• 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:
    In order to improve the mill release and green strength of an elastomeric copolymer derived from ethylene; alkyl acrylates or vinyl esters of carboxylic acids; and alpha , beta -unsatruated monoor dicarboxylic acids, which copolymer may optionally contain segments derived from carbon monoxide, sulfur dioxide or acrylonitrile, a small quantity of one or more specific chromium (III) compounds are incorporated into the copolymer. A process for the preparation of the copolymer is described and exemplified, and vulcanizable compositions containing the copolymer and vulcanized articles prepared therefrom are described.
    公开号:SU1083913A3
    申请号:SU792739299
    申请日:1979-03-15
    公开日:1984-03-30
    发明作者:Марк Коуен Гордон
    申请人:Е.И.Дюпон Де Немур Энд Компани (Фирма)；
    IPC主号:
    专利说明:

    00
    with f
    oo The invention relates to the plastics industry and concerns the development of a method for producing a polymer. A known method for producing a polymer composition by mixing carboxyl-containing polymer, for example, a copolymer of butadiene, styrene, and methacrylic acid with a building agent — metal oxide in an amount of 2-5 meq. per 100 weight parts polymer, followed by heat treatment at til, However, this method does not improve the physicomechanical properties of the composition. The purpose of the invention is to improve the physico-mechanical properties of the composition. This goal is achieved by the fact that according to the method of obtaining a polymeric composition by mixing car. a bauxyl-containing polymer with a jet (setting agent AG, followed by heat treatment, a carboxyl-containing polymer is mixed at 2050 C, a polymer selected from the group of ethylene copolymer with methyl acrylate and ethyl-H-maleate in a ratio of 42: 54: 4, ethylene copolymer with methyl acrylate and methacrylic acid in a ratio of 45g53; 2, a copolymer of ethylene with methyl acrylate, carbon monoxide and ethyl H-maleate in a ratio of 63–26: 5; 6, a copolymer of ethylene with vinyl acetate and methacrylic acid in a ratio of 66: 29: 5, a copolymer of ethylene with vinyl acetate and ethyl nemaleate in sootn 68 g30: 2, and as a structuring agent - chromium carboxylate, selected from the group 2 chromium 2-ethylhexanoate, e chromium oleate, 3- (2-hydroxyacetate) chromium, neodecanoate chromium, chromium acetate, 0,7814 mEq per 100 wt% h: polymer, and the heat treatment was carried out at SO-XZO C. Example 1 about A mixture containing h "; carbon black-16 poly (ethyleneoxy) glycol, mol 4000 4000;; ((, d-dimethylbenzyl ) diphenylamine 0.8 3- (mixed mono- and dinonylphenyl) phosphite 0.8 and ethylene copolymer obtained at high pressure by polymerization in mass (42 wt.% ethyl, 54 wt.% methyl acrylate and 4 weight ethyl H-maleate, melting index at 190 ° C. Approximately 9 g / 10 m 81 is treated with several metal salts on a double roll roller. The salts are mixed with the polymer on unheated walds, then the mixture is heated for 5 minutes at a rolling temperature to conduct a chemical reaction. Mixing is carried out continuously at 125 s by folding the rubber within the rim bands obtained by diagonal cutting the polymer strip on the roller of the rollers. Table 1 presents the salts used to treat rubber, their effect on the bulk viscosity of the polymer and adhesion to heated roller rollers. If the adhesion is so great that the rim tapes cannot be cut and cannot be folded as described above, then the mixture is indicated as inoperable. The data show that only chromium 2-ethylhexanoate (W) provides a mass that can be removed at and with which to work, chromium 2-ethylhexanoate (w) also gives a volumetric viscosity greater than the viscosity obtained with an equivalent or more other metal salts. Example 2. A mixture containing different metal salts is prepared in the compositions shown in Table 2 from ethylene (methyl acrylate) methacrylate acid of a terpolymer obtained under high pressure by bulk polymerization. All ingredients are mixed with polymer on an unheated two-roll mill. The mixture is then heated for 5 minutes at the temperature of the rolls for the hilmic reaction. Mixing is carried out at 125s by folding within the rim bands of rubber obtained by diagonal cutting of a polymer strip on a roller roller. Table 2 shows the compositions of rubbers and the effect of various metals on the bulk viscosity of the polymer and adhesion to the heated rollers of the rollers. Adhesion is determined by the impossibility of cutting loose bands in the mass (as described above) at 125 ° C and separating the mass from the rolls after 5 min of reaction. The results show that only chromium 2-ethylhexanoate leads to a mass that can be separated at. This salt results in a bulk viscosity that is noticeably greater than a non-metal control sample. Froze The mixtures with increasing volumetric ecologically are prepared according to the compositions indicated in Table 3 in a water-cooled mixer. The mixer is loaded with a half amount of thermoplastic rubber (terpolymer), then all ingredients are loaded and then the remaining terpolymer. The temperature of the tank mixer during loading 40-50 ° C. As can be seen from table 3, the increased amount of chromium 2-ethylhexanoate added leads to
    increase in bulk viscosity of rubber. In spite of the use of the organometallic salt of rubber, they do not adhere strongly to the two-roller mill, placed under the mixing chamber for the selection and transformation into a strip of hot material leaving the mixer.
    Example4. The mixture of example 1 is treated with various amounts of several salts of carboxylic acids of chromium and 2g hydroxyacetophenone chromium chelate. Additives are mixed with rubber (about 185 grams) on two roll rollers 8 without heating. In the case of a salt of acetic acid with rubber mix the aqueous solution of the additive at a temperature of rollers 60 ° C. The mixtures are heated on rollers for 5 minutes at 125 seconds to conduct a chemical reaction.
    Table 4 shows the effect on bulk viscosity and rubber adhesion. Adhesion is determined by impossibility at 125 ° C to cut rim ribbons in the mass of a strip, - co; The torus is folded over the rollers to effectively continue mixing. The adhesion is also determined by the impossibility of separating the mass from the roller, bodies at the reaction temperature. .
    It can be seen from the above data that at low chromium contents (0.8 mEq of chromium per 100 g of polymer) sticking can occur. If adhesion exists, the bulk viscosity is not significantly different from the viscosity of the raw polymer. At elevated levels of chromium, no adheside.
    Example 5. Similar to the method of mixing and reacting the various additives of metal salts to rubber, described in example 1
    Table 5 presents the salts used to treat rubber and their effect on bulk viscosity. polymer and adhesion to heated rollers. Only chromium 2-ethylhexanoate results in viscosity at low levels of additives, without causing sticking of the mass with the HarpeTHNDi roller rollers. Some salts, such as iron 2-ethylhexanoate, zinc 2-ethylhexanoate and tin 2-ethylhexanoate, cause such a large increase in viscosity at elevated levels of additives that the polymer mass does not adhere to the convertible rollers, but is not suitable for processing. Among the salts listed in Table 5, at metal concentrations of about 3.5 meq per 100 g of polymer, chromium 2-ethylhexanoate (III) results in the highest viscosity
    Example b. The properties of rolling and bulk viscosity with copolymers containing are evaluated.
    some carboxylic acids, and determine the effect of treating polymers with chromium 2-ethylhexanoate, magnesium stearate and zirconium 2-ethylhexanoate.
    The polymers are obtained by bulk polymerization at high pressures.
    Characteristics of ethylene copolymers are given in table 6.
    Raw copolymers are rolled on two-roll rollers heated to 5 minutes. Evaluate the ability to obtain diagonal cuts on a hot spread polymer mass and
    with ribbons of material that are folded on the rollers (for mixing the mass). Also evaluate the ability to separate the mass from the rollers at 100 ° C. Sticking is intended for those samples of masses of polymers
    which cannot be folded and detached from the roller without cooling.
    The copolymers are also treated with metal salts, heated on rollers for 5 minutes and then evaluated for adhesion and bulk viscosity.
    Data on adhesion and viscosity are presented in Table 7.
    Salt metal treatment. 0 Е / МА / СО / МАМЕ. 50 g of polymer are valted and treated with 0.5 g of chromium 2-ethylhexanoate (8 wt.% Chromium) at room temperature. Another portion in 50 g of polymer is treated with 5k) t in the same way at room temperature, 0.7 g of magnesium stearate. The next portion in 40 g of polymer is treated in a similar way at room temperature with 0.4 g of 2 ethyl hexanoate zirconium (17 wt.%
    zirconium).
    E / UA / MAA. A portion of 50 g of polymer is rolled on rollers at 60-70 ° C and cooled to room temperature to add 1.5 g of 2 ethylhexanoate chromium (III) (8 wt.% Chromium). Another portion of 50 g of polymer is treated in the same way with 0.7 g of magnesium stearate. Then the mass is heated to 100 ° C, but due to the fact that it
    0 stuck together with a roller. An additional 1.4 g of magnesium stearate (total 2.1 g) is added at room temperature. The following portion of 50 g of polymer
    5 rolls at 60-70 ° C, cooled before and treated with 1.5 g of 2-ethylene7 zirconium hexanoate (17 wt.% Zirconium).
    E / UA / MAME. A portion of 40 g of polymer is treated with 0.4 g of chromium 2-ethylhexano.at (8 wt.% Chromium) on valtsars heated to 65 ° C; At 65 and the mass was sticky and then heated for 5 minutes at a higher temperature, add
    0.4 g of chromium salt, heated to 100 ° C. The following portion of chromium salt 0.4 g (total 1.2 g) is added at.
    Another portion of 40 g of polymer is treated with 1.6 g of 2 zirconium ethylhexanoate (17 wt.% Zirconium).
    E / MA / MAMA. A portion of 50 g of polymer rolls on two-roll rollers at room temperature and treatment of 0.2 g of 2-ethylhexanoate chromium (III) (8 wt.% Chromium). Another 50 g portion of the polymer is treated in the same manner with 0.7 g zirconium 2-ethylhexanoate (17 wt.% Zirconium).
    Table 7 shows the effect of metal salts on bulk viscosity and adhesion of some carboxyl-containing ethylene copolymers to hot rollers.
    PRI me R 7. (Chromium 2-ethylhexanoate is included as a control).
    The rubber described in Example 1 is treated with various salts of chromium by mixing on a two roller roller at room temperature. Aqueous solutions and suspensions are added to the crushing rubber, and the rubber is rolled at. The mass is then held for 5 minutes on rollers heated to 125 ° C for a chemical reaction.
    Table 8 shows the effect of additives on bulk viscosity and rubber adhesion. A diagonal section of the heated roll polymer and rim tapes that can be folded on the rolls to mix the mass are obtained, the ability to separate the weight from the rolls at 125 ° C is evaluated. Adhesion is observed in polymer masses for which rim tapes cannot be obtained and which cannot be separated without some cooling of the gel rolls.
    The results show that most chromium compounds are ineffective, since they do not prevent sticking, but increase viscosity. In some examples, sticking is absent if the chromium content increases to such an extent that the viscosity reaches an almost inapplicable high level.
    Thus, the offered rubbers in comparison with the known ones are characterized by better physicomechanical properties.
    Table 1
    Chromium 2-ethylhexanoate (B wt.% Chromium)
    0.56
    Cobalt 2-ethylhexanoate (12 wt.% Cobalt)
    0.56 n-butyltin hydroxide 0.56 10.8 oxide Nickel acetylacetonate 0.56 4.4
    Titanium butoxide (14 wt.% Titanium)
    0.75
    Titanium (di-isopropoxide) bis (2,4-pentanedionate) (9.9 wt.% Titanium)
    2.6
    38
    Yes
    Yes
    2.3
    Not
    20
    Not
    8,8
    Not
    24
    Not
    6.2
    Not
    28
    No No No 30 No No 22
    Ethylene (methyl acrylate) methacrylic acid
    . Soot
    Poly (ethyleneoxy) glycol (mol. Weight. 4000)
    4,4-bis (ot D-dimethylben zil) -diphenylamine
    Three (mixed mono - and dinophenyl) phosphite
    Chromium 2-ethylhexanoate
    Sodium stearate
    Zinc oxide
    mEq metal / 100 g polyme
    Sticking to heated roller ()
    Viscosity Ethylene (methyl acrylate) methacrylic 45/53/2 and with a melting index of 9 Cr (III) 5.5 wt.%.
    Ethylene (methyl acrylate) ethyl-N-maleate, g
    Soot SRF N 774, g
    Poly (ethyleneoxy) glycol (mol. Weight 4000)
    4, (oC, eC-Dimethylbenzyl) diphenyls1min
    .Table 2
    150
    150
    100 30 20 30
    3.0
    3.0
    2.0 b5 1.5
    1/0 l, 5 1,5
    1.0
    1.0
    45
    1.5
    14.8 36.9
    3.2
    Not
    Yes 16
    Yes 16 74
    43,100 43,100 .43,100 43,100

    8,6208,6208,6208,620
    862
    862
    862
    862
    431
    431
    431
    431 acid in a weight ratio of g / 10 min at. T & b l and c a 3 Terpolimer contains, wt%: ethylene 42, ethyl H-maleate 4. Cg (III) 5.5 wt.%. five%
    Chromium 2-ethylhexanoate, 5.5% chromium
    Chromium oleate, chromium 4.5%
    Chromium acetate (in water) (mol. Weight; 247.2) The same
    Continued table. 3
    Table 4
    0.27 0.78 0.53 1.5 1.5, 4.3
    0.86
    1r7
    3.2
    0.86
    2.6
    3.9
    1.6 4.0 methyl acrylate 54 to
    Also
    3 (2-hydroxyacetophenone) Note ..
    Without additives
    Chromium 2-ethylhexanoate (5.5 wt.% Cr)
    2-Ethylhexanoate cerium (III) (6 wt.% Cerium)
    2-Ethylhexanoate cerium (III) (6 wt.% Cerium)
    Zinc Oxide 2,4-Zinc Pentanedionate
    Zinc 2-ethylhexanoate (18 wt.%)
    Continued table. four
    12.1
    Not
    126
    1.0
    T a b l and c a 5
    20 1/2
    Not
    11.0
    32
    Yes The terpolymer contains 42% by weight of ethylene, 54% by weight of methyl acrylate and 4% by weight of ethyl H-maleate. The acid content is 35 meq / 100 g of polymer.
    Magnesium oxide (, flax product) 1.0
    2-Ethylgee Nickel Note,
    Continuation of table.5
    49,6
    23
    Yes terpolymer contains, wt%: atilen42, methyl acrylate 54 and monoethyl maleate 4, Acid content 35 meq / 100 g of polymer.
    E / MA / CO / MA
    Not
    2-Ztilge chromium sanoate (W)
    2-ethylhexanoate zirconia
    Magnesium stearate
    Table b
    Table 7
    Yes
    57 No
    /
    13 1/2
    Yes Yes
    b
    / UA / MAA
    Not
    2-Ethylhexanoate
    chromium (W)
    (8 wt.% Chromium)
    2-ethylhexanoate zirconium (17 wt.% Zirconium) 23
    Magnesium Stearate 14 No
    / UA / MAME
    2-Ethylhexanoate
    chromium (W)
    (8 wt.% Cr.) 14
    Zirconium 2-ethylhexanoate (17 wt.% Zirconium) 30
    / MA / MA
    Not
    2Tethylhexanoate
    chromium (W)
    (8 wt.% Cr) 1.8
    2-ethylhexanoate zirconium (17 wt.% Zirconium) 10
    2 Chromium ethyl hexanoate (8 wt.% Chromium)
    CrCf 6H2O
    Continued table. 7
    74
    46 16 1
    86
    28 1/2 19
    61
    33 1/2
    Table &
    Chromium methacrylate chloride (industrial product, chromium complex, B wt.% Chromium)
    - Stearate chloride (industrial product, bwt% chromium).
    - Chromium benzoyl acetonate
    , 7
    Cr2 (003) 3 (aqueous suspension, 1 compound per 5 ml of water)
    Cr (OH)) (water suspension
    1 g of compound per 5 ml
    water)
    Cr (VOL. (Solid
    substance 21 wt.% chromium) 1.0 Note:
    Continued table. -eight
    66,112
    Well no
    40
    Yes
    106 No 16 1/2 No 39 yes
    20
    Not
    19 19
    No No terpolymer contains, wt%: ethylene 42; methyl acrylate 54; monoethyl maleate 4. The acid content is about 35 meq / 100 g of polymer
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING A POLYMERIC COMPOSITION by mixing a carboxyl-containing polymer with a structuring agent followed by heat treatment, characterized in that, in order to increase the physicomechanical properties, COMPOSITIONS / are mixed at 20-5 gC carboxyl-containing polymer selected from the Group ethylene-methyl acrylate copolymer! N-maleate in a ratio of 42: 54: 4, a copolymer of ethylene with methyl acrylate and methacrylic acid in a ratio of 45: 53: 2, a copolymer of ethylene with methyl acrylate, carbon monoxide and ethyl H-maleate in a ratio of 63: 26: 5: 6, copoly p of ethylene with vinyl acetate and methacrylic acid in a ratio of 66: 29: 5, a copolymer of ethylene with vinyl acetate and ethyl H-maleate in a ratio of 68: 30: 2, and as a structuring agent, chromium carboxylate selected from chromium 2-ethylhexanoate group, chromium oleate, 3- (2-hydroxy- § acetophenone) chromium, chromium neodecanoate, chromium acetate, chromium stearate in the amount of 0.78-14 meq. per 100 parts by weight of polymer, and heat treatment is carried out at 100-130 ° FROM.
    SU „1083913>
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3245968A|1961-12-20|1966-04-12|Minnesota Mining & Mfg|Cross-linking polymers with a chromium coordination comoplex of fluorine or chlorinesubstituted aliphatic carboxylic acid|
    US3249570A|1962-11-15|1966-05-03|Union Carbide Corp|Terpolymer of ethylene, alkyl acrylate and acrylic acid|
    US3267083A|1963-06-07|1966-08-16|Union Carbide Corp|Reprocessable crosslinked polymeric compositions|
    US3345352A|1964-02-21|1967-10-03|Allied Chem|Catalytic process for the thermal degradation of polyolefins|
    GB1141354A|1965-10-21|1969-01-29|Ici Ltd|Stabilisers for polymers|
    US4038228A|1971-11-19|1977-07-26|Owens-Illinois, Inc.|Degradable plastic composition containing a transition metal salt of a highly unsaturated organic acid|
    US3904588A|1973-08-09|1975-09-09|Du Pont|Random ethylene/alkyl acrylate 1,4-butene-dioic acid terpolymers|JPS625942B2|1983-01-12|1987-02-07|Osaka Soda Co Ltd|
    JPH06507669A|1991-05-13|1994-09-01|
    US5214108A|1992-07-10|1993-05-25|E. I. Du Pont De Nemours And Company|Process for modifying the viscosity of copolymers of ethylene and unsaturated carboxylic acids|
    US5492971A|1994-05-19|1996-02-20|E. I. Du Pont De Nemours And Company|Curable ethylene copolymer blend composition|
    US5464903A|1994-10-31|1995-11-07|E. I. Du Pont De Nemours And Company|Process for preparing ethylene copolymer plasticized PVC|
    US7153918B2|2003-07-24|2006-12-26|E. I. Du Pont De Nemours And Company|Random ethylene/alkyl acrylate copolymers, compounds and elastomeric compositions thereof with improved low temperature properties|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US05/887,330|US4304887A|1978-03-16|1978-03-16|Ethylene/carboxylic acid copolymers|
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