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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
121 ELASTOMERIC FIBRES, STRUCTURES FASHIONED THEREFROM AND ELASTOMERIC FILMS AU2116688 1988-08-18 AU2116688A 1989-02-23 HIMES GLENN ROY
122 DIRECT METHOD FOR PREPARING SYNDIOTACTIC 1,2-POLYBUTADINE ZA8700158 1987-01-09 ZA8700158B 1987-08-26 BELL ANTHONY JOSEPH
123 PREPARATION OF PBD USING CATALYST COMPOSITION OF CO- AND AL- COMPOUNDS AU6785787 1987-01-21 AU6785787A 1987-07-30 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.
124 PROCESS FOR THE PREPARATION OF HYDROPHILIC FIBRES AND FILAMENTS FROM SYNTHETIC POLYMERS GB942177 1977-03-07 GB1540976A 1979-02-21
The invention relates to a process for the production of hydrophilic filaments and fibers which comprises wet- or dry-spinning a fibre-forming synthetic polymer from a spinning solvent containing from 5 to 50% of a substance which has a higher melting or boiling point than the spinning solvent which is miscible with the spinning solvent and with a liquid suitable for use as a washing liquid and which is a non-solvent for the polymer to be spun and from 0,1 to 20% by weight of at least one substance which decomposes into a gas under heating.
125 FR62072 1966-05-18 FR1480082A 1967-05-05
126 A process for the production of shaped articles from elastomeric polymers containing reactive groups GB2940255 1955-10-14 GB785631A 1957-10-30
Shaped articles, e.g. filaments or films, are made by introducing a solution or emulsion of a synthetic elastomeric polymer containing reactive groups into a coagulating bath which contains an agent capable of reacting with the reactive groups of the polymer to give cross-linking, removing the coagulate so formed from the bath, and finally drying it. Suitable elastomeric polymers consist essentially of linear carbon chains to which are linked 0.005-0.6 mols. by weight per 100 parts by weight of the polymer of reactive groups such as carbonyl, carboxyl, sulphonic acid, amide, or basic groups, preferably basic groups containing nitrogen. These groups may be introduced by copolymerizing 15-99 per cent of such monomers as acrylic or methacrylic acid esters of aliphatic alcohols containing at least 4 and preferably 8-14 carbon atoms, vinyl alkyl ethers in which the alkyl group contains 1-8 carbon atoms, and butadiene and its homologues and derivatives, with such carbonyl-containing compounds as acrolein, a -substituted acroleins, vinyl alkyl ketones or methyl isopropenyl ketone, or acids such as acrylic or methacrylic acid, sorbic acid, maleic or fumaric acid or their monoesters, or amides such as acrylamide, a -methacrylamide, a -isopropylacrylamide, or a -chloracrylamide, or heterocyclic nitrogen bases such as 2-vinyl pyridine or sulphonic acids such as vinyl sulphonic acid. The monomers containing the reactive groups may be present in quantities of 0.5-50 per cent by weight of the monomer mixture. Other polymerizable compounds such as styrene, acrylonitrile, acrylic or methacrylic acid esters of alcohols having 1-3 carbon atoms, vinyl chloride, and 1 : 1-dichlorethylene, and small amounts (preferably 0.001-1 per cent by weight of the monomer mixture) of polyfunctional monomers containing at least two active olefinic non-conjugate double bonds, such as divinyl benzene, esters of polyhydric alcohols or phenols with unsaturated acids, di-vinyl ether, or divinyl sulphone may be incorporated. Other suitable copolymerizable compounds which contain reactive groups present in "masked" form, from which they may be liberated by hydrolysis, include acrylic and methacrylic alkyl esters, vinylsulphonic alkyl esters, unsaturated nitriles such as acrylonitrile, and such amides as have already been mentioned. Copolymers containing carboxyl groups are preferred. The monomers may be polymerized in bulk, in solution in solvents such as benzene, chlorobenzene, 2 : 4-dichlorobenzene, or ketones such as methyl ethyl ketone or emulsified with alkali metal salts of paraffin sulphonates, in the presence of catalysts, e.g. azo-dinitriles, per-compounds, redox systems, and especially with aliphatic sulphinic acid salts, and modifiers such as n-dodecyl mercaptan and diisopropyl xanthogen disulphide. The polymerization may be stopped by adding hydroquinone or sodium hydrosulphite and unreacted monomer stripped by steam distillation. The solutions should contain 8-40, preferably 10-20, per cent by weight of polymers. Stabilizers such as phenyl-b -naphthylamine or phenols should also be included in the case of butadiene polymers. The reactive agent present in the coagulating bath, in the case of copolymers containing carbonyl groups, may be a polyamine or polyamide, such as polyalkylene polyamines and diamides of dibasic aliphatic and aromatic carboxylic acids. A water-soluble hydroxide or salt of a polyvalent metal is suitable for carboxyl-containing copolymers. Other suitable cross-linking agents for such copolymers include compounds containing at least two epoxy groups, such as diglycidyl trimethylolpropane, diglycidyl glycerol, b ,b - di - (glycidyloxyphenyl) - propane and diglycidyl aniline, which are all preferably used in alcoholic solution. Copolymers containing amide groups may be reacted with aliphatic or aromatic aldehydes or with such formaldehyde-yielding compounds as hexamethylene tetramine, the sodium salt of a -hydroxymethane sulphinic acid, dimethylol urea or hexamethylol melamine, while copolymers containing basic nitrogen groups may be reacted with polybasic acids such as oxalic, maleic, citric, itaconic, fumaric, succinic, glutaconic, adipic, tartaric, 1 : 3-benzenedisulphonic or 1 : 5-naphthalene-disulphonic acid. The coagulating bath should contain the cross-linking agent in a proportion sufficient to react with at least 10 per cent of the reactive groups in the copolymer in a solvent such as water or an alcohol such as methanol or ethanol. Preferably, the cross-linking agent is present in an amount at least chemically equivalent to the reactive groups present in the copolymers, and to ensure this the cross-linking agent should comprise 1-50 per cent of the bath. In addition, the bath may also contain coagulating agents, for instance strong electrolytes such as metallic salts, in concentrations of 1-30 per cent. The pH value of the bath should be within the range 4-10, depending on the cross-linking agent used, and its temperature should be 20-70 DEG C. Thickening agents such as polyvinyl alcohol, salts of polyacrylic acid, alginic acid or carboxymethyl cellulose may also be present. After leaving the coagulating bath, the coagulate may be washed with water or alcohol at 20-70 DEG C. and finally dried at 50-150 DEG C., preferably at 90-120 DEG C. Although the process is particularly suitable for the production of threads or filaments, tubular films may also be produced by the use of annular nozzles, or alternatively the copolymer may be cast on to a mould which rotates in the coagulating bath to produce a film. The copolymer emulsions to be spun may also include natural or synthetic rubber latices or plastic emulsions, fillers, plasticizers, resins, dyes, pigments, solvents or other high polymers. Numerous examples are given. German Specification 750,330 and U.S.A. Specification 2,581,464 are referred to.
127 Improvements in and relating to the manufacture of artificial threads, fibres, filaments and the like GB863851 1951-04-13 GB705072A 1954-03-10 WILLIAMS HAROLD MALCOLM GORDON
The ultra-violet light stability of polydienesulphur dioxide threads is increased by passing the thread during its manufacture in a number of consecutive turns over one or more thread-advancing, thread-storage devices and subjecting the turns of thread to an extensive washing treatment with a liquid consisting essentially of an alcohol. The polydiene may be polybutadiene or natural rubber. The thread-storage devices are preferably reels of the type described in Specifications 413,413, 413,414, [Group IX], and 474,974. The alcohol, which may be ethanol, methanol or isopropanol, on the thread-storage device preferably flows in counter-current to the direction of travel of the thread. The washing step may be followed by the incorporation of heat-stabilizing agents such as those disclosed in Specifications 666,640 and 684,967. In examples, masticated rubber in toluene is activated with tertiary butyl hydroperoxide and then extruded into a coagulant bath containing sulphur dioxide dissolved in a mixture of ethanol and toluene; the resultant thread is passed to a take-up godet and then over three cantilever thread-advancing reels on the first two of which the thread is washed with ethanol. On the third reel the thread is washed with ethanol alone, or with ethanol containing either thiourea and hexamethylene tetramine or phenyl salicylate. Specifications 527,075, 616,276, and 679,274 also are referred to.ALSO:The ultra-violet light stability of polydiene-sulphur dioxide threads is increased by passing the thread during its manufacture in a number of consecutive turns over one or more thread-advancing, thread-storage devices and subjecting the turns of thread to an extensive washing treatment with a liquid consisting essentially of an alcohol. The thread-storage devices are preferably reels of the type described in Specifications 413,413, [Group IV], 413,414, [Group IX], and 474,974, [Group IV]. The alcohol which may be ethanol, methanol or isopropanol on the thread storage device preferably flows counter-current to the direction of travel of the thread. The washing step may be followed by the incorporation of heat stabilizing agents such as those disclosed in Specifications 666,640, [Group IV (a)], and 684,967. In Examples, masticated rubber in toluene was activated with tertiary butyl hydroperoxide and then extruded into a coagulant bath containing sulphur dioxide dissolved in a mixture of ethanol and toluene, the resultant thread was passed to a take-up godet and then over three cantilever thread-advancing reels on first two of which the thread was washed with ethanol. On the third reel the thread was washed with ethanol alone, or with ethanol containing either thiourea and hexamethylene tetramine or phenyl salicylate. Specifications 527,075, 616,276, [Group IV (a)], and 679,274 also are referred to.
128 FR1031770D 1950-12-27 FR1031770A 1953-06-26
129 FR1018635D 1950-03-08 FR1018635A 1953-01-09
130 Methods for improving the stability of threads and like products of polydiene-sulphur dioxide compounds GB670150 1950-03-17 GB684967A 1952-12-31 CARPENTER ALBERT STANLEY; WALDEN HAROLD ELBOROUGH; WILLIAMS HAROLD MALCOLM GORDON
The stability of threads and like filamentary products of polydiene-sulphur dioxide compounds is improved by incorporating in the product one or more aromatic hydroxy compounds, such as pyrogallol, quinol, catechol and b -naphthol. Mixtures of such compounds may be used, but it is preferred to use one or more of said compounds in conjunction with one or more of the stabilizing agents described in Specification 666,640, i.e. compounds containing the group such as hexamine, triethanolamine, urea and thiourea and their N,N- or N,N1-diphenyl derivatives, and the corresponding diphenyl guanidines. The threads may be first washed, e.g. with methanol to remove any sulphuric acid and are then immersed in solutions of the compounds, preferably in methanol, e.g. of 0.5 to 5 per cent total concentrations, and for times such as 16 hours at 20 DEG C. The threads are then removed from the bath and air-dried. Specifications 527,075, 616,276 and 679,274 also are referred to.ALSO:The stability of threads and like filamentary products of polydiene-sulphur dioxide compounds is improved by incorporating in the product one or more aromatic hydroxy compounds, such as pyrogallol, quinol, catechol, and betanaphthol. Mixtures of such compounds may be used, but it is preferred to use one or more of said compounds in conjunction with one or more of the stabilizing agents described in Specification 666,640, i.e. compounds containing the group such as hexamine, triethanolamine, urea and thiourea and their N,N- or N,N1-diphenyl derivatives, and the corresponding diphenyl guanidines. The threads may be first washed, e.g. with methanol, to remove any sulphuric acid and are then immersed in solutions of the compounds, preferably in methanol, e.g. of 0.5 to 5 per cent total concentrations, and for times such as 16 hours at 20 DEG C. The threads are then removed from the bath and air-dried. Specifications 527,075, 616,276 and 679,274 also are referred to.
131 Process for the incorporation or application of substances, in particular dye-stuffsand stabilizers, in or on to reaction products of sulphur dioxide with polymers or co-polymers of conjugated dienes GB1551850 1950-06-21 GB680491A 1952-10-08
Dyestuffs, stabilizers, and other substances are incorporated in or on the reaction products obtained by the action of sulphur dioxide on polymers or copolymers of conjugated dienes by soaking the reaction products in aqueous solutions or dispersions containing swelling agents of the substances to be applied. The swelling agents may be acetone, pyridine, benzene, toluene, chloroform, dichlorethane, methyl ethyl ketone, cyclohexanone, benzyl alcohol, crotonaldehyde, benzaldehyde, furfural, ethyl acetate, amyl acetate, nitro-ethane, phenol or cresol. The polymers and copolymers may be polymers of butadiene, methyl butadiene, dimethylbutadiene, and chloroprene, and copolymers of these monomers with isobutene, styrene, vinyl chloride, acrylonitrile, allyl alcohol, allyl chloride, allyl acetate, diallyl phthalate, and diallyl adipate. The dyestuffs include noir acetoquinone N.B.N. and Java red, and the stabilizers may be thiourea, melamine, hexamethylenetetramine, thiocyanates and cation-active substances such as cetyl - pyridinium bromide and sapamines. Specification 616,276 is referred to.ALSO:Dyestuffs, stabilizers, and other substances are incorporated in or on the reaction products obtained by the action of a sulphur dioxide on rubber, guttapercha or balata by soaking the reaction products in aqueous solutions or dispersions containing swelling agents of the substances to be applied. The swelling agents may be acetone, pyridine, benzene, toluene, chloroform, dichlorethane, methyl ethyl ketone, cyclohexanone, benzyl alcohol, crotonaldehyde, benzaldehyde, furfural, ethyl acetate, amyl acetate, nitro-ethane, phenol or cresol. The dyestuffs include noir acetoquinone N.B.N. and Java red, and the stabilizers may be thiourea, melamine, hexamethylenetetramine, thiocyanates and cationactive substances such as cetyl-pyridinium bromide and sapamines. In examples the effect of various swelling agents on the dyeing and stabilising of rubber-sulphur dioxide reaction products is illustrated. Specification 616,276 is referred to.
132 Improvements in and relating to the manufacture of artificial threads, fibres, filaments and the like GB669950 1950-03-17 GB679274A 1952-09-17 CARPENTER ALBERT STANLEY; HAMPSON HENRY; WALLSGROVE ERIC RICHARD
Artificial threads are produced 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 catalyst into a coagulant bath containing sulphur dioxide, the polydiene solution having a concentration of at least 10 per cent by weight, and preferably 20 to 40 per cent. The solvents and coagulant baths may be the same, or those described in Specification 679,040. The viscosity of the polydiene solution may be reduced by passing a stream of ozonized oxygen p through it. Specifications 527,075 and 616,276 also are referred to.
133 FR1015178D 1950-02-24 FR1015178A 1952-08-28
134 DEP0042745 1949-05-15 DE843899C 1952-07-14 GOPPEL JOHAN MICHAEL
135 DEN0000567 1950-02-28 DE828913C 1952-01-21 MAASKANT DR LEENDERT
136 NL139976 1948-04-16 NL71108C 1952-01-15
137 FR969154D 1948-07-13 FR969154A 1950-12-15
138 FR968137D 1948-06-22 FR968137A 1950-11-20
139 A process for manufacturing valuable reaction products of high-molecular unsaturated substances containing more than one unsaturated grouping in the molecule with inorganic acids or acid anhydrides GB3245645 1945-11-30 GB616276A 1949-01-19
Products suitable for conversion into filaments, yarns, and ribbons are obtained by reacting synthetic polymers or copolymers of dienes with sulphur dioxide or sulphurous acid in the presence of organic or inorganic hydroperoxides. The polymeric substances must have a molecular weight of at least 5,000, and contain a plurality of unsaturated carbon to carbon linkages in the molecule. Specified substances are polymers of butadiene, methyl butadiene, dimethyl butadiene, and pentadiene; and copolymers of these monomers with isobutene. A hydroperoxide is defined as having the group R-O-O-H where R is a hydrogen atom or an organic radical in which a carbon atom of the radical is directly attached to the group O-O-H. Specific hydroperoxides are tetrahydro-naphthalene peroxide, peracetic acid, tertiary butyl hydroperoxide and hydrogen peroxide. In an example a butadiene polymer in benzene solution was coagulated by peracetic acid and sulphur dioxide dissolved in alcohol and water. Specifications 527,075 and 611,919 are referred to. The Specification as open to inspection under Sect. 91 comprises also the use, in the place of the polymeric substances specified, of polymerized chloroprene and acetylene; and copolymers of butadiene, methyl butadiene, dimethyl butadiene, pentadiene, chloroprene and acetylene with acetylene, vinyl acetylene, isobutene, styrene, vinyl chloride, vinyl esters, acrylic acid, methacrylic acid, methyl isopropenyl ketone, or vinyl ethyl ether. In addition the sulphur dioxide may be replaced by any inorganic acid or inorganic acid excepting those in which the acid forming element occurs in the highest valency in cases in which more than one series of such compounds may be formed. Specified substances of this type are phosphorous trioxide, hydrogen sulphide, hydrochloric acid, and hydrobromic acid. This subject-matter does not occur in the Specification as accepted.ALSO:Products suitable for conversion into filaments, yarns, and ribbons are obtained by reacting natural or synthetic polymers or copolymers of dienes with sulphur dioxide or sulphurous acid in the presence of organic or inorganic hydroperoxides. The polymeric substances must have a molecular weight of at least 5,000, and contain a plurality of unsaturated carbon to carbon linkages in the molecule. Specified substances are natural rubber, polymers of butadiene, methyl butadiene, dimethyl butadiene and pentadiene; and copolymers of these monomers with isobutene. A hydroperoxide is defined as having the group R-O-O-H where R is a hydrogen atom or an organic radical in which a carbon atom of the radical is directly attached to the group O-O-H. Specific hydroperoxides are tetrahydro-naphthalene peroxide, peracetic acid, tertiary butyl hydroperoxide and hydrogen peroxide. In examples (1) A rubber in benzene solution containing tetrahydro naphthalene peroxide was coagulated by sulphur dioxide dissolved in alcohol and water (ii) A butadiene polymer in benzene solution was coagulated by peracetic acid and sulphur dioxide dissolved in alcohol and water. (iii) and (iv) Gaseous sulphur dioxide was passed into a benzene solution of rubber containing either tertiary butyl hydroperoxide in butyl alcohol or hydrogen peroxide in diethyl ether. Specifications 527,075 and 611,919 are referred to. The Specification as open to inspection under Sect. 91 comprises also the use, in the place of the polymeric substances specified, of polymerised chloroprene and acetylene; and copolymers of butadiene, methyl butadiene, dimethyl butadiene, pentadiene, chloroprene and acetylene with acetylene, vinyl acetylene, isobutene, styrene, vinyl chloride vinyl esters, acrylic acid, methacrylic acid, methyl isopropenyl ketone, or vinyl ethyl ether. In addition the sulphur dioxide may be replaced by any inorganic acid or inorganic acid excepting those in which the acid forming element occurs in the highest valency in cases in which more than one series of such compounds may be formed. Specified substances of this type are phosphorous trioxide, hydrogen sulphide, hydrochloric acid, and hydrobromic acid. This subject-matter does not appear in the Specification as accepted.
140 FR902016D 1944-02-17 FR902016A 1945-08-16