CN102875799A - Preparation methods of multi-benzene-ring polyether succinate and sulfonate thereof - Google Patents
Preparation methods of multi-benzene-ring polyether succinate and sulfonate thereof Download PDFInfo
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- CN102875799A CN102875799A CN2012104201621A CN201210420162A CN102875799A CN 102875799 A CN102875799 A CN 102875799A CN 2012104201621 A CN2012104201621 A CN 2012104201621A CN 201210420162 A CN201210420162 A CN 201210420162A CN 102875799 A CN102875799 A CN 102875799A
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Abstract
The invention discloses a preparation method of multi-benzene-ring polyether succinate, which comprises the following step: esterifying multi-benzene-ring polyether and maleic anhydride at 80-100 DEG C for 4-8 hours to obtain the multi-benzene-ring polyether succinate, wherein the mol ratio of the multi-benzene-ring polyether to the maleic anhydride is (1.0-2.5):1. The invention also discloses a preparation method and application of multi-benzene-ring polyether succinate sulfonate. The preparation method of multi-benzene-ring polyether succinate sulfonate comprises the following steps: adding a sulfonating agent into the multi-benzene-ring polyether succinate, sulfonating at 100-170 DEG C for 4-6 hours, and neutralizing with alkali to obtain the multi-benzene-ring polyether succinate sulfonate. The multi-benzene-ring polyether succinate sulfonate can be used in pesticide water-based preparations, synthetic resins, paint, papermaking, binding agents, fibers or construction materials.
Description
Technical field
The present invention relates to the preparation method of a kind of many phenyl ring polyethers succinate and sulfonate thereof, belong to technical field of chemical synthesis.
Background technology
Modern changes very fast, just towards the future development of environment-friendly type, Water-borne modification and solidification are its main directions, yet, domestic inert ingredient also is not very flourishing at present, what generally use at present is several nonionogenic tensides that contain a plurality of benzene ring structures, it has good emulsifying property and dispersiveness, also be weak but in the aq. type preparation, use, aspect physical stability, there is more or less certain problem, especially often occur serious demixing phenomenon on ageing stability, overall performance also has very large gap compared with developed countries.
Succinate one series products kind is more, and such as alkylphenol, Fatty Alcohol(C12-C14 and C12-C18) etc., but the modification of many phenyl ring polyethers has no report.Also more rare to be applied in the pesticide water fundamental mode preparation it.
Summary of the invention
In order to overcome the deficiencies in the prior art: the object of the present invention is to provide a kind of characteristic that nonionogenic tenside also has anion surfactant that namely has, and can in pesticide water fundamental mode preparation, have many phenyl ring polyethers succinate of good stability and the preparation method of sulfonate thereof.
Technical scheme of the present invention is:
A kind of preparation method of many phenyl ring polyethers succinate, it is characterized in that, esterification 4 ~ 8h under 80 ~ 100 ℃ temperature condition with many phenyl ring polyethers and maleic anhydride obtain many phenyl ring polyethers succinate, and the mol ratio of described many phenyl ring polyethers and maleic anhydride is: 1.0 ~ 2.5:1.
Further, described many phenyl ring polyethers generates by the oleophilic group with reactive hydrogen atom and the ethylene oxide polymerization reaction that contains a plurality of phenyl ring.
And the oleophilic group with reactive hydrogen atom of described a plurality of phenyl ring is at least a in single styroyl phenol, hexichol ethylphenol, triphen ethylphenol, four styroyl phenol, resol class product, the dihydroxyphenyl propane.
And when synthetic many phenyl ring of 1mol polyethers, need oxyethane 2 ~ 100mol.
A kind of preparation method of many phenyl ring polyethers sulphosuccinates is characterized in that, add sulphonating agent in many phenyl ring polyethers succinate after, under 100 ~ 170 ℃ temperature condition, after the sulfonation 4 ~ 6 hours, with the alkali neutralization, obtain many phenyl ring polyethers sulphosuccinates.
Further, described sulphonating agent is any one in sulfuric acid, oleum, thionamic acid, sulphite, halogenosulfonic acid, the sulphur trioxide.
Described alkali then is organic bases or mineral alkali.
The application of a kind of many phenyl ring polyethers sulphosuccinates in pesticide water fundamental mode preparation.
And, the application of a kind of many phenyl ring polyethers sulphosuccinates on synthetic resins, coating, papermaking, binding agent, fiber, material of construction.
Beneficial effect of the present invention is: the present invention is by preparing many phenyl ring polyethers succinate as nonionogenic tenside, and then with its sulfonation introducing sulfonation group, the performance that possesses simultaneously anion surfactant, the synergistic effect of a plurality of functional groups, improved the properties of tensio-active agent, in pesticide water fundamental mode preparation, use, have unrivaled advantage.
Description of drawings
Fig. 1 is the reaction process synoptic diagram of one embodiment of the invention.
Embodiment
Below in conjunction with accompanying drawing technical solution of the present invention is elaborated, but protection scope of the present invention is not limited to described embodiment.
Fig. 1 is the reaction process synoptic diagram of one embodiment of the invention.
As shown in Figure 1: the preparation method of many phenyl ring polyethers succinate is: esterification 4 ~ 8h under 80 ~ 100 ℃ temperature condition with many phenyl ring polyethers and maleic anhydride, obtain many phenyl ring polyethers succinate, and the mol ratio of described many phenyl ring polyethers and maleic anhydride is: 1.0 ~ 2.5:1.Wherein, described many phenyl ring polyethers generates by the oleophilic group with reactive hydrogen atom and the ethylene oxide polymerization reaction that contains a plurality of phenyl ring, and when synthetic many phenyl ring of 1mol polyethers, need oxyethane 2 ~ 100mol, and the oleophilic group with reactive hydrogen atom of described a plurality of phenyl ring is at least a in single styroyl phenol, hexichol ethylphenol, triphen ethylphenol, four styroyl phenol, resol class product, the dihydroxyphenyl propane.
And the preparation method of described many phenyl ring polyethers sulphosuccinates is: after adding sulphonating agent in many phenyl ring polyethers succinate, under 100 ~ 170 ℃ temperature condition, sulfonation with the alkali neutralization, obtained many phenyl ring polyethers sulphosuccinates after 4 ~ 6 hours.And described sulphonating agent is any one in sulfuric acid, oleum, thionamic acid, sulphite, halogenosulfonic acid, the sulphur trioxide.Described alkali then is organic bases or mineral alkali.
Utilize the general structure of many phenyl ring polyethers sulphosuccinates of aforesaid method preparation to be:
Wherein, middle R, R ' among above-mentioned formula Ι and the formula Π are many phenyl ring polyethers, and K then is organic bases or mineral alkali.
Specific embodiment is:
Embodiment 1:With many phenyl ring polyethers (triphen ethylphenol polyethers; molecular weight 2000 ~ 2500) with maleic anhydride in molar ratio 1:1 add in the reactor; start stirring; esterification temperature is 80 ~ 100 ℃, and without catalyzer, reaction is 4 hours under the nitrogen protection condition; obtain many phenyl ring polyethers succinate; add again sulphonating agent (sulfuric acid), 100 ~ 170 ℃ of lower reactions 3 ~ 4 hours, both got finished product: many phenyl ring polyethers sulphosuccinates.
Embodiment 2:With many phenyl ring polyethers (triphen ethylphenol polyethers; molecular weight 2000 ~ 2500) with maleic anhydride in molar ratio 1:1 add in the reactor; start stirring; esterification temperature is 80 ~ 100 ℃; without catalyzer; reaction is 4 hours under the nitrogen protection condition; and then add many phenyl ring polyethers of geometric ratio mole in the reactor; under the condition of using catalyzer, open vacuum, reaction is carried out smoothly; until the water electrode that steams few till; rethink and add sulphonating agent (oleum) in the reactor, 100 ~ 170 ℃ of lower reactions 3 ~ 4 hours, both finished product: many phenyl ring polyethers sulphosuccinates.
Embodiment 3:With many phenyl ring polyethers (triphen ethylphenol polyethers; molecular weight 1500 ~ 2000) with maleic anhydride in molar ratio 1:1 add in the reactor; start stirring; 80 ~ 100 ℃ of esterification temperatures, without catalyzer, reaction is 4 hours under nitrogen protection; obtain many phenyl ring polyethers succinate; add again sulphonating agent (thionamic acid), 100 ~ 170 ℃ of lower reactions 3 ~ 4 hours, both got finished product: phenyl ring polyethers sulphosuccinates.
Embodiment 4:With many phenyl ring polyethers (triphen ethylphenol polyethers; molecular weight 1500 ~ 2000) with maleic anhydride in molar ratio 1:1 add in the reactor; start stirring; 80 ~ 100 ℃ of esterification temperatures; without catalyzer; reaction is 4 hours under nitrogen protection; the many phenyl ring polyethers that adds again the geometric ratio mole; under the catalyzer condition; open vacuum, till the water electrode that reaction is proceeded to smoothly steam is few, add again sulphonating agent (sulphite); 100 ~ 170 ℃ of lower reactions 3 ~ 4 hours, both got finished product: phenyl ring polyethers sulphosuccinates.
Embodiment 5:With many phenyl ring polyethers (resol polyethers; molecular weight 500 ~ 1000) with maleic anhydride in molar ratio 1:1 add in the reactor; start stirring; 80 ~ 100 ℃ of esterification temperatures, without catalyzer, reaction is 4 hours under nitrogen protection; obtain many phenyl ring polyethers succinate; add again sulphonating agent (halogenosulfonic acid), 100 ~ 170 ℃ of lower reactions 3 ~ 4 hours, both got finished product: phenyl ring polyethers sulphosuccinates.
Embodiment 6:With many phenyl ring polyethers (resol polyethers; molecular weight 500 ~ 1000) with maleic anhydride in molar ratio 1:1 add in the reactor; start stirring; 80 ~ 100 ℃ of esterification temperatures; without catalyzer; reaction is 4 hours under nitrogen protection, obtains many phenyl ring polyethers succinate, adds sulphonating agent again; 100 ~ 170 ℃ of lower reactions 4; add again many phenyl ring polyethers of geometric ratio mole, under the catalyzer condition, open vacuum; till the water electrode that reaction is proceeded to smoothly steam is few; add again sulphonating agent (sulphur trioxide), 100 ~ 170 ℃ of lower reactions 3 ~ 4 hours, both got finished product: phenyl ring polyethers sulphosuccinates.
Embodiment 7:With many phenyl ring polyethers (bisphenol A polyether; molecular weight 400 ~ 800) with maleic anhydride in molar ratio 1:1 add in the reactor; start stirring; 80 ~ 100 ℃ of esterification temperatures, without catalyzer, reaction is 4 hours under nitrogen protection; obtain many phenyl ring polyethers succinate; add again sulphonating agent (oleum), 100 ~ 170 ℃ of lower reactions 3 ~ 4 hours, both got finished product: phenyl ring polyethers sulphosuccinates.
Embodiment 8:With many phenyl ring polyethers (bisphenol A polyether; molecular weight 400 ~ 800) with maleic anhydride in molar ratio 1:1 add in the reactor; start stirring; 80 ~ 100 ℃ of esterification temperatures; without catalyzer; reaction is 4 hours under nitrogen protection, obtains many phenyl ring polyethers succinate, adds sulphonating agent (halogenosulfonic acid) again; 100 ~ 170 ℃ of lower reactions 4 hours; add again many phenyl ring polyethers of geometric ratio mole, under the catalyzer condition, open vacuum; till the water electrode that reaction is proceeded to smoothly steam is few; add again sulphonating agent (halogenosulfonic acid), 100 ~ 170 ℃ of lower reactions 3 ~ 4 hours, both got finished product: phenyl ring polyethers sulphosuccinates.
The phenyl ring polyethers sulphosuccinates of above-described embodiment 1-8 preparation can be used in the pesticide water fundamental mode preparation, and specific embodiment is:
Embodiment 9:In 6.9% fenoxapropPethyl aqueous emulsion, its prescription is as follows with product application synthetic among the embodiment 1 ~ 8:
FenoxapropPethyl 6.9%;
Mefenpyrdiethyl 2.5%;
Dimethylbenzene 30%;
Finished product 5% among the embodiment 1 ~ 8;
Tensio-active agent 5%;
Ethylene glycol 5%;
Trolamine 1%;
Water surplus.
Show that through application test the physical stability of 6.9% fenoxapropPethyl aqueous emulsion all is significantly improved.
Embodiment 10: sintetics among the embodiment 1 ~ 8 is applied in the 38% G-30027 water suspending agent, and it is as follows that it uses prescription:
G-30027 38%;
Finished product 2% among the embodiment 1 ~ 8;
Tensio-active agent 2%;
Xanthan gum 0.1 ~ 0.2%;
Magnesium aluminum silicate 1%;
Ethylene glycol 5%;
Silicone antifoam agent 0.2%;
Sanitas 0.2%;
Water surplus.
Detect through application test, the indices of 38% G-30027 water suspending agent preparation all meets international food and agricultural organization standard.
By embodiment 9 ~ 10, can find out that many phenyl ring polyethers sulphosuccinates can widespread use in pesticide water fundamental mode preparation.
In addition, the phenyl ring polyethers sulphosuccinates of above-described embodiment 1-8 preparation also can be applicable on synthetic resins, coating, papermaking, binding agent, fiber, the material of construction.
As mentioned above, although the specific preferred embodiment of reference has represented and has explained the present invention that it shall not be construed as the restriction to the present invention self.Under the spirit and scope of the present invention prerequisite that does not break away from the claims definition, can make in the form and details various variations to it.
Claims (9)
1. the preparation method of the succinate of phenyl ring polyethers more than a kind, it is characterized in that, esterification 4 ~ 8h under 80 ~ 100 ℃ temperature condition with many phenyl ring polyethers and maleic anhydride obtain many phenyl ring polyethers succinate, and the mol ratio of described many phenyl ring polyethers and maleic anhydride is: 1.0 ~ 2.5:1.
2. the preparation method of a kind of many phenyl ring polyethers succinate according to claim 1 is characterized in that, described many phenyl ring polyethers generates by the oleophilic group with reactive hydrogen atom and the ethylene oxide polymerization reaction that contains a plurality of phenyl ring.
3. the preparation method of a kind of many phenyl ring polyethers succinate according to claim 2, it is characterized in that the oleophilic group with reactive hydrogen atom of described a plurality of phenyl ring is at least a in single styroyl phenol, hexichol ethylphenol, triphen ethylphenol, four styroyl phenol, resol class product, the dihydroxyphenyl propane.
4. the preparation method of a kind of many phenyl ring polyethers succinate according to claim 2 is characterized in that, when synthetic many phenyl ring of 1mol polyethers, needs oxyethane 2 ~ 100mol.
5. the preparation method of the sulphosuccinates of phenyl ring polyethers more than a kind is characterized in that, add sulphonating agent in many phenyl ring polyethers succinate after, under 100 ~ 170 ℃ temperature condition, after the sulfonation 4 ~ 6 hours, with the alkali neutralization, obtain many phenyl ring polyethers sulphosuccinates.
6. the preparation method of a kind of many phenyl ring polyethers sulphosuccinates according to claim 5 is characterized in that, described sulphonating agent is any one in sulfuric acid, oleum, thionamic acid, sulphite, halogenosulfonic acid, the sulphur trioxide.
7. the preparation method of a kind of many phenyl ring polyethers sulphosuccinates according to claim 5 is characterized in that, described alkali is organic bases or mineral alkali.
8. the application of the sulphosuccinates of phenyl ring polyethers more than a kind in pesticide water fundamental mode preparation.
9. the application of the sulphosuccinates of phenyl ring polyethers more than a kind on synthetic resins, coating, papermaking, binding agent, fiber, material of construction.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190007858A (en) | 2017-07-14 | 2019-01-23 | 순천대학교 산학협력단 | Method of producing phenol alkoxylate |
| CN113637155A (en) * | 2021-10-18 | 2021-11-12 | 常熟耐素生物材料科技有限公司 | Anionic polyether type high-molecular surfactant and preparation method thereof |
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| WO2001062828A1 (en) * | 2000-02-23 | 2001-08-30 | Asahi Kasei Kabushiki Kaisha | Modified polyphenylene ether |
| CN101692807A (en) * | 2009-10-20 | 2010-04-14 | 陕西上格之路生物科学有限公司 | Dispersible oil suspension agent containing cyproconazole |
| CN101731205A (en) * | 2010-01-27 | 2010-06-16 | 江苏省农用激素工程技术研究中心有限公司 | Suspending agent of tebuthiuron and method for preparing same |
| CN101743957A (en) * | 2010-01-27 | 2010-06-23 | 江苏省农用激素工程技术研究中心有限公司 | Bispyribac-sodium salt suspending agent and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001062828A1 (en) * | 2000-02-23 | 2001-08-30 | Asahi Kasei Kabushiki Kaisha | Modified polyphenylene ether |
| CN101692807A (en) * | 2009-10-20 | 2010-04-14 | 陕西上格之路生物科学有限公司 | Dispersible oil suspension agent containing cyproconazole |
| CN101731205A (en) * | 2010-01-27 | 2010-06-16 | 江苏省农用激素工程技术研究中心有限公司 | Suspending agent of tebuthiuron and method for preparing same |
| CN101743957A (en) * | 2010-01-27 | 2010-06-23 | 江苏省农用激素工程技术研究中心有限公司 | Bispyribac-sodium salt suspending agent and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190007858A (en) | 2017-07-14 | 2019-01-23 | 순천대학교 산학협력단 | Method of producing phenol alkoxylate |
| CN113637155A (en) * | 2021-10-18 | 2021-11-12 | 常熟耐素生物材料科技有限公司 | Anionic polyether type high-molecular surfactant and preparation method thereof |
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