CA2103694A1 - Process for preparing a polypropylene wax - Google Patents
Process for preparing a polypropylene waxInfo
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- CA2103694A1 CA2103694A1 CA002103694A CA2103694A CA2103694A1 CA 2103694 A1 CA2103694 A1 CA 2103694A1 CA 002103694 A CA002103694 A CA 002103694A CA 2103694 A CA2103694 A CA 2103694A CA 2103694 A1 CA2103694 A1 CA 2103694A1
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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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—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
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/642—Component covered by group C08F4/64 with an organo-aluminium 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
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/646—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64
- C08F4/6465—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64 containing silicium
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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
- 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
- C08F4/647—Catalysts containing a specific non-metal or metal-free compound
- C08F4/649—Catalysts containing a specific non-metal or metal-free compound organic
- C08F4/6494—Catalysts containing a specific non-metal or metal-free compound organic containing oxygen
-
- 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
- C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
- C08F4/652—Pretreating with metals or metal-containing compounds
- C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
- C08F4/6543—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof halides of magnesium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
Abstract
Abstract of the disclosure Process for preparing a polypropylene wax Polypropylene waxes of high crystallinity and good processibility can be obtained by solution polymerization at a temperature above 110°C, if a catalyst system, which has been formed from a magnesium-alkoxy compound, a tetravalent titanium compound, a silicon compound and an aluminumorganic compound, is used in the polymerization.
The polypropylene waxes prepared by the process are viscous-hard, colorless, non-tacky, heat-stable, readily grindable products having an isotacticity, determined by IR-spectroscopy, of more than 70 % and a melt viscosity of 50 to 4000 mPa.s, measured at 170°C. The waxes are suitable, for example, as base masses for pigment preparation, for an abrasion-resistant finish of printing inks, for dulling paints, as an aid in the processing of plastics, for example as lubricants and release agents, as a formulation component in photographic toners and as agents for increasing the melting point.
The polypropylene waxes prepared by the process are viscous-hard, colorless, non-tacky, heat-stable, readily grindable products having an isotacticity, determined by IR-spectroscopy, of more than 70 % and a melt viscosity of 50 to 4000 mPa.s, measured at 170°C. The waxes are suitable, for example, as base masses for pigment preparation, for an abrasion-resistant finish of printing inks, for dulling paints, as an aid in the processing of plastics, for example as lubricants and release agents, as a formulation component in photographic toners and as agents for increasing the melting point.
Description
2~ ~3~9~
HOECHST AKTIENGESELLSCEIAFT HOE 92/F 241 Dr.I:~A/-Description Process for preparing a polypropylene wax The invention relates to a process for preparing polypropylene waxes of high crystallinity by homopolymerization of propylene or copolymerization of propylen~ with a small fraction of other olefins, to the catalyst used for this purpo~e and to the waxe~ prepared by this process.
It is known that the polymerization of propylene in the presence of a catalyst, obtain~d by reacting a titanium compound with a magnesium compound, at a relatively high temperature leads to waxy polym~rs having a comparatively high melt viscosity (cf. DE 2,329,641). The crystallinity of these waxes i~ in the lower to medium range and can be influenced within certain limits by the nature o~ the aluminum-organic compound u~ed for activation, but at most only moderake degrees o~ crystallinity are obtained.
Moreover, highly crystalline poly-l-alkene waxesd in particular polypropylene waxes, are accessible by using a specific ca~alyst sy~tem composed of the reaction product of titanium tetrahalide, ma~nesium alcohvlate and an ether, alcohol, amine or a carboxylic acid or a carboxylic acid derivative ~cf. DE 3,148,229)~ Addition-ally, a further, stereoregulating component selected from the group comprising carboxylic acid e~ters, phosphoric acid amides, ethers or thioethers is added during the polymerization. The polymerization i8 carried out in solution in a temperature range from 100 to 110C. At a higher polymerization temperaturel the cry~tallinity of the products decreases. A di~advanta~e o~ this process i8 that the required low polymerization temperature~ are a~
a rule below the cloud point of the waxes formed, ~o that the Iatter precipitate and hence cause the formation of undesixed deposits in the reactor.
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Finally, a process for the preparation o~ "exclusively isotactic~ polypropylene waxes by bulk polymerization with the aid of a titanium halide and an aluminum-organic compound at a temperature in the range from 180 to 350C
and a pressure from 500 to 3000 bar is known ~cf.
DE 3,431,842). The process involves a hîgh energy con-sumption and rsquires expensive pressure and tempe.ra-ture-resistant equipment.
In addition, the preparation of highly isotactic homo-polymeric and copolymeric polypropylene waxes by a gas phase proce~s is known, in which supported catalysts containing titanium and magnesium are used in combinat.ion with aluminum-organic activators and electron donors such as, for example, alkoxysilane compounds (cf.
DE 4,030,379). The products acce~sib].e by this process are, however, comparatively high-molecular~ Their further processing by the melt technology, which is usual for waxes and presupposes low vi~aosities, is not po~ible with these, or at least difficult.
It is also known that polypropylene waxes can be prepared with the aid o~ soluble catalyst systems containing metallocene compounds ~cf. DE 3,743,321, D~ 3,904,468 and DE 3,743,320). ~he synthesis and handling of the metallo-cene components and espeGially of the al~minoxane compon~
ents used as co-catalysts in a large excess is expensive.
It has now been ~ound that polypropylene waxes of high crystallinity and good processibility can be obtained by solution polymerization at a temperature above 110C, if a specific catalyst system in combination with a silicon compound is used in the polymerization.
The invention therefore relat~s to a proceæs for prepar-ing a polyolefin wax having an IR isotacticity of ~ 70 ~
and a melt v.iscosity of 50 to 4000 mPa.s, measured at 170C, by homopolymerization of propylene or copolymeriz ation of propylene with 0.1 to 5 ~ by weight of ethylene , ' ' ' .
21036~4 or of an ol~fin of the formula R-CH=CH2, in which R is an alkyl radical having 2 to 38 carbon atoms, in solution at a temperature of 2 110C at a pressure of 2 to 100 bar in the presence of a catalyst system composed of a titanium-containing componen~ ~, a silicon-containing component B
and an aluminum~organic component C, wherein component A
has been prepared by reacting a magnesium compound of the formula I
Mg~ORl)~X~n (I), in which Rl is identical or different Cl-510-al}cyl radicalsl X is a halogen atom and n is 1 or 2, with a tetravalent ti-tanium compound of the formula II
Ti~OR2)mX
(II~, in which R2 iS identical or different Cl-C6-alkyl radicals, X is a halogen atom and m is a number from 0 to 4, a silicon compound of the formula III
R3pSi(oR4)4p (III) in which p is 1, 2 or 3 ~ ~3 is identical or di~ferent Cl-Cl6-alkyl radicals and R4 is identical or different cl-c16-alkyl radicals or unsubstitu-ted or alkyl-substituted C5-C8-cycloalkyl radicals, C6-Cla-aryl radicals or C7-C1a-aralkyl radicals, is used as compon-ent ~ and an aluminum compound of the formula IV
R5qAlCl3 g in which q is 1, 2 or 3 a~d R5 is identical or di~ferent C1-C30-al~yl radicals, i8 used as component CO
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The preparation of the cataly~t is carried out in such a way that initially the catalyst component A i~ prepared by reacting a magnesium compound, pre~erably a magnesium alcoholate, with a tetravalen~ titanium compQund, prefer-ably a titanium tetrahalide, in an in~_rt solvent. Themagnesium alcoholate used is a compound of the formula I
Mg(OR~ 2-~
(I), in which Rl is identical or different, preferably straight chain C,-C,0-alkyl radicals, preferably C,~C6-alkyl radicals, X is a halogen atom and n is 1 or 2.
~y(OCH3) 2 r Mg~oc2Hs) 2 / ~g ( ~C3H,) 2 and Mg( OC4~9 ) 2 may be mentioned as examples. ~owe~er, magnesium alcoholates of the formula MgX(OR'), in which X is halogen and R' i~ as defined above, can also be used.
The magnesium compound is reacted with a tetrclvalent titanium compound of the formula II
Ti(OR2)~X4m (II), in which R2 is identical or dif~erent C,-C6-alkyl radicals, X is a halogen atom and m is a numbar from 0 to 4, at a temperature from 0 to 200, preferably 20 to 120C. The reaction medium used i~ an inert diluent and ~uspending agent, for example a hydrocarbon. Aliphatic and cycloaliphatîc hydrocarbons ~uch as, for example~
hexane, heptane or cyclohexane and also aromatia hydro-carbons such a~ benzene, toluene etc~ are suitable.
Advantageously, the magne~ium component is introduced as a suspen~ion, and the titanium compound is added with stirring~ The magnesium compound and ti~anium com~ound are expediently and preferably used in a molar ratio of l : 0.2 to 1 : 5/ but molar ratios out~ide this range are also possible. The reaction times are in general between 1 and 10 howrs.
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The catalyst component A thus obtained axises as a solid.
It is freed of soluble fractions by xepeated washing with an inert hydrocarbon~ preferably with the medium used in its preparation. The washed catalyst can, if de~ired, be reacted with an electron donor. Suitable! electron donors are alcohols such as methanol, ethanol and propanol, ethers such as diethyl ether, di-n butyl ether or di-i-amyl ether, amines such as triethylamine, aliphatic or aromatic carboxylic acids and derivatives thereo~, for example esters, anhydrides, halides or amides su~h a~, for example, ethyl acetate, ethyl benzoate, benzoic anhydride and benzamide.
The component B used is a silicon compound of the formula III
R3pSi(oR4)4p (III~, in which p is 1, 2 or 3, ~3 iS identical or different Cl-Cl6-alkyl radicals, for example methyl, ethyl or n- or i-propyl, and R4 is identical or different Cl~C16-alkyl radicals or unsubstituted or alkylsubætituted Cs-C8-cycloalkyl radicals, Cj-Cl8-aryl radicals, for example phenyl radicals, or C7-Cl8-aralkyl radicals, for example 4-methylphenyl radicals. Methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, dimethyldimethoxy~ilane, dimethyldiethoxysilane, isobutylmethyldimethoxysilane, trimethylmethox~silane, cyclopentylmethyldimethoxysilane, cyclohexylmethyldLmeth-oxysilane, phenyltrimethoxy~ilane and diphenyldimethoxy-silane may be mentioned as examples of component B.
As the aluminum-vrganic component C, compounds of the formula IV
RsqAlCl3 q ( ~V) are used, in which q is 1, 2 or 3 and R5 is identical or different Cl-C30-alkyl radicals, preferably C2-C12-alkyl ~, . - .. . . . - - .
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radicals. The Cl/Al atomic ratio is accordingly between 2 : 1 and 0 : 1. Preferably, a ratio between 1 : 1 and 0.25 : 1 is set, which can be effected by mixing aluminum-organic compounds of different chlorine content, for example triethylaluminum and diethylaluminum chloride.
Using the catalyst system according to the invention, propylene or propylene with 0.1 to 5 % by weight of ethylene or an olefin of the formula R-C~=CH2, in which R
is an alkyl radical having 2 to 38 carbon atoms, ~or example 1-butene or 1-hexene, are polymexized.
The procedure for carrying out the polymerization is advantageously such that the catalyæt system is first prepared by reacting component C with component B by mixing in the presence of an inert hydrocarbon and then adding component A to this mixture. The quantities are to be salected here in ~uch a way that the component C
(relative to al~minum~/component B molar ratio i5 200 : 1 to 1 : 1, preferably 50 : 1 to 10 : 1, and the compon-ent C (relative to aluminum)/component A (relative to titanium) molar ratio is 1 : 1 to 30: 1, pref0rably 2 : 1 to 20 ~
The polymerization is carried out continuously or discon-tinuously in solution at a temperature above 110C, preferably ~etween 115 and 150C, particularly pre~erably between 120 and 140C, at a pressure of 2 to 100 bar, preferably 5 to 20 bar. It is also possible to polymerize in inert hydrocarbvns which are liquid at the polymeriza-tion temperature but solid at room temperature.
The molecular mass is regulated in the known m~nner by addition of hydro~en. After completion of the polymerization, the solvent is ~eparated off, pre~erably by distillation, if necessary a~ter prior decompo~ition of the catalyst with suitable decomposing a~ents, for example wat r, and subsequent fi~tration.
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2~36~q The pol~olefin waxes prepared by the process accoxding to the invention are viscous-hard, colorless, non-tac~y, heat-stable, readily grindable products having a degxee of isotacticity, determined by IR spectroscopy, of more than 70 % and a melt viscosity of 50 to 4000 mPa.s, measured at 170C. The waxes are suitable, for example, as base masses for pigment preparation, for an abrasion-resistant finish of printing inks, for dulling paints, as an aid in the processing of plastics, for example as lubrican~s and release agents, as a formulation component ia photographic toners and as agPnts for increasing the melting point~
The examples which follow serve to explain the invention in more detail.
The melt viscosities were mea~ured in a rotary visco-meter. The determination of isotacticity was carr:ied Ollt by IR spectroscopy according to J.P. Luongo, J. Appl.
Pol. Chem. 3 (9), 302 (1960), and the heat of fusion was determined by DSC spectro~copy.
Example 1 114.4 g (1.0 mol~ of magnesium ethylate were suspended in 1000 cm3 of a diesel oil fr~ction (boiling range 140 to 160C). 284.8 g (1.5 mol) of titanium tetrachloride were added dropwise to the batch with stirring ~t 85C in the course of 4 hours. 1~he suspension was then stirred for a further 30 minutes at 85C. The precipitate wa~ wash0d by repeated stirring with diesel oil, until the supernata~t diesel oil above the solid was free of titanium.
The catalyst system used for the polymerization was prepared by mixing 150 mmol of triethylaluminum, 75 mmol of diethylalu~inum chloride (catalyst component C) and 7.5 mmol of cyclohexylmethyldimethoxy~ilane (component Bl in 1.5 dm3 0~ diesel oil fraction and subse~uently stixr-ing 30 mmol (relative to Ti) of the above c~taly~t , . . .
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component A into this mixture. The molar ratio of the said componerlts was 5 : 2.5 o 0.25 : 1.
15 dm3 of a diesel oil fraction (boiling range 140 to 160C~ were introduced into a 40 dm3 vessel with impeller stirrer. After heating of the vessel contents to 130C, hydrogen gas was fixst added up to an internal pressure of 0.1 bar, and then propylene up to an internal pressure of 5 bar~ 0.5 dm3 of the catalyst described above waq pumped in at 130C. By continuou~ further addition of 3.2 kg of propylene and 0.5 dm3 of hydrogen per hour cmd intermittent addition of catalyst, the pressure was maintained at 5 bar~ The polymerization temperature wa.
130C.
A~ter 75 minutes, a total of 1~50 cm3 of the catalyst suspen6ion, corresponding to ahout 21 m~ atom of Ti, had been consumed. The reaction was stopped by addition of 15 cm3 of water, the polymer solution was filtered and khe solvent was distilled off in vacuo. This gave 3.55 kg of polypropylene wax.
Melt viscosity at 170C 1330 mPa.s; heat of fusion 83 J/g; IR isotacticity 72 %.
Comparison ~xample 1 The catalyst component A wa~ prepared according to Example 1. The catalyst system u~ed for polymerization was composed of 90 mmol of triethylaluminum, 60 mmol of diethylaluminum chloride and 30 mg atom of component A.
A silicon compound was not used.
The polymerization of propylene under the conditions described in ~xample 1 led to a wax product which had a lower crystallinity than that obtained accordincJ to ~xample 1.
Melt viscosity at 170C: 13~0 mPa.s; heat of fusion .
- ~ . -~: ' ~ 1 03~4 g 63 J/g; IR isotacticity 63 %.
Comparison Example B
A polymerization catalyst was preparled according toDE-A 3,148,229, Example 1~ For this purpose, 114.4 g (1.0 mol) of magnesium ethylate were suspended in 1000 cm3 of a diesel oil fraction (boi:Ling range 140 -160C). 380 q (2.0 mol) of titanium tetrachloride were added dropwise with stirring at 85C in the course of 4 hours. The batch was then stirred for a further 30 min utes at 85~C. The precipitate was washed by decanting and repeated stirring with diesel oil, until the dies~l oil supernatant above the solid was free of titanium.
31.7 g (O.20 mol) of di-isoamyl ether as an electron donor were then added to the suspension, and the mixture was stirred for 1 hour at 100C. The solid was freed of soluble titanium compound~ by washing with diesel oil.
Using this catalyst, propylene was polymerized according to Example 1 of DE-A 3,14~,~29, but a polymerizatiDn temperature of 130C was chosen in place of the indicated ~0 100C~ The resulting polypropylene wax showed the follow-ing characteristic data:
Melt viscosity at 170C 810 mPa.s; heat of fu~ion 79 J/g;
IR-isotacticity 71 %.
As can be seen, the isotaatiaity value of the wax i8 markedly lower than that of a product prepared ln the same manner but at 100C (85 %). If the polymerization is carried out at 100C according to DE 3,148,229, the isotacticity value is admittedly higher, but the inner wall of the polymerization vessel shows depo~its of precipitated product, which impede the removal o~ the heat of reaction.
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~369~
Example 2 The polymerization was carried out according to Example l. The cataly~t was prepared by mixing 210 mmol of triethylaluminum, 105 mmol of diethylaluminum chlor-ide, 22.5 mmol of cyclohexylmethyldime~thoxysilane and30 mg atom of the catalys~ component ~ fxom Example 1, corresponding to a molar ratio of 7 : 3.5 : 0O75 : 1.
This gave a polypropylene wax having the following characteristic data:
Melt viscosity at 170C 1990 mPaOs; heat of fu~ion 106 J/g; IR isotacticity 80 %.
Example 3 114.4 g of mag~esium ethylate were ~uspended in lO00 cm3 of a diesel oil fraction (boiling range 140 to 160C).
380 g (2.0 mol) of titanium tetrachloride were added drop~ise to the batch with ~tirri.ng at 85C in the course of 4 hours. The suspension was then stirred for a further 30 minutes at 85C. The precipitate was washed by repeat-ed stirring with diesel oil, until the diesel oil super-natant above the solid was free of titanium.
31.7 g of diisoamyl ether (200 mmol) were then added to the suspension, and the mixture was stirred for 1 hour at 100C. The solid was again freed of soluble titanium compounds by washing with diesel oil. It still contained 3.5 % of the titanium originally introduced as titanium tetrachloride.
The polymerization was carried out according to Example 1. The cataly t system was prepared by mixing 210 mmol of triethylaluminum, 105 mmol of diethylal~minum chloride/ 2~.5 mmol of cyclohexylmethyldimethoxysilane and 30 mg atom of catalyst component A, corresponding to a molar ratio of 7 : 3.5 : 0.7S : 1. This gave a polypro-pylene wax having the following characteri~tic data:
Melt viscosity at 170C 1200 mPa.~; heat o~ fusion .
-.
2~369~
110 J~g; IR isotacticity 84 ~.
Example 4 The catalyst system used for the polymerization wasprepared analogously to Example 1, diphenyldimethoxy-silane being used in place of cyclohexylmethyldimethoxy-silane. The polymerization of propylene, carried out a~
described in Example 1, gave a wax having the following characteristlc data:
Melt viscosity at 170C 1600 mPa.s; heat of fusion 82 J/g; IR isotacticity 73 ~.
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-. - .
HOECHST AKTIENGESELLSCEIAFT HOE 92/F 241 Dr.I:~A/-Description Process for preparing a polypropylene wax The invention relates to a process for preparing polypropylene waxes of high crystallinity by homopolymerization of propylene or copolymerization of propylen~ with a small fraction of other olefins, to the catalyst used for this purpo~e and to the waxe~ prepared by this process.
It is known that the polymerization of propylene in the presence of a catalyst, obtain~d by reacting a titanium compound with a magnesium compound, at a relatively high temperature leads to waxy polym~rs having a comparatively high melt viscosity (cf. DE 2,329,641). The crystallinity of these waxes i~ in the lower to medium range and can be influenced within certain limits by the nature o~ the aluminum-organic compound u~ed for activation, but at most only moderake degrees o~ crystallinity are obtained.
Moreover, highly crystalline poly-l-alkene waxesd in particular polypropylene waxes, are accessible by using a specific ca~alyst sy~tem composed of the reaction product of titanium tetrahalide, ma~nesium alcohvlate and an ether, alcohol, amine or a carboxylic acid or a carboxylic acid derivative ~cf. DE 3,148,229)~ Addition-ally, a further, stereoregulating component selected from the group comprising carboxylic acid e~ters, phosphoric acid amides, ethers or thioethers is added during the polymerization. The polymerization i8 carried out in solution in a temperature range from 100 to 110C. At a higher polymerization temperaturel the cry~tallinity of the products decreases. A di~advanta~e o~ this process i8 that the required low polymerization temperature~ are a~
a rule below the cloud point of the waxes formed, ~o that the Iatter precipitate and hence cause the formation of undesixed deposits in the reactor.
- ~ , .. , ., . ~ - ,.
- .
. . - . . . , ~ : .,, :. :
.. .. . : : - : : .:: .
~: : ... .
. . ~ . ,. : . . : : .
~io~
Finally, a process for the preparation o~ "exclusively isotactic~ polypropylene waxes by bulk polymerization with the aid of a titanium halide and an aluminum-organic compound at a temperature in the range from 180 to 350C
and a pressure from 500 to 3000 bar is known ~cf.
DE 3,431,842). The process involves a hîgh energy con-sumption and rsquires expensive pressure and tempe.ra-ture-resistant equipment.
In addition, the preparation of highly isotactic homo-polymeric and copolymeric polypropylene waxes by a gas phase proce~s is known, in which supported catalysts containing titanium and magnesium are used in combinat.ion with aluminum-organic activators and electron donors such as, for example, alkoxysilane compounds (cf.
DE 4,030,379). The products acce~sib].e by this process are, however, comparatively high-molecular~ Their further processing by the melt technology, which is usual for waxes and presupposes low vi~aosities, is not po~ible with these, or at least difficult.
It is also known that polypropylene waxes can be prepared with the aid o~ soluble catalyst systems containing metallocene compounds ~cf. DE 3,743,321, D~ 3,904,468 and DE 3,743,320). ~he synthesis and handling of the metallo-cene components and espeGially of the al~minoxane compon~
ents used as co-catalysts in a large excess is expensive.
It has now been ~ound that polypropylene waxes of high crystallinity and good processibility can be obtained by solution polymerization at a temperature above 110C, if a specific catalyst system in combination with a silicon compound is used in the polymerization.
The invention therefore relat~s to a proceæs for prepar-ing a polyolefin wax having an IR isotacticity of ~ 70 ~
and a melt v.iscosity of 50 to 4000 mPa.s, measured at 170C, by homopolymerization of propylene or copolymeriz ation of propylene with 0.1 to 5 ~ by weight of ethylene , ' ' ' .
21036~4 or of an ol~fin of the formula R-CH=CH2, in which R is an alkyl radical having 2 to 38 carbon atoms, in solution at a temperature of 2 110C at a pressure of 2 to 100 bar in the presence of a catalyst system composed of a titanium-containing componen~ ~, a silicon-containing component B
and an aluminum~organic component C, wherein component A
has been prepared by reacting a magnesium compound of the formula I
Mg~ORl)~X~n (I), in which Rl is identical or different Cl-510-al}cyl radicalsl X is a halogen atom and n is 1 or 2, with a tetravalent ti-tanium compound of the formula II
Ti~OR2)mX
(II~, in which R2 iS identical or different Cl-C6-alkyl radicals, X is a halogen atom and m is a number from 0 to 4, a silicon compound of the formula III
R3pSi(oR4)4p (III) in which p is 1, 2 or 3 ~ ~3 is identical or di~ferent Cl-Cl6-alkyl radicals and R4 is identical or different cl-c16-alkyl radicals or unsubstitu-ted or alkyl-substituted C5-C8-cycloalkyl radicals, C6-Cla-aryl radicals or C7-C1a-aralkyl radicals, is used as compon-ent ~ and an aluminum compound of the formula IV
R5qAlCl3 g in which q is 1, 2 or 3 a~d R5 is identical or di~ferent C1-C30-al~yl radicals, i8 used as component CO
:. . . . .
:, , :
. . ~ . .
,, . : . - , :
... ..
: ~ ~ . .. . . .
.- . . . : .. . .
2:~3~9~
The preparation of the cataly~t is carried out in such a way that initially the catalyst component A i~ prepared by reacting a magnesium compound, pre~erably a magnesium alcoholate, with a tetravalen~ titanium compQund, prefer-ably a titanium tetrahalide, in an in~_rt solvent. Themagnesium alcoholate used is a compound of the formula I
Mg(OR~ 2-~
(I), in which Rl is identical or different, preferably straight chain C,-C,0-alkyl radicals, preferably C,~C6-alkyl radicals, X is a halogen atom and n is 1 or 2.
~y(OCH3) 2 r Mg~oc2Hs) 2 / ~g ( ~C3H,) 2 and Mg( OC4~9 ) 2 may be mentioned as examples. ~owe~er, magnesium alcoholates of the formula MgX(OR'), in which X is halogen and R' i~ as defined above, can also be used.
The magnesium compound is reacted with a tetrclvalent titanium compound of the formula II
Ti(OR2)~X4m (II), in which R2 is identical or dif~erent C,-C6-alkyl radicals, X is a halogen atom and m is a numbar from 0 to 4, at a temperature from 0 to 200, preferably 20 to 120C. The reaction medium used i~ an inert diluent and ~uspending agent, for example a hydrocarbon. Aliphatic and cycloaliphatîc hydrocarbons ~uch as, for example~
hexane, heptane or cyclohexane and also aromatia hydro-carbons such a~ benzene, toluene etc~ are suitable.
Advantageously, the magne~ium component is introduced as a suspen~ion, and the titanium compound is added with stirring~ The magnesium compound and ti~anium com~ound are expediently and preferably used in a molar ratio of l : 0.2 to 1 : 5/ but molar ratios out~ide this range are also possible. The reaction times are in general between 1 and 10 howrs.
. . .
.
. . .~
2:L~3~9~
The catalyst component A thus obtained axises as a solid.
It is freed of soluble fractions by xepeated washing with an inert hydrocarbon~ preferably with the medium used in its preparation. The washed catalyst can, if de~ired, be reacted with an electron donor. Suitable! electron donors are alcohols such as methanol, ethanol and propanol, ethers such as diethyl ether, di-n butyl ether or di-i-amyl ether, amines such as triethylamine, aliphatic or aromatic carboxylic acids and derivatives thereo~, for example esters, anhydrides, halides or amides su~h a~, for example, ethyl acetate, ethyl benzoate, benzoic anhydride and benzamide.
The component B used is a silicon compound of the formula III
R3pSi(oR4)4p (III~, in which p is 1, 2 or 3, ~3 iS identical or different Cl-Cl6-alkyl radicals, for example methyl, ethyl or n- or i-propyl, and R4 is identical or different Cl~C16-alkyl radicals or unsubstituted or alkylsubætituted Cs-C8-cycloalkyl radicals, Cj-Cl8-aryl radicals, for example phenyl radicals, or C7-Cl8-aralkyl radicals, for example 4-methylphenyl radicals. Methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, dimethyldimethoxy~ilane, dimethyldiethoxysilane, isobutylmethyldimethoxysilane, trimethylmethox~silane, cyclopentylmethyldimethoxysilane, cyclohexylmethyldLmeth-oxysilane, phenyltrimethoxy~ilane and diphenyldimethoxy-silane may be mentioned as examples of component B.
As the aluminum-vrganic component C, compounds of the formula IV
RsqAlCl3 q ( ~V) are used, in which q is 1, 2 or 3 and R5 is identical or different Cl-C30-alkyl radicals, preferably C2-C12-alkyl ~, . - .. . . . - - .
.
.
. ' .. .
.
3~9~
radicals. The Cl/Al atomic ratio is accordingly between 2 : 1 and 0 : 1. Preferably, a ratio between 1 : 1 and 0.25 : 1 is set, which can be effected by mixing aluminum-organic compounds of different chlorine content, for example triethylaluminum and diethylaluminum chloride.
Using the catalyst system according to the invention, propylene or propylene with 0.1 to 5 % by weight of ethylene or an olefin of the formula R-C~=CH2, in which R
is an alkyl radical having 2 to 38 carbon atoms, ~or example 1-butene or 1-hexene, are polymexized.
The procedure for carrying out the polymerization is advantageously such that the catalyæt system is first prepared by reacting component C with component B by mixing in the presence of an inert hydrocarbon and then adding component A to this mixture. The quantities are to be salected here in ~uch a way that the component C
(relative to al~minum~/component B molar ratio i5 200 : 1 to 1 : 1, preferably 50 : 1 to 10 : 1, and the compon-ent C (relative to aluminum)/component A (relative to titanium) molar ratio is 1 : 1 to 30: 1, pref0rably 2 : 1 to 20 ~
The polymerization is carried out continuously or discon-tinuously in solution at a temperature above 110C, preferably ~etween 115 and 150C, particularly pre~erably between 120 and 140C, at a pressure of 2 to 100 bar, preferably 5 to 20 bar. It is also possible to polymerize in inert hydrocarbvns which are liquid at the polymeriza-tion temperature but solid at room temperature.
The molecular mass is regulated in the known m~nner by addition of hydro~en. After completion of the polymerization, the solvent is ~eparated off, pre~erably by distillation, if necessary a~ter prior decompo~ition of the catalyst with suitable decomposing a~ents, for example wat r, and subsequent fi~tration.
.. ~ - . - - .
2~36~q The pol~olefin waxes prepared by the process accoxding to the invention are viscous-hard, colorless, non-tac~y, heat-stable, readily grindable products having a degxee of isotacticity, determined by IR spectroscopy, of more than 70 % and a melt viscosity of 50 to 4000 mPa.s, measured at 170C. The waxes are suitable, for example, as base masses for pigment preparation, for an abrasion-resistant finish of printing inks, for dulling paints, as an aid in the processing of plastics, for example as lubrican~s and release agents, as a formulation component ia photographic toners and as agPnts for increasing the melting point~
The examples which follow serve to explain the invention in more detail.
The melt viscosities were mea~ured in a rotary visco-meter. The determination of isotacticity was carr:ied Ollt by IR spectroscopy according to J.P. Luongo, J. Appl.
Pol. Chem. 3 (9), 302 (1960), and the heat of fusion was determined by DSC spectro~copy.
Example 1 114.4 g (1.0 mol~ of magnesium ethylate were suspended in 1000 cm3 of a diesel oil fr~ction (boiling range 140 to 160C). 284.8 g (1.5 mol) of titanium tetrachloride were added dropwise to the batch with stirring ~t 85C in the course of 4 hours. 1~he suspension was then stirred for a further 30 minutes at 85C. The precipitate wa~ wash0d by repeated stirring with diesel oil, until the supernata~t diesel oil above the solid was free of titanium.
The catalyst system used for the polymerization was prepared by mixing 150 mmol of triethylaluminum, 75 mmol of diethylalu~inum chloride (catalyst component C) and 7.5 mmol of cyclohexylmethyldimethoxy~ilane (component Bl in 1.5 dm3 0~ diesel oil fraction and subse~uently stixr-ing 30 mmol (relative to Ti) of the above c~taly~t , . . .
~ ,. , , .,:
, ~ 1 ~3~9~
component A into this mixture. The molar ratio of the said componerlts was 5 : 2.5 o 0.25 : 1.
15 dm3 of a diesel oil fraction (boiling range 140 to 160C~ were introduced into a 40 dm3 vessel with impeller stirrer. After heating of the vessel contents to 130C, hydrogen gas was fixst added up to an internal pressure of 0.1 bar, and then propylene up to an internal pressure of 5 bar~ 0.5 dm3 of the catalyst described above waq pumped in at 130C. By continuou~ further addition of 3.2 kg of propylene and 0.5 dm3 of hydrogen per hour cmd intermittent addition of catalyst, the pressure was maintained at 5 bar~ The polymerization temperature wa.
130C.
A~ter 75 minutes, a total of 1~50 cm3 of the catalyst suspen6ion, corresponding to ahout 21 m~ atom of Ti, had been consumed. The reaction was stopped by addition of 15 cm3 of water, the polymer solution was filtered and khe solvent was distilled off in vacuo. This gave 3.55 kg of polypropylene wax.
Melt viscosity at 170C 1330 mPa.s; heat of fusion 83 J/g; IR isotacticity 72 %.
Comparison ~xample 1 The catalyst component A wa~ prepared according to Example 1. The catalyst system u~ed for polymerization was composed of 90 mmol of triethylaluminum, 60 mmol of diethylaluminum chloride and 30 mg atom of component A.
A silicon compound was not used.
The polymerization of propylene under the conditions described in ~xample 1 led to a wax product which had a lower crystallinity than that obtained accordincJ to ~xample 1.
Melt viscosity at 170C: 13~0 mPa.s; heat of fusion .
- ~ . -~: ' ~ 1 03~4 g 63 J/g; IR isotacticity 63 %.
Comparison Example B
A polymerization catalyst was preparled according toDE-A 3,148,229, Example 1~ For this purpose, 114.4 g (1.0 mol) of magnesium ethylate were suspended in 1000 cm3 of a diesel oil fraction (boi:Ling range 140 -160C). 380 q (2.0 mol) of titanium tetrachloride were added dropwise with stirring at 85C in the course of 4 hours. The batch was then stirred for a further 30 min utes at 85~C. The precipitate was washed by decanting and repeated stirring with diesel oil, until the dies~l oil supernatant above the solid was free of titanium.
31.7 g (O.20 mol) of di-isoamyl ether as an electron donor were then added to the suspension, and the mixture was stirred for 1 hour at 100C. The solid was freed of soluble titanium compound~ by washing with diesel oil.
Using this catalyst, propylene was polymerized according to Example 1 of DE-A 3,14~,~29, but a polymerizatiDn temperature of 130C was chosen in place of the indicated ~0 100C~ The resulting polypropylene wax showed the follow-ing characteristic data:
Melt viscosity at 170C 810 mPa.s; heat of fu~ion 79 J/g;
IR-isotacticity 71 %.
As can be seen, the isotaatiaity value of the wax i8 markedly lower than that of a product prepared ln the same manner but at 100C (85 %). If the polymerization is carried out at 100C according to DE 3,148,229, the isotacticity value is admittedly higher, but the inner wall of the polymerization vessel shows depo~its of precipitated product, which impede the removal o~ the heat of reaction.
, . : . :::
- . . . .
- .: ~ . ~ . , ' ' : : , , ' .
~369~
Example 2 The polymerization was carried out according to Example l. The cataly~t was prepared by mixing 210 mmol of triethylaluminum, 105 mmol of diethylaluminum chlor-ide, 22.5 mmol of cyclohexylmethyldime~thoxysilane and30 mg atom of the catalys~ component ~ fxom Example 1, corresponding to a molar ratio of 7 : 3.5 : 0O75 : 1.
This gave a polypropylene wax having the following characteristic data:
Melt viscosity at 170C 1990 mPaOs; heat of fu~ion 106 J/g; IR isotacticity 80 %.
Example 3 114.4 g of mag~esium ethylate were ~uspended in lO00 cm3 of a diesel oil fraction (boiling range 140 to 160C).
380 g (2.0 mol) of titanium tetrachloride were added drop~ise to the batch with ~tirri.ng at 85C in the course of 4 hours. The suspension was then stirred for a further 30 minutes at 85C. The precipitate was washed by repeat-ed stirring with diesel oil, until the diesel oil super-natant above the solid was free of titanium.
31.7 g of diisoamyl ether (200 mmol) were then added to the suspension, and the mixture was stirred for 1 hour at 100C. The solid was again freed of soluble titanium compounds by washing with diesel oil. It still contained 3.5 % of the titanium originally introduced as titanium tetrachloride.
The polymerization was carried out according to Example 1. The cataly t system was prepared by mixing 210 mmol of triethylaluminum, 105 mmol of diethylal~minum chloride/ 2~.5 mmol of cyclohexylmethyldimethoxysilane and 30 mg atom of catalyst component A, corresponding to a molar ratio of 7 : 3.5 : 0.7S : 1. This gave a polypro-pylene wax having the following characteri~tic data:
Melt viscosity at 170C 1200 mPa.~; heat o~ fusion .
-.
2~369~
110 J~g; IR isotacticity 84 ~.
Example 4 The catalyst system used for the polymerization wasprepared analogously to Example 1, diphenyldimethoxy-silane being used in place of cyclohexylmethyldimethoxy-silane. The polymerization of propylene, carried out a~
described in Example 1, gave a wax having the following characteristlc data:
Melt viscosity at 170C 1600 mPa.s; heat of fusion 82 J/g; IR isotacticity 73 ~.
. ; . - ~ - , .
- . . :
-. - .
Claims (5)
1. A process for preparing a polypropylene wax having an IR isotacticity of > 70 % and a melt viscosity of 50 to 4000 mPa.s, by homopolymerization of propylene or copolymerization of propylene with 0.1 to 5 % by weight of ethylene or of an olefin of the formula R-CH=CH2, in which R is an alkyl radical having 2 to 38 carbon atoms, in solution at a temperature of ? 110°C at a pressure of 2 to 100 bar in the presence of a catalyst system composed of a titanium-containing component A, a silicon-containing component B and an aluminum-organic component C, wherein component A
has been prepared by reacting a magnesium compound of the formula I
Mg(OR1)nX2-n (I), in which R1 is identical or different C1-C10-alkyl radicals, X is a halogen atom and n is 1 or 2, with a tetravalent titanium compound of the formula II
Ti(OR2)mX4-m (II), in which R2 is identical or different C1-C6-alkyl radicals, X is a halogen atom and m is a number from 0 to 4, a silicon compound of the formula III
R3pSi(OR4)4-p (III) in which p is 1, 2 or 3, R3 is identical or different C1-C16-alkyl radicals and R4 is identical or different C1-C16-alkyl radicals or unsubstituted or alkyl-substituted C5-C8-cycloalkyl radicals, C6-C18-aryl radicals or C7-C18-aralkyl radicals, is used as component B and an aluminum compound of the formula IV
R5qAlCl3-q (IV) in which q is 1, 2 or 3 and R5 is identical or different C1-C30-alkyl radicals, is used as component C.
has been prepared by reacting a magnesium compound of the formula I
Mg(OR1)nX2-n (I), in which R1 is identical or different C1-C10-alkyl radicals, X is a halogen atom and n is 1 or 2, with a tetravalent titanium compound of the formula II
Ti(OR2)mX4-m (II), in which R2 is identical or different C1-C6-alkyl radicals, X is a halogen atom and m is a number from 0 to 4, a silicon compound of the formula III
R3pSi(OR4)4-p (III) in which p is 1, 2 or 3, R3 is identical or different C1-C16-alkyl radicals and R4 is identical or different C1-C16-alkyl radicals or unsubstituted or alkyl-substituted C5-C8-cycloalkyl radicals, C6-C18-aryl radicals or C7-C18-aralkyl radicals, is used as component B and an aluminum compound of the formula IV
R5qAlCl3-q (IV) in which q is 1, 2 or 3 and R5 is identical or different C1-C30-alkyl radicals, is used as component C.
2. The process as claimed in claim 1, wherein the reaction of the magnesium compound of the formula I
with the titanium compound of the formula II has been carried out in the presence of an electron donor from the group comprising ethers, alcohols and carboxylic acids and derivatives thereof.
with the titanium compound of the formula II has been carried out in the presence of an electron donor from the group comprising ethers, alcohols and carboxylic acids and derivatives thereof.
3. A catalyst system for preparing a polyolefin wax having an IR isotacticity of > 70 % and a melt viscosity of 50 to 4000 mPa.s, measured at 170°C, composed of a titanium-containing component A, a silicon-containing component B and an aluminum organic component C, wherein component A has been prepared by reacting a magnesium compound of the formula I
Mg(OR1)nX2-n (I), in which R1 is identical or different C1-C10-alkyl radicals, X is a halogen atom and n is 1 or 2, with a tetravalent titanium compound of the formula II
Ti(OR2)mX4-m (II), in which R2 is identical or different C1-C6-alkyl radicals, X is a halogen atom and m is a number from 1 to 4, component B is a silicon compound of the formula III
R3pSi(OR4)4-p (III) in which p is 1, 2 or 3, R3 is identical or different C1-C16-alkyl radicals and R4 is identical or different C1-C16-alkyl radicals or unsubstituted or alkyl-substituted C5-C8-cycloalkyl radicals, C6-C18-aryl radicals or C7-C18-aralkyl radicals, and component C is an aluminum compound of the formula IV
R5qAlCl3-q (IV) in which q is 1, 2 or 3 and R5 is identical or different C1-C30-alkyl radicals.
Mg(OR1)nX2-n (I), in which R1 is identical or different C1-C10-alkyl radicals, X is a halogen atom and n is 1 or 2, with a tetravalent titanium compound of the formula II
Ti(OR2)mX4-m (II), in which R2 is identical or different C1-C6-alkyl radicals, X is a halogen atom and m is a number from 1 to 4, component B is a silicon compound of the formula III
R3pSi(OR4)4-p (III) in which p is 1, 2 or 3, R3 is identical or different C1-C16-alkyl radicals and R4 is identical or different C1-C16-alkyl radicals or unsubstituted or alkyl-substituted C5-C8-cycloalkyl radicals, C6-C18-aryl radicals or C7-C18-aralkyl radicals, and component C is an aluminum compound of the formula IV
R5qAlCl3-q (IV) in which q is 1, 2 or 3 and R5 is identical or different C1-C30-alkyl radicals.
4. The catalyst system as claimed in claim 3, wherein component A has been prepared from titanium tetra-chloride, a magnesium alcoholate of the formula Mg(OR1)2, in which R1 is a C1-C6-alkyl group, and a silicon compound of the formula IV is used.
5. A polyolefin wax having an IR isotacticity of > 70 %
and a melt viscosity of 50 to 4000 mPa.s, measured at 170°C, obtained as claimed in claim 1.
and a melt viscosity of 50 to 4000 mPa.s, measured at 170°C, obtained as claimed in claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4226321 | 1992-08-08 | ||
| DEP4226321.2 | 1992-08-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2103694A1 true CA2103694A1 (en) | 1994-02-09 |
Family
ID=6465172
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002103694A Abandoned CA2103694A1 (en) | 1992-08-08 | 1993-08-06 | Process for preparing a polypropylene wax |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0584586B1 (en) |
| JP (1) | JPH06157664A (en) |
| KR (1) | KR940003979A (en) |
| AT (1) | ATE152739T1 (en) |
| AU (1) | AU670105B2 (en) |
| BR (1) | BR9303275A (en) |
| CA (1) | CA2103694A1 (en) |
| CZ (1) | CZ160593A3 (en) |
| DE (1) | DE59306372D1 (en) |
| ES (1) | ES2104007T3 (en) |
| HK (1) | HK1006721A1 (en) |
| TW (1) | TW303368B (en) |
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| US7319125B2 (en) | 2002-09-20 | 2008-01-15 | Exxonmobil Chemical Patents Inc. | Supercritical polymerization process and polymers produced therefrom |
| US7910637B2 (en) | 2007-09-13 | 2011-03-22 | Exxonmobil Research And Engineering Company | In-line blending of plasticizers with a base polymer |
| US7910679B2 (en) | 2007-12-20 | 2011-03-22 | Exxonmobil Research And Engineering Company | Bulk homogeneous polymerization process for ethylene propylene copolymers |
| US7928162B2 (en) | 2007-09-13 | 2011-04-19 | Exxonmobil Research And Engineering Company | In-line process for producing plasticized polymers and plasticized polymer blends |
| US7994237B2 (en) | 2007-12-20 | 2011-08-09 | Exxonmobil Research And Engineering Company | In-line process to produce pellet-stable polyolefins |
| US8008412B2 (en) | 2002-09-20 | 2011-08-30 | Exxonmobil Chemical Patents Inc. | Polymer production at supersolution conditions |
| US8058371B2 (en) | 2002-09-20 | 2011-11-15 | Exxonmobil Chemical Patents Inc. | Super-solution homogeneous propylene polymerization |
| US8080610B2 (en) | 2007-03-06 | 2011-12-20 | Exxonmobil Research And Engineering Company | Monomer recycle process for fluid phase in-line blending of polymers |
| US8138269B2 (en) | 2007-12-20 | 2012-03-20 | Exxonmobil Research And Engineering Company | Polypropylene ethylene-propylene copolymer blends and in-line process to produce them |
| US8143352B2 (en) | 2006-12-20 | 2012-03-27 | Exxonmobil Research And Engineering Company | Process for fluid phase in-line blending of polymers |
| US8242237B2 (en) | 2006-12-20 | 2012-08-14 | Exxonmobil Chemical Patents Inc. | Phase separator and monomer recycle for supercritical polymerization process |
| US8318875B2 (en) | 2008-01-18 | 2012-11-27 | Exxonmobil Chemical Patents Inc. | Super-solution homogeneous propylene polymerization and polypropylenes made therefrom |
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| WO1996004320A1 (en) * | 1994-08-03 | 1996-02-15 | Exxon Chemical Patents, Inc. | Catalyst system containing a solid titanium component for the stereoregulation of polyolefins |
| EP0890619B1 (en) * | 1997-07-11 | 2004-10-27 | Clariant GmbH | Use of polyolefinwaxes |
| DE19729833A1 (en) * | 1997-07-11 | 1999-01-14 | Clariant Gmbh | Polypropylene wax |
| KR20020000211A (en) * | 2000-06-24 | 2002-01-05 | 박윤구 | Method of making cake coated with chocolate and the cake made therefrom |
| EP1377614A2 (en) | 2000-12-12 | 2004-01-07 | Baker Hughes Incorporated | Low molecular weight isotactic polypropylene polymers, copolymers and derivatives and materials prepared therewith |
| KR20030064553A (en) * | 2002-01-28 | 2003-08-02 | 박충호 | Multilayered rice cake and the preparation method thereof |
| DE102013221849B4 (en) * | 2012-10-30 | 2021-07-29 | Beijing Research Institute Of Chemical Industry, China Petroleum & Chemical Corporation | Process for producing a propylene polymer |
| EP4108972A1 (en) | 2021-06-21 | 2022-12-28 | B Continuity Solutions, S.L. | Method for the freezing of fluids in pipes in an invasive and/or non-invasive way, for releasing metallic elements or for making mechanical adjustments by means of a closed circuit |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2329641C3 (en) * | 1973-06-09 | 1978-09-28 | Hoechst Ag, 6000 Frankfurt | Process for the polymerization of ct-olefins |
| US4451688A (en) * | 1981-12-03 | 1984-05-29 | Nippon Oil Company, Limited | Process for preparing polyolefins |
| DE3148229A1 (en) * | 1981-12-05 | 1983-06-09 | Hoechst Ag, 6230 Frankfurt | Process for the preparation of polyolefin waxes |
| JPH072799B2 (en) * | 1988-12-16 | 1995-01-18 | 住友化学工業株式会社 | Method for producing highly stereoregular a-olefin polymer |
| DE69019046T2 (en) * | 1989-03-02 | 1995-09-07 | Mitsui Petrochemical Ind | Process for the polymerization of olefins and catalyst for olefin polymerization. |
| EP0439622A4 (en) * | 1989-08-18 | 1993-05-26 | Tonen Corporation | Catalytic component for alpha-olefin polymerization |
| JP2818264B2 (en) * | 1990-06-29 | 1998-10-30 | 三井化学株式会社 | Propylene polymerization method |
-
1993
- 1993-07-26 TW TW082105930A patent/TW303368B/zh active
- 1993-08-02 AT AT93112347T patent/ATE152739T1/en not_active IP Right Cessation
- 1993-08-02 ES ES93112347T patent/ES2104007T3/en not_active Expired - Lifetime
- 1993-08-02 BR BR9303275A patent/BR9303275A/en not_active Application Discontinuation
- 1993-08-02 DE DE59306372T patent/DE59306372D1/en not_active Expired - Fee Related
- 1993-08-02 EP EP93112347A patent/EP0584586B1/en not_active Expired - Lifetime
- 1993-08-04 JP JP5193640A patent/JPH06157664A/en active Pending
- 1993-08-05 CZ CZ931605A patent/CZ160593A3/en unknown
- 1993-08-06 AU AU44460/93A patent/AU670105B2/en not_active Ceased
- 1993-08-06 KR KR1019930015233A patent/KR940003979A/en not_active Application Discontinuation
- 1993-08-06 CA CA002103694A patent/CA2103694A1/en not_active Abandoned
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1998
- 1998-06-23 HK HK98106074A patent/HK1006721A1/en not_active IP Right Cessation
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| US7279536B2 (en) | 2002-09-20 | 2007-10-09 | Exxonmobil Chemical Patents Inc. | Polymer production at supercritical conditions |
| US7319125B2 (en) | 2002-09-20 | 2008-01-15 | Exxonmobil Chemical Patents Inc. | Supercritical polymerization process and polymers produced therefrom |
| US7354979B2 (en) | 2002-09-20 | 2008-04-08 | Exxonmobil Chemical Patents Inc. | Polymer production at supercritical conditions |
| US8008412B2 (en) | 2002-09-20 | 2011-08-30 | Exxonmobil Chemical Patents Inc. | Polymer production at supersolution conditions |
| US8058371B2 (en) | 2002-09-20 | 2011-11-15 | Exxonmobil Chemical Patents Inc. | Super-solution homogeneous propylene polymerization |
| US8143352B2 (en) | 2006-12-20 | 2012-03-27 | Exxonmobil Research And Engineering Company | Process for fluid phase in-line blending of polymers |
| US8242237B2 (en) | 2006-12-20 | 2012-08-14 | Exxonmobil Chemical Patents Inc. | Phase separator and monomer recycle for supercritical polymerization process |
| US8080610B2 (en) | 2007-03-06 | 2011-12-20 | Exxonmobil Research And Engineering Company | Monomer recycle process for fluid phase in-line blending of polymers |
| US7910637B2 (en) | 2007-09-13 | 2011-03-22 | Exxonmobil Research And Engineering Company | In-line blending of plasticizers with a base polymer |
| US7928162B2 (en) | 2007-09-13 | 2011-04-19 | Exxonmobil Research And Engineering Company | In-line process for producing plasticized polymers and plasticized polymer blends |
| US7994237B2 (en) | 2007-12-20 | 2011-08-09 | Exxonmobil Research And Engineering Company | In-line process to produce pellet-stable polyolefins |
| US8138269B2 (en) | 2007-12-20 | 2012-03-20 | Exxonmobil Research And Engineering Company | Polypropylene ethylene-propylene copolymer blends and in-line process to produce them |
| US7910679B2 (en) | 2007-12-20 | 2011-03-22 | Exxonmobil Research And Engineering Company | Bulk homogeneous polymerization process for ethylene propylene copolymers |
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Also Published As
| Publication number | Publication date |
|---|---|
| AU670105B2 (en) | 1996-07-04 |
| EP0584586B1 (en) | 1997-05-07 |
| BR9303275A (en) | 1994-03-08 |
| AU4446093A (en) | 1994-02-10 |
| TW303368B (en) | 1997-04-21 |
| ES2104007T3 (en) | 1997-10-01 |
| HK1006721A1 (en) | 1999-03-12 |
| CZ160593A3 (en) | 1994-03-16 |
| KR940003979A (en) | 1994-03-14 |
| EP0584586A3 (en) | 1994-08-17 |
| ATE152739T1 (en) | 1997-05-15 |
| JPH06157664A (en) | 1994-06-07 |
| DE59306372D1 (en) | 1997-06-12 |
| EP0584586A2 (en) | 1994-03-02 |
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