CN102173010A - Benzimidazole ionic liquid aid used in rubber processing and preparation method thereof - Google Patents
Benzimidazole ionic liquid aid used in rubber processing and preparation method thereof Download PDFInfo
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- CN102173010A CN102173010A CN2011100393971A CN201110039397A CN102173010A CN 102173010 A CN102173010 A CN 102173010A CN 2011100393971 A CN2011100393971 A CN 2011100393971A CN 201110039397 A CN201110039397 A CN 201110039397A CN 102173010 A CN102173010 A CN 102173010A
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- benzimidazole
- ionic liquid
- benzyl
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Abstract
The invention relates to a benzimidazole ionic liquid aid used in rubber processing and a preparation method thereof. The method comprises the following steps of: (1) mixing benzimidazole, aqueous solution of NaOH and (C4H9)4NBr, heating to the temperature of 55DEG C, adding a reactant of benzyl chloride, reacting for 1 to 1.5 hours, cooling, filtering, dissolving a solid by using chloroform, washing with distilled water, drying with anhydrous Na2SO4, steaming out a solvent under reduced pressure, and recrystallizing with benzene to obtain 1-benzyl-benzimidazole; and (2) dissolving the 1-benzyl-benzimidazole in a solvent, adding aqueous solution of HB for reaction, steaming out the solvent under reduced pressure, and performing washing, recrystallization and vacuum drying to obtain 1-benzyl-benzimidazole ionic liquid. Required raw materials of the benzimidazole ionic liquid aid are sold in market, wide in sources and low in prices; and the product yield in each step is high, the process is simple, and the production cost is low. The product can serve as an external lubricant, film separant and release agent in rubber processing.
Description
Technical field
The present invention relates to a kind of rubber processing aids, particularly the benzimidazole ionic liquid can be used as external lubricant, film isolating agent, releasing agent in the rubber processing process.
Background technology
In the rubber mold process, rubber will vulcanize through HTHP, just can become to have rubber product excellent mechanical properties, different shape.In process, tend to take place the sticking to mould problem during molding, cause product surface damaged, influence product quality.Sticking to mould when preventing rubber vulcanization except that rational mould design, is also taked lubricant method usually.Lubricant is divided into external lubricant and in-lubricant.It is to form separation layer that external lubricant mainly acts on, and reduces the adhesion between rubber and the mold cavity surface, makes the demoulding easy.Usually take to adorn before the glue way, but silicone oil will be through spraying, and order will spray evenly, otherwise mold sticking can take place also at mold cavity spraying silicone oil.
In the rubber production process, because the tack of elastomeric compound, sizing material can glutinously mutually connect in process, cause processing and transportation difficulty, therefore, before elastomeric compound is finally made finished product, before carrying and accumulating elastomeric compound, extrude, before extrusion and the gum stock, all can on corresponding film, be coated with the last layer interleaving agent, connect to prevent that film is glutinous mutually.The application of interleaving agent is more and more wider, and the at present existing interleaving agent that comprises solid, liquid, lotion, 4 kinds of forms of suspended substance is used by vast rubber manufacturer.The external lubricant of Shi Yonging, film isolating agent, releasing agent are generally not general mutually in the market, and have and easily stay mold deposit and vestige, mould is had corrosiveness, price than shortcomings such as costlinesses.
Summary of the invention
One of purpose of the present invention provides the benzimidazole ionic liquid auxiliary agent that uses in a kind of rubber processing, can be used as external lubricant, film isolating agent, releasing agent in the rubber processing process.This auxiliary agent has the chemical constitution shown in the general formula (I):
General formula (I)
R in the general formula (I)
1Be H, R
2Be benzyl or its homologue, [B]
-Be Cl
-, Br
-, I
-, BF
4 -, PF
6 -, NO
3 -, HSO
4 -Or H
2PO
4 -
The preparation method of a kind of benzimidazole ionic liquid auxiliary agent that two of purpose of the present invention provides.
For realizing that the technical scheme that purpose of the present invention adopts is:
1, with benzimidazole, the 40% NaOH aqueous solution and (C
4H
9)
4Three kinds of compound of NBr are heated to 55 ℃, stir, and question response liquid adds benzyl chloride after being colourless solution, reacts 1～1.5 hour.Cooling leaches white solid, and with the chloroform dissolving, organic facies is washed with distilled water to neutrality, anhydrous Na
2SO
4Dry.Remove solvent under reduced pressure, make the 1-benzyl benzimidazole with the benzene recrystallization.The material consumption of described participation reaction is benzimidazole (the g) ︰ 40% NaOH aqueous solution (mL) ︰ (C
4H
9)
4NBr(g) ︰ benzyl chloride (mL) is 1 ︰, 10～15 ︰, 0.1～0.5 ︰ 1～3.
Reaction equation is as follows:
2, the 1-benzyl benzimidazole is dissolved in solvent, slowly dripping concentration then is the HB aqueous solution of 5 ~ 10mol/L.At room temperature stirring reaction is 2～3 hours.Remove solvent under reduced pressure, obtain thick product.Thick product is washed 3 times with ether, and (70 ℃ of vacuum drying obtain colourless 1-benzyl benzimidazole ionic liquid to the alcohol-ether mixed system for V/V, 1:1) recrystallization.
Reaction equation is as follows:
B among the wherein said HB
-Be Cl
-, Br
-, I
-, BF
4 -, PF
6 -, NO
3 -, HSO
4 -Or H
2PO
4 -In a kind of.
The material consumption of wherein said participation reaction is that (g) ︰ solvent (mL) ︰ HB(mL) is 2 ︰, 30～70 ︰ 2～4 to the 1-benzyl benzimidazole.
Described solvent is methyl alcohol, ethanol, acetone, ethyl acetate or water.
Benzimidazole ionic liquid auxiliary agent of the present invention is produced required raw material and is the commercial goods, and wide material sources are cheap, and the synthetic method of employing or production technology also belong to classical organic synthesis.Each step products yield height, technology is simple, and production cost is low.Utilize the benzimidazole ionic liquid auxiliary agent of the inventive method preparation, can be used as external lubricant, film isolating agent, releasing agent in the rubber processing process, it is stable to have chemical property, and the performance of eliminating the rubber adhesion is better than present like product.Benzimidazole ionic liquid provided by the invention spreads upon the machine surface unsaturated field of force on saturated rubber surface fully, eliminates adhesion.Also can increase the mechanical performance of rubber.Benzimidazole ionic liquid of the present invention is being liquid more than 80 ℃, and the hardware of rubber toolings such as opening rubber mixing machine is had good wetability, to the then significantly not sticking glutinous phenomenon of the little various rubber of polarity.Can be used as external lubricant, film isolating agent, releasing agent in the rubber processing process.
The specific embodiment
Embodiment 1
The ion liquid preparation of 1-benzyl benzimidazole bromate
1, the preparation of 1-benzyl benzimidazole
In three-neck flask, add 2g benzimidazole, 20mL 40% NaOH and 0.2g(C
4H
9)
4NBr is heated to 55 ℃, stirs the benzyl chloride that adds 2.4mL down, reacts after 1 hour, and the adularescent solid is separated out.Reactant mixture is poured in the water of 50mL, filtered.The precipitation that leaches is dissolved with chloroform, with distilled water washing 3 times, organic facies anhydrous Na
2SO
4Drying removes solvent under reduced pressure, with benzene be recrystallized the 1-benzyl benzimidazole.
2, the ion liquid preparation of 1-benzyl benzimidazole bromate
Add 2.00g 1-benzyl benzimidazole in three-necked bottle, 30mL ethanol slowly drips 2.00mL 6.93mol/L HBr under the stirring at room.Stirring at room reaction 2 hours.Remove the second alcohol and water under reduced pressure, obtaining Chinese red grease is thick product.Thick product is with ether washing 3 times, and (70 ℃ of vacuum drying 12 hours promptly get 1-benzyl benzimidazole bromate ionic liquid to alcohol-ether for V/V, 1:1) recrystallization.
Embodiment 2
The preparation of 1-benzyl benzimidazole tetrafluoroborate ion liquid
1, the preparation of 1-benzyl benzimidazole
In three-neck flask, add 2g benzimidazole, the 30mL 40%NaOH aqueous solution and 0.3g(C
4H
9)
4NBr is heated to 55 ℃, stirs the benzyl chloride that adds 3.5mL down, reacts after 1.5 hours, and the adularescent solid is separated out.Reactant mixture is poured in the water of 50mL, filtered.Solid dissolves with chloroform, distilled water washing 3 times, anhydrous Na
2SO
4Dry.Remove solvent under reduced pressure, with benzene be recrystallized the 1-benzyl benzimidazole.
2, the preparation of 1-benzyl benzimidazole tetrafluoroborate ion liquid
Take by weighing 2.45g 1-benzyl benzimidazole, place the 100mL three-necked bottle, add 30mL acetone and make solvent, stirring at room is dissolved solid fully.Add 4mL 8mol/L HBF
4The aqueous solution, stirring at room reaction 1.5 hours removes solvent under reduced pressure and gets thick product.Thick product is with ether washing 3 times, alcohol-ether (V/V, 1:1) recrystallization, 70 ℃ of vacuum drying 12 hours, 1-benzyl benzimidazole tetrafluoroborate ion liquid.
Embodiment 3
The ion liquid preparation of 1-benzyl benzimidazole hexafluorophosphate
Take by weighing the 2g 1-benzyl benzimidazole of example 1 gained, place flask at the bottom of the 250mL, add 50ml distilled water, add 2mL 10mol/L KPF again
6The aqueous solution, stirring at room reaction 1.5 hours removes solvent under reduced pressure and gets thick product.Thick product is with ether washing 3 times, alcohol-ether (V/V, 1:1) recrystallization, 70 ℃ of vacuum drying 12 hours, 1-benzyl benzimidazole hexafluorophosphate ionic liquid.
Claims (7)
1. the benzimidazole ionic liquid auxiliary agent that uses in the rubber processing has the chemical constitution shown in the general formula (I):
General formula (I)
R in the general formula (I)
1Be H, R
2Be benzyl or its homologue, [B]
-Be Cl
-, Br
-, I
-, BF
4 -, PF
6 -, NO
3 -, HSO
4 -Or H
2PO
4 -
2. the preparation method of the benzimidazole ionic liquid auxiliary agent that uses in the rubber processing is characterized in that this method may further comprise the steps:
(1) with benzimidazole, the 40% NaOH aqueous solution and (C
4H
9)
4Three kinds of compound of NBr are heated to 55 ℃, add benzyl chloride, react after 1～1.5 hour cooling, filtration; Leach solid and dissolve with chloroform, organic facies is washed with distilled water to neutrality, anhydrous Na
2SO
4Drying removes solvent under reduced pressure, obtains the 1-benzyl benzimidazole with the benzene recrystallization;
(2) the 1-benzyl benzimidazole is dissolved in solvent, adds the HB aqueous solution then, at room temperature reaction removes solvent under reduced pressure, obtains thick product, through washing, recrystallization, 70 ℃ of vacuum drying, gets 1-benzyl benzimidazole ionic liquid.
3. the preparation method of the benzimidazole ionic liquid auxiliary agent that uses in a kind of rubber processing according to claim 2, when it is characterized in that described preparation 1-benzyl benzimidazole, the material consumption that participates in reaction is benzimidazole (g) ︰ 40%NaOH(mL) Shui Rong Ye ︰ (C
4H
9)
4NBr(g) ︰ benzyl chloride (mL) is 1 ︰, 10～15 ︰, 0.1～0.5 ︰ 1～3.
4. the preparation method of the benzimidazole ionic liquid auxiliary agent that uses in a kind of rubber processing according to claim 2, when it is characterized in that described preparation 1-benzyl benzimidazole ionic liquid, the material consumption that participates in reaction is that (g) ︰ solvent (mL) ︰ HB(mL) is 2 ︰, 30～70 ︰ 2～4 to the 1-benzyl benzimidazole.
5. the preparation method of the benzimidazole ionic liquid auxiliary agent that uses in a kind of rubber processing according to claim 2 is characterized in that the B among the described HB
-Be Cl
-, Br
-, I
-, BF
4 -, PF
6 -, NO
3 -, HSO
4 -Or H
2PO
4 -In a kind of.
6. the preparation method of the benzimidazole ionic liquid auxiliary agent that uses in a kind of rubber processing according to claim 2 is characterized in that thick product recrystallization system after washing is the alcohol-ether mixed system of equal-volume ratio.
7. the preparation method of the benzimidazole ionic liquid auxiliary agent that uses in a kind of rubber processing according to claim 2 is characterized in that described solvent is methyl alcohol, ethanol, acetone, ethyl acetate or water.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100393971A CN102173010A (en) | 2011-02-17 | 2011-02-17 | Benzimidazole ionic liquid aid used in rubber processing and preparation method thereof |
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|---|---|---|---|
| CN2011100393971A CN102173010A (en) | 2011-02-17 | 2011-02-17 | Benzimidazole ionic liquid aid used in rubber processing and preparation method thereof |
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|---|---|---|---|
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1852968A (en) * | 2003-08-15 | 2006-10-25 | 科聚亚公司 | Reactions products of mercaptobenzothiazoles, mercaptothiazolines, and mercaptobenzimidazoles with epoxides as lubricant additives |
| CN1958576A (en) * | 2006-10-27 | 2007-05-09 | 西北大学 | Acid ion liquid of benzimidazole salts, synthetic method, and application in reaction of esterification |
-
2011
- 2011-02-17 CN CN2011100393971A patent/CN102173010A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1852968A (en) * | 2003-08-15 | 2006-10-25 | 科聚亚公司 | Reactions products of mercaptobenzothiazoles, mercaptothiazolines, and mercaptobenzimidazoles with epoxides as lubricant additives |
| CN1958576A (en) * | 2006-10-27 | 2007-05-09 | 西北大学 | Acid ion liquid of benzimidazole salts, synthetic method, and application in reaction of esterification |
Non-Patent Citations (1)
| Title |
|---|
| 朱竹英 等: "1,3-二苄基苯并咪唑盐的合成研究", 《延安大学学报(自然科学版)》 * |
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Application publication date: 20110907 |