• 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:
    Metal organic compounds comprising three or four cobalt or nickel atoms, each bonded to aluminum, silicon or titanium via an oxygen atom and comprising a combination of aliphatic and aromatic carboxylic acid residues, prevent the adhesion of brass clad steel to vulcanized rubber. It is useful as an adhesion promoter for promoting.
    公开号:KR20010030938A
    申请号:KR1020007003661
    申请日:1998-10-09
    公开日:2001-04-16
    发明作者:힐튼존마이클；호킨스이안마이클；윌슨조너선콜린
    申请人:로디아 리미티드；
    IPC主号:
    专利说明:

    Rubber Adhesion Promoter {RUBBER ADHESION PROMOTERS}
    Compounds are known which each comprise a divalent metal, for example three cobalt atoms, bonded to a boron or phosphorus atom via an oxygen atom and comprising an aliphatic monocarboxylic acid residue bonded to the metal. These known compounds have been used as additives to rubber scheme stocks to improve the adhesion of rubber to metals.
    They are easy to handle and are provided in a form that is not particularly tacky or viscous in nature.
    The present invention has the advantages of the known compounds described above, but in comparison with known cobalt-containing compounds, the new compounds further improve the adhesion of rubber to brass clad steel cords and the maintenance of such adhesion in steam and salt aging conditions. To provide.
    The present invention relates to metal organic compounds, compositions containing them, and their use.
    According to the present invention, there is provided a metal-organic compound of the following average formula for use in promoting adhesion of rubber to metal.
    Chemical formula
    X (OMA ′ p ) m (OMB ′ q ) n
    In the above formula,
    X is aluminum , titanium , Zirconium , Alkyl or aryl silicone , Di-alkyl, di-aryl or alkyl, aryl silicone Or silicone ego;
    M is cobalt or nickel, preferably cobalt (II);
    A 'is an aliphatic carboxylic acid residue having 7 to 15 carbon atoms (formula R'COO);
    B 'is an aromatic carboxylic acid residue having 7 to 15 carbon atoms (formula RCOO); Or aryloxy substituted aliphatic or aromatic carboxylic acid having 8 to 15 carbon atoms;
    p and q are independently 0.5 to 1.5, preferably 1.0;
    m + n = x, where x is the valence of X and m / n is typically 0.67 to 9.0, preferably 1.5 to 4.0;
    Typically n is 0.2 to (x-1), preferably 0.5 to 3, in particular 0.5 to 1.4.
    When X is an alkyl- and / or aryl-substituted silicone, the alkyl group is preferably one having 1 to 4 carbon atoms, especially methyl, while the aryl group is preferably phenyl. Typical examples include methylsilicone, dimethylsilicone, diphenylsilicone and methylphenylsilicone.
    The aliphatic carboxylic acid (A′H) is preferably a monocarboxylic acid such as n-heptanoic acid, 2,2-dimethylpentanoic acid, 2-ethylpentanoic acid, 4,4-dimethylpentanoic acid, n-octanoic acid, 2,2-dimethylhexanoic acid, 2-ethylhexanoic acid, 4,4-dimethylhexanoic acid, 2,4,4-trimethylpentanoic acid, n-nonanoic acid, 2,2-dimethylheptanoic acid, 6,6-dimethyl With heptanoic acid, 3,5,5-trimethylhexanoic acid, n-decanoic acid, 2,2-dimethyloctanoic acid, 7,7-dimethyloctanoic acid, n-undecanoic acid, isoundecanoic acid, secanoic acid or neodecanoic acid Known mixtures of 2,2,2-trialkyl acetic acid.
    Aromatic carboxylic acids (B′-H) are, for example, benzoic acid, alkyl-, alkoxy-, amino-, halogen-, thio-, or hydroxy-substituted benzoic acid (eg 2-, 3-, or 4-methylbenzoic acid). ), Salicylic acid, 3,5-diisopropyl salicylic acid, 3,5-di-tert-butyl salicylic acid, anthranilic acid or 4-chloro-benzoic acid, phthalic acid, terephthalic acid, cinnamic acid, or a conjugated ring system It may be acid. When B'-H is an aryloxy substituted acid, it is preferably a phenoxy substituted aliphatic or aromatic acid, in particular phenoxyacetic acid and phenoxypropionic acid.
    The metal organic compound may be associated with the borate of a Group IA or Group IIA element (ie, alkali metal or alkaline earth metal) of the Periodic Table of Elements. Such borate may be present at a concentration up to 20% by weight of the metal compound. Suitable borate includes sodium borate, potassium borate, calcium borate and magnesium borate.
    Metal organic compounds may also be associated with microcrystalline waxes and / or process oils, and / or hydrocarbon resins and / or resorcinol / formaldehyde resins.
    Novel metal organic compounds can be incorporated as adhesion promoters in rubber scheme stock comprising rubber and conventional rubber compounding components. The metal organic compound is typically present in an amount of 0.2 to 2 parts by weight per 100 parts by weight of rubber, and preferably the metal organic compound provides about 0.224 parts by weight of cobalt metal per 100 parts by weight of rubber.
    The metal organic compounds of the present invention are (1) acids A'H and B'H, which produce residues A 'and B' described above, (2) cobalt or nickel sources such as oxides, hydroxides or carbonates, (3) The need for an acid, such as acetic acid or propionic acid, which can form volatile esters with lower alcohols such as aluminates, silicates or titanate esters of n-butanol, and lower alcohol residues present in the ester (4). The mixtures in the proportions thereof can be prepared by heating together and then distilling the volatile esters, preferably under reduced pressure. Both the acid (1,4) and the metal source (2) must be reacted before adding the ester (3). The reaction temperature is typically in the range from 50 to 250 ° C.
    The invention is illustrated by the following examples. Examples 1 to 4 describe a method for producing a novel metal organic compound.
    Example 1
    A solution of cobalt 99% cobalt neodecanoate propionate (891 g) in mineral spirits is heated to 50 ° C. under mechanical agitation. Propionic acid (44 g) and benzoic acid (72.5 g) are added. The reaction mass is stirred for 10 minutes and cobalt hydroxide (57 g) is added. The reaction mixture is slowly heated to 195 ° C. and water (24 g) and mineral spirits (446 g) are distilled off and the distillation is completed using a vacuum. Methyltriethoxysilane (126.1 g) is added to the reaction mixture at 170 ° C. and the reaction is held at reflux for 4 hours before ethyl propionate is distilled as the reaction temperature rises to 220 ° C. and distillation using vacuum To complete.
    The product (540 g) was a hard, weak blue solid with an average formula: MeSi [OCo (neodecanoate) 1.0 ] 2.16 [OCo (benzoate) 1.0 ] 0.84 and contained 22.9% (w / w) cobalt.
    Example 2
    A solution of cobalt neodecanoate propionate (817 g) of 9.8% (w / w) cobalt in mineral spirits is heated to 40 ° C under stirring. Propionic acid (44 g) and benzoic acid (71.8 g) are added. Cobalt hydroxide (55.4 g) is also added to the reaction mass. The reaction is heated to 190 ° C., water and mineral spirits (combined weight 415 g) are distilled off and the distillation is completed using vacuum.
    Aluminum triisopropoxide (132 g) is slowly added and the reaction mass is heated to 190 ° C. and isopropyl propionate ester is distilled off as it is formed.
    The reaction temperature is gradually raised to 240 ° C. to distill residual ester, and distillation is completed using a vacuum. A total of 159 g isopropylpropionate is collected.
    The product (533 g) was a hard, weak blue solid with an average formula: Al [OCo (neodecanoate) 1.0 ] 2.1 [OCo (benzoate) 1.0 ] 0.9 and contained 20.8% w / w cobalt.
    Example 3
    Neodecanoic acid (294 g), propionic acid (188 g) and benzoic acid (88 g) and toluene (200 g) are placed in a reaction flask and heated to 50 ° C. under mechanical stirring. Cobalt hydroxide (233 g) is added and the temperature is raised to 90 ° C. to produce a mobile blue liquid. Additional heat is applied to remove the reaction water through the Dean-Stark apparatus, whereby the reaction temperature rises to 190 ° C. and the last traces of the solvent are removed under vacuum resulting in 91 g of water and 206 g of toluene. Tetrabutyl titanate (205 g) is slowly added to the reaction mass at 160 ° C. and the reaction is maintained at reflux temperature of 160 ° C. for 3 hours. Butyl propionate (240 g) is removed by distillation upon heating to 230 ° C. and distillation is completed using vacuum.
    The product (624 g) was a hard, weak blue solid with an average formula: Ti [OCo (neodecanoate) 1.0 ] 2.8 [OCo (benzoate) 1.0 ] 1.2 and contained 22.5% (w / w) cobalt.
    Example 4
    Neodecanoic acid (193 g), benzoic acid (62 g) and toluene (420 g) are placed in a reaction flask equipped with a mechanical stirrer. To this is added cobalt hydroxide (156 g) and propionic acid (130 g).
    Gradually raising the temperature to 120 ° C. produces a viscous blue liquid and the reaction water is removed using a Dean-Stark apparatus. Further heating to distill off residual toluene. At 180 ° C., vacuum is applied to complete the distillation.
    Tetraethylorthosilicate (85 g) was slowly added to the reaction mass and the reaction was held at reflux temperature of 145 ° C. for 2 hours before ethyl propionate (136 g) was removed by distillation to a final reaction temperature of 230 ° C., After that the vacuum is applied to complete the distillation.
    The product (416 g) was a hard, weak blue solid with an average formula: Si [OCo (neodecanoate) 1.0 ] 2.75 [OCo (benzoate) 1.0 ] 1.25 and contained 22.8% (w / w) cobalt.
    The rubber scheme stock according to the invention comprises the metal organic compounds of the invention as rubber + one or more conventional rubber compounding components such as pigments, fillers, extenders, promoters, antioxidants, vulcanizing agents and the like, and adhesion promoters. A rubber scheme stock of the following composition is prepared:
    Parts by weight
    Natural Rubber SMR 10 100
    Peptizer (Renacit 12) a) 0.05
    MAF carbon black N-326 57
    Zinc oxide 8
    Antidegradant (6 PPD) b) 2.0
    Promoter DCBS c) 0.7
    Insoluble Sulfur 4.0
    a) zinc salt of pentachlorothiophenol
    b) N- (1,3-dimethylbutyl) -N'phenyl-p-phenylene diamine
    c) N, N-dicyclohexyl-2-benzthiazyl sulfenamide
    Vulcanizable compositions are prepared using the rubber scheme stock and the adhesion promoters listed below. Adhesion promoter is added to the scheme stock and seated on a Z-roll laboratory mill while mixing in a 15 liter internal laboratory mixer. All compositions are vulcanized at 153 ° C. with T90 + 8 minutes.
    Adhesion tests are performed using a modified static block tension test based on ASTM D2229 using an embedded length of 10 mm. A typical brass clad steel tire cord of structure 2 + 2 = X 0.25 from Bekaert is used, each cord having a brass cladding with an average copper content of 63.5%. Adhesion values are exemplified in Newton / 10 mm. The results are shown in Table 1.
    Aging condition
    16 hours steam @ 121 ℃
    Humidity 7 days @ 70% 95% RH
    Heating 7 days @ 85 ℃
    Salt 7 days @ R.T., 3.6% w / w NaCl in water
    The results presented in these tables show that rubber scheme stocks comprising the metal organic compounds of the present invention exhibit significantly improved adhesion of rubber to metals as compared to known boro neodecanoate compounds. This improvement is particularly noticeable in steam aging conditions. In addition, the novel metal organic compounds show equivalent performance at lower levels of use than the corresponding boro neodecanoate.
    In one aspect, the metal compound is deposited on a support, for example from an oil solution of the compound. The support is typically a silicate or silicate of a Group IA or Group IIA metal, for example sodium silicate, potassium silicate, magnesium silicate or calcium silicate.
    Table 1. Adhesion Test Results
    权利要求:
    Claims (13)
    [1" claim-type="Currently amended] Metal-organic compound of the following average formula.
    Chemical formula
    X (OMA ′ p ) m (OMB ′ q ) n
    In the above formula,
    X is aluminum, titanium, zirconium or silicon alkyl- or aryl-silicone or dialkyl-, diaryl- or alkylaryl-silicone,
    M is cobalt or nickel,
    A 'is an aliphatic carboxylic acid residue having 7 to 15 carbon atoms,
    B ′ is an aromatic carboxylic acid residue having 7 to 15 carbon atoms or an aliphatic or aromatic aryloxy carboxylic acid residue having 8 to 15 carbon atoms,
    p and q are independently 0.5 to 1.5,
    m + n = x, where x is the valence of X.
    [2" claim-type="Currently amended] The metal organic compound according to claim 1, wherein M is Co (II).
    [3" claim-type="Currently amended] The compound according to claim 1 or 2, wherein B 'is benzoic acid, 2-, 3-, or 4-methylbenzoic acid, salicylic acid, 3,5-diisopropyl salicylic acid, 3,5-di-tert-butyl salicylic acid, anthranilic acid , A metal organic compound that is a cinnamic acid, phenoxy acetic acid or phenoxy propionic acid residue.
    [4" claim-type="Currently amended] The metal organic compound according to any one of claims 1 to 3, wherein A 'is a neodecanoic acid, isoundecanoic acid, secanoic acid, or 2-ethyl hexanoic acid residue.
    [5" claim-type="Currently amended] The metal organic compound according to any one of claims 1 to 4, wherein m / n is 0.67 to 9.0.
    [6" claim-type="Currently amended] The metal organic compound according to claim 5, wherein m / n is 1.5 to 4.0.
    [7" claim-type="Currently amended] The metal organic compound of claim 1, specifically identified herein.
    [8" claim-type="Currently amended] The metal organic compound according to any one of claims 1 to 7, associated with up to 20% by weight of a borate of a Group IA or Group IIA metal of the Periodic Table of Elements.
    [9" claim-type="Currently amended] The metal organic compound according to any one of claims 1 to 7 associated with a microcrystalline wax, process oil or hydrocarbon resin or resorcinol / formaldehyde resin.
    [10" claim-type="Currently amended] The metal organic compound according to any one of claims 1 to 7, supported on silica or silicates of Group IA or Group IIA.
    [11" claim-type="Currently amended] A rubber scheme stock comprising a rubber and at least one metal organic compound according to any one of claims 1 to 7 as an adhesion promoter.
    [12" claim-type="Currently amended] The rubber scheme stock according to claim 11, comprising 0.2 to 2.0 parts by weight of the metal organic compound per 100 parts by weight of rubber.
    [13" claim-type="Currently amended] A vulcanized rubber reinforced with brass coated steel, comprising at least one metal organic compound according to any one of claims 1 to 7 as an adhesion promoter.
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    同族专利:
    公开号 | 公开日
    EP1023303B1|2003-09-03|
    BR9812758A|2000-08-29|
    DE69817849T2|2004-08-19|
    KR100572688B1|2006-04-24|
    ES2205549T3|2004-05-01|
    JP4287590B2|2009-07-01|
    ID24179A|2000-07-13|
    WO1999019336A1|1999-04-22|
    CA2305626C|2008-02-19|
    AU746070B2|2002-04-11|
    RU2218344C2|2003-12-10|
    AT248847T|2003-09-15|
    DE69817849D1|2003-10-09|
    CN1281461A|2001-01-24|
    JP2001519435A|2001-10-23|
    AU9361898A|1999-05-03|
    PT1023303E|2003-12-31|
    CA2305626A1|1999-04-22|
    CN1243762C|2006-03-01|
    EP1023303A1|2000-08-02|
    US6353047B1|2002-03-05|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1997-10-10|Priority to GB9721583.4
    1997-10-10|Priority to GBGB9721583.4A
    1997-10-24|Priority to GB9722513A
    1997-10-24|Priority to GB9722513.0
    1998-10-09|Application filed by 로디아 리미티드
    1998-10-09|Priority to PCT/GB1998/003069
    2001-04-16|Publication of KR20010030938A
    2006-04-24|Application granted
    2006-04-24|Publication of KR100572688B1
    优先权:
    申请号 | 申请日 | 专利标题
    GB9721583.4|1997-10-10|
    GBGB9721583.4A|GB9721583D0|1997-10-10|1997-10-10|Rubber adhesion promoters|
    GB9722513A|GB2330581A|1997-10-24|1997-10-24|Metal salts of carboxylic acids as adhesion promoters|
    GB9722513.0|1997-10-24|
    PCT/GB1998/003069|WO1999019336A1|1997-10-10|1998-10-09|Rubber adhesion promoters|
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