• 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 production of thermoplastic masses, which improves the transparency and surface quality of thermoplastic multilayer masses while maintaining their high toughness. This is achieved due to the fact that the emulsion polymerization is carried out in the presence of (meth) acrylic acid alkyl ester added after the initiator is added and before the aromatic vinyl monomer is added to the initial mixture as a mixture with a crosslinking agent, used in an amount of 0.01 - 5.0% of the total mass of monomers and a crosslinking agent, and an organic complexing agent, which, together with the emulsifier in the form of a solution in water, are added as a separate stream to the starting mixture simultaneously with the aromatic sludge monomer which is added together with a crosslinking agent in the form of a mixture used in an amount of 20 - 70% of the total weight of monomers and crosslinking agent. Graft copolymerization is carried out in the presence of an emulsifier added as an aqueous solution simultaneously with acrylic acid alkyl ester and a crosslinking agent, and the two-layer polymer is mixed with vinyl chloride or vinyl chloride-containing monomer mixture at a weight ratio of (2-50) :( 50 - 98 ) by stirring at a temperature of 20-50 ° C in the presence of an initiator for 30-120 minutes until a monomer conversion reaches a maximum of 10% by weight, followed by polymerization. 5 tab.
    公开号:SU1662351A3
    申请号:SU864028446
    申请日:1986-11-04
    公开日:1991-07-07
    发明作者:Штурм Гаральд；Тервонне Рольф-Вальтер；Туниг Дитер
    申请人:Хюльс Аг (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to the production of thermoplastic masses, in particular, to a method for producing thermoplastic multilayer masses.
    The aim of the invention is to increase the light transmission and surface quality of thermoplastic multilayer masses while maintaining high impact strength.
    The proposed method is carried out as follows.
    The first polymerization step is carried out in an aqueous medium in the presence of an emulsifier or a mixture of emulsifiers. At the reaction temperature, before and after the addition of the initiator, in the presence of an emulsifier, methacrylic or acrylic ester is added together with a crosslinking agent. After this, an aromatic vinyl monomer forming a core two-layer polymer is added and
     s
    a crosslinking agent. Simultaneously, an aqueous solution of the emulsifier and the organic complexing agent is added as a separate stream to the aromatic vinyl monomer. The addition process can be carried out continuously or intermittently. It is also possible to add one part at the beginning of the reaction, and the rest - during the polymerization process. The acrylic monomer, which forms the shell of the bilayer polymer, is added as a mixture with a crosslinking agent either continuously or periodically at the end of the first stage and, if necessary, during the reaction period, which is 15 to 180 minutes. Simultaneously, an emulsifier solution is added.
    Water-soluble or oil-soluble initiators are used, water-soluble initiators are added together with an emulsifier solution, and oil-soluble initiators are added together with my meter. In both stages, the monomers, the emulsifier and the initiator are added in such an amount that the formation of new particles in the polymerization process is effectively avoided, so the surface tension is kept above the critical concentration of micelles. Particle formation should occur only in the initial phase of polymerization. The use of oil-soluble ini-fs, in this case, is more advantageous.
    I
    Vinyl chloride is applied to a polymer consisting of a core and a shell in a third stage by polymerization. For this, the latex is preferably fed to an aqueous solution of the suspending agent, containing the initiator and, if necessary, auxiliary substances, such as organic complexing agents, buffers, and, if necessary, further auxiliary substances. After removal of oxygen, vinyl chloride is introduced and heated to 20-50 ° C. At this temperature, mix from 30 minutes to 2 hours, and the conversion should not exceed 10.0 wt.%, And after this time is heated to the polymerization temperature of 35 - 75 ° C. The polymerization temperature and thus the type and amount of initiator is chosen according to the desired Fikentscher constant (K value).
    0
    Q
    c 35
    up to 45 CQ
    0
    The temperature and the stirring time are chosen such that the majority of the monomers undergo conversion only at the polymerization temperature. The polymer obtained by conventional physical methods, for example, centrifugation or suction filtration, is freed from the bulk of the water and dried, for example, in a fluidized bed dryer. The average grain diameter is 80-150 microns. The processing is carried out by conventional methods, for example, extruders, injection molding machines, and the like, and, if necessary, conventional stabilizers, plasticizers, colorants and auxiliary agents are added.
    If an emulsion polymerization is carried out in the third stage, then vinyl chloride and, if necessary, further emulsifier and initiator, as well as further usual auxiliary substances are added. The rest of the process is carried out in the manner described. The isolation of the polymer is then carried out, for example, by spray drying.
    As aromatic vinyl monomers, for example, styrene, vinyltoluene, p (.-Methylstyrene, chlorostyrene, bromostyrene and the like, i.e., those that form polymers with a glass transition temperature of 25 ° C, preferably 40 ° C, and with a refractive index greater than the refractive index of polyvinyl chloride. As an alkyl ester of acrylic acid can be used alkyl esters of acrylic acid with an alkyl chain whose polymers have a glass transition temperature of -20 ° C and a parameter of Firms with a lower refractive index of polyvinyl chloride, such as, for example, ethyl acrylate, n-butyl acrylate, isobutylacrylate, n-octylacrylate, 2-ethylhexyl acrylate, etc. Especially preferred are alkyl esters with, such as n-butyl acrylate , isobutyl acrylate, n-octylacrylate, 2-ethylhexyl acrylate, etc.
    As the methacrylic acid alkyl ester (at the preliminary stage), esters with a C-CigB alkyl chain can be used, such as, for example, methyl methacrylate, etc. These monomers
    can be used both separately and as mixtures.
    In addition, up to 20% by weight of monomers that can be used with the above monomer compounds can be used, such as, for example, vinyl ether, vinyl ether, acrylo or methacrylonitrile, alkyl ester of maleic, fumaric or itaconic acids, olefins, etc. d.
    The refractive index of a polymer formed from a core with a shell would have to correspond to the refractive index of polyvinyl chloride.
    Compounds which can be copolymerized with the corresponding monomers and contain at least two non-conjugated double bonds, such as, for example, divinylbenzene, vinyl ester of (meth) acrylic, can also be used as a crosslinking agent in the first and second stages. acids, allyl ester of (meth) acrylic acid, diallyl ester of phthalic acid9 maleic acid and so on, triallyl cyanurate, polyvalent alcohols “polyvalent alcohols, such as, for example, pentazritrite, trimethylol propane, butane andiol, ethanediol, glycerin, etc., triacrylamide or trimet ™ acrylamide, etc. .
    In both stages of the emulsion polymerization, crosslinking agents are used in an amount of 0.1-7.0%, preferably 0.2-5.0%, of the mars of the crosslinkable monomer.
    As emulsifiers in both stages of the process of obtaining the polymer formed from the core and shell, and also, if necessary, in the third stage (vinyl chloride polymerization), ordinary surfactants can be used. Conventional anionic emulsifiers are suitable, such as, for example, sodium laurate, sodium lauryl sulfate, sodium alkyl benzene sulfonate, etc. Depending on the type and desired particle size, they are added in an amount of 0.20-5 May., Based on the organic phase. Preferred in the first two stages are quantities in which polymers consisting of a core and a shell are obtained with an average particle diameter of 50-500 nm, i.e. amounts from 0.30 to 2.5% by weight of the organic phase.
    0
    five
    0
    five
    with
    0
    five
    0
    five
    0
    Additionally, still unconquered surfactants can be added, such as, for example, fatty alcohol ethoxylate, polyethylene oxide fatty acid ester, polyethylene oxide fatty acid ester, polyol fatty acid ester, etc. amounts from 0.05 to 1.5 ma.ch. based on the weight of the monomers used.
    The organic complexing agents used in the first stage are alkali and ammonium salts of ethylenediaminetetraacetic acid or nitrilotriacetic acid. Further, 1,2- and 1,3-propylenediamine tetraacetic acid, diethyl acetate and others can be used, and their derivatives in the form of free acids or salts, such as sodium N-hydroxyethyl diamine tritriacetate, N-isopropanol ethylene diamine triacetic acid, and N-isopropylamine sodium, N-isopropanol di-ethylenediamine tetraacetate, and - crude sodium or o-diaminocyclohexane-tetraacetic sodium.
    As emulsion polymerization initiators, for example, water-soluble peroxide-type compounds, such as, for example, potassium persulfate, sodium, ammonium, tert-butyl hydrogen peroxide, etc. can be used. These initiators can be used alone or in the form of mixtures in amounts of 0.01 - 1, C% of the total mass of the organic phase, if necessary, in the presence of 0.01 to 1.0 wt.% Of one or several substances with reducing effect, capable of to form redox oxidation catalyst systems, such as, for example, aldehyde sulfo acid, hyposulphite, pyrosulphite, sulphite, thiosulphate, etc.
    In emulsion polymerization (in the first, second, and, if appropriate, in the third stages), oil-soluble catalysts can also be used, such as, for example, azobis- (isobutyronitrile). These catalysts have the advantage that the formation of new particles caused in the polymerization process is less than when using water-soluble catalysts, such as, for example, persulfates. The polymerization is carried out in an autoclave at 40 - 90 ° C, and with the use of redox catalyst systems - at lower temperatures.
    The polymerization of vinyl chloride in a polymer consisting of a core and a shell (third stage) is carried out preferably in suspension, but if necessary also in an emulsion. Up to 20% by weight of copolymerizable monomers, such as, for example, vinyl ether, vinyl ester, such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl halides, such as
    like vinyl fluoride, vinylidene chloride, not


    chesky phase.
    ditch - azo-bis (isobutyronitrile). The selection of the type and amount of initiator is carried out in the usual manner, and mixtures of initiators can also be used.
    Buffers and / or an organic complexing agent, such as ethylenediaminetetraacetic acid, as well as its salts, nitriletriacetic acid and its salts, etc., can be used as additives for suspension polymerization, in amounts from 0.01 to 0.5 May. . h. based on the mass of the organi
    saturated acids and their anhydrides, such as maleic, fumaric and acrylic acids, their mono- and di-esters, and maleic anhydride.
    As a suspending agent, primary protective colloids can be added in an amount of from 0.05 to 1.0 wt.% (Calculated on the total amount of the organic phase). For example, water-soluble cellulose derivatives with a viscosity of a 2% aqueous solution of 25–3000 mPa.s, such as alkyl, oxyalkyl, alkyloxyalkyl and carboxyl-cellulose, polyvinyl alcohols, partially saponified water-soluble polyvinyl acetates, copolymers of vinylpyrrolidone and ethylenically unsaturated esters, polyoxazolines, etc.
    Non-ionic surfactants such as, for example, fatty acid ethoxylates, polyol fatty acid esters, alcohol ethoxylates and similar compounds in amounts of from 0.01 to 1 can be used as additional auxiliary agents. 2 ma.ch. based on the total amount of the organic phase.
    Slurry polymerization is started with mono-soluble radical-forming agents, for example, of the peroxide type or azo compounds. As peroxide initiators, for example, diacyl peroxide, dialkyl peroxide, peroxydicarbonates, complex alkyl peroxides, etc. can be mentioned, such as bis- (2-methylbenzoyl) peroxide, di-tert.-butyl peroxide, dilururyl-5 for 1 hour. Average particle diameter
    peroxide, acetylbenzoyl peroxide, dicumshreoxide, diethyl peroxydicarbonate, tert.butyl perpivalate and the like, and 95% of zinc / aryl of a two-layer material. The content of the residual monomer in this case is 0.1% by weight (conversion 99% by weight).
    five
    0 0 5
    0 5
    Q
    Example 1. Preparation of a two-layer material consisting of a core and a shell (stage A).
    To 100 parts (based on the weight of the whole organic phase) 0.85 parts of sodium laureate as an emulsifier is added to the completely desalted water. The mixture is heated to 80 ° C and, when the solution is clear, 0.5 parts (0.87% by weight of the total monomer) of a mixture of n-butyl acrylate and diallyl phthalate are added in a ratio of 99: 1. After 10 minutes, 0.20 is added. including ammonium persulfate and after a further 10 minutes, start additions with doses of 57.0 parts of a mixture of styrene and divinylbenzene in a ratio of 99: 1 and 115 parts of emulsifier solution and ethylenediaminetetraacetic acid tetrasodium salt. The solution of emulsifier and tetrasodium salt of ethylene diamine tetraacetic acid consists of 0.425 parts sodium laurate, 1.0 parts tetrasodium salt of ethylene diamine tetra acetic acid and 113.575 parts completely demineralized water. The addition is continued for more than 2 hours. After an additional reaction for 30 minutes, the residual styrene content is 0.2% (conversion is 99%). Then for 3 hours, it was carried out at 80 ° C by adding doses of 42.5 parts of a mixture of butyl acrylate with diallyl phthalate in a ratio of 99: 1 and 85 hours, a mixture of O, 293 parts of sodium laurate with .0.130 parts of ammonium persulfate at 84, 577 hours fully demineralized water. Then continue stirring for another 1 hour. Average particle diameter
    the bilayer material is 95 nm. The content of the residual monomer in this case is 0.1% by weight (conversion 99% by weight).
    The graft polymerization of vinyl chloride is carried out on the bilayer material in the form of a latex of stage A (stage B).
    To a solution of 0.20 parts of methyloxypropylcellulose (viscosity of a 2% aqueous solution of 50 mPags) in 120 parts of completely desalinated water was added 0.08 parts of azo-bis (isobutyronitrile), 0.06 hours ethylenediaminetetraacetic acid tetrasodium salt, 40 parts of stage A latex (corresponding to 10 hours solids), and after repeated evacuation and washing with nitrogen, 90 parts of vinyl chloride. Thus, the weight ratio of the bilayer to vinyl chloride is 10:90. The mixture is heated to 40 ° C. and stirred for 60 minutes until the conversion of vinyl chloride to 4%. Then it will be polymerized at 60 ° C until the pressure reaches 3 bar. By depressurizing, the polymer is freed of residual monomer, filtered under suction and dried in a fluidized bed dryer.
    The resulting thermoplastic multilayer mass according to the method of example 7 is processed into a sample for testing.
    Example 2. It is carried out analogously to Example 1, but with the difference indicated in Table. one.
    The resulting thermoplastic multilayer mass according to the method. Example 7 is processed into a sample for testing.
    Example 3. It is carried out analogously to example 1, but in stage A, a mixture of n-butyl acrylate and diallyl phthalate is used in an amount respectively
    m
    0.05% (experiment a) and 5.0% (experiment b) from ob-40. A notched cut is determined by the mass of the monomer used. At the same time common standard. 534453, the amount of n-butyl acrylate was translucent with the help of respectively 41% (test a) and 37% of the spectral photometer per 2-milli-millimeter (test b) of the mass of the resulting two-meter plates using
    45 barium sulphate.
    layered material.
    The resulting thermoplastic multilayer mass according to the method of example 7 is processed into a sample for testing.
    Example 4. A conductor of similar-50 sheath is 56:44. When grafted to example 1, but the mixing of the bilayer – eternal polymerization of vinyl chloride material with vinyl chloride is carried out at a mass ratio of 2:98 (experiment a) and 50:50 (experiment b), respectively. The resulting thermoplastic multilayer mass according to the method of Example 7 is processed into a test specimen.
    Example 5. Analogously to Example 1 (Stage A), latex is made,
    The results are shown in Table. 2
    Example 8. It is carried out analogously to Example 5, but the ratio of the core to
    temperature vary. The polymer mass is processed and tested in example 7.
    The results are shown in Table. 3
    As the temperature increases, the graft polymerization of vinyl chloride on core and shell particles
    Yu
    - 5 15 20
    th
    662351Y
    but instead of ammonium persulfate use aeo-bis- (isobutyronitrile) as an initiator. In the first stage (preparation of the core), azo bis (isobutyronitrile) (0.20 part) is fed together with an aqueous solution of an emulsifier, and in the second stage (polymerization of the shell) it is dissolved in butyl acrylate (0.13 part -bis- (isobutyronitrile)); Suspension polymerization is carried out as in Example 1 (Step B). The resulting thermoplastic multilayer mass according to the method of example 7 is processed into a sample for testing.
    Example 6. Analogously to example 1, but in the emulsion polymerization azo-bis- (isobutyronitrile), as described in example G, is used as an initiator. In suspension polymerization, 32 parts of latex are used (which corresponds to 8 parts of a solid) and 92 parts of vinyl chloride. The resulting thermoplastic multilayer mass is processed in the manner described in Example 7 into a test specimen.
    Example 7. Obtaining samples for testing.
    To 100 parts of the thermoplastic multilayer mass of Examples 1-6, 2.5 parts of a mixture of a commercially available tin-based stabilizer, an ultraviolet stabilizer and a lubricant are commercially added and heated in a laboratory stirrer to hot mix to 110 ° C. Then the mass is processed by mixing rollers at 175 ° C into sheets, which are then processed into pressed plates. Impact viscosity ob25
    YU
    35
    The results are shown in Table. 2
    Example 8. It is carried out analogously to Example 5, but the ratio of the core to
    the shell is 56:44. With the polymerisation of vinyl chloride
    temperature vary. The polymer mass is processed and tested in example 7.
    The results are shown in Table. 3
    As the temperature increases, during the graft polymerization of vinyl chloride on particles of core and shell
    A decrease in the notched impact of the specimen is observed. The values for -, light transmissions remain constant.
    Example 9. It is carried out analogously to Example 5, but the ratio of the polystyrene core to the polybutyl acrylate shell varies. The processing and testing of polymeric masses is carried out according to example 7.
    The results are shown in Table. four.
    Example 10. It is carried out analogously to Example 9, but using 32 parts of latex (which corresponds to 8 parts of solids) and 92 hours of vinyl chloride. The processing and testing of polymeric masses is carried out according to example 7.
    The results are summarized in table. five.
    权利要求:
    Claims (1)
    [1]
    With a comparable notched toughness of a specimen with a notch manufactured by a known method, thermoplastic multilayer polymers have a much lower light transmission, i.e. at 500 nm, the best value is 72%, at 600 nm - 77% and at 700 nm - 82%. Surface gloss values range between 2 and 3. Invention
    The method of obtaining thermoplastic multilayer masses by emulsion
    Note. I - Diethylperoxycarbonate; II - dilauroyl peroxide; III - azo-bis- (isobutyronitrile).
    five
    five
    0
    0
    polymerization of an aromatic vinyl monomer in the presence of an initiator and at least one crosslinking agent, followed by graft copolymerization of an acrylic acid alkyl ester in the presence of an initiator and crosslinking agent and an organic complexing agent to obtain a two-layer material, followed by displacing it with a vinyl chloride polymer, that, in order to increase the light transmission and surface quality of thermoplastic multilayer masses while maintaining high With a good toughness of the masses, emulsion polymerization is carried out in the presence of alkyl ester (chalk) of acrylic acid, and it is added to the initiator and to the aromatic vinyl monomer to the initial mixture as a mixture with a crosslinking agent, used in an amount of 0.05-5 , 0% of the total mass of the monomer, and the mixture of the bilayer material with vinyl chloride is carried out in the form of a latex at a mass ratio of (2–50): (50–98) and at 20–50 ° C for 30–120 min before the conversion monomers maximum 10%, followed by depolymerization of the mixture.
    Table 1
    13
    1 2 3 4
    table 2
    Table 5
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    法律状态:
    优先权:
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