, and the fire retardant that can meet service requirements is wide in variety, but need to solve the series of problems such as the dispersiveness, consistency, interface property of fire retardant; Adopt the flame retardant resistance that obtains of reactive flame retardant to have relative permanent, on also less by the impact of the physicals of flame-retardant polymer.Halogenated flame retardant, particularly bromide fire retardant are based flame retardants of applying the earliest, but produce more smog and poisonous corrosive gases in the time of burning, can affect people's immunity and regeneration system rapidly, cause secondary pollution, even have strong carcinogenesis.The developed countries such as current America and Europe have started to ban use of Halogen and heavy metal fire retardant.In recent years, response type phosphorus, phosphorus-nitrogen coordinated fire-retardant agent enjoy favor, because its flame retarding efficiency is high, do not produce poisonous or corrosive gases in fire-retardant process, and the growing amount of cigarette is also less, therefore very noticeable in flame retardant area.
Summary of the invention
The object of this invention is to provide a kind of application of ring-type phosphorus nitrogen synergistic halogen-free flame retardants, using this fire retardant as hard section of chainextender, be applied to aqueous polyurethane flame-retardant modified, improve the limiting oxygen index(LOI) of polyurethane film, strengthen the thermostability of polyurethane film, carbon yield after material at high temperature decomposes is raise, reduce amount of flame-retardant agent simultaneously.
The object of the invention is to be achieved through the following technical solutions.
A kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants, name is called: 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid (ODDP); The structure of this compound is as follows:
2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid is white or faint yellow solid, and product yield is 35%～50%, fusing point is 88,7 DEG C, and thermal weight loss decomposition mechanism place temperature is 198.14 DEG C, in molecular structure, the percentage composition of P, N, H, C is respectively 20.66%, 18.66%, 7.33% and 32%, be applicable to doing fire retardant or the chainextender of macromolecular material.
A synthetic method for ring-type phosphorus nitrogen synergistic halogen-free flame retardants, concrete steps are as follows:
Step 1, under protection of inert gas condition, make solvent with organic solvent, alkali is made acid binding agent, phosphorus oxychloride and dimethylamine hydrochloride (mol ratio is 1:1～2:1) at-25～0 DEG C of temperature stirring reaction to no longer include white depositions generate; Then depart from low temperature environment, reaction system rises to room temperature naturally, and continues reaction 2～5 hours at ambient temperature; Obtain the mixture that contains intermediate product 1;
Step 2, by the mixture that contains intermediate product 1 of step 1 gained, vacuum filtration disgorging, obtains filtrate;
Step 3, under protection of inert gas condition, in the filtrate of step 2 gained, add thanomin, still do acid binding agent with alkali; Under ice-water bath, react to system color and no longer deepen; Then be warming up to 30～50 DEG C, and at this temperature, react to system no longer include throw out generate;
Step 4, vacuum filtration are removed the throw out in step 3, will after purified filtrate processing, obtain 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid.
Described rare gas element is the one in argon gas, helium, nitrogen, preferentially selects nitrogen;
Described acid binding agent is the one in triethylamine, tri-n-butylamine, sodium hydroxide, potassium hydroxide, calcium hydroxide, preferentially selects triethylamine;
Described organic solvent is the one in benzene,toluene,xylene, methylene dichloride, ether, sherwood oil, ethyl acetate, acetone, butanone, preferentially selects methylene dichloride;
Described purification process process is: first use sherwood oil wash filtrate 1-4 time, then vacuum filtration is removed insolubles, obtains product 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid after underpressure distillation vacuum-drying.
Its preparation technology's principle is shown below:
A kind of application of ring-type phosphorus nitrogen synergistic halogen-free flame retardants:
Be applied to the halogen-free flameproof modification of aqueous polyurethane emulsion using fire retardant of the present invention as hard section of chainextender, method of modifying is as follows:
Step 1, vulcabond (ADI), polyether glycol, hydrophilic chain extender join in the container that stirring, condensing works are housed, and under nitrogen protection, 75～85 DEG C of reaction 2～6h prepare base polyurethane prepolymer for use as; The mol ratio of reacting raw materials used is ADI: polyether glycol (amount of hydroxylated material): DMPA=3:1～1.5:0.6;
Step 2, add the hard section of halogen-free flameproof chainextender that accounts for performed polymer quality 10%-25% (massfraction), react 2～4h at 60～85 DEG C;
Step 3, be cooled to 20～40 DEG C, add neutralizing agent to carry out neutralization reaction and generate salt, in and time 10min; The add-on of neutralizing agent is the 3%-6% of performed polymer quality;
Step 4, add deionized water to carry out emulsify at a high speed 3～5min, obtain the flame-retardant modified halogen-free flameproof aqueous polyurethane emulsion of the hard section of two phosphonic amides.
Before adding neutralizing agent in described step 3, can also add solvent to carry out the viscosity of regulation system;
In described preparation process one, vulcabond (ADI) is tolylene diisocyanate TDI, isophorone diisocyanate IPDI, diphenylmethanediisocyanate MDI, naphthalene-1,5-vulcabond NDI, hexamethylene diisocyanate HDI, 2,6-vulcabond methyl caproate LDI, 4, one in 4 '-methylene radical-dicyclohexyl, two isocyanate H12MDI, xylylene diisocyanate XDI or 1,12-dodecyl vulcabond C12DDI; Be preferably tolylene diisocyanate;
The polyether compound of polyether glycol in described preparation process one for containing two hydroxyls (OH); The preferential polyether Glycols PPG1000 that selects;
Hydrophilic chain extender in described preparation process one is containing the dibasic alcohol of carboxyl structure or containing one or more the mixture in the dibasic alcohol of sulfonic acid structure; The preferential dimethylol propionic acid of selecting;
Hard section of halogen-free flameproof chainextender in described preparation process two is 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid (ODDP);
The described solvent of preparing is the one in acetone, butanone, tetrahydrofuran (THF), ethyl acetate, preferentially selects butanone;
Neutralizing agent in described preparation process three is the one in triethylamine, tri-n-butylamine, sodium hydroxide, potassium hydroxide, calcium hydroxide, preferentially selects triethylamine.
Beneficial effect:
1, a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants, fire retardant 2 of the present invention, 7-bis-(N, N dimethylamine base)-1, 6, 3, 8, 2, 7-octahydro dioxadiazole diphosphinic acid compound structure has good symmetry, stability, in this molecular structure of compounds, there are two functionality, can make the chainextender of polyreaction, and comprise 4 P-N structures, phosphorus nitrogen synergistic effect is strong, Heat stability is good, charring rate is high, be applicable to doing the fire retardant of polymer materials, be applied to water-base polyurethane material flame-retardant modified, show good flame retardant effect, and nontoxic, environmental protection.
2, a synthetic method for ring-type phosphorus nitrogen synergistic halogen-free flame retardants, of the present invention 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2, preparation technology is simple for 7-octahydro dioxadiazole diphosphinic acid, and cost is low, is easy to suitability for industrialized production, and market application foreground is wide.
3, an application for ring-type phosphorus nitrogen synergistic halogen-free flame retardants, by ring-type diphosphine amides fire retardant 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid is embedded in aqueous polyurethane macromolecular chain as hard section of chainextender, and research shows: the adding of this fire retardant, improve to a great extent the limiting oxygen index(LOI) of polyurethane film, strengthened the thermostability of polyurethane film, the carbon yield after material at high temperature decomposes raises, and has reduced amount of flame-retardant agent simultaneously.
Brief description of the drawings
Fig. 1 is 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2, the infrared spectrogram of 7-octahydro dioxadiazole diphosphinic acid;
Fig. 2 is 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid 1h-NMR spectrogram;
Fig. 3 is 2,7-bis-(N, N dimethylamine base-1, the mass spectrum of 6,3,8,2,7-octahydro dioxadiazole diphosphinic acid.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the present invention is described in further detail.
Embodiment 1
A kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants, name is called: 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid; The structure of this compound is as follows:
2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid is white or faint yellow solid, and product yield is 35%～50%, fusing point is 88,7 DEG C, and thermal weight loss decomposition mechanism place temperature is 198.14 DEG C, in molecular structure, the percentage composition of P, N, H, C is respectively 20.66%, 18.66%, 7.33% and 32%, be suitable for doing fire retardant or the chainextender of macromolecular material.As shown in Figure 1, Figure 2, Figure 3 shows; Fig. 1 represents, 3264cm -1place is N-H stretching vibration absorption peak; 2930～2894cm -1place is-CH 2-cH 2stretching vibration absorption peak; 1394cm -1for the stretching vibration absorption peak of-P-NH; 1213.99cm -1, 1310.41cm -1, 1004cm -1be respectively P=O ,-N-C and-charateristic avsorption band of P-N.Fig. 2 shows, at the acromion of 2.55ppm Chu You – NH-, splitting swarming in two groups of couplings at 3.3ppm and 3.5ppm place is the CH being connected with nitrogen-atoms on ring 2-on the characteristic peak of two H; Splitting swarming in two groups of couplings at 4.1ppm and 4.3ppm place is the CH being connected with O on ring 2-on the characteristic peak of two H; Near double spike 2.65ppm is-N-(CH 3) 2in H.Due to the impact of molecule ring texture, make two H on identical C atom produce multiple coupling and split point, and appear in different displacements, but H in symmetrical structure appears in same displacement, therefore 1on HNMR, only show the H of 7 different displacements, and the ratio of peak area is 1:1:1:1:6:1.Fig. 3 shows, m/z323.1[M+Na on mass spectrum] +place occurs unimodal, illustrates that molecular weight of product is 300, then coordinates nucleus magnetic hydrogen spectrum data, and deterministic adduct molecule formula is C 8h 22p 2n 4o 4.
N is being housed 2in the reactor of protector, thermometer, feeder, add 0.1mol phosphorus oxychloride and 0.1mol dimethylamine hydrochloride, add 100ml methylene dichloride to make solvent simultaneously, 0.15mol triethylamine, as in feeder, under magnetic agitation, is slowly added drop-wise to triethylamine in reactor, make this system bathe in environment and react 1 hour at-5 DEG C of cryosels, react at ambient temperature 4 hours, vacuum filtration is removed Triethylammonium chloride throw out, obtains filtrate again; Then by 0.1mol thanomin, 100ml methylene dichloride, 0.15mol triethylamine, is again placed at N is housed 2in the reactor of protector, thermometer, feeder, and under magnetic agitation effect, drip above-mentioned filtrate, 0 DEG C of reaction 1 hour, react 2 hours under room temperature; Finally be warming up to 40 DEG C of reactions after 1 hour, product is shifted out, vacuum filtration is removed Triethylammonium chloride throw out, by 400ml sherwood oil wash filtrate 2 times, then vacuum filtration is removed insolubles, and filtrate decompression is distilled, obtain white solid, after vacuum-drying, obtain product 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid, yield is 40.6%, and thermal weight loss test decomposition mechanism place temperature is 198.14 DEG C, and carbon yield is 20.12%.
Get polyether Glycols PPG1000 (20.9g), in the reactor with tetrafluoro stirring rake, 120 DEG C of vacuum hydro-extraction 1h, be cooled to 85 DEG C, logical nitrogen, installs condensing reflux pipe, adds 18.6g tolylene diisocyanate TDI and 3g dimethylol propionic acid (DMPA) reaction 2h.Add afterwards the fire-retardant chainextender ODDP of 7.5g, reaction 4h.Be cooled to again 40 DEG C, add after 40ml butanone diluted system viscosity, add in 2.0g triethylamine (TEA) and 10min, finally performed polymer is poured in dry beaker, under the rotating speed of blade dispersion machine 2000～3000r/min stirs, adding 150g, temperature is the deionized water of 0～10 DEG C, obtains white emulsion after 5min, places a night.Within second day, use Rotary Evaporators to remove the butanone in emulsion, obtain the flame-retardant modified halogen-free flameproof aqueous polyurethane emulsion of hard section.Get emulsion 40g, in tetrafluoroethylene sheet material middle berth film, naturally dry after 14 days, dry 4h in the vacuum drying oven of 90 DEG C, dried latex film is tested, and LOI value is 30.6%, 337.5 DEG C of the main catabolic phase decomposition mechanism of thermolysis place temperature, carbon residue amount: 14.18%, amount of flame-retardant agent: 15wt%.
Embodiment 2
A kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants, name is called: 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid; The structure of this compound is as follows:
2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid is white or faint yellow solid, and product yield is 35%～50%, fusing point is 88,7 DEG C, thermal weight loss decomposition mechanism place temperature is 198.14 DEG C, and in molecular structure, the percentage composition of P, N, H, C is respectively 20.66%, 18.66%, 7.33% and 32% is suitable for doing fire retardant or the chainextender of macromolecular material.
Being equipped with in the reactor of argon protective device, thermometer, feeder, add 0.15mol phosphorus oxychloride and 0.1mol dimethylamine hydrochloride, add 150ml toluene to make solvent simultaneously, 0.25mol triethylamine, as in feeder, under magnetic agitation, is slowly added drop-wise to triethylamine in reactor, make this system bathe in environment and react 1 hour at-5 DEG C of cryosels, react at ambient temperature 4 hours, vacuum filtration is removed Triethylammonium chloride throw out, obtains filtrate again; Then 0.1mol thanomin, 150ml methylene dichloride, 0.25mol triethylamine is again placed at N is housed 2in the reactor of protector, thermometer, feeder, and under magnetic agitation effect, drip above-mentioned filtrate, 0 DEG C of reaction 1 hour, react 2 hours under room temperature; Finally be warming up to 40 DEG C of reactions after 1 hour, product is shifted out, vacuum filtration is removed Triethylammonium chloride throw out, by 600ml sherwood oil wash filtrate 2 times, then vacuum filtration is removed insolubles, and filtrate decompression is distilled, obtain white solid, after vacuum-drying, obtain product 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid, yield is 46.7%, and thermal weight loss test decomposition mechanism place temperature is 198.14 DEG C, and carbon yield is 20.12%.
Get polyether Glycols PPG1000 (25.32g), in the reactor with tetrafluoro stirring rake, 120 DEG C of vacuum hydro-extraction 1h, be cooled to 85 DEG C, logical nitrogen, installs condensing reflux pipe, adds 16.7g isophorone diisocyanate and 3g dimethylol propionic acid (DMPA) reaction 2h.Add afterwards the fire-retardant chainextender ODDP of 5g, reaction 4h.Be cooled to again 40 DEG C, add after 40ml butanone diluted system viscosity, add in 2.0g triethylamine (TEA) and 10min, finally performed polymer is poured in dry beaker, under the rotating speed of blade dispersion machine 2000～3000r/min stirs, adding 150g, temperature is the deionized water of 0～10 DEG C, obtains white emulsion after 5min, places a night.Within second day, use Rotary Evaporators to remove the butanone in emulsion, obtain the flame-retardant modified halogen-free flameproof aqueous polyurethane emulsion of hard section.Get emulsion 40g, in tetrafluoroethylene sheet material middle berth film, naturally dry after 14 days, dry 4h in the vacuum drying oven of 90 DEG C, dried latex film is tested, and LOI value is 29.0%, 341.5 DEG C of the main catabolic phase decomposition mechanism of thermolysis place temperature, carbon residue amount: 12.18%, amount of flame-retardant agent: 10wt%.
Embodiment 3
A kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants, name is called: 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid; The structure of this compound is as follows:
2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid is white or faint yellow solid, and product yield is 35%～50%, fusing point is 88,7 DEG C, thermal weight loss decomposition mechanism place temperature is 198.14 DEG C, and in molecular structure, the percentage composition of P, N, H, C is respectively 20.66%, 18.66%, 7.33% and 32% is suitable for doing fire retardant or the chainextender of macromolecular material.
N is being housed 2in the reactor of protector, thermometer, feeder, add 0.6mol phosphorus oxychloride and 0.4mol dimethylamine hydrochloride, add 300ml ethyl acetate to make solvent simultaneously, 0.9mol triethylamine, as in feeder, under magnetic agitation, is slowly added drop-wise to triethylamine in reactor, make this system bathe in environment and react 1 hour at-5 DEG C of cryosels, react at ambient temperature 4 hours, vacuum filtration is removed Triethylammonium chloride throw out, obtains filtrate again; Then by 0.6mol thanomin, 200ml ethyl acetate, 1.0mol triethylamine, is again placed at N is housed 2in the reactor of protector, thermometer, feeder, and under magnetic agitation effect, drip above-mentioned filtrate, 0 DEG C of reaction 1 hour, react 2 hours under room temperature; Finally be warming up to 40 DEG C of reactions after 1 hour, product is shifted out, vacuum filtration is removed Triethylammonium chloride throw out, by 900ml sherwood oil wash filtrate 2 times, then vacuum filtration is removed insolubles, and filtrate decompression is distilled, obtain white solid, after vacuum-drying, obtain product 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid, yield is 45.3%, and thermal weight loss test decomposition mechanism place temperature is 198.14 DEG C, and carbon yield is 20.12%.
Get polyether glycol PPG2000 (29.75g), in the reactor with tetrafluoro stirring rake, 120 DEG C of vacuum hydro-extraction 1h, be cooled to 85 DEG C, logical nitrogen, installs condensing reflux pipe, adds 15.7gTDI and 3g dimethylol propionic acid (DMPA) reaction 2h.Add afterwards the fire-retardant chainextender ODDP of 6g, reaction 4h.Be cooled to again 40 DEG C, add after appropriate 40ml butanone diluted system viscosity, add in 2.0g triethylamine (TEA) and 10min, finally performed polymer is poured in dry beaker, under the rotating speed of blade dispersion machine 2000～3000r/min stirs, adding 150g, temperature is the deionized water of 0～10 DEG C, obtains white emulsion after 5min, places a night.Within second day, use Rotary Evaporators to remove the butanone in emulsion, obtain the flame-retardant modified halogen-free flameproof aqueous polyurethane emulsion of hard section.Get emulsion 40g, in tetrafluoroethylene sheet material middle berth film, naturally dry after 14 days, dry 4h in the vacuum drying oven of 90 DEG C, dried latex film is tested, and LOI value is 30.2%, 345.5 DEG C of the main catabolic phase decomposition mechanism of thermolysis place temperature, carbon residue amount: 18.18%, amount of flame-retardant agent: 20wt%.
Embodiment 4
A kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants, name is called: 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid; The structure of this compound is as follows:
2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid is white or faint yellow solid, and product yield is 35%～50%, fusing point is 88,7 DEG C, thermal weight loss decomposition mechanism place temperature is 198.14 DEG C, and in molecular structure, the percentage composition of P, N, H, C is respectively 20.66%, 18.66%, 7.33% and 32% is suitable for doing fire retardant or the chainextender of macromolecular material.
Being equipped with in the reactor of argon protective device, thermometer, feeder, add 0.6mol phosphorus oxychloride and 0.4mol dimethylamine hydrochloride, add 300ml methylene dichloride to make solvent simultaneously, 0.5mol sodium hydroxide is slowly added in reactor under magnetic agitation, make this system bathe in environment and react 1 hour at-8 DEG C of cryosels, react at ambient temperature 4 hours, vacuum filtration is removed insolubles, obtains filtrate again; Then by 0.6mol thanomin, 200ml methylene dichloride, 0.9mol triethylamine is placed in the reactor that argon protective device, thermometer, feeder are housed again, and under magnetic agitation effect, drip above-mentioned filtrate, under 0 DEG C of reaction 1 hour, room temperature, react 2 hours; Finally be warming up to 40 DEG C of reactions after 1 hour, product is shifted out, vacuum filtration is removed Triethylammonium chloride throw out, by 1000ml sherwood oil wash filtrate 2 times, then vacuum filtration is removed insolubles, and filtrate decompression is distilled, obtain white solid, after vacuum-drying, obtain product 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid, yield is 38.2%, and thermal weight loss test decomposition mechanism place temperature is 198.14 DEG C, and carbon yield is 20.12%.
Get polyether Glycols PPG1000 (16.56g), in the reactor with tetrafluoro stirring rake, 120 DEG C of vacuum hydro-extraction 1h, be cooled to 85 DEG C, logical nitrogen, installs condensing reflux pipe, adds 20.54gTDI and 3g dimethylol propionic acid (DMPA) reaction 2h.Add afterwards the fire-retardant chainextender ODDP of 10g, reaction 4h.Be cooled to again 40 DEG C, add after 50ml acetone diluted system viscosity, add in 2.0g triethylamine (TEA) and 10min, finally performed polymer is poured in dry beaker, under the rotating speed of blade dispersion machine 2000～3000r/min stirs, adding 150g, temperature is the deionized water of 0～10 DEG C, obtains white emulsion after 5min, places a night.Within second day, use Rotary Evaporators to remove the acetone in emulsion, obtain the flame-retardant modified halogen-free flameproof aqueous polyurethane emulsion of hard section.Get emulsion 40g, in tetrafluoroethylene sheet material middle berth film, naturally dry after 14 days, dry 4h in the vacuum drying oven of 90 DEG C, dried latex film is tested, and LOI value is 30.1%, 339.8 DEG C of the main catabolic phase decomposition mechanism of thermolysis place temperature, carbon residue amount: 13.11%, amount of flame-retardant agent: 13wt%.

Claims (6)

1. an application for ring-type phosphorus nitrogen synergistic halogen-free flame retardants, is characterized in that: concrete steps are as follows:
Step 1, vulcabond (ADI), polyether glycol, hydrophilic chain extender join in the container that stirring, condensing works are housed, and under nitrogen protection, 75～85 DEG C of reaction 2～6h prepare base polyurethane prepolymer for use as; The mol ratio of reacting raw materials used is ADI: polyether glycol (amount of hydroxylated material): DMPA=3:1～1.5:0.6;
Step 2, add the hard section of halogen-free flameproof chainextender that accounts for performed polymer quality 10%-25% (massfraction), react 2～4h at 60～85 DEG C;
Step 3, be cooled to 20～40 DEG C, add neutralizing agent to carry out neutralization reaction and generate salt, in and time 10min; The add-on of neutralizing agent is the 3%-6% of performed polymer quality;
Step 4, add deionized water to carry out emulsify at a high speed 3～5min, obtain the flame-retardant modified halogen-free flameproof aqueous polyurethane emulsion of the hard section of two phosphonic amides.
2. the application of a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants as claimed in claim 1, is characterized in that: before adding neutralizing agent in described step 3, can also add solvent to carry out the viscosity of regulation system.
3. the application of a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants as claimed in claim 2, is characterized in that: the described solvent of preparing is the one in acetone, butanone, tetrahydrofuran (THF), ethyl acetate, preferentially selects butanone.
4. the application of a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants as claimed in claim 1, it is characterized in that: vulcabond in described step 1 (ADI) is tolylene diisocyanate TDI, isophorone diisocyanate IPDI, diphenylmethanediisocyanate MDI, naphthalene-1,5-vulcabond NDI, hexamethylene diisocyanate HDI, 2,6-vulcabond methyl caproate LDI, 4, one in 4 '-methylene radical-dicyclohexyl, two isocyanate H12MDI, xylylene diisocyanate XDI or 1,12-dodecyl vulcabond C12DDI; Be preferably tolylene diisocyanate; The polyether compound of polyether glycol in described preparation process one for containing two hydroxyls (OH); The preferential polyether Glycols PPG1000 that selects; Hydrophilic chain extender in described preparation process one is containing the dibasic alcohol of carboxyl structure or containing one or more the mixture in the dibasic alcohol of sulfonic acid structure; The preferential dimethylol propionic acid of selecting.
5. the application of a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants as claimed in claim 1, is characterized in that: hard section of halogen-free flameproof chainextender in described step 2 is 2,7-, bis-(N, N dimethylamine base)-1,6,3,8,2,7-octahydro dioxadiazole diphosphinic acid (ODDP).
6. the application of a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants as claimed in claim 1, it is characterized in that: the neutralizing agent in described preparation process three is the one in triethylamine, tri-n-butylamine, sodium hydroxide, potassium hydroxide, calcium hydroxide, preferentially selects triethylamine.
CN201410286827.3A 2014-06-24 2014-06-24 The application of a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants Expired - Fee Related CN104017163B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410286827.3A CN104017163B (en) 2014-06-24 2014-06-24 The application of a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410286827.3A CN104017163B (en) 2014-06-24 2014-06-24 The application of a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants

Publications (2)

Publication Number Publication Date
CN104017163A true CN104017163A (en) 2014-09-03
CN104017163B CN104017163B (en) 2016-06-01

Family

ID=51434193

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410286827.3A Expired - Fee Related CN104017163B (en) 2014-06-24 2014-06-24 The application of a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants

Country Status (1)

Country Link
CN (1) CN104017163B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104530371A (en) * 2014-12-31 2015-04-22 四川大学 Halogen-free persistent form inflaming retarding water-borne polyurethane and preparation method thereof
CN108129634A (en) * 2017-12-22 2018-06-08 盐城工学院 A kind of preparation method of extinguishing waterborn polyurethane coating and its coating of preparation
CN110437421A (en) * 2019-08-08 2019-11-12 郝立勇 A kind of glycol modified polyurethane coating of flame retardant type phosphate ester-containing and its preparation method
CN112680104A (en) * 2020-12-30 2021-04-20 刘百党 Environment-friendly steel structure fireproof coating and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1367665A (en) * 1970-09-02 1974-09-18 Stauffer Chemical Co N,n-dialkyl o,o-bis/dihaloalkyl/phosphoramidates and their use as fla me retardants
US3966478A (en) * 1970-09-02 1976-06-29 Stauffer Chemical Company N,N-Dialkyl O,O-bis(haloalkyl)phosphoramidate flame retardant
WO2003006472A1 (en) * 2001-07-11 2003-01-23 Doobon, Inc. Method for manufacturing dicyclic phosphorus melamine compounds having superior fire retardancy and fire retardant material using thereof
CN102675372A (en) * 2012-04-25 2012-09-19 东华大学 Ethylenediamine bicyclo-tetra methylenemelamine phosphonate compound and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1367665A (en) * 1970-09-02 1974-09-18 Stauffer Chemical Co N,n-dialkyl o,o-bis/dihaloalkyl/phosphoramidates and their use as fla me retardants
US3966478A (en) * 1970-09-02 1976-06-29 Stauffer Chemical Company N,N-Dialkyl O,O-bis(haloalkyl)phosphoramidate flame retardant
WO2003006472A1 (en) * 2001-07-11 2003-01-23 Doobon, Inc. Method for manufacturing dicyclic phosphorus melamine compounds having superior fire retardancy and fire retardant material using thereof
CN102675372A (en) * 2012-04-25 2012-09-19 东华大学 Ethylenediamine bicyclo-tetra methylenemelamine phosphonate compound and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
RU-JONG JENG ETC.: "Flame retardant epoxy polymers based on all phosphorus containing components", <EUROPEAN POLYMER JOURNAL>, vol. 38, 31 December 2002 (2002-12-31), pages 683 - 693, XP004340237, DOI: doi:10.1016/S0014-3057(01)00246-4 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104530371A (en) * 2014-12-31 2015-04-22 四川大学 Halogen-free persistent form inflaming retarding water-borne polyurethane and preparation method thereof
CN104530371B (en) * 2014-12-31 2017-06-09 四川大学 A kind of fire-retardant water-based polyurethane of Halogen persistent form and preparation method thereof
CN108129634A (en) * 2017-12-22 2018-06-08 盐城工学院 A kind of preparation method of extinguishing waterborn polyurethane coating and its coating of preparation
CN110437421A (en) * 2019-08-08 2019-11-12 郝立勇 A kind of glycol modified polyurethane coating of flame retardant type phosphate ester-containing and its preparation method
CN112680104A (en) * 2020-12-30 2021-04-20 刘百党 Environment-friendly steel structure fireproof coating and preparation method thereof

Also Published As

Publication number Publication date
CN104017163B (en) 2016-06-01

Similar Documents

Publication Publication Date Title
CN105542160B (en) Bicyclo cage shaped macromolecular expansion type flame retardant of one-component phosphorus nitrogen and its preparation method and application
CN101643651B (en) Macromolecular intumescent flame resistance carbonizing agent with branching and crosslinking structure and preparation method and application thereof
CN104017163B (en) The application of a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants
CN110563765B (en) Synthesis method of Schiff base phosphazene double-base structure flame retardant and modified polyurethane flame retardant
CN105175735A (en) Branched phosphorus-nitrogen type flame retardant and preparation method therefor
CN102875842A (en) Phosphorus-nitrogen intumescent flame retardant and preparation method thereof
CN102816185A (en) Reaction type phosphorus-nitrogen fire retardant and preparation method thereof
CN104559204A (en) Phosphorus-containing macromolecular intumescent flame-retardant charring agent with cross-linked structure as well as preparation method and application thereof
CN110511431A (en) A kind of nitrogen of the structure containing benzoguanamine-phosphorus system efficient flame-retarding agent and its synthesis and application
CN108976418B (en) Three-dimensional structure flame retardant based on furan derivative and cyclotriphosphazene and preparation method thereof
CN112409567A (en) Preparation method of P-N type flame retardant based on DOPO
CN108794751A (en) One kind resin fire retardant of structural silicone containing phosphonitrile and preparation method thereof
CN112794987A (en) Flame-retardant polyurea-polyurethane
CN107955155B (en) Nitrogen-boron structure type flame-retardant polyether polyol and preparation method and application thereof
CN101560227B (en) Flame-retarding compound, flame-retardant prepared thereby and preparation method thereof
CN104031090B (en) A kind of preparation method of ring-type phosphorus nitrogen synergistic halogen-free flame retardants
CN110128474B (en) Preparation method and application of nitrogen-phosphorus-sulfur ternary synergistic flame retardant bis-DOPO thiazole compound
CN113337004A (en) Novel phosphorus-nitrogen DOPO derivative flame retardant and synthetic method and application thereof
CN109796496B (en) Three phosphazene derivative of ring containing alkoxy and its preparation method and application
CN102731554B (en) Flame retardant tri(chloropropyl)tribromophenoxychloropropoxyl silicate compound and preparation method thereof
CN116063353A (en) Phosphorus-nitrogen reactive flame retardant, and preparation method and application thereof
CN110092944A (en) The preparation method and applications of diphenyl sulphone (DPS) nitrogen phosphorus sulphur synergistic flame retardant containing DOPO
CN102277176A (en) Chloroalkyl polyphosphate ester fire retardant and synthetic technology thereof
CN104926875A (en) Flame retardant hydroxymethyl phosphonyl heterocyclic phenylphosphonate compound and preparation method therefor
CN104072804B (en) A kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants

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
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20160601

Termination date: 20190624