CN101643480B - Preparation method of cobalt boracylate - Google Patents
Preparation method of cobalt boracylate Download PDFInfo
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- CN101643480B CN101643480B CN2009100922107A CN200910092210A CN101643480B CN 101643480 B CN101643480 B CN 101643480B CN 2009100922107 A CN2009100922107 A CN 2009100922107A CN 200910092210 A CN200910092210 A CN 200910092210A CN 101643480 B CN101643480 B CN 101643480B
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- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 98
- 239000010941 cobalt Substances 0.000 title claims abstract description 98
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims abstract description 43
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims abstract description 43
- 239000013067 intermediate product Substances 0.000 claims abstract description 42
- 229960000583 acetic acid Drugs 0.000 claims abstract description 24
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 23
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000654 additive Substances 0.000 claims abstract description 13
- 230000000996 additive effect Effects 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 111
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 45
- 229910052796 boron Inorganic materials 0.000 claims description 45
- 238000005917 acylation reaction Methods 0.000 claims description 42
- 238000005469 granulation Methods 0.000 claims description 31
- 230000003179 granulation Effects 0.000 claims description 31
- 238000010992 reflux Methods 0.000 claims description 28
- 239000000047 product Substances 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 22
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 22
- 239000004571 lime Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 22
- 238000004821 distillation Methods 0.000 claims description 21
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 20
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- 238000005292 vacuum distillation Methods 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000012423 maintenance Methods 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 150000001642 boronic acid derivatives Chemical class 0.000 claims description 2
- 238000009775 high-speed stirring Methods 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims 1
- 239000000292 calcium oxide Substances 0.000 claims 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 30
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 4
- 235000014113 dietary fatty acids Nutrition 0.000 abstract description 3
- 229930195729 fatty acid Natural products 0.000 abstract description 3
- 239000000194 fatty acid Substances 0.000 abstract description 3
- 150000004665 fatty acids Chemical class 0.000 abstract description 3
- -1 isooctyl Chemical group 0.000 abstract description 3
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 abstract 2
- 239000000126 substance Substances 0.000 abstract 1
- 150000001868 cobalt Chemical class 0.000 description 13
- 230000032683 aging Effects 0.000 description 8
- 238000012856 packing Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 description 2
- KJONVQWTEXFKKS-UHFFFAOYSA-N cobalt;decanoic acid Chemical compound [Co].CCCCCCCCCC(O)=O KJONVQWTEXFKKS-UHFFFAOYSA-N 0.000 description 2
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 230000010062 adhesion mechanism Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of cobalt boracylate, belonging to the field of the preparation of composite material accelerating agent. The preparation method comprises the following steps: mixing neodecanoic acid, isooctyl acid, glacial acetic acid, dimethylbenzene and cobalt hydroxide, carrying out acid-base neutralization reaction, and obtaining an intermediate product after the neutralization reaction is finished; adding tributyl borate into the obtained intermediate product and carrying out boracylate reaction, adding calcium borate as additive simultaneously, and obtaininga reaction product, namely, cobalt boracylate after the boracylate reaction is finished. In the preparation method, the neodecanoic acid, the isooctyl acid, the lower fatty acid glacial acetic acid and the dimethylbenzene are matched and carry out the acid-base neutralization reaction together with the cobalt hydroxide to generate the intermediate product; the reaction velocity can be improved and the forming of the intermediate product is accelerated due to the effects of the glacial acetic acid and the dimethylbenzene; in addition, in the final boracylate reaction, as the calcium borate as the additive is added together with the tributyl borate, the reaction time is effectively shortened, and the insoluble substance performance and the anti-static property of the cobalt boracylate whichis prepared finally are improved.
Description
Technical field
The present invention relates to the preparation field of adhesion promotor, particularly relate to a kind of preparation method who can be used as the cobalt boracylate of rubber adhesion accelerating agent.
Background technology
From the adhesion mechanism of metal and rubber, so long as contain the salt of cobalt, can both be in the binding property of improving metal and rubber in varying degrees.The cobalt salt that people use the earliest is water miscible inorganic cobalt salt, as cobalt chloride, rose vitriol, these cobalt salts is blended in sizing material or is coated in the metallic surface, can improve the bounding force of metal and rubber to a certain extent, but finds simultaneously.When after thermal ageing, its bounding force sharply descends.Subsequently, people use cobalt salt instead and do rubber adhesion accelerating agent, find that after deliberation the more original inorganic cobalt salt of cobalt salt class adhesion promotor is compared, and can improve the bounding force of metal and rubber to a great extent.
The kind of common rubber composite promotor is a lot of on the market, and cobalt naphthenate (containing cobalt amount 10%), cobalt stearate (containing cobalt amount 9.5%), capric acid cobalt (containing cobalt amount 20.5%), cobalt boracylate (containing cobalt amount 22.5%) are arranged.Wherein cobalt boracylate is the rubber composite promotor of generally acknowledging with best bond properties.With regard to bonding conservation rate and binding efficiency after aging; cobalt boracylate will obviously be better than cobalt naphthenate, capric acid cobalt and cobalt stearate; improve 16.9% after making the performance hot air aging that makes rubber composite, improve 12.3% after the steam aging, the aging back of salt solution improves 22.9%.Therefore, cobalt boracylate can be widely used in and be used as rubber and the steel wire cord adhesion promotor of (comprising copper facing, zinc-plated, bare steel wire etc.) in rubber industry, the tire industry, is used for the production of rubber such as radial, rubber wire travelling belt, hydraulic pressure transition pipeline and metal composite; Also can be used for the manufacturing of static metal-powder in the coatings industry, powder coating siccative etc.
But in the existing preparation cobalt boracylate process, the general method that adopts neutralization, boron acidylate, interpolation additive, because in the method, acid-base neutralisation is not very strong, and promptly the short chain acids of Cai Yonging is other lower fatty acid, in it and the effect instability, can not realize the shortening of production time, the less stable of the finished product, therefore, make the cobalt boracylate ageing-resistant performance that makes bad, influence makes the performance of rubber composite; And the cobalt boracylate that prior art makes so there is the problem of granulation difficulty, is unfavorable for subsequent production packing and interpolation when rubber composite is produced because the selection of additive is limited.
Summary of the invention
The embodiment of the invention provides a kind of preparation method of cobalt boracylate, and it is good to make the cobalt boracylate performance, can guarantee to utilize it to make the ageing-resistant performance of rubber composite; And be easy to granulation, make things convenient for subsequent packages and in rubber composite, add.
The present invention is achieved through the following technical solutions:
The embodiment of the invention provides a kind of preparation method of cobalt boracylate, comprising:
Neodecanoic acid, isocaprylic acid, Glacial acetic acid, dimethylbenzene mixed with cobaltous hydroxide carry out acid-base neutralisation reaction, obtain intermediate product after neutralization reaction is finished;
Add tributyl borate and carry out the boron acylation reaction in the described intermediate product that obtains, add lime borate simultaneously as additive, the reaction product that obtains after the boron acylation reaction is finished is cobalt boracylate.
Among the cobalt boracylate preparation method in the embodiment of the present invention, cooperate by neodecanoic acid (long chain acid), isocaprylic acid (long chain acid), Glacial acetic acid (lower fatty acid) and dimethylbenzene (water-removal agent), carry out the acid-base neutralisation reaction with cobaltous hydroxide and generate intermediate product, because Glacial acetic acid and dimethylbenzene effect, can improve neutralization reaction speed, accelerate the removal of water, quicken the formation of intermediate product; And, in the boron acylation reaction of intermediate product and tributyl borate, add lime borate simultaneously as additive, not only effectively shortened the boron acylation reaction time, and improved the antistatic performance of the cobalt boracylate that finally makes, be used in rubber composite and can improve ageing-resistant performance; And owing to add lime borate, make the cobalt boracylate that makes be easy to granulation, be easy to when rubber composite is produced, add as additive.
Embodiment
For ease of understanding, the present invention is done further clear, careful explanation below in conjunction with specific embodiment.
Embodiment one
Present embodiment provides a kind of preparation method of cobalt boracylate, can be used as the rubber composite promotor of excellent property, and this method comprises:
Neodecanoic acid, isocaprylic acid, Glacial acetic acid, dimethylbenzene mixed with cobaltous hydroxide carry out acid-base neutralisation reaction, obtain intermediate product after neutralization reaction is finished;
Add tributyl borate and carry out the boron acylation reaction in the described intermediate product that obtains, add lime borate simultaneously as additive, the reaction product that obtains after the boron acylation reaction is finished is cobalt boracylate.
Aforesaid method specifically comprises neutralization reaction and two steps of boron acylation reaction:
Neutralization reaction: after neodecanoic acid, isocaprylic acid, Glacial acetic acid, dimethylbenzene mixed, add cobaltous hydroxide stirring and feed under the nitrogen state;
After cobaltous hydroxide adds, heat up and react; When being warmed up to 85～95 ℃, begin to distill out dimethylbenzene and water;
When being warming up to 155 ℃～165 ℃, carry out underpressure distillation, in the vacuum distillation process vacuum tightness from-0.01MPa reduce to-0.08MPa (can be progressively to reduce vacuum tightness, distillatory vacuum tightness is from-0.01MPa, per minute reduction-0.01MPa, reduce to-0.08MPa), and under vacuum tightness-0.08MPa, keep after 120 minutes up to vacuum tightness, finish the intermediate product after the acid-base neutralisation reaction obtains neutralizing;
The boron acylation reaction: add the mixture of tributyl borate and lime borate in the intermediate product that obtains after neutralization reaction under normal pressure, described mixture added at 60～120 minutes, kept the total reflux state in the reinforced process; Kept the total reflux state 60 minutes after reinforced the finishing, heating simultaneously, Heating temperature is 160 ℃～180 ℃;
When being warmed up to 165 ℃～175 ℃ afterwards; carry out underpressure distillation; in the vacuum distillation process vacuum tightness from-0.01MPa reduce to-0.08MPa (can be progressively to reduce vacuum tightness; distillatory vacuum tightness is from-0.01MPa; per minute reduction-0.01MPa; reduce to-0.08MPa), and keep under vacuum tightness-0.08MPa after 120 minutes up to vacuum tightness, the reaction product that obtains after the boron acylation reaction is finished is cobalt boracylate.
For the cobalt boracylate that makes conveniently being comprised and using, can further carry out granulation to the reaction product that obtains after the boron acylation reaction, as, can adopt revolution belt condensation tablets press to carry out granulation, the cooling temperature of granulation is 25～35 ℃.Making granular cobalt boracylate more is suitable for packing and adds in producing rubber composite.Additive in present method has adopted cheap lime borate, its stable performance, and particle is less, can not stop up pellet head in the process of granulation, and product can be existed with the round shaped grain form, and has improved the boron content in the product.
Control to cobalt contents in the production of cobalt boracylate is very important.The high more various performances of the rubber composite that makes that make of test shows, cobalt contents are good more, and general cobalt contents is not less than under 20% the situation, the requirement that the equal satisfiability of various rubber composite products that makes can be tested.But the content of cobalt generally can only reach about 18% in the existing boron acidylate.Therefore, cause utilizing the poor-performing of the rubber composite that this cobalt boracylate makes, the finished product performance that makes also is affected.
In aforesaid method, control the consumption of each raw material by following weight proportion:
Cobaltous hydroxide: 4～4.5 weight parts;
Isocaprylic acid: 3.4～3.8 weight parts;
Glacial acetic acid: 2.5～3.1 weight parts;
The dimethylbenzene add-on equates with the cobaltous hydroxide quality;
Tributyl borate: 3.2～5.1 weight parts;
Lime borate (additive): 0.7～1.5 weight part;
Because wherein neodecanoic acid, isocaprylic acid, Glacial acetic acid; the common acid-base neutralisation reaction of participating in (according to reaction mechanism) of three; realized having only two kinds of organic acids to participate in the technological breakthrough of reaction; the content of cobalt accurately is controlled at 22 ± 0.5% in the cobalt boracylate that can guarantee to make; thereby possess fine bounding force when making the cobalt boracylate that makes be used in the rubber composite, guaranteed to make the performance of rubber combined product.
Among the preparation method of the embodiment of the invention, in the acid-base neutralisation reaction, add neodecanoic acid, two kinds of high carboxylic acids of isocaprylic acid, and,, improve speed of reaction, quicken the formation of intermediate product with the reaction of cobaltous hydroxide generation acid-base neutralisation with the lower aliphatic acid+acetic acid; And utilize the intermediate product and the tributyl borate that obtain to carry out the boron acylation reaction; add lime borate simultaneously as additive; effectively shorten the boron acylation reaction time; and improved the antistatic performance of cobalt boracylate product; made things convenient for further granulation simultaneously; making granular cobalt boracylate and be easy to packing, is a kind of good rubber composite promotor, is easy to the interpolation process when rubber composite is produced.
And in the preparation method of the embodiment of the invention, as water-removal agent, and the employing add-on suitable with the cobaltous hydroxide quality guaranteed water removal effect with dimethylbenzene, and makes the quality of cobalt boracylate product at last.If the dimethylbenzene add-on is very few, the water that neutralization reaction generates fully can not be taken out of; Add-on has increased energy consumption, and part dimethylbenzene is remained in the final product if too much, then increased the reaction times, has influenced quality product, has reduced the whole fusing point of product.
Embodiment two
Present embodiment two provides a kind of preparation method of cobalt boracylate, and the cobalt boracylate that makes can be used as rubber combined promotor, and this method comprises:
Neutralization reaction: the isocaprylic acid of 3 weight part neodecanoic acids, 2.9～3.4 weight parts, the Glacial acetic acid of 2.5～3.1 weight parts and the dimethylbenzene of 4～4.5 weight parts are joined in the reactor, start the cobaltous hydroxide that high-speed stirring (150～250 rev/mins) adds simultaneously 4～4.5 weight parts at a slow speed and carry out the acid-base neutralisation reaction, add and keep feeding nitrogen in the cobaltous hydroxide process, after adding cobaltous hydroxide, temperature reaction; When temperature rose to 93 ℃, dimethylbenzene and water began to be distilled discharge from reactor;
When temperature rises to 160 ℃, material to the reaction in the reactor carries out underpressure distillation, vacuum tightness is reduced to-0.08MPa from-0.01MPa in the vacuum distillation process, whole process is the process that vacuum tightness progressively reduces, be the vacuum tightness of per minute reduction-0.01MPa, and reduce in vacuum tightness-kept 120 minutes during 0.08MPa, obtain intermediate product after finishing neutralization reaction;
Boron acylation reaction: after neutralization reaction is finished, under normal pressure, in aforesaid reaction vessel, add the tributyl borate of 3.2～5.1 weight parts and the mixture of 0.7～1.5 weight part lime borate, react with the intermediate product in the reactor, reinforced process is 60 minutes, and reinforced process keeps total reflux; Keep total reflux 60 minutes afterwards again; and heat; still-process heats up after Heating temperature is 160 ℃～180 ℃; when temperature of reaction reaches 170 ℃, distillatory vacuum tightness to be reduced to-0.08MPa from-0.01MPa, whole process is for progressively reducing the process of vacuum tightness; be the vacuum tightness of per minute reduction-0.01MPa; and in vacuum tightness be-0.08MPa kept 120 minutes, finished the boron acylation reaction, and the product that obtains is cobalt boracylate.
This cobalt boracylate can be used as rubber composite promotor, and its The performance test results is seen Table 1.It is more convenient when the cobalt boracylate that makes is used as rubber composite promotor; the product that can further make above-mentioned boron acylation reaction carries out granulation to be handled; as carrying out granulation by revolution belt condensation tablets press; the cooling temperature of granulation is about 30 ℃; granulation can obtain the cobalt boracylate particle after handling.The particulate state cobalt boracylate be suitable for packing and rubber composite to be produced the time add.
Embodiment three
Present embodiment three provides a kind of preparation method of cobalt boracylate, and the cobalt boracylate that makes can be used as rubber combined promotor, and this method comprises:
Neutralization reaction: the reactor that adopts 2000L, in reactor, add the neodecanoic acid of 3.4～3.8 weight parts, the isocaprylic acid of 2 weight parts, the Glacial acetic acid of 2.5～3.1 weight parts and the dimethylbenzene of 4～4.5 weight parts, start the cobaltous hydroxide that stirring adds 4～4.5 weight parts simultaneously slowly and carry out the acid-base neutralisation reaction, add the cobaltous hydroxide process and will keep in reactor, feeding nitrogen, after adding cobaltous hydroxide, make the reactor material reaction in it that heats up, when temperature rose to 93 ℃, dimethylbenzene and water were distilled discharge from reactor;
When temperature rises to 160 ℃, carry out underpressure distillation, vacuum degree control-0.01MPa～-0.08MPa, whole process is for progressively reducing process, i.e. per minute reduction-0.01MPa vacuum tightness.And in vacuum tightness be-0.08MPa kept 120 minutes, and finished neutralization reaction and obtain intermediate product;
The boron acylation reaction: afterwards under normal pressure in the reactor that makes intermediate product, add the tributyl borate of 3.2～5.1 weight parts and the mixture of 0.7～1.5 weight part lime borate, react with the intermediate product in the reactor, reinforced process is 120 minutes, and reinforced process keeps total reflux; Keep total reflux 60 minutes afterwards again, and heat simultaneously, Heating temperature is 160 ℃～180 ℃
Distill processing afterwards; when temperature of reaction reaches 170 ℃; distillatory vacuum tightness is reduced to-0.08MPa from-0.01MPa; whole process is for progressively reducing the process of vacuum tightness; be the vacuum tightness of per minute reduction-0.01MPa; and reduce in vacuum tightness-kept 120 minutes under the 0.08MPa state, finish the boron acylation reaction, the product that obtains is cobalt boracylate.This cobalt boracylate excellent property can be used as rubber composite promotor, and its The performance test results is seen Table 1.
Be the convenience of using, the product that can further make above-mentioned boron acylation reaction carries out granulation to be handled, and as carrying out granulation by revolution belt condensation tablets press, the cooling temperature of granulation is about 30 ℃, and granulation can obtain the cobalt boracylate particle after handling.The particulate state cobalt boracylate be suitable for packing and rubber composite to be produced the time add.
Embodiment four
Present embodiment four provides a kind of preparation method of cobalt boracylate, and the cobalt boracylate that makes can be used as rubber combined promotor, and this method comprises:
Neutralization reaction: adopt the 2000L reactor, in reactor, add the neodecanoic acid of 3.4～3.8 weight parts, the isocaprylic acid of 2.9～3.4 weight parts, the Glacial acetic acid of 2 weight parts and the dimethylbenzene of 4～4.5 weight parts, start and stir the cobaltous hydroxide that slowly adds 4～4.5 weight parts simultaneously and carry out the acid-base neutralisation reaction.Hydro-oxidation cobalt process keep to feed nitrogen, add cobaltous hydroxide after, temperature reaction, when temperature rose to 93 ℃, dimethylbenzene and water were distilled discharge from reactor;
When temperature rises to 160 ℃, carry out underpressure distillation, the vacuum tightness of underpressure distillation is reduced to-0.08MPa from-0.01MPa, whole process is for progressively reducing the process of vacuum tightness, be the vacuum tightness of per minute reduction-0.01MPa, and reduce in vacuum tightness-kept 120 minutes under the 0.08MPa state, finish neutralization reaction after the maintenance and obtain intermediate product;
Boron acylation reaction: after neutralization reaction is finished, in normal pressure downhill reaction still, add the tributyl borate of 3.2～5.1 weight parts and the mixture of 0.7～1.5 weight part lime borate, react with the intermediate product in the reactor, reinforced process is 60 minutes, reinforced process keeps total reflux, kept total reflux again 60 minutes after reinforced the finishing, and keep heating in this process, Heating temperature is 160 ℃～180 ℃;
Carry out still-process afterwards; when temperature of reaction reaches 170 ℃; the distillatory vacuum degree control-0.01MPa～-0.08MPa; whole process is for progressively reducing the process of vacuum tightness; be the vacuum tightness of per minute reduction-0.01MPa; and reduce in vacuum tightness-kept 120 minutes under the 0.08MPa state, finish the boron acylation reaction, the product that makes is cobalt boracylate.This cobalt boracylate excellent property can be used as rubber composite promotor, and its The performance test results is seen Table 1.
Be the convenience of using, the product that can further make above-mentioned boron acylation reaction carries out granulation to be handled, and as carrying out granulation by revolution belt condensation tablets press, the cooling temperature of granulation is about 30 ℃, and granulation can obtain the cobalt boracylate particle after handling.The particulate state cobalt boracylate be suitable for packing and rubber composite to be produced the time add.
Embodiment five
Present embodiment five provides a kind of preparation method of cobalt boracylate, and the cobalt boracylate that makes can be used as rubber combined promotor, and this method comprises:
Neutralization reaction: the neodecanoic acid of 3.4～3.8 weight parts, the isocaprylic acid of 2.9～3.4 weight parts, the Glacial acetic acid of 2.5～3.1 weight parts and the dimethylbenzene of 4～4.5 weight parts are joined in the reactor of 2000L, start the cobaltous hydroxide that stirring adds 4～4.5 weight parts simultaneously slowly and carry out the acid-base neutralisation reaction, add and keep in reactor, feeding nitrogen in the cobaltous hydroxide process, after adding cobaltous hydroxide, temperature reaction, when temperature rose to 93 ℃, dimethylbenzene and water were distilled discharge from reactor;
When temperature rises to 160 ℃, carry out underpressure distillation, the vacuum degree control of underpressure distillation-0.01MPa～-0.08MPa, whole process is for progressively reducing the process of vacuum tightness, be the vacuum tightness of per minute reduction-0.01MPa, and reduce in vacuum tightness-kept 120 minutes under the 0.08MPa state, finish neutralization reaction after the maintenance and obtain intermediate product;
Boron acylation reaction: under normal pressure, in the reactor of finishing neutralization reaction, add the tributyl borate of 3 weight parts and the mixture of 0.7～1.5 weight part lime borate, intermediate product in mixture and the reactor is reacted, the reinforced process of mixture is 60 minutes, keeps total reflux in the reinforced process; Kept total reflux again 60 minutes after reinforced the finishing, and keep heating in the total reflux process at this, Heating temperature is 160 ℃～180 ℃;
Carry out still-process afterwards; when temperature of reaction reaches 170 ℃; the distillatory vacuum degree control-0.01MPa～-0.08MPa; whole process is for progressively reducing the process of vacuum tightness; be the vacuum tightness of per minute reduction-0.01MPa; and in vacuum tightness be-kept 120 minutes under the 0.08MPa state, finish the boron acylation reaction, the product that obtains is cobalt boracylate.This cobalt boracylate excellent property can be used as rubber composite promotor, and its The performance test results is seen Table 1.
Be the convenience of using, the product that can further make above-mentioned boron acylation reaction carries out granulation to be handled, and as carrying out granulation by revolution belt condensation tablets press, the cooling temperature of granulation is about 30 ℃, and granulation can obtain the cobalt boracylate particle after handling.The particulate state cobalt boracylate be suitable for packing and rubber composite to be produced the time add.
Embodiment six
Present embodiment six provides a kind of preparation method of cobalt boracylate, and the cobalt boracylate that makes can be used as rubber combined promotor, and this method comprises:
Neutralization reaction: the isocaprylic acid of 3.4～3.8 weight part neodecanoic acids, 2.9～3.4 weight parts, the Glacial acetic acid of 2.5～3.1 weight parts and the dimethylbenzene of 4～4.5 weight parts are joined in the reactor of 2000L, start the cobaltous hydroxide that stirring adds 4～4.5 weight parts simultaneously slowly and carry out the acid-base neutralisation reaction, add and keep in reactor, feeding nitrogen in the cobaltous hydroxide process, after adding cobaltous hydroxide, temperature reaction, when temperature rose to 93 ℃, dimethylbenzene and water were distilled discharge from reactor;
When temperature rises to 160 ℃, carry out underpressure distillation, the vacuum degree control of underpressure distillation-0.01MPa～-0.08MPa, whole process is for progressively reducing the process of vacuum tightness, be the vacuum tightness of per minute reduction-0.01MPa, and reduce in vacuum tightness-kept 120 minutes under the 0.08MPa state, finish neutralization reaction after the maintenance and obtain intermediate product;
Boron acylation reaction: under normal pressure, in the reactor of finishing neutralization reaction, add the tributyl borate of 3.2～5.1 weight parts and the mixture of 1.8 weight part lime borates, intermediate product in mixture and the reactor is reacted, the reinforced process of mixture is 60 minutes, keeps total reflux in the reinforced process; Kept total reflux again 60 minutes after reinforced the finishing, and keep heating in the total reflux process at this, Heating temperature is 160 ℃～180 ℃;
Carry out still-process afterwards; when temperature of reaction reaches 170 ℃; the distillatory vacuum degree control-0.01MPa～-0.08MPa; whole process is for progressively reducing the process of vacuum tightness; be the vacuum tightness of per minute reduction-0.01MPa; and in vacuum tightness be-kept 120 minutes under the 0.08MPa state, finish the boron acylation reaction, the product that obtains is cobalt boracylate.This cobalt boracylate excellent property can be used as rubber composite promotor, and its The performance test results is seen Table 1.
Be the convenience of using, the product that can further make above-mentioned boron acylation reaction carries out granulation to be handled, and as carrying out granulation by revolution belt condensation tablets press, the cooling temperature of granulation is about 30 ℃, and granulation can obtain the cobalt boracylate particle after handling.The particulate state cobalt boracylate be suitable for packing and rubber composite to be produced the time add.
Table 1: each embodiment makes cobalt boracylate performance test table
| Sequence number | Cobalt contents % | Heptane insolubles % | Heat waste % | Whole fusing point ℃ | The granulation situation |
| Embodiment one | 22.5 | 8.0 | 0.3 | 100 | ○ |
| Embodiment two | 22.2 | 9.3 | 0.5 | 108 | △ |
| Embodiment three | 22.2 | 9.4 | 0.7 | 109 | △ |
| Embodiment four | 22.2 | 9.5 | 0.5 | 109 | △ |
| Embodiment five | 22.0 | 9.2 | 0.6 | 105 | × |
| Embodiment six | 22.0 | 11.2 | 0.7 | 112 | × |
In the table 1: zero: the grain circle is good; △: grain is not round, poor slightly; *: granulating not, very poor
The cobalt boracylate for preparing in the embodiment of the invention can be used as rubber composite promotor; can be used in the preparation radial; radial is compared with traditional bias tyre; has the actual service life height; fuel consumption is few; advantages such as wear resisting property is good, shock-absorbing capacity excellence, this cobalt boracylate can further improve the performance of radial.
The above; only for the preferable embodiment of the present invention, but protection scope of the present invention is not limited thereto, and anyly is familiar with those skilled in the art in the technical scope that the present invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (12)
1. the preparation method of a cobalt boracylate is characterized in that, comprising:
Neodecanoic acid, isocaprylic acid, Glacial acetic acid, dimethylbenzene mixed with cobaltous hydroxide carry out acid-base neutralisation reaction, obtain intermediate product after neutralization reaction is finished;
Add tributyl borate and carry out the boron acylation reaction in the described intermediate product that obtains, add lime borate simultaneously as additive, the reaction product that obtains after the boron acylation reaction is finished is cobalt boracylate.
2. the preparation method of cobalt boracylate as claimed in claim 1 is characterized in that, the content of calcium oxide is 15%～35% in the lime borate that uses in the described method.
3. the preparation method of cobalt boracylate as claimed in claim 1 is characterized in that, described neodecanoic acid, isocaprylic acid, Glacial acetic acid, dimethylbenzene are mixed with cobaltous hydroxide carries out acid-base neutralisation reaction and comprise:
After neodecanoic acid, isocaprylic acid, Glacial acetic acid, dimethylbenzene mixed, add cobaltous hydroxide stirring and feed under the nitrogen state;
After cobaltous hydroxide adds, heat up and react; When being warmed up to 85～95 ℃, dimethylbenzene and water are discharged in distillation;
When being warming up to 155 ℃～165 ℃, carry out underpressure distillation, vacuum tightness is reduced to-0.08MPa from-0.01MPa in the vacuum distillation process, and keeps under vacuum tightness-0.08MPa after 120 minutes, finishes the intermediate product after the acid-base neutralisation reaction obtains neutralizing.
4. the preparation method of cobalt boracylate as claimed in claim 3 is characterized in that, in the described method, carries out underpressure distillation, in the vacuum distillation process vacuum tightness from-0.01MPa reduce to-0.08MPa comprises:
After entering underpressure distillation, vacuum tightness is from-0.01MPa, and per minute reduction-0.01MPa reduces to-0.08MPa up to vacuum tightness.
5. the preparation method of cobalt boracylate as claimed in claim 1 is characterized in that, the described tributyl borate that adds in the intermediate product that obtains carries out the boron acylation reaction, adds lime borate simultaneously and comprises as additive:
Add the mixture of tributyl borate and lime borate in the intermediate product that obtains after neutralization reaction under normal pressure, described mixture added at 60～120 minutes, kept the total reflux state in the reinforced process; Kept the total reflux state 60 minutes after reinforced the finishing, heating simultaneously, Heating temperature is 160 ℃～180 ℃;
When being warmed up to 165 ℃～175 ℃ afterwards, carry out underpressure distillation, vacuum tightness is reduced to-0.08MPa from-0.01MPa in the vacuum distillation process, and keeps after 120 minutes under vacuum tightness-0.08MPa, and the reaction product that obtains after the boron acylation reaction is finished is cobalt boracylate.
6. the preparation method of cobalt boracylate as claimed in claim 5 is characterized in that, in the described method, carries out underpressure distillation, in the vacuum distillation process vacuum tightness from-0.01MPa reduce to-0.08MPa comprises:
After entering underpressure distillation, vacuum tightness is from-0.01MPa, and per minute reduction-0.01MPa reduces to-0.08MPa up to vacuum tightness.
7. the preparation method of cobalt boracylate as claimed in claim 1 is characterized in that, described method also comprises:
The step that the reaction product that obtains after the boron acylation reaction finished is carried out granulation adopts revolution belt condensation tablets press, and the cooling temperature of granulation is 25～35 ℃.
8. the preparation method of a cobalt boracylate is characterized in that, comprising:
Neutralization reaction: the isocaprylic acid of 3 weight part neodecanoic acids, 2.9～3.4 weight parts, the Glacial acetic acid of 2.5～3.1 weight parts and the dimethylbenzene of 4～4.5 weight parts are joined in the reactor, start high-speed stirring, it is 150～250 rev/mins, the cobaltous hydroxide that adds simultaneously 4～4.5 weight parts at a slow speed carries out the acid-base neutralisation reaction, add and keep feeding nitrogen in the cobaltous hydroxide process, after adding cobaltous hydroxide, temperature reaction; When temperature rose to 93 ℃, dimethylbenzene and water began to be distilled discharge from reactor;
When temperature rises to 160 ℃, material to the reaction in the reactor carries out underpressure distillation, vacuum tightness is reduced to-0.08MPa from-0.01MPa in the vacuum distillation process, whole process is the process that vacuum tightness progressively reduces, be the vacuum tightness of per minute reduction-0.01MPa, and reduce in vacuum tightness-kept 120 minutes during 0.08MPa, obtain intermediate product after finishing neutralization reaction;
Boron acylation reaction: after neutralization reaction is finished, under normal pressure, in aforesaid reaction vessel, add the tributyl borate of 3.2～5.1 weight parts and the mixture of 0.7～1.5 weight part lime borate, react with the intermediate product in the reactor, reinforced process is 60 minutes, and reinforced process keeps total reflux; Keep total reflux 60 minutes afterwards again; and heat; still-process heats up after Heating temperature is 160 ℃～180 ℃; when temperature of reaction reaches 170 ℃, distillatory vacuum tightness to be reduced to-0.08MPa from-0.01MPa, whole process is for progressively reducing the process of vacuum tightness; be the vacuum tightness of per minute reduction-0.01MPa; and in vacuum tightness be-0.08MPa kept 120 minutes, finished the boron acylation reaction, and the product that obtains is cobalt boracylate.
9. the preparation method of a cobalt boracylate is characterized in that, comprising:
Neutralization reaction: the reactor that adopts 2000L, in reactor, add the neodecanoic acid of 3.4～3.8 weight parts, the isocaprylic acid of 2 weight parts, the Glacial acetic acid of 2.5～3.1 weight parts and the dimethylbenzene of 4～4.5 weight parts, start the cobaltous hydroxide that stirring adds 4～4.5 weight parts simultaneously slowly and carry out the acid-base neutralisation reaction, add the cobaltous hydroxide process and will keep in reactor, feeding nitrogen, after adding cobaltous hydroxide, make the reactor material reaction in it that heats up, when temperature rose to 93 ℃, dimethylbenzene and water were distilled discharge from reactor;
When temperature rises to 160 ℃, carry out underpressure distillation, vacuum degree control-0.01MPa～-0.08MPa, whole process is for progressively reducing process, be per minute reduction-0.01MPa vacuum tightness, and in vacuum tightness be-0.08MPa kept 120 minutes, and finished neutralization reaction and obtain intermediate product;
The boron acylation reaction: afterwards under normal pressure in the reactor that makes intermediate product, add the tributyl borate of 3.2～5.1 weight parts and the mixture of 0.7～1.5 weight part lime borate, react with the intermediate product in the reactor, reinforced process is 120 minutes, and reinforced process keeps total reflux; Keep total reflux 60 minutes afterwards again, and heat simultaneously, Heating temperature is 160 ℃～180 ℃,
Distill processing afterwards; when temperature of reaction reaches 170 ℃; distillatory vacuum tightness is reduced to-0.08MPa from-0.01MPa; whole process is for progressively reducing the process of vacuum tightness; be the vacuum tightness of per minute reduction-0.01MPa; and reduce in vacuum tightness-kept 120 minutes under the 0.08MPa state, finish the boron acylation reaction, the product that obtains is cobalt boracylate.
10. the preparation method of a cobalt boracylate is characterized in that, comprising:
Neutralization reaction: adopt the 2000L reactor, in reactor, add the neodecanoic acid of 3.4～3.8 weight parts, the isocaprylic acid of 2.9～3.4 weight parts, the Glacial acetic acid of 2 weight parts and the dimethylbenzene of 4～4.5 weight parts, start and stir the cobaltous hydroxide that slowly adds 4～4.5 weight parts simultaneously and carry out the acid-base neutralisation reaction, hydro-oxidation cobalt process keeps feeding nitrogen, after adding cobaltous hydroxide, temperature reaction, when temperature rose to 93 ℃, dimethylbenzene and water were distilled discharge from reactor;
When temperature rises to 160 ℃, carry out underpressure distillation, the vacuum tightness of underpressure distillation is reduced to-0.08MPa from-0.01MPa, whole process is for progressively reducing the process of vacuum tightness, be the vacuum tightness of per minute reduction-0.01MPa, and reduce in vacuum tightness-kept 120 minutes under the 0.08MPa state, finish neutralization reaction after the maintenance and obtain intermediate product;
Boron acylation reaction: after neutralization reaction is finished, in normal pressure downhill reaction still, add the tributyl borate of 3.2～5.1 weight parts and the mixture of 0.7～1.5 weight part lime borate, react with the intermediate product in the reactor, reinforced process is 60 minutes, reinforced process keeps total reflux, kept total reflux again 60 minutes after reinforced the finishing, and keep heating in this process, Heating temperature is 160 ℃～180 ℃;
Carry out still-process afterwards; when temperature of reaction reaches 170 ℃; the distillatory vacuum degree control-0.01MPa～-0.08MPa; whole process is for progressively reducing the process of vacuum tightness; be the vacuum tightness of per minute reduction-0.01MPa; and reduce in vacuum tightness-kept 120 minutes under the 0.08MPa state, finish the boron acylation reaction, the product that makes is cobalt boracylate.
11. the preparation method of a cobalt boracylate is characterized in that, comprising:
Neutralization reaction: the neodecanoic acid of 3.4～3.8 weight parts, the isocaprylic acid of 2.9～3.4 weight parts, the Glacial acetic acid of 2.5～3.1 weight parts and the dimethylbenzene of 4～4.5 weight parts are joined in the reactor of 2000L, start the cobaltous hydroxide that stirring adds 4～4.5 weight parts simultaneously slowly and carry out the acid-base neutralisation reaction, add and keep in reactor, feeding nitrogen in the cobaltous hydroxide process, after adding cobaltous hydroxide, temperature reaction, when temperature rose to 93 ℃, dimethylbenzene and water were distilled discharge from reactor;
When temperature rises to 160 ℃, carry out underpressure distillation, the vacuum degree control of underpressure distillation-0.01MPa～-0.08MPa, whole process is for progressively reducing the process of vacuum tightness, be the vacuum tightness of per minute reduction-0.01MPa, and reduce in vacuum tightness-kept 120 minutes under the 0.08MPa state, finish neutralization reaction after the maintenance and obtain intermediate product;
Boron acylation reaction: under normal pressure, in the reactor of finishing neutralization reaction, add the tributyl borate of 3 weight parts and the mixture of 0.7～1.5 weight part lime borate, intermediate product in mixture and the reactor is reacted, the reinforced process of mixture is 60 minutes, keeps total reflux in the reinforced process; Kept total reflux again 60 minutes after reinforced the finishing, and keep heating in the total reflux process at this, Heating temperature is 160 ℃～180 ℃;
Carry out still-process afterwards; when temperature of reaction reaches 170 ℃; the distillatory vacuum degree control-0.01MPa～-0.08MPa; whole process is for progressively reducing the process of vacuum tightness; be the vacuum tightness of per minute reduction-0.01MPa; and in vacuum tightness be-kept 120 minutes under the 0.08MPa state, finish the boron acylation reaction, the product that obtains is cobalt boracylate.
12. the preparation method of a cobalt boracylate is characterized in that, comprising:
Neutralization reaction: the isocaprylic acid of 3.4～3.8 weight part neodecanoic acids, 2.9～3.4 weight parts, the Glacial acetic acid of 2.5～3.1 weight parts and the dimethylbenzene of 4～4.5 weight parts are joined in the reactor of 2000L, start the cobaltous hydroxide that stirring adds 4～4.5 weight parts simultaneously slowly and carry out the acid-base neutralisation reaction, add and keep in reactor, feeding nitrogen in the cobaltous hydroxide process, after adding cobaltous hydroxide, temperature reaction, when temperature rose to 93 ℃, dimethylbenzene and water were distilled discharge from reactor;
When temperature rises to 160 ℃, carry out underpressure distillation, the vacuum degree control of underpressure distillation-0.01MPa～-0.08MPa, whole process is for progressively reducing the process of vacuum tightness, be the vacuum tightness of per minute reduction-0.01MPa, and reduce in vacuum tightness-kept 120 minutes under the 0.08MPa state, finish neutralization reaction after the maintenance and obtain intermediate product;
Boron acylation reaction: under normal pressure, in the reactor of finishing neutralization reaction, add the tributyl borate of 3.2～5.1 weight parts and the mixture of 1.8 weight part lime borates, intermediate product in mixture and the reactor is reacted, the reinforced process of mixture is 60 minutes, keeps total reflux in the reinforced process; Kept total reflux again 60 minutes after reinforced the finishing, and keep heating in the total reflux process at this, Heating temperature is 160 ℃～180 ℃;
Carry out still-process afterwards; when temperature of reaction reaches 170 ℃; the distillatory vacuum degree control-0.01MPa～-0.08MPa; whole process is for progressively reducing the process of vacuum tightness; be the vacuum tightness of per minute reduction-0.01MPa; and in vacuum tightness be-kept 120 minutes under the 0.08MPa state, finish the boron acylation reaction, the product that obtains is cobalt boracylate.
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| CN103102362B (en) * | 2012-12-19 | 2016-03-02 | 于文明 | Boric acid one-step synthesis method Novel boron acidylate cobalt salt adhesion promotion agent production technique |
| CN103102363A (en) * | 2012-12-31 | 2013-05-15 | 大连爱柏斯化工有限公司 | Preparation method of low insoluble substance cobalt boroacylate |
| CN103113416B (en) * | 2012-12-31 | 2019-07-05 | 大连爱柏斯化工股份有限公司 | A kind of preparation method of low melting point cobalt boracylate |
| 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 |
| CN107986955A (en) * | 2017-11-22 | 2018-05-04 | 浙江三晟化工有限公司 | A kind of preparation method of new cobalt decanoate |
| 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 |
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