CN105348635A - Nano cooperative intumescent flame retardant and toughening polypropylene blend composite material and preparation method thereof - Google Patents
Nano cooperative intumescent flame retardant and toughening polypropylene blend composite material and preparation method thereof Download PDFInfo
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- CN105348635A CN105348635A CN201510750601.9A CN201510750601A CN105348635A CN 105348635 A CN105348635 A CN 105348635A CN 201510750601 A CN201510750601 A CN 201510750601A CN 105348635 A CN105348635 A CN 105348635A
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses a nano cooperative intumescent flame retardant and toughening polypropylene blend composite material and a preparation method thereof. The nano cooperative intumescent flame retardant and toughening polypropylene blend composite material is composed of the following components by mass: 71 parts of polypropylene, 20 parts of an octene-ethylene block copolymer, 23 parts of a modified intumescent flame retardant, 2 parts of organic modified montmorillonite, 1-11 parts of maleic anhydride grafted polypropylene. The nano cooperative intumescent flame retardant and toughening polypropylene blend composite material provided by the invention has the characteristics of sufficient and affordable raw materials and simple processing technology, the finished product has good flame retardant and toughening properties, compared with pure polypropylene, the peak heat release rate and the smoke release rate are obviously decreased, and at the same time the impact strength of the material is improved.
Description
Technical field
The present invention relates to anti-flaming polypropylene material technical field, be specifically related to a kind of nanometer cooperative expandable flame retardant tenacity-increased profax blend matrix material and preparation method thereof.
Background technology
Polypropylene (PP) is one of five large general synthetic resins, is widely used in Hyundai Motor industry, household electrical appliance, electronic product, packaging and building materials furniture.But the limiting oxygen index(LOI) (LOI) of polypropylene (PP) only has 17.8, in burning, easily there is melting, drippage produce a large amount of smog, be cause the intensity of a fire in fire spread the major reason with loss of life and personal injury fast.Halogenated flame retardant was once most economical effective polypropylene fire retardant additive, but can cause the generation of a large amount of poison gas in material combustion process, so halogenated flame retardant is prohibitted the use by various countries gradually.Expansion type flame retardant (IFR) is a kind of novel efficient, halogen-free flame retardants, general by acid source, charcoal source, source of the gas three part forms, the acid produced by acid source when being heated makes polyvalent alcohol dewater as dewatering agent and generates layer of charcoal, and the non-flammable gases produced by source of the gas makes burning molten system expanded foamed, foamed char is formed at polymer surfaces, reach isolated heat, the object of flammable volatilization gas and oxygen, polymer combustion is finally made to slow down or stop, the layer of charcoal simultaneously generated also can effectively stop polymkeric substance to melt the generation of dripping, be considered to the optimal selection replacing halogenated flame retardant, research for expansion type flame retardant (IFR) is also the trend constantly risen.But compared with halogenated flame retardant, the flame retarding efficiency of conventional expanded type fire retardant (IFR) is low, and addition is large; Simultaneously because of polarity difference, expansion type flame retardant (IFR) is difficult to form uniform dispersion in polypropylene (PP) matrix, have impact on the performance of its flame-retarded efficiency.In order to improve above-mentioned defect, domestic and international investigator has attempted a large amount of methods, comprise the new macromolecular carbon forming agent (CFA) of synthesis with alternative tetramethylolmethane (PER), dipentaerythritol (DPER), expansion type flame retardant (IFR) carried out to modification, in expansion type flame retardant (IFR), add synergist etc. to improve its flame retarding efficiency, achieve a large amount of breakthroughs.On the other hand, the most outstanding shortcoming of restriction polypropylene (PP) industrial application is exactly that its shock strength is low, and the interpolation of fire retardant also creates very large impact to polypropylene (PP) mechanical property, the particularly impact of On Impact Toughness, so the focus improving that while not affecting polypropylene (PP) mechanical property flame retardant properties becomes polypropylene (PP) flame-retardant modified research.
Summary of the invention
The object of the invention is to carry out fire-retardant and toughening modifying to polypropylene (PP), obtain the novel flame-retardant tenacity-increased profax that toughness and flame retardant properties are all better than conventional polypropylene material.
In order to achieve the above object, the present invention has following technical scheme:
A kind of nanometer cooperative expandable flame retardant tenacity-increased profax blend matrix material of the present invention, is made up of the component of following proportion by weight: polypropylene (PP) 71 parts, octene-ethylene segmented copolymer (POE) 20 parts, modified expanded type fire retardant 23 parts, organic modification montmonrillonite 2 parts, maleic anhydride inoculated polypropylene (PP-g-MA) 1-11 part.
Preferably, described maleic anhydride inoculated polypropylene proportion by weight is 7-9 part.
The preparation method of described nanometer cooperative expandable flame retardant tenacity-increased profax blend matrix material comprises the steps:
(1) in high-speed mixer, add expansion type flame retardant powder, and add KH-161 silane coupling agent in 0.3wt% ratio, high-speed mixing 30min, obtains modified expanded type fire retardant;
(2) take polypropylene, octene-ethylene segmented copolymer, modified expanded type fire retardant, organic modification montmonrillonite, maleic anhydride inoculated polypropylene mixing according to formula, add forcing machine feeding port, extrude and obtain shaping blend;
(3) blend of extruder for shaping is sent into tablets press, obtain nanometer cooperative expandable flame retardant tenacity-increased profax blend pellet;
(4) nanometer cooperative expandable flame retardant tenacity-increased profax blend pellet is after the dry 24h of loft drier, utilizes the injection moulding of high-pressure injection moulding machine
Described forcing machine is twin screw extruder, and it is 170 DEG C, 190 DEG C, 200 DEG C and 195 DEG C successively that each section of temperature from feeding mouth to discharge port forcing machine is arranged, and basal rate is 100 revs/min.
Owing to taking above technical scheme, the invention has the advantages that material is all originated abundance and moderate, complete processing is simple, finished product has good fire-retardant and toughness reinforcing performance, simultaneously expanding material (maleic anhydride inoculated polypropylene) add flame retardant properties and the toughness that can promote material further, it is not very large for affecting tensile strength, add the heat release rate of matrix material during 7-9 part maleic anhydride inoculated polypropylene, flue gas rate of release obtains reduction clearly, tensile strength is also higher simultaneously, although shock strength rises along with expanding material consumption is lasting, but consider flame retardant properties and mechanical property, can show that the preferred mass number of expanding material (maleic anhydride inoculated polypropylene) is 7-9 part.
Accompanying drawing explanation
Fig. 1 is SEM image (500X) comparison diagram that expanding material (maleic anhydride inoculated polypropylene) adds front and back material microstructure, and wherein A is the sample not adding expanding material, and B is the sample of interpolation 9 parts of expanding materials.
Fig. 2 is material XRD test result figure.Wherein 1 containing expanding material (maleic anhydride inoculated polypropylene), and in 2-7, expanding material (maleic anhydride inoculated polypropylene) mass fraction is followed successively by 1 part, 3 parts, 5 parts, 7 parts, 9 parts and 11 parts.
Fig. 3 is Heat Release Rate of Materials (HRR)-time curve, and in A, B, C, D, E, F, expanding material (maleic anhydride inoculated polypropylene) mass fraction is followed successively by 1 part, 3 parts, 5 parts, 7 parts, 9 parts and 11 parts.
Fig. 4 is material flue gas rate of release (SPR)-time curve, and in A, B, C, D, E, F, expanding material (maleic anhydride inoculated polypropylene) mass fraction is followed successively by 1 part, 3 parts, 5 parts, 7 parts, 9 parts and 11 parts.
Fig. 5 is material impact intensity, tensile strength test results.
Embodiment
Following examples for illustration of the present invention and uses thereof, but are not used for limiting the scope of the invention.
Embodiment 1
(1) in high-speed mixer, add expansion type flame retardant powder, and add KH-161 silane coupling agent in 0.3wt% ratio, high-speed mixing 30min, obtains modified expanded type fire retardant;
(2) polypropylene 71 parts, octene-ethylene segmented copolymer 20 parts, modified expanded type fire retardant 23 parts, organic modification montmonrillonite 2 parts, maleic anhydride inoculated polypropylene 1 part mixing is taken, add forcing machine feeding port, extrude and obtain shaping blend;
(3) blend of extruder for shaping is sent into tablets press, obtain nanometer cooperative expandable flame retardant tenacity-increased profax blend pellet;
(4) nanometer cooperative expandable flame retardant tenacity-increased profax blend pellet is after the dry 24h of loft drier, utilizes the injection moulding of high-pressure injection moulding machine.
Embodiment 2
(1) in high-speed mixer, add expansion type flame retardant powder, and add KH-161 silane coupling agent in 0.3wt% ratio, high-speed mixing 30min, obtains modified expanded type fire retardant;
(2) polypropylene 71 parts, octene-ethylene segmented copolymer 20 parts, modified expanded type fire retardant 23 parts, organic modification montmonrillonite 2 parts, maleic anhydride inoculated polypropylene 3 parts mixing is taken, add forcing machine feeding port, extrude and obtain shaping blend;
(3) blend of extruder for shaping is sent into tablets press, obtain nanometer cooperative expandable flame retardant tenacity-increased profax blend pellet;
(4) nanometer cooperative expandable flame retardant tenacity-increased profax blend pellet is after the dry 24h of loft drier, utilizes the injection moulding of high-pressure injection moulding machine.
Embodiment 3
(1) in high-speed mixer, add expansion type flame retardant powder, and add KH-161 silane coupling agent in 0.3wt% ratio, high-speed mixing 30min, obtains modified expanded type fire retardant;
(2) polypropylene 71 parts, octene-ethylene segmented copolymer 20 parts, modified expanded type fire retardant 23 parts, organic modification montmonrillonite 2 parts, maleic anhydride inoculated polypropylene 5 parts mixing is taken, add forcing machine feeding port, extrude and obtain shaping blend;
(3) blend of extruder for shaping is sent into tablets press, obtain nanometer cooperative expandable flame retardant tenacity-increased profax blend pellet;
(4) nanometer cooperative expandable flame retardant tenacity-increased profax blend pellet is after the dry 24h of loft drier, utilizes the injection moulding of high-pressure injection moulding machine.
Embodiment 4
(1) in high-speed mixer, add expansion type flame retardant powder, and add KH-161 silane coupling agent in 0.3wt% ratio, high-speed mixing 30min, obtains modified expanded type fire retardant;
(2) polypropylene 71 parts, octene-ethylene segmented copolymer 20 parts, modified expanded type fire retardant 23 parts, organic modification montmonrillonite 2 parts, maleic anhydride inoculated polypropylene 7 parts mixing is taken, add forcing machine feeding port, extrude and obtain shaping blend;
(3) blend of extruder for shaping is sent into tablets press, obtain nanometer cooperative expandable flame retardant tenacity-increased profax blend pellet;
(4) nanometer cooperative expandable flame retardant tenacity-increased profax blend pellet is after the dry 24h of loft drier, utilizes the injection moulding of high-pressure injection moulding machine.
Embodiment 5
(1) in high-speed mixer, add expansion type flame retardant powder, and add KH-161 silane coupling agent in 0.3wt% ratio, high-speed mixing 30min, obtains modified expanded type fire retardant;
(2) polypropylene 71 parts, octene-ethylene segmented copolymer 20 parts, modified expanded type fire retardant 23 parts, organic modification montmonrillonite 2 parts, maleic anhydride inoculated polypropylene 9 parts mixing is taken, add forcing machine feeding port, extrude and obtain shaping blend;
(3) blend of extruder for shaping is sent into tablets press, obtain nanometer cooperative expandable flame retardant tenacity-increased profax blend pellet;
(4) nanometer cooperative expandable flame retardant tenacity-increased profax blend pellet is after the dry 24h of loft drier, utilizes the injection moulding of high-pressure injection moulding machine.
Embodiment 6
(1) in high-speed mixer, add expansion type flame retardant powder, and add KH-161 silane coupling agent in 0.3wt% ratio, high-speed mixing 30min, obtains modified expanded type fire retardant;
(2) polypropylene 71 parts, octene-ethylene segmented copolymer 20 parts, modified expanded type fire retardant 23 parts, organic modification montmonrillonite 2 parts, maleic anhydride inoculated polypropylene 11 parts mixing is taken, add forcing machine feeding port, extrude and obtain shaping blend;
(3) blend of extruder for shaping is sent into tablets press, obtain nanometer cooperative expandable flame retardant tenacity-increased profax blend pellet;
(4) nanometer cooperative expandable flame retardant tenacity-increased profax blend pellet is after the dry 24h of loft drier, utilizes the injection moulding of high-pressure injection moulding machine.
The described polypropylene trade mark is S1003, and the octene-ethylene segmented copolymer trade mark is engage8150, and the expanding fire retardant trade mark is JLS-PNP1D, and the maleic anhydride inoculated polypropylene trade mark is GPM200A.
Fig. 1 shows the SEM image (500X) not adding expanding material (maleic anhydride inoculated polypropylene) Yu add 9 parts of expanding material (maleic anhydride inoculated polypropylene) sample impact fracture surfaces, known expanding material (maleic anhydride inoculated polypropylene) makes fire-retardant particles size in the base reduce, and disperses more even;
Fig. 2 shows the X-ray diffraction test result of described material, and the dispersion in the composite of known organic modification montmonrillonite reaches intercalation and exfoliated;
Fig. 3 shows the heat release rate-time curve of material, and the heat release rate of known described material significantly reduces;
Fig. 4 shows the flue gas rate of release-time curve of material, and smoke-producing amount and the product cigarette speed of known material significantly reduce;
Fig. 5 shows shock strength, the tensile strength test results of material, the known increase along with expanding material (maleic anhydride inoculated polypropylene) content, and the shock strength of material has had raising; Along with the increase of expanding material (maleic anhydride inoculated polypropylene) content, the tensile strength change of material is significantly not regular, but overall variation amplitude is not very large.
From above-described embodiment, flame retardant properties and the toughness of described expandable flame retardant tenacity-increased profax blend matrix material have all had larger lifting, simultaneously expanding material (maleic anhydride inoculated polypropylene) add flame retardant properties and the toughness that can promote material further, little on tensile strength impact, can show that the preferred mass number of expanding material (maleic anhydride inoculated polypropylene) is 7-9 part simultaneously.
Obviously, the above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here cannot give exhaustive to all embodiments.Every belong to technical scheme of the present invention the apparent change of extending out or variation be still in the row of protection scope of the present invention.
Claims (4)
1. a nanometer cooperative expandable flame retardant tenacity-increased profax blend matrix material, it is characterized in that, be made up of the component of following proportion by weight: polypropylene 71 parts, octene-ethylene segmented copolymer 20 parts, modified expanded type fire retardant 23 parts, organic modification montmonrillonite 2 parts, maleic anhydride inoculated polypropylene 1-11 part.
2. nanometer cooperative expandable flame retardant tenacity-increased profax blend matrix material according to claim 1, it is characterized in that, described maleic anhydride inoculated polypropylene proportion by weight is 7-9 part.
3. the preparation method of nanometer cooperative expandable flame retardant tenacity-increased profax blend matrix material according to claim 1, is characterized in that, comprise the steps:
(1) in high-speed mixer, add expansion type flame retardant powder, and add KH-161 silane coupling agent in 0.3wt% ratio, high-speed mixing 30min, obtains modified expanded type fire retardant;
(2) take polypropylene, octene-ethylene segmented copolymer, modified expanded type fire retardant, organic modification montmonrillonite, maleic anhydride inoculated polypropylene mixing according to formula, add forcing machine feeding port, extrude and obtain shaping blend;
(3) blend of extruder for shaping is sent into tablets press, obtain nanometer cooperative expandable flame retardant tenacity-increased profax blend pellet;
(4) nanometer cooperative expandable flame retardant tenacity-increased profax blend pellet is after the dry 24h of loft drier, utilizes the injection moulding of high-pressure injection moulding machine.
4. the preparation method of nanometer cooperative expandable flame retardant tenacity-increased profax blend matrix material according to claim 3, it is characterized in that: described forcing machine is twin screw extruder, it is 170 DEG C, 190 DEG C, 200 DEG C and 195 DEG C successively that each section of temperature from feeding mouth to discharge port forcing machine is arranged, and basal rate is 100 revs/min.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110747583A (en) * | 2019-11-06 | 2020-02-04 | 安徽瑞智福瑶环保科技有限公司 | Preparation method of high-flame-retardant non-woven fabric |
| CN110885498A (en) * | 2019-12-20 | 2020-03-17 | 广东道生科技股份有限公司 | Flame-retardant toughened polypropylene material and preparation method thereof |
| CN112961431A (en) * | 2021-02-07 | 2021-06-15 | 陈瑞英 | High-temperature-resistant flame-retardant insulating material and preparation method thereof |
| CN114685848A (en) * | 2020-12-29 | 2022-07-01 | 洛阳尖端技术研究院 | Intumescent flame retardant, plastic and preparation method and application thereof |
| CN115873293A (en) * | 2021-09-26 | 2023-03-31 | 中国石油化工股份有限公司 | Composition for preparing flame-retardant foamed polypropylene material, flame-retardant foamed polypropylene material and preparation method thereof |
| CN117261389A (en) * | 2023-09-28 | 2023-12-22 | 南通中奥车用新材料有限公司 | Composite polymer nano synthetic material with high flame retardance and preparation method thereof |
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| CN115873293B (en) * | 2021-09-26 | 2023-09-05 | 中国石油化工股份有限公司 | Composition for preparing flame-retardant foaming polypropylene material, flame-retardant foaming polypropylene material and preparation method thereof |
| CN117261389A (en) * | 2023-09-28 | 2023-12-22 | 南通中奥车用新材料有限公司 | Composite polymer nano synthetic material with high flame retardance and preparation method thereof |
| CN117261389B (en) * | 2023-09-28 | 2024-04-19 | 南通中奥车用新材料有限公司 | Composite polymer nano synthetic material with high flame retardance and preparation method thereof |
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Application publication date: 20160224 |