CN104250400B - A kind of preparation method of polypropylene foaming beads - Google Patents

A kind of preparation method of polypropylene foaming beads Download PDF

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CN104250400B
CN104250400B CN201310270422.6A CN201310270422A CN104250400B CN 104250400 B CN104250400 B CN 104250400B CN 201310270422 A CN201310270422 A CN 201310270422A CN 104250400 B CN104250400 B CN 104250400B
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weight portion
silane
electron donor
propane
external electron
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CN104250400A (en
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郭鹏
吕明福
张师军
董穆
邹浩
张丽英
刘建叶
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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
    • 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
    • C08L23/12—Polypropene
    • 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
    • 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
    • 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
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • 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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The present invention provides the preparation method of a kind of polypropylene foaming beads, and described expanded bead uses HOPP to be matrix resin, and with APP as fire retardant, foaming prepares in the presence of blowing agents；Wherein said HOPP is adopted and is prepared with the following method: in the reactor of two or more serial operations, carrying out two benches or above propylene homo closes reaction, the external electron donor used in two benches reaction is respectively silane compound and diether compound.The present invention is with the high melt strength, propylene of wide molecular weight distribution as raw material, realize the stabilisation of pp material, foaming window is effectively expanded, technique is prone to adjust, low cost, can prepare that cell diameter is uniform, abscess is fine and close, the polypropylene foaming beads of even aperture distribution, hole-closing structure, can be applicable to the occasion that foam plastic product is had relatively high fire-retardance to require by automobile component, electronic packaging and building decoration etc..

Description

A kind of preparation method of polypropylene foaming beads
Technical field
The present invention relates to field of polymer technology, say further, relate to the preparation side of a kind of halogen-free polypropylene flame redardant expanded bead Method.
Background technology
Since the eighties in last century abroad starts to research and develop polypropylene foaming beads (EPP), it is at buffering package, food bag The fields such as dress, automobile component, heat insulation and construction material are widely used, become can substitute expanded polystyrene (EPS), The novel environment friendly foamed materials of polyurathamc.EPP beadlet has uniform size and stable expansion ratio, suitable for making Molded foaming product.
But EPP beadlet belongs to combustible material, during burning, caloric value is big, and with molten drop, easily propagating flame, require fire-retardant The application of occasion is restricted.At present, polypropylene fire retardant modification great majority use Interventional flame-retardant system.Fire retardant master Including following several classes: halogenated flame retardant, inorganic matter fire retardant, phosphorus flame retardant, expansion type flame retardant.Containing halogen flame retardant The plastic application and development of agent is ripe, and flame retarding efficiency is higher, but can generate when burning substantial amounts of cigarette and poisonous, have corruption The gas of erosion property, causes harm greatly to environment.Halogen flame retardant material is referred in a lot of environmental protection appraisal reports in recent years Its processing, burning and removal process can discharge benzene, furan and two English contour poison carcinogen, serious harm environment and human body Healthy.Inorganic matter fire retardant is with magnesium hydroxide, aluminium hydroxide as representative, and its addition often just can make to gather at more than 60wt% Propylene reaches the UL94V0 flame retardant rating required by insulating trip, and this causes EPP beadlet to prepare molding processing difficulties. Use phosphorus flame retardant, need and oxy radical synergism competence exertion effect, so needing to add hydroxide in system The oxygen-containing inorganic matter such as aluminum or magnesium hydroxide can be only achieved fire retardation.Expansion type flame retardant is a class BACN, mostly is P-N Synergistic is fire-retardant.One layer of uniform heat insulation, oxygen barrier can be formed at material surface when halogen-free expanded flame-retardant polypropylene is by heat-flash or burning Porous carbonaceous foam protective layer, flame retarding efficiency can be significantly improved.But polypropylene is nonpolar, becomes hardly during burning The polymeric material of charcoal, so just can reach UL94V0 flame retardant rating, in addition by this side after needing to add more fire retardant The polypropylene fire retardant composite that method obtains, in often flame retardant rating decline after autoclave dipping batch-foamed, wherein oxygen refers to Number drops to less than 28 from 35～the 45 of polypropylene flame redardant microparticle, it is impossible to meet and flame retardant rating requires higher application neck Territory.In order to improve flame retardant effect, often increase the interpolation number of fire retardant, and this can increase goods cost, and affect EPP The preparation of beadlet and subsequent forming.
The present invention, with the high melt strength, propylene of wide molecular weight distribution as matrix resin, adds fire retardant and foaming agent prepares one Planting micropore halogen-free polypropylene flame redardant expanded bead, have simple process, abscess merges few, high density holes, and rate of closed hole is high, close Spend controlled feature.
Summary of the invention
The present invention provides the preparation method of a kind of polypropylene foaming beads, it is characterised in that described expanded bead uses homopolymerization to gather Propylene is matrix resin, and with APP as fire retardant, foaming prepares in the presence of blowing agents；Wherein, described homopolymerization poly-third Alkene is adopted and is prepared with the following method: in the reactor of two or more serial operations, carries out two benches or above propylene is equal Polyreaction, wherein, is carried out the first stage third in the presence of the Ziegler-Natta catalyst including the first external electron donor component Polyamino alkenyl closes reaction, and it is 0.01～0.4g/10min that the MFR of resulting polymers controls；Base at first stage reaction product Proceed second stage propylene homo on plinth, in the presence of hydrogen and the second external electron donor component and close reaction；Merge two sections Resulting polymers obtains described HOPP, and it is 0.2～15g/10min that its MFR controls；And outside wherein said first, give electricity Daughter is silane compound, and the second external electron donor is diether compound.
In above-mentioned preparation method, it is preferable that described silane compound is that four organic groups connected on the silicon atoms are appointed Selected from alkyl and the compound of alkoxyl.It is further preferred that described silane compound be selected from tetramethoxy-silicane, positive third Ethyl triethoxy silicane alkane, isobutyl triethoxy silane, trimethoxysilane, vinyltrimethoxy silane, just Propyl trimethoxy silicane, tetraethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, dimethylformamide dimethyl TMOS, dimethyldiethoxysilane, second, isobutyl dimethoxy silane, Cyclohexylmethyldimethoxysilane, first Base isobutyl group dimethoxysilane, Dicyclohexyldimethoxysilane, phenyltrimethoxysila,e and dicyclopentyl dimethoxyl One or more in silane.
In the present invention, it is preferable that described diether compound is 1,3-diether compound, its general structure is:
Wherein, R1And R2Identical or different, preferably R1And R2It is the straight chained alkyl of C1～C20；R3～R8Phase each other Same or different, selected from hydrogen, halogen atom, C1～the C20 alkyl of straight or branched, C3～C20 cycloalkyl, C6～C20 virtue One in base, C7～C20 alkaryl, C7～C20 aralkyl, R3～R8Group between can be bonded cyclization.
It is further preferred that described diether compound is selected from 2,2-diisobutyl-1,3-dimethoxy propane, 2,2-phenyl-1,3-diformazan Double (the ring of epoxide propane, 2,2-benzyl-1,3-dimethoxy propane, 2-isopropyl-2-isopentyl-1,3-dimethoxy propane, 2,2- Own methyl)-1,3-dimethoxy propane, 2-isopropyl-2-3,7-dimethyl octyl-dimethoxy propane, 2,2-isopropyl-1,3-diformazan Epoxide propane, 2-isopropyl-2-cyclohexyl methyl-1,3-dimethoxy propane, 2,2-diisobutyl-1,3-di ethyl propyl ether, 2,2- Diisobutyl-1,3-dipropoxy propane, 2-isopropyl-2-isopentyl-1,3-di ethyl propyl ether, 2-isopropyl-2-isopentyl-1,3- One or more in dipropoxy propane and double (the cyclohexyl methyl)-1,3-di ethyl propyl ether of 2,2-.
In the present invention it is preferred that described Ziegler-Natta catalyst includes following components, a kind of with magnesium, titanium, halogen and Internal electron donor is the ingredient of solid catalyst A of key component, a kind of organo-aluminium component B and the first external electron donor component C, Wherein the part by weight between component A and component B is calculated as 1:10～500 with titanium aluminum ratio, the weight ratio between component B and component C Example is 10～150:1.Organo-aluminium chemical combination in an instantiation of said method, in described Ziegler-Natta catalyst Thing and 1, the mol ratio of 3-diether compound external electron donor is 1:1～30:1, preferably 2:1～15:1.
In the preparation process of matrix resin HOPP of the present invention, the added hydrogen of first stage and second stage is with The requirement of whole MFR controls.Preferably, in the first phase, hydrogen content is less than or equal to 400ppmV；And second Hydrogen content during hydrogen content is higher than the first stage in stage.
In the above-mentioned methods, the described first stage is all polymerized and in Liquid-liquid, or can carry out in gas phase-gas phase, Or use liquid-gas combination technique to carry out.In a specific embodiment, its polymerization methods is liquid-phase bulk polymerization.Entering During row liquid phase polymerization, polymerization temperature is 50～100 DEG C, preferably 60～85 DEG C；Polymerization pressure should be higher than that propylene is corresponding poly- Saturated vapour pressure at a temperature of conjunction.When gas-phase polymerization, polymerization temperature is 50～100 DEG C, preferably 60～85 DEG C；Polymerization Pressure can be normal pressure or higher, preferably pressure be 1.0～3.0MPa(gauge pressures, lower with).The equal polyreaction of described second stage Generally carrying out in the gas phase, polymerization temperature is 50～100 DEG C, preferably 60～85 DEG C；Polymerization pressure can be normal pressure or more Height, preferably pressure are 1.0～3.0MPa(gauge pressures, lower same).Above-mentioned equal polyreaction can be carried out continuously, it is also possible to interval is entered OK.Continuous polymerization can be Liquid-phase reactor and/or the Gas-phase reactor of two or more series connection, and Liquid-phase reactor can be ring Pipe reactor or stirred tank reactor, Gas-phase reactor can be horizontal type agitated bed reactor or vertical mixing bed reactor or Being fluidized-bed reactor etc., above Liquid-phase reactor and Gas-phase reactor can also at random matched combined.
In the above-mentioned methods, the described catalyst comprising silanes external electron donor can be added directly in the first reactor, After the pre-contact (premixing) can also known altogether through industry and/or prepolymerization, it is then added in the first reactor.Described Prepolymerization refers to that catalyst carries out the prepolymerization of certain multiplying power at a lower temperature, to obtain preferable particle shape and kinetics Behavior-Based control.It can be the continuous prepolymerization of liquid-phase bulk, it is also possible to be batch pre-polymerization in the presence of an inert solvent.In advance Polymerization temperature usually-10～50 DEG C, preferably 5～30 DEG C.Pre-contacting steps was optionally set before prepolymerization technology； Described pre-contacting steps refers to promoter in catalyst system, external electron donor and major catalyst (solid active center component) Carry out the complex reaction of catalyst system, to obtain the catalyst system with polymerization activity.The temperature of pre-contacting steps is usual Control as-10～50 DEG C, preferably 5～30 DEG C.In the present invention, preferably give outside described first before first stage propylene homo closes Electron participates in Propylene Pre-polymerization；Preferably before second stage propylene homo closes, described second external electron donor participates in premixing.
In the present invention, it is preferred that be additionally included in the preparation method of polypropylene foaming beads interpolation silicone rubber for collaborative resistance Combustion agent.In the expanding fire retardant of expanded flame-retardant polypropylene system, add synergistic fire retardant, flame retarding efficiency can be significantly improved, and And the addition of expanding fire retardant in reduction fire retardant systems, thus be conducive to improving the preparation technology of EPP, improve finished product Mechanics and processability.
In the present invention, described foaming agent can be a kind of organic physical blowing agent or a kind of mineral-type physical blowing agent.This has Machine physical blowing agent includes aliphatic hydrocarbon such as propane, butane, pentane, hexane and heptane, alicyclic hydro carbons such as ring fourth Alkane and hexamethylene, and halogenated hydrocarbon such as chlorofluoromethane, fluoroform, 1,2-Difluoroethane, 1,2,2,2-tetrafluoroethane, Methyl chloride, ethyl chloride and dichloromethane.The example of inorganic physical blowing agent include air, nitrogen, carbon dioxide, oxygen and Water.Wherein, the water as foaming agent could be for making this acrylic resin microgranule be scattered in the water in this disperse medium.This The most organic and inorganic foaming agent can be used alone, it is also possible to two or more are used in mixed way.Owing to PP expanded bead is apparent Stability (homogeneity), low cost and the environmental friendliness problem of density, preferably carbon dioxide of the present invention and/or nitrogen are as sending out Infusion.
In the preparation method of polypropylene foaming beads of the present invention, preferably will include matrix resin, Nucleating Agent, main fire-retardant After agent APP and optional synergistic fire retardant, additive melt blending, pelletize form acrylic resin microgranule, described Acrylic resin microgranule foams in the presence of described foaming agent after mixing with auxiliary agent and prepares described polypropylene foaming beads.
This Nucleating Agent can be a kind of inorganic powder such as Firebrake ZB, silicon dioxide, Talcum, calcium carbonate, Borax or hydrogen-oxygen Change aluminum, wherein preferred boric acid zinc or silicon dioxide；According to fire-retardant compounding effect, more preferably Firebrake ZB；At matrix resin Gao Rong When body strength polypropylene is 100 weight portion, described Nucleating Agent is 0.001～1 weight portion, is preferably 0.01～0.05 weight portion. In combustion, as the Nucleating Agent of Firebrake ZB can also form vitreous body by the gap closing between block charcoal, can Hope the barriering effect improving barrier layer.
APP is as the main flame retardant in expansion type flame retardant, and it can be commercially available high polymerization degree APP, its polymerization Degree is more than 1000, P2O5Content is more than 70%, and density is 1.9g/cm3, decomposition temperature is more than 270 DEG C, and dissolubility is less than 0.1g/100ml H2O(25 DEG C), for the matrix resin of every 100 weight portions, the usage amount of this fire retardant is 1～80 Weight portion, preferably 10～35 weight portions.
Silicone rubber adds system as a kind of synergistic fire retardant, and silicone rubber is by commercially available acquisition, or according to Chinese patent ZL 01801656.1 prepares fully sulfurized silicon rubber powder (VP-601), its mean diameter≤2 μm, between preferably 0.1～0.5 μm, Described fully sulfurized silicon rubber powder granule is preferably equal phase structure.For every this matrix resin of 100 weight portions, this adds The usage amount adding agent is 0～0.1 weight portion, preferably 0.001～0.005 weight portion.The addition of silicone rubber can improve material at high temperature heat Stability, and improve material carbon yield.The addition of a small amount of silica gel makes material combustion Char Residues Structure finer and close, can effectively press down The further burning of polymer processed.
In the present invention, described additive be antioxidant, ultraviolet absorber, antistatic agent, fire retardant, metal inactivator, One or more in pigment, nucleating agent, foam controller, filler, stabilizer, reinforcing agent and lubricant.
Described auxiliary agent includes disperse medium, surfactant, dispersant and dispersion intensifier.
Any acrylic resin microgranule is made to be dispersed therein and the component of this microgranule insoluble can be used as disperse medium.This point Dispersion media can be water, ethylene glycol, glycerol, methanol, ethanol or its mixture.Preferably a kind of aqueous dispersion medium, more excellent Select water, most preferably deionized water.Relative to the reactor of 5L volume, disperse medium usage amount is 1～4L, preferably 2.5～3.5L.
In order to promote microgranule dispersion in disperse medium, a kind of surfactant is preferably used, can be stearic acid, 12 Sodium alkyl benzene sulfonate, quaternary ammonium compound, lecithin, aminoacid, glycine betaine, fatty glyceride, fatty acid Pyrusussuriensis is smooth (to be lost Water Span), Polysorbate, preferred anionic type surfactant sodium dodecyl base benzene sulfonic acid sodium salt, relative to often For this acrylic resin microgranule of 100 weight portions, the usage amount of this surfactant is generally 0.001～1 weight portion, preferably 0.01～0.5 weight portion, preferably 0.1～0.3 weight portion.
For polypropylene microparticle each other melt bonded during preventing foaming step, it is generally desirable to add one in this disperse medium Plant the dispersant belonging to fine organic or inorganic solid.For the ease of operation, preferably use a kind of inorganic powder.This point Powder can be natural or synthesis clay mineral (such as Kaolin, Muscovitum, pyrope and clay), Alumina, two Titanium oxide, basic magnesium carbonate, basic zinc carbonate, calcium carbonate, silicon dioxide, Firebrake ZB and ferrum oxide, wherein preferred kaolinite Soil.For this acrylic resin microgranule of every 100 weight portions, the usage amount of this dispersant is generally 0.01～5 weight portions, Preferably 0.1～3 weight portions, preferably 0.5～2 weight portions.
In order to improve the dispersion efficiency of this dispersant, while reducing this dispersant quantity, i.e. retain it prevent microgranule melted viscous The function closed, can add a kind of dispersion intensifier in this disperse medium.This dispersion intensifier be one be provided that bivalence or Trivalent anion or the inorganic compound of cation.The example of this dispersion intensifier include magnesium chloride, magnesium nitrate, magnesium sulfate, Aluminum chloride, aluminum nitrate, aluminum sulfate, iron chloride, iron sulfate and ferric nitrate, wherein preferably sulfuric acid aluminum.This dispersion intensifier Use and be conducive to obtaining the PP expanded bead that apparent density is 50g/L or less.Relative to every this acrylic resin of 100 weight portions For microgranule, the usage amount of this dispersion intensifier is generally 0.0001～1 weight portion, preferably 0.01～0.1 weight portion.
In the present invention, the consumption of above-mentioned foaming agent can be sent out according to the kind of this foaming agent, blowing temperature and PP to be produced The apparent density of bubble beadlet is determined.Such as when with nitrogen as foaming agent and when using water as disperse medium, foaming dress Pressure in this hermetic container when putting pressure release, this hermetic container internal upper part space gauge pressure in the range of 1～12MPa；If making Be foaming agent with carbon dioxide, then gauge is 1～7MPa.It is desirable that apparent close with PP expanded bead to be obtained Degree reduces, and the pressure in this hermetic container increases.
The present invention correspondingly provides the polypropylene foaming beads that method described in as above any one prepares.
Utilize polypropylene foaming beads prepared by the inventive method, there is low cost, abscess densification and even aperture distribution, combustion Burning oxygen index (OI) advantages of higher, can be applicable to automobile component, electronic packaging and building decoration etc. has higher to foam plastic product The occasion of flame-retardancy requirements.
Detailed description of the invention
Melt flow rate (MFR) (MFR): by ISO1133, uses CEAST company 7026 type Melt Flow Rate Measurer, 230 DEG C, measure under 2.16kg load.
Underwater pellet cutting system: Labline100, BKG company of Germany.
Melt drawn test machine: RheotensTM97, Goettfert company of Germany.
Density tester: CPA225D, density adnexa YDK01, Satorius company of Germany.Method of testing: use Satorius The density adnexa of balance, utilizes drainage to obtain the density of polypropylene matrix resin and polypropylene foaming beads.Obtain is poly- The expansion ratio of propylene expanded bead formula b=ρ1/ρ2Calculating, wherein, b is expansion ratio, ρ1For polypropylene matrix resin Density, ρ2Density for polypropylene foaming beads；Density in the present invention refers both to the apparent density of material.
Opening and closing porosity tester: ULTRAFOAM1200e, Quantachrome instrument company of the U.S..
The following example further describes the present invention, but it should be noted that the present invention is in no way limited to these embodiments.
The preparation of matrix resin HMSPP501
Polyreaction is carried out on a set of polypropylene pilot-plant.Its capital equipment includes prepolymerization reactor, the first ring canal reaction Device and the second annular-pipe reactor.
Prepolymerization: flow is about major catalyst (DQ-III catalyst, Beijing Austria of middle Effect of Catalysis In Petrochemistry agent company of 0.5g/hr Reach branch company to provide), flow be the promoter (triethyl aluminum) of 6.33g/hr, flow be the first outer to electronics of 0.63g/hr Body (dicyclopentyl dimethoxyl silane, DCPMS) through 6 DEG C, after 20min pre-contact, be added continuously continuous stirring autoclave Prepolymerization reactor carries out prepolymerization, and prepolymerization is carried out under propylene liquid-phase bulk environment, and temperature is 15 DEG C, the time of staying Being about 4min, under the conditions of this, the pre-polymerization multiple of catalyst is about 120～150 times.Enter prepolymerization reactor TEA/DCPMS mole Ratio is 20.
Propylene homo in annular-pipe reactor closes: pre-polymerization rear catalyst is continuously into completing the first rank in the first annular-pipe reactor Section propylene homo closes reaction, loop po lymerisation reaction temperature 70 DEG C, reaction pressure 4.0MPa, is not added with in the charging of annular-pipe reactor Hydrogen, the density of hydrogen 10ppmV of on-line chromatograph detection, obtain acrylic polymers.Polymer syrup at the first reactor Liquid exit adds second external electron donor 2 of 0.59g/hr, 2-diisobutyl-1,3-dimethoxy propane (DIBMP) so that it is The acrylic polymers premixing obtained with the first stage；Wherein TEA/DIBMP mol ratio is 20.Material after premixing is entered Entering the second reactor, add a certain amount of hydrogen in the second reactor, on-line chromatograph detection density of hydrogen is 4000ppmV, Second reactor continues cause propylene homo to close reaction.After having reacted, remove catalyst in reactor through wet nitrogen Activity, merge two benches produce polymer and heated be dried, obtain described HOPP.
The preparation of matrix resin HMSPP502
With the preparation of matrix resin HMSPP501, but adding a small amount of hydrogen in the first annular-pipe reactor, on-line chromatograph detects Density of hydrogen is 300ppmV, and changes the density of hydrogen in the second annular-pipe reactor into 5000ppmV；It addition, regulation makes In the first annular-pipe reactor TEA Yu DCPMS mol ratio be 10, TEA Yu DIBMP mol ratio tune in the second annular-pipe reactor Whole is 60.
Table 1 lists two kinds of matrix resin HMSPP501 and HMSPP502 and common HOPP of the prior art The analysis result of T30S.
Table 1
In the preparation process of matrix resin HOPP in the present invention, it is according to the requirement to different molecular weight fraction, The external electron donor with different qualities is added in different reactor.Specifically, in first stage that is first reactor, The present invention needs to prepare the acrylic polymers of high molecular weight block, in order to make this fraction have higher molecular weight, have selected one Plant the external electron donor with relatively low hydrogen response, i.e. silane compound；And in second stage, the present invention needs system The acrylic polymers of standby lower molecular weight fraction, in order to use lesser amount of hydrogen, have selected a kind of higher hydrogen and adjusts sensitivity The external electron donor of property, i.e. diether compound.
It addition, the two ethers external electron donors added in the present invention and the silanes in prior art (WO2011/088754) External electron donor is compared, and has the higher ability with catalyst active center's complexation, and it can be polymerized with first stage gained Catalytic active center in composition granule reacts, and generates new catalytic active center, continues to cause all polymerizations of propylene.
The acrylic polymers of the polymerization of the present invention not only available wider molecular weight, and the feature of its maximum is high point Sub-magnitude divides the content of (molecular weight be more than 5,000,000) higher, simultaneously lower molecular weight fraction (molecular weight is less than 50,000) Content also can ensure more than a certain amount of, so makes the melt strength of gained acrylic polymers have and improves significantly, but also protects Demonstrate,prove the processing characteristics of polymer.
Embodiment 1～10
First, by include the matrix resin of 100 weight portions and the Nucleating Agent (Firebrake ZB) of parts by weight as shown in table 2, Main flame retardant (APP) and the microparticle of synergistic fire retardant (silicone rubber), and additive puts in homogenizer high After speed mixing 30 seconds, adding LabLine100 microparticle preparation system, moment of torsion controls about 65%, rotating speed 300rpm, water Lower pelletizing obtains acrylic resin microgranule.Wherein, the matrix resin that embodiment 1～8 uses is HMSPP501, embodiment 9～10 The matrix resin used is HMSPP502.Additive used by embodiment 1～10 all includes the antioxidant 1010 of 0.2 weight portion The irgasfos 168 (BASF AG) of (BASF AG), 0.1 weight portion and the calcium stearate of 0.05 weight portion.Specifically, By matrix resin, Nucleating Agent, fire retardant, synergistic fire retardant, add additive and utilize homogenizer to be blended After, extruded by double screw extruder, import 75 DEG C or following, preferable 70 DEG C or less, the water of more preferable 55～65 DEG C enters Row microparticle cuts, and the length/diameter ratio making every is 0.5～2.0, preferable 0.8～1.3, more preferable 0.9～1.1, and average weight is 0.1～20mg, preferable 0.2～10mg, more preferable 1～3mg.This average weight is the meansigma methods of 200 any selection microgranules.
And in foaming prepares the step of described polypropylene foaming beads, particularly as follows: first, in autoclave, by described poly- Allyl resin microgranule (HMSPP501 or HMSPP502) and disperse medium (deionized water), surfactant (dodecane Base benzene sulfonic acid sodium salt), dispersant (Kaolin), these several auxiliary agents of dispersion intensifier (aluminum sulfate) disposably add mixing；Phase Should be in the polypropylene of 100 weight portions, the weight fraction of several auxiliary agents is shown in Table 2.Secondly, inertia foaming agent is used after covering tightly kettle cover Residual air in reactor is discharged, removes air in reactor；Inertia foaming agent is fed in this autoclave, first step Seamless power is until it is stable；It is subsequently agitated for the dispersion in this autoclave, is heated to compare expansion temperature with constant-speed heating Low 0.5～1 DEG C.Subsequently, in adjusting still, pressure reaches the desirable pressure that foams；With the average heating rate of 0.1 DEG C/min by temperature Being increased to blowing temperature, blowing temperature is lower 0.5～1 DEG C than microgranule melt temperature；Under blowing temperature and pressure condition, persistently stir Mix 0.25～0.5 hour.Finally, the discharging opening of this autoclave is opened, makes the material in reactor be excreted in collecting tank, To obtain polypropylene foaming beads；Inertia foaming agent gas is fed so that send out completely at all particles while carrying out discharging Before bubble and entrance collecting tank, the pressure in this autoclave is maintained near blow pressure.Wherein, embodiment 1～10 and comparative example The inertia foaming agent used in 1～6 is CO2。
Comparative example 1～6
The common HOPP T30S using Sinopec Qilu Branch Company to produce replaces embodiment In HMSPP501 and HMSPP502 test.
Utilize molding forming machine that the expanded bead prepared in above-described embodiment and comparative example is prepared as foaming plate, according to The specification of 10mm*10mm*150mm is processed into batten, and the method described according to GB GB T2406.2-2009 carries out oxygen Index is tested, and it the results are shown in Table 2.
Table 2
From experimental result, embodiment 1～10 with the trade mark as HMSPP501 or HMSPP502 high fondant-strength gather Propylene is matrix resin, obtains abscess dense uniform, ganoid expanded bead；It is further preferred that by adding trace Synergistic fire retardant silicone rubber, after it interacts with Nucleating Agent, can effectively reduce the interpolation of main flame retardant APP Amount, main flame retardant APP addition can produce the oxygen index (OI) flame retardant products higher than 28 when being 15～25 parts.And comparative example Using common HOPP T30S in 1～6, preparation process is temperature required higher, and the expanded bead density obtained is relatively big, bubble Hole density is low and sparse uneven, surface of beads out-of-flatness；Even and if add a large amount of main flame retardant and synergistic fire retardant still without Method meets oxygen index (OI) requirement, relatively low mainly due to the melt strength of T30S, cause foam structure to rupture and cannot be formed complete One-tenth carbon-coating.

Claims (12)

1. the preparation method of a polypropylene foaming beads, it is characterised in that described expanded bead uses HOPP to be matrix Resin, with APP as fire retardant, foaming prepares in the presence of blowing agents；Wherein, described HOPP uses as follows Method prepares: in the reactor of two or more serial operations, carries out two benches or above propylene homo closes reaction, Wherein, in the presence of the Ziegler-Natta catalyst including the first external electron donor component, carry out first stage propylene homo close anti- Should, it is 0.01～0.4g/10min that the MFR of resulting polymers controls；On the basis of first stage reaction product, at hydrogen Proceed second stage propylene homo in the presence of gas and the second external electron donor component and close reaction；Merge two sections of resulting polymers Obtaining described HOPP, it is 0.2～15g/10min that its MFR controls；And wherein said first external electron donor is silane Compounds, the second external electron donor is diether compound.
Method the most according to claim 1, it is characterised in that described silane compound is four and connects on the silicon atoms Organic group optionally from alkyl and the compound of alkoxyl.
Method the most according to claim 2, it is characterised in that described silane compound be selected from tetramethoxy-silicane, N-pro-pyl triethoxysilane, isobutyl triethoxy silane, trimethoxysilane, vinyltrimethoxy silane, N-pro-pyl trimethoxy silane, tetraethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, dimethyl two Methoxy silane, dimethyldiethoxysilane, second, isobutyl dimethoxy silane, Cyclohexylmethyldimethoxysilane, Methyl-isobutyl dimethoxysilane, Dicyclohexyldimethoxysilane, phenyltrimethoxysila,e and bicyclopentyl dimethoxy One or more in base silane.
Method the most according to claim 1, it is characterised in that described diether compound is 1,3-diether compound, its General structure is:
Wherein, R1And R2Identical or different, and R1And R2It is the straight chained alkyl of C1～C20；R3～R8Phase each other Same or different, selected from hydrogen, halogen atom, C1～the C20 alkyl of straight or branched, C3～C20 cycloalkyl, C6～C20 virtue One in base, C7～C20 alkaryl, C7～C20 aralkyl, R3～R8Group between can be bonded cyclization.
Method the most according to claim 4, it is characterised in that described diether compound is selected from 2,2-diisobutyl-1,3- Dimethoxy propane, 2,2-phenyl-1,3-dimethoxy propane, 2,2-benzyl-1,3-dimethoxy propane, 2-isopropyl-2-are different Amyl group-1,3-dimethoxy propane, 2,2-double (cyclohexyl methyl)-1,3-dimethoxy propane, 2-isopropyl-2-3,7-dimethyl octyl -dimethoxy propane, 2,2-isopropyl-1,3-dimethoxy propane, 2-isopropyl-2-cyclohexyl methyl-1,3-dimethoxy propane, 2,2-diisobutyl-1,3-di ethyl propyl ether, 2,2-diisobutyl-1,3-dipropoxy propane, 2-isopropyl-2-isopentyl-1,3- Double (the cyclohexyl methyl)-1,3-diethoxy of di ethyl propyl ether, 2-isopropyl-2-isopentyl-1,3-dipropoxy propane and 2,2- One or more in propane.
6. according to the method described in any one in Claims 1 to 5, it is characterised in that institute before first stage propylene homo closes State the first external electron donor and participate in Propylene Pre-polymerization, and/or described second external electron donor ginseng before second stage propylene homo closes With premixing.
7. according to the method described in any one in Claims 1 to 5, it is characterised in that be additionally included in polypropylene foaming beads Adding silicone rubber in preparation method is synergistic fire retardant.
Method the most according to claim 1, it is characterised in that described foaming agent is carbon dioxide and/or nitrogen.
Method the most according to claim 7, it is characterised in that matrix resin, Nucleating Agent, main flame retardant will be included After APP and optional synergistic fire retardant, additive melt blending, pelletize form acrylic resin microgranule, described poly- Allyl resin microgranule foams in the presence of blowing agents after mixing with auxiliary agent and prepares described polypropylene foaming beads.
Method the most according to claim 9, it is characterised in that described Nucleating Agent be selected from Firebrake ZB, silicon dioxide, One or more in Talcum, calcium carbonate, Borax and aluminium hydroxide；Described auxiliary agent include disperse medium, surfactant, Dispersant and dispersion intensifier；
Described disperse medium is selected from water, ethylene glycol, glycerol, methanol, ethanol or its mixture；Described surfactant is selected from Stearic acid, dodecylbenzene sodium sulfonate, quaternary ammonium compound, lecithin, aminoacid, glycine betaine, fatty glyceride, fat Acid Pyrusussuriensis is smooth, Polysorbate；Described dispersant selected from Kaolin, Muscovitum, pyrope, clay, Alumina, titanium dioxide, Basic magnesium carbonate, basic zinc carbonate, calcium carbonate, silicon dioxide, Firebrake ZB and ferrum oxide；
When matrix resin is 100 weight portion, described Nucleating Agent is 0.001～1 weight portion, and described main flame retardant is 1～80 Weight portion, described synergistic fire retardant is 0～0.1 weight portion, and described surfactant is 0.001～1 weight portion, described dispersion Agent is 0.01～5 weight portions, and described dispersion intensifier is 0.0001～1 weight portion.
11. methods according to claim 10, it is characterised in that when matrix resin is 100 weight portion, described abscess becomes Core agent is 0.01～0.05 weight portion, and described main flame retardant is 10～35 weight portions, and described synergistic fire retardant is 0.001～0.005 Weight portion, described surfactant is 0.1～0.3 weight portion, and described dispersant is 0.5～2 weight portions, described dispersion intensifier It it is 0.01～0.1 weight portion.
The polypropylene foaming beads that 12. 1 kinds of methods as described in any one in claim 1～11 prepare.
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