CN1946781A - Ethylene-alpha-olefin copolymer for extrusive expansion molding and extrusive expansion molded product - Google Patents
Ethylene-alpha-olefin copolymer for extrusive expansion molding and extrusive expansion molded product Download PDFInfo
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- CN1946781A CN1946781A CNA2005800122690A CN200580012269A CN1946781A CN 1946781 A CN1946781 A CN 1946781A CN A2005800122690 A CNA2005800122690 A CN A2005800122690A CN 200580012269 A CN200580012269 A CN 200580012269A CN 1946781 A CN1946781 A CN 1946781A
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- extrusive expansion
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- olefin copolymer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—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 chemical blowing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
- C08J2201/03—Extrusion of the foamable blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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Abstract
A product of extrusion foam molding of an ethylene-alpha-olefin copolymer having a molecular weight distribution of 5 or greater and a swell ratio of 1.15 to 1.45. This molding product excels in appearance and mechanical strength.
Description
Technical field
The present invention relates to a kind of extrusive expansion molding and extrusive expansion molded product of ethene-alpha-olefin copolymer
Background technology
The extrusive expansion molding and extrusive expansion molded product that contains polyethylene-based resin is used to various uses such as wrapping material, cushioning material, core, thermal insulation material, wrapping material, material of construction because flexibility, impact absorbency, light weight, heat insulating ability are good always.But the extrusive expansion molding and extrusive expansion molded product of widely used hp-ldpe easily is known as corrugated periodically thickness inequality, outward appearance change up to now.
The spy opens and has put down in writing a kind of hp-ldpe extrusive expansion molding and extrusive expansion molded product in the 2001-347619 communique, and it has average bubble density is 15/9mm
2Above top layer, but outward appearance is bad.In addition, these moulding product because physical strength is not enough cracky.
The spy opens the foam of having put down in writing a kind of polymer composition in the 2000-119427 communique and with thermolysis type whipping agent this polymer composition foaming having been obtained, and wherein said polymer composition contains ethene-alpha-olefin copolymer, comprises the hydride and the olefin polymer of the segmented copolymer of polymerization of aromatic vinyl thing block and conjugated diolefin polymer block.Because this foam bubble size is big, surface smoothing is poor.In addition, because that above-mentioned polymer composition dissolves tension force is low, easy follicular rupture when extrusive expansion molding and extrusive expansion molded, therefore if make the high foam molded product of expansion ratio, because follicular rupture causes the surface easily coarse, the outward appearance of the foam molded product that obtains is not good.In addition, owing to follicular rupture makes the physical strength of the foam molded product that bubble becomes thick also poor.
Summary of the invention
The purpose of this invention is to provide a kind of extrusive expansion molding and extrusive expansion molded product, it contains ethene-alpha-olefin copolymer, and outward appearance and physical strength are good.
The invention provides a kind of extrusive expansion molding and extrusive expansion molded product, it contains, and molecular weight distribution is more than 5, swelling ratio is 1.15～1.45 ethene-alpha-olefin copolymer." extrusive expansion molding and extrusive expansion molded product " is meant the moulding product of making by extruded plastic foam in addition, in the present invention.In addition, in the following description, remove special declaration, " moulding product " promptly refer to " extrusive expansion molding and extrusive expansion molded product ".
Embodiment
Moulding product of the present invention contain ethene-alpha-olefin copolymer.This ethene-alpha-olefin copolymer is that ethene and more than one carbonatomss are the multipolymer of the alpha-olefin more than 3, and contains the structural unit from ethene that surpasses 50 weight %.The preferred carbonatoms of alpha-olefin is 4～12 alpha-olefin.
As alpha-olefin, can enumerate propylene, butene-1,4-methylpentene-1, hexene-1, octene-1, decylene-1 etc., preferred butene-1 and hexene-1.Consider special optimal ethylene-hexene-1 multipolymer from the angle of moulding product physical strength.
The molecular weight distribution that constitutes the ethene-alpha-olefin copolymer of moulding product of the present invention is more than 5, is preferably more than 6, more preferably more than 7.Too small as molecular weight distribution, then bubble becomes thick, because follicular rupture makes moulding product surface produce space, the degraded appearance of moulding product.Molecular weight distribution is preferably below 30, more preferably below 25, is preferably below 20 especially.Excessive as molecular weight distribution, then extrusive expansion molding and extrusive expansion molded product easily takes place wrinkling.
" molecular weight distribution " among the present invention is meant the ratio of weight-average molecular weight (Mw) and number-average molecular weight (Mn).Mn and Mw are tried to achieve by gel permeation chromatography (GPC).
The density that constitutes the ethene-alpha-olefin copolymer of moulding product of the present invention is preferably 890～940kg/m
3, 895～935kg/m more preferably
3, 900～930kg/m more preferably
3Low excessively as density, then the rigidity of moulding product reduces.In addition, too high as density, then the physical strength of moulding product reduces.
The swelling ratio (the following SR that slightly is designated as) that constitutes the ethene-alpha-olefin copolymer of moulding product of the present invention is 1.15～1.45, is preferably 1.15～1.40, more preferably 1.20～1.35.Less than 1.15, then bubble becomes thick as SR, because follicular rupture makes moulding product surface produce space, moulding product degraded appearance.As SR greater than 1.45, then take place wrinkling, moulding product degraded appearance.
Swelling ratio among the present invention is to be that 150 ℃, velocity of shear are 60.8s in temperature
-1Condition under the value measured, following in more detail mensuration.Use capillary rheometer (for example system CAPIROGRAPH-IB of the smart machine of Japan Co., Ltd.) during mensuration, it has the kapillary of diameter 1mm, long 40mm, fluid inlet angle 90 degree.According to JIS K 7199, be that 150 ℃, velocity of shear are 60.8s in temperature
-1Condition under, extrude the ethene-alpha-olefin copolymer of molten state continuously.The wire rod of extruding is cut off at the capillary outlet place, remove.Proceed then to extrude, when the wire rod length of newly extruding reaches 20mm when above, measure from the diameter of the wire rod of the position of the downward 15mm of capillary outlet.Use the laser extensometer to measure above-mentioned diameter.
Calculate SR by following formula.
SR＝D/D
0
Here, D represents the diameter (mm) of wire rod, D
0Represent diameter capillaceous (mm).
The flow-activation energy that constitutes the ethene-alpha-olefin copolymer of moulding product of the present invention is preferably more than the 40kJ/mol, more preferably more than the 50kJ/mol, more preferably more than the 55kJ/mol, is preferably more than the 60kJ/mol especially.Low excessively as flow-activation energy, then the speed of cooling of the molten state extrudate of being extruded by shaper is accelerated.Cause bubble state heterogeneity thus, moulding product degraded appearance, physical strength reduces simultaneously.
Consider that from the outward appearance of moulding product and the angle of physical strength the flow-activation energy of ethene-alpha-olefin copolymer is preferably below the 100kJ/mol, more preferably below the 90kJ/mol.
[mensuration of dynamic viscoelastic]
(mensuration of storage modulus (G '), out-of-phase modulus (G ")) is used the determination of viscoelasticity device to dynamic viscoelastic.The representative condition determination of dynamic viscoelastic is as follows:
(1) determination part shape: parallel plate (diameter 25mm, distance between plates: about 1mm)
(2) shear strain: 5%
(3) radian frequency: the set(ting)value in 0.1～100rad/ scope second
(4) temperature: 130 ℃, 150 ℃, 170 ℃, 190 ℃ (4 point)
Adding an amount of antioxidant in working sample in advance (as 200～10000ppm), measures and all carries out in nitrogen atmosphere.
[calculating of shift factor]
Shift factor (a
T) calculation procedure as follows:
With 130 ℃ (403 ° of K) as reference temperature (T
0), make G ' (Pa) and G " principal curve (Pa) according to formula (1) and (2).
G′(ω，T)＝b
TG′(a
Tω，T
0) (1)
G″(ω，T)＝b
TG″(a
Tω，T
0) (2)
Here, ω is radian frequency (rad/ second), and T measures temperature (K), T for each
0Be reference temperature, a
TBe the translational movement of radian frequency direction, b
TBe G ', G " axial translational movement.
[calculating of activation energy]
Flow-activation energy (Ea) is obtained according to the following steps:
With Log (a
T) 1/T is mapped.This figure is carried out linear regression according to method of least squares, calculate the collinear slope.The slope that obtains is considered as Ea/2.303R, calculates Ea (kJ/mol) (but about flow-activation energy reference example such as Polymer Engineering and Science, the 8th rolls up 235 pages (nineteen sixty-eight)).
The melt flow rate (MFR) (following note make MFR) of ethene-alpha-olefin copolymer under 190 ℃ that constitutes moulding product of the present invention is preferably 0.01～5g/10 minute, and more preferably 0.05～4g/10 minute, more preferably 0.1～3g/10 minute.MFR is the value of obtaining according to JIS K 6760.Low excessively as MFR, then the surface irregularity of moulding product can not get enough expansion ratios.Too high as MFR, then the bubble in the moulding product becomes thick, makes the formed body surface produce the space.
Manufacture method as the ethene-alpha-olefin copolymer that constitutes moulding product of the present invention, can be set forth in following metallocenes series catalysts exists down, with ethene and carbonatoms is the method that the alpha-olefin copolymer more than 3 closes, and described metallocenes series catalysts obtains promotor carrier (A), cross-linking type biindyl zirconium complex (B) and organo-aluminium compound (C) contact.
Above-mentioned promotor carrier (A) is by making (a) zinc ethyl, (b) fluoridize phenol, (c) water, (d) silicon-dioxide and (e) trimethyldisilazane (((CH
3)
3Si)
2NH) contact the carrier that obtains.
Mentioned component (a) and (b) and (c) usage quantity are not had special restriction, as the mol ratio of establishing each composition usage quantity is composition (a): composition (b): composition (c)=1: y: z, then preferred y and z satisfy following formula:
|2-y-2z|≤1
In the following formula, y is preferably 0.01～1.99 number, 0.10～1.80 number more preferably, and more preferably 0.20～1.50 number most preferably is 0.30～1.00 number.
Composition (d) is with respect to the usage quantity of composition (a), be preferably and make the mole number of the zinc atom that contains in the particle that obtains by composition (a) and (b), (c), (d) and contact (e) reach every 1g this particle 0.1mmol or above amount, more preferably make it reach the amount of 0.5～20mmol.Composition (e) is with respect to the usage quantity of composition (d), is preferably to make with respect to every 1g composition (d), and composition (e) reaches the above amount of 0.1mmol, more preferably makes it reach the amount of 0.5～20mmol.
Cross-linking type biindyl zirconium complex (B) is preferably racemize-ethylenebis (1-indenyl) zirconium dichloride and racemize-ethylenebis (1-indenyl) biphenol zirconium.
As organo-aluminium compound (C), preferred triisobutyl aluminium and tri-n-octylaluminium.
With respect to 1g promotor carrier (A), the usage quantity of cross-linking type biindyl zirconium complex (B) is preferably 5 * 10
-6～5 * 10
-4Mol.The usage quantity of organo-aluminium compound (C) is preferably and makes with respect to 1 mole of the zirconium atom of cross-linking type biindyl zirconium complex (B) in addition, and the aluminium atom of organo-aluminium compound (C) reaches 1～2000 mole amount.
As the polymerization process that is used to make ethene-alpha-olefin copolymer, be preferably formed ethene-alpha-olefin copolymer particulate continuous polymerization.As, continuous gas-phase polymerization, continuous slurry polymerization, continuous bulk polymerization, preferred continuous gas-phase polymerization.The gas phase polymerization device is generally the device with fluidized bed type reactive tank, preferably has the device of the fluidized bed type reactive tank that has amplifier section.Also agitating vane can be installed in the reactive tank.
Method as each composition of metallocenes series catalysts being added polymerization reaction trough adopts rare gas elementes such as nitrogen, argon, hydrogen, ethene etc. usually as carrier, in the method that does not have to supply with under the state of moisture content; With the method for each composition with the state supply of solution or slurry.Each composition of catalyzer both can be supplied with respectively, also can make any composition contact the back in advance with random order and supply with.
In addition, before carry out this polymerization, preferably carry out prepolymerization, the pre-polymerized catalyst composition that prepolymerization is obtained is used as this polymerization catalyst component or catalyzer.
Polymerization temperature is usually less than the melt temperature of the ethene-alpha-olefin copolymer of generation, is preferably 0～150 ℃, more preferably 30～100 ℃.In addition, in order to regulate the fluidity of molten of multipolymer, can add hydrogen as molecular weight regulator.Rare gas element also can coexist in mixed gas.
The whipping agent that uses when extrusive expansion molding and extrusive expansion molded product is made does not have special qualification, can use known pneumatogen, chemical foaming agent.Also can and use multiple whipping agent.
Pneumatogen has air, oxygen, nitrogen, carbonic acid gas, ethane, propane, normal butane, Trimethylmethane, Skellysolve A, iso-pentane, normal hexane, isohexane, hexanaphthene, heptane, ethene, propylene, water, sherwood oil, methyl chloride, chloric ethane, monochlorotrifluoromethane, Refrigerant 12, dichloro tetrafluoro ethane etc.Consider preferred carbonic acid gas or the nitrogen that uses wherein from the angle of economy and security.
It is whipping agent that chemical foaming agent has volatile salt, yellow soda ash, bicarbonate of ammonia, sodium bicarbonate, ammonium nitrite, sodium borohydride, Citric Acid, usp, Anhydrous Powder list sodium etc. inorganic; Cellmic C 121, barium azodicarboxylate, azo dibutyronitrile, nitro two guanidines, N, N-dinitrosopentamethylene tetramine, N, N '-dimethyl-N, N '-dinitrosoterephthalamine, p-toluene sulfonyl hydrazide, p-toluene sulfonylsemicarbazide, p, p '-oxybis-benzenesulfonyl hydrazide, Diisopropyl azodicarboxylate, p, organic system whipping agents such as the two phenylsulfonamido ureas of p '-oxygen, 5-phenyltetrazole, trihydrazinotriazine, hydrazo-dicarbonamide etc.Consider preferred Cellmic C 121, sodium bicarbonate, the p '-oxybis-benzenesulfonyl hydrazide that uses wherein from the viewpoint of economy and security.Because the mold temperature wide ranges can obtain the fine extrusion moulding product of bubble, the preferred especially whipping agent that contains Cellmic C 121 and sodium bicarbonate that uses.
When using chemical foaming agent, using decomposition temperature usually is 140～180 ℃ chemical foaming agent.When using decomposition temperature to be higher than 180 ℃ chemical foaming agent, preferably by and use frothing aid, make decomposition temperature reduce to use below 180 ℃.As frothing aid, can enumerate metal oxides such as zinc oxide, plumbous oxide; Metal carbonates such as zinc carbonate; Metal chlorides such as zinc chloride; Urea; Zinic stearas; Lead stearate; Dibasic lead stearate; Zinc laurate; 2 ethyl hexanoic acid zinc; Metallic soaps such as two alkali formula phthalic acid lead; Organo-tin compounds such as dibutyl tin laurate, two toxilic acid dibutyl tins; Inorganic salts such as tribasic lead sulfate, dibasic lead phosphite and basic lead sulfite; Polyvinyl-chloride use one package stabilizers such as dibutyl tin laurate system, two toxilic acid dibutyl tins system, calcium-zinc system, barium-zinc system etc.Total amount with whipping agent and frothing aid is 100 weight %, and the usage quantity of frothing aid is 0.1～30 weight %, is preferably 1～20 weight %.
When using chemical foaming agent, use the master batch that constitutes by above-mentioned chemical foaming agent, frothing aid and resin usually.Be used for master batch resin kind only otherwise damage effect of the present invention, then do not have special restriction, preferably constitute the ethene-alpha-olefin copolymer of moulding product of the present invention.The chemical foaming agent that contains in the master batch and the total amount of frothing aid are generally 5～90 weight % with respect to the cooperation ratio of resin.
When using pneumatogen, by also obtaining having the more moulding product of micro bubble with sending out a kernel foaming agent.As sending out kernel foaming agent, can enumerate inorganic fillers such as talcum, silicon-dioxide, mica, zeolite, lime carbonate, Calucium Silicate powder, magnesiumcarbonate, aluminium hydroxide, barium sulfate, silico-aluminate, clay, silica powder, diatomite; The particle diameter that contains polymethylmethacrylate, polystyrene is the following pearls of 100 μ m; Metal-salts such as calcium stearate, Magnesium Stearate, Zinic stearas, Sodium Benzoate, calcium benzoate, aluminum benzoate, magnesium oxide also can being used in combination these.In addition, when using pneumatogen, also can use aforementioned chemical foaming agent as sending out kernel foaming agent.When using the chemical foaming agent conduct to send out kernel foaming agent, preferably use the low chemical foaming agent of decomposition temperature.For example, preferably with Cellmic C 121, p, p '-oxybis-benzenesulfonyl hydrazide, N, N-dinitrosopentamethylene tetramine etc. is the chemical foaming agent of principal constituent.In addition, also can and use the number of chemical whipping agent.
The addition of whipping agent can carry out suitable adjustment according to the kind of use whipping agent, the expansion ratio of manufacturing moulding product, and resin 100 weight parts with respect to constituting the moulding product are generally 0.1～10 weight part.
Among the present invention, can add linking agent when extrusive expansion molding and extrusive expansion molded.As linking agent, can enumerate for example dicumyl peroxide, 2,5-dimethyl-2,5-two (tert-butyl peroxide) hexane, 2,5-dimethyl-2,5-two (tert-butyl peroxide) hexin-3, benzoyl peroxide, 2,2-two (tert-butyl peroxide) butane, t-butyl perbenzoate, peroxidation isobutyl-, 1, two (tert-butyl peroxide sec.-propyl) benzene of 3-etc.
When using linking agent, can and use crosslinking coagent.As crosslinking coagent, can enumerate triallyl cyanurate, triallyl isocyanurate, Vinylstyrene, glycidyl methacrylate, polyethylene glycol dimethacrylate etc.
With respect to constituting moulding product resin 100 weight parts, the addition when using linking agent is generally 0.01～1.0 weight part, is preferably 0.03～0.5 weight part, more preferably 0.05～0.3 weight part.Usage quantity as linking agent is very few, and then the bubble diameter heterogeneity might can't obtain fine bubble; The usage quantity of linking agent is too much, and then mobile variation has the tendency of difficult forming.When using crosslinking coagent, be generally about 3～10 times (weight basis) of linking agent.
Formed body of the present invention can contain resin, the additive beyond the aforementioned ethene-alpha-olefin copolymer that does not damage effect degree of the present invention.
Resin beyond the ethene-alpha-olefin copolymer that can contain as moulding product of the present invention can be enumerated Alathons such as high density polyethylene(HDPE), medium-density polyethylene, new LDPE (film grade), contains the ethylene-propylene copolymer from the structural unit of propylene that surpasses 50 weight %, multipolymer such as ethylene-propylene-1-Butylene copolymer, not belong to the multipolymer of the ethene-alpha-olefin copolymer that uses among the present invention etc.When being 100% with the weight resin that constitutes these moulding product, the content of the resin beyond the ethene-alpha-olefin copolymer that uses among the present invention is generally below the 10 weight %.
As additive, can use known additive, can enumerate inorganic fillers such as glass fibre, carbon fiber; Tinting material such as dyestuff, pigment; Neutralizing agent, antioxidant, thermo-stabilizer, weather agent, lubricant, UV light absorber, antistatic agent, anti-hard caking agent, antifogging agent, dispersion agent, fire retardant, antiseptic-germicide, white dyes etc.
In the manufacturing of formed body of the present invention, when using ethene-alpha-olefin copolymer, when also using other resins, additive, can in advance they be mixed, use as resin combination.The preparation of resin combination can be used known mixing machine, mixing roll.In addition, on one side can use the weigher metering, Yi Bian ethene-alpha-olefin copolymer and other resins, additive are supplied with extrusive expansion molding and extrusive expansion molded machine respectively.
Manufacture method to moulding product of the present invention is not particularly limited, with ethene-alpha-olefin copolymer or contain its resin combination melting mixing in known shapers such as single shaft extruding machine, twin shaft extruding machine, the method for to atmosphere, extruding from the die head that is installed on the shaper front end.As die head, can from various types of die heads such as seam pattern head, circular seams die head, round mouth die head, section bar die head, select according to purpose.For making extrusion capacity stable, between shaper and die head, toothed gear pump can be set.In addition, also can between extruding machine and die head, static mixer etc. be set, so that resin and whipping agent is mixing.When using pneumatogen, after with ethene-alpha-olefin copolymer or resin combination fusion, from the pneumatogen opening for feed injection pneumatogen of shaper.
When extrusive expansion molding and extrusive expansion molded, the temperature of extruding machine is generally 100～260 ℃, and the temperature of die head is generally 90～240 ℃.Make the extrusion moulding product foaming of the molten state behind the die head extrusion molding just.By using cooling roller, cooling mandrel, cooling air, water coolant that the extrusive expansion molding and extrusive expansion molded product of this molten state is cooled off, can obtain extrusive expansion molding and extrusive expansion molded product as the finished product.
Expansion ratio to moulding product of the present invention is not particularly limited, and is generally 1.2～50 times.Even moulding product expansion ratio height of the present invention, outward appearance is also good.In addition, thickness, the shape to the moulding product also is not particularly limited.
Can will append laminated layer on moulding product of the present invention more than 1 layer in case of necessity, form multi-layer molded articles.This multi-layer molded articles can be made by the multi layer extrusion moulding; In addition, also can make by dry lamination method, heat fusing attachment method lamination by with the extrusive expansion molding and extrusive expansion molded moulding product of the present invention that obtain with append layer.
The layer that contains the good resin of gas barrier properties such as ethylene-vinyl alcohol copolymer, polyamide resin, pet resin by setting can obtain the good multi-layer molded articles of gas barrier property as appending layer, and this multi-layer molded articles is applicable to food product containers etc.In addition, also can make to have and contain the not outermost multi-layer molded articles of foamex of wood powder filling.In addition, by at the outside of the conduit that do not foam, the pipe that do not foam lining moulding extrusive expansion molding and extrusive expansion molded product of the present invention, can give conduit, pipe heat insulating ability and anti-dewing function.And, by the moulding extrusive expansion molding and extrusive expansion molded product of the present invention that around steel pipe, is covered, can improve the shock strength of steel pipe.In addition, by surrounding type extrusive expansion molding and extrusive expansion molded product of the present invention, can improve the insulativity of electric wire, optical fiber at electric wire, optical fiber isoperimetric.
[embodiment]
Below, the present invention will be described according to embodiment, but the present invention is not limited by embodiment.
The evaluation assessment of using in embodiment and the comparative example is as described below.
1. melt flow rate (MFR) (MFR)
Melt flow rate (MFR) (unit: g/10 minute) is measured under the condition of 190 ℃ of temperature, loading 21.2N according to JIS K 6760.
2. density (d)
Density (unit: kg/m
3) measure according to JIS K6760-1981.
3. molecular weight distribution
Molecular weight distribution is measured under the following conditions by gel permeation chromatography (GPC).
[condition determination]
Device: Waters corporate system 150C-CV type
Chromatographic column: the clear and system Shodex GPC AT-806MS of electrician society
Detector: differential refractometer
Column temperature: 140 ℃
Solvent: orthodichlorobenzene
Solvent flow rate: 1ml/ minute
Sample size: 400 μ l
Add sample in orthodichlorobenzene, heated 2 hours down at 140 ℃, the modulation sample concentration is 0.1% solution.This solution (400 μ l) is injected the chromatographic column (140 ℃) of GPC device.Detect the composition of wash-out on the chromatographic column with the differential refractometer, obtain color atlas.By the color atlas that obtains with obtain weight-average molecular weight (Mw), the number-average molecular weight (Mn) of sample with the GPC device correction curve that single decentralized standard polystyrene (eastern ソ one Co., Ltd.'s system, molecular weight=500～6,000,000) is made.Calculate the molecular weight distribution (Mw/Mn) of sample by Mw that obtains and Mn.(molecular weight distribution slightly is designated as MWD sometimes)
4. swelling ratio (SR)
Using to have diameter as 1mm, long capillary type viscometer capillaceous as 40mm, fluid inlet angle 90 degree (trade(brand)name: CAPIROGRAPH-IB, Japan smart machine Co., Ltd. system), according to JIS K7199, is 150 ℃, velocity of shear 60.8s in temperature
-1Condition under, the continuous extrusion sample.The wire rod of extruding is cut off at the capillary outlet place, remove.Proceed extrusion molding then, when the wire rod length of newly extruding reached the 20mm left and right sides, mensuration was by the diameter of the wire rod of the position of the downward 15mm of capillary outlet.Use the laser extensometer to measure above-mentioned diameter.To remove value that gauge or diameter of wire obtains as swelling ratio (SR) with capillary diameter.
5. the thickness of extrusive expansion molding and extrusive expansion molded product
The thickness of extrusive expansion molding and extrusive expansion molded product (unit: mm) measure with (strain) mitsutoyo system digimatic standard outside micrometer.
6. the expansion ratio of extrusive expansion molding and extrusive expansion molded product
The expansion ratio of extrusive expansion molding and extrusive expansion molded product densometer (EW-200SG type, A﹠amp; D Co., Ltd. system), adopt substitution method mensuration under 23 ℃ in the water.
7. the outward appearance of extrusive expansion molding and extrusive expansion molded product
The surface of extrusive expansion molding and extrusive expansion molded product divides 3 grades to estimate by visual according to standard shown below.
(judgement criteria)
A: no wrinkling, good luster.
B: take place slightly wrinkling.
C: take place wrinklingly, surface irregularity produces space, appearance poor.
8. the tear strength of extrusive expansion molding and extrusive expansion molded product
According to the method (A method) of ASTM D1922-67 regulation, record the Elmendorf tear strength (unit: kg/cm) of getting direction that tears of the extruded plastic foam sheet material that obtains by the aftermentioned method.
9. flow-activation energy Ea
[mensuration of dynamic viscoelastic]
(mensuration of storage modulus (G '), out-of-phase modulus (G ")) is used determination of viscoelasticity device (Rheometrics corporate system RMS-800 type) to dynamic viscoelastic.In nitrogen atmosphere, under the condition as follows, measure.
(1) determination part shape: parallel plate (diameter: 25mm, distance between plates: about 1mm)
(2) shear strain: 5%
0.1,0.15849,0.2512,0.39812,0.63098,1.00003,1.58496,2.51202,3.98132,6.31006,10.0007,15.8501,25.1206,39.8135,63.1006,100rad/ second (3) radian frequency:
(4) temperature: 130 ℃, 150 ℃, 170 ℃, 190 ℃
[calculating of shift factor]
Shift factor (a
T) calculation procedure as described below.
With 130 ℃ (403 ° of K) as reference temperature (T
0), make G ' (Pa) and G " master curve (Pa) according to formula (1) and (2).
G′(ω，T)＝b
TG′(a
Tω，T
0) (1)
G″(ω，T)＝b
TG″(a
Tω，T
0) (2)
Here, ω is radian frequency (rad/ second), and T measures temperature (° K), T for each
0Be reference temperature, a
TBe the translational movement of radian frequency direction, b
TBe G ', G " axial translational movement.
[calculating of activation energy]
Flow-activation energy (Ea) is obtained according to the following steps.
Log (a
T) 1/T is mapped.To this curve, carry out linear regression according to method of least squares, calculate the collinear slope.The slope that obtains is considered as Ea/2.303R, calculates Ea (kJ/mol).
The polymkeric substance that uses in embodiment and the comparative example is as described below.The rerum natura of each polymkeric substance is as shown in table 1.
1. ethene-1-hexene copolymer
Melt flow rate (MFR) (MFR) is that 1.1g/10 minute, density (d) are 923kg/m
3Ethene-1-hexene copolymer.
2. ethene-1-octene copolymer
Melt flow rate (MFR) is that 1g/10 minute, density (d) are 870kg/m
3Commercially available ethene-1-octene copolymer.
3. hp-ldpe
The hp-ldpe of Sumitomo Chemical (strain) system commodity Sumikathene F102-0 by name.This poly melt flow rate (MFR) (MFR) is 0.3g/10 minute, and density (d) is 922kg/m
3
4. styrene isoprene styrene block copolymer (SIS)
The styrene isoprene styrene block copolymer (SIS) of (strain) Kuraray system commodity SEPTON 2104 by name.The melt flow rate (MFR) of this multipolymer is 0.8g/10 minute, and density is 970kg/m
3
[embodiment 1]
(preparation of ethene-1-hexene copolymer)
Carry out the copolymerization of ethene and 1-hexene according to following method, obtain ethene-1-hexene copolymer.
[modulation of catalyst component]
The modulation of promotor carrier (A)
To nitrogen replacement the reactor of outfit stirrer in be added in the nitrogen gas stream, 300 ℃ of silicon-dioxide (trade(brand)names: Sylopo1948 that following heat treated is crossed; The Davison corporate system; Median size=5.5 μ m; Pore capacity=1.67ml/g; Specific surface area=325m
2/ g) 2.8kg and toluene 24kg, and stir.After being cooled to 5 ℃, keeping the temperature of reactor is 5 ℃, drips 1,1,1,3,3, the mixing solutions of 3-hexamethyldisilazane 0.91kg and toluene 1.43kg with 33 minutes.After dropwising, stirred 1 hour, stirred 3 hours, filter then at 95 ℃ at 5 ℃.The solid resultant that obtains is washed 6 times with toluene 21kg.Then, add toluene 6.9kg and make slurry, leave standstill an evening.
In the above-mentioned slurry that obtains.Hexane solution (the zinc ethyl concentration: 50wt%) 2.05kg and hexane 1.3kg, stirring that adds zinc ethyl.After being cooled to 5 ℃ then, keeping the temperature of reactor is 5 ℃, with the mixing solutions that dripped Pentafluorophenol 0.77kg and toluene 1.17kg in 61 minutes.After dropwising, stirred 1 hour, stirred 1 hour at 40 ℃ at 5 ℃.The temperature that keeps reactor then was 5 ℃, with 1.5 hours dropping water 0.11kg.After dropwising, stirred 1.5 hours, stirred 2 hours at 55 ℃ at 5 ℃.Hexane solution (the zinc ethyl concentration: 50wt%) 1.4kg and hexane 0.8kg that under room temperature, adds zinc ethyl then.After being cooled to 5 ℃, keeping the temperature of reactor is 5 ℃, drips 3,4, the mixing solutions of 5-trifluoromethyl phenol 0.42kg and toluene 0.77kg with 60 minutes.After dropwising, stirred 1 hour, stirred 1 hour at 40 ℃ at 5 ℃.The temperature that keeps reactor then was 5 ℃, with 1.5 hours dropping water 0.077kg.After dropwising, stirred 1.5 hours, stirred 2 hours, stirred 2 hours at 80 ℃ again at 40 ℃ at 5 ℃.Stop to stir, pipetting supernatant liquor, to make residual quantity be 16L.Add toluene 1.6kg, stir.Be warming up to 95 ℃, stirred 4 hours.Leave standstill and make the solids component sedimentation, settled solids component layer (lower floor) and slurry part (upper strata) remove slurry part (upper strata), then the liquid component of filtration residue (lower floor) when separation surface occurring.With the solid resultant that obtains with 20.8kg toluene wash 4 times, with 24 liters of hexane wash 3 times.Drying obtains solids component (hereinafter referred to as promotor carrier (A)) then.
[modulation of pre-polymerized catalyst composition]
Be 210 liters and have in the autoclave of agitator to the internal volume that has carried out nitrogen replacement in advance, add above-mentioned promotor carrier (A) 0.53kg, control high pressure temperature in the kettle is 25 ℃, and pressure is normal atmosphere, after adding 80 liters of 3 liters of hydrogen, butene-1 20g, butane, autoclave is warming up to 30 ℃.Adding ethene then, to make its gaseous pressure with respect to autoclave be the amount of 0.03Mpa, in the system stable after, add triisobutyl aluminium 159mmol and racemize-ethylenebis (1-indenyl) biphenol zirconium 53mmol, the beginning polymerization.Be warming up to 31 ℃, simultaneously, continuously supply with ethene and hydrogen and on one side further be warming up to 51 ℃ on one side, amount to the prepolymerization of carrying out 4 hours.Polymerization is removed ethene, butane, hydrogen etc. after finishing, and residual solid is at room temperature carried out vacuum-drying.Thus, the above-mentioned promotor carrier of every 1g (A) obtains the poly pre-polymerized catalyst composition of prepolymerization 15g.
[polymerization]
Use above-mentioned gained pre-polymerized catalyst composition, carry out the polymerization of ethene and 1-hexene, obtain ethene-1-hexene copolymer powder with continuous fluidized bed gas phase polymerization apparatus.Polymerizing condition: polymerization temperature is 75 ℃, and polymerization pressure is 2MPa, and hydrogen is 0.9% with respect to the mol ratio of ethene, and the 1-hexene is 0.9% with respect to the mol ratio of ethene.In order to keep the constant gas composition, supply with ethene, 1-hexene and hydrogen continuously in the polymerization process.In addition, supply with catalyst component and triisobutyl aluminium that above-mentioned prepolymerization finishes continuously, thereby keep the total powder weight of fluidized-bed certain (80kg).The average polymerization time is 4 hours.
[mixing]
In the ethene that obtains-1-hervene copolymer powder, add and mixing antioxidant (trade(brand)name: Sumilizer GP, Sumitomo Chemical Co's system), make concentration reach 750ppm.Use extruding machine (trade(brand)name: LCM50; Kobe Steel, Ltd society system), in input speed is 50kg/ hour, screw speed is that 450rpm, cast gate opening degree are 50%, suction pressure is that 0.1MPa, resin temperature are under 200～230 ℃ the condition, with the mixture pelleting that obtains, to obtain ethene-1-hervene copolymer composition granule.
[manufacturing of extrusive expansion molding and extrusive expansion molded product]
With ethene-1-hervene copolymer composition granule 100 weight parts and azo-2-carboxylic acid is chemical foaming agent (trade(brand)name: Cellmic MB2043; Three associations change into (strain) system) mixed 1 minute with the rotating cylinder mixing tank.This mixing raw material is supplied with the sheet forming machine, and it is 50mm, long 2.1m that these sheet forming facility have diameter, be furnished with the screw rod of 3 place's mixing sections, is that 60rpm, kneading part temperature are that 150～210 ℃, die section temperature are extrusion molding under 150 ℃ the condition at screw speed.Extrusion molding speed is 18kg/ hour.Pars intermedia at extruding machine is provided with fillup valve, injects the carbonic acid gas that is forced into 10MPa continuously by this valve, adjusts injection rate and makes it reach 0.4 weight part.It is that 80mm, internal diameter are that 79.2mm, die lip gap are the round mouth die head of 0.4mm that the extruding machine front end is provided with external diameter, and the foamex of molten state is extruded into circle by this round mouth die head.Utilization is circulating the cooling mandrel of 25 ℃ of water coolants with the cooling of the foamex of this molten state, makes its curing, tears with nip rolls and gets, and obtaining thickness is that 0.8mm, expansion ratio are 2.1 times extrusive expansion molding and extrusive expansion molded sheet material.This extrusive expansion molding and extrusive expansion molded sheet material is wrinkle resistant, and the sheet material outward appearance is good.In addition, the tear strength of this sheet material is 38kg/cm, and physical strength might as well.The result is as shown in table 2.
[embodiment 2]
Injection rate that remove to adjust carbonic acid gas makes it reach 0.5 weight part, outside injecting continuously, uses the method identical with embodiment 1 to make extrusive expansion molding and extrusive expansion molded sheet material.The gained result is as shown in table 2.This extrusive expansion molding and extrusive expansion molded sheet material is wrinkle resistant, and the sheet material outward appearance is good.In addition, the tear strength of this sheet material is 32kg/cm, and physical strength is also fine.
[comparative example 1]
Except that replace ethene-1-hexene copolymer with hp-ldpe (Sumikathene F102-0), make extrusive expansion molding and extrusive expansion molded sheet material with method similarly to Example 1.The gained result is as shown in table 2.This extrusive expansion molding and extrusive expansion molded sheet material corrugation is not the good sheet material of outward appearance.In addition, the tear strength of this sheet material is 20kg/cm, bad mechanical strength.
[comparative example 2]
Except that replace ethene-1-hexene copolymer with commercially available ethene-1-octene copolymer, make extrusive expansion molding and extrusive expansion molded sheet material with method similarly to Example 1.The gained result is as shown in table 2.Shark skin spot appears in this extrusive expansion molding and extrusive expansion molded sheet material, is not the good sheet material of outward appearance.In addition, the tear strength of this sheet material is 22kg/cm, bad mechanical strength.
[comparative example 3]
With commercially available ethene-1-octene copolymer 60 weight parts, styrene isoprene styrene block copolymer (SIS) hydride (SEPTON 2104) 30 weight parts, hp-ldpe (Sumikathene F102-0) 10 weight parts and chemical foaming agent (trade(brand)name: CellmicMB2043; Three associations change into (strain) system) azo-2-carboxylic acid is that 1 weight part mixed 1 minute in the rotating cylinder mixing tank.This mixing raw material is supplied with the sheet forming machine identical with embodiment 1, is that 60rpm, kneading part temperature are that 150～210 ℃, die section temperature are to carry out extrusion molding under 180 ℃ the condition at screw speed.Extrusion molding speed is 18kg/ hour.In the die lip gap of round mouth die head is under the condition of 0.4mm, and the foamex of molten state is extruded into circle.Utilize circulation that the foamex cooling of the cooling mandrel of 25 ℃ of water coolants with this molten state arranged, make its curing, tear with nip rolls and get, making thickness is the extrusive expansion molding and extrusive expansion molded sheet material of 0.4mm.The expansion ratio of this extrusive expansion molding and extrusive expansion molded sheet material is low, is 1.1 times, and sheet surface forms shark skin spot, appearance poor.In addition, tear strength is 14kg/cm, bad mechanical strength.
[comparative example 4]
When extrusive expansion molding and extrusive expansion molded, remove from fillup valve and inject the carbonic acid gas that is forced into 10MPa continuously, injection rate is reached beyond 0.4 weight part, use with the same method of comparative example 3 and make extrusive expansion molding and extrusive expansion molded sheet material.The thickness of this extrusive expansion molding and extrusive expansion molded sheet material is that 0.72mm, expansion ratio are 1.6 times, and sheet surface produces space, appearance poor.In addition, tear strength is 13kg/cm, bad mechanical strength.
[table 1]
| MFR (g/10 minute) | d (kg/m 3) | MWD | SR | Ea (kJ/mol) | |
| Ethene-1-hexene copolymer | 1.1 | 923 | 17.8 | 1.28 | 72 |
| Hp-ldpe | 0.3 | 923 | 4.4 | 1.53 | 70 |
| Ethene-1-octene copolymer | 1.0 | 870 | 1.7 | 1.13 | 41 |
| The styrene-isoprene-phenylethene block polymer | 0.8 | 970 | - | - | - |
[table 2]
| Embodiment | Comparative example | |||||
| 1 | 2 | 1 | 2 | 3 | 4 | |
| Ethene-1-hexene copolymer (weight part) | 100 | 100 | - | - | - | - |
| Hp-ldpe (weight part) | - | - | 100 | 10 | 10 | |
| Ethene-1-octene copolymer (weight part) | - | - | - | 100 | 60 | 60 |
| Styrene isoprene styrene block copolymer (SIS) (weight part) | - | - | - | - | 30 | 30 |
| Chemical foaming agent (weight part) | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
| Carbonic acid gas feed rate (weight part) | 0.4 | 0.5 | 0.5 | 0.5 | - | 0.5 |
| The thickness of extrusive expansion molding and extrusive expansion molded product (mm) | 0.8 | 0.8 | 0.8 | 0.7 | 0.4 | 0.7 |
| The expansion ratio of extrusive expansion molding and extrusive expansion molded product (doubly) | 2.14 | 2.25 | 2.1 | 1.7 | 1.1 | 1.6 |
| The outward appearance of extrusive expansion molding and extrusive expansion molded product | A | A | B | C | C | C |
| The tear strength of extrusive expansion molding and extrusive expansion molded product (kg/cm) | 38 | 32 | 20 | 22 | 14 | 13 |
Industrial applicability
Moulding product outward appearance of the present invention and physical strength are good, applicable to various uses, as material of construction purposes such as boards supporting substrates, thermal insulation material, adiabatic water-proof material, cushioning material, flap roof Material, health material, seam material, straw mat core enumerably; The adiabatic cushioning material of inner panel, door, ceiling etc., the core of sheet material, the automobile purposes such as adiabatic cushioning material of flexible pipe; Groceries purposes such as the wrapping material of precision instrument, toy, seat, sheet material, cold-reserving box, insulation can, book cover, cassette tape material, safety helmet cushioning material, motion protector core, kickboard; Food product pack purposes such as pallet, reticulation, fruit containers, packing bag; Medical use such as cleaning pad, keeping device etc.
Claims (3)
1. extrusive expansion molding and extrusive expansion molded product, it contains, and molecular weight distribution is more than 5, swelling ratio is 1.15～1.45 ethene-alpha-olefin copolymer.
2. the described extrusive expansion molding and extrusive expansion molded product of claim 1, wherein, the flow-activation energy of above-mentioned ethene-alpha-olefin copolymer is more than the 40kJ/mol.
3. claim 1 or 2 described extrusive expansion molding and extrusive expansion molded products, wherein, the melt flow rate (MFR) of above-mentioned ethene-alpha-olefin copolymer is 0.01～5g/10 minute.
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|---|---|---|---|
| JP2004033008 | 2004-02-10 | ||
| JP033008/2004 | 2004-02-10 |
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| CN2012102393595A Division CN102746569A (en) | 2004-02-10 | 2005-02-08 | Product of extrusion foam molding of ethylene-alpha-olefin copolymer |
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| CN2012102393595A Pending CN102746569A (en) | 2004-02-10 | 2005-02-08 | Product of extrusion foam molding of ethylene-alpha-olefin copolymer |
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| JP (1) | JP2009256690A (en) |
| CN (2) | CN1946781A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103205124A (en) * | 2013-03-04 | 2013-07-17 | 鲁奎 | Foaming agent for silicone rubber sponge |
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| JP2011132402A (en) * | 2009-12-25 | 2011-07-07 | Sumitomo Chemical Co Ltd | ETHYLENE-alpha-OLEFIN COPOLYMER FOR FOAMING, RESIN COMPOSITION FOR FOAMING, AND FOAM |
| CN102850639B (en) * | 2012-08-31 | 2015-03-25 | 泗县赛克斯科技有限公司 | Crosslinked polyethylene composition and application thereof |
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| JPS5373382A (en) * | 1976-11-25 | 1978-06-29 | Sumitomo Electric Ind Ltd | Manufacturing method of highly-foamed plastic insulated electric wire |
| JPH0755990B2 (en) * | 1989-11-02 | 1995-06-14 | 宇部興産株式会社 | Expandable polyolefin resin composition for coating electric wires |
| JPH07100745B2 (en) * | 1990-04-24 | 1995-11-01 | 日立化成工業株式会社 | Crosslinked polyethylene resin foam |
| CN1038755C (en) * | 1995-02-20 | 1998-06-17 | 三井石油化学工业株式会社 | Ethylene polymer, process for preparing the same, solid titanium catalyst component for ethylene polymerization and ethylene polymerization catalyst |
| WO2001007516A1 (en) * | 1999-07-23 | 2001-02-01 | Mitsui Chemicals, Inc. | Rubber composition for extrusion molding and for molding with mold and use thereof |
| JP3717377B2 (en) * | 2000-07-19 | 2005-11-16 | 積水化成品工業株式会社 | Non-crosslinked polyethylene resin foam, method for producing the same, and molded article using the same |
| JP2003026870A (en) * | 2001-07-23 | 2003-01-29 | Sumitomo Chem Co Ltd | Polyethylene resin composition, polyethylene resin composition for foaming and foamed product |
| JP2004082480A (en) * | 2002-08-26 | 2004-03-18 | Tosoh Corp | Manufacturing method for polyethylenic foam |
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| TW200540210A (en) | 2005-12-16 |
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