Dicyclopentadiene derivatives and polymers thereof

Abstract

Dicyclopentadiene (DCPD) derivatives of following general formula (I); their preparation and use thereof, especially as monomers in polymerization reactions, such as olefin polymerization or ring-opening metathesis polymerization (ROMP). ##STR00001##

Claims

1. A crosslinked polymer or copolymer formed by polymerizing a compound of Formula (I): ##STR00043## wherein: R is selected from the group consisting of a linear or branched alkyl (C.sub.nH.sub.2n+1); an aryl; an alkylaryl; a positively charged nitrogen-containing group in which case the compound of Formula I is provided in a form of a salt with a suitable counter-ion, wherein the positively charged nitrogen may form part of a ring system; CH.sub.2O-dicyclopentadiene; and an ester-forming group of a general formula C(O)R; wherein R is independently selected from the group consisting of a linear or branched alkyl (C.sub.nH.sub.2n+1), substituted or unsubstituted aryl; and a positively charged nitrogen-containing group, wherein the positively charged nitrogen may form part of a ring system; and the crosslinked polymer or copolymer is formed using a (1,3-Bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro-(phenylmethylene)(tricyclohexylphosphine)ruthenium catalyst or a sulfur chelated ruthenium catalyst.

2. The crosslinked polymer or copolymer according to claim 1, having Formula (V) ##STR00044## wherein: n indicates a degree of polymerization and m indicates a degree of cross-linking; m is not zero; and Ru is a catalyst residue.

3. The crosslinked polymer or copolymer according to claim 1, wherein R is a linear or branched alkyl (C.sub.nH.sub.2n+1).

4. The crosslinked polymer or copolymer according to claim 1, wherein R is an aryl.

5. The crosslinked polymer or copolymer according to claim 1, wherein R is an alkylaryl.

6. The crosslinked polymer or copolymer according to claim 1, wherein R is a positively charged nitrogen-containing group in which case the compound of Formula I is provided in a form of a salt with a suitable counter-ion, and wherein the positively charged nitrogen may form part of a ring system.

7. The crosslinked polymer or copolymer according to claim 1, wherein R is CH.sub.2O-dicyclopentadiene.

8. The crosslinked polymer or copolymer according to claim 1, wherein R is an ester-forming group of a general formula C(O)R; wherein R is independently selected from the group consisting of a linear or branched alkyl (C.sub.nH.sub.2n+1), substituted or unsubstituted aryl, and a positively charged nitrogen-containing group in which case the compound of Formula I is provided in a form of a salt with a suitable counter-ion, wherein the positively charged nitrogen may form part of a ring system.

9. The crosslinked copolymer according to claim 1, wherein the copolymer is formed by polymerizing a compound of Formula (I) and endo-hydroxydicyclopentadiene (DCPD-OH).

10. The crosslinked polymer or copolymer according to claim 1, wherein the compound of Formula (I) is selected from the group consisting of compounds of Formula 1, Formula 2, Formula 3, Formula 4, Formula 5, Formula 11 and Formula 14: ##STR00045##

11. The crosslinked copolymer according to claim 10, wherein the copolymer is formed by polymerizing a compound of Formula (I) selected from the group consisting of compounds of Formula 1, Formula 2, Formula 3, Formula 4, Formula 5, Formula 11 and Formula 14; and endo-hydroxydicyclopentadiene (DCPD-OH).

12. The crosslinked copolymer according to claim 11, formed by polymerizing a compound of Formula 3 and endo-hydroxydicyclopentadiene (DCPD-OH).

Description

BRIEF DESCRIPTION OF THE FIGURES

(1) FIG. 1A provides a .sup.1H-NMR spectrum of hydroxydicyclopentadiene (DCPD-OH).

(2) FIG. 1B shows a .sup.13C-NMR spectrum of hydroxydicyclopentadiene (DCPD-OH).

(3) FIG. 1C shows a TGA curve of hydroxydicyclopentadiene.

(4) FIG. 1D provides a HMQC spectrum of hydroxyl-dicyclopentadiene (DCPD-OH) in CDCl.sub.3.

(5) FIG. 2A shows a .sup.1H-NMR spectrum of compound of Formula 1.

(6) FIG. 2B provides a .sup.13C-NMR spectrum of compound of Formula 1.

(7) FIGS. 2C and 2D show HRMS spectra of the sodium salt of compound of Formula 1.

(8) FIG. 2E provides a TGA curve of compound of Formula 1.

(9) FIG. 2F provides a COSY NMR spectrum of compound of Formula 1 in CDCl.sub.3.

(10) FIG. 2G provides a HMQC NMR spectrum of compound of Formula 1 in CDCl.sub.3.

(11) FIG. 3A provides a .sup.1H-NMR spectrum of compound of Formula 3.

(12) FIG. 3B provides a .sup.13C-NMR spectrum of compound of Formula 3.

(13) FIGS. 3C and 3D show HRMS spectra for the sodium salt of compound of Formula 3.

(14) FIG. 3E provides a TGA curve of compound of Formula 3.

(15) FIG. 3F provides a COSY NMR spectrum of compound of Formula 3 in CDCl.sub.3.

(16) FIG. 3G provides a HMQC NMR spectrum of compound of Formula 3 in CDCl.sub.3.

(17) FIG. 4A shows a .sup.1H-NMR spectrum of compound of Formula 4.

(18) FIG. 4B shows a .sup.13C-NMR spectrum of compound of Formula 4.

(19) FIGS. 4C and 4D provide HRMS spectra for the sodium salt of compound of Formula 4.

(20) FIG. 4E provides a TGA curve of compound of Formula 4.

(21) FIG. 4F provides a COSY NMR spectrum of compound of Formula 4 in CDCl.sub.3.

(22) FIG. 4G provides a HMQC spectrum of compound of Formula 4 in CDCl.sub.3.

(23) FIG. 5A shows a .sup.1H-NMR spectrum of compound of Formula 5 in CD.sub.2Cl.sub.2.

(24) FIG. 5B shows a .sup.13C-NMR spectrum of compound of Formula 5 in CD.sub.2Cl.sub.2.

(25) FIG. 6A shows a .sup.1H-NMR spectrum of compound of Formula 6.

(26) FIG. 6B shows a .sup.13C-NMR spectrum of compound of Formula 6.

(27) FIG. 6C shows a HRMS spectrum of compound of Formula 6.

(28) FIG. 7A provides a .sup.1H-NMR spectrum of compound of Formula 7.

(29) FIG. 7B provides a .sup.13C-NMR spectrum of compound of Formula 7.

(30) FIG. 8A shows a .sup.1H-NMR spectrum of compound of Formula 8.

(31) FIG. 8B shows a .sup.13C-NMR spectrum of compound of Formula 8.

(32) FIG. 9A provides a .sup.1H-NMR spectrum of compound of Formula 9.

(33) FIG. 9B provides a .sup.13C-NMR spectrum of compound of Formula 9.

(34) FIG. 10 provides a .sup.1H-NMR spectrum of compound of Formula 10.

(35) FIG. 11A shows a .sup.1H-NMR spectrum of compound of Formula 11.

(36) FIG. 11B shows a .sup.13C-NMR spectrum of compound of Formula 11.

(37) FIGS. 11C and 11D show HRMS spectra of the sodium salt of compound of Formula 11.

(38) FIG. 11E provides a TGA curve of compound of Formula 11.

(39) FIG. 12A provides a .sup.1H-NMR spectrum of compound of Formula 12.

(40) FIG. 12B provides a .sup.13C-NMR spectrum of compound of Formula 12.

(41) FIG. 12C provides HRMS spectrum for compound of Formula 12.

(42) FIG. 13A shows a .sup.1H-NMR spectrum of compound of Formula 13.

(43) FIG. 13B shows HRMS spectrum for compound of Formula 13.

(44) FIG. 14A provides a .sup.1H-NMR spectrum of compound of Formula 14.

(45) FIG. 14B provides a .sup.13C-NMR spectrum of compound of Formula 14.

(46) FIG. 14C provides a COSY NMR spectrum of compound of Formula 14 in CDCl.sub.3.

(47) FIG. 14D provides a HMQC spectrum of compound of Formula 14.

(48) FIG. 14E provides a HRMS spectrum of compound of Formula 14.

(49) FIG. 14F provide a TGA curve of compound of Formula 14.

(50) FIG. 15 provides a TGA curve of endo-DCPD.

(51) FIG. 16A provide a DSC curve of pDCPD (the polymer of endo-DCPD).

(52) FIG. 16B provides a TGA curve of pDCPD (the polymer of endo-DCPD), after 2 hours of curing.

(53) FIG. 17A provides a DSC curve of pDCPD-OH (the polymer of hydroxy-DCPD (DCPD-OH)).

(54) FIG. 17B provides a TGA curve of pDCPD-OH (the polymer of hydroxy-DCPD (DCPD-OH)), after 2 hours of curing.

(55) FIG. 18A provides a DSC curve of pDCPD-OMe (the polymer of a compound of Formula 1).

(56) FIG. 18B provides a TGA curve of pDCPD-OMe (the polymer of a compound of Formula 1), after 2 hours of curing.

(57) FIG. 19A provides a DSC curve of pDCPD-OPr (the polymer of a compound of Formula 3).

(58) FIG. 19B provides a TGA curve of pDCPD-OPr (the polymer of a compound of Formula 3), after 2 hours of curing.

(59) FIG. 20A provides a DSC curve of pDCPD-OOc (the polymer of a compound of Formula 4).

(60) FIG. 20B provides a TGA curve of pDCPD-OOc (the polymer of a compound of Formula 4), after 2 hours of curing.

(61) FIG. 21A provides a DSC curve of pDCPD-OAc (the polymer of a compound of Formula 14).

(62) FIG. 21B provides a TGA curve of pDCPD-OAc (the polymer of a compound of Formula 14), after 2 hours of curing.

(63) FIG. 22 provides a DMA plot for pDCPD-OCH.sub.2Ph (the polymer of compound of Formula 5).

(64) FIG. 23 provides a TGA curve of pDCPD-OBz (the polymer of compound of Formula 11), after 2 hours of curing.

(65) FIG. 24 provides a DSC curve for four pDCPD-OR polymers (OROH, OMe, OPr and OBz), the polymers of DCPD-OH and of compounds of Formulae 1, 3 and 11, respectively.

(66) FIG. 25 shows a photograph of the following polymers: (i) pDCPD (the polymer of endo-DCPD), (ii) pDCPD-OH (the polymer of DCPD-OH), (iii) pDCPD-OAc (the polymer of compound of Formula 14), (iv) pDCPD-OBz (the polymer of compound of Formula 11), (v) pDCPD-OMe (the polymer of compound of Formula 1), (vi) pDCPD-OPr (the polymer of compound of Formula 3) and (vii) DCPD-OOc (the polymer of compound of Formula 4). The transparency of the polymers is shown by the lines drawn under the polymers.

(67) FIG. 26 provides an image for wetting of pDPCD-OH (the polymer of DCPD-OH), co-(pDCPD-OH-pDCPD-OPr) (copolymer of pDPCD-OH and pDCPD-OPr), and pDCPD-OPr (the polymer of compound of Formula 3).

(68) FIG. 27 provides a DMA plot for pDCPD (the polymer of endo-DCPD). DMA storage tensile modulus E and mechanical loss factor tan as a function of temperature for pDCPD.

(69) FIG. 28 provides a DMA plot for pDCPD-OH the polymer of DCPD-OH). DMA storage tensile modulus E and mechanical loss factor tan as a function of temperature for pDCPD-OH.

(70) FIG. 29 provides a DMA plot for pDCPD-OAc (the polymer of compound of Formula 14). DMA storage tensile modulus E and mechanical loss factor tan as a function of temperature for pDCPD-OAc.

(71) FIG. 30 provides a DMA plot for pDCPD-OBz (the polymer of compound of Formula 11). DMA storage tensile modulus E and mechanical loss factor tan as a function of temperature for pDCPD-OBz.

(72) FIG. 31 provides a DMA plot for pDCPD-OMe (the polymer of compound of Formula 1). DMA storage tensile modulus E and mechanical loss factor tan as a function of temperature for pDCPD-OMe.

(73) FIG. 32 provides a DMA plot for pDCPD-OPr (the polymer of compound of Formula 3). DMA storage tensile modulus E and mechanical loss factor tan as a function of temperature for pDCPD-OPr.

(74) FIG. 33 provides a DMA plot for pDCPD-OOct (the polymer of compound of Formula 4). DMA storage tensile modulus E and mechanical loss factor tan as a function of temperature for pDCPD-OOc.

(75) FIG. 34 provides the FTIR for DCPD-OH monomer.

(76) FIG. 35 provides the FTIR for DCPD-OAc monomer (compound of formula 14).

(77) FIG. 36 provides the FTIR for DCPD-OPr monomer (compound of Formula 3).

(78) FIG. 37 provides the FTIR for cross-linked pDCPD-OH thin film (the polymer of DCPD-OH).

(79) FIG. 38 provides the FTIR for cross-linked pDCPD-OAc thin film (the polymer of compound of Formula 14).

(80) FIG. 39 provides the FTIR for cross-linked pDCPD-OPr thin film (the polymer of compound of Formula 3).

(81) FIG. 40 provides the FTIR for linear pDCPD-OAc thin film (the polymer of compound of Formula 14).

(82) FIG. 41 provides the FTIR for linear pDCPD-OPr thin film (the polymer of compound of Formula 3).

(83) FIG. 42 shows the expanded FTIR spectra for polymeric films obtained using Grubb's 1.sup.st and 2.sup.nd generation catalysts.

EXAMPLES

(84) Materials

(85) All reagents were purchased from usual suppliers and were used without further purification.

(86) Solvents were dried and stored on molecular sieves or alkali metals.

(87) Yields refer to isolated compounds greater than 95% purity as determined by proton Nuclear Magnetic Resonance spectroscopy (.sup.1H-NMR) analysis.

(88) Methods

(89) .sup.1H and .sup.13C-NMR spectra were recorded either with Bruker 400 MHz or 500 MHz FT NMR (model Avance-DPX 400 or DPX 500) instruments with chemical shifts reported in ppm relative to the residual in the deuterated solvent or the internal standard tetramethylsilane. HR-MS data were obtained using a thermoscientific LTQU XL Orbitrap HR-MS equipped with APCI (atmospheric pressure chemical ionization). TGA analysis was performed using a Mettler-Toledo instrument model TGA/SDTA851. 5-7 mg sample were heated in a standard 70 L TGA alumina crucible from room temperature to 600 C., with a heating rate of 10 C./min in nitrogen atmosphere 50 ml/min. The results were analysed by STAR.sup.e software 12.00. The crosslinked thermoset polymers were also subjected to the differential scanning calorimetric analysis (DSC) with a METTLER-TOLEDO DSC 823 and results were evaluated with the STAR.sup.e software. Each sample was subjected to a 2-3 heating cooling cycles. Each cycle contained a heating segment followed by a cooling segment at a heating rate of 5 C./min. The viscoelastic properties of the pDCPD-OR were evaluated from 25 C. to lowest storage modulus (E) temperature with the heating rate of 2 C./min using dynamic mechanical analysis (DMA) (METTLER TOLEDO DMA 1 STARe system) at different frequencies e.g. 0.1 Hz, 1 Hz and 10 Hz while experimental results were evaluated using the STARe software version 14.00. However, for very soft material like pDCPDOOc (the polymer of compound of Formula 4), the measurement was performed in the temperature range 100 C. to 10 C. until the E reached a minimum value at the same frequencies. The values of the storage modulus (E), loss modulus (E) and loss tangent (tan =E/E) for multiple frequencies were measured as a function of temperature. FTIR for the thin films was measured by using a Jasco FT/IR-460 Plus Fourier transform infrared spectrometer.

Preparation 1

Preparation of endo-hydroxydicyclopentadiene (DCPD-OH)

(90) ##STR00026##

(91) Endo-dicyclopentadiene (endo-DCPD) (40.0 g, 0.303 mol) was dissolved in 120 ml of 9:1 v/v THF/H.sub.2O solution or in 120 ml of 9:1 v/v dioxane/water solution. Selenium dioxide (40.08 g, 0.361 mol) was added in one portion, the solution was refluxed for 3 hours and cooled to room temperature. The solvent was removed in vacuo and the viscous brown oil was dissolved in 200 ml of diethyl ether, dried on magnesium sulfate, filtered and the solvent again evaporated. The crude brown oil was distilled at 1.5 mbar, the fraction at 74-76 C. was collected to afford 30 g, (67%) as a pale yellow oil which crystallized at 4 C. to a pale yellow solid, M.P. at 30-35 C.

(92) .sup.1H NMR (400 MHz, CDCl.sub.3) 5.91 (dd, J=5.7, 3.0 Hz, 1H), 5.82 (dd, J=5.7, 3.0 Hz, 1H), 5.78-5.71 (m, 1H), 5.61-5.55 (m, 1H), 4.04 (dtd, J=3.3, 2.2, 1.2 Hz, 1H), 3.35 (dddt, J=7.3, 4.2, 3.0, 2.0 Hz, 1H), 3.03 (ddd, J=3.4, 2.4, 1.5 Hz, 1H), 2.77 (ddq, J=5.6, 2.9, 1.4 Hz, 1H), 2.51 (ddd, J=7.2, 4.4, 2.1 Hz, 1H), 1.95 (s, 1H), 1.54 (dt, J=8.1, 1.8 Hz, 1H), 1.37 (dddd, J=8.1, 2.1, 1.4, 0.6 Hz, 1H).

(93) .sup.13C NMR (101 MHz, CDCl.sub.3) 137.76, 135.41, 134.63, 132.38, 78.92, 54.64, 53.37, 51.23, 44.77, 44.62.

(94) .sup.1H and .sup.13C-NMR spectra of hydroxydicyclopentadiene (DCPD-OH) are provided in FIGS. 1A and 1B, respectively.

(95) TGA curve of hydroxydicyclopentadiene (DCPD-OH) is provided in FIG. 1C.

(96) HMQC spectrum of hydroxydicyclopentadiene (DCPD-OH) in CDCl.sub.3 is provided in FIG. 1D.

Example 1

Preparation of Compounds of Formulae 1, 3 and 4, as Performed for the Compound of Formula 4

(97) ##STR00027##

(98) A three necked round bottom flask was charged with hydroxydicyclopentadiene (1 gm, 6.75 mmol) and NaH (405 mg, 10.13 mmol, 60%) and subjected to vacuum and then nitrogen, consecutively three times. Then, dry DMF (20 ml) was added to the flask and the reaction mixture was stirred at 0 C. for 10 minutes. A purple colored solution was observed. After that, 1-Iodooctane (2.43 gm, 10.13 mmol) was added through syringe in drop wise fashion, purple color disappeared and a pale white solution was observed during addition. It was then kept for 12 hours stirring at room temperature. After that, it was diluted with ethyl acetate (60 ml) and washed with saturated aqueous NH.sub.4C1 solution. The organic layer was then separated and dried over MgSO.sub.4. It was finally concentrated and subjected to flash column chromatography for purification. The expected product was eluted with Ethyl acetate/Petroleum ether (1:19) on silica gel stationary phase as a light yellowish liquid.

(99) Isolated Yield: 1.03 gm (59%)

(100) All three ethers are liquid at room temperature.

(101) Following are the .sup.1H and .sup.13C-NMR spectral data for compound of Formula 1:

(102) .sup.1H NMR (500 MHz, CDCl.sub.3) 5.95 (dd, J=5.6, 2.9 Hz, 1H), 5.86 (dd, J=5.6, 3.0 Hz, 1H), 5.82 (d, J=4.9 Hz, 1H), 5.65 (d, J=5.7 Hz, 1H), 3.71 (d, J=1.1 Hz, 1H), 3.40-3.33 (m, 1H), 3.31 (s, 3H), 2.99 (s, 1H), 2.79 (s, 1H), 2.66-2.53 (m, 1H), 1.57 (d, J=8.1 Hz, 1H), 1.43 (d, J=8.1 Hz, 1H).

(103) .sup.13C NMR (126 MHz, CDCl.sub.3) 138.66, 135.57, 132.50, 131.96, 88.02, 55.75, 54.84, 51.46, 49.71, 45.36, 44.68.

(104) .sup.1H and .sup.13C-NMR spectra for compound of Formula 1 are provided in FIGS. 2A and 2B, respectively.

(105) HRMS spectrum for the sodium salt of compound of Formula 1 are provided in FIGS. 2C and 2D.

(106) TGA curve of compound of Formula 1 is provided in FIG. 2E.

(107) COSY NMR spectrum of compound of Formula 1 in CDCl.sub.3 is provided in FIG. 2F.

(108) HMQC NMR spectrum of compound of Formula 1 in CDCl.sub.3 is provided in FIG. 2G.

(109) Following are the .sup.1H and .sup.13C-NMR spectral data for compound of Formula 3:

(110) .sup.1H NMR (500 MHz, CDCl.sub.3) 5.95 (dd, J=5.6, 2.9 Hz, 1H), 5.86 (dd, J=5.6, 3.0 Hz, 1H), 5.80 (d, J=5.7 Hz, 1H), 5.72-5.58 (m, 1H), 3.77 (d, J=1.8 Hz, 1H), 3.43 (dt, J=8.8, 6.9 Hz, 1H), 3.39-3.26 (m, 2H), 2.99 (s, 1H), 2.78 (s, 1H), 2.65-2.57 (m, 1H), 1.61-1.54 (m, 3H), 1.41 (d, J=8.1 Hz, 1H).

(111) .sup.13C NMR (126 MHz, CDCl.sub.3) 138.24, 135.58, 132.54, 132.50, 86.61, 70.33, 54.85, 51.47, 50.18, 45.37, 44.67, 23.44, 10.84.

(112) .sup.1H and .sup.13C-NMR spectra for compound of Formula 3 are provided in FIGS. 3A and 3B, respectively.

(113) HRMS spectra for the sodium salt of compound of Formula 3 are provided in FIGS. 3C and 3D.

(114) TGA curve of compound of Formula 3 is provided in FIG. 3E.

(115) COSY NMR spectrum of compound of Formula 3 in CDCl.sub.3 is provided in FIG. 3F.

(116) HMQC NMR spectrum of compound of Formula 3 in CDCl.sub.3 is provided in FIG. 3G.

(117) Following are the .sup.1H and .sup.13C-NMR spectral data for compound of Formula 4:

(118) .sup.1H NMR (500 MHz, CDCl.sub.3) 5.95 (dd, J=5.5, 2.9 Hz, 1H), 5.86 (dd, J=5.6, 3.0 Hz, 1H), 5.80 (d, J=5.7 Hz, 1H), 5.63 (d, J=5.7 Hz, 1H), 3.76 (d, J=1.7 Hz, 1H), 3.50-3.43 (m, 1H), 3.40-3.35 (m, 2H), 2.99 (s, 1H), 2.78 (s, 1H), 2.67-2.55 (m, 1H), 1.55 (dd, J=14.5, 7.3 Hz, 3H), 1.42 (d, J=8.1 Hz, 1H), 1.36-1.22 (m, 10H), 0.88 (t, J=6.9 Hz, 3H).

(119) .sup.13C NMR (126 MHz, CDCl.sub.3) 138.24, 135.59, 132.56, 132.52, 86.64, 68.74, 54.86, 51.48, 50.19, 45.39, 44.69, 31.98, 30.30, 29.63, 29.41, 26.45, 22.81, 14.24.

(120) .sup.1H and .sup.13C-NMR spectra for compound of Formula 4 are provided in FIGS. 4A and 4B, respectively.

(121) HRMS spectra for the sodium salt of compound of Formula 4 are provided in FIGS. 4C and 4D.

(122) TGA curve of compound of Formula 4 is provided in FIG. 4E.

(123) COSY NMR spectrum of compound of Formula 4 in CDCl.sub.3 is provided in FIG. 4F.

(124) HMQC spectrum of compound of Formula 4 in CDCl.sub.3 is provided in FIG. 4G.

Example 2

Preparation of Compound of Formula 5

(125) ##STR00028##

(126) To a stirring suspension of NaH (421.5 mg, 17.57 mmol, hexane washed) in dry DMF (5 ml) under N.sub.2, hydroxydicyclopentadiene (DCDP-OH, 2 gm, 13.5 mmol) was added in dropwise fashion after dissolving in dry DMF (5 ml). After 10 minutes vigorous stirring at room temperature (RT), temperature was lowered to 0 C. Then benzylbromide (2.06 ml, 17.56 mmol) was dropped into the stirring suspension. The purple suspension turned white with precipitation. It was left for 15 hours stirring by that time temperature raised to RT. The solution was then diluted with diethylether (100 ml) and washed with saturated NH.sub.4Cl solution (50 ml2). The organic layer was collected and dried over MgSO.sub.4 and concentrated. Finally purification was done using diethylether/hexane (1:49, v/v) as mobile phase while silica gel was the stationary phase. The obtained product was colorless liquid. Yield: 2.63 gm (81.3%).

(127) Following are the .sup.1H and .sup.13C-NMR spectral data for compound of Formula 5:

(128) .sup.1H NMR (CD.sub.2Cl.sub.2, ppm): 7.35 (4H, d), 7.28 (1H, m), 5.95 (1H, dd), 5.87 (1H, dd), 5.83 (1H, d), 5.66 (1H, d), 4.51 (2H, dd), 3.92-3.91 (1H, m), 3.42-3.37 (1H, m), 3.0 (1H, bs), 2.81 (1H, bs), 2.71-2.68 (1H, m), 1.58 (1H, d) and 1.45 (1H, d).

(129) .sup.13C NMR (CD.sub.2Cl.sub.2, ppm): 139.22, 138.12, 135.35, 132.39, 132.30, 128.21, 127.66, 27.28, 86.27, 70.22, 54.79, 51.25, 50.12, 45.25, 44.65.

(130) .sup.1H and .sup.13C-NMR spectra for compound of Formula 5 are provided in FIGS. 5A and 5B, respectively.

Example 3

Preparation of Compounds of Formulae 6, 7 and 8

(131) Step 1

(132) ##STR00029##

(133) To a stirring suspension of NaH (81 mg, 2.03 mmol, 60%) in dry DMF (1 ml) under inert atmosphere, hydroxy dicyclopentadiene (200 mg, 1.35 mmol) was added after dissolving in DMF (1 ml). The resultant reaction mixture was stirred for 10 minutes until it appeared as purple. It was then placed in an ice bath and then 1,n-dibromoalkane (n=5, 6, 7, 3.38 mmol) was added very slowly through syringe after dissolving in DMF (1 ml). The purple color disappeared. It was then left for 5 hours stirring at room temperature. Then it was diluted with diethyl ether (20 ml) and the organic layer was washed twice with NH.sub.4Cl. The organic layer was then separated and dried over MgSO.sub.4. Finally, it was concentrated and subjected to silica gel column chromatography for purification (2.5% diethyl ether in hexane) as colorless liquid.

(134) Isolated yield: (n=5: 53%; n=6: 42%, n=7: 36%)

(135) Step 2

(136) ##STR00030##

(137) To a stirring solution of the bromoalkoxy dicyclopentadiene (200 mg, 0.67 mmol) in DMF (1.5 ml, not dry), N-methyl imidazole (61 mg, 0.76 mmol) was added. The resultant solution was stirred at room temperature for 48 hours. Then solvent was removed under vacuum and it was washed with diethyl ether (5 times) to get a white gel in its pure form (yield: 98%).

(138) Following are the .sup.1H and .sup.13C-NMR spectral data for compound of Formula 6:

(139) .sup.1H NMR (CDCl.sub.3, ppm, 400 MHz): 10.509 (1H, s), 7.356 (1H, s) 7.295 (1H, s), 5.949-5.929 (1H, q), 5.855-5.834 (1H, q), 5.797 (1H, d), 5.588 (1H, d), 4.331 (2H, t), 4.110 (3h, s), 3.740 (1H, s), 3.508-3.454 (1H, m), 3.386-3.333 (2H, m), 2.972 (1H, s), 2.780 (1H,$), 2.568-2.534 (1H, m), 1.942 (2H, quin), 1.639-1.551 (3H, m).

(140) .sup.13C NMR (CDCl.sub.3, ppm, 100 MHz): 138.52, 138.22, 135.58, 132.50, 132.25, 123.31, 121.86, 86.78, 67.81, 54.85, 51.46, 50.19, 50.09, 45.34, 44.65, 36.91, 30.20, 29.41, 23.32.

(141) .sup.1H and .sup.13C-NMR spectra for compound of Formula 6 are provided in FIGS. 6A and 6B, respectively.

(142) HRMS spectra for compound of Formula 6 are provided in FIG. 6C.

(143) Following are the .sup.1H and .sup.13C-NMR spectral data for compound of Formula 7:

(144) .sup.1H NMR (CDCl.sub.3, ppm, 400 MHz): 10.509 (1H, s), 7.399 (1H, s), 7.304 (1H, s), 5.946-5.926 (1H, q), 5.851-5.830 (1H, q), 5.787 (1H, d), 5.592 (1H, d), 4.309 (1H, t), 4.112 (3H, s), 3.736 (1H, s), 3.481-3.426 (1H, m), 3.365-3.312 (2H, m), 2.970 (1H, s), 2.771 (1H, s), 2.577-2.542 (1H. m), 1.933-1.879 (3H, m), 1.558-1.504 (2H, m), 1.412-1.370 (5H, m).

(145) .sup.13C NMR (CDCl.sub.3, ppm, 100 MHz): 138.29, 137.96, 135.45, 132.40, 132.22, 123.25, 121.65, 86.59, 68.02, 54.72, 51.34, 50.11, 50.00, 45.23, 44.53, 35.80, 30.20, 29.82, 26.08, 25.75.

(146) .sup.1H and .sup.13C-NMR spectra for compound of Formula 7 are provided in FIGS. 7A and 7B, respectively.

(147) Following are the .sup.1H and .sup.13C-NMR spectral data for compound of Formula 8:

(148) .sup.1H NMR (CDCl.sub.3, ppm, 400 MHz): 10.755 (1H, s), 7.224 (1H, s), 7.194 (1H, s), 5.961-5.941 (1H, q), 5.867-5.845 (1H, q), 5.801 (1H, d), 5.634 (1H, d), 4.316 (2H, t), 4.123 (3H, s), 3.753 (1H, s), 3.491-3.436 (1H, m), 3.377-3.322 (2H, m), 2.985 (1H, s), 2.784 (1H, s), 2.601-2.566 (1H, m), 1.922 (2H, broad s), 1.576-1.523 (3H, m), 1.415 (1H, d), 1.360 (6H, broad s).

(149) .sup.13C NMR (CDCl.sub.3, ppm, 100 MHz): 138.24, 138.20, 135.46, 132.41, 132.27, 123.07, 121.53, 86.57, 68.28, 54.73, 51.51, 50.24, 50.02, 45.24, 44.54, 36.81, 30.20, 29.94, 28.81, 26.15, 26.08.

(150) .sup.1H and .sup.13C-NMR spectra for compound of Formula 8 are provided in FIGS. 8A and 8B, respectively.

Example 4

Preparation of Compound of Formula 9

(151) Step 1

(152) Step 1 was carried out as described in detail in Step 1 of Example 3 above.

(153) Step 2

(154) ##STR00031##

(155) To a stirring solution of the bromoalkoxy dicyclopentadiene (360 mg, 1.22 mmol) in DMF (1.5 ml, not dry), 1,2-dimethylmethyl imidazole (175 mg, 1.82 mmol) was added. The resultant solution was stirred at room temperature for 48 hours. Then solvent was removed under vacuum and it was washed with diethyl ether (5 times) to get a white solid in its pure form (yield: 87%) [Melting point: 30-35 C.].

(156) Following are the .sup.1H and .sup.13C-NMR spectral data for compound of Formula 9:

(157) .sup.1H NMR (CDCl.sub.3, ppm, 400 MHz): 10.468 (1H, s), 7.304 (1H, s), 7.251 (1H, s), 5.941-5.920 (1H, dd), 5.847-5.782 (1H, dd), 5.789 (1H, d), 5.58 (1H, d), 4.322 (3H, t), 4.096 (3H,$), 3.732 (1H,$), 3.486-3.448 (1H, m), 3.379-3.326 (2H, m), 2.963 (1H, s), 2.772 (1H, s), 2.560-2.526 (1H, m), 1.990-1.895 (2H, m), 1.631-1.543 (3H, m), 1.465-1.389 (3H, m).

(158) .sup.13C NMR (CDCl.sub.3, ppm, 100 MHz): 138.39, 137.85, 135.46, 132.38, 132.13, 123.26, 121.79, 86.65, 67.69, 54.72, 51.33, 49.97, 45.22, 44.52, 36.79, 30.20, 29.30, 23.19.

(159) .sup.1H and .sup.13C-NMR spectra for compound of Formula 9 are provided in FIGS. 9A and 9B, respectively.

Example 5

Preparation of Compound of Formula 10

(160) ##STR00032##

(161) In a 3-necked RB-flask, hydroxydicyclopentadiene (400 mg, 1 eq) and NaH (162 mg, 1.5 eq) were dissolved in dry dimethylformamide (DMF) at 0 C. under nitrogen atmosphere. After stirring for 10 minutes diiodomethane (0.326 ml, 1.5 eq) was added in one portion and stirred overnight. Ethylacetate was added, washed with aqueous NH.sub.4Cl solution, organic layer was collected, dried on MgSO.sub.4, filtered and evaporated. Purified by silica gel chromatography with 5% ethyl acetate in petroleum ether.

(162) Isolated Yield: 82 mg.

(163) Following are the .sup.1H-NMR spectral data for compound of Formula 10:

(164) .sup.1H NMR (400 MHz, CDCl.sub.3) 5.91 (d, J=41.6 Hz, 4H), 5.82 (t, J=6.3 Hz, 2H), 5.62 (dd, J=12.2, 5.4 Hz, 2H), 4.85-4.70 (m, 2H), 4.08 (s, 2H), 3.39 (s, 2H), 3.01 (s, 2H), 2.80 (s, 2H), 2.65 (s, 2H), 1.57 (s, 2H), 1.42 (t, J=6.6 Hz, 2H).

(165) .sup.1H-NMR spectrum for compound of Formula 10 is provided in FIG. 10.

Example 6

Preparation of Compound of Formula 11 (DCPD-OBz)

(166) ##STR00033##

(167) A three necked round bottom flask was charged with hydroxydicyclopentadiene (1 gm, 6.75 mmol), was subjected to vacuum and then nitrogen, consecutively three times. Then, dry DCM (50 ml) and Et3N (1.5 ml) were added and the reaction mixture was stirred at 0 C. for 10 minutes. After that, benzoyl chloride (727 l, 10.13 mmol) was added through syringe in drop wise fashion. The reaction mixture was then kept for 12 hours stirring at room temperature. After that, it was washed with water. The organic layer was then separated and dried over MgSO.sub.4. It was finally concentrated and subjected to flash column chromatography for purification. The expected product was eluted with Ethyl acetate/Petroleum ether (1:19) on silica gel stationary phase as a light yellowish liquid.

(168) Isolated Yield: 1.04 gm (81%)

(169) Compound of formula 11 is solid with M.P. at 70 C.

(170) Following are the .sup.1H and .sup.13C-NMR spectral data for compound of Formula 11:

(171) .sup.1H NMR (500 MHz, CDCl.sub.3) 8.03 (dd, J=8.1, 0.9 Hz, 2H), 7.54 (t, J=7.4 Hz, 1H), 7.42 (t, J=7.7 Hz, 2H), 6.11 (dd, J=5.6, 3.0 Hz, 1H), 5.95 (d, J=5.7 Hz, 1H), 5.91 (dd, J=5.6, 3.0 Hz, 1H), 5.70 (d, J=5.7 Hz, 1H), 5.27-5.17 (m, 1H), 3.48-3.40 (m, 1H), 3.19 (s, 1H), 2.86 (s, 1H), 2.80-2.73 (m, 1H), 1.63 (d, J=8.2 Hz, 1H), 1.44 (d, J=8.2 Hz, 1H).

(172) .sup.13C NMR (126 MHz, CDCl.sub.3) 166.83, 140.28, 135.57, 132.89, 132.83, 131.00, 130.82, 129.69, 128.41, 82.90, 77.41, 77.16, 76.91, 54.84, 51.57, 50.55, 45.00, 44.93.

(173) .sup.1H and .sup.13C-NMR spectra for compound of Formula 11 are provided in FIGS. 11A and 11B, respectively.

(174) HRMS spectra for the sodium salt of compound of Formula 11 are provided in FIGS. 11C and 11D.

(175) TGA curve of compound of Formula 11 is provided in FIG. 11E.

Example 7

Preparation of Compound of Formula 12

(176) Step 1

(177) ##STR00034##

(178) To the suspension of N,N-dimethylamino benzoic acid (500 mg, 3.02 mmol) in EtOAc, thionyl chloride (540 mg, 4.52 mmol) was added and it was kept under reflux under inert conditions for 10 hours until a clear yellow solution was observed. The solvent was removed after cooling to room temperature and the obtained yellow solid was immediately dissolved in dry dichloromethane (20 ml). Then hydroxydicyclopentadiene (400 mg, 2.7 mmol) was dissolved in dry dichloromethane (10 ml) containing Et3N (1 ml) and was added into the acid chloride solution at room temperature and was left for overnight stirring. Then the solvent was removed and the ester product was purified by silica gel column chromatography using 5% EtOAc in hexane (Isolated yield: 50%).

(179) Step 2

(180) ##STR00035##

(181) To the solution of the ester product of Step 1 in DMF (2 ml), MeI (5 ml, excess) was added. The solution was stirred for 48 hours at room temperature. Then solvent was removed and diethyl ether was added to yield a white precipitate. The precipitate (compound of formula 12) was separated and washed with ether for thrice and isolated as its pure form after drying (yield: 100%).

(182) Following are the .sup.1H and .sup.13C-NMR spectral data for compound of Formula 12:

(183) .sup.1H NMR (DMSO-d.sub.6, ppm, 400 MHz): 8.142 (4H, s), 6.126 (1H, q), 6.046 (1H, d, 5.6 Hz), 5.937 (1H, q), 5.708 (1H, d), 5.159 (1H, s), 3.656 (9H, s), 3.412 (1H, s), 3.127 (1H, s), 2.903 (1H, d), 2.777-2.765 (1H, m), 1.546 (1H, d), 1.563 (1H, d).

(184) .sup.13C NMR (DMSO-d.sub.6, ppm, 100 MHz): 164.75, 150.93, 141.41, 136.18, 132.98, 132.89, 132.83, 131.83, 131.12, 130.74, 121.76, 83.60, 56.95, 54.77, 51.44, 50.16, 44.74, 34.95.

(185) .sup.1H and .sup.13C-NMR spectra for compound of Formula 12 are provided in FIGS. 12A and 12B, respectively.

(186) HRMS spectra for compound of Formula 12 are provided in FIG. 12C.

Example 8

Preparation of Compound of Formula 13

(187) ##STR00036##

(188) Compound of Formula 12 (860 mg) was dissolved in water (100 ml) and the insoluble part was filtered off. The filtrate was collected and to it was added NH.sub.4PF.sub.6 (1.5 gm) to get white precipitate. It was left for overnight stirring. Then an extraction was done with CHCl.sub.3. The organic layer was collected, dried over MgSO.sub.4 and collected as white gum after concentration. A white and pure precipitate (compound of Formula 13) was obtained after adding hexane into that gum (yield: 77%, Melting point: 150 C.).

(189) Following is the .sup.1H-NMR spectral data for compound of Formula 13:

(190) .sup.1H NMR (CDCl.sub.3, ppm, 400 MHz): 8.241 (2H, d), 7.799 (2H, d), 6.085 (1H, q), 5.972 (1H, d), 5.913 (1H, q), 5.663 (1H, d), 5.210 (1H, s), 3.677 (9H, s), 3.464 (1H, s), 3.164 (1H, s), 2.881 (1H, s), 2.747 (1H, m), 1.638 (1H, d), 1.457 (1H, d).

(191) .sup.1H-NMR spectrum for compound of Formula 13 is provided in FIG. 13A.

(192) HRMS spectra for compound of Formula 13 are provided in FIG. 13B.

Example 9

Preparation of acetoxydicyclopentadiene (DCPD-OAc)

(193) Acetoxydicyclopentadiene (DCPD-OAc) (compound of Formula 14), was prepared by following the general procedure for esterification of DCPD-OH described in Example 6 hereinabove. Briefly, a three necked round bottom flask was charged with DCPD-OH (1 gm, 6.75 mmol) and was subjected to vacuum and then nitrogen consecutively three times. Then, dry DCM (50 ml) and Et.sub.3N (1.5 ml) were added to it and the solution was stirred at 0 C. for 10 min. After that, acetyl chloride (10.13 mmol) was added through syringe in dropwise fashion. It was then kept for 12 hours stirring at room temperature. After that, it was washed with water. The organic layer was separated and dried over MgSO.sub.4. It was finally concentrated and subjected to flash column chromatography for purification. The product (compound of Formula 14) was eluted with ethyl acetate/petroleum ether (1:19) on neutral alumina stationary phase.

(194) ##STR00037##

(195) Compound of Formula 14 is a colorless liquid, isolated yield: 85%, boiling point: 224-226 C.

(196) Following are the .sup.1H and .sup.13C-NMR spectral data for compound of Formula 14:

(197) .sup.1H NMR (500 MHz, CDCl.sub.3, ppm) (3a): 6.03 (dd, J=5.5, 3.0 Hz, 1H), 5.88 (bd, J=5.5 Hz, 1H), 5.86 (dd, J=5.5, 3.0 Hz, 1H), 5.57 (bd, J=5.5 Hz, 1H), 4.96 (bs, 1H), 3.383.37 (m, 1H), 3.10 (bs, 1H), 2.82 (bs, 1H), 2.61-2.59 (m, 1H), 2.02 (s, 3H), 1.58 (bd, J=8.2 Hz, 1H), 1.40 (bd, J=8.2 Hz, 1H).

(198) .sup.13C NMR (125 MHz, CDCl.sub.3, ppm) (3a): 171.22, 140.15, 135.48, 132.68, 130.86, 82.23, 54.67, 51.47, 50.37, 44.94, 44.84 and 21.51.

(199) .sup.1H and .sup.13C-NMR spectra for compound of Formula 14 are provided in FIGS. 14A and 14B, respectively.

(200) COSY NMR spectrum of compound of Formula 14 in CDCl.sub.3 is provided in FIG. 14C.

(201) HMQC and HRMS spectra for compound of Formula 14 are provided in FIGS. 14D and 14E, respectively.

(202) TGA curve for compound of Formula 14 is provided in FIG. 14F.

Example 10

TGA Analysis of Some of the Neutral DCPD Derivatives of General Formulae (I) and (II)

(203) Some neutral DCPD derivatives of general Formulae (I) and (II) were analyzed by TGA to evaluate their weight loss at high temperatures. As shown in Table 1, all derivatives displayed maximum rate of weight loss at higher temperatures compared to endo-dicyclopentadiene (endo-DCPD), with a certain correlation to the boiling points of the derivatives.

(204) TABLE-US-00001 TABLE 1 Maximum rate of weight loss T Compound ( C.) endo-DCPD 165.7 DCPD-OH 218.2 Compound of Formula 14 230.4 Compound of Formula 11 260.1 Compound of Formula 1 212.5 Compound of Formula 3 226.9 Compound of Formula 4 254.1

(205) A TGA curve of endo-DCPD is provided in FIG. 15.

(206) The corresponding TGA curves of DCPD-OH and compounds of Formulae 1, 3, 4, 11 and 14 are provided in FIGS. 2E, 3E, 4E, 11E and 14E respectively.

Example 11

Smell and Volatility Properties of Some of the Neutral DCPD Derivatives of General Formulae (I) and (II)

(207) All of the compounds of Formulae (I) and (II) that were prepared as detailed in Examples 1-9 above, had a significantly reduced smell compared to endo-DCPD.

(208) The boiling points of some of the neutral compounds of Formulae (I) and (II) were measured and are provided in Table 2.

(209) TABLE-US-00002 TABLE 2 Compound Boiling Point T ( C.) endo-DCPD 170 DCPD-OH 216-217 Compound of Formula 14 (DCPD-OAc) 224-226 Compound of Formula 1 (DCPD-OMe) 214-217 Compound of Formula 3 (DCPD-OPr) 216-218 Compound of Formula 4 (DCPD-OOc) 220-222

(210) Without being bound by theory, it is believed that the significantly reduced smell is due to increase of intermolecular polar interactions and lowering of the compounds' volatility, as can be seen from the boiling points of some of the compounds provided in Table 2.

Example 12

Formation and Characterization of Cross-Linked Polymers of Neutral Monomers of Formula (I) and (II)

(211) A.

(212) ##STR00038##

(213) Polymerization of some neutral monomers of general Formulae (I) and (II) (was carried out according to the following general procedure: 1 mmol of monomer (RH, OH, OCOCH.sub.3, OCH.sub.3, O.sup.nC.sub.3H.sub.7 or O.sup.nC.sub.8H.sub.17) was introduced to a 4 ml glass vial and then 2.sup.nd generation Grubbs' catalyst (2.010.sup.4 mmol) dissolved in a small amount of dry CH.sub.2Cl.sub.2 (50 l) was added. After mixing the solution very quickly, the solvent was removed by gentle blowing of argon and the remaining mixture was transferred into a rectangular shaped (2 cm1 cm1 mm) aluminum mold and placed in an oven of pre-set temperature at 70 C. for 60 minutes to produce the highly cross-linked solid polymer.

(214) The following monomers were polymerized by following the above detailed procedure: endo-dicyclopentadiene (endo-DCPD), hydroxydicyclopentadiene (interchangeably identified herein as hydroxyl-DCPD or as DCPD-OH), compound of Formula 1, compound of Formula 3, compound of Formula 4 and acetoxydicyclopentadiene (compound of Formula 14). All reactions were performed with Grubbs' 2.sup.nd generation catalyst 1,3-Bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro-(phenylmethylene) (tricyclohexylphosphine)ruthenium), commercially available from Sigma Aldrich.

(215) Polymerization reactions of hydroxydicyclopentadiene (DCPD-OH), of compound of Formula 1, of compound of Formula 3 and of compound of Formula 14, resulted in a solid, hard polymer. Polymerization of the octyl derivative of Formula 4, resulted in a rubbery, flexible polymer.

(216) All of the obtained polymers were odourless.

(217) Characteristic properties of the resultant polymers were measured using Differential Scanning calorimetry (DSC) technique and by TGA, in order to evaluate the effect of the substituents on the polymers' thermal properties.

(218) DSC curve of a polymer of endo-DCPD (pDCPD) is provided in FIG. 16A.

(219) TGA curve of a polymer of endo-DCPD (pDCPD), after 2 hours of curing, is provided in FIG. 16B.

(220) DSC curve of a polymer of hydroxyl-DCPD (pDCPD-OH) is provided in FIG. 17A.

(221) TGA curve of a polymer of hydroxyl-DCPD (pDCPD-OH), after 2 hours of curing, is provided in FIG. 17B.

(222) DSC curve of a polymer of compound of Formula 1 is provided in FIG. 18A.

(223) TGA curve of a polymer of compound of Formula 1, after 2 hours of curing, is provided in FIG. 18B.

(224) DSC curve of a polymer of compound of Formula 3 is provided in FIG. 19A.

(225) TGA curve of a polymer of compound of Formula 3, after 2 hours of curing, is provided in FIG. 19B.

(226) DSC curve of a polymer of compound of Formula 4 is provided in FIG. 20A.

(227) TGA curve of a polymer of compound of Formula 4, after 2 hours of curing, is provided in FIG. 20B.

(228) DSC curve of a polymer of compound of Formula 14 is provided in FIG. 21A.

(229) TGA curve of a polymer of compound of Formula 14, after 2 hours of curing, is provided in FIG. 21B.

(230) B.

(231) Polymerization of Compound of Formula 5 (DCPD-OCH.sub.2pH)

(232) ##STR00039##

(233) Polymerization of compound of Formula 5 (DCPD-OCH.sub.2Ph) was carried out according to the following procedure:

(234) The monomer (compound of Formula 5 (DCPD-OCH.sub.2Ph)) (600 mg, 2.52 mmol) was introduced to a 4 ml glass vial and then 2.sup.nd generation Grubbs' catalyst (0.43 mg, 5.0410.sup.4 mmol) dissolved in a small amount of dry CH.sub.2Cl.sub.2 (100 l) was added. After mixing the solution very quickly, the solvent was removed by gentle blowing of argon and the remaining mixture was distributed into three rectangular shaped (2 cm1 cmmm) aluminum molds and placed in an oven of pre-set temperature at 70 C. for 60 minutes to produce the odorless cross-linked solid polymer pDCPD-OCH.sub.2Ph.

(235) The viscoelastic properties of the pDCPD-OCH.sub.2Ph were evaluated from 25 C. to lowest storage modulus (E) temperature with the heating rate of 1 C./min using dynamic mechanical analysis (DMA) (METTLER TOLEDO DMA 1 STARe system) at different frequencies e.g. 0.1 Hz and 1 Hz while experimental results were evaluated using the STAR.sup.e software version 14.00. DMA plot for pDCPD-OCH.sub.2Ph is provided in FIG. 22. The values of the storage modulus (E), loss modulus (E) and loss tangent (tan =E/E) for multiple frequencies were measured as a function of temperature. The glass transition temperatures (T.sub.g) attendant with the a peaks are commonly defined either from the onset of the decrease of the modulus or from the tan peak. The T.sub.g on the onset curve elucidates the mechanical softening useful for load-bearing applications while tan indicates the maximum mobility. T.sub.g values obtained at different frequencies are summarized in Table 3.

(236) TABLE-US-00003 TABLE 3 0.1 Hz 1 Hz Onset (Tg) ( C.) tan ( C.) Onset (Tg) ( C.) tan ( C.) 29.10 38.40 31.12 41.86
C.

(237) Polymerization of compound of Formula 11 (DCPD-OBz) was carried out according to the following procedure:

(238) ##STR00040##

(239) Polymerization of compound of Formula 11 was more challenging as it has a melting point of 70 C. Thus, the compound of Formula 11 was melted at 100 C. in an oven and then it was polymerized at this same temperature. Also in this case a latent sulphur chelated ruthenium catalyst (such as cis-RuSPh) had to be used, as compound of Formula 11 instantly polymerized with the Grubbs' 2.sup.nd generation catalyst at 100 C.

(240) Briefly, 0.252 gr of compound of Formula 11 was melted at 100 C. in an oven and then it was polymerized at this same temperature, using a 0.02 mol % latent sulphur chelated ruthenium catalyst cis-RuSPh or cis-RuS.sup.iPr (cis-RuSPh was predominantly used), described in (a) A. Ben-Asuly, A. Aharoni, C. E. Diesendruck, Y. Vidaysky, I. Goldberg, B. F. Straub and N. G. Lemcoff, Organometallics, 2009, 28, 4652-4655; (b) E. Tzur, E. Ivry, C. E. Diesendruck, Y. Vidaysky, I. Goldberg and N. G. Lemcoff, J. Organomet. Chem., 2014, 769, 24-28, dissolved in a small amount of dry CH.sub.2Cl.sub.2 (50 l). The solvent was removed by evaporation and the mixture was heated to 100 C. for 1 hour.

(241) The obtained polymer was odourless.

(242) Characteristic properties of the resultant polymers were measured using Differential Scanning calorimetry (DSC) technique and by TGA, in order to evaluate the effect of the substituents on the polymers' thermal properties.

(243) TGA curve of a polymer of compound of Formula 11 is provided in FIG. 23.

(244) DSC curve of a polymer of compound of Formula 11, as well as DSC curves of the polymers of DCPD-OH and of compounds of Formulae 1 and 3, are provided in FIG. 24.

(245) D.

(246) Transparency of polymers is important in some applications, such as, for example thin film applications, as well as for containers and formed objects. Therefore, transparency of the polymers of some neutral monomers of general Formulae (I) and (II) was examined. FIG. 25 shows a photograph of the following polymers: (i) pDCPD (the polymer of endo-DCPD), (ii) pDCPD-OH (the polymer of DCPD-OH), (iii) pDCPD-OAc (the polymer of compound of Formula 14), (iv) pDCPD-OBz (the polymer of compound of Formula 11), (v) pDCPD-OMe (the polymer of compound of Formula 1), (vi) pDCPD-OPr (the polymer of compound of Formula 3) and (vii) DCPD-OOc (the polymer of compound of Formula 4). The polymers were obtained as described in sections A and B hereinabove. The transparency of the polymers is shown by the lines drawn under the polymers. As evident from FIG. 25, all of the above polymers are quite transparent except for the polymer of compound of Formula 1 (pDCPD-OMe).

(247) E.

(248) In the TGA, a distinct behavior was observed for the ether derivatives (polymers of some neutral monomers of general Formulae (I)) and the ester derivatives (polymers of some neutral monomers of general Formulae (II)). The hydroxyl and ether derivatives displayed only one distinctive decomposition temperature, while the esters showed two decomposition steps, probably due to breakdown of the side group followed by the main chain decay pathway. Table 4 summarizes the decomposition temperatures of the new polymers. As can be seen from the data in Table 4, the new hydroxyl and ether polymers showed maximum rate decomposition temperatures very similar to that of the parent pDCPD polymer, while the esters showed greater decomposition at lower temperatures. However, pDCPD has greater stability at extreme temperatures, indicating that probably the side chains are being decomposed first.

(249) TABLE-US-00004 TABLE 4 Decomposition temperatures obtained from the TGA data for cross-linked polymers 5% 10% Main chain max Ester maximum weight weight decomposition decomposition loss loss rate rate Polymer T ( C.) T ( C.) T ( C.) T ( C.) pDCPD 212.2 451.0 474.4 pDCPD-OH 187.7 230.1 469.9 pDCPD-OAc 228.7 253.0 471.1 261.7 (the polymer of compound of Formula 14) pDCPD-OBz 212.8 219.0 473.8 231.1 (the polymer of compound of Formula 11) pDCPD-OMe 181.0 217.1 463.4 (the polymer of compound of Formula 1) pDCPD-OPr 219.4 253.8 467.1 (the polymer of compound of Formula 3) pDCPD-OOc 196.9 250.0 466.7 (the polymer of compound of Formula 4)
F.

(250) DSC analyses in Table 5 show that substitutions on DCPD significantly decreased the Tg of the resultant polymers compared to the parent pDCPD, ranging from 80 C. for pDCPD-OMe (the polymer of compound of Formula 1), up to 143 C. for pDCPD-OBz (the polymer of compound of Formula 11). For pDCPD-OOc (the polymer of compound of Formula 4) and pDCPD-OAc (the polymer of compound of Formula 14), no Tg values were found, neither at high temperatures nor by cooling to 100 C.

(251) TABLE-US-00005 TABLE 5 Glass transition temperatures from DSC analysis Polymer Tg ( C.) pDCPD 163.3 pDCPD-OH 83.5 pDCPD-OAc (the polymer of compound of N.A Formula 14) pDCPD-OBz (the polymer of compound of 142.9 Formula 11) pDCPD-OMe (the polymer of compound of 79.6 Formula 1) pDCPD-OPr (the polymer of compound of 80.9 Formula 3) pDCPD-OOc (the polymer of compound of N.A Formula 4)

(252) Unlike all other polymers which formed stiff solid materials, pDCPD-OOc appeared as a very flexible and elastic, stretchable polymer. pDCPD-OAc was also relatively soft, although not as flexible as the octyl-ether (the polymer of compound of Formula 4).

(253) G.

(254) The following wetting experiment was performed in order to understand the hydrophilic and hydrophobic nature of the polymers:

(255) Polymers of pDCPD-OH, pDCPD-OPr (the polymer of compound of Formula 3) and a copolymer of both pDCPD-OH and pDCPD-OPr, were prepared in a 4 ml glass vial. The copolymer was prepared by mixing DCPD-OH and DCPD-OPr in a 50/50 ratio. All polymers were prepared following the general polymerization procedure detailed in section A hereinabove. After polymerization was completed the vial was broken and the polymer removed. 30 l deionized water were added to the top of each of the polymers and a snapshot was taken after a few minutes.

(256) A qualitative wetting contact angle test on pDCPD-OH, pDCPD-OPr (the polymer of compound of Formula 3) and a copolymer of both, nicely showed how changing the functional group of the monomer can affect the hydrophilic properties of the surface as expected. The image for wetting of pDPCD-OH, co-(pDCPD-OH-pDCPD-OPr) and pDCPD-OPr is provided in FIG. 26. The lines are visual aids, the differences in the contact angles are quite apparent.

(257) H.

(258) In order to further study the thermal properties of the polymers, dynamic mechanical analysis (DMA) of the samples were performed at various fixed frequencies as a function of temperature to obtain the storage modulus (E), loss modulus (E) and the tangent modulus (tan =E/E). The glass transition temperatures (Tg) attendant with the a peaks are commonly defined either from the onset of the decrease of the E modulus or from the tan peak. The Tg on the onset curve elucidates the mechanical softening useful for load-bearing applications. These Tg values obtained at different frequencies are summarized in Table 6.

(259) TABLE-US-00006 TABLE 6 Onset Tg and tan values obtained from DMA measurement (10 Hz) (1 Hz) (0.1 Hz) Onset Tan Onset tan Onset tan Sample Tg Tg Tg Tg Tg Tg name ( C.) ( C.) ( C.) ( C.) ( C.) ( C.) pDCPD 64.0 77.2 62.1 75.0 59.3 70.4 pDCPD-OH 95.8 112.8 92.5 105.4 87.9 95.1 pDCPD-OAc 59.7 77.1 59.5 75.2 59.4 83.4 (the polymer of compound of Formula 14) pDCPD-OBz 59.6 77.5 54.9 75.5 50.9 68.9 (the polymer of compound of Formula 11) pDCPD-OMe 42.3 52.7 39.3 58.7 37.8 62.7 (the polymer of compound of Formula 1) pDCPD-OPr 50.2 73.7 50.7 67.8 49.7 61.3 (the polymer of compound of Formula 3) pDCPD-OOc 9.6 14.2 2.7 17.4 10.2 (the polymer of compound of Formula 4)

(260) As observed from the values in Table 6, glass transition temperatures were quite different from the Tg values obtained by DSC experiments because of the applied mechanical forces. Table 6 shows that the new polymer pDCPD-OH (the polymer of DCPD-OH) has the highest Tg values, while rubbery pDCPD-OOc (the polymer of compound of Formula 4) has the lowest. The DMA curves for each polymer are depicted in FIGS. 27-33. Overall it can be observed that the new polymers display thermal properties that fall in line with the parent polydicyclopentadiene material produced by the same ruthenium catalyst. Thus, it has now been shown that the new polymers disclosed herein possess useful physical properties, while lacking the irritating odour of the dicyclopentadiene parent monomer.

Example 13

Formation and Comparison of Linear and Cross-Linked Polymer Films of Neutral Monomers of Formula (I) and (II)

(261) The formation of cross-linked polymers was studied by carrying out infrared spectroscopy analyses on polymer films prepared with Grubbs' 1.sup.st and 2.sup.nd generation catalysts. It has been reported that the use of Grubbs' 1.sup.st generation catalyst leads to linear polymers with DCPD derivatives at low temperatures (Gong L. et al. RSC Adv., 2015, 5, 26185-26188), and it has also been shown that the catalyst devoid of the N-heterocyclic carbene ligand is much less reactive in reactions with doubly substituted olefins (such as the cyclopentene moiety in DCPD) (S. Elmer, N. G. Lemcoff and S. C. Zimmerman, Macromolecules, 2007, 40, 8114-8118). Thus, it was surmised that 1.sup.st generation catalysts would give more linear polymers, while 2.sup.nd generation catalysts should give more cross-linked material.

(262) Thin polymer films were produced according to the following general procedure: 20 mg of monomer were mixed with 0.03 mg of ruthenium catalyst dissolved in 30 L of dry CH.sub.2Cl.sub.2. The mixture was transferred onto microscope slide and was covered with second slide. Air bubbles were removed by applying pressure on the slides. For linear polymer films: Grubbs 1st generation catalyst was used [CAS Number 172222-30-9, Grubbs Catalyst, 1.sup.st Generation purchased from Sigma-Aldrich]. The setup was kept at RT (25 C.) for 2 hours. For cross-linked polymer films: Grubbs' 2.sup.nd generation catalyst was used [as specified hereinabove in Example 12A]. The setup was kept at 70 C. for 30 minutes.

(263) All of the polymers thus formed were subjected to solubility testing in several organic solvents, including THF, ethyl acetate, chloroform, methylene chloride. It was found that the above-identified linear polymer films were soluble in organic solvents, whereas the above-identified cross-linked polymer films were insoluble in organic solvents. Without being bound by theory it is believed that the insolubility of the polymers made with the Grubb's 2.sup.nd generation catalyst, in regular organic solvents, provides a proof for the formation of cross-linked polymers.

(264) All films thus formed were analysed by FTIR.

(265) A FTIR spectrum for DCPD-OH monomer is provided in FIG. 34.

(266) A FTIR spectrum for DCPD-OAc monomer (compound of Formula 14) is provided in FIG. 35.

(267) A FTIR spectrum for DCPD-OPr monomer (compound of Formula 3) is provided in FIG. 36.

(268) A FTIR spectrum for cross-linked pDCPD-OH thin film (the polymer of DCPD-OH) is provided in FIG. 37.

(269) A FTIR spectrum for cross-linked pDCPD-OAc thin film (the polymer of compound of Formula 14) is provided in FIG. 38.

(270) A FTIR spectrum for cross-linked pDCPD-OPr thin film (the polymer of compound of Formula 3) is provided in FIG. 39.

(271) A FTIR spectrum for linear pDCPD-OAc thin film (the polymer of compound of Formula 14) is provided in FIG. 40.

(272) A FTIR spectrum for linear pDCPD-OPr thin film (the polymer of compound of Formula 3) is provided in FIG. 41.

(273) Careful observation of the expanded spectra (3100-2950 cm.sup.1 region), shows that the IR absorption bands at 3000 cm.sup.1 (assigned to CH acyclic bond) were present only for polymers made with the Grubb's 2.sup.nd generation catalyst and almost negligible for those made with the Grubb's 1.sup.st generation catalyst. FIG. 42 shows the expanded FTIR spectra for polymeric films obtained using Grubb's 1.sup.st and 2.sup.nd generation catalysts. The presence of an absorption band around 3000 cm.sup.1 is indicative of cross-linking.

Example 14

Polymerization of Some Ionic Monomers of Formula (I) and (II)

(274) Polymerization of ionic monomers of general Formulae (I) and (II) was carried out according to the following procedure:

(275) ##STR00041##

(276) A mixture of hydroxydicyclopentadiene (200 mg, 1.35 mmol), ionic monomer (4 mg, 0.0105 mmol) and cis-phenyl-sulfur chelated ruthenium catalyst as shown in the scheme above (R in the cis-phenyl-sulfur chelated ruthenium catalyst is phenyl), described in Kost, T. et al, Journal of Organometallic Chemistry, 2008, 693, 2200-2203, (1.84 mg, 2.72 mol) were dissolved in 100 l of dry CHCl.sub.3. Then solvent was removed by vacuum and the reaction mixture was placed in oven at 90 C. for 1 hour to get the covalent ionic crossed linked polymer.

Example 15

Polymerization Assisted with Catalysts Responsive to UV Irradiation

(277) Polymerization of DCPD-OH was carried out with a catalyst responsive to UV irradiation according to the following procedure:

(278) ##STR00042##

(279) In a 4-ml vial, 0.228 g of DCPD-OH was mixed with 0.31 mg of S-Phenyl-Ru catalyst as shown in the scheme, (as ca. 20 methylene chloride solution). The solvent was evaporated and the mixture was layered on a template having dimensions 20 mm10 mm1 mm. The template was irradiated with 350-nm UV light for 1:40 hours, at room temperature. A hard cross-linked polymer was obtained.