CN105482252A - Halogen-free smoke-suppression flame-retardant polypropylene composite material and preparation method thereof - Google Patents
Halogen-free smoke-suppression flame-retardant polypropylene composite material and preparation method thereof Download PDFInfo
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- CN105482252A CN105482252A CN201511007791.1A CN201511007791A CN105482252A CN 105482252 A CN105482252 A CN 105482252A CN 201511007791 A CN201511007791 A CN 201511007791A CN 105482252 A CN105482252 A CN 105482252A
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- hydrotalcite
- flame retardant
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- smoke
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Abstract
The invention discloses a halogen-free smoke-suppression flame-retardant PP composite material and a preparation method thereof. The halogen-free smoke-suppression flame-retardant PP composite material comprises the following components in percentage by weight: 65%-85% of polypropylene, 6%-15% of laminate peel type hydrotalcite, 3%-6% of organosilicon modified hydrotalcite, 3%-8% of boric acid intercalated hydrotalcite, 2%-6% of a toughening agent, 0.5%-1% of an antioxidant and 0.5%-2% of a lubricant. Performance tests present that the composite material is good in smoke suppression performance and flame retardance and simultaneously preserves relatively good mechanical property.
Description
Technical field
The present invention relates to a kind of flame-proof composite material, belong to field of high polymer material modification, specifically a kind of Halogen smoke-inhibiting flame retardant polypropylene composite material and preparation method thereof.
Background technology
Polypropylene (PP) is a kind of commodity polymer material of high comprehensive performance, is widely used in the field such as electronic apparatus, automobile.Along with the expanding day of its range of application, requirements at the higher level are proposed to polyacrylic flame retardant properties.At present, halogen containing flame-retardant (particularly bromide fire retardant) is widely used in high molecular fire retardant material, and serves good fire retardation.But adopt the material of halogen containing flame-retardant can produce poisonous, corrosive gases and smog in a large number in combustion, make people be choked to death, its hazardness is even more serious than big fire itself.In view of the protection to environment, the application of halogenated flame retardant is restricted, and Halogen smoke-inhibiting flame retardant polypropylene has become current study hotspot.
Halogen-free flame retardants, mainly based on inorganic combustion inhibitor, halogen-free expansion fire retardant and organic silicon fibre retardant, is not fuming during the burning of this three based flame retardant, is not produced corrosive gases, be called as " green " fire retardant.And inorganic combustion inhibitor is because of its good stability, low toxicity or nontoxic, there is environmental protection, safety, press down cigarette and the advantage of generally acknowledging such as inexpensive.
Inorganic combustion inhibitor mainly contains: phosphorus series compound, molybdenum based compound, tin based compound, layered silicate, weisspiessglanz, borate, magnesium hydroxide, aluminium hydroxide, hydrotalcite etc.Wherein hydrotalcite and analogue thereof because of its smoke-inhibiting flame retardant functional, and there is filling properties, be the class inorganic combustion inhibitor be concerned by people in recent years, but still exist and PP poor compatibility, not easily good distribution in PP, causes the problems such as addition is higher, flame retarding efficiency is on the low side.
The mode of the inorganic fire-retarded performance of existing raising mainly contains: (1) super-refinement, fire retardant powder particle is diminished, specific surface area increases, surface energy increases, thus the reactive behavior of particle surface strengthens, be conducive to the dispersion of particle in PP material, and the interface binding power of fire retardant and PP storeroom can be improved, improve the machine-shaping property of body material and the mechanical property of goods further; (2) surface modification treatment, the condition of surface of fire-retardant particles is changed by various surface-modifying agent and fire-retardant particles surface chemical reaction and Surface coating process, to improve fire retardant surfactivity, its surface is made to produce new physics, chemical functional, thus the avidity improved between fire retardant and matrix polymer, be conducive to fire retardant dispersion in the base, improve Drawing abillity and mechanical property; (3) complex treatment, utilize the cooperative flame retardant effect between various fire retardant, two or more fire retardant is carried out compound, mixture, make composite flame-retardant agent to use, make their mutual synergy, learn from other's strong points to offset one's weaknesses, thus reach the consumption reducing fire retardant, improve the objects such as Flame Retardancy energy, processing characteristics and mechanical property.
Be difficult to, while flame retarding and smoke suppressing properties improves, and not affect the mechanical property of matrix material above by single mode, the common lifting how reaching smoke-inhibiting flame retardant and mechanical property by synergy is emphasis of the present invention.
Summary of the invention
For the deficiency that prior art exists, technical problem to be solved by this invention is, provides a kind of Halogen smoke-inhibiting flame retardant PP matrix material, can meet the requirement to smoke-inhibiting flame retardant performance and mechanical property in materials'use process simultaneously.Propose by adding laminate exfoliated hydrotalcite, organic-silicon-modified hydrotalcite, boric acid intercalated houghite simultaneously, melt blending prepares the method for the Halogen smoke-inhibiting flame retardant polypropylene composite of good dispersity.
For solving the problems of the technologies described above, the technical solution used in the present invention is, a kind of Halogen smoke-inhibiting flame retardant PP matrix material is provided, be made up of the component of following mass percent: polypropylene 65%-85%, Delamination type hydrotalcite 6-15%, organic-silicon-modified hydrotalcite 3%-6%, boric acid intercalated houghite 3-8%, toughner 2%-6%, oxidation inhibitor 0.3%-1%, lubricant 0.3-1%.
Described Delamination type hydrotalcite adopts micro emulsion legal system standby, first LGA intercalation is entered hydrotalcite layers, then in octane solution, carries out pillared stripping, and vacuum-drying obtains, for subsequent use.
Described organic-silicon-modified hydrotalcite adopts cladding process preparation, adds the silane coupling agent of 5% consumption, abundant ground and mixed in hydrotalcite, for subsequent use after cooling.
Described borate intercalation hydrotalcite adopts structure restoration legal system standby, by hydrotalcite roasting 2-5h at 400-600 DEG C, joins in borate solution, stirred at ambient temperature 1-3h after cooling, after reaction terminates, filters, in 65 DEG C of oven dry, for subsequent use.
The preparation method of described Halogen-free flame-retardant PP composite material is completed by following steps:
(1) each component is taken according to weight percent;
(2) each component fully mediated in kneader, wherein mixing temperature is 40-100 DEG C;
(3) extruded in twin screw extruder by the material mixed, temperature is 160-250 DEG C, and rotating speed controls to turn/min at 80-120.
Halogen smoke-inhibiting flame retardant PP matrix material tool of the present invention has the following advantages:
(1) Halogen smoke-inhibiting flame retardant PP matrix material of the present invention uses Delamination type hydrotalcite, make the dispersion in the material of hydrotalcite lamella and associativity better, considerably increase consistency, the mechanical property maintaining material does not decline;
(2) Halogen smoke-inhibiting flame retardant PP matrix material of the present invention uses multiple hydrotalcite fire retardant composite, introduces boric acid intercalated houghite simultaneously, greatly improves the smoke suppressing of fire-retardant PP;
(3) Halogen smoke-inhibiting flame retardant PP matrix material of the present invention is not containing halogenated flame retardant and poisonous metal oxide, has asepsis environment-protecting characteristic.
Embodiment
Embodiment 1
A kind of Halogen smoke-inhibiting flame retardant PP matrix material of the present embodiment, is made up of the component of following mass percent: polypropylene 72%, Delamination type hydrotalcite 12%, organic-silicon-modified hydrotalcite 5%, boric acid intercalated houghite 5%, toughner 5%, oxidation inhibitor 0.5%, lubricant 0.5%.
Above-mentioned matrix material is prepared from by following steps:
(1) each component is taken according to weight percent;
(2) each component fully mediated in kneader, wherein mixing temperature is 40 DEG C;
(3) extruded in twin screw extruder by the material mixed, temperature is 230 DEG C, and rotating speed controls at 90 turns/min.
Embodiment 2
A kind of Halogen smoke-inhibiting flame retardant PP matrix material of the present embodiment, is made up of the component of following mass percent: polypropylene 80%, Delamination type hydrotalcite 8%, organic-silicon-modified hydrotalcite 4%, boric acid intercalated houghite 4%, toughner 3%, oxidation inhibitor 0.5%, lubricant 0.5%.
Above-mentioned matrix material is prepared from by following steps:
(1) each component is taken according to weight percent;
(2) each component fully mediated in kneader, wherein mixing temperature is 60 DEG C;
(3) extruded in twin screw extruder by the material mixed, temperature is 200 DEG C, and rotating speed controls at 110 turns/min.
Embodiment 3
A kind of Halogen smoke-inhibiting flame retardant PP matrix material of the present embodiment, is made up of the component of following mass percent: polypropylene 65%, Delamination type hydrotalcite 15%, organic-silicon-modified hydrotalcite 6%, boric acid intercalated houghite 8%, toughner 5%, oxidation inhibitor 0.5%, lubricant 0.5%.
Above-mentioned matrix material is prepared from by following steps:
(1) each component is taken according to weight percent;
(2) each component fully mediated in kneader, wherein mixing temperature is 90 DEG C;
(3) extruded in twin screw extruder by the material mixed, temperature is 160-250 DEG C, and rotating speed controls at 120 turns/min.
Embodiment 4
A kind of Halogen smoke-inhibiting flame retardant PP matrix material of the present embodiment, is made up of the component of following mass percent: polypropylene 75%, Delamination type hydrotalcite 10%, organic-silicon-modified hydrotalcite 3%, boric acid intercalated houghite 6%, toughner 4%, oxidation inhibitor 1%, lubricant 1%.
Above-mentioned matrix material is prepared from by following steps:
(1) each component is taken according to weight percent;
(2) each component fully mediated in kneader, wherein mixing temperature is 100 DEG C;
(3) extruded in twin screw extruder by the material mixed, temperature is 210 DEG C, and rotating speed controls at 100 turns/min.
Embodiment 5
A kind of Halogen smoke-inhibiting flame retardant PP matrix material of the present embodiment, is made up of the component of following mass percent: polypropylene 85%, Delamination type hydrotalcite 6%, organic-silicon-modified hydrotalcite 3%, boric acid intercalated houghite 3%, toughner 2%, oxidation inhibitor 0.5%, lubricant 0.5%.
Above-mentioned matrix material is prepared from by following steps:
(1) each component is taken according to weight percent;
(2) each component fully mediated in kneader, wherein mixing temperature is 80 DEG C;
(3) extruded in twin screw extruder by the material mixed, temperature is 160 DEG C, and rotating speed controls at 80 turns/min.
Carry out performance test to the fire retardant material obtained by above embodiment, concrete outcome is in table 1.
Table 1 embodiment gained Halogen smoke-inhibiting flame retardant PP composite property is tested
| Test event | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Tensile strength (MPa) | 49 | 52 | 47 | 53 | 51 |
| Flexural strength (MPa) | 32.3 | 33.7 | 32.0 | 34.4 | 33.5 |
| Izod notched impact strength (Kg/m2) | 10.5 | 10.9 | 10.0 | 10.6 | 11.0 |
| Combustionproperty | V-0 | V-0 | V-0 | V-0 | V-0 |
| Limiting oxygen index(LOI) (LOI) | 30.9 | 30.6 | 33.2 | 31.3 | 30.0 |
| Smoke density grade (SDR) | 69.6 | 72.5 | 68.1 | 70.4 | 74.5 |
By testing above and can seeing, the Halogen smoke-inhibiting flame retardant PP matrix material obtained by the present invention has good smoke-inhibiting flame retardant performance, and keeps good mechanical property.
The above is only to preferred embodiment of the present invention, and be not do other forms of restriction to the present invention, any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the Equivalent embodiments of equivalent variations.But, everyly do not depart from the present invention program's content, according to technical spirit of the present invention to any simple modification made for any of the above embodiments, equivalent variations and remodeling, still belong to protection scope of the present invention.
Claims (7)
1. a Halogen smoke-inhibiting flame retardant PP matrix material, it is characterized in that, be made up of the component of following mass percent: polypropylene 65%-85%, Delamination type hydrotalcite 6-15%, organic-silicon-modified hydrotalcite 3%-6%, boric acid intercalated houghite 3-8%, toughner 2%-6%, oxidation inhibitor 0.5%-1%, lubricant 0.5-2%.
2. Halogen smoke-inhibiting flame retardant PP matrix material according to claim 1, is characterized in that, Delamination type hydrotalcite adopts micro emulsion legal system standby, first LGA intercalation is entered hydrotalcite layers, then in octane solution, carries out pillared stripping, and vacuum-drying obtains.
3. Halogen smoke-inhibiting flame retardant PP matrix material according to claim 1, is characterized in that, organic-silicon-modified hydrotalcite adopts cladding process preparation, adds the silane coupling agent of 5% consumption, abundant ground and mixed in hydrotalcite, for subsequent use after cooling.
4. Halogen smoke-inhibiting flame retardant PP matrix material according to claim 1, it is characterized in that, borate intercalation hydrotalcite adopts structure restoration legal system standby, by hydrotalcite roasting 2-5h at 400-600 DEG C, join after cooling in borate solution, stirred at ambient temperature 1-3h, after reaction terminates, filter, in 65 DEG C of oven dry, for subsequent use.
5. Halogen smoke-inhibiting flame retardant PP matrix material according to claim 1, is characterized in that, with the addition of mass percent is that the PTFE micro mist of 0.5-2% is as lubricant.
6. Halogen smoke-inhibiting flame retardant PP matrix material according to claim 5, is characterized in that, the median size of the PTFE micro mist added is 1-5 μm.
7. the preparation method of the Halogen smoke-inhibiting flame retardant PP matrix material described in above-mentioned any claim, is characterized in that, be prepared by following steps:
(1) each component is taken according to weight percent;
(2) each component fully mediated in kneader, wherein mixing temperature is 40-100 DEG C;
(3) extruded in twin screw extruder by the material mixed, temperature is 160-250 DEG C, and rotating speed controls to turn/min at 80-120.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201511007791.1A CN105482252B (en) | 2015-12-30 | 2015-12-30 | A kind of Halogen smoke-inhibiting flame retardant PP composite material and preparation method thereof |
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| CN201511007791.1A CN105482252B (en) | 2015-12-30 | 2015-12-30 | A kind of Halogen smoke-inhibiting flame retardant PP composite material and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105482461A (en) * | 2016-01-25 | 2016-04-13 | 广东工业大学 | Fire retardant and preparation method thereof |
| CN111362285A (en) * | 2020-03-29 | 2020-07-03 | 衢州学院 | Method for utilizing boron resource in salt lake brine |
| CN111410218A (en) * | 2020-03-29 | 2020-07-14 | 衢州学院 | Method for separating magnesium, lithium and boron from brine based on precipitation-ion imprinting coupling |
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| KR101186818B1 (en) * | 2012-02-17 | 2012-09-28 | (주)우진고분자 | A surface-treated hydrotalcite and a composition comprising the same |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105482461A (en) * | 2016-01-25 | 2016-04-13 | 广东工业大学 | Fire retardant 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 |
| CN111362285A (en) * | 2020-03-29 | 2020-07-03 | 衢州学院 | Method for utilizing boron resource in salt lake brine |
| CN111410218A (en) * | 2020-03-29 | 2020-07-14 | 衢州学院 | Method for separating magnesium, lithium and boron from brine based on precipitation-ion imprinting coupling |
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