CN103951876A - Environment-friendly type high-toughness and flame retardation polypropylene material as well as preparation method thereof - Google Patents
Environment-friendly type high-toughness and flame retardation polypropylene material as well as preparation method thereof Download PDFInfo
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- 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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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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- B29C48/50—Details of extruders
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- B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
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- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/505—Screws
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C2948/00—Indexing scheme relating to extrusion moulding
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- B29C2948/92504—Controlled parameter
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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
- C08J2323/02—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
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08L2312/00—Crosslinking
Abstract
The invention provides an environment-friendly type high-toughness and flame retardation polypropylene material as well as a preparation method thereof. The high-toughness and flame retardation polypropylene material is prepared by mixing 100 parts of polypropylene, 10-25 parts of crosslinking ethylene-alpha alkene copolymer, 25-35 parts of environmental protection fire retardant, 0.1-0.3 parts of maleic anhydride, 0.2-0.5 parts of anti-oxidant and 0.5-1.5 parts of lubricant through granulation for preparation; the crosslinking ethylene-alpha alkene copolymer is prepared by 100 parts of ethane-alpha alkene copolymer, 0.6-2.8 parts of crosslinking initiator, 0.3-0.45 parts of anti-oxidant and 0.3-0.45 parts of lubricant and then is performed through the steps of mixing, fusion crosslinking for extrusion, bracing and cutting. According to the invention, an in-situ two-step method is used for preparing the polypropylene material, compared with the flame retardation polypropylene material prepared by an one step method through blending, the toughening effect of the polypropylene material is better, the polypropylene material can reach UL94 flame retardation V0 grade, has excellent mechanical property, and can be widely used in the industries of household electrical appliance, electrical and electronic industry.
Description
technical field:
The present invention relates to modifying plastics field, relate in particular to a kind of environment-friendly type high-ductility, anti-flaming polypropylene material and preparation method thereof.
background technology:
Polypropylene (PP) is one of cheap general-purpose plastics of current consumption maximum, has the characteristic of a lot of excellences, as: source is wide, price is low, density is little, nontoxic, easy processing etc., thereby is widely used in automobile, household electrical appliances, the field such as electric.Especially in field of household appliances, sometimes need that PP is carried out to flame-retardant modified need and reach UL94 flame retardant rating, and according to the difference of materials'use environment, client can require to reach the different grades (as: V0, V1, V2 grade) of fire-retardant UL94.Flame-retardant modified to PP, is divided at present and has the fire-retardant and halogen-free flameproof of halogen, wherein has the fire-retardant minute environment-friendly type again of halogen (meeting RoHS Directive) and environment-friendly type (not meeting RoHS Directive) not, and halogen-free flameproof is all environment-friendly type at present.There is halogen environment friendly flame retardant to mainly contain tetrabromo-bisphenol, eight bromo ether, eight bromine bisphenol S ethers, brominated epoxy resin, brominated Polystyrene, chlorinatedpolyethylene, TDE etc.; Have halogen not environment friendly flame retardant have at present pentabromodiphenyl oxide, octabromodiphenyl ether etc.; Halogen-free environment-friendly type flame-proof agent common are nitrogen-phosphorus series expansion type halogen-free flame retardants at present.
But at present no matter have the flame-retardant modified PP of halogen or halogen-free flameproof MODIFIED PP, maximum shortcoming is exactly that the introducing of fire retardant can make the mechanical property of material significantly decline, and especially shock resistance declines the most remarkable.For fear of the decline of impact property, in polypropylene and fire retardant, directly add elastomerics to carry out toughness reinforcing, utilize single stage method to melt extrude blend and reach.Wherein conventional elastomerics is ethylene-octene copolymer (POE), ternary isopropyl rubber (EPDM), styrene-butadiene-styrene terpolymer (SBS) etc.The main shortcoming of existing single stage method is exactly to add a large amount of elastomericss just can improve impact property, so words can make the tensile strength, flexural strength of material etc. significantly decline, and the introducing of great number of elastic body can make the consumption of fire retardant increase, and cost increases.
The present invention adopts in-situ two-step legal system for environment-friendly type high-ductility, anti-flaming polypropylene material, and the anti-flaming polypropylene material of preparing than existing single stage method has better mechanical property, and especially impelling strength can be improved significantly.
summary of the invention:
The present invention is directed to the deficiencies in the prior art, a kind of environment-friendly type high-ductility, anti-flaming polypropylene material and preparation method thereof are provided, adopt standby environment-friendly type high-ductility, the anti-flaming polypropylene material of in-situ two-step legal system, its mechanical property polypropylene flame redardant that especially impelling strength is prepared than the single stage method of prior art improves a lot.
Environment-friendly type high-ductility, an anti-flaming polypropylene material, be prepared from by weight by following component:
100 parts of polypropylene,
10 ~ 25 parts of cross-linked ethylene-alpha olefin copolymers,
25 ~ 35 parts of environmental protection fire retarding agents,
0.1 ~ 0.3 part of maleic anhydride,
0.2 ~ 0.5 part, oxidation inhibitor,
0.5 ~ 1.5 part of lubricant.
Described cross-linked ethylene-alpha olefin copolymer be by 100 parts of ethylene-alpha-olefin copolymers, 0.6 ~ 2.8 part of cross-linked evocating agent, 0.3 ~ 0.45 part of oxidation inhibitor and 0.3 ~ 0.45 part of lubricant mix, melting is crosslinked extrused, tie rod, pelletizing make.
Described ethylene-alpha-olefin copolymer is ethene-α butylene copolymer or ethene-α octene copolymer.
Described cross-linked evocating agent is a kind of in dicumyl peroxide, peroxidized t-butyl perbenzoate, dibenzoyl peroxide.
Described oxidation inhibitor is that four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (anti-1010), three [2,4-di-tert-butyl-phenyl] phosphorous acid ester (anti-168) carry out composite use.
Described environmental protection fire retarding agent is that bromo-antimony is to have halogen fire retardant or nitrogen-phosphorus series non-halogen fire retardant.
It is the mixture of eight bromine bisphenol S ethers and weisspiessglanz or the mixture of TDE and weisspiessglanz that there is halogen fire retardant in described bromo-antimony system; Described nitrogen-phosphorus series non-halogen fire retardant is the expanding halide-free fire-retardant that contains ammonium polyphosphate.
Described lubricant is the mixture of silicone based lubricant and calcium stearate.
Another object of the present invention is to provide a kind of method of preparing above-mentioned environment-friendly type high-ductility, anti-flaming polypropylene material, comprises the steps:
(1) prepare cross-linked ethylene-alpha olefin copolymer
It is that 200 ~ 300 revs/min, temperature are that the high-speed mixer of 25 ~ 30 ℃ mixes 2 ~ 5 minutes that 100 parts of ethylene-alpha-olefin copolymers, 0.6 ~ 2.8 part of cross-linked evocating agent, 0.3 ~ 0.45 part of oxidation inhibitor and 0.3 ~ 0.45 part of lubricant are put into rotating speed; Then mixture is added in twin screw extruder, carry out that melting is crosslinked extrused, tie rod, pelletizing, final cross-linked ethylene-alpha olefin copolymer;
The temperature of described twin screw extruder is followed successively by 30 ℃, 40 ℃, 100 ℃, 105 ℃, 105 ℃, 108 ℃, 108 ℃, 110 ℃ from feeding section to head, twin screw length-to-diameter ratio is 25, and screw speed is 100 ~ 130 revs/min.
(2) prepare environment-friendly type high-ductility, anti-flaming polypropylene material.
First 10 ~ 25 parts of cross-linked ethylene-alpha olefin copolymers, 0.1 ~ 0.3 part of maleic anhydride are put into high-speed mixer and mixed 2 ~ 5 minutes in 50 ~ 55 ℃; Then add 100 parts of polypropylene, 0.2 ~ 0.5 part of oxidation inhibitor, 0.5 ~ 1.5 part of lubricant to mix 2 ~ 5 minutes; Then add 25 ~ 35 parts of environmental protection fire retarding agents to mix 2 ~ 5 minutes at 55 ~ 65 ℃; Finally mixture is added in twin screw extruder, carry out that fusion-grafting is extruded, tie rod, pelletizing, final environment-friendly type high-ductility, anti-flaming polypropylene material;
The rotating speed of described high-speed mixer is 200 ~ 300 revs/min; The temperature of described twin screw extruder is followed successively by 100 ℃, 185 ℃, 195 ℃, 195 ℃, 190 ℃, 190 ℃, 185 ℃, 185 ℃ from feeding section to head, twin screw length-to-diameter ratio is 30, and screw speed is 100 ~ 130 revs/min.
The present invention compared with prior art has following beneficial effect:
1, the present invention adopts in-situ two-step legal system for environment-friendly type high-ductility, anti-flaming polypropylene material, and the first step is prepared cross-linked ethylene-alpha olefin copolymer, and second step is prepared environment-friendly type high-ductility, anti-flaming polypropylene material; The various performances of the anti-flaming polypropylene material that it is prepared than existing single stage method blend are all excellent.
2, the processing parameters such as temperature in in-situ two-step method of the present invention are extremely strict, slightly high or slightly lowly all can not get desirable performance, thereby have improved the performance of the finished product.
3, in the present invention, cross-linked ethylene-alpha olefin copolymer has better toughening effect than uncrosslinked ethylene-alpha-olefin copolymer.
4, in-situ two-step method of the present invention is simple to operate, is easy to industrialization, and has widened the Application Areas of polypropylene composite material.
5, in preparation method of the present invention, raw material time is mixed in three batches, first cross-linked ethylene-alpha olefin copolymer is mixed with maleic anhydride, then add polypropylene, oxidation inhibitor, lubricant to mix; Make material premix even, thereby improve final polypropylene material toughness and flame retardant properties.
specific embodiment:
Below in conjunction with embodiment and comparative example, the invention will be further described.Below in all embodiment and comparative example, testing standard is carried out national standard, and tensile property is carried out GB/T 1040 and Elongation test speed 50mm/min, and bending property is carried out GB/T 9341 and crooked test speed 2mm/min, impact property is carried out GB/T 1843, and flame retardant properties is carried out UL-94; And test environment is 23 ℃ ± 1 ℃, 50%RH ± 3%RH.
The starting material of using in embodiment and comparative example have:
Ethene-α butylene copolymer model: POE 7467 Dow Chemicals;
Ethene-α octene copolymer model: POE 8150 Dow Chemicals;
The prosperous holy brightness chemical industry of dicumyl peroxide model: DCP;
The prosperous holy brightness chemical industry of peroxidized t-butyl perbenzoate model: TBPB;
Dibenzoyl peroxide model: Zouping, BPO Shandong Heng Tai Chemical Co., Ltd.;
Maleic anhydride model: MA Qingdao Heng Rui Chemical Co., Ltd.;
Polypropylene A model: K7726H China Petrochemical Industry Yanshan Petrochemical;
Polypropylene B model: sub-petrochemical industry is raised by S700 China Petrochemical Industry;
Fire retardant A model: eight bromine bisphenol S ether Shanghai Ao Hui Industrial Co., Ltd.s;
Fire retardant B model: TDE Shanghai Ao Hui Industrial Co., Ltd.;
Fire retardant C model: the prosperous antimony industry of weisspiessglanz Yiyang City China;
Fire retardant D model: expanding halide-free fire-retardant WR03 Suzhou peace letter is safe;
Antioxidant 1010 model: Irganox1010 Switzerland Ciba;
Irgasfos 168 model: Irganox168 Switzerland Ciba;
Silicone based lubricant model: E525 Germany Degussa;
Lubricant model: calcium stearate (premium grads) You He of Gaomi City, Shandong Province auxiliary agent company limited.
embodiment 1
(1) prepare cross-linked ethylene-alpha olefin copolymer
7467,0.6 part of DCP of 100 parts of POE, 0.15 part of anti-1010,0.15 parts of anti-168,0.2 parts of E525,0.1 part of calcium stearate are put into high-speed mixer and mixed 2 minutes, the mixture mixing is added in twin screw extruder, carry out that melting is crosslinked extrused, tie rod, pelletizing, final cross-linked ethylene-alpha olefin copolymer.
The rotating speed of high-speed mixer is that 200 revs/min, temperature are 25 ℃; The temperature of twin screw extruder is followed successively by 30 ℃, 40 ℃, 100 ℃, 105 ℃, 105 ℃, 108 ℃, 108 ℃, 110 ℃ from feeding section to head, twin screw length-to-diameter ratio is 25, and screw speed is 100 revs/min.
(2) prepare environment-friendly type high-ductility, anti-flaming polypropylene material
First 10 parts of cross-linked ethylene-alpha olefin copolymers, 0.1 part of maleic anhydride being put into temperature is that 50 ℃ of high-speed mixers mix 2 minutes; Then add 100 parts of polypropylene K7726H, 0.1 part of antioxidant 1010,0.1 part of irgasfos 168,0.4 part of E525,0.1 part of calcium stearate to continue to mix 2 minutes; Finally add 19 part of eight bromine bisphenol S ether, 6 parts of weisspiessglanzs in temperature, to be 55 ℃ and to mix 2 minutes; Finally the mixture mixing is added in twin screw extruder, carry out that fusion-grafting is extruded, tie rod, pelletizing, final environment-friendly type high-ductility, anti-flaming polypropylene material.
The rotating speed of high-speed mixer is 200 revs/min, the temperature of twin screw extruder is followed successively by 100 ℃, 185 ℃, 195 ℃, 195 ℃, 190 ℃, 190 ℃, 185 ℃, 185 ℃ from feeding section to head, twin screw length-to-diameter ratio is 30, and screw speed is 100 revs/min.Performance is as table 1.
comparative example 1
First 7467,0.1 part of maleic anhydride of 10 parts of POE being put into temperature is that 50 ℃ of high-speed mixers carry out high-speed mixing 2 minutes; Then add 100 parts of polypropylene K7726H, 0.1 part of antioxidant 1010,0.1 part of irgasfos 168,0.4 part of E525,0.1 part of calcium stearate to continue to mix 2 minutes; Finally add 19 part of eight bromine bisphenol S ether, 6 parts of weisspiessglanzs in temperature, to be 55 ℃ and to mix 2 minutes.The mixture mixing is added in twin screw extruder, carry out that fusion-grafting is extruded, tie rod, pelletizing, final environment-friendly type high-ductility, anti-flaming polypropylene material.
The rotating speed of high-speed mixer is 200 revs/min, the temperature of twin screw extruder is followed successively by 100 ℃, 185 ℃, 195 ℃, 195 ℃, 190 ℃, 190 ℃, 185 ℃, 185 ℃ from feeding section to head, twin screw length-to-diameter ratio is 30, and screw speed is 100 revs/min.Performance is as table 1.
embodiment 2
(1) prepare cross-linked ethylene-alpha olefin copolymer.
Anti-1010,0.15 parts of anti-168, the 0.35 parts of E525 of 8150,2.8 parts of TBPB of 100 parts of POE, 0.3 part, 0.1 part of calcium stearate are put into high-speed mixer and mixed 5 minutes, and the rotating speed of high-speed mixer is that 300 revs/min, temperature are 30 ℃.The mixture mixing is added in twin screw extruder, carry out that melting is crosslinked extrused, tie rod, pelletizing, final cross-linked ethylene-alpha olefin copolymer.
The temperature of twin screw extruder is followed successively by 30 ℃, 40 ℃, 100 ℃, 105 ℃, 105 ℃, 108 ℃, 108 ℃, 110 ℃ from feeding section to head, twin screw length-to-diameter ratio is 25, and screw speed is 130 revs/min.
(2) prepare environment-friendly type high-ductility, anti-flaming polypropylene material
First it is that 55 ℃ of high-speed mixers mix 5 minutes that cross-linked ethylene-alpha olefin copolymer of being prepared by 25 parts of the first steps, 0.3 part of maleic anhydride are put into temperature; Then add 100 parts of polypropylene S700,0.35 part of antioxidant 1010,0.15 part of irgasfos 168,1.2 parts of E525,0.3 part of calcium stearate to mix 5 minutes; Finally add 26 parts of TDE, 9 parts of weisspiessglanzs in temperature, to be 65 ℃ and to mix 5 minutes.The mixture mixing is added in twin screw extruder, carry out that fusion-grafting is extruded, tie rod, pelletizing, final environment-friendly type high-ductility, anti-flaming polypropylene material.
The rotating speed of high-speed mixer is 300 revs/min, the temperature of twin screw extruder is followed successively by 100 ℃, 185 ℃, 195 ℃, 195 ℃, 190 ℃, 190 ℃, 185 ℃, 185 ℃ from feeding section to head, twin screw length-to-diameter ratio is 30, and screw speed is 130 revs/min.Performance is as table 1.
comparative example 2
First 8150,0.3 part of maleic anhydride of 25 parts of POE is put into high-speed mixer and carry out high-speed mixing 5 minutes, the rotating speed of high-speed mixer is that 300 revs/min, temperature are 55 ℃; Then add 100 parts of polypropylene S700,0.35 part of antioxidant 1010,0.15 part of irgasfos 168,1.2 parts of E525,0.3 part of calcium stearate to carry out high-speed mixing 5 minutes, the rotating speed of high-speed mixer is that 300 revs/min, temperature are 55 ℃; Finally add 26 parts of TDE, 9 parts of weisspiessglanz high-speed mixing 5 minutes, the rotating speed of high-speed mixer is that 300 revs/min, temperature are 65 ℃.The mixture mixing is added in twin screw extruder, carry out that fusion-grafting is extruded, tie rod, pelletizing, final environment-friendly type high-ductility, anti-flaming polypropylene material.The temperature of twin screw extruder is followed successively by 100 ℃, 185 ℃, 195 ℃, 195 ℃, 190 ℃, 190 ℃, 185 ℃, 185 ℃ from feeding section to head, twin screw length-to-diameter ratio is 30, and screw speed is 130 revs/min.Performance is as table 1.
Table 1 embodiment 1 ~ 2 and comparative example 1 ~ 2 performance
| Test event | The pure material of PP K7726H | The pure material of PP S700 | Embodiment 1 | Comparative example 1 | Embodiment 2 | Comparative example 2 |
| Tensile strength/MPa | 25 | 35 | 24 | 21 | 28 | 25 |
| Flexural strength/MPa | 34 | 41 | 32 | 27 | 35 | 31 |
| Modulus in flexure/MPa | 1265 | 1450 | 1536 | 1320 | 1860 | 1625 |
| Socle girder notched Izod impact strength/(KJ/m2) | 8.9 | 3.5 | 9.6 | 5.4 | 11.6 | 6.8 |
| UL-94 flame retardant rating 0.8mm | Not fire-retardant | Not fire-retardant | V0 | V0 | V0 | V0 |
From above table 1, can find out, due to crosslinked between the molecular chain of cross-linked ethylene-alpha olefin copolymer, make it when receiving external impacts, than uncrosslinked molecular weight, can absorb more energy, therefore show as good toughening effect and higher stretching and flexural strength.So under the toughner condition identical with content with fire retardant kind, comparative example is not as good as toughness reinforcing effect of the present invention, and two-step approach of the present invention is also less than traditional single stage method to the impact of tensile strength and flexural strength.As: embodiment 2 and comparative example 2 can be found out, material impact intensity 11.6KJ/m2, tensile strength 28MPa, flexural strength 35MPa, modulus in flexure 1860MPa prepared by two-step approach of the present invention, and material impact intensity 6.8KJ/m2, tensile strength 25MPa, flexural strength 31MPa, modulus in flexure 1625MPa prepared by traditional single stage method.
embodiment 3
(1) prepare cross-linked ethylene-alpha olefin copolymer
Anti-1010,0.15 parts of anti-168, the 0.25 parts of E525 of 7467,1.3 parts of BPO of 100 parts of POE, 0.2 part, 0.1 part of calcium stearate are put into high-speed mixer and carried out high-speed mixing 3.5 minutes, and the rotating speed of high-speed mixer is that 220 revs/min, temperature are 27 ℃.The mixture mixing is added in twin screw extruder, carry out that melting is crosslinked extrused, tie rod, pelletizing, final cross-linked ethylene-alpha olefin copolymer.The temperature of twin screw extruder is followed successively by 30 ℃, 40 ℃, 100 ℃, 105 ℃, 105 ℃, 108 ℃, 108 ℃, 110 ℃ from feeding section to head, twin screw length-to-diameter ratio is 25, and screw speed is 110 revs/min.
(2) prepare environment-friendly type high-ductility, anti-flaming polypropylene material
First cross-linked ethylene-alpha olefin copolymer of being prepared by 14 parts of the first steps, 0.16 part of maleic anhydride are put into high-speed mixer and are carried out high-speed mixing 2.8 minutes, and the rotating speed of high-speed mixer is that 235 revs/min, temperature are 52 ℃; Then add 100 parts of polypropylene K7726H, 0.15 part of antioxidant 1010,0.1 part of irgasfos 168,0.55 part of E525,0.1 part of calcium stearate to carry out high-speed mixing 3.2 minutes, the rotating speed of high-speed mixer is that 255 revs/min, temperature are 53 ℃; Finally add 29 parts of fire retardant WR03 high-speed mixing 2.7 minutes, the rotating speed of high-speed mixer is that 265 revs/min, temperature are 58 ℃.The mixture mixing is added in twin screw extruder, carry out that fusion-grafting is extruded, tie rod, pelletizing, final environment-friendly type high-ductility, anti-flaming polypropylene material.The temperature of twin screw extruder is followed successively by 100 ℃, 185 ℃, 195 ℃, 195 ℃, 190 ℃, 190 ℃, 185 ℃, 185 ℃ from feeding section to head, twin screw length-to-diameter ratio is 30, and screw speed is 116 revs/min.Performance is as table 2.
comparative example 3
First 7467,0.16 part of maleic anhydride of 14 parts of POE is put into high-speed mixer and carry out high-speed mixing 2.8 minutes, the rotating speed of high-speed mixer is that 235 revs/min, temperature are 52 ℃; Then add 100 parts of polypropylene K7726H, 0.15 part of antioxidant 1010,0.1 part of irgasfos 168,0.55 part of E525,0.1 part of calcium stearate to carry out high-speed mixing 3.2 minutes, the rotating speed of high-speed mixer is that 255 revs/min, temperature are 53 ℃; Finally add 29 parts of fire retardant WR03 high-speed mixing 2.7 minutes, the rotating speed of high-speed mixer is that 265 revs/min, temperature are 58 ℃.The mixture mixing is added in twin screw extruder, carry out that fusion-grafting is extruded, tie rod, pelletizing, final environment-friendly type high-ductility, anti-flaming polypropylene material.The temperature of twin screw extruder is followed successively by 100 ℃, 185 ℃, 195 ℃, 195 ℃, 190 ℃, 190 ℃, 185 ℃, 185 ℃ from feeding section to head, twin screw length-to-diameter ratio is 30, and screw speed is 116 revs/min.Performance is as table 2.
embodiment 4
(1) prepare cross-linked ethylene-alpha olefin copolymer
Anti-1010,0.15 parts of anti-168, the 0.28 parts of E525 of 8150,1.8 parts of BPO of 100 parts of POE, 0.25 part, 0.1 part of calcium stearate are put into high-speed mixer and carried out high-speed mixing 3.9 minutes, and the rotating speed of high-speed mixer is that 245 revs/min, temperature are 28 ℃.The mixture mixing is added in twin screw extruder, carry out that melting is crosslinked extrused, tie rod, pelletizing, final cross-linked ethylene-alpha olefin copolymer.The temperature of twin screw extruder is followed successively by 30 ℃, 40 ℃, 100 ℃, 105 ℃, 105 ℃, 108 ℃, 108 ℃, 110 ℃ from feeding section to head, twin screw length-to-diameter ratio is 25, and screw speed is 117 revs/min.
(2) prepare environment-friendly type high-ductility, anti-flaming polypropylene material
First cross-linked ethylene-alpha olefin copolymer of being prepared by 19 parts of the first steps, 0.22 part of maleic anhydride are put into high-speed mixer and are carried out high-speed mixing 3.7 minutes, and the rotating speed of high-speed mixer is that 256 revs/min, temperature are 53 ℃; Then add 100 parts of polypropylene K7726H, 0.25 part of antioxidant 1010,0.15 part of irgasfos 168,0.75 part of E525,0.15 part of calcium stearate to carry out high-speed mixing 3.8 minutes, the rotating speed of high-speed mixer is that 289 revs/min, temperature are 54 ℃; Finally add 29 parts of fire retardant WR03 high-speed mixing 2.8 minutes, the rotating speed of high-speed mixer is that 269 revs/min, temperature are 62 ℃.The mixture mixing is added in twin screw extruder, carry out that fusion-grafting is extruded, tie rod, pelletizing, final environment-friendly type high-ductility, anti-flaming polypropylene material.The temperature of twin screw extruder is followed successively by 100 ℃, 185 ℃, 195 ℃, 195 ℃, 190 ℃, 190 ℃, 185 ℃, 185 ℃ from feeding section to head, twin screw length-to-diameter ratio is 30, and screw speed is 119 revs/min.Performance is as table 2.
embodiment 5
(1) prepare cross-linked ethylene-alpha olefin copolymer
Anti-1010,0.16 parts of anti-168, the 0.28 parts of E525 of 8150,2.4 parts of DCP of 100 parts of POE, 0.27 part, 0.13 part of calcium stearate are put into high-speed mixer and carried out high-speed mixing 4.3 minutes, and the rotating speed of high-speed mixer is that 276 revs/min, temperature are 28 ℃.The mixture mixing is added in twin screw extruder, carry out that melting is crosslinked extrused, tie rod, pelletizing, final cross-linked ethylene-alpha olefin copolymer.The temperature of twin screw extruder is followed successively by 30 ℃, 40 ℃, 100 ℃, 105 ℃, 105 ℃, 108 ℃, 108 ℃, 110 ℃ from feeding section to head, twin screw length-to-diameter ratio is 25, and screw speed is 123 revs/min.
(2) prepare environment-friendly type high-ductility, anti-flaming polypropylene material
First cross-linked ethylene-alpha olefin copolymer of being prepared by 23.7 parts of the first steps, 0.26 part of maleic anhydride are put into high-speed mixer and are carried out high-speed mixing 4.6 minutes, and the rotating speed of high-speed mixer is that 282 revs/min, temperature are 54 ℃; Then add 100 parts of polypropylene S700,0.28 part of antioxidant 1010,0.15 part of irgasfos 168,0.79 part of E525,0.15 part of calcium stearate to carry out high-speed mixing 3.8 minutes, the rotating speed of high-speed mixer is that 295 revs/min, temperature are 54 ℃; Finally add 22 part of eight bromine bisphenol S ether, 8 parts of weisspiessglanz high-speed mixing 4.2 minutes, the rotating speed of high-speed mixer is that 285 revs/min, temperature are 63 ℃.The mixture mixing is added in twin screw extruder, carry out that fusion-grafting is extruded, tie rod, pelletizing, final environment-friendly type high-ductility, anti-flaming polypropylene material.The temperature of twin screw extruder is followed successively by 100 ℃, 185 ℃, 195 ℃, 195 ℃, 190 ℃, 190 ℃, 185 ℃, 185 ℃ from feeding section to head, twin screw length-to-diameter ratio is 30, and screw speed is 127 revs/min.Performance is as table 2.
Table 2 embodiment 3 ~ 5 and comparative example 3 performances
From above table 2, can find out, under the toughner condition identical with content with fire retardant kind, the polypropylene material of comparative example 3,4 preparations all adopts the toughening effect of the standby polypropylene material of in-situ two-step legal system good not as good as the embodiment of the present invention 3,4, and two-step approach of the present invention is also less than traditional single stage method to the impact of tensile strength and flexural strength.As: embodiment 3 and comparative example 3 can be found out, material impact intensity 11.8KJ/m2, tensile strength 22MPa, flexural strength 31MPa, modulus in flexure 1512MPa prepared by two-step approach of the present invention, and material impact intensity 6.7KJ/m2, tensile strength 19MPa, flexural strength 26MPa, modulus in flexure 1298MPa prepared by traditional single stage method.Its major cause is crosslinked the making when receiving external impacts between the molecular chain of cross-linked ethylene-alpha olefin copolymer, can absorb more energy, therefore show as good toughening effect and higher stretching and flexural strength than uncrosslinked molecular weight.
In addition, fire retardant used in the present invention is the environment friendly flame retardant that meets RoHS Directive, and the environment-friendly type high-ductility of preparing, the impelling strength of anti-flaming polypropylene material are good, can be widely used in household electrical appliances, the industry such as electric.
Claims (8)
1. environment-friendly type high-ductility, an anti-flaming polypropylene material, is characterized in that: by following component, be prepared from by weight:
100 parts of polypropylene,
10 ~ 25 parts of cross-linked ethylene-alpha olefin copolymers,
25 ~ 35 parts of environmental protection fire retarding agents,
0.1 ~ 0.3 part of maleic anhydride,
0.2 ~ 0.5 part, oxidation inhibitor,
0.5 ~ 1.5 part of lubricant,
Described cross-linked ethylene-alpha olefin copolymer be by 100 parts of ethylene-alpha-olefin copolymers, 0.6 ~ 2.8 part of cross-linked evocating agent, 0.3 ~ 0.45 part of oxidation inhibitor and 0.3 ~ 0.45 part of lubricant mix, melting is crosslinked extrused, tie rod, pelletizing make.
2. environment-friendly type high-ductility according to claim 1, anti-flaming polypropylene material, is characterized in that: described ethylene-alpha-olefin copolymer is ethene-α butylene copolymer or ethene-α octene copolymer.
3. environment-friendly type high-ductility according to claim 1, anti-flaming polypropylene material, is characterized in that: described cross-linked evocating agent is a kind of in dicumyl peroxide, peroxidized t-butyl perbenzoate, dibenzoyl peroxide.
4. environment-friendly type high-ductility according to claim 1, anti-flaming polypropylene material, it is characterized in that: described oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, three [2,4-di-tert-butyl-phenyl] phosphorous acid ester carries out composite use.
5. environment-friendly type high-ductility according to claim 1, anti-flaming polypropylene material, is characterized in that: described environmental protection fire retarding agent is that bromo-antimony is to have halogen fire retardant or nitrogen-phosphorus series non-halogen fire retardant.
6. environment-friendly type high-ductility according to claim 5, anti-flaming polypropylene material, is characterized in that: it is the mixture of eight bromine bisphenol S ethers and weisspiessglanz or the mixture of TDE and weisspiessglanz that there is halogen fire retardant in described bromo-antimony system; Described nitrogen-phosphorus series non-halogen fire retardant is the expanding halide-free fire-retardant that contains ammonium polyphosphate.
7. environment-friendly type high-ductility according to claim 1, anti-flaming polypropylene material, is characterized in that: described lubricant is the mixture of silicone based lubricant and calcium stearate.
8. a method of preparing environment-friendly type high-ductility as claimed in claim 1, anti-flaming polypropylene material, is characterized in that: comprise the steps:
(1) prepare cross-linked ethylene-alpha olefin copolymer
It is that 200 ~ 300 revs/min, temperature are that the high-speed mixer of 25 ~ 30 ℃ mixes 2 ~ 5 minutes that 100 parts of ethylene-alpha-olefin copolymers, 0.6 ~ 2.8 part of cross-linked evocating agent, 0.3 ~ 0.45 part of oxidation inhibitor and 0.3 ~ 0.45 part of lubricant are put into rotating speed; Then mixture is added in twin screw extruder, carry out that melting is crosslinked extrused, tie rod, pelletizing, final cross-linked ethylene-alpha olefin copolymer;
The temperature of described twin screw extruder is followed successively by 30 ℃, 40 ℃, 100 ℃, 105 ℃, 105 ℃, 108 ℃, 108 ℃, 110 ℃ from feeding section to head, twin screw length-to-diameter ratio is 25, and screw speed is 100 ~ 130 revs/min;
(2) prepare environment-friendly type high-ductility, anti-flaming polypropylene material
First 10 ~ 25 parts of cross-linked ethylene-alpha olefin copolymers, 0.1 ~ 0.3 part of maleic anhydride are put into high-speed mixer and mixed 2 ~ 5 minutes in 50 ~ 55 ℃; Then add 100 parts of polypropylene, 0.2 ~ 0.5 part of oxidation inhibitor, 0.5 ~ 1.5 part of lubricant to mix 2 ~ 5 minutes; Then add 25 ~ 35 parts of environmental protection fire retarding agents to mix 2 ~ 5 minutes at 55 ~ 65 ℃; Mixture is added in twin screw extruder, carry out that fusion-grafting is extruded, tie rod, pelletizing, final environment-friendly type high-ductility, anti-flaming polypropylene material;
The rotating speed of described high-speed mixer is 200 ~ 300 revs/min; The temperature of described twin screw extruder is followed successively by 100 ℃, 185 ℃, 195 ℃, 195 ℃, 190 ℃, 190 ℃, 185 ℃, 185 ℃ from feeding section to head, twin screw length-to-diameter ratio is 30, and screw speed is 100 ~ 130 revs/min.
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| CN106009252A (en) * | 2016-05-22 | 2016-10-12 | 王刚 | High-toughness high cold-resistant transparent polypropylene material and preparation method thereof |
| CN112063044A (en) * | 2020-08-19 | 2020-12-11 | 上海金发科技发展有限公司 | Flame-retardant polypropylene composition capable of preventing pet from biting and preparation method thereof |
| CN112143115A (en) * | 2020-09-18 | 2020-12-29 | 会通新材料(上海)有限公司 | Preparation method of flame-retardant polypropylene material |
| CN115449152A (en) * | 2021-06-09 | 2022-12-09 | 国家能源投资集团有限责任公司 | Flame-retardant antistatic polypropylene composition, flame-retardant antistatic polypropylene material, preparation method and application of flame-retardant antistatic polypropylene material, mining pipe and application of mining pipe |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106009252A (en) * | 2016-05-22 | 2016-10-12 | 王刚 | High-toughness high cold-resistant transparent polypropylene material and preparation method thereof |
| CN112063044A (en) * | 2020-08-19 | 2020-12-11 | 上海金发科技发展有限公司 | Flame-retardant polypropylene composition capable of preventing pet from biting and preparation method thereof |
| CN112143115A (en) * | 2020-09-18 | 2020-12-29 | 会通新材料(上海)有限公司 | Preparation method of flame-retardant polypropylene material |
| CN115449152A (en) * | 2021-06-09 | 2022-12-09 | 国家能源投资集团有限责任公司 | Flame-retardant antistatic polypropylene composition, flame-retardant antistatic polypropylene material, preparation method and application of flame-retardant antistatic polypropylene material, mining pipe and application of mining pipe |
| CN115449152B (en) * | 2021-06-09 | 2024-04-02 | 国家能源投资集团有限责任公司 | Flame-retardant antistatic polypropylene composition, flame-retardant antistatic polypropylene material, preparation method and application thereof, mining pipe and application thereof |
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