CN104017163B - The application of a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants - Google Patents

The application of a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants Download PDF

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CN104017163B
CN104017163B CN201410286827.3A CN201410286827A CN104017163B CN 104017163 B CN104017163 B CN 104017163B CN 201410286827 A CN201410286827 A CN 201410286827A CN 104017163 B CN104017163 B CN 104017163B
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halogen
ring
flame retardants
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free flame
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CN104017163A (en
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罗运军
顾丽敏
李�杰
葛震
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Beijing Institute of Technology BIT
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    • 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

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Abstract

The present invention relates to the application of a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants, it is specifically related to a kind of 2,7-bis-(N, N dimethylamine base)-1,6,3,8, the application of 2,7-eight hydrogen two oxadiazoles diphosphinic acid, belongs to novel halogen-free flame-retardant synthesis of polymer material field. 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-eight hydrogen two oxadiazoles diphosphinic acid is applied to as hard section chainextender the halogen-free flameproof modification of aqueous polyurethane emulsion. The present invention is by ring-type two phosphonic amide based flame retardant 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-eight hydrogen two oxadiazoles diphosphinic acid is embedded in aqueous polyurethane macromolecular chain as hard section chainextender, research shows: adding of this fire retardant, greatly enhances the limiting oxygen index(LOI) of polyurethane film, enhances the thermostability of polyurethane film, carbon yield after material at high temperature decomposition raises, and reduces amount of flame-retardant agent simultaneously.

Description

The application of a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants
Technical field
The present invention relates to the application of a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants, it is specifically related to a kind of 2,7-bis-(N, N dimethylamine base)-1,6,3,8, the application of 2,7-eight hydrogen two oxadiazoles diphosphinic acid, belongs to novel halogen-free flame-retardant synthesis of polymer material field.
Background technology
Along with synthetic materialss such as the development of Macromolecular materials industry, plastics, rubber, fibers, more and more widely for fields such as weaving, building, chemical industry, military affairs and traffic. Meanwhile, due to the inflammableness of macromolecular material so that flame-retarded technology receives global concern.
At present, according to fire retardant with by the relation of ignition resistant substrate, fire retardant can be divided into interpolation type and the big class of response type two. Simple with the fire-retardant high polymer processing technique of additive flame retardant, the fire retardant that can meet service requirements is wide in variety, but needs to solve a series of problems such as the dispersion of fire retardant, consistency, interface property; The flame retardant resistance adopting reactive flame retardant to obtain then has relative permanent, on also less by the impact of the physicals of flame-retardant polymer. Halogenated flame retardant, particularly bromide fire retardant are the based flame retardants applied the earliest, but produce more smog and poisonous corrosive gases when burning, and can affect immunity and the regeneration system rapidly of people, cause secondary pollution, even relatively have strong carcinogenesis. The developed countries such as current America and Europe have started to prohibit the use Halogen and heavy metal fire retardant. In recent years, response type phosphorus, phosphorus-nitrogen coordinated fire-retardant agent enjoy favor, due to its flame retarding efficiency height, 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
It is an object of the invention to provide the application of a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants, using this fire retardant as hard section chainextender, it is 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 is decomposed raises, and reduces amount of flame-retardant agent simultaneously.
It is an object of the invention 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-eight hydrogen two oxadiazoles diphosphinic acid (ODDP); The structure of this compound is as follows:
2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-eight hydrogen two oxadiazoles 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%, it is 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 one, when protection of inert gas, making solvent with organic solvent, alkali makes 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 including, white depositions generates; Then departing from low temperature environment, reaction system rises to room temperature naturally, and continues reaction 2��5 hours at ambient temperature; Obtain the mixture containing intermediate product 1;
Step 2, by step one gained containing the mixture of intermediate product 1, vacuum filtration disgorging, obtains filtrate;
Step 3, when protection of inert gas, in the filtrate of step 2 gained, add thanomin, still do acid binding agent with alkali; React under ice-water bath to system color and no longer deepen; Then be warming up to 30��50 DEG C, and react at such a temperature to system no longer include throw out generate;
Throw out in step 4, vacuum filtration removing step three, will obtain 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-eight hydrogen two oxadiazoles diphosphinic acid after purified for filtrate process.
Described rare gas element is the one in argon gas, helium, nitrogen, prioritizing selection nitrogen;
Described acid binding agent is the one in triethylamine, tri-n-butylamine, sodium hydroxide, potassium hydroxide, calcium hydroxide, prioritizing selection triethylamine;
Described organic solvent is the one in benzene, toluene, dimethylbenzene, methylene dichloride, ether, sherwood oil, ethyl acetate, acetone, butanone, prioritizing selection methylene dichloride;
Described purification process process is: first by sherwood oil wash filtrate 1-4 time, and then vacuum filtration removes insolubles, underpressure distillation also after vacuum-drying product 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-eight hydrogen two oxadiazoles diphosphinic acid.
Its preparation technology's principle is shown below:
The application of a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants:
The halogen-free flameproof modification that the fire retardant of the present invention is applied to as hard section chainextender aqueous polyurethane emulsion, method of modifying is as follows:
Step one, 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 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 halogen-free flameproof chainextender accounting for performed polymer quality 10%-25% (massfraction), at 60��85 DEG C, react 2��4h;
Step 3, it is cooled to 20��40 DEG C, adds neutralizing agent and carry out neutralization reaction and generate salt, neutralization time 10min; The add-on of neutralizing agent is the 3%-6% of performed polymer quality;
Step 4, add deionized water and carry out emulsify at a high speed 3��5min, obtain the halogen-free flameproof aqueous polyurethane emulsion that the two hard sections of phosphonic amide are flame-retardant modified.
The viscosity that solvent carrys out regulation system can also be added before described step 3 adds neutralizing agent;
In described preparation process one vulcabond (ADI) be 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-dodecane diisocyanate C12DDI; It is preferably tolylene diisocyanate;
Polyether glycol in described preparation process one is the polyether compound containing two hydroxyls (-OH); Prioritizing selection polyether Glycols PPG1000;
Hydrophilic chain extender in described preparation process one be containing carboxyl structure dibasic alcohol or containing sulfonic acid structure dibasic alcohol in the mixture of one or more; Prioritizing selection dimethylol propionic acid;
Hard section halogen-free flameproof chainextender in described preparation process two is 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-eight hydrogen two oxadiazoles diphosphinic acid (ODDP);
Described solvent of preparing is the one in acetone, butanone, tetrahydrofuran (THF), ethyl acetate, prioritizing selection butanone;
Neutralizing agent in described preparation process three is the one in triethylamine, tri-n-butylamine, sodium hydroxide, potassium hydroxide, calcium hydroxide, prioritizing selection triethylamine.
Useful effect:
1, a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants, the fire retardant 2 of the present invention, 7-bis-(N, N dimethylamine base)-1, 6, 3, 8, 2, 7-eight hydrogen two oxadiazoles diphosphinic acid compound structure has good symmetry, stability, this molecular structure of compounds has two functionality, the chainextender of polyreaction can be made, and comprise 4 P-N junction structures, phosphorus nitrogen synergistic effect is strong, Heat stability is good, charring rate height, it is applicable to doing the fire retardant of polymer materials, it is applied to water-base polyurethane material flame-retardant modified, show good flame retardant effect, and it is nontoxic, environmental protection.
2, a synthetic method for ring-type phosphorus nitrogen synergistic halogen-free flame retardants, 2,7-bis-(N, the N dimethylamine base)-1 of the present invention, 6,3,8,2,7-eight hydrogen two oxadiazoles diphosphinic acid preparation technology is simple, 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 two phosphonic amide based flame retardant 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-eight hydrogen two oxadiazoles diphosphinic acid is embedded in aqueous polyurethane macromolecular chain as hard section chainextender, and research shows: adding of this fire retardant, greatly enhance the limiting oxygen index(LOI) of polyurethane film, enhancing the thermostability of polyurethane film, the carbon yield after material at high temperature decomposition raises, and reduces amount of flame-retardant agent simultaneously.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-eight hydrogen two oxadiazoles diphosphinic acid;
Fig. 2 is 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-eight hydrogen two oxadiazoles diphosphinic acid1H-NMR spectrum;
Fig. 3 is 2,7-bis-(N, the mass spectrum of N dimethylamine base-1,6,3,8,2,7-eight hydrogen two oxadiazoles 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-eight hydrogen two oxadiazoles diphosphinic acid; The structure of this compound is as follows:
2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-eight hydrogen two oxadiazoles 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%, it is 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-CH2-CH2Stretching vibration absorption peak; 1394cm-1For the stretching vibration absorption peak of-P-NH; 1213.99cm-1, 1310.41cm-1, 1004cm-1It is respectively P=O, the charateristic avsorption band of-N-C and-P-N. Fig. 2 shows, has the shoulder peak of NH-at 2.55ppm place, and it is the CH being connected with nitrogen-atoms on ring that swarming is split in two groups of couplings at 3.3ppm with 3.5ppm place2-on the characteristic peak of two H; It is the CH being connected with O on ring that swarming is split in two groups of couplings at 4.1ppm with 4.3ppm place2-on the characteristic peak of two H; Double point peak near 2.65ppm is-N-(CH3)2In H. Due to the impact of molecule ring texture so that two H on identical C atom create multiple coupling and split point, and appear in different displacements, but the H in symmetrical structure appears in same displacement, therefore1The H of HNMR upper only display 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+There is single peak in place, illustrates that molecular weight of product is 300, then coordinates nucleus magnetic hydrogen spectrum data, it is determined that compound molecule formula is C8H22P2N4O4��
N is being housed2In the reactor of protector, thermometer, feeder, add 0.1mol phosphorus oxychloride and 0.1mol dimethylamine hydrochloride, add 100ml methylene dichloride simultaneously and make solvent, by 0.15mol triethylamine as, in feeder, under magnetic stirring, triethylamine being slowly added drop-wise in reactor, make this system reaction 1 hour in-5 DEG C of ice salt bath environment, reacting 4 hours at ambient temperature, vacuum filtration removes Triethylammonium chloride throw out, obtains filtrate again; Then by 0.1mol thanomin, 100ml methylene dichloride, 0.15mol triethylamine, is again placed at and N is housed2In the reactor of protector, thermometer, feeder, and drip under magnetic agitation effect and add above-mentioned filtrate, 0 DEG C of reaction 1 hour, reaction 2 hours under room temperature; Finally being warming up to 40 DEG C of reactions after 1 hour, moved out by product, vacuum filtration removes Triethylammonium chloride throw out, by 400ml sherwood oil wash filtrate 2 times, then vacuum filtration removes insolubles, 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-eight hydrogen two oxadiazoles diphosphinic acid, receipts rate 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 four fluorine stirring rakes, 120 DEG C of vacuum hydro-extraction 1h, it is cooled to 85 DEG C, logical nitrogen, installation condensing reflux pipe, adds 18.6g tolylene diisocyanate TDI and 3g dimethylol propionic acid (DMPA) reacts 2h. Add the fire-retardant chainextender ODDP of 7.5g afterwards, reaction 4h. It is cooled to 40 DEG C again, after adding 40ml butanone diluted system viscosity, add 2.0g triethylamine (TEA) and neutralize 10min, finally performed polymer is poured in dry beaker, under the rotating speed of blade dispersion machine 2000��3000r/min stirs, add 150g, temperature is the deionized water of 0��10 DEG C, obtains white emulsion, place a night after 5min. Within 2nd day, use Rotary Evaporators to remove the butanone in emulsion, obtain the halogen-free flameproof aqueous polyurethane emulsion that hard section is flame-retardant modified. Get emulsion 40g, in tetrafluoroethylene sheet material middle berth film, naturally after drying 14 days, dry 4h in the vacuum drying oven of 90 DEG C, being tested by dried latex film, LOI value is 30.6%, thermolysis main decomposition stage decomposition mechanism place temperature 337.5 DEG C, carbon left: 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-eight hydrogen two oxadiazoles diphosphinic acid; The structure of this compound is as follows:
2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-eight hydrogen two oxadiazoles 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.
In the reactor that argon protective device, thermometer, feeder are housed, add 0.15mol phosphorus oxychloride and 0.1mol dimethylamine hydrochloride, add 150ml toluene simultaneously and make solvent, by 0.25mol triethylamine as, in feeder, under magnetic stirring, triethylamine being slowly added drop-wise in reactor, make this system reaction 1 hour in-5 DEG C of ice salt bath environment, reacting 4 hours at ambient temperature, vacuum filtration removes Triethylammonium chloride throw out, obtains filtrate again; Then 0.1mol thanomin, 150ml methylene dichloride, 0.25mol triethylamine is again placed at and N is housed2In the reactor of protector, thermometer, feeder, and drip under magnetic agitation effect and add above-mentioned filtrate, 0 DEG C of reaction 1 hour, reaction 2 hours under room temperature; Finally being warming up to 40 DEG C of reactions after 1 hour, moved out by product, vacuum filtration removes Triethylammonium chloride throw out, by 600ml sherwood oil wash filtrate 2 times, then vacuum filtration removes insolubles, 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-eight hydrogen two oxadiazoles diphosphinic acid, receipts rate 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 four fluorine stirring rakes, 120 DEG C of vacuum hydro-extraction 1h, it is cooled to 85 DEG C, logical nitrogen, installation condensing reflux pipe, adds 16.7g isophorone diisocyanate and 3g dimethylol propionic acid (DMPA) reacts 2h. Add the fire-retardant chainextender ODDP of 5g afterwards, reaction 4h. It is cooled to 40 DEG C again, after adding 40ml butanone diluted system viscosity, add 2.0g triethylamine (TEA) and neutralize 10min, finally performed polymer is poured in dry beaker, under the rotating speed of blade dispersion machine 2000��3000r/min stirs, add 150g, temperature is the deionized water of 0��10 DEG C, obtains white emulsion, place a night after 5min. Within 2nd day, use Rotary Evaporators to remove the butanone in emulsion, obtain the halogen-free flameproof aqueous polyurethane emulsion that hard section is flame-retardant modified. Get emulsion 40g, in tetrafluoroethylene sheet material middle berth film, naturally after drying 14 days, dry 4h in the vacuum drying oven of 90 DEG C, being tested by dried latex film, LOI value is 29.0%, thermolysis main decomposition stage decomposition mechanism place temperature 341.5 DEG C, carbon left: 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-eight hydrogen two oxadiazoles diphosphinic acid; The structure of this compound is as follows:
2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-eight hydrogen two oxadiazoles 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 housed2In the reactor of protector, thermometer, feeder, add 0.6mol phosphorus oxychloride and 0.4mol dimethylamine hydrochloride, add 300ml ethyl acetate simultaneously and make solvent, by 0.9mol triethylamine as, in feeder, under magnetic stirring, triethylamine being slowly added drop-wise in reactor, make this system reaction 1 hour in-5 DEG C of ice salt bath environment, reacting 4 hours at ambient temperature, vacuum filtration removes Triethylammonium chloride throw out, obtains filtrate again; Then by 0.6mol thanomin, 200ml ethyl acetate, 1.0mol triethylamine, is again placed at and N is housed2In the reactor of protector, thermometer, feeder, and drip under magnetic agitation effect and add above-mentioned filtrate, 0 DEG C of reaction 1 hour, reaction 2 hours under room temperature; Finally being warming up to 40 DEG C of reactions after 1 hour, moved out by product, vacuum filtration removes Triethylammonium chloride throw out, by 900ml sherwood oil wash filtrate 2 times, then vacuum filtration removes insolubles, 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-eight hydrogen two oxadiazoles diphosphinic acid, receipts rate 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 four fluorine stirring rakes, 120 DEG C of vacuum hydro-extraction 1h, it is cooled to 85 DEG C, logical nitrogen, installs condensing reflux pipe, adds 15.7gTDI and 3g dimethylol propionic acid (DMPA) and react 2h. Add the fire-retardant chainextender ODDP of 6g afterwards, reaction 4h. It is cooled to 40 DEG C again, after adding appropriate 40ml butanone diluted system viscosity, add 2.0g triethylamine (TEA) and neutralize 10min, finally performed polymer is poured in dry beaker, under the rotating speed of blade dispersion machine 2000��3000r/min stirs, add 150g, temperature is the deionized water of 0��10 DEG C, obtains white emulsion, place a night after 5min. Within 2nd day, use Rotary Evaporators to remove the butanone in emulsion, obtain the halogen-free flameproof aqueous polyurethane emulsion that hard section is flame-retardant modified. Get emulsion 40g, in tetrafluoroethylene sheet material middle berth film, naturally after drying 14 days, dry 4h in the vacuum drying oven of 90 DEG C, being tested by dried latex film, LOI value is 30.2%, thermolysis main decomposition stage decomposition mechanism place temperature 345.5 DEG C, carbon left: 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-eight hydrogen two oxadiazoles diphosphinic acid; The structure of this compound is as follows:
2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-eight hydrogen two oxadiazoles 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.
In the reactor that argon protective device, thermometer, feeder are housed, add 0.6mol phosphorus oxychloride and 0.4mol dimethylamine hydrochloride, add 300ml methylene dichloride simultaneously and make solvent, 0.5mol sodium hydroxide is slowly added in reactor under magnetic stirring, make this system reaction 1 hour in-8 DEG C of ice salt bath environment, reacting 4 hours at ambient temperature, vacuum filtration removes 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 drip under magnetic agitation effect and add above-mentioned filtrate, 0 DEG C of reaction 1 hour, reaction 2 hours under room temperature; Finally being warming up to 40 DEG C of reactions after 1 hour, moved out by product, vacuum filtration removes Triethylammonium chloride throw out, by 1000ml sherwood oil wash filtrate 2 times, then vacuum filtration removes insolubles, 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-eight hydrogen two oxadiazoles diphosphinic acid, receipts rate 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 four fluorine stirring rakes, 120 DEG C of vacuum hydro-extraction 1h, it is cooled to 85 DEG C, logical nitrogen, installs condensing reflux pipe, adds 20.54gTDI and 3g dimethylol propionic acid (DMPA) and react 2h. Add the fire-retardant chainextender ODDP of 10g afterwards, reaction 4h. It is cooled to 40 DEG C again, after adding 50ml acetone diluted system viscosity, add 2.0g triethylamine (TEA) and neutralize 10min, finally performed polymer is poured in dry beaker, under the rotating speed of blade dispersion machine 2000��3000r/min stirs, add 150g, temperature is the deionized water of 0��10 DEG C, obtains white emulsion, place a night after 5min. Within 2nd day, use Rotary Evaporators to remove the acetone in emulsion, obtain the halogen-free flameproof aqueous polyurethane emulsion that hard section is flame-retardant modified. Get emulsion 40g, in tetrafluoroethylene sheet material middle berth film, naturally after drying 14 days, dry 4h in the vacuum drying oven of 90 DEG C, being tested by dried latex film, LOI value is 30.1%, thermolysis main decomposition stage decomposition mechanism place temperature 339.8 DEG C, carbon left: 13.11%, amount of flame-retardant agent: 13wt%.

Claims (6)

1. the application of a ring-type phosphorus nitrogen synergistic halogen-free flame retardants, it is characterised in that: concrete steps are as follows:
Step one, 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 reacting raw materials used is ADI: polyether glycol: hydrophilic chain extender=3:1��1.5:0.6;
Step 2, add the hard section halogen-free flameproof chainextender accounting for performed polymer quality 10%-25%, at 60��85 DEG C, react 2��4h;
Step 3, it is cooled to 20��40 DEG C, adds neutralizing agent and carry out neutralization reaction and generate salt, neutralization time 10min; The add-on of neutralizing agent is the 3%-6% of performed polymer quality;
Step 4, add deionized water and carry out emulsify at a high speed 3��5min, obtain the halogen-free flameproof aqueous polyurethane emulsion that the two hard sections of phosphonic amide are flame-retardant modified;
Hard section halogen-free flameproof chainextender in described step 2 is 2,7-bis-(N, N dimethylamine base)-1,6,3,8,2,7-eight hydrogen two oxadiazoles diphosphinic acid (ODDP);
The structural formula of described ODDP is:
2. the application of a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants as claimed in claim 1, it is characterised in that: the viscosity that solvent carrys out regulation system can also be added before described step 3 adds neutralizing agent.
3. the application of a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants as claimed in claim 2, it is characterised in that: described solvent is the one in acetone, butanone, tetrahydrofuran (THF), ethyl acetate.
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: in described step one vulcabond (ADI) be tolylene diisocyanate TDI, isophorone diisocyanate IPDI, diphenylmethanediisocyanate MDI, naphthalene-1,5-vulcabond NDI, hexamethylene diisocyanate HDI, 2,6-vulcabond methyl caproate LDI, 4,4 '-methylene radical-dicyclohexyl two isocyanate H12MDI, xylylene diisocyanate XDI or 1,12-dodecane diisocyanate C12One in DDI; Polyether glycol in described preparation process one is the polyether compound containing two hydroxyls (-OH); Hydrophilic chain extender in described preparation process one be containing carboxyl structure dibasic alcohol or containing sulfonic acid structure dibasic alcohol in the mixture of one or more.
5. the application of a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants as described in claim 1 or 4, it is characterised in that: the polyether glycol in described preparation process one selects polyether Glycols PPG1000; Hydrophilic chain extender in described preparation process one selects dimethylol propionic acid.
6. the application of a kind of ring-type phosphorus nitrogen synergistic halogen-free flame retardants as claimed in claim 1, it is characterised in that: the neutralizing agent in described preparation process three is the one in triethylamine, tri-n-butylamine, sodium hydroxide, potassium hydroxide, calcium hydroxide.
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