CN105273470A - Halogen-free intumescent flame retardant and preparation method thereof - Google Patents
Halogen-free intumescent flame retardant and preparation method thereof Download PDFInfo
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- CN105273470A CN105273470A CN201510823499.0A CN201510823499A CN105273470A CN 105273470 A CN105273470 A CN 105273470A CN 201510823499 A CN201510823499 A CN 201510823499A CN 105273470 A CN105273470 A CN 105273470A
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Abstract
The invention discloses a halogen-free intumescent flame retardant. The halogen-free intumescent flame retardant comprises 93wt% of main materials and 7wt% of auxiliary materials, wherein the main materials comprise 3.5-5wt% of ammonium polyphosphate, 1.5-2.5wt% of polyethylene, 6.5-10wt% of melamine, 7-10wt% of tripentaerythritol, 9-13wt% of 2,5-dimethyl benzylamine, 1.75-3wt% of 2-azacyclononanone, 15-17wt% of propylene glycol monomethyl ether acetate, 5-10wt% of methyl linolenate, 0.5-0.75wt% of 3-methylquinoline and the balance of mixture of aluminium hydroxide and magnesium hydroxide, wherein the weight ratio of aluminium hydroxide to magnesium hydroxide is 2 to 1; and the auxiliary materials comprise 12-15wt% of 2-mercaptopyrimidine, 8-10wt% of 3,4-dihydroxytoluene, 3-4wt% of ammonium oxalate, 10-15wt% of 4-aminopyrimidine, 17-20wt% of 2-cyano-4-nitroaniline, 5-7wt% of zinc stearate and the balance of acetamidoadamantane. The invention also provides a preparation method of the flame retardant. The halogen-free intumescent flame retardant and the preparation method have the beneficial effects that the defects of the prior art can be overcome; and the flame retardant effects of the halogen-free intumescent flame retardant after the halogen-free intumescent flame retardant is mixed in base materials are improved.
Description
Technical field
The present invention relates to technical field of flame retardant, especially a kind of halogen-free expanded flame-retardant agent and preparation method thereof.
Background technology
Halogen-free expanded flame-retardant agent is a kind of fire retardant be widely used in polyolefine and coating.Fire retardant, in use procedure, needs to mix with base-material, and carries out one-body molded with base-material.Existing halogen-free expanded flame-retardant agent and base-material carry out mixing with time shaping, and the degrees of fusion of fire retardant and base-material is not high, causes the flame retardant effect of fire retardant during base-material heated combustion to play completely.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of halogen-free expanded flame-retardant agent and preparation method thereof, can solve the deficiencies in the prior art, improves the flame retardant effect of halogen-free expanded flame-retardant agent after being mixed in base-material.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows.
A kind of halogen-free expanded flame-retardant agent, comprises the major ingredient of 93wt% and the auxiliary material of 7wt%;
Major ingredient comprises the ammonium polyphosphate of 3.5wt% ~ 5wt%, the polyethylene of 1.5wt% ~ 2.5wt%, the trimeric cyanamide of 6.5wt% ~ 10wt%, the tripentaerythritol of 7wt% ~ 10wt%, 2 of 9wt% ~ 13wt%, the 2-azabicyclononanone of 5-dimethyl benzylamine, 1.75wt% ~ 3wt%, the propylene glycol methyl ether acetate of 15wt% ~ 17wt%, the Linolenic acid methylester of 5wt% ~ 10wt%, the 3-toluquinoline of 0.5wt% ~ 0.75wt%, surplus is the mixture of aluminium hydroxide and magnesium hydroxide, and the weight ratio of aluminium hydroxide and magnesium hydroxide is 2:1;
Auxiliary material comprises the 2-sulfhydryl piperidine of 12wt% ~ 15wt%, 3 of 8wt% ~ 10wt%, the ammonium oxalate of 4-orcin, 3wt% ~ 4wt%, the 4-aminopyrimidine of 10wt% ~ 15wt%, the 2 cyano 4 nitro aniline of 17wt% ~ 20wt%, the Zinic stearas of 5wt% ~ 7wt%, surplus is acetyl amantadine.
As preferably, major ingredient also comprises the 4-aminoacetophenone of 1.3wt%.
As preferably, auxiliary material also comprises the 2-methyl-3-nitro phenol of 0.35wt%.
A preparation method for above-mentioned halogen-free expanded flame-retardant agent, comprises the following steps:
A, by ammonium polyphosphate, polyethylene, trimeric cyanamide, 2, 5-dimethyl benzylamine, aluminium hydroxide and magnesium hydroxide are put into reactor and are heated, heating and temperature control is at 320 DEG C ~ 350 DEG C, at the uniform velocity stir 20min ~ 30min, then lower the temperature, cooling rate controls at 10 DEG C/min ~ 15 DEG C/min, while cooling, by propylene glycol methyl ether acetate, Linolenic acid methylester and 3-toluquinoline are evenly sprayed in reactor, and keep stir process until temperature is down to 50 DEG C, finally add remaining ingredient, and carry out heat-insulating pressurizing, pressure-controlling is at 3bar ~ 3.5bar, Keep agitation 1h ~ 1.5h, obtained major ingredient,
B, auxiliary material component is put into reactor, add methyl alcohol, heating makes methyl alcohol slowly volatilize, make in the process to keep negative pressure in reactor, after methyl alcohol volatilization, reactor is recovered malleation, heating temperatures to 750 DEG C in reactor, keep 2min ~ 3min, be then reduced to rapidly 25 DEG C, obtained auxiliary material;
Reactor put into by C, major ingredient steps A prepared, be heated to 110 DEG C ~ 120 DEG C, then the auxiliary material that step B is obtained is put into, be warming up to 270 DEG C ~ 280 DEG C and carry out mix and blend 30min ~ 40min, then continue to add liquid ether to lower the temperature rapidly, and keep stirring velocity constant, until temperature is down to 70 DEG C simultaneously, stop adding ether, leave standstill and be down to 25 DEG C.
As preferably, in steps A, stirring velocity controls at 350rad/min ~ 400rad/min.
As preferably, in step C, stirring velocity controls at 120rad/min ~ 150rad/min.
The beneficial effect adopting technique scheme to bring is: fire retardant, by improving the formula of fire retardant, is divided into major ingredient and auxiliary material to prepare respectively by the present invention.Polyethylene in major ingredient is cross-linked all the other formulas of major ingredient in preparation process, thus uniformity coefficient when improve fire retardant material and base-material mixing moulding.Propylene glycol methyl ether acetate and Linolenic acid methylester extend the deenergized period of fire retardant, improve its protection for base-material.3-toluquinoline can improve the stability of major ingredient preparation process.Tripentaerythritol and 2-azabicyclononanone form coating layer on major ingredient surface, improve the syncretizing effect of major ingredient and auxiliary material.4-aminoacetophenone can improve the mixture homogeneity in major ingredient between each component, and can realize the persistence of flame retardant effect when fire retardant discharges.Auxiliary material is mainly used in coordinating with major ingredient, improves the mixedness between major ingredient and base-material, and extends the validity period of major ingredient, simultaneously when base-material is heated, major ingredient can be made to play flame retardant effect quickly, and improve the thermotolerance of base-material, thus reduce the drip melt phenomenon occurred when base-material is heated.The preparation process of auxiliary material, by adding methyl alcohol, can improve the syncretizing effect between each component, then by rapid heating and fast cooling, makes to form hole in granules of accessories, is convenient to being mixed with of auxiliary material and major ingredient.Major ingredient and auxiliary material carry out cooling fusion by adding ether, effectively can utilize the molecular grouping structure of major ingredient particle and granules of accessories, improve effective combination of major ingredient and auxiliary material, form fire retardant.
Embodiment
A kind of halogen-free expanded flame-retardant agent, comprises the major ingredient of 93wt% and the auxiliary material of 7wt%;
Major ingredient comprises the ammonium polyphosphate of 4.1wt%, the polyethylene of 2.3wt%, the trimeric cyanamide of 7wt%, the tripentaerythritol of 8.9wt%, 2 of 11.3wt%, the Linolenic acid methylester of the 2-azabicyclononanone of 5-dimethyl benzylamine, 2.5wt%, the propylene glycol methyl ether acetate of 16wt%, 9wt%, the 3-toluquinoline of 0.52wt%, the 4-aminoacetophenone of 1.3wt%, surplus is the mixture of aluminium hydroxide and magnesium hydroxide, and the weight ratio of aluminium hydroxide and magnesium hydroxide is 2:1;
Auxiliary material comprises the 2-sulfhydryl piperidine of 14.1wt%, 3 of 8.3wt%, the 2-methyl-3-nitro phenol of the 2 cyano 4 nitro aniline of the ammonium oxalate of 4-orcin, 3.7wt%, the 4-aminopyrimidine of 12.6wt%, 18.5wt%, the Zinic stearas of 5.8wt%, 0.35wt%, surplus is acetyl amantadine.
A preparation method for above-mentioned halogen-free expanded flame-retardant agent, comprises the following steps:
A, by ammonium polyphosphate, polyethylene, trimeric cyanamide, 2, 5-dimethyl benzylamine, aluminium hydroxide and magnesium hydroxide are put into reactor and are heated, heating and temperature control is at 330 DEG C, at the uniform velocity stir 20min, then lower the temperature, cooling rate controls at 10 DEG C/min, while cooling, by propylene glycol methyl ether acetate, Linolenic acid methylester and 3-toluquinoline are evenly sprayed in reactor, and keep stir process until temperature is down to 50 DEG C, finally add remaining ingredient, and carry out heat-insulating pressurizing, the mixed gas of sulfurous gas and carbon monoxide is filled with in reactor, make pressure-controlling at 3.5bar, the mol ratio of sulfurous gas and carbon monoxide is 5:1, Keep agitation 1.3h, obtained major ingredient, stirring velocity controls at 380rad/min,
B, auxiliary material component is put into reactor, add methyl alcohol, heating makes methyl alcohol slowly volatilize, and makes in the process to keep negative pressure in reactor, after methyl alcohol volatilization, reactor is recovered malleation, the heating temperatures to 750 DEG C in reactor, keep 2min, be then reduced to rapidly 25 DEG C, obtained auxiliary material;
Reactor put into by C, major ingredient steps A prepared, be heated to 120 DEG C, then the auxiliary material that step B is obtained is put into, be warming up to 280 DEG C and carry out mix and blend 35min, then continue to add liquid ether to lower the temperature rapidly, and keep stirring velocity constant, until temperature is down to 70 DEG C simultaneously, stop adding ether, leave standstill and be down to 25 DEG C.Stirring velocity controls at 120rad/min.
In addition, at obtained fire-retardant powder surface sprinkling 2-acetylenylbenzene methyl ether, the stability of fire retardant can be improved.
Performance comparison is carried out in the halogen-free expanded flame-retardant agent provided in fire retardant in the present embodiment and prior art (using the PC-100 type expanding halide-free fire-retardant that Jinan Jin Quan Chemical Co., Ltd. produces), and result is as shown in the table:
| Test event | Prior art | The embodiment of the present invention |
| Yu Ran extinguishes speed (s) | 31 | 16 |
| Smokescope (mg/m 3) | 79 | 21 |
Test is carried out according to according to UL94 standard.
As can be seen here, fire retardant provided by the present invention improves significantly compared with prior art tool on flame retardant effect.
Foregoing description only proposes, not as the single restricted condition to its technical scheme itself as the enforceable technical scheme of the present invention.
Claims (6)
1. a halogen-free expanded flame-retardant agent, is characterized in that comprising the major ingredient of 93wt% and the auxiliary material of 7wt%;
Major ingredient comprises the ammonium polyphosphate of 3.5wt% ~ 5wt%, the polyethylene of 1.5wt% ~ 2.5wt%, the trimeric cyanamide of 6.5wt% ~ 10wt%, the tripentaerythritol of 7wt% ~ 10wt%, 2 of 9wt% ~ 13wt%, the 2-azabicyclononanone of 5-dimethyl benzylamine, 1.75wt% ~ 3wt%, the propylene glycol methyl ether acetate of 15wt% ~ 17wt%, the Linolenic acid methylester of 5wt% ~ 10wt%, the 3-toluquinoline of 0.5wt% ~ 0.75wt%, surplus is the mixture of aluminium hydroxide and magnesium hydroxide, and the weight ratio of aluminium hydroxide and magnesium hydroxide is 2:1;
Auxiliary material comprises the 2-sulfhydryl piperidine of 12wt% ~ 15wt%, 3 of 8wt% ~ 10wt%, the ammonium oxalate of 4-orcin, 3wt% ~ 4wt%, the 4-aminopyrimidine of 10wt% ~ 15wt%, the 2 cyano 4 nitro aniline of 17wt% ~ 20wt%, the Zinic stearas of 5wt% ~ 7wt%, surplus is acetyl amantadine.
2. halogen-free expanded flame-retardant agent according to claim 1, is characterized in that: major ingredient also comprises the 4-aminoacetophenone of 1.3wt%.
3. halogen-free expanded flame-retardant agent according to claim 1, is characterized in that: auxiliary material also comprises the 2-methyl-3-nitro phenol of 0.35wt%.
4. a preparation method for the halogen-free expanded flame-retardant agent described in claim 1-3 any one, is characterized in that comprising the following steps:
A, by ammonium polyphosphate, polyethylene, trimeric cyanamide, 2, 5-dimethyl benzylamine, aluminium hydroxide and magnesium hydroxide are put into reactor and are heated, heating and temperature control is at 320 DEG C ~ 350 DEG C, at the uniform velocity stir 20min ~ 30min, then lower the temperature, cooling rate controls at 10 DEG C/min ~ 15 DEG C/min, while cooling, by propylene glycol methyl ether acetate, Linolenic acid methylester and 3-toluquinoline are evenly sprayed in reactor, and keep stir process until temperature is down to 50 DEG C, finally add remaining ingredient, and carry out heat-insulating pressurizing, pressure-controlling is at 3bar ~ 3.5bar, Keep agitation 1h ~ 1.5h, obtained major ingredient,
B, auxiliary material component is put into reactor, add methyl alcohol, heating makes methyl alcohol slowly volatilize, make in the process to keep negative pressure in reactor, after methyl alcohol volatilization, reactor is recovered malleation, heating temperatures to 750 DEG C in reactor, keep 2min ~ 3min, be then reduced to rapidly 25 DEG C, obtained auxiliary material;
Reactor put into by C, major ingredient steps A prepared, be heated to 110 DEG C ~ 120 DEG C, then the auxiliary material that step B is obtained is put into, be warming up to 270 DEG C ~ 280 DEG C and carry out mix and blend 30min ~ 40min, then continue to add liquid ether to lower the temperature rapidly, and keep stirring velocity constant, until temperature is down to 70 DEG C simultaneously, stop adding ether, leave standstill and be down to 25 DEG C.
5. the preparation method of halogen-free expanded flame-retardant agent according to claim 4, it is characterized in that: in steps A, stirring velocity controls at 350rad/min ~ 400rad/min.
6. the preparation method of halogen-free expanded flame-retardant agent according to claim 4, it is characterized in that: in step C, stirring velocity controls at 120rad/min ~ 150rad/min.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510823499.0A CN105273470A (en) | 2015-11-24 | 2015-11-24 | Halogen-free intumescent flame retardant and preparation method thereof |
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| CN201510823499.0A CN105273470A (en) | 2015-11-24 | 2015-11-24 | Halogen-free intumescent flame retardant and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106926379A (en) * | 2017-04-12 | 2017-07-07 | 超达电线电缆有限公司 | A kind of processes for chemically crosslinked polyethylene insulating materials produces and processes system and its application process |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101948581A (en) * | 2010-08-31 | 2011-01-19 | 杭州高新绝缘材料有限公司 | Intumescent flame retardant polyethylene containing organosilicon compound |
| US20140107257A1 (en) * | 2012-10-12 | 2014-04-17 | David H. Blount | Inorganic phosphorus-inorganic phosphoric oxyacids compounds and compositions |
| CN104448560A (en) * | 2014-12-01 | 2015-03-25 | 黑龙江省润特科技有限公司 | Polypropylene halogen-free intumescent flame retardant |
| CN104693485A (en) * | 2015-03-18 | 2015-06-10 | 苏州安鸿泰新材料有限公司 | Halogen-free intumescent compound flame retardant and application thereof in high-density polyethylene |
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- 2015-11-24 CN CN201510823499.0A patent/CN105273470A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948581A (en) * | 2010-08-31 | 2011-01-19 | 杭州高新绝缘材料有限公司 | Intumescent flame retardant polyethylene containing organosilicon compound |
| US20140107257A1 (en) * | 2012-10-12 | 2014-04-17 | David H. Blount | Inorganic phosphorus-inorganic phosphoric oxyacids compounds and compositions |
| CN104448560A (en) * | 2014-12-01 | 2015-03-25 | 黑龙江省润特科技有限公司 | Polypropylene halogen-free intumescent flame retardant |
| CN104693485A (en) * | 2015-03-18 | 2015-06-10 | 苏州安鸿泰新材料有限公司 | Halogen-free intumescent compound flame retardant and application thereof in high-density polyethylene |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106926379A (en) * | 2017-04-12 | 2017-07-07 | 超达电线电缆有限公司 | A kind of processes for chemically crosslinked polyethylene insulating materials produces and processes system and its application process |
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