CN100535047C - Polypropylene material with high bath strength and preparation method - Google Patents

Polypropylene material with high bath strength and preparation method Download PDF

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Publication number
CN100535047C
CN100535047C CNB2007100624518A CN200710062451A CN100535047C CN 100535047 C CN100535047 C CN 100535047C CN B2007100624518 A CNB2007100624518 A CN B2007100624518A CN 200710062451 A CN200710062451 A CN 200710062451A CN 100535047 C CN100535047 C CN 100535047C
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melt strength
high melt
polypropylene material
polypropylene
organic
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CN101092500A (en
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董金勇
倪青林
范家起
徐怀书
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Hebei fuente Electrical Equipment Group Co. Ltd.
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Fuente Anti-Corrosion Control Equipment Co Ltd Tangshan City
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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
    • 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
    • B29C48/92—Measuring, controlling or regulating
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • 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
    • 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
    • B29C48/395—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
    • B29C48/40—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 using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B29C48/405—Intermeshing co-rotating screws
    • 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
    • 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
    • B29C2948/926—Flow or feed rate
    • 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
    • B29C2948/92704—Temperature
    • 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
    • B29C2948/92819—Location or phase of control
    • B29C2948/92828—Raw material handling or dosing, e.g. active hopper or feeding device
    • 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
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92866—Inlet shaft or slot, e.g. passive hopper; Injector, e.g. injector nozzle on barrel
    • 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
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92885—Screw or gear
    • 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
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895—Barrel or housing

Abstract

This invention relates to a method for preparing propylene material with high melt strength. The propylene material is composed of: propylene 100 parts, organic peroxide initiator 0.002-4 parts, multifunctional monomer 0.005-5 parts, branching promoter 0.001-4 parts, and organic clay 0.1-10 parts. The dispersion degree of organic clay is 10-100 nm. The method comprises: uniformly mixing propylene, organic peroxide initiator, multifunctional monomer, branching promoter and organic clay, adding into a twin-screw extruder, melting, extruding and granulating with temperature, rotation speed and feeding rate controlled to obtain gel-free propylene material with high melt strength. During the in-situ intercalation process, organic clay is dispersed in the polymer matrix on nanoscale. Uniformly dispersed organic clay can control the formation of branching structure, and improve the melt strength and mechanical properties of the propylene material. The propylene material is suitable for extrusion foaming and other thermal molding processes.

Description

A kind of high melt strength polypropylene material and preparation method thereof
Technical field:
The present invention relates to a kind of method of extruding with reaction and contain high melt strength polypropylene material of long branched chain structure and preparation method thereof by the polypropylene preparation of linear structure.High melt strength polypropylene material can obtain containing the expanded polypropylene material of tiny even abscess thus.
Background technology:
Porous plastics has advantages such as density is little, specific tenacity is high, energy absorption capability is strong, sound isolating and heat insulating performance is good.In thermoplastic foamed polyolefine plastic, compare with polyethylene foamed with polystyrene foamed, expanded polypropylene has the advantage of a lot of uniquenesses: (1) polyacrylic modulus in flexure approximately is 1.52GPa, be higher than poly about 200MPa far away, so the static load ability of polypropylene foam is better than polyethylene; (2) polyacrylic second-order transition temperature is lower than room temperature, and its pars amorpha at room temperature is in elastomeric state, and unbodied polystyrene (second-order transition temperature is 105 ℃) at room temperature is in vitreous state, so the impact property of polypropylene foam is better than polystyrene foam; (3) polystyrene foam takes place softening and distortion when using more than 105 ℃; Polyethylene is also seldom using more than 100 ℃, and the fusing point of polypropylene foam is than higher (165 ℃), and resistance to elevated temperatures is good.Can in hot environment, use; (4) polypropylene has very good chemical resistance energy, can match in excellence or beauty with polyethylene; (5) because the existence of pending methyl group, polypropylene is easy to degrade, and polypropylene foam is convenient to recycling, and its environment friendly is better than other foam materials.Just be based on above-mentioned advantage, expanded polypropylene material not only can substitute existing polystyrene and polyethylene, and especially has competitive power in the application of automotive industry and food packaging industry in the application of many industrial circles.
Yet, compare with polyethylene with polystyrene, polyacrylic foaming is difficulty very, its major cause is that the molecular chain of general purpose polypropylene is a linear structure, after temperature rises to its melt temperature, its melt elasticity sharply descends, and under molten state, the polypropylene of linear structure does not have strain hardening effect, and lower melt strength can't guarantee the effect of the tensile stress that cell wall is born in the bubble propagation process, causes bubble generation to subside and breaks, this makes that the process window of polypropylene extrusion foaming is very narrow, the temperature that is suitable for the general purpose polypropylene foaming to such an extent as to the percentage of open area of polypropylene foam is very high, can't satisfy service requirements only for 4-6 ℃.Therefore the polypropylene that will produce extrusion foaming at first needs high melt strength polypropylene material.
In theory, improving polyacrylic melt strength can be by increasing molecular weight, broadening molecular weight distribution or introducing long branched chain structure and realize.The technology of preparation high melt strength, propylene mainly contains radiation (superoxide) grafting, chemically crosslinked and blending and modifying etc.
Cover your company of Mount Tai in Chinese invention patent ZL94116148, introduced activity keto concentration less than 15% environment in, with energetic ray homopolymerization and Co-polypropylene or its composition are carried out 1 hour radiation, thereby and then make radiating free radical inactivation obtain the method for the high melt strength, propylene of branching.The special company of amaurosis in Chinese invention patent CN86100791, CN1105033, CN1045107 and Basel company similar method is disclosed respectively in Chinese invention patent CN1313879.It is said that the high melt strength, propylene that in this way obtains does not contain gel, melt elasticity is high also a tangible strain hardening effect, thereby in foaming and extrude occasion such as coating and have wide practical use.Thereby the main drawback of method for radio-grafting is to produce the required very big high melt strength, propylene that causes preparing of facility investment of energetic ray to cost an arm and a leg, and this has limited its widespread use.
Chinese invention patent CN1693330 has introduced thereby double bond containing long chain molecules such as unsaturated polyester have been grafted to the method that forms branched structure on the polypropylene molecular chain by initiator, the amount that the weakness of this method is the long chain molecule that needs is big (content is more than 5%), has influenced the mechanical property of material.
Chinese invention patent CN1869119 provides a kind of preparation method of partial cross-linked high melt strength, propylene, it is that hydrolysis by silane links together different polypropylene molecular chain, polyacrylic melt strength after crosslinked is significantly improved, the major defect of this method is gel content up to more than 20%, and this is for the continuous extrusion foaming of material and reclaim to reuse and to have brought very big difficulty.Chinese invention patent CN1775851 provides and maleic anhydride (ester) or acrylic ester grafted polypropylene are cross-linked into reticulated structure by the small molecules organic amine improve polyacrylic melt strength, used the graft polypropylene of high molten finger in this method in a large number, this makes the melt strength by the formed material of this method be subjected to significant limitation.
Chinese invention patent CN1594412 provides by polypropylene, compatilizer and clay blend being improved the method for melt strength, in this method, the existence of compatilizer is absolutely necessary to the homodisperse of clay, but the melt strength of compatilizer itself is generally very low, and this has had a strong impact on the melt strength of formed material.
Different with radiation grafting, the superoxide initiation grafting generally is to extrude in twin screw extruder by reaction to carry out, and facility investment is lower, and is easy to continuous production, thereby is more paid close attention to.How the difficult point of this method is control degradation and side reaction such as crosslinked.
Wang Xiaochun (Journal of Applied Polymer Science, 1996, Vol.61,1395-1404) and D.Graebling (Journal ofApplied Polymer Science, 1996, Vol.66 809-819) has reported that respectively polypropylene and more function group monomer acrylate under superoxide causes, carry out the method that fusion-grafting prepares high melt strength, propylene by twin screw extruder.D.Graebling (Macromolecules, 2002, Vol.35 4602-1410) has further reported by introducing thiuram and can control the grafting process better, is not contained the high melt strength, propylene of gel.
As described in Chinese invention patent CN1594412 and CN1869119, the introducing of nanoclay is useful for the raising of polypropylene system melt strength, but only just has this effect with the homodisperse clay of nanoscale in system.Simultaneously, the homodisperse of clay has important meaning for the bubble nucleating stage in the foaming process, it can be used as the nucleation that nucleator causes bubble, and have only homodisperse clay could make a large amount of bubbles grow up simultaneously, improve cell density and expansion ratio, homodisperse clay nano lamella can also play certain iris action to the escape of foamed gas in the air bubble growth process.In addition, well-known, nanoclay can improve the rigidity and the thermotolerance of polypropylene matrix, and this application to foaming product is very valuable.But as previously mentioned, the simple interpolation of clay can not form the homodisperse structure of nanoscale, is very disadvantageous and use compatilizer for the melt strength of system.
Summary of the invention:
The objective of the invention is to overcome the limitation of aforesaid method, the method of extruding with reaction, when forming branched structure, make the clay homodisperse, obtain not containing substantially high melt strength polypropylene material gel, that have excellent physical mechanical property and foam performance.
The technical scheme that realizes the foregoing invention purpose is:
A kind of high melt strength polypropylene material, proportioning raw materials comprise following component and content by weight:
Component (A): polypropylene 100
Component (B): organic peroxide evocating agent 0.002-4
Component (C): polyfunctional monomer 0.005-5
Component (D): branching promotor 0.001-4
Component (E): organic clay 0.1-10
In the described material, the dispersion yardstick of organic clay is at 10～100nm.
A kind of preparation method of high melt strength polypropylene material, its step is as follows:
Polypropylene, organic peroxide evocating agent, polyfunctional monomer, branching promotor, organic clay are pre-mixed evenly, feed in the twin screw extruder then, under temperature, rotating speed and the feed rate condition of control, melt extrude and granulation, be prepared into high melt strength, propylene.
The preparating mechanism of the inventive method is characterized as: organic peroxide evocating agent at high temperature decomposes the generation free radical, it sloughs hydrogen atom from polypropylene molecular chain, produce macromolecular radical, the polyfunctional monomer acrylate can be inserted between the organic clay lamella, it is when carrying out graft reaction with macromolecular radical, its reaction heat can further strut the organic clay lamella and peel off, form the nanostructure of intercal type, and make clay in system with the nanoscale homodisperse, and clay layer also can exert an influence to the graft reaction of the acrylate that carries out at interlayer; Therefore, also can control the formation of branched structure by the introducing of organic clay.So-called situ-formed graft intercalation method that Here it is.In this course, branching promotor thiuram has the effect of stable macromolecular radical, and when no thiuram existed, macromolecular radical was easy to take place degraded and waits side reaction and make melt strength greatly reduce.
When the consumption of organic peroxide initiator, polyfunctional monomer, branching promotor is lower than above-mentioned lower value, be not enough to produce the structure that contains long-chain branch, also just be not enough to improve the melt strength of material; When their consumption surpasses above-mentioned higher limit, then can produce tangible gel.Gel content is by hot gel-filtration test determination, and this polymer dissolution in 135 ℃ 1% xylene solution, and is filtered by 325 purpose copper mesh, and the ratio that calculate not by the polymkeric substance of copper mesh the oven dry back is gel content.When the consumption of organic clay was lower than 0.1 weight part, it was not enough to play control branching reaction, nucleation, obstruct and enhanced effect; When its consumption is higher than 7 weight parts, then be difficult to homodisperse in polymeric matrix.
Polypropylene described in the technical solution of the present invention is homopolymer polypropylene or polypropylene copolymer or both blends.
Organic peroxide evocating agent described in the technical solution of the present invention comprises tertbutyl peroxide, 1,1,3,3-tetramethyl--butylhydroperoxide, cumyl hydroperoxide, p-Methylisopropylbenzene base hydrogen peroxide, di-isopropylbenzene hydroperoxide, 2,5-dimethyl-2,5-two hydroperoxy hexanes, the cyclic group ketone peroxide, methyl cyclic group ketone peroxide, 3,3,5-trimethylammonium cyclic group ketone peroxide, ditertiary butyl peroxide, dicumyl peroxide, tert butyl isopropyl benzene peroxide, the peroxidation oxalic acid, peroxy dicarbonate, dipropyonyl peroxide, peroxidation two butyryl, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, two (3,5, the 5-trimethyl acetyl) superoxide, dibenzoyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane, 2,5-dimethyl-2,5-di-t-butyl peroxy-3-hexin.
Polyfunctional monomer described in the technical solution of the present invention comprises tripropylene glycol diacrylate, propylene glycol diacrylate, 1, the 6-hexanediyl ester, 1,4 butanediol diacrylate, neopentylglycol diacrylate, ethoxylated neopentylglycol diacrylate, PDDA, ethoxylated bisphenol a diacrylate, Viscoat 295, ethoxylated trimethylolpropane triacrylate, the propoxylation Viscoat 295, trimethylolpropane trimethacrylate, the glycerol propoxylate triacrylate, pentaerythritol triacrylate.
Branching promotor described in the technical solution of the present invention comprises dimethylthiuram disulfide, tetrabutylthiuram disulfide, tetraethylthiuram disulfide, dimethyl diphenylthiuram disulfide.
Organic clay described in the technical solution of the present invention is meant with organic intercalation agent, the dispersion medium clay by ion exchange treatment, or realizes the clay that organises with additive method, and its medium clay soil is meant polynite, sepiolite, tired stone, mica, illite or the beidellite of taking off, organic intercalation agent comprises alkyl amine, the alkylammonium salt, alcamines, hexanolactam, lauric acid amine, phenyl-ethyl amine, Ursol D, dispersion medium comprises water, alcohols, ketone.
The length-to-diameter ratio of the twin screw extruder described in the technical solution of the present invention is in the scope of 15-100, and rotating speed is 10-500 rev/min, and controllable temperature is between 50-500 ℃, and additional side is to drawing-in device, liquid quantitative feeding device, vacuum pumping hardware.The length-to-diameter ratio of forcing machine is preferably in the scope of 32-50; Each section temperature preferably is controlled at 150-250 ℃, and wherein the temperature of feed zone is lower than the temperature of other each section.
When prepared high melt strength, propylene is used to foam, can adopt the technology of extrusion moulding or compression moulding, whipping agent can be selected whipping agent physics or chemistry for use.
Description of drawings:
Fig. 1 is organic clay intercalation synoptic diagram in high melt strength, propylene.
Fig. 2 is the polyacrylic foam structure picture of linear structure.
Fig. 3 is the foam structure picture of high melt strength polypropylene material.
Embodiment:
Below in conjunction with drawings and Examples in detail the present invention is described in detail.
Embodiment 1:
Starting material component (by weight): component (A) is 100 parts of homo-polypropylene, Daqing petrochemical company production, and the trade mark is T30S; Component (B) is 0.08 part of a dicumyl peroxide (commercially available); Component (C) is 1.2 parts of pentaerythritol triacrylates (commercially available); Component (D) is 0.10 part of a dimethylthiuram disulfide (commercially available); Component E is 2 parts of organic claies (Nanomer I.44, U.S. Nanocor company produce).
Twin screw extruder structure and function: the forcing machine that is adopted is for rotating cord wood engagement type twin screw extruder in the same way, and screw diameter is 30mm, and length-to-diameter ratio is 40, and seven sections heating temperature controls are adopted in speed control by frequency variation, carry out vacuum exhaust the 6th section of forcing machine.
The preparation of high melt strength, propylene: use high-speed mixer, above-mentioned all components is mixed, in twin screw extruder, react extruding pelletization then and promptly make product of the present invention.150 rev/mins of control forcing machine rotating speeds, each section temperature is controlled to be from the spout to the head: 150 ℃, 170 ℃, 180 ℃, 190 ℃, 195 ℃, 195 ℃, 185 ℃.
The comparative example 1:
Except that not containing component E, other component is identical with embodiment 1 with preparation process.
Embodiment 2:
The starting material component: component (A) is 100 parts of homo-polypropylene, Daqing petrochemical company production, and the trade mark is T30S; Component (B) is 0.06 part of a dicumyl peroxide (commercially available); Component (C) is 1.0 parts of pentaerythritol triacrylates (commercially available); Component (D) is 0.08 part of a dimethylthiuram disulfide (commercially available); Component E is 2 parts of organic claies (Nanomer I.44, U.S. Nanocor company produce).
All the other operation stepss, implementation method are all with embodiment 1.
The comparative example 2:
Except that not containing component E, other component is identical with embodiment 2 with preparation process.
Material property by each embodiment gained sees Table 1.
Table 1 embodiment and comparative example's performance data table
The comparative example 1 Embodiment 1 The comparative example 2 Embodiment 2 T30S Profax-814
Melt strength (N) 0.42 0.57 0.37 0.49 0.31 0.58
MFI (g/10min) 0.145 0.169 0.427 1.75 2.79 2.92
Flexural strength (MPa) 59.9 60.1 52.6 58.5 45.2 54.8
Modulus in flexure (MPa) 1641 1710 1419 1594 1121 1388
Tensile strength (MPa) 41.4 41.8 38.8 42.0 38.8 42.3
Elongation at break (%) 42.3 324.2 58.6 338.8 436.9 97.9
Shock strength (KJ/m 2) 3.85 3.66 4.36 4.44 4.65 3.82
Melt temperature (℃) 165.2 165.7 164.6 164.6 165.2 159.7
Tc (℃) 128.6 131.8 123.6 126.6 111.2 128.5
In the data of table 1, (the roller rotating speed is 150rpm to melt strength for Germany, GOTTFERT) melt strength survey meter mensuration, and acceleration is 20mm/s with RHEDTENS71.97 2, three sections temperature of single screw rod are respectively 160 ℃, 190 ℃, 210 ℃, and die temperature is 200 ℃; Temperature rate when measuring fusion and Tc is 20 ℃/min; MFI and every mechanical property are measured according to the respective standard of ASTM.
Relatively two embodiment can find with its comparative example's performance, and the adding of organic clay can improve melt strength, increases mechanical property and promote crystallization, and this is very favorable to the performance that polypropylene expanded process reaches by the goods of its gained.
The data of last two row are respectively the performance of the high melt strength, propylene product P rofax-814 of polypropylene matrix T30S and Basell company in the table 1.As seen, with the resulting high melt strength, propylene of the inventive method, no matter be melt strength or mechanical property, all obviously be better than matrix, and suitable with the performance of the like product of Basell company.
This is the formation owing to foregoing intercal type nano structure, as shown in Figure 1. Curve 1,2,3 among the figure is respectively organic clay, embodiment 1 and comparative example's 1 X-ray diffraction curve, and comparison curves 1 and 2 can illustrate forming of intercal type nano structure by 001 diffraction peak of organic clay to moving of little angular direction.
Fig. 2 and Fig. 3 are respectively with CO 2The SEM picture of the expanded polypropylene sample that is become through extrudate haircut infusion by T30S and embodiment 1 gained material for whipping agent can be found, more even with the abscess of the high melt strength polypropylene material of embodiment 1 gained, expansion ratio is higher.

Claims (10)

1, a kind of high melt strength polypropylene material is characterized in that the proportioning raw materials of described material comprises the component with following content by weight:
Polypropylene 100
Organic peroxide evocating agent is a dicumyl peroxide 0.06～0.08
Polyfunctional monomer is a pentaerythritol triacrylate 1.0～1.2
Branching promotor is dimethylthiuram disulfide 0.08～0.1
Organic clay 0.1～10
The dispersion yardstick of described organic clay is at 10～100nm.
2, a kind of high melt strength polypropylene material according to claim 1 is characterized in that: described polypropylene is homopolymer polypropylene or polypropylene copolymer or both mixtures.
3, a kind of high melt strength polypropylene material according to claim 1 is characterized in that: its component concentration of described dicumyl peroxide is 0.06.
4, a kind of high melt strength polypropylene material according to claim 1 is characterized in that: its component concentration of described pentaerythritol triacrylate is 1.0.
5, a kind of high melt strength polypropylene material according to claim 1 is characterized in that: its component concentration of described dimethylthiuram disulfide is 0.08.
6, a kind of high melt strength polypropylene material according to claim 1, it is characterized in that: described organic clay is meant with organic intercalation agent, the dispersion medium clay by ion exchange treatment, its medium clay soil is meant polynite, sepiolite, tires out and take off stone, mica, illite or beidellite, and organic intercalation agent is an alkyl amine, the alkylammonium salt, alcamines, hexanolactam, ammonium laurate, phenyl-ethyl amine or Ursol D, dispersion medium is water, alcohols or ketone.
7, press the preparation method of the described a kind of high melt strength polypropylene material of claim 1, its step is that polypropylene, dicumyl peroxide, pentaerythritol triacrylate, dimethylthiuram disulfide, organic clay are pre-mixed evenly, feed in the twin screw extruder then, under temperature, rotating speed and the feed rate condition of control, melt extrude and granulation, be prepared into polypropylene, the length-to-diameter ratio of described twin screw extruder is in 32～50 scope, rotating speed is 10～500 rev/mins, and controllable temperature is at 150～250 ℃.
8, the preparation method of a kind of high melt strength polypropylene material according to claim 7 is characterized in that: the length-to-diameter ratio of described twin screw extruder is 40, and additional side is to drawing-in device, liquid quantitative feeding device and vacuum pumping hardware.
9, the preparation method of a kind of high melt strength polypropylene material according to claim 7 is characterized in that: the rotating speed of described twin screw extruder is 150 rev/mins.
10, the preparation method of a kind of high melt strength polypropylene material according to claim 7 is characterized in that: each of described twin screw extruder section temperature is controlled at 150～250 ℃, and wherein the temperature of feed zone is lower than the temperature of other each section.
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Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101503538B (en) * 2008-02-04 2012-05-02 上海杰事杰新材料(集团)股份有限公司 High melt strength polypropylene and preparation thereof
CN100569818C (en) * 2008-03-06 2009-12-16 中国科学院长春应用化学研究所 A kind of method that improves melt strength of polypropylene
EP2113541A1 (en) * 2008-04-28 2009-11-04 Borealis AG Adhesive propylene polymer composition suitable for extrusion coating of paper substrates
CN101302316B (en) * 2008-06-16 2011-04-13 江苏新泉汽车饰件有限公司 Production method of co-intercal type nano-polypropylene composite material
CN101376683B (en) * 2008-10-07 2011-09-21 中国科学院长春应用化学研究所 Preparation of high melt strength polypropylene
US20100087602A1 (en) * 2008-10-08 2010-04-08 Fina Technology, Inc. Long chain branched polypropylene for cast film applications
US9074062B2 (en) 2010-10-14 2015-07-07 Reliance Industries Ltd. Process for preparing high melt strength propylene polymers
CN102516655B (en) * 2011-11-29 2014-03-26 金发科技股份有限公司 Strengthening and toughening polypropylene composite and preparation method thereof
CN102558449A (en) * 2011-12-13 2012-07-11 金发科技股份有限公司 High-melt-strength polypropylene material, and preparation method and application thereof
CN105037931A (en) * 2015-07-06 2015-11-11 安徽成方新材料科技有限公司 Foamed polypropylene-high molecular absorbent composite material capable of separating high temperature liquid, and preparation method thereof
CN105037930A (en) * 2015-07-06 2015-11-11 安徽成方新材料科技有限公司 Foamed polypropylene-high molecular absorbent composite material with uniform pore distribution, and preparation method thereof
CN105061885A (en) * 2015-07-13 2015-11-18 安徽成方新材料科技有限公司 Oil-absorbing composite with magnetic adsorption function and preparation method thereof
CN105061886A (en) * 2015-07-13 2015-11-18 安徽成方新材料科技有限公司 Adsorption material with good antibacterial and oil-absorption effects and preparation method of adsorption material
CN105061883A (en) * 2015-07-13 2015-11-18 安徽成方新材料科技有限公司 Silicon-containing oil-absorbing composite material and preparation method thereof
CN105061884A (en) * 2015-07-13 2015-11-18 安徽成方新材料科技有限公司 Foamed polypropylene oil-absorbing composite material and preparation method thereof
CN105153546B (en) * 2015-10-20 2017-12-01 惠州市环美盛新材料有限公司 A kind of preparation of environment-protective water expanded polypropylene masterbatch and its manufactured extrusion fretting map sheet material
CN105252697A (en) * 2015-10-28 2016-01-20 界首市兴安塑料制品有限公司 Foam product capable of being rapidly degraded and production technology of foam product
CN105315411A (en) * 2015-11-05 2016-02-10 广州石头造环保科技股份有限公司 Nanometer modified high-strength polypropylene material and preparation method thereof
CN106084136A (en) * 2016-06-15 2016-11-09 潘海云 A kind of modified polypropylene plastic tubing and preparation method thereof
CN107603015A (en) * 2017-09-28 2018-01-19 安徽裕泰环保科技有限公司 A kind of polypropylene packaging film of low melt flow speed
CN110229278A (en) * 2019-06-26 2019-09-13 贵州省材料产业技术研究院 Composite polyolefine material and preparation method thereof and water supply and sewerage pipeline
CN112759827B (en) * 2019-10-21 2022-01-25 国家能源投资集团有限责任公司 Flame-retardant polypropylene composition, flame-retardant foamed polypropylene and preparation method thereof
CN112321981A (en) * 2020-10-28 2021-02-05 施仕全 Preparation process of polypropylene material
CN113912937B (en) * 2021-09-30 2023-06-06 成都金发科技新材料有限公司 Polypropylene nanocomposite and preparation method and application thereof
CN115340728B (en) * 2022-09-15 2023-08-01 广东锦湖日丽高分子材料有限公司 Scratch-resistant polypropylene resin material

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
聚丙烯/有机蒙脱土纳米复合材料的制备及性能研究. 王柯等.绝缘材料，第3期. 2002
聚丙烯/有机蒙脱土纳米复合材料的制备及性能研究. 王柯等.绝缘材料，第3期. 2002 *
聚丙烯/蒙脱土纳米复合材料1 制备、表征及动态力学性能. 刘晓辉等.高分子学报，第5期. 2000
聚丙烯/蒙脱土纳米复合材料1 制备、表征及动态力学性能. 刘晓辉等.高分子学报，第5期. 2000 *
长链支化制备高熔体强度PP的研究. 金阳等.中国塑料，第16卷第10期. 2002
长链支化制备高熔体强度PP的研究. 金阳等.中国塑料，第16卷第10期. 2002 *

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