• 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:
    To prepare a terpolymer containing ester and amide bonds between the monomer units, the following procedure is followed: (a) a lactam monomer of the formula: <IMAGE> (b) a polyol and (c) a polyacyllactam or acylpolylactam of the formula: <IMAGE> are reacted in the presence of a basic lactam polymerisation catalyst. The amount of polyol is from 10 to 90% by weight of the polymerisable medium. In the formulae, A, A', R, Y, n and y are as defined in Claim 1. The terpolymers can be used, for example, for the production of fibres, moisture-absorbent nonwovens, foam products, casting resins, furniture parts and automobile parts.
    公开号:SU843759A3
    申请号:SU742012459
    申请日:1974-03-13
    公开日:1981-06-30
    发明作者:Мелвин Хедрик Росс；Дэлвин Гэбберт Джеймс
    申请人:Монсанто Компани (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD FOR OBTAINING POLYESTERIDOB
    This invention relates to a process for the preparation of polyetheramides which can be used, for example, in the textile industry. A method of producing polyether amides by reacting a lactam of a polyhydric alcohol and a dicarboxylic acid in the presence of a catalyst by heating 1 is known. The purpose of the invention is to expand: an assortment of polyetheramides having a number of valuable properties, such as high heat resistance, increased strength. The goal is achieved by reacting from 10 to 90% by weight,% of lactam, from 10 to 90% by weight,% of polyhydric alcohol, from 1 to 50% by weight,% of polyacyllactam or acylpolylactam. An optional process reagent is a monofunctional alcohol, which can be added at any time before or simultaneously with the lactam polymerization catalyst. The lactam polymerization catalyst used in the inventive process is a class of compounds known as the main catalysts suitable for the anhydrous polymerization of lactogads. In general, all alkali or alkaline earth metals are effective catalysts, either in metallic form or in the form of hydrides, halides, alkyl halides, carbonates, and the like. A number of organometallic metal compounds such as metal alkyls, metal phenyls, metal amides, and the like are also suitable. These compounds include sodium hydride, potassium hydroxide, lithium oxide, ethyl magnesium bromide, calcium fluoride, strontium carbonate, barium hydroxide, methyl sodium sulphate, potassium phenyl, diphenyl barium, sodium amide, and magnesium diethyl. Catalyst concentrations can range from 1 to 15 or 20 mol.% Or more of the polymerized lactam monomer. The polyhydric alcohol, alcohol and polyacyl lactam or acyl polylactam can be reacted before the above lactam is added to the polymerized mixture. Another variant of the method is that the polyhydric alcohol, alcohol and polyacyl lactam or acyl polylactam is reacted before
    by adding a catalyst to the polymerized mixture.
    The polymerization temperature may vary depending on the melting point of the lactam or lower down to the melting point of the final polymer and higher. Depending on the specific ingredients, this ranges from 70 to and more. The preferred polymerization temperatures are from 90 to 19 ° C, most preferably from 120 to for caprolactam three-link polymers, and Ec is more preferable to polymerization, at which TeMnepaTvpa increases during the polymerization from the initial temperature, about 70100 ° C at the beginning of the polymerization to the final Temperature v ISO-ISO C.
    As lactam monomer, compounds of the general formula are used.

    where Y is an alkylene group having at least three carbon atoms, preferably from 3 to 12 or 14, and most preferably from 5 to 11 carbon atoms.
    The preferred monomer is -caprrolactam. In addition to c-caprolactam, lactam monomers include x-pyrr6 lidinone, piperidone, alerolactam, caprolactam, lauryl lactam, and the like. Also included in the scope of the invention are lactams having substitutes that do not interfere with the polymerization of the lactam.
    A large number of compounds from simple dihydric alcohols, such as ethylene glycol to such complex polymeric polyhydric alcohols, such as poly (-caprolactam) diol, are used as polyhydric alcohols. Other polyhydric alcohols are alkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, tetramethylene glycol, dipropylene glycol, hexylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-hexanediol, 1,5-pentendiol, butylene glycol, 1, 4-butanediol, dicyclopentadiene glycol, heptaethylene glycol and isopropylene bis- (p-phenyleneoxypropanol-2), such a dihydric alcohol other than alkylene glycols, such as hydroxyethyl acrylate and hydroxypropyl methacrylate; polyhydric alcohols having more than two hydroxy functions, such as glycerol, pentaerythitol, 1,2,6-hexanetriol, and 1-trimethyl propane; polymeric polyhydric alcohols such as polyethylene glycols, polypropylene glycols, polyoxypropylene diols and triols, polytetramethylene glycols, castor oils, polybutadiene glycols and polyether glycols, as well as a large number of compounds containing
    other than hydroxy groups, substituents such as 2,4-dichlorobutylene glycol. In addition to all of the aforementioned hydroxyl compounds, the scope of the invention also includes analogous for these thio compounds with sulfur atoms instead of oxygen. Some examples are hydroxyethyl thioglycolate, ethylene glycol bis- (thio-glycolate), pentaerythritol tetra-bis- (thioglycollate) and thiodiglycol.
    as polyacyl lactam or acyl polylactam, compounds of the general formula are used.

    (5; KAA- - “))„
    where A is an acyl group, preferably selected from
    Oh oh
     B
    o s o
    1de y is an alkylene group having at least about three carbon atoms; R is a hydrocarbon group; Y is an integer; n is an integer equal to O or 1.
    An optional process reagent is monofunctional alcohol. Typical alcohols useful in the proposed process for preparing at least partially terpolymer terpolymer are aliphatic alcohols, for example methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-ethyl-hexanol, 1-dodecanol, 1-octadecanol, 2-octanol, 1-decanol, etc., as well as mixtures of their isomers. Unsaturated alcohols, for example, allyl alcohol, methyl alcohol, nitro alcohols, amino spirits, for example dimethylaminoethanol, etc., are also considered to be used. Other suitable monofunctional alcohols can be selected from a polymer with one hydroxyl group, such as tridanolethylene oxide (polyoxyethylene) condensates. In addition to the alcohols listed above, alcohols with a hydroxyl group that are desirable are desirable. Aromatic alcohols such as phenol and / or cresol are unsuitable for the proposed method, however, if OH groups are indirectly attached to the aromatic group, such alcohols can be used.
    The alcohol content can vary from 0.1 to 150 mol%, eq. imide from an excess acylpolylactam or polyacyl lactam based on molar equivalents of hydroxyl of a polyhydric alcohol present in the reaction mixture.
    A polymerized product that includes the aforementioned Ko.vmoneHTbi can have a number of different structures depending on the process conditions and relative proportions of the ingredients used in the reaction system. The molecular weights of three-stranded polymers can vary widely from an average molecular weight of several thousand to one million or more. The preferred average molecular weight range for thermoplastic cross-linked polymers is from 10-20,000 to 100; 000 or 200,000. EXAMPLE 1: 2,100 g-capro lactam is heated under vacuum to remove water. Heating is continued until 100 g of caprolactum is removed from the reaction vessel. Then caprolactam is cooled, then 725 ml of pyridine is added and the mixture is cooled until sufficiently, after which 609 g of terephthalol chloride is added with a sufficient temperature to maintain the temperature from 80 to 90 ° C. The mixture is then heated at 135-140 ° C for 2 hours. The resulting solution is poured into 14 liters of ice water to precipitate the product of terephthalol bis-caprolol. The precipitate is filtered off and washed three times with cold water and once with methanol. After washing, the powder is dried at. In tab. 1 shows the number of substances, expressed in parts by weight, used to prepare a mixture of various caprolactam-polypropylene glycol terephthalol bis-caprolactams of three-stage polymers. In each of the experiments, polypropylene glycol, caprolactam, santovitov powder to terephthalol bis-caprolactam is mixed at. Bromomagnesium pyrrolidinone is added to the resulting solution to the mole of caprolactam. The reaction mixture is poured into sheet form, heated to 100 seconds, with a thickness varying between 3 and 13 mm. The form is heated to 160 ° C for 12-min. After 30 minutes, the mold is opened and the resulting polymerized composition is extracted. Samples of each composition are tested to determine their mechanical properties. The mechanical properties of the samples are presented in table. 2. Example 2. Using the amounts listed in Table. 3, a mixture of various caprolactus 1polytetramethylene glycol-terephthalol bis-caprolactam three-link polymers is obtained. In each experiment, polytetramethylene glycol, capro lactam, santobit powder, and terephthalol bis-caprolactam are mixed at 100 ° C. As in Example 1, bromomagnesium pyrrolium) 5inone is added, the mixture is heated before and cast into a preheated before mold. Then the mold is heated to and kept at this temperature for 30 minutes, after which it is opened and the samples are removed. In tab. 4 shows the mechanical properties of the compositions obtained. Note p W.- Using the amount of substances listed in table. 5. Preparing mixtures of various caprolactam cross-linked polypropylene glycol terephthalol bis-caprolactam three-link polymers according to the procedure adopted in examples 1 and 2, except that the temperature and concentration of the catalyst are changed as shown in Table. 5. The properties of the compositions obtained are given in table. 6. Example4. With 1 (1 using the substances listed in Table 7, two caprolactam polybutadiene diol-isophthalol bis-caprolactam terpolymers are prepared. At solution temperatures and form temperatures listed in Table 7, according to the procedure adopted in Examples 1 and 2, t two three-link polymers. The catalyst (magnesium magnesium pyrrolidinone) uses a concentration of 5 mol / 1 mol of caprolactam. The properties of the obtained polymers are given in Table 8. Example 5. Using the quantities of substances, the temperatures of the solutions and the forms listed in the table below, they are prepared in Om caprolactam-polyethylene glycol-terephthalol bis-caprolactam three-link polymers. The properties of the compositions are given in Table 10. The polymers obtained by the proposed method can be used as the only component of textile fiber, as three components as one of the components of the composite fiber, which ensures their use. in the production of non-wool and well-wetted products. Three-part polymers can be processed into foamed products either during or after their polymerization to obtain Rigid and ductile foams. By obtaining directly from monomer components, polymers can be used in the manufacture of furniture, its components and automobile parts. Three-part polymers can be produced in the form of suitable resins, which can be sequentially injection-molded, extruded, stamped, etc. with getting products of almost any form. Higher elastomer formulations can be used in the manufacture of car tires and tire components. In addition, polymers can be modified with fillers, fibers, pigments, paints, stabilizers, plasticizers, e-dimel ± 1 g. Material Plural as al aOlCi Caprolactam Terephthalol bis-Caprolactam Santovitovy powder
    Glycol in so68
    5647 Polymer Polyprop glycol, mol, weight. Antioxidant, 4,4-utilidene
    CT - room temperature
    ignition to change the properties, extending the scope of their application.
    28
    18
    37
    Table 2 Content, weight. % in polymer i: i:: iiL: i: i: i :: irz:; 328,4281Л163,6186,597,364,231,1 104,0169,0157,0279,0234,0273, Ь312,0 51,549,729,334,018,312,87,3 1,01,0 0,71,00,70,70,7 Table 1 2000 bis- {6 tert-butyl m-cresol).
    SantoBITA
    0.7 0.7 powder
    The content of glycol in the copolymer, wt.% 65,0
    Polytetramethylene glycol, mol, weight, l, 2000;
    xk ъ tetraphthalol bis-caprolactam.
    HP - the sample was not broken into two parts. 229.5 196.4 163.3 130.3 Niax 61-58 79.0 118.0 157.0 195.0 Caprolactam 41.2 35.6 .30.0 24.3 Tbc
    Table 3
    0.7
    0.7 OL
    0.7
    0.7
    47
    18
    37
    28
    Table 4
    Table 5 98.164.1 31.0 233.0 273.0 112.0 18.7 13.1 7.5
    Glycol copolymer
    Condition of polymerization: Dissolution temperature, with initial pouring temperature,
    - with
    Multifunctional propylene glycol, mol. Weight. 2000

    , Magnesium pyrrolidinone.
    Continued table. five
    18 9
    28
    37
    120 120
    120 120 120 120
    110 110
    Table 6
    Material
    glycol copolymer
    weight.%
    Polymerization conditions:
    Solution temperature, with
    Initially form temperature
    Final form temperature-, 00
    Polybutad1 (eidiol, mol. Weight, 2000 / Isophthalol bis-caprolactam.
    Santovitovy
     Polyethylene glycol, mog.ves. 4000;
    about vtГ T
    Tetrakis (Methyl-5-di-Tert-butyl-4-hydroxyphenyl propionate methane), an antioxidant cBMP-bromomagnesium pyrrolidinone.
    Continued table. 7
    Content, g, in polymer
    Spreadsheets
    Table 9
    ten
    T a
    faces
    权利要求:
    Claims (7)
    [1]
    The formula of the invention by heating, characterized in that, for the purpose, the assortment of poly. subject to interaction
    5, Method popp. 1 and 2, characterized in that
    1. The method of producing polyetheramides atomic alcohol, monohydroxy alcohol by the interaction of lactam and polyhydroxy-30 and polyacillactam or acylpolylactate alcohol in the presence of a catalyst with ester expansion, from 10 to 90 wt.% Lactam, 10 to 90 wt.% polyhydric alcohol, from 1 to 50 wt.% polyacillactam or acylpolylactam.
    [2]
    2. The method according to claim 1, characterized in that. monohydric alcohol is further added to the mixture.
    [3]
    3. The method according to claim 1, characterized in that an alkali metal is used as a polymerization catalyst. or alkaline earth metal lactam or halogenated alkaline earth metal lactam.
    [4]
    4. The way popp. 1 and 2, characterized in that the polyhydric alcohol, monohydroxy alcohol and polyacylpolylactam or acylpolylactam 'are subjected to interaction before adding to the polymerized mixture of lactam.
    there they are reacted before adding θ, a catalyst, to the polymerizable mixture.
    [5]
    6. The method of pop. 1, characterized in that the polymerization reaction is carried out at a temperature of 90 180 ΰ ΰ.
    [6]
    7. The method according to PP. 1 and 6, characterized in that the polymerization is carried out at an initial temperature of 70-100 ° C, which during the polymerization reaction melt to i50-180 o C.
    enlarge45 featured
    7 - mutual atomic
    The priority in paragraphs and 03/14/73 in paragraphs 1, 3, 4 and the action of lactam, alcohol and polyacillactam.
    [7]
    12/10/73 according to claims 1, 3, 4 and 7 - the difference in structures.
    12/10/73 according to claims 2-5.
    类似技术:
    公开号 | 公开日 | 专利标题
    US4031164A|1977-06-21|Lactam-polyol-polyacyl lactam terpolymers
    Cerrai et al.1989|Polyether-polyester block copolymers by non-catalysed polymerization of ɛ-caprolactone with poly |
    US4034015A|1977-07-05|Ester terminated terpolymers
    US3944629A|1976-03-16|Polyester initiated anionic catalyzed polymerization of lactam
    SU843759A3|1981-06-30|Method of preparing polyesteramides
    Kricheldorf et al.1990|Anionic and pseudoanionic polymerization of lactones‐a comparison
    US4952644A|1990-08-28|Synthesis of ABA triblock polymers and An B star polymers from cyclic ethers
    EP0067695B1|1986-10-15|Process for the preparaton of nylon block polymers
    Kricheldorf et al.1999|Macrocycles, 8. Multiblock copoly | of poly | and ϵ‐caprolactone via macrocyclic polymerization
    Kricheldorf et al.1996|Polymers of carbonic acid. XVII. Polymerization of cyclobis | by means of BuSnCl3 and Sn | 2‐ethylhexanoate
    US4590243A|1986-05-20|Process for the preparation of nylon block polymers
    EP0067693B1|1986-09-10|Acid halide and acyllactam functional materials
    CA1255039A|1989-05-30|Promotion of epsilon-caprolactam polymerization
    EP0067694B1|1986-10-15|Acid halide and acyllactam functional materials and process for the preparation of nylon block polymers therewith
    CA1246765A|1988-12-13|Process for preparing nylon block copolymers andcomposition for use in the same
    Laurienzo et al.1989|Rubber modification of polybutyleneterephthalate by reactive blending concurrently with polymerization reaction
    Mougin et al.1993|Synthesis and characterization of polysiloxane–polyamide block and graft copolymers
    US4595747A|1986-06-17|Viscosified lactam polymerization initiator solutions
    US4649177A|1987-03-10|Process for the preparation of nylon block polymers
    US4581419A|1986-04-08|Acyllactam functional materials
    US4843127A|1989-06-27|Reactive elastomeric block co-oligomer and lactam-block copolymers derived therefrom
    KR20210154982A|2021-12-21|Use of the composition for the manufacture of foam articles
    CA1255038A|1989-05-30|Promotion of epsilon-caprolactam blockcopolymerization
    EP0164535B1|1988-11-17|Acid halide functional materials and process for their preparation
    US4590244A|1986-05-20|Acid halide functional materials
    同族专利:
    公开号 | 公开日
    DE2412106A1|1974-09-19|
    DE2412106C2|1988-12-01|
    NL180758C|1987-04-16|
    NL180758B|1986-11-17|
    SE422582B|1982-03-15|
    NL7403367A|1974-09-17|
    LU69633A1|1974-10-17|
    CA1050194A|1979-03-06|
    BR7401912D0|1974-12-03|
    ES424226A1|1977-01-01|
    JPS5440120B2|1979-12-01|
    AR199246A1|1974-08-14|
    GB1472463A|1977-05-04|
    FR2221478B1|1977-09-30|
    JPS5029553A|1975-03-25|
    IL44416D0|1974-06-30|
    AU6662074A|1975-09-18|
    IT1007674B|1976-10-30|
    CH628360A5|1982-02-26|
    FR2221478A1|1974-10-11|
    IL44416A|1976-12-31|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DD36943A|
    DE1495661A1|1961-12-23|1969-08-07|Bayer Ag|Process for the production of polyamides|
    GB1067153A|1963-05-17|1967-05-03|Ici Ltd|Grafted polyamides|
    US3366608A|1965-04-15|1968-01-30|British Celanese|Anionic polymerization of caprolactam|
    DE1745238A1|1967-03-25|1971-08-12|Plate Gmbh Chem Fab Dr|Polyamide-forming, storable mixtures of lactams and catalysts|
    NL6908380A|1969-06-03|1970-12-07|JPS521038B2|1974-04-11|1977-01-12|
    JPS53103080A|1977-02-17|1978-09-07|Sachiko Aono|Cloth coloring composition|
    JPH0116086Y2|1979-01-24|1989-05-12|
    JPS63291921A|1987-05-22|1988-11-29|Sumitomo Chem Co Ltd|Polyether polyamide copolymer having ethylenically unsaturated group|
    US5223335A|1991-03-18|1993-06-29|Teijin Limited|Fiber-reinforced composite material and process for the production thereof|
    WO2011162333A1|2010-06-23|2011-12-29|ナガセケムテックス株式会社|Impact-resistant polyamide composition and process for production of same|
    KR102275688B1|2017-11-28|2021-07-12|한화솔루션 주식회사|Process for producing end-capped polyamides via anionic ring-opening polymerization|
    KR102262504B1|2017-11-28|2021-06-08|한화솔루션 주식회사|Process for producing polyamides including double activated group via anionic ring-opening polymerization|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US34121573A| true| 1973-03-14|1973-03-14|
    US42363973A| true| 1973-12-10|1973-12-10|
    US423591A|US3862262A|1973-12-10|1973-12-10|Lactam-polyol-acyl polyactam terpolymers|
    [返回顶部]