CN105566256A - Simple method for large scale production of olefine ketone dimer - Google Patents
Simple method for large scale production of olefine ketone dimer Download PDFInfo
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- CN105566256A CN105566256A CN201410524512.8A CN201410524512A CN105566256A CN 105566256 A CN105566256 A CN 105566256A CN 201410524512 A CN201410524512 A CN 201410524512A CN 105566256 A CN105566256 A CN 105566256A
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- acid halides
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Abstract
The invention relates to a simple method for large scale production of an olefine ketone dimer. According to the method, at least a fatty acid acyl halide and a tertiary amine are subjected to a reaction in a solvent medium to form a reaction mixture so as to achieve the purpose, wherein the molten state olefine ketone dimer is adopted as the solvent medium.
Description
Technical field
The present invention relates to the method for scale operation ketene dimer.
Background technology
Ketene dimer, as alkyl ketene dimer (AKD) is used as sizing agent in papermaking.Ketene dimer, as alkyl ketene dimer, is by using tertiary amine remove hydrogen halide from lipid acid carboxylic acid halides (fattyacidhalides) and produce.The reactive ketenes obtained is as intermediate generation dimerization.Reaction is generally carry out in organic solvent, and this organic solvent is inertia for parent material and end product.Conventional organic solvent is alkane, naphthenic hydrocarbon or aromatic hydrocarbon.In suitability for industrialized production, modal a kind of solvent is toluene.Regrettably, the amount of solvent is usually quite high, and this is all disadvantageous in tooling cost and environment and occupational safety.And, remove completely the more difficult AKD from producing of organic solvent.Thus, the product of acquisition may containing a small amount of organic solvent, and this is usually difficult to accept for the terminal user of product.
Therefore, all need a kind ofly not use harmful organic solvent to produce plant-scale business method of ketene dimer all the time.
Summary of the invention
An object of the present invention is reduce or even eliminate the above-mentioned problems in the prior art.
An object of the present invention is to provide the easy full-scale industrial process producing ketene dimer, it is solvent-free.
To achieve these goals, feature of the present invention is especially the content that describes in the characteristic of the independent claim of enclosing.
Preferred embodiments more of the present invention are open in dependent claims thereto.
Typical method for the production of ketene dimer of the present invention makes at least one lipid acid carboxylic acid halides with reactive tertiary amine and forming reactions mixture in solvent medium, wherein uses ketene dimer under molten state as solvent medium.
Now surprisingly find, the ketene dimer that traditional organic solvent can be melted under state as toluene substitutes.
According to an embodiment, a part for the ketene dimer that solvent medium is produced before can being, it is left in tank reactor.Then, in turn or side by side, in the melting ketene dimer wax produced before this, at least one lipid acid carboxylic acid halides and tertiary amine is added.
According to one embodiment of the invention, the weight ratio of solvent medium and lipid acid carboxylic acid halides is 0.5:1 to 5:1.The weight ratio of solvent medium and lipid acid carboxylic acid halides also can be 0.7:1 to 1.25:1.
The weight ratio of tertiary amine and lipid acid carboxylic acid halides can be 0.25:1 to 3:1, is preferably 0.3:1 to 1.5:1.Visible, a small amount of tertiary amine can be used.This all provides obvious advantage in economy and technical elements, because tertiary amine costly, and its process also has problems.
According to one embodiment of the invention, tertiary amine is added in solvent medium, then most lipid acid carboxylic acid halides is added in solvent medium within for some time, preferably dropwise or by small proportion add.This most lipid acid carboxylic acid halides comprises at least 50% of the total amount of lipid acid carboxylic acid halides used, be generally the 50-100% of the total amount of lipid acid carboxylic acid halides used, be more typically the 80-97% of the total amount of lipid acid carboxylic acid halides used, be even more typically the 85-95% of the total amount of lipid acid carboxylic acid halides used.If this major part is 100% of the total amount of lipid acid carboxylic acid halides used, this expression adds whole lipid acid carboxylic acid halides after interpolation tertiary amine.
According to a preferred embodiment of the present invention, before the most lipid acid carboxylic acid halides of interpolation, whole tertiary amine is added in solvent medium.When adding tertiary amine in one step, adding procedure more easily controls, thus provides better reaction result.
According to another embodiment, can respectively and side by side most lipid acid carboxylic acid halides and tertiary amine are added to comprise melting form ketene dimer as in the reaction mixture of solvent.
According to a typical embodiment, in 1-6 hour, lipid acid carboxylic acid halides is added in solvent medium.This ensures to form alkyl ketene dimer with suitable speed of response.
After interpolation lipid acid carboxylic acid halides, reaction is generally made to carry out 10-180 minute.
After interpolation lipid acid carboxylic acid halides, temperature of reaction can remain in the scope of 55-65 DEG C.
In the production process of ketene dimer, the viscosity of reaction mixture remains in an acceptable level.In the method for the invention, the viscosity of reaction mixture is less than 6000cps usually, is preferably less than 5000cps.The reaction conditions that especially can be selected of viscosity is as the impact of the amount of temperature and mixing and reactant.
Such as, in order to make the viscosity of mixture remain in acceptable level, in reaction process, reaction mixture is preferably made fully to mix.Mixing can be undertaken by using the frame stirrer (frame-typeagitator) be connected with high-power engine.Such as, can with the speed hybrid reaction mixture of 80-130rpm.
According to one embodiment of the invention, the temperature of reaction mixture can be controlled in the production process of ketene dimer.Such as, preferred at least reaction mixture in process lipid acid carboxylic acid halides being added into reaction mixture.Can be cooled by external heat exchange system by making reaction mixture circulation (preferably continuously) at least partially.This represents that reaction mixture at least partially leaves tank reactor and by heat exchange system, reduces the temperature of reaction mixture at this.Afterwards, tank reactor got back to by reaction mixture.By this way, by the amount regulating circulation to enter the reaction mixture of external heat exchange system, or by regulating speed of circulation, the temperature of reaction mixture can accurately be controlled.
Advantageously, under the temperature range of 48-75 DEG C, lipid acid carboxylic acid halides is added into solvent medium.
At least one lipid acid carboxylic acid halides of the present invention can be selected from the saturated of C8-C22 and undersaturated straight chain fatty acid carboxylic acid halides, and at least one in any mixture; Tertiary amine can be selected from C1-C6 trialkylamine, N-C1-C6 Alkylpiperidine, the N-C1-C6 tetramethyleneimine of straight chain, side chain and ring-type, and at least one in arbitrary mixture.According to a preferred embodiment of the present invention, at least one lipid acid carboxylic acid halides is selected from least one in the saturated of C12-C22 and undersaturated straight chain fatty acid carboxylic acid halides, and tertiary amine is selected from least one in triethylamine, tripropyl amine, ethyl-diisobutyl amine and tetramethyleneimine.Lipid acid carboxylic acid halides can be the halogenide of lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, eicosanoic acid, Zoomeric acid, oleic acid, or at least one in its any mixture.Lipid acid carboxylic acid halides is generally muriate.According to a favourable embodiment, lipid acid carboxylic acid halides is stearyl chloride, and tertiary amine is triethylamine.
After the reaction was completed, the product obtained is washed with the aqueous hydrochloric acid of 2-50 % by weight.In some embodiments, dense HCl (30%) is used to terminate reaction.Can by evaporation, such as, pass through to use distillation, film-type evaporator or other suitable modes, except anhydrating from the product obtained.
Accompanying drawing explanation
In more detail the present invention is described with reference to the schematic diagram of enclosing below, wherein:
Fig. 1 illustrates the schematic diagram of a device of the present invention.
Embodiment
Fig. 1 illustrates the schematic diagram of a device of the present invention.Device 1 comprises tank reactor 2.Stay in tank reactor 2 by a part for the ketene dimer produced before melting form, it is used as reaction medium in tank reactor 2.Solvent medium is stirred with the frame stirrer 3 being connected to high-power engine 4.Lipid acid carboxylic acid halides is fed to tank reactor 2 from the first hold-up vessel 5, and by tertiary amine from the second hold-up vessel 6 charging.Tank reactor 2 is connected to outer loop pipeline 7 via outlet 9 ', and by outer loop pipeline 7, reaction mixture at least partially can cycle through heat exchanger 8.After over-heat-exchanger 8, reaction mixture is via entrance 9 " get back to tank reactor 2.In the passage by heat exchanger 8, the temperature of reaction mixture is lowered, and namely the temperature of reaction mixture at outlet 9 ' place is higher than at entrance 9 " temperature at place.Reaction mixture is provided by pipeline pump 10 by the circulation of external circulation line 7.
Thus illustrative methods of the present invention comprises the following steps.The ketene dimer of melting form is provided in tank reactor 2.The lipid acid carboxylic acid halides of small portion such as 10 % by weight is added in the ketene dimer of solvent medium tank reactor 2 and melting form from the first hold-up vessel 5.Tertiary amine is added into comprising in the reaction mixture of lipid acid carboxylic acid halides of solvent medium and small portion tank reactor 2 from the second hold-up vessel 6.After interpolation tertiary amine, remaining most of lipid acid carboxylic acid halides dropwise or by aliquot is added in the reaction mixture tank reactor 2 from the first hold-up vessel 5.After the most of lipid acid carboxylic acid halides of interpolation, reaction is proceeded.A part of reaction mixture is made to cycle through outer loop pipeline 7 and heat exchanger 8 thereof.In the whole process of method, by using frame stirrer 3 fully stirred reaction mixture.By making reaction terminate with aqueous acid washing.Washing liq can be the aqueous hydrochloric acid of such as 2-50 % by weight.After wash, remaining water in evaporation reaction mixture, and granulation is carried out to the dry product obtained.
Those skilled in the art are obviously appreciated that the present invention is not limited to embodiment recited above and embodiment, and change in the scope of the claim that the present invention can be described below.
Claims (15)
1. produce the method for ketene dimer, the method realizes by making at least one lipid acid carboxylic acid halides and tertiary amine react also forming reactions mixture in solvent medium, it is characterized in that using the ketene dimer of molten state as described solvent medium.
2. method according to claim 1, is characterized in that described tertiary amine to be added in described solvent medium, is added in described solvent medium by most described lipid acid carboxylic acid halides afterwards within for some time.
3. method according to claim 1 and 2, is characterized in that the weight ratio of described solvent medium and described lipid acid carboxylic acid halides is 0.5:1 to 5:1.
4. method according to claim 3, is characterized in that the weight ratio of described solvent medium and described lipid acid carboxylic acid halides is 0.7:1 to 2.5:1.
5. method as claimed in any of claims 1 to 4, is characterized in that the weight ratio of described tertiary amine and described lipid acid carboxylic acid halides is 0.25:1 to 3:1.
6. method according to claim 5, is characterized in that the weight ratio of described tertiary amine and described lipid acid carboxylic acid halides is 0.3:1 to 1.5:1.
7. method as claimed in any of claims 1 to 6, is characterized in that being added in solvent medium by whole tertiary amines before the most described lipid acid carboxylic acid halides of interpolation.
8. method as claimed in any of claims 1 to 7, is characterized in that being added in described solvent medium by described lipid acid carboxylic acid halides at the temperature of 48-75 DEG C.
9. method as claimed in any of claims 1 to 8, is characterized in that being added in solvent medium by lipid acid carboxylic acid halides within the time of 1-6 hour.
10. method as claimed in any of claims 1 to 9, is characterized in that making reaction carry out 10-180 minute after the described lipid acid carboxylic acid halides of interpolation.
11. methods as claimed in any of claims 1 to 10, is characterized in that, in the production process of ketene dimer, the temperature of reaction mixture is controlled.
12. according to the method in claim 1 to 11 described in any one, it is characterized in that described at least one lipid acid carboxylic acid halides is selected from least one in the saturated and undersaturated straight chain fatty acid carboxylic acid halides of C8-C22 and any mixture thereof, described tertiary amine is selected from the C1-C6 trialkylamine of straight chain, side chain and ring-type, N-C1-C6 Alkylpiperidine, N-C1-C6 tetramethyleneimine, and at least one in any mixture.
13. methods according to claim 12, it is characterized in that described at least one lipid acid carboxylic acid halides is selected from stearic, described tertiary amine is selected from least one in triethylamine, tripropyl amine, ethyldiisopropylamine and tetramethyleneimine.
14. according to the method in claim 1 to 13 described in any one, it is characterized in that the aqueous hydrochloric acid washing of the product 2-50 % by weight obtained.
15. according to the method in claim 1 to 14 described in any one, it is characterized in that by evaporating from the described product obtained except anhydrating.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0612739A1 (en) * | 1993-02-22 | 1994-08-31 | Eka Nobel Ab | A process for the production of ketene dimers |
| CN1156724A (en) * | 1996-12-19 | 1997-08-13 | 吴县市天马化工原料厂 | Process for producing alkyl ketene dipolymer |
| WO2000034222A1 (en) * | 1998-12-04 | 2000-06-15 | Kemira Chemicals Oy | Method for the manufacture of alkyl ketene dimers |
| CN1422854A (en) * | 2002-12-13 | 2003-06-11 | 苏州天马化工有限公司 | Alkyl olefine ketene dimer production method |
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2014
- 2014-10-08 CN CN201410524512.8A patent/CN105566256A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0612739A1 (en) * | 1993-02-22 | 1994-08-31 | Eka Nobel Ab | A process for the production of ketene dimers |
| CN1156724A (en) * | 1996-12-19 | 1997-08-13 | 吴县市天马化工原料厂 | Process for producing alkyl ketene dipolymer |
| WO2000034222A1 (en) * | 1998-12-04 | 2000-06-15 | Kemira Chemicals Oy | Method for the manufacture of alkyl ketene dimers |
| CN1422854A (en) * | 2002-12-13 | 2003-06-11 | 苏州天马化工有限公司 | Alkyl olefine ketene dimer production method |
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