DE69118378T2 - Polymers containing cyclic carbonyl groups - Google Patents

Description

The present invention relates to novel polymers which are adducts of cyclic carbonyl monomers or derivatives.

Various unsaturated hydrocarbon polymers have been reacted with maleic anhydride to form a variety of maleic anhydride adducts of unsaturated hydrocarbon polymers. The reactivity of maleic anhydride with many unsaturated hydrocarbon polymers is poor and in some cases, such as with EPDM rubber, even the use of intense heating is ineffective. Free radical reactions which graft maleic anhydride to the unsaturated hydrocarbon polymer have been used as alternative routes. Free radical grafting results in chain scission, crosslinking and solvent grafting if the solvent is sufficiently reactive. The present invention seeks to overcome these deficiencies.

GB-A-1 009 785 describes a synthetic ketone resin which is prepared by reacting a synthetic rubber such as polybutadiene or a butadiene/styrene copolymer with a cyclic ketone such as methylcyclohexanone and an aldehyde such as formaldehyde. The reaction is carried out in the presence of methyl alcoholic alkali solution.

The present invention relates to novel polymers useful as solution viscosifiers. The novel polymers are prepared by reacting a cyclic carbonyl monomer having ene-reactive carbonyl groups with an unsaturated hydrocarbon to form a novel cyclic carbonyl-containing polymer having a Mn of from about 500 to about 10⁷.

The novel polymers of the invention, which are adducts of cyclic carbonyl monomers or derivatives with unsaturated organic molecules, are prepared by contacting the cyclic carbonyl monomers A and/or B with an unsaturated polymer to form the novel product. In particular, the unsaturated polymer may be a polyolefin polymer having a Molecular weight in the range of about 500 to about 10,000,000.

Typical reactions for the preparation of these new cyclic carbonyl polymers are given by the equations

wherein Ra, Rb, Rc, Rd and Re are independently selected from the group consisting of H, alkyl groups having 1 to 10⁷ carbon atoms, alkenyl groups having 3 to 10⁷ carbon atoms, wherein the alkyl and/or alkenyl groups may have one or more substituents selected from the groups consisting of alkoxy, aryloxy, Cl, CN, OH, acyl, aroyl, acyloxy, aryl and HO(CH₂CH₂O)x, where x = 1 to 10; Q = H₂O, MeOH, EtOH, n-BuOH or any suitable alcohol; n = 0, 1, > 1; and X and Y are independently selected from the group consisting of CH₂, C=O, C=NOH, provided that X and Y are not both CH₂ are; U, V and W are independently selected from the group consisting of CH₂, C=O, C=NH, C=N-alkyl, wherein the alkyl group has 1 to 18 carbon atoms ; O, NH, N-alkyl, S, C=S, CMe₂, CH-phenyl, CH-CHOH-CH₂OH; U + V = 1,2-phenylene, 1,8-naphthalenediyl, 1,2-naphthalenediyl and 1,2-dihydroxyethylene-1,2-diyl.

Typical monomers include alloxan, indantrione, tetralintrione, dehydroascorbic acid, rhodizonic acid and croconic acid, trichinoyl, Leuconic acid and keto-Meldrum's acid (A, where X = Y = C=O, U = W = O and V = CMe₂).

The acyclic carbonyl monomer is reacted at about 20°C to about 200°C, more preferably about 40 to about 180°C, and most preferably about 60 to about 160°C.

It is heated under reflux conditions at about 100°C for about 4 to about 24 hours, preferably about 6 to about 18 hours, and most preferably about 8 to about 12 hours with an unsaturated hydrocarbon, wherein the hydrocarbon is selected from EPDM terpolymers, EPR, polyisoprene, polybutadiene, butyl rubber, random and block copolymers of styrene/butadiene and styrene/isoprene, polyisobutylene, hydrocarbon resins such as Escorez® resins. Oligomers or polymers having olefin functionality near the end of the chain are of interest. Such molecules include, but are not limited to, polyisobutene and polybutenes of varying molecular weights. Vistanex and Vistanex J are examples of such polymers. Plastics such as polyethylene and polypropylene, which contain low levels of unsaturation, are also suitable polyolefins.

Olefins substituted with functionality such as CN, HO, HO(CH2CH2O)x (x = 1 to 10), alkoxy, Cl, and other groups illustrated below are examples of useful reactants.

, where G = C, N; J = O, S, SO₂; and L is selected from OH, -OR₁, NR₁R₂, R₁, where R has about 1 to about 18 carbon atoms,

, where R₂ is any alkyl and has 1 to 18 carbon atoms, -NR₃R₄, where R₃ and R₄ have 1 to 18 carbon atoms, -OR₅, where R₅ is hydrogen or an alkyl group having 1 to 18 carbon atoms, -COOR₆, where R₆ is hydrogen or an alkyl group having 1 to 18 carbon atoms, and -SR₇, where R₇ is an alkyl group having 1 to 18 carbon atoms.

The term "butyl rubber" as used in the specification and claims is intended to include copolymers prepared from a polymerization reaction mixture containing 70 to 99.5 weight percent of an isobutylene and about 0.5 to 30 weight percent of a conjugated multiolefin having about 4 to 14 carbon atoms, e.g., isoprene. The resulting copolymer typically contains 85 to 99.8 weight percent combined isoolefin and 0.2 to 15 weight percent combined multiolefin.

The EPDM terpolymers are weakly unsaturated polymers with about 0.5 to about 10.0 wt.% olefinic unsaturation, more preferably from about 2 to about 8, most preferably from about 3 to 7, weight percent olefinic unsaturation as defined in ASTM-1418-64, and is intended to mean terpolymers containing ethylene and propylene in the backbone and an olefin residue in the side chain as a result of the incorporation of multiolefin into the backbone. Illustrative processes for preparing these terpolymers can be found in US-A-3,280,082, GB-A-1,030,289, and FR-A-1,386,600. The preferred polymers contain from about 40 to about 75 weight percent ethylene and from about 1 to about 10 weight percent of a diene monomer, the balance of the polymer being propylene. Preferably, the polymer contains from about 45 to about 70 weight percent ethylene, e.g. B. 50 wt.%, and about 2.6 to about 8.0 wt.% diene monomer, e.g. 5.0 wt.%. The diene monomer is preferably a non-conjugated diene.

Examples of these non-conjugated diene monomers that can be used in the terpolymer (EPDM) are 1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-propenylnorbornene, methyltetrahydromdene and 4-methyl-5-methylene-2-norbornene.

The EPDM terpolymers of the present invention have a number average molecular weight (Mn) as measured by GPC of from about 10,000 to about 200,000, more preferably from about 15,000 to about 100,000, most preferably from about 20,000 to about 60,000. The Mooney viscosity (ML, 1+8, 212°F) of the EPDM terpolymer is from about 5 to about 60, more preferably from about 10 to about 50, most preferably from about 15 to about 40. The Mv, as measured by GPC of the EPDM terpolymer is preferably less than about 350,000, and more preferably less than about 300,000. The Mw, as measured by GPC of the EPDM terpolymer is preferably less than about 500,000, and more preferably less than about 350,000.

Other suitable olefin polymers include polymers comprising a major molar amount of C2 to C5 monoolefins, e.g., ethylene, propylene, butylene, isobutylene and pentene. The polymers may be homopolymers such as polyisobutylene as well as copolymers of two or more such olefins, such as copolymers of ethylene and propylene, butylene and isobutylene, propylene and isobutylene.

The reaction of the cyclic carbonyl monomer with the unsaturated hydrocarbon polymer can take place in solution, in a melt, and in polymer processing equipment such as a rubber mill, a Brabender, an extruder, or a Banbury mixer.

Typically, the polymer is dissolved in a suitable solvent, such as tetrahydrofuran, xylene or mineral oil, and heated to temperatures ranging from about 40°C to about 140°C. The cyclic carbonyl monomer as a hydrate or hemiketal of methanol or butanol or a suitable alcohol is dissolved in a suitable solvent, such as tetrahydrofuran, dioxane, butanol or a suitable alcohol and gradually added to the heated butanol solution. The reaction mixture is heated with stirring until infrared and/or NMR analysis of the mixture shows that ene addition of the carbonyl monomer to the unsaturated polymer is complete. Depending on temperature and concentration, reaction times of about 4 to 40 hours are sufficient to achieve high conversions to ene adducts.

Bulk reactions (reactions in the bulk phase) can be carried out at about 40ºC to about 200ºC for approximately 3 to 300 minutes, depending on the reactivity of polyolefin and carbonyl monomer.

If necessary, the products can be isolated by solvent removal by evaporation, or by adding the reaction mixture to a polar solvent such as acetone, which leads to the precipitation of the functionalized polymer.

If desired, the ene additions of cyclic carbonyl monomers to unsaturated hydrocarbon polymers can be effected in the presence of acid catalysts selected from the group consisting of kaolin, montmorillonite, silicates, SnCl₄, AlCl₃, FeCl₃ and BF₃.

Typically, 0.1 to 1 gram of acid catalyst is used per 0.01 to 1.0 mole of reactants.

The following examples illustrate the present invention without, however, limiting it thereto.

example 1

10 g of warm polyisobutylene, Mn = 950, was poured into a nitrogen-covered reactor equipped with a mechanical stirrer, thermometer and condenser. The polyisobutylene was heated to about 150°C in an oil bath and 1.6 g of alloxan monohydrate dissolved in 20 mL of dioxane was added dropwise to the stirred polymer over a period of 4 hours. Heating of the reaction mixture to 150°C was continued for about 10 hours. When cooled, the residue was dissolved in about 100 mL of cyclohexane, filtered through Celite and concentrated by bubbling with nitrogen overnight. Analysis of the residue showed 1.84% N and showed an infrared spectrum with a dominant carbonyl absorption band at about 5.85 µm. UV-GPC analysis showed that the polyisobutylene polymer was uniformly substituted with alloxan and that the MW distribution of the polyisobutylene was not affected by the ene modification.

Example 2

10 g of poly-co-ethylene/propylene/ethylidene norbornene terpolymer, Mn = 55,000, containing about 43 wt% propylene and 5 wt% ethylidene norbornene, were dissolved in 90 g of xylene and poured into a nitrogen-blanketed reactor equipped with a mechanical stirrer and reflux condenser.

Using a silicone oil bath, the reactor was heated to 120°C and 0.5 g of alloxan hydrate dissolved in 30 mL of dioxane was added all at once to the xylene solution of the terpolymer. The reaction mixture was stirred at 120°C for about 8 hours. The functionalized polymer was precipitated by adding the cooled reaction mixture to one liter of acetone. Analysis of the dried polymer showed 0.76% N and an infrared spectrum (film) with an intense carbonyl absorption band at about 5.9 µm. GPC analysis showed that, in contrast to conventional free radical methods, ene functionalization with alloxan did not affect the MW distribution of the terpolymer.

Example 3

10 g of polyisobutylene, MW = 950, and 2 g of indantrione hydrate were combined in a nitrogen-blanketed reactor equipped with a mechanical stirrer and condenser. The stirred mixture was heated in an oil bath at 140°C to 150°C for about 28 h, then cooled and dissolved in 100 mL of cyclohexane. The mixture was filtered through celite and concentrated by evaporation using a nitrogen concentrate. Analysis of the residue showed 3.96% O and the residue showed an infrared spectrum with an intense carbonyl absorption band at about 5.9 µm.

Example 4

10 g of poly-co-ethylene/propylene/ethylidene norbornene terpolymer, MN = 55,000, containing about 43 wt% propylene and 5 wt% ethylidene norbornene was dissolved in 90 g of Mylol and introduced into a nitrogen-blanketed reactor equipped with a mechanical stirrer and reflux condenser. The stirred mixture was heated to about 120°C in an oil bath and then 0.5 g of indantrione hydrate dissolved in 30 mL of 1,4-dioxane was added to the reactor in one portion. The reaction mixture was kept at 120°C for about 6 hours, then cooled and a 10 mL portion was added to 100 mL of acetone. The precipitated polymer was washed with acetone and dried under high vacuum at about 40°C. The analysis of the modified polymer showed 1.74% O and the modified polymer showed an infrared spectrum dominated by an intense carbonyl absorption at about 5.9 µm.

Similarly, the modification of terpolymer with indantrione was also accomplished in other solvents, such as tetrahydrofuran.

Claims (5)

1. Cyclic carbonyl adduct of an unsaturated hydrocarbon polymer, wherein the cyclic carbonyl component is selected from cyclic carbonyl compounds represented by the formulas wherein X or Y is independently selected from CH₂, C=O, C=NOH, provided that X and Y are not both CH₂; U, V and W are independently selected from the group consisting of CH₂, C=O, C=NH, C=N-alkyl, wherein the alkyl group has 1 to 18 carbon atoms, O, NH, N-alkyl, S, C=S, CMe₂, CH-phenyl, CHCHOH-CH₂OH; U + V = 1,2-phenylene, 1,8-naphthalenediyl, 1,2-naphthalenediyl and 1,2-dihydroxyethylene-1,2-diyl. 2. Adduct according to claim 1, wherein the unsaturated hydrocarbon polymer is selected from the group consisting of ethylene/propylene terpolymers, ethylene/propylene copolymers, polyisoprene, butyl rubber, polybutadiene and random copolymers and block copolymers of styrene/butadiene and styrene/isoprene, polypropylenes and polyisobutylenes, as well as plastic polypropylene copolymers or polyethylene copolymers. 3. Adduct according to claim 1, wherein the unsaturated hydrocarbon polymer has substituents such as CN, HO, HO(CH₂CH₂O)x (x = 1 to 10), alkoxy, Cl, , where G = C, N; J = O, S, SO₂; and L is selected from OH, -OR₁, NR₁R₂, R₁, where R has about 1 to about 18 carbon atoms, wherein R2 is any alkyl and has from about 1 to about 18 carbon atoms, -NR3R4, wherein R3 and R4 have from about 1 to about 18 carbon atoms, OR5, wherein R5 is hydrogen or an alkyl group having from about 1 to about 18 carbon atoms, -COOR6, wherein R6 is hydrogen or an alkyl group having from about 1 to about 18 carbon atoms, and -SR7, wherein R7 is an alkyl group having from about 1 to about 18 carbon atoms. 4. An adduct according to any preceding claim formed by contacting the unsaturated hydrocarbon polymer with a cyclic carbonyl compound selected from , where Q = H₂O, MeOH, EtOH, n-BuOH; n = 0, 1, > 1; X or Y are independently selected from CH₂, C=O, C=NOH with the proviso that X and Y are not both CH₂; U, V and W are independently selected from the group consisting of CH₂, C=O, C=NH, C=N-alkyl, where the alkyl group has 1 to 18 carbon atoms, O, NH, N-alkyl, S, C=S, CMe₂, CH-phenyl, CHCHOH-CH₂OH; and U + V = 1,2-phenylene, 1,8-naphthalenediyl, 1,2-naphthalenediyl and 1,2-dihydroxyethylene-1,2-diyl. 5. Adduct according to one of the preceding claims, which is formed in the presence of an acid catalyst selected from the group consisting of kaolin, montmorillonite, silicates, SnCl₄, AlCl₃, FeCl₃ and BF₃.