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序号	专利名	申请号	申请日	公开（公告）号	公开（公告）日	发明人
61	Process for the preparation of reaction products of polybutadiene and sulphur dioxide and the products so produced	GB477950	1950-02-24	GB687720A	1953-02-18
The reaction of polybutadiene with sulphur dioxide, in which a solution of polybutadiene activated by a hydroperoxide or by another oxygen-yielding substance in combination with an ether, is extruded into a sulphur dioxide solution to form threads, fibres, tapes or films, is characterized by using polybutadiene obtained by emulsion polymerization. The polymerization temperature is preferably not above 25 DEG C. The products are stated to be mechanically and chemically more stable than those obtained from sodium polybutadiene, and the stability is independent of the sulphur content. The sulphur content also is independent, within wide limits, of the sulphur dioxide concentration, which is preferably 60-200 gms./litre, and of the temperature, which may be between 12 DEG and 30 DEG C. Comparisons are given of tensile strengths, stability, elongation, &c. Plasticized rubber or unsaturated, low molecular weight compounds such as 1,5-hexadiene, allyl alcohol or diallyl phthalate, may be present in the polymer solution. Specifications 611,919, 616,276 and 666,640 are referred to.ALSO:The reaction of polybutadiene with sulphurdioxide, in which a solution of polybutadiene activated by a hydroperoxide or by another oxygen-yielding substance in combination with an ether, is extruded into a sulphur dioxide solution to form threads, fibres, tapes or films, is characterised by using polybutadiene obtained by emulsion polymerisation. The polymerisation temperature is preferably not above 25 DEG C. The products are stated to be mechanically and chemically more stable than those obtained from sodium polybutadiene, and the stability is independent of the sulphur content. The sulphur content, also, is independent, within wide limits, of the sulphur dioxide concentration, which is preferably 60-200 gms./litre, and of the temperature, which may be between 12 DEG and 30 DEG C. Comparisons are given of tensile strengths, stability, elongation, &c. Plasticised rubber or unsaturated, low molecular weight compounds such as 1,5-hexadiene, allyl alcohol or diallyl phthalate, may be present in the polymer solution. Specifications 611,919, 616,276 and 666,640 are referred to.
62		FR1018789D	1950-03-15	FR1018789A	1953-01-13

63	Improvements in and relating to the manufacture of artificial threads, fibres, filaments and the like	GB669850	1950-03-17	GB679040A	1952-09-10	CARPENTER ALBERT STANLEY; WALLSGROVE ERIC RICHARD; WILLIAMS HAROLD MALCOLM GORDON
Artificial threads are obtained by extruding a solution of a polydiene such as polybutadiene or polychloroprene or a copolymer of butadiene or chloroprene with styrene or acrylonitrile, containing a hydroperoxide as catalyst into a coagulant bath containing sulphur dioxide wherein the coagulant bath contains at least 5 per cent by weight of the solvent used to dissolve the polydiene. The solvents for the polydiene may be aromatic hydrocarbons such as benzene, toluene, xylene and cumene, and chlorinated hydrocarbons such as trichloroethylene, carbon tetrachloride, chloroform and chlorobenzene. The preferred solvents for the sulphur dioxide are mixtures of the above hydrocarbons with methanol, ethanol, a propanol or acetone. The spinning solution may contain at least 10 per cent of the polydiene as claimed in Specification 679,274, and may contain small proportions of methanol or isopropanol to reduce viscosity and is activated by a hydroperoxide such as tetralin hydroperoxide or tertiary butyl hydroperoxide. Specifications 527,075 and 616,276 also are referred to.
64		DEP0014721	1948-10-02	DE848251C	1952-09-01	RUMSCHEIDT GOTTFRIED ERNST

65		DEN0000523	1950-02-19	DE839855C	1952-05-26	RUMSCHEIDT GOTTFRIED ERNST; GOPPEL JOHAN MICHAEEL

66		DEP0014719	1948-10-02	DE838218C	1952-05-05	NIE WILLEM LEENDERT JOHANNES D

67	A process for stabilising reaction products of polymers or co-polymers of conjugated dienes with sulphur dioxide	GB1178449	1949-05-03	GB666652A	1952-02-13
Products obtained by reacting polymers or copolymers of conjugated dienes with sulphur dioxide are stabilized with compounds having at least one condensed or non-condensed aryl nucleus and at least one, preferably esterified, carboxyl group, the carbonyl oxygen atom of which may or may not be substituted by sulphur, or with homologues, derivatives or salts of these compounds. The stabilizer may be benzoic acid, a naphthoic acid, phenyl o-hexadecoxy benzoate, salicylic acid, phenyl salicylate, mono-, di- or tri-allyl phenyl salicylate, zinc or calcium di-isopropyl salicylate, o-hydroxy phenoxy acetic acid, phthalic acid, naphthalic acid, diphenyl phthalate, or thiophthalic acid anhydride. Other stabilizers such as hexamethylene tetramine may be incorporated. The conjugated diene may be butadiene, methyl butadiene, dimethyl butadiene or chloroprene, which substances may be copolymerized with each other or with isobutylene, styrene, vinyl chloride, vinyl esters, acrylic acid, methacrylic acid, acrylonitrile or methacrylonitrile. The reaction products to be stabilized may also comprise products obtained by the reaction of the polymers or copolymers and unsaturated compounds of low molecular weight with sulphur dioxide, suitable low molecular weight compounds being butadiene, 1,5-hexadiene, allyl alcohol, chloride, acetate, capronate, isothiocyanate, and oleate, diallyl phthalate and diallyl adipate. The stabilized polymers may be used in the preparation of threads, fibres, fabrics, tapes and films. Specification 666,644, [Group V], is referred to.
68	A process for stabilising products formed by the reaction of polydienes with sulphur dioxide	GB1856648	1948-07-09	GB666640A	1952-02-13
Reaction products of polydienes with sulphur dioxide are stabilized by contacting them with solutions of compounds containing the group C-NRR1 or =C=NR11, in which R, R1 and R11 are hydrogen or the same or different hydrocarbon radicals, the hydrogen atoms of which may be substituted by other atoms or radicals, the presence of oxidizing nitrogen-oxygen radicals in the compounds being avoided. The polydienes are unsaturated polymers, copolymers of conjugated dienes of 4 to 6 carbon atoms and have a molecular weight above 5000. Examples are polymers of butadiene, pentadiene, methyl and dimethyl butadienes, copolymers of mixtures of these and of one or more with alkenes, e.g. isobutene, or vinyl compounds, e.g. styrene, vinyl chloride, vinyl esters, acrylic and methacrylic acids, acrylonitrile and methacrylonitrile. Products in which compounds of molecular weight below 5000 are simultaneously reacted with sulphur dioxide, as described in Specification 659,083, are also included. Examples of stabilizers are aliphatic and aromatic primary, secondary and tertiary amines, e.g. heptadecyl and octadecyl amines, a -naphthylamine, p-phenylene diamine-benzidene, triamino benzene, cetyl aniline, diphenylamine, N - phenyl - b - naphthylamine, methyl tert.-amyl aniline, ethyl butyl and ethyl octyl aniline, ethyl cyclohexyl aniline, triphenylamine; amino acids and elcohols, e.g. triethanolamine; acid amides, e.g. acetamide, stearic acid amide, benzamide, acetanilide; urea, N,N- and N,N1-diphenyl urea, thiourea, N,N- and N,N1-diphenyl thiourea, N,N- and N,N1-diphenyl guanidine; amides of dithio acids, e.g. tetramethyl thiuram disulphide; zinc dimethyl dithiocarbamate; amidines; urethanes and thiourethanes; carbo-di-imides, e.g. diphenyl and diallyl carbo-di-imides, p,p1-dimethyl diamino diphenyl carbo-di-imide; heterocyclic nitrogen compounds, e.g. hexamethylene tetramine, melamine, phenyl melamine, (methyl-2-dodecyl)-pyridine, thiazole, mercapto-benzimidazole; halogen amines, e.g. monochlorurea, quinone dichlorimide; dicyanodiamide; quaternary ammonium compounds, e.g. cetyl pyridinium chloride. In some cases the stabilizers can be used in the form of polymers or copolymers. The stabilizers may be applied by soaking threads or other objects of the reaction product in a stabilizer solution, preferably when the product is still in the swollen state of its production, or it may be added to the liquid in which the product is formed. The stabilizer may also be added to take part in the reaction producing the products, for which purpose compounds containing an alkenyl group are essential. The adhesion may also be improved by heating after application or during incorporation of the stabilizer, and by reacting the stabilized products with compounds such as formaldehyde or iso-cyanates. Combinations of stabilizers may be used, at least two of the group of hexamethylene tetramine and its derivatives, melamine and its derivatives and urea or thiourea and their derivatives including dicyanodiamide, being very effective. The stabilization is against the separation of sulphur dioxide and in some cases is effective against the influence of light. The invention is exemplified with reaction products of rubber and sulphur dioxide.
69		FR986267D	1949-05-17	FR986267A	1951-07-30
Products obtained by reacting polymers or copolymers of conjugated dienes with sulphur dioxide are stabilized with cyanates or thiocyanates, alkali metal or ammonium cyanates or thiocyanates being preferred. Other stabilizers such as hexamethylene tetramine may be incorporated. The conjugated diene may be butadiene, methyl butadiene, dimethyl butadiene or chloroprene, which substances may be copolymerized with each other or with isobutylene, styrene, vinyl chloride, vinyl esters, acrylic acid, methacrylic acid, acrylonitrile or methacrylonitrile. The reaction products to be stabilized may also comprise products obtained by the reaction of the polymers or copolymers and unsaturated compounds of low molecular weight with sulphur dioxide, suitable low molecular weight compounds being butadiene, 1,5-hexadiene, allyl alcohol, chloride, acetate, capronate, isothiocyanate, and oleate, diallyl phthalate and diallyl adipate. The stabilized polymers may be used in the preparation of threads, fibres, fabrics, tapes and films. Specification 666,644, [Group V], is referred to.
70		FR971620D	1948-09-14	FR971620A	1951-01-19

71	Verfahren zur Verbesserung der Eigenschaften von Fäden, Fasern, Bändern, Filmen, Folien und ähnlichen Gegenständen.	CH264916D	1946-07-02	CH264916A	1949-11-15	MAATSCHAPPIJ N V DE BATAAFSCHE

72	PROCEDE DE STABILISATION DES PRODUITS DE CERTAINES REACTIONS	LU29156D	1948-07-05	LU29156A1	1948-07-15

73		FR852804D	1939-04-07	FR852804A	1940-03-04

74	Procédé pour la préparation de produits de valeur	BE437413	1939-12-19	BE437413A	1940-02-29

75		MX496287	1987-01-16	MX163988B	1992-07-07	BELL ANTHONY JOSEPH
Short fibers of syndiotactic 1,2-polybutadiene are utilized in making tires that have improved resistance against heat build-up and improved wear characteristics. The preparation of syndiotactic 1,2-polybutadiene in fibrous form has traditionally involved an extrusion and stretching step. However, the technique of the present invention circumvents the necessity of hot mill flexing and/or extrusion in making fibrous syndiotactic 1,2-polybutadiene. The present invention more specifically involves a process for preparing syndiotactic 1,2-polybutadiene fibers directly comprising polymerizing 1,3-butadiene monomer in the presence of (1) a catalyst composition which is comprised of (a) a cobalt compound and (b) an organoaluminum compound; (2) carbon disulfide; and (3) at least one member selected from the group consisting of liquid polymers and naphthenic oils.
76	DIRECT METHOD FOR PREPARING SYNDIOTACTIC 1,2- POLYBUTADIENE	CA527899	1987-01-22	CA1297231C	1992-03-10	BELL ANTHONY J
DIRECT METHOD FOR PREPARING SYNDIOTACTIC 1,2-POLYBUTADIENE Short fibers of syndiotactic 1,2-polybutadiene are utilized in making tires that have improved resistance against heat build-up and improved wear characteristics. The preparation of syndiotactic 1,2-polybutadiene in fibrous form has traditionally involved an extrusion and stretching step. However, the technique of the present invention circumvents the necessity of hot mill flexing andJor extrusion in making fibrous syndiotactic 1,2-polybutadiene. The present invention more specificallv involves a process for preparing syndiotactic 1,2-polybutadiene fibers directly comprising polymerizing 1,3-butadiene monomer in the presence of (1) a catalyst composition which is comprised of (a) a cobalt compound and (b) an organoaluminum compound; (2) carbon disulfide; and (3) at least one member selected from the group consisting of liquid polymers and naphthenic oils.
77	PROCESS FOR THE CONTINOUS PREPARATION OF HOMOGENEOUS SOLUTIONS OF HIGH-MOLECULAR WEIGHT POLYMERS	IN711MA1985	1985-09-10	IN166332B	1990-04-14	LEMSTRA PIETER JAN; MEIJER HENRICUS EDUARD HUBERTU; UNEN LAMBERT HENRY THEODOOR VA

78	PREPARATION OF PBD USING CATALYST COMPOSITION OF CO- AND AL- COMPOUNDS	AU6785787	1987-01-21	AU583235B2	1989-04-20	BELL ANTHONY JOSEPH
Short fibers of syndiotactic 1,2-polybutadiene are utilized in making tires that have improved resistance against heat build-up and improved wear characteristics. The preparation of syndiotactic 1,2-polybutadiene in fibrous form has traditionally involved an extrusion and stretching step. However, the technique of the present invention circumvents the necessity of hot mill flexing and/or extrusion in making fibrous syndiotactic 1,2-polybutadiene. The present invention more specifically involves a process for preparing syndiotactic 1,2-polybutadiene fibers directly comprising polymerizing 1,3-butadiene monomer in the presence of (1) a catalyst composition which is comprised of (a) a cobalt compound and (b) an organoaluminum compound; (2) carbon disulfide; and (3) at least one member selected from the group consisting of liquid polymers and naphthenic oils.
79		BR8700255	1987-01-21	BR8700255A	1987-12-08	BELL ANTHONY JOSEPH
Short fibers of syndiotactic 1,2-polybutadiene are utilized in making tires that have improved resistance against heat build-up and improved wear characteristics. The preparation of syndiotactic 1,2-polybutadiene in fibrous form has traditionally involved an extrusion and stretching step. However, the technique of the present invention circumvents the necessity of hot mill flexing and/or extrusion in making fibrous syndiotactic 1,2-polybutadiene. The present invention more specifically involves a process for preparing syndiotactic 1,2-polybutadiene fibers directly comprising polymerizing 1,3-butadiene monomer in the presence of (1) a catalyst composition which is comprised of (a) a cobalt compound and (b) an organoaluminum compound; (2) carbon disulfide; and (3) at least one member selected from the group consisting of liquid polymers and naphthenic oils.
80	NON-WOVEN POLYBUTADIENE FABRIC	AU6415080	1980-11-06	AU6415080A	1981-05-28	KONTOS E G
A non-woven fabric comprising an assembly of fibers of discrete length which are interconnected and, at least a portion of which are in contact with each other, said fibers comprising crystalline syndiotactic 1,2-polybutadiene (1,2 SBD).

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