CN102796318A - Synthetic method of phosphorus and nitrogen type fire retardant - Google Patents
Synthetic method of phosphorus and nitrogen type fire retardant Download PDFInfo
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Abstract
The invention relates to a synthetic method of a phosphorus and nitrogen type fire retardant, which comprises the following steps of: reacting an assistant with phosphate materials to remove water out of the phosphate materials; reacting polyhydric alcohols with the phosphate materials with water removed to obtain an intermediate; and reacting the intermediate with melamine in a solvent to obtain the phosphorus and nitrogen type fire retardant, wherein the phosphate materials can be one or more than one of phosphoric acid, pyrophosphoric acid and polyphosphoric acid. Compared with the prior art, the synthetic method provided by the invention has the advantages of shortening the esterification reaction time and increasing yield of the phosphorus and nitrogen type fire retardant, improving the purity of the phosphorus and nitrogen type fire retardant and the production process is simple in process and clean and safe.
Description
Technical field
The present invention relates to a kind of compound method of new and effective fire retardant, relate in particular to a kind of compound method of phosphorus-nitrogen type fire retardant, belong to the fire retardant material preparing technical field.
Background technology
Fire retardant is a kind of fire resistance that can improve material, stop material to ignite or suppress the auxiliary agent of propagation of flame.The sorting technique of fire retardant has a variety of, can be divided into two big types according to chemical composition: organic fire-retardant and inorganic combustion inhibitor.Wherein representative fire retardant is phosphorus system, Marinco H, weisspiessglanz class, halogen system, phosphorus-nitrogen containing flame retardant etc.
Phosphorus-nitrogen containing flame retardant is called the expansibility flame-proof agent again; It has that Halogen, flame retardant resistance are strong, the characteristics of low toxicity, low cigarette, low-corrosiveness; And interpolation just can reach higher flame retardant effect on a small quantity in macromolecular material, thereby is considered to have the BACN of development prospect.This kind fire retardant is a nucleus with phosphorus, nitrogen element, has nitrogen phosphorus synergistic effect, and effect is remarkable during fire retardant polyolefin.When the superpolymer that contains this based flame retardant was heated, the surface can generate layer of even carbonaceous foam layer, played heat insulation, oxygen barrier, pressed down the effect of cigarette, and prevent to produce the molten drop phenomenon, so have good flame retardancy.The enhancing of Along with people's environmental consciousness, this based flame retardant will have higher development prospect and marketable value.
CN1807552A discloses a kind of compound method of new environment-friendly type non-bittern combustion inhibitor; This method adopts phosphoric acid, tetramethylolmethane and trimeric cyanamide to be raw material at special conditions and not to add synthesis of pentaerythritol bis phosphoric acid melamine salt under the situation of catalyzer, and optimum process condition is n (phosphoric acid): n (tetramethylolmethane): n (trimeric cyanamide)=2: 1: 2; Esterification temperature 120-130 ℃, time 4h; 100-105 ℃ of salify temperature, time 2h, the product flame retardant effect is good.This compound method is fairly simple, process stabilizing, but the reaction times is longer relatively, temperature of reaction high (esterification temperature can not be lower than 120 ℃), and product yield is low, and energy consumption is higher.
CN101157702A discloses a kind of NEW TYPE OF COMPOSITE phosphor nitrogen combustion inhibitor, and this fire retardant makes with industrial phosphoric acid and urea, and compound method is simple, and flame retardant effect is better, has wide range of applications.But because the restriction of this fire retardant self chemical structure, its water absorbability is very strong, and ion is resolved, and reduces its flame retardant properties, and joins the physical strength reduction that can make material itself in the organic materials, influences its normal use.
(Wang Xuefeng, Sun Chunmei, Wu Rongliang, Wang Xingyi such as Wang Xingyi; Synthetic and the applied research of expanded polystyrene veneer kind phosphate ester melamine salt based flame retardant; The functional polymer journal, 2005,18 (03): be that raw material has synthesized a kind of expanded polystyrene veneer phosphate ester melamine salt fire retardant with tetramethylolmethane, Vanadium Pentoxide in FLAKES, water and trimeric cyanamide 474-478), fire retardant and polyacrylic adding proportion are 40: 100.The result finds that this product polypropylene flame redardant effect is remarkable, and its oxygen index (LOI) is 33.6, and burning density rating (SDR) is 44.2 to reach the UL94V-0 level with the vertical combustion performance.The raw material NSC 65881 of this method consumption and tripentaerythritol all are more expensive industrial raw material; And Vanadium Pentoxide in FLAKES and polyphosphoric acid reaction in can discharge a large amount of heat, bad if this step reaction is controlled, react easy temperature runaway; Cause the accident, also unfavorable for the temperature control of next step reaction.Above condition restriction the industrialization promotion of this method.
(Dong Yanmao, Bao Zhiyu, Zhao Dan, Zhao Aiming, Chen Guocai such as Dong Yanmao; Synthesizing of pentaerythrite diphosphate ester diethyl amine salt expansion type flame retardant; Suzhou Institute of Science and Technology journal (natural science edition), 2009,26 (3): be that raw material has synthesized pentaerythrite diphosphate ester diethyl amine salt 29-33) with tetramethylolmethane, POCl3, diethylamine etc.The sintetics diethylamine phosphate that has potential this method of using value in the anti-electrostatic fire retardant field of materials mainly is used to the emulsifying agent of makeup and the inhibiter of iron and steel; Research in flame retardant area does not appear in the newspapers, and its actual flame retardant effect and commercial value have to be identified.
(Baljinder K.Kandola such as Baljinder K.; A.Richard Horrocks, Peter Myler, Dana Blair; Journal of Applied Polymer Science; 2003,88 (10), 2511-2521.) reported the E-glass that comprises multi-functional epoxy resin, woven rove, the fiber of phenolic structure, the fire retardant of phosphoric acid trimeric cyanamide.Heat weight research finds that the LOI value behind the adding fire retardant is 35.2, and the amount of being fuming is few, explains that the melamine phosphate fire retardant is good anti-flaming smoke-inhibiting agent.
(Tan Zhengde, Zhou Xiaoming, Tang Li such as Tan Zhengde; N-P environment-friendly type cloth is with the development of fire retardant; Dyeing and printing auxiliary; 2008,25 (1): be that raw material is done to react under the catalyzer condition in strong basicity (sodium alkoxide) or BPO 27-30), obtain nitrogen-phosphorus (N-P) type fire retardant with the mda reaction again with dimethylphosphite, acrylic amide; Do not use formaldehyde in this fire retardant finished product, formaldehydeless pollution.The preparation technology of this fire retardant is simple, need not use linking agent just can be directly and Mierocrystalline cellulose react, adopt the common baking process(of sulfonation) that pads to carry out fire-retardant finish, just can reach fire-retardant requirement.The synthesis technique more complicated of this method, the raw material type of use is many, and reactions step is loaded down with trivial details, and the unfavorable hydrogenchloride that also can make of reaction conditions control is stranded in the liquid phase, is unfavorable for discharging, and the industriallization difficulty is high, and cost is expensive.
(Guo Yan, Liu Fan, Wang Yufeng such as Guo Yan; Textile development and application with durable flame-proof agent KX-912; Meticulous and specialty chemicals, 2006,14 (8): be raw material 26-29) with dimethylphosphite and acrylic amide; Synthesized durable flame-proof agent KX-912, discussed the influence of methylol formaldehyde and free formaldehyde content reaction.Through experiment, confirmed optimum material proportion, temperature of reaction and the catalyst levels of reaction; Record the methylol formaldehyde content near 9%, free formaldehyde content is lower than 0.17%.The raw material that this method is used contains formaldehyde, and well-known formaldehyde is very big to human harm, and this fire retardant is mainly used in fabric; Direct or indirect the contacting with human body of meeting has influence on HUMAN HEALTH, therefore; This fire retardant can only be used for research, can't be as product promotion to market.
(Zhao Hui, Tang Yong, Chen Lijiao, Han Yingchun, Yang Bing such as Yang Bing; Synthetic, the sign of Dipentaerythritol SULPHOSUCCINIC ACID ESTER and flame retardant properties test; Chemical research and application; 2009,21 (4): be raw material 521-524), adopt the direct esterification method to synthesize fire retardant Dipentaerythritol SULPHOSUCCINIC ACID ESTER with phosphoric acid and tetramethylolmethane; Sample is characterized, and synthesis technique and the flame retardant properties in polyolefine thereof are studied.The optimum synthesis condition that the document is confirmed is: YLENE is the band aqua, and temperature of reaction is 180-220 ℃, reaction times 6-27h.This fire retardant and ammonium polyphosphate are added in the polyolefine by 40: 60 (mass ratio) is composite, and during sample proportion 30%, fire-retardant rank can reach the UL94V20 level.Phosphoric acid ester fire retardant in this method is than traditional phosphorus-nitrogen containing flame retardant, and synthesis technique is simple, but owing to lack the cause of nitrogenous source, the fire-retardant effect of nitrogen phosphorus synergistic can not take place in the fire-retardant process, and its flame retardant properties is lower than phosphorus-nitrogen containing flame retardant.
(Lin Jiansheng, Zhao Chunxia, Liu Ya, Wang Deyi, Wang Yuzhong such as Lin Jiansheng; Synthetic and the applied research in anti-flaming polyvinyl alcohol of ionic P-N fire retardant; Fire retardant material and technology; 2008; 6:1) adopt solution method to synthesize the ionic fire retardant FPA of a kind of P of containing, N ignition-proof element, mainly studied of fire retardation and the thermal property influence of this fire retardant Z 150PH (PVA).Best when total addition level is 12% when FPA and APP are composite, LOI can reach 32.4.This kind fire retardant is mainly used in vinylon; Flame retardant test for the other types material has not been seen relevant report; It is the very high fire retardant of a species specificity; And it need just can reach flame retardant effect preferably with APP is composite when fire-retardant, and its market outlook are still uncertain, remains further research.
(Liu Jian, Luo Zhiqiang, Zhou Dajun, Lin Yuanbin such as Liu Jian; The new synthetic method of pentaerythritol diphosphate melamine salt; Chemistry world; 2002,43 (4): 203-205) adopt non-solvent method to synthesize expansion type flame retardant pentaerythritol diphosphate melamine salt (PDM), at first obtain pentaerythritol diphosphate two phosphoryl chlorides (PDD) with POCl3 and tetramethylolmethane reaction through the reaction of two steps; PDD reacts with water, melamine more then, prepares PDM.In the first step reaction, as n (POCl3): n (tetramethylolmethane)=6: 1, at 60 ℃ of reaction 1h, the 10h that refluxes again, the yield of PDD were 82.3%.In the second step reaction, as n (PDD): n (melamine)=1.1: 2, when return time was 2h, the yield of PDM was 79%.The total yield of products of two-step reaction is 65%.The raw material POCl3 that uses in this method belongs to the hypertoxicity raw material, and the HCl acid mist of the generation in production process corrosion reaction container not only, and also very big to the harm of environment.Thereafter work of treatment difficulty is unfavorable for that further industry is amplified.
Summary of the invention
For solving the problems of the technologies described above; The compound method that the purpose of this invention is to provide a kind of phosphorus-nitrogen type of environment-friendly type efficiently fire retardant; Solve the problem that existing yield is not high, energy consumption is bigger in the building-up process of phosphorus-nitrogen type fire retardant; And building-up process is safe and reliable, and process stabilizing is synthetic with low cost.
For achieving the above object; The invention provides a kind of compound method of phosphorus-nitrogen type fire retardant, this method is to be main raw material with polyvalent alcohol, phosphoric acid class material, auxiliary agent, trimeric cyanamide, under certain condition; Carry out " one kettle way " building-up reactions; Need not separate purification, the substep charging reaction obtains the phosphorus-nitrogen type fire retardant.Above-mentioned compound method can may further comprise the steps:
Make auxiliary agent and phosphoric acid class substance reaction, remove the water in the phosphoric acid class material;
Make polyvalent alcohol and remove the phosphoric acid class substance reaction (esterification) that anhydrates, obtain midbody;
Make midbody and trimeric cyanamide in solvent, react (salt-forming reaction), be cooled to then below the room temperature, obtain the phosphorus-nitrogen type fire retardant through washing, suction filtration, oven dry;
Wherein, above-mentioned phosphoric acid class material is one or more in phosphoric acid, tetra-sodium and the polyphosphoric acid etc.
In above-mentioned compound method provided by the invention, auxiliary agent can play catalyzer and the effect that promotes that the molecular balance forward carries out, and preferably, the auxiliary agent that the present invention adopted is POCl
3, anhydrous MgSO
4, concentration 90-98wt% H
2SO
4, P
2O
5In molecular sieve and the High hydrophilous resin (water-absorbing resin of water-intake rate＞300g/g, for example starch-grafted thing, cross-linked carboxymethyl cellulose, polyacrylate absorbent resin etc.) etc. one or more.
In the above-mentioned compound method provided by the invention, preferably, the polyvalent alcohol that is adopted is one or more the combination in tetramethylolmethane, terepthaloyl moietie and the USP Kosher etc.
In the above-mentioned compound method provided by the invention, preferably, the mol ratio of phosphoric acid class material, polyvalent alcohol and trimeric cyanamide is 1-5: 1: 1-4 (more preferably 1.5-2: 1: 2), the mass ratio of auxiliary agent and phosphoric acid class material is 1: 2.2-2.8.According to specific embodiments of the present invention, preferably, in above-mentioned compound method, the mol ratio of auxiliary agent, phosphoric acid class material, polyvalent alcohol and trimeric cyanamide is 0.41: 1.3: 1: 2.
In the above-mentioned compound method provided by the invention, preferably, in the reaction of auxiliary agent and phosphoric acid class material, temperature of reaction is 70 ℃, and the reaction times is 30min.
In the above-mentioned compound method provided by the invention, preferably, in polyvalent alcohol and the reaction except that the phosphoric acid class material that anhydrates, temperature of reaction is 80-150 ℃, and the reaction times is 1-5 hour; More preferably, temperature of reaction is 100-120 ℃, and the reaction times is 2h.
In the above-mentioned compound method provided by the invention, preferably, in the reaction of midbody and trimeric cyanamide, temperature of reaction is 60-100 ℃, and the reaction times is 1-4 hour; More preferably, temperature of reaction is 80 ℃, and the reaction times is 2h.
In the above-mentioned compound method provided by the invention, preferably, the solvent that is adopted is water and/or terepthaloyl moietie etc.
In the above-mentioned compound method provided by the invention, can cool to the finished product, crystallization is filtered.During washing, treat that the pH value of product is at 7 o'clock, stop washing.
The present invention also provides a kind of phosphorus-nitrogen type fire retardant, and it is by above-mentioned compound method synthetic.
Above-mentioned phosphorus-nitrogen type fire retardant provided by the invention can be used for polyacrylic fire-retardant; When fire retardant and polyacrylic mass ratio were 30: 100, its LOI value can reach (difficult combustion) more than 28, and fire-retardant process is nontoxic smokeless; Cleaning very, and the problem of molten drop can solve the plastics burning time.Fire retardant provided by the invention can also be applied to the fire-retardant of polyolefins plastics such as Vilaterm, PS and polyoxymethylene, has wide practical use; And its production cost is lower, has very high commercial value and market outlook.
The present invention is to provide a kind of compound method of the phosphor nitrogen combustion inhibitor of environment-friendly type efficiently, this method makes it not only play the effect of catalyzer but also promote the molecular balance forward to carry out through adding auxiliary agent, and product purity that finally obtains and yield are all higher, and energy consumption is low.
Phosphor nitrogen combustion inhibitor provided by the invention is applied to obtain good flame-retardant effect in the production of Vestolen PP 7052 etc., because the technology of its unique mechanism and environmental protection is applied to flame retardant of plastic and has great advantage.Compound method provided by the invention has the following advantages with respect to prior art: temperature of reaction reduces, and reaction time of esterification shortens, and product yield improves, and phosphorus content and theoretical value are approaching, explains that product purity improves, and production process technology is simple, clean and safe.
Embodiment
To understand in order technical characterictic of the present invention, purpose and beneficial effect being had more clearly, technical scheme of the present invention is carried out following detailed description, but but can not be interpreted as qualification at present practical range of the present invention.
Comparative Examples 1
Present embodiment provides a kind of phosphorus-nitrogen type fire retardant, and it prepares according to following steps:
In the four-hole boiling flask of being furnished with whisking appliance, TM, prolong and water trap, add 6.8ml phosphoric acid (concentration is 85wt%), slowly be warming up to 120 ℃, add the 6.8g tetramethylolmethane, reaction 2h;
Add the 12.6g trimeric cyanamide in batches, under 80 ℃, reaction 2h, cooling is washed with distilled water to pH=7 then, suction filtration, oven dry obtains white solid product 9.94g, i.e. the phosphorus-nitrogen type fire retardant.
Do not add auxiliary agent in the phosphorus-nitrogen type fire retardant that this Comparative Examples provides, product yield has only 38.8%.
Embodiment 1
Present embodiment provides a kind of phosphorus-nitrogen type fire retardant, and it prepares according to following steps:
In the four-hole boiling flask of being furnished with whisking appliance, TM, prolong and water trap, add 4.25ml phosphoric acid (concentration is 85wt%), slowly be warming up to 120 ℃, add the 6.8g tetramethylolmethane, reaction 4h;
Add 18ml aqueous solvent and 12.6g trimeric cyanamide, under 80 ℃, reaction 2h, cooling is washed with distilled water to pH=7 then, and suction filtration is dried, and obtains white solid product 13.72g, i.e. the phosphorus-nitrogen type fire retardant.
The phosphorus-nitrogen type fire retardant that present embodiment provides adds entry as solvent when salt-forming reaction, product yield is increased to 44.3%.
Embodiment 2
Present embodiment provides a kind of phosphorus-nitrogen type fire retardant, and it prepares according to following steps:
In the four-hole boiling flask of being furnished with whisking appliance, TM, prolong and water trap, add 5.10ml phosphoric acid (concentration is 85wt%), slowly be warming up to 120 ℃, add the 6.8g tetramethylolmethane; Reaction 4h adds 18ml aqueous solvent and 12.6g trimeric cyanamide again, under 80 ℃, reacts 2h; Cooling is washed with distilled water to pH=7, suction filtration then; Oven dry obtains white solid product 13.72g, i.e. the phosphorus-nitrogen type fire retardant.
Present embodiment makes product yield be increased to 48.4% through changing the ratio of raw material.
Embodiment 3
Present embodiment provides a kind of phosphorus-nitrogen type fire retardant, and it prepares according to following steps:
In the four-hole boiling flask of being furnished with whisking appliance, TM, prolong and water trap, add 6.8ml phosphoric acid (concentration is 85wt%), slowly be warming up to 120 ℃, add 3.1g terepthaloyl moietie, reaction 2h;
Add 18ml aqueous solvent and 12.6g trimeric cyanamide again, under 80 ℃, reaction 2h, cooling is washed with distilled water to pH=7 then, suction filtration, oven dry obtains white solid product 13.72g, i.e. the phosphorus-nitrogen type fire retardant.
Present embodiment replaces tetramethylolmethane with terepthaloyl moietie, and product yield is 53.6%.It is fire-retardant that this phosphorus-nitrogen type fire retardant can be used for acrylic plastering: the mass ratio of fire retardant and acrylic plastering is 30: 100; Adopt " GBT17037.1-1997 " twin screw to extrude the injection moulding sample preparation; By national standard " GB/T2406.2-2009 plastics "; With the burning behavior of oxygen index method mensuration plastics, the room temperature test.Test result shows: oxygen index is 28, and the phosphorus-nitrogen type fire retardant that this explanation present embodiment provides has good flame-retardant effect when being applied to polypropylene material fire-retardant.
Embodiment 4
Present embodiment provides a kind of phosphorus-nitrogen type fire retardant, and it prepares according to following steps:
In the four-hole boiling flask of being furnished with whisking appliance, TM, prolong and water trap, add the 12g polyphosphoric acid.Slowly be warming up to 120 ℃ again, add the 6.8g tetramethylolmethane, reaction 3h;
Add 20ml solvent ethylene glycol and 12.6g trimeric cyanamide again, under 100 ℃, reaction 2h, cooling is washed with distilled water to pH and reaches 7 then, suction filtration, oven dry obtains white solid product 15.82g, i.e. the phosphorus-nitrogen type fire retardant.
Present embodiment replaces phosphoric acid with polyphosphoric acid, and terepthaloyl moietie is made salt solvent, and product yield is 61.8%.
Embodiment 5
Present embodiment provides a kind of phosphorus-nitrogen type fire retardant, and it prepares according to following steps:
In the four-hole boiling flask of being furnished with whisking appliance, TM, prolong and water trap, add the 9.80g tetra-sodium, be warming up to 120 ℃ of reactions, add the 6.8g tetramethylolmethane again, reaction 3h;
Add 20ml solvent ethylene glycol and 12.6g trimeric cyanamide again, under 100 ℃, reaction 2h, cooling is washed with distilled water to pH=7 then, suction filtration, oven dry obtains white solid product 16.11g, i.e. the phosphorus-nitrogen type fire retardant.
Present embodiment replaces phosphoric acid with tetra-sodium, and terepthaloyl moietie is as becoming salt solvent, and product yield is 74.6%.
It is fire-retardant that this phosphorus-nitrogen type fire retardant can be used for acrylic plastering: the mass ratio of fire retardant and acrylic plastering is 30: 100; Adopt " GBT17037.1-1997 " twin screw to extrude the injection moulding sample preparation; By national standard " GB/T2406.2-2009 plastics "; With the burning behavior of oxygen index method mensuration plastics, the room temperature test.Test result shows: oxygen index is 30.4, and the phosphorus-nitrogen type fire retardant that this explanation present embodiment provides has good flame-retardant effect when being applied to polypropylene material fire-retardant.
Embodiment 6
Present embodiment provides a kind of phosphorus-nitrogen type fire retardant, and it prepares according to following steps:
In the there-necked flask of being furnished with whisking appliance, TM and water trap, add 2.93g P
2O
5With 4.4ml phosphoric acid (concentration is 85wt%), be warming up to 70 ℃, reaction 30min;
Add 6.8g tetramethylolmethane to solid in batches and dissolve fully, 120 ℃ were reacted 2 hours down; The dissolving of 12.6g trimeric cyanamide is added in the aqueous solvent of 20ml again, and add there-necked flask in batches, temperature of reaction remains on about 70 ℃, reaction 2h; Cooling is washed with distilled water to pH=7, suction filtration then; Oven dry obtains white solid product 18.96g, i.e. the phosphorus-nitrogen type fire retardant.
Add P in the phosphorus-nitrogen type fire retardant that present embodiment provides
2O
5As auxiliary agent, product yield reaches 74.1%, compares with adding assistant not, and product yield increases substantially.
Embodiment 7
Present embodiment provides a kind of phosphorus-nitrogen type fire retardant, and it prepares according to following steps:
In the there-necked flask of being furnished with whisking appliance, TM and water trap, add the dense H of 8ml
2SO
4With 44ml phosphoric acid (concentration is 85wt%), be warming up to 70 ℃, reaction 30min;
Add 68g tetramethylolmethane to solid in batches and dissolve fully, 120 ℃ were reacted 2 hours down, the 130g trimeric cyanamide were dissolved in also to add there-necked flask in the 500ml water in batches again; Temperature of reaction remains on about 70 ℃, reaction 1h, cooling then; Be washed with distilled water to pH=7, suction filtration, oven dry; Obtain white solid product 198.98g, i.e. the phosphorus-nitrogen type fire retardant.
Add dense H in the phosphorus-nitrogen type fire retardant that present embodiment provides
2SO
4As auxiliary agent, product yield reaches 77.7%, compares product yield with adding assistant not and increases substantially.
It is fire-retardant that this phosphorus-nitrogen type fire retardant is used for acrylic plastering: the mass ratio of fire retardant and acrylic plastering is 30: 100; Adopt " GBT17037.1-1997 " twin screw to extrude the injection moulding sample preparation; By national standard " GB/T2406.2-2009 plastics ", measure burning behavior with oxygen index method, the room temperature test.Test result shows: oxygen index is 29.8, and the phosphorus-nitrogen type fire retardant that this explanation present embodiment provides has good flame-retardant effect when being applied to polypropylene material fire-retardant.
Embodiment 8
Present embodiment provides a kind of phosphorus-nitrogen type fire retardant, and it prepares according to following steps:
In the there-necked flask of being furnished with whisking appliance, TM and water trap, add 7.50g MgSO
4With 30ml phosphoric acid (concentration is 85wt%), be warming up to 70 ℃, reaction 30min;
Add 30g tetramethylolmethane to solid in batches and dissolve fully, 120 ℃ were reacted 2 hours down, the dissolving of 60g trimeric cyanamide were added in the aqueous solvent of 200ml again; And adding there-necked flask in batches, temperature of reaction remains on about 70 ℃, reaction 2h; Cooling is washed with distilled water to pH=7, suction filtration then; Oven dry obtains white solid product 93.36g, i.e. the phosphorus-nitrogen type fire retardant.
Add MgSO in the phosphorus-nitrogen type fire retardant that present embodiment provides
4As auxiliary agent, product yield reaches 78.7%, compares product yield with adding assistant not and increases substantially.
In the present invention, because the effect of phosphorus nitrogen synergistic has improved the flame retardant effect of product, so phosphorus content has important value for characterizing phosphorus-nitrogen type fire retardant performance.And the phosphorus content of phosphorus-nitrogen type fire retardant also can reflect the purity of phosphorus-nitrogen type fire retardant.When the phosphorus content measured value near theoretical value, explain that the phosphorus-nitrogen type fire retardant purity that makes is higher.The phosphorus-nitrogen type fire retardant (embodiment 1-8) that the present invention has prepared the different auxiliary agents of multiple interpolation compares with the phosphorus-nitrogen type fire retardant (Comparative Examples 1) that does not add auxiliary agent; And adopting the phosphovanadomolybdic acid difference spectrophotometry to measure the phosphorus content of phosphorus-nitrogen type fire retardant, test result is as shown in table 1.Result according to table 1 can find out; The phosphorus-nitrogen type fire retardant phosphorus content that does not add auxiliary agent is 12.97%; Add phosphorus-nitrogen type fire retardant phosphorus content behind the auxiliary agent below 12.50%, individual product in addition reached 12.05%, this and theoretical value 12.11% ten minute are approaching.This result shows that adding auxiliary agent helps preparing the higher phosphorus-nitrogen type fire retardant of purity.
The test result of table 1 phosphorus content
| P，wt％ | |
| Comparative Examples 1 | 13.01 |
| Embodiment 1 | 12.97 |
| Embodiment 2 | 12.93 |
| Embodiment 3 | 12.85 |
| Embodiment 4 | 12.04 |
| Embodiment 5 | 12.44 |
| Embodiment 6 | 12.07 |
| Embodiment 7 | 12.05 |
| Embodiment 8 | 12.33 |
Claims (9)
1. the compound method of a phosphorus-nitrogen type fire retardant, it may further comprise the steps:
Make auxiliary agent and phosphoric acid class substance reaction, remove the water in the phosphoric acid class material;
Make polyvalent alcohol and remove the phosphoric acid class substance reaction that anhydrates, obtain midbody;
Midbody and trimeric cyanamide are reacted in solvent, be cooled to then below the room temperature, obtain said phosphorus-nitrogen type fire retardant through washing, suction filtration, oven dry;
Wherein, said phosphoric acid class material is one or more in phosphoric acid, tetra-sodium and the polyphosphoric acid.
2. compound method according to claim 1, wherein, said auxiliary agent is POCl
3, anhydrous MgSO
4, concentration 90-98wt% H
2SO
4, P
2O
5, in molecular sieve and the High hydrophilous resin one or more.
3. compound method according to claim 1, wherein, said polyvalent alcohol is one or more the combination in tetramethylolmethane, terepthaloyl moietie and the USP Kosher.
4. compound method according to claim 1, wherein, the mol ratio of said phosphoric acid class material, polyvalent alcohol and trimeric cyanamide is 1-5: 1: 1-4, the mass ratio of said auxiliary agent and said phosphoric acid class material is 1: 2.2-2.8.
5. compound method according to claim 1, wherein, in the reaction of said auxiliary agent and phosphoric acid class material, temperature of reaction is 70 ℃, the reaction times is 30min.
6. compound method according to claim 1, wherein, in said polyvalent alcohol and the reaction except that the phosphoric acid class material that anhydrates, temperature of reaction is 80-150 ℃, the reaction times is 1-5 hour.
7. compound method according to claim 1, wherein, in the reaction of said midbody and trimeric cyanamide, temperature of reaction is 60-100 ℃, the reaction times is 1-4 hour.
8. compound method according to claim 1, wherein, said solvent is water and/or terepthaloyl moietie.
9. phosphorus-nitrogen type fire retardant, it is by each described compound method synthetic of claim 1-8.
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| CN106589730A (en) * | 2016-12-17 | 2017-04-26 | 衢州普信新材料有限公司 | Method for preparing modified phosphorus-nitrogen flame-retardant agent |
| CN107791357A (en) * | 2017-10-31 | 2018-03-13 | 江苏佳饰家新材料有限公司 | A levels fire-proof plate and its manufacturing process |
| CN110172326A (en) * | 2019-05-30 | 2019-08-27 | 苏州拓锐新材料科技有限公司 | A kind of flame retardant type dual-component polyurethane adhesive and preparation method thereof |
| CN110172179A (en) * | 2019-05-30 | 2019-08-27 | 苏州拓锐新材料科技有限公司 | A kind of expansion type flame retardant and preparation method thereof |
| CN111892677A (en) * | 2020-05-22 | 2020-11-06 | 四川金象赛瑞化工股份有限公司 | Flame-retardant organic glass and preparation method thereof |
| CN112430381A (en) * | 2020-11-30 | 2021-03-02 | 西北师范大学 | Preparation method of intrinsic organic-inorganic smoke-suppression flame-retardant epoxy resin composite material |
| CN112480603A (en) * | 2020-11-10 | 2021-03-12 | 四川科技职工大学 | Low-smoke carbon-forming flame retardant and application thereof in preparation of flame-retardant polyurethane elastomer |
| CN114808436A (en) * | 2022-04-20 | 2022-07-29 | 江南大学 | Method for preparing flame-retardant polyester by in-situ growth of magnesium hydroxide through phosphorus-nitrogen flame retardant |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106589730A (en) * | 2016-12-17 | 2017-04-26 | 衢州普信新材料有限公司 | Method for preparing modified phosphorus-nitrogen flame-retardant agent |
| CN106589730B (en) * | 2016-12-17 | 2019-01-04 | 衢州普信新材料有限公司 | A kind of preparation method of modified Phosphorus-nitrogen flame retardant |
| CN107791357A (en) * | 2017-10-31 | 2018-03-13 | 江苏佳饰家新材料有限公司 | A levels fire-proof plate and its manufacturing process |
| CN110172326A (en) * | 2019-05-30 | 2019-08-27 | 苏州拓锐新材料科技有限公司 | A kind of flame retardant type dual-component polyurethane adhesive and preparation method thereof |
| CN110172179A (en) * | 2019-05-30 | 2019-08-27 | 苏州拓锐新材料科技有限公司 | A kind of expansion type flame retardant and preparation method thereof |
| CN111892677A (en) * | 2020-05-22 | 2020-11-06 | 四川金象赛瑞化工股份有限公司 | Flame-retardant organic glass and preparation method thereof |
| CN112480603A (en) * | 2020-11-10 | 2021-03-12 | 四川科技职工大学 | Low-smoke carbon-forming flame retardant and application thereof in preparation of flame-retardant polyurethane elastomer |
| CN112430381A (en) * | 2020-11-30 | 2021-03-02 | 西北师范大学 | Preparation method of intrinsic organic-inorganic smoke-suppression flame-retardant epoxy resin composite material |
| CN112430381B (en) * | 2020-11-30 | 2023-01-10 | 西北师范大学 | Preparation method of intrinsic organic-inorganic smoke-suppression flame-retardant epoxy resin composite material |
| CN114808436A (en) * | 2022-04-20 | 2022-07-29 | 江南大学 | Method for preparing flame-retardant polyester by in-situ growth of magnesium hydroxide through phosphorus-nitrogen flame retardant |
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Application publication date: 20121128 |