CN101608060B - Core-shell type ammonium polyphosphate synergetic flame-retardant polyurethane elastic composite material and preparation method thereof - Google Patents
Core-shell type ammonium polyphosphate synergetic flame-retardant polyurethane elastic composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a core-shell type ammonium polyphosphate synergetic flame-retardant polyurethane elastic composite material and a preparation method thereof, which is characterized in that the polyurethane elastic composite material containing core-shell type ammonium polyphosphate can be obtained by melting and co-mixing 75-94.9% of polyurethane, 5-25% of core-shell type ammonium polyphosphate and 0.1-5% of synergistic agent at the temperature of 160-220 DEG C for 5-30 minutes by weight percentage. The composite material can ensure that the adding amount of flame retardant is reduced while ensuring the flame retardance effect, and the composite material has good resistance of melt drip, simultaneously improves the shortcoming of poor water resistance of the flame-retardant composite material containing the ammonium polyphosphate, enhances the compatibility of the flame retardant and a polyurethane elastomer and improves the mechanical properties of the material, such as tensile strength, fracture strength and flame retardance performance, thereby meeting the requirements of fire protection safety and engineering applications.
Description
Technical field
The invention belongs to halogen-free expansion type flame-proof polyurethane elastomer technical field, particularly core-shell type ammonium polyphosphate synergetic flame-retardant polyurethane elastic composite material and preparation method thereof.
Background technology
According to " polyurethane elastomer and application thereof " (Fu Mingyuan, the intoxicated warp of grandson, 2006, the third edition, Chemical Industry Press) book 3-6 page or leaf introduction, thermoplastic polyurethane is a kind of resilient material between ordinary rubber and plastics, it had both had the high strength of plastics, have the snappiness of rubber again, elongation is big, and durometer level is wide, have characteristic such as excellent wear-resisting, anti-ozone and radiation hardness simultaneously and be widely used, account for 15% of world's thermoplastic elastomer consumption greatly.But thermoplastic polyurethane burns easily, and flame is violent and with strong black smoke during burning, has molten drop simultaneously and drips and drop down phenomenon.Usually the polyurethane elastomer that adds halogenated flame retardants such as brominated and chlorine has good flame retardancy, but this class Halogen flame resistance polyurethane elastomer can produce obnoxious flavour when burning, causes environmental pollution and to the injury of human body.So the New-type halide-free environmental protection fire retarding agent of exploitation polyurethane elastomer has become the emphasis of research.
At present, the halogen-free fire retardation thermoplastic polyurethane product is mainly by adding inorganic combustion inhibitor to obtain flame retardant properties.European patent EP 0389768 discloses a kind of Mg of utilization (OH)
2And Al (OH)
3, composite flame-retardant agent such as melamine aminuria cyanic acid and phosphoric acid ester method of coming flame-proof thermoplastic polyurethane.European patent EP 0508072A2 has described melamine and be used as fire retardant in thermoplastic polyurethane, when its loading level is 30～40wt%, and tensile strength 15MPa, and use UL-94V-0 to evaluate its fire-retardant rank.Patent WO 00/66658 and EP-B 617 079 have described and have adopted the combination of phosphoric acid salt, phosphonate and/or its derivative and melamine cyanurate to come flame-proof thermoplastic polyurethane, corresponding thermoplastic polyurethane tensile strength≤35MPa has evaluated the flame retardant properties of material with UL-94V-0.But all there is the big shortcoming of fire retardant consumption in these methods, can cause the thermoplastic polyurethane mechanical property to decline to a great extent, especially cause the original snappiness of its body that follows the string, resulting product can only be used for moulding, be difficult to be used for extrusion moulding, melamine aminuria cyanic acid has Degradation to thermoplastic polyurethane simultaneously, to having relatively high expectations of matrix thermoplastic polyurethane.
Patent US 4,324, and 835 have proposed to mix the expansibility flame-proof agent as thermoplastic urethane foam with tetramethylolmethane with ammonium polyphosphate, mineral acid, and JP 01/40588 has introduced the method that a kind of ammonium polyphosphate and zinc borate are used flame-proof thermoplastic polyurethane together.US 5,837,760 have proposed independent use organophosphate or have used it and method that the mixture of melamine derivative comes flame-proof thermoplastic polyurethane, and EP 0389768A2 has reported the fire retardant with melamine cyanurate and phosphoric acid ester and magnesium hydroxide flame retardant thermoplastic polyurethane.Though these methods can reduce the consumption of fire retardant to a certain extent, the poor heat stability of material after the interpolation phosphoric acid ester, flame retardant properties is poor, and the molten drop phenomenon is arranged, and oxygen index is low, can only be used for the low fire-retardant occasion that requires; The poor water resistance of material is difficult to keep its flame retardant properties in wet environment; And the consistency of fire retardant and matrix is bad.
Have not yet to see about using core-shell type ammonium polyphosphate and synergist to be used report the flame retardant properties aspect research that improves polyurethane elastomer.
Summary of the invention:
The purpose of this invention is to provide a kind of core-shell type ammonium polyphosphate synergetic flame-retardant polyurethane elastic composite material and preparation method thereof, the addition and the dripping property of refractory that reduce fire retardant when guaranteeing flame retardant effect are good, improve the shortcoming that contains ammonium polyphosphate flame-proof composite material poor water resistance simultaneously, strengthen the consistency of fire retardant and polyurethane elastomer, improve the mechanical property of material.
The preparation method of core-shell type ammonium polyphosphate synergetic flame-retardant polyurethane elastic composite material of the present invention, it is characterized in that: by weight percentage with the synergist of 75～95% urethane, 5～25% core-shell type ammonium polyphosphate and 0.1～5% 160～220 ℃ of melt blendings 5～30 minutes, promptly obtain containing the polyurethane elastic composite material of core-shell type ammonium polyphosphate.
Described core-shell type ammonium polyphosphate is made of the shell of the crosslinking polyurethane resin that accounts for 5～30wt%, starch conversion melamine formaldehyde resin, polyvinyl alcohol modification melamine formaldehyde resin, silicon gel, cross-linking aqueous urethane or cured epoxy resin and the nuclear core that accounts for the ammonium polyphosphate of 70～95wt%.
Described synergist is selected from layered silicate, metal phosphate, graphite oxide, metal oxide, double-hydroxide, silsesquioxane, carbon nanotube, titania nanotube or silica nanometer pipe; Wherein layered silicate comprises clay, talcum, mica or chrysotile, lithium base montmorillonite, fluorine lithium base montmorillonite, zeolite, iron-based polynite, ni montmorillonite or synthetic mica; Described metal phosphate comprises titanium phosphate, zirconium phosphate, aluminum phosphate, phosphoric acid vanadium, manganous phosphate, lanthanum orthophosphate, Cerium monophosphate, tertiary iron phosphate, nickelous phosphate, cupric phosphate, phosphoric acid tin or cobaltous phosphate; Described metal oxide comprises zinc oxide, ferric oxide, lanthanum trioxide, cerium oxide, zirconium white, manganese oxide, nickel oxide, cupric oxide or cobalt oxide; Described double-hydroxide comprises calcium aluminium double-hydroxide, magnalium double-hydroxide, zinc-aluminium double-hydroxide, magnesium iron double-hydroxide, zinc-iron double-hydroxide, nickel aluminium double-hydroxide or ferronickel double-hydroxide.
By the core-shell type ammonium polyphosphate synergetic flame-retardant polyurethane elastic composite material of the present invention of method for preparing, be characterised in that it is the thermoplastic elastic matrix material that contains by weight percentage the melt blending of the synergist of 5～25% core-shell type ammonium polyphosphate and 0.1～5% and 70～94.9% urethane; Described core-shell type ammonium polyphosphate is made of the shell of the crosslinking polyurethane resin that accounts for 5～30wt%, starch conversion melamine formaldehyde resin, polyvinyl alcohol modification melamine formaldehyde resin, silicon gel, cross-linking aqueous urethane or cured epoxy resin and the nuclear core that accounts for the ammonium polyphosphate of 70～95wt%; Described synergist is selected from layered silicate, metal phosphate, graphite oxide, metal oxide, double-hydroxide, silsesquioxane, carbon nanotube, titania nanotube or silica nanometer pipe.
Compared with prior art, core-shell type ammonium polyphosphate synergetic flame-retardant polyurethane elastic composite material of the present invention is because employing core-shell type ammonium polyphosphate flame retardant is environment friendly and pollution-free; This fire retardant has excellent water tolerance simultaneously; The consistency of this fire retardant and matrix thermoplastic polyurethane is also better; Further improved flame retarding efficiency owing to add synergist; Compare with ammonium polyphosphate, the flame retarding efficiency of core-shell type ammonium polyphosphate of the present invention is higher; The present invention has improved existing method because of the fire retardant addition causes shortcomings such as the polyurethane elastomer flame retarding efficiency is low, physicals difference greatly, can satisfy the requirement that security against fire and engineering are used.
Embodiment
Embodiment 1:
By weight 75% polyurethane elastomer (tensile strength 35.1Mpa), 25% polyurethane microcapsule ammonium polyphosphate are added in the Banbury mixer, melt blending is 10 minutes under 170 ℃ and 100 rev/mins of speed conditions, the granulation of lowering the temperature then, the elastic granule that obtains is flame retardant polyurethane matrix material of the present invention.
The oxygen index that records this flame retardant polyurethane matrix material is 33.5, reaches the V-0 level in the UL-94 test, soaks after 7 days in 75 ℃ water and can test by UL-94V-0.The tensile strength of this material reaches 28.4MPa, and elongation at break is 690%.Illustrate that thus this material has good flame retardant property, water tolerance and mechanical property.
Comparative Examples 1:
By weight 75% polyurethane elastomer (tensile strength 35.1Mpa), 25% ammonium polyphosphate are added in the Banbury mixer, melt blending is 10 minutes under 170 ℃ and 100 rev/mins of speed conditions, and the granulation of lowering the temperature obtains elastic granule.
The oxygen index that records this flame retardant polyurethane matrix material is 32, reaches the V-0 level in the UL-94 test, soaks after 7 days in 75 ℃ water and can not pass through the UL-94 level estimate.The tensile strength of this material is 17.8MPa, and elongation at break is 279%.
From embodiment 1 and Comparative Examples 1 as can be seen, add the polyurethane microcapsule ammonium polyphosphate of same ratio and compare with adding ammonium polyphosphate, mechanical property obviously improves, and illustrates that polyurethane microcapsule ammonium polyphosphate and matrix polyurethane elastomer have good consistency; The oxygen index of material also increases simultaneously, has improved the flame retarding efficiency of ammonium polyphosphate flame retardant to a certain extent; Material water still can be passed through UL-94V-0 after soaking, and illustrates that the polyurethane microcapsule ammonium polyphosphate has good water tolerance.
Embodiment 2:
By weight 95% polyurethane elastomer (tensile strength 35.1Mpa), 5% polyurethane microcapsule ammonium polyphosphate are added in the Banbury mixer, melt blending is 10 minutes under 170 ℃ and 100 rev/mins of speed conditions, the cooling granulation, the elastic granule that obtains is flame retardant polyurethane matrix material of the present invention.
The oxygen index that records this flame retardant polyurethane matrix material is 26, reaches the V-2 level in the UL-94 test, soaks after 7 days in 75 ℃ water and can test by UL-94V-2.The tensile strength of this material can reach 32.7MPa, and elongation at break is 890%.
Embodiment 3:
By weight 85% polyurethane elastomer (tensile strength 35.1Mpa), 15% polyurethane microcapsule ammonium polyphosphate are added in the Banbury mixer, melt blending is 10 minutes under 170 ℃ and 100 rev/mins of speed conditions, the cooling granulation, the elastic granule that obtains is flame retardant polyurethane matrix material of the present invention.
The oxygen index that records this fire-retardant poly-compound polyurethane material is 30.5, reaches the V-2 level in the UL-94 test, soaks after 7 days in 75 ℃ water and can test by UL-94V-2.The tensile strength of this material is 30.4MPa, and elongation at break is 800%.
Embodiment 4:
By weight 75% polyurethane elastomer (tensile strength 35.1Mpa), 20% polyurethane microcapsule ammonium polyphosphate and 5% nickelous phosphate are added in the Banbury mixer, melt blending is 10 minutes under 170 ℃ and 100 rev/mins of speed conditions, the cooling granulation, the elastic granule that obtains is flame retardant polyurethane matrix material of the present invention.
The oxygen index of this flame retardant polyurethane matrix material can reach the V-0 level in the UL-94 test up to 37, soaks after 7 days in 75 ℃ water and can test by UL-94V-0.The tensile strength of this material is 27.9MPa, and elongation at break is 675%.
If the synergist nickelous phosphate in the present embodiment is replaced with layered silicate, metal phosphate, graphite oxide, metal oxide, double-hydroxide, silsesquioxane, carbon nanotube, titania nanotube or silica nanometer pipe, wherein layered silicate comprises: clay, talcum, mica or chrysotile, lithium base montmorillonite, fluorine lithium base montmorillonite, zeolite, iron-based polynite, ni montmorillonite or synthetic mica; Described metal phosphate comprises: titanium phosphate, zirconium phosphate, aluminum phosphate, phosphoric acid vanadium, manganous phosphate, lanthanum orthophosphate, Cerium monophosphate, tertiary iron phosphate, cupric phosphate, phosphoric acid tin or cobaltous phosphate; Described metal oxide comprises: zinc oxide, ferric oxide, lanthanum trioxide, cerium oxide, zirconium white, manganese oxide, nickel oxide, cupric oxide or cobalt oxide; Described double-hydroxide comprises: when calcium aluminium double-hydroxide, magnalium double-hydroxide, zinc-aluminium double-hydroxide, magnesium iron double-hydroxide, zinc-iron double-hydroxide, nickel aluminium double-hydroxide or ferronickel double-hydroxide, all can obtain the flame-retardant polyurethane elastic composite material that flame retardant resistance, water tolerance, mechanical property and fire retardant and matrix consistency are obviously improved.
Embodiment 5:
By weight 75% polyurethane elastomer (tensile strength 35.1Mpa), 22.5% polyurethane microcapsule ammonium polyphosphate and 2.5% nickelous phosphate are added in the Banbury mixer, melt blending is 10 minutes under 170 ℃ and 100 rev/mins of speed conditions, the cooling granulation, the elastic granule that obtains is flame retardant polyurethane matrix material of the present invention.
This fire-retardant its oxygen index of poly-compound polyurethane material reaches the V-0 level in the UL-94 test up to 39, soaks after 7 days in 75 ℃ water and can test by UL-94V-0.The tensile strength of this material is 29.1MPa, and elongation at break is 710%.
Embodiment 6:
By weight 85% polyurethane elastomer (tensile strength 35.1Mpa), 12.5% polyurethane microcapsule ammonium polyphosphate and 2.5% nickelous phosphate are added in the Banbury mixer, melt blending is 10 minutes under 170 ℃ and 100 rev/mins of speed conditions, the cooling granulation, the elastic granule that obtains is flame retardant polyurethane matrix material of the present invention.
The oxygen index of this flame retardant polyurethane matrix material is 37, reaches the V-0 level in the UL-94 test, soaks after 7 days in 75 ℃ water and can test by UL-94V-0.The tensile strength of this material is 31.4MPa, and elongation at break is 747%.
If the core-shell type ammonium polyphosphate in the present embodiment is replaced to starch conversion melamine formaldehyde resin, polyvinyl alcohol modification melamine formaldehyde resin, silicon gel, cross-linking aqueous urethane or the cured epoxy resin that shell is 5～30wt%, when the nuclear core is the core-shell type fire retardant of ammonium polyphosphate, all can obtain the flame-retardant polyurethane elastic composite material that flame retardant resistance, water tolerance, mechanical property and fire retardant and matrix consistency are obviously improved.
Embodiment 7:
By weight 95% polyurethane elastomer (tensile strength 35.1Mpa), 4.5% polyurethane microcapsule ammonium polyphosphate and 0.5% nickelous phosphate are added in the Banbury mixer, melt blending is 10 minutes under 170 ℃ and 100 rev/mins of speed conditions, the cooling granulation, the elastic granule that obtains is flame retardant polyurethane matrix material of the present invention.
The oxygen index of this flame retardant polyurethane matrix material is 30, reaches the V-2 level in the UL-94 test, soaks after 7 days in 75 ℃ water and can test by UL-94V-2.The tensile strength of this material can reach 33.7MPa, and elongation at break is 928%.
Embodiment 8:
By weight 74.9% polyurethane elastomer (tensile strength 35.1Mpa), 25% polyurethane microcapsule ammonium polyphosphate and 0.1% nickelous phosphate are added in the Banbury mixer, melt blending is 10 minutes under 170 ℃ and 100 rev/mins of speed conditions, the cooling granulation, the elastic granule that obtains is flame retardant polyurethane matrix material of the present invention.
The oxygen index of this flame retardant polyurethane matrix material reaches the V-0 level in the UL-94 test up to 38, soaks after 7 days in 75 ℃ water and can test by UL-94V-0.The tensile strength of this material is 30.1MPa, and elongation at break is 738%.
The test data of product records by following method in the various embodiments described above:
The UL-94 vertical combustion is tested: test on CZF-3 type horizontal vertical burning determinator by GB/T 2408-1996 standard and carry out; Limiting oxygen index(LOI): on HC-2 type oxygen index instrument, test by GB/T 2406-88 standard; Compressive strength and modulus of compression: on omnipotent puller system, test by the GB/T528-98 standard.
Claims (6)
1. the preparation method of a core-shell type ammonium polyphosphate synergetic flame-retardant polyurethane elastic composite material, it is characterized in that: by weight percentage with the synergist of 75～95% urethane, 5～25% core-shell type ammonium polyphosphate and 0.1～5% 160～220 ℃ of melt blendings 5～30 minutes, promptly obtain containing the polyurethane elastic composite material of core-shell type ammonium polyphosphate, the said components sum is 100%; Described core-shell type ammonium polyphosphate is made of the shell of the crosslinking polyurethane resin that accounts for 5～30wt%, starch conversion melamine formaldehyde resin, polyvinyl alcohol modification melamine formaldehyde resin, silicon gel or cured epoxy resin and the nuclear core that accounts for the ammonium polyphosphate of 70～95wt%; Described synergist is selected from layered silicate, metal phosphate, graphite oxide, metal oxide, double-hydroxide, silsesquioxane, carbon nanotube or silica nanometer pipe.
2. the preparation method of core-shell type ammonium polyphosphate synergetic flame-retardant polyurethane elastic composite material according to claim 1 is characterised in that layered silicate is clay, talcum, mica or chrysotile, lithium base montmorillonite, fluorine lithium base montmorillonite, zeolite, iron-based polynite or ni montmorillonite.
3. the preparation method of core-shell type ammonium polyphosphate synergetic flame-retardant polyurethane elastic composite material according to claim 1 is characterised in that described metal phosphate is titanium phosphate, zirconium phosphate, aluminum phosphate, phosphoric acid vanadium, manganous phosphate, lanthanum orthophosphate, Cerium monophosphate, tertiary iron phosphate, nickelous phosphate, cupric phosphate, phosphoric acid tin or cobaltous phosphate.
4. the preparation method of core-shell type ammonium polyphosphate synergetic flame-retardant polyurethane elastic composite material according to claim 1 is characterised in that described metal oxide is selected from zinc oxide, ferric oxide, lanthanum trioxide, cerium oxide, zirconium white, manganese oxide, nickel oxide, cupric oxide or cobalt oxide.
5. the preparation method of core-shell type ammonium polyphosphate synergetic flame-retardant polyurethane elastic composite material according to claim 1 is characterised in that described double-hydroxide is selected from calcium aluminium double-hydroxide, magnalium double-hydroxide, zinc-aluminium double-hydroxide, magnesium iron double-hydroxide, zinc-iron double-hydroxide, nickel aluminium double-hydroxide or ferronickel double-hydroxide.
6. the core-shell type ammonium polyphosphate synergetic flame-retardant polyurethane elastic composite material of the described method of claim 1 preparation, be characterised in that it is the thermoplastic elastic matrix material that contains by weight percentage the melt blending of the synergist of 5～25% core-shell type ammonium polyphosphate and 0.1～5% and 75～95% urethane, the said components sum is 100%; Described core-shell type ammonium polyphosphate is made of the shell of the crosslinking polyurethane resin that accounts for 5～30wt%, starch conversion melamine formaldehyde resin, polyvinyl alcohol modification melamine formaldehyde resin, silicon gel or cured epoxy resin and the nuclear core that accounts for the ammonium polyphosphate of 70～95wt%; Described synergist is selected from layered silicate, metal phosphate, graphite oxide, metal oxide, double-hydroxide, silsesquioxane, carbon nanotube or silica nanometer pipe.
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| CN114437535B (en) * | 2022-03-23 | 2022-12-02 | 盛鼎高新材料有限公司 | Flame-retardant environment-friendly polyurethane elastomer and preparation method thereof |
| CN115109315B (en) * | 2022-06-22 | 2023-06-09 | 中国科学院福建物质结构研究所 | Jet type core-shell structure flame retardant, and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101302309A (en) * | 2008-06-06 | 2008-11-12 | 中国科学技术大学 | Microcapsule expansion flame-proof starch-based degradable material and preparation thereof |
| CN101376812A (en) * | 2008-09-28 | 2009-03-04 | 中国科学技术大学 | Kernel-shell type silicon-containing synergistic flame retardant and preparation thereof |
| CN101376811A (en) * | 2008-09-28 | 2009-03-04 | 中国科学技术大学 | Polyurethane microcapsulated inorganic phosphonium flame retardant and preparation thereof |
-
2009
- 2009-07-09 CN CN2009101440760A patent/CN101608060B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101302309A (en) * | 2008-06-06 | 2008-11-12 | 中国科学技术大学 | Microcapsule expansion flame-proof starch-based degradable material and preparation thereof |
| CN101376812A (en) * | 2008-09-28 | 2009-03-04 | 中国科学技术大学 | Kernel-shell type silicon-containing synergistic flame retardant and preparation thereof |
| CN101376811A (en) * | 2008-09-28 | 2009-03-04 | 中国科学技术大学 | Polyurethane microcapsulated inorganic phosphonium flame retardant and preparation thereof |
Non-Patent Citations (1)
| Title |
|---|
| 郝冬梅等.无卤膨胀性阻燃剂ANTI-2阻燃聚氨酯弹性体的研究.《阻燃材料与技术》.2008,(第2期),第1-3页. * |
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