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公开(公告)号：GB899717A
公开(公告)日：1962-06-27
申请号：GB2766360
申请日：1960-08-10
Applicant: BASF AG
Inventor： MEYER FERDINAND , KNOBLOCH HORST ERICH , FREYSCHLAG HERWIG , RAUSCHENBACH ROLF DIETER
Abstract: Expanded fine-pored, light weight sheets, films and bands are produced from thermoplastic synthetic resins by (1) applying to a support a solution of the resin in a mixture of a low-boiling solvent and an organic liquid which does not dissolve or only swells the plastic and of which the boiling point is at the most 30 DEG C. higher but preferably lower than that of the solvent, (2) evaporating the solvent at temperatures which lie below the softening temperature of the plastic and (3) expanding the expandable films, sheets and bands containing the non-solvent or swelling organic liquid by heating to temperatures above the softening temperature of the plastic. Specified resins include polycarbonates; polymers and copolymers prepared from vinyl monomers such as styrene, chlorstyrene, alpha-methyl styrene, N-vinyl carbazole, vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride, acrylonitrile, vinyl acetate, vinyl propionate, vinyl butyrate, esters of acrylic acid, methacrylic acid, maleic acid or fumaric acid with methyl, ethyl, propyl, isopropyl, 2-ethylhexyl, decyl or cyclohexyl alcohols; copolymers of the above monomers and aliphatic diolefins such as butadiene-1,3, 2-chlorobutadiene-1,3 or isoprene; and mixtures of such polymers and copolymers. Low boiling, non-solvent or only swelling organic liquids referred to are pentane, hexane, petroleum ether, cyclohexane, cyclohexene, cyclopentane and cyclopentene. Suitable solvents are methylene chloride, carbon disulphide, methyl formate and acetonitrile. Thicker sheets with thicknesses up to 1 cm. may be prepared from highly viscous solutions and these solutions may be prepared in kneaders. In the examples, the expanded materials are prepared from (1) a copolymer of styrene (90 parts) and butadiene (10 parts), (2) a copolymer of styrene and methyl styrene, (3) after chlorinated polyvinyl chloride, (4) a copolymer of styrene and acrylonitrile mixed with a copolymer of vinyl chloride and vinyl acetate and (5) a copolymer of vinyl chloride, diethyl maleate and dimethyl maleate. Uses: Wallpaper, heat and electrical insulation, and the production of cups.ALSO:Expanded fine-pored, light weight sheets, films and bands are produced from thermoplastic synthetic resins by (1) applying to a support a solution of the resin in a mixture of a low boiling solvent and an organic liquid which does not dissolve or only swells the plastic and of which the boiling point is at the most 30 DEG C. higher but preferably lower than that of the solvent, (2) evaporating the solvent at temperatures which lie below the softening temperature of the plastic and (3) expanding the expandable films, sheets and bands containing the non-solvent or swelling organic liquid by heating to temperatures above the softening temperature of the plastic. Specified resins include polycarbonates; polymers and copolymers prepared from vinyl monomers such as styrene, chlorstyrene, alpha-methyl styrene, N-vinylcarbazole, vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride, acryloni trile, vinyl acetate, vinyl propionate, vinyl butyrate, esters of acrylic acid, methacrylic acid, maleic acid or fumaric acid with methyl, ethyl, propyl, isopropyl, 2-ethylhexyl, decyl or cyclohexyl alcohols; copolymers of the above monomers and aliphatic diolefins such as butadiene-1, 3, 2-chloro-butadiene-1, 3 or isoprene; and mixtures of such polymers and copolymers. Low boiling, non-solvent or only swelling organic liquids referred to are pentane, hexane, petroleum ether, cyclohexane, cyclohexene, cyclopentane and cyclopentene. Suitable solvents are methylene chloride, carbon disulphide, methyl formate and acetonitrile. A substance which gives off gas when heated may also be included in the film forming solution. The expansion stage may be effected using hot water, steam, infra-red or using high frequency heating. In the examples, the expanded materials are prepared from (1) a copolymer of styrene (90 parts) and butadiene (10 parts), (2) a copolymer of styrene and methylstyrene, (3) after chlorinated polyvinyl chloride (4) a copolymer of styrene and acrylonitrile mixed with a copolymer of vinyl chloride and vinyl acetate and (5) a copolymer of vinyl chloride, diethyl maleate and dimethyl maleate. Uses. Wallpaper, heat and electrical insulation, and the production of cups.
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公开(公告)号：FR1239521A
公开(公告)日：1960-08-26
申请号：FR807562
申请日：1959-10-15
Applicant: BASF AG
Inventor： KNOBLOCH HORST ERICH , MEYER FERDINAND , STASTNY FRITZ
Abstract: In a process for the production of expandable granular thermoplastic material with a grain size of 0,2-4 mm., water containing a dispersing agent for organic liquids immiscible with water, and a solution of a thermoplastic resin in a low-boiling organic solvent which forms with water two separate phases and which also contains in solution 2-20% (based on the weight of the thermoplastic resin) of a water-insoluble expanding agent for the resin, are admixed while being kept in steady motion, the organic solvent is removed from the mixture while continuing the steady motion, and the resulting thermoplastic granules are separated from the aqueous phase. Specified thermoplastic resins are polymers of styrene, acrylic and methacrylic acid esters, vinyl chloride, vinylidene chloride, vinyl carbazole, the polycarbonate produced from butane-diol-(1,4), 2,2-di-(p-hydroxyphenyl)-propane and phosgene, a styreneacrylonitrile copolymer, and condensation products of linear polyesters or polyamides. Chlorpolystyrene may also be used: this is made, as described in Example 1, by leading chlorine into a solution of polystyrene in methylene chloride and expelling the resulting hydrogen chloride by a current of nitrogen. The resulting solution may be used directly as one component of the mixture by adjusting its pH to 8 by addition of dry ammonia, and adding an expanding agent thereto. Specified solvents are methylene chloride, ethylene chloride, carbon tetrachloride, 1,1,2-trichlorethane, benzene, ethyl acetate, diisopropyl ether and tetrahydrofuran. Specified expanding agents are the volatile liquid type, such as petroleum ether, pentane, cyclopentane, hexane, cyclohexane, heptane, diethyl ether and carbon tetrachloride, and the decomposable type such as azoisobutyronitrile, diazoaminobenzene and benzene sulphonic acid hydrazide. The solution of thermoplastic resin may also contain fillers, pigments, dyestuffs, softeners, flame-preventing additives and insecticides. In one example (2), glycol diglycidyl ether is added as a stabilizer to a chlorpolystyrene solution. Specified dispersing agents are polyvinyl pyrrolidone, a copolymer of vinyl pyrrolidone and methyl acrylate, gelatin, casein, polyvinyl alcohol, polyacrylic acid (or salts thereof), kaolin, talc, precipitated magnesium hydroxide or barium sulphate, and alkali salts of alkyl sulphonic acids, alkyl naphthalene sulphonic acids and long-chain aliphatic carboxylic acids. The solvent may be removed from the mixture either during or after mixing, e.g. by leading an inert gas such as nitrogen or carbon dioxide therethrough, or by distilling off under reduced pressure. The granules may be separated from the aqueous phase by filtering or centrifuging, and may be expanded to form a closed-cell body by heating above the softening-point of the resin and above the temperature at which the expanding agent acts.ALSO:In a process for the production of expandable granular thermoplastic material with a grain size of 0,2-4 mm., water containing a dispersing agent for organic liquids immiscible with water, and a solution of a thermoplastic resin in a low-boiling organic solvent which forms with water two separate phases and which also contains in solution 2-20% (based on the weight of the thermoplastic resin) of a water-insoluble expanding agent for the resin, are admixed while being kept in steady motion, the organic solvent is removed from the mixture while continuing the steady motion, and the resulting thermoplastic granules are separated from the aqueous phase. Specified thermoplastic resins are polymers of styrene, acrylic and methacrylic acid esters, vinyl chloride, vinylidene chloride, vinyl carbazole, the polycarbonate produced from butane-diol-(1, 4), 2, 2-di-(p-hydroxyphenyl)-propane and phosgene, a styrene-acrylonitrile copolymer, and condensation products of linear polyesters or polyamides. Chlor-polystyrene may also be used: this is made, as described in Example 1, by leading chlorine into a solution of polystyrene in methylene chloride and expelling the resulting hydrogen chloride by a current of nitrogen. The resulting solution may be used directly as one component of the mixture by adjusting its pH to 8 by addition of dry ammonia, and adding an expanding agent thereto. Specified solvents are methylene chloride, ethylene chloride, carbon tetrachloride, 1, 1, 2-trichlorethane, benzene, ethyl acetate, di-isopropyl ether and tetrahydrofuran. Specified expanding agents are the volatile liquid type, such as petroleum ether, pentane, cyclopentane, hexane, cyclohexane, heptane, diethyl ether and carbon tetrachloride, and the decomposable type such as azoisobutyronitrile, diazoamino-benzene and benzene sulphonic acid hydrazide. The solution of thermoplastic resin may also contain fillers, pigments, dyestuffs, softeners, flame-preventing additives and insecticides. In one example (2), glycol diglycidyl ether is added as a stabilizer to a chlorpolystyrene solution. Specified dispersing agents are polyvinyl pyrrolidone, a copolymer of vinyl pyrrolidone and methyl acrylate, gelatin, casein, polyvinyl alcohol, polyacrylic acid (or salts thereof), kaolin, talc, precipitated magnesium hydroxide or barium sulphate, and alkali salts of alkyl sulphonic acids, alkyl napthalene sulphonic acids and long-chain aliphatic carboxylic acids. The solvent may be removed from the mixture either during or after mixing, e.g. by leading an inert gas such as nitrogen or carbon dioxide therethrough, or by distilling off under reduced pressure. The granules may be separated from the aqueous phase by filtering or centrifuging, and may be expanded to form a closed-cell body by heating above the softening-point of the resin and above the temperature at which the expanding agent acts.
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公开(公告)号：GB1011909A
公开(公告)日：1965-12-01
申请号：GB3486864
申请日：1964-08-26
Applicant: BASF AG
Inventor： THEWIS JOSEF , MATSCHAT KARL , MEYER FERDINAND
IPC: D06M13/165 , D06M13/372 , D06M15/327
Abstract: The invention comprises compounds, used for treating synthetic fibres &c. (see Division D1), of the formula where R1 is hydrogen, an alkyl radical of 1-4 carbon atoms or hydroxy alkyl of 2-4 carbon atoms, X denotes a radical of the formula -COR2 or -A3OCOR2, R2 is an alkyl radica of 10-20 carbon atoms, (A1-O) is an ethyleneoxy and/or propylene-oxy radical, A2 is an alkylene radical of 2-5 carbon atoms, A3 is an alkylene radical of 2-4 carbon atoms and n is 5-35. The compounds may be prepared either (1) by cyanoethylating a polyalkylene glycol, hydrogenating, and reacting the resultant diamine with a long chain fatty acid or an amide-forming derivative of such an acid, or (2) by forming the dichloride of the polyalkylene glycol, reacting this with a primary alkylamine or a primary or secondary hydroxyalkylamine and acylating the resultant diamine with a long chain fatty acid or an ester- or amide-forming derivative of such an acid. In examples: (A) acrylonitrile is added to polyethylene glycol (mol. wt. 810) and sodium methylate. After neutralization the product is hydrogenated and heated with stearic acid. (B) Polyethylene glycol (mol. wt. 810) is reacted with thionyl chloride. The dichloride obtained is stirred in monoethanolamine and anhydrous sodium carbonate, and the diamine formed is reacted with stearic acid. In further examples, stearic acid is reacted with o ,o 1-di-(aminopropyl)-octadecaethylene glycol ether and with o ,o 1-di-(aminopropyl)-tridecaethylene glycol ether. The treating agent may be used in aqueous solutions or dispersions which also contain dispersing, emulsifying or stabilizing agents, e.g. adducts of ethylene oxide with long chain alcohols, mercaptans, amines, carboxylic acids or esters or amides thereof, fatty alcohol sulphonates, alkylaryl sulphonates and partial esters of polybasic organic or inorganic acids and long chain alcohol or ether alcohols.ALSO:Textile materials of synthetic macromolecular substances are treated and given an antistatic finis by polyalkylene glycolamide of the formula where R1 is hydrogen, an alkyl radical of 1-4 carbon atom or hydroxy alkyl of 2-4 carbon atoms X is a radical of the formula-COR2 or -A3-OCOR2 R2 is an alkyl radical having 10-20 carbon atoms (A (A1-O) is an ethyleneoxy and/or propyleneoxy radical, A2 is an alkylene radical having 2-5 carbon atoms, A3 is an alkylene radical haveing 2-4 carbon atoms, and n is 5-35. The treating agent is applied in the form of an aqueous solution or dispersion, or as a solution in an organic liquid. A dispersing, emulsifying or stabilising agent may also be present. Examples describe the treatment of polyester fibres, including dyed fibres and union cloth consisting of 45% wool and 55% polyester fibre, with, e.g. aqueous solutions of the reaction product of (1) stearic acid and w, w1-di-(aminopropyl)-octadeca-ethylent glycol either, (2) stearic acid and the reaction product of diethanl amine and the dichloride of a polyethylene glycol (mol wt 800).
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公开(公告)号：FR1345644A
公开(公告)日：1963-12-13
申请号：FR912526
申请日：1962-10-17
Applicant: BASF AG
Inventor： RAUSCHENBACH ROLF DIETER , MEYER FERDINAND , WINTERSBERGER KARL , DAUMILLER GUENTHER
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公开(公告)号：GB930467A
公开(公告)日：1963-07-03
申请号：GB2766560
申请日：1960-08-10
Applicant: BASF AG
Inventor： SANDER HANS , MEYER FERDINAND
IPC: C08F8/00 , C08F22/36 , C09D125/14 , C09D135/02
Abstract: A copolymer of (A) a monoamide of a C4-C6 olefinically unsaturated dicarboxylic acid, wherein the carbonamide group may be mono- or di-substituted on the N atom by an aliphatic, cycloaliphatic or aromatic radical; (B) one or more compounds containing a -CH=CH2 or group; and (C) one or more alpha-beta olefinically unsaturated mono- or di-carboxylic acids, esters or anhydrides, wherein the mol. ratio of (A):(B+C) is between 0,05 and 1 : 1 and of (B):(C) is between 10 and 0,1 : 1, has the N atoms of the carboxylic acid amide groups substituted by alkoxymethyl groups. The alkoxymethyl groups may be introduced before, during or after polymerization by means of formaldehyde and the appropriate monohydric alcohol. It is also possible to introduce the monoamide groups themselves after polymerization by treating a copolymer derived from a dicarboxylic acid or anhydride with an appropriate amount of an amine. (A) may be a monoamide of maleic or fumaric acid; (B) may be a vinyl ether, vinyl ester, e.g. the acetate, or a vinyl aromatic compound, e.g. styrene or alpha methyl styrene; (C) may be acrylic, maleic or fumaric acid, maleic anhydride, or methyl or ethyl acrylate. In forming the alkoxymethyl groups the alcohol may be used in a 5 to 10 times excess and water of condensation continuously removed to yield a p solution which can be used directly as a varnish. The solutions may also be mixed with other varnish resins, e.g. phenol, urea, melamine, epoxy or alkyd varnish resins. 2 to 20 wt. per cent of epoxy resin is said to donate practically unlimited stability in caustic soda solution. In examples:-(1) 20 parts N-butyl maleic or fumaric acid monoamide, 40 parts styrene and 40 parts ethyl acrylate are polymerized in butanol using benzoyl peroxide as catalyst and subsequently treated with formaldehyde; the resulting solution is used as a varnish alone or mixed with 10% of an epoxy resin based on dihydroxydiphenyldimethylmethane having an epoxy No. of 0,2; (2) the monomers used are 30 parts N-cyclo-hexyl-maleic acid monoamide, 30 parts ethyl acrylate and 40 parts styrene; (3) the monomers are 20 parts N-butyl-maleic acid monoamide, 40 parts styrene, 30 parts ethyl acrylate and 10 parts vinyl ethyl ether; (4) 40 parts styrene, 40 parts ethyl acrylate and 11,5 parts maleic anhydride are polymerized in toluene with benzoyl peroxide as catalyst, precipitated, amidated with 2 parts ammonia, and then treated with excess butanol and formaldehyde. Specification 792,874 is referred to.
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Patent Agency Ranking
公开(公告)号：CA640352A
公开(公告)日：1962-04-24
申请号：CA640352D
Applicant: BASF AG
Inventor： STASTNY FRITZ , MEYER FERDINAND , KNOBLOCH HORST E
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公开(公告)号：GB860285A
公开(公告)日：1961-02-01
申请号：GB1219158
申请日：1958-04-17
Applicant: BASF AG
Inventor： DEMMLER KURT , GOELZ HORST , MEYER FERDINAND , OETTEL HEINZ , WILHELM GERTRUD
Abstract: The invention comprises ethylene imine compounds of the formula wherein X represents oxygen, sulphur or the group -NR-, R being hydrogen or an aliphatic, cycloaliphatic or aromatic hydrocarbon radical, R1 is a radical having an unsaturated chain of 3-5 carbon atoms, the unsaturated linkage being between carbon atoms 2 and 3, 3 and 4 or 4 and 5 (counting from X), and each of R2 and R3 is hydrogen or an aliphatic hydrocarbon radical or R2 and R3 together form an alkylene radical, and the preparation of these compounds by reacting a compound of the formula R1.XH with epichlorhydrin to give the corresponding substituted epoxide (or a halohydrin which is converted to the epoxide), which is treated with an ethylene imine, optionally bearing substituents R2 and R3. The reactant R.XH may be an alcohol such as allyl alcohol or a butanol or a corresponding mercaptan or an amine such as propenylamine, N-methyl propenylamine, N-phenyl butenylamine or N-cyclohexyl pentenylamine. 2 : 3-Epoxypropyl alkenyl ethers and the corresponding thioethers and amines such as 1-alkylthio-, 1-N-methyl-allylamino- and 1-a -methyallyl-oxy-2 : 3-epoxypropane are obtained as intermediates in the above process.
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公开(公告)号：GB801728A
公开(公告)日：1958-09-17
申请号：GB1192856
申请日：1956-04-19
Applicant: BASF AG
Inventor： MEYER FERDINAND , DEMMLER KURT
IPC: C07D303/24
Abstract: Polyglycidyl ethers are prepared by dehydrohalogenating polyhalogen hydrin ethers of polyhydric aliphatic saturated alcohols and of polymethylol compounds of melamine at a temperature from -20 DEG to 30 DEG C. with an amount of a 25 to 60 per cent by weight aqueous solution of a strong inorganic base at least equivalent to that required for binding the hydrogen halide split off, in the presence of an aliphatic saturated monohydric alcohol which is insoluble or soluble in water up to an amount of 10 per cent by weight at the working temperature and which dissolves the epoxy compound formed and the halogenhydrin ether. The monohydric alcohol may be n-butanol, n-sec.- or tert.-amyl alcohol or ethyl hexanol, suitably used in an amount of 33-66 per cent based on the ether, and if desired in admixture with one another or with other inert water-insoluble organic solvents such as aromatic hydrocarbons. Suitable polyhalogen hydrin ethers are those derived from glycerol, butane triol, pentaerythritol, dipentaerythritol, trimethylol propane, sorbitol, hexane-triol and tri- or hexa-methylol melamine, which ethers may be obtained by reacting the polyhydric alcohol with appropriate amounts of epichlorhydrin or dichlorhydrin and the corresponding bromo compounds in the presence of a catalyst, e.g. BF3; preferably there are introduced more than 2 halogen-hydrin groups. In examples: (1) excess of 45 per cent aqueous NaOH is slowly added at -5 DEG to 0 DEG C. with stirring to a butanol solution of a chlorhydrin obtained from a 1 : 3 molar mixture of glycerol and epichlorhydrin; water and toluene are then added and the non-aqueous phase is worked up to recover a diglycidyl ether still containing chlorine and having a M.W. of 283; (2) a chlorhydrin ether obtained from a 1 : 3 molar mixture of 1 : 2 : 4-butane-triol and epichlorhydrin is similarly treated in butanol-toluene solution and yields a diglycidyl ether containing chlorine and of M.W. 350; (3) a mixture of polychlorhydrins prepared from epichlorhydrin, glycerol and pentaerythritol is similarly treated in amyl alcohol to yield a polyglycidyl ether of epoxy value 0.63. Specification 679,536 is referred to.
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29.发明专利
公开(公告)号：GB796623A
公开(公告)日：1958-06-18
申请号：GB1111356
申请日：1956-04-12
Applicant: BASF AG
Inventor： STASTNY FRITZ , MEYER FERDINAND , THEWALT JULIUS
Abstract: Shaped articles of porous styrene polymers are made by coating a porous styrene polymer with a polyglycidyl ether of an epihalohydrin and a polyhydroxy compound (see Group IV (a)) and a hardening agent therefor. Specified styrene polymers are polystyrene and copolymers of styrene with other mono- or di-vinyl compounds. The coating may be by dipping, brushing or spraying, or by coating the inner surface of the mould in which the styrene polymer is to be expanded. In Example 2 a rectangular plate of porous polystyrene is coated with a butane-triol/epichlorhydrin resin containing p,p1-diaminodiphenylmethane as hardener.ALSO:Shaped articles and filling materials of porous styrene polymers are made either by joining together particles (having a minimum particle size of about 0.5 mm.) of a porous styrene polymer with the aid of a polyglycidyl ether of an epihalohydrin and a polyhydroxy compound and a hardening agent therefor, or by coating a porous styrene polymer shaped article or filling material with such a compound. Specified styrene polymers are polystyrene and copolymers of styrene with other mono- or divinyl compounds. Specified blowing agents are sodium carbonate, azo-compounds, and volatile organic compounds, e.g. saturated hydrocarbons of b.p. 30-70 DEG C. which do not dissolve polystyrene. Specified polyhydroxy compounds are glycol, butanediols, butanetriols, glycerine, trimethylolpropane, hexanediol, pentaerythritol, hydroquinone, resorcinol, 4,41-dihydroxydiphenyl dimethyl methane or the sulphone or oxide thereof. The epoxy resins may be modified by monohydric alcohols (e.g. allyl), hardened by polybasic acids (e.g. phthalic, succinic, adipic) or amines (e.g. ethylenediamine, hexamethylenediamine, diethylenediamine, triethylenetetramine, cyclohexylamine, diaminocyclohexane, p,p1 - diaminodiphenylurea, N-cyclohexylpropylenediamine, p,p1 - diaminodiphenylmethane), and catalysed by FriedelCrafts' catalysts (e.g. aluminium chloride). Hollow spaces in boats &c. may be filled, and lifebelts, floats, plates and insulating sheets made, with these materials. In Example (I) spherical particles of porous polystyrene are mixed with an ethylene glycol/epichlorhydrin polymer and N-cyclohexylpropylene diamine, and the mixture used to insulate and give good buoyancy to the lateral walls of boats. In Example (II) a plate of porous polystyrene is coated with a butanetriol-epichlorhydrin resin containing p,p1 - diaminodiphenylmethane as hardener.
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公开(公告)号：DE884424C
公开(公告)日：1953-07-27
申请号：DEB0014089
申请日：1951-03-08
Applicant: BASF AG
Inventor： KRZIKALLA HANS , MEYER FERDINAND , TAACK-TRAKRANEN FREDERIC VAN
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