DE4030399A1 - Polymers and oligomers of propylene¨ with functional end-gps. - produced by reacting hetero-atom. cpds. with corresp. polymers or oligomers contg. unsatd.-olefinic end-gps. - Google Patents

Abstract

Polymers and oligomers (I) of propylene with 0-40 wt.% other 2-8C 1-alkenes are claimed, with Mn = 100-100,000, mol. wt. distribution Mw/Mn = 1-3 and one functional terminal gp. (X) per macromol. Also claimed the prodn. of (I), by reaction of the corresp. polymers and oligomers contg. one olefinic end-gp. (II) with organic cpds. contg. hetero-atoms. (I) pref. have Mn = 500-50,000 and Mw/Mn of 1.5-3 Gp. (X) contains B, N, O, Si, P, S or Hal. Pref., (II) are vinylidene-terminated polymers or oligomers obtd. by polymerisation at 0.1-100 bar and -50 to 150 deg C in the presence of a soluble catalyst system contg. a bridge metallocene complex and an alumoxane cocatalyst. Hetero-atom cpds. are, e.g. boranes, amines, amides, nitro cpds., carboxylic acids, anhydrides, epoxides, ethers, silanes, mercaptans, sulphones, F, Cl, Br, I, etc.. USE/ADVANTAGE - (I) are compatible with polar polymers e.g. polycarbonate, polyamide, PAN, PET and SAN and can be combined with polar polymers to give alloys or copolymers. The process is more controlled than prior-art grafting processes for the introduction of functional gps. into polypropylene. Copolymers (III) are obtd. by reaction of (I) with polar polymers. (6pp Dwg.No.0/0)

Description

The present invention relates to polymers and oligomers of propylene with 0 to 40 wt .-% of other C₂-C₈-alk-1-enes, a number average of Molar mass n from 100 to 100,000, a molar mass distribution of 1 to 3 and one functional chain end per macromolecule.

The invention also relates to a method for producing this Polymers, another process for the preparation of copolymers from these polymers and the copolymers obtainable hereafter.

For the polymerization of alk-1-enes, in addition to insoluble, mostly supported catalyst systems also soluble catalyst systems be used. Solid become insoluble catalyst systems fabric components used together with aluminum compounds, in addition to Titanium, magnesium and halogen still contain an electron donor compound. The polymers available here generally have a wide range Molar mass distribution and can chemically maintain the chain structure no longer in a so-called "polymer-analog reaction" be implemented. The soluble catalyst systems are Complex compounds of metals of subgroup IV and V. of the periodic table with organic ligands used in conjunction with oligomeric Aluminum compounds are used (EP-A 1 85 918, EP-A 2 83 739 and GB-A 22 07 136). The complex used in these catalyst systems Compounds usually contain cyclopentadienyl groups as organic ligands, that enter into the transition metal II bonds. In contrast to the insoluble catalyst systems are with these soluble catalyst systems Polymers available, some of which have vinylidene end groups have and thus be subjected to a polymer analog reaction can.

In EP-A 2 84 708 and 3 16 155 and US-A 47 94 096 soluble Catalyst systems for the polymerization of alk-1-enes described in which as a complex compound bis (cyclopentadienyl) complex of metals the IV. Subgroup of the periodic table can be used, the two Cyclopentadienyl rings through an alkyl substituted silicon or Germanium atom are connected. Such transition metal complexes can also be used are used in which the Ccylopentadienyl rings through Alkyl groups are substituted and the two other ligands to the Contain transition metal bound halogens. As an oligomeric aluminum compound are preferably linear and cyclic alumoxane ver  bindings used. With the help of such catalyst systems are polymers various alk-1-enes available, which u. a. through her Differentiate molecular weight, their molecular weight distribution and the type of chain end, some of which have an olefinically unsaturated chain end exhibit.

The polymers produced in this way are non-polar because they are aliphatic chain structures consisting only of carbon and hydrogen atoms exist, contain no other parts of the molecule. It follows that them together with polar polymers, for example with polycarbonates, Polyamides, polyacrylonitriles, polyethylene terephthalates or styrene Acrylonitrile copolymers cannot be used. For many Areas of application, however, it is necessary to use different polymers Properties together as so-called polymer alloys or to be used as copolymers in order to ensure good properties to combine the polymers involved in an advantageous manner. Because of their poor compatibility with polar polyolefins Polymers before use as components of polymer alloys or copolymers only by introducing polar groups chemically be changed, for example by grafting with unsaturated Carboxylic acids, esters or anhydrides (EP-A 50 994, US-A 40 89 794, US-A 41 37 185). Such graft reactions usually run uncontrolled and lead to polymers whose molecular structure is not can be more arbitrarily influenced, what their uses significantly restricted.

The present invention was therefore based on the object To remedy disadvantages and to develop polymers of propylene, which further copolymerizes and alloys together with polar polymers can be.

Accordingly, the new polymers and oligomers of Propylene found.

The polymers according to the invention are polymers and Oligomers of propylene with 0 to 40, preferably 0 to 20% by weight of others C₂-C₈-Alk-1-ene. As C₂ to C₈-alk-1-enes are in particular Ethylene, but-1-ene, pent-1-ene, hex-1-ene, hept-1-ene, or oct-1-ene used, the C₂ to in the preparation of these polymers C₈-Alk-1-ene both individually and in mixtures together with the Propylene can be copolymerized. However, are particularly preferred Propylene homopolymers.

Furthermore, the polymers according to the invention are by a number average the molecular weight from 100 to 100,000, in particular from 500 to 50,000,  a molecular weight distribution from 1 to 3, in particular from 1.5 to 3 and one functional chain end per macromolecule. Under "Functionality" is usually understood to mean a heteroatom-containing one Group attached to a carbon atom. Those containing heteroatoms are preferred Groups containing at least one element from the group boron, Contain nitrogen, oxygen, silicon, phosphorus, sulfur or halogen, in particular boranes, amines, imines, amides, nitro-, nitroso or azo groups, carboxylic acids, carboxylic anhydrides, carboxylic esters, Epoxies, ethers, hydroxyl groups, silanes, phosphines, mercaptans, thioethers, Sulfones, sulfonic acid and fluorine, chlorine, bromine or iodine.

The polymers according to the invention are prepared by reaction of a polymer or oligomer of propylene with 0 to 40 wt .-% others C₂-C₈-alk-1-enes and one olefinically unsaturated chain end per macromolecule, a number average molecular weight of 100 to 100,000 and a molecular weight distribution from 1 to 3 with a heteroatomic, organic compound used in the preparative organic Chemistry usually used to introduce functional groups into one unsaturated molecule is used. For example, one Borane group without difficulty by reacting a dialkyl substituted Borans with an olefinically unsaturated chain end Introduce polymers into the latter. Such reagents are known to the person skilled in the art known, so that a more detailed explanation of the exact reaction conditions spare. As examples of common reagents in addition to dialkyl-substituted boranes, nitric acid and amines for the introduction of nitrogen-containing groups, anhydrides, peroxides and substituted carboxylic acids for the introduction of oxygen-containing groups, trisubstituted silanes for the introduction of silicon-containing groups, Phosphines for the introduction of phosphorus-containing groups, mercaptarboxylic acids for the introduction of sulfur-containing groups and halogens as well Hydrogen halides called for the introduction of halogens.

This is essential for the production of the polymers according to the invention Selection of polymers or oligomers of propylene with 0 to 40% by weight other C₂-C₈-alk-1-enes and one olefinically unsaturated chain end per Macromolecule, a number average molecular weight of 100 to 100,000 and a molecular weight distribution of 1 to 3 from those in the art known polymers of propylene. Vinylidene are preferred terminated polymers or oligomers of propylene. Such polymerates are obtainable by polymerizing propylene, optionally in Presence of one or more other C₂-C₈-alk-1-enes with the help soluble catalyst systems at pressures from 0.1 to 100 bar, temperatures from -50 to 150 ° C and residence times from 0.1 to 10 hours, in the usual reactors used for the polymerization of alk-1-enes.  

Suitable reactors include a. continuously or batch operated Stirred kettle, where appropriate also a number of several in a row switched stirred kettles are used.

The polymerization can take place both in the gas phase and in liquid monomers or can also be carried out in inert solvents.

In the, used for the production of vinyl-terminated polymers soluble catalyst systems are complex compounds of metals of the IV. and V. subgroup of the periodic table with organic Ligands used together with oligomeric aluminum compounds as cocatalysts be used. Complex compounds of are preferred Titanium, zirconium, vanadium and hafnium with cyclopentadienyl groups as organic ligands and oligomeric alumoxanes as cocatalysts.

Catalyst systems that are suitable for the production of vinylid-terminated Polymers are particularly suitable and contain a metallocene complex of the general formula I

in which the substituents have the following meaning:

R¹, R² branched C₄ to C₁₀ alkyl, 5- to 7-membered cycloalkyl, which in turn can carry a C₁ to C₆ alkyl as a substituent, C₆ to C₁₅ aryl or arylalkyl;
R³-R⁶ C₁ to C₈ alkyl,
M titanium, zirconium, hafnium, vanadium;
Y silicon or germanium;
X halogen or C₁ to C₈ alkyl

an open chain or cyclic alumoxane compound of the general Formula II and III as cocatalyst

wherein R⁷ is a C₁-C₄ alkyl group and m is a number from 5 to 30 stands.

In the event that the polymer or oligomer of the invention Propylene as a functional chain end a carboxyl or an anhydride group bears, there is still the possibility of using inorganic compounds to the corresponding ionized polymers, so-called Ionomers to implement. Alkali compounds are particularly suitable and oxides and salts of alkali metals, alkaline earth metals or compounds of the zinc with organic acids (US-A 32 64 272, US-A 34 37 718). Because of the special structure of the polymers according to the invention each macromolecule only one ionized group.

Because of their functional chain end, the inventive Polymers in particular also with polar polymers to new copolymers of propylene are implemented, the link on respective chain end takes place. The implementation takes place at pressures from 1 to 100 bar and temperature from 0 to 300 ° C, preferably at Pressures from 1 to 50 bar and temperatures from 50 to 250 ° C. The implementation can be either batchwise or in the reactors customary in the art preferably be carried out continuously. Suitable reactors are u. a. stirred antoclaves.

The polar polymers to be used according to the invention are are macromolecules which, based on the monomer units, have a have uneven charge distribution, for example polycarbonates, Polycaprolactones, polyamides, polyacrylonitriles, polyethylene terephthalates, Polystyrenes, polysulfones, polyether ketones, polyurethanes or styrene-acrylonitrile Copolymers. In making this new, too inventive copolymers can both these polar polymers as also the polymers and oligomers of the functional chain end Propylene used in excess.  

There is also still the possibility of such polar polymers in one step, for example with the help of a Friedel-Crafts alkylation with polymers and oligomers of propylene with an olefinically unsaturated Chain end per macromolecule to new copolymers as well to implement. The polymers and oligomers of propylene used contain 0 to 40 wt .-% of other C₂-C₈-alk-1-enes, a number average of Molar mass from 100 to 100,000 and a molar mass distribution from 1 to 3.

The polymers and oligomers of propylene are particularly suitable for selective implementation with polar polymers. The yields Copolymers are usually quite high. Since the Invention Polymers and oligomers of propylene each have only one functional chain end per macromolecule can react with the polar Polymers are well controlled. The also available Copolymers according to the invention can in particular as components of Polymer alloys and used as an adhesion promoter.

Examples 1. Production of a polypropylene by catalysis with the help of Metallocenes

350 ml of dried toluene were placed in a stirred autoclave with a useful volume of 1 l and then a solution of 0.45 g of methylalumoxane (average chain length m = 20) in 30 ml of toluene was added. 7.6 × 10 ^-3 mol of aluminum were used per liter of the solvent. Then a solution of 2.53 · 10 ^-6 mol of diethylsilanediyl (-3-tert-butyl-5-methylcyclopentadienyl) zirconium dichloride [representation see Journal of Organometallic Chemistry, 369 (1989), 359-370] in 20 ml of toluene was added, so that the atomic ratio between aluminum and zirconium was 300: 1. This mixture was first stirred for 30 minutes and then propylene was injected at a pressure of 2 bar and polymerized at constant pressure and at a reaction temperature of 80 ° C. After a reaction time of 60 min, the unused propylene was removed and then a mixture of 1 l of methanol and 10 ml of concentrated hydrochloric acid was added to the reaction mixture. The precipitated oligomer was filtered off, washed with methanol and dried in vacuo.

18.6 g of an oligomer of propylene were obtained with a number average the molecular weight of 800, a molecular weight distribution of 2.3 and an isotacticity of 96%. The olefinically unsaturated  The end group of the oligomer obtained was by means of 1 H and 13 C nuclear re sonar spectroscopy demonstrated.

2. Production of polypropylene with a functional chain end per Macromolecule a) Anhydride-terminated polypropylene

A mixture of 40 g of the vinylidene-terminated prepared in 1 Polypropylene was added with 10 g of maleic acid under nitrogen acid anhydride at 160 ° C for 6 hours and then at 2 hours Heated at 220 ° C. Then excess maleic anhydride was in the Vacuum removed. A polypropylene with anhydride functions was obtained. The yield was 92%, based on the content of Carboxyl functions. The anhydride content was determined by 1 H nuclear reso nanzspektoskopie, infrared spectroscopy as well as by titration determined.

b) Mercaptan-terminated polypropylene

A mixture of 10 g of the polypropylene produced in 1) was made under nitrogen with 2 ml of thioacetic acid and 80 mg Azoisobutyronitrile in 50 ml of toluene at 80 ° C for 4 hours heated. The mixture obtained was then through heating for four hours with 20 ml of a 1N potassium hydroxide solution in ethanol / water (50: 50) hydrolyzed at 90 ° C and then the solvent evaporates. A polypropylene with mercaptan end groups was obtained. The yield was 88%, based on the content of mercaptan groups. This was determined by tritation.

c) epoxy-terminated polypropylene

A solution of 25 g of the polypropylene produced in 1) in 400 ml of chloroform was mixed with a solution of 10 g of m-chlorobenzoic acid stirred in 300 ml chloroform at 20 ° C for 6 hours. Then half of the solvent was distilled off Polypropylene precipitated from 1 liter of methanol and 4 hours at 60 ° C dried long in vacuo. A polypropylene was obtained Epoxy end groups. The yield was 84% based on the Epoixd group content. This was by ¹H nuclear magnetic resonance spectroscopy and determined by titration.  

d) bromine-terminated polypropylene

A solution of 25 g of the polypropylene produced in 1) in 100 ml of carbon tetrachloride was mixed with a 1 molar bromine solution titrated in carbon tetrachloride at 20 ° C. You got one Polypropylene with bromine end groups. The yield was almost 100%, based on the bromine content. This was through elemental analysis determined.

e) carboxylic acid terminated polypropylene

A mixture of 40 g of the polypropylene produced in 1), 400 ml of toluene, 10 g of thioglycolic acid and 100 mg of azoisobutyronitrile was stirred at 80 ° C for 10 hours and then to 120 ° C heated. After evaporating the volatile components in vacuo to isolate a polypropylene with carboxylic acid end groups. The Yield was 82%, based on the content of carboxylic acid groups. This was determined by titration.

f) carboxylic ester-terminated polypropylene

Analogously to Example 2e), 40 g of the polypropylene prepared in 1) was in 400 ml of toluene with 11.5 g of ethyl thioglycolate and 100 mg of azoisobutyronitrile reacted. After working up the ester was saponified with ethanolic potassium hydroxide solution and the Carboxylic acid content as determined in Example 2e). The yield was 89.5%, based on the carboxylic ester content.

g) ionomer polypropylene

A mixture of 20 g of the one produced in 2e) with carboxylic acids terminated polypropylene was at 200 ° C for 30 minutes 2.9 g of zinc acetate dihydrate heated under water pump vacuum until the content of carboxylic acid groups dropped to less than 10% was.

h) silane-terminated polypropylene

A solution of 2.5 g of the polypropylene prepared in 1) in 100 ml of toluene was at 80 ° C with 10 g of triethoxysilane and 1 ml a solution of 10 mg hexachloroplatinate in 10 ml isopropanol transferred. After 4 hours the solution was an additional 6 hours heated at 80 ° C on a rotary evaporator. You got one  Polypropylene with a silane content determined by elemental analysis of 2.7%. The yield was 93%, based on the silane content.

1) Hydroxy-terminated polypropylene

A mixture of 40 g of the polypropylene produced in 1), 200 ml of toluene, 10 mg of azoisobutyronitrile and 7 g of mercaptoethanol was heated at 80 ° C under nitrogen for 8 hours. After that the polypropylene was precipitated by adding 1 liter of methanol and the polymer was filtered off. A polypropylene was obtained Hydroxy end groups. The yield was 80% based on the Hydroxy content. This was determined by titration.

j) Borane-terminated polypropylene

A solution of 80 g in 1) manufactured polypropylene in 500 ml of toluene was mixed with a solution of 12 g of 9-borabi cyclo (3,3,1) nonane in 100 ml of tetrahydrofuran for 4 hours 20 ° C and then reacted at 40 ° C for 1 hour. The polypropylene was filled out of methanol. The yield of borane-terminated Polypropylene was 96% based on the borane content. This was determined by titration with hydrogen peroxide.

3. Implementation of the polypropylene terminated by a functional group with polar polymers a) Hydroxy-terminated polypropylene and polycaprolactone

A mixture of 20 g of the polypropylene prepared in Example 2j) and 40 g caprolactone was in the presence of 0.05 g Dibutyltin dilaurate heated to 220 ° C for 6 hours. Subsequently the remaining hydroxy groups were analogous to Example 2i) certainly. From the remaining hydroxy groups one could conclude a yield of 70% of copolymer.

b) Mercaptan-terminated polypropylene and polystyrene

A mixture of 5 g of the polypropylene prepared in Example 2b), 80 ml of toluene and 60 g of polystyrene was added under nitrogen in the presence of 0.05 g of azoisobutyrontril for 8 hours Heated 80 ° C and then the copolymer formed with methanol failed.  

c) Mercapto-terminated polypropylene and styrene / acrylonitrile

5 g of that prepared in Example 2b) were prepared analogously to Example 3b) Polypropylene implemented with 42 g styrene and 18 g acrylonitrile.

d) anhydride-terminated polypropylene and polyamide

69 g of dimethyl sebacate and 80 g of diaminododecane were added Condensed at 250 ° C under a water jet vacuum for 4 hours until an amino-terminated polyamide with an amine content of 1.2 Val / kg had formed. 10 g were then added under nitrogen this polyamide at 250 ° C for 4 hours with 10 g of the in Example 2a) prepared polypropylene heated. The received The copolymer was first ground and then with Heptane extracted. The yield was 90%.

e) polypropylene and poly (2,6-dimethylphenyl ether)

50 g of the vinylid-terminated polypropylene prepared in 1) together with 219 g of poly (2,6-dimethylphenyl ether) (Number average = 50,000) in 2 l of 1,2,4-trichlorobenzene at 40 ° C heated, mixed with 5 g of anhydrous aluminum trichloride and first reacted at 20 ° C for 4 hours and then at 78 ° C for 12 hours. The copolymer was then precipitated from methanol. 225 g of copolymer were obtained, the yield from this Friedel-Crafts alkylation was 95%.

f) polypropylene and polystyrene

A mixture of 50 g of the polypropylene produced in 1) and 200 g of polystyrene was mixed with 5 g of anhydrous aluminum trichloride in 2 l of 1,2,4-trichlorobenzene as in Example 3e) for reaction brought. 242 g of copolymer were isolated by precipitation in methanol, the yield of this Friedel-Crafts alkylation was at 96%.

Claims (8)

1. Polymers and oligomers of propylene with 0 to 40% by weight of others C₂-C₈-Alk-1-ene, a number average molecular weight from 100 to 100,000, a molecular weight distribution of 1 to 3 and one functional chain end per macromolecule. 2. Polymers and oligomers of propylene according to claim 1, which is a number average have the molecular weight from 500 to 50,000. 3. Polymers and oligomers of propylene according to claims 1 or 2, the have a molecular weight distribution of 1.5 to 3. 4. Polymers and oligomers of propylene according to claims 1 to 3, the one functional chain end with at least one per macromolecule Element from the group boron, nitrogen, oxygen, silicon, Contain phosphorus, sulfur or halogen. 5. A process for the preparation of the polymers and oligomers according to claims 1 to 4, characterized in that a polymer or Oligomer of propylene with 0 to 40 wt .-% of other C₂-C₈-alk-1-enes and one olefinically unsaturated chain end per macromolecule, one Number average molecular weight from 100 to 100,000 and one molecular weight distribution from 1 to 3 of a heteroatom-containing organic compound. 6. Copolymer of propylene, obtainable by reaction of the polymers and oligomers according to claims 1 to 4 with polar polymers. 7. A process for the preparation of the copolymers according to claim 6, characterized characterized in that the reaction at temperatures from 0 to 300 ° C. and at pressures from 1 to 100 bar. 8. Copolymers of propylene, obtainable by reacting polymers and oligomers of propylene with 0 to 40% by weight of others C₂-C₈-Alk-1-ene and one olefinically unsaturated chain end per Macromolecule, a number average molecular weight of 100 to 100,000 and a molecular weight distribution of 1 to 3 with polar Polymers.