CN101638583B - Nitrogen-phosphorus expansion flame retardant containing flame retardant synergist and preparation method thereof - Google Patents
Nitrogen-phosphorus expansion flame retardant containing flame retardant synergist and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a nitrogen-phosphorus expansion flame retardant containing a flame retardant synergist and a preparation method thereof. The nitrogen-phosphorus expansion flame retardant containing the flame retardant synergist is characterized in that 90-99.95 percent of the nitrogen-phosphorus expansion flame retardant and 0.05-10 percent of the flame retardant synergist are evenly mixed according to the mass; the nitrogen-phosphorus expansion flame retardant comprises a nitrogen-phosphorus compound expansion flame retardant or/and a nitrogen-phosphorus simple substance expansion flame retardant; and the flame retardant synergist is selected from ferric phosphate and/or ferric pyrophosphate. The nitrogen-phosphorus expansion flame retardant containing the flame retardant synergist can be suitable for anti-flaming of polyolefin, polyester or phenyl polymer, thereby overcoming the defects of low flame retardant efficiency, large addition quantity, and the like in the prior nitrogen-phosphorus expansion flame retardant, reducing the adverse effect of flame retardant property of a matrix due to the hygroscopicity of a flame retardant agent and reducing the adverse effect of mechanical property of the matrix due to the flame retardant agent with both convenience of production and use.
Description
Technical field
The invention belongs to nitrogen-phosphorus expansion fire retardant technical field, particularly contain nitrogen-phosphorus expansion fire retardant of retardant synergist and preparation method thereof.
Background technology
Polymkeric substance burns easily because of it and is widely used, and in the flammable solid fire, occupies dominant position.Though inorganic combustion inhibitor such as Marinco H and white lake have simultaneously and fire-retardantly do not produce toxic gas and corrosive gases when pressing down cigarette effect and burning, because of required addition has a strong impact on by the physics of fire retardant material, mechanical property and processing characteristics greatly.Though halogenated flame retardant has flame retardant effect preferably,,, be eliminated gradually to environment and human body harmful because of its HX that plays fire retardation is deleterious corrosive gases.Expansion type flame retardant is to serve as the main fire retardant of forming with nitrogen, Phosphorus compound, and it is not halogen-containing, is a kind of environment friendly flame retardant.According to Britain's " polymer degradation is with stable " (Polymer Degradation andStability; 90:523-534; 2005) introduce; Add the prepared polypropylene flame redardant of forming by trimeric cyanamide ammonium phosphate and tetramethylolmethane of expanding fire retardant that accounts for system total mass 40% and just can reach the UL-94V0 rank, but can cause mechanical property such as the tensile strength and the breaking tenacity decline of material greatly because of the total amount of adding expanding fire retardant.According to the U.S. " polymer science journal (Journal of Polymer Science; Part A:Ploymer chemistry 42:6163-6173; 2004) introduce; During with organo montmorillonite and expansion type flame retardant synergistic polypropylene flame redardant, when organic polynite quality accounts for system total mass percentage composition ratio and is 4%, can obviously reduce the HRR of polypropylene flame redardant; But along with the increase (surpassing 4% back) of organo montmorillonite content aggravates because of reuniting, its flame retardant effect descends on the contrary.
Though existing adopt melt-blending process to make the flame-retardant polymer that contains the nitrogen-phosphorus expansion fire retardant or contain nitrogen-phosphorus expansion fire retardant and retardant synergist to have characteristics such as LSZH and anti-dissolves droplet; But flame retardant effect is still not ideal enough; Anti-the dripping property of dissolving is still waiting to improve; Descend because of the flame retardant amount of required interpolation can make mechanical property such as the tensile strength of material, breaking tenacity greatly, and production cost is higher.
Ferric pyrophosphate and tertiary iron phosphate can be used as accessory substance (irony reinforcer); Be used to strengthen milk powder, milk formula, dairy products and other food; Its stability is better, and has free of contamination advantage, industrialization at present; The researchist mainly notes its application prospect aspect foodstuff additive at present, but does not appear in the newspapers so far in the research aspect fire-retardant for ferric pyrophosphate and tertiary iron phosphate.Lanthanum orthophosphate, Cerium monophosphate and these materials of manganese pyrophosphate do not appear in the newspapers in the research aspect fire-retardant yet simultaneously.
Summary of the invention
The present invention proposes a kind of nitrogen-phosphorus expansion fire retardant that contains retardant synergist and preparation method thereof; When guaranteeing its flame retardant effect, overcome shortcomings such as existing nitrogen-phosphorus expansion fire retardant efficient is low, the fire retardant addition is bigger, reduce the disadvantageous effect of fire retardant matrix.
The nitrogen-phosphorus expansion fire retardant that contains retardant synergist of the present invention is characterized in that containing the nitrogen-phosphorus expansion fire retardant of mass percent 90～99.95% and 0.05～10% retardant synergist.
The preparation method who contains the nitrogen-phosphorus expansion fire retardant of retardant synergist of the present invention; It is characterized in that 90～99.95% nitrogen-phosphorus expansion fire retardant and 0.05～10% retardant synergist being mixed, promptly obtain the nitrogen-phosphorus expansion fire retardant that contains retardant synergist of the present invention by quality.
Said nitrogen-phosphorus expansion fire retardant comprises the Phosphorus Compositional type expanding fire retardant of nitrogen or/and the Phosphorus simple substance type of nitrogen expanding fire retardant;
The Phosphorus Compositional type expanding fire retardant of said nitrogen is by the charcoal source: source of the gas: acid source is by mass ratio 1: 0～1.0: 1.0～3.0 composite forming;
Wherein the charcoal source is selected from one or more in tetramethylolmethane, NSC 65881 or the macro molecular triazine series carbon forming agent, or in the micro encapsulation product in above-mentioned charcoal source one or more;
Said source of the gas is selected from one or more in trimeric cyanamide, Dyhard RU 100 or the urea, or in the micro encapsulation product of above-mentioned source of the gas one or more;
Said acid source is selected from one or more in ammonium polyphosphate, ammonium phosphate, trimeric cyanamide ammonium polyphosphate or the trimeric cyanamide ammonium phosphate, or in the micro encapsulation product of above-mentioned acid source one or more;
The Phosphorus simple substance type of said nitrogen expanding fire retardant is selected from 3,9-dihydroxyl-3,9-dioxy-2; 4,8,10-four oxa-s-3; 9-two phospha volution [5,5] undecanes-3,9-two trimeric cyanamides or two (2; 6,7-trioxa-1-phospha dicyclo [2.2.2] octane-1-oxygen-4-methylene radical) one or more in the phosphate ester acid trimeric cyanamide, or in the microcapsule product of the Phosphorus simple substance type of above-mentioned nitrogen expanding fire retardant one or more;
Said micro encapsulation comprises melmac micro encapsulation, epoxy resin micro-capsuleization, siloxanes micro encapsulation or polyurethane micro-encapsulated.
Said retardant synergist is selected from one or more in lanthanum orthophosphate, Cerium monophosphate, manganese pyrophosphate, tertiary iron phosphate or the ferric pyrophosphate.
The nitrogen-phosphorus expansion fire retardant that contains retardant synergist of the present invention is applicable to polyolefine being comprised Vilaterm, Vestolen PP 7052, ethene-vinyl acetate copolymer, terpolymer EP rubber or ethylene-octene copolymer; Polyester comprises poly butylene succinate, polyphenyl dioctyl phthalate second diester, urethane or POLYACTIC ACID, and phenyl polymer comprises the fire-retardant of PS, acrylonitrile-butadiene-styrene copolymer, styrene-butadiene-styrene block copolymer or styrene-acrylonitrile copolymer.
Compared with prior art, be example with the Vestolen PP 7052, prior art polypropylene flame redardant when accounting for system total mass percentage calculation and contain 25% nitrogen-phosphorus expansion fire retardant at least just can reach the UL-94V0 rank; And adopt the nitrogen-phosphorus expansion fire retardant that contains retardant synergist of the present invention to come polypropylene flame redardant; Owing to contain retardant synergist in the system; Accounting for system total mass per-cent at the nitrogen-phosphorus expansion fire retardant is just can reach the UL-94V0 rank at 20% o'clock, and the fire retardant consumption is compared above-mentioned prior art and reduced 20%.Adopt fire retardant of the present invention to overcome shortcomings such as existing flame retarding efficiency is low, the fire retardant addition is bigger; Reduced the disadvantageous effect of fire retardant water absorbability to the matrix flame retardant properties; Reduced the disadvantageous effect of fire retardant to the mechanical property of matrix, production and use are all very convenient.
Embodiment
Further specify the present invention through embodiment below.
Embodiment 1:
The preparation that contains the nitrogen-phosphorus expansion fire retardant of retardant synergist of the present invention: the ammonium polyphosphate that will account for ferric pyrophosphate and 30.7% tetramethylolmethane and 61.3% of system total mass 8% by mass ratio is put into and is stirred well in the stirrer evenly, promptly obtains the nitrogen-phosphorus expansion fire retardant that contains retardant synergist of the present invention.
The nitrogen-phosphorus expansion fire retardant that contains retardant synergist of the present invention is carried out the flame retardant effect test:
The nitrogen-phosphorus expansion fire retardant that contains retardant synergist of the present invention with above-mentioned preparation prepares polypropylene flame redardant earlier: will account for the above-mentioned nitrogen-phosphorus expansion fire retardant that contains retardant synergist that makes of system total mass 25% and account for the Vestolen PP 7052 of system total mass 70% and 5% maleic anhydride inoculated polypropylene melt blending by mass ratio, and promptly obtain polypropylene flame redardant.
Then with the dry rear fender of this polypropylene flame redardant; Cut into the standard batten of 130mm * 13mm * 3mm and 130mm * 6.5mm * 3mm; On CZF-3 type horizontal vertical burning determinator, carry out the test of UL-94 vertical combustion by ASTM D635-77 standard, can reach the UL-94V-0 rank; Limiting oxygen index(LOI) is tested on HC-2 type oxygen index instrument by ASTM D2863-77 standard, and its limiting oxygen index(LOI) value reaches 33.0.
Comparative Examples 1:
Tetramethylolmethane and 66.7% the ammonium polyphosphate that will account for system total mass 33.3% by mass ratio are put into stirrer and are stirred, and obtain being used for the correlated nitrogen-phosphorus expansion fire retardant that does not contain retardant synergist.
The above-mentioned work that makes that will account for system total mass 25% by mass ratio contrasts the nitrogen-phosphorus expansion fire retardant that does not contain retardant synergist of usefulness and accounts for the Vestolen PP 7052 of system total mass 70% and 5% maleic anhydride inoculated polypropylene melt blending, obtains contrasting the polypropylene flame redardant of usefulness.Its laggard row of standard batten that cuts into 130mm * 6.5mm * 3mm and 130mm * 13mm * 3mm is detected, and its limiting oxygen index(LOI) value reaches 28.8, and vertical combustion can reach the UL-94V-0 rank.
Can find out with Comparative Examples 1 from top embodiment 1: keep under the 25% constant situation at nitrogen-phosphorus expansion fire retardant and ferric pyrophosphate total addition level; The oxygen index of embodiment 1 will exceed 4.2 units than the oxygen index of Comparative Examples 1; Explain and adopt the nitrogen-phosphorus expansion fire retardant that contains retardant synergist of the present invention to prepare polypropylene flame redardant, can obviously improve the flame retardant properties of polypropylene material.
Embodiment 2:
Contain the preparation of the nitrogen-phosphorus expansion fire retardant of retardant synergist: the ammonium polyphosphate that will account for ferric pyrophosphate and 30% tetramethylolmethane and 60% of system total mass 10% by mass ratio is put into stirrer and is stirred well to evenly, promptly obtains the nitrogen-phosphorus expansion fire retardant that contains retardant synergist of the present invention.
Flame retardant effect test: the nitrogen-phosphorus expansion fire retardant that present embodiment preparation above-mentioned that will account for system total mass 20% by mass ratio contains retardant synergist with account for 75% Vestolen PP 7052 and 5% maleic anhydride inoculated polypropylene melt blending, promptly obtain polypropylene flame redardant.Its standard batten that cuts into 130mm * 13mm * 3mm is detected, and vertical combustion reaches the UL-94V-0 rank.
Embodiment 3:
Ferric pyrophosphate and 33.32% ammonium polyphosphate, 33.32% tetramethylolmethane and 33.31% the trimeric cyanamide that will account for system total mass 0.05% by mass ratio are put into stirrer and are fully stirred, and promptly obtain the nitrogen-phosphorus expansion fire retardant that contains retardant synergist of the present invention.
Flame retardant effect test: will account for by mass ratio system total mass 22% the present embodiment preparation the nitrogen-phosphorus expansion fire retardant that contains retardant synergist with account for the Vestolen PP 7052 of system total mass 73% and 5% maleic anhydride inoculated polypropylene melt blending, promptly obtain polypropylene flame redardant.Its standard batten that cuts into 130mm * 13mm * 3mm is detected, and vertical combustion reaches the UL-94V-0 rank.
Embodiment 4:
Ferric pyrophosphate and 49.5% trimeric cyanamide ammonium polyphosphate, 24.75% NSC 65881 and 24.75% the trimeric cyanamide that will account for system total mass 1% by mass ratio are put into stirrer and are fully stirred, and promptly obtain the nitrogen-phosphorus expansion fire retardant that contains retardant synergist of the present invention.
Flame retardant effect test: will account for the above-mentioned nitrogen-phosphorus expansion fire retardant that contains retardant synergist that makes and 74% the Vestolen PP 7052 and 5% the maleic anhydride inoculated polypropylene melt blending of system total mass 21% by mass ratio, and promptly obtain polypropylene flame redardant.Its standard batten that cuts into 130mm * 13mm * 3mm is detected, and vertical combustion reaches the UL-94V-0 rank.
Embodiment 5:
Contain the preparation of the nitrogen-phosphorus expansion fire retardant of retardant synergist: by mass ratio will account for system total mass 10% ferric pyrophosphate and 90% 3,9-dihydroxyl-3,9-dioxy-2; 4,8,10-four oxa-s-3; 9-two phospha volutions [5; 5] undecane-3,9-two trimeric cyanamides are put into stirrer and are fully stirred, and promptly obtain the nitrogen-phosphorus expansion fire retardant that contains retardant synergist of the present invention.
Flame retardant effect test: will account for the above-mentioned nitrogen-phosphorus expansion fire retardant that contains retardant synergist that makes and 70% the Vestolen PP 7052 and 5% the maleic anhydride inoculated polypropylene melt blending of system total mass 25% by mass ratio, and promptly obtain polypropylene flame redardant.Its standard batten that cuts into 130mm * 13mm * 3mm is detected, and vertical combustion reaches the UL-94V-0 rank.
Embodiment 6:
By mass ratio will account for system total mass 8% tertiary iron phosphate and 25% tetramethylolmethane, 50% ammonium polyphosphate and 8% trimeric cyanamide, 9% 3,9-dihydroxyl-3,9-dioxy-2; 4,8,10-four oxa-s-3; 9-two phospha volutions [5; 5] undecane-3,9-two trimeric cyanamides are put into stirrer and are fully stirred, and promptly obtain the nitrogen-phosphorus expansion fire retardant that contains retardant synergist of the present invention.
Flame retardant effect test: the nitrogen-phosphorus expansion fire retardant that contains retardant synergist with the present embodiment preparation prepares polypropylene flame redardant earlier: the above-mentioned nitrogen-phosphorus expansion fire retardant that contains retardant synergist that makes that will account for system total mass 25% by mass ratio with account for 70% Vestolen PP 7052 and 5% maleic anhydride inoculated polypropylene melt blending, promptly obtain polypropylene flame redardant.Its standard batten that cuts into 130mm * 13mm * 3mm is detected, and vertical combustion reaches the UL-94V-0 rank.
If the tertiary iron phosphate in the present embodiment is replaced with in lanthanum orthophosphate, Cerium monophosphate, manganese pyrophosphate, tertiary iron phosphate or the ferric pyrophosphate one or more, the acid source ammonium polyphosphate is replaced in the micro encapsulation product of one or more or above-mentioned acid source in ammonium polyphosphate, ammonium phosphate, trimeric cyanamide ammonium polyphosphate or the trimeric cyanamide ammonium phosphate one or more, the source of the gas trimeric cyanamide is replaced in the micro encapsulation product of one or more or above-mentioned source of the gas in trimeric cyanamide, Dyhard RU 100 or the urea one or more; Charcoal source tetramethylolmethane is replaced in the micro encapsulation product of one or more or above-mentioned char-forming agent in tetramethylolmethane, NSC 65881 or the macro molecular triazine series carbon forming agent one or more, with 3,9-dihydroxyl-3; 9-dioxy-2,4,8; 10-four oxa-s-3,9-two phospha volution [5,5] undecanes-3; 9-two trimeric cyanamides change 3 into, 9-dihydroxyl-3,9-dioxy-2; 4,8,10-four oxa-s-3; 9-two phospha volutions [5; 5] undecane-3,9-two trimeric cyanamides or two (2,6; 7-trioxa-1-phospha dicyclo [2.2.2] octane-1-oxygen-4-methylene radical) one or more in the microcapsule product of one or more in the phosphate ester acid trimeric cyanamide or the Phosphorus simple substance type of above-mentioned nitrogen expanding fire retardant, also can obtain with the foregoing description in similar flame retardance results; Described micro encapsulation comprises melmac micro encapsulation, epoxy resin micro-capsuleization, siloxanes micro encapsulation or polyurethane micro-encapsulated.
Embodiment 7:
By mass ratio will account for system total mass 2% ferric pyrophosphate, 2% manganese pyrophosphate, 1% lanthanum orthophosphate and 30% ammonium polyphosphate, 10% melamine parcel ammonium polyphosphate, 10% siloxanes parcel ammonium polyphosphate, 7% epoxy resin parcel ammonium polyphosphate, 10% tetramethylolmethane, 9% NSC 65881,5% trimeric cyanamide, 5% Dyhard RU 100 and 9% two (2; 6; 7-trioxa-1-phospha dicyclo [2.2.2] octane-1-oxygen-4-methylene radical) the phosphate ester acid trimeric cyanamide is put into stirrer and is fully stirred, and promptly obtains the nitrogen-phosphorus expansion fire retardant that contains retardant synergist of the present invention.
Flame retardant effect test: will account for the above-mentioned nitrogen-phosphorus expansion fire retardant that contains retardant synergist that makes and 70% the Vestolen PP 7052 and 5% the maleic anhydride inoculated polypropylene melt blending of system total mass 25% by mass ratio, and promptly obtain polypropylene flame redardant.Its standard batten that cuts into 130mm * 13mm * 3mm is detected, and vertical combustion reaches the UL-94V-0 rank.
Comparative Examples 2:
Tetramethylolmethane and 66.7% the ammonium polyphosphate that will account for system total mass 33.3% by mass ratio are put into stirrer and are fully stirred, and obtain being used for the correlated nitrogen-phosphorus expansion fire retardant that does not contain retardant synergist.
To account for the system total mass 20% above-mentioned nitrogen-phosphorus expansion fire retardant that does not contain retardant synergist that makes and account for 75% Vestolen PP 7052 and 5% maleic anhydride inoculated polypropylene melt blending by mass ratio, promptly obtain polypropylene flame redardant.Its standard batten that cuts into 130mm * 13mm * 3mm is detected, and vertical combustion does not reach the UL-94 rank.
Comparative Examples 3:
Red stone and 30% tetramethylolmethane, 60% the ammonium polyphosphate that will account for system total mass 10% by mass ratio are put into stirrer and are fully stirred, and obtain being used for the correlated nitrogen-phosphorus expansion fire retardant that contains the red stone retardant synergist.
To account for the above-mentioned nitrogen-phosphorus expansion fire retardant that contains the red stone retardant synergist that makes and 75% the Vestolen PP 7052 and 5% the maleic anhydride inoculated polypropylene melt blending of system total mass 20% by mass ratio, promptly obtain polypropylene flame redardant.Its standard batten that cuts into 130mm * 13mm * 3mm is detected, and vertical combustion does not reach the UL-94 rank.
Comparative Examples 4:
The ammonium polyphosphate that will account for organic modification montmonrillonite and 30% tetramethylolmethane and 60% of system total mass 10% by mass ratio is put into stirrer and is fully stirred, and obtains being used for the correlated nitrogen-phosphorus expansion fire retardant that contains the organic modification montmonrillonite retardant synergist.
To account for the Vestolen PP 7052 of the system total mass 20% above-mentioned nitrogen-phosphorus expansion fire retardant that contains the organic modification montmonrillonite retardant synergist that makes and 75% and 5% maleic anhydride inoculated polypropylene melt blending by mass ratio, promptly obtain polypropylene flame redardant.Its standard batten that cuts into 130mm * 13mm * 3mm is detected, and vertical combustion does not reach the UL-94 rank.
Comparative Examples 5:
The ammonium polyphosphate that will account for zinc borate and 30% tetramethylolmethane and 60% of system total mass 10% by mass ratio is put into stirrer and is fully stirred, and obtains being used for the correlated nitrogen-phosphorus expansion fire retardant that contains the zinc borate retardant synergist.
To account for the Vestolen PP 7052 of the system total mass 20% above-mentioned nitrogen-phosphorus expansion fire retardant that contains the zinc borate retardant synergist that makes and 75% and 5% maleic anhydride inoculated polypropylene melt blending by mass ratio, promptly obtain polypropylene flame redardant.Its standard batten that cuts into 130mm * 13mm * 3mm is detected, and vertical combustion does not reach the UL-94 rank.
Embodiment 8:
Tertiary iron phosphate and 28% tetramethylolmethane, 56% ammonium polyphosphate and 8% the trimeric cyanamide that will account for system total mass 8% by mass ratio are put into stirrer and are fully stirred, and promptly obtain the nitrogen-phosphorus expansion fire retardant that contains retardant synergist of the present invention.
The flame retardant effect test: the nitrogen-phosphorus expansion fire retardant that contains retardant synergist with the present embodiment preparation prepares flame-proof polyethylene earlier: above-mentioned make of the present invention that will account for system total mass 28% by mass ratio contains the nitrogen-phosphorus expansion fire retardant of retardant synergist and accounts for 72% Vilaterm melt blending, promptly obtains flame-proof polyethylene.Its standard batten that cuts into 130mm * 13mm * 3mm is detected, and vertical combustion reaches the UL-94V0 rank.
Comparative Examples 6:
Tetramethylolmethane, 8.7% trimeric cyanamide and 60.9% the ammonium polyphosphate that will account for system total mass 30.4% by mass ratio are put into stirrer and are fully stirred, and obtain being used for the correlated nitrogen-phosphorus expansion fire retardant that does not contain retardant synergist.
To account for the above-mentioned nitrogen-phosphorus expansion fire retardant that does not contain retardant synergist that makes of system total mass 28% and account for 72% Vilaterm melt blending by mass ratio, promptly obtain flame-proof polyethylene.Its standard batten that cuts into 130mm * 13mm * 3mm is detected, and vertical combustion reaches the UL-94V2 rank.
Comparative Examples 7:
Tetramethylolmethane, 8.7% trimeric cyanamide and 60.9% the ammonium polyphosphate that will account for system total mass 30.4% by mass ratio are put into stirrer and are fully stirred, and obtain being used for the correlated nitrogen-phosphorus expansion fire retardant that does not contain retardant synergist.
To account for the above-mentioned nitrogen-phosphorus expansion fire retardant that does not contain retardant synergist that makes of system total mass 34% and account for 66% Vilaterm melt blending by mass ratio, promptly obtain flame-proof polyethylene.Its standard batten that cuts into 130mm * 13mm * 3mm is detected, and vertical combustion reaches the UL-94V0 rank.
Analyze and conclusion:
Can find out from the foregoing description 1 and Comparative Examples 1: when adding the fire-retardant additive of same amount; The polypropylene flame redardant that makes among the embodiment 1 exceeds 4.2 units than the oxygen index of the polypropylene flame redardant that makes in the Comparative Examples 1, explains that the nitrogen-phosphorus expansion fire retardant that contains retardant synergist of the present invention has higher flame retarding efficiency;
From the foregoing description 2 and Comparative Examples 1; 2 can find out: under the situation that does not contain retardant synergist of the present invention; Polypropylene flame redardant just can reach the UL-94V0 rank when accounting for system total mass percentage calculation and contain 25% nitrogen-phosphorus expansion fire retardant at least; And add the nitrogen-phosphorus expansion fire retardant that contains synergistic agent of the present invention, and accounting for system total mass per-cent at fire retardant is that 20% o'clock Vestolen PP 7052 just can reach the UL-94V0 rank, the fire retardant consumption compares ratio 1 and has reduced 20%;, explain that the present invention has overcome shortcomings such as existing nitrogen-phosphorus expansion fire retardant efficient is low, the fire retardant addition is bigger;
From embodiment 2 and Comparative Examples 3; 4; 5 can find out, the synergistic agent in the expansion type flame retardant of the present invention and traditional retardant synergist be red stone for example, and zinc borate or organic modification montmonrillonite etc. is compared has better flame retarding efficiency; Under equal addition situation, the nitrogen-phosphorus expansion fire retardant that contains synergistic agent of the present invention of the present invention can make Vestolen PP 7052 reach the U1-94V-0 rank;
From embodiment 8 and Comparative Examples 6; 7 can find out: under the situation that does not contain retardant synergist of the present invention; Flame-proof polyethylene just can reach the UL-94V0 rank when accounting for system total mass percentage calculation and contain 34% nitrogen-phosphorus expansion fire retardant at least; And add the nitrogen-phosphorus expansion fire retardant that contains synergistic agent of the present invention, and accounting for system total mass per-cent at fire retardant is that 28% o'clock Vilaterm just can reach the UL-94V0 rank, the fire retardant consumption compares ratio 7 and has reduced 17.6%;, explain that the present invention has overcome shortcomings such as existing nitrogen-phosphorus expansion fire retardant efficient is low, the fire retardant addition is bigger.
Utilize the nitrogen-phosphorus expansion fire retardant that contains retardant synergist of the present invention that polyolefine is comprised Vilaterm, ethene-vinyl acetate copolymer, terpolymer EP rubber or ethylene-octene copolymer; Polyester comprises poly butylene succinate, polyphenyl dioctyl phthalate second diester, urethane or POLYACTIC ACID; Phenyl polymer comprises that PS, acrylonitrile-butadiene-styrene copolymer, styrene-butadiene-styrene block copolymer or styrene-acrylonitrile copolymer carry out when fire-retardant; Basic identical with the specific practice in the foregoing description; All can significantly reduce nitrogen-phosphorus expansion fire retardant consumption; Compare and existing do not add the retardant synergist flame-retarded technology, nitrogen-phosphorus expansion fire retardant addition has reduced 10～25%, has overcome shortcomings such as existing nitrogen-phosphorus expansion fire retardant efficient is low, the fire retardant addition is bigger.
Claims (3)
1. a nitrogen-phosphorus expansion fire retardant that contains retardant synergist is characterized in that containing the nitrogen-phosphorus expansion fire retardant of mass percent 90～99.95% and 0.05～10% retardant synergist; Said nitrogen-phosphorus expansion fire retardant is selected from the Phosphorus Compositional type expanding fire retardant of nitrogen or/and the Phosphorus simple substance type of nitrogen expanding fire retardant; Said retardant synergist is selected from tertiary iron phosphate or/and ferric pyrophosphate.
2. the said preparation method who contains the nitrogen-phosphorus expansion fire retardant of retardant synergist of claim 1; It is characterized in that 90～99.95% nitrogen-phosphorus expansion fire retardant and 0.05～10% retardant synergist being mixed, promptly obtain the nitrogen-phosphorus expansion fire retardant that contains retardant synergist of the present invention by quality; Said nitrogen-phosphorus expansion fire retardant is selected from the Phosphorus Compositional type expanding fire retardant of nitrogen or/and the Phosphorus simple substance type of nitrogen expanding fire retardant; Said retardant synergist is selected from tertiary iron phosphate or/and ferric pyrophosphate.
3. the nitrogen-phosphorus expansion fire retardant or the described preparation method of claim 2 that contain retardant synergist according to claim 1, be characterised in that the Phosphorus Compositional type expanding fire retardant of said nitrogen is by the charcoal source: source of the gas: acid source is by mass ratio 1: 0～1.0: 1.0～3.0 composite forming;
Said charcoal source is selected from tetramethylolmethane, NSC 65881 or/and the macro molecular triazine series carbon forming agent, or in the micro encapsulation product in above-mentioned charcoal source one or more;
Said source of the gas is selected from trimeric cyanamide, Dyhard RU 100 or/and urea, or in the micro encapsulation product of above-mentioned source of the gas one or more;
Said acid source is selected from ammonium polyphosphate, ammonium phosphate, trimeric cyanamide ammonium polyphosphate or/and trimeric cyanamide ammonium phosphate, or in the micro encapsulation product of above-mentioned acid source one or more;
The Phosphorus simple substance type of said nitrogen expanding fire retardant is selected from 3,9-dihydroxyl-3,9-dioxy-2; 4,8,10-four oxa-s-3; 9-two phospha volution [5,5] undecanes-3,9-two trimeric cyanamides are or/and two (2; 6,7-trioxa-1-phospha dicyclo [2.2.2] octane-1-oxygen-4-methylene radical) phosphate ester acid trimeric cyanamide, or in the microcapsule product of the Phosphorus simple substance type of above-mentioned nitrogen expanding fire retardant one or more.
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| CN101921599B (en) * | 2010-04-30 | 2013-04-10 | 中国科学院宁波材料技术与工程研究所 | Bicyclic phosphate-based triazine derivative flame retardant and preparation method thereof |
| CN102234516B (en) * | 2010-05-06 | 2014-06-04 | 中国科学院宁波材料技术与工程研究所 | Long-chain triazine macromolecular flame retardant with bicyclic phosphate structure and preparation method thereof |
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