• 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 the manufacture of urea-formaldehyde condensation polymers containing sulpho groups. The starting material is a urea-formaldehyde precondensate, and a condensation polymer of naphthalenesulphonic acid and formaldehyde is used as the acid catalyst for the subsequent polycondensation of the urea-formaldehyde precondensate. The peculiarity of this polycondensation is that the condensation catalyst is incorporated into the polymer structure of the UF polymer.
    公开号:SU826961A3
    申请号:SU752135315
    申请日:1975-05-22
    公开日:1981-04-30
    发明作者:Реннер Альфред
    申请人:Циба-Гейги Аг (Фирма)；
    IPC主号:
    专利说明:

    urea and formaldehyde and condensation polymer IH} from naphthalene sulfonic acid and formaldehyde are subjected to polycondensation in an aqueous solution at a temperature of 20-100 ° C to a gel in such a ratio that the molar ratio of formaldehyde to urea in the reaction mixture at the time of formation of the gel is 1.25-2 , and at these values of the molar ratio, both the free and the monomeric precursors (formaldehyde and urea) that are bound to the final products should be taken into account. If necessary, the resulting gel is crushed, stirred up, neutralized and filtered, dried and the product thus obtained is ground with a mill or processed by extrusion to a granulate.
    According to the proposed method, the condensation polymer (H) is present in the reaction mixture, preferably in such an amount that 10-15 meq groups are per mole of urea. In general, especially favorable results are obtained if there are 20–50 meq groups per 1 mol of urea. Therefore, this method of operation is the preferred form of the invention.
    The concentration of the aqueous reaction mixture, in relation to the sum of the forcondensate (V) and the condensation polymer H, should preferably be 15-40% by weight, based on the solution. Especially good polymers are obtained at a concentration of 20-25 wt.%.
    Preparation of forcondensate (V) proceeds according to known methods by condensation of the components F and M in aqueous solution. According to the proposed method, it is advantageous to use such forcondensates (Y), which Φ and M contain in a molar ratio of from 1.3 to 1.8, and those that are obtained by forcondensation of the reaction components at pH values from 6 to 9 and in the temperature range from 20 to.
    The condensation polymer H should preferably contain KOMioenents in such molar ratios that there would be 0.7-2.2 mol of formaldehyde per 1 mole of naphthalenesulfonic acid. Best results are obtained if the molar ratio of Φ to naphthalene sulfonic acid is 1.01, 5. The condensation polymer (H) is obtained by lime by means of the method of condensation of naphthalene sulfonic acid with formaldehyde in an aqueous solution, using technical naphthalene phosphoric acid, which predominantly contains 2 sulfonic acid, and in addition, some free sulfuric acid. Naphthalene sulfonic acid can also be obtained in situ when preparing a condensation polymer (, H).
    The polycondensation of the proposed method can also be carried out in such a way that the comonomers are partially replaced with urea, namely up to 1/3 of the corresponding molar amount, i.e. introduced into the molecular chain. When comonomer is spoken, they are in the form of substances which are suitable together with urea for polycondensation with formaldehyde or methylol compounds. Among them are the following compounds: phenol, resorcinol, alkylphenols I, for example cresols, aniline, benzoguanidine, amides of acids (such as formamide, acrylamide, dicyandiamide and oxalic and salicylic acid diamides, biuret and hydration, for example 5,5-dimethylhydanthion). A mixture of these individual substances can also be used as a comonomer.
    Comonomer introduction can proceed in two ways: either forcondensate is introduced (U, in which up to 1/3 of the prescribed amount of urea is replaced with a corresponding molar amount of comonomer, or forcondensate (U) is introduced with a corresponding, lower urea content (up to 1/3 lower than foreseen: reno) and added to the reaction: a mixture containing forcondensate (V) and condensation polymer (, H), before or during polycondensation, the corresponding comonomer in the required amount.
    The products obtained by the proposed method have strong hydrogen bonds and therefore do not dissolve in common organic solvents. On the contrary, they are soluble in hot formic acid and in saturated aqueous solutions of lithium bromide and magnesium perchlorate. From these solutions, they can again pour. They melt at about 250 ° C with the release of formaldehyde. Products that are suitable as reinforcing fillers for elastomers, as adsorbents for wastewater treatment, especially for splitting conventional oil emulsions, as carriers for agrochemical effective substances, as well as thickeners and enhancers for varnishes, printing inks, liquid liners and t .P. This use is particularly effective due to the improved affinity of the surface while simultaneously porosity between particles.
    The products resulting from the application of the proposed method are remarkably well processed into tablets and granules, while using known methods of granulation, such as tableting, extruding or shaping using granulating plates. 3, the opposite of the known MF polycondensates, the resulting products do not crush a little.
    : According to the known methods of obtaining MP-polycondensation products, when using sulfamic acid or water-soluble ammonium acid sulfate as a catalyst, it was never possible to introduce these catalysts into a condensation polymer.
    When using the proposed method to achieve a large surface and good properties of the final products, as opposed to other known MF polycondensation methods, surfactants or protective colloids are not required. But this does not mean that such additives act negatively with the proposed method. They can be added in the case when, for example, such additives of these substances are needed for technical reasons.
    Further, the invention includes sulfo-modified, highly dispersed, solid urea-formaldehyde polycondensation products, consisting of compact, spherical, sintered primary particles with a diameter of less than 1 µm, which are obtained by the proposed method. MFP polycondensation products preferably have a specific surface area of 5-100, a sulfur content of 0.22 wt.%, An average primary particle diameter of 0.04-1 μm, MF polycondensation products can contain comonomer as a partial substitute for urea, and the mole ratio of comonomer to urea reaches i / 2.
    The method is carried out as follows.
    Preparation of a condensation polymer .H).
    a) Condensation polymer 1H) -A. .. Naphthalene: Н2.504: formaldehyde
     1: 1: 1 (molar ratio).
    128 weight.h. naphthalene and 100 weight.h. concentrated sulfuric acid is heated for 6 hours to 160c with stirring. ; 0hlazhdat to and drips from 100 weight.h. aqueous 30% formaldehyde solution. The temperature is maintained at 100 ° C due to free release to 1 of its reaction heat. After 30 minutes of boiling, 100 parts by weight are diluted. water. After 16 hours of boiling, the formaldehyde conversion is 94.5% by weight. 100 parts by weight are diluted again. water and get 510 weight.h. brown viscous solution with a solids content of 45/5 Beci% and acid 2.17 g-eq / kg. A solution of acid bold can be diluted with water as you like.
    b) Condensation polymer (H) -B. Naphthalene:.: Formaldehyde
    1: 1: 1,5.128 weight.h. naphthalene sulphate 100 weight.h. concentrated sulfuric acid for 6 h at 160 ° C and then condense with 150 weight.h. 30% aqueous solution of formaldehyde at 100-110 ° C.
    The following dilutions and determinations of the conversion of formaldehyde are carried out at 100-110 ° C after a specified time: Interval, Water Additive / Transformation
    h weight , weight.%
     40
    17.0 79.6
    155
    60
    81.7 23.5
    24.0
    100 40.0
    85
    48.0-85.2
    After cooling, 512 parts by weight are obtained. a viscous brown gum that mixes in any ratio with water and gives colloidal solutions.
    The solids content in the resin is 44.5 wt.% And the acid is 2.12 g-eq / kg.
    c) Condensation polymer (H) -B. C | gHg: CH20 1: 1: 2.
     described in the above examples, 128 parts by weight naphthalene sulphate 100 weight.h. concentrated sulfuric acid and then condensed with 200 weight.h. 30% aqueous pacTBOf) a formaldehyde 22 h at
    and diluted to 100 parts by weight. water. After. This formaldehyde conversion is up to 76.6% by weight. Get 472 weight.h. almost solid, resin, which, however, is mixed with water
    in any ratios and gives colloidal solutions. The solid content is 50 wt.% And the acid is 2.09 g-eq / / kg.
    d) Condensation polymer (H) -H; 2504: CH20 1: 1: 0.75,
    128 weight.h. naphthalene sulphate 100 weight.h. concentrated sulfuric acid for 6 h at and immediately after that condense
    29 h with 75 weight parts. 30% water
    formaldehyde solution at 110-120s. At the end of this time, the reactions are diluted twice with 100 parts by weight. water. Output 475 parts by weight, solids content 45% by weight, acids
    2.2 g-eq / kg mixed with water indefinitely.
    d) Condensation polymer (H) -0. C-gHg: HjSO rCHjO 1: 1.4: 1.1. 128 weight.h. naphthalene sulfide
    110 weight.h. concentrated sulfuric acid for 6 hours at 160 ° C and condensed with 110 parts by weight 30% aqueous formaldehyde solution at lOO-llO c. The following dilutions are carried out and
    determining the conversion of formoldehyde at lOO-llO C after a specified time:, Interval, hours 3 26.5 30 45 72 78 Water addition, parts by weight, 100 - 100 - 50 Conversion of CHOO, wt.% - 81.8; - 87.5 90.9 90 Yield 570 wt.h ,, solid content 43 wt.%, Acid 2.16 g-eq / kgJ mixed with water unlimitedly. f) Condensation polymer {R) -E Naftsinsyn sulfonic acid: СН2О 1 {molar ratio). 343.8 weight, h. technical naphthalenesulfonic acid mainly two acids, 5.82 g-eq (kg) and 200 parts by weight 30% aqueous formaldehyde solution is condensed at 100 ° C. It is followed by dilution and determination of formaldehyde at 100-102 seconds after a specified time: Interval, Addition of water. Turn h weight.h, SNGO, be 5 1000 68,01080.0 & LHOD 877 weight.h. the solids content is 42.5 wt.%, the acid is 2.255 g-eq / kg, it is mixed with water indefinitely. g) Condensation polymer (H) -Z Naphthalene sulphonic acid: CH2O 1 (molar ratio). 348 weight.h. technical naphthalene sulfonic acid (mainly two acids, 5.82 g-eq (kg) and 300 parts by weight of a 30% aqueous solution of formaldehyde are condensed at 100 ° C. The following dilutions are carried out to determine the conversion of formaldehyde at 100 ° C after a specified time Interval, hours 4.5 21.5 42.0 64 Additive of water, parts by weight 100 Turning CH, 0, wt.% - 55.8 66.7 74 Output 686 parts by weight, solid content substances 57.2 wt.%, acids 3.00 g-eq / kg, mixed with water indefinitely. e) Preparation of urea-formaldehyde polycondensation products. Examples 1-3. 900 parts by weight are dissolved. urea in 2100 weight.h. water, heated to 70 ° C, 2250 parts by weight, are added. A 30% iodine solution of formaldehyde is condensed for 30 minutes at a pH of 7, a temperature of 70 ° C, and cooled to 50 ° C. This forcondensate is divided into 3 equal parts, which are mixed under the conditions given in table. 1, with solutions of condensation polymer (H) -B at 50 ° C and turned into a polymer gel. Each gel is kept for 2 hours at 65 ° C, crushed, mixed well with 2000 parts by weight. water and set using 2H, NaOH pH 7.5. The polymer is filtered off, dried overnight with a hot stream of air with a temperature, and crushed using a blower mill with a pressure of 40 atm. A very volumetric, white polymer powder is obtained with the following indicators: 123,400,404,401 Yield, parts by weight Surface area, 67.8 80.8 78.8 Average diameter of primary particles, 600 510 520 3.7 3.8 4.4 Agglomerate, µm Resid - moisture5, 6 5.8 5.4%, wt.% Bulk weight , g / l 124 100 125 Oil absorption, 200 228 174 wt.% Sulfur content, wt.% 0.4 0.7 0.9 Oil absorption in all examples is determined by the method of Wolff and Toeldte in wt.% DWR. Examples 4-6. The Y of the forcondensate, as for Examples 1-3, is divided into 3 equal parts, mixed at 50 ° C with a condensation polymer (H) -A and converted into a polymer gel (see Table 2). After crushing the gel is crushed to 2500 parts by weight. water, but, in addition, treated the same way as gels in examples 1-3. The performance of the polymer obtained is as follows: Yield, parts by weight Specific surface area, 58.1 Average primary particle diameter, - A 3.8 3.4 Agglomerate, µm Residual moisture, total 3.5% 3.5 Bulk density, g / l 39.6 33.0 Oil absorption, weight. % 371 391 Contents ce0, 7. 0.7. ry., weight% Example 7. Forcondensate, parts by weight: urea 180, 30% formaldehyde solution 450, deionized water 300, 30 minutes, pH 7.0 and. . Condension polymer (N) -B 28.7 parts by weight dissolved in 300 parts by weight of water, gel concentration 25 wt.%, mEq SO.H / mol of urea 20. Gel formation time 18 s, a rise in temperature of 50-65 ° C, gelation pH 2.1. Gel is treated with 1500 wt.h. water, further processing, as in Examples 1-3. The drive is 237 parts by weight, the surface weight is 70, the average diameter of the primary particles is 590 A, cf. the research institute has an agglomerate diameter of 4.3 And the residual moisture is 2/1 wt.%, bulk density is 130 g / l, the oil absorption is 227 weight. DVR, the sulfur content of 0.7 wt.%. Example 8. Urea 300 weight of deionized water 700 parts by weight, .30% aqueous formaldehyde solution 750 parts by weight, 30 minutes, pH 7 and. The condensed polymer (H) -E. 57.9 parts by weight dissolved in 816 parts by weight of water, gel concentration (% U + 20, mEq SO, H / mol urea 25. Gel formation time 25 s, gelation pH (not indicated), temperature rise 5 ° -62 ° C, the gel is treated with 2500 parts by weight at pH 7.5, yes Lee is dried and treated as described in examples 1-3. The yield is 397 weight specific surface / ton, medium primary particle diameter 650.A, the average diameter of the agglomerate is 3.5 / U and residual moisture 3.5 parts by weight, dry weight 37 g / l, oil absorption 339 weight% DWR, sulfur content 0.75 weight ..%. Examples 9-20. Table 3 shows examples in which use condensation poly ep (H), type B (examples 9-14) and type G (examples 15-20). Both series show the dependence of the properties of the polycondensate obtained in this way on the molar ratio of formaldehyde / urea. 31. These examples are summarized in Table 4, d, for which various concentrations of gelation and amounts of catalyst are given, 7. Condensation polymer (H) and type G are used in various concentrations. The concentration of 3.6 24.0 424 0.8 of the gelation and catalyst also changes. Examples 32-44. These examples are explained in Table. 5 and relates to the preparation of the proposed method of urea-formaldehyde condensation products with the combined use of various comonomers. The corresponding comonomers are introduced in essence already upon receipt of the forcondensate (y), i.e. The number of comonomers is already in the reaction mixture at the forcondensate (s). C. Contrary to these methods according to examples 32-38, comonomers are added only after the forcondensate 1) and condensation polymer H) are obtained to the reaction mixture for the final polycondensation, i.e. here it is introduced into the polycondensate only at the last stage. Table 1 Condensation polymer, (H) -B, weight.h. 47.2 53.1 55.1 303 530 815 water, parts by weight 25 22.5 20 Gel M + F, wt.% Mg-SQV SOjH / mol 22.5 25 months Gel, 29 g of gel, pH of gel 2 , 1 2.1 2.1 vani Temperature rise up to, C 656463 Table 2 Condensation sample (n) A,: h.ch. 46.2 52.0 58.0 300 530 820 Water, weight.h. 25 22.5 20 Gel M + F wt.% MEq SOjH / mol 22.5 23 urea Time Formation 20. 22 no gel, with H gel 2, 0 2.0 2.0 vani
     t Table 4
    Mochzvina, weight.h. 180 180 180 180 180 weight.h. . 500 500 500 500 150 30% formaldehyde, parts by weight 510 510 .510 510 510 Voronden Satsi 30 min, pH 7 Condensation Palimer (H) -ZH /; weight.h. 33.3 29.0 25.0 22.5 20, Solubility in parts of NBO, weight.h; 998 685 450 270 472 Concentration Geleob-. rae, wt.%. 15.0 17.5 20.0 22.5 25, Mg-eq of the condensation polymer (H) per 1 mol of urea 33.3 28.6 25.0 22.5 20, Gel time. p .50.0 44 38 36 33 Temperature rise from to С 58 V 58 61 61 63 Output, parts by weight 223 224 230 230 238. Specific surface, m2 / g 53.9 68.9 78.6 76.6 74 Residual moisture, wt.% 4.2 4.8 4.3 4.3 3, Bulk, weight, g / l 280 230 133 133 122 90 Oil absorption,% DWR 121 121 203 233 319 Content of methylol groups, wt.% 252 - 2.36 - 2.0 80 180 180 180 1.80 180 50 150 10 510 510 510 510 510 70 ° WITH . 18.5 17.0 15.5 14.3 13.4 12.5 55 260 170 248 185 130 27.5 30.0 32.5 35.0 37.5 40.0 18.2 16.7 15, four. 14.3 13.3 12.5 28 25 26 23 21 19 65 66 67 G7 69 70 40 242 237 216 228 235 70.4 69.4 66.2 64.4 65.2 62.7. 5.8 5D 4.7 3.1 3.3 3.1 80 89 88 10.1 94 105 79 399 409 336 350 353. . - 2.61 2.30 3.09 3.32 3.25
    权利要求:
    Claims (1)
    [1]
    1. A method for producing highly dispersed, solid urea-formaldehyde condensation polymers, comprising reacting forcondensate from urea and formaldehyde with a reagent containing sulfo groups in an aqueous solution at a temperature from 20 to a gel that differs in that, in order to increase, the quality of the target product, as a reagent, containing sulfo groups, use condensation polymer naphthalenesulfonic acid and formaldehyde, the interaction is carried out at a concentration of pea concentrations of 15 to 40 weight,% and mole The ratio of the total amount of formaldehyde to the total amount of urea is 1.25 to 2.
    2, the method according to claim 1, characterized in that the gel obtained is crushed, crushed, neutralized, filtered, dried, and the product obtained in this way is milled using a mill or processed to extrude to a granulate.
    Sources of information taken into account during the examination
    1. British Patent 1318244, C 3 C, 1973.
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    同族专利:
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    US4010132A|1977-03-01|
    GB1501217A|1978-02-15|
    JPS5811451B2|1983-03-03|
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    US4452934A|1981-09-28|1984-06-05|Georgia-Pacific Corporation|Aminoplast resin compositions|
    FI832553A|1983-07-19|1985-01-14|Gosudarstvenny Nauchno- Issledovatelsky I Proektny Institut/Po Obogascheniju Rud Tsvetnykh Metallov Çkazmekhanobrç|POLYMER MATERIAL FOR PHYSICAL AND CHEMICAL PROCESSING OF OIL FOR FARING FRAMSTATION OF MATERIALS.|
    JPH0212352U|1988-03-11|1990-01-25|
    US5110898A|1988-11-28|1992-05-05|Georgia-Pacific Corporation|Method for manufacturing amino-aldehyde compositions|
    US4960856A|1988-11-28|1990-10-02|Georgia-Pacific Corporation|Urea-formaldehyde compositions and method of manufacture|
    US4898908A|1989-01-26|1990-02-06|Kuwait Institute For Scientific Research|Anionic polymer hydrogels and a process for making the same|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    CH780974A|CH599260A5|1974-06-07|1974-06-07|
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