CN103665567B - Co-polymer foamed bead of propylene butene and preparation method thereof - Google Patents
Co-polymer foamed bead of propylene butene and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/14—Copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/06—Biodegradable
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
Abstract
The invention provides a kind of polypropylene foaming beads, described expanded bead adopts high melt strength, propylene to be matrix resin, adopts foaming agent foam to obtain; Wherein, described high melt strength, propylene has following feature: its melting index MFR is 0.2 ~ 10g/10min, molecular weight distribution M
w/ M
nbe 6 ~ 20, the content that molecular weight is greater than 5,000,000 fractions is more than or equal to 0.8wt%, M
z+1/ M
nbe more than or equal to 70, and wherein butene content is 0.1 ~ 15wt%.The present invention with the high melt strength, propylene of wide molecular weight distribution for raw material, realize the stabilization of pp material, foaming window is effectively expanded, technique is easy to adjustment, cost is low, can prepare that cell diameter is even, abscess is fine and close, even aperture distribution, unicellular structure, density are 0.02 ~ 0.3g/cm
3polypropylene foaming beads, and n-hexane extract content is lower, can be widely used in the fields such as thermal-insulating food-drink tool, automotive upholstery, building template, camp appliances, finishing material interlayer, product damping packaging.
Description
Technical field
The present invention relates to field of polymer technology, say further, relate to a kind of propylene butene high melt strength, propylene expanded bead and preparation method thereof.
Background technology
Acrylic resin has good processibility, thermotolerance, reproducibility, environment friendly, the character that physical strength etc. are excellent, and therefore Application Areas constantly expands.Equally, acrylic resin microparticle is made to foam as expanded particle (EPP) by reactor impregnating fluid method, then in-molded polypropylene-based resin expanded particle formed body is carried out, the excellent properties of above-mentioned acrylic resin can be kept, in addition its light weight can also be given, resiliency, the characteristics such as thermal insulation, compared with polystyrene series resin expanded particle formed body, polypropylene foamed particles through molded and obtain Situation of Polypropylene Foaming body also there is chemical-resistant, high tenacity, the excellent properties such as high heat resistance and good compression resilience, therefore wrapping material are widely used in, material of construction or impact absorption material for use with vehicle etc.But, when polypropylene foamed particles is in-molded, in order to make expanded particle mutually molten glutinous, the water vapour heating with higher saturated vapor pressure must be used to make in mould, to have higher pressure; Therefore, must use the Special forming machine of high withstand voltage metal die and high punching press, this will cause energy cost to rise.If use the lower atactic copolymerized polypropene of fusing point effectively can lower the mold temperature of expanded particle as expanded particle raw material, thus reduce costs, reach the object of industrialized utilization.
Random copolymerization most widely used is at present the multipolymer of propylene with a small amount of ethene, effectively can improve polyacrylic toughness and reduce fusing point.But often ethylene content is too high for low molecular weight part in ethylene, propylene atactic copolymerized polypropene, thus add the content of the random thing of low molecule in product, cause the n-hexane extract of product higher all the time, limit its range of application, especially at food sanitation packaging field.1-butylene and propylene are all alhpa olefins, replace ethene and copolymerization of propylene, can reduce polyacrylic degree of crystallinity, the more important thing is the amount that effectively can reduce the random thing of low molecule in polymkeric substance, thus can avoid the problem that in product, n-hexane extract is too much with 1-butylene.The polypropylene foaming beads obtained like this, may be used for the production of foodstuff sanitation-stage lightweight goods.
Summary of the invention
For solving problems of the prior art, the invention provides a kind of propylene butene copolymerization high melt strength, propylene expanded bead and preparation method.Obtain meet environmental requirement degradable, uniform foam cell, rate of closed hole is high, physical heat resistance is high, density is controlled, production cost is low, meet food sanitation requires and be applicable to the polypropylene foaming beads of large-scale production.
In the present invention, described " high fondant-strength " refers to that polyacrylic melt strength is more than 0.8 newton, and its melt strength even can meet or exceed 2.2 newton.
The high melt strength, propylene used in the present invention not only molecular weight distribution is wider, and its maximum feature is that ultra high molecular weight fraction (molecular weight is greater than 5,000,000) content is higher, preferably the content of lower molecular weight fraction (molecular weight is less than 50,000) is also greater than a certain amount of simultaneously, make the melt strength of gained propene polymer have like this to improve significantly, but also ensure that the processing characteristics of polymkeric substance.
The invention provides a kind of polypropylene foaming beads, described expanded bead adopts high melt strength, propylene to be matrix resin, adopts foaming agent foam to obtain; Wherein, described high melt strength, propylene has following feature: its melting index MFR is 0.2 ~ 10g/10min, molecular weight distribution M
w/ M
nbe 6 ~ 20, the content that molecular weight is greater than 5,000,000 fractions is more than or equal to 0.8wt%, M
z+1/ M
nbe more than or equal to 70, and wherein butene content is 0.1 ~ 15wt%.
Described whipping agent can be a kind of organic pneumatogen or a kind of mineral-type pneumatogen.This organic physical blowing agents comprises aliphatic hydrocarbon such as propane, butane, pentane, hexane and heptane, alicyclic hydro carbons such as tetramethylene and hexanaphthene, and halogenated hydrocarbon such as chlorofluoromethane, trifluoromethane, 1,2-C2H4F2 C2H4F2,1,2,2,2-Tetrafluoroethane, methyl chloride, ethyl chloride and methylene dichloride.The example of inorganic pneumatogen comprises air, nitrogen, carbonic acid gas, oxygen G&W.Wherein, the water as whipping agent can be for making the water of this acrylic resin microparticulate in this dispersion medium.These organic and inorganic foaming agents can be used alone, also can two or more are used in combination.Due to the stability (homogeneity) of PP expanded bead apparent density, low cost and environmental friendliness problem, preferably carbon dioxide of the present invention and nitrogen are as whipping agent.
In the present invention, preferred described high melt strength, propylene has following feature: its melting index MFR is 1.6 ~ 6g/10min, molecular weight distribution M
w/ M
n=6 ~ 20, the content that molecular weight is greater than 5,000,000 fractions is more than or equal to 1.0wt%, M
z+1/ M
nbe more than or equal to 80, butene content is 0.5 ~ 10wt%, and the content that molecular weight is less than 50,000 fractions is 17.5 ~ 30wt%, and the dispersion index of polymkeric substance is 9.0 ~ 16.0.
The present invention also provides a kind of polypropylene foaming beads, and described expanded bead adopts high melt strength, propylene to be matrix resin, adopts foaming agent foam to obtain; Wherein, described high melt strength, propylene is adopted and is prepared with the following method: in the reactor of two or more serial operation, carry out the above propene/but-1-ene copolymerization of two benches, the wherein first stage: under the Ziegler-Natta catalyst comprising the first external electron donor component exists, under the polymerization temperature of 50 ~ 100 DEG C, carry out propene/but-1-ene copolymerization, the MFR of resulting polymers controls to be 0.01 ~ 0.3g/10min; Subordinate phase: on the basis of first stage resultant of reaction, hydrogen adds the second external electron donor component and butylene proceeds propene/but-1-ene copolymerization under existing; The MFR of final polymkeric substance controls to be 0.2 ~ 10g/10min; Wherein, described first external electron donor adjusts susceptibility low than the hydrogen of the second external electron donor.
In the present invention, preferably described Ziegler-Natta catalyst comprises following component, a kind of be main ingredient with magnesium, titanium, halogen and internal electron donor ingredient of solid catalyst A, a kind of organoaluminum B component and the first external electron donor component C, part by weight wherein between component A and B component counts 1:10 ~ 500 with titanium aluminum ratio, and the part by weight between B component and component C is 10 ~ 150:1; In subordinate phase, the part by weight between organoaluminum B component and the second external electron donor component of filling into is 1 ~ 50:1.Wherein, more preferably, in the first phase, adjust the consumption of the first external electron donor component C, the part by weight making itself and organoaluminum B component is 1:15 ~ 100; In subordinate phase, the amount of the organoaluminum B component added by the first stage is fixed and fills into the second external electron donor component, and the part by weight making itself and organoaluminum B component is 1:2 ~ 20.
In the present invention, preferably, in the first phase, hydrogen content is less than or equal to 300ppmV; In a specific embodiment, the added hydrogen of first stage and subordinate phase controls with the requirement of melting index MFR final at the end of two benches.In addition, preferably described first external electron donor be selected from dicyclopentyl dimethoxyl silane, diisopropyl dimethoxy silane, Dicyclohexyldimethoxysilane and second, isobutyl dimethoxy silane one or more, the second external electron donor be selected from tetramethoxy-silicane, tetraethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane and Cyclohexylmethyldimethoxysilane one or more.In the present invention, the polypropylene productive rate mass ratio of preferred first stage and subordinate phase is 30:70 ~ 70:30.In the present invention, preferably, described butylene adds in two stages, and first stage butylene add-on is that butylene adds 40 ~ 60% of total amount, and subordinate phase butylene add-on is that butylene adds 40 ~ 60% of total amount.
In the present invention, above-described high melt strength, propylene is applied for a patent on June 9th, 2011, and its number of patent application is 201110153451.5(High-melt-strength propylene/butene copolymer and preparation method thereof); At this, its full content is introduced as a application's part.
The present invention also provides a kind of preparation method of polypropylene foaming beads, comprises with above-mentioned high melt strength, propylene for matrix resin, obtains using carbonic acid gas or nitrogen as foaming agent foam.
In the preparation process in accordance with the present invention, preferred preparation process comprises: by after the micropartical that comprises matrix resin and Nucleating Agent and optional additive melt blending, granulation forms acrylic resin particulate, foaming in the presence of blowing agents after described acrylic resin particulate mix with auxiliary agent obtains described polypropylene foaming beads.
This Nucleating Agent can be a kind of inorganic powder as zinc borate, silicon-dioxide, talcum, calcium carbonate, borax or aluminium hydroxide, wherein preferred boric acid zinc or silicon-dioxide; When matrix resin high melt strength, propylene is 100 weight part, described Nucleating Agent is 0.001 ~ 1 weight part, is preferably 0.01 ~ 0.05 weight part.
In the present invention, described additive is one or more in oxidation inhibitor, uv-absorbing agent, antistatic agent, fire retardant, metal inactivator, pigment, nucleating agent, Foam Control, filler, stablizer, toughener and lubricant; Described auxiliary agent comprises dispersion medium, tensio-active agent, dispersion agent and dispersion intensifier.
Any acrylic resin microparticulate that makes can be used as dispersion medium in the component of wherein and not dissolving this particulate.This dispersion medium can be water, ethylene glycol, glycerine, methyl alcohol, ethanol or its mixture.Preferred a kind of aqueous dispersion medium, more preferably water, most preferably deionized water.Relative to the reactor of 5L volume, dispersion medium usage quantity is 1 ~ 4L, preferably 2.5 ~ 3.5L.
In order to promote the dispersion of particulate in dispersion medium, a kind of tensio-active agent of preferred use, it can be stearic acid, Sodium dodecylbenzene sulfonate, quaternary ammonium compound, Yelkin TTS, amino acid, trimethyl-glycine, glycerin fatty acid ester, lipid acid sorb is smooth, polysorbate, preferred anionic type surfactant sodium dodecyl base benzene sulfonic acid sodium salt, for this acrylic resin particulate of every 100 weight parts, the usage quantity of this tensio-active agent is generally 0.001 ~ 1 weight part, is better 0.01 ~ 0.5 weight part, preferably 0.1 ~ 0.3 weight part.
In order to each other melt bonded of polypropylene microparticle during preventing foaming step, it is desirable in this dispersion medium, add a kind of dispersion agent belonging to fine organic or inorganic solid.For the ease of operation, be preferably and use a kind of inorganic powder.This dispersion agent can be clay mineral (such as kaolin, mica, vogesite and clay) that is natural or that synthesize, alumina, titanium dioxide, magnesium basic carbonate, zinc subcarbonate, calcium carbonate, silicon-dioxide, zinc borate and ferric oxide, wherein preferred kaolin.For this acrylic resin particulate of every 100 weight parts, the usage quantity of this dispersion agent is generally 0.01 ~ 5 weight part, is better 0.1 ~ 3 weight part, preferably 0.5 ~ 2 weight part.
In order to improve the dispersion efficiency of this dispersion agent, namely while this dispersion agent quantity of minimizing, retaining its function preventing particulate melt bonded, a kind of dispersion intensifier can be added in this dispersion medium.This dispersion intensifier is that one can provide divalence or trivalent anion or cationic mineral compound.The example of this dispersion intensifier comprises magnesium nitride, magnesium nitrate, magnesium sulfate, aluminium nitride, aluminum nitrate, Tai-Ace S 150, iron(ic) chloride, ferric sulfate and iron nitrate, wherein preferably sulfuric acid aluminium.The use of this dispersion intensifier is conducive to obtaining the PP expanded bead that apparent density is 50g/L or less.For this acrylic resin particulate of every 100 weight parts, the usage quantity of this dispersion intensifier is generally 0.0001 ~ 1 weight part, preferably 0.01 ~ 0.1 weight part.
In the present invention, the consumption of whipping agent can be determined according to the apparent density of the kind of whipping agent, blowing temperature and the PP expanded bead that will produce.Such as, when with nitrogen as whipping agent and when using water as dispersion medium, the pressure (gauge pressure) in pressure during foam device pressure release in this encloses container, this encloses container internal upper part space is within the scope of 1 ~ 12MPa; If use carbonic acid gas as whipping agent, then gauge is at 1 ~ 7MPa.In general, the pressure in this encloses container internal upper part space increases with the apparent density reduction of the PP expanded bead that will obtain ideally.
As the present invention adopt carbonic acid gas or nitrogen as whipping agent time, compared with organic whipping agent, there is environmental friendliness, safety etc. advantage.
In the present invention, particularly, granulation is and the material after blended is extruded into wire rod and cuts.In the granulation underwater step forming acrylic resin particulate, the one or more extrusion via twin screw or single screw extruder become wire rod and cut, and obtain acrylic resin particulate.This process is passed through matrix resin and Nucleating Agent, add after the additives such as optional antistatic agent and oxidation inhibitor utilize homogenizer blended, extruded by twin screw extruder, import 75 DEG C or following, better 70 DEG C or following, in the water of better 55 ~ 65 DEG C, carry out micropartical cutting, make the length/diameter of every ratio be 0.5 ~ 2.0, better 0.8 ~ 1.3, better 0.9 ~ 1.1, and weight in average is 0.1 ~ 20mg, better 0.2 ~ 10mg, better 1 ~ 3mg.This weight in average is 200 mean values selecting arbitrarily particulate.
And in the step of the obtained described high melt strength, propylene expanded bead of foaming, be specially: first, in autoclave, the auxiliary agents such as described acrylic resin particulate and dispersion medium, tensio-active agent, dispersion agent, dispersion intensifier are mixed disposable adding.Then, use inertia whipping agent (nitrogen or carbonic acid gas) to be discharged by residual air in reactor, remove in reactor and cover tightly kettle cover after air; Be fed into by inertia whipping agent in this autoclave, preliminary adjustment pressure is until it is stablized; Be stirred in the dispersion in this autoclave subsequently, stirring velocity is 50 ~ 150rpm, preferably 90 ~ 110rpm; Be heated lower than expansion temperature 0.1 ~ 5 DEG C with constant-speed heating, preferably low 0.5 ~ 1 DEG C.3rd step, adjustment still internal pressure reaches the required pressure of foaming, and this pressure is 1 ~ 10MPa, preferably 3 ~ 5MPa; With the average heating rate of 0.1 DEG C/min, temperature is elevated to blowing temperature, blowing temperature is lower than particulate melt temperature 0.1 ~ 5 DEG C, preferably low 0.5 ~ 1 DEG C; Under blowing temperature and pressure condition, Keep agitation 0.1 ~ 2 hour, preferably 0.25 ~ 0.5 hour.Finally, the discharge port of this autoclave is opened, make the material in reactor be excreted in holding tank, obtain polypropylene foaming beads; While carrying out discharging, feed inertia foaming agent gas, make before all particles foams completely and enters holding tank, the pressure in this autoclave remains near blow(ing) pressure.
The present invention with the high melt strength, propylene of wide molecular weight distribution for raw material, realize the stabilization of pp material, foaming window is effectively expanded, technique is easy to adjustment, cost is low, can prepare that cell diameter is even, abscess is fine and close, even aperture distribution, unicellular structure, density are 0.02 ~ 0.3g/cm
3polypropylene foaming beads, and n-hexane extract content is lower, can be widely used in the fields such as thermal-insulating food-drink tool, automotive upholstery, building template, camp appliances, finishing material interlayer, product damping packaging; And the expanded polypropylene beads of manufacture of the present invention is non-crosslinking structure, can recycles according to general polypropylene modified material, not cause secondary pollution, meet the requirement of recycling economy.
Embodiment
The following example further describes the present invention, but should illustrate, the present invention is in no way limited to these embodiments.
Underwater pellet cutting system: LabLine 100, German BKG company;
Melt drawn test machine: Rheotens
tM97, German Goettfert company;
Density tester: CPA225D, density annex YDK01, German Satorius company.Testing method: the density annex using Satorius balance, utilizes drainage to obtain the density of polypropylene matrix resin and polypropylene foaming beads.Expansion ratio formula b=ρ 1/ ρ 2 of the polypropylene foaming beads obtained calculates, and wherein, b is expansion ratio, and ρ 1 is the density of polypropylene matrix resin, and ρ 2 is the density of polypropylene foaming beads; Density in the present invention all refers to the apparent density of material;
Opening and closing porosity tester: ULTRAFOAM 1200e, Quantachrome instrument company of the U.S..
The preparation of matrix resin HMSPP301
Polyreaction is carried out on a set of polypropylene pilot plant.Its major equipment comprises prepolymerization reactor, first ring pipe reactor and the second annular-pipe reactor.
Prepolymerization: Primary Catalysts (the solid catalyst active ingredient of titaniferous) adopts the method that in Chinese patent CN93102795, embodiment 1 describes to obtain, and its Ti content is 2.4wt%, Mg content is 18.0wt%, and n-butyl phthalate content is 13wt%.Primary Catalysts, promotor (triethyl aluminum), the first external electron donor (dicyclopentyl dimethoxyl silane, DCPMS) through 10 DEG C, after 20min pre-contact, add prepolymerization reactor continuously and carry out pre-polymerization reactor, prepolymerization is carried out under propylene liquid-phase bulk environment, temperature is 15 DEG C, the residence time is about 4min, and under this condition, the pre-polymerization multiple of catalyzer is about 120 ~ 150 times.The triethyl aluminum flow entering prepolymerization reactor is 6.33g/hr, and bicyclopentyl dimethoxy silane flow is 0.33g/hr, and Primary Catalysts flow is about 0.5g/hr.
The copolymerization of propene/but-1-ene: pre-polymerization rear catalyst enters in the annular-pipe reactor of two series connection, and complete the copolymerization of propene/but-1-ene in annular-pipe reactor, wherein the butylene add-on of the first endless tube is 5mol%, and the butylene add-on of the second endless tube is 4mol%.Two loop po lymerisation temperature of reaction are 70 DEG C, and reaction pressure is 4.0MPa.The processing condition of gate ring pipe reactor, make the productivity ratio of first, second endless tube for about 45:55.Not hydrogenation in the charging of first ring pipe reactor, the density of hydrogen < 10ppmV that on-line chromatograph detects, adds a certain amount of hydrogen in the second annular-pipe reactor charging, and the density of hydrogen that on-line chromatograph detects is 4500ppmV.
Because these catalyst components directly enter first ring pipe reactor after prepolymerization, first ring pipe reactor no longer includes other charging any except propylene, butylene, therefore, triethyl aluminum in first ring pipe reactor/dicyclopentyl dimethoxyl silane ratio (Al/Si-I) ratio be in catalyst prepolymer is 19.0(weight ratio).In the second annular-pipe reactor, add the tetraethoxysilane (TEOS) into 0.67g/hr, therefore, in the second annular-pipe reactor, triethyl aluminum/tetraethoxysilane ratio (Al/Si-II) is 9.4(weight ratio).Concrete technology condition is in table 1.Go out after propylene and butylene through flash separation from the second endless tube polymkeric substance out, then remove the activity of catalyst in reactor through wet nitrogen, polymkeric substance, through heat drying, obtains polymer powders.
Is added IRGAFOS 168 additive of 0.1wt%, IRGANOX 1010 additive of 0.2wt% and the calcium stearate of 0.05wt% in the powder that polymerization is obtained, use twin screw extruder granulation.Gained pellet is carried out performance test by existing relevant ASTM standard.
The preparation of matrix resin HMSPP302
With the preparation of matrix resin HMSPP301, just the butylene add-on of first ring pipe reactor is become 25mol%, the butylene add-on of the second annular-pipe reactor is adjusted to 20mol%; And the second annular-pipe reactor density of hydrogen is adjusted to 8500ppmV.
Table 2 ~ 4 list analytical results and its physicals of two kinds of matrix resin HMSPP301 and HMSPP302; The partial parameters contrast of common atactic propene butene polypropylene SP179 is also listed in table 2 ~ 4.
Table 1
Table 2
Table 3
Table 4
Embodiment 1 ~ 30
The high melt strength, propylene of 100 weight parts, Nucleating Agent (silicon-dioxide or zinc borate) and additive are put into after homogenizer high speed mixes 30 seconds, add LabLine100 micropartical preparation system, moment of torsion controls about 65%, rotating speed 300rpm, underwater cutpellet obtains acrylic resin particulate.Wherein, additive comprises the antioxidant 1010 (BASF AG) of 0.2 weight part and the irgasfos 168 (BASF AG) of 0.1 weight part; The consumption of Nucleating Agent is in table 5.
Wherein, the polypropylene kind that embodiment 1 ~ 15 uses is HMSPP301, and the polypropylene kind that embodiment 16 ~ 30 uses is HMSPP302; The Nucleating Agent that embodiment 1 ~ 4,9 ~ 12,16 ~ 19 and 24 ~ 27 uses is silicon-dioxide, and the Nucleating Agent that embodiment 5 ~ 8,13 ~ 15,20 ~ 23 and 28 ~ 30 uses is zinc borate.
Use deionized water for dispersion medium in concrete foaming process, be tensio-active agent with Sodium dodecylbenzene sulfonate, take kaolin as dispersion agent and be dispersion intensifier with Tai-Ace S 150; Corresponding to the polypropylene of 100 weight parts, the weight fraction of several auxiliary agent is in table 5.In addition, CO is used
2or nitrogen is inertia whipping agent, specifically in table 5.Gained expanded particle density adopts GB/T1033.1-2008 to measure, concrete data sheet 5.
Comparative example 1 ~ 10
The propylene butene impact copolymer polypropylene SP179 adopting Qilu Petrochemical branch office of SINOPEC to produce replaces HMSPP301 or HMSPP302 in embodiment to test.
Table 5
Can be found by table 4 ~ 5, fusing point and the blowing temperature of HMSPP301 and HMSPP302 are starkly lower than SP179, thus reduce production energy consumption; In addition, the normal hexane extraction rate of HMSPP301 and HMSPP302 meets GB 9693-1988, food packaging acrylic resin hygienic standard, and this bead may be used for the production of food grade tr and medical facilities lightweight plastics.The expanded bead of embodiment 1 ~ 30 gained is carried out to the test of opening and closing porosity, find that rate of closed hole all reaches 100%.In addition, the propylene butene high melt strength, propylene of HMSPP301 and HMSPP302 two trades mark, as matrix resin, utilizes autoclave pickling process, all can obtain abscess dense uniform, ganoid expanded bead; Can obtain density by adjustment blow(ing) pressure and temperature is 0.02 ~ 0.3g/cm
3expanded bead, carbonic acid gas or nitrogen all can reach good foaming effect as whipping agent.Can be found out by comparative example 1 ~ 10, compare high melt strength, propylene HMSPP301 and HMSPP302, the density that propylene butene impact copolymer polypropylene SP179 obtains goods is comparatively large, and abscess is uneven, surface of beads unfairness, the melt strength mainly due to SP179 is lower caused.
Claims (11)
1. a polypropylene foaming beads, is characterized in that, described expanded bead adopts high melt strength, propylene to be matrix resin, adopts foaming agent foam to obtain; Wherein, described high melt strength, propylene has following feature: its melting index MFR is 0.2 ~ 10g/10min, molecular weight distribution M
w/ M
nbe 6 ~ 20, the content that molecular weight is greater than 5,000,000 fractions is more than or equal to 0.8wt%, M
z+1/ M
nbe more than or equal to 70, and wherein butene content is 0.1 ~ 15wt%.
2. polypropylene foaming beads according to claim 1, is characterized in that, described high melt strength, propylene has following feature: its melting index MFR is 1.6 ~ 6g/10min, molecular weight distribution M
w/ M
n=6 ~ 20, the content that molecular weight is greater than 5,000,000 fractions is more than or equal to 1.0wt%, M
z+1/ M
nbe more than or equal to 80, butene content is 0.5 ~ 10wt%, and the content that molecular weight is less than 50,000 fractions is 17.5 ~ 30wt%, and the dispersion index of polymkeric substance is 9.0 ~ 16.0.
3. a polypropylene foaming beads, is characterized in that, described expanded bead adopts high melt strength, propylene to be matrix resin, adopts foaming agent foam to obtain; Wherein, described high melt strength, propylene is adopted and is prepared with the following method: in the reactor of two or more serial operation, carry out the above propene/but-1-ene copolymerization of two benches, the wherein first stage: under the Ziegler-Natta catalyst comprising the first external electron donor component exists, under the polymerization temperature of 50 ~ 100 DEG C, carry out propene/but-1-ene copolymerization, the MFR of resulting polymers controls to be 0.01 ~ 0.3g/10min; Subordinate phase: on the basis of first stage resultant of reaction, hydrogen adds the second external electron donor component and butylene proceeds propene/but-1-ene copolymerization under existing; The MFR of final polymkeric substance controls to be 0.2 ~ 10g/10min; Wherein, described first external electron donor adjusts susceptibility low than the hydrogen of the second external electron donor.
4. polypropylene foaming beads according to claim 3, it is characterized in that, described Ziegler-Natta catalyst comprises following component, a kind of be main ingredient with magnesium, titanium, halogen and internal electron donor ingredient of solid catalyst A, a kind of organoaluminum B component and the first external electron donor component C, part by weight wherein between component A and B component counts 1:10 ~ 500 with titanium aluminum ratio, and the part by weight between B component and component C is 10 ~ 150:1; In subordinate phase, the part by weight between organoaluminum B component and the second external electron donor component of filling into is 1 ~ 50:1.
5. polypropylene foaming beads according to claim 4, is characterized in that, in the first phase, adjusts the consumption of the first external electron donor component C, and the part by weight making itself and organoaluminum B component is 1:15 ~ 100; In subordinate phase, the amount of the organoaluminum B component added by the first stage is fixed and fills into the second external electron donor component, and the part by weight making itself and organoaluminum B component is 1:2 ~ 20.
6. polypropylene foaming beads according to claim 3, it is characterized in that, described first external electron donor be selected from dicyclopentyl dimethoxyl silane, diisopropyl dimethoxy silane, Dicyclohexyldimethoxysilane and second, isobutyl dimethoxy silane one or more, the second external electron donor be selected from tetramethoxy-silicane, tetraethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane and Cyclohexylmethyldimethoxysilane one or more.
7. according to the polypropylene foaming beads in claim 3 ~ 6 described in any one, it is characterized in that, described butylene adds in two stages, and first stage butylene add-on is that butylene adds 40 ~ 60% of total amount, and subordinate phase butylene add-on is that butylene adds 40 ~ 60% of total amount.
8. a preparation method for polypropylene foaming beads, comprises with the high melt strength, propylene in claim 1 ~ 7 described in any one for matrix resin, obtains using carbonic acid gas or nitrogen as foaming agent foam.
9. method according to claim 8, it is characterized in that, preparation process comprises: by after the micropartical that comprises matrix resin and Nucleating Agent and optional additive melt blending, granulation forms acrylic resin particulate, foaming in the presence of blowing agents after described acrylic resin particulate mix with auxiliary agent obtains described polypropylene foaming beads.
10. method according to claim 9, is characterized in that, described Nucleating Agent be selected from zinc borate, silicon-dioxide, talcum, calcium carbonate, borax and aluminium hydroxide one or more; Described auxiliary agent comprises dispersion medium, tensio-active agent, dispersion agent and dispersion intensifier; When matrix resin is 100 weight part, described Nucleating Agent is 0.001 ~ 1 weight part, and described tensio-active agent is 0.001 ~ 1 weight part, and described dispersion agent is 0.01 ~ 5 weight part, and described dispersion intensifier is 0.0001 ~ 1 weight part.
11. methods according to claim 10, it is characterized in that, when matrix resin is 100 weight part, described Nucleating Agent is 0.01 ~ 0.05 weight part, described tensio-active agent is 0.1 ~ 0.3 weight part, described dispersion agent is 0.5 ~ 2 weight part, and described dispersion intensifier is 0.01 ~ 0.1 weight part.
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| CN110105677A (en) * | 2019-05-27 | 2019-08-09 | 苏州市炽光新材料有限公司 | PP foam material and preparation method thereof based on recycled plastic |
| CN110183713B (en) * | 2019-06-25 | 2022-06-10 | 中国科学院青岛生物能源与过程研究所 | Preparation method of polybutylene expanded beads (EPB) |
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| CN101274968A (en) * | 2007-03-28 | 2008-10-01 | 中国石油化工股份有限公司 | Composite catalytic for producing polyethylene having wide molecular weight distribution |
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| US8101685B2 (en) * | 2008-12-15 | 2012-01-24 | Exxonmobil Chemical Patents Inc. | Thermoplastic elastomer polyolefin in-reactor blends and molded articles therefrom |
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| CN101724110A (en) * | 2002-10-15 | 2010-06-09 | 埃克森美孚化学专利公司 | Multiple catalyst system for olefin polymerization and polymers produced therefrom |
| CN101104716A (en) * | 2006-07-13 | 2008-01-16 | 中国石油化工股份有限公司 | Expandable polypropylene beading, preparation method thereof, and its foaming beading and foaming molding products |
| CN101274968A (en) * | 2007-03-28 | 2008-10-01 | 中国石油化工股份有限公司 | Composite catalytic for producing polyethylene having wide molecular weight distribution |
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