• 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 urea derivatives, in particular, to the preparation of a crosslinking component for containing hydroxyl groups and / or primary and / or secondary amino groups of a binder for aminopolyol based electrical submersible varnishes. The purpose of the invention is to increase the hardness and resistance to solvents of cathode deposited, protonated and water-thinned coatings. Preparation of lead from 3-isocyanatmethyl-3,5,5-trimethylcyclohexyl isocyanate (in which the free isocyanate groups are blocked by compounds containing methylene groups reactive with isocyanate groups) and dimethyl or diethyl malonic acid ester or ethyl acetic ester until a cyanoacetic acid ester is reached, and the cytokine ester is ethyl acetate or ethyl acetate. corresponding to semi-blocked isocyanate, at their molar ratio of 1: 1, 0-1.2, in the presence of 0.1-0.5% by weight sodium or sodium phenol (catalyst) at room temperature e. The process is carried out with the subsequent addition of the obtained product at 30-40 ° C to a solution of diethylenetriamine or amino alcohol obtained from tetraethylenepentamine and 4 - methyl - 1,3 - dioxolane - 2 - it in a 1: 2 ratio, or diethanolamine containing an equivalent amount of isocyanate groups the pre-product is the amount of primary or secondary amino groups or OH groups in an inert organic solvent medium and the reaction is carried out to an NCO value of 0.1 wt.%. 1 tab.
    公开号:SU1475485A3
    申请号:SU864027540
    申请日:1986-05-28
    公开日:1989-04-23
    发明作者:Плюм Хельмут；Паар Виллибальд
    申请人:Вианова Кунстхарц Аг (Фирма)；
    IPC主号:
    专利说明:

    -i The invention concerns a process for the preparation of a crosslinking component for containing hydroxyl and / or primary and / or secondary amino groups of a lacquer bond, used

    cm
    for electric dip coating (EBR).
    The purpose of the invention is to increase the hardness and resistance to solvents
    3147
    cathodic deposited, protonated and water-borne coatings,
    The reaction products obtained from the active CH groups of alkyl esters, diisocyanates and polyamines and / or polyamino alcohols, in combination with those containing
    oxyl groups and / or amino groups with synthetic resins already at tempo-vO
    The form below forms a coating with excellent lacotechnical properties. If methyl or ethyl ether is used as having the active CH-groups of the alkyl ester, then the losses resulting from cleavage are particularly small, and ethyl ether, moreover, is the most favorable, taking into account the cleavage products. The curing components are stable for long periods of time in systems for cathodic electroplating by immersion.
    The crosslinking components obtained in accordance with the invention react with polymers containing hydroxyl groups and / or amino groups already at a temperature below 120 ° C, and during the reaction, transesterification or reamidation occurs.
    As a leaving product, only alcohol is formed from the alkyl ether containing active CH groups. Cleavage of the alkyl ether containing active CH groups during the formation of free isocyanate groups and the subsequent formation of a dimensional network, in which urethane groups or carbamide residues are formed, does not occur.
    Despite the high content of urea groups obtained in accordance with the invention, the products can be diluted with the usual ones. solvents for sakas to form clear solutions.


    50
    In the examples given, all data, expressed in parts or percentages, are, if there are no additional indications, weight units,
    Example 1 but). Getting a hardener
    To a mixture consisting of 222 g of 3-iso-5 cyanatomethyl-3,3,5-trimethylcyclohexyl isocyanate and 176 g of diethylene glycol dimethyl ether for 8 hours
    five
    0
    five
    five
    176 g of malonic acid diethyl ester and 0.8 g of phenolate were continuously added at room temperature. on three . The reaction is then continued at room temperature until the isocyanate content becomes 6.6%. The reaction mixture is then introduced into a mixture consisting of 0 30.9 g of diethylenetriamine and 220 g of diethylene glycol dimethyl ether at such a rate that the temperature of the reaction mixture does not exceed 30 ° C. Immediately after this, the reaction mixture is heated at 60 ° C until when the isocyanate content becomes less than 0.1%.
    at). Getting a binder. In a known manner, an amino polyether polyol is obtained from 65.5% bisphenol A ester and an epoxy resin with an epoxy equivalent weight of 480, 18.8% polyester from trimethylolpropane, adipic acid, isononanoic acid and tetrahydrophthalic anhydride with an acid number of 65 mg KOH / g and hydroxyl number 310 mg KOH / g, 6.1% diethanol-amine, 4.4% 2-ethylhexylamine, and 5.2% diethylaminopropylamine.
    The product is dissolved in propylene glycol monomethyl ether to obtain a 65% solution, and the amino number is 96 mg KOH / g.
    with). Dip electropacking and testing,
    5 in
    0
    0
    five
    108 g of the binder obtained in accordance with paragraph 1c is mixed with 60 g of hardener obtained in paragraph 1a and 15 g of a 3N solution of formic acid, after which the mixture is diluted with 817 g of completely demineralized water. The varnish solution is stirred for 24 hours, as a result of which it has the following characteristics: solid content 10% by weight. pH value of 5.7, the conductivity of the solution 1060 / US cm MEQ value of 38,
    On a steel sheet that is phosphated and connected as a cathode, is obtained after deposition at a solution temperature of 25 ° C for 1 min at 150 V and after curing
    V and after (30 min, 120 C) a smooth coating with a layer thickness of 15 μm and a solvent resistance of more than 500 double strokes in methyl isobutyl ketone.
    514
    11 p and m about r 2. l). Aminoopyr preparation.
    To a mixture consisting of 189 g of tetra-ethylene peptamine and 168 g of diethylene glycol dimethyl ether, 204 g of 4-methyl-1.3 dioxolan-2-one is added dropwise at a rate such that the temperature of the reaction mixture does not exceed 60 ° C. Immediately after this reaction mixture is heated at 60 ° C until reaching the amine number of 300 mg KOH / g.
    at). Getting hardener.
    To a mixture consisting of 222 g of 3-iso-cyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate and 176 g of diethylene glycol dimethyl ether, over time 8 hours, 176 g of malonic acid diethyl ester and 0.8 g of phenol and sodium. The reaction is then continued at room temperature until the isocyanate content becomes 6.6%. The reaction mixture is then introduced into a mixture consisting of 101 g of a 70% aqueous alcohol solution obtained in paragraph 2a and 0.5 g of dibutylamine sulphate, the introduction being made at such a rate that the temperature of the reaction mixture does not exceed 40 ° C. . Immediately after this, the reaction mixture is heated at 60 ° C until the isocyanate content becomes less than 0.1% by weight.
    with). Dip electropacking and testing.
    108 g of the binder obtained in paragraph 1c are mixed with 43 g of hardener obtained in Example 2c and 15 g of 3N. a formic acid solution, after which the mixture is diluted by adding 834 g of completely desalted water. The varnish solution is stirred for 24 hours, after which it has the following characteristics: solid content 10 wt.%, PH value 5.8, electrical conductivity of the solution 1060 jUS, MEQ value 45.
    56
    On phosphated and undercranded steel as a cathode, steel is obtained after ossaldrum for 1 min at 150 V and a raspor rastor 25 ° C and after curing (30 min, 120 C) a smooth coating with a 23 μm thick layer and solvent resistance more than 500 double
    courses in methyl isobutyl ketone. Comparative example. 108 g of the amino polyether polyol obtained in paragraph 1c are mixed with 43 g of the preparation prepared according to
    with the well-known method of the reaction of malonic acid diethyl ester, trimethylolpropane and 3-isocyanato-3,5,5-trimethylcyclohexyl esocyanate (70% solution in diethylene glycol) and 11.7 g of 3N. formic acid solution, after which the mixture is diluted with the addition of 237 g of completely desalted water. Lacquer solution is stirred
    within 24 hours, after which it has the following characteristics: solid content 10 wt.%; pH value 5.8, electrical conductivity of the solution 980 US, MEQ value 37.
    On a steel plate that is phosphated and connected as a cathode, is obtained after deposition for 1 min at 150 V and a solution temperature of 25 ° C and after curing (30 min,
    140 C) smooth coating with a layer thickness of 19 μm and solvent resistance of less than 200 double strokes in methyl isobutyl ketone. Hardener 1a.
    Product interaction on average
    1 mol of diethylenetriamine H2H-CHg-CH2-NH-CH-CHz-NHa and 3 mol of sub-blocking 3-isocyanatomethyl-3,5,5-trimethyl-cyclohexyl isocyanate (α-isophorone diisocyanate-IPDI) diethyl malonic acid ester.
    The product is used as a 50% solution in diethylene glycol dimethyl ether.
    Hardener 2c.
    The product of the interaction on average 1 mol of amino alcohol
    ABOUT
    it
    sngsn-sng-o-c-kn- (sn2-sn2-mn-s-o-cng-snsn3
    he
    I
    with 5 mol of the indicated for 1a semi-blocked GRL1, which is dissolved
    ABOUT
    s-sng-snon
    I
    in diethyl glycol dimethyloro - tfire in the form of a 70% solution.
    Aminoalcohol is the reaction product of 1 mole of tetraethylenepentamine.
    2 CH2-CH-CH3 - «- H2N- (CH2-CH
    v °
    II
    about
    Hardener Over.
    The product of the interaction is, on average, 1 mol of diethanolamine HO-CHZ CHZ-NH-CH2 SNYON with 3 mol of semi-blocked IPDI malonic acid dimethyl ester, which is taken as a 50% solution in diethylene glycol dimethyl ether.
    Hardener 4a.
    The product of the interaction is 1 mol of diethanolamine and 3 mol of semi-blocked acetoacetic acid ethyl ether, CH3-CO-CH3, -COOCHH5-IPDI, which is taken as a 50% solution in diethylene glycol dimethyl ether.
    Hardener for comparison.
    The product is with a mixture of polyisocyanates obtained by reacting 0.2 mol of trimethylolpropane and 1.23 mol of IPDI, followed by blocking this product in an amount corresponding to a NCO equivalent of 1.88, malonic acid diethyl ester, taken in an amount 1.96 mole. To facilitate further processing, the product is diluted with diethylene glycol dimethyl ether to a solids content of 70%.
    The test results for resistance to methyl isobutyl ketone of cathode-deposited films using hardeners in accordance with the proposed method are as follows.
    The hardeners of examples 1, 2, 3 and comparative example are tested in varnishes, in which the ratio of hardeners to amino polyether polyol is 30:70 (calculated on the solid resin). In example 4, the ratio was 23.5: 76.5.
    Resistance to solvents is tested using methyl isobutyl ketone, each time after 50 double strokes.
    Resistance to solvent is determined by the usual letter with methyl isobutyl ketone (MIBK). At the same time, a lump of cotton wool or tissue under pressure corresponding to a load of 1 kg is impregnated with MIEK rchad-forward (twice) and 2 mol of 4-methyl-1,3 dioxolan-2-one (-propylene carbonate)
    2-NH) 3-CH2-CH2-NH2
    on the test surface. The test can be carried out by hand or by an appropriate apparatus, if necessary also with another solvent.
    The table shows the data for which the films were still intact, as well as the data for lacquer films applied cathodically on phosphated steel sheets that are stitched at two different curing temperatures (120 and 140 ° C) f for the same time of 30 minutes.
    Sheets are exposed to the solvent after 2 hours at room temperature. The test is continued for as long as the film begins to soften, as determined by pressure with a finger. The estimate is the amount at which the film remains unchanged.
    The lacquer for comparison (by a known method) gives the film, even at the beginning of tests, of already insufficient hardness. After several specified double strokes (wiping) with the MIBK, the film dissolves to a large degree.
    The proposed method allows to obtain products characterized by good resistance to hydrolysis, which can be used as a component of water-soluble varnishes,
    in particular, in a composition capable of being deposited on the cathode in the implementation of the electroplating process by immersion. /
    The products obtained can be applied in a two component system in conjunction with a synthetic resin, which is capable of forming amides and / or esters with carboxylic acid.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    The method of producing a cross-linking component for containing hydroxyl groups and / or primary and / or secondary amino groups of a binder for electro-submersible aminopolyol based lacquers from H-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, in which the free isocyanate groups are blocked by compounds containing methylene groups reactive to isocyanate groups, characterized in that, in order to increase the hardness and resistance to cathode deposited, protonated and water-soluble solvents, nd, 3 izotsianatometil- 3,5,5-trimethylcyclohexyl isocyanate
    0
    with
    0
    five
    react with dimethyl or diethyl malonic acid ester or ethyl acetate acetic acid to achieve a value of the isocyanate number corresponding to a semi-blocked 3-isopyanate-methyl-3,5,5-trimethylcyclohexylcate, with a molar ratio equal to 1: 1, from 1.2, in the presence of 0.1– 0.5 wt.% Sodium or sodium phenol as a catalyst at room temperature, followed by adding the product obtained at 30–40 ° C to a solution of diethylenetriamine or amino alcohol prepared from tetraethyl n-pentamine and 4-methyl-1,3-dioxolan-2- it in a 1: 2 ratio, or diethanol-amine containing an equivalent amount of the isocyanate groups of the pre-product, the number of primary or secondary amino groups or hydroxyl groups, in an inert organic medium, solvent and carry out the reaction to a value of SO-counts equal to 0.1 wt.%.
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