CN103435952A - Phosphate nano composite flame-retardant masterbatch and preparation method thereof - Google Patents
Phosphate nano composite flame-retardant masterbatch and preparation method thereof Download PDFInfo
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- CN103435952A CN103435952A CN2013103248521A CN201310324852A CN103435952A CN 103435952 A CN103435952 A CN 103435952A CN 2013103248521 A CN2013103248521 A CN 2013103248521A CN 201310324852 A CN201310324852 A CN 201310324852A CN 103435952 A CN103435952 A CN 103435952A
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Abstract
The invention relates to a phosphate nano composite flame-retardant masterbatch and a preparation method thereof, and belongs to the technical field of high polymer materials. The phosphate nano composite flame-retardant masterbatch comprises the following raw materials in percentage by weight: 40-75% of phosphate/organic clay nano composite fire retardant, 3-20% of flame-retardant synergist, 20-40% of carrier resin and 0.1-0.5% of antioxidant. The flame-retardant masterbatch keeps plasticization of the phosphate fire retardant; but mechanical properties and thermal properties of a matrix are not reduced greatly; additional liquid feeding equipment is not required for solid addition; a compatilizer serves as a carrier and has good compatibility with the matrix; and the influence of the addition of the fire retardant on the mechanical properties of the matrix is avoided.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of phosphoric acid ester nano composite fire retardant master batch and preparation method thereof.
Background technology
Phosphate flame retardant is applied widely as a kind of halogen-free flame retardants, but its major part is liquid, complex process during use, and the optional equipment cost is high; And the phosphate flame retardant poor heat resistance, volatility is large, serious to the Effect of Thermal Performance of base material, and this has also limited phosphoric acid ester and has been widely used.In view of the shortcoming of phosphoric acid ester, new phosphorus, nitrogen combustion inhibitor are developed in succession, but are subject to the impact of technology, and its major part also exists defect.
Nano material technology, particularly nanometer organo-clay add mechanical property and the resistance toheat that not only can improve macromolecule matrix in polymer due to it, can also improve the flame retardant properties of matrix, in macromolecular material, are widely used.But it is applied to separately in plastic material, and flame retardant properties also can't reach the requirement of actual use, this just affected its as a kind of fire retardant material large-scale promotion application in practice.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide a kind of phosphoric acid ester nano composite fire retardant master batch and preparation method thereof.Be intended to the characteristics in conjunction with phosphate flame retardant and organo-clay nano flame retardant, solve existing phosphate flame retardant liquid and add, poor heat resistance, the serious shortcoming to the Effect of Thermal Performance of base material.
Described a kind of phosphoric acid ester nano composite fire retardant master batch, is characterized in that consisting of the raw material of following weight percent: phosphoric acid ester/organic clay nano composite flame-retardant agent 40～75%, fire retarding synergist 3～20%, vector resin 20～40% and oxidation inhibitor 0.1～0.5%.
Described a kind of phosphoric acid ester nano composite fire retardant master batch, is characterized in that consisting of the raw material of following weight percent: phosphoric acid ester/organic clay nano composite flame-retardant agent 45～65%, fire retarding synergist 5～20%, vector resin 25～35% and oxidation inhibitor 0.2～0.4%.
Described a kind of phosphoric acid ester nano composite fire retardant master batch, is characterized in that consisting of the raw material of following weight percent: phosphoric acid ester/organic clay nano composite flame-retardant agent 53～60%, fire retarding synergist 10～15%, vector resin 27～32% and oxidation inhibitor 0.25～0.35%.
Described a kind of phosphoric acid ester nano composite fire retardant master batch is characterized in that described phosphoric acid ester/organic clay nano composite flame-retardant agent makes by following step:
According to phosphate flame retardant 80～100 weight parts, organo-clay 1～20 weight part and silane coupling agent 0.1～2 weight part, prepared burden; Phosphate flame retardant is heated to 90～100 ℃, adds organo-clay and silane coupling agent, keep temperature to stir 3～6 hours, obtain phosphoric acid ester/organic clay nano composite flame-retardant agent.
Described a kind of phosphoric acid ester nano composite fire retardant master batch, is characterized in that described fire retarding synergist is one or more in linear phenolic resin, zinc borate, hypo-aluminum orthophosphate and silicon-dioxide.
Described a kind of phosphoric acid ester nano composite fire retardant master batch, is characterized in that described vector resin is one or more in maleic anhydride grafted polyethylene, maleic anhydride inoculated polypropylene and maleic anhydride grafted ethene-acetate ethylene copolymer.
Described a kind of phosphoric acid ester nano composite fire retardant master batch, is characterized in that described oxidation inhibitor is one or more in antioxidant 1010, antioxidant 300 and irgasfos 168.
Described a kind of phosphoric acid ester nano composite fire retardant master batch, is characterized in that described phosphate flame retardant is one or more in BDP, RDP and TPP, and described silane coupling agent is one or more in KH550, KH560 and KH570.
Described a kind of phosphoric acid ester nano composite fire retardant master batch, is characterized in that being prepared burden according to phosphate flame retardant 85～95 weight parts, organo-clay 5～15 weight parts and silane coupling agent 0.5～1.5 weight part.
The preparation method of described a kind of phosphoric acid ester nano composite fire retardant master batch is characterized in that comprising following processing step:
By the phosphoric acid ester of described weight percent/organic clay nano composite flame-retardant agent, fire retarding synergist, vector resin and oxidation inhibitor are put into kneader, are uniformly mixed 10～15 minutes, after a material, at vacuum, 60 ℃ of temperature, dry, and obtain Preblend; Preblend is put into to twin screw incorporates, extrudes, granulation, obtain phosphoric acid ester nano composite fire retardant master batch.
Raw material in the present invention is currently available products, all can on market, form, and wherein organo-clay is by the production and sales of Zhejiang Feng Hong clay chemical industry company limited.
A kind of phosphoric acid ester nano composite fire retardant of the present invention master batch, both kept phosphorus flame retardant in the flame retardant of plastic performance, kept again the increase of nano imvite in the mechanical property of plastics, used the over-all properties of bi-material.Compare with traditional phosphate flame retardant, following advantage arranged:
Fire-retardant master granule of the present invention has kept the plastification of phosphate flame retardant, but does not sharply reduce again mechanical property and the thermal characteristics of matrix; Solid adds, and does not need extra liquid feeding equipment; Use compatilizer as carrier, with matrix, there is good consistency, solved the impact of the interpolation of fire retardant on the matrix mechanical property.
Embodiment
Further illustrate the present invention below in conjunction with embodiment.
Embodiment 1
1) preparation of phosphoric acid ester/organic clay nano composite flame-retardant agent
100 parts of BDP are heated to 100 ℃ under stirring action, add respectively 2 parts of coupling agent KH550 and 20 parts of organo-clay, under 100 ℃, high-speed stirring 5 hours, obtain phosphoric acid ester/organic clay nano composite flame-retardant agent (BDP/OMMT).
2) preparation of phosphoric acid ester/organic clay nano composite flame-proof master batch
700g BDP/OMMT, 47g hypo-aluminum orthophosphate, 250g maleic anhydride inoculated polypropylene, 3g antioxidant 1010 are added in kneader, be uniformly mixed, rise after material under 60 ℃, vacuum and dry, then through the twin screw extruder melting, extrude, granulation, make 1000g phosphoric acid ester nano composite fire retardant master batch (FRWS-1).
The product performance contrast
| Test event | Testing method | Unit | The BDP fire retardation PC | The FRWS-1 fire retardation PC |
| Vertical combustion (1.6mm) | GB/T 2408-2008 | / | V-0 | V-0 |
| Oxygen index | GB/T 2406-2008 | % | 38 | 39 |
| Shock strength | GB/T 1043-2008 | kJ/m 2 | 7 | 15 |
| Heat-drawn wire | GB/T 1634-2004 | ℃ | 90 | 120 |
* the fire retardant addition is all 8%
In this embodiment, to replace to silane coupling agent be one or more in KH550, KH560 and KH570 to coupling agent KH550; Antioxidant 1010 replaces to one or more in antioxidant 1010, antioxidant 300 and irgasfos 168; Maleic anhydride inoculated polypropylene replaces to one or more in maleic anhydride grafted polyethylene, maleic anhydride inoculated polypropylene and maleic anhydride grafted ethene-acetate ethylene copolymer; Hypo-aluminum orthophosphate replaces to one or more in linear phenolic resin, zinc borate, hypo-aluminum orthophosphate and silicon-dioxide.Finally also can reach the technique effect identical with embodiment 1.
Embodiment 2
1) preparation of phosphoric acid ester/organic clay nano composite flame-retardant agent
90 parts of RDP are heated to 95 ℃ under stirring action, add respectively 1.5 parts of coupling agent KH550 and 15 parts of organo-clay, under 95 ℃, high-speed stirring 6 hours, obtain phosphoric acid ester/organic clay nano composite flame-retardant agent (RDP/OMMT).
2) preparation of phosphoric acid ester/organic clay nano composite flame-proof master batch
500g RDP/OMMT, 95g linear phenolic resin, 400g maleic anhydride grafted ethene-acetate ethylene copolymer, 5g antioxidant 300 are added in kneader, be uniformly mixed, rise after material under 60 ℃, vacuum and dry, then through the twin screw extruder melting, extrude, granulation, make 1000g phosphoric acid ester nano composite fire retardant master batch (FRWS-2).
The product performance contrast
| Test event | Testing method | Unit | The RDP fire retardation PC | The FRWS-2 fire retardation PC |
| Vertical combustion (1.6mm) | GB/T 2408-2008 | / | V-0 | V-0 |
| Oxygen index | GB/T 2406-2008 | % | 38 | 39 |
| Shock strength | GB/T 1043-2008 | kJ/m 2 | 7 | 15 |
| Heat-drawn wire | GB/T 1634-2004 | ℃ | 85 | 115 |
* the fire retardant addition is all 10%
Adopt 750g RDP/OMMT, 45g linear phenolic resin, 200g maleic anhydride grafted ethene-acetate ethylene copolymer, 5g antioxidant 300 are added in kneader in this embodiment, be uniformly mixed, rise after material under 60 ℃, vacuum and dry, then through the twin screw extruder melting, extrude, granulation, make 1000g phosphoric acid ester nano composite fire retardant master batch.This phosphoric acid ester nano composite fire retardant master batch also can reach the technique effect identical with embodiment 2.
Embodiment 3
1) preparation of phosphoric acid ester/organic clay nano composite flame-retardant agent
80 parts of TPP are heated to 90 ℃ under stirring action, add respectively 0.1 part of coupling agent KH550 and 1 part of organo-clay, under 90 ℃, high-speed stirring 3 hours, obtain phosphoric acid ester/organic clay nano composite flame-retardant agent (TPP/OMMT).
2) preparation of phosphoric acid ester/organic clay nano composite flame-proof master batch
600g TPP/OMMT, 199g linear phenolic resin, 200g maleic anhydride grafted ethene-acetate ethylene copolymer, 1g antioxidant 300 are added in kneader, be uniformly mixed, rise after material under 60 ℃, vacuum and dry, then through the twin screw extruder melting, extrude, granulation, make 1000g phosphoric acid ester nano composite fire retardant master batch (FRWS-3).
The product performance contrast
| Test event | Testing method | Unit | The TTP fire retardation PC | The FRWS-3 fire retardation PC |
| Vertical combustion (1.6mm) | GB/T 2408-2008 | / | V-2 | V-0 |
| Oxygen index | GB/T 2406-2008 | % | 35 | 39 |
| Shock strength | GB/T 1043-2008 | kJ/m 2 | 6 | 16 |
| Heat-drawn wire | GB/T 1634-2004 | ℃ | 75 | 105 |
* the fire retardant addition is all 10%
Adopt 400g TPP/OMMT, 200g linear phenolic resin, 395g maleic anhydride grafted ethene-acetate ethylene copolymer, 5g antioxidant 300 are added in kneader in this embodiment, be uniformly mixed, rise after material under 60 ℃, vacuum and dry, then through the twin screw extruder melting, extrude, granulation, make 1000g phosphoric acid ester nano composite fire retardant master batch.Phosphoric acid ester nano composite fire retardant master batch finally also can reach the technique effect identical with embodiment 3.
Claims (10)
1. a phosphoric acid ester nano composite fire retardant master batch, is characterized in that consisting of the raw material of following weight percent: phosphoric acid ester/organic clay nano composite flame-retardant agent 40～75%, fire retarding synergist 3～20%, vector resin 20～40% and oxidation inhibitor 0.1～0.5%.
2. a kind of phosphoric acid ester nano composite fire retardant master batch as claimed in claim 1, is characterized in that consisting of the raw material of following weight percent: phosphoric acid ester/organic clay nano composite flame-retardant agent 45～65%, fire retarding synergist 5～20%, vector resin 25～35% and oxidation inhibitor 0.2～0.4%.
3. a kind of phosphoric acid ester nano composite fire retardant master batch as claimed in claim 1, is characterized in that consisting of the raw material of following weight percent: phosphoric acid ester/organic clay nano composite flame-retardant agent 53～60%, fire retarding synergist 10～15%, vector resin 27～32% and oxidation inhibitor 0.25～0.35%.
4. as claim 1 or 2 or 3 described a kind of phosphoric acid ester nano composite fire retardant master batches, it is characterized in that described phosphoric acid ester/organic clay nano composite flame-retardant agent makes by following step:
According to phosphate flame retardant 80～100 weight parts, organo-clay 1～20 weight part and silane coupling agent 0.1～2 weight part, prepared burden; Phosphate flame retardant is heated to 90～100 ℃, adds organo-clay and silane coupling agent, keep temperature to stir 3～6 hours, obtain phosphoric acid ester/organic clay nano composite flame-retardant agent.
5. as claim 1 or 2 or 3 described a kind of phosphoric acid ester nano composite fire retardant master batches, it is characterized in that described fire retarding synergist is one or more in linear phenolic resin, zinc borate, hypo-aluminum orthophosphate and silicon-dioxide.
6. as claim 1 or 2 or 3 described a kind of phosphoric acid ester nano composite fire retardant master batches, it is characterized in that described vector resin is one or more in maleic anhydride grafted polyethylene, maleic anhydride inoculated polypropylene and maleic anhydride grafted ethene-acetate ethylene copolymer.
7. as claim 1 or 2 or 3 described a kind of phosphoric acid ester nano composite fire retardant master batches, it is characterized in that described oxidation inhibitor is one or more in antioxidant 1010, antioxidant 300 and irgasfos 168.
8. a kind of phosphoric acid ester nano composite fire retardant master batch as claimed in claim 4, is characterized in that described phosphate flame retardant is one or more in BDP, RDP and TPP, and described silane coupling agent is one or more in KH550, KH560 and KH570.
9. a kind of phosphoric acid ester nano composite fire retardant master batch as claimed in claim 4, is characterized in that being prepared burden according to phosphate flame retardant 85～95 weight parts, organo-clay 5～15 weight parts and silane coupling agent 0.5～1.5 weight part.
10. as the preparation method of claim 1 or 2 or 3 described a kind of phosphoric acid ester nano composite fire retardant master batches, it is characterized in that comprising following processing step:
By the phosphoric acid ester of described weight percent/organic clay nano composite flame-retardant agent, fire retarding synergist, vector resin and oxidation inhibitor are put into kneader, are uniformly mixed 10～15 minutes, after a material, at vacuum, 60 ℃ of temperature, dry, and obtain Preblend; Preblend is put into to twin screw incorporates, extrudes, granulation, obtain phosphoric acid ester nano composite fire retardant master batch.
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| CN104448948A (en) * | 2014-12-10 | 2015-03-25 | 山东川君化工股份有限公司 | Preparation method of modified aluminium hypophosphite |
| CN106977874A (en) * | 2017-02-28 | 2017-07-25 | 绵阳朗迪新材料有限公司 | Halogen-free environment-friendly flame-proof ABS/PC resin alloys |
| CN108587035A (en) * | 2018-04-08 | 2018-09-28 | 慈溪市山今高分子塑料有限公司 | A kind of halogen-free flameproof optical fiber tail sleeve TPE material and preparation method thereof |
| CN112480534A (en) * | 2020-11-26 | 2021-03-12 | 上海明克包装制品有限公司 | Heat-resistant flame-retardant paper-plastic composite bag and preparation method thereof |
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| CN104448948A (en) * | 2014-12-10 | 2015-03-25 | 山东川君化工股份有限公司 | Preparation method of modified aluminium hypophosphite |
| CN106977874A (en) * | 2017-02-28 | 2017-07-25 | 绵阳朗迪新材料有限公司 | Halogen-free environment-friendly flame-proof ABS/PC resin alloys |
| CN108587035A (en) * | 2018-04-08 | 2018-09-28 | 慈溪市山今高分子塑料有限公司 | A kind of halogen-free flameproof optical fiber tail sleeve TPE material and preparation method thereof |
| CN112480534A (en) * | 2020-11-26 | 2021-03-12 | 上海明克包装制品有限公司 | Heat-resistant flame-retardant paper-plastic composite bag and preparation method thereof |
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