CA2010064A1 - Polypropylene wax and process for the production thereof - Google Patents
Polypropylene wax and process for the production thereofInfo
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- CA2010064A1 CA2010064A1 CA002010064A CA2010064A CA2010064A1 CA 2010064 A1 CA2010064 A1 CA 2010064A1 CA 002010064 A CA002010064 A CA 002010064A CA 2010064 A CA2010064 A CA 2010064A CA 2010064 A1 CA2010064 A1 CA 2010064A1
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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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- 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
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/63912—Component covered by group C08F4/62 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- 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
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/6392—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/63922—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/63927—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/943—Polymerization with metallocene catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S585/00—Chemistry of hydrocarbon compounds
- Y10S585/929—Special chemical considerations
- Y10S585/946—Product is waxy polymer
Abstract
Abstract Polypropylene wax and process for the production thereof Polyolefin waxes are obtained in high yield by copoly-merizing propylene with small amounts of other olefins in the presence of a catalyst composed of a metallocene of the formula I:
(I) and an alumoxane The waxes are produced as compact, spherical particles having a narrow particle size distri-bution and high apparent density. In addition, the physical data of these waxes such as, for example, hardness, melting point, melt viscosity etc., are vari-able within wide limits.
The polymer chains are noteworthy for a homogeneous and uniform structure, the comonomer units being pre-dominantly arranged individually between polypropylene blocks.
(I) and an alumoxane The waxes are produced as compact, spherical particles having a narrow particle size distri-bution and high apparent density. In addition, the physical data of these waxes such as, for example, hardness, melting point, melt viscosity etc., are vari-able within wide limits.
The polymer chains are noteworthy for a homogeneous and uniform structure, the comonomer units being pre-dominantly arranged individually between polypropylene blocks.
Description
HOECHST AKTIENGESELLSCH~FT DA/~e HOE B9~F 052 Description Polypropylene wax and process for the production thereof The invention relates to a polypropylene wax whose polymer chains are of high uniformity as regards chain length and chain structure.
S The production of isotactic polyolefin waxe~ (isotactic index 80 to 85~, enthalpy of fusion 63 J/g, mixture of atactic and isotactic polyolefin chains) by means of supported catalysts, cocatalysts and stereoregulators at a temperature of over 95~C is knvwn (cf. DE 3,148,229).
Large amounts of hydrogen have ~o be employed as molar mass regulator.
Furthermore/ an MgCl2 supported contact catalyst which results in crystalline PP waxes with a narrow molar mass distribution is also known tcf. JP 59/206,409). This catalyst, too, has the typical disadvanta~es of catalyst systems which have been developed for the production of high-molecular-weight polyolefins and consequently have a low activity in the produc~ion of low-molecular-weight polyolefins. Furthermore, here again, an undesirable mixture o i~otactic and atactic chains is present in the wax product.
Wax-type random ethylene copolymers which contain an ~-olefin fraction of 1-15 mol~ and which are produced using a catalyst system based on zirconium hydride metallo-cene/alumox~ne (cf. JP 62/12g,303) are also known. Such metallocenes are not, however, suitable for producing isotactic polypropylene; in addition, their activity in polypropylene polymerization is very low.
Owinq to the low catalytic activity under the necessary reaction conditions, relatively high chlorine contents of, in some cases, over 1000 ppm are found in the pol~mer waxes if the catalyst residues are not removed by an expensive special post-treatment.
The use of metallocene/alumo~an~ catalyst system3 has also been proposed for the production of highly isotactic l-olefin polymer waxes (cf. DE 3,743J321).
Although it was possible to overcome the disadvantages of the processes described above with th:is catalyst, the high isotacticity of the products resulted in the har~-ness of the waxes being extremely high, and this i5 undesirable for a number of wax applications.
It is possible in principle to reduce the hardness by subseguently adding atactic poly-1 olefin wax. Apart from the high costs which are unacceptable and uneconomical on a large scale, this addition results in nonuniform and sticky products.
There is consequently the ob~ect of finding a process wlth which polyolafin waxes having lower hardness can be produced using metallocene/alumXane catalysts.
It was found that the object can be achieved by copoly-merizing propylene with other olefins in the presence ofcertain metallocene catalysts.
The invention consequently relates to a polypropylene wax composed of 80 to 99.75~ by weight, based on the ~o~al polymer, of propylene units and 0.25 to 20~ by weight, based on the total polymer, of units which are derived from ethylene or an olefin containing not less than 4 carbon atoms of the formula R15-CH=CH-Rl6, in which R15 and R16 are identical or different and are a hydrogen atom or an alky radical containing 1 to 28 carbon atoms or Rl5 and Rl6 form a ring containing 4 to 28 carbon atoms with the carbon atoms joining them, which polypropylene wax has a molar mass N~ of 1,000 to 50,000 g/mol, a poly-dispersity M~/M~ of 1.8 to S.0, a viscosity number of 2 to - 3 ~ 4 60 cm3/g~ a mel~ing point of 50 to 150C, an enthalpy of fusion ~ of less than 100 J/g, a dropping point of 60 to 160C, a melt viscosity at 170C of 100 to 20,000 mPa.s and a regular distribution of the comonomer uni~s in the polymer chain, the mean block length n being less than 1.25.
The inven~ion furthermore relates to a process ~or the production of the polypropylene wax as claimed in claLm 1 by polymerizing 70 ~o 99.9~ by weightl based on the total amount of the monomers, of propylene and 0.1 to 3D%
by weight, based on the total amount of the monomers, of not less than one represen~ative of the group comprising ethylene and olefins containing not less than 4 carbon atoms of the formula ~ CH=CH~Rls, in which Rl5 and Rl6 have the meaning sta~ed in claIm 1, at a temperature of -60~C to 100C, at a pressure of 0.5 to 120 bar, in solution, in suspension or in the ga~ phase, in the presence of hydrogen as a molar mass regulator and of a catalyst which is composed of a metallocene and an alum oxane wherein the hydrogen partial pres~ure is 0.05 to 50 bar and the molax ratio of olefin to hydrogen is 3 to 3,000:1, and wherein the metallocene is a com-pound of the formula I:
R4--~-( CR~R9 ~ m R1~1 R7 R2 R5~1R3R9)n (I) in which M1 is a metal of the group IVb, Vb or VIb of the periodic system, R1 and R2 are identical or different and are a hydrogen atom, a (C1-C10)alkyl group, a tC1-ClO)alkoxy group, a (C6-C1O)aryl group, a (C~-C1O)aryloxy group, a (C2-C10)alkenyl gxoup, a (C7-C40)arylal~yl group, a (C7-C40)alkylaryl group, a (C8-C40)arylalXenyl group or a halogen atom, R3, R4, R5 and R6 are identical or differen~ and are a hydrogen atom, a halogen atom, a (Cl-cl0)alkyl group~ a (Cl-CI0)alkoxy group, a (C6-C10)aryl group, or an -NR2, -SRl, -OSiR3,-SiR3, or-PR2 radical, in which Rl is a (Cl-C1O)alkyl group, a (C6-C1O)aryl group or alternatively, in the case of radicals containing silicon or phofiphorus, a halogen atom, or two ad~acen~ R3, R4, R5 or R6 radicals each form a ring with the carbon atoms ~oining them, R7 is Rll R~ ll Rll Rll M2 _ l2 _ , - M? _ CR2 _ , _ O _ ~2 _ o -R12 R12 ~12 ~12 R12 - C - , _ O ~ ~2 _ , - M2 _ o - M2 _ ~12 ~lZ ~12 i12 =BR11, =AlR11, -Ge-, -Sn-, -O-, -S-, =SO, -S02, =NR~ CO, =PRll or =P(O)R
where R11, R12 and R13 are identical or different and are a hydrogen atom, a halogen atom, a (Cl-C30)alkyl group, a (C1-C10)fluoroalkyl group, a (C~-C1O)aryl group, a (C6-C10)fluoroaryl group, a ~Cl-C10~alkoxy group, a (C2-C10)alkenyl group, a (C7-C40)arylalkyl group, a (C8-C40)arylalkenyl group, a (C7-C40)alkylaryl group, or R11 and Rl2 or Rll and Rl3 in each case form a ring with the atoms joining them, M2 is silicon~ germanium or tin, R8 and R9 are identical or different and have the meaning stated for Rl1, m and n are identical or different and are zero, 1 or 2, m plus n being zero, 1 or 2, and the alumo;ane is a compound of the formula (II):
X~ 6'~
R~4 ~ Rl4 R14 Al - o - A1 - O - Al /
R14 ~~ ' p \ R14 (II) for ~he linear type and~or of the formula (III) -lAl - o (III) p+2 for the cyclic type, Rl4 being a (Cl-C6)alkyl group in the formulae (II) and (III3 and p beiny an in~eger fxom 2 to 50.
The polypropylene wax according ~o the invention is composed of 80 to 9~.75, preferably 90 to 99.5% by weight, based on the total pol~mer, of propylene units and of 0.25 to 20, preferably 0.5 to 15% by weight, bcised on the total polymer, of unlts which are derived ~rom ethylene or an olefin containing at least 4 carbon at:oms of the formula Rl5-CH=CH-RlB. In this formula, R1s and Rl6 are identical or dif~erent and are a hydrogen atom or an alkyl radical containing l to 28 carbon atoms. Rls and Rl6 may, howe~er, also form a ring contai~ing 4 to 28 carbon atoms with the carbon atoms joining them. Examples of such olefins are l-butene, l-hexene, 4-methyl-1-pentene, l~pentene, l octene, norbornene, norbornadiene, 6-pentene, cyclohexene or cyclooctene.
Preferred copolymer waxes are propylene/ethylene, propy-lene/l-hexene, propylene/l-butene and propylene/4-methyl-l-pentene polymers.
Copolymeræ of three different monomers are preferably propylene/ethylene/l-hexene and propylene/ethylene/l-butene terpolymer waxes.
The copolymer wax according to the invention has a molar mass M~ of 1,000 to 50,000 g/mol, preferably 8,000 to 45,000 g/mol, a polydispersity M~/M~ of 1.8 to 5.0, - 6 ~
preferably 2.0 to 4.0, a visco~ity number of 2 to 60 cm3/g, preferably 10 to 50 cm3/g, a melting point of 50 to 150C, preferably 70 to 140Cr an enthalpy fusion ~H of less than 100 J/g, a dropping point of 60 to 160C, preferably 80 to 150C, a melt vi~cosity of 100 to 20,000 mPa.s, preferably 120 to 7,000 mPa.3, at 170C and a regular distribution of the comonomer units in the polymer chain, the me~ium ccmonc~er block length n being less ~han 1.25, preferably le~s than 1.2.
The catalyst to be used for the process according to the invention is composed of an alum o~ane and a metallocene of the formula I:
R4--~( CRBR9 ) m R6 R6 (I) In formula I, M1 is a metal of the group IVb, Vb or VIb of the periodic system, for example titanium, zirconium, hafnium~ vanadium, niobium, tantalum, chromium, mol-ybdenum or tungsten, preferably zirconium and hafnium.
R1 and R2 are identical or different and are a hydrogen atom, a (C1-C~0)-, preferably a (C1-C3)alkyl group, a (Cl-C10)-, preferably a (C~-C3)al~oxy group, a (C6-C~O)-, preferably a (C6-Ca)aryl group, a (C6-C10), preferably a (C6-C8)aryloxy group, a tC2-C10)-, preferably a (C2-C4) alkenyl group, a (C7-C40)-, preferably a (C7-C1O)arylalkyl group, a (C7-C40)-, preferably a (C7-C~z)alkylaryl group, a (C8-C40)-, preferably a (C8-C,2)arylalkenyl group or a halogen atom, preferably chlorine.
R3, R4, R5 and R6 are identical or different and are a hydrogen atom, a halogen atom, preferably a fluorine, chlorine or bromine atom, a (C~-C~0)-, preferably a tC~-C3)alkyl group, a (C6-C~0)-, preferably a (C6-C8)aryl - 7 ~ 0 group, a (C~-C~0)-, pre~erably a (Cl-C3)alkoxy group, or an -NR2, -SR10, -OSiR3, ~SiR3, or -PR2 radical, in which Rl is a (Cl-C,0)-, preferably a (Cl-C3)alkyl group or a (C6-Cl0~-, preferably a ~C6-C8)aryl group, or alter-natively, in the case of radicals containing silicon or phosphorus, a halogen atom, preferably a chlorine atom, or two adjacent radicals R3, R4, R5 or R6 each form a ring with the carbon atoms joining them. Particularly pre-ferred ligands are indenyl, fluorenyl and cyclopenta-dienyl.
R7 i~
Rll ~11 Rll ~11 Rll - M2 _ , _ ~2 _ l2 _ , - M2 _ CR~ _ , _ o - M2 _ o -R12 R12 R12 l12 ~12 Rll ~11 Rll ~,11 ~ _ , - O - M2 _ , - M~ - O - M2 R12 Rl~ R12 R12 =BRll, =AlRll, -Ge-, -Sn-, -O-, -S-, =SO, =SO2, =NRIl, =CO, =PRl1 or =P(O)R11, where R1l, R12 and R13 are identical or different and are a hydrogen atom, a halogen atom, a (Cl-C30)-, preferably a (Cl-C4)alkyl group, in particular a methyl group, a (Cl-C10)fluoroalkyl group~ preferably a CF3 group, a (C6-C10)fluoroaryl group, preferably a penta-fluorophenyl group, a (C6-C10)-, preferably a tC6-C8)aryl group, a (Cl-C10)-, preferably a (C1-C4)alkoxy group, in particular a methoxy group, a ~Cz-Cl0)~~ preferably (C2-Cb)alkenyl group, a ~C7-C40)-, preferably a (C7-C10)-arylalkyl group, a (Ca-C40) , preferably a (C8-C12)aryl-alkenyl group or a (C7-C40)-, preferably a (C7-Cl2)alkylaryl group, or R11 and R12 or R11 and Rl3 together form in each case a ring with the atoms ~oining them.
M2 is silicon, germanium or tin, preferably silicon and germanium.
R is preferably =CR11R12, =siRl1R12 =GeR11R12 =S0, -PRl1 or =P(O)R11.
- 8 ~ 64 R~ and R9 are identical or different and have the meaning sta~ed for R1l.
m and n are identical or differen~ and are æerol 1 or ~, preferably zero or 1, m plus n being zero, 1 ox 2, preferably zero or 1.
The metallocenes described above can be prepared by the following general reaction scheme:
H2Ra+ButylLi-->HRaLi ¦
X- (CR8R9)m-R7- (CR8R9)n-X
H2Rb)~utylLi ~HRbLiJ ~~
HRa-(CR~R9)m-R7-(CR8R9)n-RbH 2 ButylLi~
LiRa- (C~8R9)m-R7- (CR8R9)n-RbLi MlCl~ ~
(CRjR9)m-Ra (CRjR9)m-~a (CR¦R9)n~ Ra 77 ~f RlLl~ j7 1~1 R2Li~ R7 (CR8R9)n-Rb (CR8R9)n-Rb (CR R9)n-lb (X = Cl, Br, J, O-Tosyl, HRa _ R3 ~ , HRb = R5 ~ H) Metallocene compounds which are preferably employed are dialkylsilylbisindenylzirconium dichloride, alkylalkylenebisindenylzirconium dichloride, alkylenebisindenylzirconium dichloride, diarylalkylenebisindenylzirconium dichloride, alkylenebisindenylhafnium dichloride, o diarylsilylbisindenyl2irconium dichloride, ~ar~l)(al~yl)bisindenylzirconium dichloride, dialkylgermylbisindenylzirconium dichloride, (alkyl)(alkenyl)silylbisindenylzirconium dichloride and (aryl)(alkenyl~silylbisindenylzirconium dichloride.
In this connection, ~he following are particularly preferred:
dimethylsilylbisindenyl2irconium dichloride, ethylenebisindenylzirconium dichloride, diphenylsilylbisindenylzirconium dichloride, dimethylgermylbisindenylzirconium dichloride, (phenyl)(vinyl)silylbisindenyl~irconium dichloride and ethylenebisindenylhafnium dichloxide.
The cocatalyst i8 an alum~xane of the fo~mula II:
R14 \ R14 ~ R
Al - O - Al _ o - Al R14 ~ . \ R14 ~II) for the linear type and/or of the formula (III)s _ Al - O ~ (III) ~ p~,~
for the cyclic type. In these formulae, Rl4 is a ~C1-C6)-alkyl group, preferably methyl, ethyl or isobutyl, in particular methyl, and p is an int~ger from 2 to 50, preferably 5 to 40O The precise structure of the alum oxane is, however, not known.
The alum~ane can be prepared in various ways.
One possibility is to add water carefully to a dilute solution of trialkylaluminum, the solution of the tri-alkylaluminum, preferably trimethylaluminum, and the water each being introduced in small portions into a larger amount of an inert solvent which has been taken and the cessation of gas development always being awaited - 10 ~ 0 inbetween.
In another process, finely powdered coppex sulfate pentahydrate i8 suspended in toluene and mixed in a glass flask under inert gas a~ about -20~C with enough tri-alkylaluminum for about 1 mol of CUSO4 .5H20 to be avail-able for every 4 Al atoms. ~fter ~low hydrolysis invol-ving alkane detachment, the reaction mixture is left for 24 to 48 hours at room temperature, it possibly being necessary to cool it in order to prevent the temperatura rising ahove 30C. Then the alum oxane dissolved in the toluene is filtered off from the copper sulfate and the solution is e~aporated down in vacuo. It is assumed that, in this process of preparation, the low-molecular-weight alum o~ane condense to form higher oligomers with the detachment of trialkylaluminum.
Furthermore, alum oxane are obtained if dis olved trialkylaluminum, preferably trimethylaluminum, is reacted with aluminum salts, preferably aluminum ~ulfate, containing water of crystallization at a temperature of -20 to 100C in an inert aliphatic or aromatic solvent, preferably heptane or toluene. In this ca~e, the volu-metric ratio between solvent and the alkylaluminum used is 1:1 to 50:1 - preferably 5:1 ~ and the reaction tLme, which can be monitored by the detachment of the alkane, is 1 to 200 hours - preferably 10 to 40 hours.
Am~ng the ~luminum salts containing water of cxystalli-zation, in particular those are used which have a hi~h content of water of crystallization. Particularly pre-ferred is aluminum sulfate hydrate, e~pecially the compounds Al2(SO4)3.16~lzO and Al2tSO4)3.18HzO, which have the particularly high content of water of crystallization of 16 or 18 mol of H2O/mol of Al2(SO4)3, respectively.
A further variant of the preparation of alum o~ane is to dissolve trialkylalumlnum, preferably trimethyl-aluminum, in the suspending agent contained in the polymarization vessel, preferably in the liquid monomer, in heptane or toluene and then to react the aluminum compound with water.
In addition to the processes described ahove for prepar-ing alumoxane there are further processes which can be used. Regardless of the type of preparation, a varying content of unreacted trialkylaluminum, w,hich is present in free form ox as an adduct, is common to all alurn~
oxane solutions.
It is possible to pre-activate the metallocene with an alumo~ane of the formula ~II) and/or (III) before use in the polymerization reaction. This markedly increases the polymerization activity and Lmproves the partic:le morphology.
The transition metal compound is preactivated in 801u-tion. In this connection, the metallocene i9 pre~erably dissolved in a 601uticn of the alumoxane in an ine:rt hydrocarbon. A suitable inert hydrocarbon i6 an aliphatic or aromatic hydrocarbon.
Preferably toluene is employed.
The concentration of the alum o~ane in the solution is in the range from approximately 1 part` by weight up to the saturation limit, preferably from 5 to 30% by weight, based in all cases on the total solution. The metallocene may be employed in the same concentration, preferably, however, it is employed in an amount of 10-4 - 1 mol per mol of alum oxane The preactivation time is 5 minutes to 60 hours, preferably 5 to 60 minutes. A temperature of -78C to 100C, preferably 0 to 70C, is employed.
The polymerization i8 carried out in a known manner in solution, in suspension or in the gas phase, continuously or batchwise, in one s~ep or several steps at a temperature of -60 to 150C, preferably 0 to 80C. The polymerization involves propylene and, as comonomer, - 12 - 2~
at least one member of the group c~sisting of ethylene and olefins containing at least 4 carbon atoms of the formula R15-CH=CH-R1~. In this formula, R15 and Rl6 have the meaning already stated. 70 to 99.9, preferably 80 to 99.7% by weigh~, based on the total amount of the monomers, of propylene and 0.1 to 30, preferably 0.3 to 20~ by weight, based on the total amount of the monomers, of at least one comonomer are employed.
~ydrogen is added as molar mass regulator, the hydrogen partiAl pressure being in the range from 0.05 to 50 bar, preferably 0.1 to 25 bar, in particular 0.2 to 10 bar.
The molar ratio of the olefins to hydrogen is 3 to 3,000, preferably 6 to 1,500l in particular 15 to 300.
The total pressure in the polymeri2a~ion system i9 0.5 to 120 bar. Polymerization in the industrially particularly attractive pre~sure range from 5 to 64 bar i~ preferred.
In this connection, the metallocene compound is employed in a concentration, based on the transition metal, of 10-3 to 10-7, preferably 10-4 to 10-6 mol of transition metal per dm3 o F solvent or per dm3 of reactor volume. The alum-oxane is used in a concentration of 10-5 to 10-~ mol, preferably 10-4 to 10-2 mol per dm3 of solvent or per dm3 of reactor volume, respectively. In principle, however, even higher concentrations are possible.
If the polymerization is carried out as a suspen6ion or solution polymerization, an inert solvent which is normal for the Ziegler low-pressure process is used. For example, an aliphatic or cycloaliphatic hydrocarbon is employed; as such, mention may be made, for example, of butane, pentane, hexane, heptane, isooctane, cyclohexane and methylcyclohexane.
Furthermore, a gasoline or hydrogenated diesel oil fraction maybe used. Toluene is also useable. Preferably, - 13 - Z ~ ~0 polymerization is carried out in the liquid monomer. If inert solvents are usedt the monomers are added in gaseous or liquid form. If only one monomer is u~ed as suspending agent, the comonomer is/ or the comonomers are, added in gaseous or liquid form. It i~ furthermore possible to polymerize in a mixture of different monomers as suspending agent; a further monomer can then be added in liquid or gaseous form.
The polymerization time is indefinite since ~he catalyst system to be used according to the invention exhibits only a slight time-dependent drop in the polymerization activity.
Chemically highly uniform copolymer waxes can be produced by the process according to the invention.
In generall the chain ends are constructed of saturated hydrocarbon groups. The polydispersity M~/M~ i~ extremely narrow, with typical values of ~.0-3Ø The comonomar or the comonomers are almost exclusively incorporated individually between polypropylene blocks, and this results in an optimum reduction in the crystallinity and hardness of the copolymer waxes. Associated with this is 2 reduction in the enthalpy of fusion and enthalpy of crystallization, and also of the melting point and crystallization point. Depending on the process, these parameters, and in addition the melt vi~cosity, can be controlled precisely over a wide range by varying the amount of hydrogen and by varying the comonomers. In addition, colorless, highly transparent waxes can also be produced by means of the process according to the inven-tion. The polymer powder~ produced according to theinvention are composed of nonadhering, compact spherical particles having a narrow particle size distribution and high apparent density. The wax powder is noteworthy for its very good free-flowing property and can consequently be handled in an optimum manner.
.
iO~i4 Tha cataly~t activities are very high, and this means low catalyst residue contents in the polymer for high ~pace-tLme yields.
The following examples are intended to explain the invention in more detail.
Key to symbols:
VN - Viscosity number in cm3/g N~ = Weight average of molar mass `determined by gel N~ = Number average of molar mass permeation chromatography N~/M~ = Polydispersity ~ (numerical data in gtmol) MY = Melt viscosity determined by means of ro~ational viscometer at 170C
AD = Apparent density of the polymer powder in y/dm3 npp = Medium polypropylene- block length np~ polyethylene block length np~ = polyhexene block length np~ = " polybutene block length N~ poly-4-methy-1-pentene block lenyth (the block length were determined by means of 13C NMR
spectroscopy) Melting points~ crystallization points, their full widths at half maximum, the enthalpies of fusion and crystalliz-ation, and also the ~lass transition temperature~ (Tg) were determined by DSC measurements (heating~cooling rate 20C/min).
~xamples 1-16 A dry 16 dm3 vessel was flushed with nitrogen and filled with 40 Ndm3 (equivalent to 2.5 bar) of hydrogen and also with 10 dm3 of liquid propylene. Then 30 cm3 of toluenic methylalumoxane ~olution (equivalent to 40 mmol of Al, a~erage degree of oligomerization of the methylalumoxane n=20) and also 25% by weight of the desired total amount - 15 - 2~00~.4 of ~thylene (see Table 1 for amounts) were added and the mixkure was stirred for 15 minutes at 30C.
In parallel with this, the amount shown in Table 1 of the zirconocene dimethylsilylbisindenylzirconium dichloride was dissolved in 15 cm3 of toluenic methylalumo~ane solution (20 mmol of Al) and preactivated by being allowed to stand for 15 minu~es. The orange-red solution was then introduced in~o the vessel. ~he polymerization system was brought to ~he polymeriza~ion temperature shown in Table 1 and was kept at this temperature by suitable cooling during the polymerization time (Table 1). The remaining amount of ethylene was added uniformly during the polymerization time.
Product amounts, metallocene activities and also the ethylene content of ~he polymers produced are summarized in Table l. The product properties are to be found in Table 2.
Exa~plea 17-1~
The procedure was analogous to that of Examples 1-16, but the amount of hydrogen used as molar mass regu}ator was varied. Instead of 40 Ndm3, the amounts specified in Table 3 were added. The polymerization conditions are to be found in Table 3 and the product properties in Table 4.
~a~ple~ 20-24 The procedure was analogous to that in Examples 1-16, but the metallocenes ethylenebisindenylzirconium dichloride (Example 20), diphenylsilylbisindeny}zirconium dichloride (Example 21), dimethylgermylbisindenylzirconium dichloride (Example 22), ethylenebisindenylhafnium d i c h l o r i d e ( E x a m p l e 2 3 ) a n d (vinyl)(phenyl)silylbisindenylzirconium dichloride (Example24) were used instead of dimethylsilylbisindenyl-zirconium dichloride. The polymerization conditions are - 16 - 2~
to be foun~ in Table 5 and the product properties in ~able 6.
E~mples 25-27 The procedure was analogous to tha~ of Ex~mples 1-16, but the comonomers 1-hexene (Example 25), 1-butene (~xample 26) and 4-methyl-1-pentane (Example 27) were used instead of the comonomer ethylene. The polymerization conditions are to be found in Table 7 and the product properties in Table 8.
~xample 28 A dry 16 dm3 vessel was flushed with nitrogen and filled with 10 dm3 of liquid propylene. Then 30 cm3 of ~oluanic methylalumo~ane - ~olution (equivalent to 40 mmol of Al, aV~age degree of oligomerization of the methylalum oxane n=20) wera added and the mixture was stirred for 15 minutes.
In parallel with this, 8.5 mg (O.019 mmol) of dimethyl-silylbisindenylzirconium dichloride were di~solved in 15 cm3 of toluenic methylalumXane solution ~20 mmol of Al). After 15 minutes, the orange-red solution was introduced into the vessel. The polymerization system was brought to 50C and then 85 g of ethylene were continu-ously adding during the 60-minute polymerization tLme.
1.1 kg of polymer powder, equivalent to a metallocene activity of 129.4 kg of polymer/g of catalyst x h wexe obtained.
The ethylene incorporated was 7.1% by weight.
Block length: npp = 9.2, npE = 1.05, VN = 39 cm3/g;
M~ = 24,750, M~ = 9,850, M~ = 2.5; AD = 330 g/dm3;
MV = 1,350 mPa.s;
Dropping point 128C; melting point 108C, Crystallization point 69C, glass transition temperature -24C, Enthalpy of f~sion 52.8 J/g, enthalpy of crystallization -40.1 J/g.
Comparison ex~mple A
A dry 16 dm3 vessel was flushed with nitrogen and filled with 40 Ndm3 (equivalent to 2.5 bar) of hyclrogen, with 10 dm3 of liquid propylene and 140 g of ethylene. Then 30 cm3 of toluenic methylalumoxane ~olution ~aquivalent to 40 mmol of Al,avera~edegree of oligomerization of khe aluminoxane n=20) were added and the mixture was stirred for 15 minutes.
In parallel with this, 8.5 mg (0.019 mmol) of dimethyl-silylbisindenylzirconium dichloride were dissolved in 15 cm3 of ~oluenic methylalumoxane solution (20 mmol of Al). After 15 minutes, the orange-red solution was introduced into the vessel. Polymerization was carried out for 60 minutes at 50C. 2.0 k~ of polymer powder were lS obtained, equivalent to a ~etallocene activity of 235.3 kg of polymer/g of catalyst x h. The ethylene incorporated was 6.8% by weight. VN = 38 cm3/g~
M~ = 24,950, M~ - 10,150, M~/M~ = 2.5, ~D 310 g~dnl31 NV = 1~220 m~a.s;
dropping point 141~C; melting point 128C, crystallization point 91C, glass transition temperature enthalpy of fusion 63.5 J/g, enthalpy of crystallization -50.7 J/g.
Taking the entire amount of comonomer results in a con-siderably different product from ~hat which is obtained by taking 25% of the total amount of monomer and con-tinuously adding the remaining comonomer during the polymeri~ation (Examples 8 and 9) or which is obtained by exclusively adding the comonomer during the polymeriz-ation (Example 28). Dropping point, melting point, crystallization point, enthalpy of fusion and also enthalpy of crystallization are considerably higher.
According to 13C NMR, a product with a higher medium block length npE is obtained.
Example 29 A dry 16 dm3 vessel was flushed with nitrogen and filled with 40 Ndm3 (equivalent to 2.5 bar) of hydrogen, with 10 dm3 of liquid propylene, with 300 g of l-hexene and 17.5 g of ethylene. Then 30 cm3 of toluenic methylalum~
oxane solu~ion (equivalent to 40 mmol of Al, average de3ree of oligomerization n=20) were added and the mixture was stirred for 15 minutes.
In parallel with this, 8.5 mg (0.019 mmol) of dimethyl-silylbisindenylzirconium dichloride were dissolved in 15 cm3 of toluenic methylalum~Xane solution (20 mmol of Al).
After 15 minutes, the orange-red solution was introduced into the vessel. Polymerization was carried out for S0 minutes at 60C, 52.5 g of ethylene being added continu ously. 2.1 kg of polymer powder, equivalent to a matal-locene activity o~ 247.0 kg of polymer/g of cataly~t x h, were obtained.
The polymer contained 2.6~ by weight of hexene units, 2.5% by weight of ethylene unit~ and 94.9% by weight of propylene units. Mean block length of the copolymers, np~ = 1.0: npE - 1.02; VN = 29.1 cm3/g~ M~ = 17,400, Mn = 8,050, ~/M~ = 2.2; AD = 410 g/dm3; MV = 760 mPa.~;
dropping point 118C, melting point 106~C, crystallization point 68C~ enthalpy of fusion 70.4 3/g, enthalpy of crystalliz~tion -52.6 J/g, glass transition temperature Example 30 The procedure was as in Example 29, but 500 g of 1-butene were taken instead of 300 g of l-hexene. 1.92 kg of polymer powder, equivalent to a metallocene activity of 225.9 kg of polymer/g of catalyst x h, were obtained.
The polymer contained 4.1~ by weight of butene units, 2.9% by weight of ethylene units and 93.0% by weight of propylene units. The mean block lengths of the copolymers were: npE = 1.04 and npB = 1003. VN - 30 cm3/y; M~ = 19,100~
M~ = 9,100, M~ = 2.1; AD = 370 g~dm3, MV = 760 mPa.s;
dropping point 120C, melting point 110C, crystalliæation point 70C, enthalpy of fusion 76.1 J/g, enthalpy of S crystallization -62.0 J/g~ qlas~ txansi~ion temperature -21C.
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S The production of isotactic polyolefin waxe~ (isotactic index 80 to 85~, enthalpy of fusion 63 J/g, mixture of atactic and isotactic polyolefin chains) by means of supported catalysts, cocatalysts and stereoregulators at a temperature of over 95~C is knvwn (cf. DE 3,148,229).
Large amounts of hydrogen have ~o be employed as molar mass regulator.
Furthermore/ an MgCl2 supported contact catalyst which results in crystalline PP waxes with a narrow molar mass distribution is also known tcf. JP 59/206,409). This catalyst, too, has the typical disadvanta~es of catalyst systems which have been developed for the production of high-molecular-weight polyolefins and consequently have a low activity in the produc~ion of low-molecular-weight polyolefins. Furthermore, here again, an undesirable mixture o i~otactic and atactic chains is present in the wax product.
Wax-type random ethylene copolymers which contain an ~-olefin fraction of 1-15 mol~ and which are produced using a catalyst system based on zirconium hydride metallo-cene/alumox~ne (cf. JP 62/12g,303) are also known. Such metallocenes are not, however, suitable for producing isotactic polypropylene; in addition, their activity in polypropylene polymerization is very low.
Owinq to the low catalytic activity under the necessary reaction conditions, relatively high chlorine contents of, in some cases, over 1000 ppm are found in the pol~mer waxes if the catalyst residues are not removed by an expensive special post-treatment.
The use of metallocene/alumo~an~ catalyst system3 has also been proposed for the production of highly isotactic l-olefin polymer waxes (cf. DE 3,743J321).
Although it was possible to overcome the disadvantages of the processes described above with th:is catalyst, the high isotacticity of the products resulted in the har~-ness of the waxes being extremely high, and this i5 undesirable for a number of wax applications.
It is possible in principle to reduce the hardness by subseguently adding atactic poly-1 olefin wax. Apart from the high costs which are unacceptable and uneconomical on a large scale, this addition results in nonuniform and sticky products.
There is consequently the ob~ect of finding a process wlth which polyolafin waxes having lower hardness can be produced using metallocene/alumXane catalysts.
It was found that the object can be achieved by copoly-merizing propylene with other olefins in the presence ofcertain metallocene catalysts.
The invention consequently relates to a polypropylene wax composed of 80 to 99.75~ by weight, based on the ~o~al polymer, of propylene units and 0.25 to 20~ by weight, based on the total polymer, of units which are derived from ethylene or an olefin containing not less than 4 carbon atoms of the formula R15-CH=CH-Rl6, in which R15 and R16 are identical or different and are a hydrogen atom or an alky radical containing 1 to 28 carbon atoms or Rl5 and Rl6 form a ring containing 4 to 28 carbon atoms with the carbon atoms joining them, which polypropylene wax has a molar mass N~ of 1,000 to 50,000 g/mol, a poly-dispersity M~/M~ of 1.8 to S.0, a viscosity number of 2 to - 3 ~ 4 60 cm3/g~ a mel~ing point of 50 to 150C, an enthalpy of fusion ~ of less than 100 J/g, a dropping point of 60 to 160C, a melt viscosity at 170C of 100 to 20,000 mPa.s and a regular distribution of the comonomer uni~s in the polymer chain, the mean block length n being less than 1.25.
The inven~ion furthermore relates to a process ~or the production of the polypropylene wax as claimed in claLm 1 by polymerizing 70 ~o 99.9~ by weightl based on the total amount of the monomers, of propylene and 0.1 to 3D%
by weight, based on the total amount of the monomers, of not less than one represen~ative of the group comprising ethylene and olefins containing not less than 4 carbon atoms of the formula ~ CH=CH~Rls, in which Rl5 and Rl6 have the meaning sta~ed in claIm 1, at a temperature of -60~C to 100C, at a pressure of 0.5 to 120 bar, in solution, in suspension or in the ga~ phase, in the presence of hydrogen as a molar mass regulator and of a catalyst which is composed of a metallocene and an alum oxane wherein the hydrogen partial pres~ure is 0.05 to 50 bar and the molax ratio of olefin to hydrogen is 3 to 3,000:1, and wherein the metallocene is a com-pound of the formula I:
R4--~-( CR~R9 ~ m R1~1 R7 R2 R5~1R3R9)n (I) in which M1 is a metal of the group IVb, Vb or VIb of the periodic system, R1 and R2 are identical or different and are a hydrogen atom, a (C1-C10)alkyl group, a tC1-ClO)alkoxy group, a (C6-C1O)aryl group, a (C~-C1O)aryloxy group, a (C2-C10)alkenyl gxoup, a (C7-C40)arylal~yl group, a (C7-C40)alkylaryl group, a (C8-C40)arylalXenyl group or a halogen atom, R3, R4, R5 and R6 are identical or differen~ and are a hydrogen atom, a halogen atom, a (Cl-cl0)alkyl group~ a (Cl-CI0)alkoxy group, a (C6-C10)aryl group, or an -NR2, -SRl, -OSiR3,-SiR3, or-PR2 radical, in which Rl is a (Cl-C1O)alkyl group, a (C6-C1O)aryl group or alternatively, in the case of radicals containing silicon or phofiphorus, a halogen atom, or two ad~acen~ R3, R4, R5 or R6 radicals each form a ring with the carbon atoms ~oining them, R7 is Rll R~ ll Rll Rll M2 _ l2 _ , - M? _ CR2 _ , _ O _ ~2 _ o -R12 R12 ~12 ~12 R12 - C - , _ O ~ ~2 _ , - M2 _ o - M2 _ ~12 ~lZ ~12 i12 =BR11, =AlR11, -Ge-, -Sn-, -O-, -S-, =SO, -S02, =NR~ CO, =PRll or =P(O)R
where R11, R12 and R13 are identical or different and are a hydrogen atom, a halogen atom, a (Cl-C30)alkyl group, a (C1-C10)fluoroalkyl group, a (C~-C1O)aryl group, a (C6-C10)fluoroaryl group, a ~Cl-C10~alkoxy group, a (C2-C10)alkenyl group, a (C7-C40)arylalkyl group, a (C8-C40)arylalkenyl group, a (C7-C40)alkylaryl group, or R11 and Rl2 or Rll and Rl3 in each case form a ring with the atoms joining them, M2 is silicon~ germanium or tin, R8 and R9 are identical or different and have the meaning stated for Rl1, m and n are identical or different and are zero, 1 or 2, m plus n being zero, 1 or 2, and the alumo;ane is a compound of the formula (II):
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R~4 ~ Rl4 R14 Al - o - A1 - O - Al /
R14 ~~ ' p \ R14 (II) for ~he linear type and~or of the formula (III) -lAl - o (III) p+2 for the cyclic type, Rl4 being a (Cl-C6)alkyl group in the formulae (II) and (III3 and p beiny an in~eger fxom 2 to 50.
The polypropylene wax according ~o the invention is composed of 80 to 9~.75, preferably 90 to 99.5% by weight, based on the total pol~mer, of propylene units and of 0.25 to 20, preferably 0.5 to 15% by weight, bcised on the total polymer, of unlts which are derived ~rom ethylene or an olefin containing at least 4 carbon at:oms of the formula Rl5-CH=CH-RlB. In this formula, R1s and Rl6 are identical or dif~erent and are a hydrogen atom or an alkyl radical containing l to 28 carbon atoms. Rls and Rl6 may, howe~er, also form a ring contai~ing 4 to 28 carbon atoms with the carbon atoms joining them. Examples of such olefins are l-butene, l-hexene, 4-methyl-1-pentene, l~pentene, l octene, norbornene, norbornadiene, 6-pentene, cyclohexene or cyclooctene.
Preferred copolymer waxes are propylene/ethylene, propy-lene/l-hexene, propylene/l-butene and propylene/4-methyl-l-pentene polymers.
Copolymeræ of three different monomers are preferably propylene/ethylene/l-hexene and propylene/ethylene/l-butene terpolymer waxes.
The copolymer wax according to the invention has a molar mass M~ of 1,000 to 50,000 g/mol, preferably 8,000 to 45,000 g/mol, a polydispersity M~/M~ of 1.8 to 5.0, - 6 ~
preferably 2.0 to 4.0, a visco~ity number of 2 to 60 cm3/g, preferably 10 to 50 cm3/g, a melting point of 50 to 150C, preferably 70 to 140Cr an enthalpy fusion ~H of less than 100 J/g, a dropping point of 60 to 160C, preferably 80 to 150C, a melt vi~cosity of 100 to 20,000 mPa.s, preferably 120 to 7,000 mPa.3, at 170C and a regular distribution of the comonomer units in the polymer chain, the me~ium ccmonc~er block length n being less ~han 1.25, preferably le~s than 1.2.
The catalyst to be used for the process according to the invention is composed of an alum o~ane and a metallocene of the formula I:
R4--~( CRBR9 ) m R6 R6 (I) In formula I, M1 is a metal of the group IVb, Vb or VIb of the periodic system, for example titanium, zirconium, hafnium~ vanadium, niobium, tantalum, chromium, mol-ybdenum or tungsten, preferably zirconium and hafnium.
R1 and R2 are identical or different and are a hydrogen atom, a (C1-C~0)-, preferably a (C1-C3)alkyl group, a (Cl-C10)-, preferably a (C~-C3)al~oxy group, a (C6-C~O)-, preferably a (C6-Ca)aryl group, a (C6-C10), preferably a (C6-C8)aryloxy group, a tC2-C10)-, preferably a (C2-C4) alkenyl group, a (C7-C40)-, preferably a (C7-C1O)arylalkyl group, a (C7-C40)-, preferably a (C7-C~z)alkylaryl group, a (C8-C40)-, preferably a (C8-C,2)arylalkenyl group or a halogen atom, preferably chlorine.
R3, R4, R5 and R6 are identical or different and are a hydrogen atom, a halogen atom, preferably a fluorine, chlorine or bromine atom, a (C~-C~0)-, preferably a tC~-C3)alkyl group, a (C6-C~0)-, preferably a (C6-C8)aryl - 7 ~ 0 group, a (C~-C~0)-, pre~erably a (Cl-C3)alkoxy group, or an -NR2, -SR10, -OSiR3, ~SiR3, or -PR2 radical, in which Rl is a (Cl-C,0)-, preferably a (Cl-C3)alkyl group or a (C6-Cl0~-, preferably a ~C6-C8)aryl group, or alter-natively, in the case of radicals containing silicon or phosphorus, a halogen atom, preferably a chlorine atom, or two adjacent radicals R3, R4, R5 or R6 each form a ring with the carbon atoms joining them. Particularly pre-ferred ligands are indenyl, fluorenyl and cyclopenta-dienyl.
R7 i~
Rll ~11 Rll ~11 Rll - M2 _ , _ ~2 _ l2 _ , - M2 _ CR~ _ , _ o - M2 _ o -R12 R12 R12 l12 ~12 Rll ~11 Rll ~,11 ~ _ , - O - M2 _ , - M~ - O - M2 R12 Rl~ R12 R12 =BRll, =AlRll, -Ge-, -Sn-, -O-, -S-, =SO, =SO2, =NRIl, =CO, =PRl1 or =P(O)R11, where R1l, R12 and R13 are identical or different and are a hydrogen atom, a halogen atom, a (Cl-C30)-, preferably a (Cl-C4)alkyl group, in particular a methyl group, a (Cl-C10)fluoroalkyl group~ preferably a CF3 group, a (C6-C10)fluoroaryl group, preferably a penta-fluorophenyl group, a (C6-C10)-, preferably a tC6-C8)aryl group, a (Cl-C10)-, preferably a (C1-C4)alkoxy group, in particular a methoxy group, a ~Cz-Cl0)~~ preferably (C2-Cb)alkenyl group, a ~C7-C40)-, preferably a (C7-C10)-arylalkyl group, a (Ca-C40) , preferably a (C8-C12)aryl-alkenyl group or a (C7-C40)-, preferably a (C7-Cl2)alkylaryl group, or R11 and R12 or R11 and Rl3 together form in each case a ring with the atoms ~oining them.
M2 is silicon, germanium or tin, preferably silicon and germanium.
R is preferably =CR11R12, =siRl1R12 =GeR11R12 =S0, -PRl1 or =P(O)R11.
- 8 ~ 64 R~ and R9 are identical or different and have the meaning sta~ed for R1l.
m and n are identical or differen~ and are æerol 1 or ~, preferably zero or 1, m plus n being zero, 1 ox 2, preferably zero or 1.
The metallocenes described above can be prepared by the following general reaction scheme:
H2Ra+ButylLi-->HRaLi ¦
X- (CR8R9)m-R7- (CR8R9)n-X
H2Rb)~utylLi ~HRbLiJ ~~
HRa-(CR~R9)m-R7-(CR8R9)n-RbH 2 ButylLi~
LiRa- (C~8R9)m-R7- (CR8R9)n-RbLi MlCl~ ~
(CRjR9)m-Ra (CRjR9)m-~a (CR¦R9)n~ Ra 77 ~f RlLl~ j7 1~1 R2Li~ R7 (CR8R9)n-Rb (CR8R9)n-Rb (CR R9)n-lb (X = Cl, Br, J, O-Tosyl, HRa _ R3 ~ , HRb = R5 ~ H) Metallocene compounds which are preferably employed are dialkylsilylbisindenylzirconium dichloride, alkylalkylenebisindenylzirconium dichloride, alkylenebisindenylzirconium dichloride, diarylalkylenebisindenylzirconium dichloride, alkylenebisindenylhafnium dichloride, o diarylsilylbisindenyl2irconium dichloride, ~ar~l)(al~yl)bisindenylzirconium dichloride, dialkylgermylbisindenylzirconium dichloride, (alkyl)(alkenyl)silylbisindenylzirconium dichloride and (aryl)(alkenyl~silylbisindenylzirconium dichloride.
In this connection, ~he following are particularly preferred:
dimethylsilylbisindenyl2irconium dichloride, ethylenebisindenylzirconium dichloride, diphenylsilylbisindenylzirconium dichloride, dimethylgermylbisindenylzirconium dichloride, (phenyl)(vinyl)silylbisindenyl~irconium dichloride and ethylenebisindenylhafnium dichloxide.
The cocatalyst i8 an alum~xane of the fo~mula II:
R14 \ R14 ~ R
Al - O - Al _ o - Al R14 ~ . \ R14 ~II) for the linear type and/or of the formula (III)s _ Al - O ~ (III) ~ p~,~
for the cyclic type. In these formulae, Rl4 is a ~C1-C6)-alkyl group, preferably methyl, ethyl or isobutyl, in particular methyl, and p is an int~ger from 2 to 50, preferably 5 to 40O The precise structure of the alum oxane is, however, not known.
The alum~ane can be prepared in various ways.
One possibility is to add water carefully to a dilute solution of trialkylaluminum, the solution of the tri-alkylaluminum, preferably trimethylaluminum, and the water each being introduced in small portions into a larger amount of an inert solvent which has been taken and the cessation of gas development always being awaited - 10 ~ 0 inbetween.
In another process, finely powdered coppex sulfate pentahydrate i8 suspended in toluene and mixed in a glass flask under inert gas a~ about -20~C with enough tri-alkylaluminum for about 1 mol of CUSO4 .5H20 to be avail-able for every 4 Al atoms. ~fter ~low hydrolysis invol-ving alkane detachment, the reaction mixture is left for 24 to 48 hours at room temperature, it possibly being necessary to cool it in order to prevent the temperatura rising ahove 30C. Then the alum oxane dissolved in the toluene is filtered off from the copper sulfate and the solution is e~aporated down in vacuo. It is assumed that, in this process of preparation, the low-molecular-weight alum o~ane condense to form higher oligomers with the detachment of trialkylaluminum.
Furthermore, alum oxane are obtained if dis olved trialkylaluminum, preferably trimethylaluminum, is reacted with aluminum salts, preferably aluminum ~ulfate, containing water of crystallization at a temperature of -20 to 100C in an inert aliphatic or aromatic solvent, preferably heptane or toluene. In this ca~e, the volu-metric ratio between solvent and the alkylaluminum used is 1:1 to 50:1 - preferably 5:1 ~ and the reaction tLme, which can be monitored by the detachment of the alkane, is 1 to 200 hours - preferably 10 to 40 hours.
Am~ng the ~luminum salts containing water of cxystalli-zation, in particular those are used which have a hi~h content of water of crystallization. Particularly pre-ferred is aluminum sulfate hydrate, e~pecially the compounds Al2(SO4)3.16~lzO and Al2tSO4)3.18HzO, which have the particularly high content of water of crystallization of 16 or 18 mol of H2O/mol of Al2(SO4)3, respectively.
A further variant of the preparation of alum o~ane is to dissolve trialkylalumlnum, preferably trimethyl-aluminum, in the suspending agent contained in the polymarization vessel, preferably in the liquid monomer, in heptane or toluene and then to react the aluminum compound with water.
In addition to the processes described ahove for prepar-ing alumoxane there are further processes which can be used. Regardless of the type of preparation, a varying content of unreacted trialkylaluminum, w,hich is present in free form ox as an adduct, is common to all alurn~
oxane solutions.
It is possible to pre-activate the metallocene with an alumo~ane of the formula ~II) and/or (III) before use in the polymerization reaction. This markedly increases the polymerization activity and Lmproves the partic:le morphology.
The transition metal compound is preactivated in 801u-tion. In this connection, the metallocene i9 pre~erably dissolved in a 601uticn of the alumoxane in an ine:rt hydrocarbon. A suitable inert hydrocarbon i6 an aliphatic or aromatic hydrocarbon.
Preferably toluene is employed.
The concentration of the alum o~ane in the solution is in the range from approximately 1 part` by weight up to the saturation limit, preferably from 5 to 30% by weight, based in all cases on the total solution. The metallocene may be employed in the same concentration, preferably, however, it is employed in an amount of 10-4 - 1 mol per mol of alum oxane The preactivation time is 5 minutes to 60 hours, preferably 5 to 60 minutes. A temperature of -78C to 100C, preferably 0 to 70C, is employed.
The polymerization i8 carried out in a known manner in solution, in suspension or in the gas phase, continuously or batchwise, in one s~ep or several steps at a temperature of -60 to 150C, preferably 0 to 80C. The polymerization involves propylene and, as comonomer, - 12 - 2~
at least one member of the group c~sisting of ethylene and olefins containing at least 4 carbon atoms of the formula R15-CH=CH-R1~. In this formula, R15 and Rl6 have the meaning already stated. 70 to 99.9, preferably 80 to 99.7% by weigh~, based on the total amount of the monomers, of propylene and 0.1 to 30, preferably 0.3 to 20~ by weight, based on the total amount of the monomers, of at least one comonomer are employed.
~ydrogen is added as molar mass regulator, the hydrogen partiAl pressure being in the range from 0.05 to 50 bar, preferably 0.1 to 25 bar, in particular 0.2 to 10 bar.
The molar ratio of the olefins to hydrogen is 3 to 3,000, preferably 6 to 1,500l in particular 15 to 300.
The total pressure in the polymeri2a~ion system i9 0.5 to 120 bar. Polymerization in the industrially particularly attractive pre~sure range from 5 to 64 bar i~ preferred.
In this connection, the metallocene compound is employed in a concentration, based on the transition metal, of 10-3 to 10-7, preferably 10-4 to 10-6 mol of transition metal per dm3 o F solvent or per dm3 of reactor volume. The alum-oxane is used in a concentration of 10-5 to 10-~ mol, preferably 10-4 to 10-2 mol per dm3 of solvent or per dm3 of reactor volume, respectively. In principle, however, even higher concentrations are possible.
If the polymerization is carried out as a suspen6ion or solution polymerization, an inert solvent which is normal for the Ziegler low-pressure process is used. For example, an aliphatic or cycloaliphatic hydrocarbon is employed; as such, mention may be made, for example, of butane, pentane, hexane, heptane, isooctane, cyclohexane and methylcyclohexane.
Furthermore, a gasoline or hydrogenated diesel oil fraction maybe used. Toluene is also useable. Preferably, - 13 - Z ~ ~0 polymerization is carried out in the liquid monomer. If inert solvents are usedt the monomers are added in gaseous or liquid form. If only one monomer is u~ed as suspending agent, the comonomer is/ or the comonomers are, added in gaseous or liquid form. It i~ furthermore possible to polymerize in a mixture of different monomers as suspending agent; a further monomer can then be added in liquid or gaseous form.
The polymerization time is indefinite since ~he catalyst system to be used according to the invention exhibits only a slight time-dependent drop in the polymerization activity.
Chemically highly uniform copolymer waxes can be produced by the process according to the invention.
In generall the chain ends are constructed of saturated hydrocarbon groups. The polydispersity M~/M~ i~ extremely narrow, with typical values of ~.0-3Ø The comonomar or the comonomers are almost exclusively incorporated individually between polypropylene blocks, and this results in an optimum reduction in the crystallinity and hardness of the copolymer waxes. Associated with this is 2 reduction in the enthalpy of fusion and enthalpy of crystallization, and also of the melting point and crystallization point. Depending on the process, these parameters, and in addition the melt vi~cosity, can be controlled precisely over a wide range by varying the amount of hydrogen and by varying the comonomers. In addition, colorless, highly transparent waxes can also be produced by means of the process according to the inven-tion. The polymer powder~ produced according to theinvention are composed of nonadhering, compact spherical particles having a narrow particle size distribution and high apparent density. The wax powder is noteworthy for its very good free-flowing property and can consequently be handled in an optimum manner.
.
iO~i4 Tha cataly~t activities are very high, and this means low catalyst residue contents in the polymer for high ~pace-tLme yields.
The following examples are intended to explain the invention in more detail.
Key to symbols:
VN - Viscosity number in cm3/g N~ = Weight average of molar mass `determined by gel N~ = Number average of molar mass permeation chromatography N~/M~ = Polydispersity ~ (numerical data in gtmol) MY = Melt viscosity determined by means of ro~ational viscometer at 170C
AD = Apparent density of the polymer powder in y/dm3 npp = Medium polypropylene- block length np~ polyethylene block length np~ = polyhexene block length np~ = " polybutene block length N~ poly-4-methy-1-pentene block lenyth (the block length were determined by means of 13C NMR
spectroscopy) Melting points~ crystallization points, their full widths at half maximum, the enthalpies of fusion and crystalliz-ation, and also the ~lass transition temperature~ (Tg) were determined by DSC measurements (heating~cooling rate 20C/min).
~xamples 1-16 A dry 16 dm3 vessel was flushed with nitrogen and filled with 40 Ndm3 (equivalent to 2.5 bar) of hydrogen and also with 10 dm3 of liquid propylene. Then 30 cm3 of toluenic methylalumoxane ~olution (equivalent to 40 mmol of Al, a~erage degree of oligomerization of the methylalumoxane n=20) and also 25% by weight of the desired total amount - 15 - 2~00~.4 of ~thylene (see Table 1 for amounts) were added and the mixkure was stirred for 15 minutes at 30C.
In parallel with this, the amount shown in Table 1 of the zirconocene dimethylsilylbisindenylzirconium dichloride was dissolved in 15 cm3 of toluenic methylalumo~ane solution (20 mmol of Al) and preactivated by being allowed to stand for 15 minu~es. The orange-red solution was then introduced in~o the vessel. ~he polymerization system was brought to ~he polymeriza~ion temperature shown in Table 1 and was kept at this temperature by suitable cooling during the polymerization time (Table 1). The remaining amount of ethylene was added uniformly during the polymerization time.
Product amounts, metallocene activities and also the ethylene content of ~he polymers produced are summarized in Table l. The product properties are to be found in Table 2.
Exa~plea 17-1~
The procedure was analogous to that of Examples 1-16, but the amount of hydrogen used as molar mass regu}ator was varied. Instead of 40 Ndm3, the amounts specified in Table 3 were added. The polymerization conditions are to be found in Table 3 and the product properties in Table 4.
~a~ple~ 20-24 The procedure was analogous to that in Examples 1-16, but the metallocenes ethylenebisindenylzirconium dichloride (Example 20), diphenylsilylbisindeny}zirconium dichloride (Example 21), dimethylgermylbisindenylzirconium dichloride (Example 22), ethylenebisindenylhafnium d i c h l o r i d e ( E x a m p l e 2 3 ) a n d (vinyl)(phenyl)silylbisindenylzirconium dichloride (Example24) were used instead of dimethylsilylbisindenyl-zirconium dichloride. The polymerization conditions are - 16 - 2~
to be foun~ in Table 5 and the product properties in ~able 6.
E~mples 25-27 The procedure was analogous to tha~ of Ex~mples 1-16, but the comonomers 1-hexene (Example 25), 1-butene (~xample 26) and 4-methyl-1-pentane (Example 27) were used instead of the comonomer ethylene. The polymerization conditions are to be found in Table 7 and the product properties in Table 8.
~xample 28 A dry 16 dm3 vessel was flushed with nitrogen and filled with 10 dm3 of liquid propylene. Then 30 cm3 of ~oluanic methylalumo~ane - ~olution (equivalent to 40 mmol of Al, aV~age degree of oligomerization of the methylalum oxane n=20) wera added and the mixture was stirred for 15 minutes.
In parallel with this, 8.5 mg (O.019 mmol) of dimethyl-silylbisindenylzirconium dichloride were di~solved in 15 cm3 of toluenic methylalumXane solution ~20 mmol of Al). After 15 minutes, the orange-red solution was introduced into the vessel. The polymerization system was brought to 50C and then 85 g of ethylene were continu-ously adding during the 60-minute polymerization tLme.
1.1 kg of polymer powder, equivalent to a metallocene activity of 129.4 kg of polymer/g of catalyst x h wexe obtained.
The ethylene incorporated was 7.1% by weight.
Block length: npp = 9.2, npE = 1.05, VN = 39 cm3/g;
M~ = 24,750, M~ = 9,850, M~ = 2.5; AD = 330 g/dm3;
MV = 1,350 mPa.s;
Dropping point 128C; melting point 108C, Crystallization point 69C, glass transition temperature -24C, Enthalpy of f~sion 52.8 J/g, enthalpy of crystallization -40.1 J/g.
Comparison ex~mple A
A dry 16 dm3 vessel was flushed with nitrogen and filled with 40 Ndm3 (equivalent to 2.5 bar) of hyclrogen, with 10 dm3 of liquid propylene and 140 g of ethylene. Then 30 cm3 of toluenic methylalumoxane ~olution ~aquivalent to 40 mmol of Al,avera~edegree of oligomerization of khe aluminoxane n=20) were added and the mixture was stirred for 15 minutes.
In parallel with this, 8.5 mg (0.019 mmol) of dimethyl-silylbisindenylzirconium dichloride were dissolved in 15 cm3 of ~oluenic methylalumoxane solution (20 mmol of Al). After 15 minutes, the orange-red solution was introduced into the vessel. Polymerization was carried out for 60 minutes at 50C. 2.0 k~ of polymer powder were lS obtained, equivalent to a ~etallocene activity of 235.3 kg of polymer/g of catalyst x h. The ethylene incorporated was 6.8% by weight. VN = 38 cm3/g~
M~ = 24,950, M~ - 10,150, M~/M~ = 2.5, ~D 310 g~dnl31 NV = 1~220 m~a.s;
dropping point 141~C; melting point 128C, crystallization point 91C, glass transition temperature enthalpy of fusion 63.5 J/g, enthalpy of crystallization -50.7 J/g.
Taking the entire amount of comonomer results in a con-siderably different product from ~hat which is obtained by taking 25% of the total amount of monomer and con-tinuously adding the remaining comonomer during the polymeri~ation (Examples 8 and 9) or which is obtained by exclusively adding the comonomer during the polymeriz-ation (Example 28). Dropping point, melting point, crystallization point, enthalpy of fusion and also enthalpy of crystallization are considerably higher.
According to 13C NMR, a product with a higher medium block length npE is obtained.
Example 29 A dry 16 dm3 vessel was flushed with nitrogen and filled with 40 Ndm3 (equivalent to 2.5 bar) of hydrogen, with 10 dm3 of liquid propylene, with 300 g of l-hexene and 17.5 g of ethylene. Then 30 cm3 of toluenic methylalum~
oxane solu~ion (equivalent to 40 mmol of Al, average de3ree of oligomerization n=20) were added and the mixture was stirred for 15 minutes.
In parallel with this, 8.5 mg (0.019 mmol) of dimethyl-silylbisindenylzirconium dichloride were dissolved in 15 cm3 of toluenic methylalum~Xane solution (20 mmol of Al).
After 15 minutes, the orange-red solution was introduced into the vessel. Polymerization was carried out for S0 minutes at 60C, 52.5 g of ethylene being added continu ously. 2.1 kg of polymer powder, equivalent to a matal-locene activity o~ 247.0 kg of polymer/g of cataly~t x h, were obtained.
The polymer contained 2.6~ by weight of hexene units, 2.5% by weight of ethylene unit~ and 94.9% by weight of propylene units. Mean block length of the copolymers, np~ = 1.0: npE - 1.02; VN = 29.1 cm3/g~ M~ = 17,400, Mn = 8,050, ~/M~ = 2.2; AD = 410 g/dm3; MV = 760 mPa.~;
dropping point 118C, melting point 106~C, crystallization point 68C~ enthalpy of fusion 70.4 3/g, enthalpy of crystalliz~tion -52.6 J/g, glass transition temperature Example 30 The procedure was as in Example 29, but 500 g of 1-butene were taken instead of 300 g of l-hexene. 1.92 kg of polymer powder, equivalent to a metallocene activity of 225.9 kg of polymer/g of catalyst x h, were obtained.
The polymer contained 4.1~ by weight of butene units, 2.9% by weight of ethylene units and 93.0% by weight of propylene units. The mean block lengths of the copolymers were: npE = 1.04 and npB = 1003. VN - 30 cm3/y; M~ = 19,100~
M~ = 9,100, M~ = 2.1; AD = 370 g~dm3, MV = 760 mPa.s;
dropping point 120C, melting point 110C, crystalliæation point 70C, enthalpy of fusion 76.1 J/g, enthalpy of S crystallization -62.0 J/g~ qlas~ txansi~ion temperature -21C.
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Claims (3)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A polypropylene wax composed of 80 to 99.75% by weight, based on the total polymer, of propylene units and 0.25 to 20% by weight, based on the total polymer, of units which are derived from ethylene or an olefin containing not less than 4 carbon atoms of the formula R15-CH=CH-R16, in which R15 and R16 are identical or dif-ferent and are a hydrogen atom or an alkyl radical containing 1 to 28 carbon atoms or R15 and R16 form a ring containing 4 to 28 carbon atoms with the carbon atoms joining them, which polypropylene wax has a molar mass Mw of 1,000 to 50,000 g/mol, a polydispersity MW/Mn of 1.8 to 5.0, a viscosity number of 2 to 60 cm3/g, a melting point of 50 to 150°C, an enthalpy of fusion .DELTA.H of less than 100 J/g, a dropping point of 60 to 160°C, a melt viscosity at 170°C of 100 to 20,000 mPa.s and a regular distribution of the comonomer units in the polymer chain, the mean block length n being less than 1.25.
A process for the production of the polypropylene wax as claimed in claim 1 by polymerizing 70 to 99.9% by weight, based on the total amount of the monomers, of propylene and 0.1 to 30% by weight, based on the total amount of the monomers, of not less than one representative of the group comprising ethylene and olefins containing not less than 4 carbon atoms of the formula R15-CH=CH-R16, in which R15 and R16 have the meaning stated in claim 1, at a temperature of -60°C to 100°C, at a pressure of 0.5 to 120 bar, in solution, in suspension or in the gas phase, in the presence of hydrogen as a molar mass regulator and of a catalyst which is composed of a metallocene and an alum oxane wherein the hydrogen partial pressure is 0.05 to 50 bar and the molar ratio of olefin to hydrogen is 3 to 3,000:1, and wherein the metallocene is a com-pound of the formula I:
(I) in which M1 is a metal of the group IVb, Vb or VIb of the periodic system, R1 and R2 are identical or different and are a hydrogen atom, a (C1-C10)alkyl group, a (C1-C10)alkoxy group, a (C6-C10)aryl group, a (C6-C10)aryloxy group, a (C2-C10)-alkenyl group, a (C7-C40)arylalkyl group, a (C7-C40)-alkylaryl group, a (C8-C40)arylalkenyl group or a halogen atom, R3, R4, R5 and R6 are identical or different and are a hydrogen atom, a halogen atom, a (C1-C10)alkyl group, a (C6-C10)aryl group, a (C1-C10)alkoxy group, or an -NR??, -SR10, -OSiR?0, -SiR?0, or -OR?0 radical, in which R10 is a (C1-C10)alkyl group, a (C6-C10)aryl group or alternatively, in the case of radicals containing silicon or phosphorus, a halogen atom, or two adjacent radicals R3, R4, R5 or R3 each form a ring with the carbon atoms joining them, R7 is , , , , , , where R11, R12 and R13 are identical or different and are a hydrogen atom, a halogen atom, a (C1-C30)alkyl group, a (C1-C10)fluoroalkyl group, a (C6-C10)aryl group, a (C6-C10)fluoroaryl groups a (C1-C10)alkoxy group, a (C2-C10)alkenyl group, a (C7-C40)arylalkyl group, a (C8-C40)arylalkenyl group, a (C7-C40)alkylaryl group, or R11 and R12 or R11 and R13 in each case form a ring with the atoms joining them, M2 is silicon, germanium or tin, R8 and R9 are identical or different and have the meaning stated for R11, m and n are identical or different and are zero, 1 or 2, m plus n being zero, 1 or 2, and the alum oxane is a compound of the formula (II):
(II) for the linear type and/or of the formula (III) (III) for the cyclic type, R14 being a (C1-C6)alkyl group in the formulae (II) and (III) and p being an integer from 2 to 50.
(I) in which M1 is a metal of the group IVb, Vb or VIb of the periodic system, R1 and R2 are identical or different and are a hydrogen atom, a (C1-C10)alkyl group, a (C1-C10)alkoxy group, a (C6-C10)aryl group, a (C6-C10)aryloxy group, a (C2-C10)-alkenyl group, a (C7-C40)arylalkyl group, a (C7-C40)-alkylaryl group, a (C8-C40)arylalkenyl group or a halogen atom, R3, R4, R5 and R6 are identical or different and are a hydrogen atom, a halogen atom, a (C1-C10)alkyl group, a (C6-C10)aryl group, a (C1-C10)alkoxy group, or an -NR??, -SR10, -OSiR?0, -SiR?0, or -OR?0 radical, in which R10 is a (C1-C10)alkyl group, a (C6-C10)aryl group or alternatively, in the case of radicals containing silicon or phosphorus, a halogen atom, or two adjacent radicals R3, R4, R5 or R3 each form a ring with the carbon atoms joining them, R7 is , , , , , , where R11, R12 and R13 are identical or different and are a hydrogen atom, a halogen atom, a (C1-C30)alkyl group, a (C1-C10)fluoroalkyl group, a (C6-C10)aryl group, a (C6-C10)fluoroaryl groups a (C1-C10)alkoxy group, a (C2-C10)alkenyl group, a (C7-C40)arylalkyl group, a (C8-C40)arylalkenyl group, a (C7-C40)alkylaryl group, or R11 and R12 or R11 and R13 in each case form a ring with the atoms joining them, M2 is silicon, germanium or tin, R8 and R9 are identical or different and have the meaning stated for R11, m and n are identical or different and are zero, 1 or 2, m plus n being zero, 1 or 2, and the alum oxane is a compound of the formula (II):
(II) for the linear type and/or of the formula (III) (III) for the cyclic type, R14 being a (C1-C6)alkyl group in the formulae (II) and (III) and p being an integer from 2 to 50.
3. The polypropylene wax as claimed in claim 1, and substantially as described herein.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3904468A DE3904468A1 (en) | 1989-02-15 | 1989-02-15 | POLYPROPYLENE WAX AND METHOD FOR THE PRODUCTION THEREOF |
| DEP3904468.8 | 1989-02-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2010064A1 true CA2010064A1 (en) | 1990-08-15 |
Family
ID=6374090
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002010064A Abandoned CA2010064A1 (en) | 1989-02-15 | 1990-02-14 | Polypropylene wax and process for the production thereof |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5081322A (en) |
| EP (1) | EP0384264B1 (en) |
| JP (1) | JP3086469B2 (en) |
| AU (1) | AU623491B2 (en) |
| CA (1) | CA2010064A1 (en) |
| DE (2) | DE3904468A1 (en) |
| ES (1) | ES2041059T3 (en) |
| ZA (1) | ZA901114B (en) |
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| DE3148229A1 (en) * | 1981-12-05 | 1983-06-09 | Hoechst Ag, 6230 Frankfurt | Process for the preparation of polyolefin waxes |
| JPS59206409A (en) * | 1983-05-11 | 1984-11-22 | Mitsui Petrochem Ind Ltd | Polyolefin wax and its production |
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| DE3443087A1 (en) * | 1984-11-27 | 1986-05-28 | Hoechst Ag, 6230 Frankfurt | METHOD FOR PRODUCING POLYOLEFINES |
| EP0200351B2 (en) * | 1985-03-26 | 1996-10-16 | Mitsui Petrochemical Industries, Ltd. | Liquid ethylene-type random copolymer, process for production thereof, and use thereof |
| JPS62129303A (en) * | 1985-12-02 | 1987-06-11 | Mitsui Petrochem Ind Ltd | Ethylenic random copolymer wax and production thereof |
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| JP2546859B2 (en) * | 1987-10-08 | 1996-10-23 | 東燃株式会社 | Ethylene polymerization catalyst |
| DE3743320A1 (en) * | 1987-12-21 | 1989-06-29 | Hoechst Ag | 1-OLEFIN STEREO BLOCK POLYMER WAX AND METHOD FOR THE PRODUCTION THEREOF |
| DE3743321A1 (en) * | 1987-12-21 | 1989-06-29 | Hoechst Ag | 1-OLEFIN POLYMER WAX AND METHOD FOR THE PRODUCTION THEREOF |
| US4914253A (en) * | 1988-11-04 | 1990-04-03 | Exxon Chemical Patents Inc. | Method for preparing polyethylene wax by gas phase polymerization |
| DE3904469A1 (en) * | 1989-02-15 | 1990-08-16 | Hoechst Ag | METHOD FOR PRODUCING A STATISTICAL PROPYLENE COPOLYMER |
-
1989
- 1989-02-15 DE DE3904468A patent/DE3904468A1/en not_active Withdrawn
-
1990
- 1990-02-13 ES ES199090102762T patent/ES2041059T3/en not_active Expired - Lifetime
- 1990-02-13 DE DE9090102762T patent/DE59001092D1/en not_active Expired - Lifetime
- 1990-02-13 US US07/479,401 patent/US5081322A/en not_active Expired - Lifetime
- 1990-02-13 JP JP02029752A patent/JP3086469B2/en not_active Expired - Lifetime
- 1990-02-13 EP EP90102762A patent/EP0384264B1/en not_active Expired - Lifetime
- 1990-02-14 AU AU49397/90A patent/AU623491B2/en not_active Ceased
- 1990-02-14 ZA ZA901114A patent/ZA901114B/en unknown
- 1990-02-14 CA CA002010064A patent/CA2010064A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| DE3904468A1 (en) | 1990-08-16 |
| AU4939790A (en) | 1990-08-23 |
| ES2041059T3 (en) | 1993-11-01 |
| DE59001092D1 (en) | 1993-05-06 |
| ZA901114B (en) | 1990-10-31 |
| US5081322A (en) | 1992-01-14 |
| EP0384264B1 (en) | 1993-03-31 |
| JP3086469B2 (en) | 2000-09-11 |
| AU623491B2 (en) | 1992-05-14 |
| EP0384264A1 (en) | 1990-08-29 |
| JPH03197516A (en) | 1991-08-28 |
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