CN101982481B - Preparation method of alkyl blocked allyl polyether - Google Patents
Preparation method of alkyl blocked allyl polyether Download PDFInfo
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- CN101982481B CN101982481B CN201010503322.XA CN201010503322A CN101982481B CN 101982481 B CN101982481 B CN 101982481B CN 201010503322 A CN201010503322 A CN 201010503322A CN 101982481 B CN101982481 B CN 101982481B
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- 125000000217 alkyl group Chemical group 0.000 title claims abstract description 31
- 229920000570 polyether Polymers 0.000 title claims abstract description 31
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 28
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims description 19
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical group ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 150000008044 alkali metal hydroxides Chemical class 0.000 abstract description 5
- 230000001804 emulsifying effect Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 2
- 239000002736 nonionic surfactant Substances 0.000 abstract 1
- 230000006911 nucleation Effects 0.000 abstract 1
- 238000010899 nucleation Methods 0.000 abstract 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract 1
- 239000000047 product Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- -1 propylene halide Chemical class 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- BQODPTQLXVVEJG-UHFFFAOYSA-N [O].C=C Chemical compound [O].C=C BQODPTQLXVVEJG-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 5
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 238000004611 spectroscopical analysis Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 description 1
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001447 alkali salts Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006561 solvent free reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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 wetting ability and superior emulsifying capacity, is a kind of nonionogenic tenside of excellent performance, because its end group has two keys, therefore in Polymer Synthesizing, has very consequence.
Chinese patent CN 101099926A (January 9 2008 publication date), a kind of preparation method of alkyl blocked allyl polyether is provided, that employing vinyl carbinol and oxyethane and propylene oxide are raw material, under bimetallic catalyst six cobalt oxides acid zinc compounds exist, under the condition such as pressure≤0.2MPa, make allyl-terminated polyether, and then obtain blocking modification polyethers with the hydroxyl that alkoxyl group replaces the other end.If but allyl polyether directly produced by downstream industry as intermediates and apply to that next step is synthetic, this method is comparatively loaded down with trivial details, and this method has certain requirement to the pressure of reaction.Chinese patent CN 101543747A (September 30 2009 publication date) provides a kind of method of preparing allyl alkylphenol ethoxylate in solvent medium, this method is used solvent, its shortcoming is that aftertreatment bothers, and it is many with alcohols, to do solvent side reaction, productive rate is reduced, and the 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 (January 20 2010 publication 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 relatively high.
Chinese patent CN1563146, the patents such as CN1311264 disclose employing allyl alcohol polyether, alkaline slow releasing microcapsule and methyl-sulfate/ethyl sulfate single stage method polyoxyalkylene alkyl have been carried out to end-blocking, the method has moisture to generate in alcohol salinization reaction process, while causing etherified sealed end reaction, side reaction increases, cause the consumption of end-capping reagent to increase and product purification trouble, increased production cost.
Lack at present the preparation method of the alkyl blocked allyl polyether that a kind of applicable downstream industry direct production and production cost are lower.
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, the method has raw materials used cheap and easy to get, and reaction conditions is gentle, reaction yield is high, pollution is few, is applicable to the advantages such as production of downstream industry.
Above-mentioned purpose of the present invention is achieved by following technical solution:
A preparation method for alkyl blocked allyl polyether, is characterized in that comprising the steps: take that alkyl, polyether, propylene halide are raw material, and under the effect of alkali metal hydroxide, a step solvent-free reaction generates alkyl blocked allyl polyether.
A preparation method for alkyl blocked allyl polyether, is characterized in that comprising the steps:
(1) in reactor, add alkyl, polyether and alkali metal hydroxide, heating, stirs, and drips propylene halide;
(2) after dropwising, continue heating, without adding under solvent, carrying out insulation reaction;
(3) reaction solution is neutralized to neutrality after having reacted, low-boiling-point substance is pulled out in underpressure distillation, the salt of filtering separation organism and generation, and gained organism is 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) is for adopting Glacial acetic acid or concentrated hydrochloric acid to neutralize, 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 as shown in formula I:
R(OCH
2CH
2)
nOH
(Ⅰ)；
Wherein: n=2～30, n is integer; R is that carbonatoms is 6～20 straight chain or isomery chain alkyl, or for thering is structure as 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 to be described herein, this ratio does not affect enforcement of the present invention, but reduces yield lower than aforementioned proportion scope, higher than aforementioned proportion scope, can increase cost, and alkali too much can affect quality product.
An alkyl blocked allyl polyether compound of preparing according to described preparation method, has structure as shown in formula III:
Wherein: n=2～30, n is integer; R is that carbonatoms is 6～20 straight chain or isomery chain alkyl, or for thering is structure as 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, reaction conditions is gentle, preparation method's of the present invention reaction is carried out under normal pressure, and temperature of reaction is lower than 120 ℃, reaction yield is high, pollution is few, is applicable to the production of downstream industry and directly applies to next step reaction; The target product that single stage method of the present invention makes does not have a significant effect to its application, with respect to the two-step approach of prior art, has simplified reaction conditions, has saved cost;
(2) in prior art, reaction system will be used solvent, and the shortcoming causing is that aftertreatment bothers, and may cause side reaction many, productive rate is reduced, and reaction of the present invention is without being used solvent, Main By product is alkali salt, convenient post-treatment is simple, pollute low, more friendly to environment.
Embodiment
Below in conjunction with embodiment, further explain the present invention, but embodiment does not limit in any form to the present invention.
Raw material reagent and experimental instrument and equipment that the embodiment of the present invention adopts are all conventional commercial product.
Embodiment 1
In the four-hole boiling flask of whipping appts, reflux exchanger, thermometer and dropping funnel is 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, then at 100 ℃, react 5 hours, reacted rear and be neutralized to neutrality with 2g Glacial acetic acid, at 100～110 ℃, underpressure distillation is 1.5 hours, pulls out low-boiling-point substance, until chlorallylene is pulled out totally substantially, the salt of filtering separation organism and generation, obtain target compound 240g, yield is 90%, light yellow transparent liquid.
Target compound spectroscopic analysis:
IR (KBr cm
-1): 2917 (C-H), 1645 (C=C), the division belonging to by charateristic avsorption band, proves and in product structure, contains carbon carbon unsaturated double-bond C=C, the primary product that obtains our target compound has just been described, it has the structure shown in formula III.
1h-NMR (CDCl
3, ppm): δ 5.86～5.94 (CH=CH
2, 3H), δ 4.01～4.03 (CH2-C=C, 2H), δ 3.42～3.67 (OCH
2cH
2o-), the division according to characteristic peak ownership, has illustrated that the product obtaining has the structure shown in formula III equally.
Embodiment 2
In the four-hole boiling flask of whipping appts, reflux exchanger, thermometer and dropping funnel is housed, adding R is C
12isomery alkyl polyoxyethylenated alcohol (I) (oxygen ethene is counted n=9) 188g, KOH 18g, stirring is warming up to approximately 30 ℃, in 0.5 hour, drip chlorallylene 25g, then at 70 ℃, react 6 hours, react the rear hydrochloric acid soln with 10g 35% and be neutralized to neutrality, at 100～110 ℃, underpressure distillation is 1 hour, pulls out low-boiling-point substance, until chlorallylene is pulled out totally substantially, the salt of filtering separation organism and generation, obtain target compound 165g, yield is 83%, yellow transparent liquid.
Target compound spectroscopic analysis:
IR (KBr cm
-1): 2924 (C-H), 1647 (C=C), the division belonging to by charateristic avsorption band, proves and in product structure, contains carbon carbon unsaturated double-bond C=C, the primary product that obtains our target compound has just been described, it has the structure shown in 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 characteristic peak ownership, has illustrated that the product obtaining has the structure shown in formula III equally.
Embodiment 3
In the there-necked flask of whipping appts, reflux exchanger, thermometer and dropping funnel is 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, then at 90 ℃, react 3.5 hours, reacted rear and be neutralized to neutrality with 7.5g Glacial acetic acid, at 100～110 ℃, underpressure distillation is 1.5 hours, pulls out low-boiling-point substance, until chlorallylene is pulled out totally substantially, the salt of filtering separation organism and generation, obtain target compound 463g, yield is 93%, light yellow transparent liquid.
Target compound spectroscopic analysis:
IR (KBr cm
-1): 2923 (C-H), 1647 (C=C), the division belonging to by charateristic avsorption band, proves and in product structure, contains carbon carbon unsaturated double-bond C=C, the primary product that obtains our target compound has just been described, it has the structure shown in 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 characteristic peak ownership, has illustrated that the product obtaining has the structure shown in formula III equally.
Embodiment 4
In the four-hole boiling flask of whipping appts, reflux exchanger, thermometer and dropping funnel is 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, then at 85 ℃, react 5 hours, react the rear hydrochloric acid soln with 11g 35% and be neutralized to neutrality, at 105～120 ℃, underpressure distillation is 1 hour, pulls out low-boiling-point substance, until chlorallylene is pulled out totally substantially, the salt of filtering separation organism and generation, obtain target compound 418g, yield is 85%, yellow transparent liquid.
Target compound spectroscopic analysis:
IR (KBr cm
-1): 2920 (C-H), 1642 (C=C), the division belonging to by charateristic avsorption band, proves and in product structure, contains carbon carbon unsaturated double-bond C=C, the primary product that obtains our target compound has just been described, it has the structure shown in 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 characteristic peak ownership, has illustrated that the product obtaining has the structure shown in formula III equally.
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, then at 90 ℃, react 5 hours, react the rear hydrochloric acid soln with 10g 35% and be neutralized to neutrality, at 100～110 ℃, underpressure distillation is 1 hour, pull out low-boiling-point substance, until chlorallylene is pulled out totally substantially, the salt of filtering separation organism and generation, obtain target compound 160g, yield is 91%, yellow transparent liquid.
Target compound spectroscopic analysis:
IR (KBr cm
-1): 2876 (C-H), 1610 (C=C), 1462,1512 (phenolic group, bimodal), the division belonging to by charateristic avsorption band, proof contains carbon carbon unsaturated double-bond C=C in product structure, and the primary product that obtains our target compound has just been described, it has the structure shown in 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 characteristic peak ownership, has illustrated that the product obtaining has the structure shown in formula III equally.
Embodiment 6
In the there-necked flask of whipping appts and thermometer is housed, add the prepared target product 50g of embodiment 1, allyl group polyoxy alkyl oxide (F-6) 70g, the side group containing hydrogen silicone oil 80g that is 0.2% containing hydrogen number, 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.This organic silicon surfactant that is 6% with massfraction, the 500cSt silicone oil that emulsion quality mark is 20%, obtains milky white liquid, and 2500r/min * 15min is centrifugal not stratified, illustrates that this emulsifying agent has good emulsifying capacity to polydimethylsiloxane.
Comparative example 1
In the four-hole boiling flask of whipping appts, reflux exchanger, thermometer and dropping funnel is 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, then at 100 ℃, react 5 hours, after having reacted, 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.
From comparative example, can obviously find out, solventless method productive rate of the present invention is better than traditional solvent method, and has avoided, except this loaded down with trivial details technique of desolventizing, reducing production costs, and is more suitable for a large amount of direct production alkyl blocked allyl polyethers of downstream industry.
Claims (1)
1. a preparation method for alkyl blocked allyl polyether, is characterized in that comprising the steps:
(1) in reactor, add alkyl, polyether and sodium hydroxide, heating, stirs and is warming up to 40 ℃, in 1.5 hours, drips chlorallylene;
(2) after dropwising, continue heating, without adding under solvent, at 100 ℃, reacting 5 hours;
(3) reacted and in backward reaction solution, added Glacial acetic acid and be neutralized to neutrality, at 100 ~ 110 ℃, low-boiling-point substance is pulled out in underpressure distillation, the salt of filtering separation organism and generation, and gained organism is alkyl blocked allyl polyether compound;
Wherein, described alkyl, polyether has structure as shown in formula I:
Wherein: n=7; R is that carbonatoms is 12 fatty alcohol-polyoxyethylene ether,
The molar ratio of described alkyl, polyether, chlorallylene, three kinds of raw materials of sodium hydroxide is 1:1～1.5:1～1.2.
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| 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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| CN1204163C (en) * | 2002-11-28 | 2005-06-01 | 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 |
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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 |
| CN101628976A (en) * | 2009-08-27 | 2010-01-20 | 浙江皇马科技股份有限公司 | Preparation method of butyl-terminated allyl polyoxyethylene ether |
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