WO2014197150A1

WO2014197150A1 - Cross-linkable cyclopentadiene epoxide oligomer compositions

Info

Publication number: WO2014197150A1
Application number: PCT/US2014/036770
Authority: WO
Inventors: Mun Fu Tse; Man Kit Ng; Kirk C. Nadler; Kathleen E. Edwards
Original assignee: ExxonMobil Chemical Patents Inc
Current assignee: ExxonMobil Chemical Patents Inc
Priority date: 2013-06-06
Filing date: 2014-05-05
Publication date: 2014-12-11
Anticipated expiration: 2015-12-06

Abstract

An adhesive blend made from a cyclopentadiene epoxide oligomer composition comprising the epoxidized oligomers of multi-cyclic conjugated dienes and a functionalized oligomer comprising functionality selected from the group consisting of a carboxylate group, a hydroxyl group, amine groups, and combinations thereof.

Description

TITLE; CROSS-LINKABLE CYCLOPENTADIENE EPOXIDE OLIGOMER

COMPOSITIONS

INVENTOR(S): Mun F. TSE, Man K. NG, Kirk C. NADLER, Kathleen E. EDWARDS

FIELD OF THE INVENTION

[0001] The present invention(s) relate to cyclopentadiene-type oligomer compositions that are epoxidized to enhance their use as heat curable adhesives, coatings and other applications.

BACKGROUND OF THE INVENTION

[0002] The applications for epoxy-based materials are very broad. They include paints and coatings, adhesives, and composite materials such as those using carbon fiber and fiberglass reinforcements. The chemistry of epoxies and the range of commercial variations allow cross-linked polymers to be produced with a very broad range of properties. In general, epoxies have excellent adhesion, chemical and heat resistance, good-to-excellent mechanical properties and very good electrical insulating properties. Variations offering high thermal insulation, or thermal conductivity combined with high electrical resistance for electronics applications, are available.

[0003] In US 5,095,046, Tse disclosed a curable hot melt adhesive system, which was a blend of acid- or hydroxyl-containing polyolefin, a tackifier, and an epoxide with functionality of at least two. The epoxide used was a prepolymer made by condensing epichlorodydrin and bisphenol A (2,2'-bis(4-hydroxyphenyl)propane) with degree of polymerization varied to produce liquids or solids which soften at temperatures up to 140°C. What would be useful is to develop a simpler cross-linkable epoxide tackifier with better properties.

[0004] Also related are EP 0 845 486 Al ; US 2008/132643; GB 0 882 147 A; GB 1 096 856 A; WO 2001/02382; PCT/US2013/060723; US 7,417,093 and US 7,622,534 which describe compositions with dicyclopentadiene type oligomers.

SUMMARY OF THE INVENTION

[0005] Described herein is an adhesive blend comprising the epoxidized oligomers of multi-cyclic conjugated dienes, and a functionalized oligomer/polymer comprising functionality selected from the group consisting of a carboxylate groups, a hydroxyl groups, amine groups, and combinations thereof. An example of the epoxidation is as follows: other epoxidized

oligomers cyclopentadiene oligomer . . .. . . ..

cyclopentadiene epoxide oligomer composition (CEOC)

[0006] The cross-linked ("cross-linked" or "cured" can be used interchangeably as used herein, but "cross-linked" will be used hereinafter) CEOC/functionalized oligomer compositions have many desirable uses such as adhesives, hot melt adhesives, encapsulating media, coatings and paint additives, and as additives in compositions suitable as adhesives and coatings.

BRIEF DESCRIPTION OF THE DRAWING

[0007] Figure 1 is an ^lR NMR spectrum (400 MHz, CDC1₃) of a cyclopentadiene oligomer starting material obtained after steam stripping of solvent.

[0008] Figure 2 is an lH NMR spectrum (400 MHz, CDC1₃) of the crude CEOC product obtained after roto-evaporation of solvent.

[0009] Figure 3 is a Dynamic Mechanical Thermal Analysis (DMTA) of the three molded plaques of Escor 5200.

[00010] Figure 4 is a DMTA curve of Escor™ 5200 blended with the cyclopentadiene oligomer.

[00011] Figure 5 is a DMTA curve of Escor 5200 blended with the CEOC.

[00012] Figure 6 is a comparison of storage modulus (Ε') curves of polymers in Figures

2-5.

[00013] Figure 7 is a comparison of stress-strain curves of polymers in Figures 2-5.

[00014] Figure 8 is a GC-FIMS of the example CEOC.

[00015] Figure 9 is an APPI-FTICR-MS of the example CEOC.

DETAILED DESCRIPTION

[00016] The present invention(s) relate to "epoxy" compositions, in particular, cyclopentadiene epoxide oligomer compositions ("CEOC") that are cross-linkable with functional polymers, making the resulting compositions suitable for curable, hot melt applications. When referring to "cyclopentadiene oligomers" or "cyclopentadiene epoxide oligomers" this may also refer to multi-cyclic structures, for instance, those commonly referred to as dicyclopentadiene oligomers, etc. In any case, the resulting CEOC's, when combined with functionalized oligomers or polymers, such as polyethylene acrylic acid copolymers or polyethyleneimines, will produce high modulus materials with a high strain at break.

[00017] More particularly, the epoxidized oligomers of cyclic or multi-cyclic conjugated dienes form the cyclopentadiene epoxide oligomer, wherein the multi-cyclic conjugated dienes are preferably selected from the group consisting of multiples of cyclopentadiene, for example: tetrahydroindene; methyltetrahydroindene; dicyclopentadiene (DCPD); bicyclo- (2,2, l)-hepta-2,5-diene; alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes such as 5-methylene-2-norbornene (MNB), 5-ethylidene-2-norbornene (ENB), 5-propenyl-2- norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene, 5-vinyl-2- norbornene (VNB), and combinations thereof, most preferably dicyclopentadiene.

[00018] Described another way, CEOC is as a composition comprising the following general structures (1):

wherein the "R" above the bracket represents that each structure can be substituted in any one, two, or three positions with the R group in place of a hydrogen, where the R group is a Ci to C₄ or CIQ alkyl or alkene; and where n is an integer from 1 or 2 to 8 or 10 or 12 or 16 or 20 or 30; wherein from 80 or 85 or 90 wt% to 95 or 98 wt% of the composition comprises components where n is within the range of from 3 or 4 to 14 or 16.

[00019] Desirably, the CEOC's have an average weight average molecular weight within the range of from 250 or 300 or 400 or 500 g/mole to 700 or 800 or 900 or 1000 or 5000 or 10,000 or 20,000 g/mole.

[00020] The CEOCs are derived from "cyclopentadiene oligomers" that are described further here. They are referred to as being "cross-linkable" or "curable" since the components of the CEOC can potentially be cross-linked to themselves, and adhesive blends (blends of CEOCs with functionalized oligomers or polymers) that include the CEOC's are also "cross-linkable" or "curable".

Cyclopentadiene Oligomers

[00021] The copolymeric materials which are epoxidized in accordance with the invention(s) herein are copolymers comprising (1) at least one a-olefin and/or olefin comonomer and (2) at least one cyclic or multi-cyclic diene-derived comonomer. Accordingly, for purposes of this invention, an "oligomer" is a material which is prepared by copolymerizing at least two different co-monomer types including the essentially present co- monomers derived from a-olefins and cyclic dienes. One or more other different comonomer types may also be included in the copolymers herein such that the copolymer definition includes terpolymers as well as copolymers comprising four or more different comonomer types.

[00022] The first a-olefin or olefin components utilized herein are generally those acyclic unsaturated materials comprising C2 to hydrocarbons. Such materials may be linear or branched and have one double bond in the alpha position. Illustrative non-limiting examples of preferred a-olefins and olefins are ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1- octene, piperylene, butadiene, or other linear conjugated dienes and 1-dodecene. Combinations of olefins may also be used, such as a combination of ethylene with piperylene, 1-octene, 1-hexene and/or 1-butene. The olefin(s) will generally be incorporated into the cyclopentadiene oligomers herein to the extent of from 5 or 10 or 20 mole% to 50 or 60 or 70 or 80 or 95 mole % of the cyclopentadiene oligomer.

[00023] The second component of the cyclopentadiene oligomers used in the epoxidation process herein comprises one or more diene-derived comonomers which are copolymerized with the olefin comonomers(s). Such dienes may be conjugated or non-conjugated cyclic structures. Typical non-limiting examples of non-conjugated dienes useful in the practice of this invention are:

(a) single-ring dienes such as: 1 ,4-cyclohexadiene; 1,5-cyclooctadiene; and 1,5- cyclododecadiene; and

(b) multi-cyclic fixed and fused ring dienes such as: tetrahydroindene; methyltetrahydroindene; dicyclopentadiene (DCPD); bicyclo-(2,2, l)-hepta-2,5-diene; alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes such as 5- methylene-2-norbornene (MNB), 5-ethylidene-2-norbornene (ENB), 5-propenyl-2- norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene, and 5-vinyl-2-norbornene (V B). [00024] When cyclopentadiene oligomers, which are high temperature elastomeric materials resistant to oil, are desired, flexible dienes are used to form the cyclopentadiene oligomers herein. Preferred flexible dienes include 7-methyl-l,6-octadiene; 1 ,4-hexadiene; and 4-vinyl-l-cyclohexene. When cyclopentadiene oligomers, which are rigid, structural polyolefins, are desired, rigid dienes are used to form the cyclopentadiene oligomers herein. Preferred rigid dienes include dicyclopentadiene (DCPD), 5-methylene-2-norbornene (MNB), and 5-ethylidene-2-norbornene (ENB). Dicyclopentadiene (DCPD) is the most preferred comonomer used to form the oligomers used in this invention. The cyclic or multi- cyclic comonomer will generally be incorporated into the cyclopentadiene oligomers herein to the extent of from 10 or 15 or 20 mole% to 55 or 60 or 70 or 85 or 90 mole% of the cyclopentadiene oligomer.

[00025] The cyclopentadiene oligomers may also optionally comprise additional ancillary comonomers, which are none of a-olefins, olefins or dienes. Such optional ancillary comonomers will generally be acyclic, monocyclic or polycyclic mono-olefins containing from 4 to 18 carbon atoms.

[00026] Preferred ancillary comonomers are the acyclic monoolefins, such as cyclohexene and cyclooctene, and the polycylic mono-olefins, such as those described in US 6,627,714, incorporated herein by reference. Specific examples of such polycylic mono-olefins include 2-norbornene, l,4,5,8-dimethano-l,2,3,4,4a,5,8,8a-octahydronaphthalene, 5-methyl-2- norbornene, 5-ethyl-2-norbornene, 5-propyl-2-norbornene, 5-phenyl-2-norbornene, 5-benzyl- 2-norbornene, 5-chloro-2-norbornene, 5 -fluoro-2 -norbornene, 5-chloromethyl-2-norbornene, 5-methoxy-2-norbornene, 7-methyl-2-norbornene, 5 -is obutyl-2 -norbornene, 5,6-dimethyl-2- norbornene, 5,5-dichloro-2-norbornene, 5,5,6-trimethyl-2-norbornene, 5,5,6-trifluoro-6- trifluoromethylnorbornene, 2-methyl-l, 4,5, 8-dimethano-l,2,3,4,4a,5, 8,8a- octahydronaphthalene, 2-ethyl-l,4,5,8-dimethano-l,2,3,4,4a,5,8,8a-octahydronaphthalene and 2,3-dimethyl-l,4,5,8-dimethano-l,2,3,4,4a,5,8,8a-octahydronaphthalene. The most preferred optional ancillary comonomers for use in preparing the cyclopentadiene oligomers are 2-norbornene and 5-methyl-2-norbornene.

[00027] The introduction of a third type of ancillary comonomer into the cyclopentadiene oligomers used herein permits one to adjust the thermal, optical or rheological characteristics (such as glass transition temperature) of these cyclopentadiene oligomers independently of the extent of functional characteristics of the copolymers introduced via epoxidation of the residual double bonds of the diene-derived comonomers. The resulting copolymer materials containing these ancillary commoners can thus be characterized as terpolymers comprising three distinct types of comonomers within their polymer structure. If utilized, the optional ancillary comonomers will generally comprise from 5 or 10 or 20 mole% to 50 or 60 or 70 or 85 mole%, of the cyclopentadiene oligomer.

[00028] For cyclopentadiene oligomers which are formed from rigid dienes (and optionally also rigid ancillary comonomers), the copolymer precursor component of the present invention will generally have a weight average molecular weight, M_w, of from 500 or

600 or 700 or 1000 g/mole to 2000 or 4000 or 10,000 or 20,000 g/mole, as measured versus polystyrene standards by Gel Permeation Chromatography analysis. As noted, weight average molecular weight for these copolymer materials can be determined in standard fashion using Gel Permeation Chromatography.

[00029] Commercial examples of desirable cyclopentadiene oligomers include Escorez™ resins from ExxonMobil Chemical Co.

[00030] These cyclopentadiene oligomers are epoxidized by methods known in the art to form the CEOC's of the invention, and most preferably by using organic oxidizing agents, such as 3-chloroperbenzoic acid. It is preferable to carry out the epoxidation in organic media, such as methylene chloride or other medium that is mildly dielectric, and with some cooling, or no heating, or gentle heating to 40 or 50°C.

Cross-linkable functionalized oligomer or polymer component

[00031] The CEOC's described herein are particularly useful as adhesives, coatings, encapsulating agents and other such uses when combined with a cross-linkable oligomer or polymer (hereinafter "oligomer"), which is typically a functionalized oligomer with a functional group that, when contacted under suitable conditions, will react with the epoxide moiety(s) of the CEOC's to form covalent bonds between the two oligomers or polymers. The functionalized oligomer, preferably, is one having a molecular weight of at least 400 or 500 or 800 or 1000 g/mole and comprising at least one carboxylate group, hydroxide group, amine group, halogen group, or some combination thereof. Preferably, the functionalized oligomer is selected from the group consisting of poly(vinyl alcohol), ethylene/vinyl alcohol copolymer, poly(propylene glycol) bis(2-aminopropyl ether), amine-terminated polybutadiene, amine-terminated butadiene/acrylonitrile copolymer, polyethyleneimines, acid anhydrides, thiols, phenols and polyphenols, and combinations thereof.

[00032] So called "suitable conditions" for cross-linking include radiant heating, exposure to radiation, exposure to air, or other means known in the art. The CEOC's may be reacted with themselves in the presence of an anionic catalyst (a Lewis base such as tertiary amines or imidazoles) or a cationic catalyst (a Lewis acid such as a boron trifluoride complex) to form a cross-linked network. This process is known as catalytic homopolymerisation. The resulting network contains only ether bridges, and exhibits high thermal and chemical resistance, but is brittle and often requires elevated temperature to effect curing, so it finds only niche applications industrially. Epoxy homopolymerisation is often used when there is a requirement for UV curing, since cationic UV catalysts may be employed.

[00033] Most desirably, the adhesive cyclopentadiene epoxide oligomer compositions are a combination of the CEOC and a polyethylene acrylic acid co-oligomer or copolymer, or "ethylene polymer." The ethylene polymer component possesses carboxylic acid functionality or is capable of modification to have carboxylic acid functionality. The ethylene polymer component may comprise a plurality of reactive species, for example, a hydroxyl functional polymer and a dicarboxylic acid anhydride, which react to provide an ethylene polymer with carboxylic acid functionality, or the ethylene polymer component may comprise a copolymer of ethylene and an α,β-ethylenically unsaturated carboxylic acid. In this latter embodiment of the invention, the ethylene-carboxylic acid copolymers will have polymerized therein at least 40 and preferably at least 60 wt% ethylene, with the balance of the copolymer being, for example, an α,β-ethylenically unsaturated carboxylic acid, and optionally one or more termonomers polymerizable therewith such as, for example, olefins, vinyl monomers, such as vinyl esters of carboxylic acids, and alkyl esters of α,β-ethylenically unsaturated carboxylic acids, and the like.

[00034] The α,β-ethylenically unsaturated carboxylic acid is preferably present in the copolymer in an amount of from 1 to 50 wt% of the copolymer, more preferably from 5 to 30 wt%, and particularly from 10 to 20 wt% of the copolymer. Specific representative examples of suitable α,β-ethylenically unsaturated carboxylic acids include acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, vinyl acetic acid, angelic acid, maleic acid, fumaric acid and the like. Of these, acrylic acid and methacrylic acid are preferred.

[00035] The melt viscosity of the ethylene copolymer is influenced primarily by molecular weight, termonomer content, and also by the acid content. The ethylene copolymer, preferably, has a melt index of at least 2 dg/min, more preferably at least 40 dg/min, and especially at least 100 dg/min at 190°C. As used herein, melt index (MI) is determined according to ASTM D-1238, condition E (190°C/2.16 kg), unless otherwise stated. The ethylene copolymer preferably has a 190°C Brookfield viscosity of from 100 to 7000 cps, more preferably from 100 to 3000 cps. As used herein, Brookfield viscosity is determined according to ASTM D-3236, unless otherwise stated. Particularly, preferred ethylene copolymers include ethylene-acrylic acid copolymer, ethylene-methyl acrylate-acrylic acid terpolymer and ethylene-vinyl acetate-acrylic acid terpolymer. The ester-containing terpolymers are preferred in applications wherein reduced stiffness at low temperature is desired.

[00036] The ethylene polymer component of the adhesive blends may also comprise a hydroxyl functional ethylene polymer, and a dicarboxylic acid anhydride is included with the composition. As hydroxyl functional ethylene polymers, there may be mentioned copolymers of ethylene and vinyl alcohol, hydroxyalkyl acrylates, and/or hydroxyalkyl methacrylates, preferably containing the hydroxyl functional comonomer in an amount of from 1 to 50 wt% of the copolymer, more preferably from 5 to 30 wt%, and particularly from 10 to 20 wt% of the copolymer. These ethylene-alcohol copolymers may further include up to 20 wt%, preferably up to 10 wt%, of an optional additional polymerized vinyl termonomer, preferably alkyl esters of ethylenically unsaturated carboxylic acids or vinyl esters of carboxylic acids, such as, for example, vinyl acetate, methyl acrylate, methyl methacrylate and the like. These copolymers may be obtained by interpolymerizing a mixture of the monomers, or by partial hydrolysis of copolymers of ethylene and vinyl acetate. Exemplary of the preferred ethylene-alcohol copolymers are ethylene-vinyl acetate-vinyl alcohol terpolymer (EVAVOH), ethylene/2-hydroxy ethyl acrylate copolymer (EHEA), ethylene/2- hydroxyethyl methacrylate copolymer (EHEMA), ethylene/methyl acrylate/2-hydroxy ethyl methacrylate terpolymer (EMAHEMA), and the like.

[00037] Dicarboxylic acid anhydrides may also be used in the adhesive blends with the ethylene-alcohol copolymers, there may be mentioned the commercially common phthalic anhydride, although other dicarboxylic anhydrides may be used such as, for example, maleic anhydride, pyromellitic dianhydride, dodecylsuccinic anhydride, 4-aminophthalic anhydride, and the like. The anhydride serves to convert the hydroxyl functionality of the ethylene polymer to carboxylic acid functionality for crosslinking by the epoxy crosslinking agent, and selection of the particular anhydride employed is not otherwise critical. The dicarboxylic anhydride is generally used in an amount to provide an equivalent ratio of anhydride groups to hydroxyl groups in the hydroxyl functional ethylene copolymer of from 0.1 : 1 to 10: 1, more preferably from 0.5: 1 to 2.5: 1 and especially from 0.9: 1 to 1.5: 1. The dicarboxylic acid anhydride is, preferably, microencapsulated by a high-melting (for example, in the range of 120°C to 140°C) microcrystalline wax, a high-melting natural wax, a non-reactive polyolefin material, or the like. Microencapsulation is discussed below in connection with the epoxy crosslinking agent. [00038] Commercial examples of desirable functionalized oligomers include Escor™ and Escorene™ resins from ExxonMobil Chemical Co.

Cross-linked adhesive/coating composition

[00039] The adhesive blends that include the blend of the CEOC and functionalized oligomer/polymer are uncross-linked blends until cross-linked. The CEOC is present in the composition within a range of from 5 or 8 or 10 or 15 wt% to 20 or 25 or 30 or 40 or 50 wt% of the composition (the blend of CEOC and functionalized oligomer/polymer).

[00040] The adhesive blends have many desirable properties, especially once "cross- linked". For example, the crystallization temperature T_c of the cross-linked composition, as measured by DSC, is within the range of from 20 or 25 or 30 or 35 or 40°C to 80 or 85 or 90 or 95°C. Also, the melting point temperature T_m of the cross-linked composition, by DSC, is within the range of from 60 or 65 or 70 or 75°C to 100 or 105 or 110 or 1 15°C. Further, the heat of fusion Hf of the cross-linked composition, by DSC, is within the range of from 10 or

15 or 20 or 25 or 30 J/g to 50 or 55 or 60 or 65 or 70 J/g.

[00041] The adhesive blend has many desirable Tensile properties as well as its thermal properties. For example, the cross-linked adhesive cyclopentadiene epoxide oligomer composition has a storage modulus (Ε') at 150°C of at least 10 or 20 or 40 or 80 or 100 kPa; preferably within a range from 10 or 20 or 40 or 80 kPa to 1.0 or 5.0 or 10.0 MPa. Also, the strain at break (e¾) of the cross-linked composition is greater than 90 or 100 or 1 10%, or within the range of from 90 or 100 or 1 10% to 140 or 150 or 160 or 200 or 250%. Finally, the tensile strength (σ¾) of the cross-linked composition is greater than 10 or 12 or 15 MPa, or within the range of from 10 or 12 or 15 MPa to 25 or 30 or 25 MPa. Significantly, the inventive cross-linked adhesive blends have a storage modulus that is the same or within 5 or 10 or 15% of the values above at a temperature of 200°C or 250°C. Also, the inventive cross- linked adhesive blends have a Nominal Stress value of from 15-20 MPa at a strain level of 100%, or a Nominal Stress value of from 18 or 20 MPa to 23 or 25 MPa at a strain level of 135%.

[00042] As mentioned, the cross-linked CEOC/functionalized oligomer compositions have many desirable uses, such as adhesives, hot melt adhesives, encapsulating media, coatings and paint additives, and as additives in compositions suitable as adhesives and coatings.

[00043] In particular, the applications for epoxy-based materials are extensive and include coatings, adhesives and composite materials, such as those using carbon fiber and fiberglass reinforcements. The chemistry of epoxies and the range of commercially available variations allows cross-link polymers to be produced with a very broad range of properties. In general, epoxies are known for their excellent adhesion, chemical and heat resistance, good-to- excellent mechanical properties and very good electrical insulating properties. Many properties of epoxies can be modified (for example silver-filled epoxies with good electrical conductivity are available, although epoxies are typically electrically insulating). Variations offering high thermal insulation, or thermal conductivity combined with high electrical resistance for electronics applications, can be achieved.

[00044] Commercially, the CEOC portion of the adhesive/coating/encapsulating composition may be kept in a separate compartment or container from the functionalized polymer portion, and the two are then combined at the point of desired use and blended together in situ. Alternatively, the CEOC and functionalized polymer may be pre-blended then activated by heat or other radiation at the point of use.

[00045] The various descriptive elements and numerical ranges disclosed herein for the CEOCs, cross-linkable compositions including the CEOC's and method of making them, can be combined with other descriptive elements and numerical ranges to describe the invention(s); further, for a given element, any upper numerical limit can be combined with any lower numerical limit described herein. The features of the invention are described in the following non-limiting examples.

EXAMPLES

[00046] The following scheme is a representation of one way in which the epoxidation of a cyclopentadiene epoxide oligomer composition is achieved, and the resulting cyclopentadiene epoxide oligomer composition ("CEOC"):

+ other epoxidized

oligomers cyclopentadiene oligomer

cyclopentadiene epoxide oligomer composition (CEOC)

[00047] In the present examples, to a solution of cyclopentadiene oligomer (an oligomer of cyclopentadiene (minor), dicyclopentadiene (major), piperylene and minor amounts of C2 to C₅ olefins) (5.00g) in methylene chloride (50ml) cooled in an ice-water bath was added 3- chloroperbenzoic acid (purity < 77%, 5.09g) in small portions over 5 minutes. The resulting mixture was stirred at 0°C for an additional 15 minutes and then at room temperature for 16 hours. The mixture was diluted with chloroform (25ml), washed with 10% aqueous sodium bicarbonate (50ml), water (50ml), and brine (25ml), dried with anhydrous MgS0₄, filtered and concentrated on a rotary evaporator to afford a light yellow solid as crude product (5.53 g). ^lR NMR of the epoxide product, shown in Figure 1, indicated a substantially reduced absorption signal of the vinylic protons (δ 4.7-6.2 ppm) relative to the aliphatic protons (δ 0.5-3.4 ppm). Residual solvent peaks in the epoxide crude product are those of CH₂Ci2 and CHCI3. This crude product was further dried in air for removal of residual solvents.

[00048] Blends of Escor 5200 and a cyclopentadiene oligomer, or the CEOC, were prepared at 200°C as follows: all the Escor 5200 pellets (12g) were put in a test tube placed inside the thermal cell of a Brookfield viscometer equipped with an electrically driven stirrer. It took 3-5 min to melt the pellets. Cyclopentadiene oligomer, or CEOC (2g), was then added. The mixing was continued for 1 min and the blend was poured and cooled on a piece of Teflon-coated aluminum foil. These blends and the neat polymer of Escor 5200 were then compression-molded at 200°C for 30 min into pads with a thickness of approximately 0.4mm. Dynamic Mechanical Thermal Analysis (DMT A) of these three molded plaques was then performed. In the DMTA experiment, a sample with dimensions 25.0mm by 5.0mm is die-cut from each of the above compression-molded plaques. Samples are analyzed on the Rheometrics Solids Analyzer (RSA3) produced by TA Instruments (New Castle, DE) in tension using auto-tension capabilities with the Film and Fiber Tool geometry. Each sample is tested under the appropriate strain as determined by a strain sweep prior to the temperature ramp (*). The temperature ramp is performed at lHz (6.2834 rad/s) and a ramp rate of 2.0°C/min starting at -100°C and testing to 200°C or sample failure.

• * Escor 5200 = 0.029%

• Escor 5200 + CEOC (aks: 26421-58) = 0.057%

• Escor 5200 + cyclopentadiene oligomer (aks: 26421-73) = 0.136%

[00049] Figures 3-5 show the DMTA curves of the three materials, where E' and E" denote the storage and loss moduli, respectively, and loss tangent is simply equal to E"/E'. For Escor 5200 (Figure 3) and Escor 5200 + cyclopentadiene oligomer (Figure 4), the scattered data points at high temperatures (> 100°C) indicate melting and they do not represent the absolute values of the moduli as the normal forces measured were out of the limits of the DMTA. For Escor 5200 + CEOC (Figure 5), the E' curve shows a constant plateau value up to 200°C. This suggests the behavior of a cross-linked network. Therefore, the epoxy groups in the modified cyclopentadiene oligomer did react with the acid groups in Escor 5200. [00050] Figure 6 compares the E' curves of Escor 5200, Escor 5200 + CEOC, and Escor 5200 + cyclopentadiene oligomer. It clearly demonstrates the cross-linkable reaction between the CEOC and Escor 5200.

[00051] Figure 7 shows the stress-strain curves of the various polymers described in Figures 2-5. In the stress-strain experiments, the molded plaque with a thickness of 0.4 mm was die-cut into micro-dumbbell specimens (the base was 1 cm x 1 cm and the center, narrow strip was 0.6 cm x 0.2 cm). Stress-strain measurements under tension were then performed in an INSTRON™ tester (available from Instron, Norwood MA). Measurements (using triplicate samples, conditioned under ambient conditions for 24 hours prior to tests) were performed at room temperature (25°C) and at a separation speed of 2"/min = 850 μιη/s until each dumbbell sample was broken. The stress was calculated based on the undeformed cross-sectional area of the test specimen. Strain measurements were based on clamp separation. From these stress-strain data points, the whole stress-strain curve was constructed. Tensile parameters, such as the strain at break (e¾), the tensile strength (σ¾), and the tensile toughness (U, calculated as the total area under the stress-strain curve) were then determined, Table 1. As noted, adding 14.3 wt% inventive CEOC in Escor 5200 decreased e¾, σ¾, and U because they are compatible. However, adding the same amount of CEOC in Escor 5200 restored part of the tensile properties of Escor 5200 back. Also, shown in Table 1 are the DSC second melt data of these three polymers described in Figures 2-5. After cross- linked, Escor 5200 still retains its crystallinity partially.

Table 1. DSC and Tensile Data pai aimii r Escor 5200 Escor 5200 + Escor 5200 +

c 'lopcnlariiciu- oligomer CEOC

T_c, °C 61 57 60

T_m, °C 91 89 88

Hf, J/g 67 45 47

e_b, % 207 1 12 135

o_b, MPa 26 15 22

U, MJ/m³ 31 13 20

[00052] The acid-containing polymers (EAA, etc.), such as Escor 5200, are just one type of functionalized oligomer that can be combined with the cyclopentadiene epoxide oligomer. The epoxidized cyclopentadiene epoxide oligomers can form cross-linked networks with hydroxyl-containing polymers, such as poly(vinyl alcohol), ethylene/vinyl alcohol copolymer, etc., amine-terminating polymers, such as poly(propylene glycol) bis(2- aminopropyl ether), amine-terminated polybutadiene, amine-terminated butadiene/acrylonitrile copolymer, etc., polyfunctional primary (RNH2) and secondary (R₂NH) amines (polyethyleneimines), or acid anhydrides. Experimental work in these areas is in progress.

[00053] GC-FIMS. A Waters GCT Classic is used for the GC-FIMS analysis shown in

Figure 8. Samples were prepared in toluene or methylene chloride at the 1-2 wt% level and Ι μΐ_^ of the solution is introduced to the heated injection port (325°C) via a GC autosampler. In GC-FIMS, a GC was used to separate species by boiling point (DB- 1HT 30 m 0.25 mm

0.25 um). The oven was ramped from 50°C to 350°C at 10°C/min. Field ionization provides soft ionization of the species as they elute the GC column forming intact molecular ions or protonated ions. Time-of-Flight (TOF) MS accurately determines the masses of the components (with an error of less than 3 mDa). Elemental compositions of the masses can thus be determined.

[00054] APPI-FTICR-MS. A Bruker Apex-Qe 12T Fourier Transform Ion Cyclotron Resonance Mass Spectrometer is used for the APPI-FTICR-MS analysis in Figure 9. Samples were dissolved in toluene to form a 200-2000 ppm solution depending on analyte concentration. The solution was introduced into the APPI source using a syringe pump controlled at 120 μΐ/hour. The source is manufactured by Syagen and comprised of a heated capillary needle and Krypton UV lamp with ionization energy of 10.6 eV. Nitrogen was used for both nebulizing gas and drying gas. Nebulizing gas flow rate is normally between 1 to 3 L/min, while drying gas flow rate is normally between 2 to 7 L/min. The flow rates were adjusted to maximize APPI-FTICR signals. Nebulizing gas temperature varies from 350°C to 450°C. Toluene was used as both solvent and chemical ionization agent. Ionization takes place via UV photoionization of the toluene solvent followed by ion-neutral collisions with the analyte molecules. The predominant ionization mechanism is charge transfer to the analyte molecules. An external calibration was performed to provide mass accuracy to 2ppm followed by an internal calibration to provide exact mass accuracy to 0.5ppm or better. Elemental compositions of the masses can thus be determined.

[00055] Now, having described the CEOC's and their adhesive/coating compositions, described herein in numbered embodiments is:

1. A cross-linkable cyclopentadiene epoxide oligomer composition with components having the general structures (1):

wherein the "R" above the bracket represents that each structure can be substituted in any one, two, or three positions with the R group in place of a hydrogen, where the R group is a Ci to Cio alkyl or alkene; and where n is an integer from 1 or 2 to 8 or 10 or 12 or 16 or 20 or 30; wherein from 80 or 85 or 90 wt% to 95 or 98 wt% of the composition comprises components where n is within the range of from 3 or 4 to 14 or 16.

2. The cross-linkable cyclopentadiene epoxide oligomer composition of numbered paragraph 1, wherein the composition (1) has a weight average molecular weight within the range of from 250 or 300 or 400g/mole to 700 or 800 or 900 or lOOOg/mole.

3. The cross-linkable cyclopentadiene epoxide oligomer composition of numbered paragraphs 1 or 2, further comprising (a blend with) a functionalized oligomer comprising functionality selected from the group consisting of a carboxylate groups, a hydroxyl groups, amine groups, and combinations thereof.

4. The cross-linkable cyclopentadiene epoxide oligomer composition of numbered paragraph 3, wherein the functionalized oligomer comprises a polyethylene acrylic acid co- oligomer or copolymer.

5. The cross-linkable cyclopentadiene epoxide oligomer composition of numbered paragraph 3, wherein the functionalized oligomer is selected from the group consisting of poly(vinyl alcohol), ethylene/vinyl alcohol copolymer, poly(propylene glycol) bis(2- aminopropyl ether), amine-terminated polybutadiene, amine-terminated butadiene/acrylonitrile copolymer, polyethyleneimines, acid anhydrides, and combinations thereof.

6. The cross-linkable cyclopentadiene epoxide oligomer composition of any one of the previous numbered paragraphs 3-5, wherein the crystallization temperature T_c of the cross- linked composition, by DSC, is within the range of from 20 or 25 or 30 or 35 or 40°C to 80 or 85 or 90 or 95°C.

7. The cross-linkable cyclopentadiene epoxide oligomer composition of any one of the previous numbered paragraphs 3-6, wherein the melting point temperature T_m of the cross- linked composition, by DSC, is within the range of from 60 or 65 or 70 or 75°C to 100 or 105 or 110 or 1 15°C.

8. The cross-linkable cyclopentadiene epoxide oligomer composition of any one of the previous numbered paragraphs 3-7, wherein the heat of fusion H_f of the cross-linked composition, by DSC, is within the range of from 10 or 15 or 20 or 25 or 30 J/g to 50 or 55 or 60 or 65 or 70 J/g.

9. The cross-linkable cyclopentadiene epoxide oligomer composition of any one of the previous numbered paragraphs 3-8, wherein the cross-linked composition has a storage modulus (Ε') at 150°C of at least 10 or 20 or 40 or 80 or 100 kPa; preferably within a range from 10 or 20 or 40 or 80 kPa to 1.0 or 5.0 or 10.0 MPa.

10. The cross-linkable cyclopentadiene epoxide oligomer composition of any one of the previous numbered paragraphs 3-9, wherein the cyclopentadiene epoxide oligomer is present in the composition within a range of from 5 or 8 or 10 or 15 wt% to 20 or 25 or 30 or 40 or 50 wt% of the composition.

1 1. The cross-linkable cyclopentadiene epoxide oligomer composition of any one of the previous numbered paragraphs 3-10, wherein the strain at break (e¾) of the cross-linked composition is greater than 90 or 100 or 110%, or within the range of from 90 or 100 or 1 10% to 140 or 150 or 160 or 200 or 250%.

12. The cross-linkable cyclopentadiene epoxide oligomer composition of any one of the previous numbered paragraphs 3-1 1, wherein the tensile strength (σ¾) of the cross-linked composition is greater than 10 or 12 or 15 MPa, or within the range of from 10 or 12 or 15 MPa to 25 or 30 or 25 MPa.

13. The cross-linkable cyclopentadiene epoxide oligomer composition of claim 1, wherein (1) is described alternately as the epoxidized oligomers of multi-cyclic conjugated dienes forming a cyclopentadiene epoxide oligomer; the multi-cyclic conjugated dienes selected from the group consisting of tetrahydroindene; methyltetrahydroindene; dicyclopentadiene (DCPD); bicyclo-(2,2, l)-hepta-2,5-diene; alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes such as 5-methylene-2-norbornene (M B), 5-ethylidene-2- norbornene (ENB), 5-propenyl-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5- cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene (VNB), and combinations thereof; most preferably dicyclopentadiene.

14. An adhesive, a coating, or an encapsulating agent comprising the cross-linkable cyclopentadiene epoxide oligomer composition of any one of the previous numbered paragraphs 3-12.

[00056] The invention(s) also include the use of the cross-linkable cyclopentadiene epoxide oligomer composition as an adhesive, coating, or encapsulating agent as described in any one of the previous numbered paragraphs 3-12.

Claims

wherein the "R" above the bracket represents that each structure can be substituted in any one, two, or three positions with the R group in place of a hydrogen, where the R group is a Ci to Cio alkyl or alkene; and where n is an integer from 1 to 30; wherein from 80 wt% to

98 wt% of the composition comprises components where n is within the range of from 3 to 16.

2. The cross-linkable cyclopentadiene epoxide oligomer composition of claim 1, wherein the composition (1) has a weight average molecular weight within the range of from 250 g/mole to 1000 g/mole.

3. The cross-linkable cyclopentadiene epoxide oligomer composition of claims 1 or 2, further comprising a functionalized oligomer comprising functionality selected from the group consisting of a carboxylate group, a hydroxyl group, amine groups, and combinations thereof.

4. The cross-linkable cyclopentadiene epoxide oligomer composition of any one of the previous claims, wherein the functionalized oligomer comprises a polyethylene acrylic acid co-oligomer or copolymer.

5. The cross-linkable cyclopentadiene epoxide oligomer composition of claims 3 or 4, wherein the functionalized oligomer is selected from the group consisting of poly(vinyl alcohol), ethylene/vinyl alcohol copolymer, poly(propylene glycol) bis(2-aminopropyl ether), amine-terminated polybutadiene, amine-terminated butadiene/acrylonitrile copolymer, polyethyleneimines, acid anhydrides, and combinations thereof.

6. The cross-linkable cyclopentadiene epoxide oligomer composition of any one of claims 3 to 5, wherein the crystallization temperature T_c of the cross-linked composition, by DSC, is within the range of from 20°C to 95°C.

7. The cross-linkable cyclopentadiene epoxide oligomer composition of any one of claims 3 to 6, wherein the melting point temperature T_m of the cross-linked composition, by

DSC, is within the range of from 60°C to 1 15°C.

8. The cross-linkable cyclopentadiene epoxide oligomer composition of any one of claims 3 to 7, wherein the heat of fusion H_f of the cross-linked composition, by DSC, is within the range of from 10 J/g to 70 J/g.

9. The cross-linkable cyclopentadiene epoxide oligomer composition of any one of claims 3 to 8, wherein the cross-linked composition as a storage modulus (Ε') at 150°C of at least 10 kPa.

10. The cross-linkable cyclopentadiene epoxide oligomer composition of any one of claims 3 to 9, wherein the cyclopentadiene epoxide oligomer is present in the composition within a range of from 5 wt% to 50 wt% of the composition.

11. The cross-linkable cyclopentadiene epoxide oligomer composition of any one of claims 3 to 10, wherein the strain at break (e¾) of the cross-linked composition is greater than 90%.

12. The cross-linkable cyclopentadiene epoxide oligomer composition of any one of claims 3 to 11, wherein the tensile strength (σ¾) of the cross-linked composition is greater than 10 MPa.

13. The cross-linkable cyclopentadiene epoxide oligomer composition of any one of claims 3 to 12, wherein,

the epoxidized oligomers of the multi-cyclic conjugated dienes forming cyclopentadiene epoxide oligomers, the multi-cyclic conjugated dienes selected from the group consisting of tetrahydroindene; methyltetrahydroindene; dicyclopentadiene (DCPD); bicyclo-(2,2, l)-hepta-2,5-diene; alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes, and combinations thereof; and the functionalized oligomer comprising functionality selected from the group consisting of a carboxylate group, a hydroxyl group, amine groups, and combinations thereof.

14. An adhesive, a coating, or an encapsulating agent comprising the cross-linkable cyclopentadiene epoxide oligomer composition of any one of claims 3 to 13.