• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
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  • 优先权
    • 专利摘要:
    1530580 Phenolic resins CPC INTERNATIONAL Inc 15 July 1977 [22 July 1976] 29853/77 Heading C3R A resin is made by reacting, in the presence of an acid catalyst, (1) an aldose saccharide, (2) a phenol, and (3) urea or a di-primary amine. Use.-Making resoles as laminating adhesives.
    公开号:SU784787A3
    申请号:SU772505305
    申请日:1977-07-21
    公开日:1980-11-30
    发明作者:П. Гиббонс Джон；Вондоловски Лоренс
    申请人:Спс Интернэшнл Инк (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD FOR OBTAINING CARBON DOPER
    one
    The invention relates to the field of production of thermosetting X Cl-1; ol, in particular a carbohydrate-phenol resin.
    A known method for producing a carbohydrate-phenolic resin by condensation of 5 dextrose or starch, phenol and an amine in the presence of a mineral acid by heating. However, the resin obtained in a known manner does not have sufficient water capacity and elastic modulus.
    The aim of the invention is to increase the water resistance and the modulus of elasticity .15
    This goal is achieved by using a compound selected from the group: urea, toluene, amine, ethylenediamine, with the following molar 20 ratio of components, respectively, dextrose (starch): amine: phenol-1: 0, 25- 1: 1, as a mineral acid, sulfuric and condensation is carried out at 95-194 "C.25
    If the reaction is stopped in the liquid phase, then this resin can be reacted with an aldehyde to form a resole resin. You can get a solid, smooth resin, 30
    if given the opportunity to continue the first stage of the reaction.
    Solid fusible resins obtained by the proposed method are characterized by good water resistance and high durability.
    In carrying out the invention, the preferred carbohydrate is dextrose, although, if desired, many other carbohydrates can be used. In general, aldososaccharides containing from 1 to 10 saccharide moieties in a molecule can be used, with hexose being the preferred aldose. You can use dextrose, maltose and maltotriose, lactose, sucrose, glycogen, glucosyls, corn syrup, hydrolyzed dry residues of elans with a low degree of elasticity, etc.
    Also suitable for use in the practice of the present invention are various starches containing up to 10 repeating fragments. Starches suitable for the use of the proposed method include all possible starch varieties, such as corn starch, tapioca starch, wheat starch, lepeH sorghum starch, and potato starch.
    R.: Igo starch, sago starch, etc., as well as all its types and varieties, including unprocessed starch with a high amylose content, chemically modified starches, dextrins, narrow-boiling starches and pre-kelatinized ones. This includes raw starches, such as factory starch, flour made from grain, flour made from wheat, choux grains, ground rice, etc.
    Acid catalysts used in the practice of the invention are typical acid catalysts used in the condensation of aldehydes with phenols and urinary. These include strong mineral acids, for example, sulfuric, hydrochloric, etc .; sulfonic acids, including i-toluenesulfonic acid, naphthalenesulfonic acid, etc .; sulfur trichloride, antimony chloride.
    Condensation is carried out at a temperature of from 70 to 200 ° C, and the reaction time depends on the reaction temperature.
    The resulting solid smelting resin is a brittle material that can be thermally structured by adding an appropriate amine ti crosslinking agent, preferably hexamethylene tetramine, the resins thus obtained are thermosetting and find wide use as a molding resin and a resin for cortical casting. They are distinguished by excellent water resistance and improved qualities, in particular elasticity.
    It is easy to work with the liquid resin used to make the resole resins, and it has the necessary viscosity when mixing and adding an aldehyde reactant and an alkaline catalyst to produce a resole resin. Moreover, it was found that the liquid state of the resin can be controlled by controlling the amount of water produced. It is preferable to control the amount of water produced by condensation to a level not exceeding 5.0 M MOL in the reaction. Attempts to dissolve solid fusible-resins, when interacting with formaldehyde, were difficult, as the viscosity remained unsuitable for use levels.
    Example. In this example, the implementation of the proposed method is illustrated when dextrose, urea and phenol are used as a reagent.
    In the reaction vessel with a capacity of 1000 ml, equipped with a condenser, a stirrer and a thermometer, loaded 360 g of dekostrose, 60 g of urea
    and 208 g of 90% phenol, which corresponds to the molar ratio of dextrose: urea: phenol - 1: 0.5: 1
    To the reaction vessel was added 2.5 ml of 5N sulfuric acid as a catalyst, and the vessel was heated to a temperature in the range of 123-182; Within 8.6 hours, 171 ml of water was removed from the reaction vessel over a period of time,
    As a result, the obtained resin was extracted from the reaction vessel, which at room temperature had the appearance of a solid black material.
    Example2. This example illustrates the use of starch as a carbohydrate in the preparation of a carbohydrate-phenolic condensation resin.
    In a 500 ml reaction vessel, starch (Ag Code 3005) was loaded with 104 g of 90% phenol, 100 g of water and 14 g of 5H. .
    The resulting mixture was first stirred at a temperature of 95-114 ° C to hydrolyze the starch and form a black solution, from which 105 ml of water was separated.
    At this stage, 30 g of urea was added to the vessel and a condensation reaction was performed at a temperature of from 114 to 183 s for 6.4 hours. During this time, another 101 ml of water was obtained from the reaction vessel.
    The resulting resin weighed 210
    The room temperature was a brittle solid material.
    PRI me R 3. Using the methods and installation of example 2, in the reaction vessel was loaded 360 g of dextrose 60 g of urea, 204 g of 90% phenol and 9.6 g 5i. . In about 9.1 hours, only 206 ml of condensed water was collected, and the reaction temperature in the vessel varied from 118 to 185 ° C.
    380 g of black resin, fragile at room temperature, was recovered from the reaction vessel.
    Example4. In this example, a method is illustrated in which a resin is prepared in the presence of an amine fatty acid to increase the water resistance of the resin and the fusibility of the final thermosetting resin.
    180 g of dextrose, 30 g of urea, 104 g of 90% phenol, 9 g of ARMEEN-T-Ta11oN amine and 1.4 g of 5N are charged into a 500m reaction vessel. Hjso. The reactants interact in the reaction vessel at a temperature of from 129 to 189s for 4.9 hours; during this time, 97.5 ml of condensation water was collected.
    The resulting resin was removed from the reaction vessel in the form of black material, brittle at room temperature.
    EXAMPLE 5 This example shows the effect of the change in the molar ratio of dextrose-urea-phenol on the physical properties, namely the water resistance and fusibility of the resin.
    A. Dextrose-urea-phenol 1: 1: 1 molar ratio was used when 60 g of urea, 104 g of 90% phenol and 2.8 g of 5H were loaded into the reaction vessel. The reaction temperature ranged from 127 to
    194 C, and during the reaction time of 6.1 h 112 ml of condensed water was collected.
    B. Used dextrose-urea-phenol molar ratio
    1: O, 75: 1, which was obtained by placing in a reaction vessel 180 g of dextrose, 45 g of urea, 104 g of 90% phenol and 1.4 g of 5N. H. The condensation reaction lasted for 4.7 hours at a temperature of 130 to 180 ° C., while 98.5 ml of condensation water was collected.
    C. The molar ratio of dextrose-urea to phenol, corresponding to 1: 0.25: 1, was achieved when 180 g of dextrose, 15 g of urea, 104 g of 90% phenol, 9 g of ARMEENT and 1.4 g were placed in a reaction vessel. 5H. Within 4.8 hours, the temperature of the reaction vessel was in the range from 129 to, while 91 ml of condensation water was collected,
    PRI me R b. This example illustrates the use of toluene diamine as a nitrogen-containing crosslinking agent.
    In Example 1, 180 g of dextrose, 61.1 g of toluene diamines, 104 g of 90% phenol and 1.4 g of 5H were loaded into a 500 ml flask. . The reagents were kept at a temperature of from 113 to 4.2 hours, during which 79 ml of condensation water was collected.
    Received 200 g of black resin, brittle at room temperature.
    Example. This example illustrates the use of ethylene diamine as a crosslinking agent in the implementation of the proposed method.
    According to the method described in Example 6, the reaction mixture was obtained from 180 g of dextrose, 300 g of ethylenediamine, 104 g of 90% phenol and 1.4 g
    five"
    a.SO as a catalyst.
    The reaction lasted 5 hours and the temperature of the mixture changed during this time.
    o from 111 to 178 ° C.
    At the same time allocated only 56 ml of condensation water. The resulting resin was a black material, fragile at room temperature.
    PRI me R 8. This example illustrates the use of resins, obtained by the proposed spisobu.
    Each of the resins obtained in accordance with the methods of examples 1-4, 5A, 5B, 5c, bi7 was incorporated into the following composition, g:
    Resin4 6
    Hexamethylenetet- Different ko5
    humanism
    Calcium Stearate 2.0
    Calcium Oxide 2.0
    Wood flour 46,
    Each of the resins introduced into the specified composition and melted at 200 ° C ()
    0 for 2 min. Then, the resulting composition was molded in the form of bars (5 0.5 X 1/8) by melting at 350 ° F (177 ° C) for 5 minutes.
    The test bars obtained were subjected to tests to determine their water resistance, first the test bars were brought into contact with boiling water for 2 hours, and in another experiment, by immersing them in water for 24 hours, in accordance with the requirements of AS TMO 57063 (6a ).
    Testing was also conducted to determine the elastic moduli of these bars.
    The results of these tests are given in Table 1 (in a pa-account for the weight of compounds).
    iT a l and c a 1Note. Data for the sample and therefore omitted. As can be seen in Table 1, the resins obtained according to the method of the invention do not have good water resistance and durability. EXAMPLE 9 This example was carried out for comparison with HssiecT methods and illustrates the use of monofunctional aa, aniline, A. In a 1000 ml reaction vessel of the type used in Example 1, 183 g of dextrose were placed. 93 g of aniline, 103 g of 90% phenol and 1.5 g of 5H .H LSClj,, Reac. Continuation of table. 1 were considered uncharacteristic condensation continued for 145 minutes, at a temperature that varied from 109 to. Total collected 95 ml of condensation water. B. In the same way as described above, 180 g of dextrose, 53 g of 90% phenol, 94 g of aniline and 1.3 g of 5N were placed in a reaction vessel. The reaction lasted 4.7 hours at temperatures ranging from 113 to 16 ° C. In total, 83 ml of condensation water was collected during the reaction.
    C. According to the method described in prize winner 8, the resin was introduced into the composition, crushed, melted into bars, as indicated in Example 8. As follows from the data of Table 2, the use of analytes, as in the previously known methods, results in The bars with good water resistance, however, the strength, expressed in moduli of elasticity, is lower in these bars than in those that were obtained using urea as a crosslinking agent. An example. This example illustrates the use of corn flour as a carbohydrate in the proposed method. The following ingredients were loaded into a 500-volume reaction vessel: 184 starch (yellow corn flour), 104
    Example 11 This example illustrates the preparation of a resole resin according to the method of the present invention by reacting a dextrozoamine phenolic liquid resin and formaldehyde to form a resole resin.
    Bars were tested in Example 8.
    The results are shown in table 2
    Table 2
    The reaction vessel was placed. 270 if dextrose, 45 g urea and 156 g phenol (90% by weight), and 13.5 g 5.0 was added as a catalyst. H2, SO. The reaction proceeded at a temperature of from 125 to 153 ° C for 4 hours of phenol (90%), 30 g of urea and 40 g of 5N. Starch was added to the vessel in two portions, hydrolysis reactions were allowed to proceed for 3 hours, after which urea was added. The condensation reaction proceeded for 8.2 hours at a temperature of from 112 to 186 ° C, while 118 ml of water was collected. A solid black material was obtained, brittle at room temperature (yield 223 g). The resulting product was introduced into the composition, crushed and tested for water resistance and durability. The results are presented in Table 3. Table 3 and ja this time collected 112 g of water using a water-cooled fridge. The resulting resin had a dark liquid. The liquid resin was cooled to about 90 ° C and the condensed water was again poured into the reaction vessel. At this point, 13,, O g of calcium hydroxide was added to neutralize the acid and create a basic catalytic system. The reaction temperature was lowered to about and added 450 g of aqueous (by weight) formaldehyde. The reaction was carried out with stirring until heat generation ceased. Then the reaction cNKJCb was kept for about an hour at the temperature. Then, the resol resin was cooled to room temperature and a liquid product with a viscosity of about 500 cP was obtained. The final solids content was 49.4% by weight. Thus, the molar ratio of reagents in this example to form an intermediate resin is V1 mole of dextrose; 0.5 mol of urea: 1 mol of phenol, and for the step of producing a resole resin, about 3.5 mol of formaldehyde per mol of phenol. Example 12. Resolar resin prepared in Example 12 was used as a glue for plywood, the composition of the glue was as follows, g Distilled water 86.3 Durum wheat flour 9.0 Norparfil (filler) 27.0 Resol resin (49.4 %) 34.3 50% NaOH .9.4 Sodium carbonate 3.6 Resolymer resin (49.4%) 121.9 The final viscosity of the adhesive was about 2100 cP. Then, the glue was applied on three sheets of 12 Oouqlas Fir of Southern Pine plywood size 0.3 once. Plates were folded together and cured in the process with heating (285 ° F, 140 C) at a pressure (12.23 kg / cm). ) to reduce the curing time of the glue (about 4.5 minutes). The laminates obtained using the new resole resins of this example demonstrate excellent water resistance in boiling water for 18 hours without delamination. Example 13 This example illus 1: trials the preparation of the resole resin of the present invention when starch drolysate or corn syrup is taken as the starting position. 332 g of starch hydrolyzate with a dry content of about 81% by weight was placed in a reaction vessel at a temperature of about and added 8.1 g of 5N, H, acid. The reaction was carried out for 2 hours before decomposition of the dextrose began, and then 45 g of urea and 156 g of phenol (90%) by weight were added. The reaction proceeded at a temperature of about 112-163 C for 6 hours, during which time 152 g of water was collected in a water-cooled refrigerator. Got the resin in the form of a dark liquid product. This liquid resin was cooled to about 90 ° C, and the condensed water was again poured into the reaction vessel. At this time, 13.0 calcium hydroxide was added to neutralize the acid and to form the main catalytic system. The reaction temperature was lowered to about 70 s, after which 375 g of aqueous 35% (by weight) formaldehyde was added. The reaction was carried out with stirring until heat generation ceased. Then the reaction was continued for one hour at about. Then, the resol resin was cooled to room temperature and a liquid product with a viscosity of about 500 cP was obtained. The final solids content was about 51.4% by weight. The composition of the plywood adhesive was made according to Example 13. The final laminates obtained, flattered using resole resin, demonstrated good water resistance in boiling water for 2 hours without exfoliation. Example14. This example illustrates the production of resole resins using the proposed method, where formaldehyde is added to the dextrose-amino-phenolic liquid resin at a different molar ratio of reagents, and results obtained in the manufacture of layered plywood using new resole resins. The compositions LIQUID; OH resin and rezol resin of Example 11 were used, with the exception that other molar ratios were used. The results are presented in tab.4.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    A method for producing a carbohydrate phenol resin by condensation of dextrose or starch, phenol or amine in the presence of a mineral acid when heated, characterized in that, in order to increase the water resistance of the elastic modulus, an amine uses a compound selected from the group: urea, toluene diamine, ethyleneTab 1itsa4
    diamine, with the following molar ratio of components, respectively, dextrose or starch: amine: phenol 1: 0, 25-1: 1, as mineral acid, sulfuric acid and condensation is carried out at 95-194 s.
    Sources of information taken into account in the examination of 35 1. US Patent No. 1753030, cl. 260-67, publ. 1929.
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    同族专利:
    公开号 | 公开日
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    MY7900164A|1979-12-31|
    US4085076A|1978-04-18|
    SE7707501L|1978-01-23|
    NO146474B|1982-06-28|
    ZA774445B|1978-06-28|
    FR2359168A1|1978-02-17|
    SE8204645D0|1982-08-11|
    ES460911A1|1978-05-16|
    GB1530580A|1978-11-01|
    SE8204645L|1982-08-11|
    BE856965A|1978-01-20|
    NO772603L|1978-01-24|
    FI772250A|1978-01-23|
    NL7708038A|1978-01-24|
    NO146474C|1982-10-20|
    FR2359168B1|1984-04-13|
    DE2732992A1|1978-02-02|
    FI64612B|1983-08-31|
    FI64612C|1983-12-12|
    AT368765B|1982-11-10|
    CH633815A5|1982-12-31|
    US4048127A|1977-09-13|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US05/707,600|US4048127A|1976-07-22|1976-07-22|Carbohydrate-based condensation resin|
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