CN1233263A - A method of compounding a multimodal polymer composition - Google Patents
A method of compounding a multimodal polymer composition Download PDFInfo
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- CN1233263A CN1233263A CN97198698A CN97198698A CN1233263A CN 1233263 A CN1233263 A CN 1233263A CN 97198698 A CN97198698 A CN 97198698A CN 97198698 A CN97198698 A CN 97198698A CN 1233263 A CN1233263 A CN 1233263A
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- 239000000203 mixture Substances 0.000 title claims abstract description 58
- 238000013329 compounding Methods 0.000 title claims abstract description 52
- 229920000642 polymer Polymers 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 22
- 229920000573 polyethylene Polymers 0.000 claims abstract description 36
- 230000002902 bimodal effect Effects 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims description 33
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 24
- 239000005977 Ethylene Substances 0.000 claims description 18
- 238000010008 shearing Methods 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 7
- 230000000630 rising effect Effects 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims 1
- -1 polyethylene Polymers 0.000 claims 1
- 238000002844 melting Methods 0.000 abstract description 9
- 230000008018 melting Effects 0.000 abstract description 7
- 239000000470 constituent Substances 0.000 description 13
- 238000002156 mixing Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000007863 gel particle Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 229920006158 high molecular weight polymer Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/40—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/40—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft
- B29B7/42—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft with screw or helix
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/005—Processes for mixing polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
A method of compounding a multimodal, preferably a bimodal polymer composition comprising a low molecular weight ethylene polymer and a high molecular weight ethylene polymer is described. The composition is compounded during a relatively long time at a low temperature which lies in a narrow temperature range including the melting point of the low molecular weight ethylene polymer. More particularly, the polymer composition is compounded, without addition of a beat transfer medium, in a temperature range from about 10 DEG C. below to about 10 DEG C. above the melting point of the low molecular weight ethylene polymer during a time of more than 10 seconds. The viscosity ratio between the ethylene polymers in said temperature range preferably is from about 5:1 to about 1:5.
Description
The present invention relates to the method for compounding of multimodal polymer composition, relate more specifically to a kind of method of compounding that contains the multimodal polymer composition of low-molecular ethylene polymers and high molecular weight ethylene polymkeric substance.
For the present invention, term " ethene polymers " comprises Alathon and ethylene copolymer.
In addition, for the present invention, the molecular weight of polymkeric substance is according to ISO1133, and (MFR) defines by its melt flow index.As a kind of tolerance to polymer viscosity, melt flow index (mistake is called melting index usually) is under specified temp, pressure and mould condition, " restraining/10 minutes " value with polymer flow rate is represented, therefore, for every kind of polymkeric substance, this value not only is subjected to its molecular weight distribution, but also is subjected to the influence of its degree of branching etc.For specific polymkeric substance, its MFR value is high more, and its molecular-weight average is just low more.
So term " low-molecular ethylene polymers " is meant to have high melt flow index (MFR) MFR
2.16/ 10 minutes ethene polymers of=about 0.1-5000 gram, this is according to ISO1133, condition 4 records.
Similarly, term " high molecular weight ethylene polymkeric substance " is meant to have mobile index (MFR) MFR of low melt
21.6/ 10 minutes ethene polymers of=about 0.01-10.0 gram, this is according to ISO1133, condition 7 records.
When making polymer composition, in order to obtain composition as far as possible uniformly, its various compositions are answered uniform mixing as different polymkeric substance, filler, additive etc.This uniform mixing is undertaken by each composition of compounding in continuous or intermittent type compounding machine; Preceding type example has single screw rod or twin screw extruder.When composition comprised two or more different polymkeric substance, they are thorough mixing mutually, and they can form complete homogeneous polymer mixture ideally like this.For this reason, polymkeric substance can heat or not have to mix under the outer situation about heating outside, the fusible like this liquid that changes into, and these liquid polymerses carry out thorough mixing under high shear rate then.
In order to obtain uniform composition, on the one hand, should carry out compounding under the following conditions: a) high temperature, be easy to the blended low-viscosity (mobile) liquid so that polymeric constituent is transformed into, b) high as far as possible shearing rate is to provide the macro-mixing energy, and c) time of growing as far as possible, but then, be necessary limit temperature, shearing rate and time, because too exacting terms easily causes the decomposition of polymkeric substance.
In order to break the balance between the low Decomposition of excellent fit silver mixing spare and polymkeric substance, when the compounding composition, generally as quickly as possible temperature is risen to more than the fusing point of polymeric constituent, make it in the short as far as possible time, stand high shear rate then.This generally means, in forcing machine, comes the compounding said composition by heating combination, and wherein the fusion ethene polymers is in being warmed up to 130-160 ℃ temperature range below 10 seconds.
Although the above-mentioned ordinary method of compounding polymer composition can produce the result that can accept in many cases, run into variety of issue at multimodal polymer composition, when more specifically comprising the multimodal polymer composition batch mixing of low-molecular ethylene polymers and high molecular weight ethylene polymkeric substance.Therefore, for example, when being used for tubing, in the compounding so-called " white point " can appear at the compounding polymer composition.The about 10-50 μ of the size of these white points m is by the abundant high-molecular weight polymer granulometric composition of compounding not in the composition.Except outward appearance is destroyed, these white points also have a negative impact to the intensity of composition.In addition, for example, when making film, the gel particle of the about 0.01-1 millimeter of size often appears at the compounding polymer composition.These gel particles have destroyed outward appearance, cause the ununiformity of finished film, and by the high-molecular weight polymer granulometric composition that fully is not compounded in the composition.
Above-mentioned white point and gel particle are existing serious problems in the polymer industry, and the solution of this problem will mean, eliminate and use otherwise the obstacle during multimodal polymer composition of excellent performance.
In EP645232, a kind of method that reduces or avoid this problem by the heat-transfer material that adds liquid nitrogen or liquid state or solid carbon dioxide and so in polymer raw material has been described.Feed rate with polymkeric substance is a benchmark, add heat-transfer material amount be about 5-30% weight, preferably about 10-20% weight.But this adding mode cost of heat-transfer material is higher, and when preferably using solid carbon dioxide, the problem of relevant processing environment also occurs.
Now be surprisingly found out that, carry out compounding by adopting a kind of novel method, more specifically by than under the low melting glass, the compounding multimodal polymer composition reduces or eliminates the problems referred to above in a long time, the temperature range of described temperature is narrower, and in fact polymeric constituent in this temperature range fusion takes place mostly.
Therefore, the invention provides a kind of in single screw rod or twin screw extruder compounding comprise the multimodal polymer composition of low-molecular ethylene polymers and high molecular weight ethylene polymkeric substance, and the method for " white point " or gel particle can not appear in the finished product mixture, wherein, in the main region of carrying out compounding processing, shearing rate is the highest 100 seconds
-1According to method of the present invention, in polymer composition, do not add any heat-transfer material, and, the melt temperature by the low-molecular ethylene polymers fusing point below 10 ℃ when rising to more than the fusing point 10 ℃, the residence time will be longer than 10 seconds, preferably be longer than 15 seconds, more preferably be longer than 20 seconds, most preferably be longer than 25 seconds.Under these conditions, melt compounded at first takes place in more low-melting high molecular weight ethylene polymeric constituent, the low-molecular ethylene polymers component of higher melt just begins fusing then, and so most of compounding processing will be at more low-melting high molecular weight ethylene polymeric constituent.
These and other advantage and feature of the present invention can be found out from following specification sheets and appended claims.
As mentioned above, the polymer composition according to compounding of the present invention is a kind of multi-modal, preferred bimodal polymer composition.About " form " of polymkeric substance, this term is meant the shape of its molecular weight distribution curve, that is, and and the outside drawing of forming as the polymer weight of its molecular weight function.If this polymkeric substance is in the continuous processing step, by adopting tandem reactor and adopting different condition to obtain in each reactor, the different integral parts that produce in different reactor so will have the molecular weight distribution of himself.When the molecular weight distribution curve of these integral parts was overlapped into the molecular weight distribution curve of whole resulting polymers product, this curve had two or more summits, or obviously wideer than the curve of each integral part at least.This polymeric articles of making in two or more series of steps is called bimodal or multi-modal, and this depends on the number of step.Below, this polymkeric substance of all that make in two or more consecutive steps all is called " multi-modal ".The chemical ingredients that should be noted that different integral parts can be different.Therefore, one or more integral parts can comprise ethylene copolymer, and other one or more integral parts then can comprise Alathon.
People are known for a long time in placed in-line two or more polymerization reactors, prepare multi-modal, bimodal olefin polymer particularly, preferred multi-modal ethene polymers.As this prior art, can mention EP040992, EP041796, EP022376 and WO92/12182, at this with its reference content as relevant preparation multi-modal polymer.According to these reference contents, each polymerization stage all can carry out in liquid phase, slurries or gas phase.Particularly preferably being, is product when carrying out this polyreaction in two or more tandem reactors according to the polymer composition of compounding of the present invention.
But the polymeric constituent that multimodal polymer composition alternately comprises at least two kinds of differences and separates at first, according to the present invention, mixing of their meltings or compounding are in multimodal polymer composition.
Also have, the present invention is defined in the method for compounding of the multimodal polymer composition that comprises low-molecular ethylene polymers and high molecular weight ethylene polymkeric substance.As mentioned above, the polymericular weight among the present invention is by its melt flow rate definition.In general, the MFR of low-molecular ethylene polymers
2.16About 0.1-5000 gram/10 minutes, preferably about 50-500 gram/10 minutes; And the MFR of high molecular weight ethylene polymkeric substance
21.6About 0.01-10.0 gram/10 minutes, preferably about 0.1-5.0 gram/10 minutes.
Another distinguishing characteristics of this ethylene polymer component is that its density should be in certain scope.The density of low-molecular ethylene polymers should about 0.935-0.970 gram per centimeter
3, preferred 0.940-0.965 gram per centimeter
3And the density of high molecular weight ethylene polymkeric substance should about 0.875-0.945 gram per centimeter
3, preferred 0.875-0.935 gram per centimeter
3Therefore, preferably, low-molecular ethylene polymers is high density polyethylene(HDPE) (HDPE), and the high molecular weight ethylene polymkeric substance is linear low density polyethylene (LLDPE).
As mentioned above, under the low-molecular ethylene polymers fusing point about 10 ℃ to the fusing point about 10 ℃, in about 5 ℃ of temperature ranges about 5 ℃ to the fusing point, polymer composition of the present invention will carry out the compounding of long period under the preferred fusing point.Under the used condition of forcing machine, in the scope that this temperature range covered, high molecular low melting point ethylene polymer component obviously begins fusing, and the major portion in lower molecular weight high-melting-point ethylene polymer component also is melted in the mixture.
In the main forcing machine zone that compounding takes place, the ratio of the viscosity of the viscosity of low-molecular ethylene polymers and high molecular weight ethylene polymkeric substance should preferably be about 5: 1-1: 5, more preferably from about 3: 1-1: 3.Have now found that, if viscosity ratio outside this scope, just is difficult to obtain having well distributed and the dispersive polymeric constituent.
It is believed that if in the said temperature scope, come the compounding multimodal polymer composition according to the present invention, at first low-molecular ethylene polymers and low-molecular ethylene polymers all should be solid-state.In this step, the anti-deformability of high molecular weight polymer components is relatively poor, because its crystallization is bad and fusing point is lower than other component.Therefore, need to absorb most of shearing force and could begin fusing.Along with the rising of temperature, the high-melting-point lower-molecular-weight component begins to be melted to gradually in the matrix that melts high molecular weight component.In case fusing, lower-molecular-weight component should have than low viscosity.As mentioned above, in this step, it is the highest about 5: 1 that viscosity ratio should reach, that is, in order to make each component good dispersion, it is too big that the viscosity between polymeric constituent should not differ.The viscosity of two kinds of materials is near more, shearing force easy more from a phase transition to other mutually, produce distortion/dispersion so good mixing.
Therefore in the compounding process, have than low melting point high molecular weight ethylene polymkeric substance and at first begin fusing, and low molecular weight part keeps solid-state.In this step, differences in viscosity between two kinds of polymeric constituents is reversed, promptly, when the high molecular weight ethylene polymer melted, its viscosity is higher than the unexpected viscosity degradation of high molecular weight ethylene polymkeric substance of low-molecular ethylene polymers under normal operation, and becoming is lower than the viscosity of still solid-state low-molecular ethylene polymers.This " counter-rotating " viscosity relationship can remain to the low-molecular ethylene polymers component and melt, because in liquid phase and under identical temperature, wanting of the viscosity ratio low-molecular ethylene polymers of high molecular weight ethylene polymkeric substance is high.Therefore, along with the rising of temperature, the viscosity differences between polymeric constituent can be inverted to standard state when polymeric constituent all melts fully.
Polymeric constituent by the solid-state zone of intersection that becomes liquid phase in, these two kinds of materials are approaching relatively on hardness/viscosity, therefore can carry out good homogeneous and mix.In order to optimize mixed effect and corresponding compositions homogeneity, should be in the zone of intersection, that is, under about 10 ℃ of melt temperature about 10 ℃ to the fusing point under the low-molecular ethylene polymers fusing point, carry out compounding as far as possible for a long time.According to the present invention, to be longer than 10 seconds in the compounding time of the zone of intersection, preferably be longer than 15 seconds, more preferably be longer than 20 seconds, most preferably be longer than 25 seconds.But the time in the zone of intersection should be above about 1 minute.This and conventional method of compounding form contrast, just attempt usually to melt composition as far as possible soon and fully, carry out the high temperature compounding with liquid state then.
For above-mentioned ethene polymers, the about 125-140 of its fusing point ℃.But the temperature that begins to melt depends on heating rate, and in high heating rate, and under may occur during as compounding polymer composition in forcing machine about 300-400 ℃/minute, the temperature that begins to melt can rise to about 140-155 ℃.Also have, the delay fusing effect of high molecular weight ethylene polymkeric substance is eager to excel than low-molecular ethylene polymers.This means that carry out the actual zone of intersection of compounding or temperature range greatly between 125-155 ℃ according to the present invention, this depends on polymkeric substance and heating rate.
Another important factor is the shearing rate that polymer composition is stood when compounding.Although should carry out more effective mixing by improving shearing rate in principle, too high shearing rate easily causes the decomposition of polymkeric substance.Therefore, in the present invention, the shearing rate that carries out in the main region of compounding processing should be about at most 100 seconds
-1, preferably about 10-100 second
-1Be lower than about 10 seconds
-1Shearing rate often do not have effect, and be higher than 100 seconds
-1The shearing rate danger that then brings polymer degradation.About shearing rate, term " carries out the main region of compounding processing " and considers that when carrying out compounding in forcing machine, the polymeric constituent of different piece stands different shearings rate.Therefore, although will stand high shear rate by the small part composition of helical land in the screw rod, most compositions is carried out compounding in the helical channel between the screw rod land under low shearing rate.In the present invention, being also referred to as this shearing rate of average shear rate should be about at most 100 seconds
-1
According on the methodological principle of the present invention at conventional compounding device, as single screw rod or double-screw type, carry out in the preferred counter rotating double screw type compounding device.But at the appointed time, said composition is in the specified for temperature ranges, has necessity and add cooling.
According to this polymer composition of compounding of the present invention the time, if desired, can further carry out compounding according to conventional method of compounding.This means that said composition can be at about 150-300 ℃, under preferably about 160-250 ℃ high temperature and about 200-1000 second
-1Shearing rate under stand other compounding step.This compounding step of optionally replenishing can be directly and combine according to compounding step of the present invention and to carry out, and perhaps carries out separately after a while.
According to the present invention, although preferably in single stepping, carry out compounding,, also can in two or more independent steps, mix this polymkeric substance by allowing twice in polymkeric substance or repeatedly flow through viscosity and intersect phase, that is, each step is meant and carries out independent compounding operation in mixing tank or forcing machine.
Claims (10)
- One kind in single screw rod or twin screw extruder compounding comprise the method for the multimodal polymer composition of low-molecular ethylene polymers and high molecular weight ethylene polymkeric substance, it is characterized in that: in described polymer composition, do not add any heat-transfer material; Described polymer composition is the highest about 100 seconds -1Shearing rate under carry out compounding; And the temperature of described polymer composition below by the low-molecular ethylene polymers fusing point about 10 ℃ when rising to more than the fusing point about 10 ℃, the residence time was longer than 10 seconds.
- 2. according to the process of claim 1 wherein below temperature at described polymer composition is by the low-molecular ethylene polymers fusing point about 5 ℃ when rising to more than the fusing point about 5 ℃, the described residence time was longer than 10 seconds.
- 3. according to the method for claim 1 or 2, the wherein said residence time was longer than 15 seconds.
- 4. according to any one method among the claim 1-3, the wherein said residence time was longer than 20 seconds.
- 5. according to any one method among the claim 1-4, wherein below the low-molecular ethylene polymers fusing point about 10 ℃ to temperature range about 10 ℃ more than the fusing point, the ratio of the viscosity of the viscosity of described low-molecular ethylene polymers and described high molecular weight ethylene polymkeric substance is about 5: 1-1: 5.
- 6. according to the method for claim 5, wherein said viscosity ratio is about 3: 1-1: 3.
- 7. according to any one method among the claim 1-6, the density of wherein said low-molecular ethylene polymers is about the 0.935-0.970 gram per centimeter 3
- 8. according to any one method among the claim 1-7, the density of wherein said high molecular weight ethylene polymkeric substance is about 0.875-0.945cm 3/ g.
- 9. according to any one method among the claim 1-8, wherein said polymer composition is the polyethylene bimodal composition.
- 10. according to the method for claim 6, wherein said composition carries out compounding in counter rotating twin screW extruder.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE9603683A SE9603683L (en) | 1996-10-09 | 1996-10-09 | Methods for compounding a multimodal polymer composition |
| SE96036835 | 1996-10-09 | ||
| SE9603683-5 | 1996-10-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1233263A true CN1233263A (en) | 1999-10-27 |
| CN1066469C CN1066469C (en) | 2001-05-30 |
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ID=20404180
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97198698A Expired - Fee Related CN1066469C (en) | 1996-10-09 | 1997-10-03 | A method of compounding a multimodal polymer composition |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0931106A1 (en) |
| JP (1) | JP2001502370A (en) |
| CN (1) | CN1066469C (en) |
| AU (1) | AU4641397A (en) |
| SE (1) | SE9603683L (en) |
| WO (1) | WO1998015591A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100369729C (en) * | 2001-06-14 | 2008-02-20 | 英尼奥斯制造业比利时有限公司 | Method of compounding multimodal polyethylene composition |
Families Citing this family (22)
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| EP1319685A1 (en) * | 2001-12-14 | 2003-06-18 | ATOFINA Research | Physical blends of polyethylenes |
| EP1473137A1 (en) * | 2003-04-30 | 2004-11-03 | Coperion Werner & Pfleiderer GmbH & Co. KG | Process for melting and homogenizing bimodal or multimodal polyolefins |
| EP1648671A1 (en) * | 2003-07-29 | 2006-04-26 | Basell Polyolefine GmbH | Process for granulating powders of thermoplastic polymers under improved economic conditions |
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| DE102007014621A1 (en) * | 2007-03-23 | 2008-09-25 | Innogel Ag | Process for the preparation of short-chain molecular weight distributions by post-reactor extrusion |
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| EP2182524A1 (en) | 2008-10-31 | 2010-05-05 | Borealis AG | Cable and Polymer composition comprising a multimodal ethylene copolymer |
| EP2182525A1 (en) | 2008-10-31 | 2010-05-05 | Borealis AG | Cable and polymer composition comprising a multimodal ethylene copolymer |
| EP2182526A1 (en) | 2008-10-31 | 2010-05-05 | Borealis AG | Cable and polymer composition comprising an multimodal ethylene copolymer |
| ES2381849T3 (en) | 2008-11-17 | 2012-06-01 | Borealis Ag | Multi-stage procedure to produce polyethylene with reduced gel formation |
| EP2256159A1 (en) | 2009-05-26 | 2010-12-01 | Borealis AG | Polymer composition for crosslinked pipes |
| PL2256158T3 (en) | 2009-05-26 | 2014-09-30 | Borealis Ag | Polymer composition for crosslinked articles |
| DE102010006965A1 (en) | 2010-02-05 | 2011-08-11 | Continental Automotive GmbH, 30165 | Apparatus and method for determining a range of a battery characteristic |
| US10208196B2 (en) | 2010-03-17 | 2019-02-19 | Borealis Ag | Polymer composition for W and C application with advantageous electrical properties |
| KR20130016285A (en) | 2010-03-17 | 2013-02-14 | 보레알리스 아게 | Polymer composition for w&c application with advantageous electrical properties |
| CN107000257B (en) * | 2014-12-04 | 2019-10-11 | 巴塞尔聚烯烃股份有限公司 | The method for being used to prepare polyolefin composition |
| PL3567061T3 (en) | 2018-05-09 | 2024-02-26 | Borealis Ag | Polypropylene pipe composition |
| EP4023711A1 (en) | 2020-12-29 | 2022-07-06 | Borealis AG | Highly track resistant polyethylene compounds for wire and cable applications |
| EP4023712A1 (en) | 2020-12-29 | 2022-07-06 | Borealis AG | Highly track resistant polyethylene compositions for wire and cable applications |
| EP4257640B1 (en) | 2022-04-04 | 2024-08-28 | Borealis AG | Pipe comprising a polypropylene composition |
| EP4393989A1 (en) | 2022-12-27 | 2024-07-03 | Borealis AG | Use of a magnesium hydroxide filler in highly track resistant polyethylene compositions |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1604396A1 (en) * | 1966-03-26 | 1970-09-17 | Werner & Pfleiderer | Method and device for the production of thermoplastic mixtures by continuously homogenizing several parts of the mixture |
| CA2099750C (en) * | 1992-09-01 | 1996-05-07 | William Richard Coutant | Process for producing polymer blends |
| US5409646A (en) * | 1993-09-29 | 1995-04-25 | Union Carbide Chemicals & Plastics Technology Corporation | Method for compounding a polymerized alpha-olefin resin |
-
1996
- 1996-10-09 SE SE9603683A patent/SE9603683L/en not_active IP Right Cessation
-
1997
- 1997-10-03 WO PCT/SE1997/001659 patent/WO1998015591A1/en not_active Application Discontinuation
- 1997-10-03 EP EP97945139A patent/EP0931106A1/en not_active Withdrawn
- 1997-10-03 CN CN97198698A patent/CN1066469C/en not_active Expired - Fee Related
- 1997-10-03 JP JP10517447A patent/JP2001502370A/en active Pending
- 1997-10-03 AU AU46413/97A patent/AU4641397A/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100369729C (en) * | 2001-06-14 | 2008-02-20 | 英尼奥斯制造业比利时有限公司 | Method of compounding multimodal polyethylene composition |
Also Published As
| Publication number | Publication date |
|---|---|
| SE506754C2 (en) | 1998-02-09 |
| WO1998015591A1 (en) | 1998-04-16 |
| AU4641397A (en) | 1998-05-05 |
| CN1066469C (en) | 2001-05-30 |
| EP0931106A1 (en) | 1999-07-28 |
| SE9603683D0 (en) | 1996-10-09 |
| SE9603683L (en) | 1998-02-09 |
| JP2001502370A (en) | 2001-02-20 |
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