CN1202180A - Copolymer of olefinic monomer and 1,2-polybutadiene - Google Patents

Copolymer of olefinic monomer and 1,2-polybutadiene Download PDF

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Publication number
CN1202180A
CN1202180A CN96198385A CN96198385A CN1202180A CN 1202180 A CN1202180 A CN 1202180A CN 96198385 A CN96198385 A CN 96198385A CN 96198385 A CN96198385 A CN 96198385A CN 1202180 A CN1202180 A CN 1202180A
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polyhutadiene
polyolefine
weight
olefinic monomer
alpha
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J·A·M·范贝克
N·H·弗里德里赫斯
J·A·哈恩拉思
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Koninklijke DSM NV
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DSM NV
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2420/00—Metallocene catalysts
    • C08F2420/01—Cp or analog bridged to a non-Cp X neutral donor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound

Abstract

The invention relates to a thermoplastic polyolefin which is a copolymer of at least one olefinic monomer and from 0.005 to 10 wt.% 1,2-polybutadiene referred to the copolymer and a process for producing a copolymer of at least one olefinic monomer and 1,2-polybutadiene under the influence of a cyclopentadienyl-containing transition metal complex.

Description

Olefinic monomer and 1, the multipolymer of 2-polyhutadiene
The present invention relates to TPO, it is an at least a olefinic monomer and 0.005～10% (weight) 1, the multipolymer of 2-polyhutadiene.
One of polyolefinic characteristic parameter is its molecular weight distribution, and molecular weight distribution is represented with the merchant of weight-average molecular weight Mw and number-average molecular weight Mn.This parameter is to product performance, and is for example all influential to tensile strength and shock resistance.An important parameter that influences the polyolefine processing characteristics is that melt flow is than (MFR).The method of calculation of melt flow ratio are normally: according to ASTM (ASTM (American society for testing materials)) standard D-1238, adopt 21.6 kilograms weight determination to go out melt index, divided by the melt index that the weight that adopts 2.16 kilograms is measured, resulting merchant is the melt flow ratio.Known, common polyolefinic MFR broadens with molecular weight distribution and improves, and in other words, increases with the numerical value of Mw/Mn and to raise.As a result, in some application scenario, when wishing that for the needs of processing characteristics specific MFR is arranged, and when wishing specific Mw/Mn ratio is arranged, just need seek certain compromise for the requirement of product performance.
Learn a kind of method from WO-A-93/08221 by geometry location Catalyst Production TPO.Disclosed this method allows keeping the molecular weight distribution width almost to change MFR under the constant situation.Yet as if disclosed polyolefine all has very the molecular weight distribution near 2 in this application of mentioning.Do not mention and how to produce polyolefine with other molecular weight distribution values.
Yet, selecting so that adapt to purposes widely in order to make best materials, people need such TPO, and this performance combination that provides according to prior art is provided in the combination of its MFR and molecular weight distribution.
Purpose of the present invention just provides such polyolefine.
This purpose of the present invention is that the multipolymer of 2-polyhutadiene reaches by at least a olefinic monomer and 0.005～10% (weight) 1.This 1, the 2-polyhutadiene is also referred to as (copolymerization) monomer hereinafter.Above-mentioned 1, the content of 2-polyhutadiene is for the total amount of multipolymer.
Participate in the method for copolymerization from the known a kind of polyhutadiene that the process of ethylene-propylene-elastoprene of producing available sulfur cross-linking, allows of DE-A-2.123.911.In this application, not mentioned 1, the 2-polyhutadiene is to the issuable influence of polyolefinic above-mentioned key property, and not to the type of polyhutadiene, for example is 1,4-, or be 1, the 2-polyhutadiene is distinguished.
DE-A-2.917.403 discloses a class and has contained 10～20%1, and the unsaturated structure of 2-(vinyl), molecular weight are 10 5～10 6The propylene of gram/mole and the multipolymer of polyhutadiene.Difference between the also not mentioned dissimilar polyhutadiene of this application.Described copolymer sheet reveals the behavior of the thermoplastic material with rubber elastomer characteristics.
By contrast, polyolefine of the present invention then is essentially thermoplastic, does not have tangible rubber elastomer characteristics.Polyolefine of the present invention contains at least a olefinic monomer.As olefinic monomer, use ethene, randomly unite again and use one or more C 4～C 20Alpha-olefin.This olefinic monomer can contain 0～50% (weight) C with respect to the olefinic monomer total amount that exists in the polyolefine of the present invention 4～C 20Alpha-olefin.
The alpha-olefin of uniting use with ethene is C preferably 4～C 10Alpha-olefin.The example of this type of alpha-olefin is butylene, hexene and octene.Known, particularly those wherein again copolymerization as the ethene of the 3rd monomeric diene and the multipolymer of one or more alpha-olefins, have rubber elastomer characteristics.Because polyolefine of the present invention has thermoplasticity, therefore remove and come from 1, beyond the unit of 2-polyhutadiene, it no longer contains any remarkable quantity diene deutero-unit.Preferably, this type of is at most 1% (weight) of polymkeric substance total amount by the unitary content of other diene deutero-, does not most preferably then contain this type of fully by other diene deutero-unit.
Polyolefine of the present invention does not contain remarkable quantity and removes olefinic monomer described above and 1, the monomer outside the 2-polyhutadiene.
This polyolefinic molecular weight Mw and Mn adopt size exclusion chromatography method and cooperate viscosity detector to measure, and adopt the polyethylene calibration sample as reference simultaneously.
For realizing purpose of the present invention, 1, the 2-polyhutadiene is interpreted as a kind of like this butadiene polymer, wherein [CH 2-CH-] unitary number is greater than by other divinyl deutero-number of unit,
And so-called other divinyl deutero-unit for example are [CH 2-CH=CH-CH 2-] unit and those wherein no longer contain the unit of any unsaturated structure.
The chain length of the polyhutadiene of introducing is represented with polymeric butadiene unit number, should be 4 at least, and preferably this chain length is at least 10, more preferably is at least 25.1 of each molecular chain, the number of the unsaturated structure of 2-vinyl is 3 at least, preferably is 6 at least, more preferably is 13 at least.Under the relevant condition that the requirement of chain length and the unsaturated structure number of vinyl is met, also allow this 1, the 2-polyhutadiene is a fractional saturation, this situation still belongs to scope of the present invention.Make it saturated by for example hydrogenation, perhaps the copolyreaction of divinyl and alpha-olefin realizes.The chain length of polyhutadiene preferably is not more than 5000.Chain length causes the deterioration of polyolefine traditional performance than this longer meeting, and this moment, polyolefine will begin to show the heterogeneous behavior of intensive.
Find, MFR to introduce 1, the 2-polybutadiene content has stronger dependency, shows as MFR and raises with the increase of polybutadiene content, then susceptibility is less to this for Mw/Mn ratio.Yet Mw/Mn ratio also has really with 1, and the 2-polybutadiene content increases and trend of rising is especially true for those comprise the unitary multipolymer of different 'alpha '-olefin monomers, and therefore, this content's index can be used to control this ratio again.
Generally speaking, the polyolefinic Mw/Mn ratio of the present invention is higher than those any 1 except not introducing, this ratio of (copolymerization) polymkeric substance of producing under other conditions that equate fully outside the 2-polyhutadiene.Preferably this ratio is brought up to and be not more than coefficient 3.5.Further improve this ratio and will cause the danger that forms gel in the multipolymer.After processing, particularly be processed into after the film, the made finished product outward appearance of this multipolymer can variation.Consider from requiring Mw/Mn ratio to improve the finite value this point, if 1, the chain length of 2-polyhutadiene is for being 4 at least, then 1, and the content of 2-polyhutadiene preferably is 10% (weight) at the most; More preferably be, when chain length is 10 or higher; Then its content is 5% (weight) at the most, most preferably, and when chain length is 25 or longer, then this content is 3% (weight) at the most, even 1, the 2-polybutadiene content be at the most 5% (weight), chain length be 10 or higher condition under 1, the effect of 2-polyhutadiene also very easily displays.Contain and surpass 10% high level 1, the polyolefine of 2-polyhutadiene may show bigger oxidation sensitive.
And, also find, 1 of fractional saturation, the existence of 2-polyhutadiene can cause Mw/Mn ratio to raise, and shows as Mw/Mn ratio and reduces along with double key number purpose in the polyhutadiene and raise.In addition, in this case, MFR also will be along with 1 of fractional saturation, the increase of 2-polybutadiene content and raising.
Polyolefine of the present invention has good processibility and melt strength, thereby is fit to wider product application, both can be used for thin-walled articles, and for example film also can be used for the heavy wall article.
The invention still further relates to a kind of method of making TPO, it comprises allows ethene reach, randomly, and one or more C 4～C 20Alpha-olefin contacts under certain condition with the transition metal complex that contains cyclopentadienyl as catalyzer, above-mentioned monomer under this condition can be in the presence of this catalyzer polymerization reaction take place.
It is well-known containing the polyolefinic method of non-cyclopentadiene deutero-ligand Catalyst Production by for example philip catalyst and Z-type catalyst and so on.The polyolefinic molecular weight distribution mw/mn of producing like this demonstrates complementary relation with the melt flow ratio.When Mw/Mn ratio was a certain set-point, MFR in fact just had been fixed, and therefore when plan production has the polymkeric substance of particular requirement Mw/Mn ratio, had just no longer included the leeway of the specific MFR of selection.
From WO-A-93/08221, learn a kind of produce under as the influence that contains cyclopentadienyl transition metal compounds of catalyzer ethene polymers and with the method for the multipolymer of alpha-olefin.The polyolefine of producing with the disclosed method of this application has 1.86～2.32 Mw/Mn ratio, and its a kind of parameter value that is equivalent to MFR is 5.6～16.Do not mention and how just can produce polyolefine with other molecular weight distribution.
Therefore, exist the needs to a kind of TPO production method, the TPO that this method is produced has the Mw/Mn ratio that is different from known polyolefins and the combination of MFR.
The present invention carries out polymerization and has just satisfied this needs by 1 under the existence of 2-polyhutadiene.
Find, this MFR and Mw/Mn ratio can by exist in the polymerisation medium 1, the content and the type of 2-polyhutadiene are controlled.This content to every Effect on Performance rule of mentioning in front about pointing out in this polyolefinic discussion.
1 of copolymerization, 2-polybutadiene content are 10% (weight) at the most, preferably are 5% (weight) at the most, more preferably are 3% (weight) at the most.If copolymerization too much 1, the 2-polyhutadiene, then the polyolefinic every thermoplastic property of gained will reduce.Surprisingly, even seldom measure 1 when adding, the 2-polyhutadiene also can be observed the influence that obviously can survey to resulting polymers structure and end properties during as comonomer and/or the 3rd monomer.The content that allows depends on 1, and 2-polyhutadiene chain length is as pointed in the top relevant polyolefinic description of the present invention.
For obtaining to contain appropriate quantity copolymer-1, the polyolefine of 2-polyhutadiene, must have in the reaction mixture 1, the 2-polybutadiene content especially depends on the activity of catalyst system therefor, this content can be determined by experiment easily.1, the 2-polybutadiene content is to the influence of for example MFR, will understand after having read the example that foregoing and this paper provides.Those skilled in the art just can determine this relation according to a few experimental result under selected reaction conditions, and determine to obtain the required correct consumption of multipolymer and/or the suitable molecular weight of estimated performance in view of the above.
1, the 2-polyhutadiene is seemingly entered according to a kind of mode efficiently is combined.This is unexpected, because the unsaturated side group of vinyl can be counted as a kind of γ-substituted olefine, has an alkyl substituent on its 3-position.This substituting group it is reported because it is to having had strong inhibitory effects around the so-called steric effect of ethylene linkage to the reactivity of alkene in the catalyzed alkene process.Therefore, realize 1 when requiring high conversion, in the polyolefin process process of the high introducing degree of 2-polyhutadiene, the alkene that this kind γ replaces should obviously be chosen as comonomer originally.
And only a small amount of 1, the introducing of 2-polyhutadiene just demonstrates the unusual effect to MFR.Here saidly be meant on a small quantity: the lacking of its consumption, so that the detected unsaturated link(age) number in the polyolefine of the present invention, and except not containing copolymer-1, the unsaturated link(age) number outside the 2-polyhutadiene in other all roughly the same TPO is in same scope.
Another advantage of the present invention is just like following.In WO-A-93/08221, change MFR and realize by suitable selecting catalyst consumption.This just requires also must adjust reaction conditions.Different therewith is that method of the present invention can and remove 1 at constant catalyst levels, implements under the situation that other conditions are all identical outside the 2-polybutadiene content, its reason is, say in principle, 1 in the reaction mixture, the 2-polybutadiene content is the parameter of decision.
About the definition of the related multipolymer of the inventive method and to will participating in 1 of copolymerization, the requirement of 2-polyhutadiene can be referring to above.
The enforcement of polyreaction comprises allows ethene reach, randomly, and one or more C 4～C 20Alpha-olefin contacts with the transition metal complex that contains cyclopentadienyl as catalyzer.
This metal complexes contains the periodic system of elements the 3rd that preferably is selected from IUPAC (IUPAC) redaction or the transition metal of the 4th family, this periodic system for example can be referring to 1989～nineteen ninety of CRC publishing company publication, the 70th edition " front cover of chemistry and physics handbook.If the valency of metal is 3 +, then this title complex can be expressed as R 1MX 1X 2Or R 1R 2MX 1If the valency of metal is 4 +, then this title complex can be expressed as R 1R 2MX 1X 2Or R 1MX 1X 2X 3
In the general formula that provides, R 1Be that replace or unsubstituted cyclopentadienyl ligand, for example indenyl, fluorenyl, methyl-cyclopentadienyl, pentamethyl-cyclopentadienyl, or the cyclopentadienyl ligand contain the heteroatoms derivative.In this group of in the end mentioning, heteroatoms can be the element that is selected from the 15th or the 16th family of periodic system of elements, for example N, P, As, O or S.This heteroatoms can constitute the part of this cyclopentadienyl rings, perhaps is positioned at outside the ring.R 2Can be as to R 1Definition in be cyclopentadienyl derivative like that, but also can be the substituting group that contains the dvielement of for example N, the P, As, O or the S that are selected from periodic system of elements, wherein contained assorted element links to each other with metal by covalent linkage or dative bond.R 1And R 2Can pass through-Si (R) 2Group, wherein R represents aliphatic group or aryl, and is by aliphatic group or aryl, perhaps interconnection by containing the group that is selected from periodic system of elements the 15th or the 16th family's element.
If R 2Be neutral and be not, simultaneously again with one of above-mentioned all modes and R by the cyclopentadiene derived compounds 1Link to each other then this R 1With R 2Combination be considered to as about R 1Description in the sort of derivative that contains heteroatomic cyclopentadienyl ligand of indication.
X 1, X 2And X 3Can be identical or different, all can be selected from:
-halogen
-aliphatic series or aromatic substituent
-contain the substituting group that is selected from periodic system of elements the 15th or the 16th family's element, for example OR 3, NR 3Deng, R wherein 3Can be aliphatic series or the aromatic substituent that randomly contains silicon.
As catalyzer, preferably use general formula to be R 4MX 1X 2The transition metal complex that contains cyclopentadienyl, wherein M is that the non-maximum that is selected from periodic system the 4th family is closed the transition metal of valency form, preferably Ti 3+, X wherein 1And X 2Meaning with top identical, and R 4Equal
[Cp’-Y-Z(R 5) n] -
Wherein Cp ' is by aliphatic group or aryl, and perhaps by containing the cyclopentadienyl derivative that heteroatom group replaces, Y is aliphatic group or aryl, and perhaps siliceous or heteroatomic group, Z are the elements that is selected from periodic system of elements the 15th or the 16th family, preferred N or P, R 5Be aliphatic group, aryl or siliceous group, subtract 1 and n equals the valency of Z.
Usually, this metal complexes is united use as catalyzer and a kind of activator.As activator, select the known material that is suitable for the object of the invention for use, aluminium trimethide oxyethane (MAO) for example, or possible (entirely) fluoro boron compound, for example three-phenyl-pentafluoride base borane and four-phenyl-pentafluoride ylboronic acid salt compound.In addition, in this catalyst system, can also adopt its metal to be selected from the organometallic compound of the 1st, 2,12 or 13 families, preferred alkyl aluminum compound or alkyl magnesium compound, for example trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, diethylaluminum ethoxide, magnesium ethide, dibutylmagnesium, ethyl-dibutyl magnesium and butyl-octyl group magnesium.The activity of catalyst system can be further enhanced by adding these main group metal/alkylates.
The condition that olefinic monomer contacts with catalyzer should make these monomers in the presence of this catalyzer polymerization to take place.By such as metal catalysts such as classical Z-N or philip catalysts and itself be the olefinic polyreaction of the reaction conditions chosen in the known technology, also can be applicable under the effect of the selected catalyzer of the inventive method, carry out olefinic polymerization.
This polyreaction for example can be in gas phase, carry out at suspensoid or in solution, or adopts (partly) continuous mode or employing intermittent mode.And, can also adopt a plurality of reactors of arranging according to parallel connection, series connection or the two array mode.Preferred adopt solution method because this method be particularly suitable for being used for producing be dissolved at least to a certain extent hydro carbons, the low-down polymkeric substance of degree of crystallinity.
As the dispersion agent or the solvent of polyreaction, can use any liquid that the catalyst system activity is not had negative impact.Therefore, can use saturated line style or branched aliphatic hydrocarbons, for example butane, pentane, heptane, five methylheptane, or use petroleum fractions, for example lightweight or common gasoline, petroleum naphtha, kerosene or gas oil, the perhaps mixture of above-mentioned substance.Aromatic hydrocarbons, for example benzene and toluene are suitable for, but owing to the reason of cost and safety is not preferred.With regard to the polymerization of plant size, preferred aliphatic hydrocrbon or its mixture that is provided by petrochemical industry that adopt is dried and purifies afterwards as dispersion agent or solvent.
The polymkeric substance that adopts the inventive method to obtain can adopt this to process as known method.Usually, certain of process segment of this polymkeric substance a bit adopt this as known mode with catalyst deactivation.
This polyreaction can be carried out under normal pressure, but also can carry out adding to depress.If polyreaction is carried out adding to depress, then the polymer output of unit time also can further improve.Preferably allow polyreaction in 0.1～60MPa (MPa), especially under the pressure of 1～30 MPa, carry out.When carrying out in so-called autoclave, polyreaction can adopt up to 100 MPas, even higher high pressure.
The molecular weight of polymkeric substance can adopt common mode to be controlled, and for example by adding hydrogen or other chain terminators, perhaps controls by regulating polymerizing condition.1, the 2-polyhutadiene preferably adds with its solution form in a kind of suitable dispersion agent that polymerization process is not had a negative impact.In continuous processing, 1, the 2-polyhutadiene preferably joins in the polymerization reactor in a continuous manner.In the system that adopts a plurality of reactors, also can be only with 1, the 2-polyhutadiene joins in some reactor used reactor.In batchwise polymerization, 1, the 2-polyhutadiene can add before the polyreaction or between polymerization period.1, the consumption and the molecular weight of 2-polyhutadiene illustrate in the above.
Below, will the present invention be described in conjunction with example, yet the present invention is not limited in these examples.
Measured density D according to ASTM standard D792～66 23Melt index MI is according to ASTM standard D1238, adopts 2.16 kilograms weight to measure.Melt flow is according to ASTM D1238 than the measuring method of MFR, adopts 21.6 and 2.16 kilograms weight respectively, measures melt index, and the merchant who obtains the two is MFR.Mw/Mn ratio is to adopt the Waters M150C gel permeation chromatograph that has been equipped with the DRI detector to measure the size exclusion chromatography, and select for use Viscotek502 type viscometer to measure ordinatedly as viscosity detector, also adopt the polyethylene calibration sample as reference simultaneously.
Example I～IV
Some kinds of polyolefine of the present invention have been prepared as follows.
In capacity is the autoclave of 2 liters, inject special boiling point spirits (boiling range is 65～70 ℃), remain on 160 ℃ temperature then.The mixture that in this autoclave, adds special boiling point spirits (5.5 kilograms/hour) and ethene (1.2 kilograms/hour) continuously.In addition, add the molar mass of hydrogen in some cases to obtain to require.Adjusting is to the inlet amount of autoclave, so that make autoclave keep being full of by reaction medium fully.Also in autoclave, add catalyst solution, activator suspensoid and triethyl aluminium solution continuously.Control conversion of ethylene by the add-on of regulating catalyzer and activator, make the transformation efficiency of every batch of experiment material reach about 95%.
As catalyzer, add ethylidene-dimethylamino-tetramethyl--cyclopentadienyl-titanium-dimethyl, Cp *(CH 2CH 2) N (CH 3) 2Ti (CH 3) 2, with preparation ethene and 1, the multipolymer of 2-polyhutadiene.For reaching 95% conversion of ethylene, need the catalyst concn that adds to be every liter 20 micromole approximately.
With four phenyl-pentafluoride ylboronic acids of xylidine salt as activator.For reaching 95% conversion of ethylene, need the activator concentration that adds to be every liter 40 micromole approximately.The triethyl aluminum concentration that adds in autoclave is about 40 micromoles per liter.In another container, prepared the following mixture of composition: the Mn that each molecular chain contains 50 vinyl groups is 1 of about 3000 gram/moles, 2-polyhutadiene (the grade B-3000 that Messrs NSSOH IWAI company produces) and special boiling point spirits.With 1 of some amount, 2-polyhutadiene solution pumps into autoclave continuously from this container.1, the setting speed that the 2-polyhutadiene adds is by in the suitable selection solution 1, and the concentration of 2-polyhutadiene and being adjusted to requires numerical value.Here, 1 Grams Per Hour 1, the 2-polyhutadiene corresponding to, by with respect to the ethene that transforms, 0.088% (weight).Different 1, the character that the 2-polyhutadiene adds the multipolymer that obtains under the speed is stated from table 1.
Table 1
Example 1, the 2-polyhutadiene adds speed MI MFR Mw/Mn D23
Grams Per Hour
I 0 6.1 25.8 2.5 958.9
II 0.25 4.7 27.8 2.5 959.6
III 2.5 4.7 30.2 2.6 959.1
IV 5 4.1 33.0 2.8 959.1
This result shows that MFR can be by 1, and the adding speed of 2-polyhutadiene is controlled.
Example V～IX
Ethene, 1-octene and 1, the terpolymer of 2-polyhutadiene:
Copy example I～IV, when polymerization, in autoclave, add octene-1, as extra monomer by 0.2 kilogram/hour.Different 1, the character that the 2-polyhutadiene adds the multipolymer that obtains under the speed is stated from table 2.The polymkeric substance of making contains 15% (weight) octene.
Table 2
Example 1, the 2-polyhutadiene adds speed MI MFR Mw/Mn D23
Grams Per Hour
V 0 4.2 29.1 2.5 914.9
VI 1.0 2.8 33.4 2.6 915.4
VII 5 2.4 39.8 3.2 915.6
VIII 15 0.68 56.7 5.0 916.2
IX 25 0.16 79.4 8.2 917.7
Fact proved that method of the present invention also is applicable to the production terpolymer.MFR numerical value is adding fewly to 1 Grams Per Hour 1, and the 2-polyhutadiene promptly is equivalent to just show tangible raising by after ethene 0.088% (weight) polyhutadiene that transforms.
Instance X～XIII
Copy top example, with 1 of two kinds of different grades, the 2-polyhutadiene has prepared ethene, 1-octene and 1, the terpolymer of 2-polyhutadiene, to study 1, the molar mass of 2-polyhutadiene is to this ethene, octene and 1, the influence of the MFR of the terpolymer of 2-polyhutadiene.Used already mentioned grade B-3000 among example V～IX and from same supplier's per minute subchain contain about 33 vinyl unsaturated units, Mn is the grade B-2000 of 2000 gram/moles.The result is stated from table 3.
Table 3
Example 1, the 2-polyhutadiene MI MFR ?Mw/Mn ?D23 1,2-polyhutadiene grade
Grams Per Hour
X 0 4.2 29.1 2.4 ?914.9 -
XI 2.5 4.1 31.1 2.7 ?917.0 B-2000
XII 5.0 2.2 38.6 3.0 ?915.6 B-2000
XIII 2.5 2.3 36.5 2.8 ?917.0 B-3000
VII 5.0 2.4 39.8 3.2 ?915.6 B-3000
Instance X IV～XVIII
Copy example I～IV to carry out polyreaction, different is to have adopted phenylbenzene methylene radical-fluorenyl-cyclopentadienyl-hafnium-dimethyl { [(C 6H 5) 2C] FluCpZrMe 2As catalyzer.
As 1, the 2-polyhutadiene, the grade of having used Messrs Aldrich company to supply,
Its Mn is about 1300 gram/moles, and degree of unsaturation is about 99%, its vinyl: trans insatiable hunger
Equal 40: 30 with structure (trade mark is grade A), and a kind of grade of same company supply,
Its Mn is about 1800 gram/moles, and degree of unsaturation is about 60%, unsaturated structure various can
Distribution between can configuration, use vinyl: trans: cis represents, (the trade mark that equals 45: 10: 5
Be grade B).The result is stated from table 4.
Table 4
Example 1,2-polyhutadiene add-on MI MFR Mw/Mn ?D23 Grade
% (mole)
XIV 0 12 Do not survey 3.5 ?956.7
XV 0.30 2.5 52 5.6 ?951.5 B
XVI 0.60 0.5 98 4.6 ?949.7 B
XVII 0.09 42 Do not survey 3.8 ?955.8 A
XVIII 0.19 9.6 38 3.8 ?956.7 A

Claims (12)

1. TPO, it be at least a olefinic monomer with, in the multipolymer total amount, 0.005～10% (weight) 1, the multipolymer of 2-polyhutadiene.
2. according to the thermoplastic polymer of claim 1, wherein olefinic monomer is an ethene.
3. according to the thermoplastic polymer of claim 1, wherein olefinic monomer comprise ethene and, by the olefinic monomer total amount that exists, 0～50% (weight) C 4～C 20Alpha-olefin.
4. according to the thermoplastic polymer of claim 3, wherein alpha-olefin is C 4～C 10Alpha-olefin.
5. according to any one polyolefine in the claim 1～4, wherein 1, the chain length of 2-polyhutadiene is represented with polymeric butadiene unit number, is not more than 5000.
6. according to any one polyolefine in the claim 1～5, it contains 0.01～5% (weight) polyhutadiene.
7. according to any one polyolefine in the claim 1～6, wherein 1, the chain length of 2-polyhutadiene is at least 10.
8. according to any one polyolefine in the claim 1～7, wherein 1 of each polyhutadiene chain, the number of the unsaturated structure of 2-vinyl is at least 3.
9. a method of producing the TPO of at least a olefinic monomer comprises allowing ethene reach, randomly, and one or more C 4～C 20Alpha-olefin, contact under certain condition with the transition metal complex that contains cyclopentadienyl as catalyzer, with this understanding this monomer can be in the presence of this catalyzer polymerization reaction take place, be characterised in that, this polyreaction is 1, carries out under the existence of 2-polyhutadiene.
10. according to the method for claim 9, wherein be R with the general formula 4MX 1X 2The transition metal complex that contains cyclopentadienyl as catalyzer, wherein M is that the non-maximum that is selected from periodic system the 4th family is closed the transition metal of valency form, preferred Ti 3+, X wherein 1And X 2Can be identical or different, all can be selected from:
-halogen
-aliphatic series or aromatic substituent
-contain the substituting group that is selected from periodic system of elements the 15th or the 16th family's element, for example OR 3, NR 3Deng, R wherein 3Can be aliphatic series or the aromatic substituent that randomly contains silicon, wherein R 4Equal
[Cp '-Y-Z (R 5) n] -Wherein Cp ' is by aliphatic group or aryl, and perhaps by containing the cyclopentadienyl derivative that heteroatomic group replaces, Y is aliphatic group or aryl, and is perhaps siliceous or contain heteroatomic group, and Z is the element that is selected from periodic system of elements the 15th or the 16th family, preferred N or P, R 5Be aliphatic group, aryl or siliceous group, subtract 1 and n equals the valency of Z.
11. according to any one method in the claim 9～10, wherein polyreaction is in 0.01～10% (weight) 1, carries out under the existence of 2-polyhutadiene.
12. according to any one method in the claim 9～11, wherein polyreaction is in 0.01～5% (weight) 1, carries out under the existence of 2-polyhutadiene.
CN96198385A 1995-09-19 1996-09-18 Copolymer of olefinic monomer and 1,2-polybutadiene Pending CN1202180A (en)

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