CN105418675A - Triazine charring agent, preparation method therefor and application thereof - Google Patents

Triazine charring agent, preparation method therefor and application thereof Download PDF

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CN105418675A
CN105418675A CN201510973115.3A CN201510973115A CN105418675A CN 105418675 A CN105418675 A CN 105418675A CN 201510973115 A CN201510973115 A CN 201510973115A CN 105418675 A CN105418675 A CN 105418675A
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reaction
forming agent
formula
char
acid
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CN105418675B (en
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岳涛
邢文国
陈琦
冯维春
周倜
张健
孟宪兴
李培培
游淇
杨旭
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Jinan Ift Science & Technology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D251/00Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40Nitrogen atoms
    • C07D251/54Three nitrogen atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D251/00Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40Nitrogen atoms
    • C07D251/54Three nitrogen atoms
    • C07D251/56Preparation of melamine
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02Phosphorus compounds
    • C07F9/28Phosphorus compounds with one or more P—C bonds
    • C07F9/30Phosphinic acids R2P(=O)(OH); Thiophosphinic acids, i.e. R2P(=X)(XH) (X = S, Se)
    • C07F9/301Acyclic saturated acids which can have further substituents on alkyl
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/32Phosphorus-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • C08K5/51Phosphorus bound to oxygen
    • C08K5/53Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313Phosphinic compounds, e.g. R2=P(:O)OR'
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/32Phosphorus-containing compounds
    • C08K2003/321Phosphates
    • C08K2003/322Ammonium phosphate
    • C08K2003/323Ammonium polyphosphate
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The present invention discloses a triazine charring agent, a preparation method therefor and application thereof. The preparation method comprises the following steps: performing an Mannich reaction on hypophosphorous acid, diethanol amine, and formaldehyde catalyzed by hydrochloric acid in an aqueous phase; after the reaction, adding melamine to the reaction solution to react sequentially; and obtaining the triazine charring agent with the following structural formula. The present invention also provides application of the charring agent as a raw material of a flame retardant, as well as a preparation method of the flame retardant. According to the method disclosed by the present invention, reaction conditions are mild, a process flow of operations is simple, a reaction period is short, and post treatment is simple. The resulting charring agent has good expansibility, high thermal stability, a large amount of carbon residue, a good charring effect, and good compatibility with a polymer. The charring agent can be made into the flame retardant by mixing with ammonium polyphosphate, polypropylene, and the like, with excellent inflaming retarding performance and little influence on mechanical properties.

Description

A kind of triazines char-forming agent and its preparation method and application
Technical field
The present invention relates to a kind of triazines char-forming agent and preparation method thereof, also relate to the preparation method of fire retardant containing this triazines char-forming agent and fire retardant, belong to field of material technology.
Background technology
The halogen-free flame retardants that expansion type flame retardant (IFR) is is main component with phosphorus, nitrogen, it is one of environment-friendly flame retardant agent type of widespread use in recent years, the shortcoming that halogenated flame retardant easily releases pungency and corrosive gas and smog when burning because it not only overcomes, many molten drops, the easily personnel that cause suffocate, and also overcome inorganic combustion inhibitor because addition is greatly to the detrimentally affect that the mechanics of materials, processibility the subject of knowledge and the object of knowledge bring.Expansion type flame retardant can effectively stop the characteristics such as polymkeric substance molten drop because of the carbon-coating of the fire retardant mechanism of its uniqueness and Halogen, low cigarette, low toxicity, generation; meet the requirement of preserving the ecological environment now; therefore halogen-free intumescent flame-retardant technology is described as a revolution in flame-retarded technology, becomes one of flame retardant area enlivened the most in recent years.
Generally speaking, IFR comprises three parts, i.e. carbon source (being often polyol, as tetramethylolmethane), acid source (as ammonium polyphosphate) and source of the gas (trimeric cyanamide).Triazine derivative is rich in the compound of tertiary N structure as a class, and it has excellent foaming effect and becomes charcoal effect, and tool has the following advantages: (1) Halogen, low toxicity; (2) decomposition temperature is high; (3) little on the physical and mechanical properties impact of material; (4) exudation resistance; (5) flame retarding efficiency is high.In recent years, the preparation of some pyrrolotriazine derivatives and the patent constantly open (CN1314898A as char-forming agent or fire retardant application, CN101586033A, CN101007953, CN201010165863.6, CN200710071927.4, WO9744377, JP0583065A1, ZL200510010243.4, EP0475418A2), substantially all there is consumption of organic solvent large (organic solvent is mainly acetone) in these patents, environmental pollution is serious, or subsequent disposal difficulty, product thermostability is not high, the shortcomings such as charcoal residual quantity is low, and reaction time is generally oversize, at more than 20h.Therefore study a kind of simple, that efficient, performance is good triazine derivative char-forming agent and there is good using value.
Summary of the invention
The invention provides a kind of triazines char-forming agent, this char-forming agent has good one-tenth charcoal and flame retardant effect.
Present invention also offers the preparation method of this char-forming agent, the method reaction conditions is gentle, and technical operation flow is simple, raw materials used safely, be easy to get, be convenient to suitability for industrialized production.
Present invention also offers the application of this char-forming agent in flame retardant area, be specially the preparation method of fire retardant containing this char-forming agent and fire retardant.
The concrete technical scheme of the present invention is as follows:
Triazines char-forming agent provided by the invention, has the structural formula shown in following formula II:
The above-mentioned char-forming agent of the present invention not only has carbon source (poly-hydroxy group), and also has acid source (Hypophosporous Acid, 50 structure) and source of the gas (trimeric cyanamide), becomes charcoal and good flame retardation effect, fine with polymer compatibility, little to mechanical impact.
The preparation method of above-mentioned triazines char-forming agent, comprises the following steps:
(1) there is Mannich reaction in Hypophosporous Acid, 50, diethanolamine and formaldehyde under aqueous phase, hydrochloric acid catalysis, and obtain the product shown in formula I, reaction formula is as follows:
(2) in the reaction solution of step (1), add trimeric cyanamide, make the product shown in formula I and trimeric cyanamide generation salt-forming reaction, obtain the product shown in formula II, the product shown in formula II is triazines char-forming agent, and reaction formula is as follows:
The present invention is with Hypophosporous Acid, 50, diethanolamine, formaldehyde, trimeric cyanamide for raw material, and side reaction is few, and oh group is many, and gained char-forming agent is simultaneously containing carbon source, acid source and source of the gas, and become charcoal and good flame retardation effect, thermostability is high.In addition, the method is simple to operate, be reaction medium with water, avoids the use of organic solvent, simplifies last handling process.
In step (1), Hypophosporous Acid, 50, diethanolamine and formaldehyde generation Mannich reaction (Mannich reaction), also known as Mannich reaction, concrete operating process is: first Hypophosporous Acid, 50, water and diethanolamine are mixed, then hydrochloric acid is added, after mixing, system temperature is risen to temperature of reaction, then under agitation slowly add formaldehyde and react, obtain the product shown in formula I.
In above-mentioned steps (1), formaldehyde adds in form of an aqueous solutions.Formaldehyde solution is commercially available prod, and concentration is generally at about 37wt%.
In above-mentioned steps (1), temperature of reaction is 95-100 DEG C, is preferably 100 DEG C.
In above-mentioned steps (1), formaldehyde slowly adds in solution system, and the general joining day is 0.5-1h.After treating that formaldehyde adds, then continue stirring reaction 2-4h, preferably continue reaction 3h.
In above-mentioned steps (1), the mol ratio of Hypophosporous Acid, 50, diethanolamine and formaldehyde is 1:2:2-2.2, is preferably 1:2:2.1.
In above-mentioned steps (1), add hydrochloric acid as catalyzer, that play katalysis is H in acid +, the concentration of hydrochloric acid can choose at random, and considers the discharge of saving waste water, preferably adopts the hydrochloric acid that concentration is high.In the specific embodiment of the present invention, the HCl in hydrochloric acid and Hypophosporous Acid, 50 (H 3pO 2) weight ratio of composition is 1:8-25, preferred weight ratio is 1:12.5.
In above-mentioned steps (1), water, as reaction medium, has solubilizing reaction material, provides the effect of reaction environment.The consumption of water can not very little, otherwise the intermediate product (product shown in formula I) generated is difficult to dispersion, the carrying out of impact reaction.In the present invention, water and Hypophosporous Acid, 50 (H 3pO 2) weight ratio be 16-24:1, preferred weight ratio is 20:1, and water herein refers to the pure water added, do not comprise other raw materials introduce water.
Further, the specific operation process of step (2) for: after being obtained by reacting the product shown in formula I, keeping the temperature of reaction identical with step (1), in the reaction solution of step (1), add trimeric cyanamide react, cooling after reaction, filtration, drying, obtain the product shown in formula II.
In above-mentioned steps step (2), the mol ratio that the consumption of trimeric cyanamide meets trimeric cyanamide and Hypophosporous Acid, 50 is the requirement of 1:1.
In step (2), the reaction times is 1-3h, is preferably 2h.
Further, gained char-forming agent of the present invention can be mixed with other materials, makes fire retardant, to play better flame retardant effect.The effective constituent of fire retardant provided by the invention is above-mentioned triazines char-forming agent, ammonium polyphosphate and polyacrylic mixture.Preferably, in fire retardant, char-forming agent of the present invention, ammonium polyphosphate, polyacrylic mass ratio are 5:20:75.
The preparation method of above-mentioned fire retardant is: first, and obtained triazines char-forming agent, then mixes triazines char-forming agent, ammonium polyphosphate and polypropylene, obtain fire retardant according to the method described above.In addition, as required, fire retardant prior art can be made different shapes.
The inventive method with Hypophosporous Acid, 50, diethanolamine, formaldehyde, trimeric cyanamide for primitive reaction thing, triazines macromolecular cpd has been synthesized in whole water phase, reaction conditions is gentle, technical operation flow is simple, and reaction time is short, and aftertreatment is simple, raw materials used safely, be easy to get, be suitable for industrialization scale operation, avoid existing technological reaction overlong time and the shortcoming such as consumption of organic solvent is large, there is good environmental protection and economic worth.
Gained char-forming agent swelling property of the present invention is good, thermostability is high, carbon residue allowance large, and become charcoal effective, fine with polymer compatibility, can make fire retardant with ammonium polyphosphate and polypropylene etc. are used in combination, flame retardant properties is outstanding, little to mechanical impact.
Accompanying drawing explanation
The infrared spectrum of Fig. 1 char-forming agent of the present invention.
Fig. 2 is the thermogravimetric analysis figure of each char-forming agent, and X-coordinate is temperature, and ordinate zou is weight.
Embodiment
Below in conjunction with specific embodiment, the present invention is further described, so that those skilled in the art more understands the present invention, but does not therefore limit the present invention.In following embodiment, if no special instructions, percentage composition is mass percentage.
embodiment 1
Get the 2L tetra-mouthfuls of round-bottomed flasks with agitator, thermometer, prolong and constant pressure funnel, 132g aqueous hypophosphorous acid (content 50%), 210.6g diethanolamine (content 99.7%), 1056g water are joined in flask, open and stir, add 17g hydrochloric acid (content 31%), then 95-100 DEG C is warming up to, 0.5-1h drips formalin 170.3g(content 37%), dropwise after continuing reaction 3h and add trimeric cyanamide 126g, lower the temperature after continuing reaction 2h, filter, dry, obtain char-forming agent 412.1g, collect rate 96.7% with Hypophosporous Acid, 50.
Fig. 1 is the infrared spectrum of gained char-forming agent, as can be seen from the figure there is trimeric cyanamide group, diethanolamine group and phosphorus-oxygen groups, coincide with the structure of synthesized novel char-forming agent.
embodiment 2
Get four mouthfuls of round-bottomed flasks of the 2L with agitator, thermometer, prolong and constant pressure funnel, 132g aqueous hypophosphorous acid (content 50%), 210.6g diethanolamine, 1320g water are joined in flask, open and stir, add 17g hydrochloric acid (content 31%), then 95-100 DEG C is warming up to, 0.5-1h drips formalin 170.3g(content 37%), dropwise after continuing reaction 3h and add trimeric cyanamide 126g, lower the temperature after continuing reaction 2h, filter, dry, obtain novel char-forming agent 418.1g, collect rate 98.1% with Hypophosporous Acid, 50.
embodiment 3
Get four mouthfuls of round-bottomed flasks of the 2L with agitator, thermometer, prolong and constant pressure funnel, 132g aqueous hypophosphorous acid (content 50%), 210.6g diethanolamine, 1584g water are joined in flask, open and stir, add 17g hydrochloric acid (content 31%), then 95-100 DEG C is warming up to, 0.5-1h drips formalin 170.3g(content 37%), dropwise after continuing reaction 3h and add trimeric cyanamide 126g, lower the temperature after continuing reaction 2h, filter, dry, obtain novel char-forming agent 417.9g, collect rate 98.1% with Hypophosporous Acid, 50.
embodiment 4
Get four mouthfuls of round-bottomed flasks of the 2L with agitator, thermometer, prolong and constant pressure funnel, 132g aqueous hypophosphorous acid (content 50%), 210.6g diethanolamine, 1320g water are joined in flask, open and stir, add 8.5g hydrochloric acid (content 31%), then 95-100 DEG C is warming up to, 0.5-1h drips formalin 170.3g(content 37%), dropwise after continuing reaction 3h and add trimeric cyanamide 126g, lower the temperature after continuing reaction 2h, filter, dry, obtain novel char-forming agent 401.2g, collect rate 94.2% with Hypophosporous Acid, 50.
embodiment 5
Get four mouthfuls of round-bottomed flasks of the 2L with agitator, thermometer, prolong and constant pressure funnel, 132g aqueous hypophosphorous acid (content 50%), 210.6g diethanolamine, 1320g water are joined in flask, open and stir, add 25.5g hydrochloric acid (content 31%), then 95-100 DEG C is warming up to, 0.5-1h drips formalin 170.3g(content 37%), dropwise after continuing reaction 3h and add trimeric cyanamide 126g, lower the temperature after continuing reaction 2h, filter, dry, obtain novel char-forming agent 418.3g, collect rate 98.2% with Hypophosporous Acid, 50.
embodiment 6
Get four mouthfuls of round-bottomed flasks of the 2L with agitator, thermometer, prolong and constant pressure funnel, 132g aqueous hypophosphorous acid (content 50%), 210.6g diethanolamine, 1320g water are joined in flask, open and stir, add 17g hydrochloric acid (content 31%), then 95-100 DEG C is warming up to, 0.5-1h drips formalin 162.2g(content 37%), dropwise after continuing reaction 3h and add trimeric cyanamide 126g, lower the temperature after continuing reaction 2h, filter, dry, obtain novel char-forming agent 403.1g, collect rate 94.6% with Hypophosporous Acid, 50. embodiment 7
Get four mouthfuls of round-bottomed flasks of the 2L with agitator, thermometer, prolong and constant pressure funnel, 132g aqueous hypophosphorous acid (content 50%), 210.6g diethanolamine, 1320g water are joined in flask, open and stir, add 17g hydrochloric acid (content 31%), then 95-100 DEG C is warming up to, 0.5-1h drips formalin 178.4g(content 37%), dropwise after continuing reaction 3h and add trimeric cyanamide 126g, lower the temperature after continuing reaction 2h, filter, dry, obtain novel char-forming agent 418.5g, collect rate 98.2% with Hypophosporous Acid, 50.
embodiment 8
Get four mouthfuls of round-bottomed flasks of the 2L with agitator, thermometer, prolong and constant pressure funnel, 132g aqueous hypophosphorous acid (content 50%), 210.6g diethanolamine, 1320g water are joined in flask, open and stir, add 17g hydrochloric acid (content 31%), then 95-100 DEG C is warming up to, 0.5-1h drips formalin 170.3g(content 37%), dropwise after continuing reaction 2h and add trimeric cyanamide 126g, lower the temperature after continuing reaction 2h, filter, dry, obtain novel char-forming agent 398.1g, collect rate 93.5% with Hypophosporous Acid, 50.
embodiment 9
Get four mouthfuls of round-bottomed flasks of the 2L with agitator, thermometer, prolong and constant pressure funnel, 132g aqueous hypophosphorous acid (content 50%), 210.6g diethanolamine, 1320g water are joined in flask, open and stir, add 17g hydrochloric acid (content 31%), then 95-100 DEG C is warming up to, 0.5-1h drips formalin 170.3g(content 37%), dropwise after continuing reaction 4h and add trimeric cyanamide 126g, lower the temperature after continuing reaction 2h, filter, dry, obtain novel char-forming agent 418.0g, collect rate 98.1% with Hypophosporous Acid, 50.
embodiment 10
Get four mouthfuls of round-bottomed flasks of the 2L with agitator, thermometer, prolong and constant pressure funnel, 132g aqueous hypophosphorous acid (content 50%), 210.6g diethanolamine, 1320g water are joined in flask, open and stir, add 17g hydrochloric acid (content 31%), then 95-100 DEG C is warming up to, 0.5-1h drips formalin 170.3g(content 37%), dropwise after continuing reaction 3h and add trimeric cyanamide 126g, lower the temperature after continuing reaction 1h, filter, dry, obtain novel char-forming agent 386.5g, collect rate 90.7% with Hypophosporous Acid, 50.
embodiment 11
Get four mouthfuls of round-bottomed flasks of the 2L with agitator, thermometer, prolong and constant pressure funnel, 132g Hypophosporous Acid, 50 (content 50%), 210.6g diethanolamine, 1320g water are joined in flask, open and stir, add 17g hydrochloric acid (content 31%), then 95-100 DEG C is warming up to, 0.5-1h drips formalin 170.3g(content 37%), dropwise after continuing reaction 3h and add trimeric cyanamide 126g, lower the temperature after continuing reaction 3h, filter, dry, obtain novel char-forming agent 418.3g, collect rate 98.2% with Hypophosporous Acid, 50.
comparative example 1
Get four mouthfuls of round-bottomed flasks of the 2L with agitator, thermometer, prolong and constant pressure funnel, 132g aqueous hypophosphorous acid (content 50%), 122g thanomin, 1320g water are joined in flask, open and stir, add 17g hydrochloric acid (content 31%), then 100 DEG C are warming up to, 0.5-1h drips formalin 162.2g(content 37%), dropwise after continuing reaction 3h and add trimeric cyanamide 126g, after continuing reaction 3h.Cooling, filtration, oven dry, obtain char-forming agent 295.9g, collect rate 96.1% with Hypophosporous Acid, 50.Because with thanomin as raw material, containing two reactive hydrogens on the nitrogen of thanomin, these two hydrogen can with Hypophosporous Acid, 50 and formaldehyde reaction, the reaction that can occur like this is more, and therefore product component is complicated, is mixture, and be difficult to purify, thermostability is not high.
Reaction equation is:
Wherein A 1for H or ; A 2for H or .
comparative example 2
Get four mouthfuls of round-bottomed flasks of the 2L with agitator, thermometer, prolong and constant pressure funnel, 83.2g phosphorous acid (content 98.5%), 105g diethanolamine, 1320g water are joined in flask, open and stir, add 17g hydrochloric acid (content 31%), then 100 DEG C are warming up to, 0.5-1h drips formalin 81.1g(content 37%), dropwise after continuing reaction 3h.Add trimeric cyanamide 126g, after continuing reaction 3h.Cooling, filtration, oven dry, obtain novel char-forming agent 313.6g, collect rate 96.5% with Hypophosporous Acid, 50.
Reaction equation is:
Gained char-forming agent molecular weight is little, becomes charcoal poor.
application examples 1
The char-forming agent of Example 1, comparative example 1 and comparative example 2, adds in thermogravimetric analyzer and carries out thermogravimetric analysis, along with the rising of temperature, Fig. 2 is shown in the change of each char-forming agent weight, and as can be seen from the figure, the heat decomposition temperature of the char-forming agent of the present invention's synthesis is high, carbon left is large, and thermostability is strong.
The char-forming agent of embodiment 2-11 is also carried out thermogravimetric analysis, and result shows, and the char-forming agent weight variation with temperature situation of embodiment 2-11 is similar to Example 1, is all obviously better than the product of comparative example 1 and comparative example 2.
application examples 2
In order to verify the effect of char-forming agent prepared by above-described embodiment and comparative example, carry out following experiment:
According to the formula in table 1, char-forming agent, ammonium polyphosphate and polypropylene are re-dubbed fire retardant, after mixing on the twin screw extruder 180 DEG C extrude, on injection moulding machine, inject sample batten (size of sample: 120mm × 13mm × 3.2mm) after extruding pellet drying.Each for gained sample batten is carried out vertical combustion rank test, tests and carry out according to UL94-2013 standard test methods.The burning grade of each sample batten sees the following form 1.
Table 1 each sample batten vertical combustion test result
As can be seen from the above table: the consumption of formaldehyde, hydrochloric acid and reaction times affect the flame retardant effect of products obtained therefrom, and the char-forming agent molecular weight of comparative example 2 is little, become charcoal poor, flame retardant effect is not good.

Claims (10)

1. a triazines char-forming agent, is characterized in that: have the structural formula shown in following formula II:
2. a preparation method for triazines char-forming agent according to claim 1, is characterized in that comprising the following steps:
(1) there is Mannich reaction in Hypophosporous Acid, 50, diethanolamine and formaldehyde under aqueous phase, hydrochloric acid catalysis, and obtain the product shown in formula I, reaction formula is as follows:
(2) in the reaction solution of step (1), add trimeric cyanamide, make the product shown in formula I and trimeric cyanamide generation salt-forming reaction, obtain the product shown in formula II, the product shown in formula II is triazines char-forming agent, and reaction formula is as follows:
3. preparation method according to claim 2, it is characterized in that: the specific operation process of step (1) is: first Hypophosporous Acid, 50, water and diethanolamine are mixed, then hydrochloric acid is added, after mixing, system temperature is risen to temperature of reaction, then under agitation slowly add formaldehyde to react, obtain the product shown in formula I.
4. preparation method according to claim 3, is characterized in that: in step (1), and the joining day of formaldehyde is 0.5-1h, reacts 2-4h again, preferably react 3h again after adding; In step (1), formaldehyde used is formalin.
5. the preparation method according to any one of claim 2-4, is characterized in that: in step (1), and the mol ratio of Hypophosporous Acid, 50, diethanolamine and formaldehyde is 1:2:2-2.2, is preferably 1:2:2.1; In step (2), the mol ratio of trimeric cyanamide and Hypophosporous Acid, 50 is 1:1.
6. the preparation method according to any one of claim 2-5, is characterized in that: in step (1), and the HCl in hydrochloric acid and the weight ratio of Hypophosporous Acid, 50 are 1:8-25, and preferred weight ratio is 1:12.5.
7. the preparation method according to any one of claim 2-6, is characterized in that: in step (1), and the pure water added and the weight ratio of Hypophosporous Acid, 50 are 16-24:1, and preferred weight ratio is 20:1; In step (1), temperature of reaction is 95-100 DEG C.
8. the preparation method according to any one of claim 2-7, it is characterized in that: the specific operation process of step (2) is: keep the temperature of reaction identical with step (1), in the reaction solution of step (1), add trimeric cyanamide react, cooling after reaction, filtration, drying, obtain the product shown in formula II.
9. the preparation method according to claim 2 or 8, is characterized in that: in step (2), and the reaction times is 1-3h, is preferably 2h.
10. fire retardant and preparation method thereof, is characterized in that: the effective constituent of fire retardant is triazines char-forming agent according to claim 1, ammonium polyphosphate and polyacrylic mixture; The preparation method of fire retardant comprises the following steps:
(1) triazines char-forming agent is obtained according to the preparation method of the triazines char-forming agent according to any one of claim 2-9;
(2) triazines char-forming agent, ammonium polyphosphate and polypropylene are mixed, obtain fire retardant.
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Cited By (5)

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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
CN111647200A (en) * 2020-06-15 2020-09-11 中国科学技术大学 Acetal structure-containing flame retardant and preparation method and application thereof
CN111647200B (en) * 2020-06-15 2021-07-06 中国科学技术大学 Acetal structure-containing flame retardant and preparation method and application thereof

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