CN102888055A - High-melt strength polypropylene foam material and preparation method thereof - Google Patents
High-melt strength polypropylene foam material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-melt strength polypropylene foam material and a preparation method thereof. The matrix resin of the foam material is high-melt strength polypropylene. The high-melt strength polypropylene foam material has the following characteristics: (1) the melt index (190 DEGC/2.16kg) is 1.0-10g/min; (2) the molecular weight distribution Mw/Mn is 6-20; (3) the content of the molecules with molecular weight over 5 million is greater than or equal to 0.8% by weight; and (4) (Mz+1)/Mn is greater than or equal to 70. The foam material is prepared by premix melting, blending and foaming of the following components in parts by weight: 100 parts of high-melt strength polypropylene and 1-15 parts of foaming agent. The obtained foam material meets the environmental protection requirements of degradability, uniform cell, high physical heat resistance, low production cost and smooth surface, and is suitable for continuous large-scale production.
Description
Technical field
The present invention relates to field of polymer technology, say further, relate to a kind of high melt strength, propylene foam material and preparation method.
Background technology
The polymer foaming plastics mainly comprise urethane, polystyrene and polyethylene etc. soft with the rigid foam three major types.Polyurethane foamed material is a kind of foam materials commonly used, but not as comprising the easy thermoforming of thermoplastic polymer foam of polypropylene (PP).Polystyrene foamed goods rebound resilience is poor, and extrusion foaming product rigidity is high, easily efflorescence, and waste is lightweight, and volume is large, and is ageing-resistant, anticorrosive, stable chemical nature, be difficult for being degraded by microorganisms, enter soil after, soil property is degenerated, method with burning is processed, carbonic acid gas and other obnoxious flavour can be produced, also disadvantageous Greenhouse effect can be caused, also can polluted air.Polyethylene foamed has overcome that common expanded plastic is frangible, the shortcoming of distortion, and the plurality of advantages such as have water proof protection against the tide, shockproof, sound insulation, insulation, plasticity is good, toughness is strong also has good chemical resistance.But compare the polypropylene-base foam material, the modulus in flexure that polyethylene is lower causes product surface rigidity and rebound resilience relatively poor, and polyethylene foam-material often uses the crosslinking preparation, so the waste chemical stable in properties, be difficult for being degraded by microorganisms, and the recovery that can not circulate is used.By contrast, non-cross-linking PP foam material is with its good mechanical property and environmental-protecting performance: good thermotolerance, use temperature can reach 130 ℃; Product size stability under the high temperature, Vicat softening point can reach 160 ℃; Good mechanical property, modulus in flexure is high, and has good impact resistance; Environment friendly is outstanding, emits without poison gas during burning, is easy to reclaim, and can reuse; And has a good chemical resistance.
The raw material base resin of polypropylene foamed plate adopts grafting or blend to obtain more, and the mechanical properties of polymer that exists the kneading of the degradation modification of polypropylene basis resin and multiple poly-platform thing to cause descends, and makes the problem such as tooling cost rising.Recently, high melt strength, propylene (HMSPP) is considered to make the best base resin of polypropylene foam material.Compare with general purpose polypropylene, high melt strength, propylene has higher extension and shear viscosity under melted state.When making foam material, this characteristic is particularly important, because the air bubble expansion stage under the depressurization, high fondant-strength allows the whole polynuclear plane of polymer support foam, reduce the relevant problems such as bubble merging, specific rheology allows the stable increase of the bubble in the foam expansion process.1994, BASELL (Basel) company released high bath strength acrylic resin and successfully is used for the polypropylene expanded technique of serialization, and this is so that the polypropylene expanded technique of serialization obtains important breakthrough.But the Basel has used the x ray irradiation x modifying process, because the uncontrollability of each irradiation process, cause the polyacrylic product performance of the high melt of grafting long-chain branch unstable, step is comparatively loaded down with trivial details, has also increased undoubtedly cost, and is difficult to promote in PP foaming plate field.The Dapoly of Borealis series high melt strength, propylene product, by being lower than near the melt temperature, add the virgin pp particle that the propylene monomer polymerization of superoxide obtains, obtain noncrosslinking long-chain branch polypropylene, but aftertreatment technology is unstable, causes foamed products unstable.Therefore, adopting the reactor of a plurality of series connection to prepare broad molecular weight distribution polypropylene commonly uses the most, it is normally selecting different amounts of hydrogen, different comonomers, namely be conducive to produce the polypropylene that obtains wide molecular weight distribution (MWD) in the different reactor of differing molecular weight polymers by the series connection polymerization, for example: wherein a kind of reactor is conducive to produce the polymkeric substance of higher molecular weight, and another kind of reactor then is conducive to produce the polymkeric substance of lower molecular weight.In order to obtain the performance of best propene polymer, the polymer product of optimization should contain a certain amount of very high-molecular weight polymer and a certain amount of low-molecular weight polymer.So the high melt strength, propylene that use reactor original position mass polymerization obtains has broad application prospects in PP foaming field owing to its excellent product stability and over-all properties.
The PP foaming plate mainly adopts extrusion method to carry out forming process.Extrusion moulding has very high production efficiency, and easily realizes automatization.Early stage PP foaming plate mostly is and adopts two step foam shaping by extrusion methods of crosslinking process prepared.Being about to the PP resin fully mixes with whipping agent, linking agent, nucleator etc., then extrude at forcing machine and be sheet material, the PP sheet material that will not foam subsequently carries out crosslinked, in foaming furnace, carry out again foaming, crosslinkedly can adopt radiation crosslinking and two kinds of methods of chemically crosslinked, the crosslinked speed that its melt viscosity along with temperature raise and reduce of resin before foaming is slack-off, thereby has suitable melt viscosity in wide temperature range.This method is separately carried out batch mixing and foaming, and forcing machine only carries out the mixing of foaming component, and the polypropylene foam material that the method obtains easily pollutes environment owing to crosslinked not reproducible utilization.Chinese patent CN201010134664.9 (application on March 26th, 2010) discloses a kind of novel high-rate crosslinking foaming polypropylene board and preparation method thereof.This high-rate crosslinking foaming polypropylene board comprises acrylic resin, linking agent, antiaging agent and whipping agent master batch, utilize irradiation method to overcome temperature and be higher than the rapid downward trend of melt strength of polypropylene behind the fusing point, prepared the product of excellent property, the performance such as tensile strength, elongation at break of material all is significantly improved.But the method is a kind of crosslinking prepares polypropylene foam material, obtains expanded polypropylene and does not have returnability, not recyclable as packing and automotive material use, will cause environmental pollution.Similar patent also has Chinese patent CN101081914A and CN1131277C.
In recent years, the direct extrusion foaming forming method sheet material of PP is in widespread attention.Directly the extrusion foaming method is directly to finish mixing, melting and the foaming process of each component of foaming in forcing machine, can be referred to as again a step foam shaping by extrusion method.Difference according to the employing whipping agent, directly the foam shaping by extrusion method can be divided into again physical blowing and two kinds of methods of chemical foaming, no matter which kind of method of employing, common control elements is to set up sufficiently high head pressure to suppress near foaming system in advance foaming extrusion neck ring mold, in case foaming system admission port mould will the release of pressure foaming.According to publication, be not quite similar on concrete expressing technique, energy consumption and the equipment requirements.
It is 4 times or larger polypropylene-base foaming plate that Chinese patent CN99123626.2 (application on October 28th, 1999) discloses a kind of ratio of expansion, has good light weight performance and the harmony of rigidity.CN01145171.8 (application on November 28 calendar year 2001) discloses and has a kind ofly wherein effectively prevented the sheet material abscess breakage, the surface smoothness excellence in the foaming layer, and the method for this sheet material of stably manufactured.Although above two kinds of technical schemes can both be prepared the polypropylene foamed plate of surfacing, need at least one surface layer to press one deck surface lining, this has increased the requirement of machinery and the complicacy of technique.
Chinese patent CN99111834.0 (application on July 30th, 1999) discloses a kind of method of producing the non-cross-linking PP based resin foam sheet, the extrusion foaming device that is located between forcing machine and die head and is taken over the toothed gear pump that is connected by die head is used in this invention, so that might produce the foam piece of Aphron and good appearance, have remarkable productivity and extrude stability and boost productivity, reduce the corrugated or the accordion-like defective that occur in the sheet material end.But before the mouth mould, increase toothed gear pump, improved production cost and the energy consumption of foaming plate.
US Patent No. 6251319 (application on April 30th, 1999) discloses a kind of method for preparing polypropylene foamed plate, use high bath strength acrylic resin and the inflammable whipping agent butane of volatility, expansion ratio is 4-56 times, but owing to using combustiblematerials as whipping agent, equipment and corresponding factory building must be through special technological processing for explosion protection features, so the cost of polypropylene foam material is higher.
Summary of the invention
For solving problems of the prior art, the invention provides a kind of high melt strength, propylene foam material and preparation method.The degradable, abscess that the foam material that obtains meets environmental requirement evenly, the physics thermotolerance is high, production cost is low, the polypropylene foamed plate of smooth surface and suitable serialization scale production.
One of purpose of the present invention provides a kind of high melt strength, propylene foam material.
The matrix resin of described foam material is high melt strength, propylene;
Described high melt strength, propylene has following characteristics:
(1) melting index (190 ℃/2.16kg) be 1.0-10g/min, be preferably 1.6-6g/min, more preferably 2.5-6g/min;
(2) molecular weight distribution M
w/ M
n=6-20; Preferred 9.0-16.0;
(3) molecular weight greater than the content of 5,000,000 fractions more than or equal to 0.8wt%, preferably greater than or equal to 1.0wt%, more preferably greater than or equal 1.5wt%;
(4) M
Z+1/ M
nMore than or equal to 70, preferably greater than or equal to 80;
Preferably,
The molecular weight of described high melt strength, propylene more than or equal to 15.0wt%, is less than or equal to 40wt% less than the content of 50,000 fractions, more preferably greater than or equal 17.5wt%, be less than or equal to 30wt%.
Above-described high melt strength, propylene, its melt strength can be greater than 0.8 newton, even can surpass 2.2 newton, mainly can be used for preparing foaming product, biaxially oriented film, articles thermoformed therefrom and blow-molded article.
The polypropylene of described high fondant-strength is realized by the following method:
At the different propylene polymerization of serial operation in the stage, requirement according to the different molecular weight fraction, by external electron donor component in the control Ziegler-Natta catalyst system in kind and the ratio in differential responses stage, the preferably control of binding molecule amount conditioning agent consumption, can prepare the polypropylene that has wide molecular weight distribution and contain the ultra high molecular weight fraction, have good mechanical property, particularly have very high melt strength.
Be included in the reactor of two or more serial operations, carry out the equal polymerization reaction of two stages or above propylene of two stages:
Fs: Ziegler-Natta catalyst exists lower, under the polymerization temperature, lower hydrogen content (less than or equal to 300ppmV) or no hydrogen, carry out the equal polymerization reaction of propylene, obtaining MFR is 0.01-0.3g/10min, described Ziegler-Natta catalyst is the reaction product of following component basically, (1) a kind of a kind of organoaluminum component in ingredient of solid catalyst, (2), (3) first external electron donor components take magnesium, titanium, halogen and internal electron donor as main ingredient; Wherein the ratio between component (1) and the component (2) is counted with aluminium/titanium ratio: 10～500 (weight ratios); Ratio between organoaluminum (2) and the first external electron donor component is 10～150 (weight ratios).
Subordinate phase: on the basis of fs resultant of reaction, hydrogen exists lower, adds the equal polymerization reaction that the second external electron donor component is carried out propylene, and the MFR of final polymkeric substance is 0.1-10g/min; The amount that fills into the second external electron donor component is definite by the amount of the organoaluminum component of fs adding, and the ratio between organoaluminum component and the second external electron donor component is 1～50 (weight ratio).
The first external electron donor component such as R wherein
1 nSi (OR
2)
4-nShown in, R is identical or different in the formula, is C
3-C
6Aliphatic group branching or ring-type; R
2Be C
1-C
3Linear aliphatic group, for example methyl, ethyl or propyl group; N is 1 or 2.
The second external electron donor component such as general formula R wherein
3 nSi (OR
4)
4-nShown in, n is 0 or 1 or 2, R in the formula
3And R
4Be identical or different C
1-C
3The linear aliphatic group; Or be R such as general formula
5R
6Si (OR
7)
2Shown in, R in the general formula
7Be C
1-C
3The linear aliphatic group, R
5Be C
1-C
3The linear aliphatic group, R
6Be C
3-C
6Aliphatic group branching or ring-type.
The hydrogen add-on of fs and subordinate phase is controlled with the requirement of final melting index.
Wherein the productivity ratio of fs and subordinate phase is 30: 70～70: 30, is preferably 65: 35～55: 45.
In polymerisation process of the present invention, the catalyzer of propylene polymerization includes but are not limited to Ziegler-Natta catalyst.The Ziegler-Natta catalyst that uses is by open in a large number, the catalyzer that preferably has high stereoselective, " Ziegler-Natta catalyst of high stereoselective " described herein refer to prepare isotactic index greater than 95% alfon.This type of catalyzer contains (1) ingredient of solid catalyst usually, is preferably the solid catalyst active ingredient of titaniferous; (2) organo-aluminium compound cocatalyst component; (3) external electron donor component.
The specific examples that operational this class contains active solid catalyst component (1) is disclosed in Chinese patent CN85100997, CN98126383.6, CN98111780.5, CN98126385.2, CN93102795.0, CN00109216.2, CN99125566.6, CN99125567.4, CN02100900.7.Described catalyzer can directly use, also can be through adding after pre-complexing and/or the prepolymerization.Catalyzer described in Chinese patent CN85100997, CN93102795.0, CN98111780.5 and the CN02100900.7 is used for high melt strength, propylene preparation method of the present invention and has especially advantage.
Described cocatalyst component (2) is organo-aluminium compound, the preferred alkyl aluminum compound, more preferably trialkylaluminium, as: triethyl aluminum, triisobutyl aluminium, three n-butylaluminum etc., the ratio of solids containing titanium catalyst component and organo-aluminium compound cocatalyst component wherein is take the Ti/Al molar ratio computing as 1: 25～1: 100.
According to the requirement to the different molecular weight fraction, in different reactor, add the external electron donor with different qualities.Particularly, in fs namely in the first reactor, the present invention need to prepare the propene polymer of high molecular weight block, has the taxis of higher molecular weight and Geng Gao in order to make this fraction, selected a kind of have than low hydrogen transfer the susceptibility external electron donor, it is such as R
1 nSi (OR
2)
4-nShown in, R is identical or different in the formula, is C
3-C
6Aliphatic group branching or ring-type, preferred R
1Be cyclopentyl, sec.-propyl or cyclohexyl; R
2Be C
1-C
3Linear aliphatic group, for example methyl, ethyl or propyl group; N is 1 or 2, is preferably 2.Particular compound is such as dicyclopentyl dimethoxyl silane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane etc.
The MFR value of fs resulting polymers is controlled at 0.01-0.3g/10min, according to actual needs, usually be chosen in the molecular weight regulator that the first reactor does not add molecular weight regulator or adds minute quantity (less than or equal to 300ppmV), such as hydrogen, in order to obtain the fraction of higher molecular weight.
On the basis of fs polyreaction resultant, add the second external electron donor component and molecular weight regulator (hydrogen) carries out the polyreaction of subordinate phase, and the MFR value of controlling final polymkeric substance is controlled to be 0.1-10g/min.
The general formula of the second external electron donor component is R
3 nSi (OR
4)
4-n, n is 0 or 1 or 2 in the formula.R in the general formula
3And R
4Be identical or different C
1-C
3Linear aliphatic group, for example methyl, ethyl or propyl group.Specifically can include but are not limited to tetramethoxy-silicane, tetraethoxysilane, trimethylammonium methoxy silane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane etc.The general formula of the second external electron donor component is R
5R
6Si (OR
7)
2, R in the general formula
7Be C
1-C
3The linear aliphatic group, R
5Be C
1-C
3The linear aliphatic group, R
6Be C
3-C
6Aliphatic group branching or ring-type, for example methylcyclohexyl dimethoxy silane.
The polyreaction of the different steps described in the polymerization process of high melt strength, propylene of the present invention can be carried out in different reactors respectively.A concrete embodiment is: the polyreaction of fs is carried out in the first reactor, and the polyreaction of subordinate phase is carried out in the second reactor.In the first reactor, add: (1) a kind of a kind of organoaluminum component in ingredient of solid catalyst, (2), (3) first external electron donor components take magnesium, titanium, halogen and internal electron donor as main ingredient, under the condition of no hydrogen, carry out the equal polymerization reaction of propylene, the gained polymerisate is introduced the second reactor, add the second external electron donor component, in the presence of certain hydrogen, carry out the equal polymerization reaction of further propylene.
In the first reactor, described three kinds of catalyst components can directly join in the first reactor, after the pre-complexing and/or prepolymerization that also can know altogether through industry, join in the first reactor again.Wherein the form of the reactor of pre-complex reaction can be various, its objective is and make catalyst components can obtain fully effectively to mix, can be continuous stirred tank reactor, annular-pipe reactor, contain one section pipeline of static mixer, even also can be the pipeline that one section material is in turbulence state.
The temperature control of pre-complexing is between-10～60 ℃, and preferred temperature is 0～30 ℃.The time of pre-complexing is controlled at 0.1～180min, and the preferred time is 5～30min.
Through or can also carry out randomly prepolymerization without the catalyzer of pre-complexing and process.Prepolymerization can be carried out under the liquid phase bulk conditions continuously, also can the inert solvent discontinuous carry out.Pre-polymerization reactor can be continuous stirred tank, annular-pipe reactor etc.Prepolymerized temperature control is between-10～60 ℃, and preferred temperature is 0～40 ℃.Prepolymerized multiple is controlled at 0.5～1000 times, and preferred multiple is 1.0～500 times.
Described polyreaction can be in the propylene liquid phase, or carries out in gas phase, or adopts liquid-gas combination technique to carry out.When carrying out liquid polymerization, polymerization temperature is 0～150 ℃, with 40～100 ℃ for well; Polymerization pressure should be higher than the saturated vapour pressure of propylene under corresponding polymerization temperature.Polymerization temperature is 0～150 ℃ when vapour phase polymerization, with 40～100 ℃ for well; Polymerization pressure can be normal pressure or higher, and preferred pressure is 1.0～3.0MPa (gauge pressure).
Polymerization can be to carry out continuously, also may be carried out batchwise.Successive polymerization can be Liquid-phase reactor or the Gas-phase reactor of two or more series connection, Liquid-phase reactor can be annular-pipe reactor or stirred-tank reactor, Gas-phase reactor can be horizontal type agitated bed reactor or vertical mixing bed bioreactor or fluidized-bed reactor etc., and above Liquid-phase reactor and Gas-phase reactor be matched combined at random also.
Above-described high melt strength, propylene is applied for a patent on January 22nd, 2010, the patent No. 201010000975.6 (a kind of preparation method of high melt strength, propylene), 201010000974.1 (polypropylene and goods thereof with high fondant-strength).All be incorporated herein by reference at this.
Described foam material is to be made by the Preblend melt blending foaming that comprises following component:
High melt strength, propylene 100 weight parts;
Whipping agent, 1～15 weight part, preferred 1～10 weight part, more preferably 5～7 weight parts;
Described whipping agent is azo foaming agent, a kind of in nitroso group foaming agent or the hydrazides class whipping agent, be preferably Cellmic C 121 (AC), Diisopropyl azodicarboxylate (AIBN), Barium azodicarboxylate (BaAC) and azodiformate, dinitroso pentamethylene tetramine (DPT), N, N '-dinitrosopentamethylene tetramine, N, N '-dimethyl-N, N-dinitrosoterephthalamine (NTA) and trinitroso-trimethylene triamine, 4,4 ' one OBSH (OBSH), tolylsulfonyl Urea,amino-(TSSC), three phosphorus base triazines (CTHT), a kind of in the 5-phenyltetrazole; Cellmic C 121 (AC) more preferably.
In the acrylic resin matrix, add whipping agent, can produce expanded polypropylene.The whipping agent that adds decomposes release gas under specified temp and pressure, form the structure of the blister of porous in the expandability materials such as resin.The most frequently used chemical foaming agent is the organic chemistry whipping agent, specifically comprise Cellmic C 121 (AC), Diisopropyl azodicarboxylate (AIBN), Barium azodicarboxylate (BaAC) and azodiformate, dinitroso pentamethylene tetramine (DPT), N, N '-dinitrosopentamethylene tetramine, N, N '-dimethyl-N, N-dinitrosoterephthalamine (NTA) and trinitroso-trimethylene triamine, 4,4 ' one OBSH (OBSH), tolylsulfonyl Urea,amino-(TSSC), three phosphorus base triazines (CTHT), 5-phenyltetrazole etc.The characteristics such as chemical foaming agent prepares foaming plate and has surfacing, and abscess is evenly fine and close, and expansion ratio is low and controlled are widely used in automotive trim, food, household electrical appliances and electronic packaging etc.
In order to control foaming, need to add the abscess control agent, the abscess control agent is the abscess control agent that usually adopts in polypropylene expanded, as: a kind of or combination in talcum powder, aluminium hydroxide, silicon-dioxide, zeolite, the borax; The consumption of abscess control agent also is the common consumption in polypropylene expanded, can preferred 5～20 weight parts, more preferably 5～15 weight parts.
Can also be according to the needs of concrete processing, in prescription, add polypropylene expanded in processing aid commonly used, such as oxidation inhibitor, aid anti-oxidants, lubricant, pigment etc., its consumption is conventional amount used, or adjusts according to the requirement of practical situation.
Two of purpose of the present invention provides a kind of preparation method of described high melt strength, propylene foam material.Comprise: described component is made described high melt strength, propylene foam material after by described consumption melt blending, shaping foam.
Concrete steps are as follows:
Adopt high speed agitator with high melt strength, propylene, whipping agent, various processing aids carry out batch mixing by the weight ratio of prescription, obtain the Preblend of polypropylene foamed plate, Preblend is dropped in the hopper of extruding machine, the temperature of forcing machine is raised to 150～280 ℃, make polypropylene expanded material melting, preferred range is 160～180 ℃, make the particle melting, screw speed is 15-180rpm, makes the plasticized polypropylene resin to 150～280 ℃, preferred 160～180 ℃ T connector die extrusion, flow in the plate squeezing unit two roller board splittves and go, after being rolled into the sheet material, naturally cooling to room temperature, be cut on demand certain specification sheet material, be the polypropylene foamed plate finished product.
The forcing machine that adopts among the preparation method can be a kind of in the single screw extrusion machine, parallel dual-screw extruding machine, parallel dual-screw extruding machine Series Sheet screw extrusion press, counter rotation twin screw extruder, conical double screw extruder, three-screw extruder of single screw extrusion machine, two series connection forms.The mouth mould can be the flat port mould according to actual needs, T shape mouth mould, the various shapes such as circular orifices mould or annular mouth mould.The polypropylene resin composite of melting expands after discharging from the flat port mould, and the three-roller calendar by can the dancer rools spacing, and is big or small by control mouthful mould, obtains polypropylene foamed plate or the sheet material of desired thickness.In addition, the polypropene composition of melting expands after annular mouth mould is discharged, and after inflation and inside and outside cooling, dissects vertically rear rolling, obtains the polypropylene foamed plate of desired thickness.For the work to forcing machine is controlled better, the forcing machine of selling on the market now all is section to its internal separation, and can control each section temperature.
In the polypropylene material extrusion and foaming process of the present invention, material melt blending temperature is used blending temperature in the common homo-polypropylene processing, should select not only guaranteeing the complete melting of homo-polypropylene matrix but also can not make in the scope of its decomposition, be generally 160 ℃～250 ℃.But therefore the decomposition temperature of industrial AC whipping agent, considers the decomposition temperature of processibility and AC whipping agent at 150～205 ℃, the processing temperature that the processing temperature optimization polypropylene is lower, namely 160～180 ℃.
Utilize the polypropylene foam material of present method preparation, have that cost is low, abscess is fine and close, the advantage such as even aperture distribution and surfacing can be applicable to the occasions that lightweight has higher requirements to plastics such as trolley part, food and electronic packaging and building decoration.
Compared with prior art the present invention has following beneficial effect:
1) high melt strength, propylene that obtains of the multistep mass polymerization used of the present invention has higher melt strength, greater than 0.8 newton, even can surpass 2.2 newton.
2) the present invention is take the high melt strength, propylene of the wide molecular weight distribution of mass polymerization as raw material, realize the stabilization of pp material, so that the foaming window effectively enlarges, technique is easy to adjust, can prepare the surface smooth from skinning, cell diameter is even, the closed pore hard structure, and density is 0.4-0.8g cm
-3, thickness is the polypropylene foam material of 0.1-40mm, 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.
2) to adopt general azo be the AC whipping agent in the present invention, compares with using the fluorinated whipping agent in the prior art, has environmental friendliness, do not destroy the advantages such as atmospheric layer.
3) foaming polypropylene sheet of making is the non-crosslinked structure, can recycle according to general polypropylene modified material, does not cause secondary pollution, meets the requirement of recycling economy.
Description of drawings
The high melt strength, propylene foam material surface electromicroscopic photograph of Fig. 1 embodiment 1
The high melt strength, propylene foam material cross section electromicroscopic photograph of Fig. 2 embodiment 1
The polypropylene foam material surface electromicroscopic photograph of Fig. 3 Comparative Examples 1
The polypropylene foam material cross section electromicroscopic photograph of Fig. 4 Comparative Examples 1
Embodiment
Below in conjunction with embodiment, further specify the present invention.
Raw material in following examples and the comparative example and the instrument that uses and equipment comprise:
Common high melt strength, propylene
Borealis (Borealis), the trade mark, Daploy series, WB140HMS.
Plain polypropylene:
The China petroleum Chemicals Co., Ltd. Town Hai Lian Hua branched Corporation, trade mark T30S;
Sub-petrochemical industry branch office, trade mark F401 raise in Sinopec Group.
Cellmic C 121: technical grade, Shenzhen Jitian's chemical industry company limited, blowing temperature 160-180 ℃;
Dinitroso pentamethylene tetramine: Sigma-Aldrich;
4,4 '-OBSH: Sigma-Aldrich;
High molecular polysiloxane MB50-002: Dow corning company;
Other are raw materials used be commercially available.
Produce and testing apparatus:
Twin screw extruder: ZSK-25, German WP company;
Melt stretching testing machine: Rheotens
TM97, German Goettfert company;
Density tester: CPA225D, density annex YDK01, German Satorius company.
Density measurement: use the density annex of Satorius balance, utilize drainage to obtain the density of polypropylene basis resin and polypropylene foamed plate.The expansion ratio of the polypropylene foam material that obtains calculates with formula: b=ρ 1/ ρ 2, and wherein, b is expansion ratio, and ρ 1 is the density of polypropylene basis resin, and ρ 2 is the apparent density of foam material.
The preparation of high melt strength, propylene:
HMSPP101
Polyreaction is carried out at a cover polypropylene pilot plant.Its major equipment comprises prepolymerization reactor, first ring pipe reactor and the second annular-pipe reactor.Polymerization process and step are as follows:
(1) prepolymerization:
Primary Catalysts (the solid catalyst active ingredient of titaniferous) adopts the method that embodiment 1 describes among the Chinese patent CN93102795 to obtain its Ti content: 2.4wt%, Mg content 18.0wt%, n-butyl phthalate content: 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 and 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 the pre-polymerization multiple of catalyzer is that approximately 120-150 is doubly under this condition.The triethyl aluminum flow that advances prepolymerization reactor is 6.33g/hr, and two cyclopentyl dimethoxy silane flows are 0.33g/hr, and the Primary Catalysts flow is about 0.01g/hr.
(2) the equal polymerization of propylene:
The pre-polymerization rear catalyst enters in the annular-pipe reactor of two series connection, finishes the equal polymerization reaction of propylene in annular-pipe reactor.70 ℃ of two endless tube polymeric reaction temperatures, reaction pressure 4.0MPa.The processing condition of gate ring pipe reactor, the productivity ratio that makes first, second endless tube is approximately 45: 55.
Do not add hydrogen in the charging of first ring pipe reactor, 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 the first ring pipe reactor after prepolymerization, the first ring pipe reactor no longer includes any other charging except propylene, therefore, triethyl aluminum/dicyclopentyl dimethoxyl silane (Al/Si-I) is 19.0 (weight ratios) than the ratio that is in the catalyst prepolymer in the first ring pipe reactor.
Add the tetraethoxysilane (TEOS) into 0.67g/hr in the second annular-pipe reactor, therefore, triethyl aluminum/tetraethoxysilane in the second annular-pipe reactor (Al/Si-II) is than being 9.4 (weight ratios).The concrete technology condition sees Table 1,
Through after flash separation goes out propylene, remove again the active and heat drying of the catalyzer of unreacted device from the second endless tube polymkeric substance out through wet nitrogen, obtain high melt strength, propylene.Performance perameter sees Table 2.
HMSPP102
With embodiment 1, just in the additional propylene feed of first ring pipe reactor, add a small amount of hydrogen, the density of hydrogen that on-line chromatograph detects is 230ppmV.The hydrogen feed amount is adjusted into 8500ppmV in the additional propylene feed of the second annular-pipe reactor.By adjusting the external electron donor inlet amount, Al/Si-I is adjusted into 45 (weight ratios), Al/Si-II is adjusted into 4.2 (weight ratios).The add-on of promotor triethyl aluminum is constant.
Table 1
Table 2
Embodiment 1～12
Formula ratio high melt strength, propylene, whipping agent, abscess control agent and processing aid etc. are put into the homogenizer high speed mixed 1 minute, rear adding middle layer twin screw, moment of torsion are controlled at about 65%, rotating speed: 10-170rpm.Described processing aid comprises antioxidant 1010 (BASF AG), irgasfos 168 (BASF AG) etc., and the prescription consumption sees Table 3.Adopt concrete GB/T 1033.1-2008 to carry out density measurement, referring to table 3.
Table 3
Zero is smooth or abscess is fine and close, and * surface irregularity or abscess are sparse inhomogeneous
Comparative Examples 1-3:
Adopt Borealis to produce high melt strength, propylene WB140HMS and replace HMSPP, specifically fill a prescription referring to table 3.
Comparative Examples 4-6:
Adopt homo-polypropylene T30S to replace high melt polypropylene HMSPP, specifically fill a prescription referring to table 3.
Comparative Examples 7-9
Adopt homo-polypropylene F401 to replace high melt polypropylene HMSPP, specifically fill a prescription referring to table 3.
Can find out by embodiment 1～12, foam material take homemade high melt strength, propylene as base resin, all have good foaming effect, just can prepare surfacing, the polypropylene foam material of foam structure homogeneous when adding 1 part of technical grade AC whipping agent.In the situation that foaming agent consumption is identical, the more common high melt strength, propylene of foaming effect is better, and density is less, can obviously find out by electromicroscopic photograph, and high melt strength, propylene foam material of the present invention surfacing, abscess is fine and close.Can find out by Comparative Examples 1-9, compare high melt strength, propylene HMSPP, the density that obtains goods with WB140HMS is larger, under differing temps, obtain foaming plate density larger and rough, abscess is inhomogeneous, be that building-up process adds the high melt strength, propylene that superoxide obtains mainly due to WB140HMS, product is unstable to be caused.In addition, high melt strength, propylene HMSPP has wider blowing temperature window with respect to general purpose polypropylene T30S and F401, and more smooth with the surface of HMSPP goods under the addition, abscess is more even.
Claims (17)
1. high melt strength, propylene foam material is characterized in that:
The matrix resin of described foam material is high melt strength, propylene;
Described high melt strength, propylene has following characteristics:
(1) melting index (190 ℃/2.16kg) be 1.0-10g/min;
(2) molecular weight distribution M
w/ M
n=6-20;
(3) molecular weight greater than the content of 5,000,000 fractions more than or equal to 0.8wt%;
(4) M
Z+1/ M
nMore than or equal to 70.
2. high melt strength, propylene foam material as claimed in claim 1 is characterized in that:
The molecular weight of described high melt strength, propylene greater than the content of 5,000,000 fractions more than or equal to 1.0wt%.
3. high melt strength, propylene foam material as claimed in claim 2 is characterized in that:
The molecular weight of described high melt strength, propylene greater than the content of 5,000,000 fractions more than or equal to 1.5wt%.
4. high melt strength, propylene foam material as claimed in claim 1 is characterized in that:
The M of described high melt strength, propylene
Z+1/ M
nMore than or equal to 80.
5. high melt strength, propylene foam material as claimed in claim 1 is characterized in that:
The melting index of described high melt strength, propylene (190 ℃/2.16kg) be 1.6-6g/min.
6. high melt strength, propylene foam material as claimed in claim 5 is characterized in that:
The melting index of described high melt strength, propylene (190 ℃/2.16kg) be 2.5-6g/min.
7. high melt strength, propylene foam material as claimed in claim 1 is characterized in that:
The molecular weight of described high melt strength, propylene more than or equal to 15.0wt%, is less than or equal to 40% less than the content of 50,000 fractions.
8. high melt strength, propylene foam material as claimed in claim 7 is characterized in that:
The molecular weight of described high melt strength, propylene more than or equal to 17.5wt%, is less than or equal to 30% less than the content of 50,000 fractions.
9. high melt strength, propylene foam material as claimed in claim 1 is characterized in that:
The molecular weight distribution M of described high melt strength, propylene
w/ M
n=9.0-16.0.
10. high melt strength, propylene foam material as claimed in claim 1 is characterized in that:
Described high melt strength, propylene is by in the reactor of two serial operations, carries out the equal polymerization of two stage propylene and reacts to prepare, wherein:
Fs: Ziegler-Natta catalyst exists lower, under 50～100 ℃ the polymerization temperature, hydrogen content is less than or equal to 300ppmV, or under the no hydrogen condition, carry out the equal polymerization reaction of propylene, the MFR of resulting polymers is controlled to be 0.01-0.3g/10min, described Ziegler-Natta catalyst is the reaction product of following component: (1) a kind of ingredient of solid catalyst take magnesium, titanium, halogen and internal electron donor as main ingredient, (2) a kind of organoaluminum component, (3) first external electron donor components; Wherein the ratio between component (1) and the component (2) is counted with aluminium/titanium ratio: 10: 1～500: 1 (weight ratio); Ratio between organoaluminum and the first external electron donor component is 10: 1～150: 1 (weight ratio);
Subordinate phase: on the basis of fs resultant of reaction, hydrogen exists lower, adds the equal polymerization reaction that the second external electron donor component is proceeded propylene, and the MFR of final polymkeric substance is controlled to be 0.1-10g/min; The amount that fills into the second external electron donor component is definite by the amount of the organoaluminum component of fs adding, and the ratio between organoaluminum component and the second external electron donor component is 1: 1～50: 1 (weight ratio).
11. high melt strength, propylene foam material as claimed in claim 10 is characterized in that:
Described the first external electron donor is dicyclopentyl dimethoxyl silane and/or diisopropyl dimethoxy silane, and the second external electron donor is tetraethoxysilane and/or Cyclohexylmethyldimethoxysilane.
12. such as the described high melt strength, propylene foam material of one of claim 1～11, it is characterized in that:
Described foam material is to be made by the Preblend melt blending foaming that comprises following component:
High melt strength, propylene 100 weight parts;
Whipping agent 1～15 weight part.
Described whipping agent is a kind of in azo foaming agent, nitroso group foaming agent or the hydrazides class whipping agent.
13. high melt strength, propylene foam material as claimed in claim 12 is characterized in that:
Whipping agent 1～10 weight part.
14. high melt strength, propylene foam material as claimed in claim 13 is characterized in that:
Whipping agent 5～7 weight parts.
15. high melt strength, propylene foam material as claimed in claim 12 is characterized in that:
Described whipping agent is Cellmic C 121 (AC), Diisopropyl azodicarboxylate (AIBN), Barium azodicarboxylate (BaAC) and azodiformate, dinitroso pentamethylene tetramine (DPT), N, N '-dinitrosopentamethylene tetramine, N, N '-dimethyl-N, N-dinitrosoterephthalamine (NTA) and trinitroso-trimethylene triamine, 4,4 '-OBSH (OBSH), tolylsulfonyl Urea,amino-(TSSC), three phosphorus base triazines (CTHT), a kind of in the 5-phenyltetrazole.
16. high melt strength, propylene foam material as claimed in claim 15 is characterized in that:
Described whipping agent is Cellmic C 121 (AC).
17. the preparation method such as the described high melt strength, propylene foam material of one of claim 1～16 comprises:
Described component is made described high melt strength, propylene foam material after by described consumption melt blending, shaping foam.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1765976A (en) * | 2004-10-29 | 2006-05-03 | 中国石油化工股份有限公司 | Polypropylene foaming premix and its preparation method |
| CN101058654A (en) * | 2006-04-20 | 2007-10-24 | 中国石油化工股份有限公司 | Method of preparing high-performance polypropylene composition |
| US7365136B2 (en) * | 1997-09-26 | 2008-04-29 | Borealis Technology Oy | High melt strength polypropylene |
-
2011
- 2011-07-21 CN CN201110205680.7A patent/CN102888055B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7365136B2 (en) * | 1997-09-26 | 2008-04-29 | Borealis Technology Oy | High melt strength polypropylene |
| CN1765976A (en) * | 2004-10-29 | 2006-05-03 | 中国石油化工股份有限公司 | Polypropylene foaming premix and its preparation method |
| CN101058654A (en) * | 2006-04-20 | 2007-10-24 | 中国石油化工股份有限公司 | Method of preparing high-performance polypropylene composition |
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