• 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:
    The invention relates to amines, in particular, a process for the preparation of a mixture of substituted methylene bis-anilines (SZMA) consisting of 2,2-dichloro-6, b-diethylmethylene bis-aniline and a compound of the general formula 3R, 4 Shg, 5RjC6H.2., j-3Rj, 4NH, 5R, where K, Rj, Ke, R are the same or different straight or branched alkyl, C2-C4, or R, and / or R, -C1, and R and R have the indicated values used as hardeners in the process of producing polyurethanes and epoxy resins, as well as for lengthening the chain or cross-linking of polymers (polyurethanes). The goal is to obtain less toxic compounds of the specified class. Synthesis of SZMA is carried out by condensation of a mixture containing 30-99 mol% of 2-methyl-6-chloro-1-h and a aniline derivative of the formula, -3-R5, 4-NH, 5-R, where Ry and Rg are the same or different straight or branched alkyl-C-C, in a solution of xylene in an acidic medium with formaldehyde or a compound that forms it. Exit 97%. SZMA is used to lengthen the polymer chain of polyurethane or to cure epoxy resin in an amount of 0.4-0.6 mol per 1 mol of groups. Viability based on a new elastomer mixture is 11-82 s, and SZMA does not have either carcinogenicity or mutagenicity. which reduces the toxicity of production. 3 tab. § CO 00 ISD
    公开号:SU1375122A3
    申请号:SU853915009
    申请日:1985-07-04
    公开日:1988-02-15
    发明作者:Фелькер Теодор；Альтхаус Ханс
    申请人:Лонца Аг (Фирма)；
    IPC主号:
    专利说明:

     s
    The invention relates to organic chemistry, namely to a method for producing a new mixture of substituted P, P - methylene bis-anilines, which can be used as hardeners in the process of producing polyurethanes and epoxy resins, as well as chain extenders or crosslinkers.
    The aim of the invention is to develop an accessible method for producing hardeners for epoxy resins that have neither mutagenic nor carcinogenic properties.
    The proposed condensate is obtained as follows.
    1 mol of 2-ethyl-6-chloroaniline or its mixture with o-alkylated aromatic amines is diluted with xylene in a 1: 1 weight ratio, after which 3 g or 33 g are added (in the case of condensation with diisopropylaniline) 47.8% sulfuric acid and, stirring and heating under reflux, are reacted with 47.1 tons of a 30% formaldehyde solution (formalin, 0.472 mol). Then the reaction mass is neutralized with an excess of sodium hydroxide solution, after which it is continued to mix for 30 minutes with a reflux condenser. After separation of the phases at 50 ° C, the organic phase is again washed with 150 ml of water and again separated in phases at 50 ° C. Under pressure of the torr, first the mixture of xylene isomers is distilled off and at a flask temperature of 220 ° C and pressure of 5 torr, unreacted aniline is removed - derivative. The yield of the methylene bis compounds in almost all cases amounts to 97% of the theoretical or baseline.
    Example 1. 92.2 mol% of 2-ethyl-6-chloroaniline (CEA) and 7.8 mol% of 2,6-diethylaniline (DEA) are subjected to a condensation reaction. A light brown product is obtained with a mp. 100-105 With the following composition, mol.%:
    2,2-diethyl-6,6 gdichlorometilen-bis-aniline. 89.3
    2,6,2-triethyl-6 chloromethylene bis-aniline 10,1
    2,6,2, b-tetraethylmethyl
    tylen bis aniline 0.65
    In Ames test, the product does not show a mutagenic effect.
    Example 2. 89.6 mol.% CEA and 10.4 mol.% DEA are subjected to a condensation reaction. Get crystalline
    product brown with so pl. 95- of the following composition, mol.%:
    2,2-diethyl-6,6 dichloromethylene bis-aniline 80.3
    .I
    2.6, .2-triethyl-6-chloromethylene bis-aniline 18.6
     (2,6,2, 6-tetraethylmethylene bis-aniline 1,1) In the Ames test, the product does not show a mutagenic effect.
    Example 3. 79.7 mol.% CEA and 20.3 mol.% DEA are subjected to a condensation reaction. A light brown product is obtained with a mp. 91-101 With the following composition, mol.%:
    2,2-diethyl-6,6-dichloromethylene-bis-aniline 73 j 9 2,6,2 -triethyl-6-chloromethylene-bis-aniline 21.1 2,6,2,6-tetraethylmethylene-bis- aniline5.0 In the Ames test, the product has no mutagenic effect.
    Example 4. 70.3 mol.% CEA and 29.7 mol.% DEA are subjected to a condensation reaction. A light brown product is obtained with mp. 83-94 With the following composition, mol.%: 2,2 -DIETSH1-6,6 -di
    chloromethylene bis-aniline 2,6,2-triethyl-6-chlorine 56, 7 32.6
    10, .7
    methylene bis-aniline 2,6,2,6-tetraethylmethylene-bis-aniline In the Ames test, the product has no mutagenic effect.
    Example 5. 64.0 mol.% CEA and 36.0 mol.% DEA is subjected to a condensation reaction. A light-brown product is obtained with a melting point of 78-91 C of the following composition, mol%: 2,2-diethyl-6,6-dichloromethylene-bis-aniline 43.3 2,6,2 -triethyl-6-chloromethylene α-bis-aniline 2, 5 2,6,2, b-tetraethylmethyl-bis-aniline 14,2 In the Ames test, the product does not show a mutagenic effect.
    Example 6. 55.3 mol.% CEA and 44.7 mol.% DEA are subjected to a condensation reaction. A light-brown product is obtained with mp. 70-73 With the following composition, mol.%: 2,2-diethyl-6,6-dichloromethylene-bis-aniline 26,6 2,6,2 -triethyl-6-chloromethylene-bis-aniline 54,9
    not 2,6,2,6-tetraethyl-methylene bis-aniline
    In the Ames test, the product has a mutagenic effect.
    Example 7. 39,8 mol and 60,2 mol.% DEA is subjected to condensation. Get brown with so pl. 73-74 C follow, mol.%:
    2,2-diethyl-6,6-dichloromethylene bis-aniline
    2,6,2 -triethyl-6-dichloromethylene bis-aniline
    2,6,2, b-tetraethylmethylene bis-aniline
    In the Ames test, the product does not have a mutagenic effect.

    For the following condensation reactions, a mixture of 90 h. Is used as the initial standard mixtures (unless otherwise indicated). 2-ethyl-6-chloroanlene (89.6 mol.%) And 10 hours 2,6-diethyl aniline (10.4 mol.%).
    Example 8. 100 h. Standard mixtures are mixed and condensed with 40 parts of 2-ethyl-6-sec-butylaniline. The resulting product has the following composition, mol.%:
    2,2-diethyl-6,6-dichloromethylene-bis-aniline 2,6,2-triethyl-b-chlorine 43, 7 10.6
    methylene bis aniline
    2,2-Diethyl-6-Vtorbutil-6-chloromethylenebis-aniline34, 2
    2,6,2, 6-tetraethylmethylene bis-aniline 0.6
    2,6,2 -triethyl-6-sec-butylmethylene bis-aniline 4,1
    2,2-diethyl-6,6-di-Vetbutylmethylene bis-aniline 6,7
    In the Ames test, the product has no mutagenic effect.
    Example 9. 100 parts of a standard mixture are mixed with 80 parts of 2-ethyl-6-sec-butylaniline. The resulting mixture contains 52.3 mol% of 2-ethyl-6-chloroaniline. The resulting product has the following composition, mol.%:
    2,2-diethyl-6, b-dichloromethylene-bis-aniline 27,6 2,6,2 -triethyl-6-chloromethylene-bis-aniline 6,7 2,2-diethyl-6-btc) -bootsh1 - 6-chloromethylene bis-aniline 43.2 2,6,2, 6-tetraethylmethylene-bis-aniline0,4
    0
    five
    0
    five
    2,6,2 -triethyl-6-second-butylmethylene bis-aniline 5,3 2,2 -dieth1-6, b-di-sec-butylmethylene bis-aniline 16.9 In the Ames test, the product does not show mutagenic action.
    Example 10. 100 parts of a standard mixture are mixed with 20 parts of 2,6-di-isopropylaniline and condensed with formalin. The resulting product has the following composition, mol%: 2,2-diethyl-6,6-di-chloromethylene-bis-aniline 57,6 2,6,2 -triethyl-b-chloromethylene-bis-aniline 14.0 2- ethyl 6-chloro-2, 6-diisopropylmethylene bis-aniline 22,6
    2,6,2, b-tetraethylmethylene bis-aniline0,8
    2,6,2, 6 -tetraisopropylmethylene-bis-aniline 2,2 2,6-DIETHIL-2, b-diisopropylmethylene-bis-aniline 2,7
    In the Ames test, the product has no mutagenic effect.
    Example t1. 2-chloro-6-ethyl-aniline is condensed with formaldehyde. The resulting 2,2-dichloro-6,6-diethylmethylene-bis-aniline has so pl. . In the Ames test, he shows a negative reaction.
    Example 12. Condensation was carried out similarly to Example 1, but using 14.2 g (0.47 mol) of p-form. Maldehyde, instead of 47.1 g of a 30% formaldehyde solution.
    Example 13. Condensation is carried out as in Example 1, but using 14.2 g (0.157 mol) of trioxane, instead of 7.1 g of formaldehyde solution (30%).
    Example 14. 30 small.% CEA and 70 mol.% DEA is subjected to condensation reaction. Get brown product
    from m.p. 68-71 With the following composition, mol.%:
    2,2-diethyl-6,6-dichloromethylene-bis-aniline 7.9 2,6,2-triethyl-6-chloromethylene-bis aniline 48.2 2,6,2,6-tetraethylmethyl tylen bis-aniline 43.9 Example 15. 99 mol.% CEA and 1 mol.% DEA are subjected to a condensation reaction. Get light brown
    product with so pl. 103-108 With the following composition, mol.%:
    I.
    2,2-diethyl-6,6-dichloromethylene-bis-aniline 98,0 2,6,2-triethyl-6-chloromethylene-bis-and NILIN 1,9 2,6,2, 6-tetraethylme - tylen bis-aniline 0,1
    The amount of injected condensates introduced and the type of their addition depends on the properties of specific starting products and the type of target products manufactured.
    By changing the composition of the mixture of the proposed chain extenders or crosslinkers in the Ames test in the reaction system, the viability time of the polyurethane reaction mass, i.e. for a period of time T, after which the polyurethane reaction mass, when submerged in it, is a uniformly advancing horizontal spatula in the thread.
    Time Determination Results
    The proposed negative in the test of the 15 viability of the initial mixtures for
    Ames chain extenders or staplers for polyurethane elastomers
    are introduced into polyurethanes one by one in Table 1. common for the manufacture of polyurea- 1 mol of polytetramethylene glycol
    For example, by means of reactivity (mol. weight 1000), heat to 80 ° C and, efficient casting under pressure (Р1М), 20
    stirring for 2 h under a pressure of 12 mm 12 mm Hg, evacuated and dehydrated. Then, at 45-50 ° C, 2.1 mol of molten methylenediphenyldiisocyanate (so-called MDI pure) with m.p. 40 ° C, subjecting to erq reaction under nitrogen atmosphere with stirring at 80 ° C. The obtained pre-polymer with an NCO content of 6 mol% prior to its use is degassed at 60 ° C in a water-jet vacuum for 1 hour. An equimolar amount of diamine (or condensate, respectively) is added to this prepolymer, after which the resulting mixture is mixed evenly with a spatula at 50 ° C, then the reaction mixture is poured into aluminum form heated to 100 ° C (with internal dimensions 120x10x5 mm). Time lapse t
    by coating or dipping with conventional reaction systems including polyisocyanates, polyoxy compounds, catalysts and other additives.
    11odhod br 1mi polyisocyanates into- 25L are aromatic polyisocyanates such as metilenfenilendiizotsia- tension (MDI), tolylene diisocyanate (TDI) naphthalene diisocyanate (NDI), or such aliphatic and cycloaliphatic polyisocyanates 30 as izoforondiizotsia- tension and hexamethylene respectively.
    Polyoxy compounds can be, for example, polyglycols and simple, half esters - polyols, as well as complex half esters-polyols.
    All used catalysts can be used, for example, tetramethylbouling for 2 hours under a pressure of 12 m 12 mm Hg, evacuated and dehydrated. Then, at 45-50 ° C, 2.1 mol of molten-methylene di-nyl diisocyanate (so-called MDI pure) with m.p. 40 ° C, subjecting the reaction to nitrogen in an atmosphere of nitrogen with stirring at 80 ° C. The obtained polymer, with an NCO content of 6 mol.%, Is degassed at 60 ° C in a water jet in Kuum for 1 hour. An equimolar amount of diamine (or condensate, respectively) is added to this prepolymer, and the resulting mixture is mixed with a spatula at 50 ° C for 10 s, then the reaction mixture is poured into an aluminum heated to 100 C (with internal dimensions 120x10x5 mm). Time lapse t
    tandiamine (TMBDA), diazabicyclo octane in seconds, after which
    (DABCO) and dibutyl tin dilaurate (.DBTC) or mixtures of these compounds, and additives such as plasticizers, gas formers, flame retardants, etc.
    Chain extenders or crosslinkers are added in amounts of 0.4-0.6 mol, preferably 0.5 mol per 1 mol of NCO groups, i.e. in equivalent amounts in the case of a prepolymer reaction system, or in proportionate amounts in the case of the addition of polyols.
    45
    50
    the mixture on a spatula t evenly immersed in it is nets into the threads, conventionally called the mixture viability time.
    Preference is given to the condensate of Example 1.
    When this substance is introduced into a standard polyurethane elastomer, products are obtained which, at 70 ° C, are recyclable on all commonly used machines.
    These products are different in suitable physical properties (compared to MOSA) and are listed in Table 2.
    The reaction systems are processed by conventional methods for producing polyurethane, for example, by a single injection method or by a method using prepolymers.
    (mol. weight 1000) is heated to 80 C. and
    stirring for 2 h under a pressure of 12 mm 12 mm Hg, evacuated and dehydrated. Then, at 45-50 ° C, 2.1 mol of molten methylenediphenyldiisocyanate (so-called MDI pure) with m.p. 40 ° C, subjecting to erq reaction under nitrogen atmosphere with stirring at 80 ° C. The obtained pre-polymer with an NCO content of 6 mol% prior to its use is degassed at 60 ° C in a water-jet vacuum for 1 hour. An equimolar amount of diamine (or condensate, respectively) is added to this prepolymer, after which the resulting mixture is mixed evenly with a spatula at 50 ° C, then the reaction mixture is poured into aluminum form heated to 100 ° C (with internal dimensions 120x10x5 mm). Time lapse t
    five
    0
    five
    the mixture on a spatula t evenly immersed in it is nets into the threads, conventionally called the mixture viability time.
    Preference is given to the condensate of Example 1.
    When this substance is introduced into a standard polyurethane elastomer, products are obtained which, at 70 ° C, are recyclable on all commonly used machines.
    These products have favorable physical properties (compared to MOSA) and are listed in Table 2.
    As can be seen from Table 1, the use of condensate in Example 1 allows for an increase in load of 15-20%, while providing an increase in structure.
    strength with increasing temperature and starting at 70 ° C - its superiority to MOS.
    The proposed chain extenders or crosslinkers are also useful as amine hardeners for epoxy resins. Amine hardeners are introduced into conventional resins formed, for example, from bisphenol A and epichlorohydrin by conventional methods. It is also advisable to add amine hardeners to the epoxy resin in amounts of 0.2-0.4 equivalents, preferably 0.25 equivalents, based on the equivalent of the epoxy group.
    Using the proposed negative test in Ames amine hardeners get cured epoxy Resins with heat resistance, similar to the heat resistance of the known carcinogenic and mutagenic hardeners MOSA and MDA.
    When testing the applicability of the proposed agents as curing agents for epoxy resins, the latter is derived from Epichlorohydrin and Bisphenol H Ep 928 (manufactured by: Shell Chemical Co) with an equivalent weight of epoxide 190 (mol. Weight 380).
    Equivalent weights of amine hardeners are calculated by dividing their molar weights by 4 (according to the presence of 4 active hydrogen atoms). The equivalent weight of the described substance is 2,2-diethyl-6,6-dichloromethylene-bis-aniline (the condensate of example (6) is, for example, 8 g. The resin heated to 80 ° C (EProp 828) and the molten hardener are mixed, degassed by centrifugation, and finally poured into a mold with internal dimensions of 178x12.7x12.7 MML. The mixture of resins and hardener is cured, heating them for 2 hours at and then 1 hour at 175 C.
    The test results of the heat resistance of solidified molded products in accordance with the requirements of me
    eight
    Table D648-56 of the ASTM American Standard are listed in Table 3.
    Thus, the proposed mixture of the located P, p-methylene-bis-anilino has neither carcinogenicity nor mutagenicity, and in addition, the viability of the elastomer obtained on the basis of this mixture can vary widely.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    A process for the preparation of a mixture of substituted methylene bis-anilines consisting of 2,2-dichloro-6,6-diethylmethylene-bis-aniline and a compound of the general formula
    TSi Rj
    H2T - @ bCH - (
    EC R / i
    where R ,, R, R ,, R. are the same or
    various unbranched or branched. -app or R, and / or R-chloro, and R2 and K have the indicated meanings,
    different. the fact that the mixture containing 30-99 mol.% 2-ethyl-6-chloroaniline and aniline derivative of the formula
    where RC and R are the same or different unbranched or branched C2-C4-alkyl
    condensed in an acidic medium with formaldehyde or a formaldehyde-forming compound.
    137512210
    j.Table 1
    (Comparative) Diethyltoluoyl diamine
    2,2 6, b-Tetraethylmethyl-bis-aniline
    2.2 6.6 -Tetraisopropylmethylene bis-aniline
    2,2-Diethyl-6, b-divalent-butylmethylene-bisaniline
    2.2 -Diclormethylene bisVID test
    Chain extension or stapler
    MOSA
    Shore hardness
    Tensile strength, N / mm:
    before cracking
    to elongation,% 3
    5 9
    12
    table 2
    Condensate in example 1
    53
    27.32
    6.09 7.44
    Ultimate elongation, N / mm
    Structural strength:
    at room
    236
    246
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    DD236539A5|1986-06-11|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
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