CN1172924C - Alkyl olefine ketene dimer production method - Google Patents
Alkyl olefine ketene dimer production method Download PDFInfo
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- CN1172924C CN1172924C CNB021485364A CN02148536A CN1172924C CN 1172924 C CN1172924 C CN 1172924C CN B021485364 A CNB021485364 A CN B021485364A CN 02148536 A CN02148536 A CN 02148536A CN 1172924 C CN1172924 C CN 1172924C
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- Prior art keywords
- ketene dimer
- alkyl ketene
- reaction
- still
- production method
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 title description 3
- 125000000217 alkyl group Chemical group 0.000 title 1
- -1 alkyl ketene dimer Chemical compound 0.000 claims abstract description 62
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 28
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000008117 stearic acid Substances 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 9
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims abstract description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- FDEQQCOTLPPCAO-UHFFFAOYSA-N Cl.OC(O)=O Chemical compound Cl.OC(O)=O FDEQQCOTLPPCAO-UHFFFAOYSA-N 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 9
- 235000013305 food Nutrition 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 238000004513 sizing Methods 0.000 abstract description 4
- VUQPJRPDRDVQMN-UHFFFAOYSA-N 1-chlorooctadecane Chemical compound CCCCCCCCCCCCCCCCCCCl VUQPJRPDRDVQMN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract description 2
- 230000001133 acceleration Effects 0.000 abstract 1
- 230000036632 reaction speed Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a non-solvent production method of an alkyl ketene dimer. After stearic acid is melted, a catalyst and carbonyl chloride are added for reaction, and stearyl chloride is acquired by filtration; triethylamine is put in a reaction vessel, heated to 50 to 65 DEG C, and then, stirred at 65 to 70 DEG C for 30 minutes by adding acylchloride stearate in drops; an alkyl ketene dimer is acquired by extractive separation in a diluted hydrochloric acid solution; after being stirred in water, the alkyl ketene dimer stands and layered; after a water layer is separated and removed, materials are decompressed, distilled and dehydrated at 90 to 100 DEG C and-0.095MPa to acquire an alkyl ketene dimer product. Compared with the traditional method, the method has the advantages of no need of adding benzene solvent in the synthetic reaction of the alkyl ketene dimer, reaction speed acceleration by the temperature improvement of the synthetic reaction, product purity improvement and no benzene solvent pollution and is capable of sizing agents of food wrap paper. The present invention also comprises a special reaction vessel for the synthetic reaction in order to adapt to the reaction of high-viscosity materials.
Description
(one) technical field
The present invention relates to a kind of by stearic acid acyl chlorides and the synthetic method of producing alkyl ketene dimer of triethylamine.
(two) background technology
Alkyl ketene dimer is a kind of wax, and molecular structure is
Fusing point 40-52 ℃, the sizing agent as paper making pulp does not seep water the paper that makes, and is used for food wrapper or other corresponding use.
Reaction formula with stearic acid acyl chlorides and triethylamine synthesis of alkyl ketene dimer is as follows:
Above-mentioned raw materials stearic acid acyl chlorides is by passing to carbonyl chloride gas after the stearic acid melting, and reaction and getting under catalyst action.
In the production of present domestic synthesis of alkyl ketene dimer, synthesis reaction temperature is lower than the fusing point of product alkyl ketene dimer, generally about 25 ℃.Under this temperature, speed of response is slow, need soaking time long (3 hours), and material viscosity is big under this temperature, needs in the reaction mass to add a large amount of toluene solvants, could reduce material viscosity, and reaction is carried out smoothly.Yet itself has moisture toluene, and a large amount of toluene and the moisture of bringing into are very harmful to alkyl ketene dimer, makes product content be difficult to improve.And the boiling point height of toluene, need distillation at high temperature to remove, increase energy consumption, and influenced product purity.The more important thing is that benzene kind solvent is harmful, therefore the alkyl ketene dimer of producing with solvent method can not be used for food wrapper and paper for daily use.
(three) summary of the invention
The purpose of this invention is to provide a kind of solvent-free production Alkyl Ketene Dimer Production Method, it can avoid using solvent, to accelerate the synthesising reacting speed of alkyl ketene dimer, improve product purity, the alkyl ketene dimer that makes can be used as safe sizing agent and is used for food wrapper.
Another object of the present invention is for above solvent-free Alkyl Ketene Dimer Production Method provides a kind of special reactor, realizes smoothly to guarantee solvent-free synthesis method of the present invention.
Alkyl ketene dimer synthetic method of the present invention is as follows:
Will be after the stearic acid melting add the catalyzer dimethyl formamide, stir and feed a certain amount of carbonyl chloride gas reaction down, catch up with unnecessary to the greatest extent carbonyl chloride after the reaction, filter the stearic acid acyl chlorides; Triethylamine and stearic acid acyl chlorides are added reactor, reaction generates triethylamine hydrochloride and alkyl ketene dimer, with dilute hydrochloric acid solution the alkyl ketene dimer extracting and separating is come out, it is characterized in that said triethylamine adds in the reactor earlier, be warming up to 50～65 ℃ in the still, drip the stearic acid acyl chlorides then, after dropwising, stir insulation 30 minutes down at 65～70 ℃, feed-5～-10 ℃ of refrigerating fulids in the reaction process in the reacting kettle jacketing and remove reaction heat; Said extraction is 2.5～4% with the dilute hydrochloric acid solution weight concentration, pumps into fast in the still after being warmed to 70～75 ℃, stirs 15 minutes, leaves standstill 30 minutes, isolates lower floor's triethylamine hydrochloride solution recycling; Add 70 ℃ of hot water in the alkyl ketene dimer in the still and stir the back standing demix, separate and remove bottom water, then material 90～100 ℃ ,-0.095Mpa under underpressure distillation dehydration, till no overhead product, the alkyl ketene dimer product is filtered while hot cooling back slice packaging through 300 order filter clothes.
The present invention drops into gac after the reaction of stearic acid and carbonyl chloride finishes, make the stearic acid acyl chlorides remove look, and input amount is 0.2～0.35% of a raw material stearic acid weight.
The reactor of the inventive method special use, contain kettle cover, still body, still body and be provided with cooling jacket outward, be provided with electric mixer in the still, the invention is characterized in: still is as leptosomic type, aspect ratio 1.4～2: 1, be provided with metal fin in the chuck, the rotating shaft lower end of agitator links to each other with still body bottom, stirring rake is near still body inwall, and its spacing only is 10～15mm, and the upper end of stirring rake extends upwardly to 70～80% position of still height degree; Be provided with the stearic acid acyl chlorides that inserts deep in the still in addition and drip pipe.
Solubilizing agent not in the building-up process of alkyl ketene dimer of the present invention, at solvent-free operational characteristic, the present invention adds the stearic acid acyl chlorides in the triethylamine in the dropping mode, thereby guarantees that the stearic acid acyl chlorides fully reacts with triethylamine.Owing to without toluene, reduced the moisture content of reaction mass in the technological process of the present invention, product purity improved; The temperature of building-up reactions is brought up to 50～70 ℃ by former 25 ℃, accelerated speed of response, reacted soaking time reduced to 30 minutes by former 3 hours, the production cycle of alkyl ketene dimer is shortened greatly, in addition, solubilizing agent not in the still improves the reactor treatment capacity, thereby improved batch output and day output, reduced cost.The product alkyl ketene dimer that the present invention makes is the containing benezene solvent not, can be used as nontoxic sizing agent and is used for food wrapper.
In the Alkyl Ketene Dimer Production Method of the present invention special-purpose reactor at material viscosity height in the still again not the condition of solubilizing agent design, it has adopted the leptosomic type still body of high length-diameter ratio, increased the chuck cooling area, install metal fin in the chuck additional, can remove the heat that reaction produces as early as possible; Agitator adopts the titanium material to mix oar in the still in addition, and the stirring rake upper end extends to the top of still, and the lower end of stir shaft links to each other with the still lower curtate, has strengthened the stirring dynamics, adapts to the stirring load of high-viscosity material; Stirring rake outer rim and still inwall gap are very little, prevent that the alkane ketene dimer from condensing in the still wall and reducing heat-transfer effect; The stearic acid acyl chlorides splashes into pipe and stretches into depths in the still, can prevent that volatile triethylamine from overflowing from blow-down pipe.As seen the agitator of this reactor structurally can adapt to the needs of the high strength stirring load of high-viscosity material, still body and jacket structuredly accelerate removing of reaction heat, thereby this reactor has been guaranteed effective enforcement of the solvent-free synthetic alkane ketene dimer reaction of the present invention.
(four) description of drawings
Accompanying drawing is the structural representation of special reactor of the present invention.
As shown in the figure, reactor is made by the titanium material, contains still body 6 and kettle cover 4, and electric mixer is housed in the still, and it comprises stir shaft 2-1 and stirring rake 2-2, by electric motor 2 driven rotary.The still body is tall and thin, in the chuck 5 radiator element is arranged.Stir 2-2 and make with the titanium material, its upper end extends upwardly to about 4/5 place of still height degree, and the lower end of stir shaft 2-1 links to each other with still body bottom, adapts to the stirring intensity of high-viscosity material.The stearic acid acyl chlorides drips manages 3 deeps of stretching in the still 6.
(five) embodiment
Embodiment one
1. prepare intermediate stearic acid acyl chlorides
In 2500 kilograms of input reactors of stearic acid, the intensification melting treats that temperature begins when reaching 80 ℃ to stir.In reactor, add 50 kilograms of catalyzer dimethyl formamides, stir.Under 80 ± 3 ℃, in still, feed 1500 kilograms of carbonyl chlorides, catch up with and remove unnecessary carbonyl chloride gas, qualified to free acid, add gac 5-8 kilogram, suction filtration, filter then stearyl chloride.
2. alkyl ketene dimer is synthetic
Take by weighing 245～250 kilograms of triethylamines, add in the reactor, stir, be warming up to 50～60 ℃, chuck feeds refrigerating fulid, drips 600～630 kilograms of stearic acid acyl chlorides, temperature is controlled at 55～65 ℃, drips off in 2～3 hours, then 65～70 ℃ of insulation reaction 30 minutes.With 300 kg of water and 30 kilogram weights of concentration is that 31% technical hydrochloric acid is mixed with dilute hydrochloric acid, be heated to 70～75 ℃ after, add in the reactor, survey its water pH and reach 2-4, stirred 15 minutes, left standstill 30 minutes, separate triethylamine hydrochloride solution except that sub-cloud.Add the alkyl ketene dimer in 70 ℃ of hot water wash stills, stirred 5 minutes, left standstill 30 minutes, separate the water layer remove the bottom, remove moisture in the finished product through underpressure distillation, to 90～100 ℃ of dischargings, after the filtration of 300 order filter clothes, get 550～555 kilograms of alkyl ketene dimer products.By freezing pelleter section, packing.
Claims (9)
1. Alkyl Ketene Dimer Production Method, as follows:
To add catalyzer after the stearic acid melting, stir and to feed a certain amount of carbonate chloride gas reaction down, after reaction is finished, catch up with unnecessary to the greatest extent carbonyl chloride, filter the stearic acid acyl chlorides; Triethylamine and stearic acid acyl chloride reaction are generated triethylamine hydrochloride and alkyl ketene dimer, get alkyl ketene dimer, it is characterized in that said catalyzer is a dimethyl formamide with the dilute hydrochloric acid solution extracting and separating; Said triethylamine adds in the reactor earlier, is warming up to 50～65 ℃ in the still, drips the stearic acid acyl chlorides then, at 65～70 ℃ of following stirring reactions; Add hot water in the alkyl ketene dimer of extraction gained and stir the back standing demix, separate and to remove bottom water, then material 90～100 ℃ ,-0.09Mpa under the underpressure distillation dehydration, till no overhead product, with alkyl ketene dimer product filtered while hot, cooling back slice packaging.
2. according to the Alkyl Ketene Dimer Production Method of claim 1, it is characterized in that after the reaction of stearic acid and carbonyl chloride finishes that drop into gac, input amount is 0.2～0.35% of a raw material stearic acid weight.
3. according to the Alkyl Ketene Dimer Production Method of claim 1, it is characterized in that feeding-5～-10 ℃ of refrigerating fulids in the reaction chuck in the reaction process removes reaction heat.
4. according to the Alkyl Ketene Dimer Production Method of claim 1, it is characterized in that the soaking time 30 minutes of said stearic acid acyl chlorides and triethylamine.
5. according to the Alkyl Ketene Dimer Production Method of claim 1 or 2 or 3 or 4, method is characterized in that said extraction with hydrochloric acid soln weight percent concentration 2.5～4%, pumps into fast in the still after being warmed to 70～75 ℃, stirs 15 minutes, leaves standstill 30 minutes.
6. according to the Alkyl Ketene Dimer Production Method of claim 5, it is characterized in that lower floor's triethylamine hydrochloride solution recycling that extracting and separating goes out.
7. the special reactor of the Alkyl Ketene Dimer Production Method of a claim 1 contains kettle cover, still body, and cooling jacket is established in the still body outside, is provided with electric mixer in the still, it is characterized in that still as leptosomic type, and aspect ratio is 1.4～2: 1; Be provided with metal fin in the chuck, the rotating shaft lower end of agitator links to each other with still body bottom, and stirring arm is near still body inwall, and its spacing is 10～15mm, is provided with the stearic acid acyl chlorides that stretches into deep in the still and drips pipe.
8. according to the special reactor of the Alkyl Ketene Dimer Production Method of claim 7, the upper end that it is characterized in that stirring arm extends upwardly to 70～80% position of still height degree.
9. according to the special reactor of the Alkyl Ketene Dimer Production Method of claim 7 or 8, it is characterized in that stirring arm made by the titanium material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021485364A CN1172924C (en) | 2002-12-13 | 2002-12-13 | Alkyl olefine ketene dimer production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021485364A CN1172924C (en) | 2002-12-13 | 2002-12-13 | Alkyl olefine ketene dimer production method |
Publications (2)
| Publication Number | Publication Date |
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| CN1422854A CN1422854A (en) | 2003-06-11 |
| CN1172924C true CN1172924C (en) | 2004-10-27 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB021485364A Expired - Fee Related CN1172924C (en) | 2002-12-13 | 2002-12-13 | Alkyl olefine ketene dimer production method |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101575322B (en) * | 2009-03-30 | 2011-01-19 | 上海东升新材料有限公司 | Alkyl ketene, preparation method and application thereof |
| CN103449595B (en) * | 2012-06-04 | 2016-03-30 | 丰益特种化学（连云港）有限公司 | The reuse of washes during AKD produces |
| CN103102333B (en) * | 2013-01-25 | 2015-01-21 | 甘肃银光聚银化工有限公司 | Production method for alkyl ketene dimer |
| CN105566256A (en) * | 2014-10-08 | 2016-05-11 | 凯米罗总公司 | Simple method for large scale production of olefine ketone dimer |
| CN104478734B (en) * | 2014-12-28 | 2016-09-14 | 甘肃银光聚银化工有限公司 | The method that in AKD production, crude product triethylamine recycles |
| CN104496941B (en) * | 2014-12-29 | 2016-10-05 | 甘肃银光聚银化工有限公司 | A kind of method of AKD mixture continuous treating |
| CN105294421A (en) * | 2015-10-20 | 2016-02-03 | 安徽广信农化股份有限公司 | Refining method for stearoyl chloride |
| CN106916119B (en) * | 2015-12-24 | 2020-05-15 | 丰益表面活性材料（连云港）有限公司 | Method and apparatus for producing alkyl ketene dimer |
| CN108148019A (en) * | 2016-12-02 | 2018-06-12 | 丰益表面活性材料（连云港）有限公司 | A kind of preparation method of AKD |
| CN111485450A (en) * | 2020-04-28 | 2020-08-04 | 济宁明升新材料有限公司 | Preparation method of high-melting-point AKD sizing agent |
| CN114539190B (en) * | 2022-04-27 | 2022-07-29 | 山东奥赛新材料有限公司 | Preparation method of alkyl ketene dimer |
-
2002
- 2002-12-13 CN CNB021485364A patent/CN1172924C/en not_active Expired - Fee Related
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| CN1422854A (en) | 2003-06-11 |
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