CA2154643A1 - Cycloolefin copolymers and a process for their preparation - Google Patents
Cycloolefin copolymers and a process for their preparationInfo
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- CA2154643A1 CA2154643A1 CA002154643A CA2154643A CA2154643A1 CA 2154643 A1 CA2154643 A1 CA 2154643A1 CA 002154643 A CA002154643 A CA 002154643A CA 2154643 A CA2154643 A CA 2154643A CA 2154643 A1 CA2154643 A1 CA 2154643A1
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- cyclic
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- olefin
- cycloolefin copolymer
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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
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to a cycloolefin copolymer having a solution viscosity (eta) < 0.25 dl/g (measured in accordance with DIN 53728 in decalin at 135°C), which comprises polymerized units (A) of at least one cyclic olefin and (B), if desired, of one or more acyclic olefins, wherein (C) polymerized units are present which contain at least one functionalized structural unit which a) is derived from a cyclic olefin and contains at least one heteroatom which is attached directly to a ring atom of the cyclic olefin, or b) is derived from a cyclic or acyclic olefin and contains at least one group ofatoms which has two heteroatoms both of which are attached to the same carbon atom, or c) is derived from a cyclic or acyclic olefin and contains at least one aldehydegroup, or d) is derived from a cyclic or acyclic olefin and contains at least one group ofatoms in which a nitrogen atom is attached via a double bond to a carbon atom, and, where the functionalized structural unit is derived from a cyclic olefin, exactly two adjacent carbon atoms of this functionalized cyclic structural unit are incorporated into the polymer main chain. The cycloolefin copolymer is suitable as coating material or as adhesion promoter.
Description
21~4~43 HOECHST AKTIENGESELLSCHAFT HOE 94/F 213 Dr.SK/St DESCRIPTION
5 Cycloolefin copolymers and a process for their preparation The invention relates to functionalized cycloolefin copolymers ~COCs) having a solution viscosity (eta) < 0.25 dl/g, which are suitable for the production of highly mar-resistant coating materials, for example paints, or as adhesion 10 promoters, for example in coating compositions containing one- or two-component binders. The invention relates further to a process for the prepara-tion of COCs functionalized in this way.
In the sector of the automobile industry, bodywork topcoats and clearcoats are 15 assigned, in addition to the conventional function of preventing corrosion and of decoration, a central role in relation to the resistance to environmental effects.
As external coat, the clear- coat, for example, must be resistant to light, acidic components, and chemicals, such as grit, oil black, fuels and detergents, but also against mechanical stress (e.g. in automatic washing equipment). Further 20 requirements are good gloss retention, and chalking resistance and constancy of color. The individual coats of paint must, moreover, be matched to one another such that there is no detachment of individual components resulting in an impairment of the function of the overall coating system. A decisive role in this context is assigned to the substrate to be coated, too. The coating material 25 must exhibit adequate adhesion to the surface of the workpiece.
With particular regard to environmental concerns, in recent years new topcoats and/or clearcoats have been developed. Particular emphasis in this context should be placed on the so-called high-solids and waterborne coating materials, 30 whose low or zero content of organic solvents means that they assure lower polluting emissions in the course of processing (Organic coatings, Science and Technology, 8, (1986), G.D. Parfitt, A.V. Patsis (ed.)). In addition to alkyd-melamine resin coating materials, heat-curable acrylic resins in particular are 215~3 employed in this application. The outstanding performance of these systems in relation, for example, to processability, gloss retention and color stability iscountered by low resistance to hydrolysis and a degree of surface hardness which is not satisfactory in every respect. Moreover, the adhesion properties ofthe coating systems are very sensitive to the substrate to be coated. In the majority of cases, appropriate pretreatment of the substrate surface is necessary.
The development of new coating systems having substrate-specific properties continues to be of great importance.
From EP 283 164 it is known that, by copolymerizing ~-olefins with cyclic polyenes and, if desired, cycloolefins, it is possible to provide COCs containing double bonds, the cyclic polyenes used being, for example, unconjugated dienes or trienes containing norbornene as structural element. JP 05279412-A
discloses that, in such COCs containing double bonds, it is possible by epoxidiz-ation to introduce hydroxyl and/or epoxy groups, the functionalized COCs obtained being used as compatibilizers for olefinic polymer blends.
JP 2269760-A, JP 3072558-A and JP 3106962-A disclose polycyclic monomers which contain carboxyl groups and are reacted by metathesis polymerization to give homopolymers and copolymers. The disadvantage of a ring-opening polymerization of this kind, however, is that the polymer initiallyobtained has double bonds, which may lead to uncontrolled and unwanted chain crosslinking reactions, and thus considerably restrict the ability of the material to be processed by extrusion or injection molding.
EP-A-203 799 discloses COCs onto which, in a polymer-analogous reaction, o"B-unsaturated carboxylic acids such as, for example, acrylic acid are grafted. EP-A-570 126, furthermore, describes the grafting of COCs containing double bonds with monomers suitable for free-radical polymerization, for example styrene, vinyl chloride, acrylonitrile or vinyl acetate. These polymer-analogous 21546~3 grafting reactions, however, have the disadvantage that the products obtained lack uniformity with respect to the grafting yield, the grafting sites and the chain length of the graft branches. Moreover, the actual grafting reaction is often accompanied by homopolymerization of the monomer employed. The 5 homopolymers and the grafting product are, in the majority of cases, no longercapable of separation. The reaction products obtained therefore have a very wide molecular weight distribution and, in addition, are chemically heterogenous. For the development of coating materials having a high solids content (high-solids coating materials), however, it is desired to have products10 whose molecular weight distribution is as narrow as possible and in which the number of functional groups can be controlled.
The object was therefore to provide a polymer which shows ready miscibility with other substances, especially polymers, and which is suitable for the 15 production of highly mar-resistant, acid-resistant and base-resistant coatings, for example automotive finishes, having improved adhesion to the substrate surface.
It has surprisingly been found that this object can be achieved by the provision20 of specific functionalized COCs. The functionalized COCs according to the invention contain polymerized units comprising functional groups which are introduced by a polymer-analogous ozonolysis reaction, with subsequent working up, and, if desired, by specific subsequent reactions.
25 The invention therefore relates to a cycloolefin copolymer having a solution viscosity (eta) < 0.25 dl/g (measured in accordance with DIN 53728 in decalin at 135C) which comprises polymerized units (A) of at least one cyclic olefin and (B), if desired, of one or more acyclic olefins, wherein (C) polymerized units are present which contain at least one functionalized structural unit which a) is derived from a cyclic olefin and contains at least one heteroatom which is attached directly to a ring atom of the cyclic olefin, or 215~6~3 b) is derived from a cyclic or acyclic olefin and contains at least one group of atoms which has two heteroatoms both of which are attached to the same carbon atom, or 5 c) is derived from a cyclic or acyclic olefin and contains at least one aldehyde group, or d) is derived from a cyclic or acyclic olefin and contains at least one group of atoms in which a nitrogen atom is attached via a double bond to a carbon atom, and, where the functionalized structural unit is derived from a cyclic olefin, exactly two adjacent carbon atoms of this functionalized cyclic structural unit are incorporated into the polymer main chain.
The groups of atoms of the functionalized structural units in b) and d) and/or the aldehyde group of the functionalized structural unit in c) may be attached directly or via a hydrocarbon group of 1 to 20 carbon atoms, preferably an unsubstituted, alkyl-substituted or aryl-substituted C1-C10-alkylene group, to the 20 cyclic or acyclic olefin components.
The term heteroatom refers, with the exception of carbon and hydrogen, to all elements in the Periodic Table of the elements, preferably oxygen, sulfur, nitrogen, phosphorous and silicon and especially oxygen, sulfur and nitrogen. In25 strict accordance with the IUPAC nomenclature, the polymer main chain is understood as being the continuous main chain of the polymer which may possess a substitution pattern (G. Odian: "Principles of Polymerization", secondedition, 1981, p. 12). For example, in accordance with this nomenclature polypropylene possesses a polyethylene main chain on which, at every other 30 carbon atom, a hydrogen atom is substituted by a methyl group.
The cycloolefin copolymer according to the invention preferably contains 21546~3 0.1-99.89 % by weight, based on the overall mass of the cycloolefin copolymer, of polymerized units (A) of at least one cyclic olefin, 0-80 % by weight, based on the overall mass of the cycloolefin copolymer of polymerized units (B) of at least one acyclic olefin, and 0.01-50 % by weight, based on the overall mass of the cycloolefin copolymer, of polymerized units (C) which contain at least one functionalized structural unit which a) is derived from a cyclic olefin and contains at least one heteroatom which is attached directly to a ring atom of the cyclic olefin, or b) is derived from a cyclic or acyclic olefin and contains at least group of atoms which has two heteroatoms both of which are attached to the same carbon atom, or c) is derived from a cyclic or acyclic olefin and contains at least one aldehyde group, or d) is derived from a cyclic or acyclic olefin and contains at least one group of atoms in which a nitrogen atom is attached via a double bond to a carbon atom, and, where the functionalized structural unit is derived from a cyclic olefin, exactly two adjacent carbon atoms of this functionalized cyclic structural unit are incorporated into the polymer main chain.
The polymerized units (A) are preferably derived from cycloolefins of the formulae (I), (Il), (Ill), (IV), (V), (Vl) and (Vll) 215~6~3 H C/ ¦ \C H/
¦¦R3-C R~
H C\I /C H\R 2 CH
H C/ ¦ \C H
¦¦R3--C R~ ¦ CH2 ( I I ) .
H C\ /C H
cH cH /R
¦ I R 3 C--~ ~ ¦ R S C R ( I I I ) \I H/ \CH/ \ 2 H C/ ¦ \C H/ ¦ \C H/ ¦ \C H/
¦¦R3--C--R~ ¦ RS C R6 ¦ R7- C-RS ( rV) .
\C H/ \C H/ \C H/ \ 2 Rs / ¦ \
¦¦R3--C R~ ¦ ( V) \I H \C H \ R 2 R S
H C/ ¦ \C H/ \C H/ ¦ \C H/ ( V I ) ¦¦R'--C R~ ¦ ¦ R7- C R8 ¦
\ I H / \ 2 21~4643 CH CH
( V l 1 ) , ( CH2 ) n in which R1, R2, R3, R4, R5, R6, R7 and R8 are identical or different and are a hydrogen atom or a C1-C30-hydrocarbon radical, such as a C1-C8-alkyl group or 10 a C6-C14-aryl group, where identical radicals in the different formulae may have different meanings, and n is a number from 2 to 10. The polymerized units (A) are particularly preferably derived from norbornene.
The polymerized units (B) are preferably derived from acyclic monoolefins, for 15 example a-olefins of 2 to 20 carbon atoms, especially ethylene and propylene.
The polymerized units (C) are preferably derived from compounds of the formulae (XIV), (XV), (XVI), (XVII), (XVIII) and (XIX) HC ~ CH ---- _ CH- . CH ~ C/
R 1 ~ _ ¦-- R 1 7 R --C-- R ( X I V ) C H ~ C H ~ R 2 -- m HC ~ CH~ CH~ CH ~ R20 R16--C--R17 R18--C-- R19 (XV) HC~ CH~CH ~ CH ~ R21 --m H :~- CH~ CH~ CH ~ R20 R1 _ C--Rl7 (XVI ) HC~ CH~CH ~ R21 -- m HC ~ CH~ CH . CH ~ R22 R l --C--R 1 7 R 1 8--C-- R l 9 ( XV I I ) HC CH~CH ~ CH ~ \ R2 --m R 1 6\ / R 1 8 / C C \ (XVIII) Rl7 Rl9 \ / \ /
R 1 7 R R 21 R ( X I X ) -- --n -- -- I
in which R16, R17, R18, R19, R20 and R21 are identical or different, identical 10 radicals in the different formulae may have different meanings and are hydrogen, a C1-C30-hydrocarbon radical, such as a C1-C8-alkyl group or a 21a4543 C6-C14-aryl group, a primary, secondary or tertiary amino group, a substituted or unsubstituted ammonium group, a hydroxyl group, an alkyloxy group, an aryloxy group, an aralkyloxy group or a group -(X)p-Y in which X is a branched or unbranched C2-C20-alkylene group or a branched or unbranched C8-C20-arylalkylene group and p = 0 or 1 and Y is a carboxyl group, an alkyloxycarbonyl group, a carbamoyl group, a mono- or bisalkylcarbamoyl group, a chloroformyl group, an acyloxycarbonyl group, a thiocarboxy group, an alkylthiocarbonyl group, a formyl group, an alkylformyl group, a hydroxybis(alkyloxy)methyl group, a tris(alkyloxy)methyl group, a hydroxyiminomethyl group, a hydrazonomethyl group or a semicarbazonomethyl group, where in the formulae (XIV) and (XVIII) at least one of the radicals R16,R17, R13, R19, R20 and R21, in the formulae (XV), (XVI) and (XIX) at least two of the radicals R16 R17 R18 R19, R20 and R21, and in formula (XVII) none of the radicals R16 R17 R13 R19, R20 and R21 must be a group -(X)p-Y, a primarY~
secondary or tertiary amino group, a substituted or unsubstituted ammonium group, a hydroxyl group, an alkyloxy group, an aryloxy group or an aralkyloxy group.
R22 is a carbonyl group, a hydroxyiminomethyl group, a hydrazonomethyl group or a semicarbazonomethyl group.
In the formulae (XV) and (XVI) p = 0 if R20 or R21 is a group -(X)p-Y. In formula (XIX) R20 and R21 are not hydrogen or a C1-C30-hydrocarbon radical, such as a C1-C8-alkyl group or a C6-C14-aryl group.
The polymerized units (C) are derived particularly preferably from compounds of the formulae (XIV) to (XIX) in which R22 is a carbonyl group and R16, R17, R13, R19, R20 and R21 are identical or different, identical radicals in the differentformulae may have different meanings and are a primary, secondary or tertiary amino group, a hydroxyl group or a group -(X)p-Y in which X is a branched or unbranched C2-C20-alkylene group or a branched or unbranched C8-C20-arylalkylene group and p = 0 or 1 and Y is a carboxyl group or a formyl group, where in the formulae (XIV) and (XVIII) at least one of the radicals R16, R17, 21546~3 R18, R19, R20 and R21, in the formulae (XV), (XVI) and (XIX) at least two of theradicals R16 R17 R18 R19, R20 and R21, and in formula (XVII) none of the radicals R16, R17, R18, R19, R20 and R21 is or are a primary, secondary or tertiary amino group, a hydroxyl group or a group -(X)p-Y in which X is a 5 branched or unbranched C2-C20-alkylene group or a branched or unbranched C8-C20-arylalkylene group and p = O or 1 and Y is a carboxyl group or a formyl group.
The invention relates furthermore to a process for the preparation of a10 cycloolefin copolymer having a solution viscosity (eta) < 0.25 dl/g, which comprises reacting a cycloolefin copolymer containing double bonds in an inert solvent with ozone.
To carry out the process according to the invention, the COC containing double 15 bonds is dissolved in an inert solvent. Inert solvents which can be employed are aliphatic hydrocarbons, for example decalin, halogenated aliphatic hydrocarbons,for example chloroform or carbon tetrachloride, methanol or glacial acetic acid.Gassing with ozone is carried out in a suitable reaction vessel, for example a gas-fed stirred reactor or a bubble column. In this vessel, a quantity of ozone 20 equimolar with the double bond content of the COC is passed into the solution.
The ozone is prepared using an ozone generator in dry air or oxygen. The concentration of ozone in the carrier gas, air or oxygen, is not critical for the reaction procedure according to the invention. It is typically from 1 to 180 g/m3, preferably from 1Q to 50 g/m3. In practice it is chosen such that the 25 uptake of ozone is as complete as possible. The uptake of ozone can be monitored by means of a suitable meter, for example a UV photometer. In order to avoid a reduction in molecular mass of the COC, it is advantageous to carry out the gassing with ozone at a low temperature, between -78 and + 10C, preferably between -10 and 0C.
30 Owing to the tendency of the double-bond-containing COCs used as starting materials to crosslink at relatively high temperatures, the addition of a suitable inhibitor which is not chemically reactive under the chosen conditions may be 215454~
advantageous. Suitable examples are phenothiazine and aromatic nitro compounds such as nitrobenzene and dinitrobenzene (US 4,082,493).
After the end of the ozonolysis, in order to avoid the formation of so-called 5 ozonides, a small quantity of alcohol, for example methanol, or water is added to the solution.
Oxidative working up is carried out using peroxy carboxylic acids, for example those of formic, acetic or propionic acid. In this context it is possible to use the 10 equilibrium peracid or to prepare the peracid in situ by addition of carboxylic acid, an appropriate quantity of hydrogen peroxide and a catalytic amount of mineral acid. The peracid is employed in excess, the excess becoming smaller as the batch size increases. For each mole of double bond in the COC, from 1 to 3 mole equivalents, preferably from 1.1 to 1.8 mole equivalents, of peracid are 15 employed. In order to complete the oxidative working up, the solution is heated at reflux for a number of hours. The primary products of the oxidative working up are COCs containing carboxyl groups.
The reductive working up is carried out with reducing agents such as zinc dust 20 in acetic acid, or by way of catalytic hydrogenation with palladium on calcium carbonate or sodium dithionite. The reducing agent is employed in excess. For each mole of double bond, from 1 to 4 mole equivalents, preferably from 1.2 to 2.2 mole equivalents, of reducing agent are employed. In order to be assured of complete reaction, the mixture is boiled at reflux for from 1 to 4 hours. The 25 primary products of this reductive working up are COCs containing aldehyde and/or keto groups.
Both after the oxidative and after the reductive working up, the polymer solution can be passed on for further use directly. If the polymer is to be 30 isolated as such, then it can be freed from the solvent by known methods:
1. stripping off the solvent, for example by steam distillation, 2. evaporating off the solvent, for example by spray drying or thickening in a falling-film evaporator, which may be operated with a vacuum, and preferably by 5 3. precipitating in a nonsolvent which is miscible with the polymer solvent, the nonsolvent being, for example, methanol or acetone.
With particular preference, the isolation of the functionalized COC is carried out by precipitation with acetone. In order to avoid the formation of cyclic peroxides 10 of the acetone, care must be taken here that there is no longer any oxidizingagent in the solution; if required, any remaining oxidizing agent must be removed by the appropriate addition of reducing agent.
By washing with solvents which do not dissolve the polymer it is readily 15 possible to remove extraneous substances, for example by-products. Drying canbe carried out at atmospheric pressure or reduced pressure, optionally with inert gas blanketing, at a temperature which must be below T~ in order to avoid sintering. Preference is given to drying in a stream of nitrogen at mild temperatures .
All compounds obtained by oxidative or reductive working up can be subjected to subsequent reactions by means of which further functional groups are introduced into the COCs.
25 From the corresponding carboxylic acids it is possible by conventional laboratory methods to prepare acid chlorides, esters, anhydrides, amides or hydrazides [J.
March: "Advanced Organic Chemistryn, third edition].
The corresponding aldehydes and ketones can be reduced, for example, to 30 alcohols. Reduction can be carried out catalytically over nickel or palladium, or using nascent hydrogen which is prepared in situ by reaction of sodium amalgam and water or sodium and alcohol. Particularly preferred reducing agents for preparing the corresponding alcohols are lithium aluminum hydride and sodium borohydride. Also suitable are aluminum alcoholates, for example aluminum isopropylate. The reactions may optionally be catalyzed by addition of acids or bases. If the hydrogenation is carried out in the presence of ammonia, 5 primary or secondary amines, then the corresponding primary, secondary or tertiary amines are obtained. For the preparation of these systems, the amine component is employed in excess. In this context the preferred ratio of the number of moles of aldehyde to that of amine is 1:10, and a ratio of 1.1:5.5 is particularly preferred. The direct addition of ammonia, primary or secondary 10 amines with subsequent elimination of water produces imines, azomethines, enamines or aminals [J. March: "Advanced Organic Chemistry", third edition].
The derivatives obtained can be employed as crosslinking agents in powder coating systems or in other coating compositions. In this utility it may be 15 necessary to convert the amino groups of the COC derivative into the isocyanate groups. A further conceivable application of these derivatives is as polymer supports for immobilized catalysts, for example for the fixation of enzymes by way of the hydroxyl and/or amino groups for use in modern synthesis processes.
Employing basic catalysis, the addition of hydrocyanic acid onto the aldehyde groups of the COC backbone gives rise to the formation of cyanohydrins (a-hydroxy nitriles), which can be reacted to a-hydroxy carboxylic acids. If thereaction is carried out in the presence of equimolar quantities of ammonia or 25 primary and secondary amines, then the hydrocyanic acid is added onto the imino compounds which are formed initially. The resulting amino nitriles, when subjected subsequently to acid hydrolysis, give a-amino acids. In this way it ispossible to achieve a biocompatibility which may be particularly advantageous, especially for the application of these materials in the medical field, for example 30 as membranes.
215~643 In order to prepare the acetals and hemiacetals, the aldehyde- and/or ketone-functionalized COCs are reacted in the presence of anhydrous mineral acids with the corresponding alcohols. It is advisable to carry out the reaction in the presence of water-binding agents. For the preparation of the diethyl acetals of 5 keto groups in particular, it is possible to use triethyl orthoformate. In place of the alcohols, thiols can also be used, which react to give the corresponding mercaptans.
In addition to this, all known reactions can be carried out on the aldehyde 10 and/or ketone functionalities. The formation of oximes, semicarbazones and hydrazones is mentioned only by way of example, these compounds being able to be prepared by the conventional methods from the corresponding COCs with aldehyde and/or ketone groups. Reference may likewise be made to the possible variants which can be achieved by aldol condensation [J. March: "Advanced 15 Organic Chemistry", third edition]. The reactions described may, moreover, also be configured as crosslinking reactions. If the corresponding bifunctional compounds are employed - for example diols, diamines, etc. - then intermolecular reaction may lead to the formation of a polymer network. For the subsequent crosslinking of a coating material comprising functionalized COCs, 20 this gives rise to a host of possibilities. The double-bond-containing cycloolefin copolymers employed in the process according to the invention preferably contain 0.1-99.89 % by weight of polymerized units of a cycloolefin of the formula (I), (Il), (Ill), (IV), (V), (Vl) or (Vll) H C/ ¦ \C H/
¦¦R3-C R~ ¦ ( I ) .
H C\I /C H\R 2 C H
21.~4~43 H C/ C H
¦¦R C R ¦ CH2 ( I I ) H C/ ¦ \C H/ ¦ \ /
¦¦R3--C R4 ¦ RS C R6 ( I I I ) .
\C H/ \J H/ \ 2 1 0 H C/ \ C H / ¦ \C H / \C H/
¦¦R3--C--R4 ¦ RS C R6 R7- `-R8 ( I V ) R s / \ / \ /
¦IR3--C--RI ¦ (V) .
\
R S
HC/ ¦ \CH/ \~H/f \CH/ ( V I ) ¦¦R3--C R4 ¦ R7- C R8 H C\ /C H /~ H ¦ /C H\
CH CH
(V l l ), ( C H 2 ) n in which R1, R2, R3, R4, R5, R6, R7 and R8 are identical or different and are a hydrogen atom or a C1-C30-hydrocarbon radical, such as a C1-C8-alkyl group or a C6-C14-aryl group, where identical radicals in the different formulae may havedifferent meanings, and n is a number from 2 to 10, and 0-80 % by weight, based on the overall mass of the cycloolefin copolymer, of polymerized units of at least one acylic monoolefin, preferably of an a-olefin of 2-20 carbon atoms, particularly preferably ethylene or propylene, and 0.01-50 % by weight, based on the overall mass of the cycloolefin copolymer, of polymerized units of at least one olefin which has at least one double bond, preferably of at least one olefin of the formulae (Vlll), (IX), (X), (Xl), (Xll) and (Xlll) / CH ~CH ~ CH ~ CH /
H C
¦¦R11 I _ R12 RI3 C R (Vl I I ) HC CH ~_ CH CH~ \ R10 --m / CH ~CH ~ jH ~ C
¦IR11-- C_ R12 R13 C R1~ ( IX) -- m CH ~ R 10 21~4643 I
/ CH ~CH / CH \
¦¦ R 11 _ C_ R 1 2 C _ R 9 ( X ) C H ~ C H C
c C H / C H ~ \ R 1 O
¦¦R 1 C R12 1 3 --C-- R1~
(X I ) H C ~ C H ~ C H ~ C H ~ C H \ R 1 5 --m C C ( X I I ) R 12 / \R 10 C C (X I I I ) R10 \_/ \R1O
- -n - - I
in which R9, R10, R11, R12, R13, R14 and R15 are identical or different and are a hydrogen atom, a C1-C30-hydrocarbon radical, such as a C1-C8-alkyl group or a C6-C14-aryl group, a C2-C20-alkenyl group or a C8-C20-arylalkenyl group, where identical radicals in the different formulae may have different meanings, and in 21~4613 the formulae (IX) and (X) R9 and R10 are a hydrogen atom, a C1-C30-hydrocarbon radical, such as a C1-C8-alkyl group or a C6-C14-aryl group, in the formula (Vlll) at least one of the radicals R9, R10, R11, R12, R13 and R14 is analkenyl group, in the formula (Xll) at least one of the radicals R9, R10, R1 1 and 5 R12 is an alkenyl group, and m is a number from 0 to 10 and n and I are each a number from 0 to 10, with the proviso that n = I = 0 does not apply.
The double-bond-containing cycloolefin copolymers employed in the process according to the invention can be prepared at temperatures of from -78 to 200C under a pressure of from 0.01 to 64 bar in the presence of a catalyst system comprising at least one metallocene, which is preferably stereorigid, and at least one cocatalyst, which is preferably an aluminoxane, inparticular of the formula (XX) R22\ IR22 R22 Al-0-- Al-0 Al (XX) R22 - r for the linear type and/or of the formula (XXI) -- --A 1-0 A I (XX I ) - - r+2 for the cyclic type, where in the formulae (XX) and (XXI) R22 is a C1-C20-hydrocarbon radical, for example a C1-C6-alkyl group, a C6-C14-aryl group, phenyl or benzyl, and r is an integer from 2 to 50.
Preference is given to stereorigid metallocenes as described in P 43 44 631.0, to which express reference is made hereby.
2154~
Also preferred are metallocenes of the formula (XXII) R 2 s /, ~R23 R27 M1~ (XX I I ) in which 10 Ml j5 a metal from the group consisting of titanium, zirconium, hafnium, vanadium, niobium and tantalum, preferably zirconium or hafnium, R23 and R24 are identical or different and are a hydrogen atom, a C1-C10-alkyl group, preferably a C1-C3-alkyl group, a C1-C10-alkoxy group, preferably a C1-C3-alkoxy group, a C6-C10-aryl group, preferably a C6-C8-aryl group, a C6-C10-aryloxy group, preferably a C6-C8-aryloxy group, a C2-C~O-alkenyl group, preferably a C2-C4-alkenyl group, a C7-C40-arylalkyl group, preferably a C7-C10-arylalkyl group, a C7-C40-alkylaryl group, preferably a C7-C12-alkylaryl group, a C8-C40-arylalkenyl group, preferably a C8-C12-arylalkenyl group or a halogen atom, preferably chlorine, 0 R25 and R26 are identical or different and are a mono- or polycyclic hydrocarbon radical which is able with the central atom M1 to form a sandwich structure, R27 is a single- or multi-membered bridge which links the radicals R25 and R26 and is -M2- -M2 M2 M2 CR230- !c -1-M2-, -C - C-, =BR28, =AIR28, -Ge-, -Sn-, -O-, -S-, = SO, = S02, = NR28, = CO, = PR28 or = P(O)R28, in which R28, R29 and R30 are identical or different and are a hydrogen atom, a halogen atom, preferably chlorine, a C1-C10-alkyl group, preferably a C1-C3-alkyl group, ~1546~3 especially methyl group, a C1-C10-fluoroalkyl group, preferably CF3 group, a C6-C10-fluoroaryl group, preferably pentafluorophenyl group, a C6-C10-aryl group, preferably a C6-C8-aryl group, a C1-C10-alkoxy group, preferably a C~-C4-alkoxy group, especially methoxy group, a C2-C10-alkenyl group, preferably a C2-C4-alkenyl group, a C7-C40-arylalkyl group, preferably a C7-C10-arylalkyl group, a C8-C40-arylalkenyl group, preferably a C8-C12-arylalkenyl group, or a C7-C40-alkylaryl group, preferably a C7-C12-alkylaryl group, or R28 and R29 or R28 and R30, together with the atoms connecting them, form a ring, and M2 is silicon, germanium or tin, preferably silicon or germanium.
Metallocenes of this type are described in EP 0 407 870, to which express reference is made hereby.
In formula (XXII), M1 is preferably zirconium or hafnium. R23 and R24 are identical or different and are preferably a C1-C10-alkyl group, especially a methyl group, or a halogen atom, especially chlorine. R25 and R26 are identical or different and are preferably cyclopentadienyl, 3-methylcyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, 4,7-tert-butylfluorenyl or benzoindenyl. R27 is preferably = CR23R29, = SiR23R29, = GeR23R29, -0-, -S- = S0 = PR23 or =P(o)R23, in which R23 and R29 are a hydrogen atom, a C1-C10-alkyl group or a C6-C10-aryl group.
Particular preference is given to metallocenes such as 4-(175-cyclopentadienyl)-4,7,7-trimethyl(1754,5,6,7-tetrahydroindenyl)ZrCI2 or dimethylsilanediylbis( 1 -indenyl)ZrCI2.
In order to prepare the functionalized COCs according to the invention, COCs containing double bonds are employed which have been prepared by polymerization with ring retention; in other words, polymers obtained by ",etalhesis polymerization are not employed in this case.
In the context of the process according to the invention it is an advantage that 2 1 ~4643 the COCs containing double bonds can be functionalized without a reduction in the molecular mass of the polymer. The molecular weight distribution of the functionalized COCs accessible in this way is thus determined decisively by the polymer-building reaction. Furthermore, the functionalized COCs possess a well-5 defined number of functional groups, which can likewise be controlled withinbroad ranges by the quantities of the monomer units employed in the polymerization reaction.
The functionalized COCs obtained by ozonolysis of double-bond-containing 10 COCs with oxidative or reductive working up are distinguished by an outstanding adhesion to plastics, aluminum, steel and zinc-plated steel. For this reason, the COCs according to the invention are particularly suitable as direct coating compositions for the production of acid-resistant and mar-resistant protective coats on the substrates mentioned. Coating compositions of this kind 15 contain at least one cycloolefin compolymer according to the invention and, if desired, one or more binders, conventional paint additives, pigments and/or fillers.
Owing to their good compatibility and homogeneous miscibility with the coating 20 compositions which are commonly used in coatings technology, which compositions contain one- or two-component binders, the COCs according to the invention are also suitable, furthermore, as adhesion promoters for the coating of, for example, plastics with these coating compositions. After applica-tion to the workpiece to be coated, curing using the corresponding crosslinking 25 agents is possible. The films prepared in this way possess high transparency,heat deformation resistance and hardness, and a high surface gloss. Moreover, in comparison with the standard coatings, they exhibit improved acid resistance and a higher level of mar resistance.
30 Examples of binders which can be employed in this context are one- or two-component polyurethane systems, epoxy resins, alkyd resins, melamine resins, saturated or unsaturated polyester resins, acrylate systems which can be 21~4643 crosslinked by means of irradiation, thermal treatment or free-radical initiators, two-component OH-functional acrylate-polyurethane systems, thermoplastic polyacrylates such as polymethyl methacrylate, nitrocellulose, rubber grades or polyamide resins. In principle it is also possible to use binder mixtures which 5 comprise more than one type of binder of the type mentioned above. Preference is given to the use of polyurethane systems or polyacrylate systems as one- or two-component binders. Such polyacrylate systems are described in the as yet unpublished German Patent Applications bearing the file references P 43 44 515 and P 43 44 516, to which express reference is made hereby. To the extent 10 that they are employed as adhesion promoters, the functionalized COCs are employed in quantities of from 2 to 60% by weight, preferably from 15 to 40%
by weight, based on the weight of the binder.
The coating compositions are preferably processed from solution, with the use 15 of organic solvents such as, for example, butyl acetate, methyl ethyl ketone,methyl isobutyl ketone, methoxypropyl acetate, toluene, xylene or mixtures of such solvents being possible. It is possible, moreover, to employ the systems inlow-solvent or solvent-free coating compositions, especially aqueous coating compositions. With this in mind, their use as adhesion promoters in powder 20 coating applications is also conceivable. A good overview of the possible coating compositions can be found in "Organic Coatings, Science and technologyn, Volume 8 (1986).
The invention is illustrated in more detail by the following examples.
25 Examples:
In the examples:
eta = solution viscosity (decalin, 135C, in accordance with DIN 53728) in dl/g, 30 Mw = weight-average molecular weight in g/mol, MW/Mn = polydispersity, measured by gel permeation chromatography (o-dichlorobenzene,135 C, polystyrene standard), ~154643 Equivalent weight (EW) = g of polymer / mol of functional group (determined titrimetrically) IN = iodine number (g of iodine / 100 9 of polymer) AN = acid number (mg of KOH / g of polymer) Examples 1-3 describe the preparation of the starting compounds:
Example 1 A clean and dry 1.5 dm3 polymerization reactor with stirrer was flushed with nitrogen and then with ethylene and filled with 0.6 dm3 of an 85% strength solution of norbornene in toluene. 60 ml of 5-vinyl-2-norbornene were added.
The ethylene pressure was adjusted to 6 bar gauge. 180 cm3 of hydrogen were also added and the temperature was adjusted to 70C. 12 mg of diphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconiumdichloride were dissolved in 20 cm3 of a solution of methylaluminoxane in toluene (10% by weight of methylaluminoxane of molecular mass 1300g/mol by cryoscopic determination) and then the solution was metered into the reactor. By subsequent injection the ethylene pressure was maintained at 6 bar. After a polymerization time of one hour the reactor contents were run off into a vessel,20 and 5 cm3 of isopropanol were added.
10 9 of XCelite 545 (LuV, Hamburg) and 5 cm3 of water were added to the solution, which was stirred at 60C for 30 min. A filter cake consisting of 10 9of ~Celite suspended in 0.5 dm3 of toluene was built up on the filter mesh of a 25 2 I pressure suction filter. The polymer solution was filtered through the pressure suction filter, with a nitrogen pressure of about 1 bar being developed.
The clear solution was introduced into 5 dm3 of acetone using a disperser (from Kotthoff). The solid was isolated by filtration, dispersed twice in acetone and then dried at 100C and under reduced pressure (0.2 bar) for 15 hours. 90 9 of 30 polymer was obtained, comprising 50 mol% of ethylene, 45 mol% of norbornene and 5 mol% of vinylnorbornene repeating units. The glass transition temperature was 151 C and eta was 0.15 dl/g (DIN 53728). Mw = 9700 215~3 g/mol and MW/Mn = 2.2. An iodine number of 15.5 was determined (EW =
1640 g/mol C=C).
Example 2 A clean and dry 1.5 dm3 polymerization reactor with stirrer was flushed with nitrogen and then with ethylene and filled with 0.6 dm3 of an 85% strength solution of norbornene in toluene. 60 ml of 2,5-norbornadiene were added. The ethylene pressure was adjusted to 6 bar gauge. 180 cm3 of hydrogen were also added and the temperature was adjusted to 70C. 12 mg of diphenyl-methylene(cyclopentadienyl) (9-fluorenyl)zirconium dichloride were dissolved in 20 cm3 of a solution of methylaluminoxane in toluene (10% by weight of methylaluminoxane of molecular mass 1300g/mol by cryoscopic determination) and then the solution was metered into the reactor. By subsequent injection the ethylene pressure was maintained at 6 bar. After a polymerization time of one hour the reactor contents were run off into a vessel, and 5 cm3 of isopropanol were added.
10 9 of ~Celite 545 (LuV, Hamburg) and 5 cm3 of water were added to the solution, which was stirred at 60C for 30 min. A filter cake consisting of 10 9of ~Celite suspended in 0.5 dm3 of toluene was built up on the filter mesh of a 2 I pressure suction filter. The polymer solution was filtered through the pressure suction filter, with a nitrogen pressure of about 1 bar being developed.
The clear solution was introduced into 5 dm3 of acetone using a disperser (from Kotthoff). The solid was isolated by filtration, dispersed twice in acetone and then dried at 100C and under reduced pressure (0.2 bar) for 15 hours. 78 9 of polymer was obtained, comprising 50 mol% of ethylene, 46 mol% of norbornene and 6 mol% of 5-norbornene repeating units. The glass transition temperature was 168C and eta was 0.20 dl/g (DIN 53728). Mw = 10,300 g/mol and MW/Mn = 2.1. An iodine number of 22 was determined (EW =
1218 g/mol C = C).
Example 3 21546~3 A clean and dry 1.5 dm3 polymerization reactor with stirrer was flushed with nitrogen and then with ethylene and filled with 0.6 dm3 of an 85% strength solution of norbornene in toluene. 60 ml of 5-ethylidene-2-norbornene were added. The ethylene pressure was adjusted to 6 bar gauge. 180 cm3 of 5 hydrogen were also added and the temperature was adjusted to 70C. 12 mg of diphenylmethyl(methylenebisindenyl)zirconium dichloride were dissolved in 20 cm3 of a solution of methylaluminoxane in toluene (10% by weight of methylaluminoxane of molecular mass 1300g/mol by cryoscopic determination) and then the solution was metered into the reactor. By subsequent injection the 10 ethylene pressure was maintained at 6 bar. After a polymerization time of onehour the reactor contents were run off into a vessel, and 5 cm3 of isopropanol were added.
10 9 of ~Celite 545 (LuV, Hamburg) and 5 cm3 of water were added to the solution, which was stirred at 60C for 30 min. A filter cake consisting of 10 9of ~Celite suspended in 0.5 dm3 of toluene was built up on the filter mesh of a 2 I pressure suction filter. The polymer solution was filtered through the pressure suction filter, with a nitrogen pressure of about 1 bar being developed.
The clear solution was introduced into 5 dm3 of acetone using a disperser (from Kotthoff). The solid was isolated by filtration, dispersed twice in acetone and then dried at 100C and under reduced pressure (0.2 bar) for 15 hours. 85 9 of polymer was obtained, comprising 50 mol% of ethylene, 44 mol% of norbornene and 6 mol% of vinylnorbornene repeating units. The glass transition temperature was 151 C and eta was 0.23 dl/g (DIN 53728). Mw = 11,500 g/mol and MW/Mn = 2.1. An iodine number of 16.2 was determined (EG =
1587 g/mol C=C).
Examples 4-6 describe the preparation of functionalized COCs Example 4 80 9 (0.65 mol) of COC from Example 1 are dissolved in a mixture of 500 ml of chloroform and 50 ml of methanol. The solution is cooled to a temperature of 215~693 from -7 to -10C. This temperature is also maintained during the gassing with ozone which follows. At a flow rate of 100 liters per hour and at an ozone concentration of from 49 to 61 g of ozone per cubic meter of oxygen, a quantity of ozone which is equimolar with the double bond content of the COC
5 is passed in. The ozone is prepared with an ozone generator (model 503 from Fischer in Mekkenheim, Bonn, and ozone meter, Ozontron 23 from the same manufacturer) in dry air or oxygen. After the end of gassing, a further 85 ml ofmethanol are added at -5C and then 43 ml of peracetic acid at 0C.
Subsequently, the temperature is slowly raised to 50C. At this temperature, 10 the reaction solution is stirred for 2 hours. lt is then cooled, washed with 200 ml of water and heated at reflux with 100 ml of water for one hour. The aqueous phase is separated off and the organic phase is washed with 100 ml of water. The carboxy-functionalized COC is isolated by precipitation with acetone followed by drying under vacuum at mild temperatures.
Product weight: 82 g; iodine number: < 1; acid number: 35 Example 5 50 9 (0.41 mol) of COC from Example 2 are dissolved in a mixture of 500 ml of chloroform and 50 ml of methanol. The solution is cooled to a temperature of from -7 to -10C. This temperature is also maintained during the gassing with ozone which follows. At a flow rate of 100 liters per hour and at an ozone concentration of from 49 to 61 g of ozone per cubic meter of oxygen, a quantity of ozone which is equimolar with the double bond content of the COC
is passed in. The ozone is prepared with an ozone generator (model 503 from Fischer in Mekkenheim, Bonn, and ozone meter, Ozontron 23 from the same manufacturer) in dry air or oxygen. After the end of gassing, a further 85 ml ofmethanol are added at -5C and then 43 ml of peracetic acid at 0C.
Subsequently, the temperature is slowly raised to 50C. At this temperature, the reaction solution is stirred for 2 hours. lt is then cooled, washed with 200 ml of water and heated at reflux with 100 ml of water for one hour. The aqueous phase is separated off and the organic phase is washed with 100 ml of water. The carboxy-functionalized COC is isolated by precipitation with acetone 21~4543 followed by drying under vacuum at mild temperatures.
Product weight: 53 9, iodine number: < 1; acid number: 90 Example 6 75 9 (0.61 mol) of COC from Example 3 are dissolved in a mixture of 500 ml of chloroform and 50 ml of methanol. The solution is cooled to a temperature of from -7 to -10C. This temperature is also maintained during the gassing with ozone which follows. At a flow rate of 100 liters per hour and at an ozone concentration of from 49 to 61 9 of ozone per cubic meter of oxygen, a quantity of ozone which is equimolar with the double bond content of the COC
is passed in. The ozone is prepared with an ozone generator (model 503 from Fischer in Mekkenheim, Bonn, and ozone meter, Ozontron 23 from the same manufacturer) in dry air or oxygen. After the end of gassing, a further 85 ml ofmethanol are added at -5C and then 43 ml of peracetic acid at 0C.
Subsequently, the temperature is slowly raised to 50C. At this temperature, the reaction solution is stirred for 2 hours. lt is then cooled, washed with 200 ml of water and heated at reflux with 100 ml of water for one hour. The aqueous phase is separated off and the organic phase is washed with 100 ml of water. The carboxy-functionalized COC is isolated by precipitation with acetone followed by drying under vacuum at mild temperatures.
Product weight: 78 9; iodine number: < 1 Investigating the adhesion properties of the functionalized COCs prepared 10 9 of each of the polymers from Examples 4-6 are dissolved in 100 ml of toluene at 80C and the solutions are knife-coated onto glass plates or steel plates or polypropylene plates respectively. These plates are dried initially atroom temperature for 4 h in a convection drying cabinet and then at 80C for 24 h in a vacuum drying cabinet.
In order to assist the adhesion of these films to the various substrates, the following qualitative tests are carried out:
a: Fingernail test: testing for mechanical detachment of the film using the fingernail.
b: ~Tesa-Film test: testing for mechanical detachment of the film by removal, with a sharp jerk, of a stuck-on section of ~Tesa-Film (Scotch tape test).
c: Cross-hatch test: the films are marked a number of times in a crosswise pattern using a sharp knife. Subsequently, the film is tested for mechanical detachment by removal, with a sharp jerk, of a section of ~Tesa-Film stuck on to this cross-hatch.
The results of these tests are compiled in Table 1. The table also gives the results for the unmodified COCs.
Table 1: Investigating the adhesion properties of COC films ExampleCOC Substrat Fingernail Scotc Cross-e test h tape hatch 7 COC IV glass + + + + + +
8 COC IV steel + + + + + +
9 COC lV PP ++ ++ ++
COC V glass + + + + + +
11 COC V steel + + + + + +
12 COCV PP ++ ++ ++
13 COC Vl glass + + + + + +
14 COC Vl steel + + + + + +
COC Vl PP + + + + + +
16 COC I glass -- -- --17 COC I steel -- -- --19 COC ll glass -- -- --COC ll steel -- -- --21 COC ll PP -- -- --20 Key to Table 1:
Polymer from Example 1 = COC I
Polymer from Example 2 = COC ll Polymer from Example 3 = COC lll 21~613 Polymer from Example 4 = COC IV
Polymer from Example 5 = COC V
Polymer from Example 6 = COC Vl 5 + + = very good adhesion. The films withstand the test method indicated without damage.
-- = very poor adhesion. The films are partially destroyed by the test method ind icated .
The polypropylene sheet used was a 200*50 mm sheet of commercial EPDM-modified polypropylene from Hoechst AG.
5 Cycloolefin copolymers and a process for their preparation The invention relates to functionalized cycloolefin copolymers ~COCs) having a solution viscosity (eta) < 0.25 dl/g, which are suitable for the production of highly mar-resistant coating materials, for example paints, or as adhesion 10 promoters, for example in coating compositions containing one- or two-component binders. The invention relates further to a process for the prepara-tion of COCs functionalized in this way.
In the sector of the automobile industry, bodywork topcoats and clearcoats are 15 assigned, in addition to the conventional function of preventing corrosion and of decoration, a central role in relation to the resistance to environmental effects.
As external coat, the clear- coat, for example, must be resistant to light, acidic components, and chemicals, such as grit, oil black, fuels and detergents, but also against mechanical stress (e.g. in automatic washing equipment). Further 20 requirements are good gloss retention, and chalking resistance and constancy of color. The individual coats of paint must, moreover, be matched to one another such that there is no detachment of individual components resulting in an impairment of the function of the overall coating system. A decisive role in this context is assigned to the substrate to be coated, too. The coating material 25 must exhibit adequate adhesion to the surface of the workpiece.
With particular regard to environmental concerns, in recent years new topcoats and/or clearcoats have been developed. Particular emphasis in this context should be placed on the so-called high-solids and waterborne coating materials, 30 whose low or zero content of organic solvents means that they assure lower polluting emissions in the course of processing (Organic coatings, Science and Technology, 8, (1986), G.D. Parfitt, A.V. Patsis (ed.)). In addition to alkyd-melamine resin coating materials, heat-curable acrylic resins in particular are 215~3 employed in this application. The outstanding performance of these systems in relation, for example, to processability, gloss retention and color stability iscountered by low resistance to hydrolysis and a degree of surface hardness which is not satisfactory in every respect. Moreover, the adhesion properties ofthe coating systems are very sensitive to the substrate to be coated. In the majority of cases, appropriate pretreatment of the substrate surface is necessary.
The development of new coating systems having substrate-specific properties continues to be of great importance.
From EP 283 164 it is known that, by copolymerizing ~-olefins with cyclic polyenes and, if desired, cycloolefins, it is possible to provide COCs containing double bonds, the cyclic polyenes used being, for example, unconjugated dienes or trienes containing norbornene as structural element. JP 05279412-A
discloses that, in such COCs containing double bonds, it is possible by epoxidiz-ation to introduce hydroxyl and/or epoxy groups, the functionalized COCs obtained being used as compatibilizers for olefinic polymer blends.
JP 2269760-A, JP 3072558-A and JP 3106962-A disclose polycyclic monomers which contain carboxyl groups and are reacted by metathesis polymerization to give homopolymers and copolymers. The disadvantage of a ring-opening polymerization of this kind, however, is that the polymer initiallyobtained has double bonds, which may lead to uncontrolled and unwanted chain crosslinking reactions, and thus considerably restrict the ability of the material to be processed by extrusion or injection molding.
EP-A-203 799 discloses COCs onto which, in a polymer-analogous reaction, o"B-unsaturated carboxylic acids such as, for example, acrylic acid are grafted. EP-A-570 126, furthermore, describes the grafting of COCs containing double bonds with monomers suitable for free-radical polymerization, for example styrene, vinyl chloride, acrylonitrile or vinyl acetate. These polymer-analogous 21546~3 grafting reactions, however, have the disadvantage that the products obtained lack uniformity with respect to the grafting yield, the grafting sites and the chain length of the graft branches. Moreover, the actual grafting reaction is often accompanied by homopolymerization of the monomer employed. The 5 homopolymers and the grafting product are, in the majority of cases, no longercapable of separation. The reaction products obtained therefore have a very wide molecular weight distribution and, in addition, are chemically heterogenous. For the development of coating materials having a high solids content (high-solids coating materials), however, it is desired to have products10 whose molecular weight distribution is as narrow as possible and in which the number of functional groups can be controlled.
The object was therefore to provide a polymer which shows ready miscibility with other substances, especially polymers, and which is suitable for the 15 production of highly mar-resistant, acid-resistant and base-resistant coatings, for example automotive finishes, having improved adhesion to the substrate surface.
It has surprisingly been found that this object can be achieved by the provision20 of specific functionalized COCs. The functionalized COCs according to the invention contain polymerized units comprising functional groups which are introduced by a polymer-analogous ozonolysis reaction, with subsequent working up, and, if desired, by specific subsequent reactions.
25 The invention therefore relates to a cycloolefin copolymer having a solution viscosity (eta) < 0.25 dl/g (measured in accordance with DIN 53728 in decalin at 135C) which comprises polymerized units (A) of at least one cyclic olefin and (B), if desired, of one or more acyclic olefins, wherein (C) polymerized units are present which contain at least one functionalized structural unit which a) is derived from a cyclic olefin and contains at least one heteroatom which is attached directly to a ring atom of the cyclic olefin, or 215~6~3 b) is derived from a cyclic or acyclic olefin and contains at least one group of atoms which has two heteroatoms both of which are attached to the same carbon atom, or 5 c) is derived from a cyclic or acyclic olefin and contains at least one aldehyde group, or d) is derived from a cyclic or acyclic olefin and contains at least one group of atoms in which a nitrogen atom is attached via a double bond to a carbon atom, and, where the functionalized structural unit is derived from a cyclic olefin, exactly two adjacent carbon atoms of this functionalized cyclic structural unit are incorporated into the polymer main chain.
The groups of atoms of the functionalized structural units in b) and d) and/or the aldehyde group of the functionalized structural unit in c) may be attached directly or via a hydrocarbon group of 1 to 20 carbon atoms, preferably an unsubstituted, alkyl-substituted or aryl-substituted C1-C10-alkylene group, to the 20 cyclic or acyclic olefin components.
The term heteroatom refers, with the exception of carbon and hydrogen, to all elements in the Periodic Table of the elements, preferably oxygen, sulfur, nitrogen, phosphorous and silicon and especially oxygen, sulfur and nitrogen. In25 strict accordance with the IUPAC nomenclature, the polymer main chain is understood as being the continuous main chain of the polymer which may possess a substitution pattern (G. Odian: "Principles of Polymerization", secondedition, 1981, p. 12). For example, in accordance with this nomenclature polypropylene possesses a polyethylene main chain on which, at every other 30 carbon atom, a hydrogen atom is substituted by a methyl group.
The cycloolefin copolymer according to the invention preferably contains 21546~3 0.1-99.89 % by weight, based on the overall mass of the cycloolefin copolymer, of polymerized units (A) of at least one cyclic olefin, 0-80 % by weight, based on the overall mass of the cycloolefin copolymer of polymerized units (B) of at least one acyclic olefin, and 0.01-50 % by weight, based on the overall mass of the cycloolefin copolymer, of polymerized units (C) which contain at least one functionalized structural unit which a) is derived from a cyclic olefin and contains at least one heteroatom which is attached directly to a ring atom of the cyclic olefin, or b) is derived from a cyclic or acyclic olefin and contains at least group of atoms which has two heteroatoms both of which are attached to the same carbon atom, or c) is derived from a cyclic or acyclic olefin and contains at least one aldehyde group, or d) is derived from a cyclic or acyclic olefin and contains at least one group of atoms in which a nitrogen atom is attached via a double bond to a carbon atom, and, where the functionalized structural unit is derived from a cyclic olefin, exactly two adjacent carbon atoms of this functionalized cyclic structural unit are incorporated into the polymer main chain.
The polymerized units (A) are preferably derived from cycloolefins of the formulae (I), (Il), (Ill), (IV), (V), (Vl) and (Vll) 215~6~3 H C/ ¦ \C H/
¦¦R3-C R~
H C\I /C H\R 2 CH
H C/ ¦ \C H
¦¦R3--C R~ ¦ CH2 ( I I ) .
H C\ /C H
cH cH /R
¦ I R 3 C--~ ~ ¦ R S C R ( I I I ) \I H/ \CH/ \ 2 H C/ ¦ \C H/ ¦ \C H/ ¦ \C H/
¦¦R3--C--R~ ¦ RS C R6 ¦ R7- C-RS ( rV) .
\C H/ \C H/ \C H/ \ 2 Rs / ¦ \
¦¦R3--C R~ ¦ ( V) \I H \C H \ R 2 R S
H C/ ¦ \C H/ \C H/ ¦ \C H/ ( V I ) ¦¦R'--C R~ ¦ ¦ R7- C R8 ¦
\ I H / \ 2 21~4643 CH CH
( V l 1 ) , ( CH2 ) n in which R1, R2, R3, R4, R5, R6, R7 and R8 are identical or different and are a hydrogen atom or a C1-C30-hydrocarbon radical, such as a C1-C8-alkyl group or 10 a C6-C14-aryl group, where identical radicals in the different formulae may have different meanings, and n is a number from 2 to 10. The polymerized units (A) are particularly preferably derived from norbornene.
The polymerized units (B) are preferably derived from acyclic monoolefins, for 15 example a-olefins of 2 to 20 carbon atoms, especially ethylene and propylene.
The polymerized units (C) are preferably derived from compounds of the formulae (XIV), (XV), (XVI), (XVII), (XVIII) and (XIX) HC ~ CH ---- _ CH- . CH ~ C/
R 1 ~ _ ¦-- R 1 7 R --C-- R ( X I V ) C H ~ C H ~ R 2 -- m HC ~ CH~ CH~ CH ~ R20 R16--C--R17 R18--C-- R19 (XV) HC~ CH~CH ~ CH ~ R21 --m H :~- CH~ CH~ CH ~ R20 R1 _ C--Rl7 (XVI ) HC~ CH~CH ~ R21 -- m HC ~ CH~ CH . CH ~ R22 R l --C--R 1 7 R 1 8--C-- R l 9 ( XV I I ) HC CH~CH ~ CH ~ \ R2 --m R 1 6\ / R 1 8 / C C \ (XVIII) Rl7 Rl9 \ / \ /
R 1 7 R R 21 R ( X I X ) -- --n -- -- I
in which R16, R17, R18, R19, R20 and R21 are identical or different, identical 10 radicals in the different formulae may have different meanings and are hydrogen, a C1-C30-hydrocarbon radical, such as a C1-C8-alkyl group or a 21a4543 C6-C14-aryl group, a primary, secondary or tertiary amino group, a substituted or unsubstituted ammonium group, a hydroxyl group, an alkyloxy group, an aryloxy group, an aralkyloxy group or a group -(X)p-Y in which X is a branched or unbranched C2-C20-alkylene group or a branched or unbranched C8-C20-arylalkylene group and p = 0 or 1 and Y is a carboxyl group, an alkyloxycarbonyl group, a carbamoyl group, a mono- or bisalkylcarbamoyl group, a chloroformyl group, an acyloxycarbonyl group, a thiocarboxy group, an alkylthiocarbonyl group, a formyl group, an alkylformyl group, a hydroxybis(alkyloxy)methyl group, a tris(alkyloxy)methyl group, a hydroxyiminomethyl group, a hydrazonomethyl group or a semicarbazonomethyl group, where in the formulae (XIV) and (XVIII) at least one of the radicals R16,R17, R13, R19, R20 and R21, in the formulae (XV), (XVI) and (XIX) at least two of the radicals R16 R17 R18 R19, R20 and R21, and in formula (XVII) none of the radicals R16 R17 R13 R19, R20 and R21 must be a group -(X)p-Y, a primarY~
secondary or tertiary amino group, a substituted or unsubstituted ammonium group, a hydroxyl group, an alkyloxy group, an aryloxy group or an aralkyloxy group.
R22 is a carbonyl group, a hydroxyiminomethyl group, a hydrazonomethyl group or a semicarbazonomethyl group.
In the formulae (XV) and (XVI) p = 0 if R20 or R21 is a group -(X)p-Y. In formula (XIX) R20 and R21 are not hydrogen or a C1-C30-hydrocarbon radical, such as a C1-C8-alkyl group or a C6-C14-aryl group.
The polymerized units (C) are derived particularly preferably from compounds of the formulae (XIV) to (XIX) in which R22 is a carbonyl group and R16, R17, R13, R19, R20 and R21 are identical or different, identical radicals in the differentformulae may have different meanings and are a primary, secondary or tertiary amino group, a hydroxyl group or a group -(X)p-Y in which X is a branched or unbranched C2-C20-alkylene group or a branched or unbranched C8-C20-arylalkylene group and p = 0 or 1 and Y is a carboxyl group or a formyl group, where in the formulae (XIV) and (XVIII) at least one of the radicals R16, R17, 21546~3 R18, R19, R20 and R21, in the formulae (XV), (XVI) and (XIX) at least two of theradicals R16 R17 R18 R19, R20 and R21, and in formula (XVII) none of the radicals R16, R17, R18, R19, R20 and R21 is or are a primary, secondary or tertiary amino group, a hydroxyl group or a group -(X)p-Y in which X is a 5 branched or unbranched C2-C20-alkylene group or a branched or unbranched C8-C20-arylalkylene group and p = O or 1 and Y is a carboxyl group or a formyl group.
The invention relates furthermore to a process for the preparation of a10 cycloolefin copolymer having a solution viscosity (eta) < 0.25 dl/g, which comprises reacting a cycloolefin copolymer containing double bonds in an inert solvent with ozone.
To carry out the process according to the invention, the COC containing double 15 bonds is dissolved in an inert solvent. Inert solvents which can be employed are aliphatic hydrocarbons, for example decalin, halogenated aliphatic hydrocarbons,for example chloroform or carbon tetrachloride, methanol or glacial acetic acid.Gassing with ozone is carried out in a suitable reaction vessel, for example a gas-fed stirred reactor or a bubble column. In this vessel, a quantity of ozone 20 equimolar with the double bond content of the COC is passed into the solution.
The ozone is prepared using an ozone generator in dry air or oxygen. The concentration of ozone in the carrier gas, air or oxygen, is not critical for the reaction procedure according to the invention. It is typically from 1 to 180 g/m3, preferably from 1Q to 50 g/m3. In practice it is chosen such that the 25 uptake of ozone is as complete as possible. The uptake of ozone can be monitored by means of a suitable meter, for example a UV photometer. In order to avoid a reduction in molecular mass of the COC, it is advantageous to carry out the gassing with ozone at a low temperature, between -78 and + 10C, preferably between -10 and 0C.
30 Owing to the tendency of the double-bond-containing COCs used as starting materials to crosslink at relatively high temperatures, the addition of a suitable inhibitor which is not chemically reactive under the chosen conditions may be 215454~
advantageous. Suitable examples are phenothiazine and aromatic nitro compounds such as nitrobenzene and dinitrobenzene (US 4,082,493).
After the end of the ozonolysis, in order to avoid the formation of so-called 5 ozonides, a small quantity of alcohol, for example methanol, or water is added to the solution.
Oxidative working up is carried out using peroxy carboxylic acids, for example those of formic, acetic or propionic acid. In this context it is possible to use the 10 equilibrium peracid or to prepare the peracid in situ by addition of carboxylic acid, an appropriate quantity of hydrogen peroxide and a catalytic amount of mineral acid. The peracid is employed in excess, the excess becoming smaller as the batch size increases. For each mole of double bond in the COC, from 1 to 3 mole equivalents, preferably from 1.1 to 1.8 mole equivalents, of peracid are 15 employed. In order to complete the oxidative working up, the solution is heated at reflux for a number of hours. The primary products of the oxidative working up are COCs containing carboxyl groups.
The reductive working up is carried out with reducing agents such as zinc dust 20 in acetic acid, or by way of catalytic hydrogenation with palladium on calcium carbonate or sodium dithionite. The reducing agent is employed in excess. For each mole of double bond, from 1 to 4 mole equivalents, preferably from 1.2 to 2.2 mole equivalents, of reducing agent are employed. In order to be assured of complete reaction, the mixture is boiled at reflux for from 1 to 4 hours. The 25 primary products of this reductive working up are COCs containing aldehyde and/or keto groups.
Both after the oxidative and after the reductive working up, the polymer solution can be passed on for further use directly. If the polymer is to be 30 isolated as such, then it can be freed from the solvent by known methods:
1. stripping off the solvent, for example by steam distillation, 2. evaporating off the solvent, for example by spray drying or thickening in a falling-film evaporator, which may be operated with a vacuum, and preferably by 5 3. precipitating in a nonsolvent which is miscible with the polymer solvent, the nonsolvent being, for example, methanol or acetone.
With particular preference, the isolation of the functionalized COC is carried out by precipitation with acetone. In order to avoid the formation of cyclic peroxides 10 of the acetone, care must be taken here that there is no longer any oxidizingagent in the solution; if required, any remaining oxidizing agent must be removed by the appropriate addition of reducing agent.
By washing with solvents which do not dissolve the polymer it is readily 15 possible to remove extraneous substances, for example by-products. Drying canbe carried out at atmospheric pressure or reduced pressure, optionally with inert gas blanketing, at a temperature which must be below T~ in order to avoid sintering. Preference is given to drying in a stream of nitrogen at mild temperatures .
All compounds obtained by oxidative or reductive working up can be subjected to subsequent reactions by means of which further functional groups are introduced into the COCs.
25 From the corresponding carboxylic acids it is possible by conventional laboratory methods to prepare acid chlorides, esters, anhydrides, amides or hydrazides [J.
March: "Advanced Organic Chemistryn, third edition].
The corresponding aldehydes and ketones can be reduced, for example, to 30 alcohols. Reduction can be carried out catalytically over nickel or palladium, or using nascent hydrogen which is prepared in situ by reaction of sodium amalgam and water or sodium and alcohol. Particularly preferred reducing agents for preparing the corresponding alcohols are lithium aluminum hydride and sodium borohydride. Also suitable are aluminum alcoholates, for example aluminum isopropylate. The reactions may optionally be catalyzed by addition of acids or bases. If the hydrogenation is carried out in the presence of ammonia, 5 primary or secondary amines, then the corresponding primary, secondary or tertiary amines are obtained. For the preparation of these systems, the amine component is employed in excess. In this context the preferred ratio of the number of moles of aldehyde to that of amine is 1:10, and a ratio of 1.1:5.5 is particularly preferred. The direct addition of ammonia, primary or secondary 10 amines with subsequent elimination of water produces imines, azomethines, enamines or aminals [J. March: "Advanced Organic Chemistry", third edition].
The derivatives obtained can be employed as crosslinking agents in powder coating systems or in other coating compositions. In this utility it may be 15 necessary to convert the amino groups of the COC derivative into the isocyanate groups. A further conceivable application of these derivatives is as polymer supports for immobilized catalysts, for example for the fixation of enzymes by way of the hydroxyl and/or amino groups for use in modern synthesis processes.
Employing basic catalysis, the addition of hydrocyanic acid onto the aldehyde groups of the COC backbone gives rise to the formation of cyanohydrins (a-hydroxy nitriles), which can be reacted to a-hydroxy carboxylic acids. If thereaction is carried out in the presence of equimolar quantities of ammonia or 25 primary and secondary amines, then the hydrocyanic acid is added onto the imino compounds which are formed initially. The resulting amino nitriles, when subjected subsequently to acid hydrolysis, give a-amino acids. In this way it ispossible to achieve a biocompatibility which may be particularly advantageous, especially for the application of these materials in the medical field, for example 30 as membranes.
215~643 In order to prepare the acetals and hemiacetals, the aldehyde- and/or ketone-functionalized COCs are reacted in the presence of anhydrous mineral acids with the corresponding alcohols. It is advisable to carry out the reaction in the presence of water-binding agents. For the preparation of the diethyl acetals of 5 keto groups in particular, it is possible to use triethyl orthoformate. In place of the alcohols, thiols can also be used, which react to give the corresponding mercaptans.
In addition to this, all known reactions can be carried out on the aldehyde 10 and/or ketone functionalities. The formation of oximes, semicarbazones and hydrazones is mentioned only by way of example, these compounds being able to be prepared by the conventional methods from the corresponding COCs with aldehyde and/or ketone groups. Reference may likewise be made to the possible variants which can be achieved by aldol condensation [J. March: "Advanced 15 Organic Chemistry", third edition]. The reactions described may, moreover, also be configured as crosslinking reactions. If the corresponding bifunctional compounds are employed - for example diols, diamines, etc. - then intermolecular reaction may lead to the formation of a polymer network. For the subsequent crosslinking of a coating material comprising functionalized COCs, 20 this gives rise to a host of possibilities. The double-bond-containing cycloolefin copolymers employed in the process according to the invention preferably contain 0.1-99.89 % by weight of polymerized units of a cycloolefin of the formula (I), (Il), (Ill), (IV), (V), (Vl) or (Vll) H C/ ¦ \C H/
¦¦R3-C R~ ¦ ( I ) .
H C\I /C H\R 2 C H
21.~4~43 H C/ C H
¦¦R C R ¦ CH2 ( I I ) H C/ ¦ \C H/ ¦ \ /
¦¦R3--C R4 ¦ RS C R6 ( I I I ) .
\C H/ \J H/ \ 2 1 0 H C/ \ C H / ¦ \C H / \C H/
¦¦R3--C--R4 ¦ RS C R6 R7- `-R8 ( I V ) R s / \ / \ /
¦IR3--C--RI ¦ (V) .
\
R S
HC/ ¦ \CH/ \~H/f \CH/ ( V I ) ¦¦R3--C R4 ¦ R7- C R8 H C\ /C H /~ H ¦ /C H\
CH CH
(V l l ), ( C H 2 ) n in which R1, R2, R3, R4, R5, R6, R7 and R8 are identical or different and are a hydrogen atom or a C1-C30-hydrocarbon radical, such as a C1-C8-alkyl group or a C6-C14-aryl group, where identical radicals in the different formulae may havedifferent meanings, and n is a number from 2 to 10, and 0-80 % by weight, based on the overall mass of the cycloolefin copolymer, of polymerized units of at least one acylic monoolefin, preferably of an a-olefin of 2-20 carbon atoms, particularly preferably ethylene or propylene, and 0.01-50 % by weight, based on the overall mass of the cycloolefin copolymer, of polymerized units of at least one olefin which has at least one double bond, preferably of at least one olefin of the formulae (Vlll), (IX), (X), (Xl), (Xll) and (Xlll) / CH ~CH ~ CH ~ CH /
H C
¦¦R11 I _ R12 RI3 C R (Vl I I ) HC CH ~_ CH CH~ \ R10 --m / CH ~CH ~ jH ~ C
¦IR11-- C_ R12 R13 C R1~ ( IX) -- m CH ~ R 10 21~4643 I
/ CH ~CH / CH \
¦¦ R 11 _ C_ R 1 2 C _ R 9 ( X ) C H ~ C H C
c C H / C H ~ \ R 1 O
¦¦R 1 C R12 1 3 --C-- R1~
(X I ) H C ~ C H ~ C H ~ C H ~ C H \ R 1 5 --m C C ( X I I ) R 12 / \R 10 C C (X I I I ) R10 \_/ \R1O
- -n - - I
in which R9, R10, R11, R12, R13, R14 and R15 are identical or different and are a hydrogen atom, a C1-C30-hydrocarbon radical, such as a C1-C8-alkyl group or a C6-C14-aryl group, a C2-C20-alkenyl group or a C8-C20-arylalkenyl group, where identical radicals in the different formulae may have different meanings, and in 21~4613 the formulae (IX) and (X) R9 and R10 are a hydrogen atom, a C1-C30-hydrocarbon radical, such as a C1-C8-alkyl group or a C6-C14-aryl group, in the formula (Vlll) at least one of the radicals R9, R10, R11, R12, R13 and R14 is analkenyl group, in the formula (Xll) at least one of the radicals R9, R10, R1 1 and 5 R12 is an alkenyl group, and m is a number from 0 to 10 and n and I are each a number from 0 to 10, with the proviso that n = I = 0 does not apply.
The double-bond-containing cycloolefin copolymers employed in the process according to the invention can be prepared at temperatures of from -78 to 200C under a pressure of from 0.01 to 64 bar in the presence of a catalyst system comprising at least one metallocene, which is preferably stereorigid, and at least one cocatalyst, which is preferably an aluminoxane, inparticular of the formula (XX) R22\ IR22 R22 Al-0-- Al-0 Al (XX) R22 - r for the linear type and/or of the formula (XXI) -- --A 1-0 A I (XX I ) - - r+2 for the cyclic type, where in the formulae (XX) and (XXI) R22 is a C1-C20-hydrocarbon radical, for example a C1-C6-alkyl group, a C6-C14-aryl group, phenyl or benzyl, and r is an integer from 2 to 50.
Preference is given to stereorigid metallocenes as described in P 43 44 631.0, to which express reference is made hereby.
2154~
Also preferred are metallocenes of the formula (XXII) R 2 s /, ~R23 R27 M1~ (XX I I ) in which 10 Ml j5 a metal from the group consisting of titanium, zirconium, hafnium, vanadium, niobium and tantalum, preferably zirconium or hafnium, R23 and R24 are identical or different and are a hydrogen atom, a C1-C10-alkyl group, preferably a C1-C3-alkyl group, a C1-C10-alkoxy group, preferably a C1-C3-alkoxy group, a C6-C10-aryl group, preferably a C6-C8-aryl group, a C6-C10-aryloxy group, preferably a C6-C8-aryloxy group, a C2-C~O-alkenyl group, preferably a C2-C4-alkenyl group, a C7-C40-arylalkyl group, preferably a C7-C10-arylalkyl group, a C7-C40-alkylaryl group, preferably a C7-C12-alkylaryl group, a C8-C40-arylalkenyl group, preferably a C8-C12-arylalkenyl group or a halogen atom, preferably chlorine, 0 R25 and R26 are identical or different and are a mono- or polycyclic hydrocarbon radical which is able with the central atom M1 to form a sandwich structure, R27 is a single- or multi-membered bridge which links the radicals R25 and R26 and is -M2- -M2 M2 M2 CR230- !c -1-M2-, -C - C-, =BR28, =AIR28, -Ge-, -Sn-, -O-, -S-, = SO, = S02, = NR28, = CO, = PR28 or = P(O)R28, in which R28, R29 and R30 are identical or different and are a hydrogen atom, a halogen atom, preferably chlorine, a C1-C10-alkyl group, preferably a C1-C3-alkyl group, ~1546~3 especially methyl group, a C1-C10-fluoroalkyl group, preferably CF3 group, a C6-C10-fluoroaryl group, preferably pentafluorophenyl group, a C6-C10-aryl group, preferably a C6-C8-aryl group, a C1-C10-alkoxy group, preferably a C~-C4-alkoxy group, especially methoxy group, a C2-C10-alkenyl group, preferably a C2-C4-alkenyl group, a C7-C40-arylalkyl group, preferably a C7-C10-arylalkyl group, a C8-C40-arylalkenyl group, preferably a C8-C12-arylalkenyl group, or a C7-C40-alkylaryl group, preferably a C7-C12-alkylaryl group, or R28 and R29 or R28 and R30, together with the atoms connecting them, form a ring, and M2 is silicon, germanium or tin, preferably silicon or germanium.
Metallocenes of this type are described in EP 0 407 870, to which express reference is made hereby.
In formula (XXII), M1 is preferably zirconium or hafnium. R23 and R24 are identical or different and are preferably a C1-C10-alkyl group, especially a methyl group, or a halogen atom, especially chlorine. R25 and R26 are identical or different and are preferably cyclopentadienyl, 3-methylcyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, 4,7-tert-butylfluorenyl or benzoindenyl. R27 is preferably = CR23R29, = SiR23R29, = GeR23R29, -0-, -S- = S0 = PR23 or =P(o)R23, in which R23 and R29 are a hydrogen atom, a C1-C10-alkyl group or a C6-C10-aryl group.
Particular preference is given to metallocenes such as 4-(175-cyclopentadienyl)-4,7,7-trimethyl(1754,5,6,7-tetrahydroindenyl)ZrCI2 or dimethylsilanediylbis( 1 -indenyl)ZrCI2.
In order to prepare the functionalized COCs according to the invention, COCs containing double bonds are employed which have been prepared by polymerization with ring retention; in other words, polymers obtained by ",etalhesis polymerization are not employed in this case.
In the context of the process according to the invention it is an advantage that 2 1 ~4643 the COCs containing double bonds can be functionalized without a reduction in the molecular mass of the polymer. The molecular weight distribution of the functionalized COCs accessible in this way is thus determined decisively by the polymer-building reaction. Furthermore, the functionalized COCs possess a well-5 defined number of functional groups, which can likewise be controlled withinbroad ranges by the quantities of the monomer units employed in the polymerization reaction.
The functionalized COCs obtained by ozonolysis of double-bond-containing 10 COCs with oxidative or reductive working up are distinguished by an outstanding adhesion to plastics, aluminum, steel and zinc-plated steel. For this reason, the COCs according to the invention are particularly suitable as direct coating compositions for the production of acid-resistant and mar-resistant protective coats on the substrates mentioned. Coating compositions of this kind 15 contain at least one cycloolefin compolymer according to the invention and, if desired, one or more binders, conventional paint additives, pigments and/or fillers.
Owing to their good compatibility and homogeneous miscibility with the coating 20 compositions which are commonly used in coatings technology, which compositions contain one- or two-component binders, the COCs according to the invention are also suitable, furthermore, as adhesion promoters for the coating of, for example, plastics with these coating compositions. After applica-tion to the workpiece to be coated, curing using the corresponding crosslinking 25 agents is possible. The films prepared in this way possess high transparency,heat deformation resistance and hardness, and a high surface gloss. Moreover, in comparison with the standard coatings, they exhibit improved acid resistance and a higher level of mar resistance.
30 Examples of binders which can be employed in this context are one- or two-component polyurethane systems, epoxy resins, alkyd resins, melamine resins, saturated or unsaturated polyester resins, acrylate systems which can be 21~4643 crosslinked by means of irradiation, thermal treatment or free-radical initiators, two-component OH-functional acrylate-polyurethane systems, thermoplastic polyacrylates such as polymethyl methacrylate, nitrocellulose, rubber grades or polyamide resins. In principle it is also possible to use binder mixtures which 5 comprise more than one type of binder of the type mentioned above. Preference is given to the use of polyurethane systems or polyacrylate systems as one- or two-component binders. Such polyacrylate systems are described in the as yet unpublished German Patent Applications bearing the file references P 43 44 515 and P 43 44 516, to which express reference is made hereby. To the extent 10 that they are employed as adhesion promoters, the functionalized COCs are employed in quantities of from 2 to 60% by weight, preferably from 15 to 40%
by weight, based on the weight of the binder.
The coating compositions are preferably processed from solution, with the use 15 of organic solvents such as, for example, butyl acetate, methyl ethyl ketone,methyl isobutyl ketone, methoxypropyl acetate, toluene, xylene or mixtures of such solvents being possible. It is possible, moreover, to employ the systems inlow-solvent or solvent-free coating compositions, especially aqueous coating compositions. With this in mind, their use as adhesion promoters in powder 20 coating applications is also conceivable. A good overview of the possible coating compositions can be found in "Organic Coatings, Science and technologyn, Volume 8 (1986).
The invention is illustrated in more detail by the following examples.
25 Examples:
In the examples:
eta = solution viscosity (decalin, 135C, in accordance with DIN 53728) in dl/g, 30 Mw = weight-average molecular weight in g/mol, MW/Mn = polydispersity, measured by gel permeation chromatography (o-dichlorobenzene,135 C, polystyrene standard), ~154643 Equivalent weight (EW) = g of polymer / mol of functional group (determined titrimetrically) IN = iodine number (g of iodine / 100 9 of polymer) AN = acid number (mg of KOH / g of polymer) Examples 1-3 describe the preparation of the starting compounds:
Example 1 A clean and dry 1.5 dm3 polymerization reactor with stirrer was flushed with nitrogen and then with ethylene and filled with 0.6 dm3 of an 85% strength solution of norbornene in toluene. 60 ml of 5-vinyl-2-norbornene were added.
The ethylene pressure was adjusted to 6 bar gauge. 180 cm3 of hydrogen were also added and the temperature was adjusted to 70C. 12 mg of diphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconiumdichloride were dissolved in 20 cm3 of a solution of methylaluminoxane in toluene (10% by weight of methylaluminoxane of molecular mass 1300g/mol by cryoscopic determination) and then the solution was metered into the reactor. By subsequent injection the ethylene pressure was maintained at 6 bar. After a polymerization time of one hour the reactor contents were run off into a vessel,20 and 5 cm3 of isopropanol were added.
10 9 of XCelite 545 (LuV, Hamburg) and 5 cm3 of water were added to the solution, which was stirred at 60C for 30 min. A filter cake consisting of 10 9of ~Celite suspended in 0.5 dm3 of toluene was built up on the filter mesh of a 25 2 I pressure suction filter. The polymer solution was filtered through the pressure suction filter, with a nitrogen pressure of about 1 bar being developed.
The clear solution was introduced into 5 dm3 of acetone using a disperser (from Kotthoff). The solid was isolated by filtration, dispersed twice in acetone and then dried at 100C and under reduced pressure (0.2 bar) for 15 hours. 90 9 of 30 polymer was obtained, comprising 50 mol% of ethylene, 45 mol% of norbornene and 5 mol% of vinylnorbornene repeating units. The glass transition temperature was 151 C and eta was 0.15 dl/g (DIN 53728). Mw = 9700 215~3 g/mol and MW/Mn = 2.2. An iodine number of 15.5 was determined (EW =
1640 g/mol C=C).
Example 2 A clean and dry 1.5 dm3 polymerization reactor with stirrer was flushed with nitrogen and then with ethylene and filled with 0.6 dm3 of an 85% strength solution of norbornene in toluene. 60 ml of 2,5-norbornadiene were added. The ethylene pressure was adjusted to 6 bar gauge. 180 cm3 of hydrogen were also added and the temperature was adjusted to 70C. 12 mg of diphenyl-methylene(cyclopentadienyl) (9-fluorenyl)zirconium dichloride were dissolved in 20 cm3 of a solution of methylaluminoxane in toluene (10% by weight of methylaluminoxane of molecular mass 1300g/mol by cryoscopic determination) and then the solution was metered into the reactor. By subsequent injection the ethylene pressure was maintained at 6 bar. After a polymerization time of one hour the reactor contents were run off into a vessel, and 5 cm3 of isopropanol were added.
10 9 of ~Celite 545 (LuV, Hamburg) and 5 cm3 of water were added to the solution, which was stirred at 60C for 30 min. A filter cake consisting of 10 9of ~Celite suspended in 0.5 dm3 of toluene was built up on the filter mesh of a 2 I pressure suction filter. The polymer solution was filtered through the pressure suction filter, with a nitrogen pressure of about 1 bar being developed.
The clear solution was introduced into 5 dm3 of acetone using a disperser (from Kotthoff). The solid was isolated by filtration, dispersed twice in acetone and then dried at 100C and under reduced pressure (0.2 bar) for 15 hours. 78 9 of polymer was obtained, comprising 50 mol% of ethylene, 46 mol% of norbornene and 6 mol% of 5-norbornene repeating units. The glass transition temperature was 168C and eta was 0.20 dl/g (DIN 53728). Mw = 10,300 g/mol and MW/Mn = 2.1. An iodine number of 22 was determined (EW =
1218 g/mol C = C).
Example 3 21546~3 A clean and dry 1.5 dm3 polymerization reactor with stirrer was flushed with nitrogen and then with ethylene and filled with 0.6 dm3 of an 85% strength solution of norbornene in toluene. 60 ml of 5-ethylidene-2-norbornene were added. The ethylene pressure was adjusted to 6 bar gauge. 180 cm3 of 5 hydrogen were also added and the temperature was adjusted to 70C. 12 mg of diphenylmethyl(methylenebisindenyl)zirconium dichloride were dissolved in 20 cm3 of a solution of methylaluminoxane in toluene (10% by weight of methylaluminoxane of molecular mass 1300g/mol by cryoscopic determination) and then the solution was metered into the reactor. By subsequent injection the 10 ethylene pressure was maintained at 6 bar. After a polymerization time of onehour the reactor contents were run off into a vessel, and 5 cm3 of isopropanol were added.
10 9 of ~Celite 545 (LuV, Hamburg) and 5 cm3 of water were added to the solution, which was stirred at 60C for 30 min. A filter cake consisting of 10 9of ~Celite suspended in 0.5 dm3 of toluene was built up on the filter mesh of a 2 I pressure suction filter. The polymer solution was filtered through the pressure suction filter, with a nitrogen pressure of about 1 bar being developed.
The clear solution was introduced into 5 dm3 of acetone using a disperser (from Kotthoff). The solid was isolated by filtration, dispersed twice in acetone and then dried at 100C and under reduced pressure (0.2 bar) for 15 hours. 85 9 of polymer was obtained, comprising 50 mol% of ethylene, 44 mol% of norbornene and 6 mol% of vinylnorbornene repeating units. The glass transition temperature was 151 C and eta was 0.23 dl/g (DIN 53728). Mw = 11,500 g/mol and MW/Mn = 2.1. An iodine number of 16.2 was determined (EG =
1587 g/mol C=C).
Examples 4-6 describe the preparation of functionalized COCs Example 4 80 9 (0.65 mol) of COC from Example 1 are dissolved in a mixture of 500 ml of chloroform and 50 ml of methanol. The solution is cooled to a temperature of 215~693 from -7 to -10C. This temperature is also maintained during the gassing with ozone which follows. At a flow rate of 100 liters per hour and at an ozone concentration of from 49 to 61 g of ozone per cubic meter of oxygen, a quantity of ozone which is equimolar with the double bond content of the COC
5 is passed in. The ozone is prepared with an ozone generator (model 503 from Fischer in Mekkenheim, Bonn, and ozone meter, Ozontron 23 from the same manufacturer) in dry air or oxygen. After the end of gassing, a further 85 ml ofmethanol are added at -5C and then 43 ml of peracetic acid at 0C.
Subsequently, the temperature is slowly raised to 50C. At this temperature, 10 the reaction solution is stirred for 2 hours. lt is then cooled, washed with 200 ml of water and heated at reflux with 100 ml of water for one hour. The aqueous phase is separated off and the organic phase is washed with 100 ml of water. The carboxy-functionalized COC is isolated by precipitation with acetone followed by drying under vacuum at mild temperatures.
Product weight: 82 g; iodine number: < 1; acid number: 35 Example 5 50 9 (0.41 mol) of COC from Example 2 are dissolved in a mixture of 500 ml of chloroform and 50 ml of methanol. The solution is cooled to a temperature of from -7 to -10C. This temperature is also maintained during the gassing with ozone which follows. At a flow rate of 100 liters per hour and at an ozone concentration of from 49 to 61 g of ozone per cubic meter of oxygen, a quantity of ozone which is equimolar with the double bond content of the COC
is passed in. The ozone is prepared with an ozone generator (model 503 from Fischer in Mekkenheim, Bonn, and ozone meter, Ozontron 23 from the same manufacturer) in dry air or oxygen. After the end of gassing, a further 85 ml ofmethanol are added at -5C and then 43 ml of peracetic acid at 0C.
Subsequently, the temperature is slowly raised to 50C. At this temperature, the reaction solution is stirred for 2 hours. lt is then cooled, washed with 200 ml of water and heated at reflux with 100 ml of water for one hour. The aqueous phase is separated off and the organic phase is washed with 100 ml of water. The carboxy-functionalized COC is isolated by precipitation with acetone 21~4543 followed by drying under vacuum at mild temperatures.
Product weight: 53 9, iodine number: < 1; acid number: 90 Example 6 75 9 (0.61 mol) of COC from Example 3 are dissolved in a mixture of 500 ml of chloroform and 50 ml of methanol. The solution is cooled to a temperature of from -7 to -10C. This temperature is also maintained during the gassing with ozone which follows. At a flow rate of 100 liters per hour and at an ozone concentration of from 49 to 61 9 of ozone per cubic meter of oxygen, a quantity of ozone which is equimolar with the double bond content of the COC
is passed in. The ozone is prepared with an ozone generator (model 503 from Fischer in Mekkenheim, Bonn, and ozone meter, Ozontron 23 from the same manufacturer) in dry air or oxygen. After the end of gassing, a further 85 ml ofmethanol are added at -5C and then 43 ml of peracetic acid at 0C.
Subsequently, the temperature is slowly raised to 50C. At this temperature, the reaction solution is stirred for 2 hours. lt is then cooled, washed with 200 ml of water and heated at reflux with 100 ml of water for one hour. The aqueous phase is separated off and the organic phase is washed with 100 ml of water. The carboxy-functionalized COC is isolated by precipitation with acetone followed by drying under vacuum at mild temperatures.
Product weight: 78 9; iodine number: < 1 Investigating the adhesion properties of the functionalized COCs prepared 10 9 of each of the polymers from Examples 4-6 are dissolved in 100 ml of toluene at 80C and the solutions are knife-coated onto glass plates or steel plates or polypropylene plates respectively. These plates are dried initially atroom temperature for 4 h in a convection drying cabinet and then at 80C for 24 h in a vacuum drying cabinet.
In order to assist the adhesion of these films to the various substrates, the following qualitative tests are carried out:
a: Fingernail test: testing for mechanical detachment of the film using the fingernail.
b: ~Tesa-Film test: testing for mechanical detachment of the film by removal, with a sharp jerk, of a stuck-on section of ~Tesa-Film (Scotch tape test).
c: Cross-hatch test: the films are marked a number of times in a crosswise pattern using a sharp knife. Subsequently, the film is tested for mechanical detachment by removal, with a sharp jerk, of a section of ~Tesa-Film stuck on to this cross-hatch.
The results of these tests are compiled in Table 1. The table also gives the results for the unmodified COCs.
Table 1: Investigating the adhesion properties of COC films ExampleCOC Substrat Fingernail Scotc Cross-e test h tape hatch 7 COC IV glass + + + + + +
8 COC IV steel + + + + + +
9 COC lV PP ++ ++ ++
COC V glass + + + + + +
11 COC V steel + + + + + +
12 COCV PP ++ ++ ++
13 COC Vl glass + + + + + +
14 COC Vl steel + + + + + +
COC Vl PP + + + + + +
16 COC I glass -- -- --17 COC I steel -- -- --19 COC ll glass -- -- --COC ll steel -- -- --21 COC ll PP -- -- --20 Key to Table 1:
Polymer from Example 1 = COC I
Polymer from Example 2 = COC ll Polymer from Example 3 = COC lll 21~613 Polymer from Example 4 = COC IV
Polymer from Example 5 = COC V
Polymer from Example 6 = COC Vl 5 + + = very good adhesion. The films withstand the test method indicated without damage.
-- = very poor adhesion. The films are partially destroyed by the test method ind icated .
The polypropylene sheet used was a 200*50 mm sheet of commercial EPDM-modified polypropylene from Hoechst AG.
Claims (10)
1. A cycloolefin copolymer having a solution viscosity (eta) < 0.25 dl/g (measured in accordance with DIN 53728 in decalin at 135°C), which comprises polymerized units (A) of at least one cyclic olefin and (B), if desired, of one or more acyclic olefins, wherein (C) polymerized units are present which contain at least one functionalized structural unit which a) is derived from a cyclic olefin and contains at least one heteroatom which is attached directly to a ring atom of the cyclic olefin, or b) is derived from a cyclic or acyclic olefin and contains at least one group of atoms which has two heteroatoms both of which are attached to the same carbon atom, or c) is derived from a cyclic or acyclic olefin and contains at least one aldehyde group, or d) is derived from a cyclic or acyclic olefin and contains at least one group of atoms in which a nitrogen atom is attached via a double bond to a carbon atom, and, where the functionalized structural unit is derived from a cyclic olefin, exactly two adjacent carbon atoms of this functionalized cyclic structural unit are incorporated into the polymer main chain.
2. A cycloolefin copolymer as claimed in claim 1, which contains 0.1-99.89 % by weight, based on the overall mass of the cycloolefin copolymer, of polymerized units (A) of at least one cyclic olefin, 0-80 % by weight, based on the overall mass of the cycloolefin copolymer of polymerized units (B) of at least one acyclic olefin, and 0.01-50 % by weight, based on the overall mass of the cycloolefin copolymer, of polymerized units (C) which contain at least one functionalized structural unit.
3. A cycloolefin copolymer as claimed in claim 1 or 2, wherein the polymerized units (A) are derived from at least one compound of the formulae (I), (II), (III), (IV), (V), (VI) and (VII) (I), (II), (III), (IV), (V), (VI), (VII), in which R1, R2, R3, R4, R5, R6, R7 and R8 are identical or different and are a hydrogen atom or a C1-C30-hydrocarbon radical, such as a C1-C8-alkyl group or a C6-C14-aryl group, where identical radicals in the different formulae may have different meanings, and n is a number from 2 to 10.
4. A cycloolefin copolymer as claimed in one or more of claims 1 to 3, wherein the polymerized units (B) are derived from an .alpha.-olefin having 2 to20 carbon atoms.
5. A cycloolefin copolymer as claimed in one or more of claims 1 to 4, wherein the polymerized units (C) are derived from at least one compound of the formulae (XIV), (XV), (XVI), (XVII), (XVIII) and (XIX) (XIV) (XV) (XVI) (XVII) (XVIII) (XIX) in which R22 is a carbonyl group, a hydroxyiminomethyl group, a hydrazonomethyl group or a semicarbazonomethyl group and R16, R17, R18, R19, R20 and R21 are identical or different, identical radicals in the differentformulae may have different meanings and are hydrogen, a C1-C30-hydrocarbon radical, a primary, secondary or tertiary amino group, a substituted or unsubstituted ammonium group, a hydroxyl group, an alkyloxy group, an aryloxy group, an aralkyloxy group or a group -(X)p-Y in which X is a branched or unbranched C2-C20-alkylene group or a branched or unbranched C8-C20-arylalkylene group and p = 0 or 1 and Y is a carboxyl group, an alkyloxycarbonyl group, a carbamoyl group, a mono- or bisalkyl-carbamoyl group, a chloroformyl group, an acyloxycarbonyl group, a thio-carboxy group, an alkylthiocarbonyl group, a formyl group, an alkylformyl group, a hydroxybis(alkyloxy)methyl group, a tris(alkyloxy)methyl group, a hydroxyiminomethyl group, a hydrazonomethyl group or a semicarbazono-methyl group, where in the formulae (XIV) and (XVIII) at least one of the radicals R16, R17, R18, R19, R20 and R21, in the formulae (XV), (XVI) and (XIX) at least two of the radicals R16, R17, R18, R19, R20 and R21, and in formula (XVII) none of the radicals R16, R17, R18, R19, R20 and R21 is or are a group -(X)p-Y, a primary, secondary or tertiary amino group, a substituted or unsubstituted ammonium group, a hydroxyl group, an alkyloxy group, an aryloxy group or an aralkyloxy group, where in the formulae (XV) and (XVI) p = 0 when R20 or R21 is a group -(X)p-Y and in formula (XIX) R20 and R21 are not hydrogen or a C1-C30-hydrocarbon radical.
6. A cycloolefin copolymer as claimed in one or more of claims 1 to 5, wherein the polymerized units (C) are derived from compounds of the formulae (XIV) to (XIX) in which R22 is a carbonyl group and R16, R17, R18, R19, R20 and R21 are identical or different, identical radicals in the different formulae may have different meanings and are a primary, secondary or tertiary amino group, a hydroxyl group or a group -(X)p-Y in which X is a branched or unbranched C2-C20-alkylene group or a branched or unbranched C8-C20-arylalkylene group and p = 0 or 1 and Y is a carboxyl group or a formyl group, where in the formulae (XIV) and (XVIII) at least one of the radicals R16, R17, R18, R19, R20 and R21, in the formulae (XV), (XVI) and (XIX) at least two of the radicals R16, R17, R18, R19, R20 and R21, and in formula (XVII) none of the radicals R16, R17, R18, R19, R20 and R21 is or are a primary, secondary or tertiary amino group, a hydroxyl group or a group -(X)p-Y and in the formulae (XV) and (XVI) p =
0 if R20 or R21 is a group -(X)p-Y.
0 if R20 or R21 is a group -(X)p-Y.
7. A process for the preparation of a cycloolefin copolymer having a solution viscosity (eta) < 0.25 dl/g (measured in accordance with DIN 53728 in decalin at 135°C), which comprises polymerized units (A) of at least one cyclic olefin and (B), if desired, of one or more acyclic olefins, and (C) polymerized units are present which contain at least one functionalized structural unit which a) is derived from a cyclic olefin and contains at least one heteroatom which is attached directly to a ring atom of the cyclic olefin, or b) is derived from a cyclic or acyclic olefin and contains at least one group ofatoms which has two heteroatoms both of which are attached to the same carbon atom, or c) is derived from a cyclic or acyclic olefin and contains at least one aldehyde group, or d) is derived from a cyclic or acyclic olefin and contains at least one group ofatoms in which a nitrogen atom is attached via a double bond to a carbon atom, and, where the functionalized structural unit is derived from a cyclic olefin, exactly two adjacent carbon atoms of this functionalized cyclic structural unit are incorporated into the polymer main chain, which comprises reacting a cycloolefin copolymer containing double bonds in an inert solvent with ozone.
8. The process as claimed in claim 7, wherein the cycloolefin copolymer containing double bonds contains 0.1-99.9% by weight of polymerized units of a cycloolefin of the formula (I), (II), (III), (IV), (V), (VI) or (VII) ( I ), (II), ( I I I ) (IV), ( V ) , (VI), (VII) 0-80% by weight, based on the overall mass of the cycloolefin copolymer, of polymerized units of at least one acyclic monoolefin, and 0.1-99.9% by weight, based on the overall mass of the cycloolefin copolymer, of polymerized units of at least one olefin which has at least one double bond, preferably of at least one olefin of the formulae (VIII), (IX), (X), (XI), (XII) and (XIII) (VIII) (IX) ( X ) (X I ) (X I I ) (XIII)
9. A coating material comprising at least one cycloolefin copolymer as claimed in one or more of claims 1 to 6 and, if desired, one or more binders, conventional paint additives, pigments and/or fillers.
10. An adhesion promoter comprising at least one cycloolefin copolymer as claimed in one or more of claims 1 to 6.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4426399A DE4426399A1 (en) | 1994-07-26 | 1994-07-26 | Cycloolefin copolymers and a process for their preparation |
| DEP4426399.6 | 1994-07-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2154643A1 true CA2154643A1 (en) | 1996-01-27 |
Family
ID=6524145
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002154643A Abandoned CA2154643A1 (en) | 1994-07-26 | 1995-07-25 | Cycloolefin copolymers and a process for their preparation |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0694567A2 (en) |
| JP (1) | JPH0859744A (en) |
| KR (1) | KR960004385A (en) |
| CN (1) | CN1122341A (en) |
| AU (1) | AU2507995A (en) |
| CA (1) | CA2154643A1 (en) |
| DE (1) | DE4426399A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19905093A1 (en) * | 1999-02-01 | 2000-08-03 | Ivoclar Ag Schaan | Low shrinkage dental materials |
| US6403742B2 (en) | 1999-12-27 | 2002-06-11 | Jsr Corporation | Olefin copolymer having functional group, production process thereof and rubber composition |
| EP1138595A1 (en) * | 2000-03-30 | 2001-10-04 | Tetra Laval Holdings & Finance SA | Packaging machine for producing sealed packages of a pourable food and featuring a level detecting device |
| US6713582B2 (en) | 2001-12-14 | 2004-03-30 | Uniroyal Chemical Company, Inc. | Process for the oligomerization of α-olefins having low unsaturation, the resulting polymers, and lubricants containing same |
| US8057852B2 (en) | 2006-11-23 | 2011-11-15 | National Research Council Of Canada | Microdevice for a fluorescence-based assay, and a method for making the microdevice |
| JP5551263B2 (en) * | 2010-10-06 | 2014-07-16 | 三井化学株式会社 | Cyclic olefin copolymer and cross-linked product thereof |
| DE102011015150A1 (en) * | 2011-03-25 | 2012-09-27 | Evonik Degussa Gmbh | Syntesis of alpha, omega-dicarboxylic acids and their esters from unsaturated fatty acid derivatives |
| JP7168412B2 (en) * | 2017-10-31 | 2022-11-09 | 三井化学株式会社 | Cyclic olefin copolymer, cyclic olefin copolymer composition and crosslinked product |
| JP7218176B2 (en) * | 2018-12-27 | 2023-02-06 | 三井化学株式会社 | Cyclic olefin copolymer, cyclic olefin copolymer composition and crosslinked product |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4082493A (en) | 1977-01-19 | 1978-04-04 | Cam-Stat Incorporated | Gas burner control system |
| CA1278899C (en) | 1985-05-24 | 1991-01-08 | Mitsui Chemicals, Inc. | Random copolymer, and process for production thereof |
| US5003019A (en) | 1987-03-02 | 1991-03-26 | Mitsui Petrochemical Industries, Ltd. | Cyclo-olefinic random copolymer, olefinic random copolymer, and process for producing cyclo-olefinic random copolymers |
| JP3016561B2 (en) | 1989-04-12 | 2000-03-06 | ジェイエスアール株式会社 | Heat resistant resin composition |
| JP2940014B2 (en) | 1989-05-08 | 1999-08-25 | ジェイエスアール株式会社 | Thermoplastic resin composition |
| DE3922546A1 (en) | 1989-07-08 | 1991-01-17 | Hoechst Ag | METHOD FOR THE PRODUCTION OF CYCLOOLEFINPOLYMERS |
| JPH03106962A (en) | 1989-09-20 | 1991-05-07 | Japan Synthetic Rubber Co Ltd | Thermoplastic resin composition |
| JPH05279412A (en) | 1992-04-03 | 1993-10-26 | Mitsubishi Petrochem Co Ltd | Production of modified copolymer |
| JPH05306311A (en) | 1992-04-30 | 1993-11-19 | Mitsubishi Petrochem Co Ltd | Production of graft-modified copolymer |
| DE4344631A1 (en) | 1993-12-24 | 1995-06-29 | Hoechst Ag | Stereo-rigid metallocenes useful in catalyst for cyclo-olefin copolymer prodn. |
| DE4344516C2 (en) | 1993-12-24 | 1997-08-07 | Herberts Gmbh | Binders based on peroxygenated cycloolefinic copolymers, their production and their use |
| DE4344515C2 (en) | 1993-12-24 | 1998-01-29 | Herberts Gmbh | Binding agents based on cycloolefinic copolymers, their production and their use |
-
1994
- 1994-07-26 DE DE4426399A patent/DE4426399A1/en not_active Withdrawn
-
1995
- 1995-07-11 EP EP95110784A patent/EP0694567A2/en not_active Withdrawn
- 1995-07-19 AU AU25079/95A patent/AU2507995A/en not_active Abandoned
- 1995-07-24 CN CN95108630A patent/CN1122341A/en active Pending
- 1995-07-25 KR KR1019950021977A patent/KR960004385A/en not_active Application Discontinuation
- 1995-07-25 CA CA002154643A patent/CA2154643A1/en not_active Abandoned
- 1995-07-26 JP JP7190408A patent/JPH0859744A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0859744A (en) | 1996-03-05 |
| DE4426399A1 (en) | 1996-02-01 |
| EP0694567A2 (en) | 1996-01-31 |
| AU2507995A (en) | 1996-02-08 |
| KR960004385A (en) | 1996-02-23 |
| CN1122341A (en) | 1996-05-15 |
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