CN1069038A - Ethene polymers of high fondant-strength and its production and use - Google Patents
Ethene polymers of high fondant-strength and its production and use Download PDFInfo
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- CN1069038A CN1069038A CN92104989A CN92104989A CN1069038A CN 1069038 A CN1069038 A CN 1069038A CN 92104989 A CN92104989 A CN 92104989A CN 92104989 A CN92104989 A CN 92104989A CN 1069038 A CN1069038 A CN 1069038A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F10/02—Ethene
Abstract
The present invention has disclosed the normality solid, high molecular, gel-free.Density be 0.89～0.97g/cc through irradiated ethene polymers, it is characterized in that owing to strain hardening has formed high fondant-strength, and think that strain hardening is that free-end long chain branches by the molecular chain that constitutes polymkeric substance forms.
The present invention has also disclosed a kind of method for preparing polymkeric substance, it is by use high-energy irradiation normality solid, high-molecular weight ethene polymers in reductive active oxygen environment, to in this environment, keep one section specified time through irradiated material, make the radical inactivation in the material then.
Description
The present invention relates to chemical preparations.It relates to the chemical preparations that the synthetic resins of deriving is out made from alpha-olefin or 1-alkene particularly, and it is particularly related to the synthetic resins that forms by the independent polymerization of ethene or ethene and other olefinic polymerization.
Be called polyethylene by the ethene synthetic resins that polymerization forms as only monomer.Although term " polyethylene " repeatedly is used on the multipolymer that comprises ethene and a small amount of another kind of monomer (as 1-butylene) in the prior art, do not comprise such implication with this noun here.
Commercially available polyethylene is as new LDPE (film grade) (LDPE) and high density polyethylene(HDPE) (HDPE) and ethene and C
3～10The multipolymer of alpha-olefin (being commonly referred to as linear low density ethylene (LLDPE)) is generally solid, the soft thermoplastic polymkeric substance that they form the specific monomer polymerization by the known various methodologies of prior art.For example, by the radical polymerization under the high pressure or by low pressure method,, and prepare this base polymer with catalyst with base of molybdenum, chromium-based catalysts or Z-N (Ziehler-Natta) catalyst system as fluidized-bed, gaseous techniques.High pressure method is produced the polymkeric substance with long-chain branch, and low pressure method is produced the in check polymkeric substance that is linearity substantially of short-chain branch.In Z-N (Ziegler-Natta) catalyst system, catalyzer is to use the mineral compound (for example, aluminum alkyls) and the periodictable IV-VIII group transition metal compound (for example, the halogenide of titanium) of periodictable I～III family metal to prepare.Adopt Wunderlick ﹠amp; Guar, J.phys.Chem.Ref.Data, the 10th volume, the method for No. 1 (1981), its typical degree of crystallinity are about 21～75%(weight).The typical melting index of described ethylene homo body or multipolymer is 0.2～50g/10 minute (according to ASTM1238, condition E measures).In addition, the fusing point of the crystallization phases of commercially available normality solid polyethylene is about 135 ℃.
Though commercially available linear polyethylene has many desirable advantageous properties, their melt strength deficiency.During fusion, their no strain hardenings (the stretching tolerance that during stretch the melt material position, increases).Like this, linear polyethylene has the shortcoming of many melt-processed, is included in to extrude at a high speed when being coated on paper or other matrix and can form edge waviness suddenly, matrix occurs and hang down and contract and local attenuation fluid instability in laminate structures is extruded jointly in hot melt molding.As a result, they are such as extruding that coating, blowing, section bar are squeezed and the potential application of aspect such as thermoforming is restricted.
Prior art has been made some effort, to overcome the melt strength deficiency of commercial polyethylene.
Prior art has pair polyethylene to carry out irradiation, but this class irradiation impinges upon on the goods that polyethylene makes at first, on film, fiber and sheet material, and (promptly makes polyethylene crosslinking greater than 2 megarads with high dosage.For example, United States Patent (USP) 4,668,577 have disclosed crosslinked to polyethylene filaments, United States Patent (USP) 4,705,714 and 4,891,173 have disclosed the sheet material that high density polyethylene(HDPE) is made, and to carry out differential crosslinked.According to reports,, improved melt strength, reduced solubleness and melt flow by the crosslinked polyethylene of these methods.But, this crosslinked unnecessary minimizing of extension generation that makes polyethylene melt, thus limited the tensile elongation of special requirement is arranged on film or the fiber applications.
At United States Patent (USP) 3,563, set forth by linear polyethylene being exposed on the low dosage level of high-energy irradiation in 870, promptly 0.05 to 0.3 megarad attempts to improve poly melt strength and melt unit elongation.
European patent application 047171 has disclosed ethene polymers has been carried out irradiation, it reduces oxygen level in the particle to come the thermal aging ethylene polymer particles by it is carried out pre-treatment with the steam atmosphere, come the polymkeric substance of the treated mistake of irradiation to be less than 1.5 megarad dosage, give the radiation polymerization thing logical steam then.
English Patent the 2nd, 019 relates to for No. 412 linear low density polyethylene (LLDPE) film is carried out irradiation in 2～80 megarad scope, to increase its elongation at break.
United States Patent (USP) 4,586,995 and 4,598,128 relate to a kind of method that long " Y " side chain is arranged in the ethene polymers for preparing, it is by heating ethene polymers under non-gelling, non-oxide condition, thereby in not having the ethene polymers of unsaturated end group, form the unsaturated ethylene end group, perhaps in containing the polyethylene of unsaturated end group, increased the unsaturated ethylene end group, come irradiation through heat treated ethene polymers with 0.1 to 4 megarad dosage, cool off gradually or rapidly then, thereby made through irradiated polymkeric substance.
United States Patent (USP) 4,525,257 irradiation doses that disclosed with 0.05 to 2 megarad (Mrad) come irradiation narrow molecular-weight, linearity, low-density ethene/C
3～18Alpha-olefin copolymer does not have the agglomerative cross-linking copolymer with generation, and this crosslinking degree is enough to make this multipolymer to be compared with corresponding uncrosslinked polyethylene, has higher elongational viscosity and suitable substantially shear viscosity.The irradiation multipolymer reduces or eliminates the radical intermediate without deactivating.
One aspect of the present invention comprises a kind of normally normality solid, high molecular and gel-free through irradiated polyethylene, its density is 0.89 to 0.97g/cc, its molecular chain has the long-chain branch of a large amount of free-ends, the branching rate is less than 1, and it has sufficient strain hardening elongational viscosity.
Be widely, the present invention includes a kind of normality solid, gel-free, high molecular, through irradiated ethene polymers material, its branching rate is less than 1, and it has competent strain hardening elongational viscosity.
Polymkeric substance of the present invention has reduced melting index and (has used I under 190 ℃
2Confirm that the reduction of this melting index has proved the increase of molecular weight, melting index ratio (I
10/ T
2) increase show the expansion of molecular weight distribution, and improved melt tension and strain hardening elongational viscosity, its branching rate is less than 1.
Ethene polymers of the present invention prepares by low dose irradiation under controlled conditions.
Terminology used here " ethene polymers material " is represented by (a) Alathon, (b) ethene and a kind of by C
3-10The random copolymers of the alpha-olefin of choosing in the cohort that alpha-olefin constitutes, the about 20wt%(of its polymeric alpha-olefin content better is about 16wt%), (c) the random trimer of ethene and described alpha-olefin, condition is that polymeric alpha-olefin maximum level is about 20wt%(and better is about 16wt%), the ethene polymers material of selecting in such cohort that constitutes.C
3～10Alpha-olefin comprises linear and α-side chain collateralization.As propylene, 1-butylene, iso-butylene, 1-amylene, 3-methyl-1-butene, 1-hexene, 3,4-dimethyl-1-butylene, 1-heptene, 3-methyl isophthalic acid-hexene, 1-octene and so on.
When ethene polymers is the homopolymer of ethene, its typical density is 0.960g/Cm
3Or bigger, when ethene polymers is ethene and C
3～10The multipolymer of alpha-olefin, its density typically is 0.91g/Cm
3Or bigger, but less than 0.94g/Cm
3Suitable ethylene copolymer comprises ethylene/butylene-1, ethylene/hexene-1, ethylene/octene-1 and ethene/4-methyl-1-pentene.Ethylene copolymer can be the linear low density polyethylene (LLDPE) of high density polyethylene(HDPE) (HDPE) or short-chain branch, and Alathon can be high density polyethylene(HDPE) (HDPE) or new LDPE (film grade) (LDPE).The density of typical linear low density polyethylene (LLDPE) and new LDPE (film grade) (LDPE) is 0.910g/Cm
3Or greatly to being no more than 0.940g/Cm
3, and the density of high density polyethylene(HDPE) (HDPE) is greater than 0.940g/Cm
3, often be 0.950g/Cm
3Or it is bigger.In a word, density be 0.89 to 0.97g/cc ethene polymers material be applicable to of the present invention.Ethene polymers is that density is 0.89 to 0.97g/cc linear low density polyethylene (LLDPE) and high density polyethylene(HDPE) (HDPE) preferably.
In present patent application, term " high molecular " expression molecular-weight average is at least about 50,000.
The branching rate is the degree of branching of long-chain quantitatively, and the branching rate is less than approximately 0.9 in example preferably, and is preferably about 0.2～0.8.It defines with following equation:
Wherein g ' is the branching rate, (IV)
BrBe the ethene polymers properties of materials viscosity through branching, (IV)
Lin(promptly normality solid normally has the ethene polymers properties of materials viscosity of identical molecular-weight average basically, and for multipolymer and trimer, the unitary corresponding molecule ratio of its body is basic identical for corresponding ethene polymers material.
Limiting viscosity is known to be used for limiting viscosity number, it is generally acknowledged that this is to be used for measuring the ability that polymer molecule increases soltion viscosity.It depends on dissolved polymer beads size and shape.Therefore, the essentially identical linear polymer of non-linear polymer and molecular-weight average is compared, it has the non-linear polymer molecular configuration.Really, the ratio of above-mentioned limiting viscosity is a kind of method of tolerance non-linear polymer degree of branching.J.App.Poly Sci. has described the method for measuring the ethene polymers limiting viscosity in 21,3331～3343 pages (1977).
Molecular-weight average can be measured by the whole bag of tricks.And used here method is the laser light scattering photometer, and this method is set forth in the article of Mc Connell being entitled as in Am.Lab1978 5 months " polymericular weight and by low angle laser light scattering dispersive molecular weight distribution ".
Resistibility when elongational viscosity is fluid or semi-fluid substance stretching.It is the melt property of thermoplastic material, and it is measured when applying tension strain with given pace by instrument, the stress of the sample under the molten state and strain.At Munstedt, J.Rheology 23(4), has set forth this quasi-instrument in 421～425(1979), and has showed at Fig. 1.Similar commercially available instrument extends rheometer for Rheonetrics RER-9000.To fused, high molecular weight ethylene polymer materials from a point of fixity with the given pace elongation or when stretching, demonstrate its elongational viscosity and in certain distance, trend towards increasing with rate of extension, being thinned at it does not then have the back-and be that so-called ductile failure or necking down destroy back minimizing rapidly.On the other hand, fusion ethene polymers material of the present invention is basic identical with molecular-weight average in contrast, fused high molecular weight ethylene polymer materials, and under the essentially identical condition of test temperature, it is stretched with essentially identical rate of extension from a point of fixity, demonstrate its elongational viscosity and trend towards in longer distance range, increasing, and owing to fracture fractures or destroys-so-called brittle rupture or elastic failure.These mark sheets are understood strain hardening.In fact, the ethene polymers material that chain component more how long arranged of the present invention has the tendency that bigger elongational viscosity increases when destroying being stretched to.When the branching rate less than about 0.8 the time, this tendency is the most obvious.
Melt tension has also shown the melt strength of material, melt tension is measured with the Gottfert Rheotens melt tension instrument that Gottfert company produces, and it measures the tension force (centimetre) of fusion ethene polymers wire rod by method as described below: extrude tested polymkeric substance by the kapillary of long 20mm, diameter 2mm under 180 ℃; With sustained acceleration is 0.3cm/ second
2Tensioning system wire rod is stretched.Measure the tension force that above-mentioned stretching produces (centimetre).Higher melt tension is represented bigger melt strength values, and it also shows the strain hardening capacity of certain material.
Another aspect of the present invention provides a kind of method normality solid, high molecular, ethene polymers material is converted into the ethene polymers material of normality solid, gel-free, and its branching rate is less than 1, and has competent strain hardening elongational viscosity.
This method comprises
(1) the described ethene polymers material of irradiation
(a) be held at less than the 15%(volume of environment at activity keto concentration) described environment in, and
(b) with about 1～10
4Megarad/minute dosage speed with high energy ion irradiation for some time, make irradiation reach 2.0 megarads, but be not enough to cause the material production gel;
What (2) will obtain like this keeps grace time so that the capacity long chain branches forms through irradiated material in this class environment; And
(3) in this class environment, handle then through irradiated material, so that all radicals that exist in irradiated material deactivate.
The ethene polymers material of handling according to the inventive method can be any normality solid, high molecular weight ethylene polymer materials.In general, initial ethene polymers properties of materials viscosity can show molecular weight, and the logical case button of this limiting viscosity is 1～25, is 1～6 preferably, is that 0.8～25(is 1～3 preferably with the limiting viscosity that obtains the finished product).But, have the big or little ethene polymers material of the general value of limiting viscosity ratio also in the scope of broad of the present invention.Can use melting index to be about 0.01 or higher ethene polymers material.
The ethene polymers material that the inventive method under the wideest notion is handled can be any physical form, for example, and subparticle, fine particle, pellet, film, sheet material and so on.In the preferred embodiment of the inventive method, be particulate state or spherolitic ethene polymers material and can obtain satisfied result.Mean diameter is better greater than the spherical particle of 0.4mm.
The active o content of the environment in three method stepss is a critical factor." active oxygen " represent here oxygen be can with the irradiation material, preferably and the form of the free radical reaction in the material.It comprises molecular oxygen (it is for generally being present in airborne oxygen).Require can be by using vacuum or using rare gas element such as nitrogen to replace that some or all air reach in the environment for required active o content in the inventive method.
The ethene polymers material of just having made is non-activity oxygen at that time generally.Therefore, polymerization and the polymer processing step (when the ethene polymers material is not exposed in the air) according to the inventive method is in notion of the present invention.But, owing to the ethene polymers material being stored in the air or owing to some other reason, this ethene polymers material in most of the cases contains active oxygen.Consequential is in the better embodiment of the inventive method, at first ethene polymers material in small, broken bits to be handled, to reduce its active o content.Mode is that material is put into the bed that is filled with nitrogen preferably, and active o content is equal to or less than the 0.004%(volume in nitrogen).The residence time of material in bed generally should be at least 5 minutes, to guarantee removing active oxygen effectively from the space of material granule, better was to stop the sufficiently long time, made material and environment reach balance.
Between preparation and irradiation steps, the ethene polymers material of preparation gained should be kept at activity keto concentration and be less than in 15% the environment, is less than 5% preferably in gas transport system, is preferably the 0.004%(volume).In addition, the temperature of ethene polymers material should remain on the glass transition temp that is higher than the material pars amorpha, but is not higher than about 70 ℃, better about 60 ℃.
In irradiation steps, the activity keto concentration of environment better is less than the 5%(volume), better be less than the 1%(volume).Best activity keto concentration should be less than the 0.004%(volume).
In irradiation steps, the ionization irradiation source should have competent energy to penetrate radiation exposed vinyl polymerization object, the required degree that reaches.This energy must be enough to make molecular structure ionization and excited atom structure, but also is not enough to bombard the atomic nucleus.Ionization irradiation can be any kind of, the most practical stream of electrons and the gamma-rays of comprising.Being preferably from accelerating potential is 500～4, the stream of electrons of getting in the electronic generator of 000KV.For the ethene polymers material, with about 0.2-2.0 megarad, be preferably 0.3～be less than 2.0 megarads, be preferably the ionization irradiation of the low dosage of 0.5～1.5 megarad, with general about 1～10,000 megarad/minute, better about 18～2,000 megarad/minute dose rates discharge, can obtain satisfied result like this.
Term " rad " is commonly defined as the numerical value of ionization irradiation, the result of ionization irradiation be every gram by the irradiation absorbed energy of 100 ergs, this and irradiation source are irrelevant.For the present invention, normally indefinite by the energy of ethene polymers absorbed during irradiation.In general practice, prepare the energy absorption in the ionization irradiation with known routine dose instrument (a kind of measuring apparatus, the fabric strip that wherein contains the radiation sensitive dyestuff are the energy absorption sensors).Therefore, be used for the term " rad " of this specification sheets no matter expression causes being placed on the amount of radiation exposed its ionization irradiation when quite absorbing 100 erg energy for the every gram fabric strip in the dosimeter on the ethene polymers material surface of the bed of particle or film or sheet material or layer form.
In about 1 minute to 1 hour, in about 2～30 minutes, carry out preferably as second step 1 of the inventive method.The time that needs lowest limit degree guarantees to make the ethene polymers segment partly to migrate to the radical position and is combined to form complete chain again, or forms long side chain on chain.The radical transition time is less than 1 minute, and for example about half a minute, this is in broad notion of the present invention, but is not preferred, because the quantity of the long chain branches with free-end of gained is quite low like this.
The final step of present method, promptly radical deactivation or quencher step can be used heating method, and generally heating is at least 60 ℃ to 280 ℃, or has the additive that captures the radical effect by adding, carries out as adding methyl mercaptan.
In the method example of application of heat, it comprises and melt extruding through irradiated ethene polymers material.As a result, the quencher radical is very complete basically.In this example, extrude or melt composition before, if need, then through irradiated ethene polymers can with other polymkeric substance, and the fusion together of the additive such as stablizer, pigment, filler.Interchangeablely be that this class additive can be used as the side line component and adds to and carry out fusion in the forcing machine.
Another example of the inventive method of application of heat is by will putting into fluidized-bed or the staged fluidized bed system carries out through irradiated ethene polymers material, and wherein fluidizing medium is such as nitrogen or other rare gas element.Setting up fluidized-bed and make temperature range remain at least 60 ℃ until the temperature that is no more than melting point polymer, is about 5 minutes to about 120 minutes through the mean time that irradiated ethene polymers is detained in fluidized-bed, and the best is 20～30 minutes.
The product of gained often is the normality solid like this, the ethene polymers material of high molecular, gel-free, and its strain hardening is its feature.The feature of this material is that also the ratio of melting index is greater than 10.
Though method of the present invention can intermittently be carried out, be that continous way is carried out preferably.In the example that continous way is carried out, according to the material activity oxygen level, have preparation process or not with the ethene polymers material in small, broken bits of preparation process in desired environment on travelling belt stratification.The layer thickness depend on the desired degree of ionization irradiation penetrating layer, and in final product through the shared ratio of irradiated ethene polymers material.Choose the speed of travelling belt, so that the speed of ethene polymers material layer dosage ion irradiation that required receiving in small, broken bits is through the bundle of rays of ionization irradiation.After obtaining the ionization irradiation of required dosage, allow and on the conveying belt of irradiated layer, stay for some time so that its radical migration and combination at described environment, leave from being with then, advance forcing machine, under the melt temperature of irradiated material, processing, perhaps, in another special case, enter and add hott bed or classification adds hott bed, make grain fluidized through irradiated material with nitrogen or other rare gas element.In another is implemented, after treating it all radicals deactivating at least basically, this class is put into normal atmosphere and is cooled to room temperature rapidly through irradiated material.In another example, will be transferred in the storage vessel from being with under required environment through irradiated ethene polymers material, the inside of storage vessel has required environment, material is saved to radical moves complete required time in container.Enter forcing machine through irradiated material then, under the melt temperature of irradiated material, processing, perhaps the ethene polymers material granule is put into heating, rare gas element fluidisation bed or staged fluidized bed, behind the quencher radical, will put into atmosphere through irradiated polyethylene.
Another aspect of the present invention comprises that ethene polymers material strain of the present invention is hardened in the purposes in the expansion flow.When making ethene polymers material under the molten state, then expand stream to stretch at one or more directions place than the fireballing speed of proper flow.Expansion flow takes place extruding to apply in the operation, applies in the operation extruding, and the fused coating material is extruded on the substrate such as the mobile base-material of paper or metal sheet, and the rate travel of forcing machine or substrate is than rate of extrusion height.When fused films is extruded, when being stretched to required thickness then, expansion flow takes place in film production.Expansion flow is present in the thermal-setting operation, makes fused sheet material matched moulds on the plug mould in this operation, and the employing vacuum also is pressed into sheet material in the mould.This takes place in whipping agent expansible foaming product at manufacturing fused ethene polymers material.The ethene polymers material of strain hardening of the present invention with part (as few to 0.5wt%, as many as 95wt%) or whole basically melted plastic material carry out these or other melt-processed (as the profile extrusion in the fibers melt spinning), thereby be useful especially when making useful goods.
The present invention is further elaborated by integral part-accompanying drawing of this explanation and the following example.
Fig. 1 makes for continuation method, and for example normality solid polyethylene changes into the schema of a poly preferred embodiment of normality solid with strain hardening, gel-free.
The figure that Fig. 2 is depicted as the elongation time for the elongational viscosity of two samples of the high density polyethylene(HDPE) of the free-end long chain branches that makes with the inventive method and high density polyethylene(HDPE) contrast.
The implication of each symbol is as follows among Fig. 2:
Fig. 3 is the figure that the elongational viscosity of the new LDPE (film grade) sample of the free-end long chain branches that makes with method of the present invention and linear low density polyethylene (LLDPE) contrast was depicted as the elongation time.
The implication of each symbol is as follows among Fig. 3:
LLDPE-0.5 second-1
◆ LLDPE-1.0 second-1
◇ 1.5 megarads-0.5 second-1
■ 1.5 megarads-1.0 second-1
1.5 megarads-2.0 second-1
In more detail, Fig. 1 depicts the fluid-bed unit 10 of conventional structure and routine operation, by pipeline 11 to wherein introducing polyethylene in small, broken bits, that molecular weight is high, by pipeline 13 to wherein introducing nitrogen, the High molecular weight polyethylene of non-activity oxygen is by disposing solids discharge nozzle 15 dischargings of solid velocity controller 16, and solid discharge nozzle 15 leads to conveyer belt feed hopper 20.
Conveyer belt feed hopper 20 is the structures of covering of a kind of routinely design. Its inside is filled with nitrogen during operation. A solids discharging opening is arranged at its bottom, and polyethylene particle mouthful is removed by this outlet material, and on the top levels of the continuous cycloconveyor belt 21 of operation stratification.
What link to each other with radiation chamber 22 is to design routinely and the electron stream generator 25 of routine operation. Under common operating condition, the polyethylene particle layer of this generator on the conveyer belt 21 Send a branch of high-energy electron. One solids collector 28 is arranged below the conveyer belt discharging end, and when conveyer belt turned to work oppositely to move, this solids collector 28 was just collected the radiation exposed polyethylene particle that falls from conveyer belt 21. From solids collector 28, remove radiation exposed polyethylene particle and be transferred on the solids pipeline 30 by rotary valve or star-wheel 29.
But the extruder hopper 35 of giving extruder 36 feedings is conventional structure and routine operation. It also is closed in an inside and is filled with and keeps in the structure of blanket of nitrogen. Extruder 36 is conventional formations, and by the normal method operation. Solids in extruder hopper 35 is sent into extruder, and extruder is with the operation of certain extruded velocity, thus so that poly irradiation and enter time cycle between the extruder and be enough to form the long chain branches of the free-end of sufficient quantity. Therefore in case of necessity, choose the volume of extruder hopper 35, meet the requirements of numerical value with the period of storage that guarantees hopper, thereby satisfy this condition. The design of extruder 36 (length of extruder barrel and screw rod) and operation are according to being enough to make the polyethylene that contains free radical that basically deactivation of chien shih exists when sufficient all free radicals is arranged under melt temperature under residing pressure within it.
Processed like this, poly feature in small, broken bits is basic gel-free, and its density is 0.89-0.97g/cc, and by the abundant branching of free-end long-chain of ethylene unit. It can just in statu quo remove with or directly enter pelletizing and cooling unit 37, and transfers out with the solid grain form by solids supply line 38, and this solid grain can be stored for using later on or using without just storing.
In the other particular instance of processing HMW, ethene polymers material according to above-mentioned continuation method, can obtain similar result.
The following example set forth High molecular weight polyethylene of the present invention and with aforementioned to its preferable methods example that is prepared.
Measure melting index according to ASTM D-1238, I
2And I
10, the melting index ratio passes through I
10Divided by I
2And record.This ratiometer is understood molecular weight distribution, and this ratio is higher, and then molecular weight distribution is wideer.
Embodiment 1
Soltex T50-200 polyethylene pellet melting index MI is 2, and density is 0.95, puts it into sealing radiation chamber 22, and is 40ppm by nitrogen until making oxygen content.
With distribution of material on the stainless steel conveying belt 21 that is moving, to form 1.3cm height and the wide polyethylene powder bed of 15cm.The electron beam that this powder bed sends by the 2MeV Van de Graff producer of operating under 50 milliamperes of electric currents with conveying belt 21.The absorbed surface dose of result is 0.40 megarad.In addition, at the radiation chamber 22 of sealing with go out environment in the remainder of the system that stockline 34 formed or the active o content in the atmosphere by irradiated polyethylene transfer limes 30, gas-solid separator 31 and separator and will keep and be lower than 140ppm.
Behind the irradiation, polyethylene falls from conveying belt 21 ends, enters conveying belt discharging collector 28, and enters transfer limes 30 by rotary valve 29.After from the radiation polymerization thing, isolating gas, the go out stockline 34 of polymkeric substance by separator entered in the bag that is filled with nitrogen.
Make through irradiated polyethylene and under anaerobic and room temperature, kept 30 minutes.Material is put into the forcing machine hopper that is filled with nitrogen, under 260 ℃, " extrude in the single screw extrusion machine then 2.5.
Summarized the character of the final product of gel-free among the embodiment 1 in the table 1.
Embodiment 2～4
Except absorption dose was followed successively by 0.6,0.9 and 1.0 megarads, method and the component of embodiment 2～4 usefulness embodiment 1 were made.Transport line 30 at enclosed chamber 22, irradiated polyethylene, the content that gas-solid separator 31 and separator go out oxygen in the stockline 34 remains on below the 60ppm.Summarized the character of the gel-free final product of embodiment 2～4 in the table I.
Embodiment 5～8
Except the melting index MI of Dow04052N polyethylene pellet is 4, density is 0.952, and absorption dose is followed successively by outside 0.5,0.7,0.8 and 1.0 megarads, and embodiment 5-8 makes with method and the component of embodiment 1.The oxygen level that goes out in the stockline 34 at the radiation chamber 22, irradiated polyethylene transfer limes 30, gas-solid separator 31 and the separator that seal is maintained at below the 100ppm.Summarized the character of the gel-free final product of embodiment 5～8 in the table I.
Comparative examples 1 and 2
Comparative examples 1 and 2 is respectively without the Soltex T50-200 of irradiation and Dow04052N polyethylene pellet sample.
The table I
Embodiment dosage I
10I
2I
10/ I
2
(megarad)
C-1 0 4.1 1.8 2.27
1 0.4 10.9 1.0 10.4
2 0.6 10.0 0.89 11.2
3 0.9 8.7 0.67 13.0
4 1.0 7.9 0.64 12.5
C-2 0 31.5 4.30 7.32
5 0.5 15.6 1.27 12.3
6 0.7 9.70 0.682 14.2
7 0.8 8.48 0.521 20.7
8 1.0 6.49 0.333 19.5
Embodiment 9 and comparative examples 3～8
Irradiation steps (1) corresponding to present method, it is the criticality that demonstrates irradiation atmosphere, second step (2) corresponding to present method, to be free radical intermediate (RIA) carry out ageing in oxygen level is less than 15% controlled environment for it, last step corresponding to the method for the invention, it is the step of deactivating (RID) of free radical intermediate, and except following exception, the method for embodiment 9 and comparative examples 4～8 usefulness embodiment 1 is made:
-be that 6.90 high density polyethylene(HDPE) spherical pellets (being produced by Italian amaurosis spy (HIMONT) company limited) replaces Soltex T50-200 pellets of high density polyethylene with melting index MI;
-absorption dose is 1.1 megarads;
The processing environment of-comparative examples 3～8 changes shown in the table II; And
-in the time of about 260 ℃, " carry out the free radical deactivation in the Brabender forcing machine 3/4.
The result is shown in the following table II
The table II
Ⅰ
2@ Ⅰ
2@ Ⅰ
2@
Example I A RIA RID 1 day 3 days 13 days
C-3 - - - 6.90 - -
C-4 N
2Air air 3.56 3.13 3.23
C-5 N
2- - 2.44 3.67 4.58
C-6 air air air 4.62 4.30 4.51
C-7 air N
2N
24.39 4.14 4.13
C-8 air--4.56 5.90 9.40
9 N
2N
2N
22.86 2.63 2.60
Compare with embodiments of the invention 9, comparative examples 5 and 8 demonstrates the poor stability of melt flow rate (MFR) after 13 days.Comparative examples 4,6 and 7 better slightly than the stability of the melt flow rate (MFR) of comparative examples 5 and 8, but its melt flow rate (MFR) is little unlike embodiment 9.
Embodiment 10-15 and comparative examples 9 and 10
Embodiment 10-15 makes with method and the component of embodiment 1, wherein different places be: used ethene polymers goes out stockline 34 and enters to be filled with 3/4 of nitrogen and " in the hopper of Brabender forcing machine; 210 ℃ is first district in this forcing machine; 215 ℃ is second district; the die head place is 220 ℃, and then to use the ordinary method granulation through separator among the embodiment 10-15.With disposed the Maddoch mixing machine 1～1/4 " the Killian single screw extrusion machine makes pellet carry out secondary with 0.1%Irganox 1010 stablizers on the flat profile of 100rpm and 420F and extrudes.Irradiation and extrude between about 15 minutes of hold-time average out to.Table has been summarized the character of the final product of embodiment 10～15 in the III, set forth among Fig. 2 and 3 embodiment 10,12 and 14 and comparative examples 9 and 10 be 0.05-2.0 second 180 ℃ and strain rate
-1The following elongational viscosity that records with Rheometrics RER 9000 extension rheometers.
(1) the Gottfert Rheotens melt tension instrument of producing with Gottfert company is measured, the process of tension force (li newton) of measuring fusion ethene polymers line material is as follows: polymkeric substance to be measured is long by 20mm under 180 ℃, the kapillary of 2mm diameter and extruding; With constant acceleration is 0.3Cm/ second
2Tensioning system this line material that stretches.Tension force is high more, and visco-elasticity is good more, thereby the processibility of polymkeric substance under molten state is also good more.
(2) limiting viscosity that in 135 ℃ naphthalane, records.
(3) molecular-weight average that records by laser light scattering of the Wyatt Dawn laser light scattering instrument of in 135 ℃ trichlorobenzene, producing with Wyatt technology company.
(4) branching rate, (IV)
Lin=2.77 * 10
-4Mw
0.25
(5) contain the high density polyethylene(HDPE) of 0.5% propylene monomer units, produced by Dow chemical company, it is that melting index (MI) is 3.9 pellet.
(6) linear low density polyethylene (LLDPE) contains 6.1% butene-1 monomeric unit, and it is that melting index MI is 7.9 pellet that it and 200 parts of Irganox1076 stablizer/percentage parts mix it, covers special (HIMONT) company limited by Italy and produces.
Last table result shows that the ratio of polyvinyl melting index of the present invention increases, and this shows that its molecular weight distribution increases, and melt tension increases, and the branching rate that melt strength and expression form long chain branches also increases.
Fig. 2 and result shown in Figure 3 show: polyvinyl elongational viscosity of the present invention indicates this material strain hardening capacity.Trend is the strain hardening elongational viscosity to be increased with the minimizing of branching rate, i.e. increase with the long chain branching degree increases.
The ethene polymers of free-end long chain branches of the present invention can be used for melt-processed to be formed with the goods of usefulness, and for example foam article such as foam sheet and thermoset sheet material and thermoformed articles are extruded coated article and fiber etc.In fact, strain hardening ethene polymers material of the present invention is useful in all melt-processed, needs high-molecular weight, vinyl polymerization material that melt strength is high when melt-processed.
Aforementioned disclosure makes further feature of the present invention, advantage and example apparent to the personnel of this technical field.Thus, since described special case of the present invention in detail, change and modification that these special cases are made do not deviate from the spirit and scope of specification sheets and claims yet.
This specification sheets " in fact by ... constitute " speech got rid of this not this material of statement, the concentration of this material has been enough to influence in fact the essential characteristic and the character of defined composition here, yet it allows the existence of one or more this materials of not stating, the concentration of this kind material is not enough to influence in fact described essential property and feature.
Claims (16)
1, a kind of normality solid, high molecular, gel-free through irradiated ethene polymers material, its branching rate is characterized in that less than 1 it has the strain hardening elongational viscosity.
2, a kind of normality solid, high molecular, gel-free through irradiated ethene polymers material, its branching rate is less than 1, density is 0.89～0.97g/cc, it is characterized in that it has the strain hardening elongational viscosity.
3, ethene polymers material according to claim 2, it is characterized in that this material in fact by density greater than 0.94g/cc, the branching rate constitutes less than 0.9 high molecular weight ethylene polymkeric substance.
4, ethene polymers material according to claim 3 is characterized in that branching rate wherein is about 0.2～0.8.
5, ethene polymers material according to claim 2, it is characterized in that this material in fact by density less than 0.94g/cc, the branching rate constitutes less than 0.9 high molecular weight ethylene polymkeric substance.
6, ethene polymers material according to claim 5 is characterized in that branching rate wherein is 0.2～0.8.
7, ethene polymers material according to claim 2 is characterized in that ethene polymers wherein is a particle form.
8, a kind of with normality solid, high molecular, density be 0.89～0.97g/cc, no strain hardening elongational viscosity ethene polymers material preparation normality solid, high molecular, gel-free, the method through irradiated ethene polymers material of strain hardening elongational viscosity is arranged, it is characterized in that this method comprises:
(1) the described ethene polymers material of irradiation
(a) be held at less than the 15%(volume of environment at activity keto concentration) described environment in, and
(b) with about 1～1 * 10
4Megarad/minute dosage speed with high energy ion irradiation for some time, make irradiation reach 2.0 megarads, but be not enough to cause the material production gel;
What (2) will obtain like this keeps grace time so that the capacity long chain branches forms through irradiated material in this class environment; And
(3) in this class environment, handle then through irradiated material, so that all radicals that exist in irradiated material deactivate.
9, method according to claim 8 is characterized in that at pre-irradiation, and described ethene polymers material is maintained in the described reducing activity oxygen environment.
10, method according to claim 8 is characterized in that the active o content in the described environment is lower than about 0.004%(volume).
11, method according to claim 8, the absorption dose that it is characterized in that high energy ion irradiation wherein is 1～12 megarad.
12, method according to claim 8, the time that it is characterized in that step (2) is about 1 minute to 1 hour.
13, a kind of is 0.89～0.97g/cc, branching rate less than 1 the film composite that constitutes through irradiated ethene polymers by normality solid, high molecular, gel-free, density in fact, it is characterized in that this material has the strain hardening elongational viscosity.
14, a kind of in fact by normality solid, high molecular, gel-free, density be 0.89～0.97g/cc, branching rate less than 1 through the film that irradiated ethene polymers constituted, it is characterized in that this material has the strain hardening elongational viscosity.
15, a kind of method for preparing blown film, this method is that vinyl composition is clamp-oned in the pipe, blowing is subsequently gone in the film bubble, described composition in fact by normality solid, high molecular, gel-free, density by 0.89～0.97g/cc, branching rate less than 1 constituted through irradiated ethene polymers material, it is characterized in that this material has the strain hardening elongational viscosity.
16, a kind of useful article of forming by polyvinyl composition, said composition by a large amount of normality solids, high molecular, gel-free, density by 0.89～0.97g/cc, branching rate less than 1 constituted through irradiated ethene polymers material, it is characterized in that this material has the strain hardening elongational viscosity.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US71895191A | 1991-06-21 | 1991-06-21 | |
| US07/718,951 | 1991-06-21 | ||
| US72003691A | 1991-06-24 | 1991-06-24 | |
| US07/720,036 | 1991-06-24 | ||
| US89747292A | 1992-06-18 | 1992-06-18 | |
| US07/897,472 | 1992-06-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1069038A true CN1069038A (en) | 1993-02-17 |
| CN1045210C CN1045210C (en) | 1999-09-22 |
Family
ID=27418987
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92104989A Expired - Fee Related CN1045210C (en) | 1991-06-21 | 1992-06-20 | High melt strength ethylene polymer process for making it and use thereof |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JP3386150B2 (en) |
| KR (1) | KR100266044B1 (en) |
| CN (1) | CN1045210C (en) |
| AU (1) | AU1846692A (en) |
| BR (1) | BR9202331A (en) |
| CA (1) | CA2071779C (en) |
| FI (1) | FI922879A (en) |
| MX (1) | MX9203077A (en) |
| NO (1) | NO922435L (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105143288A (en) * | 2013-03-28 | 2015-12-09 | 陶氏环球技术有限责任公司 | An ethylene/alpha-olefin interpolymer composition |
| CN106632784A (en) * | 2016-10-27 | 2017-05-10 | 段恒宇 | Preparation method of ethylene/alpha-olefin copolymer, and application of ethylene/alpha-olefin copolymer in pipeline transmission |
| CN107660222A (en) * | 2015-04-30 | 2018-02-02 | Sabic环球技术有限责任公司 | High density polyethylene (HDPE) |
| CN108463496A (en) * | 2016-01-12 | 2018-08-28 | Sabic环球技术有限责任公司 | The injection molding product of foaming |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08269262A (en) * | 1995-03-30 | 1996-10-15 | Showa Denko Kk | Polypropylene resin composition |
| JPH1067871A (en) * | 1996-08-28 | 1998-03-10 | Asahi Chem Ind Co Ltd | Production of microporous polyethylene film |
| DE69922435T2 (en) * | 1998-06-10 | 2005-12-08 | Depuy Products, Inc., Warsaw | Method for producing crosslinked, molded plastic bearings |
| JP4140107B2 (en) * | 1998-12-28 | 2008-08-27 | 東ソー株式会社 | Ethylene resin composition and foam comprising the same |
| AU2004263737A1 (en) * | 2003-08-12 | 2005-02-17 | Basell Poliolefine Italia s.r.l.% | Irradiated butene-1 polymer compositions |
| JP2005146129A (en) * | 2003-11-17 | 2005-06-09 | Mitsui Chemicals Inc | ETHYLENE-alpha-OLEFIN COPOLYMER, RESIN COMPOSITION COMPOSED OF THE SAME, AND FILM OR SHEET MADE OF IT |
| JP2010276128A (en) * | 2009-05-29 | 2010-12-09 | Sumitomo Chemical Co Ltd | Tube |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4586995A (en) * | 1982-09-17 | 1986-05-06 | Phillips Petroleum Company | Polymer and irradiation treatment method |
| IN166935B (en) * | 1985-01-31 | 1990-08-11 | Himont Inc | |
| NO167039C (en) * | 1985-01-31 | 1991-09-25 | Himont Inc | PROCEDURE FOR MANUFACTURING THE POLYPROPYLLE WITH LONG-CHAINED BRANCHES AND APPLICATION OF THIS |
-
1992
- 1992-06-18 FI FI922879A patent/FI922879A/en not_active Application Discontinuation
- 1992-06-19 MX MX9203077A patent/MX9203077A/en not_active IP Right Cessation
- 1992-06-19 NO NO92922435A patent/NO922435L/en unknown
- 1992-06-19 KR KR1019920010649A patent/KR100266044B1/en not_active IP Right Cessation
- 1992-06-19 BR BR929202331A patent/BR9202331A/en not_active IP Right Cessation
- 1992-06-20 CN CN92104989A patent/CN1045210C/en not_active Expired - Fee Related
- 1992-06-22 CA CA002071779A patent/CA2071779C/en not_active Expired - Fee Related
- 1992-06-22 AU AU18466/92A patent/AU1846692A/en not_active Abandoned
- 1992-06-22 JP JP16291692A patent/JP3386150B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105143288A (en) * | 2013-03-28 | 2015-12-09 | 陶氏环球技术有限责任公司 | An ethylene/alpha-olefin interpolymer composition |
| CN105143288B (en) * | 2013-03-28 | 2017-10-13 | 陶氏环球技术有限责任公司 | Ethylene/alpha-olefin interpolymer composition |
| CN107660222A (en) * | 2015-04-30 | 2018-02-02 | Sabic环球技术有限责任公司 | High density polyethylene (HDPE) |
| CN107660222B (en) * | 2015-04-30 | 2021-04-16 | Sabic环球技术有限责任公司 | High density polyethylene |
| CN108463496A (en) * | 2016-01-12 | 2018-08-28 | Sabic环球技术有限责任公司 | The injection molding product of foaming |
| CN108463496B (en) * | 2016-01-12 | 2021-03-23 | Sabic环球技术有限责任公司 | Foamed injection molded article |
| CN106632784A (en) * | 2016-10-27 | 2017-05-10 | 段恒宇 | Preparation method of ethylene/alpha-olefin copolymer, and application of ethylene/alpha-olefin copolymer in pipeline transmission |
Also Published As
| Publication number | Publication date |
|---|---|
| KR930000547A (en) | 1993-01-15 |
| AU1846692A (en) | 1992-12-24 |
| NO922435L (en) | 1992-12-22 |
| JPH0693033A (en) | 1994-04-05 |
| MX9203077A (en) | 1994-06-30 |
| FI922879A0 (en) | 1992-06-18 |
| BR9202331A (en) | 1993-01-19 |
| CN1045210C (en) | 1999-09-22 |
| NO922435D0 (en) | 1992-06-19 |
| CA2071779A1 (en) | 1992-12-22 |
| KR100266044B1 (en) | 2000-09-15 |
| FI922879A (en) | 1992-12-22 |
| CA2071779C (en) | 1997-01-21 |
| JP3386150B2 (en) | 2003-03-17 |
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| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C53 | Correction of patent for invention or patent application | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: PATENTEE; FROM: HIMONT INC. TO: MONTELL NORTH AMERICA INC. |
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| CP01 | Change in the name or title of a patent holder |
Patentee after: Montell North America Inc. Patentee before: Himont Inc. |
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| C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
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