• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    1508164 Preparation of esters, ester-amides and amides of isophthalic acid MONSANTO CO 21 July 1975 [22 July 1974] 30416/75 Heading C2C [Also in Division C3] An alcohol (A) is condensed with a poly- (N-acyl) lactam (L) in the presence of a catalyst (C) being a Group Ia, IIa, IIb or IIIa metal (M) or compound of (M). A large number of each of (A), (L) and (C) are listed. (C) may be inorganic, organic or organometallic, including lactam, halolactam, haloalkyl or alkoxide derivatives. The products may be esters or esteramides. (M) may be, e.g., Li, Na, K, Mg, Ca, Sr, Ba, Zn, Cd, or Al. (A) may be saturated or unsaturated, unsubstituted or substituted, aliphatic or aromatic, carbohydrate, ether, or ester. The reaction medium may contain a lactam, e.g. 1-methyl-2-pyrrolidone or caprolaetam. In the Example (1), (L) is N,N<SP>1</SP>-isophthaloyl-bis-caprolactam; (A) is ethanol; and (C) is C 2 H 5 MgBr; the products are diethyl isophthalate, m - carbethoxy - [N - (5 - carbethoxy - n - amyl)]benzamide, and N,N<SP>1</SP> - bis- (5-carbethoxy-n-amyl)isophthalamide.
    公开号:SU843760A3
    申请号:SU752159076
    申请日:1975-07-21
    公开日:1981-06-30
    发明作者:Мельвин Хенрик Росс；Дельвин Гэбберт Джеймс
    申请人:Монсанто Компани (Фирма)；
    IPC主号:
    专利说明:

    METHOD OF OBTAINING POLYAMIDOESTERS
    This invention relates to the field of the chemistry of high molecular weight compounds, in particular, the catalytic method of condensing imides with alcohols. A known method for the preparation of polyamides is dopesters by the condensation reaction of acyl lactams with alcohols in the reaction medium in the absence of 1 and 1 catalysts. The disadvantages of the method include the use of high temperatures and low speed of interaction. The purpose of the invention is to accelerate the reaction, as well as to conduct it at lower temperatures. The goal is accomplished by the addition of at least one metal or a compound of a metal of groups IA, HA, 118, III as a catalyst to the reaction. The base metals of group IA, PA, CV, and P1A have a proper effect, either in metallic form or in the hydrides, halides, alkyl halides, oxides, hydroxides, peroxides, carbonates and similar types of compounds. Other useful catalysts may be derived from a variety of organometallic compounds of these metals, such as alkyls, phenols, metal amides, alkoxides, glycoxides, and the like. As an example, it is possible to use a Soda , diethyl aluminum bromide and the like. The catalyst can be obtained in situ by reacting one of the above-listed metals or its compounds with the alcohol link of the imido-alcohol condensation reagent. The concentration of the catalyst may range from 1 mol. % to 15 or 20 mol.% alcohol, link and more. The expression alcohol unit refers, in the scope of the present invention, to a compound containing at least one hydroxyl radical associated with an aliphatic carbon. The polymers obtained by the catalyzed condensation of an imide with an alcohol according to the present invention can be used as prepolymers, for example, for the polymerization of lactam in the preparation of a three-stage polymer. Catalysts that can be used for the condensation of an imide with an alcohol in the presence of lactam and which do not easily polymerize the lactam medium include zinc caprolactam, caprolactam: calcium, caprolactam barium, aluminum-tri-caprol act, wild aprolactyl-alumi; bis- (bromo ethyl and caprolactam magnesium. Alcohol units include simple and / or polyhydric alcohols, starting with monomeric or polymeric compounds, where the hydroxyl radical is bound to the compound with aliphatic carbon. Alcohol The units may contain one or more hydroxyl radicals bonded by aliphatic carbon. Typical alcohols that can be used according to this invention include, for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, tert. -butanol, 2-ylhexanol, 1-dodecanol, 1 octadecanol; saturated alcohol such as allyl alcohol and metal alcohol; halogenated alcohols, for example, ethylene chlorohydrin nitroalcohol, for example 2-nitro-butanol-1f ether alcohols, for example ethylene glycol; p and diethylene glycol monoethyl ETHER cycloalkanols, for example, cyclohexanol; aralkyl alcohols, for example benzyl alcohol; tertiary amino alcohols, for example triethanolamine, cyclic combinations, for example, cyanoethanol; polyhydric alcohols, such as ethylene glycol, polyethylene glycols, polymeric alcohol 5, obtained by oxidation followed by reduction of the isoolefin; conjugated diolefin copolymers, alkyl resins containing terminal alcoholic hydroxyl groups, glycerol, pentahertyrol, cellulose, starch, glucose, sucrose, sorbitol, polyvinyl alcohol, and their partial ethers and esters; monoglycerides; diglycerides; triglycerides containing one or more alcoholic hydroxyl groups, for example, castor oil and blown oils obtained from soybean and flaxseed oils; methanolphenols, for example, 2, b, dimethylol-4-alkylphenols and their condensed polymers, N-methylol compounds, for example, N-methylol maleimide and N, N-dimethylolurea; and alcohols containing sulfo groups, for example, alcohols derived from glycol and divinyl sulfone. Available in the trade of polyhydric alcohols, which are suitable reagents for. This method is obtained.
    for example, by reacting propylene oxide or ethylene oxide with glycols, glycerol, pentaerythritol, glucose; amines and the like. The class of compounds listed also includes a large number of relevant compounds from simple diols, like ethylene glycol, to complex polymeric polyhydric alcohols, like a poly (6-caprolactone) -diol. Other polyhydric alcohols include alkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, tetramethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, 1,2-propanediol, 1,3-propandiol, 1,3-hexanediol, 1 .. 5-pentaidiol, butylene glycol, 1,3-propandiol, 1,3-hexanediol, 1 .. 5-pentadiol, butylene glycol, 1,3-propandiol, 1,3-hexanediol, 1 .. 5-pentaidiol, butylene glycol, 1,3-propandiol, 1,3-hexanediol, 1. 4-loaf, cyol, dicyclopentagdiglycol, gegggaetk..englykol, isopropylidene-bis- {phenyleneoxypropanol-2); diols other than alkylene glycols such as hydroxyethyl acrylate and hydroxypropyl methacrylate; polyhydric alcohols contain more than two hydroxyl functions, such as glycerol, pentaerythritol, 1,2-hexantriol, 1-trimethylolpropane) polymeric polyhydric alcohols, such as polyethylene glycol, polypropylene glycols, polyoxypropylene diols and -triols, castor oils, polybutadiene glycols, polytoxypropylene diols and triols, castor oils; of all the abovementioned oxo compounds, thio compounds are also included in the volume - analogues of the above compounds with sulfur atoms instead of oxygen. As individual examples, hydroxyethyl thioglycolate, ethylene glycol bis (thioglycolate), pentaerythol, tetrakis (thioglycolate) and thiodiglycol can be given.
    If the intermediate polyhydric alcohol is a polymer, the molecular weight of this alcohol is any. Polyhydric alcohols available in trade have a molecular weight of 200 to 5000, but polymers with a molecular weight outside this range can also be used in the scope of the present invention. If the intermediate polyhydric alcohol is one single mo-. a two hydroxyl radicals, such as ethylene glycol, the corresponding polyhydric alcohol according to this invention will have a molecular weight of at least 62, although simple methyl alcohol with a molecular weight of 32 is also applicable.
    A number of imides are suitable for catalyzed condensation of an imide with an alcohol, however, the preferred imides are acyl-lactams, acylpolylactams, polyacyl-lactams; below, they are indicated; within the scope of this invention, acyl lactams.
    According to the catalyzed condensation of an imide with an alcohol, typical polymers are obtained, and the polyacyl-lactam component is reacted with a polyethylene glycol component. In the structural formula expressing the polyacyl-lactam used, the group R can designate any hydrocarbon group containing the necessary number of valences available for the compound with all acyl groups contained in the compound. The hydrocarbon group can be of any size, however, preferably contains no more than 8-10 C atoms. The corresponding R groups include, for example, phenylene, biphenylene, methylene, hexylene, polyoxyethylene, polyoxypropylene, and similar hydrocarbons containing more than 2 possibilities for zy with acyl groups. Groups A and A can denote carbonyl, thiocarbonyl, sulphuryl, phosphoryl. The group Y can designate any alkylene chain with 3-10 C atoms. Preferred compounds of the polyacyl-lactam class included in the scope of the following structural formula are those, where A and A are carbonyl groups. In particular, compounds in which A and A are carbonyl are preferred, R is either alkylene or phenylene, U is a 5-member on an alkylene group, and the integer is 1. The structure formula expresses polyacyl-lactamic , which may contain imkdnaya link condensation of the imide with alcohol H (-A- (k) b- (A-1t), 1 and VY acyl groups, selected from A to 0 from 0.0 And 11 IIR-C-, -C- , -S - or -P and -i Oh About
    ( WITH
    . oh oh
    / C II and
    (Cc – O – c where C is an alkylene group containing at least about 3 C atoms, f is an aromatic unit, B is an integer equal to 1
    or more.
    The preferred catalyst may be selected from compounds of metals of groups IA, PA, IIB, 111A, Kakhch lactam salts, halo-lactam salts, and alcoholoids, for example, caprolactammagnesium bromide, bromomagnesium caprolactam.
    //ABOUT
    hhfh fffWAUSOTOP
    БС С 0С-15) -
     H U
    Chu
    Vy /
    sodium caprolactam, calcium caprolactam, zinc caprolactam, aluminum-tri-caprolactam, aluminum-bis- (bromomethyl caprolacta-aluminum chloride, dicaprolacto-aluminum chloride, and similar compounds.
    The consumption rate of acyl-lactam, necessary for the preparation of copolymers, depends on the amount of alcohol or polyhydric alcohol used. For a preferred embodiment of the polymerization, a primer is required; where Y is an alkylene group containing at least about 3 C atoms; divalent or multivalent group; an integer equal to at least 1 integer. These compounds include, for example, terephthaloyl bis-caprolactam oxalyl bis-caprolactam; isoftsshoyl bis-caprolactam; adipoyl bis-caprolactam; malonyl bis-pyrrolidinone, succinoyl bis-pyrrolidinone, glutaroyl bis bis-piperidone; glutaconoyl bis bis-piperidone, 2-ethyl-2-phenylglutaroyl bis-valerolactam; 2,3-diethylsuccinoyl bis-caprolactam; pimeloyl bis-caprilactam; sebacil bis caprolactam, phthaloyl bis bispiperidone, isophthaloyl bis bis dodecanolactam; trimesoyl-tris-caprolactam; 1,2,3,5-benzenetetracarbonyltetrakine prolactam; 1,2,3,4-naphthalene-tetracarbonyl-tetrakipiperidone and 1,4-cyclohexanedicarbonyl bis-caprolactam; 1,3-benzene-disulfonyl-caprolactam; 3- (sulfonyl-caprolactam) -benzoyl-caprolactam; phosphoryl tris caprolactam; benol-phosphoryl bis-caprolactam; and dithioterephthaloyl bis-caprolactam. The characteristic catalyzed condensation of an imide with an alcohol is expressed by the formula-scheme outside the acyl-lactam in an amount from 10 to 200 mol.% Of alcohol or a polyhydric alcohol. The preferred ratio of the two polymer forms of substances, t.a. imide and alcohol, depends on 6m of the final destination of the target polymers. In the event that al final application requires elastomeric properties, such as elongation, the ratio of both monomers can be set in such a way that the polymerization medium contains 60 or BP or 90% or more polyhydric alcohol. Polymers containing approximately equal amounts of acyl lactam and polyhydric alcohol are preferred for a very large number of applications due to the advantageous combination of properties obtained with such polymers. Variations in the properties of the target products can be made by appropriate selection of reagents for catalyzed condensation of alcohol with alcohol, namely, the use of a polyacyl lactam with an aromatic hydrocarbon group between acyl lactam groups as opposed to a long chain aliphatic group. Shlborom aromatic groups reach greater hardness and stiffness of the product. Similarly, copolymers can have a large number of cross-links if polyatomic alcohols containing more than two hydroxy-BS groups are used. Thanks to the application of all the above methods suitable for modifying and regulating properties, they can find application in a whole number of areas. and in particular, in general, a number of textile and other wobbly regions. As regards the textile industry, these polymers find use in the production of nonwovens and high-moisture content fibers. The copolymers can be used to produce peoplasts, to manufacture molding resins, which can immediately be processed by injection molding, extrusion, heat treatment, and other means for the manufacture of products of any shape. Highly elastomeric copolymers can also be used in the manufacture of automobile tires and tire parts. The polymers can be modified with aggregates, fibers, pigments, dyes, stabilizers, plasticizers, agents for imparting fire to the bone and other modifiers in order to change and vary the properties of the polymers and thereby expand the field of application. One of the ways of modifying this type involves reinforcement with fillers or fibers, which were processed by combination agents that can enhance the bond between the fillers and the polymer molecules. A whole series of organic compounds of silicon-hydrogen have been found, particularly well performing the function of enhancing the bond between the polymer and the filler or fiber, such adhesion agents suitable for use in polymers include, for example, 3-aminopropyl-triethoxycarboxylic hydrogen, glycido-oxypropyl, trimethoxycarbonyl and N -trimethoxysilylpropyl-Na-amino-ztil-amine. Preferred fillers and fibers include quartz, wollastonite, feldspar, calcined kaolin clay, fiberglass and other good performance fibers, such as graphite, boron, steel, etc. The concentration of filler and fiber can vary in a wide range; from small amounts as 1 or 2% by volume, up to 70 or 80% by volume or higher. Catalyzed amide condensation with alcohol is carried out at temperatures from about -20 ° C to or higher, depending on the components used. Preferred polymerization temperatures range from about 20 to about, and the duration of condensation varies depending on the reaction temperatures and the reagents used. The total duration of polymerization can be as low as 0.5 seconds and fluctuate within a range from a few seconds to about 1 hour. This duration can be extended to any length, for example, several hours or longer, however, in total, catalyzed amide condensation. with alcohol can be completed in a few minutes. In the method of catalyzed condensation of an amide with an alcohol, it is advisable to use mainly anhydrous reagents and solvents. It is also recommended to operate an inert gas atmosphere, such as nitrogen, to achieve an anhydrous atmosphere. The reaction of catalyzed condensation of amcd with alcohol is carried out; at atmospheric pressure, however, if the application of high temperatures requires pressure to liquefy the reagents, pressures of various sizes can be used. Example. In a 1 L flask equipped with a stirrer, an inlet for nitrogen and a reflux condenser, installed together with a q drip catcher, 35.6 g of isophthaloyl bis-caprolactam and 400 ml of toluene are charged. The mixture is dried by heating toluene under reflux until the trapping of water into the trap is stopped. The resulting solution is cooled under nitrogen until 14.1 g of ethanol is added, heating the mixture gently under reflux. Then 1.5 ml of ethyl magnesium bromide (3 molar solution in diethyl ether) is added to this solution, and the mixture is then heated under reflux for another 15 minutes. The solution is cooled and mixed with 400 ml of a 10% hydrochloric acid solution. The toluene solution is separated from the aqueous solution and dried by heating under reflux to catch azeotropic water. Toluene is removed by distillation, the residual liquid is distilled under vacuum at OD mm Hg. Three products are obtained: Fractions Point Weight in boiling grams 1 85-120 ° C 6.60 2. 162-2050С 10.55 3 residue 11.70 Product identifications Fraction 1 - diethylisophthalate%%% Wetane sample Carbon Hydrogen Nitrogen Calculated: 64, 85 6.35 O Found: 64.67 6.41 0.39 fraction 2 - meta-carbethoxy (N- (5-carbethoxy-p-amyl) benzamide%%% Sokra sample Carbon Hydrogen Nitrogen Calculated: 64.46 7, 51 4.18 Found: 64.62 7.69 4.21 64.75 7.62 4.16 Fraction 3 - residue; N, N-bis- (5-carbethoxy-p-amyl) and phthalamide,%% Mokra sample Carbon Hydrogen Nitrogen Calculated: 64.26 8.09 .6.24 Found: 64.43 8.17 5.92 64.26 8.24 6.01 The product of fraction 1 is the result ata obtained by reacting an alcohol with both phthalic carbonyl groups by caprolactam cleavage The product of fraction 2 is the product obtained by reacting one part of the alcohol in the lactam carbonyl group with ring opening, and the second part of the alcohol reacts with the left carbonyl group of the remaining imidnry group , chipped off caprolactam. Fraction 3 is formed by the interaction of the alcohol in both lactam carbonyl groups with ring opening. Example 2. A mixture of 3.1 g (0.05 mol) of ethylene glycol and 8.9 g (0.025 mol) of isophthaloyl bis-caprolactam is heated under nitrogen to 120 ° C. 1.5 ml of ethylmagnesium bromide (3 molar solution in diethyl ether) is added to the resulting solution with vigorous stirring. The reaction temperature rapidly rises to 180 ° C due to the heat of reaction, after which the mixture is cooled 1 minute to. After additional cooling to room temperature, the mixture is evacuated in order to remove the esters and the liberated ethane from the catalyst. In order to control the outgassing, the mixture is heated under vacuum to. The resulting product is a viscous oil. Analysis - found: 5.65% nitrogen, calculated: 5.83%. According to chromatographic analysis, 33.6% of free caprolactam was found in the mixture. The excreted caprolactam shows that the interaction of the alcohol occurs with a phthalic carbonyl group in a volume of 75%, and with a lactam carbonyl group. In a volume of 25%. Example 3. A mixture of 150 rVoranol. P-2000 (polyoxypropylene glycol), 29.4 g of isophthaloyl bis-caprolactam, 146 g of caprolactam and 1.5 g of Santowhite powder are heated in vacuo to distill 25 ml of caprolactam. The temperature of the solution is adjusted to, then stirred under a nitrogen atmosphere / by adding 0.37 ml of magnesium di-caprolactam (2 molar solution in 1-methyl-2-pyrrolidone). The catalyzed mixture is diluted at 45 minutes by adding 0.3 g of lauric acid to deactivate the catalyst. The solution thus obtained in caprolactam can be catalyzed additionally by using Grignard compound or an alkali metal lactam, to obtain a 50% polypropylene glycol / nylon-6 three-unit polymer. EXAMPLE 4 A mixture of 195 g of Vorano I P-2000 (polyoxypropylene glycol), 93 g of caprolactam, 37.1 g of isophthaloyl bis-caprolactam and 0.6 g of Fleetot H are heated under vacuum to distill off 25 ml of caprolactam. The mixture is cooled to 65 ° C. under a nitrogen atmosphere, then adding 2.4 g of magnesium di-caprolactam (2 MOLAR1 solution in 1-methyl-2-pyrrolidone). Within 10 seconds, the viscosity increases with a simultaneous increase in temperature to 77 ° C due to the exothermicity of the reaction. The polymer solution is stirred at 700 s for 1 h in a vacuum, then ice glacial acetic acid is added in order to deactivate the catalyst. The polymer solution has a viscosity of 31.4 SO cP (according to Brookfield RVF) at and 7.300 cP at. The solution thus obtained in caprolactam can be further catalyzed by means of a catalyst based on a Grignard compound or an alkali metal, to obtain a 65% polypropylene glycol / nylon-6 3-unit: polymer. EXAMPLE 5 A mixture of 90 g of Carbwax 4000 (polyoxyethylene glycol), 216 g of caprolactam, 18.7 g of terephthaloyl bis-caprolactam and 0.6 g of Electol H is heated under vacuum to distill 25 ml of caprolactam. The mixture is cooled to 75 seconds under a nitrogen atmosphere, then adding 1.3 ml of magnesium di-caprolactam (2 molar solution in 1-methyl-2-pyrrolidone). Within 1 minute, the viscosity increases due to polymer formation. The solution is stirred for another 1 h under vacuum to ensure completion of the reaction, then 0.17 ml of glacial acetic acid is added to deactivate the catalyst. The polymer solution thus obtained in caprolactam can be catalyzed further, obtaining a 30% polyethylene glycol / milonic three-part polymer. Example 6, a solution of 227.5 g of Voranol P-4000 (polyoxypropylene glycol), 23.1 g of terephthaloyl bis-caprolactam and 1 g of Electol H in 300 ml of toluene are dried by heating with a reverse HbnvT cooler to form azeotropic water. The solution is catalyzed by the addition of O, 2 molar. ethyl magnesium bromide in toluene / diethyl ether, a noticeable viscosity increase occurs over 15 minutes. After further heating under reflux, 0.4 g of lauric acid is added over 15 minutes to deactivate the catalyst. The resulting polymer can be isolated by removal of the solvent by distillation, as well as
    sixteen
    Cast sheet 97
    Pressed film 95 10
    Example 8 A mixture of 36.72 g of isophthaloyl bis-caprolactam and 50.0 g of Polymeg 1000 (polytetramethylene glycol with a hydroxyl number of 113.5) was stirred for 30 minutes under vacuum at 1500 ° C, then cooled to room temperature. To this mixture was added 39, 4 g of Polymeg 2000 with a hydroxyl number of 57.6 and 61.15 g of Niah 61-58 (a multifunctional polyoxypropylene polyhydric alcohol with a hydroxyl number of 55.7), thoroughly mixing the ingredients. Into the resulting plant, 5 ml of bromag122 is added.
    600 2896
    1115
    313
    niypyrrolidone (2-molar solution in 1-methyl-2-pyrrolidone), stirring the catalyzed mixture for 1 min in vacuum. The solution is poured into the bottle, where it is gelatinized for 30 minutes. After curing overnight at room temperature, an elastomeric crosslinked polymer having a Shore A 43 hardness is obtained,
    权利要求:
    Claims (10)
    [1]
    Example 9, A mixture of 36.72 g of isophthaloyl bis-caprolactam and 50.0 g of Polymeg 1000 (polytetramethylene glycol with a hydroxyl number of 113.5) is used for subsequent polymerization with caprolactam using alkali metal lactams or a Grignard compound, Example 7, Mixture 33.6 g of terephthaloyl bis-caprolactam, 141.6 g of Carbowax 4000 (polyoxyethylene glycol) and 0.6 g of Zgdapoh 1010 are heated for 45 minutes under vacuum at 170 ° C. Then the mixture is cooled to 100 ° C, by adding another 141.5 g of Carbowax, The mixture is evacuated and heated for another 15 minutes at 120-s. After that, the mixture is poured into a vertical form of 0.32x25.4x25.4 cm, heated to 120 ° C. Casting is carried out using a metering pump. The mixture is catalyzed by injecting bromomagnesium pyrrolidone (2 molar solution in 1-methyl-2-pyrrolidone) into the stream using a second metering pump. The catalyst concentration is 7.8 mol% based on terephthaloyl bis caprolactam. After pouring, the mold is heated to 15 minutes, holding at this temperature for 75 minutes, after which the mold is cooled, removing the polymer sample. Samples for tensile testing are cut from a cast sheet, and a part of the remaining polymer is made by compressing the film into molds. Subminiature specimens are cut from the film for stretching testing. Both forms of copolymer are water soluble. The mechanical properties of the copolymer are presented in the table. They are heated under vacuum for 60 minutes and cooled to room temperature. To this mixture is added .41.83 g of P1 of cola P-2010 (polyoxypropylene glycol with a hydroxyl number of 54.3). and 60.14 g of Pluracol GP-3030 (polyoxypropylene triol with a hydroxyl number of 56.6). To the resulting solution was added 2.5 ml of bromo-magnesium pyrrolidone {2-molar solution in 1-methyl-2-pyrrolidone), stirring in vacuo. The catalyzed mixture is poured into the bottle and cured by heating in a furnace for 1 hour. The resulting elastomer has a Shore hardness. The above techniques are repeated, except for curing the mixture, not in a furnace, but at room temperature for. 18 h, obtaining an elastomer with Shore hardness. Example 10. A mixture of 71 g of capro. Lactam, 14.0 g of isophtapoyl bis bis-capro lactam and 75 g of Voranol P-2000 (polyoxypropylene glycol) is heated in vacuum to distill 10 ml of caprolactam. The resulting solution was cooled to nitrogen and catalyzed by the addition of 0.5 ml of diisobutyl aluminum chloride. After the completion of this interaction with the imide with glycol, the viscosity is measured using a Vrukfil-RVF viscometer. In 30 minutes, the viscosity rises to 54,000 cP, after 1 hour to 450,000 SP after 2 hours to 1,100,100 cP After 2 hours, the viscosity no longer changes from. The resulting polymer solution can be used to obtain 50% polypropylene-glycol / nylon-6 three-unit polymer by means of additional catalysis using Grignard compound or alkaline metal based catalysts. Example 11. A sodium glycollate catalyst solution is prepared by mixing 5 g of Pluracol GP-3030 (polyoxypropylene triol) with 0.06 g of sodium hydrate (60% solution in mineral oil), followed by heating in vacuo to remove hydrogen. A second solution of 2.7 g of terephthaloyl bis-caprolactam in 10 g of Pluracol P-2010 (polyoxypropylene glycol) is obtained by heating to 190 ° C. Both solutions are mixed with an unmixed rubbery rubber for 5 seconds. The resulting resin is soft and sticky due to an incomplete degree of mixing, due to the high reactivity of the system. The proposed method allows polyamidoesters to be poured at a faster rate, as well as to reduce the temperature of the process. Claim 1. Method for producing polyamido esters by condensation of acyl lactams with alcohols in a reaction medium, characterized in that, in order to accelerate the reaction, a. also carried out at lower temperatures, at least one metal or compounds of a metal of groups IA, NA, 1ГВ, and П1А are additionally introduced into the reaction as a catalyst.
    [2]
    2. A method according to claim 1, characterized in that a metal compound is used consisting of at least a lactam salt, a halo-lactam salt and an alkoxide.
    [3]
    3. Method according to pl, I differ. u and with the use of a metal selected from the group consisting of sodium, potassium, lithium, magnesium, calcium, -strontium, barium, zinc, cadmium and aluminum.
    [4]
    4. The method according to claim 1, wherein the catalyzed condensation of acyl lactams with alcohol is carried out at a temperature of from 230 ° C,
    [5]
    5. Method POP1, characterized in that acyl lactam is used in an amount of from 10 to 200 mol. in terms of alcohol.
    [6]
    6. Method POP.1, distinguished in that the catalyzed condensation of acyl lactam with alcohol is carried out in a lactam reaction medium, and the catalysts are selected from the group including zinc caprolactam, magnesium caprolactam, calcium caprolactam, aluminum bis (bromomethyl) , caprolactam-aluminum chloride, dicaprolactam-aluminum chloride, aluminum-trick to aprolactam and bromomagnesium caprolactam.
    [7]
    7. Method POP.1, differing from the fact that isophthaloyl bis-caprolactus is used as acyllactam, and polymeric polyhydric alcohol is used as alcohol.
    [8]
    8. Method POP.1, which is also distinguished by the fact that terephthaloyl bis bis-caprolactam is used as an acyl lactam, and a polymeric polyhydric alcohol as alcohol.
    [9]
    9. The method according to claim 7, differing in 10ad and in that a cataty is used. Selected from the group including magnesium bromide caprolactam and magnesium aprolactam.
    1584376016
    10. The method according to claim 8, distinguish-sources of information,
    [10]
    yi and with the fact that they use catalysts taken into account in the examination of a licenser selected from the group including magnesium bromide caprolactam and magnesium- 1. US Patent 2682526,
    Dicaprolactam. 260 - 75, 1952 (prototype).
    类似技术:
    公开号 | 公开日 | 专利标题
    KR100877087B1|2009-01-07|Polymer material containing chains bearing imidazolidone functions
    KR100266501B1|2000-09-15|Process for preparing alkoxy-terminated organosiloxane fluid
    US6344538B1|2002-02-05|Functionalized diene monomers and polymers containing functionalized dienes and methods for their preparation
    SE429134B|1983-08-15|PROCEDURE FOR THE PREPARATION OF POLYETER ESTERAMIDS
    CN104011081B|2016-01-20|The preparation method of modified conjugated diene class rubber
    JP2004131620A|2004-04-30|Branch-type polar group-containing olefin copolymer, and method for producing the same
    USRE30371E|1980-08-12|Catalytic process for imide-alcohol condensation
    SU843760A3|1981-06-30|Method of preparing polyesteramides
    EP0067693A1|1982-12-22|Acid halide and acyllactam functional materials
    US4587305A|1986-05-06|Composition for use in preparing nylon block copolymer
    KR900004792B1|1990-07-05|Process for the preparation of nylon block copolymer
    EP0067694A1|1982-12-22|Acid halide and acyllactam functional materials and process for the preparation of nylon block polymers therewith
    US3567696A|1971-03-02|Storable polyamide-forming compositions and process for the production of polyamides
    US4431795A|1984-02-14|Copolymers of cyclic carbonic acid esters and lactams and their production
    US5399662A|1995-03-21|Strong non-ionic base catalyzed ring opening polymerization of lactams
    RU2041889C1|1995-08-20|Polyhydroxyalkylenephthalyllactam alkylphthalates and a method of their synthesis
    US4596865A|1986-06-24|Promotion of ε-caprolactam block copolymerization
    US4214065A|1980-07-22|Reinforced polylactams
    JP2874738B2|1999-03-24|Method for producing 2-pyrrolidone polymer
    US4171426A|1979-10-16|Triarylmethylhalide-accelerated lactam polymerization
    US3647764A|1972-03-07|Polymerization of 2-pyrrolidone in the presence of carbonyl sulfide
    CH679046A5|1991-12-13|
    JP2914537B2|1999-07-05|Method for producing 2-pyrrolidone polymer
    KR900004796B1|1990-07-05|Composition of co-polymerizable caprolactam
    US3631223A|1971-12-28|Lactam polymerization with polythiolactone initiators
    同族专利:
    公开号 | 公开日
    NL7508552A|1976-01-26|
    IL47746D0|1975-10-15|
    LU73026A1|1976-07-01|
    JPS5148628A|1976-04-26|
    ATA562075A|1977-10-15|
    JPS6132334B2|1986-07-26|
    US3922254A|1975-11-25|
    BR7504642A|1976-07-06|
    NL181023B|1987-01-02|
    CA1042431A|1978-11-14|
    ES439517A1|1977-02-01|
    DE2532596C2|1988-11-17|
    SE427754B|1983-05-02|
    CH621137A5|1981-01-15|
    IL47746A|1979-05-31|
    NL181023C|1987-06-01|
    GB1508164A|1978-04-19|
    FR2279791B1|1980-11-07|
    AT343912B|1978-06-26|
    AU498734B2|1979-03-22|
    IT1040035B|1979-12-20|
    SE7508272L|1976-01-23|
    AU8320575A|1977-01-20|
    NL8601102A|1986-08-01|
    DE2532596A1|1976-02-05|
    BE831510A|1976-01-19|
    FR2279791A1|1976-02-20|
    AR217394A1|1980-03-31|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2682526A|1950-07-28|1954-06-29|Goodyear Tire & Rubber|Interlinking polymers with polylactams|
    US3018273A|1958-04-21|1962-01-23|Monsanto Chemicals|Process of polymerizing higher lactams|
    US3120503A|1959-12-03|1964-02-04|Monsanto Chemicals|Copolymers of caprolactam and aminocyclohexane carboxylic acid|
    FR1437020A|1964-06-05|1966-04-29|Hoechst Ag|Process for the preparation of polyester amides and polythio-ester amides|
    US3366608A|1965-04-15|1968-01-30|British Celanese|Anionic polymerization of caprolactam|
    US3631006A|1965-09-01|1971-12-28|Cities Service Co|Process for the anionic polymerization of unsaturated hydrocarbon monomers|
    US3526604A|1965-09-01|1970-09-01|Cities Service Co|Polymerization of unsaturated monomers with catalysts formed from the reaction of metals and derivatives of groups i-a and ii-a with compounds of group iii-a|
    NL6908380A|1969-06-03|1970-12-07|
    US3740379A|1971-01-08|1973-06-19|Polymer Corp|Method for introducing metal cations into lactam polymers|
    DE2124497A1|1971-05-18|1972-11-30|Bayer Ag|Process for improving the polymerizability of lactams|US4150674A|1977-12-27|1979-04-24|Monsanto Company|Three-component blends of a polyamide, and a polyester and a lactam terpolymer|
    US4148960A|1977-12-27|1979-04-10|Monsanto Company|Polyester having improved antistatic properties|
    US4625002A|1983-01-03|1986-11-25|The Standard Oil Company|Binuclear catalyst for the preparation of polyamide|
    NL8900937A|1989-04-14|1990-11-01|Stamicarbon|PROCESS FOR THE CONDENSATION OF IMIDES AND ALKOHOLS OR AMINES|
    US5223335A|1991-03-18|1993-06-29|Teijin Limited|Fiber-reinforced composite material and process for the production thereof|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US490439A|US3922254A|1974-07-22|1974-07-22|Catalytic process for imide-alcohol condensation|
    [返回顶部]