CN101982481A - Preparation method of alkyl blocked allyl polyether - Google Patents
Preparation method of alkyl blocked allyl polyether Download PDFInfo
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- CN101982481A CN101982481A CN201010503322XA CN201010503322A CN101982481A CN 101982481 A CN101982481 A CN 101982481A CN 201010503322X A CN201010503322X A CN 201010503322XA CN 201010503322 A CN201010503322 A CN 201010503322A CN 101982481 A CN101982481 A CN 101982481A
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Abstract
The invention discloses a preparation method of alkyl blocked allyl polyether. The preparation method comprises the following steps: carrying out reaction on alkyl polyether and halogenated propylene under the action of alkali metal hydroxides without solvent to generate the alkyl blocked allyl polyether. The reaction of the preparation method is carried out under ordinary pressure, the reaction temperature is lower than 120 DEG C, and the preparation method has the advantages of high reaction yield and little pollution, and is suitable for production in downstream industry and directly used for next reaction. Compared with the traditional technology, the preparation method simplifies the reaction conditions and saves the cost. The prepared alkyl blocked allyl polyether is suitable for preparing blocked non-ionic surfactant with low surface tension, favorable emulsifying property and favorable nucleation property.
Description
Technical field
The invention belongs to technical field of chemistry, be specifically related to a kind of preparation method of alkyl-blocked allyl polyether.
Background technology
Allyl polyether has good hydrophilicity and superior emulsifying capacity, is a kind of nonionogenic tenside of excellent performance, because its end group has two keys, therefore has very consequence in Polymer Synthesizing.
Chinese patent CN 101099926A (open January 9 2008 date), a kind of preparation method of alkyl-blocked allyl polyether is provided, be that employing vinyl carbinol and oxyethane and propylene oxide are raw material, in the presence of the bimetallic catalyst six cobalt oxides acid zinc compounds, make allyl-terminated polyether under the condition such as pressure≤0.2MPa, and then obtain the blocking modification polyethers with the hydroxyl of the alkoxyl group replacement the other end.But if directly by downstream industry production and apply to that next step is synthetic, this method is comparatively loaded down with trivial details as intermediates for allyl polyether, and this method has certain requirement to the pressure of reaction.Chinese patent CN 101543747A (open September 30 2009 date) provides a kind of method for preparing the allyl group alkylphenol polyoxyethylene in solvent medium, this method is used solvent, its shortcoming is trouble of aftertreatment, and it is many to do the solvent side reaction with alcohols, productive rate is reduced, and this method is unfavorable for suitability for industrialized production.Chinese patent CN 101628976A provides a kind of preparation method of butyl end-capping allyl polyethenoxy ether on (open January 20 2010 date), adopting allyl polyethenoxy ether and n-butyl bromide is raw material, select two-step approach, this method is had relatively high expectations to the pressure of reaction, and cost is higher relatively.
Chinese patent CN1563146, patent disclosures such as CN1311264 employing allyl alcohol polyether, alkaline slow releasing microcapsule and methyl-sulfate/ethyl sulfate single stage method polyoxyalkylene alkyl is carried out end-blocking, this method has moisture to generate in pure salinization reaction process, side reaction increases when causing the etherified sealed end reaction, cause the consumption of end-capping reagent to increase and the product purification trouble, increased production cost.
The preparation method who lacks the lower alkyl-blocked allyl polyether of a kind of suitable downstream industry direct production and production cost at present.
Summary of the invention
An object of the present invention is to overcome the deficiencies in the prior art, a kind of preparation method of alkyl-blocked allyl polyether is provided, this method has raw materials used cheap and easy to get, and reaction conditions gentleness, reaction yield height, pollution are lacked, and are fit to the advantages such as production of downstream industry.
Above-mentioned purpose of the present invention is achieved by following technical solution:
A kind of preparation method of alkyl-blocked allyl polyether is characterized in that comprising the steps: that with alkyl, polyether, propylene halide be raw material, and under the effect of alkali metal hydroxide, a step solvent-free reaction generates alkyl-blocked allyl polyether.
A kind of preparation method of alkyl-blocked allyl polyether is characterized in that comprising the steps:
(1) add alkyl, polyether and alkali metal hydroxide in reactor, heating is stirred, and drips propylene halide;
(2) dropwise after, continue heating, carry out insulation reaction not having under the solvent of interpolation;
(3) after reaction is finished reaction solution is neutralized to neutrality, low-boiling-point substance is pulled out in underpressure distillation, and the salt of filtering separation organism and generation, gained organism are alkyl-blocked allyl polyether compound.
The temperature of the described dropping propylene halide of step (1) is 30～90 ℃, is preferably 30～60 ℃.
The temperature of the described reaction of step (2) is 60～110 ℃, is preferably 70～100 ℃; The described reaction times is 3～6h, is preferably 5h.
The described neutralization of step (3) neutralizes for adopting Glacial acetic acid or concentrated hydrochloric acid, and preferably adopting massfraction is that 35% concentrated hydrochloric acid neutralizes.
The temperature of the described underpressure distillation of step (3) is 60～120 ℃.
Described alkyl, polyether has structure shown in formula I:
R(OCH
2CH
2)
nOH
(Ⅰ)；
Wherein: n=2～30, n is an integer; R is that carbonatoms is 6～20 straight chain or isomery chain alkyl, or for having structure shown in formula II:
Wherein: Rx is preferably octyl group, nonyl or dodecyl.
Rx also can be known other groups in this area.
Described propylene halide is preferably any one or its mixture of chlorallylene or allyl bromide 98; Described alkali metal hydroxide is preferably any one or its mixture of sodium hydroxide or potassium hydroxide.
The molar ratio of described alkyl, polyether, propylene halide, three kinds of raw materials of alkali metal hydroxide is 1: 1～1.5: 1～1.2.Need this explanation be, this ratio does not influence enforcement of the present invention, then reduces yield but be lower than the aforementioned proportion scope, being higher than the aforementioned proportion scope then can increase cost, and alkali too much can influence quality product.
A kind of alkyl-blocked allyl polyether compound according to described preparation method's preparation has structure shown in formula III:
Wherein: n=2～30, n is an integer; R is that carbonatoms is 6～20 straight chain or isomery chain alkyl, or for having structure shown in formula II:
Wherein: Rx is preferably octyl group, nonyl or dodecyl.
Compared with prior art, the present invention has following beneficial effect:
(1) directly to adopt chain alkyl polyethers and chlorallylene be raw material in the present invention, raw materials used cheap and easy to get, the reaction conditions gentleness, being reflected under the normal pressure of preparation method of the present invention carried out, and temperature of reaction is lower than 120 ℃, reaction yield height, pollution are lacked, and the production that is fit to downstream industry also directly applies to next step reaction; The target product that single stage method of the present invention makes is used not obviously influence to it, with respect to the two-step approach of prior art, has simplified reaction conditions, has saved cost;
(2) in the prior art, reaction system will be used solvent, and the shortcoming that causes is trouble of aftertreatment, and may cause side reaction many, productive rate is reduced, and reaction of the present invention need not to use solvent, main by product is an alkali salt, convenient post-treatment is simple, pollute low, more friendly to environment.
Embodiment
Further explain the present invention below in conjunction with embodiment, but embodiment does not do any type of qualification to the present invention.
Raw material reagent and experimental instrument and equipment that the embodiment of the invention adopts are all conventional commercial product.
Embodiment 1
In the four-hole boiling flask that whipping appts, reflux exchanger, thermometer and dropping funnel are housed, adding R is C
12Fatty alcohol-polyoxyethylene ether (I) (oxygen ethene is counted n=7) 247g, NaOH21g stirs and to be warming up to 40 ℃, in 1.5 hours, drip chlorallylene 57g, reacted 5 hours down at 100 ℃ then, after finishing, reaction is neutralized to neutrality with the 2g Glacial acetic acid, 100～110 ℃ of following underpressure distillation 1.5 hours, pull out low-boiling-point substance, pull out substantially totally until chlorallylene, the salt of filtering separation organism and generation, obtain target compound 240g, yield is 90%, light yellow transparent liquid.
The target compound spectroscopic analysis:
IR (KBr cm
-1): 2917 (C-H), 1645 (C=C), the division by charateristic avsorption band ownership proves and contains carbon carbon unsaturated double-bond C=C in the product structure, and the primary product that obtains our target compound just has been described, it has the structure shown in the formula III.
1H-NMR (CDCl
3, ppm): δ 5.86～5.94 (CH=CH
2, 3H), and δ 4.01～4.03 (CH2-C=C, 2H), δ 3.42～3.67 (OCH
2CH
2O-), the division according to the characteristic peak ownership has illustrated that equally the product that obtains has the structure shown in the formula III.
Embodiment 2
In the four-hole boiling flask that whipping appts, reflux exchanger, thermometer and dropping funnel are housed, adding R is C
12Isomery alkyl polyoxyethylenated alcohol (I) (oxygen ethene is counted n=9) 188g, KOH 18g stirs and to be warming up to about 30 ℃, in 0.5 hour, drip chlorallylene 25g, reacted 6 hours down at 70 ℃ then, hydrochloric acid soln with 10g 35% after reaction is finished is neutralized to neutrality, 100～110 ℃ of following underpressure distillation 1 hour, pull out low-boiling-point substance, pull out substantially totally until chlorallylene, the salt of filtering separation organism and generation, obtain target compound 165g, yield is 83%, yellow transparent liquid.
The target compound spectroscopic analysis:
IR (KBr cm
-1): 2924 (C-H), 1647 (C=C), the division by charateristic avsorption band ownership proves and contains carbon carbon unsaturated double-bond C=C in the product structure, and the primary product that obtains our target compound just has been described, it has the structure shown in the formula III.
1H-NMR (CDCl
3, ppm): δ 5.87～5.95 (CH=CH
2, 3H), δ 4.01～4.03 (CH
2-C=C, 2H), δ 3.43～3.72 (OCH
2CH
2O-), the division according to the characteristic peak ownership has illustrated that equally the product that obtains has the structure shown in the formula III.
Embodiment 3
In the there-necked flask that whipping appts, reflux exchanger, thermometer and dropping funnel are housed, adding R is C
18Fatty alcohol-polyoxyethylene ether (I) (oxygen ethene is counted n=3) 502g, NaOH60g stirs and to be warming up to 50 ℃, in 3.0 hours, drip chlorallylene 143g, reacted 3.5 hours down at 90 ℃ then, after finishing, reaction is neutralized to neutrality with the 7.5g Glacial acetic acid, 100～110 ℃ of following underpressure distillation 1.5 hours, pull out low-boiling-point substance, pull out substantially totally until chlorallylene, the salt of filtering separation organism and generation, obtain target compound 463g, yield is 93%, light yellow transparent liquid.
The target compound spectroscopic analysis:
IR (KBr cm
-1): 2923 (C-H), 1647 (C=C), the division by charateristic avsorption band ownership proves and contains carbon carbon unsaturated double-bond C=C in the product structure, and the primary product that obtains our target compound just has been described, it has the structure shown in the formula III.
1H-NMR (CDCl
3, ppm): δ 5.81～6.00 (CH=CH
2, 3H), δ 3.36～3.93 (OCH
2CH
2O-), the division according to the characteristic peak ownership has illustrated that equally the product that obtains has the structure shown in the formula III.
Embodiment 4
In the four-hole boiling flask that whipping appts, reflux exchanger, thermometer and dropping funnel are housed, adding R is C
6Fatty alcohol-polyoxyethylene ether (I) (oxygen ethene is counted n=20) 491g, NaOH20g stirs and to be warming up to 40 ℃, in 1.0 hours, drip chlorallylene 46g, reacted 5 hours down at 85 ℃ then, hydrochloric acid soln with 11g 35% after reaction is finished is neutralized to neutrality, 105～120 ℃ of following underpressure distillation 1 hour, pull out low-boiling-point substance, pull out substantially totally until chlorallylene, the salt of filtering separation organism and generation, obtain target compound 418g, yield is 85%, yellow transparent liquid.
The target compound spectroscopic analysis:
IR (KBr cm
-1): 2920 (C-H), 1642 (C=C), the division by charateristic avsorption band ownership proves and contains carbon carbon unsaturated double-bond C=C in the product structure, and the primary product that obtains our target compound just has been described, it has the structure shown in the formula III.
1H-NMR (CDCl
3, ppm): δ 5.85～6.02 (CH=CH
2, 3H), δ 3.40～3.75 (OCH
2CH
2O-), the division according to the characteristic peak ownership has illustrated that equally the product that obtains has the structure shown in the formula III.
Embodiment 5
Whipping appts is being housed, reflux exchanger, in the four-hole boiling flask of thermometer and dropping funnel, add polyoxyethylene nonylphenol ether (I) (oxygen ethene is counted n=8) 168g, NaOH 13g, stirring is warming up to 40 ℃, in 1.0 hours, drip chlorallylene 32g, reacted 5 hours down at 90 ℃ then, the hydrochloric acid soln with 10g 35% after reaction is finished was neutralized to neutrality, 100～110 ℃ of following underpressure distillation 1 hour, pull out low-boiling-point substance, substantially pull out totally until chlorallylene, the salt of filtering separation organism and generation obtains target compound 160g, yield is 91%, yellow transparent liquid.
The target compound spectroscopic analysis:
IR (KBr cm
-1): 2876 (C-H), 1610 (C=C), 1462,1512 (phenolic group, bimodal), the division by the charateristic avsorption band ownership proves and contains carbon carbon unsaturated double-bond C=C in the product structure, the primary product that obtains our target compound just has been described, it has the structure shown in the formula III.
1H-NMR (CDCl
3, ppm): δ 7.12～7.26 (phenolic group, 3H), δ 6.82～6.84 (CH=CH
2, 3H), δ 4.00～4.12 (CH
2-C=C, 2H), δ 3.59～3.85 (OCH
2CH
2O-), the division according to the characteristic peak ownership has illustrated that equally the product that obtains has the structure shown in the formula III.
Embodiment 6
In the there-necked flask that whipping appts and thermometer are housed, add embodiment 1 prepared target product 50g, allyl group polyoxy alkyl oxide (F-6) 70g, contain hydrogen number and be 0.2% side group containing hydrogen silicone oil 80g, when stirring is warming up to 90 ℃, add 2 chloroplatinic acid catalysts, and continue to be warming up to 150 ℃ of reactions, can obtain light yellow transparent organic silicon surfactant.With massfraction is this organic silicon surfactant of 6%, and the emulsion quality mark is 20% 500cSt silicone oil, obtains milky white liquid, and 2500r/min * 15min is centrifugal not stratified, illustrates that this emulsifying agent has good emulsifying capacity to polydimethylsiloxane.
Comparative Examples 1
In the four-hole boiling flask that whipping appts, reflux exchanger, thermometer and dropping funnel are housed, adding R is C
12Fatty alcohol-polyoxyethylene ether (I) (oxygen ethene is counted n=7) 247g, NaOH21g, dimethyl sulfoxide (DMSO) (DMSO) 39.6g, stirring is warming up to 40 ℃, in 1.5 hours, drips chlorallylene 57g, reacted 5 hours down at 100 ℃ then, after reaction is finished, the solids removed by filtration by product, filtrate is carried out underpressure distillation, remove excessive chlorallylene and solvent DMSO, filter again, just obtain target compound 186g, yield is 70%, light yellow transparent liquid.
Can find out obviously that from Comparative Examples solventless method productive rate of the present invention is better than traditional solvent method, and avoid removing this loaded down with trivial details technology of desolvating, reduce production costs, be more suitable for the alkyl-blocked allyl polyether of a large amount of direct production of downstream industry.
Claims (10)
1. the preparation method of an alkyl-blocked allyl polyether is characterized in that comprising the steps: that with alkyl, polyether, propylene halide be raw material, and under the effect of alkali metal hydroxide, solvent-free reaction generates alkyl-blocked allyl polyether.
2. the preparation method of an alkyl-blocked allyl polyether is characterized in that comprising the steps:
(1) add alkyl, polyether and alkali metal hydroxide in reactor, heating is stirred, and drips propylene halide;
(2) dropwise after, continue heating, carry out insulation reaction not having under the solvent of interpolation;
(3) after reaction is finished reaction solution is neutralized to neutrality, low-boiling-point substance is pulled out in underpressure distillation, and the salt of filtering separation organism and generation, gained organism are alkyl-blocked allyl polyether compound.
3. preparation method as claimed in claim 2 is characterized in that the temperature of the propylene halide of dropping described in the step (1) is 30～90 ℃; The temperature of reaction is 60～110 ℃ described in the step (2); The time of described reaction is 3～6h.
4. preparation method as claimed in claim 3 is characterized in that the temperature of the propylene halide of dropping described in the step (1) is 30～60 ℃; The temperature of reaction is 70～100 ℃ described in the step (2); The time of described reaction is 5h.
5. preparation method as claimed in claim 2, its feature is that 35% concentrated hydrochloric acid neutralizes in neutralization described in the step (3) for adopting Glacial acetic acid or massfraction.
6. preparation method as claimed in claim 2, its feature is 60～120 ℃ in the temperature of underpressure distillation described in the step (3).
7. as any described preparation method of claim in the claim 1～6, it is characterized in that described alkyl, polyether has structure shown in formula I:
R(OCH
2CH
2)
nOH
(Ⅰ)；
Wherein: n=2～30, n is an integer; R is that carbonatoms is 6～20 straight chain or isomery chain alkyl, or for having structure shown in formula II:
Wherein: Rx is octyl group, nonyl or dodecyl.
8. as any described preparation method of claim in the claim 1～6, it is characterized in that described propylene halide is any one or its mixture of chlorallylene or allyl bromide 98.
9. as any described preparation method of claim in the claim 1～6, it is characterized in that described alkali metal hydroxide is any one or its mixture of sodium hydroxide or potassium hydroxide.
10. as any described preparation method of claim in the claim 1～6, it is characterized in that the molar ratio of described alkyl, polyether, propylene halide, three kinds of raw materials of alkali metal hydroxide is 1: 1～1.5: 1～1.2.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492130A (en) * | 2011-12-07 | 2012-06-13 | 南京德美世创化工有限公司 | Capped polyether prepared by alkaline catalytic one-step method and preparation method for capped polyether |
| CN102585194A (en) * | 2011-12-14 | 2012-07-18 | 中国日用化学工业研究院 | Method for synthesizing allyl fatty alcohol-polyoxyethylene ether or allyl alkylphenol ethoxylate |
| CN110283325A (en) * | 2019-07-01 | 2019-09-27 | 上海麦浦新材料科技有限公司 | A kind of preparation method for the organic silicon surfactant being used to prepare hard polyurethane foam |
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| GB1273552A (en) * | 1968-06-28 | 1972-05-10 | Ici Ltd | Unsaturated ethers of sterols and copolymers thereof |
| GB1566655A (en) * | 1977-03-03 | 1980-05-08 | Texaco Development Corp | Process for making ether sulphonates |
| CN1504492A (en) * | 2002-11-28 | 2004-06-16 | 中国石化上海石油化工股份有限公司 | Method for preparing alkyl end capping polyether using alkyl halide as end capping reagent |
| CN101628976A (en) * | 2009-08-27 | 2010-01-20 | 浙江皇马科技股份有限公司 | Method for preparing butyl end-capping allyl polyethenoxy ether |
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2010
- 2010-10-08 CN CN201010503322.XA patent/CN101982481B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| GB1273552A (en) * | 1968-06-28 | 1972-05-10 | Ici Ltd | Unsaturated ethers of sterols and copolymers thereof |
| GB1566655A (en) * | 1977-03-03 | 1980-05-08 | Texaco Development Corp | Process for making ether sulphonates |
| CN1504492A (en) * | 2002-11-28 | 2004-06-16 | 中国石化上海石油化工股份有限公司 | Method for preparing alkyl end capping polyether using alkyl halide as end capping reagent |
| CN101628976A (en) * | 2009-08-27 | 2010-01-20 | 浙江皇马科技股份有限公司 | Method for preparing butyl end-capping allyl polyethenoxy ether |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492130A (en) * | 2011-12-07 | 2012-06-13 | 南京德美世创化工有限公司 | Capped polyether prepared by alkaline catalytic one-step method and preparation method for capped polyether |
| CN102492130B (en) * | 2011-12-07 | 2014-01-01 | 江苏美思德化学股份有限公司 | Capped polyether prepared by alkaline catalytic one-step method and preparation method for capped polyether |
| CN102585194A (en) * | 2011-12-14 | 2012-07-18 | 中国日用化学工业研究院 | Method for synthesizing allyl fatty alcohol-polyoxyethylene ether or allyl alkylphenol ethoxylate |
| CN110283325A (en) * | 2019-07-01 | 2019-09-27 | 上海麦浦新材料科技有限公司 | A kind of preparation method for the organic silicon surfactant being used to prepare hard polyurethane foam |
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