CN105061510A - Reaction type water-soluble fire retardant as well as preparation method and application thereof - Google Patents
Reaction type water-soluble fire retardant as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a compound shown in a formula 1 or a formula 2, a corresponding water-soluble ionic compound shown in a formula 3 or a formula 4 as well as a preparation method and an application of the compound. In the formula 1, the formula 2, the formula 3 and the formula 4, R 1 represents C1-C4 alkylene, and x ranges from 4 to 10; in the formula 3 and the formula 4, M<y+> represents a monovalent metal ion or a bivalent metal ion, and y is 1 or 2. The preparation method comprises steps as follows: 1), a compound shown in a formula 5 and a compound shown in a formula 6 react in a solvent, and a compound shown in a formula 7 or a formula 8 is obtained; 2), the compound shown in the formula 7 or the formula 8 and a compound shown in a formula 9 have a reflux reaction in the solvent, the compound shown in the formula 1 or the formula 2 is obtained and has an acid-base reaction with inorganic base in the solvent, and the compound shown in the formula 3 or the formula 4 is obtained. The preparation method is simple, a reaction product has good water solubility, water is taken as the solvent, other special solvents are not required, solubility and uniformity are guaranteed, and the solvent is easy to recover.
Description
Technical field
The invention belongs to fire retardant preparation field, be specifically related to a kind of reactive type water-solubility fire retardant and preparation method thereof and application.
Background technology
The current major part of exploitation of Flameproof polyamide also rests on polyamide substrate and carries out in blended granulation to blended fire retardant and relevant synergistic flame retardant, this mode is owing to adding the restriction of the factor such as flame retardant amount many, the dispersiveness of fire retardant in polyamide substrate, consistency, interface characteristics, weather resistance, cause many performances of polymeric amide self to be limited, reduce its range of application.And reactive flame retardant well solves these problems, reactive flame retardant and monomer of polyamide react, flame retarding construction unit becomes a part for polymeric amide macromolecular chain, there are not the various problems that blending fire retardant agent brings, long-acting reliable flame retardant properties can be provided within the materials'use cycle.Therefore developing reactive flame retardant in-situ polymerization fire-retardant nylon is a urgently research topic for challenge.
Patent application 201410056761.9 discloses a kind of high flame retardant nylon resin and preparation method thereof, and synthesizing polyamides has good flame retardant properties, but synergistic flame retardant does not participate in home position polymerization reaction, is just distributed in polymerisate.Patent CN101663374A discloses a kind of DOPO flame retardant composition, and it comprises the mixture of phosphinates and dihydro-oxa--phospho hetero phenanthrene derivative, has good flame retardant effect.But the reactive flame retardant that current polymeric amide is conventional is mostly water-insoluble fire retardant, is solvent, there is the problems such as recycled solvent with ethanol,
Summary of the invention
The object of the present invention is to provide a kind of reactive type water-solubility fire retardant and preparation method thereof.
The general structure of fire retardant provided by the present invention such as formula shown in 1 or formula 2 and corresponding water soluble ion salt such as formula shown in 3 or formula 4:
In shown formula 1, formula 2, formula 3 and formula 4, R
1be the alkylidene group of C1 ~ C4; X is 4 ~ 10.
Shown in formula 3 and formula 4, M
y+for the metal ion of monovalence or divalence, specifically can be Na
+, K
+, Ca
2+or Mg
2+in any one; Y is 1 or 2.
The preparation method of fire retardant provided by the present invention is as follows:
When fire retardant is for compound shown in formula 1 or formula 2, preparation method comprises the steps:
1) under an inert atmosphere, compound shown in compound and formula 6 shown in formula 5 is reacted in solvent, obtains compound shown in compound shown in formula 7 or formula 8,
In described formula 5, formula 7 and formula 8, R
1be the alkylidene group of C1 ~ C4; In described formula 6, formula 7 and formula 8, x is 4 ~ 10;
2) compound shown in compound and formula 9 shown in compound shown in formula 7 or formula 8 is carried out back flow reaction in solvent, obtains compound shown in formula 1 or formula 2,
In above-mentioned preparation method, step 1) in, described inert atmosphere is nitrogen atmosphere and/or argon gas atmosphere.
Shown in described formula 5, shown in compound and described formula 6, the mol ratio of compound is (1-1.5): 1, specifically can be 1:1.
The temperature of reaction of described reaction is 20 ~ 70 DEG C, specifically can be 25-60 DEG C, and the reaction times is 0.5-3h.
Described solvent is water or ethanol.
In above-mentioned preparation method, step 2) in, shown in compound shown in described formula 7 or formula 8, shown in compound and formula 9, the mol ratio of compound is (1-2): 1, specifically can be 1:1.
The temperature of reaction of described back flow reaction is 50-100 DEG C, specifically can be 85-95 DEG C, and the reaction times is 2-3h.
Described solvent is water or ethanol.
Compound shown in formula 9 is 6H-dibenzo [c, e] [1,2] oxygen phospha cyclohexane-6-oxide compound (6H-dibenz [c, e] [1,2] oxaphosphorin-6-oxide), be abbreviated as DOPO (C.A.RN35948-25-5).
When fire retardant is for compound shown in formula 3 or formula 4, preparation method comprises the steps: compound shown in formula 1 or formula 2 and mineral alkali to react in solvent, obtains compound shown in formula 3 or formula 4.
In above-mentioned preparation method, shown in described formula 1 or formula 2, the mol ratio of compound and mineral alkali is (0.5-1): 1, specifically can be 1:1.
Described mineral alkali is the alkali that the metal pair of monovalence or divalence is answered, and specifically can be NaOH, KOH, Ca (OH)
2or Mg (OH)
2in any one.
The temperature of reaction of described reaction is 50-100 DEG C, specifically can be 80-90 DEG C, and the reaction times is 0.5-2h, specifically can be 0.5-1h.
Described solvent is water.
In addition, compound shown in compound shown in the preparation-obtained formula 1 of the present invention and/or formula 2 and corresponding water soluble ion salt formula 3 thereof and/or formula 4 also belongs to protection scope of the present invention preparing the application in fire retardant material.
In above-mentioned application, described fire retardant material specifically can be Flameproof polyamide.
The preparation-obtained fire retardant of the present invention is reactive type water-solubility fire retardant, be mainly the mixture of compound shown in formula 1 and formula 2, reaction process easily controls, exploitativeness is strong, the good water solubility of the reaction product obtained, and compound shown in formula 1 and formula 2 has amino and carboxyl both-end based structures, be applicable to the synthesis of all kinds of Flameproof polyamide, react obtained flame-retardant polymeric amide with monomer of polyamide to there is permanent fire retardant (" permanent fire retardant " is the advantage of copoly type Flameproof polyamide compared to blended based flame retardant, mainly refer to that in use As time goes on flame retardant properties can not change), react with monomer of polyamide (compound shown in formula 7 or formula 8 shown in compound) and only need be solvent in a kettle. with water, without the need to other special solvents, ensure that fire retardant solvability in a kettle. and homogeneity, solvent recuperation is easy, by compound shown in formula 1 and formula 2 and monovalence or divalent-metal ion alkaline solution being reacted, obtaining reactive type water-solubility ion salt fire retardant, being mainly the mixture that formula 3 and formula 4 show compound.
Accompanying drawing explanation
Fig. 1 is the reacting flow chart in embodiment 1.
Fig. 2 is the reacting flow chart in embodiment 2.
Fig. 3 is the reacting flow chart in embodiment 3.
Fig. 4 is the reacting flow chart in embodiment 4.
Embodiment
Below by specific embodiment, method of the present invention is described, but the present invention is not limited thereto.
Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
Embodiment 1, preparation feedback type water-soluble flame retardant:
Undertaken by the reacting flow chart shown in Fig. 1:
1) by methylene-succinic acid and hexanediamine in molar ratio for 1:1 joins in the four-hole boiling flask with agitator, thermometer, reflux exchanger and logical nitrogen pipe, pass into nitrogen, make both in water, at 60 DEG C, react 0.5h, obtain methylene-succinic acid hexanediamine salt brine solution;
2) 6H-dibenzo [c, e] [1,2] oxygen phospha cyclohexane-6-oxide compound (DOPO) is slowly joined methylene-succinic acid hexanediamine salt brine solution, the mol ratio of DOPO and methylene-succinic acid hexanediamine salt is made to be 1:1, back flow reaction 2.5h at 90 DEG C, cool to room temperature, filters reaction gains, and with deionized water dissolving recrystallize 5 times, in order to remove impurity, be drying to obtain reactive type water-solubility fire retardant, be compound shown in formula 1 and/or formula 2, wherein, R
1for methylene radical; X is 6.
3) by step 2) in the reactive type water-solubility fire retardant that obtains and sodium hydroxide in water, carry out acid-base reaction for 1:1 in molar ratio, temperature of reaction is 80 DEG C, and the reaction times is 1h, obtain reactive type water-solubility ion salt fire retardant, be compound shown in formula 3 and/or formula 4, wherein, M
y+for monovalence Na
+; Y is 1.
Embodiment 2, preparation feedback type water-soluble flame retardant:
Undertaken by the reacting flow chart shown in Fig. 2:
1) by methylene-succinic acid and quadrol in molar ratio for 1:1 joins in the four-hole boiling flask with agitator, thermometer, reflux exchanger and logical nitrogen pipe, pass into nitrogen, make both in water, at 25 DEG C, react 0.5h, obtain the methylene-succinic acid ethylenediamine salt aqueous solution;
2) 6H-dibenzo [c, e] [1,2] oxygen phospha cyclohexane-6-oxide compound (DOPO) is slowly joined the methylene-succinic acid ethylenediamine salt aqueous solution, the mol ratio of DOPO and methylene-succinic acid ethylenediamine salt is made to be 1:1, back flow reaction 2h at 85 DEG C, cool to room temperature, filters reaction gains, and with deionized water dissolving recrystallize 5 times, in order to remove impurity, be drying to obtain reactive type water-solubility fire retardant, be compound shown in formula 1 and/or formula 2, wherein, R
1for methylene radical; X is 2.
3) by step 2) in the reactive type water-solubility fire retardant that obtains and potassium hydroxide in water, carry out acid-base reaction for 1:1 in molar ratio, temperature of reaction is 80 DEG C, and the reaction times is 1h, obtain reactive type water-solubility ion salt fire retardant, be compound shown in formula 3 and/or formula 4, wherein, M
y+for monovalence K
+; Y is 1.
Embodiment 3, preparation feedback type water-soluble flame retardant:
Undertaken by the reacting flow chart shown in Fig. 3:
1) by methylene-succinic acid and pentamethylene diamine in molar ratio for 1:1 joins in the four-hole boiling flask with agitator, thermometer, reflux exchanger and logical nitrogen pipe, pass into nitrogen, make both in water, at 60 DEG C, react 0.5h, obtain methylene-succinic acid pentamethylene diamine salt brine solution;
2) 6H-dibenzo [c, e] [1,2] oxygen phospha cyclohexane-6-oxide compound (DOPO) is slowly joined methylene-succinic acid pentamethylene diamine salt brine solution, the mol ratio of DOPO and methylene-succinic acid pentamethylene diamine salt is made to be 1:1, back flow reaction 3h at 95 DEG C, cool to room temperature, filters reaction gains, and with deionized water dissolving recrystallize 5 times, in order to remove impurity, be drying to obtain reactive type water-solubility fire retardant, be compound shown in formula 1 and/or formula 2, wherein, R
1for methylene radical; X is 5.
3) by step 2) in the reactive type water-solubility fire retardant that obtains and calcium hydroxide in water, carry out acid-base reaction for 2:1 in molar ratio, temperature of reaction is 85 DEG C, and the reaction times is 1h, obtain reactive type water-solubility ion salt fire retardant, be compound shown in formula 3 and/or formula 4, wherein, M
y+for divalence Ca
2+; Y is 2.
Embodiment 4, preparation feedback type water-soluble flame retardant:
Undertaken by the reacting flow chart shown in Fig. 4:
1) by methylene-succinic acid and heptamethylene diamine in molar ratio for 1:1 joins in the four-hole boiling flask with agitator, thermometer, reflux exchanger and logical nitrogen pipe, pass into nitrogen, make both in water, at 25 DEG C, react 0.5h, obtain methylene-succinic acid heptamethylene diamine salt brine solution;
2) 6H-dibenzo [c, e] [1,2] oxygen phospha cyclohexane-6-oxide compound (DOPO) is slowly joined methylene-succinic acid heptamethylene diamine salt brine solution, the mol ratio of DOPO and methylene-succinic acid heptamethylene diamine salt is made to be 1:1, back flow reaction 2.5 at 95 DEG C, cool to room temperature, filters reaction gains, and with deionized water dissolving recrystallize 5 times, in order to remove impurity, be drying to obtain reactive type water-solubility fire retardant, be compound shown in formula 1 and/or formula 2, wherein, R
1for methylene radical; X is 7.
3) by step 2) in the reactive type water-solubility fire retardant that obtains and magnesium hydroxide in water, carry out acid-base reaction for 2:1 in molar ratio, temperature of reaction is 90 DEG C, and the reaction times is 0.5h, obtain reactive type water-solubility ion salt fire retardant, be compound shown in formula 3 and/or formula 4, wherein, M
y+for divalence Mg
2+; Y is 2.
Embodiment 5, reactive type water-solubility fire retardant is utilized to prepare Flameproof polyamide:
1) reactive type water-solubility fire retardant prepared by embodiment 1 is dissolved in deionized water, is made into the aqueous solution, and join in autoclave; Slowly be added in autoclave by hexanodioic acid, the mol ratio making reactive flame retardant and hexanodioic acid is 1:1, in adding procedure open stir, temperature is elevated to 223 DEG C from room temperature gradually, and at 223 DEG C insulation reaction 45min, obtain performed polymer;
2) again hexanediamine and hexanodioic acid are joined in autoclave, make hexanediamine, the mol ratio of hexanodioic acid and performed polymer three is 1:1:1, temperature and pressure is slowly risen to 245 DEG C and 2.0MPa, suitably regulates vent valve, pressure is made to maintain 2.0MPa, pressurize reaction 1.5h;
3), after pressurize has been reacted, regulate vent valve, make autoclave internal pressure be down to normal pressure gradually in 25min, and at ambient pressure, draining 20min at 245 DEG C, by decompression drainage except early stage add water and react the water of generation;
4) finally the temperature in autoclave is risen to 264 DEG C; shut vent valve; vacuum is evacuated to by still; after 23min, limiting viscosity reaches about 1.68dL/g and gets final product discharging; after water quench tank cooling, cross dicing machine pelletizing obtain copolymerization flame resistant polyamide resin particle product, recording gained copolymerization flame resistant polyamide resin particle product oxygen index by limiting oxygen index(LOI) is 30.
Embodiment 6, reactive type water-solubility fire retardant is utilized to prepare Flameproof polyamide:
1) reactive type water-solubility fire retardant prepared by embodiment 2 is dissolved in deionized water, is made into the aqueous solution, and join in autoclave; Slowly be added in autoclave by hexanodioic acid, the mol ratio making reactive flame retardant and hexanodioic acid is 1:1, in adding procedure open stir, temperature is elevated to 224 DEG C from room temperature gradually, and at 224 DEG C insulation reaction 35min, obtain performed polymer;
2) again hexanediamine and hexanodioic acid are joined in autoclave, make hexanediamine, the mol ratio of hexanodioic acid and performed polymer three is 1:1:1, temperature and pressure is slowly risen to 243 DEG C and 2.0MPa, suitably regulates vent valve, pressure is made to maintain 2.0MPa, pressurize reaction 100min;
3), after pressurize has been reacted, regulate vent valve, make autoclave internal pressure be down to normal pressure gradually in 25min, and at ambient pressure, draining 25min at 243 DEG C, by decompression drainage except early stage add water and react the water of generation;
4) finally the temperature in autoclave is risen to 265 DEG C; shut vent valve; vacuum is evacuated to by still; after 20min, limiting viscosity reaches about 1.7dL/g and gets final product discharging; after water quench tank cooling, cross dicing machine pelletizing obtain copolymerization flame resistant polyamide resin particle product, recording gained copolymerization flame resistant polyamide resin particle product oxygen index by limiting oxygen index(LOI) is 30.3.
Embodiment 7, reactive type water-solubility fire retardant is utilized to prepare Flameproof polyamide:
1) reactive type water-solubility fire retardant prepared by embodiment 3 is dissolved in deionized water, is made into the aqueous solution, and join in autoclave; Slowly be added in autoclave by hexanodioic acid, the mol ratio making reactive flame retardant and hexanodioic acid is 1:1, in adding procedure open stir, temperature is elevated to 220 DEG C from room temperature gradually, and at 220 DEG C insulation reaction 45min, obtain performed polymer;
2) again hexanediamine and hexanodioic acid are joined in autoclave, make hexanediamine, the mol ratio of hexanodioic acid and performed polymer three is 1:1:1, temperature and pressure is slowly risen to 245 DEG C and 2.0MPa, suitably regulates vent valve, pressure is made to maintain 2.0MPa, pressurize reaction 1.5h;
3), after pressurize has been reacted, regulate vent valve, make autoclave internal pressure be down to normal pressure gradually in 30min, and at ambient pressure, draining 25min at 245 DEG C, by decompression drainage except early stage add water and react the water of generation;
4) finally the temperature in autoclave is risen to 264 DEG C; shut vent valve; vacuum is evacuated to by still; after 20min, limiting viscosity reaches about 1.66dL/g and gets final product discharging; after water quench tank cooling, cross dicing machine pelletizing obtain copolymerization flame resistant polyamide resin particle product, recording gained copolymerization flame resistant polyamide resin particle product oxygen index by limiting oxygen index(LOI) is 29.8.
Embodiment 8, reactive type water-solubility fire retardant is utilized to prepare Flameproof polyamide:
1) reactive type water-solubility fire retardant prepared by embodiment 4 is dissolved in deionized water, is made into the aqueous solution, and join in autoclave; Slowly be added in autoclave by hexanodioic acid, the mol ratio making reactive flame retardant and hexanodioic acid is 1:1, in adding procedure open stir, temperature is elevated to 221 DEG C from room temperature gradually, and at 221 DEG C insulation reaction 45min, obtain performed polymer;
2) again hexanediamine and hexanodioic acid are joined in autoclave, make hexanediamine, the mol ratio of hexanodioic acid and performed polymer three is 1:1:1, temperature and pressure is slowly risen to 246 DEG C and 2.0MPa, suitably regulates vent valve, pressure is made to maintain 2.0MPa, pressurize reaction 1.5h;
3), after pressurize has been reacted, regulate vent valve, make autoclave internal pressure be down to normal pressure gradually in 30min, and at ambient pressure, draining 20min at 246 DEG C, by decompression drainage except early stage add water and react the water of generation;
4) finally the temperature in autoclave is risen to 265 DEG C; shut vent valve; vacuum is evacuated to by still; after 20min, limiting viscosity reaches about 1.65dL/g and gets final product discharging; after water quench tank cooling, cross dicing machine pelletizing obtain copolymerization flame resistant polyamide resin particle product, recording gained copolymerization flame resistant polyamide resin particle product oxygen index by limiting oxygen index(LOI) is 29.
Claims (9)
1. compound shown in compound shown in formula 1 or formula 2 and corresponding water soluble ion salt formula 3 thereof or formula 4:
In shown formula 1, formula 2, formula 3 and formula 4, R
1be the alkylidene group of C1 ~ C4; X is 4 ~ 10;
Shown in formula 3 and formula 4, M
y+for the metal ion of monovalence or divalence, be Na
+, K
+, Ca
2+or Mg
2+in any one; Y is 1 or 2.
2. the preparation method of compound shown in formula 1 according to claim 1 or formula 2, comprises the steps:
1) under an inert atmosphere, compound shown in compound and formula 6 shown in formula 5 is reacted in solvent, obtains compound shown in compound shown in formula 7 or formula 8,
In described formula 5, formula 7 and formula 8, R
1be the alkylidene group of C1 ~ C4; In described formula 6, formula 7 and formula 8, x is 4 ~ 10;
2) compound shown in compound and formula 9 shown in compound shown in formula 7 or formula 8 is carried out back flow reaction in solvent, obtains compound shown in formula 1 or formula 2,
3. preparation method according to claim 2, is characterized in that: step 1) in, described inert atmosphere is nitrogen atmosphere and/or argon gas atmosphere;
Shown in described formula 5, shown in compound and described formula 6, the mol ratio of compound is (1-1.5): 1;
The temperature of reaction of described reaction is 20 ~ 70 DEG C, and the reaction times is 0.5-3h.
Described solvent is water or ethanol.
4. the preparation method according to Claims 2 or 3, is characterized in that: step 2) in, shown in compound shown in described formula 7 or formula 8, shown in compound and formula 9, the mol ratio of compound is (1-2): 1;
The temperature of reaction of described back flow reaction is 50-100 DEG C, and the reaction times is 2-3h;
Described solvent is water or ethanol.
5. the preparation method of compound shown in formula 3 according to claim 1 or formula 4, comprises the steps: compound shown in formula 1 or formula 2 and mineral alkali to react in solvent, obtains compound shown in formula 3 or formula 4.
6. preparation method according to claim 5, is characterized in that: shown in described formula 1 or formula 2, the mol ratio of compound and mineral alkali is (0.5-1): 1;
Described mineral alkali is the alkali that the metal pair of monovalence or divalence is answered;
The temperature of reaction of described acid-base reaction is 50-100 DEG C, and the reaction times is 0.5-2h;
Described solvent is water.
7. preparation method according to claim 6, is characterized in that: described mineral alkali is NaOH, KOH, Ca (OH)
2or Mg (OH)
2in any one.
8. compound shown in compound shown in formula 1 according to claim 1 and/or formula 2 and corresponding water soluble ion salt formula 3 thereof and/or formula 4 is preparing the application in fire retardant material.
9. application according to claim 8, is characterized in that: described fire retardant material is Flameproof polyamide.
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Application publication date: 20151118 |