CN107011369A - A kind of preparation method of high-performance compound cobalt boracylate - Google Patents
A kind of preparation method of high-performance compound cobalt boracylate Download PDFInfo
- Publication number
- CN107011369A CN107011369A CN201710254240.8A CN201710254240A CN107011369A CN 107011369 A CN107011369 A CN 107011369A CN 201710254240 A CN201710254240 A CN 201710254240A CN 107011369 A CN107011369 A CN 107011369A
- Authority
- CN
- China
- Prior art keywords
- reaction
- cobalt
- acid
- steel cord
- rubber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 42
- 239000010941 cobalt Substances 0.000 title claims abstract description 42
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 150000001875 compounds Chemical class 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 36
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims abstract description 19
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 18
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052796 boron Inorganic materials 0.000 claims abstract description 15
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 10
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 9
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000008117 stearic acid Substances 0.000 claims abstract description 9
- 238000005917 acylation reaction Methods 0.000 claims abstract description 7
- 238000006073 displacement reaction Methods 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 14
- 150000001868 cobalt Chemical class 0.000 claims description 9
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 claims description 9
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 8
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 7
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical group C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- TZWGXFOSKIHUPW-UHFFFAOYSA-L cobalt(2+);propanoate Chemical compound [Co+2].CCC([O-])=O.CCC([O-])=O TZWGXFOSKIHUPW-UHFFFAOYSA-L 0.000 claims description 4
- 229910020647 Co-O Inorganic materials 0.000 claims description 2
- 229910020704 Co—O Inorganic materials 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 2
- 235000021050 feed intake Nutrition 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims description 2
- 239000011833 salt mixture Substances 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 abstract description 38
- 239000010959 steel Substances 0.000 abstract description 38
- 229920001971 elastomer Polymers 0.000 abstract description 29
- 239000005060 rubber Substances 0.000 abstract description 29
- 239000003292 glue Substances 0.000 abstract description 16
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 125000000217 alkyl group Chemical group 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 description 10
- 239000002351 wastewater Substances 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 7
- 229910001868 water Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 238000007664 blowing Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000003679 aging effect Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 229910001369 Brass Inorganic materials 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 2
- 239000002085 irritant Substances 0.000 description 2
- 231100000021 irritant Toxicity 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- -1 acids cobalt salts Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 230000000739 chaotic effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/55—Boron-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of preparation method of high performance compound boronation cobalt, mainly include salt-forming reaction, acid displacement reaction, boron acylation reaction, it is controllable with the degree that stearic acid and propionic acid replace neodecanoic acid to realize that boron is acylated, the carbon number of alkyl includes 3 in cobalt boracylate molecule, 10, 18, and mean control is 10, improve the dispersiveness of product cobalt boracylate, improve the uniformity coefficient on rubber covering steel cord surface, solve point-like in attached glue, wire, the exposed actual application problem of planar, the binding efficiency of rubber and steel cord is set to reach more than 90%, promote rubber and the bond properties of steel cord, extend the service life of tire.
Description
Technical field
The present invention relates to the preparation method of cobalt boracylate.
Background technology
Cobalt boracylate, its Theoretical molecular formula is：（RmCO-Co- O-）3B,（M=3~11 in formula, based on 9）.Boron is acylated
Cobalt is a kind of higher adhesion promotor of activity, is mainly used in natural rubber, synthetic rubber or these glue and brass, zinc, naked copper
And the all-steel cord of brass plating or zinc, rope, the adhesion promotion of metallic plate.It is using cobalt hydroxide and acetic acid and Related organic acid as
Raw material, first carries out acid-base reaction, and boron acylation reaction is then carried out again.The cobalt boracylate amount containing cobalt prepared by this method compared with
Height, they are in the vulcanization of rubber, and reactivity is big, and the bonding enhancing to rubber and steel wire plays a major role, but have the disadvantage its
Bad dispersibility in rubber and cause attached glue（Binding efficiency：Rubber osmosis covers the degree on steel cord surface into steel cord）No
Uniformly, directly affect rubber and steel cord bonding strength and ageing-resistant performance it is unstable.
Publication No. CN103113416A patent discloses a kind of preparation method of low melting point cobalt boracylate, its neutralization reaction
It is that neodecanoic acid, propionic acid, valeric acid, stearic acid, rosin, dimethylbenzene are mixed into progress acid-base neutralization reaction with cobalt hydroxide, neutralizes anti-
Intermediate product is obtained after the completion of answering.Because species sour in raw material in neutralization reaction is more, and the cooking-pot type of neutralization reaction one is carried out, in
Chaotic with replacing in reaction product, after boron acylation reaction below, the substitution of the alkyl in product is irregular, and single boron is acylated
The carbon number of alkyl is distributed more widely in cobalt, and whole boron is acylated degree and is difficult to control to, and causes the bad dispersibility of cobalt boracylate.
The content of the invention
Inventor provides a kind of preparation of high performance compound boronation cobalt in view of the shortcomings of the prior art
Method, realizes that the degree that boron is acylated is controllable, the carbon number of alkyl includes 3,10,18 in cobalt boracylate molecule, and mean control exists
10, improve the dispersiveness of product cobalt boracylate, improve the uniformity coefficient on rubber covering steel cord surface, solve point-like in attached glue,
The exposed actual application problem of wire, planar, makes rubber and the binding efficiency of steel cord reach more than 90%, promotes rubber and steel curtain
The bond properties of line, extends the service life of tire.
The present invention the used technical scheme that solves the above problems is：A kind of preparation side of high-performance compound cobalt boracylate
Method, comprises the following steps,
Step 1: salt-forming reaction
Using cobalt hydroxide and propionic acid as raw material, in atmospheric pressure sealed container, 100~150 DEG C of temperature, time >=2 hour, reaction life
Into Cobaltous propionate, its reaction equation is：
CO(OH)2 + CH3CH2COOH à CH3CH2- CO-O-Co-O-CO-CH3CH2 +2 H2O；
Step 2: acid displacement reaction
Neodecanoic acid and stearic acid are added in above-mentioned reaction system, 150~190 DEG C of temperature is controlled, time >=2 hour, reaction is put
The propionic acid swapped out in Cobaltous propionate molecule；Its reaction equation is：
+ CH3(CH2)8COOH àRn+CH3CH2COOH
+ CH3(CH2)16COOH àRm+CH3CH2COOH
Wherein：N=9, m=17
The salt-mixture of following three cobalt salt is obtained after above-mentioned steps one and two:
1、
2、
3、
Wherein n=9, m=17
At least provided with a propionic acid in cobalt salt molecular formula in step 2 products therefrom；
Step 3: boron acylation reaction
Butyl borate is added in the compound mixing cobalt salt generated in above-mentioned reaction system, 190~200 DEG C of temperature is controlled,
Time >=1 hour, reaction generation high-performance compound cobalt boracylate, byproduct is butyl propionate, and its reaction equation is：
(R4O)3B+ Rm à (RmO-O-Co-O)3B+
Wherein m=3,10,18；
This reaction key is that control boron is acylated degree, and boron is acylated degree not enough, then product fusing point is too high, and residual propionic acid is more, to glue
Based article is corrosion-resistant unfavorable with ageing properties, if boron acylation reaction is excessively, reaction product molecular species is complicated, it is impossible to control, then
Product is excessively soft, and also influence is used.
Step 4: finished product is made
By the temperature control of above-mentioned reaction system at 180~190 DEG C, shaping packaging, be made high-performance compound cobalt boracylate into
Product.
The high-performance compound cobalt boracylate amount containing cobalt of the application is high, and reactivity is big, and the bonding to rubber and steel wire increases
Play a major role by force；The dispersiveness of product is strong, is uniformly dispersed in the vulcanization of rubber, can greatly improve rubber covering steel cord table
The uniformity coefficient in face, solves the exposed actual application problem of point-like, wire, planar in attached glue, makes rubber and the attached glue of steel cord
Rate reaches more than 90%, promotes rubber and the bond properties of steel cord, extends the service life of tire.
Prepare each material performance of the present invention and require as follows：
Cobalt hydroxide：Molecular formula Co (OH)2, molecular weight 93.
Character：Co(OH)2Pinkiness powder, water content ＜ 2% can be slowly oxidized generation brown in atmosphere
Hydrous oxide, can also occur this change at high temperature.
Propionic acid：Molecular formula CH3CH2COOH, molecular weight 74.
Character:Colourless liquid, irritant smell, content >=99.5%, acid number 758mgKOH/g, proportion（d20 4℃）
0.9942, -20.8 DEG C of fusing point, 140.7 DEG C of boiling point, refractive index 1.3862, flash-point 1300F, it is water-miscible, it is dissolved in ethanol, chlorine
Imitative and ether.This product low toxicity.It is same with glacial acetic acid to stimulate eyes, it is mucocutaneous, and after having on bactericidal properties, attachment skin, can use
Water is rinsed, and mask has been dressed during operation, equipment will be sealed.
Neodecanoic acid：Molecular formula C10H20O2, mean molecule quantity about 172.
Character：Slightly yellow transparency liquid, is a kind of mixed organic acid with branched structure, and its main component is neodecanoic acid
（C10Acid）, next to that new n-nonanoic acid（C9Acid）With a small amount of high carbon chain（CnAcid >=11）The mixture of acid.The acid number of the organic acid is general
327 or so, minimum is not less than 315, and it is transparent that mean molecule quantity, which is generally under 171.5 or so, not more than 178, normal temperature,
Liquid, color and luster（Pt-C0）Not more than 4, water content not more than 0.4%, density（20℃）0.915,120 DEG C of flash-point, boiling
223-323 DEG C of point, -30 DEG C of freezing point, the solubility in water（25℃）620mg/L, it is irritant with skin to eyes.
Stearic acid：Molecular formula：C18H36O2, molecular weight 284.48, character：Outward appearance is the wax-like small crystalline substance of white slightly gloss
Body, density is about 0.94, index of refraction 1.429,63 DEG C of fusing point, and 232 DEG C of boiling point is nontoxic.
Butyl borate：Molecular formula：C12H27BO3, molecular weight 203.16, character：Outward appearance is colourless transparent liquid, and density is about
For 0.8530, index of refraction 1.407,230 DEG C of boiling point is easily moist, can be miscible with the common solvent such as methanol, meets water decomposition.
The mass parts that feed intake of the primary chemical raw material of the application are,
31~33 parts of cobalt hydroxide
25~27 parts of propionic acid
30~32 parts of neodecanoic acid
30~32 parts of stearic acid
26~28 parts of butyl borate.
Compared with prior art, the advantage of the invention is that：It is characteristic of the invention that being substituted with stearic acid and propionic acid part
2 parts of neodecanoic acid, under the premise for ensureing finished product cobalt content, improves the dispersiveness of product, and with boron acylating reagent pair
Two acids cobalt salts carry out boron acylation reaction, improve the amount containing cobalt and reactivity of this kind of cobalt salt, realize the acyl group carbon of cobalt boracylate
Content is controllable, is maintained at 9 or so, has significantly enhanced rubber and the binding efficiency and bonding force of steel cord.
Embodiment
The present invention is described in further detail with reference to embodiments.
Embodiment 1：
With moisture content collector, return and evaporate the 500ml three-necked flasks of condenser pipe, vavuum pump, be separately added into propionic acid 50g, hydrogen-oxygen
Change the g of cobalt 66, controlling reaction temperature in 2 hours reaction time, releases waste water at 100-150 DEG C, adds neodecanoic acid 60g and hard
The g of resin acid 100, controlling reaction temperature in 2 hours reaction time, releases waste water, adds butyl borate 55 at 150-190 DEG C
G is stirred, and heating and temperature control steamed butyl propionate, temperature control is 180~190 in 190-195 DEG C of insulation reaction 1 hour
DEG C, blowing after half an hour.Reaction product amount containing cobalt：23%, fusing point：125 DEG C, outward appearance is in bluish violet solid.
Embodiment 2：
With moisture content collector, return and evaporate the 1000ml three-necked flasks of condenser pipe, vavuum pump, be separately added into propionic acid 74g, hydrogen-oxygen
Change the g of cobalt 93, controlling reaction temperature is at 120-170 DEG C, in 2.5 hours reaction time, release waste water, add neodecanoic acid 84g and
The g of stearic acid 134, controlling reaction temperature in 1.5 hours reaction time, releases waste water, adds the fourth of boric acid three at 170-190 DEG C
The g of ester 75 is stirred, and heating and temperature control steamed propionic acid fourth fat in 190-195 DEG C of insulation reaction 1 hour, temperature control 180 DEG C ~
190 DEG C, blowing after half an hour.Reaction product amount containing cobalt：22.5%, fusing point：122 DEG C, outward appearance is in bluish violet solid.
Embodiment 3：
With moisture content collector, return and evaporate the 500ml three-necked flasks of condenser pipe, vavuum pump, be separately added into propionic acid 52g, hydrogen-oxygen
Change the g of cobalt 66, controlling reaction temperature in 2 hours reaction time, releases waste water at 100-150 DEG C, adds neodecanoic acid 62g and hard
The g of resin acid 62, controlling reaction temperature in 3 hours reaction time, releases waste water, adds butyl borate 50g at 150-190 DEG C
Stirring, heating and temperature control steamed butyl propionate in 190-195 DEG C of insulation reaction 1 hour, temperature control at 180~190 DEG C,
Blowing after half an hour.Reaction product amount containing cobalt 24%, fusing point：125 DEG C, outward appearance is strong bluish violet solid.
Embodiment 4：
With moisture content collector, return and evaporate the 1L three-necked flasks of condenser pipe, vavuum pump, be separately added into propionic acid 75g, hydroxide
The g of cobalt 96, controlling reaction temperature in 3 hours reaction time, releases waste water, adds neodecanoic acid 90g and tristearin at 100-150 DEG C
96 g of acid, controlling reaction temperature in 3 hours reaction time, releases waste water, adds butyl borate 78g and stir at 150-190 DEG C
Mix, heating and temperature control steamed butyl propionate, temperature control is at 180~190 DEG C in 190-195 DEG C of insulation reaction 2 hours, half
Blowing after hour.Reaction product amount containing cobalt 24%, fusing point：124 DEG C, outward appearance is strong bluish violet solid.
Embodiment 5：
With moisture content collector, return and evaporate the 500ml three-necked flasks of condenser pipe, vavuum pump, be separately added into propionic acid 52g, hydrogen-oxygen
Change the g of cobalt 64, controlling reaction temperature in 2 hours reaction time, releases waste water at 100-150 DEG C, adds neodecanoic acid 64g and hard
Resin acid 60g, controlling reaction temperature in 2 hours reaction time, releases waste water, adds butyl borate 55g and stir at 150-190 DEG C
Mix, heating and temperature control steamed butyl propionate, temperature control is at 180~190 DEG C in 190-195 DEG C of insulation reaction 1 hour, half
Blowing after hour.Reaction product amount containing cobalt 24%, fusing point：128 DEG C, outward appearance is strong bluish violet solid.
Contrast and experiment：
According to GB-T 16586-1996《Vulcanize rubber and the measure of all-steel cord bonding strength》, to the high property of the addition present invention
The compound cobalt boracylate of energy and the common cobalt boracylate of addition and the rubber of cobaltous octadecanate and the bonding strength of all-steel cord are carried out
Determine.Test general principle：Vulcanized in the rubber that all-steel cord is embedded in definite shape, then measured on puller system
Every steel wire pumps to required power of being released from rubber along steel wire.And the binding efficiency in Steel Wire Surface is observed or determines, use
Extraction force and binding efficiency two parameters characterize sizing material level of adhesion.
According to identical sizing compound formula, the wherein deal of cobalt salt is calculated according to actual cobalt content.Glue is refined under equal conditions
Material, vulcanization, aging and extraction.
Experimental result（Average value）Such as following table：
The binding efficiency of steel cord judges：
Rubber osmosis into steel cord and be completely covered steel cord surface for 100% attached glue；
Rubber osmosis point-like Naked into steel cord reveal steel cord surface for more than 95% attached glue；
Rubber osmosis point-like into steel cord be linked to be wire Naked dew steel cord surface for more than 90% attached glue；
Rubber osmosis into steel cord point-like+wire Naked dew steel cord surface for more than 85% attached glue；
Rubber osmosis into steel cord continuous wire Naked dew steel cord surface for more than 80% attached glue；
Rubber osmosis be wired into steel cord facet cumuliformis Naked dew steel cord surface for more than 75% attached glue；
Rubber osmosis larger area Naked into steel cord reveal steel cord surface for more than 70% attached glue；
Rubber osmosis large area Naked into steel cord reveal steel cord surface for more than 60% attached glue；
As seen from the above table：In the case of equal conditions, high-performance compound cobalt boracylate of the invention is in binding efficiency, extraction
Power, thermal aging property and salt solution ageing properties are excellent in common cobaltous octadecanate and common cobalt boracylate.
In addition to the implementation, present invention additionally comprises have other embodiment, all use equivalent transformation or equivalent replacements
The technical scheme that mode is formed, all should fall within the scope of the hereto appended claims.
Claims (2)
1. a kind of preparation method of high-performance compound cobalt boracylate, it is characterised in that：Comprise the following steps,
Step 1: salt-forming reaction
Using cobalt hydroxide and propionic acid as raw material, in atmospheric pressure sealed container, 100~150 DEG C of temperature, time >=2 hour, reaction life
Into Cobaltous propionate, its reaction equation is：
CO(OH)2 + CH3CH2COOH à CH3CH2- CO-O-Co-O-CO-CH3CH2 +2 H2O；
Step 2: acid displacement reaction
Neodecanoic acid and stearic acid are added in above-mentioned reaction system, 150~190 DEG C of temperature is controlled, time >=2 hour, reaction is put
The propionic acid swapped out in Cobaltous propionate molecule；Its reaction equation is：
+ CH3(CH2)8COOH àRn+CH3CH2COOH
+ CH3(CH2)16COOH àRm+CH3CH2COOH
Wherein：N=9, m=17
The salt-mixture of following three cobalt salt is obtained after above-mentioned steps one and two:
1、
2、
3、
Wherein n=9, m=17
At least provided with a propionic acid in cobalt salt molecular formula in step 2 products therefrom；
Step 3: boron acylation reaction
Butyl borate is added in the compound mixing cobalt salt generated in above-mentioned reaction system, 190~200 DEG C of temperature is controlled,
Time >=1 hour, reaction generation high-performance compound cobalt boracylate, byproduct is butyl propionate, and its reaction equation is：
(R4O)3B+ Rm à (RmO-O-Co-O)3B+
Wherein m=3,10,18；
Step 4: finished product is made
By the temperature control of above-mentioned reaction system at 180~190 DEG C, shaping packaging, be made high-performance compound cobalt boracylate into
Product.
2. the preparation method of high-performance compound cobalt boracylate according to claim 1, it is characterised in that：Primary raw material
The mass parts that feed intake are,
31~33 parts of cobalt hydroxide
25~27 parts of propionic acid
30~32 parts of neodecanoic acid
30~32 parts of stearic acid
26~28 parts of butyl borate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710254240.8A CN107011369A (en) | 2017-04-18 | 2017-04-18 | A kind of preparation method of high-performance compound cobalt boracylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710254240.8A CN107011369A (en) | 2017-04-18 | 2017-04-18 | A kind of preparation method of high-performance compound cobalt boracylate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107011369A true CN107011369A (en) | 2017-08-04 |
Family
ID=59448415
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710254240.8A Pending CN107011369A (en) | 2017-04-18 | 2017-04-18 | A kind of preparation method of high-performance compound cobalt boracylate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107011369A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107955028A (en) * | 2017-11-22 | 2018-04-24 | 浙江三晟化工有限公司 | A kind of preparation method of cobalt boracylate |
| CN109828065A (en) * | 2019-03-26 | 2019-05-31 | 江阴市三良橡塑新材料有限公司 | The measuring method of n-butyl propionate content in a kind of cobalt boracylate |
| CN114507489A (en) * | 2022-01-26 | 2022-05-17 | 江苏卡欧化工股份有限公司 | Cobalt boracylate adhesive and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60109591A (en) * | 1983-11-18 | 1985-06-15 | Nippon Mining Co Ltd | Production of complex organometallic compound of boron |
| US4609499A (en) * | 1984-01-30 | 1986-09-02 | Daninippon Ink and Chemicals, Inc. | Rubber-steel cord adhesion promoter |
| US5276172A (en) * | 1990-07-10 | 1994-01-04 | Rhone-Poulenc Chemicals Ltd. | Metal organic compounds |
| CN1844213A (en) * | 2006-04-10 | 2006-10-11 | 徐美华 | Process for preparing organic cobalts mixed salt finished product with cobalt neodecanoate as main raw material |
| CN103113206A (en) * | 2012-12-31 | 2013-05-22 | 大连爱柏斯化工有限公司 | Preparation method of neodecanoic acid cobalt |
| CN103897216A (en) * | 2014-03-28 | 2014-07-02 | 江阴市三良化工有限公司 | High-performance organic cobalt mixed salt and preparation method thereof |
| CN104788718A (en) * | 2015-04-15 | 2015-07-22 | 江阴市三良化工有限公司 | Preparation method for high-stability cobalt neocaprate mixed salt |
-
2017
- 2017-04-18 CN CN201710254240.8A patent/CN107011369A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60109591A (en) * | 1983-11-18 | 1985-06-15 | Nippon Mining Co Ltd | Production of complex organometallic compound of boron |
| US4609499A (en) * | 1984-01-30 | 1986-09-02 | Daninippon Ink and Chemicals, Inc. | Rubber-steel cord adhesion promoter |
| US5276172A (en) * | 1990-07-10 | 1994-01-04 | Rhone-Poulenc Chemicals Ltd. | Metal organic compounds |
| CN1844213A (en) * | 2006-04-10 | 2006-10-11 | 徐美华 | Process for preparing organic cobalts mixed salt finished product with cobalt neodecanoate as main raw material |
| CN103113206A (en) * | 2012-12-31 | 2013-05-22 | 大连爱柏斯化工有限公司 | Preparation method of neodecanoic acid cobalt |
| CN103897216A (en) * | 2014-03-28 | 2014-07-02 | 江阴市三良化工有限公司 | High-performance organic cobalt mixed salt and preparation method thereof |
| CN104788718A (en) * | 2015-04-15 | 2015-07-22 | 江阴市三良化工有限公司 | Preparation method for high-stability cobalt neocaprate mixed salt |
Non-Patent Citations (1)
| Title |
|---|
| 肖英等: "钴盐粘合增进剂的生产与需求分析", 《橡胶科技》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107955028A (en) * | 2017-11-22 | 2018-04-24 | 浙江三晟化工有限公司 | A kind of preparation method of cobalt boracylate |
| CN109828065A (en) * | 2019-03-26 | 2019-05-31 | 江阴市三良橡塑新材料有限公司 | The measuring method of n-butyl propionate content in a kind of cobalt boracylate |
| CN114507489A (en) * | 2022-01-26 | 2022-05-17 | 江苏卡欧化工股份有限公司 | Cobalt boracylate adhesive and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107011369A (en) | A kind of preparation method of high-performance compound cobalt boracylate | |
| CN103059696B (en) | A kind of powder coating containing modified meerschaum powder and preparation method thereof | |
| CN102559047B (en) | Organosilicon coating and preparation method thereof | |
| CN100344683C (en) | Process for preparing organic cobalts mixed salt finished product with cobalt neodecanoate as main raw material | |
| CN105440333A (en) | Cobalt salt-free tire steel wire framework material formula and preparation method thereof | |
| CN1072655A (en) | Zinc borate | |
| CN103013296A (en) | Powder coating containing modified attapulgite and preparation method of powder coating | |
| CN101003544A (en) | Method for preparing finished products of salt mixture of organic cobalt class of giving priority to cobalt boroacidate | |
| CN103013298A (en) | Powder coating containing modified nanocarbon and preparation method of powder coating | |
| CN102965033B (en) | Nano-mica powder modified compound adhesive for packaging | |
| CN107382710A (en) | A kind of polyalcohol for being grafted antioxygen agent molecule | |
| CN103265917A (en) | Adhesive containing nano attapulgite for packaging and preparation method thereof | |
| CN102965050B (en) | A kind of adhesive for packaging of nano diatomite modification | |
| CN101016396A (en) | Method of preparing polyvinylchloride composite processing auxiliary agent | |
| CN103173140A (en) | Neoprene adhesive for woodworking | |
| CN107216577A (en) | A kind of novel PVC liquid Ca-Zn composite heat stabilizer and preparation method for adding modified Nano carbon ball | |
| CN104788718A (en) | Preparation method for high-stability cobalt neocaprate mixed salt | |
| CN105153798B (en) | A kind of photocuring solder mask | |
| CN116622244A (en) | Rubber based on N, N' -di-sec-butyl-p-phenylenediamine and preparation method thereof | |
| CN105131704B (en) | A kind of heat resistance photocuring solder mask | |
| CN109777154A (en) | A kind of response type white carbon black functional additive and its preparation method and application based on vegetable fatty acids | |
| CN105199480B (en) | A kind of photocuring solder mask ink composition | |
| CN103045104A (en) | Phenolic resin-chloroprene rubber adhesive and preparation method thereof | |
| CN113912960A (en) | Transparent PVC composite film and preparation method thereof | |
| CN115028942A (en) | Impact-resistant overhead insulated conductor with protective sleeve and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170804 |