CN1257886A - Process for synthesizing polyether p-toluenesulfonate - Google Patents
Process for synthesizing polyether p-toluenesulfonate Download PDFInfo
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- CN1257886A CN1257886A CN 98124012 CN98124012A CN1257886A CN 1257886 A CN1257886 A CN 1257886A CN 98124012 CN98124012 CN 98124012 CN 98124012 A CN98124012 A CN 98124012A CN 1257886 A CN1257886 A CN 1257886A
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- polyethers
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- 229920000570 polyether Polymers 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims description 12
- 239000004721 Polyphenylene oxide Substances 0.000 title abstract description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 title abstract 2
- 230000002194 synthesizing effect Effects 0.000 title description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- -1 cyclopentadienyl compound Chemical class 0.000 claims abstract description 40
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 14
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 38
- 238000007306 functionalization reaction Methods 0.000 claims description 23
- 150000002148 esters Chemical class 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 18
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 13
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 13
- 239000011591 potassium Substances 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- 239000003086 colorant Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- IJJSYKQZFFGIEE-UHFFFAOYSA-N naphthalene;potassium Chemical compound [K].C1=CC=CC2=CC=CC=C21 IJJSYKQZFFGIEE-UHFFFAOYSA-N 0.000 claims description 2
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012454 non-polar solvent Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- OHUVHDUNQKJDKW-UHFFFAOYSA-N sodium;cyclopenta-1,3-diene Chemical compound [Na+].C=1C=C[CH-]C=1 OHUVHDUNQKJDKW-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 abstract description 4
- 229920001223 polyethylene glycol Polymers 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- CBQKGISIWKPJMB-UHFFFAOYSA-N naphthalene;oxolane;sodium Chemical compound [Na].C1CCOC1.C1=CC=CC2=CC=CC=C21 CBQKGISIWKPJMB-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- ZMHMECOYLWGPJB-UHFFFAOYSA-N O1CCCC1.[K].C1=CC=CC2=CC=CC=C12 Chemical compound O1CCCC1.[K].C1=CC=CC2=CC=CC=C12 ZMHMECOYLWGPJB-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-Lutidine Substances CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 1
- LKXXNEZQESKGMW-UHFFFAOYSA-N O1CCCC1.C1=CC=CC1.[Na] Chemical compound O1CCCC1.C1=CC=CC1.[Na] LKXXNEZQESKGMW-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229950009789 cetomacrogol 1000 Drugs 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229960003511 macrogol Drugs 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- Polyethers (AREA)
Abstract
A process for preparing the polyether p-toluene sulfonate as an important intermediate for preparing other functional polyethers (aminopolyglycol, for example) includes the reaction of single- or double-end polyether (polyethylene glycol, polypropanediol, or polybutanediol) as raw material with the colour naththalene compound or cyclopentadienyl compound of Na or K to obtain active intermediate, and the reaction with p-toluene sulfonyl chloride.
Description
The present invention relates to the synthetic method of polyethers p-toluenesulfonic esters, particularly the synthetic method of polyoxyethylene glycol p-toluenesulfonic esters.
The functionalization polyethers is the functional polyethylene glycol derivative especially, many-sides such as the sustained-release and controlled release of, Polymer Synthesizing synthetic in organic synthesis, polypeptide as polyoxyethylene glycol p-toluenesulfonic esters, amido polyoxyethylene glycol, carboxy polyethylene glycol and ethylene glycol copolymer etc. and medicine, target dispenser are with a wide range of applications, and relevant its report synthetic and that use increases day by day.It has become the focus of domestic and international research at present.
In the polyethers p-toluenesulfonic esters, more easily leave away owing to the tosic acid ester group, make it have high reaction activity and high, be the important intermediate of other functionalization polyethers of preparation such as amido polyoxyethylene glycol etc., and the polyethers p-toluenesulfonic esters itself is exactly to cause the initiator that the class monomer polymerization prepares multipolymer.Although the external reagent of polyethers p-toluenesulfonic esters company has the reagent production marketing at present, it costs an arm and a leg, and can not guarantee 100% functionality, is unfavorable for the industrialization of derived product.For a long time, many scholars are seeking high functionality always, high conversion, the preparation method of low-cost polyethers p-toluenesulfonic esters, Mutter (Tetrahydron Lett, 1978,2839) and Suzaki (Journal of Polymer Science:Polymer ChemistryEdition, 1979,17,241) report uses the Tosyl chloride of exsiccant polyoxyethylene glycol and ten times of amounts in dichloromethane solvent, do acid absorber with pyridine and obtain polyoxyethylene glycol-p-toluenesulfonic esters, in this way, the hydroxyl transformation efficiency has only 80%, and unreacted polyoxyethylene glycol is difficult to remove from product, and can produce the fracture of polymkeric substance chain link in the reaction process, cause the molecular weight of polyoxyethylene glycol approximately to reduce by 30%, long reaction time, aftertreatment complexity.(Journal of Polymer Science:Polymer Chemistry Edition such as Xavier, 1984,22,1623) aforesaid method is improved, directly make solvent with pyridine, 0 ℃ of prepared in reaction, but this method also exists need low-temp reaction, aftertreatment and purifying complex, productive rate low (60%) etc. to lack-point.Harris (J.Org.Chem., 1982,47,4789) etc. also make the polyoxyethylene glycol p-toluenesulfonic esters with polyoxyethylene glycol and Tosyl chloride reaction in the presence of sodium hydride, the shortcoming of this method maximum is the cost height, needs low-temp reaction, is unfavorable for industrialization production.(Makromol.Chem., Rapid Commun., 1985,6,53) such as De Vos have adopted two kinds of methods to come synthesizing polyethylene glycol-p-toluenesulfonic esters.Shortcomings such as a kind of method is to use the alkali N stronger than pyridine, and the N-lutidine substitutes pyridine, and productive rate increases but still has aftertreatment and purifying complex, and the functionalization degree is incomplete.The limitation of people's such as De Vos, Xavier, Mutter and Suzaki method maximum is that also it is lower to monohydroxy polyethers and high molecular weight polyether (Mw＞5000) functionalization degree.Another kind method is to form active intermediate with n-Butyl Lithium and end hydroxy polyether earlier, and active intermediate obtains product with the Tosyl chloride reaction again.This method is an ideal comparatively in the aforesaid method, but its cost is higher, and the active intermediate of formation is a gel, influence the further raising of functionalization, especially to high molecular weight polyether, the lithium chloride that generates in the reaction can be dissolved in the organic solvent in right amount, makes troubles to aftertreatment and purifying.
In order to overcome above-mentioned shortcoming, the present invention aims to provide the polyethers p-toluenesulfonic esters of a kind of low cost, high degree of functionalization, high conversion, the particularly preparation method of polyoxyethylene glycol p-toluenesulfonic esters.This method is quantitative to the functionalized of polyethers substantially.
The object of the present invention is achieved like this: with the polyethers (polyoxyethylene glycol of single end or two ends, polypropylene glycol, polytetramethylene glycol etc.) for raw material in solvent with the naphthalene compound with the sodium of color or potassium, cyclopentadienyl compounds reaction, form the sodium salt or the sylvite active intermediate of polyethers, obtain product with the Tosyl chloride reaction again.
The polyether structure of indication of the present invention is:
HO-[(CH
2)xO]y-H
RO-[(CH
2)xO]y-H(R＝CH
3，CH
3CH
2，.....)
x＝1～3，y＝10～1000
The molecular weight of polyethers is 400-50000.
Naphthalene compound, the cyclopentadienyl compounds of used coloured sodium of the present invention or potassium are meant naphthalene potassium, naphthalene sodium, cyclopentadienyl sodium, the purpose of using the naphthalene compound of coloured sodium or potassium is that they also play indicator, can determine the degree of functionalization of polyethers terminal group according to change in color, and the Repone K or the sodium-chlor that generate in the reaction process are insoluble in organic solvent, are easy to by removing by filter.
Solvent for use of the present invention is polarity or the non-polar solvent that benzene, toluene, tetrahydrofuran (THF), dioxane etc. can dissolve polyethers.The concentration of polyethers in solvent is 3～30%, and suitable concentration is 10～20%.
The mall of each reaction mass is than being the polyethers terminal hydroxyl among the present invention: the naphthalene compound of sodium or potassium, cyclopentadienyl compounds: Tosyl chloride=1: 0.9～1.5: 0.9～1.5, preferred ratio is the polyethers terminal hydroxyl: the naphthalene compound of sodium or potassium, cyclopentadienyl compounds: Tosyl chloride=1: 1～1.2: 1～1.2.The consumption of each material determines that according to the naphthalene compound of sodium or potassium, the colour-change of cyclopentadienyl compounds 30 minutes colors do not disappear and indicate that degree of functionalization has reached 90-100% behind the naphthalene compound that adds sodium or potassium, cyclopentadienyl compounds.
Enforcement temperature of the present invention is 0～80 ℃, and preferred temperature of reaction is 20～50 ℃.
The present invention can use inert gas replacement reactor afterreaction, and perhaps direct reaction reacts but be preferably under the protection of rare gas element.
Embodiments of the invention are as follows:
Embodiment one
In reaction flask, add the two terminal hydroxyl polypropylene glycols 5000 of 80g, 1000ml benzene, the naphthalene sodium tetrahydrofuran solution of 74.8ml0.5M was stirring at room reaction 30 minutes, if the color of naphthalene sodium tetrahydrofuran solution does not disappear, illustrate that then the sodium salt active intermediate transformation efficiency of polyethers has reached 100%.If the color of naphthalene sodium tetrahydrofuran solution disappears, then add an amount of naphthalene sodium tetrahydrofuran solution to the color of naphthalene sodium tetrahydrofuran solution and do not disappear in 30 minutes.Add the Tosyl chloride with mall amount such as naphthalene sodium tetrahydrofuran solution, continued stirring reaction 5 hours, filter in room temperature, filtrate with ether sedimentation, filter the solid head product, head product gets pure product with ethyl alcohol recrystallization.Productive rate 95%,
1H-NMR identifies that degree of functionalization is 100%.
Embodiment two
In reaction flask, add the two terminal hydroxyl poly(oxyethylene glycol) 400 of 100g, 1000ml toluene, the naphthalene sodium tetrahydrofuran solution of 1000ml0.5M was stirring at room reaction 30 minutes.All the other operations are with embodiment one.Productive rate 80%,
1H-NMR identifies that degree of functionalization is 90%.
Embodiment three
In reaction flask, add 200g methoxyl group list terminal hydroxyl cetomacrogol 1000 0, the 3000ml tetrahydrofuran (THF), the naphthalene potassium tetrahydrofuran solution of 60ml0.5M was stirring at room reaction 30 minutes.All the other operations are with embodiment one.Productive rate 79%,
1H-NMR identifies that degree of functionalization is 80%.
Embodiment four
In reaction flask, add the two terminal hydroxyl polytetramethylene glycols 6000 of 40g, the 400ml dioxane, the cyclopentadiene sodium tetrahydrofuran solution of 18ml1M was 40 ℃ of stirring reactions 30 minutes.All the other operations are with embodiment one.Productive rate 90%,
1H-NMR identifies that degree of functionalization is 98%.
Embodiment five
In reaction flask, add the two terminal hydroxyl polyoxyethylene glycol 35000 of 70g, 1000ml benzene, the naphthalene potassium tetrahydrofuran solution of 5ml1M was 0 ℃ of stirring reaction 30 minutes.All the other operations are with embodiment one.Productive rate 60%,
1H-NMR identifies that degree of functionalization is 75%.
Embodiment six
In reaction flask, add 200g methoxyl group list terminal hydroxyl polyoxyethylene glycol (Mw=5000), 2000ml benzene, the naphthalene potassium tetrahydrofuran solution of 40ml1M was 25 ℃ of stirring reactions 30 minutes.All the other operations are with embodiment one.Productive rate 96%,
1H-NMR identifies that degree of functionalization is 99%.
Embodiment seven
In reaction flask, add the two terminal hydroxyl polyoxyethylene glycol 800 of 400g, 2000ml toluene, the naphthalene potassium tetrahydrofuran solution of 1000ml1M was 25 ℃ of stirring reactions 30 minutes.All the other operations are with embodiment one.Productive rate 93%,
1H-NMR identifies that degree of functionalization is 99%.
Embodiment eight
In reaction flask, add the two terminal hydroxyl polyethylene glycol 1500s of 200g, 2000ml toluene, the naphthalene potassium tetrahydrofuran solution of 300ml1M was 25 ℃ of stirring reactions 30 minutes.All the other operations are with embodiment one.Productive rate 85%,
1H-NMR identifies that degree of functionalization is 95%.
Embodiment nine
In reaction flask, add the two terminal hydroxyl Macrogol 4000s of 200g, 2000ml toluene, the naphthalene potassium tetrahydrofuran solution of 150ml1M was 25 ℃ of stirring reactions 30 minutes.All the other operations are with embodiment one.Productive rate 87%,
1H-NMR identifies that degree of functionalization is 99%.
Claims (5)
1, the preparation method of the polyethers p-toluenesulfonic esters of low cost, high degree of functionalization, high conversion, especially the method for polyoxyethylene glycol p-toluenesulfonic esters, it is characterized in that polyethers (polyoxyethylene glycol with single end or two ends, polypropylene glycol, polytetramethylene glycol etc.) for raw material in solvent with the naphthalene compound with the sodium of color or potassium, cyclopentadienyl compounds reaction, form the sodium salt or the sylvite active intermediate of polyethers, obtain product with the Tosyl chloride reaction again.The polyethers of indication of the present invention is characterised in that structure is:
HO-[(CH
2)xO]y-H
RO-[(CH
2)xO]y-H(R＝CH
3，CH
3CH
2，.....)
x＝1～3，y＝10～1000
The molecular weight of polyethers is 400-50000.
2, according to the preparation method of the polyethers p-toluenesulfonic esters of the described low cost of claim 1, high degree of functionalization, high conversion, it is characterized in that naphthalene compound, the cyclopentadienyl compounds of used coloured sodium or potassium is meant naphthalene potassium, naphthalene sodium, cyclopentadienyl sodium.
3, according to the preparation method of the polyethers p-toluenesulfonic esters of the described low cost of claim 1, high degree of functionalization, high conversion, it is characterized in that solvent for use is polarity or the non-polar solvent that benzene, toluene, tetrahydrofuran (THF), dioxane etc. can dissolve polyethers.The concentration of polyethers in solvent is 3～30%, and preferred concentration is 10～20%.
4, according to the preparation method of the polyethers p-toluenesulfonic esters of the described low cost of claim 1, high degree of functionalization, high conversion, the mall that it is characterized in that each reaction mass is than being the polyethers terminal hydroxyl: the naphthalene compound of sodium or potassium, cyclopentadienyl compounds: Tosyl chloride=1: 0.9～1.5: 0.9～1.5, preferred ratio is the polyethers terminal hydroxyl: the naphthalene compound of sodium or potassium, cyclopentadienyl compounds: Tosyl chloride=1: 1～1.2: 1～1.2.The consumption of each material determines that according to the naphthalene compound of sodium or potassium, the colour-change of cyclopentadienyl compounds 30 minutes colors do not disappear and indicate that degree of functionalization has reached 90-100% behind the naphthalene compound that adds sodium or potassium, cyclopentadienyl compounds.
5, according to the preparation method of the polyethers p-toluenesulfonic esters of the described low cost of claim 1, high degree of functionalization, high conversion, it is characterized in that implementing temperature is 0～80 ℃, and preferred temperature of reaction is 20～50 ℃.
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|---|---|---|---|
| CN 98124012 CN1257886A (en) | 1998-12-18 | 1998-12-18 | Process for synthesizing polyether p-toluenesulfonate |
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|---|---|---|---|
| CN 98124012 CN1257886A (en) | 1998-12-18 | 1998-12-18 | Process for synthesizing polyether p-toluenesulfonate |
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1998
- 1998-12-18 CN CN 98124012 patent/CN1257886A/en active Pending
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| CN106188552B (en) * | 2016-08-09 | 2019-05-03 | 武汉工程大学 | The preparation method of chitosan class natural macromolecule modification crude oil desalting demulsifier |
| CN106279706B (en) * | 2016-08-09 | 2019-05-03 | 武汉工程大学 | A kind of preparation method of polyether grafted chitosan derivative crude oil desalting demulsifier |
| CN106279708B (en) * | 2016-08-09 | 2019-05-03 | 武汉工程大学 | A kind of preparation method of chitosan crude oil desalting demulsifier |
| WO2023201805A1 (en) * | 2022-04-22 | 2023-10-26 | 天津凯莱英制药有限公司 | Method for preparing polyethylene glycol-glycerol derivative and intermediate thereof |
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