• 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 flame resistant and self-extinguishing copolyester composition is made by copolycondensing a dicarboxylic aromatic acid or its diester, a saturated aliphatic diol, a tetrabrominated diol and a sulphonated aromatic compound, preferably in the presence of a phosphor derivative as a complexing and stabilizing agent. Preferably the acid is terephthalic acid and the saturated diol is ethylene or butylene glycol. The viscosity of the copolyester is from 0.3 to 0.6 dl/g and preferably not less than 0.4 or more preferably 0.45 dl/g and its bromine and sulphur contents are 0.1-12% and 0.05-1% by weight respectively, the phosphor, if any, not exceeding 1%. A marked synergic effect of the concurrent presence of bromine and sulphur is evidenced by combustion tests.
    公开号:SU973030A3
    申请号:SU782579599
    申请日:1978-02-15
    公开日:1982-11-07
    发明作者:Чаперони Альдемаро；Куалья Джузеппе
    申请人:Сниа Вискоза Сочиета Национале Индустриа Аппликационе Вискоза С.П.А. (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to the production of synthetic fibers, in particular to the preparation of a composition for forming polyether fibers.
    A method is known for preparing a composition for forming fibers by transesterification of terephthalic acid or its dimethyl ether with ethylene glycol and a sulfonated compound at 200-220 seconds followed by polycondensation under vacuum in the presence of antimony oxide until the characteristic viscosity of the composition is 0.49-0.52 dl / g l.
    However, the fibers obtained by molding a known composition are not flame resistant and do not have a sufficient degree of whiteness.
    The purpose of the invention is to obtain fire-resistant fibers with a high degree of whiteness.
    The goal is achieved in that according to the method of preparing a composition for forming fibers by transesterification of terephthalic acid or its dimethyl ether with ethylene glycol and a sulfonated compound at 200-220 ° C, followed by polycondensation under vacuum in the presence of
    Antimony oxides, until the intrinsic viscosity of the coagulation is 0.490.52 dl / g, dimethyl ester of 1-sulfobenzene-3,5-dicarboxylic acid or its sodium salt is used as the sulfonated compound and 2,2-bis g is additionally introduced at the transesterification stage , 3-dibromo-4- (2-hydroxyethoxy) phenyl-pro10 pan, and at the stage of polycondensation phosphorous acid in the following ratio of components, mol:
    Terephthalic acid
    or her dimethyl
    15
    ether
    2.17-2.19
    Ethylene glycol
    Dimethyl complex
    1-sulfobenzene-3, 5-dicarboxylic ester
    20
    acid or its sodium salt0,0231-0,0421
    2, 2-bis (3,3-dibromo-4 (2-hydroxyethoxy
    0,0197-0,0232
    (phenyl) propane
    25 0.489 10 Phosphorous acid
    Example 1. Preparation of a copolyester of dimethyl terephthalate, ethylene glycol, 2,2-bis 3, 3-dibrom-4 (2-hydroxy-ethoxy) -phenyl-3-propane and 1-sulfobenzene-3,5-dicarboxylic acid monosodium salt, having the calculated contents bromine and sulfur, equal to, respectively, 5 and 0.35%. In an autoclave equipped with a stirrer and suitable for an exchange reaction involving air 1 O, resulting in the formation of poly (ethylene terephthalate) from dimethyl terephthalate and ethylene glycol, are introduced at 150 hours in a stream of nitrogen (1 mol) of dimethyl terephthalate, 105 parts (2.17 mol ) ethylene glycol 16.76 parts (0.0343 mol) 2,2-bisSC3, 3-dibromo-4 (2-hydroxyethoxy) f.enil.3-propa (molar ratio 3.4% with respect to dimethyl terephthalate) , 5.3 parts (0.0232 mol) of 1-sulfobenzene-3 dimethyl ester, 5-dicarboxylic acid (molar ratio 2, relative to dimethyl terephthalate) dimethyl ester 0.112.4. (O, 5 9-10-5 mol) of manganese acetate; 0.6 h (9.71 Yumol) of titanium dioxide and 0.019 h (2.5 x X) potassium acetate. By putting these substances into the autoclave, they create a nitrogen atmosphere in it. The entire system is heated while being stirred until reaching 185 minutes. during this period, 47.9 parts {9.36 mo of methyl alcohol (96% of the theoretical amount) are distilled. The mixture formed as a result of an ester exchange reaction is fed to the polycondensation autoclave, in which 06 hours {0,2661СГ mol) a half of antimony oxide and 0,046 h. I O, 334) monosodium phosphate with stirring at. After that, an incomplete and gradually increasing vacuum is created within 45 minutes. During this period of time, excess ethylene glycol is removed. When the residual pressure in the autoclave reaches 30-50 mm Hg, 0.031 parts (0.489-10 mol) of phosphoric acid dispersed in a small amount of ethylene glycol are injected. After stirring for 5-6-4 at 265 ° C and a residual pressure of 0.2 mm Hg. extrude a mass of copolyester containing compounds br. ma and sulfur, for 3040 min. The resulting copolymer has the following characteristics: Viscosity1}, dl / g0.49 Acid groups, equivalent / t41 Content of diethylene glycol, mol.% 2.2 By (found), S4.8 S (found),% 0.35 Degree of lightness43 Whiteness58 Degree of yellowness11. Duration of the subsequent combustion (TC), c1.4 Average burning length (LB) 11.2 Example 2. Prepare the copolymer as described in Example 1, but this copolyester has a calculated bromine and sulfur content of 3.5 and 0.3%, respectively. 15 parts (1 mol) of dimethyl terephthalate are introduced into the autoclave described in example 1; 105 parts (2.19 mol) of ethylene glycol; 11.3 parts (0.0231 mol) 2.2bis Cz, W-dibrom-4 (2-oxyethoxy) phenylJ-propane (molar ratio of & to dimethyl terephthalate 2.3%); 4J5 parts (0.0197 mol) of 1-sulfobenzene-3,5-dicarboxylic acid dimethyl ether monosodium salt (molar ratio to dimethyl terephthalate 1.98), 0.112 parts (0.59-10 5 mol) of magnesium acetate, 0, 6 hL9.71-10 mol) titanium dioxide and 0.019 h (2.5-10 mol) of potassium acetate. The exchange reaction with the complex ETHEROME and the polycondensation reaction is carried out in the same manner as described in example 1. The polymer obtained has the following characteristics: Viscosity G, dl / g 0.52 Acid groups, equivalent / ton 38 Content of diethylene glycol, mol% 2.5 Vg (found),% 3.4. S (found), 0.31 Degree of lightness 51 Degree of whiteness - 64 Degree of yellowness 8 TC, SO LB, cm, 12.3 Example 3. Prepare a copolyester from terephthalic acid, ethylene glycol, 2,2-bis 3, 3-dibromo-4 (2-hydroxyethoxy) phenyl-3-propane and 1-sulfobenzene-3 monosodium salt, 5-dicarbonic strength, the calculated contents of bromine and sulfur in this copolyester are 6 and 0.34%, respectively. 128 parts (1 mol) of terephthalic acid 105 h (2.19 mol) of ethylene glycol, 20.5 h, (0.0421 mol) of the brominated derivative specified in examples 1 and 2 were introduced into the autoclave described in example 1. (molar ratio to terephthalic acid, 4.2%), 60 parts (0.024 mol) of 1-sulfobenzene-3, 5-dicarboxylic acid monosodium salt (molar ratio to terephthalic acid, 2.4%) and 0.6 hours (9,738 x X) titanium dioxide. After the products have been introduced, the temperature is quickly adjusted while simultaneously stirring; the ester exchange reaction was initiated at this temperature with the removal of water.
    After 90–93% (of the theoretical amount) of water accumulates for 200– 215 min, this material is fed to the second autoclave. In the second autoclave, the products specified in example 1 are introduced, in the same quantities, the polycondensation is continued in the same manner as indicated in example 1. The resulting polymer has the following characteristics:
    Viscosity H, dl / g 0.49 Acid groups, equivalent / m45
    Content, diethylene glycol, mol.% 2.1
    Br (found),% 5.9
    S (found),% 0.34
    Degree of lightness 40 degree of whiteness53
    The degree of yellowness 13 TC, SO
    LB, cm10., 8
    Example 5. A flammability test was carried out on test specimens obtained from an opolyester yarn prepared according to Example 2.
    The polymer is chemically molded and fibers drawn. Fibers have the following characteristics:
    Viscosity, dl / g 0.5 Gluteness (or bonding strength), g / den 4,1
    Elongation,% 19.2
    Weight number 70/24 The same initial sample prepared from fiber and ten prototypes prepared from it are subjected to fire resistance test. Average TS - O s, average LB - 12.3 cm.
    Consequently, despite the lower content of Cg and S in this polyester, the behavior of the samples when tested is similar to the behavior of the sample described in example 4.
    Example b. The synergistic effect of compositions containing bromine and sulfur when comparing the characteristics of self-extinguishing and retardation flames inherent in this copolyester.
    The test is to determine the number of ignitions necessary for the complete burning of a 50 cm long twisted yarn made of fibers consisting of various copolyesters, including the proposed copolyester and regular polyethylene terephthalate. Each twisted yarn is prepared by twisting 100 yarns having a weight of 70/24 denier (.10 twists per cm).
    The following composite samples are used: sample A - a co-ethylene terephthalate yarn containing 0.35% sulfur (obtained from the monosodium salt of sulfobenzene-1,3-dicarboxylic acid dimethyl ester) having a viscosity of l / ri
    Sample B — Conventional polyethylene terephthalate thread having a viscosity of 6.63 dL / g kJJQ;
    Sample C - a thread of copolyethene terephthalate containing 4% bromine (obtained from a brominated compound) and a viscosity of 0, b1 dl / g;
    sample D - a co-polyethylene terephthalate yarn prepared according to example 1, containing 0.35% sulfur and 5% bromine, with a viscosity of 0.50 dl / g.
    Before testing, the twisted yarns are kept in an oven with the purpose of conditioning them for 15 hours at. The amounts of ignition required for combustion listed in Table 1 are the averaged values of five measurements.
    Table 1
    I Sample 1 Ignition Number
    Since it was found that the presence of a sulfur-containing compound (Sample A) only affects the worse combustion of the polyester compared to conventional polyethylene terephthalate (Sample B), Sample D containing both bromine and sulfur should have less fire resistance than Sample C, which contains only bromine, i.e. Sample D should show the number of ignitions in the range from 10 to 19 if there were no synergistic effect between bromine and sulfur. The fact that instead of the indicated limit the number is ignited in the case of sample D is 25, it is indisputable that the simultaneous presence of components containing bromine and sulfur gives a synergistic effect when polyethylene terephthalates modified according to the invention are subjected to burning.
    Comparative data on the properties of modified fibers are given in table. 2
    table 2
    58 64 53 39
    one
    43 51 40 32 2 3
    40
    31
    Thus, the invention makes it possible to obtain co-uzations for forming fibers with a higher degree of lightness (40-51 and whiteness (53-64), less yellowness and improved fire resistance than the known fibers.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    A method for preparing a composition for forming fibers by transesterification of terephthalic acid or its dimethyl ether with ethylene glycol and a sulfated compound at 200-220 ° C, followed by polycondensation under vacuum in the presence of antimony oxide until the characteristic viscosity of the composition is 0.49-0.52 dl / g, About tl and h and y and by the fact that, in order to obtain fire-resistant fibers with a high degree of whiteness, the dimethyl ester 1-sulfobenzene 1, 4 is used as the sulfonated compound
    11.2 O O 17 12.3 10.8 19.3
    sixteen
    18.6
    -3,5-dicarboxylic acid or its sodium salt, and in addition 2.2ois -3,3-Dibrom-4 (2-hydroxyethoxy) -phenyl3-propane is introduced at the transesterification stage, and phosphorous acid at the polycondensation stage at the following ratio önie components, mol:
    Terephthalic acid
    or her dimethyl
    ether
    2.17-2.19
    Ethylene glycol
    Dimethyl complex
    1-sulfobenzene-3, 5-dicarboxylic ester
    acids or its nat0,02-0-0,0421 salt of riev
    2,2-bis (3,3-dibromo-4 (2-hydroxyethoxy (fe0, 0197-0.0232 nyl) propane)
    Phosphorist
    gz
    0,489-10
    acid
    Sources. Information taken into account during the examination 5 1. Japanese patent 48-5256,
    cl. 25 (1) 032, publ. 1973 (prototype),
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    同族专利:
    公开号 | 公开日
    GB1590238A|1981-05-28|
    JPS53118495A|1978-10-16|
    US4209606A|1980-06-24|
    NL7801607A|1978-08-17|
    IT1075572B|1985-04-22|
    FR2380311A1|1978-09-08|
    AR223957A1|1981-10-15|
    DE2806944A1|1978-08-17|
    CA1111187A|1981-10-20|
    PL115324B2|1981-03-31|
    SE7801688L|1978-08-15|
    ES466946A1|1978-10-01|
    FR2380311B1|1985-03-22|
    BR7800831A|1978-10-10|
    CS214768B2|1982-05-28|
    PL204614A1|1978-10-09|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    RU2533675C1|2011-09-26|2014-11-20|Канека Корпорейшн|Fire resistant yarn, fabric, clothing and fire resistant workwear|US3794617A|1972-03-15|1974-02-26|Emery Industries Inc|Copolyester fiber compositions having improved flame retardant properties|
    US3935166A|1973-06-08|1976-01-27|Teijin Limited|Aromatic polyester of 2,6 and/or 2,7 naphthalene dicarboxylic acid|
    US3873504A|1973-10-03|1975-03-25|Fmc Corp|Flame-retardant copolyester resin containing dialkyl tetrabromo diphenoxyalkane dicarboxylates|
    IT1045047B|1975-10-20|1980-04-21|Snia Viscosa|THERMOSTABLE FIREPROOF AGENT FOR COPOLIESTER|AT365182T|2003-12-22|2007-07-15|Amcor Ltd|PREFORMS AND SOLID CONTAINERS FROM AROMATIC POLYESTER COMPOSITIONS AND METHOD FOR PRODUCING SUCH CONTAINERS|
    BRPI0417296A|2003-12-22|2007-03-13|Amcor Ltd|rigid parison or container made from at least one polyester resin, and process for producing a container|
    US20080167440A1|2007-01-10|2008-07-10|Pickel Deanna L|Use of copolymerizable sulfonate salts to promote char formation in polyesters and copolyesters|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    IT20278/77A|IT1075572B|1977-02-15|1977-02-15|SELF-EXTINGUISHING AND THERMO-STABLE COLOPYESTERS AND PROCEDURE TO OBTAIN THEM|
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