CN106279965A - A kind of physical blowing fills anti-flaming polypropylene material and preparation method thereof - Google Patents
A kind of physical blowing fills anti-flaming polypropylene material and preparation method thereof Download PDFInfo
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- 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
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/30—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- 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 present invention provides a kind of physical blowing to fill anti-flaming polypropylene material and preparation method thereof, and it is, extrusion, frothing injection gained blended by polipropene 25-84 parts, high melt-strength polyethylene 5-20 part, inorganic filler 1-15 part, fire retardant 5-20 part, fire retarding synergist 3-10 part, compatilizer 2-10 part, primary antioxidant 0.1-1 part, auxiliary antioxidant 0.1-1 part, dispersant 0.5-1 part.The viscosity of described high melt-strength polyethylene is 5.0*104-1.0*105 pascal second, its temperature be 190 DEG C, load be the melt index under 2.16kg be 0.5-2g/10min.The present invention adds a certain amount of high melt-strength polyethylene in polypropylene and is modified polypropylene, improve the cryogenic property of material, and use supercritical nitrogen to foam, thus avoid melt to rupture, and reduce the density of end article, improve the fire resistance of goods simultaneously, reach loss of weight and ensure that its rigidity and specious requirement.
Description
Technical field
The invention belongs to technical field of polymer processing, be specifically related to a kind of physical blowing and fill anti-flaming polypropylene material and preparation method thereof.
Background technology
Polypropylene (PP) is the crystalline polymer of a kind of compound with regular structure, is often white pellet or powder, is tasteless, nontoxic, the thermoplastic resin of light weight.Polypropylene possesses the advantages such as easily processing, impact strength, flexibility and electrical insulating property are good, and has good chemical-resistance, has a wide range of applications at aspects such as auto industry, household electrical appliance, electronics, packaging, building materials and furniture.In place of but PP there is also some shortcomings, disconnected, the defect such as shrinkage factor is big, creep resistance is poor, the most inflammable as poor in tolerance to cold, fragile under low temperature, it is therefore desirable to being modified polypropylene, the especially polypropylene of high flame retardant is also always the research emphasis of modified polypropene.
In recent years, many industries all suffer from dropping the problem of this loss of weight, especially automobile industry, expanded material is to be passed through a certain amount of gas in injection moulding process, the density of goods is reduced, thus reach the purpose of loss of weight, fall can be carried out originally on the basis of existing product, the problem solving rigidity from mould structure, and do not affect automobile product dermatoglyph outward appearance, both ensure that the performance of goods, maintain again the aesthetic property of its outward appearance.
Current foaming material shaped typically have two ways: one is chemical blowing, and it is to add a certain amount of foaming agent in product matrix formulation to be shaped, and chemical blowing is strict to the technological requirement of molding；Another kind is physical blowing, is to be passed through gas in the melt to obtain foaming product.
Chinese patent (CN 102040775A) discloses a kind of anti-flaming polypropylene material, it is made up of high fluidity HOPP 25-50%, High Flowability Polypropylene Copolymers 25-50%, fire retardant 10-33%, inorganic strengthening agent 5-30%, barrier additive 1-10%, heat-resisting reinforcing agent 0.1-3%, antioxidant and nucleator 0.1-4%, composite pigment 0.1-3%, inside and outside lubricant agent 1-5%, this patent falls within inorganic filler modified flame-retardant polypropylene material, but its final molding mode is not foaming, and high fluidity material also cannot be carried out foaming..
Chinese patent (CN 102372855A) discloses a kind of supercritical method for preparing pre-foamed polypropylene, this patent is to use supercritical fluid method, utilizes physical blowing agent, polypropylene is made increase melt strength and processes, and by special pre-expansion process, prepare pre-foamed polypropylene material；Its preparation method mainly uses PP Yu PE to cross-link, increase its melting range by interpolation inorganic filler and elastomer simultaneously and reach to increase the purpose of melt strength, but this patent addO-on therapy is complicated, the compatibility of polarity and non-polar component can affect the stable performance of its expanded polypropylene material, so matrix needed the surface of long period to process before being blended.
Summary of the invention
For the limitation of above prior art, it is an object of the invention to provide a kind of physical blowing and fill anti-flaming polypropylene material and preparation method thereof.
Technical scheme is as follows:
A kind of physical blowing fills anti-flaming polypropylene material, and this material is to be prepared from by weight by following components:
Polipropene 25-84 parts；
High melt-strength polyethylene 5-20 part；
Inorganic filler 1-15 part；
Fire retardant 5-20 part；
Fire retarding synergist 3-10 part；
Compatilizer 2-10 part；
Primary antioxidant 0.1-1 part；
Auxiliary antioxidant 0.1-1 part；
Dispersant 0.5-1 part.
The viscosity of described high melt-strength polyethylene is 5.0*104-1.0*105 pascal second, its temperature be 190 DEG C, load be the melt index under 2.16kg be 0.5-2g/10min.
Described polypropylene temperature be 230 DEG C, load be the melt index under 2.16kg be 1-15g/10min, its average weight-molecular mass is 1.0 × 105～6.0 × 105。
Described inorganic filler be particle diameter be the Pulvis Talci of 1250-2500 mesh.
Described compatilizer is maleic anhydride grafted ethene-octene copolymer.
Described fire retardant is double (2, the 3-dibromopropyl) ether of TDE, decabromodiphenyl oxide or tetrabromobisphenol A.
Described fire retarding synergist is antimony oxide, zinc oxide or manganese dioxide.
Described primary antioxidant is single phenol antioxidant, bis-phenolic antioxidants or polyhydric phenols antioxidant in Hinered phenols；Described auxiliary antioxidant is selected from phosphite ester kind antioxidant or sulfur-containing compound.
Described phosphite ester kind antioxidant is selected from alkyl phosphite, aryl phosphite or alkyl aryl ester；Described sulfur-containing compound is selected from monothioester, thioether, disulphide or mercaptan.
Described dispersant is selected from Tissuemat E or ethylene bis stearamide.
Another object of the present invention is to provide a kind of physical blowing and fills the preparation method of anti-flaming polypropylene material, and the method comprises the following steps:
(1) polipropene 25-84 parts, high melt-strength polyethylene 5-20 part, inorganic filler 1-15 part, fire retardant 5-20 part, fire retarding synergist 3-10 part, compatilizer 2-10 part, primary antioxidant 0.1-1 part, auxiliary antioxidant 0.1-1 part, dispersant 0.5-1 part are put in high mixer, carry out mixing 3-8min in 60-80 DEG C of temperature；
(2) mixed material is added in the double screw extruder that each district temperature is 180-200 DEG C and carry out extruding pelletization；
(3) particle in (2) is added foaming special injection molding, and be passed through and account for the supercritical nitrogen that its percentage by weight is 15%-30% and carry out foam injection molding, described foaming special injection molding each district temperature is 175-190 DEG C, pressure is 25-65MPa, dwell pressure is 15-40MPa.
The present invention compared with the existing technology, has the advantages that
1, the present invention adds a certain amount of high melt-strength polyethylene in polypropylene, and polythene material itself is better than the resistance to low temperature of polypropylene material, can improve the resistance to low temperature of goods；And melt strength can be increased, it is to avoid melt fracture occurs in foaming process.
2, the present invention uses supercritical nitrogen to foam, nitrogen pour the density that can reduce end article, to reach the purpose of loss of weight；The flame retardant effect of goods can also be strengthened simultaneously.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further illustrated.
Draw ratio 30:1 of double screw extruder used in the embodiment of the present invention, manufacturer is BRABEBDER company of Germany.
Each district temperature of following embodiment foaming used special injection molding is 175-190 DEG C, pressure is 25-65MPa, dwell pressure is 15-40MPa.
The viscosity of described high melt-strength polyethylene is 5.0*104-1.0*105 pascal second, its temperature be 190 DEG C, load be the melt index under 2.16kg be 0.5-2g/10min.
Described polypropylene temperature be 230 DEG C, load be the melt index under 2.16kg be 1-15g/10min, its average weight-molecular mass is 1.0 × 105～6.0 × 105。
The product of the present invention uses the standard of GB to test, and extrusion pellet obtains test bars through injection machine molding, 23 DEG C, stablize 24h under the conditions of relative humidity 50% after carry out performance test, the physical and mechanical properties carried out is tested to be had:
Anti-flammability: according to testing level method and the normal beam technique of GB/T 2408(combustibility) test；
Melt index: test according to GB/T 3682 standard sample preparation；
Density: test according to GB/T 1033 standard sample preparation.
Embodiment 1
1) polipropene 25 part, high melt-strength polyethylene 20 parts, 15 parts of Pulvis Talci 1250 mesh, TDE 20 parts, antimony oxide 10 parts, maleic anhydride grafted ethene-octene copolymer 10 parts, single 1 part of phenol antioxidant, alkyl phosphite 1 part, 0.5 part of polyethylene of dispersing agent wax are put in high mixer, carry out mixing 3min in 80 DEG C of temperature；
2) mixed material is added extruding pelletization in the double screw extruder that each district temperature is 180-200 DEG C；
3) by 2) in particle add foaming special injection molding, and be passed through and account for the supercritical nitrogen that its percentage by weight is 15% and carry out foam injection molding.
Embodiment 2
1) polypropylene 84 parts, high melt-strength polyethylene 5 parts, 1 part of Pulvis Talci 2000 mesh, decabromodiphenyl oxide 5 parts, zinc oxide 3 parts, maleic anhydride grafted ethene-octene copolymer 2 parts, bis-phenolic antioxidants 0.1 part, aryl phosphite 0.1 part, dispersant ethylene bis stearamide 1 part are put in high mixer, carry out mixing 8min in 60 DEG C of temperature；
2) mixed material is added extruding pelletization in the double screw extruder that each district temperature is 180-200 DEG C；
3) by 2) in particle add foaming special injection molding, and be passed through and account for the supercritical nitrogen that its percentage by weight is 30% and carry out foam injection molding.
Embodiment 3
1) by polypropylene 50 parts, high melt-strength polyethylene 10 parts, 10 parts of Pulvis Talci 2500 mesh, tetrabromobisphenol A double (2,3-dibromopropyl) 15 parts of ether, manganese dioxide 10 parts, maleic anhydride grafted ethene-octene copolymer 5 parts, 0.5 part of polyhydric phenols antioxidant, alkyl aryl ester 0.5 part, 0.8 part of polyethylene of dispersing agent wax puts in high mixer, carries out mixing 5min in 70 DEG C of temperature；
2) mixed material is added extruding pelletization in the double screw extruder that each district temperature is 180-200 DEG C；
3) by 2) in particle add foaming special injection molding, and be passed through and account for the supercritical nitrogen that its percentage by weight is 25% and carry out foam injection molding.
Embodiment 4
1) polypropylene 29 parts, high melt-strength polyethylene 20 parts, 15 parts of Pulvis Talci 1250 mesh, TDE 20 parts, antimony oxide 6 parts, maleic anhydride grafted ethene-octene copolymer 10 parts, 0.3 part of polyhydric phenols antioxidant, monothioester 0.7 part, 0.6 part of polyethylene of dispersing agent wax are put in high mixer, carry out mixing 5min in 70 DEG C of temperature；
2) mixed material is added in the double screw extruder that each district temperature is 180-200 DEG C and carry out extruding pelletization；
3) by 2) in particle add foaming special injection molding, and be passed through and account for the supercritical nitrogen that its percentage by weight is 20% and carry out foam injection molding.
Embodiment 5
1) polypropylene 47 parts, high melt-strength polyethylene 15 parts, 12 parts of Pulvis Talci 1250 mesh, TDE 10 parts, antimony oxide 8 parts, maleic anhydride grafted ethene-octene copolymer 8 parts, 0.6 part of polyhydric phenols antioxidant, thioether 0.3 part, 0.7 part of polyethylene of dispersing agent wax are put in high mixer, carry out mixing 5min in 60 DEG C of temperature；
2) mixed material is added in the double screw extruder that each district temperature is 180-200 DEG C and carry out extruding pelletization；
3) by 2) in particle add foaming special injection molding, and be passed through and account for the supercritical nitrogen that its percentage by weight is 20% and carry out foam injection molding.
Embodiment 6
1) polypropylene 39 parts, high melt-strength polyethylene 15 parts, 15 parts of Pulvis Talci 1250 mesh, TDE 18 parts, antimony oxide 6 parts, maleic anhydride grafted ethene-octene copolymer 7 parts, 0.2 part of polyhydric phenols antioxidant, disulphide 0.5 part, 0.5 part of polyethylene of dispersing agent wax are put in high mixer, carry out mixing 6min in 70 DEG C of temperature；
2) mixed material is added in the double screw extruder that each district temperature is 180-200 DEG C and carry out extruding pelletization；
3) by 2) in particle add foaming special injection molding, and be passed through and account for the supercritical nitrogen that its percentage by weight is 15% and carry out foam injection molding.
Embodiment 7
1) polypropylene 39 parts, high melt-strength polyethylene 15 parts, 15 parts of Pulvis Talci 1250 mesh, TDE 18 parts, antimony oxide 6 parts, maleic anhydride grafted ethene-octene copolymer 7 parts, 0.2 part of polyhydric phenols antioxidant, 0.5 part of mercaptan, 0.5 part of polyethylene of dispersing agent wax are put in high mixer, carry out mixing 6min in 70 DEG C of temperature；
2) mixed material is added in the double screw extruder that each district temperature is 180-200 DEG C and carry out extruding pelletization；
3) by 2) in particle add foaming special injection molding, and be passed through and account for the supercritical nitrogen that its percentage by weight is 15% and carry out foam injection molding.
Polypropylene fire retardant particle prepared by above-described embodiment 1-6 and the performance test results of product after its foam injection molding is shown in Table 1:
Table 1
| Embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Density/the g/cm of polypropylene fire retardant particle3 | 1.33 | 0.966 | 1.25 | 1.266 | 1.188 | 1.25 |
| Melt flow rate (MFR)/the g/10min of polypropylene fire retardant particle | 7.6 | 13.7 | 9.4 | 8.0 | 11.2 | 12.5 |
| The anti-flammability (batten thickness 3.2mm, vertical checkout) of polypropylene fire retardant particle | V-0 | V-2 | V-1 | V-1 | V-1 | V-1 |
| Density/the g/cm of product after foaming3 | 1.13 | 0.68 | 0.94 | 1.01 | 0.95 | 1.06 |
| The anti-flammability (batten thickness 2mm, vertical checkout) of product after foaming | V-0 | V-2 | V-1 | V-0 | V-1 | V-0 |
As can be seen from Table 1, in polypropylene fire retardant system, add high melt-strength polyethylene be prepared as the fire-retardant particle of modified polypropene, account for the supercritical nitrogen that its percentage by weight is 15%-30% and can be prepared as expanded polypropylene material by being passed through in injection moulding process again, significantly reduce material weight, if embodiment 1 Midst density is from 1.13 g/cm3Drop to 1.13 g/cm3；And the nitrogen being passed through the most more can strengthen the flame retardant effect of product, as shown in embodiment 4,6, product anti-flammability all brings up to V-level 0 from V-1 level, thus ensure that the surface aesthetic of product.
The above-mentioned description to embodiment is to be understood that for ease of those skilled in the art and apply the present invention.These embodiments obviously easily can be made various amendment by person skilled in the art, and General Principle described herein is applied in other embodiments without through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art should be within protection scope of the present invention according to the announcement of the present invention, the improvement made without departing from scope and amendment.
Claims (10)
1. a physical blowing fills anti-flaming polypropylene material, it is characterised in that: this material is to be prepared from by weight by following components:
Polipropene 25-84 parts；
High melt-strength polyethylene 5-20 part；
Inorganic filler 1-15 part；
Fire retardant 5-20 part；
Fire retarding synergist 3-10 part；
Compatilizer 2-10 part；
Primary antioxidant 0.1-1 part；
Auxiliary antioxidant 0.1-1 part；
Dispersant 0.5-1 part；
The viscosity of described high melt-strength polyethylene is 5.0*104-1.0*105 pascal second, its temperature be 190 DEG C, load be the melt index under 2.16kg be 0.5-2g/10min.
Physical blowing the most according to claim 1 fills anti-flaming polypropylene material, it is characterised in that: described polypropylene temperature be 230 DEG C, load be the melt index under 2.16kg be 1-15g/10min, its average weight-molecular mass is 1.0 × 105～6.0 × 105。
Physical blowing the most according to claim 1 fill anti-flaming polypropylene material, it is characterised in that: described inorganic filler be particle diameter be the Pulvis Talci of 1250-2500 mesh.
Physical blowing the most according to claim 1 fills anti-flaming polypropylene material, it is characterised in that: described compatilizer is maleic anhydride grafted ethene-octene copolymer.
Physical blowing the most according to claim 1 fills anti-flaming polypropylene material, it is characterised in that: described fire retardant is double (2, the 3-dibromopropyl) ether of TDE, decabromodiphenyl oxide or tetrabromobisphenol A.
Physical blowing the most according to claim 1 fills anti-flaming polypropylene material, it is characterised in that: described fire retarding synergist is antimony oxide, zinc oxide or manganese dioxide.
Physical blowing the most according to claim 1 fills anti-flaming polypropylene material, it is characterised in that: described primary antioxidant is single phenol antioxidant, bis-phenolic antioxidants or polyhydric phenols antioxidant in Hinered phenols；Described auxiliary antioxidant is selected from phosphite ester kind antioxidant or sulfur-containing compound.
Physical blowing the most according to claim 7 fills anti-flaming polypropylene material, it is characterised in that: described phosphite ester kind antioxidant is selected from alkyl phosphite, aryl phosphite or alkyl aryl ester；Described sulfur-containing compound is selected from monothioester, thioether, disulphide or mercaptan.
Physical blowing the most according to claim 1 fills anti-flaming polypropylene material, it is characterised in that: described dispersant is selected from Tissuemat E or ethylene bis stearamide.
10. a physical blowing as described in any one of claim 1-9 fills the preparation method of anti-flaming polypropylene material, it is characterised in that: the method comprises the following steps:
(1) polipropene 25-84 parts, high melt-strength polyethylene 5-20 part, inorganic filler 1-15 part, fire retardant 5-20 part, fire retarding synergist 3-10 part, compatilizer 2-10 part, primary antioxidant 0.1-1 part, auxiliary antioxidant 0.1-1 part, dispersant 0.5-1 part are put in high mixer, carry out mixing 3-8min in 60-80 DEG C of temperature；
(2) mixed material is added in the double screw extruder that each district temperature is 180-200 DEG C and carry out extruding pelletization；
(3) particle in (2) is added foaming special injection molding, and be passed through and account for the supercritical nitrogen that its percentage by weight is 15%-30% and carry out foam injection molding；Described foaming special injection molding each district temperature is 175-190 DEG C, pressure is 25-65MPa, dwell pressure is 15-40MPa.
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| CN114044974A (en) * | 2021-11-20 | 2022-02-15 | 南京聚隆科技股份有限公司 | Flame-treatment-free high-foaming-ratio polypropylene foam material and preparation method thereof |
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| CN109306114A (en) * | 2018-08-09 | 2019-02-05 | 南京聚隆科技股份有限公司 | A kind of hollow blow molding automobile inlet manifold material and preparation method thereof |
| CN110511482A (en) * | 2019-08-15 | 2019-11-29 | 合肥市和裕达塑业有限公司 | A kind of ultrahigh flame-retardant, physical blowing squeeze out PP composite material and preparation method |
| CN110564043A (en) * | 2019-09-18 | 2019-12-13 | 合肥市和裕达塑业有限公司 | Flame-retardant glass fiber reinforced polypropylene composite material and preparation method thereof |
| CN110919956A (en) * | 2019-10-23 | 2020-03-27 | 江苏聚核高分子功能材料研究院有限公司 | EPP material manufacturing method and manufacturing equipment |
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| CN115448449A (en) * | 2021-06-08 | 2022-12-09 | 中国石油化工股份有限公司 | Denitrification carrier and preparation method, device and application thereof |
| CN115448449B (en) * | 2021-06-08 | 2024-02-13 | 中国石油化工股份有限公司 | Denitrification carrier, and preparation method, device and application thereof |
| CN114044974A (en) * | 2021-11-20 | 2022-02-15 | 南京聚隆科技股份有限公司 | Flame-treatment-free high-foaming-ratio polypropylene foam material and preparation method thereof |
| CN114044974B (en) * | 2021-11-20 | 2023-10-27 | 南京聚隆科技股份有限公司 | Flame-treatment-free high-foaming-rate polypropylene foaming material and preparation method thereof |
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