CN104974367B - A kind of preparation method of antistatic polypropylene foaming plate or sheet material - Google Patents
A kind of preparation method of antistatic polypropylene foaming plate or sheet material Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of antistatic polypropylene foaming plate or sheet material, including first obtaining polypropylene by the following method, then it is antistatic additive as matrix resin, addition CNT using gained polypropylene and the polypropylene foamed plate or sheet material is made using foaming agent foam；Wherein, the polyacrylic preparation method is：In the reactor of two or more serial operations, two benches or more propylene polymerization is carried out, the external electron donor used in two benches reaction is respectively silane compound and diether compound.The PP foam material prepared using this method, there is the advantages that antistatic, abscess is fine and close, even aperture distribution and surfacing, can be applied to the occasion having higher requirements antistatic to plastic products lightweight such as Aero-Space and electronic packaging.
Description
Technical field
The present invention relates to field of polymer technology, further says, is to be related to a kind of antistatic polypropylene foaming plate or sheet material
Preparation method.
Background technology
Expanded material mainly includes the apparent forms such as expanded bead, foaming plate or sheet material；Foaming plate or sheet material are extensive
For fields such as container, construction material, auto parts and impact energy absorbing materials.
Polypropylene foam is a kind of new material, and it contains a large amount of bubbles using polypropylene as solvent.With matter
Gently, material-saving, thermal conductivity are low, heat-proof quality is good, can absorb shock loading, have excellent shock-absorbing capacity, sound insulation value it is good, than strong
Spend high good performance.But PP expanded material static electricity resistances are poor, make its application aspects such as chemical pipeline, container there is
Defect, electrostatic charge is also easy to produce when rubbing or peeling off with the external world, and electric charge is not easy to leak, and can constantly be gathered on surface.Poly- third
After alkene surface is powered, if without effective leakage path, the dust and dirt in air can be adsorbed.As human contact to static electrification
Polypropylene when, the sensation of electric shock can be produced, and electrostatic can also cause the malfunction of electronic equipment, more seriously electrostatic
Electrostatic attraction will occur for accumulation（Or repulsion）, electric shock or Spark Discharges, this meeting under inflammable, explosive material environmental condition
Lead to huge disaster.In order to avoid the influence of electrostatic, it is necessary to it is antistatic modified to polypropylene progress, to adapt to some particular fields
Close.Conductive functional filler is added in polymeric matrix（Such as conductive black）Or antistatic agent is that to prepare polymer matrix antistatic compound
One of main method of material, but generally, form the loading or antistatic agent of the conductive filler that conductive network needs
Addition it is all bigger, cause mechanical property of polymer etc. to reduce more apparent, and improve the production cost and work of material
Skill difficulty, therefore the dosage for reducing conductive filler is the important content of antistatic composite material exploitation and application.
Chinese patent application 200710192215.8 reports antistatic, conductive polyacrylic preparation method, obtains
The surface intrinsic resistance rate of polypropylene board is 1010-1011Ω·cM, the addition of carbon black is 5-40%, apparent due to carbon black
Density is low, and addition is larger, and difficult, the complexity and product cost of increased technique are blended with polypropylene base resin.In recent years
Come, it is more using CNT or graphene as the report of antistatic filler, but due to scattered and interface cohesion problem, shadow
Its extensive use is rung.For example, CNT has specific surface energy high, easily reunite, bad dispersibility, the complete light in its surface in addition
Sliding, dangling bonds are few, very poor with the wellability of other materials, are practically insoluble in any solvent, and easily assemble bunchy in the solution,
This several respects strong influence CNT it is scattered so as to influenceing its electric conductivity.Currently used surface modification of carbon nanotube
Method includes physics coating modification and grafting modification.Because the surface of CNT is smooth, additive and carbon are relied solely on
Physical interaction power between nanotube, which carries out coating modification, has significant limitations, so more researchs concentrate on chemistry
In graft modification.Using effective surface modifying method, promote CNT scattered in matrix resin, so as to improve matrix
The antistatic effect of resin.
Therefore, this area it is also required to provide a kind of excellent antistatic polypropylene foaming plate or sheet material.
The content of the invention
Antistatic additive CNT is added using resin based on the high melt strength, propylene voluntarily researched and developed in the present invention,
The antistatic polypropylene foaming plate or sheet material of function admirable are obtained, it meets degradable environmental requirement, uniform foam cell, thing
Manage heat resistance height, production cost is low, surface is smooth, mechanical property is good and suitable serialization large-scale production.Further, it is preferable to make
When the modified carbon nano-tube for being modified to obtain by the use of three steps of microwave radiation under ball milling, acidifying and reducing atmosphere is as antistatic filler,
Obtain antistatic additive and disperse extraordinary antistatic polypropylene foaming plate.
Therefore, the present invention provides a kind of preparation method of antistatic polypropylene foaming plate or sheet material, including elder generation is under
The method of stating obtains polypropylene, then is antistatic additive as matrix resin, addition CNT using gained polypropylene and uses foaming agent
The polypropylene foamed plate or sheet material is made in foaming；Wherein, the polyacrylic preparation method is：In two or more series connection
In the reactor of operation, the propylene polymerization of two benches or more is carried out, wherein, including the first external electron donor component
Carry out first stage propylene polymerization in the presence of Ziegler-Natta catalyst, the MFR controls of resulting polymers for 0.01~
0.4g/10min；Continue in the first stage on the basis of reaction product, in the presence of hydrogen and the second external electron donor component
Carry out second stage propylene polymerization；Merge two sections of resulting polymers and obtain the polypropylene, its MFR controls for 0.2~
15g/10min；And wherein described first external electron donor is silane compound, the second external electron donor is two ethers chemical combination
Thing；The polypropylene is the COPP that HOPP or propylene obtain with butylene and/or ethylene copolymer.
In the present invention, comonomer ethylene and/or the ratio of butylene and propylene can adjust according to the difference of target.Such as
The weight percent of monomer ethylene and butylene in polypropylene is 0.1~20wt%, preferably 0.5~10wt%.
The characteristics of molecular weight distribution of the high melt strength, propylene used in the present invention is wider, and its is maximum is high
While the content of molecular weight fraction is higher the content of lower molecular weight fraction can also ensure be more than it is a certain amount of, so make gained third
The melt strength of alkene polymer, which has, significantly to be improved, more than 0.8 newton, or even can be more than 2.2 newton, and also assures that poly-
The processing characteristics of compound.
Foaming agent is added in matrix resin, polypropylene foamed plate or sheet material can be produced.Foaming agent can be inorganic
Foaming agent or organic foaming agent, inorganic foaming agent are, for example, air, nitrogen, carbon dioxide, oxygen and water, and organic foaming agent is one
Determine to decompose release gas under temperature and pressure, porous balloon-shaped structure is formed in the expandability material such as resin.
In above-mentioned preparation method, it is preferable that the silane compound is the organic group of four connections on the silicon atoms
Group is optionally from the compound of alkyl and alkoxy.It is further preferred that the silane compound is selected from tetramethoxy-silicane, just
Propyl-triethoxysilicane, isobutyl triethoxy silane, trimethoxysilane, vinyltrimethoxy silane, just
Propyl trimethoxy silicane, tetraethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, dimethylformamide dimethyl oxygen
Base silane, dimethyldiethoxysilane, second, isobutyl dimethoxy silane, Cyclohexylmethyldimethoxysilane, methyl are different
Butyldimethoxysilane, Dicyclohexyldimethoxysilane, phenyltrimethoxysila,e and dicyclopentyl dimethoxyl silane
In one or more.
In the present invention, it is preferable that the diether compound is 1,3- diether compounds, and its general structure is：
Wherein, R1And R2It is identical or different, preferably R1And R2It is C1~C20 straight chained alkyl；R3~R8It is mutually the same
Or it is different, selected from hydrogen, halogen atom, C1~C20 alkyl of straight or branched, C3~C20 cycloalkyl, C6~C20 aryl, C7~
One kind in C20 alkaryls, C7~C20 aralkyl, R3~R8Group between can key be linked to be ring.
It is further preferred that the diether compound is selected from 2,2- diisobutyls -1,3- dimethoxy propane, 2,2- hexichol
Base -1,3- dimethoxy propanes, 2,2- benzhydryl -1,3- dimethoxy propanes, 2- isopropyl -2- isopentyl -1,3- diformazans
Epoxide propane, 2,2- are double（Cyclohexyl methyl）- 1,3- dimethoxy propanes, 2- isopropyls -2-3,7- dimethyl octyls-dimethoxy third
Alkane, 2,2- diisopropyl -1,3- dimethoxy propanes, 2- isopropyl -2- cyclohexyl methyl -1,3- dimethoxy propanes, 2,2- bis-
Isobutyl group -1,3- di ethyl propyl ethers, 2,2- diisobutyl -1,3- dipropoxies propane, 2- isopropyl -2- isopentyl -1,3-
Di ethyl propyl ether, 2- isopropyls -2- isopentyl -1,3- dipropoxies propane and 2,2- are double（Cyclohexyl methyl）- 1,3- diethoxies
One or more in base propane.
In the present invention it is preferred that the Ziegler-Natta catalyst includes following components, one kind is with magnesium, titanium, halogen
Ingredient of solid catalyst A, a kind of organo-aluminium component B and the first external electron donor component C with internal electron donor for key component,
Part by weight between wherein component A and component B is calculated as 1 with titanium aluminum ratio：10~500, the weight ratio between component B and component C
Example is 10~150：1.In an instantiation of the above method, the organo-aluminium chemical combination in the Ziegler-Natta catalyst
The mol ratio of thing and 1,3- diether compound external electron donors is 1:1~30:1, preferably 2:1~15:1.
In the polyacrylic preparation process of matrix resin of the present invention, the added hydrogen of first stage and second stage is with most
Whole MFR requirement controls.Preferably, in the first phase, hydrogen content is less than or equal to 400ppmV；And in second stage
Hydrogen content is higher than hydrogen content in the first stage.
In the above-mentioned methods, polymerization of described first stage can be in Liquid-liquid, or is carried out in gas phase-gas phase,
Or carried out using liquid-gas combination technique.In a specific embodiment, its polymerization methods is liquid-phase bulk polymerization.Carry out
During liquid phase polymerization, polymerization temperature is 50~100 DEG C, preferably 60~85 DEG C；Polymerization pressure should be higher than that propylene in corresponding polymerization temperature
Saturated vapour pressure under degree.In gas-phase polymerization, polymerization temperature is 50~100 DEG C, preferably 60~85 DEG C；Polymerization pressure can
To be normal pressure or higher, preferably pressure is 1.0~3.0MPa（Gauge pressure, similarly hereinafter）.The second stage polymerisation is generally in gas
Carried out in phase, polymerization temperature is 50~100 DEG C, preferably 60~85 DEG C；Polymerization pressure can be normal pressure or higher, preferably pressure
For 1.0~3.0MPa（Gauge pressure, similarly hereinafter）.Above-mentioned polymerisation can be carried out continuously, and can also intermittently be carried out.Continuous polymerization can be with
It is the Liquid-phase reactor and/or Gas-phase reactor of two or more series connection, Liquid-phase reactor can be annular-pipe reactor or stirring
Kettle reactor, Gas-phase reactor can be horizontal type agitated bed reactor vertical mixing bed reactor or fluidized-bed reactor
Can also arbitrarily matched combined Deng, above Liquid-phase reactor and Gas-phase reactor.
In the above-mentioned methods, the described catalyst comprising silanes external electron donor can be added directly into the first reaction
In device, the known pre-contact of industry can also be passed through（Premixing）And/or prepolymerization and then it is added in first reactor.
The prepolymerization refers to that catalyst carries out the prepolymerization of certain multiplying power at a lower temperature, to obtain preferable particle shape and move
Mechanical behavior controls.It can be the continuous prepolymerization of liquid-phase bulk, can also be batch pre-polymerization in the presence of an inert solvent.
Prepolymerization temperature is usually -10~50 DEG C, preferably 5~30 DEG C.Optionally pre-contact is set to walk before prepolymerization technology
Suddenly；The pre-contacting steps refers to co-catalyst in catalyst system, external electron donor and major catalyst（Solid active central. set
Point）The complex reaction of catalyst system is carried out, to obtain the catalyst system with polymerization activity.The temperature of pre-contacting steps is led to
Often control is -10~50 DEG C, preferably 5~30 DEG C.In the present invention, preferably given in the first stage before propylene polymerization outside described first
Electron participates in Propylene Pre-polymerization；It is preferred that second external electron donor participates in premixing before second stage propylene polymerization.
Above-mentioned high melt strength, propylene is applied for a patent on October 30th, 2012, and number of patent application is
A kind of 201210422726.5 entitled polyacrylic preparation method with high fondant-strength.In its description and this Shen
On the premise of description please does not collide, its content is all incorporated in the present application as reference.
In a kind of embodiment of the present invention, the foaming agent is organic chemistry foaming agent；And the polypropylene
The preparation method of foaming plate or sheet material is：By matrix resin polypropylene, antistatic additive CNT, organic chemistry foaming agent,
The polypropylene expanded plate is made in Cell-controlling agents and optional additive melt blending, extrusion and foaming at 150~280 DEG C
Material or sheet material.Foaming plate or sheet material prepared by CBA has a surfacing, abscess dense uniform, expansion ratio it is low and
The features such as controllable, it is widely used in the field such as automotive trim, food, household electrical appliances and electronic packaging.
Antistatic additive CNT in the present invention can also pass through arc discharge method, laser evaporation with commercially available
Any one method in method, chemical vapour deposition technique is prepared；Its a diameter of 10~100nm, length are 0.5~500 μm,
Can be single wall or multi-walled carbon nanotube.In the present invention, it is antistatic corresponding to the high melt strength, propylene of 100 parts by weight
Agent is 0.5~2 parts by weight.
It is preferred that antistatic additive of the present invention is to change by including three steps of microwave radiation under ball milling, acidifying and reducing atmosphere
The modified carbon nano-tube obtained after property.Wherein, preferably described ball milling is to use weight ratio as 150~400:1 agate ball and carbon
With 170-290rpm rotating speed ball milling 0.5h-2h on ball mill after nanotube mixing.It is preferred that microwave spoke under the reducing atmosphere
Penetrate and be included in microwave radiation processing under one or more reducing atmospheres in hydrogen, methane, ethane, acetylene and carbon monoxide
The carboxylic carbon nano-tube that acidification step obtains.
Modified carbon nano-tube in the present invention is specifically obtained by the following steps：
Ball milling：With 250:Agate ball is well mixed by 1 ratio of grinding media to material with CNT, is expert at 170-290rpm rotating speed
Ball milling 0.5h-2h on planetary ball mill, obtain the CNT that is chopped.Shearing force in mechanical milling process is advantageous under electrostatic force
The carbon nanotube separation of reunion and surface produce the defects of sp3 structures position, not only contribute to CNT inside resin matrix
It is scattered, also improve the adhesion with resin matrix；In addition, defective bit is advantageous to the aggregation of electric charge, so as to improve the biography of electric charge
It is defeated, play anlistatig effect.In mechanical milling process, there are obvious shadow rotational speed of ball-mill and time to the CNT performance of preparation
Ring.Rotational speed of ball-mill is too small or Ball-milling Time is too short, and the CNT of reunion can not be fully dispersed；On the other hand, rotating speed is too
Big either Ball-milling Time is oversize, causes defective bit excessive so that the conductive capability of CNT declines.
Acidification：CNT after ball milling is mixed with acid solution, back flow reaction is carried out, products therefrom is filtered,
Carboxylic carbon nano-tube is obtained after washing and drying.Specifically, CNT is mixed with acid solution, acid used is strong for what is commonly used
Sulfuric acid, the 65~70wt% nitric acid of acid solution or nitration mixture, such as 50~98wt%, and sulfuric acid/nitric acid, hydrochloric acid/nitric acid, dioxygen
At least one of mixed acid solutions such as water/nitric acid.It is preferred that the CNT presses carbon nanotube mass with acid solution：Acid solution body
Product is 2~10g：0.2~0.5L ratio mixing.Advantageously, the mixed liquor is subjected to magnetic agitation 30 at normal temperatures successively
~60 minutes and 20~40 KHz ultrasonic echographies are handled 20~30 minutes, then enter mixed liquor introducing back flow reaction device
Row reaction, makes CNT carboxylated.The temperature of back flow reaction is usually 80~120 DEG C, and the time is 2~4 hours.Reaction terminates
After filter products therefrom, preferably filtered using 0.22 micrometer Millipore filter membrane.Then product is washed with water, preferably uses deionization
Water washed product repeatedly, until eluate is in neutrality.Product can be dried in vacuo 12~24 hours at 60~100 DEG C, obtain carboxylic
Base carbon nano tube.
Microwave radiation under reducing atmosphere：Microwave radiation processing CNT is utilized under reducing atmosphere, so as to be modified
Product.It is preferred that reducing atmosphere is hydrogen, and methane, ethane, acetylene, carbon monoxide etc., it is so that and is changed using the purpose of reducing atmosphere
Property carbon nano tube surface there are suitable sp2 and sp3 constituent carbon atoms to exist, while ensureing electric conductivity, meet dispersiveness and
With the interfacial bonding property of matrix resin；It is preferred that the reaction time of microwave radiation is 15~60 minutes, temperature is 110~130 DEG C, micro-
Wave power is 100~400W.
Preferably, the organic chemistry foaming agent is selected from azo foaming agent, nitroso group foaming agent and the foaming of hydrazides class
Agent；It is chosen in particular from azodicarbonamide (AC), azodiisobutyronitrile (AIBN), Barium azodicarboxylate (BaAC) and azoformic acid
Ester, dinitroso pentamethylene tetramine (DPT), N, N '-dinitrosopentamethylene tetramine, N, N'- dimethyl-N, N- dinitroso
Terephthalamide (NTA) and trinitroso-trimethylene triamine, 4,4' mono- OBSHs (OBSH), tosyl ammonia
Base urea (TSSC), three phosphorus base triazines (CTHT), the one or more in 5- phenyltetrazoles；More preferably azodicarbonamide
(AC).The azo system AC foaming agents preferably used in the present invention, compared with using fluorinated foaming agent, have it is environment-friendly, no
The advantages that destroying atmosphere.
The Cell-controlling agents be talcum powder, aluminium hydroxide, silica, zeolite and borax in one or more, institute
Stating additive includes the one or more in antioxidant, aid anti-oxidants, acid-acceptor, lubricant and pigment；Corresponding to 100 parts by weight
Polypropylene；Organic foaming agent is 1~15 parts by weight, preferably 5~7 parts by weight；The dosage of Cell-controlling agents is 5~20 weight
Part, preferably 5~15 parts by weight.The dosage of the additive is conventional amount used, or is adjusted according to actual requirement.
In another embodiment of the present invention, the foaming agent is inorganic gas foaming agent；And described poly- third
The preparation method of alkene foaming plate or sheet material is：By matrix resin polypropylene, inorganic gas foaming agent, Cell-controlling agents and optionally
Additive be placed in the foaming dedicated extruder with gas injection apparatus, in the extruder be blended, extrude and foaming be made
The polypropylene foamed plate or sheet material.The inorganic gas foaming agent is, for example, one kind in carbon dioxide, nitrogen, air and water
It is or a variety of.When it is foaming agent to select carbon dioxide, corresponding to the matrix resin of 100 parts by weight, 1~10 weight is preferably
Part.
Using this method prepare PP foam material, have it is antistatic, abscess is fine and close, even aperture distribution and table
The advantages that face is smooth, it can be applied to the field having higher requirements antistatic to plastic products lightweight such as Aero-Space and electronic packaging
Close.
Embodiment
Melt flow rate (MFR)（MFR）：By ISO1133, using the type Melt Flow Rate Measurer of CEAST companies 7026,230
DEG C, determined under 2.16kg load.
Double screw extruder：ZSK-25, German WP companies.
Melt drawn test machine：RheotensTM97, German Goettfert companies.
Density tester：CPA225D, density annex YDK01, German Satorius companies.Method of testing：Use
The density annex of Satorius balances, polypropylene matrix resin and polypropylene foamed plate or sheet material are obtained using drainage
Density.Obtained polypropylene foamed plate or the expansion ratio formula of sheet materialCalculate, wherein,For expansion ratio, ρ
1 be polypropylene matrix resin density, ρ2For the density of PP foam material；Density in the present invention refers both to the apparent of material
Density.
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.
Matrix resin HMSPP501 preparation
Polymerisation is carried out on a set of polypropylene pilot-plant.Its capital equipment includes prepolymerization reactor, the first endless tube
Reactor and the second annular-pipe reactor.
Prepolymerization：Flow is about 0.5g/hr major catalyst（DQ-III catalyst, sinopec catalyst Co. north
Jing Aoda branch companies provide）, flow be 6.33g/hr co-catalyst（Triethyl aluminum）, flow be 0.63g/hr first outside give
Electron（Dicyclopentyl dimethoxyl silane, DCPMS）After 6 DEG C, 20min pre-contact, it is added continuously and continuously stirs autoclave
Prepolymerization reactor carries out prepolymerization, and prepolymerization carries out under propylene liquid-phase bulk environment, and temperature is 15 DEG C, and the residence time is
About 4min, pre-polymerization multiple of catalyst is about 120~150 times under the conditions of this.The TEA/DCPMS mol ratios for entering prepolymerization reactor are
20。
Propylene homo in annular-pipe reactor closes：Pre-polymerization rear catalyst is continuously into completing in the first annular-pipe reactor
One stage propylene homo, which closes, to react, 70 DEG C, reaction pressure 4.0MPa of loop po lymerisation reaction temperature, in the charging of annular-pipe reactor not
Hydrogenation, the density of hydrogen ﹤ 10ppmV of on-line chromatograph detection, obtains acrylic polymers.In the polymer slurries of first reactor
Exit adds 0.59g/hr the second external electron donor 2,2- diisobutyl -1,3- dimethoxy propanes（DIBMP）, make its with
The acrylic polymers premixing that first stage obtains；Wherein TEA/DIBMP mol ratios are 20.Material after premixing is entered the
Two reactors, a certain amount of hydrogen is added in second reactor, on-line chromatograph detection density of hydrogen is 4000ppmV, anti-second
Answer and continue to trigger propylene homo to close reaction in device.After the completion of reaction, the activity of catalyst in reactor is removed through wet nitrogen, is merged
Polymer caused by two benches and heated drying, obtain the HOPP.
Matrix resin HMSPP502 preparation
With matrix resin HMSPP501 preparation, but a small amount of hydrogen is added in the first annular-pipe reactor, on-line chromatograph inspection
Survey density of hydrogen is 300ppmV, and the density of hydrogen in the second annular-pipe reactor is changed into 5000ppmV；In addition, regulation causes
TEA and DCPMS mol ratios are 10 in first annular-pipe reactor, and TEA and DIBMP mol ratios are adjusted in the second annular-pipe reactor
60。
Table 1 lists two kinds of matrix resin HMSPP501 and HMSPP502 and common HOPP of the prior art
T30S analysis result.
Table 1
It is requirement of the basis to different molecular weight fraction in the polyacrylic preparation process of matrix resin in the present invention,
The external electron donor with different qualities is added in different reactor.Specifically, in the first stage i.e. in first reactor, this
Invention needs to prepare the acrylic polymers of high molecular weight block, in order that the fraction has higher molecular weight, have selected one kind
External electron donor with relatively low hydrogen response, i.e. silane compound；And in second stage, the present invention need prepare compared with
The acrylic polymers of low molecular weight fraction, in order to which lesser amount of hydrogen can be used, it have selected a kind of higher hydrogen and adjust sensitiveness
External electron donor, i.e. diether compound.
In addition, the two ethers external electron donors and prior art that are added in the present invention（WO2011/088754）In silane
Class external electron donor is compared, and has the stronger ability being complexed with catalyst active center, and it can be poly- with first stage gained
Catalytic active center in polymer beads reacts, and generates new catalytic active center, continues to trigger the polymerization of propylene.
The characteristics of polymerization of the present invention not only can obtain the acrylic polymers of wider molecular weight, and its is maximum is pole
High molecular weight block（Molecular weight is more than 5,000,000）Content it is higher, while lower molecular weight fraction（Molecular weight is less than 50,000）Contain
Amount can also ensure to be more than a certain amount of, so make the melt strength of gained acrylic polymers have and significantly improve, but also ensure
The processing characteristics of polymer.
The preparation of foaming plate or sheet material
The preparation method of polypropylene foamed plate or sheet material is, for example, in the present invention：It is using high speed agitator that high melt is strong
Polypropylene, antistatic additive, foaming agent, Cell-controlling agents and the additive of degree carry out batch mixing, obtain the pre- of polypropylene foamed plate
Batch mixing, premix being put into the hopper of extruding machine, the temperature of extruder, which is raised to 150~280 DEG C, makes polypropylene expanded material melting,
Preferred range is that 160~180 DEG C of screw speeds are 15~180rpm, makes plasticized polypropylene resin to 150~280 DEG C, excellent
160~180 DEG C of T connector die extrusion is selected, is flowed in the roller board splitter of plate squeezing unit two, through roll-in slabbing material, natural cooling
To after room temperature, certain specification sheet material, as polypropylene foamed plate or finished sheet material are cut on demand.
Extruder employed in preparation method can be single screw extrusion machine, in the same direction series connection single screw extrusion machine, double spiral shells
Bar extruder, parallel dual-screw extruding machine, series connection single screw extrusion machine, counter rotation twin screw extruder, conical double screw extruder,
One kind in three-screw extruder.Mouth mold can be flat mouth mold, T-shaped mouth mold, circular hole mouth mold or annular according to being actually needed
The various shapes such as mouth mold.The polypropylene resin composite of melting expands after the discharge of flat mouth mold, and by can be between regulating roller
Away from three-roller calendar, by controlling mouth mold size, obtain the polypropylene foamed plate or sheet material of desired thickness.It is in addition, molten
The polypropene composition melted expands after the discharge of annular mouth mold, after inflation and inside and outside cooling, is wound vertically after cutting,
Obtain desired thickness and the polypropylene foamed plate or sheet material of size.In order to which the work to extruder better controls over,
The extruder sold currently on the market is all divided into section to its inside, and each section of temperature can be controlled.
In the polypropylene material extrusion and foaming process of the present invention, material melts blending temperature is in usual polypropylene processing
Blending temperature used, it should selected in the range of not only ensureing polypropylene matrix melting completely but also will not decompose it, generally
For 160~250 DEG C.But the decomposition temperature of industrial AC foaming agents is at 150~205 DEG C, therefore, consider processability and
The decomposition temperature of AC foaming agents, the relatively low processing temperature of the preferred polypropylene of processing temperature, i.e., 150~200 DEG C.
Embodiment 1~8
1）Prepare modified carbon nano-tube：Weigh 0.5g CNTs（Multi-walled carbon nanotube, 15~30nm of diameter）, with 125g
It is placed in after agate ball is well mixed in agate jar, with rotating speed ball milling listed in table 21 hour in planetary ball mill,
Obtain dispersing Nano carbon tubes.It is molten to weigh dispersing Nano carbon tubes addition 500ml nitric acid/hydrogen peroxide mixing that the above-mentioned ball millings of 5.0g obtain
In liquid（The concentration of nitric acid is 65wt%, hydrogen peroxide concentration 45wt%, volume ratio H2O2：HNO3=1:3）, by solution at normal temperatures
Magnetic agitation 30 minutes, then handled 30 minutes through 40 KHz ultrasonic echographies, solution is then accessed into back flow reaction device, in
120 DEG C of return stirrings react 2 hours.Products therefrom is filtered with 0.22 micrometer Millipore filter membrane, washs production repeatedly with deionized water
Thing 10 times, it is dried in vacuo 12 hours at 80 DEG C, obtains carboxylic carbon nano-tube.In atmospheric conditions, above-mentioned carboxylated carbon is received
Mitron is positioned in hydrogen atmosphere, and microwave power is shown in Table 2, processing time 10min, that is, obtains the modified carbon nano-tube.
Table 2
2）Prepare polypropylene foamed plate：By the HOPP HMSPP501 or HMSPP502 of 100 parts by weight, antistatic
Agent, foaming agent（Azodicarbonamide, i.e. technical grade AC foaming agents）, Cell-controlling agents（Talcum powder）High-speed stirring is put into additive
Mix after machine high speed mixes 1 minute, add intermediate layer double screw extruder, moment of torsion control is 65% or so, rotating speed 10-170rpm.
Wherein, additive includes acid-acceptor calcium stearate, antioxidant（Part by weight is 1:2:2 calcium stearate, BASF antioxidant
1010 compound with irgasfos 168, account for 0.2 parts by weight altogether）With lubricant MB50-002（High molecular weight silicone）1 part, bubble
The parts by weight of hole controlling agent, foaming agent and antistatic additive are shown in Table 3；The density of blowing temperature and product sheet material is shown in Table 3, specifically adopts
Density measure is carried out with GB/T1033.1-2008.In addition, the use of embodiment 1~4 HMSPP501 is matrix resin, embodiment 5~
8 use HMSPP502 are matrix resin.
Comparative example 1~4
The common HOPP produced using the Sinopec Qilu Branch Company of 100 parts by weight
T30S is tested instead of the HMSPP501 in embodiment 1~8 or HMSPP502.And comparative example 1~2 using respectively with embodiment
Identical modified carbon nano-tube in 1 and 2, comparative example 3~4 use unmodified CNT as antistatic additive.
Table 3
Note："○" represents that abscess is fine and close, and "×" represents that abscess is sparse uneven；
By embodiment 1~8 as can be seen that using the present invention high melt strength, propylene HMSPP501 or HMSPP502 as
Expanded material obtained by matrix resin is respectively provided with good foaming effect, can just be prepared when adding 5 parts of technical grade AC foaming agents
Go out surfacing, the homogeneous PP foam material of foam structure.In the case of foaming agent consumption identical, its foaming effect compared with
Common HOPP is good, and product density is small, and surface is more smooth, and deflection is high.By comparative example 1~4 as can be seen that with T30S
It is larger to obtain the density of product, and product surface is rough and/or abscess is uneven, it is relatively low mainly due to T30S melt strengths,
Caused by abscess reservation is bad in extrusion and foaming process.In addition, the high melt strength, propylene HMSPP of the present invention is relative to logical
It is equal in the range of 150~200 DEG C because it is with wider molecular weight distribution and with wider foaming window with polypropylene
The excellent expanded material of abscess can be obtained；And under identical foaming agent addition HMSPP products surface it is more smooth, abscess is more
Add uniformly.In addition, only adding 0.5~2 part of antistatic additive in the present invention, gained foaming product can meet antistatic need
Ask.And abscess is caused to develop bad, the electric charge of the CNT of obstruction because the melt strength of matrix resin is relatively low in comparative example
Effectively transmit, therefore antistatic requirement can not be met.
Claims (12)
1. the preparation method of a kind of antistatic polypropylene foaming plate or sheet material, including first polypropylene is obtained by the following method,
It is antistatic additive as matrix resin, addition CNT using gained polypropylene again and the polypropylene is made using foaming agent foam
Foaming plate or sheet material；Wherein, the polyacrylic preparation method is：In the reactor of two or more serial operations, enter
The propylene polymerization of row two benches or more, wherein, including the Ziegler-Natta catalyst of the first external electron donor component
In the presence of carry out first stage propylene polymerization, resulting polymers MFR control be 0.01~0.4g/10min, the MFR
Determined under 230 DEG C, 2.16kg load；In the first stage on the basis of reaction product, in hydrogen and the second external electron donor
Continue second stage propylene polymerization in the presence of component；Merge two sections of resulting polymers and obtain the polypropylene, its MFR
Control and determined for 0.2~15g/10min, the MFR under 230 DEG C, 2.16kg load；And wherein described first external electron donor
For silane compound, the second external electron donor is diether compound；The polypropylene is HOPP or propylene and fourth
The COPP that alkene and/or ethylene copolymer obtain；The diether compound is 1,3- diether compounds.
2. according to the method for claim 1, it is characterised in that the silane compound is four and connected on the silicon atoms
Organic group optionally from the compound of alkyl and alkoxy.
3. according to the method for claim 2, it is characterised in that the silane compound be selected from tetramethoxy-silicane,
N-propyl triethoxysilane, isobutyl triethoxy silane, trimethoxysilane, vinyltrimethoxy silane,
N-propyl trimethoxy silane, tetraethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, dimethylformamide dimethyl
TMOS, dimethyldiethoxysilane, second, isobutyl dimethoxy silane, Cyclohexylmethyldimethoxysilane, methyl
Isobutyl group dimethoxysilane, Dicyclohexyldimethoxysilane, phenyltrimethoxysila,e and dicyclopentyl dimethoxyl silicon
One or more in alkane.
4. according to the method for claim 1, it is characterised in that the diether compound is 1,3- diether compounds,
Its general structure is：
Wherein, R1And R2It is identical or different；R3~R8It is mutually the same or different, selected from hydrogen, halogen atom, straight or branched C1
One kind in~C20 alkyl, C3~C20 cycloalkyl, C6~C20 aryl, C7~C20 alkaryls, C7~C20 aralkyl, R3~R8
Group between can key be linked to be ring.
5. according to the method for claim 4, it is characterised in that the R1And R2It is C1~C20 straight chained alkyl.
6. according to the method for claim 4, it is characterised in that the diether compound be selected from 2,2- diisobutyls-
1,3- dimethoxy propanes, 2,2- diphenyl -1,3- dimethoxy propanes, 2,2- benzhydryl -1,3- dimethoxy propanes, 2-
Double (the cyclohexyl methyl) -1,3- dimethoxy propanes of isopropyl -2- isopentyl -1,3- dimethoxy propanes, 2,2-, 2,2- diisopropyls
Base -1,3- dimethoxy propanes, 2- isopropyl -2- cyclohexyl methyl -1,3- dimethoxy propanes, 2,2- diisobutyls -1,3- two
Ethoxy propane, 2,2- diisobutyl -1,3- dipropoxies propane, 2- isopropyl -2- isopentyl -1,3- di ethyl propyl ethers,
One kind in 2- isopropyls -2- isopentyl -1,3- dipropoxies propane and double (the cyclohexyl methyl) -1,3- di ethyl propyl ethers of 2,2-
It is or a variety of.
7. the method according to any one in claim 1~6, it is characterised in that institute before propylene polymerization in the first stage
State the first external electron donor and participate in Propylene Pre-polymerization, second external electron donor participates in premix before second stage propylene polymerization
Close.
8. the method according to any one in claim 1~6, it is characterised in that by matrix resin polypropylene, antistatic
Agent CNT, organic chemistry foaming agent, Cell-controlling agents and optional additive melt blending, extrusion at 150~280 DEG C
The polypropylene foamed plate or sheet material is made with foaming.
9. the method according to any one in claim 1~6, it is characterised in that the antistatic additive is by including
The modified obtained modified carbon nano-tube of three steps of microwave radiation under ball milling, acidifying and reducing atmosphere.
10. according to the method for claim 9, it is characterised in that the ball milling is to use weight ratio as 150~400:1
Agate ball mixed with CNT after on ball mill with 170-290rpm rotating speed ball milling 0.5h-2h.
11. according to the method for claim 9, it is characterised in that microwave radiation is included in selected from hydrogen under the reducing atmosphere
Microwave radiation processing acidification step obtains under one or more reducing atmospheres in gas, methane, ethane, acetylene and carbon monoxide
Carboxylic carbon nano-tube.
12. it is a kind of such as any one methods described is prepared in claim 1~11 antistatic polypropylene foaming plate or
Sheet material.
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| CN1298887A (en) * | 1999-12-06 | 2001-06-13 | 中国石油化工集团公司 | Catalyst system for polymerization or copolymerization of olefine |
| CN102532380A (en) * | 2010-12-24 | 2012-07-04 | 中国石油化工股份有限公司 | Method for preparing high-fluidity anti-impact polypropylene |
| CN102888055A (en) * | 2011-07-21 | 2013-01-23 | 中国石油化工股份有限公司 | High-melt strength polypropylene foam material and preparation method thereof |
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| CN1298887A (en) * | 1999-12-06 | 2001-06-13 | 中国石油化工集团公司 | Catalyst system for polymerization or copolymerization of olefine |
| CN102532380A (en) * | 2010-12-24 | 2012-07-04 | 中国石油化工股份有限公司 | Method for preparing high-fluidity anti-impact polypropylene |
| CN102888055A (en) * | 2011-07-21 | 2013-01-23 | 中国石油化工股份有限公司 | High-melt strength polypropylene foam material and preparation method thereof |
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