CN104311876A - Polymerization type phosphorus-containing flame retardant as well as preparation method and application thereof as epoxy resin flame retardant - Google Patents
Polymerization type phosphorus-containing flame retardant as well as preparation method and application thereof as epoxy resin flame retardant Download PDFInfo
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Abstract
The invention discloses a polymerization type phosphorus-containing flame retardant as well as a preparation method and application thereof as an epoxy resin flame retardant, relates to a hydrolysis-resisting phosphorus-containing flame retardant and a preparation method thereof, and solves the problems that a conventional phosphorus-containing flame retardant is low in thermal stability, easy to hydrolyte and hard to process. The structural formula of the phosphorus-containing flame retardant is as shown in the specification. The preparation method comprises the following steps: by taking phosphoric acid or sulfuric acid as a catalyst, adding a trisphosphine oxide solution or a tertphosphine oxide solution, a reaction solvent and an additive into a reaction container, adding a melamine or amine compound at the room temperature, adjusting the pH value, heating at a certain stirring speed, reacting at certain temperature, performing backflow reaction, cooling to be the room temperature, sequentially performing suction filtration, washing in water and drying, thereby obtaining white powder solid, that is, the polymerization type phosphorus-containing flame retardant. The polymerized type phosphorus-containing flame retardant can be used as the epoxy resin flame retardant which is added into epoxy resin.
Description
Technical field
The present invention relates to phosphonium flame retardant of a kind of hydrolysis and preparation method thereof and the application as Fire Retardant of The Expoxy Resin.
Background technology
Polymer materials has excellent over-all properties and is widely used in the fields such as aerospace, electronic apparatus, automotive industry, but the harm such as the inflammableness of polymer materials and burning release toxic gas hinders them applies widely.Fire retardant is the functional aid that a class can give polymer materials flame retardancy, and halogenated flame retardant especially brominated flame-retardant has the advantages such as flame retarding efficiency is high, cheap and is widely used.But halogenated flame retardant can generate a large amount of dense smoke and corrosive toxic gas when thermo-cracking or burning, as: polybrominated dibenzo-furan, dioxin etc., based on the requirement of environmental protection and Sustainable development, some halogen containing flame-retardants are disabled, from the promulgation of European Union RoHS and WEEE in 2003 two instructions, make the cry of developing green halogen-free environment-friendlyflame flame retardant more and more higher.
Organic phosphonium flame retardant has low cigarette, the advantage such as nontoxic in combustion, more environmental protection during use, and being recognized is one of the staple product of alternative halogen containing flame-retardant, has good development prospect.Current organic phosphonium flame retardant great majority are liquid, as BDP, RDP, TPP etc., and poor heat resistance and facile hydrolysis.Simultaneously along with the enforcement of RoHS instruction, make that material is unleaded becomes trend, and the use temperature containing lead system than tradition is improve 30 ~ 50 DEG C by the use temperature of leadless welding material, require that material can bear higher processing temperature, this just requires that fire retardant material has good thermostability and processing characteristics, and some traditional phosphorus flame retardants cannot reach such requirement.Fire retardant material is out of doors or when using in the environment of humidity, and the decline of the surface that fire retardant hydrolysis occurs or the moves to material performance such as material then can be caused fire-retardant, worsens the performance of material.In recent years along with the fast development of electronic industry, people have higher requirement to electric industrial material, the requirement of environmental protection improved further, simultaneously obtained flame retardant products demand fulfillment fire retardant addition is few, good mechanical property, thermostability are high, hydrolysis, the feature such as not move.For this reason, in the urgent need to research and development, there is highly effective flame-retardant, consistency is good, thermostability is high and the phosphorus flame retardant of hydrolysis, to adapt to fast-developing high-technology field to the high request of fire retardant material.
Summary of the invention
The object of the invention is to solve that the thermostability that existing phosphonium flame retardant exists is low, the problem of facile hydrolysis, processing difficulties, and polymeric phosphorus-containing flame retardant and preparation method thereof and the application as Fire Retardant of The Expoxy Resin are provided.
Polymeric phosphorus-containing flame retardant, its general structure is:
The preparation method of above-mentioned polymeric phosphorus-containing flame retardant, specifically prepares according to the following steps:
Adopt water as reaction solvent, with the trishydroxymethyl phosphorus oxide aqueous solution for starting raw material, using phosphoric acid or sulfuric acid as catalyzer, at room temperature by the trishydroxymethyl phosphorus oxide aqueous solution, reaction solvent and catalyzer add in reaction vessel, then at room temperature trimeric cyanamide is added, again pH value is adjusted to 4 ~ 6, low whipping speed is that 300r/min ~ 400r/min stirs, then low whipping speed be under 300r/min ~ 400r/min with temperature rise rate 5 DEG C/min from room temperature to 85 DEG C ~ 95 DEG C, 10min ~ 15min is reacted at temperature is 85 DEG C ~ 95 DEG C, then be 85 DEG C ~ 95 DEG C with temperature rise rate 2 DEG C/min from temperature and be warming up to reaction solvent reflux temperature, sustained reaction 2h ~ 3h under reaction solvent reflux temperature, after being cooled to room temperature, then suction filtration is carried out successively, white powdery solids is obtained after washing and oven dry, the massfraction of the described trishydroxymethyl phosphorus oxide aqueous solution is 97%, the mass ratio of described trimeric cyanamide and the trishydroxymethyl phosphorus oxide aqueous solution is 1:(1 ~ 1.1), the described quality of the trishydroxymethyl phosphorus oxide aqueous solution and the volume ratio of water are 1g:(1 ~ 2) mL, the described quality of the trishydroxymethyl phosphorus oxide aqueous solution and the volume ratio of catalyzer are 50g:(3 ~ 4) mL,
The general structure of described polymeric phosphorus-containing flame retardant is:
Polymeric phosphorus-containing flame retardant, its general structure is:
The preparation method of above-mentioned polymeric phosphorus-containing flame retardant, specifically prepares according to the following steps:
Adopt water as reaction solvent, with the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution for starting raw material, using phosphoric acid or sulfuric acid as catalyzer, at room temperature by the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution, reaction solvent and catalyzer add in reaction vessel, then at room temperature trimeric cyanamide is added, again pH value is adjusted to 4 ~ 6, low whipping speed is stir under 300r/min ~ 400r/min, then low whipping speed be under 300r/min ~ 400r/min with temperature rise rate 5 DEG C/min from room temperature to 85 DEG C ~ 95 DEG C, 10min ~ 15min is reacted at temperature is 85 DEG C ~ 95 DEG C, then be 85 DEG C ~ 95 DEG C with temperature rise rate 2 DEG C/min from temperature and be warming up to reaction solvent reflux temperature, sustained reaction 2h ~ 3h under reaction solvent reflux temperature, after being cooled to room temperature, then suction filtration is carried out successively, white solid is obtained after washing and oven dry, described tetrakis hydroxymetyl phosphonium sulfuric aqueous solution massfraction is 75%, the mass ratio of described trimeric cyanamide and the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution is 1:(1.5 ~ 1.7), the quality of the described tetrakis hydroxymetyl phosphonium sulfuric aqueous solution and the volume ratio of water are 1g:(1 ~ 1.2) mL, the quality of the described tetrakis hydroxymetyl phosphonium sulfuric aqueous solution and the volume ratio of catalyzer are 50g:(3 ~ 4) mL,
The general structure of described polymeric phosphorus-containing flame retardant is:
Polymeric phosphorus-containing flame retardant, its general structure is:
n=2,3,4 in general structure ..., in general structure, R is
or
and
middle m=2,3,4 ...
The preparation method of above-mentioned polymeric phosphorus-containing flame retardant, specifically prepares according to the following steps:
Adopt water as reaction solvent, with the trishydroxymethyl phosphorus oxide aqueous solution for starting raw material, using phosphoric acid or sulfuric acid as catalyzer, at room temperature by the trishydroxymethyl phosphorus oxide aqueous solution, reaction solvent and catalyzer add in reaction vessel, then at room temperature aminated compounds is added, again pH value is adjusted to 4 ~ 6, low whipping speed is stir under 300r/min ~ 400r/min, then low whipping speed be under 300r/min ~ 400r/min with temperature rise rate 5 DEG C/min from room temperature to 85 DEG C ~ 95 DEG C, 15min is reacted at temperature is 85 DEG C ~ 95 DEG C, then be 85 DEG C ~ 95 DEG C with temperature rise rate 2 DEG C/min from temperature and be warming up to reaction solvent reflux temperature, sustained reaction 2h ~ 3h under reaction solvent reflux temperature, after being cooled to room temperature, then suction filtration is carried out successively, pale yellow powder is obtained after washing and oven dry, described trishydroxymethyl phosphorus oxide aqueous solution massfraction is 97%, the mol ratio of described aminated compounds and the trishydroxymethyl phosphorus oxide aqueous solution is 3:2, the described quality of the trishydroxymethyl phosphorus oxide aqueous solution and the volume ratio of water are 100g:(30 ~ 40) mL, the described quality of the trishydroxymethyl phosphorus oxide aqueous solution and the volume ratio of catalyzer are 50g:(3 ~ 4) mL, described aminated compounds is quadrol or urea,
The general structure of described polymeric phosphorus-containing flame retardant is:
n=2,3,4 in general structure ...
Polymeric phosphorus-containing flame retardant, its general structure is:
n=2,3,4 in general structure ...
The preparation method of above-mentioned polymeric phosphorus-containing flame retardant, specifically prepares according to the following steps:
Adopt water as reaction solvent, with the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution for starting raw material, using phosphoric acid or sulfuric acid as catalyzer, at room temperature by the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution, reaction solvent and catalyzer add in reaction vessel, then at room temperature aminated compounds is added, again pH value is adjusted to 4 ~ 6, low whipping speed is stir under 300r/min ~ 400r/min, then low whipping speed be under 300r/min ~ 400r/min with temperature rise rate 5 DEG C/min from room temperature to 85 DEG C ~ 95 DEG C, 10min is reacted at temperature is 85 DEG C ~ 95 DEG C, then be 85 DEG C ~ 95 DEG C with temperature rise rate 2 DEG C/min from temperature and be warming up to reaction solvent reflux temperature, sustained reaction 2h ~ 3h under reaction solvent reflux temperature, after being cooled to room temperature, then suction filtration is carried out successively, solid is obtained after washing and oven dry, described tetrakis hydroxymetyl phosphonium sulfuric aqueous solution massfraction is 75%, the mol ratio of described aminated compounds and the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution is 4:1, the quality of the described tetrakis hydroxymetyl phosphonium sulfuric aqueous solution and the volume ratio of water are 100g:(30 ~ 40) mL, the quality of the described tetrakis hydroxymetyl phosphonium sulfuric aqueous solution and the volume ratio of catalyzer are 50g:(3 ~ 4) mL, described aminated compounds is quadrol or urea,
The general structure of described polymeric phosphorus-containing flame retardant is:
n=2,3,4 in general structure ...
Polymeric phosphorus-containing flame retardant, its general structure is:
n=2,3,4 in general structure ...
The preparation method of above-mentioned polymeric phosphorus-containing flame retardant, specifically prepares according to the following steps:
Adopt distilled water as reaction solvent, with the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution for starting raw material, using phosphoric acid or sulfuric acid as catalyzer, at room temperature by piperazine, distilled water and catalyzer join in reaction vessel, low whipping speed is be stirred under 300r/min ~ 400r/min to dissolve completely, then constant pressure funnel is adopted to drip the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution that massfraction is 75%, dropwise rear heating in water bath and be warming up to 85 DEG C ~ 95 DEG C, and 2h is reacted under temperature is 85 DEG C ~ 95 DEG C and stirring velocity is 300r/min ~ 400r/min, after being cooled to room temperature, decompress filter obtains white solid powder, distilled water is utilized to wash 3 times to white solid powder, then at temperature is 105 DEG C, 2h ~ 3h is dried, obtain pale yellow powder, the mass ratio of described piperazine and the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution is 1:(1.5 ~ 1.6), the quality of the described tetrakis hydroxymetyl phosphonium sulfuric aqueous solution and the volume ratio of distilled water are 1g:(1 ~ 3) mL, the quality of the described tetrakis hydroxymetyl phosphonium sulfuric aqueous solution and the volume ratio of catalyzer are 50g:(3 ~ 4) mL,
The general structure of described polymeric phosphorus-containing flame retardant is:
n=2,3,4 in general structure ...
Polymeric phosphorus-containing flame retardant is as the application of Fire Retardant of The Expoxy Resin, add in epoxy resin as Fire Retardant of The Expoxy Resin and mphenylenediamine as epoxy curing agent, obtain fire retarding epoxide resin cured article, when polymeric phosphorus-containing flame retardant addition reaches 10wt% ~ 15wt%, the test of fire retarding epoxide resin cured article vertical combustion is by UL-94V-0 level.
Advantage of the present invention: contain P-C key in the polymeric phosphorus-containing flame retardant molecular structure that, prepared by the present invention, heat-resisting hydrolysis, product is white or flaxen powder, productive rate is more than 94%, 1% thermal weight loss decomposition temperature is all more than 210 DEG C, in a nitrogen atmosphere, 800 DEG C time neat coal amout all more than 35%.Product expands at foamable, and final generation is expanded and loosened and the layer of charcoal of good strength, and it has into charcoal and swelling capacity is strong, the advantage of Heat stability is good; Two, the present invention adopts water to make solvent, and reaction process is continuous reaction, and synthesis technique is simple, and the reaction times is short, usually only needs 3 ~ 4h, has greatly saved energy consumption, improve production efficiency, reduced production cost; Three, compared with prior art, the Heat stability is good of polymeric phosphorus-containing flame retardant prepared by the present invention, and there is good anti-hydrolytic performance, the fire retardant of synthesis is boiled in the water of 100 DEG C filtering drying after 2 hours, the mass loss of fire retardant is only about 0.6wt%; The consistency of polymeric phosphorus-containing flame retardant prepared by the present invention and blended polymeric substrate is good, not easily move, can ensure Flame Retardancy can weather resistance, overcome small molecules phosphate flame retardant heat decomposition temperature low, with polymeric matrix poor compatibility and the shortcoming of easily moving.Compared with existing aggretion type phosphorus flame retardant, it has the carbon-forming performance that well expands, flame retarding efficiency is high, during for fire retarding epoxide resin, when the addition of polymeric phosphorus-containing flame retardant is only 10 ~ 15%, the limiting oxygen index(LOI) of epoxide resin material has brought up to more than 30% by 17.8%, and vertical combustion grade reaches UL-94V-0 level.
Accompanying drawing explanation
Fig. 1 is to the polymeric phosphorus-containing flame retardant infrared spectrum of test seven preparation;
Fig. 2 is the polymeric phosphorus-containing flame retardant of this test preparation
13c-NMR spectrogram;
Fig. 3 be this test preparation polymeric phosphorus-containing flame retardant
31p-NMR spectrogram.
Embodiment
Embodiment one: present embodiment is polymeric phosphorus-containing flame retardant, its general structure is:
Embodiment two: present embodiment is the preparation method of polymeric phosphorus-containing flame retardant, specifically prepares according to the following steps:
Adopt water as reaction solvent, with the trishydroxymethyl phosphorus oxide aqueous solution for starting raw material, using phosphoric acid or sulfuric acid as catalyzer, at room temperature by the trishydroxymethyl phosphorus oxide aqueous solution, reaction solvent and catalyzer add in reaction vessel, then at room temperature trimeric cyanamide is added, again pH value is adjusted to 4 ~ 6, low whipping speed is that 300r/min ~ 400r/min stirs, then low whipping speed be under 300r/min ~ 400r/min with temperature rise rate 5 DEG C/min from room temperature to 85 DEG C ~ 95 DEG C, 10min ~ 15min is reacted at temperature is 85 DEG C ~ 95 DEG C, then be 85 DEG C ~ 95 DEG C with temperature rise rate 2 DEG C/min from temperature and be warming up to reaction solvent reflux temperature, sustained reaction 2h ~ 3h under reaction solvent reflux temperature, after being cooled to room temperature, then suction filtration is carried out successively, white powdery solids is obtained after washing and oven dry, the massfraction of the described trishydroxymethyl phosphorus oxide aqueous solution is 97%, the mass ratio of described trimeric cyanamide and the trishydroxymethyl phosphorus oxide aqueous solution is 1:(1 ~ 1.1), the described quality of the trishydroxymethyl phosphorus oxide aqueous solution and the volume ratio of water are 1g:(1 ~ 2) mL, the described quality of the trishydroxymethyl phosphorus oxide aqueous solution and the volume ratio of catalyzer are 50g:(3 ~ 4) mL,
The general structure of the polymeric phosphorus-containing flame retardant described in present embodiment is:
Present embodiment is reacted reaction system in 10min ~ 15min process and is become clear by white opacity at temperature is 85 DEG C ~ 95 DEG C, then produces the solid particulate of white gradually.
Embodiment three: present embodiment is polymeric phosphorus-containing flame retardant, its general structure is:
Embodiment four: present embodiment is the preparation method of polymeric phosphorus-containing flame retardant, specifically prepares according to the following steps:
Adopt water as reaction solvent, with the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution for starting raw material, using phosphoric acid or sulfuric acid as catalyzer, at room temperature by the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution, reaction solvent and catalyzer add in reaction vessel, then at room temperature trimeric cyanamide is added, again pH value is adjusted to 4 ~ 6, low whipping speed is stir under 300r/min ~ 400r/min, then low whipping speed be under 300r/min ~ 400r/min with temperature rise rate 5 DEG C/min from room temperature to 85 DEG C ~ 95 DEG C, 10min ~ 15min is reacted at temperature is 85 DEG C ~ 95 DEG C, then be 85 DEG C ~ 95 DEG C with temperature rise rate 2 DEG C/min from temperature and be warming up to reaction solvent reflux temperature, sustained reaction 2h ~ 3h under reaction solvent reflux temperature, after being cooled to room temperature, then suction filtration is carried out successively, white solid is obtained after washing and oven dry, described tetrakis hydroxymetyl phosphonium sulfuric aqueous solution massfraction is 75%, the mass ratio of described trimeric cyanamide and the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution is 1:(1.5 ~ 1.7), the quality of the described tetrakis hydroxymetyl phosphonium sulfuric aqueous solution and the volume ratio of water are 1g:(1 ~ 1.2) mL, the quality of the described tetrakis hydroxymetyl phosphonium sulfuric aqueous solution and the volume ratio of catalyzer are 50g:(3 ~ 4) mL,
The general structure of the polymeric phosphorus-containing flame retardant described in present embodiment is:
Embodiment five: present embodiment is polymeric phosphorus-containing flame retardant, its general structure is:
n=2,3,4 in general structure ..., in general structure, R is
or
and
middle m=2,3,4 ...
Embodiment six: present embodiment is the preparation method of polymeric phosphorus-containing flame retardant, specifically prepares according to the following steps:
Adopt water as reaction solvent, with the trishydroxymethyl phosphorus oxide aqueous solution for starting raw material, using phosphoric acid or sulfuric acid as catalyzer, at room temperature by the trishydroxymethyl phosphorus oxide aqueous solution, reaction solvent and catalyzer add in reaction vessel, then at room temperature aminated compounds is added, again pH value is adjusted to 4 ~ 6, low whipping speed is stir under 300r/min ~ 400r/min, then low whipping speed be under 300r/min ~ 400r/min with temperature rise rate 5 DEG C/min from room temperature to 85 DEG C ~ 95 DEG C, 15min is reacted at temperature is 85 DEG C ~ 95 DEG C, then be 85 DEG C ~ 95 DEG C with temperature rise rate 2 DEG C/min from temperature and be warming up to reaction solvent reflux temperature, sustained reaction 2h ~ 3h under reaction solvent reflux temperature, after being cooled to room temperature, then suction filtration is carried out successively, pale yellow powder is obtained after washing and oven dry, described trishydroxymethyl phosphorus oxide aqueous solution massfraction is 97%, the mol ratio of described aminated compounds and the trishydroxymethyl phosphorus oxide aqueous solution is 3:2, the described quality of the trishydroxymethyl phosphorus oxide aqueous solution and the volume ratio of water are 100g:(30 ~ 40) mL, the described quality of the trishydroxymethyl phosphorus oxide aqueous solution and the volume ratio of catalyzer are 50g:(3 ~ 4) mL, described aminated compounds is quadrol or urea,
The general structure of the polymeric phosphorus-containing flame retardant described in present embodiment is:
n=2,3,4 in general structure ...
Embodiment seven: present embodiment is polymeric phosphorus-containing flame retardant, its general structure is:
n=2,3,4 in general structure ...
Embodiment eight: present embodiment is the preparation method of polymeric phosphorus-containing flame retardant, specifically prepares according to the following steps:
Adopt water as reaction solvent, with the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution for starting raw material, using phosphoric acid or sulfuric acid as catalyzer, at room temperature by the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution, reaction solvent and catalyzer add in reaction vessel, then at room temperature aminated compounds is added, again pH value is adjusted to 4 ~ 6, low whipping speed is stir under 300r/min ~ 400r/min, then low whipping speed be under 300r/min ~ 400r/min with temperature rise rate 5 DEG C/min from room temperature to 85 DEG C ~ 95 DEG C, 10min is reacted at temperature is 85 DEG C ~ 95 DEG C, then be 85 DEG C ~ 95 DEG C with temperature rise rate 2 DEG C/min from temperature and be warming up to reaction solvent reflux temperature, sustained reaction 2h ~ 3h under reaction solvent reflux temperature, after being cooled to room temperature, then suction filtration is carried out successively, solid is obtained after washing and oven dry, described tetrakis hydroxymetyl phosphonium sulfuric aqueous solution massfraction is 75%, the mol ratio of described aminated compounds and the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution is 4:1, the quality of the described tetrakis hydroxymetyl phosphonium sulfuric aqueous solution and the volume ratio of water are 100g:(30 ~ 40) mL, the quality of the described tetrakis hydroxymetyl phosphonium sulfuric aqueous solution and the volume ratio of catalyzer are 50g:(3 ~ 4) mL, described aminated compounds is quadrol or urea,
The general structure of the polymeric phosphorus-containing flame retardant described in present embodiment is:
n=2,3,4 in general structure ...
Embodiment nine: present embodiment is polymeric phosphorus-containing flame retardant, its general structure is:
n=2,3,4 in general structure ...
Embodiment ten: present embodiment is the preparation method of polymeric phosphorus-containing flame retardant, specifically prepares according to the following steps:
Adopt distilled water as reaction solvent, with the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution for starting raw material, using phosphoric acid or sulfuric acid as catalyzer, at room temperature by piperazine, distilled water and catalyzer join in reaction vessel, low whipping speed is be stirred under 300r/min ~ 400r/min to dissolve completely, then constant pressure funnel is adopted to drip the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution that massfraction is 75%, dropwise rear heating in water bath and be warming up to 85 DEG C ~ 95 DEG C, and 2h is reacted under temperature is 85 DEG C ~ 95 DEG C and stirring velocity is 300r/min ~ 400r/min, after being cooled to room temperature, decompress filter obtains white solid powder, distilled water is utilized to wash 3 times to white solid powder, then at temperature is 105 DEG C, 2h ~ 3h is dried, obtain pale yellow powder, the mass ratio of described piperazine and the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution is 1:(1.5 ~ 1.6), the quality of the described tetrakis hydroxymetyl phosphonium sulfuric aqueous solution and the volume ratio of distilled water are 1g:(1 ~ 3) mL, the quality of the described tetrakis hydroxymetyl phosphonium sulfuric aqueous solution and the volume ratio of catalyzer are 50g:(3 ~ 4) mL,
The general structure of described polymeric phosphorus-containing flame retardant is:
n=2,3,4 in general structure ...
Embodiment 11: present embodiment is the application of polymeric phosphorus-containing flame retardant as Fire Retardant of The Expoxy Resin, polymeric phosphorus-containing flame retardant adds in epoxy resin as Fire Retardant of The Expoxy Resin and mphenylenediamine as epoxy curing agent, obtain fire retarding epoxide resin cured article, when polymeric phosphorus-containing flame retardant addition reaches 10wt% ~ 15wt%, the test of fire retarding epoxide resin cured article vertical combustion is by UL-94V-0 level.
Adopt following verification experimental verification effect of the present invention
Test one: the preparation method of polymeric phosphorus-containing flame retardant, specifically prepare according to the following steps:
Adopt water as reaction solvent, with the trishydroxymethyl phosphorus oxide aqueous solution for starting raw material, using phosphoric acid as catalyzer, at room temperature by the 50.0g trishydroxymethyl phosphorus oxide aqueous solution, 100mL reaction solvent and 4mL catalyzer add in reaction vessel, then 49.2g trimeric cyanamide is at room temperature added, again pH value is adjusted to 5, low whipping speed is that 300r/min stirs, then low whipping speed be under 300r/min with temperature rise rate 5 DEG C/min from room temperature to 92 DEG C, 10min is reacted at temperature is 92 DEG C, then be 92 DEG C with temperature rise rate 2 DEG C/min from temperature and be warming up to reaction solvent reflux temperature, sustained reaction 2h under reaction solvent reflux temperature, after being cooled to room temperature, then suction filtration is carried out successively, white powdery solids is obtained after washing and oven dry, the massfraction of the described trishydroxymethyl phosphorus oxide aqueous solution is 97%,
The general structure of the polymeric phosphorus-containing flame retardant described in this test is:
Known by calculating, the polymeric phosphorus-containing flame retardant productive rate that this test obtains is 95.2%.Be 317 DEG C by testing the initial heat decomposition temperature of the polymeric phosphorus-containing flame retardant that known test obtains, carbon left when 800 DEG C is 33.5%.
Test two: polymeric phosphorus-containing flame retardant is as the application of Fire Retardant of The Expoxy Resin, polymeric phosphorus-containing flame retardant adds in epoxy resin as Fire Retardant of The Expoxy Resin and mphenylenediamine as epoxy curing agent, obtain fire retarding epoxide resin cured article, when polymeric phosphorus-containing flame retardant addition is 10wt%, the test of fire retarding epoxide resin cured article vertical combustion is by UL-94V-0 level.
Polymeric phosphorus-containing flame retardant described in this test is prepared by test one.
Polymeric phosphorus-containing flame retardant embody rule process described in this test is as follows:
Polymeric phosphorus-containing flame retardant (polymeric phosphorus-containing flame retardant is as Fire Retardant of The Expoxy Resin) is added in 50g epoxy resin, after being uniformly mixed at 120 DEG C, add 7.42g mphenylenediamine (mphenylenediamine is as the solidifying agent of epoxy resin), continue to be stirred to mphenylenediamine to dissolve, be poured into after mixing in Standard Module, under 150 DEG C of conditions, solidify 2h, be cooled to room temperature rear demoulding, obtain fire retarding epoxide resin cured article; In described fire retarding epoxide resin cured article, polymeric phosphorus-containing flame retardant addition is 10wt%.
To fire retarding epoxide resin cured article by limiting oxygen index(LOI) and vertical combustion test, when the addition of polymeric phosphorus-containing flame retardant is 10wt%, the vertical combustion test of material just can reach UL-94V-0 level, and limiting oxygen index(LOI) reaches 30.4%.Fire retarding epoxide resin cured article is put in constant temperature 70 DEG C of water baths and keep 168h, water is changed every 24h, take out post-drying, limiting oxygen index(LOI) and vertical combustion test are carried out to this material, the vertical combustion test of this material is still by UL-94V-0 level, limiting oxygen index(LOI) slightly declines, and is 29.1%.
Test three: the preparation method of polymeric phosphorus-containing flame retardant, specifically prepare according to the following steps:
Adopt water as reaction solvent, with the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution for starting raw material, using sulfuric acid as catalyzer, at room temperature by the 50.0g tetrakis hydroxymetyl phosphonium sulfuric aqueous solution, 60mL reaction solvent and 4mL catalyzer add in reaction vessel, then 17.0g trimeric cyanamide is at room temperature added, again pH value is adjusted to 5, low whipping speed is stir under 300r/min, then low whipping speed be under 300r/min with temperature rise rate 5 DEG C/min from room temperature to 92 DEG C, 10min is reacted at temperature is 92 DEG C, then be 92 DEG C with temperature rise rate 2 DEG C/min from temperature and be warming up to reaction solvent reflux temperature, sustained reaction 2h under reaction solvent reflux temperature, after being cooled to room temperature, then suction filtration is carried out successively, white solid is obtained after washing and oven dry, described tetrakis hydroxymetyl phosphonium sulfuric aqueous solution massfraction is 75%,
The general structure of the polymeric phosphorus-containing flame retardant described in this test is:
chemical name is trimeric cyanamide tetramethylene sulfuric acid phosphorus oligopolymer.
Known by calculating, polymeric phosphorus-containing flame retardant (the trimeric cyanamide tetramethylene sulfuric acid phosphorus oligopolymer) productive rate that this test obtains is 94.15%.Be 313 DEG C by testing the initial heat decomposition temperature of the polymeric phosphorus-containing flame retardant that known test obtains, carbon left when 800 DEG C reaches 43.5%.
Test four: polymeric phosphorus-containing flame retardant is as the application of Fire Retardant of The Expoxy Resin, polymeric phosphorus-containing flame retardant adds in epoxy resin as Fire Retardant of The Expoxy Resin and mphenylenediamine as epoxy curing agent, obtain fire retarding epoxide resin cured article, when polymeric phosphorus-containing flame retardant addition is 11 ~ 15wt%, the test of fire retarding epoxide resin cured article vertical combustion is by UL-94V-0 level.
Polymeric phosphorus-containing flame retardant described in this test is prepared by test three.
Polymeric phosphorus-containing flame retardant embody rule process described in this test is as follows:
Polymeric phosphorus-containing flame retardant (polymeric phosphorus-containing flame retardant is as Fire Retardant of The Expoxy Resin) is added in 25g epoxy resin, 30min is stirred at 120 DEG C, add 3.18g mphenylenediamine (mphenylenediamine is as the solidifying agent of epoxy resin), continue to be stirred to mphenylenediamine to dissolve, be poured into after mixing in Standard Module, under 150 DEG C of conditions, solidify 2h, naturally cool to room temperature, after demoulding, obtain fire retarding epoxide resin cured article.
The addition of polymeric phosphorus-containing flame retardant and the relation of fire retarding epoxide resin Solidified enzyme as shown in table 1.As can be seen from Table 1, when the addition of polymeric phosphorus-containing flame retardant is only 11wt%, the oxygen index of material has brought up to 31.1% by 17.8%, and the vertical combustion grade of material have passed UL-94V-0 level.
Fire retarding epoxide resin cured article is put in constant temperature 70 DEG C of water baths, change water every 24h, keep 168h, by sample drying after taking-up, test limiting oxygen index(LOI) and the vertical combustion of this sample, as shown in table 1.In table 1, data show, flame-retardant epoxide resin material is after water-fast test, with the addition of the fire retarding epoxide resin cured article of the polymeric phosphorus-containing flame retardant of 11wt% still by UL-94V-0 level, the limiting oxygen index(LOI) of material remains unchanged substantially, show that material still maintains extraordinary flame retardant properties after poach test, fire retardant has good water resistance.
The addition of table 1 polymeric phosphorus-containing flame retardant and fire retarding epoxide resin Solidified enzyme
Test five: the preparation method of polymeric phosphorus-containing flame retardant, specifically prepare according to the following steps:
Adopt water as reaction solvent, with the trishydroxymethyl phosphorus oxide aqueous solution for starting raw material, using phosphoric acid as catalyzer, at room temperature by the 100.0g trishydroxymethyl phosphorus oxide aqueous solution, 40mL reaction solvent and 4mL catalyzer add in reaction vessel, then 32.26g aminated compounds is at room temperature added, again pH value is adjusted to 5, low whipping speed is stir under 300r/min, then low whipping speed be under 300r/min with temperature rise rate 5 DEG C/min from room temperature to 90 DEG C, 15min is reacted at temperature is 90 DEG C, then be 90 DEG C with temperature rise rate 2 DEG C/min from temperature and be warming up to reaction solvent reflux temperature, sustained reaction 2h under reaction solvent reflux temperature, after being cooled to room temperature, then suction filtration is carried out successively, pale yellow powder is obtained after washing and oven dry, described trishydroxymethyl phosphorus oxide aqueous solution massfraction is 97%, described aminated compounds is quadrol,
The general structure of the polymeric phosphorus-containing flame retardant described in present embodiment is:
n=2,3,4 in general structure ...
Known through calculating, the polymeric phosphorus-containing flame retardant productive rate of this test preparation is 96.26%.Be 212 DEG C by testing the initial heat decomposition temperature of polymeric phosphorus-containing flame retardant of known test preparation, the carbon left 800 DEG C time is 30.4%.
Test six: polymeric phosphorus-containing flame retardant is as the application of Fire Retardant of The Expoxy Resin, polymeric phosphorus-containing flame retardant adds in epoxy resin as Fire Retardant of The Expoxy Resin and mphenylenediamine as epoxy curing agent, obtain fire retarding epoxide resin cured article, when polymeric phosphorus-containing flame retardant addition is 12wt%, the test of fire retarding epoxide resin cured article vertical combustion is by UL-94V-0 level.
Polymeric phosphorus-containing flame retardant described in this test is prepared by test five.
Polymeric phosphorus-containing flame retardant embody rule process described in this test is as follows:
Polymeric phosphorus-containing flame retardant (polymeric phosphorus-containing flame retardant is as Fire Retardant of The Expoxy Resin) is added in 50g epoxy resin, 30min is stirred at 120 DEG C, add 7.42g mphenylenediamine (mphenylenediamine is as the solidifying agent of epoxy resin), continue to be stirred to mphenylenediamine to dissolve, be poured into after mixing in Standard Module, 1h is kept in the baking oven of 105 DEG C, then under 150 DEG C of conditions, 2h is kept, naturally cool to room temperature, after demoulding, obtain fire retarding epoxide resin cured article; In described fire retarding epoxide resin cured article, polymeric phosphorus-containing flame retardant addition is 12wt%.
To fire retarding epoxide resin cured article by limiting oxygen index(LOI) and vertical combustion test, when the addition of polymeric phosphorus-containing flame retardant is 12wt%, the vertical combustion test of material just can reach UL-94V-0 level, and limiting oxygen index(LOI) brings up to 30.1% from 17.8%.Put into by fire retarding epoxide resin cured article in constant temperature 70 DEG C of water baths and keep 168h, change water every 24h, take out post-drying, carry out limiting oxygen index(LOI) and vertical combustion test to this material, the vertical combustion test of this material is still by UL-94V-0 level.
Test seven: the preparation method of polymeric phosphorus-containing flame retardant, specifically prepare according to the following steps:
Adopt water as reaction solvent, with the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution for starting raw material, using sulfuric acid as catalyzer, at room temperature by the 100.00g tetrakis hydroxymetyl phosphonium sulfuric aqueous solution, 30mL reaction solvent and 8mL catalyzer add in reaction vessel, then 26.61g aminated compounds is at room temperature added, again pH value is adjusted to 4 ~ 6, low whipping speed is stir under 300r/min, then low whipping speed be under 300r/min with temperature rise rate 5 DEG C/min from room temperature to 90 DEG C, 10min is reacted at temperature is 90 DEG C, then be 90 DEG C with temperature rise rate 2 DEG C/min from temperature and be warming up to reaction solvent reflux temperature, sustained reaction 2h under reaction solvent reflux temperature, after being cooled to room temperature, then suction filtration is carried out successively, solid is obtained after washing and oven dry, described tetrakis hydroxymetyl phosphonium sulfuric aqueous solution massfraction is 75%, described aminated compounds is urea,
The general structure of the polymeric phosphorus-containing flame retardant described in present embodiment is:
n=2,3,4 in general structure ...
Known through calculating, the polymeric phosphorus-containing flame retardant productive rate of this test preparation is 98.84%.Be 211.5 DEG C by testing the initial heat decomposition temperature of polymeric phosphorus-containing flame retardant of known test preparation, the carbon left 800 DEG C time is 38.1%.
Utilize Fourier infrared spectrograph to characterize polymeric phosphorus-containing flame retardant prepared by this test, as shown in Figure 1, Fig. 1 is to the polymeric phosphorus-containing flame retardant infrared spectrum of test seven preparation; Can find out from figure: 3250cm
-1locate the stretching vibration peak that wide absorption peak is N-H; 2973cm
-1, 2914cm
-1two place's absorption peaks are methylene radical stretching vibration peak; 1671cm
-1place's absorption peak is C=O stretching vibration; 1551cm
-1place's absorption peak is N-H flexural vibration; 1391cm
-1place's absorption peak is C-N stretching vibration; 1248cm
-1place's absorption peak is P-C stretching vibration; 1107cm
-1, 1043cm
-1two place's absorption peaks are C-O stretching vibration, 866cm
-1place's absorption peak is S-O stretching vibration; As can be seen from infrared spectrum, at 3400cm
-1, 3500cm
-1near there is not the symmetrical and asymmetric stretching vibration particular peaks of the N-H of two medium tenacitys of primary amide, illustrate that primary amide take part in dehydration reaction, to sum up tentatively determining target product is that part of hydroxyl and amino carry out shrink and reacts and generate.
Fig. 2 is the polymeric phosphorus-containing flame retardant of this test preparation
13c-NMR spectrogram, as can be seen from the figure, is positioned at the chemical shift that peak, 159.2ppm place is the carbonyl of product; Be positioned at 32.6ppm-52.6ppm place and occurred that multiplet is methylene radical (-CH
2-) chemical shift.
Fig. 3 be this test preparation polymeric phosphorus-containing flame retardant
31p-NMR spectrogram.In figure, 28.4ppm place has a very strong peak to be the chemical shift of P in product, illustrates that in product, most of P is present in this chemical environment.In addition, having occurred three small peaks at 66.39ppm ,-8.55ppm and-38.02ppm place, is due under certain conditions, and a small amount of tetra methylol phosphorus oxide is converted into the material such as tris(hydroxymethyl)phosphine and trishydroxymethyl phosphine oxide in reaction process.
Determining target product is in sum that part of hydroxyl and amino carry out shrink and reacts and generate, and structural formula is
chemical name is tetrakis hydroxymetyl phosphonium sulfuric-quadrol oligopolymer.
Test eight: polymeric phosphorus-containing flame retardant is as the application of Fire Retardant of The Expoxy Resin, polymeric phosphorus-containing flame retardant adds in epoxy resin as Fire Retardant of The Expoxy Resin and mphenylenediamine as epoxy curing agent, obtain fire retarding epoxide resin cured article, when polymeric phosphorus-containing flame retardant addition is 11wt% ~ 15wt%, the test of fire retarding epoxide resin cured article vertical combustion is by UL-94V-0 level.
Polymeric phosphorus-containing flame retardant described in this test is prepared by test seven.
Polymeric phosphorus-containing flame retardant embody rule process described in this test is as follows:
Polymeric phosphorus-containing flame retardant (polymeric phosphorus-containing flame retardant is as Fire Retardant of The Expoxy Resin) is added in 50g epoxy resin, 30min is stirred at 120 DEG C, add 7.42g mphenylenediamine (mphenylenediamine is as the solidifying agent of epoxy resin), continue to be stirred to mphenylenediamine to dissolve, be poured into after mixing in Standard Module, 1h is kept in the baking oven of 105 DEG C, then under 150 DEG C of conditions, 2h is kept, naturally cool to room temperature, after demoulding, obtain fire retarding epoxide resin cured article.
Relation between the addition of polymeric phosphorus-containing flame retardant and fire retarding epoxide resin Solidified enzyme is shown in as shown in table 2.As can be seen from Table 2, when the interpolation of fire retardant is only 12wt%, the limiting oxygen index(LOI) of material has brought up to 28.0% from 17.8%, and the burning rank of material reaches UL-94V-0 level.
Fire retarding epoxide resin cured article is put in constant temperature 70 DEG C of water baths, change water every 24h, keep 168h, by sample drying after taking-up, test limiting oxygen index(LOI) and the vertical combustion of this sample, as shown in table 2.In table 2, data show, flame-retardant epoxide resin material is after water-fast test, with the addition of the fire retarding epoxide resin cured article of the polymeric phosphorus-containing flame retardant of 12wt% still by UL-94V-0 level, the limiting oxygen index(LOI) of material slightly declines, show that material still maintains extraordinary flame retardant properties after poach test, fire retardant has good water resistance.
The addition of table 2. polymeric phosphorus-containing flame retardant and fire retarding epoxide resin Solidified enzyme
Test nine: the preparation method of polymeric phosphorus-containing flame retardant, specifically prepare according to the following steps:
Adopt distilled water as reaction solvent, with the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution for starting raw material, using sulfuric acid as catalyzer, at room temperature by 191.8g piperazine, 900mL distilled water and 24mL catalyzer join in reaction vessel, low whipping speed is be stirred under 300r/min to dissolve completely, then constant pressure funnel is adopted to drip the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution that 300g massfraction is 75%, dropwise rear heating in water bath and be warming up to 90 DEG C, and 2h is reacted under temperature is 90 DEG C and stirring velocity is 300r/min, after being cooled to room temperature, decompress filter obtains white solid powder, distilled water is utilized to wash 3 times to white solid powder, then at temperature is 105 DEG C, 2h is dried, obtain pale yellow powder,
The general structure of described polymeric phosphorus-containing flame retardant is:
n=2,3,4 in general structure ...
Known through calculating, the polymeric phosphorus-containing flame retardant productive rate of this test preparation is 96.8%.The polymeric phosphorus-containing flame retardant fusing point prepared by detecting this test is 286.0 ~ 289.7 DEG C.By thermogravimetric analyzer, polymeric phosphorus-containing flame retardant prepared by this test is tested, the initial heat decomposition temperature of the polymeric phosphorus-containing flame retardant of this test preparation is 217.5 DEG C, maximum heat rate of decomposition peak appears at 275.3 DEG C, and the carbon left 800 DEG C time is 22.3%.
Test ten: polymeric phosphorus-containing flame retardant is as the application of Fire Retardant of The Expoxy Resin, polymeric phosphorus-containing flame retardant adds in epoxy resin as Fire Retardant of The Expoxy Resin and mphenylenediamine as epoxy curing agent, obtain fire retarding epoxide resin cured article, when polymeric phosphorus-containing flame retardant addition is 11wt%, the test of fire retarding epoxide resin cured article vertical combustion is by UL-94V-0 level.
Polymeric phosphorus-containing flame retardant described in this test is prepared by test nine.
Polymeric phosphorus-containing flame retardant embody rule process described in this test is as follows:
Polymeric phosphorus-containing flame retardant (polymeric phosphorus-containing flame retardant is as Fire Retardant of The Expoxy Resin) is added in 50g epoxy resin, 30min is stirred at 120 DEG C, add 7.42g mphenylenediamine (mphenylenediamine is as the solidifying agent of epoxy resin), continue to be stirred to mphenylenediamine to dissolve, be poured into after mixing in Standard Module, 1h is kept in the baking oven of 105 DEG C, then under 150 DEG C of conditions, 2h is kept, naturally cool to room temperature, after demoulding, obtain fire retarding epoxide resin cured article; In described fire retarding epoxide resin cured article, polymeric phosphorus-containing flame retardant addition is 11wt%.
To fire retarding epoxide resin cured article by limiting oxygen index(LOI) and vertical combustion test, when the addition of polymeric phosphorus-containing flame retardant is 11wt%, the vertical combustion test of material just can reach UL-94V-0 level, and limiting oxygen index(LOI) brings up to 30.4% from 17.8%.Fire retarding epoxide resin cured article is put in constant temperature 70 DEG C of water baths and keep 168h, water is changed every 24h, take out post-drying, limiting oxygen index(LOI) and vertical combustion test are carried out to this material, the vertical combustion test of this material is still by UL-94V-0 level, the limiting oxygen index(LOI) of material drops to 29.7% from 30.4%, maintains good flame retardant properties.
Claims (10)
1. polymeric phosphorus-containing flame retardant, is characterized in that the general structure of polymeric phosphorus-containing flame retardant is:
2. the preparation method of polymeric phosphorus-containing flame retardant as claimed in claim 1, is characterized in that the preparation method of polymeric phosphorus-containing flame retardant is prepared according to the following steps:
Adopt water as reaction solvent, with the trishydroxymethyl phosphorus oxide aqueous solution for starting raw material, using phosphoric acid or sulfuric acid as catalyzer, at room temperature by the trishydroxymethyl phosphorus oxide aqueous solution, reaction solvent and catalyzer add in reaction vessel, then at room temperature trimeric cyanamide is added, again pH value is adjusted to 4 ~ 6, low whipping speed is that 300r/min ~ 400r/min stirs, then low whipping speed be under 300r/min ~ 400r/min with temperature rise rate 5 DEG C/min from room temperature to 85 DEG C ~ 95 DEG C, 10min ~ 15min is reacted at temperature is 85 DEG C ~ 95 DEG C, then be 85 DEG C ~ 95 DEG C with temperature rise rate 2 DEG C/min from temperature and be warming up to reaction solvent reflux temperature, sustained reaction 2h ~ 3h under reaction solvent reflux temperature, after being cooled to room temperature, then suction filtration is carried out successively, white powdery solids is obtained after washing and oven dry, the massfraction of the described trishydroxymethyl phosphorus oxide aqueous solution is 97%, the mass ratio of described trimeric cyanamide and the trishydroxymethyl phosphorus oxide aqueous solution is 1:(1 ~ 1.1), the described quality of the trishydroxymethyl phosphorus oxide aqueous solution and the volume ratio of water are 1g:(1 ~ 2) mL, the described quality of the trishydroxymethyl phosphorus oxide aqueous solution and the volume ratio of catalyzer are 50g:(3 ~ 4) mL,
The general structure of described polymeric phosphorus-containing flame retardant is:
3. polymeric phosphorus-containing flame retardant, is characterized in that the general structure of polymeric phosphorus-containing flame retardant is:
4. the preparation method of polymeric phosphorus-containing flame retardant as claimed in claim 3, is characterized in that the preparation method of polymeric phosphorus-containing flame retardant is prepared according to the following steps:
Adopt water as reaction solvent, with the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution for starting raw material, using phosphoric acid or sulfuric acid as catalyzer, at room temperature by the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution, reaction solvent and catalyzer add in reaction vessel, then at room temperature trimeric cyanamide is added, again pH value is adjusted to 4 ~ 6, low whipping speed is stir under 300r/min ~ 400r/min, then low whipping speed be under 300r/min ~ 400r/min with temperature rise rate 5 DEG C/min from room temperature to 85 DEG C ~ 95 DEG C, 10min ~ 15min is reacted at temperature is 85 DEG C ~ 95 DEG C, then be 85 DEG C ~ 95 DEG C with temperature rise rate 2 DEG C/min from temperature and be warming up to reaction solvent reflux temperature, sustained reaction 2h ~ 3h under reaction solvent reflux temperature, after being cooled to room temperature, then suction filtration is carried out successively, white solid is obtained after washing and oven dry, described tetrakis hydroxymetyl phosphonium sulfuric aqueous solution massfraction is 75%, the mass ratio of described trimeric cyanamide and the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution is 1:(1.5 ~ 1.7), the quality of the described tetrakis hydroxymetyl phosphonium sulfuric aqueous solution and the volume ratio of water are 1g:(1 ~ 1.2) mL, the quality of the described tetrakis hydroxymetyl phosphonium sulfuric aqueous solution and the volume ratio of catalyzer are 50g:(3 ~ 4) mL,
The general structure of described polymeric phosphorus-containing flame retardant is:
5. the preparation method of polymeric phosphorus-containing flame retardant, is characterized in that the preparation method of polymeric phosphorus-containing flame retardant is prepared according to the following steps:
Adopt water as reaction solvent, with the trishydroxymethyl phosphorus oxide aqueous solution for starting raw material, using phosphoric acid or sulfuric acid as catalyzer, at room temperature by the trishydroxymethyl phosphorus oxide aqueous solution, reaction solvent and catalyzer add in reaction vessel, then at room temperature aminated compounds is added, again pH value is adjusted to 4 ~ 6, low whipping speed is stir under 300r/min ~ 400r/min, then low whipping speed be under 300r/min ~ 400r/min with temperature rise rate 5 DEG C/min from room temperature to 85 DEG C ~ 95 DEG C, 15min is reacted at temperature is 85 DEG C ~ 95 DEG C, then be 85 DEG C ~ 95 DEG C with temperature rise rate 2 DEG C/min from temperature and be warming up to reaction solvent reflux temperature, sustained reaction 2h ~ 3h under reaction solvent reflux temperature, after being cooled to room temperature, then suction filtration is carried out successively, pale yellow powder is obtained after washing and oven dry, described trishydroxymethyl phosphorus oxide aqueous solution massfraction is 97%, the mol ratio of described aminated compounds and the trishydroxymethyl phosphorus oxide aqueous solution is 3:2, the described quality of the trishydroxymethyl phosphorus oxide aqueous solution and the volume ratio of water are 100g:(30 ~ 40) mL, the described quality of the trishydroxymethyl phosphorus oxide aqueous solution and the volume ratio of catalyzer are 50:(3 ~ 4) mL, described aminated compounds is quadrol or urea,
The general structure of described polymeric phosphorus-containing flame retardant is:
n=2,3,4 in general structure ...
6. polymeric phosphorus-containing flame retardant, is characterized in that the general structure of polymeric phosphorus-containing flame retardant is:
n=2,3,4 in general structure ...
7. the preparation method of polymeric phosphorus-containing flame retardant as claimed in claim 6, is characterized in that the preparation method of polymeric phosphorus-containing flame retardant is prepared according to the following steps:
Adopt water as reaction solvent, with the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution for starting raw material, using phosphoric acid or sulfuric acid as catalyzer, at room temperature by the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution, reaction solvent and catalyzer add in reaction vessel, then at room temperature aminated compounds is added, again pH value is adjusted to 4 ~ 6, low whipping speed is stir under 300r/min ~ 400r/min, then low whipping speed be under 300r/min ~ 400r/min with temperature rise rate 5 DEG C/min from room temperature to 85 DEG C ~ 95 DEG C, 10min is reacted at temperature is 85 DEG C ~ 95 DEG C, then be 85 DEG C ~ 95 DEG C with temperature rise rate 2 DEG C/min from temperature and be warming up to reaction solvent reflux temperature, sustained reaction 2h ~ 3h under reaction solvent reflux temperature, after being cooled to room temperature, then suction filtration is carried out successively, solid is obtained after washing and oven dry, described tetrakis hydroxymetyl phosphonium sulfuric aqueous solution massfraction is 75%, the mol ratio of described aminated compounds and the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution is 4:1, the quality of the described tetrakis hydroxymetyl phosphonium sulfuric aqueous solution and the volume ratio of water are 100g:(30 ~ 40) mL, the quality of the described tetrakis hydroxymetyl phosphonium sulfuric aqueous solution and the volume ratio of catalyzer are 50g:(3 ~ 4) mL, described aminated compounds is quadrol or urea,
The general structure of described polymeric phosphorus-containing flame retardant is:
n=2,3,4 in general structure ...
8. polymeric phosphorus-containing flame retardant, is characterized in that the general structure of polymeric phosphorus-containing flame retardant is:
n=2,3,4 in general structure ...
9. the preparation method of polymeric phosphorus-containing flame retardant as claimed in claim 8, is characterized in that the preparation method of polymeric phosphorus-containing flame retardant is prepared according to the following steps:
Adopt distilled water as reaction solvent, with the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution for starting raw material, using phosphoric acid or sulfuric acid as catalyzer, at room temperature by piperazine, distilled water and catalyzer join in reaction vessel, low whipping speed is be stirred under 300r/min ~ 400r/min to dissolve completely, then constant pressure funnel is adopted to drip the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution that massfraction is 75%, dropwise rear heating in water bath and be warming up to 85 DEG C ~ 95 DEG C, and 2h is reacted under temperature is 85 DEG C ~ 95 DEG C and stirring velocity is 300r/min ~ 400r/min, after being cooled to room temperature, decompress filter obtains white solid powder, distilled water is utilized to wash 3 times to white solid powder, then at temperature is 105 DEG C, 2h ~ 3h is dried, obtain pale yellow powder, the mass ratio of described piperazine and the tetrakis hydroxymetyl phosphonium sulfuric aqueous solution is 1:(1.5 ~ 1.6), the quality of the described tetrakis hydroxymetyl phosphonium sulfuric aqueous solution and the volume ratio of distilled water are 1g:(1 ~ 3) mL, the quality of the described tetrakis hydroxymetyl phosphonium sulfuric aqueous solution and the volume ratio of catalyzer are 50g:(3 ~ 4) mL,
The general structure of described polymeric phosphorus-containing flame retardant is:
n=2,3,4 in general structure ...
10. the polymeric phosphorus-containing flame retardant as described in claim 1,3,5,6 or 8 is as the application of Fire Retardant of The Expoxy Resin, it is characterized in that polymeric phosphorus-containing flame retardant adds in epoxy resin as Fire Retardant of The Expoxy Resin and mphenylenediamine as epoxy curing agent, obtain fire retarding epoxide resin cured article, when polymeric phosphorus-containing flame retardant addition reaches 10wt% ~ 15wt%, the test of fire retarding epoxide resin cured article vertical combustion is by UL-94V-0 level.
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