• 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:
    A method for preparing a low molecular weight polymer in an aqueous medium from a monomer mixture mainly composed of vinyl chloride monomer, comprising: adding an organic compound containing at least one mercapto group and at least one hydroxy or carboxyl group per molecule to the aqueous medium, and wherein at least 50 weight percent of the organic compound is added to the aqueous medium when the monomer conversion is between 1% and 30%. Polymers produced by the method disclosed have a relatively low degree of polymerization, good heat stability and desirable particle size distribution.
    公开号:SU841592A3
    申请号:SU782585304
    申请日:1978-02-24
    公开日:1981-06-23
    发明作者:Кувата Сатоси；Азума Коудзи；Куримото Казухико；Огава Кинья
    申请人:Син-Эцу Кемикал Ко.,Лтд (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to the technology of vinyl chloride polymers and can be used in the chemical industry. A known method for the preparation of ninchloride polymers by the aqueous polymerization of vinyl chloride in the presence of emulsifiers, radical initiators and as β-agents of chain transfer of mercaptans, carbon tetrachloride or trichlorethylene flj. The closest to the present invention is a method for producing vinyl chloride polymers by aqueous suspension polymerization of vinyl chloride or its copolymerization with vinyl acetate in the presence of suspending agents, radical initiators and as chain transfer agents 0.001-0.5% (by weight of monomers) mercaptoalkanols Cg-Cj or thioglycolic acid which are introduced into the reaction zone before the onset of polymerization 2. The disadvantage of this method is the relatively low heat resistance of polymers, the wide distribution of particle size Leamer and relatively high oderzhanie the polymer remains exactly monomer. The purpose of the invention is to increase the warm resistance of polymers and the uniformity of particle size, as well as a decrease in the content of residual monomer in the polymer. The goal is achieved by the fact that in the process of producing vinyl chloride polymers by water-suspension polymerization of vinyl chloride or copolymerisation of it with vinyl acetate in the presence of suspending agents, radical initiators, and as chain transfer agents, 0.001-0.5% (by weight of monomers) mercaptoalkanols of SL-Chol. thioglycolic acid, chain transfer agents are introduced into the reaction mixture at a monomer conversion of 1-30%. In addition, 0.1-50% of the chain transfer agent may be introduced into the reaction mixture when the monomers are converted to less than 1%. The polymerization process is carried out in an aqueous medium containing suspending agents selected from water-soluble polymeric substances such as partially saponified methylcarbonate polyvinyl alcohol, polyvinylpyrolidone, copolymers of vinyl acetate (maleic anhydride, starch, gelatin, possibly in combination with anion or non-ionic surface. The initiator of the polymerization reaction is usually organic peroxide dissolved in the monomer, such as, for example, diisopropyl peroxy dicarbonate, acetyl glass eksilsulfonil peroxide / tertiary butilperokisiivalat and lauryl peroxide and azo compounds such as a.zo bisizobutironitril, d ,, of -azobis-2, 4-dimetilvaleroni TRIL and with, o / -azobis-4-methoxy-2, 4 -dimetilvaleronytril . In the examples, all quantities are given in parts by weight, and the procedures for determining the average molecular weight, the amount of residual vinyl chloride monomer, absorption of dioctyl phthalate and heat resistance are as follows: Average molecular weight: in accordance with the method detailed in JIS K 6721. Residual in inyl chloride: chromatographic analysis of the gas for a solution of 1 g of polymer in 25 ml of tetrahydrofuran. The procedure for: 4 and the degree of absorption of dioctyl phthalate are as follows. 20 g of 1-octyl phthalate is added to 10 g of the vinyl chloride polymer obtained according to an example, resulting in a mixture that is kept at room temperature for one hour, followed by the separation of excess dioctyl phthalate unabsorbed in the polymer by the centrifugal method. The amount of dioctyl phthalate absorbed in the polymer is determined (wt.%) Relative to the weight of the polymers. The procedure for determining the heat resistance is as follows. A mixture consisting of 100 g of vinyl chloride polymer obtained in accordance with the examples, 0.5 g of organostananate mercaptide (product manufactured by Nit to Cemical Co Japan, called TVS-8831) and 0.5 g of stearic acid are milled on a roller mill for 5 minutes at a roller temperature equal to, and this material is shaped like a sheet with a thickness of 0.8 mm. The sheet obtained in this way is kept in the oven for a period of 40 minutes and, after being removed from the oven, the appearance of the sample is evaluated visually on a five-sided scale as follows; a) the appearance of the sample is the same (even after exposure for 60 minutes when heated in a furnace); c) slight staining; c) dyeing in brown color; e) dyeing in a dark-brown color; e) the sample is completely black. In the tables given in the examples, the abbreviations DMVN.PV and LPO are used for c1 / o -azobis-2,4-dimethylvaleronitrile, tertiary butyl peroxypivalate and lauryl peroxide, respectively. Example 1. In a 50 L polymerization reactor made of stainless steel, 30 kg of deionized water are introduced; 20 g partially saponified polyvinyl alcohol; 15 kg of vinyl chloride monomer and a polymerization reaction initiator in an amount as shown in Table 1, and the polymerization process is started by increasing the temperature. While the conversion of myomer reaches the value indicated in% in the table, the organic compound containing the mercapto group is placed in the polymerization mixture and the polymerization is reacted at the temperature indicated in the table. After the total polymerization reaction time indicated in the table elapses, the polymerization reaction stops, and after removing the 4ie-reacted monomer - vinyl chloride, and the resulting polymer in the aqueous slurry is dehydrated and dried to form polyvinyl chloride. Polyvinyl chloride thus obtained is subjected to a study to determine the average degree of polymerization, determine the particle size distribution, the amount of residual monomer - vinyl chloride, the degree of absorption of dioctyl phthalate and heat resistance. Experiments 9 and 10 (listed in Table 1) are presented for comparison purposes, and according to which 10 g of 2 mercapto ethanol is introduced into the polymerization mixture, either during the period of time when the monomer conversion reaches about 50% (experiment 9), or before initiation of the polymerization reaction, and this input is made together with deionized water, partially saponified polyvinyl alcohol, vinyl chloride monomer and the initiator of the polymerization reaction (experiment 10). Table
    Continued table. one
    Polymerization reaction temperature, C62626258 Conversion of the monomer,% (when the addition of the agent-chain sensor 1712158 is made, in hours from the moment of the start of polymerization) (1.0) (1.0) (1.0) (1.0
    Total polymerization time, h888 1LIN45 Average degree of polymerization 680 700 710 720 Polymer particle size distribution,% passing through sieve No. 60100.0 100.0 100.0 100.0 1.5 2.0 1.2 1.2 2.5 3, 9 1.5 1.0
    The residual amount of monomer, ppm (ppm) 15 13 14 10 Absorption of dioctyl phthalate,% 17.5 16.5 17.0 18 18
    Heat resistance The Other conditions of these experiments and the results of testing samples of polymer products in these comparative experiments are also shown in the table. Chain transfer agents are as follows: (a) 2-mercaptoethanol; - (b) mercaptopropanol; (c) thioglycolic acid; (d) 2-mercaptopropanol. Example 2. In the same polymerization reactor as in example 1, made of stainless steel, 30 kg of deionized water, 20 g of partially saponified polyvinyl alcohol, 15 kg of monomer — vinyl chloride, and o, L-azobis — are loaded 2,4-dimethylvaleronitrile in the amount indicated in the table. the polymerization reaction starts at
    99 9 9 8 8 9 3010 40 30 jQ
    9 10 30 42 50
    B 58 58 566458 58 420101250О Со, 5) (2.0) (1.5) (1.0) (4.0) (0) 680 700 690 720 830 690 / 98.8 100.0 100.0 100.0 100.0 60.5 (rep. Dia.) 0.9 2.5 2.2 (dia, response) 18.0 19.0 19.5 17.0 16.2 19.5 as a result of an increase in temperature. During the polymerization reaction, 2-mercaptoethanol is added to the polymerization mixture at the time when the conversion is in the range indicated in the table, and the polymerization reaction continues at 625:; or 58 C. After the entire polymerization reaction time is 8 or 9 hours from the start of the polymerization reaction, the polymerization process is stopped, and after removal of the unreacted vinyl chloride monomer, the polymer obtained in the aqueous slurry is dehydrated and dried to obtain the final product, polyvinyl chloride, The properties of the resulting products are listed in table 2. 2-Merck Agent-transmitter ethanol chain, g Initiator-dimethylvaleronitrile, g 4.5 Polymerization reaction temperature g-62 Conversion of the monomer,% at the time when the agent of the transmitter is added to the chain (in hours from 15-25 the beginning of the polymerization reaction) (1-2) Total polymerization reaction time, h 8 Average degree of polymerization 700 Polymer particle size distribution,% passed through sieve No. 60100.0 2000.8 Residual monomer concentration in the polymer, ppm (ppm) ) 12 Absorption of dioctyl phthalate,% 18.0 Heat resistance C.
    Experiment 13 (Table 2) is given for the purpose of comparison, and in this experiment 2-mercaptoethanol is introduced into the polymerization reactor together with deionized water, partially saponified with polyvinyl alcohol and the vinyl chloride monomer.
    Example 3. In the same polymerization reactor made of stainless steel, 30 kg of deionized water, 20 g of partially saponified polyvinyl alcohol and a mixture of monomers consisting of 12.7 kg of vinyl chloride monomer and 2.3 kg of vinyl acetate monomer and 7.5 g o / jf, o 4-azobis-2,4-dimethylvaleronitrile and the polymerization reaction begins. At that point in time when the monomer conversion reaches 12%, 15.0 g of 2-mercaptoethanol is added to the polymerizate mixture and the process
    Table 2
    the polymerization proceeds further. After a total polymerization reaction time of 11 hours and 20 minutes from the beginning of the polymerization reaction, the polymerization reaction is stopped and, after removal of unreacted monomers, the resulting copolymer in the aqueous slurry is subjected to dehydration and drying, resulting in a finished vinyl chloride copolymer and vinyl acetate. The properties of the copolymer product thus obtained are listed in Table 3. Experiment 15 is shown for comparative purposes and in this experiment 15 g of 2-mercaptoethanol is introduced into the polymerization reactor along with deionized water, partially saponified with polyvinyl alcohol, vinyl chloride monomer and other ingredients, and the total polymerization reaction time is increased to 12 hours.
    Table 3
    2-mercap-. 2-mertoethanol kapto15, 0 ethanol 15.0
    7.5.
    7.5,
    56 o
    56 12
    (1) 12 550
    11.2 560
    16.5
    100.0. 2.8 Chain Transfer Agent First addition of Chain Transfer Agent, relative to monome0, 010 0.015 0.005 0.010%,% Secondary addition of transfer agent,%, (relative to monomer with monomer conversion),% 0.020 0.020 0.085 0.060 (15) (10 ) (25) (15)
    Example 4. In a 100.0 L polymerization reactor made of stainless steel, 500 kg of deionized water, 120 g of partly saponified polyvinyl alcohol, 60 g of hydroxypropylmethyl cellulose, 350 kg of vinyl chloride monomer, a chain transfer agent and a polymerization initiator are given, Table 4. The polymerization process begins with an increase in temperature. When
    0, the conversion rate of the monomer, the higher percentage of S, reaches the value indicated in the table, an additional amount of the same agent is added to the polymerization reactor. ta-chain transmitter, while the polymerization reaction continues at the same polymerization temperature of the other nopJs, until the pressure inside the polymerization reactor drops to 7 kg / cm, and the polymerization reaction stops when the unreacted vinyl chloride monomer is removed.
    The resulting polymers of vinyl chloride chloride are dehydrated and dried in a fluidizing dryer, which is dried with hot air having a temperature of 75 s for 20 minutes after the temperature of the polymer has reached 70 ° C.
    For comparison, experiments are carried out in which the same steps are carried out, except that 2-mercaptoethanol is completely added before the start of the polymerization reaction (experiment 23) and part of the chain transfer agent is added before the start of the polymerization reaction and the wasp is added when the power of
    0 rotation is 0.5% (experiment 1, 5 ment 24).
    Table4
    0.030 0.010
    0.025 (0.5) 0.007 0.015 0.028 0.025 0.030 (5) (2) (15) Polymerization initiator (attributable to monomer),%
    62
    55
    62
    The size distribution of the portion% passing through a mesh sieve. 60
    100 200
    Heat resistance
    Residual monomer in polNsepe, ppm 1.5
    1.0 1.8
    650
    670
    640
    Example 5. In a polymerization reactor, similar to that used in Example 4, 600 kg of deionized water, 120 g, are fed.
    Agent chain transmitter
    Initial addition of a chain transfer agent, relative to my number,%
    Secondary addition of a chain transfer agent% relative to the monomer (degree of monomer conversion),%
    Reaction initiator
    polymerization (% relative to monomer)
    Polymerization temperature
    Continued table. four
    63
    63
    63
    62
    0.9
    18
    50
    23
    640
    650
    660
    670
    methylcellulose, 250 kg of vinyl chloride monomer, agent-transmitter circuit and the polymerization reaction, which are listed in table.5. Table 5
    (but)
    (but)
    (but)
    0,0150,030
    .0,010
    0,005
    0.020
    0,025О
    (20) (10)
    DM DM, (0.04) (0.04)
    63
    62 DMVN DMVN (0.05) {0.040) {0.05) (0.04) (0.04) (0.04) (0.04) (0.04) DMVN DMVN DMVN OMVN
    Particle size distribution,% passage through a type sieve, mesh
    60
    100
    200
    Heat resistance
    © monomer stock
    polymer, ppm 0.8 1,5
    Medium polymerization degree660 680
    The polymerization reaction starts as the temperature rises. When the degree of conversion of the monomer reaches the values expressed in percentages listed in the table, an additional amount of the same chain transfer agent is added, while the polymerization reaction continues at the same temperature until the pressure inside the polymerization reactor drops 30 up to a value of 7 kg / cm; wherein the polymerization reaction is terminated using a chain of unreacted vinyl chloride monomer. Processing of the polymerizate after completion of the polymerization reaction is carried out in accordance with Example 4.
    Transfer agent
    chains, g
    Initiator, g
    Polymerization temperature, C
    Conversion of monomer,%, with the addition of a chain transfer agent (h from the beginning of the polymerization)
    The total duration of polymerization
    Medium Polymerization
    Particle size distribution
    Continued table. five
    100 90 0.8
    1 & 0 78
    98 45 3.5. 1.5
    AT
    1.5. 20
    660
    650
    For comparison, an experiment is carried out in which all 2-mercaptoethanol is added before the start of the polymerization reaction (experiment 28) while all other conditions are maintained.
    Example 6. The operations described in example 1 are repeated, except that 2-mercaptoheptanol is used as the chain transfer agent, and the time of addition of such agents is varied over a wide range.
    . Information about this experiment is summarized in table. The following chain transfer agents are: (a) 2-mercaptoethepol, (b) 3-mercaptrethanol, (c) 2-mercaptoethanol.
    Table 6
    3.8
    75 3.8 4.5, 6.5 4.5
    62
    55
    62
    21 1.0
    30 (2.5)) (1.5) (0.2)
    8,680
    12 8 430 670
    passing% through
    strainer type, mesh.
    60100.0 100.0
    2002.0 1.5
    The residual amount of monomer in the polymer, h / m
    Dioctylblock Absorption Example 7. The operations described in Example 4 are repeated except that the amount of the first added chain transfer agent is reduced to 0.0005% of the amount of monomer. Detailed information about this experiment is discussed below. Chain transfer agent - 2-mercaptoethanol) amount of the first added chain transfer agent - 0.0005% (relative to the monomer) amount of the second chain transfer agent added to the monomer 0.0295%, (at a monomer conversion of 15); polymerization initiator (% to monomer - DMI) 0.04%; polymerization temperature, particle size distribution, (in%) passing through a sieve: 60 mesh. . 100 100 87. 2000.8 Thermal stability B: residual monomer content in polymer 30 PPMJ average degree of polymerization 650. As follows from these examples, the proposed method improves the heat resistance of polymers and the uniformity of its particle size and also reduces the residual monomer content in the polymer.
    Continued table. 6
    100.0 100.0 100.0 6.0 3.0 2.0
    nineteen
    17
    权利要求:
    Claims (2)
    [1]
    20 Claim 1. Method for producing vinyl chloride polymers (d / d) by suspension polymerization of vinyl chloride or by copolymerizing it with vinyl acetate in the presence of radical initiating suspending agents - and chain transfer agents of 0.001-0.5% (by weight of monomers) mercaptoalkanole CL-C7 or thioglycolic acid, characterized in that, in order to increase the heat resistance of polymers and uniformity in particle size, as well as to reduce the content of residual monomer in the polymer, chain transfer agents are introduced into the reaction the mixture at 1-30% conversion of the monomers. 2. The method of claim 1, wherein 0, the chain transfer agent, is introduced into the reaction mixture when the monomer conversion is less than .1%. Sources of information taken into account in the examination 1.Zilberman E.N. Preparation and properties of polyvinyl chloride. M., Himi, 1968, p.78.
    [2]
    2. The patent of the USSR on the application 2395310/05, c. 08 F 14/06, 1976 (prototype).
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    同族专利:
    公开号 | 公开日
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    SE440784C|1989-12-04|
    HU178740B|1982-06-28|
    JPS53104684A|1978-09-12|
    NO780590L|1978-08-25|
    PT67691B|1979-07-23|
    SE440784B|1985-08-19|
    NO152754C|1985-11-13|
    PL204854A1|1978-11-06|
    NL181659B|1987-05-04|
    NL7802025A|1978-08-28|
    GB1596689A|1981-08-26|
    FR2381792B1|1980-09-12|
    PL107759B1|1980-03-31|
    IT1094154B|1985-07-26|
    FR2381792A1|1978-09-22|
    SE7801919L|1978-08-25|
    DE2807180A1|1978-09-21|
    IT7820524D0|1978-02-22|
    BR7801118A|1978-10-10|
    NO152754B|1985-08-05|
    ATA126678A|1981-04-15|
    CA1126449A|1982-06-22|
    JPS5533804B2|1980-09-03|
    CU34877A|1979-08-20|
    ES467284A1|1978-10-16|
    BE864149A|1978-06-16|
    NL181659C|1987-10-01|
    DE2807180C2|1991-12-05|
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    引用文献:
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    GB579353A|1943-03-20|1946-07-31|Du Pont|Polymerisation of unsaturated compounds in the presence of thiols and derivatives thereof|
    DE2051317A1|1970-10-20|1972-04-27|Basf Ag|Radical polymerisation using regulator - of bifunctional mercaptan or organic sulphide type|
    JPS5313515B2|1975-09-11|1978-05-10|
    JPS52138583A|1976-04-19|1977-11-18|Mitsui Toatsu Chem Inc|Preparation of vinyl chloride polymers|
    JPS5372089A|1976-12-09|1978-06-27|Nippon Zeon Co Ltd|Preparation of polyvinyl chloride type resin|DE3029907A1|1980-08-07|1982-03-18|Hoechst Ag, 6000 Frankfurt|CONTINUOUS METHOD AND DEVICE FOR PRODUCING A VINYL CHLORIDE POLYMERISATE IN AQUEOUS SUSPENSION|
    JPS6248703A|1985-08-27|1987-03-03|Chisso Corp|Production of vinyl chloride polymer having low polymerization degree|
    US4797458A|1986-09-02|1989-01-10|The B.F. Goodrich Company|Colloidal stable vinyl halide polymerizations with mercaptan chain transfer agents|
    DE10309857A1|2003-03-06|2004-09-23|Wacker Polymer Systems Gmbh & Co. Kg|Epoxy-modified vinyl chloride-vinyl ester copolymer solid resins|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP1969177A|JPS5533804B2|1977-02-24|1977-02-24|
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