CN103665567A - Propylene-butylene copolymer foamed bead and preparation method thereof - Google Patents

Propylene-butylene copolymer foamed bead and preparation method thereof Download PDF

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CN103665567A
CN103665567A CN201210324294.4A CN201210324294A CN103665567A CN 103665567 A CN103665567 A CN 103665567A CN 201210324294 A CN201210324294 A CN 201210324294A CN 103665567 A CN103665567 A CN 103665567A
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polypropylene
electron donor
propylene
weight
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CN103665567B (en
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郭鹏
吕明福
张师军
宋文波
刘有鹏
邹浩
邵静波
李�杰
高达利
权慧
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/06—CO2, N2 or noble gases
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • 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 polypropylene foamed bead. The foamed bead is prepared by foaming a base resin high-melt-strength polypropylene with a foaming agent, wherein the high-melt-strength polypropylene has the following characteristics: the melt index MFR is 0.2-10 g/10 minutes, the molecular weight distribution Mw/Mn is 6-20, the content of substances with the molecular weight of greater than 5 million is greater than or equal to 0.8 wt%, the M[z+1]/Mn is greater than or equal to 70, and the butylene content is 0.1-15 wt%. The high-melt-strength polypropylene with wide molecular weight distribution is utilized as the raw material to implement stabilization of the polypropylene raw material, so that the foaming window is effectively enlarged, the technique is easy to adjust, and the cost is low; the method can be used for preparing the polypropylene foamed bead with the density of 0.02-0.3 g/cm<3>, which has the advantages of uniform pore diameter, compact pores, uniform pore size distribution, closed cell structure and lower content of n-hexane extract; and the polypropylene foamed bead can be widely used in the fields of thermal insulation tableware, automobile interior ornaments, architectural moldboards, camping supplies, decorating material interlayers, product damping packages and the like.

Description

Co-polymer foamed bead of propylene butene and preparation method thereof
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, so Application Areas constantly expands.Equally, by reactor, flooding gas method makes the foaming of acrylic resin microparticle for expanded particle (EPP), then carry out the in-molded polypropylene-based resin expanded particle formed body forming, the excellent properties that can keep above-mentioned acrylic resin, in addition can also give its light weight, resiliency, the characteristics such as thermal insulation, compare with polystyrene series resin expanded particle formed body, polypropylene foamed particles also has chemical-resistant through Situation of Polypropylene Foaming body molded and that obtain, high tenacity, high heat resistance and the good excellent properties such as compression resilience, therefore be widely used in wrapping material, 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, must to use the water vapour with higher saturated vapor pressure to heat to make, in mould, there is higher pressure; Therefore, essential high withstand voltage metal die and the Special forming machine of high punching press of using, this will cause energy cost to rise.If use the lower atactic copolymerized polypropene of fusing point can effectively lower the mold temperature of expanded particle as expanded particle raw material, thereby reduce costs, reach the object of industrialized utilization.
Most widely used random copolymerization is at present the multipolymer of the same a small amount of ethene of propylene, can effectively improve polyacrylic toughness and reduce fusing point.But in ethylene, propylene atactic copolymerized polypropene, often ethylene content is too high for low molecular weight part, thereby increased the content of the random thing of low molecule in product, cause the n-hexane extract of product higher all the time, limited its range of application, especially at food sanitation packaging field.1-butylene and propylene are all alhpa olefins, with 1-butylene, replace ethene and copolymerization of propylene, can reduce polyacrylic degree of crystallinity, the more important thing is the amount that can effectively reduce the random thing of low molecule in polymkeric substance, thereby can avoid the too much problem of n-hexane extract in product.The polypropylene foaming beads obtaining like this, can be 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.The degradable, the abscess that have obtained meeting environmental requirement are even, rate of closed hole is high, physics thermotolerance is high, density is controlled, production cost is low, meet the polypropylene foaming beads that food sanitation required and be applicable to 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 using 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 like this melt strength of gained propene polymer have raising significantly, but also guaranteed the processing characteristics of polymkeric substance.
The invention provides a kind of polypropylene foaming beads, it is matrix resin that described expanded bead adopts high melt strength, propylene, adopts whipping agent foaming to make; 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 pneumatogen comprises aliphatic hydrocarbon for example propane, butane, pentane, hexane and heptane, alicyclic hydro carbons is tetramethylene and hexanaphthene for example, and halogenated hydrocarbon for example 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 this acrylic resin microparticulate in the water of this dispersion medium.These organic and inorganic foaming agents can be used separately, also can two or more mix and use.Due to stability (homogeneity), low cost and the environmental friendliness problem of PP expanded bead apparent density, 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 it is matrix resin that described expanded bead adopts high melt strength, propylene, adopts whipping agent foaming to make; Wherein, described high melt strength, propylene is adopted with the following method and is prepared: in the reactor of more than two serial operation, carry out two above propene/but-1-ene copolymerizations of stage, first stage wherein: under the Ziegler-Natta catalyst that comprises the first external electron donor component exists, under the polymerization temperature of 50 ~ 100 ℃, carry out propene/but-1-ene copolymerization, it is 0.01 ~ 0.3g/10min that the MFR of resulting polymers controls; Subordinate phase: on the basis of first stage resultant of reaction, hydrogen adds the second external electron donor component and butylene to proceed propene/but-1-ene copolymerization under existing; It is 0.2 ~ 10g/10min that the MFR of final polymkeric substance controls; Wherein, described the 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 ofly take ingredient of solid catalyst A, a kind of organoaluminum B component and the first external electron donor component C that magnesium, titanium, halogen and internal electron donor be main ingredient, wherein the part by weight between component A and B component is counted 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 stage, adjust the consumption of the first external electron donor component C, making the part by weight of itself and organoaluminum B component is 1:15 ~ 100; In subordinate phase, the amount of the organoaluminum B component adding by the first stage is fixed and fills into the second external electron donor component, and making the part by weight of itself and organoaluminum B component is 1:2 ~ 20.
In the present invention, preferably, in the first stage, hydrogen content is less than or equal to 300ppmV; In embodiment, when the hydrogen add-on of first stage and subordinate phase finished with two stages, the requirement of final melting index MFR is controlled.In addition, preferably described the first external electron donor is to be selected from one or more in dicyclopentyl dimethoxyl silane, diisopropyl dimethoxy silane, Dicyclohexyldimethoxysilane and second, isobutyl dimethoxy silane, and the second external electron donor is to be selected from one or more in tetramethoxy-silicane, tetraethoxysilane, trimethylammonium methoxy silane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane and Cyclohexylmethyldimethoxysilane.In the present invention, preferably the polypropylene productive rate mass ratio of first stage and subordinate phase is 30:70 ~ 70:30.In the present invention, preferably, described butylene adds in two stages, first stage butylene add-on be butylene add total amount 40 ~ 60%, subordinate phase butylene add-on be butylene add total amount 40 ~ 60%.
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 fondant-strength propene/but-1-ene copolymer and preparation method thereof); At this, its full content is introduced as to the application's a part.
The present invention also provides a kind of preparation method of polypropylene foaming beads, comprises and take above-mentioned high melt strength, propylene as matrix resin, usings carbonic acid gas or nitrogen to make as whipping agent foaming.
In preparation method of the present invention, preferably preparation process comprises: by comprising after the micropartical and optional additive melt blending of matrix resin and Nucleating Agent, granulation forms acrylic resin particulate, after described acrylic resin particulate mixes with auxiliary agent whipping agent existence issue brewed must 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, be 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, deionized water most preferably.With respect 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, preferably use a kind of tensio-active agent, 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 tensio-active agent Sodium dodecylbenzene sulfonate, 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 prevent each other melt bonded of polypropylene microparticle during foaming step, it is desirable to add a kind of dispersion agent that belongs to fine organic or inorganic solid in this dispersion medium.For the ease of operation, be preferably and use a kind of inorganic powder.This dispersion agent can be natural or synthetic clay mineral (for example kaolin, mica, vogesite and clay), 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, when reducing this dispersion agent quantity, retain the function that it prevents that particulate is melt bonded, can in this dispersion medium, add a kind of dispersion intensifier.This dispersion intensifier is a kind ofly can provide divalence or trivalent negatively charged ion 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 obtain apparent density for 50g/L or less PP expanded bead.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.For example, when with nitrogen as whipping agent and water during 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, gauge pressure scope 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.
While adopting carbonic acid gas or nitrogen as whipping agent as the present invention, compare with organic whipping agent, there is environmental friendliness, the advantages such as safety.
In the present invention, particularly, granulation is the material after blend is extruded into wire rod cutting.In forming the granulation underwater step of acrylic resin particulate, via one or more die heads of twin screw or single screw extruder, be extruded into wire rod cutting, obtain acrylic resin particulate.This process is passed through matrix resin and Nucleating Agent, adding the additives such as optional antistatic agent and oxidation inhibitor utilizes after homogenizer blend, by twin screw extruder, extrude, import 75 ℃ or following, better 70 ℃ or following, carry out micropartical cutting in the water of better 55 ~ 65 ℃, the length/diameter ratio that makes every is 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 of selecting arbitrarily particulate.
And make in the step of described high melt strength, propylene expanded bead in foaming, be specially: first, in autoclave, described acrylic resin particulate is mixed with auxiliary agents such as dispersion medium, tensio-active agent, dispersion agent, dispersion intensifiers disposable adding.Then, use inertia whipping agent (nitrogen or carbonic acid gas) that residual air in reactor is discharged, remove in reactor and cover tightly kettle cover after air; Inertia whipping agent is fed in this autoclave, tentatively adjusts pressure until it is stable; Be stirred in subsequently the dispersion in this autoclave, stirring velocity is 50 ~ 150rpm, preferably 90 ~ 110rpm; With constant-speed heating, be heated lower 0.1 ~ 5 ℃ than expansion temperature, preferably low 0.5 ~ 1 ℃.The 3rd step, adjusts still internal pressure and reaches the required pressure of foaming, and this pressure is 1 ~ 10MPa, preferably 3 ~ 5MPa; Average rate of heating with 0.1 ℃/min is elevated to blowing temperature by temperature, and blowing temperature is lower 0.1 ~ 5 ℃ than particulate melt temperature, preferably low 0.5 ~ 1 ℃; Under blowing temperature and pressure condition, continue to stir 0.1 ~ 2 hour preferably 0.25 ~ 0.5 hour.Finally, the discharge port of this autoclave is opened, the material in reactor is excreted in holding tank, obtain polypropylene foaming beads; When carrying out discharging, feed inertia foaming agent gas, make foam completely and enter before holding tank at all particles, the pressure in this autoclave remains near blow(ing) pressure.
It is raw material that the high melt strength, propylene of wide molecular weight distribution is take in the present invention, realize the stabilization of pp material, the window that makes to foam effectively expands, technique is easy to adjust, cost is low, can prepare that cell diameter is even, abscess is fine and close, even aperture distribution, unicellular structure, density be 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 packing; And the expanded polypropylene bead of manufacture of the present invention is non-crosslinked structure, can recycle according to general polypropylene modified material, do 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 embodiment.
Underwater pellet cutting system: LabLine 100, German BKG company;
Melt stretching testing machine: Rheotens tM97, German Goettfert company;
Density tester: CPA225D, density annex YDK01, German Satorius company.Testing method: use the density annex of Satorius balance, utilize drainage to obtain the density of polypropylene matrix resin and polypropylene foaming beads.The expansion ratio of the polypropylene foaming beads obtaining calculates with formula b=ρ 1/ ρ 2, and wherein, b is expansion ratio, and ρ 1 is the density of polypropylene matrix resin, the density that ρ 2 is polypropylene foaming beads; Density in the present invention all refers to the apparent density of material;
Open and close porosity tester: ULTRAFOAM 1200e, U.S. Quantachrome instrument company.
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%, and 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) after the pre-contact of 10 ℃, 20min, add continuously prepolymerization reactor to carry out pre-polymerization reactor, prepolymerization is carried out under propylene liquid phase bulk environment, temperature is 15 ℃, the residence time is about 4min, and under this condition, the pre-polymerization multiple of catalyzer is approximately 120 ~ 150 times.The triethyl aluminum flow that enters prepolymerization reactor is 6.33g/hr, and two cyclopentyl dimethoxy silane flows are 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, completes the copolymerization of propene/but-1-ene in annular-pipe reactor, wherein the butylene add-on of the first endless tube is 5mol%, the butylene add-on of the second endless tube is 4mol%.Two endless tube polymeric reaction temperatures are 70 ℃, and reaction pressure is 4.0MPa.The processing condition of gate ring pipe reactor, the productivity ratio that makes first, second endless tube is about 45:55.In the charging of first ring pipe reactor, do not add hydrogen, 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 any other charging except propylene, butylene, therefore the ratio that, in first ring pipe reactor, triethyl aluminum/dicyclopentyl dimethoxyl silane is in catalyst prepolymer than (Al/Si-I) 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 is 9.4(weight ratio than (Al/Si-II)).Concrete technology condition is in Table 1.From the second endless tube polymkeric substance out, after flash separation goes out propylene and butylene, then through wet nitrogen, remove the activity of catalyst in reactor, polymkeric substance, through heat drying, obtains polymer powders.
In the powder that polymerization is obtained, add IRGAFOS 168 additives of 0.1wt%, IRGANOX 1010 additives of 0.2wt% and the calcium stearate of 0.05wt%, use twin screw extruder granulation.Gained pellet is carried out to 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 to 25mol%, the butylene add-on of the second annular-pipe reactor is adjusted into 20mol%; And the second annular-pipe reactor density of hydrogen is adjusted into 8500ppmV.
Analytical results and its physicals of two kinds of matrix resin HMSPP301 and HMSPP302 listed in table 2 ~ 4; The partial parameters contrast of common atactic propene butylene Co-polypropylene SP179 is also listed in table 2 ~ 4.
Table 1
Table 2
Figure BDA00002099042100062
Table 3
Figure BDA00002099042100063
Table 4
Figure BDA00002099042100064
Embodiment 1 ~ 30
The high melt strength, propylene of 100 weight parts, Nucleating Agent (silicon-dioxide or zinc borate) and additive are put into homogenizer high speed to be mixed after 30 seconds, add LabLine100 micropartical preparation system, moment of torsion is controlled at 65% left and right, 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 is used is HMSPP301, and the polypropylene kind that embodiment 16 ~ 30 is used is HMSPP302; Embodiment 1 ~ 4,9 ~ 12,16 ~ 19 and 24 ~ 27 Nucleating Agents that use are silicon-dioxide, and embodiment 5 ~ 8,13 ~ 15,20 ~ 23 and 28 ~ 30 Nucleating Agents that use are zinc borate.
In concrete foaming process, use deionized water for dispersion medium, take Sodium dodecylbenzene sulfonate as tensio-active agent, take kaolin as dispersion agent and take Tai-Ace S 150 as dispersion intensifier; Corresponding to the polypropylene of 100 weight parts, the weight fraction of several auxiliary agents is in Table 5.In addition, use CO 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
Adopt the propylene butene crushing-resistant copolymerization polypropylene SP179 that Qilu Petrochemical branch office of SINOPEC produces to replace HMSPP301 or HMSPP302 in embodiment to test.
Table 5
Figure BDA00002099042100071
Figure BDA00002099042100081
By table 4 ~ 5, can find, fusing point and the blowing temperature of HMSPP301 and HMSPP302 are starkly lower than SP179, thereby have reduced production energy consumption; In addition, the normal hexane extraction rate of HMSPP301 and HMSPP302 meets GB 9693-1988, used for packing foods acrylic resin hygienic standard, and this bead can be for the production of food grade tr and medical facilities use lightweight plastics.The expanded bead of embodiment 1 ~ 30 gained is opened and closed to the test of porosity, find that rate of closed hole all reaches 100%.In addition, the propylene butene high melt strength, propylene of HMSPP301 and two trades mark of HMSPP302, as matrix resin, utilizes autoclave pickling process, all can obtain abscess evenly fine and close, ganoid expanded bead; By adjustment blow(ing) pressure and temperature, can obtain density is 0.02 ~ 0.3g/cm 3expanded bead, carbonic acid gas or nitrogen all can reach good foaming effect as whipping agent.By comparative example 1 ~ 10, can find out, compare high melt strength, propylene HMSPP301 and HMSPP302, the density that propylene butene crushing-resistant copolymerization polypropylene SP179 obtains goods is larger, and abscess is inhomogeneous, surface of beads unfairness is mainly because the melt strength of SP179 is lower caused.

Claims (10)

1. a polypropylene foaming beads, is characterized in that, it is matrix resin that described expanded bead adopts high melt strength, propylene, adopts whipping agent foaming to make; 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, it is matrix resin that described expanded bead adopts high melt strength, propylene, adopts whipping agent foaming to make; Wherein, described high melt strength, propylene is adopted with the following method and is prepared: in the reactor of more than two serial operation, carry out two above propene/but-1-ene copolymerizations of stage, first stage wherein: under the Ziegler-Natta catalyst that comprises the first external electron donor component exists, under the polymerization temperature of 50 ~ 100 ℃, carry out propene/but-1-ene copolymerization, it is 0.01 ~ 0.3g/10min that the MFR of resulting polymers controls; Subordinate phase: on the basis of first stage resultant of reaction, hydrogen adds the second external electron donor component and butylene to proceed propene/but-1-ene copolymerization under existing; It is 0.2～10g/10min that the MFR of final polymkeric substance controls; Wherein, described the 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 ofly take ingredient of solid catalyst A, a kind of organoaluminum B component and the first external electron donor component C that magnesium, titanium, halogen and internal electron donor be main ingredient, wherein the part by weight between component A and B component is counted 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 stage, adjusts the consumption of the first external electron donor component C, and making the part by weight of itself and organoaluminum B component is 1:15 ~ 100; In subordinate phase, the amount of the organoaluminum B component adding by the first stage is fixed and fills into the second external electron donor component, and making the part by weight of itself and organoaluminum B component is 1:2 ~ 20.
6. polypropylene foaming beads according to claim 3, it is characterized in that, described the first external electron donor is to be selected from one or more in dicyclopentyl dimethoxyl silane, diisopropyl dimethoxy silane, Dicyclohexyldimethoxysilane and second, isobutyl dimethoxy silane, and the second external electron donor is to be selected from one or more in tetramethoxy-silicane, tetraethoxysilane, trimethylammonium methoxy silane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane and Cyclohexylmethyldimethoxysilane.
7. according to the polypropylene foaming beads described in any one in claim 3 ~ 6, it is characterized in that, described butylene adds in two stages, first stage butylene add-on be butylene add total amount 40 ~ 60%, subordinate phase butylene add-on be butylene add total amount 40 ~ 60%.
8. a preparation method for polypropylene foaming beads, comprises that take the high melt strength, propylene described in any one in claim 1 ~ 7 is matrix resin, and foaming makes as whipping agent to using carbonic acid gas or nitrogen.
9. method according to claim 8, it is characterized in that, preparation process comprises: by comprising after the micropartical and optional additive melt blending of matrix resin and Nucleating Agent, granulation forms acrylic resin particulate, after described acrylic resin particulate mixes with auxiliary agent whipping agent existence issue brewed must described polypropylene foaming beads.
10. method according to claim 9, is characterized in that, described Nucleating Agent is to be selected from one or more in zinc borate, silicon-dioxide, talcum, calcium carbonate, borax and aluminium hydroxide; 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, be preferably 0.01 ~ 0.05 weight part, described tensio-active agent is 0.001 ~ 1 weight part, preferred 0.1 ~ 0.3 weight part, described dispersion agent is 0.01 ~ 5 weight part, preferred 0.5 ~ 2 weight part, and described dispersion intensifier is 0.0001 ~ 1 weight part, preferred 0.01 ~ 0.1 weight part.
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