• 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:
    1524890 Media for the polymerization of acrylonitrile JAPAN EXLAN CO Ltd 8 Nov 1976 [7 Nov 1975] 46441/76 Heading C3P A mixture of acrylonitrile and a comonomer is polymerized at 80-120‹ C. under a pressure which is slightly less than self-generated in the presence of an organic solvent-free system in which water is present in an amount of 3 to 60% by wt. of the total amount of monomer and water, to a conversion of at least 45%. The resulting melt can be spun directly, or heat treated, or mixed with solvents for spinning.
    公开号:SU738513A3
    申请号:SU762416908
    申请日:1976-11-05
    公开日:1980-05-30
    发明作者:Кобаси Тосиюки；Озаки Масахико；Оно Кениги
    申请人:Джапан Икслан Компани Лимитед (Фирма)；
    IPC主号:
    专利说明:

    methacrylate, phenyl methacrylate, cyclohexyl methacrylate; unsaturated ketones, such as methyl vinyl ketone, phenylethyl ketone, methyl isopropenyl ketone; vinyl esters such as formic acid vinyl ester, vinyl acetate, vinyl propionate, butyric acid vinyl ester, vinyl benzoate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether; acrylamide and its alkyl substituted unsaturated sulfonic acids, such as vinyl sulfonic acid, metal sulfonic acid amyl sulfonic acid, p-styrene sulfonic acid, and their salts; styrenes, such as styrene, ct-methylstyrene, chlorostyrene, and their alkyl or halo-substituted compounds, allyl alcohol and its esters or ethers; basic vinyl compounds, such as vinylpyridine, vinylimidazole, dimethyl-, aminoethyl methacrylic ester; unsaturated aldehydes, such as acrolein, methacrolein; unsaturated nitrites, such as methacrylonitrile, vinylidene cyanide; crosslinked vinyl compounds, such as glycidyl ether of methacrylic acid, N-methyl acrylamide, hydroxyethyl methacrylate, divinyl benzene, ethylene glycol diacrylate.
    In case the ratio of acrylonitrile in the monomer mixture increases to 98%, it becomes difficult to obtain a polymer melt under the polymerization conditions of the invention. In order to obtain an acrylonitrile polymer melt used to form products, a monomer mixture is usually used, in which acrylonitrile is in excess of 50 mol%. In particular, however, if a monomer mixture containing more than 80 mol% of acrylonitrile is used, the distinctive features of the polymerization process of the present invention are better manifested.
    In the polymerization process of the present invention, when using such a monomer mixture, it is necessary that the water content is from 3 to 6% by weight, preferably from 5 to 50% by weight. %, and for best results about 10 to 35 wt.%, based on the total amount of monomer and water. If the polymerization system contains less than 3% by weight of water, then melting the acrylonitrile polymer becomes very difficult. On the other hand, if the amount of water in the polymerization system is too large / it will be difficult to obtain a homogeneous melt, which is accompanied by further problems, such as low productivity. It is necessary to maintain the polymerization system under a pressure exceeding the self-sustaining pressure, in particular under a pressure exceeding the pressure of the vapors formed in the polymerization system under the conditions of polymerization. It is also necessary to use for polymerization a temperature in the range from 80 to 120 ° C, preferably from 85 to 115 ° C, more preferably from 90 to IO ° C. The use of too high temperature causes a deterioration in the quality of the polymer obtained, for example, its decomposition and discoloration. In addition, such temperatures create different problems in energy consumption and industrial use. On the other hand, the polymerization temperature of less than 80 ° C makes it difficult to melt the obtained polymer.
    In order to obtain an acrylonitrile polymer melt according to the proposed method, under such conditions of polymerization it is necessary to continue polymerization until the degree of conversion into polymer (i.e. the degree of polymerization) of the monomer mixture fed to the polymerization system becomes more than 45% by weight preferably more than 50% by weight, and most preferably more than 55% by weight. Only when this degree of polymerization is achieved, the obtained acrylonitrile polymer, even under the indicated low-temperature conditions and under pressure, can be transformed into a transparent polymer liquid in a substantially molten state. On the other hand, if the degree of polymerization does not reach 45%, the polymer obtained is separated in a polymerization system, giving a pasty or melamy polymer.
    The polymerization according to the inventive method is carried out in a hermetic system or in a polymerization device equipped with appropriate means of increasing pressure in order to maintain a pressure higher than the vapor pressure generated in the polymerization system under polymerization conditions (self-sustaining pressure), usually from 2 to 3 atm or higher. As a polymerization pressure, any pressure that is higher than said vapor pressure (self-sustaining pressure) can be used. For example, high pressure — above 100 atm. Or even above 1000 atm. Can be used as the polymerization pressure of the proposed method. However, it is convenient to carry out the polymerization, usually under a pressure of from 3 to 5 atm in view of the ease of industrial work, as well as in order to facilitate the removal of the polymer melt obtained to form it into fibers or films.
    As a means of initiating the polymerization, for the process of the present invention, all known methods can be used, for example, rational polymerization using radical-forming agents such as azo-compound peroxides, etc .; direct photopolymerization by ultraviolet irradiation or photosensitized polymerization in the presence of photosensitizers; polymerization by irradiation. The choice of any of these agents is determined according to the polymerization conditions and the polymerization device used, as well as the conditions of use of the polymer obtained. Among the radical-agents may be mentioned here re Kis hydrogen, Greta -butilperoksipivalat, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, stearoyl peroxide, propionyl peroxide, succinic acid peroxide, acetyl peroxide, t-butilperoksi- 2-ethylhexanoate, benzoyl peroxide, tert-butyl peroximeleic acid, azo bis isobutyronitrile, p-chlorine-benzoyl peroxide, tert-butyl peroxide cyclohexanol peroxide, tert-butyl peroxyisopropyl carbonate, 2,5-dimethyl-2, 5-di (2,5-dimethyl-2, 5-di (3) oilperoksi) hexane, Thr, g -butilpereksiatset.at tert -butilperoksibenzoat, di-tert butylperoxy phthalate, metiletipketona peroxide, rakis dikumanila ne, 2, 5-dimethyl-2, 5-rre pi-butylperoxy) hexane peroxide, tert-butylcumenyl, 7ct-butyl hydroperoxide, di-butyl peroxide, etc. These radical-forming agents can be used individually or in combinations of two or more reagents. In addition, one or more of these radical-forming agents are often used in combination with one or more compounds selected from the group consisting mainly of tertiary amines, formic acid, phenylhydrogen, reducing sulfoxys (acid sulfide, sulfites, hydrosulfites, bisulfites, metabisulfites, etc.), phenylsulfonic acid, tetraphenylhydrazine, etc. The amount when using such a triggering agent is chosen in the range of about 0.01 to 3 wt.%, preferably from 0.1 to 2 in % by weight of the monomer mixture. Well-known chain transfer agents such as amines, alcohols, substituted benzenes, chloroform, mercapto compounds, ketones, as well as a method of changing the amount of catalyst added to the system, can be used to control the molecular weight of the polymer produced by the proposed method. and a method for changing the intensity of irradiation with light or X-rays. In order to suppress the rapid polymerization reaction in the early polymerization stage and thus avoid a rapid pressure jump, it is often practiced to add a polymerization inhibitor to the polymerization system. In addition, various additives can be added to the polymerization system to improve the properties of the polymer obtained, for example anti-bleaching agents, stabilizers against thermal decomposition, flame retardants, antistatic agents, stabilizers against ultraviolet rays, pigments, etc., in such quantities as they are does not adversely affect the polymerization. The polymerization time in the process of the invention varies depending on the means of initiation of the polymerization, the type and amount of the catalyst used, the polymerization temperature, etc., but using a duration of generally from 5 minutes to 2 hours, preferably from 20 minutes up to 1 hour. The advantage of the present invention is also a short time of low temperature polymerization under pressure. The polymerization reaction of the present invention can be carried out batchwise or in a continuous way, or a combination of these methods. The clear, homogeneous liquid of the acrylonitrile polymer in the molten state, obtained by the proposed polymerization method, is released directly or after separation of the polymer melt from the aqueous phase, for stretching the filaments, for forming a film, and for forming. Thus, this melt is suitable for direct extrusion into a zone characterized by lower temperature and pressure than in a reactor for forming filaments or films. In addition, a polymer melt after adding a solvent to an acrylonitrile polymer (for example, an aqueous solution of an inorganic salt, such as zinc chloride, thiocyanate; an inorganic solvent, such as nitric acid; an organic solvent, such as dimethylformamide, dimethylacetamide) under pressure and mixing with it. , dimethyl sulfoxide, ethylene carbonate, etc.), can be molded into filaments in the usual way by wet molding or dry molding, or it can be molded into films. Further, if the pressure inside the reactor containing the melt of a hot polymer is reduced, then a polymer casting can be obtained there. As a real degree of polymerization, values in the range from 55 to 97% are used. Therefore, a certain amount of unreacted monomer remains in the resulting molten polymer. But the unreacted monomer is recovered in some acceptable manner at the stage of yarn drawing, film or molding, and can be reused. Using this method, one can substantially simplify the polymerization stage and at the same time, the amount of water used and the amount of heat energy consumed can be significantly reduced. In addition, it is possible to obtain molded products without using any solvents. Thus, the method has the advantage that the release of the solvent and the problems of its high-quality purification can be avoided. Because the polymerization is carried out in a homogeneous phase, heat transfer is facilitated. Accordingly, it is possible to suppress heat accumulation in the polymerization system and side reactions, and the polymerization product can be made homogeneous. Finally, due to the fact that the polymer becomes liquid at the same time as polymerization, transportation (transfer) of the polymer is facilitated. Due to the fact that this method is carried out in the Comparatively Low-Temperature Range (80-120s), inexpensive, safe heat sources can be used. Simultaneous carrying out the polymerization and melting steps is a very great advantage for simplifying the process. vania (yellowness) of the polymer and homogeneous. the molecular weight of the polymer obtained. In the examples, parts and percentages are decimal & by weight, unless otherwise specified. The number of APHA (number of the American Public Health Association) indicated in the examples is a calculated value, using the standard APHA curve, the degree of absorption of transmitted light at a wavelength of 430 nm through a sample of 0.4 gpolymer in 20 ml of dimethylformamide. The higher this number, the greater the degree of bleaching (yellowness)., Example 1. With a monomer mixture consisting of 91 mol% acrylonitrile () and 9 mol% methyl acrylate (Ma), mixed per 0.5 monomer mixture % di-treg-butyl peroxide, as a catalyst, and dissolved in it. After that, 8 parts of this monomer solution and 2 parts of water were placed in strong glass tubes, each of which had an inner diameter of 5 and a length of 15.0 mm, with sealed ends. After replacing the air flow in the empty space of the glass tubes with nitrogen gas, the glass tubes fill up. Each glass tube containing the reaction mixture was allowed to stand in an oil bath and the dissolved mixture was polymerized under the various conditions listed in Table 1. In each case, a transparent viscous polymer was obtained in a substantially molten state. The results of the polymerization are shown in Table. 1, As can be seen from the results table. 1, the degree of discoloration (yellowness) of the polymers obtained can be significantly suppressed, using a polymerization temperature below 120 s. If only one monomer solution (without water) is enclosed in glass tubes and polymerization is carried out under the same conditions as in Table. 1, each time at the polymerization temperature, a white or yellow chalky polymer was obtained, which does not have a flowability. Example 2 To the monomer mixture consisting of 91 mol% acrylonitrile and 9 mol% methyl acrylate, respectively, various initiators listed in Table 2 were added. 2. Eight parts of this monomer solution and two parts of water were placed in glass tubes in the same way as in Example 1 and the fuses. The reaction mixture in glass tubes was polymerized at different temperatures and for various times, as indicated in table. 2, and obtained the polymerization results shown in the same table. It can be seen from the results table. 2, that a polymerization temperature of more than 80 ° C and a degree of polymerization of more than 45% are required to obtain an acrylonitrile polymer melt, Example 3. 0.5% of AIBN was dissolved in a monomer mixture consisting of 91 mol% acrylonitrile and 9 mol% methyl acrylate (see . Definition in Table 2) (based on the monomer mixture) or 0.6% (based on the monomer mixture) BPO (see definition in Table 2). The monomer solution was enclosed in glass tubes with water; in various ratios, as indicated in table. 3. The polymerization mixture in glass tubes was polymerized under the various conditions indicated in table. 3, and the results of the polymerization obtained are shown in the same table. As can be seen from the results in Table 3, a polymer melt can be obtained only if there is a certain amount of water and when the degree of polymerization is reached above a certain value. Example 4.8 parts of solutions of various monomer mixtures indicated in Table. 4 in which 0.8% (based on the monster mixture) AIBN or 0.6% (based on the monomer mixture) BPO was dissolved as an initiator, respectively, mixed with 2 parts of water. These solutions of the monomer mixture were then sealed into glass tubes and polymerized at 100 or 60 minutes. The polymers thus obtained, with the exception of Polymer 24, were homogeneous transparent liquids in substantially molten state and substantially free oV bleaching. Example 5. In a monomer mixture consisting of 91 mol% acrylonitrile and 9 mol% methyl methacryl, tert-butyl peroxybenzoate (0.7% (based on the monomer mixture)) was dissolved as a catalyst. Then, 8.5 parts of the monster solution and 1.5 parts of water are fused in a strong glass tube. The glass tube was left to stand in an oil bath at 110 ° C for 60 minutes in order to polymerizate
    a monomer mixture .. A colorless transparent polymer was obtained in a substantially molten state. When the glass tube containing the polymer was heated for 60 minutes at 150 ° C, the flowability of the polymer increased. On the other hand, for comparison, the monomer mixture was polymerized at 150 ° C for 60 minutes. A molten polymer was obtained, but it had: a yellow color. The indicated results of the polymerization and the degree of bleaching (the number of APHA) of the polymers thus obtained are listed in Table. 5. As can be seen from the results table. 5 Polymer 34, obtained by the proposed method, is much less colored than polymer 36, obtained by a known high-temperature method under pressure. Even in the case of polymer 35 (in accordance with the present invention), which has undergone a much greater thermal prehistory than polymer 36, the discoloration is much lower.
    100 115 120 140 160
    6 7 8 9
    0.5
    AIBN
    75 VO
    0.5
    AIBN 90
    1.2
    AIBN
    1.0 100
    AVN
    0 11
    0.5
    AIBN 100
    0.5 100
    AIBN 2
    0.6 110
    VRO
    ;Table 2
    Cretaceous
    79.3 87.1
    130,500 Melted 83,200 89,5
    The same 43,6 61,000 Melobrazny 42,9
    The same 65.7
    75,600 Molten 68,000 70.2
    Same Note;
    AN / MA-100/0
    AIBN
    AN / MA-94/6
    VRO
    AN / MA-95/15
    VRO
    AN / AA-92/8
    AIBN I I
    AN / BA-85/15
      I
    AN / AAM 92/8 I I
    AN / ST-95/5
    Continuation
    tab. 2
    Table 4
    93,8
    Non-melted 75.6 Melted 64.1
    The same I 1 79.6 74.6 84.3 81.8 AIBN - azobisisobutyronitrile; AVN - azobisvaleronitrile; BPO - benzoyl peroxide; Ovr - peroxide di-gret butyl. In experiments No. 14 and 15, 0.8% benzylamine was added (based on the monomer mixture). Table 3
    YES - Acrylic. Acid
    YES - acrylamide
    MFA-methyl methacrylate
    VDC-vinylidene chloride
    34110 С X 60 min
    权利要求:
    Claims (5)
    [1]
    35NO C X 60 min + Claim 1. Method for the preparation of an acrylonitrile polster melt by radical polymerization of a mixture consisting of 50-98 mol% acrylonitrile and 2-50 mol% of at least one ethylenically unsaturated comonomer when heated under pressure 3-1000 ATM in the presence of 3-60% by weight of water based on the weight of the monsters and water, which is the fact that, in order to obtain a less colored sol. the polymer lava and the economical process, the polymerization is carried out at 80-120 ° C.
    Continued table. four
    DB - sec-butyl acrylate
    ST - styrene
    Vods - vinyl acetate
    g
    Table 5
    90,8
    239
    [2]
    2. Method pop, 1, which is also distinguished by the fact that, in order to improve the process technology, after the monomer is converted to polymer at least 45 wt.%, The reaction mixture is heated at 130-250 ° C.
    [3]
    3. The method according to claim 1, wherein the polymerization is carried out at 85-115 seconds.
    [4]
    4. The method according to claim 1, characterized in that the polymerization is carried out at 90-110 ° C.
    [5]
    5. The method according to claim 1, wherein the polymerization is carried out in a mixture containing 10-35% by weight of water.
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    同族专利:
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    JPS543784B2|1979-02-27|
    JPS5258785A|1977-05-14|
    US4062857A|1977-12-13|
    引用文献:
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    US3701761A|1968-07-03|1972-10-31|Nitto Chemical Industry Co Ltd|Temperature control in suspension polymerisation|
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    GR72246B|1978-08-30|1983-10-04|American Cyanamid Co|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP13451675A|JPS543784B2|1975-11-07|1975-11-07|
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