Showing papers on "Norbornene published in 1975"

Novel copolymer and process for producing same

Abstract: A novel copolymer is obtained by reacting [A] at least one norbornene derivative having at least one polar group or polar-group-containing substituent with [B] at least one unsaturated polymer having carbon-to-carbon double bonds in the presence of a metathesis catalyst. This copolymer is excellent in chemical and mechanical properties. Particularly, when 50% by weight or more of the component [A] is contained, the resin is distinguished for its high impact strength.

Über die Autoxydation von Norbornenderivaten

Abstract: Norbornen, Bicyclo[2, 2, 1]hepten-(2)-carbonsaure-(5)-methylester, Bicyclo[2, 2, 1]hepten-(2)-carbonsaure-(5)-nitril, 5-Methylbicyclo[2, 2, 1]hepten-(2)-carbonsaure-(5)-methylester und Dicyclopentadien werden von molekularem Sauerstoff leicht oxydiert; als Hauptprodukte bilden sich unter Angriff auf die Norbornendoppelbildung die entsprechenden exo-Epoxide. On the Autoxidation of Derivatives of Norbornenen Norbornene, bicyclo[2, 2, 1]2-heptene-5-carboxylic acid methyl ester, bicyclo-[2, 2, 1]2-heptene-5-carbonitril, 5-methylbicyclo[2, 2, 1]2-heptene-5-carboxylic acid methyl ester and dicyclopentadiene are easily oxidized by molecular oxygen; the corresponding exo-epoxides are formed as main products by attack on the norbornene double bond.

High heat stability composition of ring-opening polymerization product

Abstract: High stability composition of ring-opening polymerization product which is formed of (A) 100 parts by weight of at least one ring-opening polymerization product selected from the group consisting of (a) ring-opening polymerization homopolymers of norbornene derivatives containing at least one cyano group, (b) ring-opening polymerization homopolymers of norbornene derivatives containing at least one ester group, (c) ring-opening polymerization homopolymers of norbornene derivatives containing at least one ether group, (d) ring-opening polymerization homopolymers containing at least one N-substituted cyclic imide group, (e) ring-opening polymerization interpolymers of the above-mentioned types of norbornene derivatives, and (f) other ring-opening polymerization copolymers obtained by the ring-opening copolymerization of said various types of norbornene derivatives and 50 mol% at most of other unsaturated cyclic compounds; and (B) 0.01 to 10.0 parts by weight of specified phenolic compounds.

The Chlorination of Norbornene by Metal Chlorides and the Product Isomerization

Abstract: The reaction of norbornene with CuCl2, TlCl3·4H2O, PbCl4, SeCl4, SbCl5, and VCl4 in CCl4, CH2Cl2, or CH3CN gave a mixture of nortricyclyl chloride (1), and six isomeric dichloronorbornanes [trans-2,3-(2), exo-2-anti-7-(3), trans-2,5-(4), exo-cis-2,5-(5), exo-cis-2,3-(6), and exo-2-syn-7-(7)], the product distribution depending very much on metal chlorides and reaction conditions. The reactions did not show any participation of a chlorine molecule which may be released from metal chlorides. The ability of SeCl4 and VCl4 to chlorinate olefins was found for the first time. From a synthetic viewpoint CuCl2 was a good reagent for obtaining 2, while TlCl3·4H2O and SbCl5 were recommended for either 3 or 7. The reactions with the following metal chlorides did not give any dichloronorbornanes; SnCl4, BiCl3, TiCl4, FeCl3, NbCl5, TaCl5, and WCl6. It was revealed that isomerization of 2 or 7 to a mixture of 3, 4, and 5 occurred very rapidly by SbCl5 and smoothly by TlCl3·4H2O. The chlorination of norbornene and their...

Process for substantially gel-free polymerization of norbornene with dicyclopentadiene

Abstract: A norbornene-type monomer is copolymerized with about 0% to about 95% by weight of dicyclopentadiene, based upon total polymer weight. The polymerization is conducted in the presence of (1) a catalyst comprising (a) at least one compound selected from the group consisting of dialkyl-aluminum iodides, alkylaluminum diodides 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.

Novel polymer containing cyclopentanylvinylene units

Abstract: Processes for preparing novel polymers containing carboxyl or carboxylate groups which comprises hydrolyzing starting polymers containing acid anhydride groups in the presence of acids or alkalies, the starting polymers being prepared by ring-opening polymerization of acid anhydride-type norbornene derivatives, and the characteristics and utility of these novel polymers are disclosed.

Blends of acrylonitrile copolymers with graft copolymers containing rubber and acrylonitrile copolymer

Abstract: A graft copolymer comprises a substrate of a diene rubber, and a homogeneous superstrate containing units of acrylonitrile and at least one aromatic olefin having a molar ratio of acrylonitrile to olefin between 2 and 9. The superstrate may also contain a minor amount (preferably less than 10 mole %) of at least one other comonomer selected from acenaphthylene, vinyl carbazole and its derivatives, maleimide and its N-substituted derivatives and norbornene and its derivatives.

Oxymetallation. Part VII. Peroxymercuration of terminal, medial, and cyclic alkenes without accompanying acyloxymercuration

Abstract: Ethylene, propene, styrene, cis- and trans-but-2-ene, trans-hex-3-ene, cis- and trans-stilbene, trans-prop-1-enylbenzene, cyclohexene, norbornene, and 2-methylpropene each react with mercury(II) trifluoroacetate and t-butyl hydroperoxide in dichloromethane to provide the peroxymercurials R1R3C(OOBut)·CH(HgO2C·CF3)R2. Unlike the corresponding reactions with mercury(II) acetate, competitive acyloxymercuration does not occur. The products are obtained in high yield (ca. 85%) and require little or no purification; they have been characterized by elemental analysis and 1H n.m.r. spectroscopy.A mixture of positional isomers is obtained from prop-1-enylbenzene but the compound PhCH(OOBut)·CH(HgO2C·CF3)Me (84%) predominates. Diastereoisomeric products are obtained from the cis/trans-pairs and the spectra of the crude materials show that the reactions are stereospecific. When treated with mercury(II) trifluoroacetate and t-butyl hydroperoxide or methanol, the peroxy- and methoxy-mercurials from both cis- and trans-stilbene undergo oxidative demercuration with rearrangement to give the compounds Ph2CH·CH(OR)2, where R = OBut or Me.

Some reactions of Quinoline-8- and Ureidobenzene-sulphonyl chlorides

Abstract: Quinoline-8-sulphonyl chloride (1) with hydrazine, phenylhydrazine and sodium azide gave the corresponding hydrazide (3); phenylhydrazide (4); and azide (12). The hydrazide (3) undergoes facile hydrolysis, in contrast to the rather inert sulphonyl azide (12). Chlorosulphonation of m- and p-chlorophenylureas was unsuccessful. However, the N,N-di-methylurea (18) reacted with chlorosulphonic acid to give p-(N,N-dimethy1ureido)benzenesulphonyl chloride (19), which has been converted into the hydrazide (21) and the azide (20). Both 3- methyl-4-ureidobenzenesulphonyl azide (25) and the azide (20) failed to add to norbornene, although they did react with triphenylphosphine.

Ring opening polymerisation of norbornene derivs. - using catalyst contg. organometallic cpd. and prod. of metal oxide and halide

Abstract: Polymer is prepd. by ring opening >=1 norbornene deriv. contg. (i) >=1 polar gp. consisting of a nitrile, ester, ether imide, acid anhydride or amide gp., Cl or Br, or (ii) a 20C hydrocarbyl gp. and polar gp. Catalyst system is prepd. from an organometallic cpd. (I) of a Gp. IA, IIA, IIB, IIIB, IVA or IVB and the reaction prod. of >=1 W oxide and Mo oxide and >=1 halogen-contg. cpd., e.g. PCl5, PF5, PBr5, POCL3, PCl3, AlCl3, AlBr3, All3, BF3, TiCl4, SnCl4, VOCl3, VCl4 or SiCl4. Polymers, graft-and block copolymers may be used as such or as compressed articles, e.g. pellets, films, foils pipes, rods, containers. Uses include bottles, bags, machine parts, lamp parts, agricultural devices. Other uses are as ion exchanger resins, coagulants, adhesives and coatings. The catalyst activity is high. In an example 0.152 mol WO3 and 0.182 mil PCl5 were reacted in o-dichlorobenzene for 60 min. at 120 degrees C. 1 ml (0.4 mmol W) of liquid residue of WO3/PCl5 prod., 250 ml 1,2-dichloroethane, 150 g 5-cyano-bicyclo- 2,2,1 - heptene-2 and 6 ml Et2AlCl in 1,2-C2Cl4Cl2 (1 mol/1) were added. Polymerisation took 60 min at 70 degrees C. Degree of conversion for polymer (w.r.t. monomer) was 52%.

N-(o or p-thiophenyl) substituted polyhalo-5-norbornene-2,3,-dicarboximide flame retardants and polymers containing said imides

Abstract: This invention relates to N-(o- or p-thiophenyl) substituted polyhalo-5-norbornene-2,3-dicarboximides, their preparation via a one-step process and their use as flame retardants for polyurethane elastoplastics and other polymeric materials.

Morphology of random and non‐random olefin copolymers of ethylene

Abstract: Studies have been published relating the mechanical properties of ethylene copolymers with short chain branching structures. Other work has emphasized that crystallites in these copolymer systems participate in superstructures and that stress distribution during mechanical testing depends on the arrangement of these structures, the morphology. While developing structure-property correlations, morphologies of some random and non-random olefin copolymers have been examined. Surprising morphological differences were found depending on the length, concentration and degree of randomness of the n-alkyl branch and on vicinal substitution with norbornene derivatives as comonomers. X-ray diffraction yielded unexpected results which can be explained by a change in the direction of chain folding. Linear side chains randomly introduced into an otherwise high density polyethylene result in a two to three fold increase in the 110:200 x-ray intensity ratios, a slight reduction in the 110:020 intensity and a 5 to 10 fold decrease in the 200:02 intensities. These results cannot be explained by orientations introduced in sample preparation. There are associated morphological changes. Vincinal substitution with norbornene comonomers has little effect on crystal habit but does change the morphology, tending to shift superstructures from lamellar to fibrillar in nature.

Oxymetallation. Part IX. Bromodemercuration of peroxymercurials derived from terminal, medial, and cyclic alkenes to give β-bromoperoxides

Abstract: Each of the peroxymercurials R1R3C(OOBut)·CH(HgBr)R2 derived from ethylene, propene, 2-methylpropene, but-2-ene, hex-3-ene, stilbene, prop-1-enylbenzene, cyclohexene, and norborn-2-ene reacts with bromine in dichloromethane to afford the corresponding β-bromo-peroxide R1R3C(OOBut)·CHBrR2, in ca. 85% yield; the new compounds have been characterised by 1H n.m.r. spectroscopy. The bromo-peroxides derived from non-terminal alkenes are obtained as 1 : 1 mixtures of diastereoisomers except for the norbornene derivative where the ratio of isomers is 65 : 35. The extent of racemisation is considerably reduced by carrying out the bromodemercuration in pyridine; isomer ratios of 4 : 1 are thus readily obtained.

High impact composition of ring-opening polymerization product

Abstract: High impact composition of ring-opening polymerization product formed of (A) 100 parts by weight of at least one ring-opening polymerization product selected from the group consisting of (a) ring-opening polymerization homopolymers of norbornene derivatives containing at least one nitrile group or a substituent including said nitrile group, (b) ring-opening polymerization homopolymers of norbornene derivatives containing at least one ester group or a substituent including said ester group, (c) ring-opening polymerization copolymers of combination of said norbornene derivatives, and (d) other ring-opening polymerization copolymers of any of said norbornene derivatives and 50 mol% at most of other unsaturated cyclic compounds; and (B) 0.05 to 10.0 parts by weight of specified metal salts of fatty acids.

Photoreaction of Nitroso Compounds in Solution. Part XXXII: Synthesis and Reaction of 2-Nitrato-3-Aminonorbornanes

Abstract: Oxidative photoaddition of nitrosamines to norbornene gave both cis-exo- and trans-2-nitrato-3-aminonorbornanes that were stable in their protonated form under photolysis conditions. The free bases...

Oxymetallation. Part VIII. The stereochemistry of peroxymercuration of cyclohexene, norbornene, but-2-ene, and stilbene; intramolecular co-ordination in β-peroxyalkylmercury trifluoroacetates

Abstract: The configurations of peroxymercurials, RCHA(OOBut)CHB(HgTFA)R, prepared from mercuric trifluoroacetate have been assigned on the basis of vicinal proton–proton coupling constants (JAB). The structures of the cyclohexene and norbornene products are readily assigned from spectral similarity with other oxymercurials and they result from trans- and cis-addition respectively. In the but-2-ene (R = Me) and stilbene (R = Ph) products the assignments depend on comparisons between cis- and trans-derived diastereoisomers. The relative magnitudes of JAB and their behaviour upon addition of pyridine or replacement of trifluoroacetate by bromide indicate that there is intramolecular ButO ⋯ Hg co-ordination in the adducts and that the peroxymercurations involve trans-addition.

Olefinic copolymer compositions

Abstract: A composition comprising 90 to 20 % by might of at least one diene rubber or butyl rubber and 10 to 80 % by weight of halogen-containing, sulfur-curable, normally amorphous quadripolymer produced by contacting a mixture of (1) ethylene, (2) an α-olefin having the formula, R--CH=CH2 , wherein R is a hydrocarbon radical having 1 to 20 carbon atoms, (3) a hydrocarbon compound having a plurality of non-conjugated unsaturated bonds capable of polymerizing with a coordinated catalyst, and (4) a halogenated norbornene compound represented by the formula, ##SPC1## Wherein R1, R2, R3 and R4 are hydrogen atoms, hydrocarbon radicals having 1 to 20 carbon atoms, halogen atoms, or halogenated hydrocarbon radicals having 1 to 20 carbon atoms and containing at least one halogen atom as substituent, provided that R1, R2, R3 and R4 have as a whole at least one halogen atom, with a coordinated catalyst comprising an organoaluminum compound of the formula, AlR'n X3 -n, wherein R' is a hydrocarbon radical having 1 to 20 carbon atoms, X is a halogen atom, and n is any number of from 1.5 to 3, and a transition metal compound selected from the group consisting of vanadium compounds and titanium compounds, the molar ratio of said organoaluminum compound to said transition metal compound being from 5 : 1 to 0.5 : 1. The rate of vulcanization of the said quadripolymer is freely controllable by varying the non-conjugated diene content thereof.

Stereochemistry of the t-butylcyanoketen cycloaddition to norbornene

Abstract: The stereochemistry of the title cycloaddition has been determined by lanthanide-induced shift experiments; the cyclobutanone ring is exo, while the t-butyl group is pointing towards the methylene bridge of norbornane.

Photoreaction of Nitroso Compounds in Solution. Part XXXI. Mechanisms of Intramolecular Acid Catalyzed Cleavage Reactions and a Hydride Initiated Rearrangement of C-Nitroso Alkanes

Abstract: Two novel rearrangements of nitroso alkanes, one intramolecular acid catalyzed cleavage reaction and the other ring enlargement during hydride reduction, are described. Aminium radical initiated addition to norbornene under nitrogen gave cis-exo- and trans-2-nitroso-3-ammonium norbornanes in a good yield. Whereas the trans isomer underwent the usual nitroso group reactions, i.e., tautomerization, dimerization, and HNO addition, the cis-exo isomer and its hydroxy analog cleaved extremely readily to give 1,3-bisformylcyclopentane derivatives. The stereoelectronic driving force in this cleavage is interpreted as the intramolecular proton transfer and the electron reorganization via a cyclic transition state. Metal hydride reduction of the trans isomer was accompanied by ejection of the neighboring amino group and an expansion of the ring to form an azabicyclic compound. A sequence involving an intramolecular displacement to form aziridine followed by the reductive cleavage is proposed.

A process for manufacturing animpact resistant thermoplastic resin

Abstract: PURPOSE: To manufacture an impact resistant thermoplastic resin by reacting a polar group substituted norbornene derivative with an unsaturated polymer in the presence of a metathesis catalyst COPYRIGHT: (C)1976,JPO&Japio

Molybdenum(v) chloride as a reagent for cis chlorination of olefins

Abstract: Treatment of nonconjugated olefins such as cis- and trans-2-butenes, cis-2-octene, and cyclohexene with MoCl5 in CCl4 gave vic-dichloroalkanes whose cis-isomer was formed predominantly, the ratio of cis- to trans-addition being 4.9–12.1, together with monochloroalkanes. Preferential formation of exo-cis-dichloride was observed in the case of norbornene and norbornadiene. Bromochlorination and chloroiodination of olefins, and aromatic bromination and iodination were carried out with mixtures of MoCl5 and halogens. The reaction scheme for chlorination is discussed.