CN102391581A - Halogen-free flame-retarding polypropylene nano composite material and preparation method thereof - Google Patents
Halogen-free flame-retarding polypropylene nano composite material and preparation method thereof Download PDFInfo
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- CN102391581A CN102391581A CN201110306154XA CN201110306154A CN102391581A CN 102391581 A CN102391581 A CN 102391581A CN 201110306154X A CN201110306154X A CN 201110306154XA CN 201110306154 A CN201110306154 A CN 201110306154A CN 102391581 A CN102391581 A CN 102391581A
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- halogen
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- flame redardant
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Abstract
The invention discloses a halogen-free flame-retarding polypropylene nano composite material, which comprises the following components in part by weight: 60 to 80 weight parts of polypropylene, 15 to 30 weight parts of nano laminar double hydroxide, 1 to 8 weight parts of organic silicon resin, 1 to 5 weight parts of compatilizer, and 0.1 to 1 weight part of antioxygen. The invention also discloses a method for preparing the halogen-free flame-retarding polypropylene nano composite material. In the method, the adopted nano laminar double hydroxide, organic silicon resin and polypropylene form a stable carbon layer at a high temperature, and thus, heat and flammable gases are prevented from permeating effectively, and the flame retardant property of the material is improved. In the preparation process of the composite material, the adopted flame retardant is halogen-free flame retardant; and toxic and corrosive gases are not generated in the preparation process, and the preparation method meets an environment-protection requirement.
Description
Technical field
The present invention relates to the modifying plastics technical field, be specifically related to a kind of halogen-free polypropylene flame redardant nano composite material and preparation method thereof.
Background technology
Vestolen PP 7052 (PP) is a kind of thermoplastic resin, and its raw material sources are abundant, and are cheap, have better comprehensive performance simultaneously, in industries such as automobile, electrical equipment, daily necessities and furniture, packing, building, obtained increasingly extensive application.Yet polyacrylic flame retardant properties is poor, very easily burning, and its limiting oxygen index(LOI) (LOI) is 18.5; Belong to inflammable substance, thermal value is high when meeting fire burns, combustionvelocity is 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 receives great restriction.At present, widely used Vestolen PP 7052 is through flame-retardant modified mostly.In addition, owing to contain some and the inconsistent small-molecule substance of polypropylene matrix mostly in the Halogen polypropylene flame redardant, 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 people's is to environmental protection and healthy pay attention to day by day, and the halogen-free flameproof performance of goods also more and more is 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 in patent CN03131694.8, proposes 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.
It is main chain with the Si-O-Si key that silicone resin is one type, directly connects the polymkeric substance of organic radical on the Siliciumatom, has had concurrently organic and characteristic inorganic materials.Silicone resin is mainly used in fire-retardant polycarbonate at present, is used on the Vestolen PP 7052 little to the flame retardant properties influence separately.The present invention has adopted cooperative flame retardant, finally prepares the good matrix material of flame retardant effect.
Summary of the invention
The object of the present invention is to provide a kind of halogen-free polypropylene flame redardant nano composite material and preparation method thereof.Prepared halogen-free polypropylene flame redardant nano composite material overcome existing single halogen-free flame retardants flame retardant effect not obvious with problem such as affect the mechanical properties; The nano layered double hydroxides, silicone resin and the Vestolen PP 7052 that adopt at high temperature form stable carbon-coating; Effectively intercept the infiltration of heat and inflammable gas, improved the flame retardant properties of material.The fire retardant that adopts in this Composite Preparation process is a halogen-free flame retardants, and its preparation process does not produce poisonous and corrosive gases, meets environment protection requirement.
The present invention for realizing the technical scheme that above-mentioned purpose adopted is:
A kind of halogen-free polypropylene flame redardant nano composite material, its component and mass percent are following:
Said Vestolen PP 7052 is a kind of or mixture among HOPP or the COPP.
The particle diameter of said nano layered double hydroxides is 20～80nm.
The general formula of said silicone resin is (R
nSiO
4-n/2)
m, the organic radical R in this silicone resin is methyl, ethyl, propyl group, butyl or phenyl, and n is the organic radix that connects on the Siliciumatom, and this n=1,2 or 3, m are the polymerization degree, this m＞2.
Said compatilizer is polypropylene grafted maleic anhydride PP-g-MAH.
Said oxidation inhibitor is antioxidant 1010, and chemical constitution is: four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester.
A kind of preparation method of aforesaid halogen-free polypropylene flame redardant nano composite material, it may further comprise the steps:
(1) take by weighing raw material by following component and mass percent:
(2) place high-speed mixer to mix discharging 2～5 minutes the raw material that is taken by weighing in this step (1);
(3) mixed raw materials in the step (2) is placed the extrusion equipment extruding pelletization, obtain this halogen-free polypropylene flame redardant nano composite material.
Said extrusion equipment is a parallel double-screw extruder, and in the technological process of extruding pelletization, the temperature of this forcing machine is 180～200 ℃, and the engine speed of this forcing machine is 150～500RPM.
Described Vestolen PP 7052 is a kind of or its mixture among HOPP or the COPP; The particle diameter of said nano layered double hydroxides is 20～80nm.
The general formula of described silicone resin is (R
nSiO
4-n/2)
m, the organic radical R in this silicone resin is methyl, ethyl, propyl group, butyl or phenyl, and n is the organic radix that connects on the Siliciumatom, and this n=1,2 or 3, m are the polymerization degree, this m＞2; Said compatilizer is polypropylene grafted maleic anhydride PP-g-MAH; Said oxidation inhibitor is antioxidant 1010, and chemical constitution is: four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester.
Beneficial effect of the present invention is: halogen-free polypropylene flame redardant nano composite material of the present invention and preparation method thereof; Be on cooperative flame retardant basis, adopt common melt-blending process to obtain nanometer composite polypropylene material again through organic silicon resin fire retardant and layered double-hydroxide.Compared with prior art; The present invention is because with organic silicon resin fire retardant and nano layered double hydroxides cooperative flame retardant; Compare the flame retardant effect of single fire retardant and want much obvious, and the fire retardant that the present invention adopts is halogen-free flame retardants, meet environment protection requirement fully.Because the laminated double hydroxide nanometer lamella can be dispersed in the Vestolen PP 7052, realize the application of nanotechnology simultaneously, improved the mechanical property of material.
In the matrix material of the present invention, lowered the thermal destruction speed of PP composite material in thermal destruction or combustion processes owing to added silicone resin; The product that silicone resin decompose to produce can same layered double-hydroxide, Vestolen PP 7052 reacts the generation compact carbon layer; Organosilyl in addition decomposition can also form unbodied silicon-dioxide, improves the thermostability of charcoal layer, thereby realizes polyacrylic fire-retardant.
Embodiment
Embodiment 1: a kind of halogen-free polypropylene flame redardant nano composite material of the present invention, and its component and mass percent are following:
Said Vestolen PP 7052 is a kind of or mixture among HOPP or the COPP.
The particle diameter of said nano layered double hydroxides is 20～80nm.
The general formula of said silicone resin is (R
nSiO
4-n/2)
m, the organic radical R in this silicone resin is methyl, ethyl, propyl group, butyl or phenyl, and n is the organic radix that connects on the Siliciumatom, and this n=1,2 or 3, m are the polymerization degree, this m＞2.
Said compatilizer is polypropylene grafted maleic anhydride PP-g-MAH.
Said oxidation inhibitor is antioxidant 1010, and chemical constitution is: four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester.
A kind of preparation method of aforesaid halogen-free polypropylene flame redardant nano composite material, it may further comprise the steps:
(1) take by weighing raw material by following component and mass percent:
(2) place high-speed mixer to mix discharging 2～5 minutes the raw material that is taken by weighing in this step (1);
(3) mixed raw materials in the step (2) is placed the extrusion equipment extruding pelletization, obtain this halogen-free polypropylene flame redardant nano composite material.
Said extrusion equipment is a parallel double-screw extruder, and in the technological process of extruding pelletization, the temperature of this forcing machine is 180～200 ℃, and the engine speed of this forcing machine is 150～500RPM.
Described Vestolen PP 7052 is a kind of or its mixture among HOPP or the COPP; The particle diameter of said nano layered double hydroxides is 20～80nm.
The general formula of described silicone resin is (R
nSiO
4-n/2)
m, the organic radical R in this silicone resin is methyl, ethyl, propyl group, butyl or phenyl, and n is the organic radix that connects on the Siliciumatom, and this n=1,2 or 3, m are the polymerization degree, this m＞2; Said compatilizer is polypropylene grafted maleic anhydride PP-g-MAH; Said oxidation inhibitor is antioxidant 1010, and chemical constitution is: four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester.
Concrete, be matrix resin with the Vestolen PP 7052, nano layered double hydroxides and silicone resin are fire retardant, and PP-g-MAH is a compatilizer, and antioxidant 1010 is an oxidation inhibitor.Concrete mass percent is following: 70 weight part Vestolen PP 7052,20 weight part nano layered double hydroxides, 6 weight part silicone resins, 3 weight part PP-g-MAH and 1 weight part antioxidant 1010.All raw materials were put into high-speed mixer and mixing 3 minutes, and discharging places the twin screw extruder extruding pelletization with raw materials mixed, and the engine speed of twin screw extruder is 250RPM, and temperature is 190 ℃, obtains the halogen-free polypropylene flame redardant nano composite material.
Embodiment 2: halogen-free flameproof propylene nano composite material of present embodiment and preparation method thereof is basic identical with embodiment 1; Its difference is following: concrete; With the Vestolen PP 7052 is matrix resin; Nano layered double hydroxides and silicone resin are fire retardant, and PP-g-MAH is a compatilizer, and antioxidant 1010 is an oxidation inhibitor.Concrete mass percent is following: 65 weight part Vestolen PP 7052,25 weight part nano layered double hydroxides, 7 weight part silicone resins, 2.5 weight part PP-g-MAH and 0.5 weight part antioxidant 1010.All raw materials were put into high-speed mixer and mixing 3 minutes, and discharging places the twin screw extruder extruding pelletization with raw materials mixed, and the engine speed of twin screw extruder is 250RPM, and temperature is 190 ℃, obtains the halogen-free polypropylene flame redardant nano composite material.
Embodiment 3: halogen-free flameproof propylene nano composite material of present embodiment and preparation method thereof is basic identical with embodiment 1,2; Its difference is following: concrete; With the Vestolen PP 7052 is matrix resin; Nano layered double hydroxides and silicone resin are fire retardant, and PP-g-MAH is a compatilizer, and antioxidant 1010 is an oxidation inhibitor.Concrete mass percent is following: 75 weight part Vestolen PP 7052,18 weight part nano layered double hydroxides, 5 weight part silicone resins, 1.5 weight part PP-g-MAH and 0.5 weight part antioxidant 1010.All raw materials were put into high-speed mixer and mixing 3 minutes, and discharging places the twin screw extruder extruding pelletization with raw materials mixed, and the engine speed of twin screw extruder is 250RPM, and temperature is 190 ℃, obtains the halogen-free polypropylene flame redardant nano composite material.
Embodiment 1-3 gained halogen-free polypropylene flame redardant nano composite material is carried out performance test by following standard: mechanics, oxygen index and thermal property are according to the ASTM standard, and the vertical combustion performance is pressed the UL-94 standard.
The performance table of table 1 embodiment 1-3 gained sample
Halogen-free polypropylene flame redardant nano composite material of the present invention and preparation method thereof is on the cooperative flame retardant basis through organic silicon resin fire retardant and layered double-hydroxide, adopts common melt-blending process to obtain nanometer composite polypropylene material again.Compared with prior art; The present invention is because with organic silicon resin fire retardant and nano layered double hydroxides cooperative flame retardant; Compare the flame retardant effect of single fire retardant and want much obvious, and the fire retardant that the present invention adopts is halogen-free flame retardants, meet environment protection requirement fully.Because the laminated double hydroxide nanometer lamella can be dispersed in the Vestolen PP 7052, realize the application of nanotechnology simultaneously, improved the mechanical property of material.
In the matrix material of the present invention, lowered the thermal destruction speed of PP composite material in thermal destruction or combustion processes owing to added silicone resin; The product that silicone resin decompose to produce can same layered double-hydroxide, Vestolen PP 7052 reacts the generation compact carbon layer; Organosilyl in addition decomposition can also form unbodied silicon-dioxide, improves the thermostability of charcoal layer, thereby realizes polyacrylic fire-retardant.
Of the embodiment of the invention, with other halogen-free polypropylene flame redardant nano composite materials of the same or similar structure of the present invention and preparation method thereof, all in protection domain of the present invention.
Claims (10)
1. a halogen-free polypropylene flame redardant nano composite material is characterized in that, its component and mass percent are following:
2. halogen-free polypropylene flame redardant nano composite material according to claim 1 is characterized in that, said Vestolen PP 7052 is a kind of or mixture among HOPP or the COPP.
3. halogen-free polypropylene flame redardant nano composite material according to claim 1 is characterized in that, the particle diameter of said nano layered double hydroxides is 20～80nm.
4. halogen-free polypropylene flame redardant nano composite material according to claim 1 is characterized in that, the general formula of said silicone resin is (R
nSiO
4-n/2)
m, the organic radical R in this silicone resin is methyl, ethyl, propyl group, butyl or phenyl, and n is the organic radix that connects on the Siliciumatom, and this n=1,2 or 3, m are the polymerization degree, this m＞2.
5. halogen-free polypropylene flame redardant nano composite material according to claim 1 is characterized in that, said compatilizer is polypropylene grafted maleic anhydride PP-g-MAH.
6. halogen-free polypropylene flame redardant nano composite material according to claim 1 is characterized in that, said oxidation inhibitor is antioxidant 1010, and chemical constitution is: four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester.
7. the preparation method of the described halogen-free polypropylene flame redardant nano composite material of claim 1 is characterized in that it may further comprise the steps:
(1) take by weighing raw material by following component and mass percent:
(2) place high-speed mixer to mix discharging 2～5 minutes the raw material that is taken by weighing in this step (1);
(3) mixed raw materials in the step (2) is placed the extrusion equipment extruding pelletization, obtain this halogen-free polypropylene flame redardant nano composite material.
8. preparation method according to claim 7 is characterized in that, said extrusion equipment is a parallel double-screw extruder, and in the technological process of extruding pelletization, the temperature of this forcing machine is 180～200 ℃, and the engine speed of this forcing machine is 150～500RPM.
9. preparation method according to claim 7 is characterized in that, described Vestolen PP 7052 is a kind of or its mixture among HOPP or the COPP; The particle diameter of said nano layered double hydroxides is 20～80nm.
10. preparation method according to claim 7 is characterized in that, the general formula of described silicone resin is (R
nSiO
4-n/2)
m, the organic radical R in this silicone resin is methyl, ethyl, propyl group, butyl or phenyl, and n is the organic radix that connects on the Siliciumatom, and this n=1,2 or 3, m are the polymerization degree, this m＞2; Said compatilizer is polypropylene grafted maleic anhydride PP-g-MAH; Said oxidation inhibitor is antioxidant 1010, and chemical constitution is: four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110306154XA CN102391581A (en) | 2011-10-11 | 2011-10-11 | Halogen-free flame-retarding polypropylene nano composite material and preparation method thereof |
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| CN201110306154XA CN102391581A (en) | 2011-10-11 | 2011-10-11 | Halogen-free flame-retarding polypropylene nano composite material and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103992563A (en) * | 2014-05-19 | 2014-08-20 | 安徽嘉木橡塑工业有限公司 | Flame retardant polypropylene masterbatch |
| CN105482461A (en) * | 2016-01-25 | 2016-04-13 | 广东工业大学 | Fire retardant and preparation method thereof |
| CN105504757A (en) * | 2016-01-25 | 2016-04-20 | 广东工业大学 | Flame-retardant PC plastic and preparation method thereof |
| CN112300466A (en) * | 2019-07-29 | 2021-02-02 | 合肥杰事杰新材料股份有限公司 | Polyolefin flame-retardant master batch and preparation method and application thereof |
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| JPH09165478A (en) * | 1995-12-15 | 1997-06-24 | Ube Ind Ltd | Polypropylene resin composition for automobile component part |
| CN101724198A (en) * | 2009-12-22 | 2010-06-09 | 上海大学 | Halogen-free flame-retardant and low-odor polypropylene/layered double-hydroxide nanocomposite and preparation method thereof |
| CN102181099A (en) * | 2011-03-07 | 2011-09-14 | 黑龙江省润特科技有限公司 | Ultraviolet deep crosslinked halogen-free flame-retardant ethylene propylene rubber cable material and preparation method of insulating or sheathing layer thereof |
-
2011
- 2011-10-11 CN CN201110306154XA patent/CN102391581A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09165478A (en) * | 1995-12-15 | 1997-06-24 | Ube Ind Ltd | Polypropylene resin composition for automobile component part |
| CN101724198A (en) * | 2009-12-22 | 2010-06-09 | 上海大学 | Halogen-free flame-retardant and low-odor polypropylene/layered double-hydroxide nanocomposite and preparation method thereof |
| CN102181099A (en) * | 2011-03-07 | 2011-09-14 | 黑龙江省润特科技有限公司 | Ultraviolet deep crosslinked halogen-free flame-retardant ethylene propylene rubber cable material and preparation method of insulating or sheathing layer thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103992563A (en) * | 2014-05-19 | 2014-08-20 | 安徽嘉木橡塑工业有限公司 | Flame retardant polypropylene masterbatch |
| CN105482461A (en) * | 2016-01-25 | 2016-04-13 | 广东工业大学 | Fire retardant and preparation method thereof |
| CN105504757A (en) * | 2016-01-25 | 2016-04-20 | 广东工业大学 | Flame-retardant PC plastic and preparation method thereof |
| CN105482461B (en) * | 2016-01-25 | 2018-09-14 | 广东工业大学 | A kind of fire retardant and preparation method thereof |
| CN112300466A (en) * | 2019-07-29 | 2021-02-02 | 合肥杰事杰新材料股份有限公司 | Polyolefin flame-retardant master batch and preparation method and application thereof |
| CN112300466B (en) * | 2019-07-29 | 2022-04-26 | 合肥杰事杰新材料股份有限公司 | Polyolefin flame-retardant master batch and preparation method and application thereof |
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Application publication date: 20120328 |