• 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:
    Disclosed herein is a method for stabilizing the viscosity of polyvinyl acetal resins, especially those resins used as interlayers for laminated safety glass. The disclosed process comprises incorporating a buffer having a pH in the range of from 3 to 7 into the plasticized polyvinyl acetal.
    公开号:SU900815A3
    申请号:SU762390473
    申请日:1976-08-12
    公开日:1982-01-23
    发明作者:Эдвард Монт Джордж；Артур Снельгроув Джеймс
    申请人:Монсанто Компани (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to a method for stabilizing the viscosity of polyvinyl acetate resins, in particular, used as intermediate layers for laminated safety glass, 5 which has found application in various kinds of means of transport, for example for wind-proof glass for automobiles, as well as for architectural purposes.
    There is a method of stabilizing polyvinyl butyral resins in their bones during their processing into sheet material. In this case, plasticizers are introduced in the preparation of shatterproof glass. The polyvinyl acetal intermediate layers are subjected during the extrusion process to elevated temperatures, as well as during the drying of the obtained sheets and to the manufacture of the layered product 20 from sheets 1.
    However, elevated temperatures cause the destruction of polyvinyl acetal, which is reflected in a decrease in viscosity and yellowing.
    Bones can also occur during the aging process.
    The purpose of the invention is to obtain polyvinyl acetal intermediate layers with increased viscosity stability.
    This goal is achieved by the fact that before processing 0.002-0.13 by weight of the initial resin buffer with a pH of 3-7 is introduced into the resin.
    Figure 1 shows a graph of the percentage decrease in viscosity relative to the pH of the buffer compound; Fig. 2 is a graph showing the different components included in the citrate buffer system at different pH values.
    The buffers used include citric acid (curve A), monosodium citrate (curve B), disodium citrate (curve C) and trisodium citrate (curve D).
    Polyvinyl butyral resins have a Staudinger molecular weight of 50,000-600,000, preferably 150000-270000, and contain SZO by weight,% hydroxyl groups (considered polyvinyl alcohol ohm), and wt% of sloe ester groups (preferably acetate), and the alignment compound is mainly acetal, If the acetal is butyl aldehyde acetal, the polyvinyl acetal resin preferably contains 12–25 veCo% hydroxyl groups (considered polyvinyl alcohol) and 0–3% by weight of ester groups (for example, acetate, and vinyl ester), while the equilibrating compound is mainly butyraldehyde acetal To polyvinyl butyral resin may contain 20-80 parts by weight. plasticizer per 100 parts by weight; resin, in the case of a change for wind-proof glasses, usually up to 20-50 weight. Cho (especially for polyvinyl butyrals containing 1223 weight. of vinyl alcohol). Plasticizers are esters of polybasic acids or a polyhydric alcohol, in particular triethylene glycol di (2-ethyl butyrate), di butyl sebacate, dihexyl adipate and a combination of dihexylamine with a phosphate plasticizer. Buffer compounds for pH adjustment are systems that prevent changes in pH when acids or bases are added to the system. The buffer should not contain hydrochloric, nitric, and sulfuric acids, which can cause resin degradation. buffer components include phosphates (sodium acid phosphate, disodium phosphate, dipotassium phosphate, ethyl acetate and the corresponding pyrophosphates, tripolyphosphates and tetraphosphates); citrates (sodium citrate, disodium citrate, dipotassium citrate, tri-potassium citrate, tac-monopotassium citrate, acid ethyl citrate and dimethyl citrate); orthophthalate (acid sodium orthophthalate, disodium orthophthalate, acid potassium orthophthalate, citrate, glyphite); borates, (acid borate, sodium disodium borate, dipotassium borate, acid borate of ethyl, and corresponding meta and tetraborates); potassium compounds (potassium tetraoxalate, potassium hydrotartrate, acid potassium succinate, potassium succinate, acid potassium phenylsuccinate, potassium silicate, potassium sulfosalicylate, acidic 1.2, cyclohexane-potassium dicarboxylate, acidic 2, Znaphthalin dicarboxylate, potassium, two-acid 1, i, 5, 8 - neftaline tetracarboxylate diqually); phosphoric acid monoesters and partially neutralized amino salts. Preferred buffer systems include phosphates, citrates, phthalates and borates of alkali and alkaline earth metals and a combination of citrate / phosphate. Preparation of buffer solutions. The purity of the material, Sol acid acid 0.2 n. and 0.1 n. usually chemically pure, prepared and standardized according to the usual titrimetric procedure. Sodium hydroxide 0.1 n., Prepared free of carbonates and standardized according to the usual titrometric procedure. Acidic phthalate of potassium KNS5NtsNts, 2. A chemically pure product, available in stock, is fairly pure. It can be recrystallized from water and dried at 110-120 ° C. Purity should be checked by titration with standardized sodium hydroxide using phenolphthalein or thymol blue as an indicator. O, 1M salt solution is prepared as the main solution. Monopotassium phosphate KHjROts, M 136.2. The chemically pure salt available, recrystallized twice from water and dried at 110-120 ° C. A 0.1 M salt solution is prepared as the main solution. Potassium chloride KS,, 6. A chemically pure product is twice recrystallized from water and dried at 120F. Boric acid H BOj,, 0. The chemically pure product is twice recrystallized from water and dried at 120 ° C. Borne acid HjBOj,, 0. The chemically pure product is recrystallized and air dried. A 6.1 M solution of boric acid in O, 1 M potassium chloride is prepared as the main solution. Table 1 shows the composition and pH of the Clark and Labs buffer mixtures with the Composition and pH of McIlwein buffer mixtures. The main solution (A) is 0.2 M di-sodium phosphate. Dissolve g of chemically pure crystals in 2 liters of COj-free water., Titrate 10 ml with 0.1 and. IS1 and a drop of methyl orange indicator to achieve a color given by a 30 ml solution containing 2.28 g of chemically pure, and 1.0 g of chemically pure NaCI and 250 ml. Adjust solution A to obtain 20.00 ml of 0.1 N. NA in the re-titration. The main solution (B) is 0.1 M citric acid. Dissolve kS g of chemically pure crystals and dilute to 2 liters. Titrate 10 ml with 0.1 N, NaOH (free of carbonates) and phenolphthalein indicator a to adjust solution B to obtain 30 ml in the repeated titration. 0.1% toluene may be added to store Solutions A and 8. To prepare the buffer mixtures, mark the required volume of solution A for the desired pH in the measuring pipette as shown in Table 2 and add the appropriate solution B to obtain an amount of 10.00 ml. Buffer systems are usually complex systems containing more than one class of chemical compounds for any value of p. The nature of the classes of compounds present is pH dependent. On the graph (figure 2) at pH k there are four different classes: citric acid (8.5 wt.); monosodium citrate (77.0 wt.); disodium citrate (H, 0 wt,) and trisodium citrate (0.5 wt. 1). The buffers used are pH 3-7. Lower pH values should be avoided in order to prevent the destruction of the resin. At pH values above 7, the stabilization of viscosity is less pronounced. The amount of the buffer compound used is 0.002-0.13 S based on the weight of the initial resin, 8 if a larger amount of the buffered compound is used, the required physical properties or optical properties of the intermediate layer made of laminated safety glass can be lost. The buffer must be compatible with the polyvinyl acetal resin and should not have any adverse effect on the physical or optical properties of laminated safety glass made of polyvini acetal resin. Buffer compounds can be added to the polyvinyl acetal resin during any conventional resin treatment process (washing, drying, etc.). Buffers can also be added to the plasticizer used for the resin, while being added to the resin in the plasticization step. The buffer can also be added to the resin during molding, for example, extruding the resin to form a sheet. Preferably, the buffer compounds are added to the resin before it is processed to form a sheet product. The buffer is introduced simultaneously with the introduction of the plasticizer into the polymer or prior to the supply of the plasticizer. Buffer is prepared with 8 aqueous solution in order to achieve a pH of 3-7. After that, the buffer solution is added to the polyvinyl acetal resin. During extrusion or drying-in-air in a thermally unstable resin, viscosity is significantly reduced and yellowing occurs, indicating destruction of the resin. In the resins buffered according to the invention, the initial viscosity is maintained a significant extent, and in many cases the yellowing does not exceed that of the unbuffered resins. Example 1. Experience in the oxidation of plastic. 100 weight.h. the resins are mixed with the calculated amount of plasticizer and buffer compounds in the flask to obtain a homogeneous system. A sample of plasticized resin is placed in an air circulating oven at 130 ° C for S min. The control sample is maintained at room temperature. The viscosity of the control and heat treatment sample is measured in a methanol solution containing 7-1 to 2% resinous solids. Viscosity measurements were carried out at 20 ° C using an Ostwald-FensKe Viscometer viscometer. The percentage retention of the viscosity of the heat-treated sample is then calculated to determine the thermal-oxidative stability of the buffered resin. The change in viscosity is calculated as follows:
    The initial viscosity-viscosity on processing "." "O,
    --- EAX 1004 and changes
    original eco
    The plastic oxidation test is intended primarily for shielding. Under the conditions of the experiment, no attempts are made to eliminate the air; therefore, changes in viscosity and yellowing are more significant than in the case of measurements under extrusion conditions.
    Determination of the percentage yellowing. Percent yellowing is determined using a 7.5% resin solution in methanol and a KlettSumraer-Son Photoelectric CoJorimeter colorimeter. Absorbance is measured at 2Q MMK using a blue filter and at 660 MMK using redo Data are converted to percentages. By subtracting the read results at 2G microns from the read results at 660 microns, a percentage yellowing is obtained. These values indicate the amount of yellowing of the resin. .
    The mixture in the plasticizer Braben dera. An appropriate amount of plasticizer is added to tO.O g of polyvinyl butyral resin, then the mixture is mixed by hand to form a homogeneous mixture. The plasticized resin is then placed in a mixing chamber of the Erabender plastograph (model (f 537) equipped with sigmoid blades, manufactured by Brabender Corp., Roche lie Park, NeWSers) The sample is then mixed for 7 minutes at 150 C and 50 rpm (blade speed). The sample is then tested for viscosity reduction and percent yellowing.
    Examples 2-21. A series of buffer solutions is prepared (the compounds used in the examples are the buffer mixtures according to Clark and Lubs, the citrate / phosphate buffers used in the examples are those with the buffer mixtures according to Us Ivaine). Buffer solutions are added to a polyvinyl butyral resin with a viscosity of 230 centipoise with a ratio of 1000 parts by weight. buffer (in terms of dry weight) per 1,000,000 weight.h. resin (0.1%). The butyral resin contains 18-2U polyvinyl alcohol, the residual acetate is less than 2.5 wt.%, And is balanced.
    resin mainly butyral groups. The resin titer level is 106 cm due to the presence of potassium acetate. The resin and the buffer mixture is then mixed with 2 parts by weight. triztilenglikol-di (2-ethyl butyrate) plasticizer per 100 weight parts of resin. The resin, buffer and plasticizer are thoroughly mixed, the resulting plasticized mixture is subjected to experience in the oxidation of plastic. By conducting this test, viscosity measurements were performed on the treated sample.
    The results of the experiments are given on table.3.
    Examples 22-27. Carry out as described. The resulting waste is used, and in examples 2 and 27 to 20 weight. the resulting waste and 30% by weight of commercial waste (the waste contains a triethylene glycol-di- (2-butybutyrate) plasticizer.
    The results are shown in Table.
    As can be seen from the table, in polyvinyl butyral compositions buffered according to the invention, the yellowing is less than in the corresponding unbuffered samples.
    Examples 28-31. The resin used is polyvinyl butyral resin, plasticized using t42 wt.Cho per 100 wt, h „resin of a plasticizer based on triethylene glycol col di (2-ethyl butyrate). 100 parts by weight are added to the sheet product. per 1,000,000 weight.h. Macllvain citrate / phosphate buffer system (0.1%) with a pH value of 3. The extruded sheet is subjected to a decrease in viscosity and yellowing.
    The results are shown in table.5.
    As can be seen from Table 5, the sheet product extruded from polyvinyl butyral resin, buffered according to the invention, has a greater viscosity and less yellowing than control samples that do not contain a buffer compound.
    Table 6 shows the effect of buffer (pH 3) on the change in viscosity when applying the plastic oxidation test. Resin and buffer system according to example 29.
    Examples 32-37. Polyvinyl butyral resin, plasticized 33 weight.h. dihexylapipate per 100 weight of parts of resin, subjected to experience in the oxidation of plastic. Three different pieces of this material from two different sources are used. The plasticized resin is treated with a buffer containing 100 parts by weight. (0,0li) Macllvaine buffer system (citrate / phosphate, pH 6). Samples are tested for a percentage reduction in viscosity. The results are shown in Table 7.
    As can be seen from Table 7, in the plasticized resin buffered according to the invention, there is less viscosity change during the plastic oxidation test.
    Example 38. A two-layered unit (separate glass) is connected to a sheet with a thickness of 7 x 2 µm from plasticized polyvinyl butyral and tested for strength (resistance in mold for accelerated aging). In poivini butyral resin plasticized with kZ, weight.h. triethylene glycol di- (2-etibuticate), 100 parts by weight are added. buffer systems of examples 32-37 with a pH of 5.5. Applies also to the control, where the polyvinyl butyral sheet contains 38 weight.h, plasticizer. Samples are processed in air circulation at 65.6 ° C. At certain intervals, the samples are tested for resin viscosity, plasticizer content and alkaline titer levels.
    Alkaline titer - the number of milliliters of 0.01% of the usual hydrochloric acid needed to neutralize 100 g of polyvinyl acetal resin. This test is standard and is used to determine the alkalinity of the resin. Alkaline titer is determined with a solution of 7 g of polyvinyl acetal sheath in 250 cm of pre-neutralized ethyl alcohol and titrated with 0.005 n hydrochloric acid to the final point using bromophenol blue indicator. The calculation is made taking into account the results obtained in order to determine the number of milliliters of 0.01 n. acid required for 100 g of resin. The results are shown in table.8.
    As can be seen from Table 8, when the resin is treated with a buffer compound according to the invention, the stability of the resin is increased.
    Example 39. The procedure is carried out analogously to example 38, however, polyvinyl l acelium ci-yula in a bilayer product is coated on the inside with a film of polyethylene terephthalate. There is no change in the content of the plasticizer, since the film of polyethylene terephthalate prevents the plasticizer from being lost. However, changes in viscosity and titer levels are observed.
    The results are shown in Table 2.
    As can be seen from Table 9, the resin, which is blacked out according to the invention, is characterized by an increased stability of viscosity.
    Table 1
    0.2 n. HCt +0.2 n. KS 1, diluted
    ,five
    32.25
    20.75
    13,15
    8.3 to 100 ml
    1.0 1.2
    1, 1.6
    1.8
    15
    / acetic acid
    900815
    16 Table 2
    Table 3
    60.5 26.9 36.9 36.9 C2, () 30, 37L 35.2 39.6 "5.6 57. 58.7
    69.5
    17
    Buffer amount
    Buffer on
    1,000,000 weight.h. resin, parts by weight (%}
    22
    23
    2k
    25 26
    27
    7,6
    +7.6
    90081518
    Continuation of table 3
    Table3 C
    Otkryzheldy, smoldering,
    %
    Table 5
    Oh oh
    50 50
    nineteen
    900815
    20 T a blitz 6
    Table 7
    21
    Control
    160 Viscosity resin, spP
    The content of the plasticizer, parts per 100
    Caption, cm
    Buffered system Viscosity of resin, spP
    The content of the plasticizer, parts per 100
    Title, note, partial
    Control
    Resin viscosity
    Titer,
    Bumpy
    Resin viscosity
    Caption, cm
    权利要求:
    Claims (1)
    [1]
    The invention of the sources of information.
    The method of stabilization of viscosity poly-taken into account in the examination of vinyl butyral resins in the process of processing them into sheet material, 1. Ushakov S.N. Polyvinyl
    the implication is that before the interstate and its derivatives, M.-L.,
    0.002-0.13% of the USSR Academy of Sciences, 19b9, v.2, P.832-8M was introduced into the resin by working.
    by weight of the original resin buffer with a pH of 3-7. (prototype).
    22 Table 8
    900815
    40
    62
    18
    23 16
    158
    U8
    3 39
    2C 23
    27 З
    107 1029693
    A7
    kk kS28kQ. 52
    18519 190
    178
    50 486i 6A insolubility. Table 9
    RI Syepepmzo CONNECT Fuz.1
    5G
    "one
    “A
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    法律状态:
    优先权:
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