• 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 of producing an amideimide polymer without using an acid having an acyl halide group which comprises reacting a composition comprising an aromatic diprimary amine and a tricarboxylic acid compound in an alcoholic solvent comprising an alkanol containing from 4 to 10 carbon atoms. In those cases where only diprimary aromatic amine is reacted, a tertiary amine is required. If desired, a glycol can be present.
    公开号:SU973028A3
    申请号:SU772455514
    申请日:1977-02-23
    公开日:1982-11-07
    发明作者:Густав Кески Роберт；Реджис Стефенс Джеймс
    申请人:Стандарт Ойл Компани (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD FOR OBTAINING POLYAMIDOIMIDES
    The invention relates to the production of heat-resistant polymers, in particular polyamidoimides.
    A method of producing polyamidoimides is known, which consists in the reaction of an aromatic diamine and hemillic acid or its dianhydride in the presence of a tertiary amine and / or an aliphatic diamine. The reaction is carried out by heating to 65 s, as a result of which a solid polymer is formed, which can precipitate from the water-tertiary amine system on the substrate as a coating.
    However, all attempts to isolate the reaction product from the reaction solution by distilling off water and a tertiary amine result in a non-meltable substance that cannot be used to form heat-resistant products using the casting method. An inert solvent, (N-, N -dimethylacetamide) can be used to solvate the reaction reagents. In this case, a low molecular weight prepolymer is obtained which, when heated, is converted to a high molecular weight product. However, such a polymer does not possess the necessary physicomechanical properties.
    The purpose of the invention is to improve the physico-mechanical characteristics of the polymer, as well as giving it the ability to be processed by casting.
    This goal is achieved by the fact that, according to the production method,. by the reaction of an aromatic diamine and hemellitic acid or its dianhydride in the presence of a tertiary amine and / or aliphatic diamine, the reaction is carried out in an alkanol medium having 4-6 atoms
    15 carbon.
    In addition, glycol is additionally introduced in an amount of 8-12 wt.% Of the total concentration of glycol and alkanol.
    20
    In addition, the tertiary amine and alkanol are used in a weight ratio of 1: 19-1: 1.
    In the absence of a tertiary amine, hemellitic acid and an aromatic diamine cannot react effectively with each other, since these reagents do not form a homogeneous solution in an alcohol solvent. The tertiary amine forms a solid salt with free carboxyl groups that solvates aromatic acid and the initial reaction products. In addition, the final reaction product does not contain fragments of a monohydric alcohol or a tertiary amine, which could enhance its properties and the properties of the molded products obtained on its basis. The method consists in the reaction of an aromatic diamine and hemellitic acid or its dianhydride in the presence of a tertiary amine in an alcohol solvent to form a solid polymer with a low molecular weight, which can be converted into a high molecular weight polymer by polymerization in a solid state. Used aromatic diamines include m-phenylenediamine, hydroxybisaniline, methylene bisaniline, 4,4-diaminodiphenylpropane, diamizr diphenyl sulfide, 4,4-diaminodiphenyl sulfone, 4,4-diaminobenzophenone, etc. Aromatic diamines are preferably used for optimum properties, since the heat resistance of the molded products is reduced when using aliphatic diamines. Trimethylamine, tretylamine pyridine, triisopropylamine, tripropylamine, etc. are suitable treogical. Triethylag in is preferred because its acid salts have a high boiling point, as a result of which they can be kept in the reaction medium during the initial stage of condensation, whereas the free amine has a sufficiently low boiling point, and therefore it can easily be removed after the formation of a polyamidoimide polymer of relatively low molecular weight, together with pirtovym solvent. Alcohol solvents (alkanols} contain 4-6 carbon atoms, for example butanol, sec-butanol, pentanol, hexanol. Among them are normal alkanols containing 4-5 a MOH of carbon (butanol or pentanol are preferred: boil down in order to not be released during the initial condensation reaction, but these foam temperatures are low enough for these alcohols to be easily removed after the formation of the polyamine t-shdny polymer with a relatively low molecular weight without ethereal of the free carboxyl groups of the aminoimide poly; pa. If the | terminal groups of the amidoimide polymer are esterified with an alcohol solvent, it is much more difficult to increase the molecular weight of the polyamidoimide polymer during the solid state polymerization. The higher boiling alcoholic solvents (hexanol and t, Substrates must be rapidly removed from the amido-imide polymer with a relatively low molecular weight. If higher boiling alcohol solvents are removed by maintaining the reaction medium at a rate of Aturi beginning runoff reflux for a prolonged period of time, intensive esterification occurs more high boiling alkanol. Such difficulties are eliminated with the use of a low-boiling alkanol, for example, butanol or pentanol. Lower alkanols are not suitable due to the low boiling point. Glycols - ethylene glycol, 1,2-propylene glycol or 1,3-propylene glycol are also used as reactive solvents. In this: case, it is also desirable to quickly remove unreacted alcohol solvent and glycol from a low molecular weight polyamidoimide polymer. The reaction of the glycol with the carboxyl group of the amidoimide polymer does not have the disadvantage of drying the alkanol, since the glycol is not a chain breaker in the subsequent solid phase polymerization stage. The molar ratio of aromatic diamine to acid is in the range of 1.2: 1: 1.2. However, it is preferable to use equimolar concentrations. The weight ratio of tertiary amine to alkanol is in the range of 1: 19-1: 1, depending on the molecular weight of the used tertiary amine and alkanol. In those cases where glycol is used, the latter is present in a concentration of 8-12% by weight of the total concentration of glycol and alkanol. Above this concentration it is difficult to remove the glycol and the polyamidoimide tends to acquire the properties of the amido-imide ester polymer. In addition, an excess of glycol leads to non-habitual foaming at high temperature, necessary for molding polymers or gas formation during annealing. Polyamidimide can be obtained by adding all reagents (alkanol / trialkylamine, aromatic diamine, hemellitic acid and any glycol) to the reactor in any order and heating the mixture under reflux. However, it is generally preferred to heat all reagents with the exception of hemellitic acid to form a homogeneous solution, and then quickly add hemellitic acid to the reactor. Such a technique usually results in a simultaneous product and prevents the formation of insoluble products. In any case, the reagents are maintained at reflux to reflux of the alkanse, tertiary amine, and substantially all glycol, if present. Typically, about 50% of the alkanol, tertiary amine, and glycol is removed in 30-60 minutes with refluxing. Then the reaction mass is heated to 200-350 ° C. The imide formation occurs when the reactants are heated to lOO-C ° while the amide formation takes place at 200-300 ° C. As a rule, after completion of the reaction, all solvents are removed by distillation and the melt of pilamidoimide remains, having an internal viscosity of 0.1 -0.3 dl / g. After the polyamidoimide is cooled, it is milled and then polymerized in the solid phase at 190-350 ° C. Because of the crosslinking during the solid-phase polymerization, the exact molecular weight is difficult to determine. The resulting polyamidoimide can be used for high temperature forming.
    Example 1. The contents of a three-liter flask equipped with a mechanical stirrer and a distillation head with a condenser consisting of 74.6 g of m-phenI Lediamine, 326 g of oxybisaniline, 56 g of ethylene glycol, 400 g of butanol, and 140 g of triethylamine are mixed for 7 minutes by heating the flask from the bottom half with a spherical heating grid up to 149 ° C. After the reagents are dissolved, 442.3 g of hemellitic anhydride are added to the stirred contents of the flask within 8 minutes. Then nitrogen is bubbled and the temperature of the heating grid is raised to. After heating for 45 minutes, g of distillate (glycol, triethylamine and butanol) was collected. The upper half of the heating jacket was then placed around the flask and its temperature was raised to 293 ° C. After heating the viscous polymer for another 1.1 h, the heating jacket was turned off, cooled and milled. The amidimide polymer had an intrinsic viscosity of about 0.22 dl / g (0.5 wt.%), the volume in the phenol: tetrachloroethane system was 60:40 at 25 ° C. The molecular weight of the amide imide polymer increased in polymerization in solid phase e by placing the composition
    into the circulating air oven for 16 hours at, for 3 hours at and 45 minutes at 316 ° C. The amidimide polymer in the solid phase is molded into disks at. The stretchable bars 5 have a tensile strength of 843.7 kg / cm, and the discs do not show gas formation or deformation after heating at 232 ° for 24 hours, followed by Harg eBa10 at 260 ° C for 24 hours. Consequently, the resulting molded products have high tensile strength, do not emit gas, and do not deform when heated or annealed during
    15 high temperature.
    Example 2. Preparation of fully aromatic amidimide polymers using 1 hexanol as alkanol.
    2Q Conducted according to Example 1, using an initial charge consisting of 396 g of methylenebisaniline, 35 g of ethylene glycol, 400 g of 1-hexanol, 140 g of triethylamine and 384 g of gemelli25 anhydride. Nitrogen sparging is carried out at a rate of 250 cm / day to the bottom of the spherical heating jacket and the temperature is maintained at 260 s. 15 minutes after the start of heating30
    neither starts distillation. Include the upper half of the heating jacket. After another 5 minutes, 100 ml of hexanol are taken from the transparent reaction mass as a condensate and
    35 shirt temperature set
    equal to. After 20 minutes, collect 449.3 g of condensate. 30 minutes later, a temperature of 5 97.7 g of condensate is taken away and a vacuum is created in the system (381 mm Hg).
    0 After 5 minutes, the heating and vacuum are turned off and the polymer is allowed to cool. The resulting amidimide polymer has an internal viscosity of 0.22 dl / g at a concentration of 0.5 wt.%
    45 volume in the system phenol: tetrachloroethane in the ratio 60:40,
    Example 3. The use of pyridine as a tertiary aromatic and aliphatic diamines. Carried out analogously to example 1 when changing the initial load of 66.8 g of hexamethylenediamine, 442.3 g of hemellitic anhydride, 338.1 g
    ,, methylenebisaniline, 100 g of pyridine, 300 g of 1-butanol and 2 g of trisnonylphenylphosphite catalyst. The bottom half of the spherical heating jacket is maintained at 327 ° C and nitrogen sparging begins.
     After 1 min after the start of heating, the upper half of the heating jacket is turned on. Distillation of the solvents is stopped after 50 min with obtaining an extremely viscous
    权利要求:
    Claims (3)
    [1]
    5 polymers. The heating is turned off, the polymer is allowed to cool and grind it. A polymer having an internal viscosity of 0.21 dL / g is polymerized overnight under polymerization conditions in the solid phase at 222 ° C under high vacuum. Example 4, Using a secondary as alkanol, and a mixture of aromatic and aliphatic diamines in the absence of a tertiary amine. Carry out a taxation example of the initial load of 66.8. hexymethylenediamine, 442.3 hemellitic anhydride, 342 g methylenebi 3aniline and 400 g secondary butyl alcohol. A few minutes after the temperature of the spherical heating jacket reaches 211 ° C, an exothermic reaction starts. 25 minutes after the start of heating, 300 ml of condensate is collected. After another 5 minutes, 1.9 trisnonyl phenylphosphite catalyst was added. Then include the upper half of the heating jacket and begin bubbling nitrogen. After 5 minutes, 480 ml of condensate was collected and the temperature of the heating jacket was set to 327 ° C. After 30 minutes, the heating is turned off, the amidimide polymer is cooled and ground. This polymer, having an internal viscosity of 0.29 dl / g, is polymerized overnight in the solid phase under high vacuum. Example 5. Using a mixture of aromatic and aliphatic diamines using 1-pentanol as an alcohol and in the absence of a tertiary amine as in example 1, using an initial charge of 66.8 g of hexamethylenediamine, 442.3 g of hemellitic anhydride, 800 g of 1-pentanol, 342 g of methylene bisaniline, 1.6 g of a 50% aqueous solution of sodium hydroxide and 2.64 g of 50% aqueous solution of hypophosphoric acid. Sodium hydroxide and hypophosphoric acid constitute the catalyst for the reaction. The temperature of the bottom half of the heating jacket is set equal and after 80 minutes the theoretical amount of imidization water is collected. Nitrogen sparging is started and the temperature is set at the top and bottom; Noah. After another 80 minutes, 940 ml of distillate is taken out to produce a very viscous amimide imide polymer. In the reaction vessel, the heating is DISCONNECTED and the amidimide polymer is cooled and ground to form a polymer having an internal viscosity of 0.22 dl / g. This polymer is polymerized in the solid phase overnight at 232 s under high vacuum. Claim 1. A method for producing polyamide diimides by reacting aromatic diamie and hemellitic acid or its dianhydride in the presence of a tertiary amine and / or aliphatic diamine, characterized in that, in order to improve the physicomechanical properties, the reaction is carried out in an alkanol medium having 4-6 carbon atoms.
    [2]
    2. The method according to claim 1, wherein, in the reaction medium, glycol is additionally introduced in an amount of 8-12% by weight of the total concentration of glycol and alkanol.
    [3]
    3. The method according to claim 1, characterized in that the tertiary amine and alkanol are used in a weight ratio of 1: 19-1: 1. Sources of information taken into account in the examination 1. US patent No. 3440197, cl. C 08 g 20/32, 1969 (prototype).
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    同族专利:
    公开号 | 公开日
    JPS5952662B2|1984-12-20|
    AU2189477A|1978-08-10|
    AU498148B2|1979-02-15|
    NL184113B|1988-11-16|
    JPS52104596A|1977-09-02|
    FR2341609A1|1977-09-16|
    IE44776B1|1982-03-24|
    FR2341609B1|1981-01-16|
    NL7701566A|1977-08-25|
    IT1082694B|1985-05-21|
    GB1559892A|1980-01-30|
    DE2705823C3|1982-03-25|
    BE851207A|1977-08-08|
    DE2705823A1|1977-09-08|
    IE44776L|1977-08-23|
    DE2759884C2|1982-12-23|
    CA1095643A|1981-02-10|
    NL184113C|1989-04-17|
    DE2705823B2|1981-05-21|
    DK73177A|1977-08-24|
    LU76724A1|1977-08-18|
    US4045407A|1977-08-30|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE4129325A1|1991-09-04|1993-03-11|Chemie Linz Deutschland|New bis--benzophenone imino:di:imide - useful as monomers for prodn. of poly:ester and poly:amide with high thermal stability, low Tg, good solubility and thermoplastic processability|
    DE4205685A1|1992-02-25|1993-08-26|Chemie Linz Deutschland|New readily processable thermally stable polyamideimide ester] polymers - prepd. from new amide-imide bisphenol cpds. and bifunctional acid chloride gp. carboxylic ester cpds.|
    US5453515A|1991-08-13|1995-09-26|Chemie Linz Gesellschaft M.B.H.|Benzophenone iminodiimides and heat-stable polymers derived therefrom|US3480588A|1963-08-20|1969-11-25|Monsanto Co|Stable coating composition of a tricarboxylic acid or its partial or full ester and a diamine|
    US3440197A|1966-05-05|1969-04-22|Gen Electric|Coating solutions and methods for preparing and using the same|
    US3663728A|1968-07-25|1972-05-16|Gen Electric|Process for producing polyamide acid and polyimides|
    JPS4814194B1|1969-06-13|1973-05-04|
    US3607838A|1970-01-28|1971-09-21|Jorg Strickrodt|Process for producing polyimides in glycol|
    US3677992A|1971-04-07|1972-07-18|Standard Oil Co|Polyamide-imide compositions containing coatability aids|US4183870A|1974-01-26|1980-01-15|May & Baker Limited|Cyclopentane derivatives|
    US4233435A|1978-01-09|1980-11-11|General Electric Company|Polyesterimide resins and synthesis thereof|
    US4459383A|1980-07-25|1984-07-10|General Electric Company|Polyamide-imide resin compositions and electrical conductors insulated therewith|
    AT397799B|1991-08-13|1994-06-27|Chemie Linz Gmbh|BENZOPHENONIMINODIIMIDES AND DERIVED THERMOSTABLE POLYMERS|
    US5324813A|1992-07-22|1994-06-28|International Business Machines Corporation|Low dielectric constant fluorinated polymers and methods of fabrication thereof|
    KR0128814B1|1993-07-05|1998-04-07|강박광|Polyamideimide resins containing isophorone diamine strncture|
    KR970006897B1|1993-11-12|1997-04-30|재단법인 한국화학연구소|The method of polyamide imide pesin|
    KR0162275B1|1995-01-16|1999-01-15|강박광|Polyamic acid prepolymer, heat-resistance polyamideimide foam produced by it and process for preparing the same|
    US8420583B2|2008-01-24|2013-04-16|Afton Chemical Corporation|Olefin copolymer dispersant VI improver and lubricant compositions and uses thereof|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US05/660,715|US4045407A|1976-02-23|1976-02-23|Process for preparing amideimide polymers in the presence of alcoholic solvent|
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