• 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 bond strength between a sulphur-vulcanisable rubber and a metal, especially brass, is increased by using as bonding promoter an organic substance containing one or more groups of the formula -S-S02R where R represents (a) a radical -OM where M is a monovalent metal, the equivalent of a multivalent metal, a monovalent ion derived by the addition of a proton to a nitrogenous base or the equivalent of a multivalent ion derived by the addition of two or more protons to a nitrogenous base, or (b) an organic radical. Preferred promoters include sodium, zinc, nickel and cobalt organothiosulphates.
    公开号:SU1398777A3
    申请号:SU833654051
    申请日:1983-10-20
    公开日:1988-05-23
    发明作者:Дельсет Жан-Марк；Эмиль Мауер Даниель；Жераф Моньотт Филипп
    申请人:Монсанто Юроп С.А. (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to the field of producing a composite material based on rubber and metal, in particular, to a method for attaching rubber to brass.
    The purpose of the invention is to increase the strength of the connection with aging.
    Prepare a vulcanizable rubber (monomer of the following composition j mac.:Natural rubber 100 Carbon black type HAF55
    Zinc Oxide8
    Stearic acid 2 M gchitel3
    Amplifier stickiness 3 Antiozonant2
    Antioxidant I
    Sulfur4
    Accelerator0.7
    Clutch promoter
    , As an antiozonant
    ,one
    3
    use coziness, 3-dimethylbut: il-L-fensh1-p-freshlandamine, as an antioxidant - a - polymerized 2,2,4-trimethyl-j, 2-dihydroquinoline, as usko- | It is 2- (morphochganthio) benzthiazole9, ia with the exception of the case noted in (tabl. 1 asterisk, where the accelerator is N-dicyclohexylbenzothiazole-2-sulfenamide.
    In comparative experiments with the use of kobafat naphthenate, 1.5 May is used as an ikpoMOTopa clutch. cobalt naphthenate, containing 10 May. % cobalt
    The components are mixed with the exception of sulfur and the accelerator are carried out with a laboratory mixer with Venbury of 1.57 liters with a filling factor of 0.8 and a rotor rotational speed. And 7 rpm in a lightly blended mode:
    Time, min
    0Downloading rubber into the mixer and turning on the rotors
    1 Addition of half carbon black and zinc oxide 2.5 Introduction of carbon black residue, stearic acid, softener, tackifier, 1 antiozonant, antioxidant, promoter, adhesion
    4 scraping
    5Discharge at 150-5 0 Then the initial mixture at 75-70 С
    translated into a map, al rollout0
    five
    0
    five
    0
    five
    0
    five
    0
    five
    nor, after which sulfur and accelerator are introduced into separate portions of the initial mixture in the mill.
    The metal component of the proposed composite material is a typical tire metal cord coated with brass and having a structure of 3 + 9 + 15 x 0.175 + 1. In most cases, the thickness of the brass cord coating is 0.20 µm with a copper content of 63.5 ± 3 wt.% The results, indicated by: an asterisk, are obtained using a cord, the brass coating thickness of which is 0.18 µm with a copper content of 67.5 - 3 wt.%.
    The adhesion strength of rubber with megatall is determined by testing adhesion according to ASTM D-2229, but using clamping plates to hold cords in shape and maintain straightening during vulcanization and a frame to preload the cord and evenly distribute the stress across its surface. Before preparing the molds, appropriate packages of rubber and cord layers adhering to one another are prepared, which include a strip of rubber, one edge of which has one end of each: several of the cord pieces located at the same distance, with one end of each pieces of the cord are embedded in the edge of the strip opposite to the first edge, with the last pieces of the cord arranged in ledges relative to the first in the first edge of the rubber strip.
    The strength of the clutch bag is measured using a tensile tester, positioning the bag so that the cords run vertically and the rubber strip horizontally, holding the lower two wires and pulling out the upper wire between them at a crosshead speed of 5 cm / min. . The recorded pull force is the average of each of the lower cords, with the exception of the cords located at each end of the strip, which are not taken into account in order to eliminate possible end effects. Those cases when, when tested, the pulling force exceeds the breaking load of one or several wires. The box is indicated in the tables by the symbol, Rubber coating on the extract 1398777
    Priced cords are rated based
    scales from O (bare cord) to 10I
    (100% coverage) by comparing 7-NaO, S ,, - {CH), - C-O- (CH)., S:, 0, Na
    with standards. High percentage of coverage
    indicates to a greater extent the failure of iNaO SiCCHj) ,,, COO (CHj) J o
    in the work of the rubber phase than on | yk
    rubber surface separation section-9.KoOs82 H2 O / CH2 $ 20s C
    metal, and may mean rubber;
    has poor physical properties, IQCHoS OlNfl
    if it is not affected by high-jl
    attracting effort .tO ff) l
    The data given in the tables are from-rtr to -kg
    aging, steam aging and ig
    aging in salt bath obtained
    with respect to the initial adhesion, air aging, steam aging and aging in a salt bath are obtained with composite material packages, where the rubber was vulcanized at JAS C for T, d + 5 min, where T is the period CH2 $ 20 from C1
    time, min, required to reach - 20 wives 90% of the maximum modulus for
    sample of this rubber, vulcanized-2.aS2,0-j () S02 (CE) in the rheometer according to the British method
    Standard Test Method 1673 Part 10., - -. ",", With l "h
     I3.O C (CH ,, S-OaNa),
    Packages designed for air - 25 g
    before aging after the test
    vulcanization at 85 ° C is maintained in. 14. j-n f
    conditions according to the British method
    Standard Method 903, Part A. 19, (1975). R
    Packages designed for steam AOR
    aging, kept in steam atmog (P - -COCH CHjSjOjNa)
    Sphere under pressure for 8 hours at
    120 С, and the packages intended for Table 2 show the results of the estrusion in the salt bath after the torture when used as
    Canization and before testing, adhesion promoters of the mixture and match into 5% solution of chloride of sodium sodium bis-thionate. The data given in the table of sulfates and nickel salts of the following
    in the column labeled 2 T-, formulas (excluding the possible presence of
    get with packages, vulcanized water of crystallization):
    during the double period t. 40
    B Table 1 shows the test data of j pg g (cn) g about the scientific research institute when using di- and trisodium salt of the J salts of the salts as promoters of z., .4 +
    the following formulas (excluding 2. {, OjS2 (CH, j) g, J Ni, the possible presence of crystallization
    . O SJCH2) ,,

    1.NaO, Sj (CHj)., S, 0, Na4. 0, Si- (CH, j) 4-0- (CH ,,)
    2.NaO, S, (CH,), S, 0, Na50 - „. (. (CH,), S,
    3.NaOjSiCCHz),, Na
    6. 0, S, - (CH,), -COO (CH), O N3
    4.NaOjt; St-tCHj) -0- (CH2) 4, Na
    5j &
    5.NaO, S «- (CHt) -0-CH ,, - 0- (CHj) 4S20, Na - 05Sj (CH, i) 0-CH2-0 (CH.,) S O jNi
    +44
    +44
    6. NaO, S4- (CH) -0-CH., - 0- (CHj) 8. O.S (CH) SO (CH), - Ni
    .f +
    Os8, CH, - O CHaSiO-3 wi
    w + - CHgSgOg
    The mixtures are obtained by passing a solution of sodium salt through a cation column, loaded with nickel, and by vaporizing the elgaate. An elemental analysis of the products obtained shows that about 50% of the original sodium is extruded by nickel, except for promoter 2, where about 30% has been supplanted.
    In tab. 3-results are given using 5. 5, S jCH, CH-jSjO, 2Na
    tortures obtained with different adhesion promoters of the following formulas or names (excluding the possible presence of crystallization water):
    6. Barium salt hexamethylene-1, bis (thiosulfate)
    .. +
    1.lc Vi OOCCE Cll.
    2. A mixture of CHj (CHj)., Ni and.
    CH, (CH,). S,
    3, (CHi) s, o; with
    4. -8gOz (SNa) b8gO; BUT,
    where A is H-benzyl K1, 1,3,3-tetramethylbutylammonlautrate nickel
    5.Laurat nickel
    II
    6. Mix 2 mac. nickel laurata and 2 ma.ch. NaO, | S.j (CH ,,) gS, 03Na
    From a comparison of the results obtained with promoter 3 in Table 3, with the 12 Gs H CH S O N results, obtained with l 6 -z g 3 j cobalt naphthenate (tab.), It is clear that the negative effect on aging can be prevented if at the same time
    cobalt and anions are present in the organic-50 feHj-CH S Oj of cell thiosulfate.
    The results in table 4, are obtained using the described vulcanizable rubber composition, N, N + 414. nC, H ,, s,
    dicyclohexylbenzthiazole-2-sulfenamide as a vulcanization accelerator, a cord e coated with brass with a copper content of 63.5–3 May.% and
    S 5 87776
    adhesion promoters of the following formulas or names (excluding the possible presence of water of crystallization):
     I. CH OOCCHSj OjNad.e parts by weight /
    I / 100 mah.ch.ukuchuka) CH,
    2.2,2,4-Trimethyl-1,2-dihydroquinoline salt of hexamethen-1,6-bis- (thiosulfate)
    3.Y-Isopropyl-Y - (p-phenylaminopheg NIL) -ammonium salt hexamethylene-1,6-bis- (thiosulfate)
    4. | icH-OTj-lCH-CH2) i-Ctt-CHj 1 (mean | ococHj he bco CHajsSjOjTfoJ formula)

    6. Barium salt of hexamethylene-1,6-bis (thiosulfate)
    7. Magnesium salt of hexamethylene-1,6-bis (thiosulfate)
    8. Zinc salt of hexamethylene-1,6-bis (thiosulfate)
    9. A mixture of 3 ma.h. disodium salt of hexamethylene-1,6-bis (thiosulfate) and 1 wt. nickel chloride
    9A. Nickel chloride (1.0 parts by weight / / 100 parts by weight of rubber)
    V4
    HE,
    10. rCH, OOC-CH-S o; 1 N3 (1.41 mas.h./ - - - / UOmas.ch.
    rubber)
    II

    + (1.33 parts per unit hours / / 100 parts units rubber)
    (1.36 parts per hour / / May 100 h. Rubber)
    14. n-C, H ,, S,
    4 +
    55
    (1, 36 mash./100 mash of rubber)
    The results shown in table 5, are obtained by the use of vulcanized
    rubber composition having the same components, except that the rubber is a mixture of 80 wt.h. natural rubber and 20 ma.ch. polybutadiene-1220, accelerator - H, K-dicyclohexylbenzthiazol-2-sulfenamide (1.0 parts by weight, per 100 parts by weight of rubber), in experiments 1-3 the cord is made of steel wire coated with brass with copper content 63 , 5%, in experiments 4-6 - from steel wire coated with a three-component alloy of 70% copper, 4% cob alto and 26Z zinc.
    The results presented in Table 6 are obtained with the following rubber mixture, iTaBOM, w.ch .: Natural rubber 30
    25,

    five




    67.5
    60 (61 mach., On
    May 100 ..h rubber)
    (5.1 parts by weight per 100 parts of rubber)
    (1.53 parts per 100 parts per rubber)
    (10.2 parts per hour per 100 parts per rubber)
    (3.07 parts by weight per 100 parts of rubber)
    1.5
    .ten
    (4.1 parts by weight per 100 parts of rubber)

    (3.07 parts by weight per 100 parts of rubber)
    N-1,3-dimethylbutythyl-N-phenyl-n-phenylenediamine is used as an antidegra- dant, and polymerized 2,4,4-trimethyl is used as an antioxidant.
    -
    ten
    15
    a 20
    987778
    Tyl-1,2-dihydroquinoline, as a vulcanization accelerator - S, H-dicyclohexylbenzthiazole-2-sulfenamide.
    Table 7 shows the results of experiments on the study of the effect of different amounts of sulfur in vulcanizable compositions. In these experiments, the clutch promoter serves as a heahydrate of nickel eol 1,6-heceamethylene (thioyl sulfate) (1.0 mas.h. per 100 mas.h. kaut1uk), otherwise it does not differ from that used to obtain the results given in Table 1, for the results indicated by an asterisk, and with the exception that the accelerator is N-tert-butylbenzthiazole-2-sulfenamide. The brass coating on the cord contains 63.5-3 May.% Copper. Results, indicated with an asterisk, are obtained with application-. Eat composition containing 0.5 wt. stearic acid at 100 ma.ch. rubber Results show optimal properties with sulfur content of 3-4 May, h. on 100 ma.ch. rubber
    Table 8 shows the results of experiments on the study of the action of different amounts of the coagula of the coagula with the metal — the hexahydrate of the nickel salt of 1,6-hexamethylene bis (thiosulfate) (HTSNi). The rubber composition is otherwise not different from that used to obtain the results shown in Table 1, c2- (morpholinthio) benzthiazole as an accelerator. The values enclosed in brackets are obtained for a brass-coated cord containing 67.5 ± 3 wt.% Copper. Other values are obtained for a cord with a brass coating containing 63.5- ± 3 wt.% Copper.
    The high activity of promoting adhesion of the rubber to the metal appears already at 0.75 wt.h. HTSNi on
    25
    thirty
    35
    40
    45
    50
    55,100 ma.h. rubber, and the optimum activity - at 1.0 mach. HTSNi.
    In other experiments, the results of which are given in Table 9, the promotion of adhesion of brass with rubber to hexahydrate of nickel salt of 1,6-hexamethylene bis (thiosulfate) and other nickel compounds is equalized, and the clutch promoter is used in an amount of 1.0 May. h on 100 ma.ch. rubber The rubber composition does not otherwise differ from that used to obtain the results given in
    Table 1, with N, H-dicyclohexylbenzthiazole-2-sulfenamide being used as an accelerator. The cord has a brass coating with a copper content of 63.5 ± 3 wt.%,
    HTSNi exhibits better promoting activity than other nickel J compounds, in particular with aging salt bath 3.
     Table 10 shows the evaluation results of various rubber-metal adhesion promoters used
    : in the amount of 1.0 mach., per 100 mach.
    ; rubber (rubber composition analogues: chen composition used in Table 1
    and 2, moreover, 2- (morpholinthio) benzthiazole cord is used as an accelerator and has a brass coating with a copper content of 63.5-3% by weight), using the promoters of the following formulas (excluding the presence of crystallization of: water)
    II
    12.
    (C ,,) Ni
    C ,, Na
    CH2 CHCH2 8.05 Ma CH,
    SN-CHCHN CH 2 S., O 3 Ka
    sixteen.
    (,, 5гО,
    ) Ni
    Cl (CH2) j 0, S (CH,),
     Sj
    Ob mn
    Consider methods for preparing individual monothiosulfates.
    Benzylthiosulfur nickel.
    57.5 g of sodium benzylthiosulfate and 14.2 g of anhydrous nickel chloride are mixed in absolute methanol (150 ml) at room temperature. The resulting mixture is then stirred for 24 hours, filtered and the methanol is evaporated, separated from the filtrate. In order to remove residual methanol, the residue is treated with 50 ml of water, after which the resulting solution in vacuum at a temperature not exceeding 50 ° C is evaporated by dosztha.
    Analytical data of the residue,%: Ni (by titration) 10.23; Ben
    five
    0
    five
    five
    0
    zylthiosulfate (NMR spectrum) 68.8, water (NMR spectrum) 21.2.
    The obtained analytical data correspond to the formula
    SbN5CH 520-.K 7 N,., 0. Yield 62%. In a similar way, cobalt benzylthiosulfate, nickel p-heptyl thiosulfate, nickel 2,5-dioxyphenyl thiosulfate (from potassium salt) are obtained. Nickel dodecylthiosulfate, nickel 1- (methoxycarbonyl) ethyl nicotriosulfate, nickel 2-phenylethylthiosulfate, nickel p-butylthiosulfate and 2- (ethoxycarbonyl) ethyl I-thiosulfate of nickel are prepared by ion exchange from sodium salts.
    Sodium allyl thiosulfate. A mixture of 100 g of allyl bromide, 212.5 g of sodium thiosulfate, 90 ml of ethanol and 40 ml of water is stirred and heated to reflux for 15 minutes to obtain a homogeneous solution. Then, the resulting solution is cooled a little, and then NOL and water are released under vacuum.
    The solid residue is added to the absolutized ethanol, after which the solvent is evaporated in vacuo to remove additional water. The residue is then stirred with hot ethanol (800 ml) and the suspension thus obtained is filtered. After cooling, a white solid (109.2 g) precipitated from the filtrate.
    The NMR spectrum of the solid shows that it contains, in wt.%: Sodium allyl thiosulfate, 80; water 11; inorganic salt 9.
    Sodium 3-chloropropyl thiosulfate is obtained by reacting 1-iodo-3-chloropropane with sodium pentahydrate-thiosulfate in aqueous ethanol under conditions that ensure the primary substitution of iodine in the starting material, although the product contains some amount of propane-bis-thiosulfate, sodium salt .
    IR spectrum: 1610; 1430; 1200; 1030; 640.
    Sodium 2- (ethoxycarbonyl) -tiltyosulfate is obtained by reacting ethyl 3-chloropropionate and sodium thiosulfate in iodine ethanol, the product is evaporated off under reduced pressure, the residue is treated with hot ethanol and the ethanol extract is added after filtration.
    0
    0
    five
    The IR spectrum corresponds to the target structure of the product, HgCl titration shows the presence of 97.1% of theory. groups -.
    Sodium 1- (methoxycarbonyl) ethylthiosulphate is obtained by reacting methyl 2-chloropropionate with sodium thiosulfate in aqueous ethanol, and the product is isolated in the same way as for 2- (ethoxycarbonyl) ethylthiosulfate. The NMR spectrum shows%: thiosulfate 77.3; water 2.2, methanol 0.7; a mixture of inorganic and organic impurities - the rest.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    The method of attaching a rubber mixture to a brass surface by coating a rubber mixture on the surface, including rubber, accelerator, carbon black, zinc oxide, stearic acid, antioxidant, sulfur, softener and adhesion promoter, followed by heating to vulcanization temperature, characterized in that, in order to increase the strength of the fastening of the compound during aging, use is made of a rubber mixture containing natural rubber as rubber or its mixture with butadiene rubber in the ratio of 80:20, or a mixture of natural rubber from buta diene and butadiene styrene rubber in the ratio of 30:: 25: 42.2, as the accelerator - 2- (morpholinthio) benzthiazole, N-tert- (bu- .tylbenzthiazole-2-sulfenamide and H, H-dicyclohexylbenzthiazole) 2-sulfenamide, as an adhesion promoter, is a compound selected from the group containing a compound of the formula
    R-S-SO, M,
    where R is Cj-Cje-alkyl, allyl, 3-chloropropyl, benzyl, 2-phenylethyl, 2,5-dioxyphenyl or a group of the formula R, OOCR2, where R is methyl, ethyl; R is 1-ethyl or 2-ethyl;
    M - sodium, cobalt, nickname.,
    the compound of the formula MOZZ-8-X, -Y-50, M, where X, is CJ-GIO -alkylene;
    - (CH2) 4-o- (,
    - (CH.,) - 0-CH ,, - 0 (CH) - ,, -CH, COCH.jj-, - (CHj), COO (GH.j) -, (CH.), O COO (CH ) -0- (CH.j) -.
    -OOC (SNg), o -, - (CH2) SO (CH, j) j-, -,
    M is sodium, nickel, cobalt, N-benzyl-N-1,1,3,3-tetramethyl butyl ammonium nickel, 2,2,4-trimethyl-1,2-dihydroquinoline,
    N-isopropyl-N-p-phenylamino-phenylammonium, the compound of the formula
     I
    I. J N
    R
    where P is COCH2CH.j.-S20, Na, compound of formula
    CH-CH.;, - (CH-CH2) -CH-CH,
    OOSN, OH
    OCO (CH,) j-SjO Na,
    0 5 о.
    five
    compound of the formula -0, S, CH., CH., 0; 2Na,
    as well as magnesium, barium and zinc salts of hexamethylene-1,6-bistiosulfate in the following ratio of components, wt.h .:
    Rubber
    Accelerator
    Soot
    Zinc oxide
    Stearinova
    acid
    Antioxidant
    Sulfur
    Antifreeze
    Adhesion promoter
    100 0.7-1.0
    55-61 5.1-8.0
    0.5-2 3.0-3.07
    2-8
    3-10.2 0.5-3.1
    17
    1398777
    18 Table 2
    nineteen
    1398777
    20 Continuation of table 4
    21
    1398777
    "
    MBS - 2- (morpholinthio) benzthiazole; DCBS - N, N-AH4HiaioreKCHn-benzthiazole-2-sulfenamide; TBS - N-tert-butylbenzthiazole-2-sulfenamide.

    600 (570)
    -530 (540)
    520 (-5bO)
    520 (560)
    420 (480) 450
    22 T. Abliya 7
    Table 8
    I § 5jj 5 SiS2Promotor. Pulling force, N / cm
    Baseline I Steam Aging in Saline Scene I Aging j Bath (48 h)
    HTSNi580 530 470
    Laurat Nickel 430 270 170
    Acetylacetonate
    nickel 350 380 360
    Comprehensive
    the phosphonate compound is not,
    cel 370 530 200
    Bis (0-ethyl-3, 5 di-tert-butyl-4-hydroxybenzene 1phosphonate) nickel (see for example. 3, US A3 991130)
    T a b l and c a 10
    Promo-Pulling force, tor-N / cm
    Original steam aging in
    coupled with old salt
    Infusion bath (48 hrs)
    490 490 570 520 590 500
    Over 500
    520

    310 390 230 360 240 420 300
    320
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    同族专利:
    公开号 | 公开日
    CA1246306A1|1988-12-13|
    CS238650B2|1985-12-16|
    ZA837797B|1984-06-27|
    EP0109955B1|1988-01-20|
    AU565303B2|1987-09-10|
    ES8600344A1|1985-10-01|
    EP0109955A3|1985-08-14|
    IE54615B1|1989-12-06|
    IE832461L|1984-04-21|
    US4532080A|1985-07-30|
    DE3375401D1|1988-02-25|
    JPS5991140A|1984-05-25|
    JPH052697B2|1993-01-13|
    DD210235A5|1984-06-06|
    AT32084T|1988-02-15|
    EP0109955A2|1984-05-30|
    ES526598A0|1985-10-01|
    AU2040983A|1984-05-03|
    CA1268476C|1990-05-01|
    US4704334A|1987-11-03|
    BR8305812A|1984-05-29|
    引用文献:
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    GB8230136|1982-10-21|
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