Functionalized dicyclopentadiene polymer and process of making the same

Abstract

This invention relates to a functionalized dicyclopentadiene polymer and a process of making the same. The functionalized dicyclopentadiene polymer of the present invention exhibits good mechanical properties, high Tg, good resistance to non-polar solvent and improved adhesion to glass surface and metal surface.

Description

FUNCTIONALIZED DICYCLOPENTADIENE POLYMER AND PROCESS OF MAKING THE SAME CROSS-REFERENCE TO RELATD APPLICATIONS

[0001] This application claims the benefit of and priority to US Provisional Application No. 63 / 625670 filed January 26, 2024, the disclosure of which is incorporated herein by reference. FIELD OF THE INVENTION

[0002] This invention relates to a functionalized dicyclopentadiene polymer and a process of making the same. BACKGROUND OF THE INVENTION

[0003] Polydicyclopentadiene (pDCPD) is a linear or heavily crosslinked organic polymer produced by ring-opening metathesis polymerization (ROMP) of dicyclopentadiene (DCPD). Crosslinked pDCPD has a very high impact resistance, coupled with a large resistance to chemical corrosion, and a high heat deflection temperature. These properties make pDCPD attractive for use to make automotive body panels and components for engineering applications.

[0004] However, the significant limitations to polydicyclopentadienes relate to the poor resistance to non-polar solvent and low surface energy of the polymer, which makes them difficult to robustly adhere to glass surface and metal surface.

[0005] It has now been found that certain functionalized polydicyclopentadienes (also referred to as “f-pDCPD”) possess an important advantage from the environmental, health, safety and industrial handling aspects and present greatly improved physical properties.

[0006] US 11059939B2 discloses functionalized (co)polydicyclopentadienes obtained by a ring opening metathesis polymerization of the monomer DCPD-OR, wherein R represents a variety of substituents. The resulting functionalized (co)polydicyclopentadienes are useful in commercial and industrial applications, including, for example, body panels for cars, trucks, buses and all types of off-highway equipment, wastewater treatment equipment, sewage plants, pipeline valves, filters and more.

[0007] Saha, S. et al. (2016) “Cross-linked ROMP Polymers Based on Odourless Dicyclopentadiene Derivatives,” Polym. Chem., v.7(18), pp.3071-3075 discloses functionalized polydicyclopentadienes obtained by a ring opening metathesis polymerization of the monomer DCPDOH and some esters and ethers. The resulting polymers degrade at somewhat lower temperatures and retain similar thermal properties compared with pDCPD andmay provide for a more appealing alternative for domestic use in the field of thermoset polymers produced by ROMP.

[0008] However, these prior arts fail to mention the good resistance to non-polar solvent and low surface energy of the functionalized polydicyclopentadienes.

[0009] As such, there exists a need in the art for new forms of functionalized polydicyclopentadienes with good mechanical properties, high Tg, good resistance to non- polar solvent and improved adhesion to glass surface and metal surface. SUMMARY OF THE INVENTION

[0010] In one aspect, embodiments of the invention provide a functionalized dicyclopentadiene polymer comprising in polymerized form dicyclopentadiene derivative of Formula (I) and optionally dicyclopentadiene of Formula (II): (I),(II), wherein: Rato Rhare independently of each other selected from the group consisting of H, OH, halogen, CN, NO2, C1-C6-alkyl, C1-C6-alkoxy, C1-C6-alkylthio, C1-C6-alkylsulfinyl, C1-C6- alkylsulfonyl, C2-C6-alkenyl, tri-C1-C6-alkylsilyl, C2-C6-alkynyl, C1-C6-alkoxy-C1-C6-alkyl, C1-C6-alkoxy-C1-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-cycloalkoxy, C3-C6-cycloalkylthio, C3-C6-cycloalkyl-C1-C6-alkyl, C3-C6-cycloalkoxy-C1-C6-alkyl, C6-C12-aryl, C6-C12-aryloxy, C6-C12-arylcarbonyl, C6-C12-arylthio or C6-C12-aryl-C1-C6-alkyl, wherein the aliphatic or aromatic moieties are unsubstituted or substituted by one or more substituents from the groupconsisting of halogen, OH, CN, NO2, C1-C6-alkyl, C1-C6-alkoxy, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-alkoxy-C1-C6-alkyl, C1-C6-alkoxy-C1-C6-alkoxy, C3-C6-cycloalkyl, C3-C6- cycloalkoxy, C3-C6-cycloalkyl-C1-C6-alkyl or C3-C6-cycloalkoxy-C1-C6-alkyl; provided that at least one of Rgand Rhis not H.

[0011] In another aspect, embodiments of the invention provide a process of preparing the functionalized dicyclopentadiene polymer of the present invention, comprising polymerizing dicyclopentadiene derivative of Formula (I) and optionally dicyclopentadiene of Formula (II) through ring-opening metathesis polymerization. DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 shows the casting sample (ISO 37 type 3 specimen) used to test the tensile and flexural behaviors of the f-pDCPD materials.

[0013] Figure 2 shows SEM images of pDCPD-GB (a, b) and 30%DCPDOH-pDCPD-GB (c, d).

[0014] Figure 3 shows assembly of the test specimen for metal adhesion test for pDCPD and 30%DCPDOH-pDCPD.

[0015] Figure 4 shows adhesion Failure Modes: (a) Adhesion Failure (b) Adhesion / Cohesion Failure (c) Cohesion Failure and (d) Substrate Failure.

[0016] Figure 5 shows solvent swelling results for pDCPD and 30%DCPDOH-pDCPD in polar (methanol) or non-polar (xylene) solvent. DETAILED DESCRIPTION OF THE INVENTION

[0017] Various specific embodiments, versions, and examples are described herein; including exemplary embodiments and definitions that are adopted for purposes of understanding the claimed invention. While the following detailed description gives specific preferred embodiments, those skilled in the art will appreciate that these embodiments are exemplary only and that the invention can be practiced in other ways. For purposes of determining infringement, the scope of the invention will refer to any one or more of the appended claims, including their equivalents, and elements or limitations that are equivalent to those that are recited. Any reference to the “invention” may refer to one or more, but not necessarily all, of the inventions defined by the claims.

[0018] All numerical values within the detailed description and the claims herein are modified by “about” the indicated value, and take into account experimental error and variations that would be expected by those skilled in the art.

[0019] As used herein, unless noted otherwise, weight percent (wt%) means a percent by weight of a particular component based on the total weight of the composition containing each component. Functionalized dicyclopentadiene polymer

[0020] In the present invention, the functionalized dicyclopentadiene polymer comprises in polymerized form dicyclopentadiene derivative of Formula (I) and optionally dicyclopentadiene of Formula (II):wherein: Rato Rhare independently of each other selected from the group consisting of H, OH, halogen, CN, NO2, C1-C6-alkyl, C1-C6-alkoxy, C1-C6-alkylthio, C1-C6-alkylsulfinyl, C1-C6- alkylsulfonyl, C2-C6-alkenyl, tri-C1-C6-alkylsilyl, C2-C6-alkynyl, C1-C6-alkoxy-C1-C6-alkyl, C1-C6-alkoxy-C1-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-cycloalkoxy, C3-C6-cycloalkylthio, C3- C6-cycloalkyl-C1-C6-alkyl, C3-C6-cycloalkoxy-C1-C6-alkyl, C6-C12-aryl, C6-C12-aryloxy, C6- C12-arylcarbonyl, C6-C12-arylthio or C6-C12-aryl-C1-C6-alkyl, wherein the aliphatic or aromatic moieties are unsubstituted or substituted by one or more substituents from the group consisting of halogen, OH, CN, NO2, C1-C6-alkyl, C1-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6- alkoxy-C1-C6-alkyl, C1-C6-alkoxy-C1-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-cycloalkoxy, C3- C6-cycloalkyl-C1-C6-alkyl or C3-C6-cycloalkoxy-C1-C6-alkyl; provided that at least one of Rgand Rhis not H.

[0021] The organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members. The prefix Cn-Cmindicates in each case the possible number of carbon atoms in the group.

[0022] The term “halogen” denotes in each case F, Br, Cl or I, in particular F, Br or Cl.

[0023] The term “alkyl” as used herein and in the alkyl moieties of alkylthio, alkylsulfinyl, alkylsulfonyl and alkylsilyl denotes in each case a straight-chain or branched alkyl group having usually from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably from 1 to 3 carbon atoms. Examples of an alkyl group are CH3, C2H5, n-propyl, iso-propyl, n-butyl, 2-butyl, iso-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, and 1-ethyl-2-methylpropyl.

[0024] The term “alkoxy” as used herein denotes in each case a straight-chain or branched alkyl group which is bonded via an oxygen atom and has usually from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Examples of an alkoxy group are methoxy, ethoxy, n-propoxy, iso-propoxy, n-butyloxy, 2-butyloxy, iso-butyloxy, tert.-butyloxy, and the like.

[0025] The term “alkylthio” (alkylsulfanyl: alkyl-S-) as used herein refers to a straight- chain or branched saturated alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms (= C1-C4-alkylthio), more preferably 1 to 3 carbon atoms, which is attached via a sulfur atom. Examples include methylthio, ethylthio, propylthio, isopropylthio, and n-butylthio.

[0026] The term “alkylsulfinyl” (alkylsulfoxyl: C1-C6-alkyl-S(=O)-) as used herein refers to a straight-chain or branched saturated alkyl group (as mentioned above) having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms (= C1-C4-alkylsulfinyl), more preferably 1 to 3 carbon atoms bonded through the sulfur atom of the sulfinyl group at any position in the alkyl group.

[0027] The term “alkylsulfonyl” (alkyl-S(=O)2-) as used herein refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms (= C1-C4-alkylsulfonyl), preferably 1 to 3 carbon atoms, which is bonded via the sulfur atom of the sulfonyl group at any position in the alkyl group.

[0028] The term “alkenyl” as used herein denotes in each case a singly unsaturated hydrocarbon radical having usually 2 to 6, preferably 2 to 4 carbon atoms, wherein the double bond can be present in any position, e.g. vinyl, allyl (2-propen-1-yl), 1-propen-1-yl, 2-propen-2-yl, methallyl (2-methylprop-2-en-1-yl), 2-buten-1-yl, 3-buten-1-yl, 2-penten-1-yl, 3-penten- 1-yl, 4-penten-1-yl, 1-methylbut-2-en-1-yl, 2-ethylprop-2-en-1-yl and the like.

[0029] The term “alkynyl” as used herein denotes in each case a singly unsaturated hydrocarbon radical having usually 2 to 6, preferably 2 to 4 carbon atoms, wherein the triple bond can be present in any position, e.g. ethynyl, propargyl (2-propyn-1-yl), 1-propyn-1-yl, 1-methylprop-2-yn-1-yl, 2-butyn-1-yl, 3-butyn-1-yl, 1-pentyn-1-yl, 3-pentyn-1-yl, 4-pentyn-1- yl, 1-methylbut-2-yn-1-yl, 1-ethylprop-2-yn-1-yl and the like.

[0030] The term “cycloalkyl” as used herein and in the cycloalkyl moieties of cycloalkoxy and cycloalkylthio denotes in each case a monocyclic cycloaliphatic radical having usually from 3 to 6 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl, preferably cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0031] The term “aryl” as used herein and in the aryl moieties of aryloxy, arylcarbonyl and arylthio denotes in each case an aromatic carbocyclic radical comprising only one ring or several, optionally fused, rings having usually 6 to 12, preferably 6 to 10 ring member atoms, such as phenyl, 1- naphthyl, 2-naphthyl, biphenylyl or ferrocenyl.

[0032] The term “substituted” if not specified otherwise refers to substitutions by 1, 2 or maximum possible number of substituents. If substituents as defined in the dicyclopentadiene derivative of Formula (I) are more than one, then they are independently from each other same or different if not mentioned otherwise.

[0033] In one embodiment, the functionalized dicyclopentadiene polymer comprises in polymerized form dicyclopentadiene derivative of Formula (Ia) and optionally dicyclopentadiene of Formula (II): (Ia),(II),wherein: Riis selected from the group consisting of OH, halogen, CN, NO2, C1-C6-alkyl, C1-C6- alkoxy, C1-C6-alkylthio, C1-C6-alkylsulfinyl, C1-C6-alkylsulfonyl, C2-C6-alkenyl, tri-C1-C6- alkylsilyl, C2-C6-alkynyl, C1-C6-alkoxy-C1-C6-alkyl, C1-C6-alkoxy-C1-C6-alkoxy, C3-C6- cycloalkyl, C3-C6-cycloalkoxy, C3-C6-cycloalkylthio, C3-C6-cycloalkyl-C1-C6-alkyl, C3-C6- cycloalkoxy-C1-C6-alkyl, C6-C12-aryl, C6-C12-aryloxy, C6-C12-arylcarbonyl, C6-C12-arylthio or C6-C12-aryl-C1-C6-alkyl, wherein the aliphatic or aromatic moieties are unsubstituted or substituted by one or more substituents from the group consisting of halogen, OH, CN, NO2, C1- C6-alkyl, C1-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy-C1-C6-alkyl, C1-C6-alkoxy- C1-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-cycloalkoxy, C3-C6-cycloalkyl-C1-C6-alkyl or C3-C6- cycloalkoxy-C1-C6-alkyl.

[0034] In one preferred embodiment, in Formula (Ia), Riis selected from the group consisting of OH, halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C6-alkylthio, C3-C6-cycloalkyl or C6-C12-aryl, wherein the aliphatic or aromatic moieties are unsubstituted or substituted by one or more substituents from the group consisting of halogen, C1-C6-alkyl or C3-C6-cycloalkyl.

[0035] In one preferred embodiment, in Formula (Ia), Riis selected from the group consisting of OH, halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C6-alkylthio or C6-C12-aryl, wherein the aliphatic or aromatic moieties are unsubstituted or substituted by one or more substituents from the group consisting of halogen, C1-C6-alkyl or C3-C6-cycloalkyl.

[0036] In one preferred embodiment, in Formula (Ia), Riis selected from the group consisting of OH, halogen, C1-C6-alkyl or C1-C6-alkoxy, wherein the aliphatic moieties are unsubstituted or substituted by one or more substituents from the group consisting of halogen or C1-C6-alkyl.

[0037] In one preferred embodiment, in Formula (Ia), Riis selected from the group consisting of OH, C1-C6-alkyl or C1-C6-alkoxy, wherein the aliphatic moieties are unsubstituted.

[0038] In one preferred embodiment, the functionalized dicyclopentadiene polymer comprises in polymerized form dicyclopentadiene derivative of Formula (Ib) and optionally dicyclopentadiene of Formula (II):.

[0039] The dicyclopentadiene derivative of Formula (I), (Ia) or (Ib) and dicyclopentadiene of Formula (II) are commercially available or can be prepared in accordance with the procedures known in literature.

[0040] In some embodiments, the functionalized dicyclopentadiene polymer may comprise more than 0 up to 100 wt%, for example from 1 to 100 wt% of units derived from dicyclopentadiene derivative of Formula (I), (Ia) or (Ib), based on the weight of the functionalized dicyclopentadiene polymer. In some embodiments, the functionalized dicyclopentadiene polymer may comprise from 1 to 5 wt%, or 5 to 10 wt%, or from 10 to 15 wt%, or from 15 to 20 wt%, or from 20 to 25 wt%, or from 25 to 30 wt%, or from 30 to 35 wt%, or from 35 to 40 wt%, or from 40 to 45 wt%, or from 45 to 50 wt%, or from 50 to 55 wt%, or from 55 to 60 wt%, or from 60 to 65 wt%, or from 65 to 70 wt%, or from 70 to 75 wt%, or from 75 to 80 wt%, or from 80 to 85 wt%, or from 85 to 90 wt%, or from 90 to 95 wt%, or 95 to 100 wt% of units derived from dicyclopentadiene derivative of Formula (I), (Ia) or (Ib), based on the weight of the functionalized dicyclopentadiene polymer.

[0041] In some embodiments, the weight ratio of the units derived from dicyclopentadiene derivative of Formula (I), (Ia) or (Ib) to the units derived from dicyclopentadiene of Formula (II) in the functionalized dicyclopentadiene polymer is 1:100 to 100:1, or 1:90 to 90:1, or 1:80 to 80:1, or 1:70 to 70:1, or 1:60 to 60:1, or 1:50 to 50:1, or 1:40 to 40:1, or 1:30 to 30:1, or 1:20 to 20:1, or 1:19 to 19:1, or 1:18 to 18:1, or 1:17 to 17:1, or 1:16 to 16:1, or 1:15 to 15:1, or 1:14 to 14:1, or 1:13 to 13:1, or 1:12 to 12:1, or 1:11 to 11:1, or 1:10 to 10:1, or 1:9 to 9:1, or 1:8 to 8:1, or 1:7 to 7:1, or 1:6 to 6:1, or 1:5 to 5:1, or 1:4 to 4:1, or 1:3 to 3:1, or 1:2 to 2:1.

[0042] In a particular embodiment, the functionalized dicyclopentadiene polymer as defined therein further comprises units derived from other cyclic olefines, such as tricyclopentadiene, norbornene derivatives, cyclic alkenes with or without heteroatoms etc.

[0043] In one embodiment, the other cyclic olefines are selected from the group consisting of tricyclopentadiene, norbornene, norbornadiene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, and theirderivatives substituted with one or more substituents selected from the group consisting of OH, halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C6-alkylthio, C3-C6-cycloalkyl or C6-C12-aryl.

[0044] In one preferred embodiment, the other cyclic olefines are selected from the group consisting of cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 5-methylcyclo- pentene, cyclopentene, norbornene, and norbornadiene.

[0045] In one more preferred embodiment, the other cyclic olefines are selected from the group consisting of norbornene, 2-methyl-5-norbornene, 2-ethyl-5-norbornene, 2-butyl-5- norbornene, 2-hexyl-5-norbornene, and norbornadiene.

[0046] In some embodiments, the functionalized dicyclopentadiene polymer may comprise from 0.1 to 10 wt% of units derived from other cyclic olefines, based on the weight of the functionalized dicyclopentadiene polymer. In some embodiments, the functionalized dicyclopentadiene polymer may comprise from 0.5 to 1.0 wt%, or from 1.0 to 1.5 wt%, or from 1.5 to 2.0 wt%, or from 2.0 to 2.5 wt%, or from 2.5 to 3.0 wt%, or from 3.0 to 3.5 wt%, or from 3.5 to 4.0 wt%, or from 4.0 to 4.5 wt%, or from 4.5 to 5.0 wt%, or from 5.0 to 5.5 wt%, or from 5.5 to 6.0 wt%, or from 6.0 to 6.5 wt%, or from 6.5 to 7.0 wt%, or from 7.0 to 7.5 wt%, or from 7.5 to 8.0 wt%, or from 8.0 to 8.5 wt%, or from 8.5 to 9.0 wt%, or from 9.0 to 9.5 wt% of units derived from other cyclic olefines, based on the weight of the functionalized dicyclopentadiene polymer.

[0047] The functionalized dicyclopentadiene polymer of the present invention can be a random copolymer, alternating copolymer or block copolymer.

[0048] The functionalized dicyclopentadiene polymer of the present invention can be a linear or a crosslinked network, preferably a crosslinked thermoset.

[0049] The functionalized dicyclopentadiene polymer of the present invention exhibit good mechanical properties, high Tg, good resistance to non-polar solvent and improved adhesion to glass surface and metal surface.

[0050] The glass transition temperature (Tg) of the functionalized dicyclopentadiene polymer can range from 120°C to 220°C. In some embodiments, the glass transition temperature (Tg) of the functionalized dicyclopentadiene polymer can range from 120°C to 220°C, or from 130°C to 210°C, or from 140°C to 200°C, or from 150°C to 190°C, or from 160°C to 185°C, or from 165°C to 180°C, or from 170°C to 178°C. The glass transition temperature is measured by dynamic mechanical thermal analysis (DMTA). The testing was performed in torsion fixture at a frequency of 1 Hz in the temperature range from 35°C to 350°C with a heating rate of 5°C / min in N2atmosphere.

[0051] The tensile modulus of the functionalized dicyclopentadiene polymer can range from 1500 MPa to 2100 MPa. In some embodiments, the tensile modulus of the functionalized dicyclopentadiene polymer can range from 1550 MPa to 2050 MPa, or from 1600 MPa to 2000 MPa, or from 1650 MPa to 1950 MPa, or from 1700 MPa to 1900 MPa, or from 1750 MPa to 1850 MPa, or from 1780 MPa to 1820 MPa. The tensile modulus is as measured by INSTRON 5966 Universal Testing Systems at 25°C under a tensile rate of 50 mm / min.

[0052] The tensile strength of the functionalized dicyclopentadiene polymer can range from 50 to 100 MPa. In some embodiments, the tensile strength of the functionalized dicyclopentadiene polymer can range from 51 MPa to 95 MPa, or from 53 MPa to 90 MPa, or from 55 MPa to 88 MPa, or from 57 MPa to 85 MPa, or from 60 MPa to 80 MPa, or from 63 MPa to 75 MPa, or from 65 MPa to 70 MPa. The tensile strength was measured by INSTRON 5966 Universal Testing Systems at 25°C under a tensile rate of 50 mm / min. Process for the preparation of the functionalized dicyclopentadiene polymer

[0053] The functionalized dicyclopentadiene polymer of the present invention is prepared by a ring-opening metathesis polymerization.

[0054] In particular, the functionalized dicyclopentadiene polymer of the present invention is prepared by a process comprising polymerizing a monomer mixture through ring-opening metathesis polymerization (ROMP), wherein the monomer mixture comprises dicyclopentadiene derivative of Formula (I), preferably Formula (Ia), more preferably Formula (Ib), and optionally dicyclopentadiene of Formula (II), and optionally other cyclic olefines as defined therein. Ring-opening metathesis polymerization catalysts

[0055] The ring-opening metathesis polymerization can be carried out in the presence of a catalyst. The catalyst for ring-opening metathesis polymerization of the present invention is a compound that catalyzes the ring-opening metathesis polymerization, and will be selected by those skilled in the art.

[0056] Examples of the catalyst include metal compounds, preferably compounds of Group 8 metal, more preferably metal compounds of titanium (Ti), molybdenum (Mo), tungsten (W), rhenium (Re), osmium (Os) and ruthenium (Ru).

[0057] In some embodiments of the invention, the ring-opening metathesis polymerization catalyst is represented by the formula:wherein: M is a Group 8 metal, preferably Ru or Os, more preferably Ru; X and X1are, independently, any anionic ligand, preferably a halogen (preferably chlorine), an alkoxide or a triflate, or X and X1can be joined to form a dianionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non- hydrogen atoms; L and L1are, independently, a neutral two electron donor, preferably a phosphine or a N- heterocyclic carbene, L and L1can be joined to form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms; L and X can be joined to form a multidentate monoanionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non- hydrogen atoms; L1and X1can be joined to form a multidentate monoanionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non- hydrogen atoms; R and R1are, independently, hydrogen, halogen, or C1to C20substituted or unsubstituted hydrocarbyl (preferably C1to C20substituted or unsubstituted alkyl or a substituted or unsubstituted C6to C20aryl) which may contain at least one atom selected from halogen, oxygen, nitrogen, sulfur, phosphorus and silicon atoms; R1and L1or X1can be joined to form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms; and R and L or X can be joined to form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms.

[0058] Preferred alkoxides include those where the hydrocarbyl group is C1to C10hydrocarbyl, preferably C1to C10alkyl group, preferably methyl, ethyl, propyl, or butyl.

[0059] Preferred phosphines are represented by the formula: PR’ R’’ R’’’, where R’ is a secondary alkyl or cycloalkyl (preferably a C3to C12secondary alkyl or cycloalkyl), and R’’ and R’’’ are aryl, C1to C10primary alkyl, secondary alkyl, or cycloalkyl. R’’ and R’’’ can be the same or different. Preferred phosphines include P(cyclohexyl)3, P(cyclopentyl)3, and / or P(isopropyl)3.

[0060] Preferred triflates are represented by the formula:wherein R2is hydrogen or C1to C30alkyl group, preferably C1to C12alkyl group, preferably methyl, ethyl, propyl, butyl, or phenyl.

[0061] Preferred N-heterocyclic carbenes are represented by the formulae of:wherein: each R4is independently a hydrocarbyl group or substituted hydrocarbyl group having 1 to 40 carbon atoms, preferably methyl, ethyl, propyl, butyl (including isobutyl and n-butyl), pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, cyclooctyl, nonyl, decyl, cyclodecyl, dodecyl, cyclododecyl, mesityl, adamantyl, phenyl, benzyl, tolulyl, or chlorophenyl; and each R5is hydrogen, a halogen, or C1to C12hydrocarbyl group, preferably hydrogen, bromine, chlorine, methyl, ethyl, propyl, butyl, or phenyl. In other useful embodiments, one of the N atoms bound to the carbene in these formulae can be replaced with an S, O, or P atom, preferably an S atom.

[0062] Other useful N-heterocyclic carbenes include the compounds described in Hermann, W. A., Chem. Eur. J., 1996, v.2, pp.772 and 1627; Enders, D. et al. Angew. Chem. Int. Ed., 1995, v.34, pg.1021; Alder R. W., Angew. Chem. Int. Ed., 1996, v.35, pg.1121; and Bertrand, G. et al., Chem. Rev., 2000, v.100, pg.39.

[0063] In some embodiments of the invention, the ring-opening metathesis polymerization catalyst is one or more of tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)imidazol-2- ylidene][3-phenyl-1H-inden-1-ylidene]ruthenium(II)dichloride, tricyclohexylphosphine[3- phenyl-1H-inden-1-ylidene][1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydro-imidazol-2- ylidene]ruthenium(II) dichloride, tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5- dihydroimidazol-2-ylidene] [(phenylthio)methylene]ruthenium(II) dichloride, and 1,3- bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(isopropoxy)-5-(N,N- dimethylaminosulfonyl)phenyl]methylene ruthenium(II) dichloride. In some embodiments,the ring-opening metathesis polymerization catalyst is 1,3-bis(2,4,6-trimethylphenyl)-4,5- dihydroimidazol-2-ylidene[2-(isopropoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methylene ruthenium(II) dichloride and / or tricyclohexylphosphine[3-phenyl-1H-inden-1-ylidene][1,3- bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene]ruthenium(II) dichloride.

[0064] In some embodiments of the invention, the ring-opening metathesis polymerization catalyst is an organoruthenium compound having formula ofCy= Cyclohexyl Ph=Phenyl .

[0065] In an embodiment of the invention, the ring-opening metathesis polymerization catalyst is Grubbs 2nd catalyst.

[0066] The quantity of the ring-opening metathesis polymerization catalyst that is employed in the process of the invention is any quantity that provides an operable ring-opening metathesis polymerization. Preferably, the mole ratio of the monomers to the ring-opening metathesis polymerization catalyst is typically not less than 10:1; or not less than 100:1; or not less than 1,000:1; or not less than 10,000:1; or not less than 25,000:1; or not less than 50,000:1; or not less than 100,000: 1; or not less than 200,000:1; or not less than 300,000:1; or not less than 400,000: 1; and not more than 800,000:1; or not more than 700,000:1; or not more than 600,000:1; or not more than 500,000:1. In an embodiment of the invention, the mole ratio of the monomers to the ring-opening metathesis polymerization catalyst is typically in the range from 100:1 to 800,000:1, or from 300:1 to 500,000:1, or from 300:1 to 100,000:1, or from 400:1 to 80,000:1, or from 500:1 to 70,000:1, or from 800:1 to 60,000:1, or from 1,000:1 to 55,000:1, or from 1,500:1 to 50,000:1, or from 2,000:1 to 45,000:1, or from 2,500:1 to 40,000:1, or from 3,000:1 to 35,000:1, or from 3,500 to 30,000:1, or from 4,000:1 to 25,000:1, or from 4,500:1 to 20,000:1, or from 5,000:1 to 15,000:1, or from 5,500 to 10,000:1, or from 6,000:1 to 9,000:1, or from 6,500:1 to 8,000:1, or from 6,700:1 to 7,500:1. Reaction Regulators (Inhibitors)

[0067] In the present invention, the ring-opening metathesis polymerization can be carried out in the presence of a reaction regulator, which can be used in order to inhibit the production of low molecular weight components (oligomers, especially cyclic oligomers). That is, atleast one compound selected from the group consisting of nitriles, ketones, ethers, esters and organic phosphorus compounds is allowed to be present in the reaction system as reaction regulators.

[0068] The nitriles are compounds represented by the formula R6CN, wherein R6is a hydrocarbon group such as an alkyl group or an aryl group. The alkyl groups include those of 1-20, preferably 3-15, more preferably 4-10 carbon atoms. Preferred are, for example, i-propyl group, t-butyl group, n-pentyl group, t-pentyl group, hexyl group, heptyl group and octyl group. Examples of the aryl groups are phenyl group, alkyl-substituted phenyl groups (such as tolyl group and xylyl group), naphthyl group and alkyl-substituted naphthyl groups. Preferred examples of the nitriles are t-butylnitrile and benzonitrile.

[0069] The ketones are compounds represented by the formula R7-C(=O)-R8, wherein R7and R8are hydrocarbon groups such as alkyl group and aryl group. Carbon number of the alkyl group is usually 1-20, preferably 1-10. As the aryl groups, phenyl group is preferred. Preferred examples of the ketones are acetone, methyl ethyl ketone, methyl isobutyl ketone and methyl phenyl ketone.

[0070] The ethers are compounds represented by the formula R9-O-R10, wherein R9and R10are hydrocarbon groups such as alkyl group and aryl group. Carbon number of the alkyl group is usually 1-20, preferably 1-10. As the aryl group, phenyl group is preferred. Examples of the ethers are dimethyl ether, diethyl ether, methylethyl ether, methylphenyl ether and diisopropyl ether.

[0071] The esters are compounds represented by the formula R11-COO-R12, wherein R11and R12are hydrocarbon groups such as alkyl group and aryl group. Carbon number of the alkyl group is usually 1-20, preferably 1-10. As the aryl group, phenyl group is preferred. Examples of the esters are methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, isopropyl butyrate, butyl butyrate, methyl benzoate and ethyl benzoate.

[0072] Non-limiting examples of organic phosphorus compounds include trimethylphosphine (PMe3), triethylphosphine (PEt3), tributylphosphine (PBu3), tri(ortho- tolyl)phosphine (P-o-tolyl3), tri-tert-butylphosphine (P-tert-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), trioctylphosphine (POct3), triisobutylphosphine (P-i-Bu3), triphenylphosphine (PPh3), tri(pentafluorophenyl)phosphine (P(C6F5)3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), diethylphenylphosphine (PEt2Ph), trimethylphosphite (P(OMe)3), triethylphosphite (P(OEt)3), triisopropylphosphite (P(O-i-Pr)3), ethyldiphenylphosphinite (P(OEt)Ph2), tributylphosphite (P(OBu)3), triphenylphosphite (P(OPh)3,diethylphenylphosphonite (P(OEt)2Ph), and tribenzylphosphine (P(CH2Ph)3), and triphenylphosphine oxide. Preferred organic phosphorus compounds include triphenylphosphine, tricyclohexylphosphine, tributylphosphine and tributylphosphite. The more preferred organic phosphorus compound is triphenylphosphine or tributylphosphite. The most preferred organic phosphorus compound is tributylphosphite.

[0073] These reaction regulators may be used each alone or in combination of two or more. Amount of the reaction regulators used is optionally selected depending on the reaction conditions, but is usually from 0.001 to 10 moles, preferably from 0.005 to 5 moles, more preferably from 0.01 to 2 moles, most preferably from 0.05 to 0.5 moles based on 100 moles of the total monomers.

[0074] Preferably, the mole ratio of the reaction regulator to the ring-opening metathesis polymerization catalyst is in the range from 1:100 to 100:1, or 1:90 to 90:1, or 1:80 to 80:1, or 1:70 to 70:1, or 1:60 to 60:1, or 1:50 to 50:1, or 1:40 to 40:1, or 1:30 to 30:1, or 1:20 to 20:1, or 1:19 to 19:1, or 1:18 to 18:1, or 1:17 to 17:1, or 1:16 to 16:1, or 1:15 to 15:1, or 1:14 to 14:1, or 1:13 to 13:1, or 1:12 to 12:1, or 1:11 to 11:1, or 1:10 to 10:1, or 1:9 to 9:1, or 1:8 to 8:1, or 1:7 to 7:1, or 1:6 to 6:1, or 1:5 to 5:1, or 1:4 to 4:1, or 1:3 to 3:1, or 1:2 to 2:1.

[0075] The ring-opening metathesis polymerization catalyst and the reaction regulator can be added separately or as a mixture. Polymerization conditions

[0076] Conditions for ring-opening metathesis polymerization can be determined by a skilled person according to practical operation. The polymerization temperature in the present invention is not particularly limited, and can be selected from -30°C to 200°C, such as -25°C, -20°C, -15°C, -10°C, -5°C, 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, and any temperature between these values. In an embodiment of the present invention, the polymerization temperature in the present invention is in the range from 0°C to 180°C. In an embodiment of the present invention, the polymerization temperature in the present invention is in the range from 10°C to 100°C, such as 20°C to 80°C.

[0077] The polymerization time in the present invention is usually in the range from 1 minute to 100 hours, such as 1 minute to 100 minutes, 5 to 60 minutes, 10 to 50 minutes, 30 to 90 minutes, 50 to 90 minutes, 2 to 100 minutes, 3 to 100 minutes, 10 to 100 m minutes in, 15 to 100 minutes, 20 to 100 minutes, 10 to 90 minutes, 15 to 90 minutes, 20 to 90 minutes, 2 to80 hours, 10 to 80 hours, 15 to 80 hours, 20 to 80 hours, 2 to 70 hours, 10 to 70 hours, 15 to 70 hours, 20 to 70 hours, 2 to 60 hours, 10 to 60 hours, 15 to 60 hours, 20 to 60 hours, 30 to 60 hours, 40 to 80 hours, 60 to 90 hours, 60 to 100 hours, and can be any time between these values. In an embodiment of the present invention, the polymerization time in the present invention is in the range from 10 to 100 minutes, such as in the range from 10 to 90 minutes.

[0078] The polymerization according to the process of the present invention can be carried out in inert solvent or under solvent-free conditions. The term “inert solvent” means that the solvent does not react with the catalyst and can be capable of dissolving the obtained polymer. Examples of the solvent for polymerization according to the process of the present invention include alcohols, such as methanol, ethanol or isopropanol; ketones, such as acetone or methyl ethyl ketone; straight and branched-chain hydrocarbons, such as isobutane, butane, pentane, isopentane, n-hexane, isohexane, heptane, octane or dodecane; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane or methylcycloheptane, such as commercial product (Isopar™); aromatic compounds, such as benzene, toluene, mesitylene, ethyl benzene or xylene; halogenated hydrocarbons, such as dichloromethane, chloroform, dichloroethane, tetrachloroethane, chlorobenzene or trichlorobenzene; ethers, such as tetrahydrofuran; amides, such as dimethylformamide; sulfoxides, such as dimethyl sulfoxide; or mixtures thereof.

[0079] In some embodiments of the present invention, the solvent for polymerization according to the process of the present invention can be selected from the group consisting of methanol, ethanol, isopropanol, dichlormethane, chloroform, acetone, n-hexane, isohexane or cyclohexane.

[0080] For polymerization according to the process of the present invention, the concentration of the monomers added for the polymerization on the basis of the solvent is in the range from 0.01 to 5 mol / L, such as 0.01 to 4.5 mol / L, 0.01 to 4 mol / L, 0.01 to 3.5 mol / L, 0.01 to 3 mol / L, 0.01 to 2.5 mol / L, 0.01 to 2 mol / L, 0.01 to 1.5 mol / L, 0.01 to 1 mol / L, 0.01 to 0.5 mol / L, 0.02 to 4.5 mol / L, 0.02 to 4 mol / L, 0.02 to 3.5 mol / L, 0.02 to 3 mol / L, 0.02 to 2.5 mol / L, 0.02 to 2 mol / L, 0.02 to 1.5 mol / L, 0.02 to 1 mol / L, 0.02 to 0.5 mol / L, 0.03 to 4.5 mol / L, 0.03 to 4 mol / L, 0.03 to 3.5 mol / L, 0.03 to 3 mol / L, 0.03 to 2.5 mol / L, 0.03 to 2 mol / L, 0.03 to 1.5 mol / L, 0.03 to 1 mol / L, 0.03 to 0.5 mol / L, 0.05 to 4.5 mol / L, 0.05 to 4 mol / L, 0.05 to 3.5 mol / L, 0.05 to 3 mol / L, 0.05 to 2.5 mol / L, 0.05 to 2 mol / L, 0.05 to 1.5 mol / L, 0.05 to 1 mol / L, 0.05 to 0.5 mol / L, 0.1 to 4.5 mol / L, 0.1 to 4 mol / L, 0.1 to 3.5 mol / L, 0.1 to 3 mol / L, 0.1 to 2.5 mol / L, 0.1 to 2 mol / L, 0.1 to 1.5 mol / L, 0.1 to 1 mol / L, 0.1 to 0.5 mol / L, or any concentration between these values. In an embodiment of the invention, for polymerization according tothe process of the present invention, the concentration of the monomer added for the polymerization on the basis of the solvent is in the range from 0.01 to 2 mol / L, such as 0.05 to 1 mol / L. In some embodiments of the invention, for polymerization according to the process of the present invention, the concentration of the monomer added for the polymerization on the basis of the solvent is in the range from 0.1 to 0.5 mol / L.

[0081] In a preferred embodiment of the present invention, the polymerization according to the process of the present invention is carried out under solvent-free conditions.

[0082] In some embodiments of the process of the present invention, the functionalized dicyclopentadiene polymer can undergo separation.

[0083] After polymerization, the polymerization catalyst and by-products thereof can be removed by a known process, including a filtration or a process using an adsorbent for adsorptive removal.

[0084] After the removal of the polymerization catalyst and by-products thereof, the obtained functionalized dicyclopentadiene polymer can be precipitated and then be collected by filtration, washed and dried. Post-cured materials of functionalized dicyclopentadiene polymer

[0085] The post-cured materials of functionalized dicyclopentadiene polymer comprise in polymerized form dicyclopentadiene derivative of Formula (I), (Ia) or (Ib) and optionally dicyclopentadiene of Formula (II), which can be obtained by thermoset manufacturing process, such as reaction injection molding, compression molding, pultrusion, resin transfer molding etc.

[0086] Depending on the applications, various additives, which include but are not limited to impact modifiers, antioxidants, reinforcing materials, density modifiers, flame retardants, fillers etc., can be added to dicyclopentadiene derivative of Formula (I), (Ia) or (Ib) and optionally dicyclopentadiene of Formula (II).

[0087] Suitable impact modifiers include, but are not limited to, natural rubber, butyl rubber, polyisoprene, polybutadiene, polyisobutylene, ethylene-propylene copolymer, styrene- butadiene-styrene triblock rubber, random styrene-butadiene rubber, including styrene- isoprene-styrene triblock rubbers, styrene-ethylene / butylene-styrene copolymers, styrene- ethylene / propylene-styrene copolymers, ethylene-propylene-diene terpolymers, ethylene-vinyl acetate copolymers, and nitrile rubbers.

[0088] Suitable antioxidants include, but are not limited to, 2,6-di-tert-butyl-4- methylphenol (BHT); 2- and 3-tert-butyl-4-methoxyphenol; alkylated hindered phenols; 4-hydroxymethyl-2,6-di-tert-butylphenol; 2,6-di-tert-butyl-4-sec-butylphenol; 2,2’-methylenebis(4-methyl-6-tert-butylphenol); 2,2’-methylenebis(4-ethyl-6-tert-butylphenol); 4,4’-methylenebis(2,6-di-tert-butylphenol); 2,2’-methylenebis(4-methyl-6-(1- methylcyclohexyl)phenol); 4,4’-butylidenebis(6-tert-butyl-3-methylphenol) polybutylated bisphenol A; 4,4’-thiobis(6-tert-butyl-3-methylphenol); 4,4’-methylenebis(2,6- dimethylphenol); 1,1’-thiobis(2-naphthol); 2,2’-thiobis(4-methyl-6-tert-butylphenol); 4,4’-methylenebis(2,6-di-tertiary butylphenol); 1,3,5-tris(3,5-di-tert-butyl-4- hydroxybenzyl)isocyanurate; 2,5-di-tert-amylhydroquinone, tert-butylhydroquinone, tris(nonylphenyl)phosphite, bis(2,4-di-tert-butyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite; 1,6-hexamethylenebis(3-(3,5-di-tert-butyl-4- hydroxyphenylpropionate) and octadecyl-3,5-di-tert-.butyl-4-hydroxyhydrocinnamate, tetrakis(2,4-di-tert-butylphenyl)4,4’-biphenylenediphosphonite, diphenylamine, and 4,4’-dimethoxydiphenylamine.

[0089] Suitable reinforcing materials include those that can add strength or stiffness to the post-cured materials. The reinforcing material can be in the form of filaments, fibers, rovings, mats, textiles, knit materials, fabrics or other known structures. Suitable reinforcing materials include glass fibers and fabrics, carbon fibers and fabrics, aramid fibers and fabrics, polyolefin fibers and fabrics.

[0090] Suitable density modifiers include, but are not limited to, glass, metals, thermoplastics or thermoset and / or ceramic / silicate microspheres; glass, plastic or ceramic beads; metal rods, chunks, pieces or shots; hollow glass, ceramic, plastic or metal spheres or tubes, and the like.

[0091] Suitable flame retardants include, but are not limited to various chlorine and bromine flame retardants, preferred are as follows: hexabromobenzene, pentabromoethylbenzene, hexabromobiphenyl, decabromobiphenyl, hexabromodiphenyl oxide, octabromodiphenyl oxide, decabromodiphenyl oxide, pentabromocyclohexane, tetrabromobisphenol A and derivatives thereof [for example, tetrabromobisphenol A-bis(hydroxyethyl ether), tetrabromobisphenol A-bis(2,3-dibromopropyl ether), tetrabromobisphenol A-bis(bromoethyl ether), and tetrabromobisphenol A-bis(allyl ether)], tetrabromobisphenol S and derivatives thereof [for example, tetrabromobisphenol S-bis(hydroxyethyl ether) and tetrabromobisphenol S-bis(2,3-dibromopropyl ether)], tetrabromophthalic anhydride and derivatives thereof [for example, tetrabromo-phthalimide and ethylenebistetrabromophthalimide], ethylenebis(5,6-dibromonorbornene-2,3- dicarboximide), tris-(2,3-dibromopropyl-1)-isocyanurate, Diels-Alder reaction adducts of hexachlorocyclopentadiene, tribromophenylglycidyl ether, tribromophenyl acrylate, ethylene- bistribromophenyl ether, ethylenebispentabromophenyl ether,tetradecabromodiphenoxybenzene, brominated polystyrene, brominated polyphenylene oxide, brominated epoxy resin, brominated polycarbonate, polypentabromobenzyl acrylate, octabromonaphthalene, hexabromocyclododecane, bis(tribromophenyl)-fumaramide, and N-methylhexabromodiphenylamine.

[0092] Suitable fillers include, but are not limited to, finely divided inorganic solid materials such as glass beads, silica, fumed silica, diatomaceous earth, calcium carbonate, calcium silicate, aluminum silicate, kaolin, talc, bentonite, clay and carbon black.

[0093] Such additives can be used in effective amounts, which vary depending upon the property required. Depending on the type of additives, they can be added in an amount of 0.001 wt% to 10.0 wt%, based on the weight of the post-cured materials of the functionalized dicyclopentadiene polymer.

[0094] In one embodiment, the initial molding temperature in the thermoset manufacturing process can be in the range from 0°C to 200°C with air, or with controlled exposure time to air, or without air exposure. Preferably, the molding temperature ranges from 40°C to 70°C without air exposure.

[0095] In one embodiment, the initial molding time in the thermoset manufacturing process can range from 1 minute to 1 hour, preferably from 5 minutes to 15 minutes.

[0096] In one embodiment, the thermoset manufacturing process can be performed via one- stage or multiple-stage post curing with air, or with controlled exposure time to air, or without air exposure, preferably one-stage or two-stage post curing, more preferably one-stage post curing with polyimide film to seal the sample.

[0097] In one embodiment, the curing temperature in the thermoset manufacturing process can range from 50°C to 400°C, or 60°C to 380°C, or from 70°C to 370°C, or from 80°C to 360°C, or from 90°C to 340°C, or from 100°C to 350°C, or from 120°C to 340°C, or from 140°C to 330°C, or from 150°C to 320°C, or from 180°C to 310°C, or from 190°C to 300°C, or from 200°C to 290°C, or from 210°C to 280°C, or from 220°C to 270°C, or from 230°C to 260°C, or from 240°C to 260°C, or from 250°C to 260°C.

[0098] In one embodiment, the curing time in the thermoset manufacturing process can range from 15 minutes to 96 hours, preferably from 30 minutes to 24 hours, more preferably from 30 minutes to 12 hours, most preferably from 30 minutes to 6 hours.

[0099] The glass transition temperature (Tg) of the post-cured materials of the functionalized dicyclopentadiene polymer can range from 170°C to 400°C. In some embodiments, the glass transition temperature (Tg) of the post-cured materials of the functionalized dicyclopentadiene polymer can range from 178°C to 390°C, or from 180°C to380°C, or from 185°C to 370°C, or from 190°C to 360°C, or from 195°C to 350°C, or from 200°C to 340°C, or from 205°C to 330°C, or from 210°C to 320°C, or from 215°C to 310°C, or from 220°C to 300°C, or from 225°C to 290°C, or from 230°C to 280°C, or from 235°C to 275°C, or from 240°C to 270°C, or from 245°C to 265°C, or from 250°C to 260°C. The glass transition temperature is measured by dynamic mechanical thermal analysis (DMTA). The testing was performed in torsion fixture at a frequency of 1 Hz in the temperature range from 35°C to 350°C with a heating rate of 5°C / min in N2atmosphere.

[0100] The tensile modulus of the post-cured materials of the functionalized dicyclopentadiene polymer can range from 1600 MPa to 4000 MPa. In some embodiments, the tensile modulus of the post-cured materials of the functionalized dicyclopentadiene polymer can range from 1620 to 3800 MPa, or from 1650 to 3600 MPa, or from 1680 to 3400 MPa, or from 1700 to 3200 MPa, or from 1720 to 3000 MPa, or from 1750 to 2900 MPa, or from 1780 to 2800 MPa, or from 1800 to 2700 MPa, or from 1820 to 2600 MPa, or from 1850 to 2500 MPa, or from 1880 to 2400 MPa, or from 1900 to 2350 MPa, or from 1920 to 2300 MPa, or from 1950 to 2250 MPa, or from 1980 to 2200 MPa, or from 2000 to 2150 MPa, or from 2050 to 2100 MPa. The tensile modulus is as measured by INSTRON 5966 Universal Testing Systems at 25°C under a tensile rate of 50 mm / min.

[0101] The tensile strength of the post-cured materials of the functionalized dicyclopentadiene polymer can range from 53 MPa to 120 MPa. In some embodiments, the tensile strength of the post-cured materials of the functionalized dicyclopentadiene polymer can range from 54 to 115 MPa, or from 55 to 110 MPa, or from 56 to 105 MPa, or from 57 to 100 MPa, or from 58 to 90 MPa, or from 59 to 85 MPa, or from 60 to 80 MPa, or from 61 to 75 MPa, or from 62 to 70 MPa, or from 63 to 65 MPa. The tensile strength was measured by INSTRON 5966 Universal Testing Systems at 25°C under a tensile rate of 50 mm / min.

[0102] The resulting post-cured materials can be used in a wide range of applications, such as adhesives, composites, coating, especially chemical resistance applications etc.

[0103] The resulting post-cured materials can be used for obtaining various molded products, such as auto-parts, electronic materials, aerospace materials, etc. The resulting post-cured materials can be used to replace PI, PEEK, PBI, etc. in some typical applications including molded or machined parts for the automotive and aerospace industry such as non- lubricating bearings, seals, bushings, pistons, gears, and thrust washers.

[0104] The various descriptive elements and numerical ranges disclosed herein for the functionalized dicyclopentadiene polymer or composition thereof described herein 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, including the examples. The features of the invention are demonstrated in the following non-limiting examples. Examples

[0105] The present invention is now further illustrated by reference to the following examples, however, the examples are used for the purpose of explanation and not intended to limit the scopes of the invention. Synthesis of DCPDOH from 1:1 mole ratio of DCPD and SeO2:

[0106] Under N2protection, 150 g DCPD (available from Guangdong New Huayue Petrochemical Incorporated Company), 126 g SeO2(available from Adamas) and 600 mL dry THF were mixed in 1 L flask. The reaction mixture was refluxed at 80°C for 20 hours. The reaction mixture was cooled to 0°C. 300 mL distilled water was added, and the mixture was stirred for 4 hours. After filtration, volatiles were removed with rotary evaporator. After extraction with ethyl acetate, all volatiles were removed under vacuum. Vacuum distillation: oil bath: 110°C, boiling point: 65°C – 70°C, viscous liquid. Recrystallization: hexane, freezer -18°C, white solid, DCPDOH yield: 72.9%. DCPDOH:1H NMR (700 MHz, Chloroform-d) δ 5.90 (dd, J = 5.7, 3.0 Hz, 1H), 5.81 (dd, J = 5.7, 3.0 Hz, 1H), 5.74 (d, J = 5.6 Hz, 1H), 5.57 (m, 1H), 4.03 (s, 1H), 3.34 (m, 1H), 3.03 (s, 1H), 2.76 (s, 1H), 2.50 (ddd, J = 7.0, 4.4, 2.1 Hz, 1H), 2.07 (s, 1H), 1.53 (d, J = 8.1 Hz, 1H), 1.36 (d, J = 8.2 Hz, 1H). DMTA and mechanical tests

[0107] Dynamic mechanical thermal analysis (DMTA) was carried out by ARES-G2 according to EM method. The testing was performed in torsion fixture at a frequency of 1 Hz in the temperature range from 35°C to 350°C with a heating rate of 5°C / min in N2atmosphere. DMTA experiment was performed to evaluate the Tg of the material.

[0108] To test the tensile and flexural behaviors, casting samples were prepared (ISO 37 type 3 specimen, shown in Figure 1) and conditioned at 25°C for 48 hours before tests. The stress-strain curve was collected by INSTRON 5966 Universal Testing Systems at 25°C under a tensile rate of 50 mm / min. The flexural testing method is developed based upon ASTM D790, Method A, denoted as EM method. Example 1

[0109] 10 g DCPD and 34.5 mg P(Ph)3were injected to a 20 mL vacuum bottle at ambient conditions, and later transferred to mix with 9.6 mg G2 catalyst available from Adamas in ultrasonic, during which the process was operated without exposure to air and moisture. The ISO 37 type 3 specimen mold was placed on the polyimide (PI) film at the bottom and pre-heated at 50°C. After the catalyst was totally dissolved, the mixture was injected to the mold and then sealed by polyimide (PI) film on the top. Once witnessing the obvious curing phenomena of sample bar, the sample was held for 15 minutes. Example 2

[0110] 10 g DCPD and 34.5 mg P(Ph)3were injected to a 20 mL vacuum bottle at ambient conditions, and later transferred to mix with 9.6 mg G2 catalyst in ultrasonic, during which the process was operated without exposure to air and moisture. The ISO 37 type 3 specimen mold was placed on the polyimide (PI) film at the bottom and pre-heated at 50°C. After the catalyst was totally dissolved, the mixture was injected to the mold and then sealed by polyimide (PI) film on the top. Once witnessing the obvious curing phenomena of sample bar, the sample was held for 15 minutes. Then the mold with resulting polymer was directly moved to a 200°C oven for 3 hours as post-curing. Example 3

[0111] 7 g DCPD, 3 g DCPDOH and 34.5 mg P(Ph)3were injected to a 20 mL vacuum bottle at ambient conditions, and later transferred to mix with 9.6 mg G2 catalyst in ultrasonic, during which the process was operated without exposure to air and moisture. The ISO 37 type 3 specimen mold was placed on the polyimide (PI) film at the bottom and pre-heated at 50°C. After the catalyst was totally dissolved, the mixture was injected to the mold and then sealed by polyimide (PI) film on the top. Once witnessing the obvious curing phenomena of sample bar, the sample was held for 15 minutes. Example 4

[0112] 7 g DCPD, 3 g DCPDOH and 34.5 mg P(Ph)3were injected to a 20 mL vacuum bottle at ambient conditions, and later transferred to mix with 9.6 mg G2 catalyst in ultrasonic, during which the process was operated without exposure to air and moisture. The ISO 37 type 3 specimen mold was placed on the polyimide (PI) film at the bottom and pre-heated at 50°C. After the catalyst was totally dissolved, the mixture was injected to the mold and then sealed by polyimide (PI) film on the top. Once witnessing the obvious curing phenomena of sample bar, the sample was held for 15 minutes. Then the mold with resulting polymer was directly moved to a 90°C oven for 4 h as post-curing. Example 5

[0113] 7 g DCPD, 3 g DCPDOH and 11.7 mg P(Ph)3were injected to a 20 mL vacuum bottle at ambient conditions, and later transferred to mix with 9.6 mg G2 catalyst in ultrasonic, during which the process was operated without exposure to air and moisture. The ISO 37type 3 specimen mold was placed on the polyimide (PI) film at the bottom and pre-heated at 50°C. After the catalyst was totally dissolved, the mixture was injected to the mold and then sealed by polyimide (PI) film on the top. Once witnessing the obvious curing phenomena of sample bar, the sample was held for 15 minutes. Then the mold with resulting polymer was directly moved to a 150°C oven for 4 hours as post-curing. Example 6

[0114] 7 g DCPD, 3 g DCPDOH and 34.5 mg P(Ph)3were injected to a 20 mL vacuum bottle at ambient conditions, and later transferred to mix with 9.6 mg G2 catalyst in ultrasonic, during which the process was operated without exposure to air and moisture. The ISO 37 type 3 specimen mold was placed on the polyimide (PI) film at the bottom and pre-heated at 50°C. After the catalyst was totally dissolved, the mixture was injected to the mold and then sealed by polyimide (PI) film on the top. Once witnessing the obvious curing phenomena of sample bar, the sample was held for 15 minutes. Then the mold with resulting polymer was directly moved to a 200°C oven for 3 hours as post-curing. Example 7

[0115] 7 g DCPD, 3 g DCPDOH and 34.5 mg P(Ph)3were injected to a 20 mL vacuum bottle at ambient conditions, and later transferred to mix with 9.6 mg G2 catalyst in ultrasonic, during which the process was operated without exposure to air and moisture. The ISO 37 type 3 specimen mold was placed on the polyimide (PI) film at the bottom and pre-heated at 50°C. After the catalyst was totally dissolved, the mixture was injected to the mold and then sealed by polyimide (PI) film on the top. Once witnessing the obvious curing phenomena of sample bar, the sample was held for 15 minutes. Then the mold with resulting polymer was directly moved to a 250°C oven for 0.5 hour as post-curing. Table 1. Tensile properties of the polymerExample 8

[0116] SEM was performed to study the morphology of filler-resin composite. SEM images were collected at the accelerating voltage of 15 kV with BSE detector by HITACHI FlexSEM 1000II equipment. Two samples were prepared for this study.

[0117] pDCPD with glass beads filler (pDCPD-GB): 4.25 g DCPD, 4.1 mg G2 catalyst, 2.3 mg P(OBu)3and 0.75 g glass beads were well mixed and injected to a sample bottle, followed by heating at 60°C on a heat plate until the mixture was cured, then cured at 200°C for 1 hour in an oven.

[0118] 30% DCPDOH-pDCPD with glass beads filler (30% DCPDOH-pDCPD-GB): 2.98 g DCPD, 1.27 g DCPDOH, 3.9 mg G2 catalyst, 2.3 mg P(OBu)3and 0.75 g glass beads were well mixed and injected to a sample bottle, followed by followed by heating at 60°C on a heat plate until the mixture was cured, then cured at 200°C for 1 hour in an oven.

[0119] The SEM samples were prepared by cutting the polymer bars into films with a thickness < 0.3 mm, followed by Au coating process for 1 minute.

[0120] Figure 2 shows that glass beads were better dispersed and embedded in 30%DCPDOH-pDCPD matrix. As a contrast, most of the beads were aggregated in pDCPD- GB, giving weak interaction at the resin-filler interface. Example 9

[0121] Lap shear test was performed to evaluate the improved metal adhesion of the system. The test specimen was assembled according to Figure 3. Two formulations were used in this experiment for comparing metal adhesion improvement after addition of DCPDOH to the system:

[0122] pDCPD: 10 g DCPD, 9.6 mg G2 catalyst, 4.6 mg P(OBu)3was mixed. The mixture was added dropwise to the surface of metal, and the other piece of metal plate was placed on top of the mixture to cover it. The resulting material was cured at 70°C on heat plate for 15 minutes, then moved to an oven for curing at 200°C for 1 hour.

[0123] 30%DCPDOH-pDCPD: 7 g DCPD, 3 g DCPDOH, 9.3 mg G2 catalyst, 4.6 mg P(OBu)3was mixed. The mixture was added dropwise to the surface of metal, and the other piece of metal plate was placed on top of the mixture to cover it. The resulting material was cured at 70°C on heat plate for 15 minutes, then moved to an oven for curing at 200°C for 1 hour.

[0124] The mechanical test was performed on INSTRON 5966 system using a force- programmed mode. The grips should be moved into alignment with the test specimen as soonas the load is applied, so that the long axis of the test specimen will coincide with the direction of the applied pull through the center line of the grip assembly.

[0125] Figure 4 shows Adhesion Failure Modes.

[0126] The lap shear test results are shown in Table 3. Table 3. the lap shear test resultsExample 10: Solvent swelling experiment

[0127] Two sample bars were used in this experiment:

[0128] pDCPD: 10 g DCPD, 9.6 mg G2 catalyst, 4.6 mg P(OBu)3was mixed. The mixture was injected to a mold covered by two glass plates and cured at 57°C on heat plate for 15 minutes, then moved to an oven for curing at 150°C for 24 hours.

[0129] 30%DCPDOH-pDCPD: 7 g DCPD, 3 g DCPDOH, 9.3 mg G2 catalyst, 4.6 mg P(OBu)3was mixed. The mixture was injected to a mold covered by two glass plates and cured at 57°C on heat plate for 15 minutes, then moved to an oven for curing at 150°C for 24 hours.

[0130] 12 samples (10 mm * 12 mm * 3 mm) were cut from the sample bar. The samples were pre-evacuated in an oven under vacuum at 40°C for 4 hours. The solvent swelling experiments were conducted by immersing samples in 4 mL different solvents (xylene or methanol). The samples were removed from the solvent, gently dabbed dry and weighed. Samples were then placed back into the solvent.Table 4. Swelling of pDCPD and 30%DCPDOH-pDCPD in methanol (polar) and xylene (nonpolar)

[0131] Figure 5 shows solvent swelling results for pDCPD and 30%DCPDOH-pDCPD in polar (methanol) or non-polar (xylene) solvent.

[0132] The results in Table 4 and Figure 5 show that pDCPD samples swelled rapidly in xylene but did not absorb any amount of methanol. By contrast, 30%DCPDOH-pDCPD samples took up small amounts of both xylene and methanol. It indicated the increased polarity within the polymer matrix, resulting from incorporation of the OH functional group.

[0133] It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. Thus, it is intended that the present invention cover such modifications and variations as come within the scope of the appended claims and their equivalents.

Claims

CLAIMS 1. A functionalized dicyclopentadiene polymer comprising in polymerized form dicyclopentadiene derivative of Formula (I) and optionally dicyclopentadiene of Formula (II): (I),(II), wherein: Rato Rhare independently of each other selected from the group consisting of H, OH, halogen, CN, NO2, C1-C6-alkyl, C1-C6-alkoxy, C1-C6-alkylthio, C1-C6-alkylsulfinyl, C1-C6- alkylsulfonyl, C2-C6-alkenyl, tri-C1-C6-alkylsilyl, C2-C6-alkynyl, C1-C6-alkoxy-C1-C6-alkyl, C1-C6-alkoxy-C1-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-cycloalkoxy, C3-C6-cycloalkylthio, C3- C6-cycloalkyl-C1-C6-alkyl, C3-C6-cycloalkoxy-C1-C6-alkyl, C6-C12-aryl, C6-C12-aryloxy, C6- C12-arylcarbonyl, C6-C12-arylthio or C6-C12-aryl-C1-C6-alkyl, wherein the aliphatic or aromatic moieties are unsubstituted or substituted by one or more substituents from the group consisting of halogen, OH, CN, NO2, C1-C6-alkyl, C1-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6- alkoxy-C1-C6-alkyl, C1-C6-alkoxy-C1-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-cycloalkoxy, C3- C6-cycloalkyl-C1-C6-alkyl or C3-C6-cycloalkoxy-C1-C6-alkyl; provided that at least one of Rgand Rhis not H.

2. The functionalized dicyclopentadiene polymer according to claim 1, comprising in polymerized form dicyclopentadiene derivative of Formula (Ia) and optionally dicyclopentadiene of Formula (II):wherein: Riis selected from the group consisting of OH, halogen, CN, NO2, C1-C6-alkyl, C1-C6- alkoxy, C1-C6-alkylthio, C1-C6-alkylsulfinyl, C1-C6-alkylsulfonyl, C2-C6-alkenyl, tri-C1-C6- alkylsilyl, C2-C6-alkynyl, C1-C6-alkoxy-C1-C6-alkyl, C1-C6-alkoxy-C1-C6-alkoxy, C3-C6- cycloalkyl, C3-C6-cycloalkoxy, C3-C6-cycloalkylthio, C3-C6-cycloalkyl-C1-C6-alkyl, C3-C6- cycloalkoxy-C1-C6-alkyl, C6-C12-aryl, C6-C12-aryloxy, C6-C12-arylcarbonyl, C6-C12-arylthio or C6-C12-aryl-C1-C6-alkyl, wherein the aliphatic or aromatic moieties are unsubstituted or substituted by one or more substituents from the group consisting of halogen, OH, CN, NO2, C1- C6-alkyl, C1-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy-C1-C6-alkyl, C1-C6-alkoxy- C1-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-cycloalkoxy, C3-C6-cycloalkyl-C1-C6-alkyl or C3-C6- cycloalkoxy-C1-C6-alkyl.

3. The functionalized dicyclopentadiene polymer according to claim 2, wherein Riis selected from the group consisting of OH, halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C6-alkylthio, C3-C6- cycloalkyl or C6-C12-aryl, wherein the aliphatic or aromatic moieties are unsubstituted or substituted by one or more substituents from the group consisting of halogen, C1-C6-alkyl or C3-C6-cycloalkyl.

4. The functionalized dicyclopentadiene polymer according to claim 2, wherein Riis selected from the group consisting of OH, halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C6-alkylthio or C6-C12- aryl, wherein the aliphatic or aromatic moieties are unsubstituted or substituted by one or more substituents from the group consisting of halogen, C1-C6-alkyl or C3-C6-cycloalkyl.

5. The functionalized dicyclopentadiene polymer according to claim 2, wherein Riis selected from the group consisting of OH, halogen, C1-C6-alkyl or C1-C6-alkoxy, wherein the aliphaticmoieties are unsubstituted or substituted by one or more substituents from the group consisting of halogen or C1-C6-alkyl.

6. The functionalized dicyclopentadiene polymer according to claim 2, wherein Riis selected from the group consisting of OH, C1-C6-alkyl or C1-C6-alkoxy, wherein the aliphatic moieties are unsubstituted.

7. The functionalized dicyclopentadiene polymer according to claim 1, comprising in polymerized form dicyclopentadiene derivative of Formula (Ib) and optionally dicyclopentadiene of Formula (II): (Ib),(II).

8. The functionalized dicyclopentadiene polymer according to any of claims 1 to 7, comprising from 5 to 95 wt % of units derived from dicyclopentadiene derivative of Formula (I), (Ia) or (Ib), based on the weight of the functionalized dicyclopentadiene polymer.

9. The functionalized dicyclopentadiene polymer according to any of claims 1 to 8, wherein the weight ratio of the units derived from dicyclopentadiene of Formula (II) to the units derived from dicyclopentadiene derivative of Formula (I), (Ia) or (Ib) in the functionalized dicyclopentadiene polymer is 1:19 to 19:

1.

10. The functionalized dicyclopentadiene polymer according to any of claims 1 to 9, further comprising units derived from other cyclic olefines.

11. The functionalized dicyclopentadiene polymer according to claim 10, wherein the other cyclic olefines are tricyclopentadiene, norbornene derivatives, or cyclic alkenes with or without heteroatoms.

12. The functionalized dicyclopentadiene polymer according to any of claims 1 to 11, wherein the glass transition temperature (Tg) of the functionalized dicyclopentadiene polymer ranges from 120°C to 240°C.

13. A process of preparing the functionalized dicyclopentadiene polymer according to any of claims 1 to 12, comprising polymerizing dicyclopentadiene derivative of Formula (I), (Ia) or (Ib) and optionally dicyclopentadiene of Formula (II) through ring-opening metathesis polymerization.

14. The process according to claim 13, wherein a catalyst is used for ring-opening metathesis polymerization and includes metal compounds, preferably compounds of Group 8 metal, more preferably metal compounds of titanium (Ti), molybdenum (Mo), tungsten (W), rhenium (Re), osmium (Os) and ruthenium (Ru).

15. The process according to claim 14, wherein the catalyst is an organoruthenium compound having formula of.

16. The process according to claim 13, wherein the catalyst is Grubbs 2ndcatalyst.

17. The process according to any of claims 13 to 16, wherein the ring-opening metathesis polymerization is carried out in the presence of a reaction regulator, which is selected from the group consisting of nitriles, ketones, ethers, esters and organic phosphorus compounds.

18. A post-cured material of functionalized dicyclopentadiene polymer, comprising in polymerized form dicyclopentadiene derivative of Formula (I), (Ia) or (Ib) as defined in any of claims 1 to 9 and optionally dicyclopentadiene of Formula (II) as defined in any of claims 1 to 9.

19. The post-cured material according to claim 18, wherein the glass transition temperature (Tg) of the post-cured material ranges from 170°C to 400°C.

20. The post-cured material according to claim 18 or 19, which is obtained from dicyclopentadiene derivative of Formula (I), (Ia) or (Ib) as defined in any of claims 1 to 9 and optionally dicyclopentadiene of Formula (II) as defined in any of claims 1 to 9 by thermoset manufacturing process.

21. The post-cured material according to claim 20, wherein the thermoset manufacturing process is performed via one-stage or multiple-stage post curing with air, or with controlled exposure time to air, or without air exposure, preferably one-stage or two-stage post curing, more preferably one-stage post curing with polyimide film to seal the sample.

22. The post-cured material according to claim 21, wherein the curing temperature in the thermoset manufacturing process ranges from 50°C to 400°C.

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