CN105037708A - Preparation method and application of high-polymerization degree fatty alcohol block polyether - Google Patents
Preparation method and application of high-polymerization degree fatty alcohol block polyether Download PDFInfo
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- CN105037708A CN105037708A CN201510383986.XA CN201510383986A CN105037708A CN 105037708 A CN105037708 A CN 105037708A CN 201510383986 A CN201510383986 A CN 201510383986A CN 105037708 A CN105037708 A CN 105037708A
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- fatty alcohol
- block polyether
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Abstract
The invention relates to a preparation method and an application of high-polymerization degree fatty alcohol block polyether. The method comprises the following steps: adding fatty alcohol to a reaction kettle, adding a catalyst adopting homogeneous gold complex (AuL), slowly introducing epoxide, and reacting at a polymerization temperature of 100-140DEG C under a reaction pressure being smaller than 0.3Mpa, and introducing another epoxide after the epoxide is completely absorbed in order to obtain the fatty alcohol block polyether product. The relative molecular weight of the prepared product is greater than 4000, the molecular weight distribution is smaller than 1.14, and the content of free glycol is smaller than 1%. The product prepared through the method can be applied in pesticide missible oil, suspensions or emulsions in water to improve the emulsification stability and enhance the hard water resistance.
Description
Technical field
The present invention is a kind of method and application thereof of high-polymerization degree fatty alcohol block polyether, and it is applied in emulsifiable concentrates for agricultural chemicals, suspension agent or aqueous emulsion, can improve emulsifying stability, strengthen resistance to hard water.
Background technology
Low melting point agricultural chemicals as pendimethalin or containing low melting point high-boiling-point impurity agricultural chemicals as emamectin benzoate process suspension agent time, usually in sand grinding process or storage process, preparation loses flowability, this is unfavorable for sand milling because low melting point easily softens or becomes liquid state in the course of processing, or the livering phenomenon promoting oil phase, aqueous phase, solid phase three-phase to exist and cause.High molecular narrow distribution aliphatic alcohol block polyether effectively emulsification can wrap up low melting point composition, and Long carbon chain is easy to intercept different alternate contact, stablizing of favourable low melting point suspension system;
High concentration agricultural chemical aqueous emulsion, as in the 450 grams per liter prochloraz EW courses of processing, because oil phase content reaches about 60%, often shows as viscosity and becomes large, cannot process further in the course of processing, and the phenomenon such as easy breakdown of emulsion in storage process.High molecular weight fatty alcohol block polyether oleophylic segment fatty alcohol polyoxypropylene ether firmly can deeply embed oil phase inside, and Soxylat A 25-7 hydrophilic segment can guarantee that emulsified particle dispersion is in aqueous phase, improves aqueous emulsion processing smoothness and package stability.
Cream preparation prepared by emulsifiable concentrates for agricultural chemicals, particularly solid pesticide often shows low temperature and easily separates out, and be diluted in high hardness water, emulsifying property does not reach requirement.Amphipathy macromolecule fatty alcohol block polyether and agricultural chemicals particle play good eutectic effect, stop the precipitation of agricultural chemicals, simultaneously by regulating hydrophilic polyethylene oxide segment ratio, effectively can improve the anti-performance of hard water of preparation.
Normal fat alcohol block polyether is that catalyzer synthesizes by sodium hydroxide or potassium hydroxide, product relative molecular weight is generally 500 ~ 2000, more than molecular weight distribution >1.3, free polyoxyethylene glycol >3%, it is sterically hindered preferably that too low molecular weight is difficult to formation, be difficult to embed agricultural chemicals drop internal, too high molecular weight distribution, reduce the designability of product structure, free polyethyleneglycol content is high in addition, actually reduce the effective content of product, therefore the synthesis of high-polymerization degree butanols polyoxyethylene poly-oxygen propylene aether is very important.
Moreover traditional method uses sodium hydroxide or potassium hydroxide as the trapping agent of proton, thus form a small amount of water, the water of this generation is a good epoxy addition reagent, thus cause the generation of ethylene glycol (reacting with EO) and 1,2-PD, then using these two kinds of alcohol as epoxy addition reagent, react with EO, PO, to a lot of complicated by products be formed, finally reduce us and expect and the quality of the Fatty alcohol polyoxyethylene polyoxypropylene ether wanted cause the reduction of the polymerization degree.
Traditional method side reaction produces reaction equation and is illustrated as:
。
Summary of the invention
The invention provides a kind of novel method, namely gold catalyzes and synthesizes high-polymerization degree fatty alcohol polyoxypropylene Soxylat A 25-7, molecular weight product reaches more than 4000, molecular weight distribution <1.1, free polyethyleneglycol content <1%, it is applied to the formulations such as emulsifiable concentrates for agricultural chemicals, suspension agent, aqueous emulsion, solves in the pesticide preparation such as water suspending agent, aqueous emulsion and missible oil the common problems such as some processing, storage and use.
The technical solution used in the present invention is for this reason: the present invention for raw material, adopts homogeneous phase gold complex AuL to be that catalyzer obtains with fatty alcohol and epoxide.
Described fatty alcohol is carbon number is 4 ~ 18 alcohol or its mixture.
Gold in described gold complex is+1 valency gold or+3 valencys gold, and ligand L is halogen, containing Phosphine ligands, containing n-donor ligand or containing oxygen part.
Described ligand L is containing Phosphine ligands.
The addition of described gold complex AuL is 0.5-100 milligram/every kilogram of fatty alcohol.
Described epoxide comprises oxyethane, propylene oxide, its base of butylene oxide ring do arbitrary proportion mixture.
The present invention carries out according to following steps specifically:
1) preheating: homogeneous phase gold complex AuL catalyzer and fatty alcohol are added reactor, mixes, vacuumizes and high pure nitrogen is replaced 2-4 time, is warming up to 100-140
oc stablizes;
2) epoxide is passed into: slowly passed into by epoxide in described reactor, carry out ring-opening polymerization, stable reaction controls at 100-140
oc, reaction pressure controls be less than 0.3Mpa, stablizes, aging 1-3 hour etc. reaction pressure;
3) 2 are repeated) step press same process, then passes into epoxide, formation block polyether.
The present invention can be applicable in agricultural chemicals suspension agent, aqueous emulsion, cream preparation.
The present invention uses the gold complex (AuL) of homogeneous phase as epoxy addition activating reagent, thus avoid the generation of water, and then avoid the generation of numerous side reaction, and gold complex (AuL) can activate the Sauerstoffatom of epoxy compounds, ring-opening polymerization can be made to be more prone in the latter stage of polymerization, form the butanols polyoxyethylene poly-oxygen propylene aether of high-polymerization degree, thus improve the quality of product.
The inventive method reaction equation is schematically as follows:
Accompanying drawing explanation
The block polyether analysis of spectra of Fig. 1 obtained by the embodiment of the present invention 1.
Embodiment
Embodiment 1: butanols, propylene oxide (PO), oxyethane (EO), ring-opening polymerization catalyst AuL
1, step is as follows:
(1) preheating, by appropriate ring-opening polymerization catalyst AuL
1(Au is+1 valency, L
1=PPh
3cl, for containing Phosphine ligands 1), add reactor with 74g butanols, mix, vacuumize also high pure nitrogen displacement 2-4 time, be warming up to 100-140
oc stablizes.(2) pass into propylene oxide (PO), slowly pass in described reactor by 70-75 equivalent PO, carry out ring-opening polymerization, stable reaction controls at 100-140
oc, reaction pressure controls be less than 0.3Mpa, stablizes, aging 1-3 hour etc. reaction pressure.(3) pass into oxyethane (EO), the EO of 40-50 equivalent is slowly passed in the reaction of described butanols and PO, carry out ring-opening polymerization, answer stability contorting at 100-140
oc, reaction pressure controls be less than 0.3Mpa, stablizes, aging 1-3 hour etc. reaction pressure.Obtained finished product, obtains product by describedly washing with PO/EO open-loop products, filtering.
Embodiment 2: butanols, propylene oxide (PO), oxyethane (EO), ring-opening polymerization catalyst AuL
2(Au is+1 valency, L
2=
tbuXPhosNTf
2, for containing Phosphine ligands 2), step is as follows:
(1) preheating, by appropriate ring-opening polymerization catalyst AuL
2add reactor with 74g butanols, mix, vacuumize also high pure nitrogen displacement 2-4 time, be warming up to 100-140
oc stablizes; (2) pass into propylene oxide (PO), slowly pass in described reactor by 70-75 equivalent PO, carry out ring-opening polymerization, stable reaction controls at 100-140
oc, reaction pressure controls be less than 0.3Mpa, stablizes, aging 1-3 hour etc. reaction pressure.(3) pass into oxyethane (EO), the EO of 40-50 equivalent is slowly passed in the reaction of described butanols and PO, carry out ring-opening polymerization, answer stability contorting at 100-140
oc, reaction pressure controls be less than 0.3Mpa, stablizes, aging 1-3 hour etc. reaction pressure.Obtained finished product, obtains product by describedly washing with PO/EO open-loop products, filtering.
Embodiment 3: butanols, propylene oxide (PO), oxyethane (EO), ring-opening polymerization catalyst AuL
3(Au is+1 valency, L
3=(CO) Cl, for containing oxygen part), step is described above;
Embodiment 4: butanols, propylene oxide (PO), oxyethane (EO), ring-opening polymerization catalyst AuL
4(Au is+1 valency, L
4=C
6h
4nCO
2cl
2(pyridine-2-carboxyphenyl) is containing n-donor ligand), step is described above;
Embodiment 5: butanols, propylene oxide (PO), oxyethane (EO), ring-opening polymerization catalyst AuL
5(Au is+1 valency, L
5=Cl, L
5for halogen 1), step is described above;
Embodiment 6: butanols, propylene oxide (PO), oxyethane (EO), ring-opening polymerization catalyst AuL
6(Au is+1 valency, L
6=Cl, L
6for halogen 1), step is described above;
Embodiment 7: butanols, propylene oxide (PO), oxyethane (EO), ring-opening polymerization catalyst AuL
7(Au is+3 valencys, L
7=Cl, L
7for halogen 1), step is described above;
Embodiment 8: butanols, propylene oxide (PO), oxyethane (EO), ring-opening polymerization catalyst AuL
8(Au is+1 valency, L
8=I, L
8for halogen 2), step is described above; Product prepared by above-mentioned employing AuL1-AuL8 ring-opening polymerization catalyst, molecular weight is about 5000, and molecular weight distribution is between 1.1-1.14.In block polyether structure, fatty alcohol and PO ratio are about 1:43-47, and PO and EO ratio is between for 1.7:1-1.9:1.As follows:
Embodiment 9:
450g/L prochloraz EW preparation
Component title Content content
Prochloraz (98%) 42%42%42%
Commercial emulsifier 6%6%6%
Import emulsifying agent 1%
Emulsifying agent one (embodiment 1 obtains) 1%
Emulsifying agent two (embodiment 2 obtains) 1%
Solvent 20%20%20%
Xanthan gum 0.05%0.05%0.05%
Defoamer 0.05%0.05%0.05%
Sanitas 0.05%0.05%0.05%
Ethylene glycol 4%4%4%
Water complements to 100% and complements to 100% and complement to 100%;
Detected result:
Appearance milky white thickness oyster white thickness oyster white thickness
Fluxion fluxion fluxion
Emulsifying dispersivity is qualified excellent
Emulsion dilution stability is qualified excellent
(diluting 200 times)
Cold storage qualified stability is qualified
Thermodynamic stability is qualified qualified
Embodiment 10
25% pyraclostrobin SC preparation
Component title Content content
Pyraclostrobin (98%) 25.5%25.5%25.5%
Dispersion moisture agent 8%5%5%
Auxiliary agent one (embodiment 1 obtains) 1%
Auxiliary agent two (embodiment 2 obtains) 1%
Xanthan gum 0.2%0.2%0.2%
Neusilin 0.5%0.5%0.5%
The appropriate appropriate 0.06%0.06%0.06% of defoamer
Sanitas 0.06%0.06%0.06%
Ethylene glycol 4%4%4%
Water complements to 100% and complements to 100% and complement to 100%
Detected result:
Outward appearance thickness, fluxion fluxion fluxion;
Suspensibility % >=92%95.294.6
Cold storage stability is defective qualified
Thermodynamic stability is defective qualified
Embodiment 11
1.8% abamectin emulsifiable concentrate preparation
Ingredient names Content content
Avrmectin (90%) 2%2%2%
Emulsifying agent 15%10%10%
Assistant for emulsifying agent (embodiment 1 obtains) 2%
Assistant for emulsifying agent (embodiment 2 gained) 2%
Dimethylbenzene complements to 100% and complements to 100% and complement to 100%
Detected result:
Appearance stablity is stable
Homogeneous liquid homogeneous liquid homogeneous liquid
Effective content % >=1.9%1.851.92
Dilution stability (diluting 200 times) is defective qualified
Cold storage stability is defective qualified
Thermodynamic stability is defective qualified
Embodiment 12
2.5% lambda-cyhalothrin microemulsion formulation
Ingredient names Content content
Lambda-cyhalothrin (95%) 2.6%2.6%2.6%
Emulsifying agent 12%8%8%
Assistant for emulsifying agent (embodiment 1 obtains) 2%
Assistant for emulsifying agent (embodiment 2 gained) 2%
Solvent 8%8%8%
Frostproofer 5%5%5%
Water complements to 100% and complements to 100% and complement to 100%
Detected result:
Appearance transparent liquid-transparent liquid-transparent liquid
Effective content % >=2.62%2.552.60
Dilution stability (diluting 200 times) is qualified qualified
Frost resistance is qualified qualified
Cold storage stability is defective qualified
Thermodynamic stability is qualified qualified
Embodiment 13
70% imidacloprid water dispersible granule
Ingredient names Content content
Provado (96%) 73%73%73%
Dispersion agent 10%8%8%
Auxiliary agent (embodiment 1 obtains) 1%
Auxiliary agent (embodiment 2 gained) 1%
Wetting agent 2%2%2%
Disintegrating agent 4%4%4%
Carrier complements to 100% and complements to 100% and complement to 100%
Detected result:
The full granulation of the not full granulation of granulation performance granulation is full
Effective content %70.5%70.2%70.4%
Suspensibility % >=939697
Disintegration time s≤301515
Cold storage qualified stability is qualified
Thermodynamic stability is defective qualified.
Claims (8)
1. a preparation method for high-polymerization degree fatty alcohol block polyether, is characterized in that, with fatty alcohol and epoxide for raw material, adopts homogeneous phase gold complex AuL to be that catalyzer obtains.
2. the preparation method of a kind of high-polymerization degree fatty alcohol block polyether according to claim 1, is characterized in that, described fatty alcohol is carbon number is 4 ~ 18 alcohol or its mixture.
3. the preparation method of a kind of high-polymerization degree fatty alcohol block polyether according to claim 1, is characterized in that, the gold in described gold complex is+1 valency gold or+3 valencys gold, and ligand L is halogen, containing Phosphine ligands, containing n-donor ligand or containing oxygen part.
4. the preparation method of a kind of high-polymerization degree fatty alcohol block polyether according to claim 3, is characterized in that, described ligand L is containing Phosphine ligands.
5. the preparation method of a kind of high-polymerization degree fatty alcohol block polyether according to claim 1, is characterized in that, the addition of described gold complex AuL is 0.5-100 milligram/every kilogram of fatty alcohol.
6. the preparation method of a kind of high-polymerization degree fatty alcohol block polyether according to claim 1, is characterized in that, described epoxide comprises oxyethane, propylene oxide, its base of butylene oxide ring do arbitrary proportion mixture.
7. the preparation method of a kind of high-polymerization degree fatty alcohol block polyether according to claim 1, is characterized in that, carry out according to following steps:
1) preheating: homogeneous phase gold complex AuL catalyzer and fatty alcohol are added reactor, mixes, vacuumizes and high pure nitrogen is replaced 2-4 time, is warming up to 100-140
oc stablizes;
2) epoxide is passed into: slowly passed into by epoxide in described reactor, carry out ring-opening polymerization, stable reaction controls at 100-140
oc, reaction pressure controls be less than 0.3Mpa, stablizes, aging 1-3 hour etc. reaction pressure;
Repeating 2) step press same process, then passes into epoxide, formation block polyether.
8. the application of the high-polymerization degree fatty alcohol block polyether prepared according to above-mentioned arbitrary claim, is characterized in that,
Be applied in agricultural chemicals suspension agent, aqueous emulsion, cream preparation.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106380589A (en) * | 2016-08-31 | 2017-02-08 | 江苏擎宇化工科技有限公司 | Environmentally-friendly pesticide wetting dispersant, modified dispersant, and preparation method and application of pesticide wetting dispersant |
| CN107868241A (en) * | 2017-11-24 | 2018-04-03 | 威海翔泽新材料科技有限公司 | A kind of fatty alcohol block polyether class tar ammonia demulsifier and preparation method thereof |
| CN110408017A (en) * | 2019-07-15 | 2019-11-05 | 佳化化学科技发展（上海）有限公司 | It is a kind of fat alcohol block polyether, for dispersing agent of pesticide suspension concentrate and preparation method thereof, pesticide suspension concentrate |
| CN110540638A (en) * | 2019-08-21 | 2019-12-06 | 佳化化学科技发展（上海）有限公司 | Preparation method of emulsifier and application of emulsifier in preparation of pesticide emulsifiable concentrate |
| CN111675804A (en) * | 2020-05-06 | 2020-09-18 | 南京威尔生物科技有限公司 | Plant source block polyether and oil suspension agent and water emulsion prepared from same |
| CN114957644A (en) * | 2022-04-20 | 2022-08-30 | 河北盛鹏化工有限公司 | Block polyether and preparation method and application thereof |
| CN115322360A (en) * | 2022-09-14 | 2022-11-11 | 南京太化化工有限公司 | Preparation method and application of monol high-molecular block polyether |
| CN115340671A (en) * | 2021-05-12 | 2022-11-15 | 联泓(江苏)新材料研究院有限公司 | Low-pour-point block polyether and preparation method and application thereof |
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2015
- 2015-07-03 CN CN201510383986.XA patent/CN105037708A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106380589A (en) * | 2016-08-31 | 2017-02-08 | 江苏擎宇化工科技有限公司 | Environmentally-friendly pesticide wetting dispersant, modified dispersant, and preparation method and application of pesticide wetting dispersant |
| CN107868241A (en) * | 2017-11-24 | 2018-04-03 | 威海翔泽新材料科技有限公司 | A kind of fatty alcohol block polyether class tar ammonia demulsifier and preparation method thereof |
| CN110408017A (en) * | 2019-07-15 | 2019-11-05 | 佳化化学科技发展（上海）有限公司 | It is a kind of fat alcohol block polyether, for dispersing agent of pesticide suspension concentrate and preparation method thereof, pesticide suspension concentrate |
| CN110408017B (en) * | 2019-07-15 | 2022-03-22 | 佳化化学科技发展（上海）有限公司 | Fatty alcohol block polyether, dispersing agent for pesticide aqueous suspension agent, preparation method of dispersing agent and pesticide aqueous suspension agent |
| CN110540638A (en) * | 2019-08-21 | 2019-12-06 | 佳化化学科技发展（上海）有限公司 | Preparation method of emulsifier and application of emulsifier in preparation of pesticide emulsifiable concentrate |
| CN110540638B (en) * | 2019-08-21 | 2022-03-22 | 佳化化学科技发展（上海）有限公司 | Preparation method of emulsifier and application of emulsifier in preparation of pesticide emulsifiable concentrate |
| CN111675804A (en) * | 2020-05-06 | 2020-09-18 | 南京威尔生物科技有限公司 | Plant source block polyether and oil suspension agent and water emulsion prepared from same |
| CN115340671A (en) * | 2021-05-12 | 2022-11-15 | 联泓(江苏)新材料研究院有限公司 | Low-pour-point block polyether and preparation method and application thereof |
| CN114957644A (en) * | 2022-04-20 | 2022-08-30 | 河北盛鹏化工有限公司 | Block polyether and preparation method and application thereof |
| CN115322360A (en) * | 2022-09-14 | 2022-11-11 | 南京太化化工有限公司 | Preparation method and application of monol high-molecular block polyether |
| CN115322360B (en) * | 2022-09-14 | 2024-04-19 | 南京太化化工有限公司 | Preparation method and application of unit alcohol polymer block polyether |
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