CN101724198A - Halogen-free flame-retardant and low-odor polypropylene/layered double-hydroxide nanocomposite and preparation method thereof - Google Patents
Halogen-free flame-retardant and low-odor polypropylene/layered double-hydroxide nanocomposite and preparation method thereof Download PDFInfo
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- CN101724198A CN101724198A CN200910200537A CN200910200537A CN101724198A CN 101724198 A CN101724198 A CN 101724198A CN 200910200537 A CN200910200537 A CN 200910200537A CN 200910200537 A CN200910200537 A CN 200910200537A CN 101724198 A CN101724198 A CN 101724198A
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Abstract
The invention relates to a halogen-free flame-retardant and low-odor polypropylene/layered double-hydroxide nanocomposite and a preparation method thereof. The halogen-free flame-retardant and low-odor polypropylene/layered double-hydroxide nanocomposite is characterized by comprising the following raw materials in percentage by weight (wt%): 70 to 99 of polypropylene and 1 to 30 of nano halogen-free flame-retardant system. The nano halogen-free flame-retardant system is a two-component nano halogen-free flame-retardant system of the layered double-hydroxide of the intercalation of 3-hydroxyphenyl phosphoroso-propanoic acid (CEPPA), which has an obviously synergistic flame-retardant effect. The material and the preparation method thereof have the characteristics of simple process, low cost, good flame-retardant effect, low odor and good mechanical property, and can be used in the industries of automobiles, construction, household electric appliances and the like.
Description
Technical field
The present invention relates to the modifying plastics technical field, be specifically related to polypropylene/layered double hydroxide nano composite material and preparation method thereof.
Background technology
Polypropylene (PP) is a kind of thermoplastic resin, and its raw material sources are abundant, and are cheap, have better comprehensive performance simultaneously, obtained increasingly extensive application in industries such as automobile, electrical equipment, daily necessities and furniture, packing, building.Yet polyacrylic flame retardant properties is poor, very easily burning, its limiting oxygen index(LOI) (LOI) is 18.5, belong to inflammable substance, thermal value height when meeting fire burns, combustionvelocity are fast, and be fuming, drip phenomenon, presence of fire easily, flame propagation speed is difficult for extinguishing, and causes great injury for people's life, property.Therefore unmodified polyacrylic Application Areas is subjected to great restriction.At present, widely used polypropylene is through flame-retardant modified mostly.In addition, owing to contain some and the inconsistent small-molecule substance of polypropylene matrix in the modified polypropene mostly, therefore, its goods in use can produce volatile matter, influence the use of product, also produce certain bad smell simultaneously, air, especially room air produces detrimentally affect, and user's health and environment caused certain infringement.Along with the pay attention to day by day of people to environmental protection and health, the low volatilization of goods, low odor properties also more and more are much accounted of, and need detect and control it when dispatching from the factory.
Layered double-hydroxide (LDH) is meant that ideal consists of [N
2+ 1-xM
3+ x(OH)
2]
X+(A
H-)
X/hMH
2The anionic intercalation material of the quasi-representative of O, wherein N
2+Be divalent-metal ion, comprise: Mg
2+, Ca
2+, Ba
2+, Fe
2+, Zn
2+, Cu
2+, Cr
2+, Co
2+, Ni
2+M
3+Be trivalent metal ion, comprise Al
3+, Fe
3+, Co
3+, Ni
3+A is a negatively charged ion, comprises NO
3 -, Cl
-, CO
3 2-, SO
4 2-And the dodecyl sodium sulfonate root, note by abridging and be N
nM/A-LDH, n are N
2+With M
3+Mol ratio.Layered double-hydroxide has important use as a kind of nano modifier at polymeric material field, can be used as anti-flaming smoke-inhibiting agent, biology/medical material, ultraviolet/infrared absorbing material etc.Polymer/laminated double-hydroxide nanocomposite that proposes in patent CN03131694.8 and preparation method thereof has solved and has disperseed inhomogeneous and compatibility problem, but the flame retardant resistance of layered double-hydroxide do not done special research.
Summary of the invention
The object of the present invention is to provide a kind of halogen-free flameproof, low odor polypropylene/layered double hydroxide nano composite material and preparation method thereof.
Halogen-free flameproof of the present invention, low odor polypropylene/layered double hydroxide nano composite material is characterized in that matrix material is made up of the raw material of following weight percent (wt%):
Polypropylene 70～99
Nanometer halogen-free anti-flaming system 1～30
Described polypropylene is homopolymerization or block copolymerization polypropylene, and consumption is 70wt%～99wt%.
Described nanometer halogen-free anti-flaming system is the nanometer halogen-free anti-flaming system of layered double-hydroxide two constituent elements of a kind of 3-hydroxy phenyl phosphoroso-propionic acid (CEPPA) intercalation.
The preparation method of halogen-free flameproof of the present invention, low odor polypropylene/layered double hydroxide nano composite material is characterized in that the preparation method comprises the steps:
The preparation of step 1, nanometer halogen-free anti-flaming system
Divalent-metal ion and trivalent metal ion mol ratio n=1～3, metal ion total concn be 0.1～1mol/L mixing salt in the aqueous solution, be added dropwise to the 3-hydroxy phenyl phosphoroso-propionic acid CEPPA that contains 0.5～1.5 times of trivalent metal ion integral molar quantity, dripping weight concentration is the mixing solutions of 5～50% alkali, to pH value 7～12, at N
2Protection is down stirred 1～2h, and 60 ℃～80 ℃ ageing 24～72h cool off, filtration, washing, drying then, the nanometer halogen-free anti-flaming system.
Step 2, mixing
The nanometer halogen-free anti-flaming system of polypropylene and above-mentioned preparation is mixed in twin screw extruder, and extrusion temperature is set in 180 ℃～220 ℃ scopes, vacuum tightness-0.08Pa, engine speed 80～280r/min.
Described mixing salt the divalent-metal ion in the aqueous solution be Mg
2+, Ca
2+, Zn
2+Or Ni
2+In a kind of, trivalent metal ion is Al
3+, Fe
3+Or Cr
3+In a kind of.
Described alkaline solution is the aqueous solution of sodium hydroxide or potassium hydroxide.
Halogen-free flameproof of the present invention, low odor polypropylene/layered double hydroxide nano composite material and preparation method thereof, be by on the basis of organic phosphorus flame retardant intercalation modifying layered double-hydroxide, adopt common melt-blending process to obtain polypropylene/layered double hydroxide nano composite material again.Compared with prior art, the present invention since with the organic phosphorus flame retardant intercalation to the layered double-hydroxide interlayer, make the hydrophilic surface of layered double-hydroxide be transformed into lipophilicity, can be well compatible with polypropylene, do not produce reunion, the laminated double hydroxide nanometer lamella can be dispersed in the polypropylene, fire retardant CEPPA is fixed on the laminated double hydroxide nanometer lamella by electrostatic interaction simultaneously, control the organophosphorus small molecules effectively and be seeped into composite material surface outward, significantly reduce micromolecular volatilization, reduced the smell of matrix material, and organophosphorous fire retardant also has the cooperative flame retardant effect with layered double-hydroxide, improves the flame retardant properties of matrix material greatly.In addition, the interpolation of nanometer halogen-free anti-flaming system has also improved physical chemistry over-all properties, the mechanical property of matrix material.
Embodiment
In conjunction with following specific embodiment, the present invention is described in further detail.
Embodiment 1
The preparation of step 1, nanometer halogen-free anti-flaming system
Zn (NO
3)
26H
2O and Al (NO
3)
39H
2O mol ratio n=3, metal ion total concn be 0.4mol/L mixing salt in the aqueous solution, be added dropwise to Al (NO
3)
39H
2The 3-hydroxy phenyl phosphoroso-propionic acid CEPPA that the O integral molar quantity is 1.2 times, dripping weight concentration is the mixing solutions of 20%NaOH, to the pH value be 9, at N
2Protection is down stirred 2h, and 60 ℃ of ageing 24h cool off, filtration, washing, drying then, the Zn of nanometer CEPPA intercalation
3Al/NO
3-LDH nanometer halogen-free anti-flaming system.
Step 2, mixing
Zn with the nanometer CEPPA intercalation of 93 weight part homo-polypropylene and the above-mentioned preparation of 3 weight parts
3Al-LDH nanometer halogen-free anti-flaming system is mixed in twin screw extruder, and extrusion temperature is set at 180 ℃, vacuum tightness-0.08Pa, engine speed 240r/min.
The performance of this halogen-free flameproof, low odor polypropylene/layered double hydroxide nano composite material is as follows: tensile strength: 25MPa (testing method: ISO 527); Modulus in flexure: 1600MPa (testing method: ISO 178); ASTM D2863-00), UL94V-0 level (testing method: UL 94-2004) flame retardant properties: limiting oxygen index(LOI) LOI=32 (testing method:; Smell: 3.5 (testing method: PV 3900C).
Embodiment 2-6
Concrete implementation step is consistent with embodiment 1, and difference is different raw materials and parameter setting, specifically sees Table 1 and table 2.The performance test results sees Table 3.
Table 1 nanometer halogen-free anti-flaming system preparation (step 1)
Table 2 mixes (step 2)
Annotate: the umber in the table all refers to weight part
Table 3 The performance test results
Claims (2)
1. a halogen-free flameproof, low odor polypropylene/layered double hydroxide nano composite material is characterized in that the composition of this matrix material is by weight percentage: polypropylene 70～99wt%, nanometer halogen-free anti-flaming system 1～30wt%; Described polypropylene is homopolymerization or block copolymerization polypropylene, and described nanometer halogen-free anti-flaming system is a kind of nanometer halogen-free anti-flaming system of layered double-hydroxide two constituent elements of 3-hydroxy phenyl phosphoroso-propionic acid intercalation.
2. preparation method who is used for the described halogen-free flameproof of claim 1, low odor polypropylene/layered double hydroxide nano composite material is characterized in that this method has following processing step:
A. the preparation of nanometer halogen-free anti-flaming system
Divalent-metal ion and trivalent metal ion mol ratio n=1～3, metal ion total concn be 0.1～1mol/L mixing salt in the aqueous solution, be added dropwise to the 3-hydroxy phenyl phosphoroso-propionic acid that contains 0.5～1.5 times of trivalent metal ion integral molar quantity, dripping weight concentration is the mixing solutions of 5～50% alkali, to the pH value be 7～12, at N
2Protection is down stirred 1～2h, and 60～80 ℃ of ageing 24～72h cool off, filtration, washing, drying then, the nanometer halogen-free anti-flaming system; Described mixing salt the divalent-metal ion in the aqueous solution be Mg
2+, Ca
2+, Zn
2+Or Ni
2+In a kind of, trivalent metal ion is Al
3+, Fe
3+Or Cr
3+In a kind of, described alkaline solution is the aqueous solution of sodium hydroxide or potassium hydroxide;
B. mix
The nanometer halogen-free anti-flaming system of polypropylene and step a preparation is mixed in twin screw extruder, and extrusion temperature is set in 180～220 ℃ of scopes, vacuum tightness-0.08Pa, engine speed 80～280r/min.
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|---|---|---|---|
| CN2009102005371A CN101724198B (en) | 2009-12-22 | 2009-12-22 | Halogen-free flame-retardant and low-odor polypropylene/layered double-hydroxide nanocomposite and preparation method thereof |
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|---|---|---|---|
| CN2009102005371A CN101724198B (en) | 2009-12-22 | 2009-12-22 | Halogen-free flame-retardant and low-odor polypropylene/layered double-hydroxide nanocomposite and preparation method thereof |
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| CN101724198B CN101724198B (en) | 2011-10-26 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391581A (en) * | 2011-10-11 | 2012-03-28 | 东莞上海大学纳米技术研究院 | Halogen-free flame-retarding polypropylene nano composite material and preparation method thereof |
| CN103275398A (en) * | 2013-04-10 | 2013-09-04 | 东莞上海大学纳米技术研究院 | Low-density flame-retardant polypropylene nano-composite material and preparation method thereof |
| CN105176074A (en) * | 2015-10-26 | 2015-12-23 | 厦门理工学院 | Nano hybridized flame-retardant polyamide 6 and preparation method thereof |
| CN105175776A (en) * | 2015-10-26 | 2015-12-23 | 厦门理工学院 | Nanometer halogen-free flame-retardant thermoplastic polyurethane elastomer and preparation method thereof |
| CN105271149A (en) * | 2015-10-26 | 2016-01-27 | 厦门理工学院 | Nano-hybrid flame retardant and preparation method thereof |
| CN107880480A (en) * | 2016-09-29 | 2018-04-06 | 航天特种材料及工艺技术研究所 | A kind of nano material modified phenolic resins and preparation method thereof |
| CN107880481A (en) * | 2016-09-29 | 2018-04-06 | 航天特种材料及工艺技术研究所 | A kind of layered double-hydroxide and preparation method thereof |
| CN109082017A (en) * | 2018-07-11 | 2018-12-25 | 河南科技大学 | A kind of phosphorus doping carbon nanotube/organically-modified layered double hydroxide/polyolefin flame-retardant material and preparation method thereof |
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- 2009-12-22 CN CN2009102005371A patent/CN101724198B/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391581A (en) * | 2011-10-11 | 2012-03-28 | 东莞上海大学纳米技术研究院 | Halogen-free flame-retarding polypropylene nano composite material and preparation method thereof |
| CN103275398A (en) * | 2013-04-10 | 2013-09-04 | 东莞上海大学纳米技术研究院 | Low-density flame-retardant polypropylene nano-composite material and preparation method thereof |
| CN105271149B (en) * | 2015-10-26 | 2018-01-23 | 厦门理工学院 | Nano hybridization fire retardant and preparation method thereof |
| CN105175776A (en) * | 2015-10-26 | 2015-12-23 | 厦门理工学院 | Nanometer halogen-free flame-retardant thermoplastic polyurethane elastomer and preparation method thereof |
| CN105271149A (en) * | 2015-10-26 | 2016-01-27 | 厦门理工学院 | Nano-hybrid flame retardant and preparation method thereof |
| CN105175776B (en) * | 2015-10-26 | 2018-01-12 | 厦门理工学院 | Nanometer halogen-free anti-flaming TPUE and preparation method thereof |
| CN105176074A (en) * | 2015-10-26 | 2015-12-23 | 厦门理工学院 | Nano hybridized flame-retardant polyamide 6 and preparation method thereof |
| CN105176074B (en) * | 2015-10-26 | 2019-01-25 | 厦门理工学院 | Nano hybridization Flameproof polyamide 6 and preparation method thereof |
| CN107880480A (en) * | 2016-09-29 | 2018-04-06 | 航天特种材料及工艺技术研究所 | A kind of nano material modified phenolic resins and preparation method thereof |
| CN107880481A (en) * | 2016-09-29 | 2018-04-06 | 航天特种材料及工艺技术研究所 | A kind of layered double-hydroxide and preparation method thereof |
| CN107880480B (en) * | 2016-09-29 | 2019-12-10 | 航天特种材料及工艺技术研究所 | Nano material modified phenolic resin and preparation method thereof |
| CN107880481B (en) * | 2016-09-29 | 2019-12-10 | 航天特种材料及工艺技术研究所 | Layered double hydroxide and preparation method thereof |
| CN109082017A (en) * | 2018-07-11 | 2018-12-25 | 河南科技大学 | A kind of phosphorus doping carbon nanotube/organically-modified layered double hydroxide/polyolefin flame-retardant material and preparation method thereof |
| CN109082017B (en) * | 2018-07-11 | 2020-11-20 | 河南科技大学 | Phosphorus-doped carbon nanotube/organic modified layered double hydroxide/polyolefin flame-retardant material and preparation method thereof |
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