Showing papers on "Norbornene published in 1977"
TL;DR: In this article, the polymerization of norbornene in the presence of either radical catalysts having a short half-life at polymerization temperature or ethylaluminum dichloride yields a saturated polymer having a rearranged structure with 2,7 linkages.
Abstract: The polymerization of norbornene in the presence of either radical catalysts having a short half-life at the polymerization temperature or ethylaluminum dichloride yields a saturated polymer having a rearranged structure with 2,7 linkages. Polymerization in the presence of either Pd(C6H5CN)2Cl2 or Ziegler-Natta catalysts containing TiCI4 and A1R3 or R2 A1C1 yields a saturated polymer with 2,3 linkages.
109 citations
TL;DR: In this paper, the rates of hydration of various alkenes, including propene, cyclohexene, 1-methylcyclohexenes and norbornene, were measured at 25/sup 0/C.
Abstract: The rates of hydration of ethylene, propene, 1-hexene, cyclohexene, 1-methylcyclohexene, 1-methylcyclopentene, and norbornene catalyzed by H/sub 2/SO/sub 4/ and D/sub 2/SO/sub 4/, and the hydration of cyclohexene catalyzed by HClO/sub 4/ and DClO/sub 4/, all at 25/sup 0/C, were measured. Ethylene is only a factor of 24 less reactive than p-nitrostyrene at H/sub 0/ = -7.37, but has a very steep slope of log k/sub obsd/ vs. H/sub 0/ of -1.54 so that ethylene rates extrapolated to low acidities appear quite small relative to other alkenes. All of the substrates are interpreted to react by rate-determining protonation on carbon to give the corresponding carbonium ions (the A/sub SE/2 mechanism). Solvent isotope effects k/sub H/sup +///k/sub D/sup +// range from 2.82 for propene to 1.06 for cyclohexene, and are only tenuously related to absolute reactivity. Norbornene is 770 times more reactive than cyclohexene, and at least part of this difference is attributed to the unsymmetrical ..pi.. bond in this molecule endowing it with enhanced nucleophilicity on the exo face.
49 citations
TL;DR: The molecular structure of norbornene has been investigated in the gas phase by combining electron diffraction data with microwave spectroscopic rotational constants as discussed by the authors, and the interatomic distances (rg) and bond angles were obtained by applying a least squares program to the refined experimental molecular diffraction intensities.
40 citations
TL;DR: The reaction of substituted (difluoroiodo)arenes with 1-phenyl-1-(m-chlorophenyl)ethylene results in 1,1-diffluoro-1-mchlorphenyl)2-phenylethane as mentioned in this paper.
Abstract: The reaction of substituted (difluoroiodo)arenes with 1-phenyl-1-(m-chlorophenyl)ethylene results in 1,1-difluoro-1-(m-chlorophenyl)2-phenylethane, with 1-phenyl-1-(p-methoxyphenyl)ethylene in 1,1-difluoro-1-phenyl-2-(p-methoxyphenyl) ethane, and with 1-phenylcyclopentene and 1-phenylcyclohexene in rearranged gem-difluoro compounds. The reaction with norbornene results in three products: fluoronortricyclane (9–12%), 2-exo-7-syn-difluoronorbornane (75–86%), and 2-exo-7-anti-difluoronorbornane (5–15%) depending upon the substituent on the phenyl ring in (difluoroiodo)arenes.
38 citations
Patent•
04 Mar 1977TL;DR: In this article, a two-stage process is described for the graft polymerization of acrylate graft copolymers, which comprises from about 5 to about 80 weight percent of the backbone polymer with the balance being furnished by the Acrylate monomer.
Abstract: Acrylate graft copolymers prepared in a two-stage process by first reacting a backbone polymer, such as 1,2-polybutadiene, an alkylidene norbornene polymer or an ethylene/propylene/alkylidene norbornene terpolymer, with, for example, a mixture of dinitrogen tetroxide and oxygen to form a nitrooxidized polymer having incorporated therein nitro and peroxy nitrate functions which serve, in the second stage of the process, as sites for the subsequent graft polymerization of an acrylate monomer are disclosed. The thus-formed graft copolymers comprise from about 5 to about 80 weight percent of the backbone polymer with the balance being furnished by the acrylate monomer.
24 citations
Patent•
05 Dec 1977
TL;DR: In this article, a 1,2-Dihydrodicyclopentadiene is copolymerized by ring opening with (1) norbornene, at least one alkylnorbornene or a mixture thereof and (2) acyclic monoolefin or nonconjugated acyCLic olefin.
Abstract: 1,2-Dihydrodicyclopentadiene is copolymerized by ring opening with (1) norbornene, at least one alkylnorbornene or a mixture thereof and (2) at least one acyclic monoolefin or nonconjugated acyclic olefin. The copolymers can be calendered and thermoformed, for example, to make rigid automotive goods such as glovebox covers, hubcaps, and the like.
22 citations
TL;DR: In this paper, the effects of the reaction conditions (the pressure of carbon monoxide, the temperature, and the molar ratio of cyclohexene to Et 2 MeSiH) were examined.
19 citations
Patent•
16 May 1977
TL;DR: In this article, the cold flow of the EP polymer is improved with resultant improvement in recoverability and handling without noticeable modification in molecular weight distribution or shear stability and without interfering with the use thereof as an oil additive, and without so much as to decrease oil solubility rate.
Abstract: EP polymer of low molecular weight containing 0.02% to 0.6% by weight vinyl norbornene or norbornadiene whereby the cold flow of the EP polymer is improved with resultant improvement in recoverability and handling without noticeable modification in molecular weight distribution or shear stability and without interfering with the use thereof as an oil additive, and without so much as to decrease oil solubility rate.
16 citations
TL;DR: In this paper, the cyclopentanone was always formed in these reactions and the reaction of disubstituted acetylenes such as dimethyl acetylenedicarboxylate and ethyl phenylpropiolate, respectively.
Abstract: Photochemical reactions of norbornadiene with substituted acetylenes in the presence of Fe(CO)5 gave various products of different types, depending on the nature of the acetylene. The results are summarized in Table 1. The cyclopentanone 1 was always formed in these reactions. In the reaction of disubstituted acetylenes such as dimethyl acetylenedicarboxylate and ethyl phenylpropiolate, the cyclopentenones 2 and 5 were formed, respectively. By contrast, propiolic esters produced the cyclohexenones 3 and 4, in which the ester group was attached on the β carbon with respect to the keto group. Plausible mechanisms for the formation of these products are shown in Schemes 7 and 8. The reaction of diphenylacetylene gave the cyclohexendione 7 as well as the cyclopentenone 6. Two enedione products 8 and 9 were obtained from the reaction of phenylacetylene. Compound 9 was converted to the aromatic diacetate 13 by heating with acetic anhydride in pyridine. On irradiation in the presence of Fe(CO)5 norbornene reacted similarly with dimethyl acetylenedicarboxylate and phenylacetylene to give the cyclopentenone 14 and the cyclohexenone 15, respectively. Compound 15, upon heating, isomerized to hydroquinone 16, which on acetylation gave the diacetate 17.
15 citations
Patent•
27 Sep 1977
TL;DR: In this paper, a reaction mixture of at least one member selected from the group consisting of compounds of W, Mo, Re and Ta, and (B) at least two members selected from groups consisting of organometallic compounds of elements of Groups IA, IIA, IIB and IIIA of the Deming Periodic Table, has a very high activity in the ring-opening polymerization of norbornene derivatives.
Abstract: A catalyst composition consisting essentially of a reaction mixture of (A) at least one member selected from the group consisting of compounds of W, Mo, Re and Ta, (B) at least one member selected from the group consisting of organometallic compounds of elements of Groups IA, IIA, IIB and IIIA of the Deming Periodic Table, and (C) at least one member selected from the group consisting of compounds of V, Cr, Mn, and elements of Groups IVB and VIII of the Deming Periodic Table, has a very high activity in the ring-opening polymerization of norbornene derivatives having at least one polar substituent selected from the group consisting of ester groups, nitrile groups, amide groups, imide groups, carboxylic acid anhydride groups and halogens. The metal atom ratio of (C)/(A) is usually 0.001-50, and the molar ratio of (B)/(A) is usually 1-10. At least one said norbornene derivative and at least one cycloolefin other than cyclohexene can also successfully be subjected to ring-opening copolymerization with said catalyst.
15 citations
TL;DR: The product formed from cyclopentadiene and the cyclo-octatetraene dimer 5a has been shown to possess structure 6a, probably resulting from Cope rearrangement of an initial adduct 4a.
Patent•
04 Apr 1977TL;DR: In this article, the copolymers of maleic anhydride and cyclic conjugated dienes such as cyclopentadiene were obtained by heating either cyclic adducts and maleic ahydride in the presence of a free radical precursor, such as a peroxygen compound, at a temperature at which endo-exo isomerization of the adduct occurs.
Abstract: Novel copolymers of maleic anhydride and the endo and exo cyclic adducts of maleic anhydride and cyclic conjugated dienes such as cyclopentadiene. The copolymers are prepared by heating either of the cyclic adducts and maleic anhydride in the presence of a free radical precursor, such as a peroxygen compound, at a temperature at which endo-exo isomerization of the adduct occurs.
TL;DR: Oxygen transfer from dioxygenbis(triphenyl-phosphine) platinum to form cyclohexene and norbornene oxides from olefins is induced by acid halides under mild conditions.
Abstract: Oxygen transfer from dioxygenbis(triphenyl-phosphine) platinum to form cyclohexene and norbornene oxides from olefins is induced by acid halides under mild conditions
Patent•
12 Oct 1977TL;DR: In this article, a tackifier is prepared by polymerizing using a Friedel Crafts catalyst: (1) a petroleum resin feed comprising C 5 olefins and diolefs, (2) an additive comprising vinyl norbornene or tetrahydroindene.
Abstract: A resin suitable as a tackifier is prepared by polymerizing using a Friedel Crafts catalyst: (1) a petroleum resin feed comprising C 5 olefins and diolefins, C 6 olefins and diolefins or a mixture of C 5 and C 6 olefins and diolefins, said feed being obtained from the cracking of petroleum feedstock, and (2) an additive comprising vinyl norbornene or tetrahydroindene. The resin thus prepared may be mixed with a natural or synthetic rubber.
Patent•
10 Jan 1977
TL;DR: In this article, a ring-opening polymerization of cyano-substituted norbornene derivatives having at least one nitrile group or substituents is described.
Abstract: A resin composition is prepared from 5 to 95 parts by weight of a polymer prepared by ring-opening polymerization of cyano-substituted norbornene derivatives having at least one nitrile group or substituents including nitrile group and 95 to 5 parts by weight of graft copolymer obtained by grafting at least one elastomer with at least one vinyl compound selected from the group consisting of styrene, acrylonitrile and methyl methacrylate.
TL;DR: In this paper, the Ziegler-Natta catalyst VOCl3 Al2(C2H5)3Cl3 continuously in hexane at 50°C was used to produce copolymers with high tensile strength and elongation.
Abstract: Athylen-Propylen-Copolymere (EPM) werden mit dem loslichen Ziegler-Natta-Katalysator VOCl3/Al2(C2H5)3Cl3 in Hexan kontinuierlich bei 50°C hergestellt. In Gegenwart von Perchlorcrotonsaureestern CCl3CClCClCOOR (RCH3, C4H9) als Reaktivator entstehen bei geringer Vanadium-Konzentration in hohen Ausbeuten Copolymere, die bis zu 17 Gew.-% kristalline
-Segmente enthalten und gunstige Roheigenschaften zeigen. Ein gesattigtes Terpolymeres aus Athylen, Propylen und 15% Bicyclo(2,2,1)-hepten-(2) (Norbornen) besitzt hohe Werte fur Festigkeit und Dehnung.
Ethylene-propylene-copolymers (EPM) are prepared with the soluble Ziegler-Natta catalyst VOCl3 Al2(C2H5)3Cl3 continuously in hexane at 50°C. In presence of perchlorocrotonic esters CCl3CClCClCOOR (RCH3, C4H9) with small concentration of vanadium high yields of copolymers resulted, which contain cristalline
-segments and possess good properties of raw products. A saturated terpolymer of ethylene, propylene and 15% bicyclo(2.2.1)heptene-(2) (norbornene) possesses high tensile strength and elongation.
Patent•
28 Mar 1977TL;DR: In this paper, a norbornene-type monomer is copolymerized with about 0% to about 95% by weight of dicyclopentadiene, based upon total polymer weight.
Abstract: At least one norbornene-type monomer is copolymerized with about 0% to about 95% by weight of dicyclopentadiene, based upon total polymer weight. The polymerization is primarily by ring opening and is conducted in the presence of (1) a catalyst comprising (a) at least one compound selected from the group consisting of dialkylaluminum iodides, alkylaluminum diiodides and mixtures of trialkylaluminum compounds with iodine, (b) at least one dialkylaluminum chloride or alkylaluminum dichloride and (c) at least one monomer- or solvent-soluble tungsten compound, and (2) at least one nonconjugated acyclic olefin having at least one hydrogen on each double-bonded carbon atom. Catalyst components (a) and (b) are charged before catalyst component (c). Use of a catalyst containing components (a), (b) and (c) produces easy-processing and substantially gel-free polymers, whereas a catalyst containing only (a) and (c) or only (b) and (c) produces heavily gelled polymers.
TL;DR: A norbornyl iodide is shown to undergo oxidative elimination to yield a norbornene, the double bond of which is sufficiently hindered not to react with oxidizing species present in the reaction mixture.
Abstract: A norbornyl iodide is shown to undergo oxidative elimination to yield a norbornene, the double bond of which is sufficiently hindered not to react with oxidizing species present in the reaction mixture.
Patent•
28 Apr 1977
TL;DR: In this paper, a cycloalkene monomer having reactive silyl group as a copolymerizing unit was used to improve the adhesivity of a particular ring opening polymer to hydroxide, silicat, or glass.
Abstract: PURPOSE:To improve the adhesivity of a particular ring opening (co)polymer to hydroxide, silicat, or glass, by the incorporation of cycloalkene monomer having reactive silyl group as a copolymerizing unit.
TL;DR: In this paper, the cyclobutane adduct was converted into methyl 2-o-hydroxybenzoylcyclohexylacetate and not the desired oxocin.
Abstract: Irradiation of 4-hydroxycoumarin in the presence of an excess of cyclohexene leads to the cyclobutane adduct, 6a,6b,7,8,9,10,10a,10b-octahydro-10b-hydroxybenzo[3,4]cyclobuta[1,2-c]chromen-6-one, in high yield. Analogous additions occur with cyclopentene, cycloheptene, cyclo-octene, norbornene, and 2,3-dimethylbut-2-ene. On treatment with triethylamine in methanol, the cyclohexene adduct is converted into methyl 2-o-hydroxybenzoylcyclohexylacetate and not the desired oxocin.
Patent•
25 Apr 1977
TL;DR: In this paper, a cycloalkene was used to copolymerize a norbornene derivative possessing polar groups or substitutents having the polar groups with a cycloencoder.
Abstract: PURPOSE:To prepare a copolymer which gives a high-impact thermoplastic resin and rubber, etc. having improved green strength, processability, and oil resistance by copolymerizing a norbornene derivative possessing polar groups or substitutents having the polar groups with a cycloalkene.
Patent•
15 Aug 1977
TL;DR: In this article, an oxygenated tricyclic derivative of norbornene was used for improving, enhancing or modifying the organoleptic properties of perfumes or perfume products as well as of foodstuffs in general.
Abstract: Method for improving, enhancing or modifying the organoleptic properties of perfumes or perfume products as well as of foodstuffs in general, beverages and tobacco, by incorporating therein an oxygenated tricyclic derivative of norbornene.
TL;DR: In this paper, the configurational and conformational relationship at C-2 and C-α in the two racemic diastereomeric endo-α-methyl-5-norbornene-2-methanols and the corresponding saturated endo-, α-α,methyl-2,norbornanemethanol were determined by first-order analysis of the 1H n.m. spectra of these compounds and of their cyclization ether products.
Abstract: The configurational and conformational relationship at C-2 and C-α in the two racemic diastereomeric endo-α-methyl-5-norbornene-2-methanols and the corresponding saturated endo-α-methyl-2-norbornanemethanols were determined by first-order analysis of the 1H n.m.r. spectra of these compounds and of their cyclization ether products, i.e. 3-methyl-2-oxatricyclo[4.2.1.04,8]nonanes and 5-methyl-4-oxatricyclo[4.3.0.03,8]nonanes. In addition, the conformational preference of the hydroxyl group in the unsaturated and saturated alcohols was confirmed by the lanthanide induced shift technique, using Eu(fod)3 as shift reagent, combined with a computer program involving various conformations of the –CHOHMe group.
Patent•
22 Mar 1977TL;DR: A high impact resin composition which comprises 100 parts by weight of polymers obtained by ring-opening polymerization of cyano- or ester-substituted norbornene derivatives bearing at least one nitrile group, a substituent containing the nitriles group, an ester group or a substitution containing the ester groups and 2 to 25 parts of rubber-like materials is defined in this paper.
Abstract: A high impact resin composition which comprises 100 parts by weight of polymers obtained by ring-opening polymerization of cyano- or ester-substituted norbornene derivatives bearing at least one nitrile group, a substituent containing the nitrile group, an ester group or a substituent containing the ester group and 2 to 25 parts by weight of rubber-like materials.
Patent•
04 Mar 1977TL;DR: In this paper, a two-stage process is described for the graft polymerization of acrylate graft copolymers, which comprises from about 5 to about 80 weight percent of the backbone polymer with the balance being furnished by the Acrylate monomer.
Abstract: Acrylate graft copolymers prepared in a two-stage process by first reacting a backbone polymer, such as 1,2-polybutadiene, an alkylidene norbornene polymer or an ethylene/propylene/alkylidene norbornene terpolymer, with, for example, a mixture of dinitrogen tetroxide and oxygen to form a nitrooxidized polymer having incorporated therein nitro and peroxy nitrate functions which serve, in the second stage of the process, as sites for the subsequent graft polymerization of an acrylate monomer are disclosed. The thus-formed graft copolymers comprise from about 5 to about 80 weight percent of the backbone polymer with the balance being furnished by the acrylate monomer.
TL;DR: In this paper, the reaction of norbornene with iodoform in the inert solvent under irradiation resulted in Kharasch type addition to give endo-3-iodo-exo-2-diiodomethyl-bicyclo[2.2.1]heptane, and a carbene addition was used to give tricyclic compound, anti-3 -iodo -exo -tricyclo [3.1.4]octane.
Abstract: The reaction of norbornene with iodoform in the inert solvent under irradiation resulted in Kharasch type addition to give endo-3-iodo-exo-2-diiodomethyl-bicyclo[2.2.1]heptane, and a carbene addition to give tricyclic compound, anti-3-iodo-exo-tricyclo[3.2.1.02,4]octane. The structural assignments of these adducts are based on elemental analyses, ir, nmr, and mass spectral studies.
TL;DR: The solution and bulk copolymerization of dicyclopentadiene (DCP) and maleic anhydride (MAH) occurs over the temperature range 80 −240°C, upon the addition of a free-radical catalyst which has a short half-life at the reaction temperature as discussed by the authors.
Abstract: The solution and bulk copolymerization of dicyclopentadiene (DCP) and maleic anhydride (MAH) occurs over the temperature range 80–240°C, upon the addition of a free-radical catalyst which has a short half-life at the reaction temperature. An unsaturated 1/1 MAH/DCP copolymer, derived from the copolymerization of MAH with the norbornene double bond, followed by a Wagner-Meerwein rearrangement, is obtained in the presence of a large excess of DCP at 80° C, while a saturated 2/1 MAH/ DCP copolymer, derived from the cyclocopolymerization of the residual cyclopentene unsaturation, is obtained at higher temperatures or in the presence of excess MAH. The copolymers prepared under other conditions with intermediate MAH/DCP mole ratios contain both 1/1 and 2/1 repeating units. The copolymer obtained from bulk copolymerization above 170° C contains units derived from cyclopentadiene-MAH cyclocopolymerization as well as DCP-MAH copolymerization.
Patent•
12 Mar 1977
TL;DR: In this article, a metathesis catalyst system based on a phosphine as a promotor in the ring opening polymerization of norbornene derivatives was proposed to increase yields of the polymer.
Abstract: PURPOSE:To increase yields of the polymer by the use of a metathesis catalyst system based on a phosphine as a promotor in the ring opening polymerization of norbornene derivatives.
Patent•
28 Oct 1977
TL;DR: In this paper, the authors proposed a method for the extraction of perfumes from formula I by alkylation, halides cyclization, and addition by dienophiles to form compounds of formula III.
Abstract: NEW MATERIAL:Norbornene derivatives of formula I: (R is 3-8C alkyl group at any one of the 1,- 4,- 5-, and 6-positions; X and Y form a corbonyl group together with the corbon atom at the 2-position, one of them is OH and the other is H). EXAMPLE: 1-Pentyl-5-norbornene-2-one. USE: Flower like fragrance components in compounded perfumes of general cosmetics, and mixed perfumes, e.g. perfumed water, etc. Physically and chemically stable and free from irritation and toxicity. PROCESS: Compounds of formula II are subjected to alkylation by alkyl halides cyclization, and addition by dienophiles to form compounds of formula III: (A and B are substituents equivalent to ketones). The substituents equivalent to ketones are changed to ketones to form alkyl-5-norbornene-2-ones, which are reduced to give alkyl-5-norbornene-2-ols of formula I, if necessary. COPYRIGHT: (C)1979,JPO&Japio