• 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:
    Process for preparing diesterdiamides, consisting of reacting a diester with a diamine under wet conditions in the presence of suitable solvents and catalysts, to give the diester diamide, together with an ester salt derivative as impurity. The reaction product is then filtered to give a diesterdiamide cake and a mother solution of the reagents which also contains the solvent, the catalyst and the ester salt product. The cake is washed with a solvent of the ester salt, which also dissolves the reagents and catalysts. The mother solution and wash solution are then distilled, the two fractions obtained being recycled to the synthesis and to the wash.
    公开号:SU1389676A3
    申请号:SU802957756
    申请日:1980-08-06
    公开日:1988-04-15
    发明作者:Коньиньи Франко；Мариано Армандо
    申请人:Аник С.П.А., (Фирма)；
    IPC主号:
    专利说明:

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    The invention relates to organic chemistry, namely to a method for producing N, N-bis para-carbomethoxy-benzoylhexamethylenediamine, which is used in the preparation of polymers, in particular fibers, similar to silk.
    The aim of the invention is to simplify the process.
    Example 1. 779 kg of toluene (HjO 10 ppm), 79 kg of methanol (HjO 70 h, ppm), 230 kg of dimethyl terephthalate (DMT) (HjO 200 ppm) and 25 eq. LiOCHj is fed to a 2 m reactor equipped with a stirrer and nitrogen injected.
    The mixture is heated to 70 ° C and 42 kg of hexamethylenediamine (800 ppm) are fed to obtain 6 NT (N, N-bis-para-carbomethoxybenzoyl-hexamethylenediamine). Methanol, which is released in the reaction, is simultaneously distilled off as an azeotropic mixture with toluene.
    At the end of the reaction, the product has the following composition,%: toluene 70.3; methanol 7, 2; DMT 8.63; 6nt 13.9; LCOCH 19 eq., Lithium terephthalate (LiTe) 6 eq. Then, 6 NT is isolated by filtration under pressure and washed on the filter with 600 l of a mixture of methanol and toluene at a volume ratio of 75:25 (content of 40 ppm).
    The wet monomer is dried at 100 ° C under normal pressure in a stream of nitrogen. The monomer has the following characteristics: mp. 232 ° C; N 6.4%; From 65.4%; H 6.5%; lithium 3 mEq./kg (LiTe 0.005%).
    The mother liquor and the washing liquid are combined and the following composition is obtained,%: DMT 7.2; toluene 65.8; methanol 27; LiOS, LiTe. 8 equiv.
    The solvents used for rinsing (except for the amount left in the filter cake) are removed in an evaporator containing a ramming column until a residue of about 950 kg is obtained with the following composition,%: DMT 10; toluene 81.7; methanol 8.3.
    EXAMPLE 2 The remainder of Example 1 is completely recycled to the 6 NT synthesis reactor under the same conditions as in Example 1 after the addition of the constituents.
    At the end of the reaction, the mass has approximately the same composition as in Example 1 and contains 21 eq. LiOCHg and 12 eq. lithium terephthalate.
    When performing filtration and washing operations, similarly to the example
    1 get dry monomer with a lithium content of 25 mEq / kg (LiTe 0.45%),
    whereas the mixture of mother liquor and washes contains about 19 eq. LiOCHj and 11 eq. lithium terephthalate. After distilling off the washing solvent, the residue composition is approximately equivalent to the residue of Example 1.
    Example 3. The remainder of the example.
    2 following compositions,%: DMT 10.1; toluene ei, 5; methanol 8.4; LiOCH
    19 eq .; lithium terephthalate 11 eq., is purified from the solvent (methanol – toluene mixture 75:25) until a composition of the following composition is obtained,%: DMT 10.6; toluene
    84; methanol 5.4; LiOCHj 21 meq / kg, lithium terephthalate 12 meq / kg, and then passed at 60 ° C through a centrifugal decanter to obtain a mass of 900 kg with a composition equivalent to
    initial composition (LiOCH,
    21 mEq / kg, LiTe 3.4 mEqUcg). After adding 135 kg DMT, .23 kg methanol and 6 equivalents of LiOCH 3, 42 kg of hexamethylenediamine are added to this mass and the new synthesis 6 NT is carried out, as in the example 1, until a weight of the following composition is obtained,%: toluene 70.15; methanol 7.2; DMT 9.9; b NT 13.9; LiOCHj 21 eq .;
    LiTe 7.1 eq.
    Monomer 6 NT with a lithium content of less than 3 meq / kg after filtration, washing and drying were separated from this mass.,
    The reaction mixture in the synthesis of diester diamide at the end of the reaction has the following composition, kg: diester diamide 254 kg; DMT 127; toluene 1225; methanol 144; lithium methylate:
    29 eq; LiTe 18.5 eq.
    The diester diamide is collected on a filter press and the filter residue thus obtained is washed with a 1100 L azeotropic mixture of methanol and toluene (75:25 by volume). The wet residue is dried, resulting in a dry di-ether diamide, which contains 3.5 meq. LiTe per 1 kg of the product.
    The combined mother liquor and wash liquid have the following composition, kg dimethyl terephthalate 127; toluene 1420; methanol 676; lithium methylate, 29 eq .; LiTe 18 eq.
    This mixture was distilled in a column at a pressure of 1020 atm with a flame number of 2: 1, while collecting 1060 L of azeotrope (methanol-toluene ratio 75:25 by volume). The temperature of the head of the column is 65 ° C, the temperature of the boiler at the start of the distillation and 71 ° C at the end of the distillation. The aze-prope thus collected is used to flush the precipitate filter, which is a diester di-amide.
    At the end of the distillation, a residue of the following composition is contained in the boiler, kg: dimethyl terephthalate 127; to-: lul 1190; methanol 49; lithium methylate, 29 eq .; LiTe 18 eq. The composition of the solvent remaining in the boiler (a mixture of toluene and methanol 95: 5 by volume) corresponds to the solubility of LiTe (ester salt), equal to about 2 of the 18 equivalents that remained. Thus, about 16 eq. LiTe precipitates and can be removed by filtering the residue on a basket filter. As a result, a composition is obtained which has the following composition, kg: dimethyl terephthalate 127; toluene 1185; methanol 49; lithium methylate, 29 eq .; LiTe approximately 2 equiv.
    This mixture can be directly introduced into the synthesis reaction, replenishing it if necessary with appropriate amounts of solvents, reagents and catalyst.
    The concentration of the LiTe ester salt in the diester di-amide has a significant effect on the quality of the polymer (obtained as a result of its polycondensation), in particular on the quality of the fiber obtained from this polymer, as well as on the spinning process.
    If the concentration of LiTe in the diester di-amide used for this purpose exceeds a certain limit value, spinning of the polymer fibers may not be possible.
    The following is the spin data for polycondensation-derived polymers using
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    five
    the use of hexanediol and diester diamides at various LiTe contents,
    The viscosity in solution of various polymers obtained in this way is approximately the same and is 2.30-2.33 (1% solution in a mixture of phenol and tetrachloroethane at 25 ° C; the mixture of solvents consists of equal amounts by weight). The yarns produced in this way consist of 24 three-pistilled fibers, their characteristic corresponds to 50 denier after the stretching, with a stretching ratio of 2.8.
    As the LiTe content increases in a polymer intended for spinning, the number of burrs produced during drawing and in monofilaments increases, resulting in more frequent replacement of the spinning heads. This can be judged by the LR values given in the table.
    权利要求:
    Claims (1)
    [1]
    Thus, the proposed method provides the possibility of almost complete regeneration of unreacted compounds, catalyst and solvent and their reuse at the stage of synthesis. This prevents the accumulation of the by-product in the reaction mixture and its entry into the final product, which improves the quality of the polymers and fibers obtained from it. Invention Formula
    The method of obtaining H, s-bis-para-carbomethoxybenzoylhexamethylenediamine by reacting dimethyl terephthalate with hexamethylenediamine in a mixture of toluene and methanol by heating the reaction mixture in the presence of a catalyst - methylate lithium, followed by separating the reaction product by filtration and washing it with a solvent, in that in order to simplify the process, the latter is carried out at 70 ° C under the conditions of the presence of moisture, a mixture of toluene and methanol is used in a volume ratio of 98:10, and the resulting product is washed from The lice salt of the ester, the catalyst, and the unreacted starting materials are conducted with a mixture of methanol and toluene at a volume ratio of 75:25, followed by distilling off the solvent until precipitation of the ester salt, while leaving the mother liquor and the washing solution. B process.
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    同族专利:
    公开号 | 公开日
    BE884650A|1981-02-06|
    NO802196L|1981-03-11|
    DK313380A|1981-03-11|
    HU191172B|1987-01-28|
    DK158660B|1990-07-02|
    GB2058053B|1983-10-05|
    ZA804455B|1981-07-29|
    NO151197B|1984-11-19|
    YU192580A|1984-02-29|
    CA1172650A|1984-08-14|
    JPS5640649A|1981-04-16|
    DK158660C|1991-01-21|
    IT7925570D0|1979-09-10|
    NO151197C|1985-02-27|
    JPH021136B2|1990-01-10|
    NL8004512A|1981-03-12|
    DE3029970C2|1984-10-04|
    IT1123574B|1986-04-30|
    DE3029970A1|1981-03-12|
    SE8005346L|1981-03-11|
    SE439304B|1985-06-10|
    LU82686A1|1981-03-24|
    YU41446B|1987-06-30|
    US4614815A|1986-09-30|
    CH650769A5|1985-08-15|
    FR2468583A1|1981-05-08|
    CS221975B2|1983-04-29|
    AU6068680A|1981-03-19|
    DD152336A5|1981-11-25|
    FR2468583B1|1984-02-17|
    AU536158B2|1984-04-19|
    GB2058053A|1981-04-08|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2861055A|1955-04-26|1958-11-18|Eastman Kodak Co|Copolyesters of a glycol and an alkylene diamine dicarboxylate containing isophthalate modifier and their preparation|
    US2925405A|1955-04-26|1960-02-16|Eastman Kodak Co|Linear polyesters containing an alkylene diamine group and manufacture thereof|
    US2839508A|1955-04-26|1958-06-17|Eastman Kodak Co|Copolyesters of a glycol, an alkylene diamine dicarboxylate and a sulfone ester|
    US2848439A|1955-04-26|1958-08-19|Eastman Kodak Co|Linear polyesters of bis alkylene diamides and manufacture thereof|
    US2851443A|1955-04-26|1958-09-09|Eastman Kodak Co|Quenchable copolyesters of a glycol, terephthalic acid and an alkylene diamine dicarboxylate and their preparation|
    US2856385A|1956-05-10|1958-10-14|Eastman Kodak Co|Polyester-amides of n,n'-bis- alkylenediamines, glycols and diamines|
    SU1069623A3|1970-10-13|1984-01-23|Снам Прогетти С.П.А. |Process for preparing diamidodiesters|US4767839A|1987-07-06|1988-08-30|Allied-Signal Inc.|Alternating aliphatic-aromatic poly|
    US5608108A|1988-11-14|1997-03-04|Sloan-Kettering Institute For Cancer Research|Potent inducers of terminal differentiation and method of use thereof|
    CA2002853A1|1988-11-14|1990-05-14|Ronald Breslow|Potent inducers of terminal differentiation and method of use thereof|
    DE4024466C2|1990-07-30|1995-04-20|Dainippon Ink & Chemicals|Thermally curable mixtures of polyfunctional formamides and aromatic mono-, di- or polyglycidyl ethers and their use|
    USRE38506E1|1991-10-04|2004-04-20|Sloan-Kettering Institute For Cancer Research|Potent inducers of terminal differentiation and methods of use thereof|
    US5369108A|1991-10-04|1994-11-29|Sloan-Kettering Institute For Cancer Research|Potent inducers of terminal differentiation and methods of use thereof|
    US5700811A|1991-10-04|1997-12-23|Sloan-Kettering Institute For Cancer Research|Potent inducers of terminal differentiation and method of use thereof|
    CA2189072A1|1994-06-17|1995-12-28|Exxon Chemical Patents Inc.|Amidation of ester functionalized hydrocarbon polymers|
    US5852155A|1995-03-01|1998-12-22|General Electric Company|Compositions of polyesteramides|
    US5744068A|1996-01-24|1998-04-28|General Electric Company|Blends of polyphenylene ethers and polyesteramides|
    US5731389A|1996-04-24|1998-03-24|General Electric Company|Blends of polyesters and polyesteramides, optionally with polycarbonates|
    EP0835896A4|1996-04-30|2004-12-08|Toray Industries|Polyester amide copolymer and process for the production thereof, polyester amide monomer and process for the production thereof, and polyester amide resin composition|
    IL148497D0|1999-09-08|2002-09-12|Sloan Kettering Inst Cancer|Novel class of cytodifferentiating agents and histone deacetylase inhibitors, and methods of use thereof|
    US7199134B2|2003-04-01|2007-04-03|Sloan-Kettering Institute For Cancer Research|Hydroxamic acid compounds and methods of use thereof|
    JPWO2013153754A1|2012-04-11|2015-12-17|出光興産株式会社|Process for producing β-alkoxypropionamides|
    US10040904B2|2013-08-16|2018-08-07|Dsm Ip Assets B.V.|Process for producing a thermoplastic polymer containing segments of a diamide|
    KR101568357B1|2013-11-25|2015-11-12|롯데케미칼 주식회사|Novel compound and method for preparing the same|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    IT25570/79A|IT1123574B|1979-09-10|1979-09-10|PROCESS FOR THE PRODUCTION OF DIESTEREDIAMIDES|
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