CN102816185A - Reaction type phosphorus-nitrogen fire retardant and preparation method thereof - Google Patents
Reaction type phosphorus-nitrogen fire retardant and preparation method thereof Download PDFInfo
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Abstract
本发明公开的反应型磷氮阻燃剂，其结构通式如下：式（Ⅰ）中，R1为氢原子或苯基；R2为氧原子或硫原子；R3为含有氮元素的化合物，该类化合物拥有一个伯胺基和两个羟基，其中的伯胺基可与异硫氰酸基（-NCS）反应，两个羟基可用于后续与聚合物单体的反应基团。本发明还公开了该反应型磷氮阻燃剂的制备方法。本发明阻燃剂不仅集酸源、碳源和气源为一体，且还拥有两个反应活性很高的羟基，既可很容易通过化学键合使阻燃剂结构嵌入聚合物链中，避免了现有技术采用的引发剂或光辐射手段所带来的问题，又能很好地发挥膨胀型阻燃剂的功效，较大幅度提高高分子材料的阻燃效果。制备方法简单、成熟，易于操作，反应温度低，节能。The reactive phosphorus nitrogen flame retardant disclosed by the present invention has a general structural formula as follows:
In the formula (I), R 1 is a hydrogen atom or a phenyl group; R 2 is an oxygen atom or a sulfur atom; R 3 is a compound containing nitrogen, which has a primary amino group and two hydroxyl groups, and the primary amine The group can react with isothiocyanate group (-NCS), and the two hydroxyl groups can be used for subsequent reaction groups with polymer monomers. The invention also discloses a preparation method of the reactive phosphorus nitrogen flame retardant. The flame retardant of the present invention not only integrates the acid source, carbon source and gas source, but also has two highly reactive hydroxyl groups, which can easily embed the flame retardant structure into the polymer chain through chemical bonding, avoiding the The problem caused by the initiator or light radiation method adopted in the prior art can also give full play to the effect of the intumescent flame retardant, and greatly improve the flame retardant effect of the polymer material. The preparation method is simple and mature, easy to operate, low in reaction temperature and energy-saving.
Description
Technical field
The invention belongs to phosphor nitrogen combustion inhibitor and preparing technical field thereof, be specifically related to a kind of novel response type phosphor nitrogen combustion inhibitor and preparation method thereof.
Background technology
After the 1950's; Macromolecular material industry begins development; But the fire that causes owing to the combustibility of macromolecular material has brought property damage and life-threatening safety to people, and macromolecular material is carried out one of flame-retardant modified important topic that becomes scientific worker's research.
Traditional fire retardant is halogenated flame retardant (especially bromine system) and halogen system and other synergist blended synergistic fire retardants; But in combustion processes, generate easily more cigarette, corrosive gases and poisonous gas because bromine is a flame-retardant system, and be restricted gradually and forbid.Make halogen-free flame-retardant system become the research focus of flame retardant area gradually.
Halogen-free flame-retardant system has phosphorus system, nitrogen system, phosphorus nitrogen system, silicon system etc.; Surface energy formed porous foam carbon-coating when wherein the polymer materials after flame-retardant modified was because of burning with phosphorus-nitrogen containing flame retardant; Heat insulation, oxygen barrier is arranged and press down the effect of cigarette; And can effectively prevent the molten drop phenomenon, and become comparatively active fire-retardant research direction of 21 century.
US4491644 discloses the synthesis preparation method of fire retardant Melabis and with its fire-retardant to PP, the structure of this fire retardant is following:
When in PP, adding 20% Melabis, the limiting oxygen index(LOI) of system can rise to 31.7% from 17.5%, and the vertical combustion grade can reach UL 94V-0.Wherein two amino are as the ratio of improving fire retardant carbon source, acid source and source of the gas, effect optimization when making it as additive flame retardant, but do not see report as reactive flame retardant.
Disclosed a kind of phosphorous, the sulphur of viscose fiber, the phosphorus-nitrogen containing flame retardant of three kinds of elements of nitrogen of being used for of CN101701423A, called after N, N '-two (two phenoxy thiophosphoryl bases) rubeanic acid, structure is following:
Because its tape base group reactive behavior is not high, so can only be applied to polymkeric substance as additive flame retardant.
CN101086136A discloses a kind of called after 1, the fire retardant of the phosphorous sulphur nitrogen element of 4-(O, O-diethyl sulfo-phosphoryl imido grpup) benzene, and structure is following:
This patented invention person uses it for the flame-retardant acrylic fibre fiber, and the fire retardant addition is 20% o'clock, and the limiting oxygen index(LOI) of acrylic fibers reaches 28%.Because of its tape base group reactive behavior is not high, so can only use as additive flame retardant.
CN102225953A discloses a kind of response type phosphorus-nitrogen containing flame retardant, and structure is following:
Wherein but reactive group is a secondary amine, so because of the sterically hindered reason, its reactive behavior is still lower.
CN 101831082A discloses a kind of response type phosphorus-nitrogen containing flame retardant, is named as 2-alkene alkoxyl group-4,6-dialkyl amino-1,3,5-triazines (gathering) phosphoric acid salt, and structure is following:
Annotate: R
1, R
2, R
3=H, CH
3
Because need under the initiation of superoxide, just can make two key groups of alkene alkoxyl group and polymkeric substance generation chemically bonded in the fire retardant, bonding process is complicated, is difficult in the industry realizing.
CN 101597307A discloses a kind of phosphorous nitrogen flame retardant of uV curable, and structure is following:
(R is the functional group of part propylene acidifying or part methyl acrylated in the formula; R ' is for having the nitrogen-containing functional group of two tertiary amines or secondary amine) but owing to reactive group in its structure has the activity double key of R part and the secondary amine of R ' part; Wherein activity double key inserts in the curable resinous substrates through uv-radiation only; Therefore bonding process is also comparatively complicated, is difficult for industriallization.
In addition; More than disclosed additive flame retardant because of being to mix with matrix with physics mode; Both occurred the phenomenon that fire retardant moves out of matrix in time easily, and the flame retardant rating of fire retardant material is descended, and the consistency of small molecules fire retardant and polymkeric substance had been generally all relatively poor; With the mechanical property that influences base material, the use at specific area is impacted.And for additive flame retardant, the group though reactive flame retardant responds is can react with monomer or prepolymer; In flame-retardant compound structure embedded polymer thing chain, not only ignition-proof element does not move, and flame retardant properties is lasting; And can overcome the phase tolerance problem; Little to the base material influence, but the disclosed three kinds of response type phosphorus-nitrogen containing flame retardants of above prior art are not fully up to expectations, all exist reactive group active low or with the complicated shortcoming of polymer chemistry bonding mode.
Summary of the invention
The objective of the invention is shortcoming to the prior art existence; A kind of new response type phosphor nitrogen combustion inhibitor at first is provided; This fire retardant not only contains all good phosphorus, nitrogen and the three kinds of ignition-proof elements of sulphur of flame retardant effect, can produce the synergistic fire retarding effect, and also contain the higher hydroxyl of reactive behavior; Can be directly as chainextender and monomer reaction, the bonding mode is simple.
Another object of the present invention provides a kind of preparation method of above-mentioned response type phosphor nitrogen combustion inhibitor.
Response type phosphor nitrogen combustion inhibitor provided by the invention, its general structure is following:
In the formula I, R
1Be Wasserstoffatoms or phenyl; R
2Be Sauerstoffatom or sulphur atom; R
3For
Wherein x, y, n, m are 0,1,2 or 3, and can not be 0 simultaneously, or do
Wherein x, y are 0,1,2 or 3, R
3' be phenyl or p-nitrophenyl.
The preparation method of above-mentioned response type phosphor nitrogen combustion inhibitor provided by the invention is when this method prepares R in the logical formula I of said structure
1Be Wasserstoffatoms, R
2During for the phosphor nitrogen combustion inhibitor of Sauerstoffatom, its process step and condition are following:
1) earlier NSC 6366 is added solvent ⅰ dissolving, slowly drip POCl3 then at normal temperatures while stirring, the mol ratio of POCl3 and NSC 6366 is 1:1.05～1.5; The hydrogen chloride gas body and function sodium bicarbonate aqueous solution that reaction generates absorbs, and is warming up to 40 ~ 83 ℃ after dropwising, and reacts 2～7 hours; Rotary evaporation removes the ⅰ that desolvates, and the solid that obtains obtains 5,5-dimethyl--1 after washing successively with normal hexane and anhydrous diethyl ether respectively; 3, phosphoryl chloride in the 2-dioxa is own;
2) with 5,5-dimethyl--1,3, phosphoryl chloride and Rhocya were dissolved in respectively among the solvent ⅱ 1:1 ~ 1.1 in molar ratio in the 2-dioxa was own; Be warming up to 40 ~ 56 ℃ then, dissolved Rhocya drips of solution added 5,5-dimethyl--1,3; In the solution of oneself interior phosphoryl chloride of 2-dioxa, reacted 4 ~ 9 hours, suction filtration is removed Repone K, and the filtrating rotary evaporation removes the ⅱ that desolvates and promptly gets the 2-isothiocyano-5 with following structure; 5-dimethyl--1,3, the 2-dioxaphosphorinane;
3) earlier respectively with 2-isothiocyano-5,5-dimethyl--1,3; The 2-dioxaphosphorinane is dissolved among the solvent ⅲ, contains two hydroxyl primary amine compounds and is dissolved among the solvent ⅳ, then at room temperature; Two kinds of solution mixing stirring reactions were got final product 2-isothiocyano-5 wherein, 5-dimethyl--1 in 6～15 hours; 3, the 2-dioxaphosphorinane is 1:1.1 ~ 1.5 with the mol ratio that contains two hydroxyl primary amine compounds.Reaction formula is following:
R in the logical formula I of preparation said structure
1Be Wasserstoffatoms, R
2During for the phosphor nitrogen combustion inhibitor of sulphur atom, its process step and condition are following:
1) earlier NSC 6366 is added solvent ⅰ dissolving, slowly drip phosphorus thiochloride then at normal temperatures while stirring, the mol ratio of phosphorus thiochloride and NSC 6366 is 1:1.05～1:1.5; The hydrogen chloride gas body and function sodium bicarbonate aqueous solution that reaction generates absorbs, and is warming up to 40 ~ 83 ℃ after dropwising, and reacts 2～7 hours; Rotary evaporation removes the ⅰ that desolvates, and the solid that obtains obtains 2-sulfo--5,5-dimethyl--1 after washing successively with normal hexane and anhydrous diethyl ether respectively; 3, phosphoryl chloride in the 2-dioxa is own;
2) with 2-sulfo--5,5-dimethyl--1,3; Phosphoryl chloride and Rhocya were dissolved in respectively among the solvent ⅱ 1:1～1.1 in molar ratio in the 2-dioxa was own, were warming up to 40～56 ℃ then, and dissolved Rhocya drips of solution is added 2-sulfo--5; 5-dimethyl--1,3 is in the solution of oneself interior phosphoryl chloride of 2-dioxa; Reacted 4～9 hours, suction filtration is removed Repone K, and the filtrating rotary evaporation removes the ⅱ that desolvates and promptly gets the 2-sulfo--2-isothiocyano-5 with following structure; 5-dimethyl--1,3, the 2-dioxaphosphorinane;
3) earlier respectively with 2-sulfo--2-isothiocyano-5,5-dimethyl--1,3; The 2-dioxaphosphorinane is dissolved among the solvent ⅲ, contains two hydroxyl primary amine compounds and is dissolved among the solvent ⅳ, then at room temperature; Two kinds of solution mixing stirring reactions were got final product 2-sulfo--2-isothiocyano-5 wherein, 5-dimethyl--1 in 6～15 hours; 3, the 2-dioxaphosphorinane is 1:1.1 ~ 1.5 with the mol ratio that contains two hydroxyl primary amine compounds.Reaction formula is following:
R in the logical formula I of preparation said structure
1Be phenyl, R
2During for the phosphor nitrogen combustion inhibitor of Sauerstoffatom, its process step and condition are following:
1) (this compound is by reference: Wolter ten Hoeve with 1-phenyl-2 earlier; Hans Wynberg.The Design of Resolving Agents.Chiral Cyclic Phosphoric Acids.J.Org.Chem.1985,50, disclosed method prepares among the 4508-4514.) dissolve with solvent ⅰ; Slowly drip POCl3, POCl3 and 1-phenyl-2,2-dimethyl--1 then at normal temperatures while stirring; The mol ratio of ammediol is 1:1.05～1.5, and the hydrogen chloride gas body and function sodium bicarbonate aqueous solution that reaction generates absorbs, and is warming up to 40 ~ 83 ℃ after dropwising; Reacted 2～7 hours, rotary evaporation removes and desolvates, and the solid that obtains is washed with normal hexane and anhydrous diethyl ether respectively successively promptly get 4-phenyl-5 again; 5-dimethyl--1,3, phosphoryl chloride in the 2-dioxa is own;
2) with 4-phenyl-5,5-dimethyl--1,3, phosphoryl chloride and Rhocya were dissolved in respectively among the solvent ⅱ by 1:1～1.1 in the 2-dioxa was own; Be warming up to 40 ~ 56 ℃ then, dissolved Rhocya drips of solution added 4-phenyl-5,5-dimethyl--1,3; In the solution of oneself interior phosphoryl chloride of 2-dioxa, reacted 4～9 hours, suction filtration is removed Repone K, and the filtrating rotary evaporation removes the ⅱ that desolvates and promptly gets the 2-isothiocyano-4-phenyl-5 with following structure; 5-dimethyl--1,3, the 2-dioxaphosphorinane;
3) earlier with 2-isothiocyano-4-phenyl-5,5-dimethyl--1,3; The 2-dioxaphosphorinane is dissolved among the solvent ⅲ, contains two hydroxyl primary amine compounds and is dissolved among the solvent ⅳ, then at room temperature; Two kinds of solution mixing stirring reactions were got final product 2-isothiocyano-4-phenyl-5 wherein, 5-dimethyl--1 in 6～15 hours; 3, the 2-dioxaphosphorinane is 1:1.1 ~ 1.5 with the mol ratio that contains two hydroxyl primary amine compounds.Reaction formula is following:
R in the logical formula I of preparation said structure
1Be phenyl, R
2During for the phosphor nitrogen combustion inhibitor of sulphur atom, its process step and condition are following:
1) earlier 1-phenyl-2 is dissolved with solvent ⅰ; Slowly drip phosphorus thiochloride, phosphorus thiochloride and 1-phenyl-2,2-dimethyl--1 then at normal temperatures while stirring; The mol ratio of ammediol is 1:1.05～1.5, and the hydrogen chloride gas body and function sodium bicarbonate aqueous solution that reaction generates absorbs, and is warming up to 40 ~ 83 ℃ after dropwising; Reacted 2～7 hours, rotary evaporation removes and desolvates, and the solid that obtains is washed with normal hexane and anhydrous diethyl ether respectively successively promptly get 2-sulfo--4-phenyl-5 again; 5-dimethyl--1,3, phosphoryl chloride in the 2-dioxa is own;
2) with 2-sulfo--4-phenyl-5,5-dimethyl--1,3; Phosphoryl chloride and Rhocya were dissolved in respectively among the solvent ⅱ by 1:1～1.1 in the 2-dioxa was own, were warming up to 40 ~ 56 ℃ then, and dissolved Rhocya drips of solution is added 2 sulfo-4-phenyl-5; 5-dimethyl--1,3 is in the solution of oneself interior phosphoryl chloride of 2-dioxa; Reacted 4～9 hours, suction filtration is removed Repone K, and the filtrating rotary evaporation removes the ⅱ that desolvates and promptly gets the 2-sulfo--2-isothiocyano-4-phenyl-5 with following structure; 5-dimethyl--1,3, the 2-dioxaphosphorinane;
3) earlier with 2-sulfo--2-isothiocyano-4-phenyl-5,5-dimethyl--1,3; The 2-dioxaphosphorinane is dissolved among the solvent ⅲ, contains two hydroxyl primary amine compounds and is dissolved among the solvent ⅳ, then at room temperature; Two kinds of solution mixing stirring reactions were got final product 2-sulfo--2-isothiocyano-4-phenyl-5 wherein, 5-dimethyl--1 in 6～15 hours; 3, the 2-dioxaphosphorinane is 1:1.1～1.5 with the mol ratio that contains two hydroxyl primary amine compounds.Reaction formula is following:
Used solvent ⅰ is trichloromethane, methylene dichloride, 1 in the above method; In 2-ethylene dichloride, tetracol phenixin, acetone, butanone, benzene,toluene,xylene, tetraline, propyl ether, isopropyl ether or the butyl ether any; Preferred trichloromethane, methylene dichloride or 1, any in the 2-ethylene dichloride; Solvent ⅱ is acetonitrile or acetone, preferred acetone; Solvent ⅲ is acetone, ETHYLE ACETATE, trichloromethane, methylene dichloride, 1, any in 2-ethylene dichloride or the tetracol phenixin, ethyl acetate; Solvent ⅳ is methyl alcohol or ethanol, particular methanol.
In the above method the 2nd) product of step reaction gained is crude product, and this crude product both can directly use, but used behind the purifying again, and did not all influence the back reaction result in one step.
In the above method the 1st) preferred 3 ~ 5 hours of the reaction times of step; The 2nd) preferred 5 ~ 8 hours of the reaction times of step; The 3rd) preferred 10 ~ 13 hours of the reaction times of step; The 1st) the step temperature of reaction is preferred 75 ℃ ~ 83 ℃; The 2nd) the step temperature of reaction is preferred 50 ~ 56 ℃.
The general structure that contains two hydroxyl primary amine compounds in the above method is following:
Wherein x, y, n, m are 0,1,2 or 3, and can not be 0 simultaneously, or do
Wherein x, y are 0,1,2 or 3, R
3' be phenyl or p-nitrophenyl.
The present invention compared with prior art has following positively effect:
1, be one owing to response type phosphor nitrogen combustion inhibitor provided by the invention not only collects acid source, carbon source and source of the gas; And have two hydroxyls that reactive behavior is very high; Thereby both can be easy to make in the fire retardant structure embedded polymer thing chain structure (because secondary amine has steric effect through chemically bonded; There is not hydroxyl strong for Hydrogen Energy power; So with isocyano (in addition reaction NCO), the hydrogen in the response type phosphor nitrogen combustion inhibitor hydroxyl provided by the invention is more active than secondary amine hydrogen in the existing fire retardant), can bring into play the effect of expansion type flame retardant again.
2. when being applied to prepare in corresponding urethane as chainextender response type phosphor nitrogen combustion inhibitor provided by the invention; Can be directly add in the reaction system, under high temperature and strong mixing, just can make the fire retardant powder be dissolved in the system gradually with the pressed powder state; Make wherein hydroxyl and isocyano (NCO) addition reaction take place and embed polyurethane backbone; Avoided the initiator of prior art employing or the problem that the optical radiation means are brought, thereby the bonding mode is simple, operation is easy to industriallization.
3. owing to contain all good phosphorus, nitrogen and the three kinds of ignition-proof elements of sulphur of flame retardant effect in the response type phosphor nitrogen combustion inhibitor provided by the invention; These three kinds of elements also have fire-retardant synergistic effect in addition; Thereby, it is applied to have flame retardant effect preferably behind the macromolecular materials such as flame retardant polyurethane and POLYACTIC ACID when can be used as chainextender; The LOI that when flame retardant agent content only has 4.43wt%, just can make polyurethane elastomer brings up to 31% from 26%, and this fire retardant has broad application prospects.
4. preparation method provided by the invention is simple, ripe, easy handling, and temperature of reaction is low, and is energy-conservation.
Description of drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of synthetic fire retardant in the embodiment of the invention 12.Four of 3.58 ~ 4.27ppm place peaks are to the Wasserstoffatoms in should the fire retardant methylene radical among the figure; 4.83ppm the peak of locating is to the Wasserstoffatoms in should the fire retardant hydroxyl; 8.46ppm the peak of locating is to the Wasserstoffatoms on the secondary amine that should fire retardant connecting carbon atom, the peak of 9.28ppm is to should fire retardant connecting the Wasserstoffatoms of the secondary amine of phosphorus atom.This explanation institute synthetic fire retardant is that phosphorous nitrogen and sulphur of the present invention is plain and with the reactive flame retardant of two hydroxyls.
Fig. 2 is the nucleus magnetic hydrogen spectrum figure of obtained flame-retardant agent in the embodiment of the invention 1.The peak at 3.57 ~ 4.46ppm place is to the Wasserstoffatoms on should the fire retardant methylene radical among the figure; 4.85ppm the peak of locating is to hydroxyl that should fire retardant; 5.57ppm the peak of locating is to the Wasserstoffatoms on should the fire retardant methyne; 7.24 the multiplet at ~ 7.43ppm place is to the Wasserstoffatoms on should the fire retardant phenyl, the peak at 8.35ppm place is to the Wasserstoffatoms on the secondary amine that should fire retardant connecting carbon atom, and the peak of 9.37ppm is to should fire retardant connecting the Wasserstoffatoms of the secondary amine of phosphorus atom.This explanation institute synthetic fire retardant is that phosphorous nitrogen and sulphur of the present invention is plain and with the reactive flame retardant of two hydroxyls.
Embodiment
Through embodiment the present invention is specifically described below.Be necessary to be pointed out that at this following examples only are used for the present invention is further specified; Can not be interpreted as the restriction to protection domain of the present invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to the foregoing invention content.
What be worth explanation is, the limiting oxygen index(LOI) of the flame resistance polyurethane elastomer that following application examples is prepared (LOI) is by GB/T2406, and the 2-2009 standard is measured, and sample size is 100 * 10 * 4mm
3
With 47.4g (0.44mol) phenyl aldehyde and 64.0g (0.88mol) isobutyric aldehyde, mix earlier, get 24.8g (0.44mol) Pottasium Hydroxide and be dissolved in 400ml ethanol; Slowly drip in the system through tap funnel; Exothermic heat of reaction stops dropping liquid when temperature reaches 70 ℃, accelerate to drip the ethanolic soln of Pottasium Hydroxide when making system fast cooling to 50 ℃ with water-bath again; Dropwise the back to the system heating, remain on 50～60 ℃ and reacted 5 hours down.Revolve after reaction finishes to steam and obtain yellow thickness crude product; Extract with the chloroform/water system; The gained chloroform layer is used anhydrous magnesium sulfate drying, and the clear liquor that obtains after the drying revolves to steam removes chloroform, obtains 61.0g (0.34mol) 1-phenyl-2 with toluene/normal hexane system recrystallization; 2-dimethyl--1, ammediol.
36.0g (0.20mol) 1-phenyl-2 is added 1 of 200ml; Dissolve in the 2-ethylene dichloride, slowly drip 27.5g (0.18mol) POCl3 through constant pressure funnel while stirring at normal temperatures then, the hydrogen chloride gas body and function sodium bicarbonate aqueous solution that reaction generates absorbs; Be warming up to 83 ℃ of reaction 7h after dropwising, reaction finishes the back rotary evaporation and removes 1, the 2-ethylene dichloride; The solid that obtains obtains 36.4g (0.14mol) 4-phenyl-5 after washing successively with normal hexane and anhydrous diethyl ether respectively; 5-dimethyl--1,3, phosphoryl chloride in the 2-dioxa is own.With 4-phenyl-5,5-dimethyl--1,3, oneself is dissolved in the 2-dioxa in the 150ml acetone by interior phosphoryl chloride 36.4g (0.14mol); Get 13.6g (0.14mol) Rhocya again and be dissolved in the 50ml acetone, be warming up to 56 ℃ then, dissolved Rhocya drips of solution is added 4-phenyl-5; 5-dimethyl--1,3 is in the solution of oneself interior phosphoryl chloride of 2-dioxa; Reaction 6h, suction filtration is removed Repone K, and the filtrating rotary evaporation is removed acetone and is promptly got 2-isothiocyano-4-phenyl-5; 5-dimethyl--1,3, the crude product 36.7g of 2-dioxaphosphorinane (about 0.13mol).Whole crude products are used the 100ml acetic acid ethyl dissolution, and with 14.7g (0.14mol) 2-amino-2-methyl-1, ammediol is used the 100ml dissolve with methanol; Then at room temperature; With two kinds of solution mixing stirring reaction 12h, reaction finishes the back suction filtration and gets white solid, with the washing of 150ml ETHYLE ACETATE once; Use the 50ml methanol wash again one time, obtain described fire retardant 42.7g.
The used 1-phenyl-2 synthetic operation steps of present embodiment is with embodiment 1.Dissolve in the YLENE with 36.0g (0.20mol) 1-phenyl-2 adding 200ml; Slowly drip 19.9g (0.13mol) POCl3 through constant pressure funnel while stirring at normal temperatures then; The hydrogen chloride gas body and function sodium bicarbonate aqueous solution that reaction generates absorbs, and is warming up to 75 ℃ of reaction 2h after dropwising, and reaction finishes the back rotary evaporation and removes removal xylene; The solid that obtains obtains 23.4g (0.09mol) 4-phenyl-5 after washing successively with normal hexane and anhydrous diethyl ether respectively; 5-dimethyl--1,3, phosphoryl chloride in the 2-dioxa is own.With 4-phenyl-5,5-dimethyl--1,3, oneself is dissolved in the 2-dioxa in the 150ml acetonitrile by interior phosphoryl chloride 23.4g (0.09mol); Get 9.7g (0.10mol) Rhocya again and be dissolved in the 50ml acetonitrile, be warming up to 40 ℃ then, dissolved Rhocya drips of solution is added 4-phenyl-5; 5-dimethyl--1,3 is in the solution of oneself interior phosphoryl chloride of 2-dioxa; Reaction 4h, suction filtration is removed Repone K, and the filtrating rotary evaporation is removed acetonitrile and is promptly got 2-isothiocyano-4-phenyl-5; 5-dimethyl--1,3, the crude product 25.4g of 2-dioxaphosphorinane (about 0.09mol).Whole crude products with the dissolving of 100ml methylene dichloride, are used the 100ml dissolve with ethanol with amino-1,2 Ucar 35 of 10.0g (0.11mol) 3-; Then at room temperature; With two kinds of solution mixing stirring reaction 15h, reaction finishes the back suction filtration and gets white solid, with the washing of 150ml ETHYLE ACETATE once; Use the 50ml methanol wash again one time, obtain described fire retardant 29.8g.
The used 1-phenyl-2 synthetic operation steps of present embodiment is with embodiment 1.Dissolve in the acetone with 36.0g (0.20mol) 1-phenyl-2 adding 200ml; Slowly drip 21.4g (0.14mol) POCl3 through constant pressure funnel while stirring at normal temperatures then; The hydrogen chloride gas body and function sodium bicarbonate aqueous solution that reaction generates absorbs, and is warming up to 56 ℃ of reaction 3h after dropwising, and reaction finishes the back rotary evaporation and removes acetone; The solid that obtains obtains 28.6g (0.11mol) 4-phenyl-5 after washing successively with normal hexane and anhydrous diethyl ether respectively; 5-dimethyl--1,3, phosphoryl chloride in the 2-dioxa is own.With 4-phenyl-5,5-dimethyl--1,3, oneself is dissolved in the 2-dioxa in the 150ml acetone by interior phosphoryl chloride 28.6g (0.11mol); Get 11.6g (0.12mol) Rhocya again and be dissolved in the 50ml acetone, be warming up to 53 ℃ then, dissolved Rhocya drips of solution is added 4-phenyl-5; 5-dimethyl--1,3 is in the solution of oneself interior phosphoryl chloride of 2-dioxa; Reaction 9h, suction filtration is removed Repone K, and the filtrating rotary evaporation is removed acetone and is promptly got 2-isothiocyano-4-phenyl-5; 5-dimethyl--1,3, the crude product 28.2g of 2-dioxaphosphorinane (about 0.10mol).Whole crude products are used the 100ml acetone solution, and with 29.7g (0.14mol) 1-nitrophenyl-2-amino-1, ammediol is used the 100ml dissolve with methanol; Then at room temperature; With two kinds of solution mixing stirring reaction 10h, reaction finishes the back suction filtration and gets white solid, with the washing of 150ml ETHYLE ACETATE once; Use the 50ml methanol wash again one time, obtain described fire retardant 44.5g.
The used 1-phenyl-2 synthetic operation steps of present embodiment is with embodiment 1.Dissolve in the isopropyl ether with 36.0g (0.20mol) 1-phenyl-2 adding 200ml; Slowly drip 29.1g (0.19mol) POCl3 through constant pressure funnel while stirring at normal temperatures then; The hydrogen chloride gas body and function sodium bicarbonate aqueous solution that reaction generates absorbs, and is warming up to 40 ℃ of reaction 4h after dropwising, and reaction finishes the back rotary evaporation and removes isopropyl ether; The solid that obtains obtains 36.4g (0.14mol) 4-phenyl-5 after washing successively with normal hexane and anhydrous diethyl ether respectively; 5-dimethyl--1,3, phosphoryl chloride in the 2-dioxa is own.With 4-phenyl-5,5-dimethyl--1,3, oneself is dissolved in the 2-dioxa in the 150ml acetonitrile by interior phosphoryl chloride 36.4g (0.14mol); Get 13.6g (0.14mol) Rhocya again and be dissolved in the 50ml acetonitrile, be warming up to 50 ℃ then, dissolved Rhocya drips of solution is added 4-phenyl-5; 5-dimethyl--1,3 is in the solution of oneself interior phosphoryl chloride of 2-dioxa; Reaction 8h, suction filtration is removed Repone K, and the filtrating rotary evaporation is removed acetonitrile and is promptly got 2-isothiocyano-4-phenyl-5; 5-dimethyl--1,3, the crude product 36.7g of 2-dioxaphosphorinane (about 0.13mol).Whole crude products are used 100ml1, and the dissolving of 2-ethylene dichloride is with 18.2g (0.20mol) 2-amino-1; Ammediol is used the 100ml dissolve with methanol, then at room temperature, and with two kinds of solution mixing stirring reaction 6h; Reaction finishes the back suction filtration and gets white solid; With the washing of 150ml ETHYLE ACETATE once, use the 50ml methanol wash again one time, obtain described fire retardant 41.0g.
Embodiment 5
The used 1-phenyl-2 synthetic operation steps of present embodiment is with embodiment 1.Dissolve in the YLENE with 36.0g (0.20mol) 1-phenyl-2 adding 200ml; Slowly drip 26.0g (0.17mol) POCl3 through constant pressure funnel while stirring at normal temperatures then; The hydrogen chloride gas body and function sodium bicarbonate aqueous solution that reaction generates absorbs, and is warming up to 77 ℃ of reaction 5h after dropwising, and reaction finishes the back rotary evaporation and removes removal xylene; The solid that obtains obtains 31.2g (0.12mol) 4-phenyl-5 after washing successively with normal hexane and anhydrous diethyl ether respectively; 5-dimethyl--1,3, phosphoryl chloride in the 2-dioxa is own.With 4-phenyl-5,5-dimethyl--1,3, oneself is dissolved in the 2-dioxa in the 150ml acetone by interior phosphoryl chloride 31.2g (0.12mol); Get 12.6g (0.13mol) Rhocya again and be dissolved in the 50ml acetone, be warming up to 56 ℃ then, dissolved Rhocya drips of solution is added 4-phenyl-5; 5-dimethyl--1,3 is in the solution of oneself interior phosphoryl chloride of 2-dioxa; Reaction 5h, suction filtration is removed Repone K, and the filtrating rotary evaporation is removed acetone and is promptly got 2-isothiocyano 4-phenyl-5; 5-dimethyl--1,3, the crude product 33.8g of 2-dioxaphosphorinane (about 0.12mol).With the dissolving of 100ml trichloromethane, with 26.7g (0.16mol) 2-amino-1-phenyl-1, ammediol is used the 100ml dissolve with methanol with whole crude products; Then at room temperature; With two kinds of solution mixing stirring reaction 13h, reaction finishes the back suction filtration and gets white solid, with the washing of 150ml ETHYLE ACETATE once; Use the 50ml methanol wash again one time, obtain described fire retardant 47.4g.
Earlier 62.4g (0.60mol) NSC 6366 is added 1 of 350ml, dissolve in the 2-ethylene dichloride, slowly drip 96.3g (0.57mol) phosphorus thiochloride through constant pressure funnel while stirring at normal temperatures then; Be warming up to 83 ℃ of reaction 5h after dropwising, reaction finishes the back rotary evaporation and removes 1, the 2-ethylene dichloride; The solid that obtains obtains 88.0g (0.44mol) 2-sulfo--5 after washing successively with normal hexane and anhydrous diethyl ether respectively; 5-dimethyl--1,3, phosphoryl chloride in the 2-dioxa is own.With the 2-sulfo--5 that obtains, 5-dimethyl--1,3; Oneself is dissolved in the 2-dioxa in the 300ml acetonitrile by interior phosphoryl chloride 88.0g (0.44mol), gets 43.7g (0.45mol) Rhocya again and is dissolved in the 50ml acetonitrile, is warming up to 45 ℃ then; Dissolved Rhocya drips of solution is added 2-sulfo--5,5-dimethyl--1,3; React 9h in the solution of oneself interior phosphoryl chloride of 2-dioxa, suction filtration is removed Repone K, and the filtrating rotary evaporation is removed acetonitrile and promptly got 2-sulfo--2-isothiocyano-5; 5-dimethyl--1,3, the crude product 93.2g of 2-dioxaphosphorinane (about 0.42mol).With the dissolving of 150ml methylene dichloride, with 117.0g (0.55mol) 1-p-nitrophenyl-2-amino-1, ammediol is used the 150ml dissolve with methanol with whole crude products; Then at room temperature; With two kinds of solution mixing stirring reaction 10h, reaction finishes the back suction filtration and gets white solid, with the washing of 300ml ETHYLE ACETATE once; Use the 50ml methanol wash again one time, promptly get described fire retardant 142.2g.
Embodiment 7
Dissolve in the methylene dichloride with 62.4g (0.60mol) NSC 6366 adding 350ml earlier; Slowly drip 72.7g (0.43mol) phosphorus thiochloride through constant pressure funnel while stirring at normal temperatures then, be warming up to 40 ℃ of reaction 2h after dropwising, reaction finishes the back rotary evaporation and removes methylene dichloride; The solid that obtains obtains 64.0g (0.32mol) 2-sulfo--5 after washing successively with normal hexane and anhydrous diethyl ether respectively; 5-dimethyl--1,3, phosphoryl chloride in the 2-dioxa is own.With the 2-sulfo--5 that obtains, 5-dimethyl--1,3; Oneself is dissolved in the 2-dioxa in the 300ml acetone by interior phosphoryl chloride 64.0g (0.32mol), gets 34.0g (0.35mol) Rhocya again and is dissolved in the 50ml acetone, is warming up to 56 ℃ then; Dissolved Rhocya drips of solution is added 2-sulfo--5,5-dimethyl--1,3; React 4h in the solution of oneself interior phosphoryl chloride of 2-dioxa, suction filtration is removed Repone K, and the filtrating rotary evaporation is removed acetone and promptly got 2-sulfo--2-isothiocyano-5; 5-dimethyl--1,3, the crude product 68.8g of 2-dioxaphosphorinane (about 0.31mol).Whole crude products are used the 150ml acetone solution, and with 30.9g (0.34mol) 2-amino-1, ammediol is used the 150ml dissolve with ethanol; Then at room temperature; With two kinds of solution mixing stirring reaction 15h, reaction finishes the back suction filtration and gets white solid, with the washing of 300ml ETHYLE ACETATE once; Use the 50ml methanol wash again one time, promptly get described fire retardant 84.5g.
Dissolve in the tetracol phenixin with 62.4g (0.60mol) NSC 6366 adding 350ml earlier; Slowly drip 84.5g (0.50mol) phosphorus thiochloride through constant pressure funnel while stirring at normal temperatures then, be warming up to 60 ℃ of reaction 7h after dropwising, reaction finishes the back rotary evaporation and removes tetracol phenixin; The solid that obtains obtains 86.0g (0.43mol) 2-sulfo--5 after washing successively with normal hexane and anhydrous diethyl ether respectively; 5-dimethyl--1,3, phosphoryl chloride in the 2-dioxa is own.With the 2-sulfo--5 that obtains, 5-dimethyl--1,3; Oneself is dissolved in the 2-dioxa in the 300ml acetone by interior phosphoryl chloride 86.0g (0.43mol), gets 41.7g (0.43mol) Rhocya again and is dissolved in the 50ml acetone, is warming up to 40 ℃ then; Dissolved Rhocya drips of solution is added 2-sulfo--5,5-dimethyl--1,3; React 8h in the solution of oneself interior phosphoryl chloride of 2-dioxa, suction filtration is removed Repone K, and the filtrating rotary evaporation is removed acetone and promptly got 2-sulfo--2-isothiocyano-5; 5-dimethyl--1,3, the crude product 88.8g of 2-dioxaphosphorinane (about 0.40mol).Whole crude products are used the 150ml acetic acid ethyl dissolution, with 63.0g (0.60mol) 2-amino-2-methyl--1, ammediol is used the 150ml dissolve with methanol; Then at room temperature; With two kinds of solution mixing stirring reaction 6h, reaction finishes the back suction filtration and gets white solid, with the washing of 300ml ETHYLE ACETATE once; Use the 50ml methanol wash again one time, promptly get described fire retardant 107.8g.
Earlier 62.4g (0.60mol) NSC 6366 is added 1 of 350ml, dissolve in the 2-ethylene dichloride, slowly drip 72.7g (0.43mol) phosphorus thiochloride through constant pressure funnel while stirring at normal temperatures then; Be warming up to 75 ℃ of reaction 4h after dropwising, reaction finishes the back rotary evaporation and removes 1, the 2-ethylene dichloride; The solid that obtains obtains 70.0g (0.35mol) 2-sulfo--5 after washing successively with normal hexane and anhydrous diethyl ether respectively; 5-dimethyl--1,3, phosphoryl chloride in the 2-dioxa is own.With the 2-sulfo--5 that obtains, 5-dimethyl--1,3; Oneself is dissolved in the 2-dioxa in the 300ml acetone by interior phosphoryl chloride 70.0g (0.35mol), gets 35.9g (0.37mol) Rhocya again and is dissolved in the 50ml acetone, is warming up to 55 ℃ then; Dissolved Rhocya drips of solution is added 2-sulfo--5,5-dimethyl--1,3; React 6h in the solution of oneself interior phosphoryl chloride of 2-dioxa, suction filtration is removed Repone K, and the filtrating rotary evaporation is removed acetone and promptly got 2-sulfo--2-isothiocyano-5; 5-dimethyl--1,3, the crude product 73.3g of 2-dioxaphosphorinane (about 0.33mol).Whole crude products are used the 150ml acetic acid ethyl dissolution, and with 34.6g (0.38mol) 3-amino-1, the 2-Ucar 35 is used the 150ml dissolve with methanol; Then at room temperature; With two kinds of solution mixing stirring reaction 11h, reaction finishes the back suction filtration and gets white solid, with the washing of 300ml ETHYLE ACETATE once; Use the 50ml methanol wash again one time, promptly get described fire retardant 88.8g.
Earlier 62.4g (0.60mol) NSC 6366 is added 1 of 350ml, dissolve in the 2-ethylene dichloride, slowly drip 93.0g (0.55mol) phosphorus thiochloride through constant pressure funnel while stirring at normal temperatures then; Be warming up to 78 ℃ of reaction 3h after dropwising, reaction finishes the back rotary evaporation and removes 1, the 2-ethylene dichloride; The solid that obtains obtains 86.0g (0.43mol) 2-sulfo--5 after washing successively with normal hexane and anhydrous diethyl ether respectively; 5-dimethyl--1,3, phosphoryl chloride in the 2-dioxa is own.With the 2-sulfo--5 that obtains, 5-dimethyl--1,3; Oneself is dissolved in the 2-dioxa in the 300ml acetonitrile by interior phosphoryl chloride 86.0g (0.43mol), gets 41.7g (0.43mol) Rhocya again and is dissolved in the 50ml acetonitrile, is warming up to 50 ℃ then; Dissolved Rhocya drips of solution is added 2-sulfo--5,5-dimethyl--1,3; React 5h in the solution of oneself interior phosphoryl chloride of 2-dioxa, suction filtration is removed Repone K, and the filtrating rotary evaporation is removed acetonitrile and promptly got 2-sulfo--2-isothiocyano-5; 5-dimethyl--1,3, the crude product 88.8g of 2-dioxaphosphorinane (about 0.40mol).With the dissolving of 150ml methylene dichloride, with 80.2g (0.48mol) 2-amino-1-phenyl-1, ammediol is used the 150ml dissolve with methanol with whole crude products; Then at room temperature; With two kinds of solution mixing stirring reaction 13h, reaction finishes the back suction filtration and gets white solid, with the washing of 300ml ETHYLE ACETATE once; Use the 50ml methanol wash again one time, promptly get described fire retardant 128.4g.
Dissolve in the toluene with 62.4g (0.60mol) NSC 6366 adding 350ml earlier; Slowly drip 76.5g (0.5mol) POCl3 through constant pressure funnel while stirring at normal temperatures then; The hydrogen chloride gas body and function sodium bicarbonate aqueous solution that reaction generates absorbs, and is warming up to 75 ℃ of reaction 2h after dropwising, and reaction finishes the back rotary evaporation and removes toluene; The solid that obtains obtains 69.9g (0.38mol) 5 after washing successively with normal hexane and anhydrous diethyl ether respectively; 5-dimethyl--1,3, phosphoryl chloride in the 2-dioxa is own.With obtain 5,5-dimethyl--1,3; Oneself is dissolved in the 2-dioxa in the 300ml acetonitrile by interior phosphoryl chloride 69.9g (0.38mol), gets 36.9g (0.38mol) Rhocya again and is dissolved in the 50ml acetonitrile, is warming up to 40 ℃ then; Dissolved Rhocya drips of solution is added 5,5-dimethyl--1,3; React 9h in oneself the interior phosphoryl chloride solution of 2-dioxa, suction filtration is removed Repone K, and the filtrating rotary evaporation is removed acetonitrile and promptly got 2-isothiocyano-5; 5-dimethyl--1,3, the crude product 76.1g of 2-dioxaphosphorinane (about 0.37mol).Whole crude products are dissolved with the 150ml trichloromethane; With 40.0g (0.44mol) 3-amino-1, the 2-Ucar 35 is used the 150ml dissolve with ethanol, then at room temperature; With two kinds of solution mixing stirring reaction 15h; The white solid that suction filtration obtained after reaction finished with the washing of 300ml ETHYLE ACETATE is once used the 50ml methanol wash one time again, promptly gets described fire retardant 79.5g.
Earlier 62.4g (0.60mol) NSC 6366 is added 1 of 350ml, dissolve in the 2-ethylene dichloride, slowly drip 87.2g (0.57mol) POCl3 through constant pressure funnel while stirring at normal temperatures then; The hydrogen chloride gas body and function sodium bicarbonate aqueous solution that reaction generates absorbs; Be warming up to 83 ℃ of reaction 5h after dropwising, reaction finishes the back rotary evaporation and removes 1, the 2-ethylene dichloride; The solid that obtains obtains 86.5g (0.47mol) 5 after washing successively with normal hexane and anhydrous diethyl ether respectively; 5-dimethyl--1,3, phosphoryl chloride in the 2-dioxa is own.With obtain 5,5-dimethyl--1,3; Oneself is dissolved in the 2-dioxa in the 300ml acetone by interior phosphoryl chloride 86.5g (0.47mol), gets 47.5g (0.49mol) Rhocya again and is dissolved in the 50ml acetone, is warming up to 56 ℃ then; Dissolved Rhocya drips of solution is added 5,5-dimethyl--1,3; React 6h in oneself the interior phosphoryl chloride solution of 2-dioxa, suction filtration is removed Repone K, and the filtrating rotary evaporation is removed acetone and promptly got 2-isothiocyano-5; 5-dimethyl--1,3, the crude product 94.8g of 2-dioxaphosphorinane (about 0.46mol).Whole crude products are used the 150ml acetic acid ethyl dissolution; With 72.5g (0.69mol) 2-amino-1, ammediol is used the 150ml dissolve with methanol, then at room temperature; With two kinds of solution mixing stirring reaction 11h; The white solid that suction filtration obtained after reaction finished with the washing of 300ml ETHYLE ACETATE is once used the 50ml methanol wash one time again, promptly gets described fire retardant 112.3g.
Embodiment 13
Dissolve in the trichloromethane with 62.4g (0.60mol) NSC 6366 adding 350ml earlier; Slowly drip 61.2g (0.40mol) POCl3 through constant pressure funnel while stirring at normal temperatures then; The hydrogen chloride gas body and function sodium bicarbonate aqueous solution that reaction generates absorbs, and is warming up to 40 ℃ of reaction 7h after dropwising, and reaction finishes the back rotary evaporation and removes trichloromethane; The solid that obtains obtains 58.9g (0.32mol) 5 after washing successively with normal hexane and anhydrous diethyl ether respectively; 5-dimethyl--1,3, phosphoryl chloride in the 2-dioxa is own.With obtain 5,5-dimethyl--1,3; Oneself is dissolved in the 2-dioxa in the 300ml acetone by interior phosphoryl chloride 58.9g (0.32mol), gets 34.0g (0.35mol) Rhocya again and is dissolved in the 50ml acetone, is warming up to 50 ℃ then; Dissolved Rhocya drips of solution is added 5,5-dimethyl--1,3; React 4h in oneself the interior phosphoryl chloride solution of 2-dioxa, suction filtration is removed Repone K, and the filtrating rotary evaporation is removed acetone and promptly got 2-isothiocyano-5; 5-dimethyl--1,3, the crude product 61.3g of 2-dioxaphosphorinane (about 0.32mol).Whole crude products are used the 150ml acetone solution; With 74.2g (0.35mol) 1-p-nitrophenyl-2-amino-1, ammediol is used the 150ml dissolve with methanol, then at room temperature; With two kinds of solution mixing stirring reaction 6h; The white solid that suction filtration obtained after reaction finished with the washing of 300ml ETHYLE ACETATE is once used the 50ml methanol wash one time again, promptly gets described fire retardant 104.5g.
Embodiment 14
Earlier 62.4g (0.60mol) NSC 6366 is added 1 of 350ml, dissolve in the 2-ethylene dichloride, slowly drip 70.4g (0.46mol) POCl3 through constant pressure funnel while stirring at normal temperatures then; The hydrogen chloride gas body and function sodium bicarbonate aqueous solution that reaction generates absorbs; Be warming up to 80 ℃ of reaction 4h after dropwising, reaction finishes the back rotary evaporation and removes 1, the 2-ethylene dichloride; The solid that obtains obtains 71.8g (0.39mol) 5 after washing successively with normal hexane and anhydrous diethyl ether respectively; 5-dimethyl--1,3, phosphoryl chloride in the 2-dioxa is own.With obtain 5,5-dimethyl--1,3; Oneself is dissolved in the 2-dioxa in the 300ml acetone by interior phosphoryl chloride 71.8g (0.39mol), gets 39.8g (0.41mol) Rhocya again and is dissolved in the 50ml acetone, is warming up to 53 ℃ then; Dissolved Rhocya drips of solution is added 5,5-dimethyl--1,3; React 5h in oneself the interior phosphoryl chloride solution of 2-dioxa, suction filtration is removed Repone K, and the filtrating rotary evaporation is removed acetone and promptly got 2-isothiocyano-5; 5-dimethyl--1,3, the crude product 76.1g of 2-dioxaphosphorinane (about 0.37mol).Whole crude products are used the 150ml acetic acid ethyl dissolution; With 40.0g (0.44mol) 2-amino-1, ammediol is used the 150ml dissolve with methanol, then at room temperature; With two kinds of solution mixing stirring reaction 10h; The white solid that suction filtration obtained after reaction finished with the washing of 300ml ETHYLE ACETATE is once used the 50ml methanol wash one time again, promptly gets described fire retardant 101.0g.
Embodiment 15
Earlier 62.4g (0.60mol) NSC 6366 is added 1 of 350ml, dissolve in the 2-ethylene dichloride, slowly drip 76.5g (0.50mol) POCl3 through constant pressure funnel while stirring at normal temperatures then; The hydrogen chloride gas body and function sodium bicarbonate aqueous solution that reaction generates absorbs; Be warming up to 75 ℃ of reaction 5h after dropwising, reaction finishes the back rotary evaporation and removes 1, the 2-ethylene dichloride; The solid that obtains obtains 77.3g (0.42mol) 5 after washing successively with normal hexane and anhydrous diethyl ether respectively; 5-dimethyl--1,3, phosphoryl chloride in the 2-dioxa is own.With obtain 5,5-dimethyl--1,3; Oneself is dissolved in the 2-dioxa in the 300ml acetone by interior phosphoryl chloride 77.3g (0.42mol), gets 44.6g (0.46mol) Rhocya again and is dissolved in the 50ml acetone, is warming up to 50 ℃ then; Dissolved Rhocya drips of solution is added 5,5-dimethyl--1,3; React 8h in oneself the interior phosphoryl chloride solution of 2-dioxa, suction filtration is removed Repone K, and the filtrating rotary evaporation is removed acetone and promptly got 2-isothiocyano-5; 5-dimethyl--1,3, the crude product 82.4g of 2-dioxaphosphorinane (about 0.40mol).Whole crude products are dissolved with the 150ml trichloromethane; With 86.8g (0.50mol) 2-amino-1-phenyl-1, ammediol is used the 150ml dissolve with methanol, then at room temperature; With two kinds of solution mixing stirring reaction 13h; The white solid that suction filtration obtained after reaction finished with the washing of 300ml ETHYLE ACETATE is once used the 50ml methanol wash one time again, promptly gets described fire retardant 140.2g.
Embodiment 16
The used 1-phenyl-2 synthetic operation steps of present embodiment is with embodiment 1.Dissolve in the trichloromethane with 36.0g (0.20mol) 1-phenyl-2 adding 200ml; Slowly drip 22.0g (0.13mol) phosphorus thiochloride through constant pressure funnel while stirring at normal temperatures then; The hydrogen chloride gas body and function sodium bicarbonate aqueous solution that reaction generates absorbs, and is warming up to 40 ℃ of reaction 7h after dropwising, and reaction finishes the back rotary evaporation and removes trichloromethane; The solid that obtains obtains 27.6g (0.10mol) 2-sulfo--4-phenyl-5 after washing successively with normal hexane and anhydrous diethyl ether respectively; 5-dimethyl--1,3, phosphoryl chloride in the 2-dioxa is own.With the 2-sulfo--4-phenyl-5 that obtains, 5-dimethyl--1,3; Oneself is dissolved in the 2-dioxa in the 150ml acetone by interior phosphoryl chloride 27.6g (0.10mol), gets 10.7g (0.11mol) Rhocya again and is dissolved in the 50ml acetone, is warming up to 56 ℃ then; Dissolved Rhocya drips of solution is added 2-sulfo--4-phenyl-5,5-dimethyl--1,3; React 4h in the solution of oneself interior phosphoryl chloride of 2-dioxa, suction filtration is removed Repone K, and the filtrating rotary evaporation is removed acetone and promptly got 2-sulfo--2-isothiocyano-4-phenyl-5; 5-dimethyl--1,3, the crude product 26.8g of 2-dioxaphosphorinane (about 0.09mol).Whole crude products are used the 100ml acetone solution, and with 9.1g (0.10mol) 3-amino-1, the 2-Ucar 35 is used the 100ml dissolve with ethanol; Then at room temperature; With two kinds of solution mixing stirring reaction 15h, reaction finishes the back suction filtration and gets white solid, with the washing of 150ml ETHYLE ACETATE once; Use the 50ml methanol wash again one time, obtain described fire retardant 31.1g.
Embodiment 17
The used 1-phenyl-2 synthetic operation steps of present embodiment is with embodiment 1.36.0g (0.20mol) 1-phenyl-2 is added 1 of 200ml; Dissolve in the 2-ethylene dichloride, slowly drip 32.1g (0.19mol) phosphorus thiochloride through constant pressure funnel while stirring at normal temperatures then, the hydrogen chloride gas body and function sodium bicarbonate aqueous solution that reaction generates absorbs; Be warming up to 75 ℃ of reaction 5h after dropwising, reaction finishes the back rotary evaporation and removes 1, the 2-ethylene dichloride; The solid that obtains obtains 38.6g (0.14mol) 2-sulfo--4-phenyl-5 after washing successively with normal hexane and anhydrous diethyl ether respectively; 5-dimethyl--1,3, phosphoryl chloride in the 2-dioxa is own.With the 2-sulfo--4-phenyl-5 that obtains, 5-dimethyl--1,3; Oneself is dissolved in the 2-dioxa in the 150ml acetone by interior phosphoryl chloride 38.6g (0.14mol), gets 13.6g (0.14mol) Rhocya again and is dissolved in the 50ml acetone, is warming up to 50 ℃ then; Dissolved Rhocya drips of solution is added 2-sulfo--4-phenyl-5,5-dimethyl--1,3; React 5h in the solution of oneself interior phosphoryl chloride of 2-dioxa, suction filtration is removed Repone K, and the filtrating rotary evaporation is removed acetone and promptly got 2-sulfo--2-isothiocyano-4-phenyl-5; 5-dimethyl--1,3, the crude product 41.7g of 2-dioxaphosphorinane (about 0.14mol).Whole crude products are used the 100ml acetic acid ethyl dissolution, and with 9.1g (0.21mol) 1-p-nitrophenyl-2-amino-1, ammediol is used the 100ml dissolve with methanol; Then at room temperature; With two kinds of solution mixing stirring reaction 12h, reaction finishes the back suction filtration and gets white solid, with the washing of 150ml ETHYLE ACETATE once; Use the 50ml methanol wash again one time, obtain described fire retardant 66.3g.
Embodiment 18
The used 1-phenyl-2 synthetic operation steps of present embodiment is with embodiment 1.Dissolve in the toluene with 36.0g (0.20mol) 1-phenyl-2 adding 200ml; Slowly drip 28.7g (0.17mol) phosphorus thiochloride through constant pressure funnel while stirring at normal temperatures then; The hydrogen chloride gas body and function sodium bicarbonate aqueous solution that reaction generates absorbs, and is warming up to 83 ℃ of reaction 2h after dropwising, and reaction finishes the back rotary evaporation and removes toluene; The solid that obtains obtains 30.4g (0.11mol) 2-sulfo--4-phenyl-5 after washing successively with normal hexane and anhydrous diethyl ether respectively; 5-dimethyl--1,3, phosphoryl chloride in the 2-dioxa is own.With the 2-sulfo--4-phenyl-5 that obtains, 5-dimethyl--1,3; Oneself is dissolved in the 2-dioxa in the 150ml acetonitrile by interior phosphoryl chloride 30.4g (0.11mol), gets 11.6g (0.12mol) Rhocya again and is dissolved in the 50ml acetonitrile, is warming up to 40 ℃ then; Dissolved Rhocya drips of solution is added 2-sulfo--4-phenyl-5,5-dimethyl--1,3; React 9h in the solution of oneself interior phosphoryl chloride of 2-dioxa, suction filtration is removed Repone K, and the filtrating rotary evaporation is removed acetonitrile and promptly got 2-sulfo--2-isothiocyano-4-phenyl-5; 5-dimethyl--1,3, the crude product 32.8g of 2-dioxaphosphorinane (about 0.11mol).With the dissolving of 100ml methylene dichloride, with 11.8g (0.13mol) 2-amino-1, ammediol is used the 100ml dissolve with methanol with whole crude products; Then at room temperature; With two kinds of solution mixing stirring reaction 6h, reaction finishes the back suction filtration and gets white solid, with the washing of 150ml ETHYLE ACETATE once; Use the 50ml methanol wash again one time, obtain described fire retardant 38.9g.
Embodiment 19
The used 1-phenyl-2 synthetic operation steps of present embodiment is with embodiment 1.Dissolve in the acetone with 36.0g (0.20mol) 1-phenyl-2 adding 200ml; Slowly drip 25.4g (0.15mol) phosphorus thiochloride through constant pressure funnel while stirring at normal temperatures then; The hydrogen chloride gas body and function sodium bicarbonate aqueous solution that reaction generates absorbs, and is warming up to 56 ℃ of reaction 3h after dropwising, and reaction finishes the back rotary evaporation and removes acetone; The solid that obtains obtains 24.8g (0.09mol) 2-sulfo--4-phenyl-5 after washing successively with normal hexane and anhydrous diethyl ether respectively; 5-dimethyl--1,3, phosphoryl chloride in the 2-dioxa is own.With the 2-sulfo--4-phenyl-5 that obtains, 5-dimethyl--1,3; Oneself is dissolved in the 2-dioxa in the 150ml acetone by interior phosphoryl chloride 24.8g (0.09mol), gets 8.7g (0.09mol) Rhocya again and is dissolved in the 50ml acetone, is warming up to 55 ℃ then; Dissolved Rhocya drips of solution is added 2-sulfo--4-phenyl-5,5-dimethyl--1,3; React 7h in the solution of oneself interior phosphoryl chloride of 2-dioxa, suction filtration is removed Repone K, and the filtrating rotary evaporation is removed acetone and promptly got 2-sulfo--2-isothiocyano-4-phenyl-5; 5-dimethyl--1,3, the crude product 23.8g of 2-dioxaphosphorinane (about 0.08mol).With the dissolving of 100ml tetracol phenixin, with 10.5g (0.10mol) 2-amino-2-methyl-1, ammediol is used the 100ml dissolve with methanol with whole crude products; Then at room temperature; With two kinds of solution mixing stirring reaction 10h, reaction finishes the back suction filtration and gets white solid, with the washing of 150ml ETHYLE ACETATE once; Use the 50ml methanol wash again one time, obtain described fire retardant 25.8g.
Embodiment 20
The used 1-phenyl-2 synthetic operation steps of present embodiment is with embodiment 1.Dissolve in the YLENE with 36.0g (0.20mol) 1-phenyl-2 adding 200ml; Slowly drip 32.1g (0.19mol) phosphorus thiochloride through constant pressure funnel while stirring at normal temperatures then; The hydrogen chloride gas body and function sodium bicarbonate aqueous solution that reaction generates absorbs, and is warming up to 80 ℃ of reaction 4h after dropwising, and reaction finishes the back rotary evaporation and removes removal xylene; The solid that obtains obtains 38.6g (0.14mol) 2-sulfo--4-phenyl-5 after washing successively with normal hexane and anhydrous diethyl ether respectively; 5-dimethyl--1,3, phosphoryl chloride in the 2-dioxa is own.With the 2-sulfo--4-phenyl-5 that obtains, 5-dimethyl--1,3; Oneself is dissolved in the 2-dioxa in the 150ml acetone by interior phosphoryl chloride 38.6g (0.14mol), gets 13.6g (0.14mol) Rhocya again and is dissolved in the 50ml acetone, is warming up to 52 ℃ then; Dissolved Rhocya drips of solution is added 2-sulfo--4-phenyl-5,5-dimethyl--1,3; React 8h in the solution of oneself interior phosphoryl chloride of 2-dioxa, suction filtration is removed Repone K, and the filtrating rotary evaporation is removed acetone and promptly got 2-sulfo--2-isothiocyano-4-phenyl-5; 5-dimethyl--1,3, the crude product 38.7g of 2-dioxaphosphorinane (about 0.13mol).With the dissolving of 100ml trichloromethane, with 25.1g (0.15mol) 2-amino-1-phenyl-1, ammediol is used the 100ml dissolve with methanol with whole crude products; Then at room temperature; With two kinds of solution mixing stirring reaction 13h, reaction finishes the back suction filtration and gets white solid, with the washing of 150ml ETHYLE ACETATE once; Use the 50ml methanol wash again one time, obtain described fire retardant 51.2g.
Application examples 1
1) with synthetic fire retardant among the embodiment 12 as chainextender and tolylene diisocyanate (TDI) and polyether Glycols (PPG1000) TDI in molar ratio: fire retardant: PPG=4:2.94:1.5, and wherein group molar ratio is a NCO:OH=0.9:1 synthesis of polyurethane oligopolymer.Concrete operations are following: PPG1000 is being vacuumized; 100 ℃ with down dehydration one hour of agitation condition, be cooled to 35 ~ 65 ℃ then, add fire retardant to stir; Add the TDI high-speed stirring again and be warming up to 100 ℃; Stirred 3 ~ 4 minutes, and, when " pole-climbing " effect occurring it was poured out to polyfluortetraethylene plate when system viscosity increases; The oligopolymer that generates placed in 100 ℃ the baking oven slaking 24 hours, and promptly obtained yellowish green flame retardant polyurethane oligopolymer.This oligopolymer structure is as follows:
The massfraction of fire retardant wherein of the present invention in oligopolymer is 29.5wt%.
2) flame retardant polyurethane oligopolymer 2.5g and commercial polyether(poly)urethane elastomerics 47.5g (Huntsman Corporation's production) blend are obtained flame resistance polyurethane elastomer TPU1, again pressing mold, be cut into limiting oxygen index(LOI) (LOI) batten be used for the test, the result sees the following form.
Application examples 2
Should use-case operation steps and the condition of synthetic flame retardant polyurethane oligopolymer with application examples 1.Flame retardant polyurethane oligopolymer 5g and commercial polyether(poly)urethane elastomerics 45g blend are obtained flame resistance polyurethane elastomer TPU2, again pressing mold, cut into the limiting oxygen index(LOI) batten be used for the test, the result sees the following form.
Application examples 3
Should use-case operation steps and the condition of synthetic flame retardant polyurethane oligopolymer with application examples 1.Flame retardant polyurethane oligopolymer 7.5g and commercial polyether(poly)urethane elastomerics 42.5g blend are obtained flame resistance polyurethane elastomer TPU3, again pressing mold, cut into the limiting oxygen index(LOI) batten be used for the test, the result sees the following form.
Application examples 4
Should use-case operation steps and the condition of synthetic flame retardant polyurethane oligopolymer with application examples 1.Flame retardant polyurethane oligopolymer 10g and commercial polyether(poly)urethane elastomerics 40g blend are obtained flame resistance polyurethane elastomer TPU4, again pressing mold, cut into the limiting oxygen index(LOI) batten be used for the test, the result sees the following form.
Table: the prescription of flame resistance polyurethane elastomer and oxygen index test result
From table 1, can find out; The limiting oxygen index(LOI) of pure commercial polyether(poly)urethane elastomer 0 is 26%; And in TPU3, when flame retardant agent content was merely 4.43wt%, the oxygen index of urethane just rose to 31% from 26%; Hence one can see that, and synthetic fire retardant of the present invention can be used as reactive flame retardant is applied in the urethane, has flame retardant effect preferably.
Claims (7)
1. response type phosphor nitrogen combustion inhibitor, its general structure is following:
In the formula I, R
1Be Wasserstoffatoms or phenyl; R
2Be Sauerstoffatom or sulphur atom; R
3For
Wherein x, y, n, m are 0,1,2 or 3, and can not be 0 simultaneously, or do
Wherein x, y are 0,1,2 or 3, R
3' be phenyl or p-nitrophenyl.
2. the preparation method of the response type phosphor nitrogen combustion inhibitor described in claim 1 is led to R in the formula I when this method prepares said structure
1Be Wasserstoffatoms, R
2During for the phosphor nitrogen combustion inhibitor of Sauerstoffatom, its process step and condition are following:
1) earlier NSC 6366 is added solvent ⅰ dissolving, slowly drip POCl3 then at normal temperatures while stirring, the mol ratio of POCl3 and NSC 6366 is 1:1.05～1.5; The hydrogen chloride gas body and function sodium bicarbonate aqueous solution that reaction generates absorbs, and is warming up to 40 ~ 83 ℃ after dropwising, and reacts 2～7 hours; Rotary evaporation removes the ⅰ that desolvates, and the solid that obtains obtains 5,5-dimethyl--1 after washing successively with normal hexane and anhydrous diethyl ether respectively; 3, phosphoryl chloride in the 2-dioxa is own;
2) with 5,5-dimethyl--1,3, phosphoryl chloride and Rhocya were dissolved in respectively among the solvent ⅱ 1:1～1.1 in molar ratio in the 2-dioxa was own; Be warming up to 40～56 ℃ then, dissolved Rhocya drips of solution added 5,5-dimethyl--1,3; In the solution of oneself interior phosphoryl chloride of 2-dioxa, reacted 4～9 hours, suction filtration is removed Repone K, and the filtrating rotary evaporation removes the ⅱ that desolvates and promptly gets 2-isothiocyano-5; 5-dimethyl--1,3, the 2-dioxaphosphorinane;
3) earlier respectively with 2-isothiocyano-5,5-dimethyl--1,3; The 2-dioxaphosphorinane is dissolved among the solvent ⅲ, contains two hydroxyl primary amine compounds and is dissolved among the solvent ⅳ, then at room temperature; Two kinds of solution mixing stirring reactions were got final product 2-isothiocyano-5 wherein, 5-dimethyl--1 in 6～15 hours; 3, the 2-dioxaphosphorinane is 1:1.1 ~ 1.5 with the mol ratio that contains two hydroxyl primary amine compounds
R in the logical formula I of preparation said structure
1Be Wasserstoffatoms, R
2During for the phosphor nitrogen combustion inhibitor of sulphur atom, its process step and condition are following:
1) earlier NSC 6366 is added solvent ⅰ dissolving, slowly drip phosphorus thiochloride then at normal temperatures while stirring, the mol ratio of phosphorus thiochloride and NSC 6366 is 1:1.05～1:1.5; The hydrogen chloride gas body and function sodium bicarbonate aqueous solution that reaction generates absorbs, and is warming up to 40 ~ 83 ℃ after dropwising, and reacts 2～7 hours; Rotary evaporation removes the ⅰ that desolvates, and the solid that obtains obtains 2-sulfo--5,5-dimethyl--1 after washing successively with normal hexane and anhydrous diethyl ether respectively; 3, phosphoryl chloride in the 2-dioxa is own;
2) with 2-sulfo--5,5-dimethyl--1,3, phosphoryl chloride and Rhocya were dissolved in respectively among the solvent ⅱ 1:1 ~ 1.1 in molar ratio in the 2-dioxa was own; Be warming up to 40～56 ℃ then, dissolved Rhocya drips of solution added 2-sulfo--5,5-dimethyl--1,3; In the solution of oneself interior phosphoryl chloride of 2-dioxa, reacted 4～9 hours, suction filtration is removed Repone K, and the filtrating rotary evaporation removes the ⅱ that desolvates and promptly gets 2-sulfo--2-isothiocyano-5; 5-dimethyl--1,3, the 2-dioxaphosphorinane;
3) earlier respectively with 2-sulfo--2-isothiocyano-5,5-dimethyl--1,3; The 2-dioxaphosphorinane is dissolved among the solvent ⅲ, contains two hydroxyl primary amine compounds and is dissolved among the solvent ⅳ, then at room temperature; Two kinds of solution mixing stirring reactions were got final product 2-sulfo--2-isothiocyano-5 wherein, 5-dimethyl--1 in 6～15 hours; 3, the 2-dioxaphosphorinane is 1:1.1～1.5 with the mol ratio that contains two hydroxyl primary amine compounds
R in the logical formula I of preparation said structure
1Be phenyl, R
2During for the phosphor nitrogen combustion inhibitor of Sauerstoffatom, its process step and condition are following:
1) earlier 1-phenyl-2 is dissolved with solvent ⅰ; Slowly drip POCl3, POCl3 and 1-phenyl-2,2-dimethyl--1 then at normal temperatures while stirring; The mol ratio of ammediol is 1:1.05～1.5, and the hydrogen chloride gas body and function sodium bicarbonate aqueous solution that reaction generates absorbs, and is warming up to 40 ~ 83 ℃ after dropwising; Reacted 2～7 hours, rotary evaporation removes and desolvates, and the solid that obtains is washed with normal hexane and anhydrous diethyl ether respectively successively promptly get 4-phenyl-5 again; 5-dimethyl--1,3, phosphoryl chloride in the 2-dioxa is own;
2) with 4-phenyl-5,5-dimethyl--1,3, phosphoryl chloride and Rhocya were dissolved in respectively among the solvent ⅱ by 1:1～1.1 in the 2-dioxa was own; Be warming up to 40 ~ 56 ℃ then, dissolved Rhocya drips of solution added 4-phenyl-5,5-dimethyl--1,3; In the solution of oneself interior phosphoryl chloride of 2-dioxa, reacted 4～9 hours, suction filtration is removed Repone K, and the filtrating rotary evaporation removes the ⅱ that desolvates and promptly gets 2-isothiocyano-4-phenyl-5; 5-dimethyl--1,3, the 2-dioxaphosphorinane;
3) earlier with 2-isothiocyano-4-phenyl-5,5-dimethyl--1,3; The 2-dioxaphosphorinane is dissolved among the solvent ⅲ, contains two hydroxyl primary amine compounds and is dissolved among the solvent ⅳ, then at room temperature; Two kinds of solution mixing stirring reactions were got final product 2-isothiocyano-4-phenyl-5 wherein, 5-dimethyl--1 in 6～15 hours; 3, the 2-dioxaphosphorinane is 1:1.1～1.5 with the mol ratio that contains two hydroxyl primary amine compounds
R in the logical formula I of preparation said structure
1Be phenyl, R
2During for the phosphor nitrogen combustion inhibitor of sulphur atom, its process step and condition are following:
1) earlier 1-phenyl-2 is dissolved with solvent ⅰ; Slowly drip phosphorus thiochloride, phosphorus thiochloride and 1-phenyl-2,2-dimethyl--1 then at normal temperatures while stirring; The mol ratio of ammediol is 1:1.05～1.5, and the hydrogen chloride gas body and function sodium bicarbonate aqueous solution that reaction generates absorbs, and is warming up to 40 ~ 83 ℃ after dropwising; Reacted 2～7 hours, rotary evaporation removes and desolvates, and the solid that obtains is washed with normal hexane and anhydrous diethyl ether respectively successively promptly get 2-sulfo--4-phenyl-5 again; 5-dimethyl--1,3, phosphoryl chloride in the 2-dioxa is own;
2) with 2-sulfo--4-phenyl-5,5-dimethyl--1,3; Phosphoryl chloride and Rhocya were dissolved in respectively among the solvent ⅱ by 1:1 ~ 1.1 in the 2-dioxa was own, were warming up to 40 ~ 56 ℃ then, and dissolved Rhocya drips of solution is added 2-sulfo--4-phenyl-5; 5-dimethyl--1,3 is in the solution of oneself interior phosphoryl chloride of 2-dioxa; Reacted 4～9 hours, suction filtration is removed Repone K, and the filtrating rotary evaporation removes the ⅱ that desolvates and promptly gets 2-sulfo--2-isothiocyano-4-phenyl-5; 5-dimethyl--1,3, the 2-dioxaphosphorinane;
3) earlier with 2-sulfo--2-isothiocyano-4-phenyl-5,5-dimethyl--1,3; The 2-dioxaphosphorinane is dissolved among the solvent ⅲ, contains two hydroxyl primary amine compounds and is dissolved among the solvent ⅳ, then at room temperature; Two kinds of solution mixing stirring reactions were got final product 2-sulfo--2-isothiocyano-4-phenyl-5 wherein, 5-dimethyl--1 in 6～15 hours; 3, the 2-dioxaphosphorinane is 1:1.1～1.5 with the mol ratio that contains two hydroxyl primary amine compounds.
3. the preparation method of response type phosphor nitrogen combustion inhibitor as claimed in claim 2; Used solvent ⅰ is trichloromethane, methylene dichloride, 1 in this method, any in 2-ethylene dichloride, tetracol phenixin, acetone, butanone, benzene,toluene,xylene, tetraline, propyl ether, isopropyl ether or the butyl ether; Solvent ⅱ is acetonitrile or acetone; Solvent ⅲ is acetone, ETHYLE ACETATE, trichloromethane, methylene dichloride, 1, any in 2-ethylene dichloride or the tetracol phenixin; Solvent ⅳ is methyl alcohol or ethanol.
4. the preparation method of response type phosphor nitrogen combustion inhibitor as claimed in claim 2, used solvent ⅰ is trichloromethane, methylene dichloride or 1 in this method, any in the 2-ethylene dichloride; Solvent ⅱ is an acetone; Solvent ⅲ is an ETHYLE ACETATE; Solvent ⅳ is a methyl alcohol.
5. like the preparation method of claim 2 or 3 or 4 described response type phosphor nitrogen combustion inhibitors, in this method the 1st) reaction times in step is 3 ~ 5 hours; The 2nd) reaction times in step is 5 ~ 8 hours; The 3rd) reaction times in step is 10 ~ 13 hours; The 1st) going on foot temperature of reaction is 75 ℃ ~ 83 ℃; The 2nd) going on foot temperature of reaction is 50 ~ 56 ℃.
6. like the preparation method of claim 2 or 3 or 4 described response type phosphor nitrogen combustion inhibitors, the general structure that contains two hydroxyl primary amine compounds in this method is following:
Wherein x, y, n, m are 0,1,2 or 3, and can not be 0 simultaneously, or do
Wherein x, y are 0,1,2 or 3, R
3' be phenyl or p-nitrophenyl.
7. the preparation method of response type phosphor nitrogen combustion inhibitor as claimed in claim 5, the general structure that contains two hydroxyl primary amine compounds in this method is following:
Wherein x, y, n, m are 0,1,2 or 3, and can not be 0 simultaneously, or do
Wherein x, y are 0,1,2 or 3, R
3' be phenyl or p-nitrophenyl.
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