CN104250375A - Disproportionated rosin amine polyoxyethylene polyoxypropylene ether and preparation method thereof - Google Patents
Disproportionated rosin amine polyoxyethylene polyoxypropylene ether and preparation method thereof Download PDFInfo
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- CN104250375A CN104250375A CN201410488600.7A CN201410488600A CN104250375A CN 104250375 A CN104250375 A CN 104250375A CN 201410488600 A CN201410488600 A CN 201410488600A CN 104250375 A CN104250375 A CN 104250375A
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Abstract
The invention relates to a preparation method of disproportionated rosin amine polyoxyethylene polyoxypropylene ether, and belongs to the technical field of polymer synthesis. The method comprises the steps as follows: first, disproportionated rosin amine is taken as an initiator to be subjected to polymerization reaction with ethylene oxide under autocatalysis, so that 2-hydroxyethyl disproportionated rosin amine is obtained; secondly, the 2-hydroxyethyl disproportionated rosin amine obtained is continuously polymerized with ethylene oxide and propylene epoxide, so that the disproportionated rosin amine polyoxyethylene polyoxypropylene ether is obtained. The method is simple in processes, green and environment-friendly, and can meet the requirement of chemical fiber operation application.
Description
Technical field
The present invention relates to a kind of preparation method of disproportionated rosin amine polyoxyethylene poly-oxygen propylene aether, introduce poly(propylene oxide) chain group in disproportionated rosin amine molecule segment, it is more close to natural resin, environmental protection more.
Background technology
At Current surface promoting agent, there is lack of raw materials, price increase, and environmental requirement is tending towards strict, and conventional process for synthesizing surfactant cannot meet the demand of environmental protection and cost; In addition, when rosin Amine D and oxyethane carry out polyreaction, harsher to the requirement of reaction conditions, its reaction conditions, reaction environment are extremely important.Otherwise, containing unreacted rosin Amine D and by product polyoxyethylene glycol in reaction product.It is muddy that this unreacted rosin Amine D can make the aqueous solution of dilution produce, and can irritate skin, unfavorable to product application.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of disproportionated rosin amine polyoxyethylene poly-oxygen propylene aether, the present invention has simple for process, environmental protection, can meet the needs of chemical fibre job applications.
For achieving the above object, technical scheme of the present invention is:
A preparation method for disproportionated rosin amine polyoxyethylene poly-oxygen propylene aether, comprises the steps: 1) take disproportionated rosin amine as initiator, under autocatalysis, carry out polyreaction with oxyethane, obtain dihydroxy ethyl disproportionated rosin amine; 2) add alkaline catalysts and propylene oxide, and continue to add oxyethane, the obtained disproportionated rosin amine polyoxyethylene poly-oxygen propylene aether of polymerization.
Further, as preferably:
In step 1), described disproportionated rosin amine (Guilin Song Quan woods chemical industry limited liability company, 90%Min, i.e. purity 90%) is 1:2 with the mol ratio of oxyethane, and temperature of reaction is 90 ~ 150 DEG C, and the reaction times is 2 ~ 10 hours;
Step 2) in, described alkaline catalysts adopt in KOH, NaOH or sodium methylate one or more; The add-on of basic catalyst is 0.1 ~ 1.5% of disproportionated rosin amine and ethylene oxide propylene oxide total mass, and the oxyethane again added is 10 ~ 50:1 with the interpolation ratio of propylene oxide, disproportionated rosin amine; Temperature of reaction is 90 ~ 150 DEG C, and the reaction times is 2 ~ 10 hours.
Adopt the disproportionated rosin amine polyoxyethylene poly-oxygen propylene aether that above-mentioned preparation method obtains, its structure is:
。
Reaction equation is:
，
Wherein n+m=10-50.
The present invention selects this natural product of disproportionated rosin amine to carry out the synthesis of tensio-active agent as starting raw material, the dependence to oil and synthetic resins can be reduced, product has good ecological performance, meets " raw material greenization " requirement of " green " tensio-active agent; And rosin Amine D abundance, low price, China is again rosin Amine D producing country maximum in the world, and output accounts for 1/3rd of Gross World Product, is a huge available natural regeneration resource.Make full use of the renewable resources that this is abundant, increase economic efficiency, enrich the kind of tensio-active agent, promote the development of rosin-based surfactant, these are all significant.
Embodiment
embodiment 1
The present embodiment adds 285.0g disproportionated rosin amine in 2.5L pressure reaction still, is connected by oxyethane test tank with autoclave pressure.With nitrogen replacement air 3 times, treat that still temperature rises to 125 ~ 130 DEG C, keep system pressure 0.2 ~ 0.3MPa, start to pass into 88.0g oxyethane, within 0.5 hour, lead to, continue reaction 1.0 hours, drop into 4.0g KOH solid catalyst,-0.1MPa dehydrated under vacuum 1.0 hours, at 150 ~ 160 DEG C, keep system pressure 0.2 ~ 0.3MPa, pass into 132.0g oxyethane, within 3.5 hours, lead to after completion of the reaction, be cooled to 110 DEG C of pressure releases degassed, at 120 ~ 125 DEG C, keep system pressure 0.2 ~ 0.3MPa, continue to pass into propylene oxide 290.0g, within 5 hours, lead to after completion of the reaction, cooling, release, obtain brown color thick liquid.The present embodiment adopts natural product disproportionated rosin amine to be raw material, has simple for process, environmental protection, can meet the needs of chemical fibre job applications.
embodiment 2
The present embodiment adds 310.0g disproportionated rosin amine in 2.5L pressure reaction still, is connected by oxyethane test tank with autoclave pressure.With nitrogen replacement air 3 times, treat that still temperature rises to 125 ~ 130 DEG C, keep system pressure 0.2 ~ 0.3MPa, start to pass into 95.0g oxyethane, within 0.5 hour, lead to, continue reaction 1.0 hours, drop into 14.3g sodium methylate solid catalyst, separating methanol 1.0 hours under-0.1MPa vacuum, at 150 ~ 160 DEG C, keep system pressure 0.2 ~ 0.3MPa, pass into 142.0g oxyethane, within 3.5 hours, lead to after completion of the reaction, be cooled to 110 DEG C of pressure releases degassed, at 120 ~ 125 DEG C, keep system pressure 0.2 ~ 0.3MPa, continue to pass into propylene oxide 1250.0g, within 10 hours, lead to after completion of the reaction, cooling, release, obtain brown color thick liquid.The present embodiment adopts natural product disproportionated rosin amine to be raw material, has simple for process, environmental protection, can meet the needs of chemical fibre job applications.
embodiment 3
The present embodiment adds 280.0g disproportionated rosin amine in 2.5L pressure reaction still, is connected by oxyethane test tank with autoclave pressure.With nitrogen replacement air 3 times, treat that still temperature rises to 125 ~ 130 DEG C, keep system pressure 0.2 ~ 0.3MPa, start to pass into 87.0g oxyethane, within 0.5 hour, lead to, continue reaction 1.0 hours, drop into 24.8g NaOH solid catalyst,-0.1MPa dehydrated under vacuum 1.0 hours, at 150 ~ 160 DEG C, keep system pressure 0.2 ~ 0.3MPa, pass into 1233.0g oxyethane, within 8 hours, lead to after completion of the reaction, be cooled to 110 DEG C of pressure releases degassed, at 120 ~ 125 DEG C, keep system pressure 0.2 ~ 0.3MPa, continue to pass into propylene oxide 1160.0g, within 10 hours, lead to after completion of the reaction, cooling, release, obtain brown color thick liquid.The present embodiment adopts natural product disproportionated rosin amine to be raw material, has simple for process, environmental protection, can meet the needs of chemical fibre job applications.
After tested, specific targets are as shown in table 1 for disproportionated rosin amine polyoxyethylene poly-oxygen propylene aether prepared by the various embodiments described above 1-3.
The test result of each embodiment of table 1
In the present invention, by controlling the ratio of each reactant in preparation process, and be aided with specific reaction conditions, when making rosin Amine D and oxyethane carry out polyreaction, remain in good reaction atmosphere, thus in the final reaction product obtained, the by-products content such as moisture controls in lower scope, unreacted rosin Amine D and by product polyethyleneglycol content less, avoid the safety risks that these residues are brought into use procedure; Simultaneously, different with mode according to the object of final utilization, rosin Amine D and oxyethane are reacted under different conditions, to obtain the disproportionated rosin amine polyoxyethylene poly-oxygen propylene aether of different molecular weight distribution, molecular weight as embodiment 1 is lower, when using for environmental protection paint with other compositions are composite, its viscosity is lower, and addition can suitably increase; And the molecular weight of embodiment 3 gained disproportionated rosin amine polyoxyethylene poly-oxygen propylene aether is higher, corresponding viscosity is also higher, and in compound process, addition just can control in less scope, with the requirement that satisfied different environmental protection paint is composite to viscosity, composition, it is more convenient to use.
Above content is the further description done provided technical scheme in conjunction with the preferred embodiment of the present invention; can not assert that the present invention specifically implements to be confined to these explanations above-mentioned; for general technical staff of the technical field of the invention; without departing from the inventive concept of the premise; some simple deduction or replace can also be made, all should be considered as belonging to protection scope of the present invention.
Claims (5)
1. the preparation method of a disproportionated rosin amine polyoxyethylene poly-oxygen propylene aether, it is characterized in that: comprise the steps: 1) take disproportionated rosin amine as initiator, polyreaction is carried out with oxyethane under autocatalysis, the mol ratio of disproportionated rosin amine and oxyethane is 1:2, temperature of reaction is 90 ~ 150 DEG C, reaction times is 2 ~ 10 hours, obtains dihydroxy ethyl disproportionated rosin amine; 2) alkaline catalysts and propylene oxide is added, the add-on of basic catalyst is 0.1 ~ 1.5% of disproportionated rosin amine and ethylene oxide propylene oxide total mass, and continue to add oxyethane, oxyethane, propylene oxide are 10 ~ 50:1 with the interpolation ratio of disproportionated rosin amine, controlling temperature of reaction is 90 ~ 150 DEG C, reaction times is 2 ~ 10 hours, the obtained disproportionated rosin amine polyoxyethylene poly-oxygen propylene aether of polymerization, described alkaline catalysts adopt in KOH, NaOH or sodium methylate one or more.
2. the preparation method of a kind of disproportionated rosin amine polyoxyethylene poly-oxygen propylene aether as claimed in claim 1, is characterized in that: in pressure reaction still, add 285.0g disproportionated rosin amine, is connected by oxyethane test tank with autoclave pressure, nitrogen replacement air 3 times, treat that still temperature rises to 125 ~ 130 DEG C, keep system pressure 0.2 ~ 0.3MPa, passed into 88.0g oxyethane in 0.5 hour after, continue reaction 1.0 hours, drop into 4.0g KOH solid catalyst,-0.1MPa dehydrated under vacuum 1.0 hours, at 150 ~ 160 DEG C, keep system pressure 0.2 ~ 0.3MPa, pass into 132.0g oxyethane, within 3.5 hours, lead to after completion of the reaction, be cooled to 110 DEG C of pressure releases degassed, at 120 ~ 125 DEG C, keep system pressure 0.2 ~ 0.3MPa, continue to pass into propylene oxide 290.0g, within 5 hours, lead to after completion of the reaction, cooling, release, obtain brown color thick liquid and be finished product disproportionated rosin amine polyoxyethylene poly-oxygen propylene aether.
3. the preparation method of a kind of nilox resin polyoxyethylene poly-oxygen propylene aether as claimed in claim 1, is characterized in that: in pressure reaction still, add 310.0g disproportionated rosin amine, is connected by oxyethane test tank with autoclave pressure, with nitrogen replacement air 3 times, treat that still temperature rises to 125 ~ 130 DEG C, keep system pressure 0.2 ~ 0.3MPa, after passing into 95.0g oxyethane in 0.5 hour, continue reaction 1.0 hours, drop into 14.3g sodium methylate solid catalyst, separating methanol 1.0 hours under-0.1MPa vacuum, at 150 ~ 160 DEG C, keep system pressure 0.2 ~ 0.3MPa, pass into 142.0g oxyethane, within 3.5 hours, lead to after completion of the reaction, be cooled to 110 DEG C of pressure releases degassed, at 120 ~ 125 DEG C, keep system pressure 0.2 ~ 0.3MPa, continue to pass into propylene oxide 1250.0g, within 10 hours, lead to after completion of the reaction, cooling, release, obtain brown color thick liquid and be finished product disproportionated rosin amine polyoxyethylene poly-oxygen propylene aether.
4. the preparation method of a kind of nilox resin polyoxyethylene poly-oxygen propylene aether as claimed in claim 1, is characterized in that: in pressure reaction still, add 280.0g disproportionated rosin amine, is connected by oxyethane test tank with autoclave pressure, with nitrogen replacement air 3 times, treat that still temperature rises to 125 ~ 130 DEG C, keep system pressure 0.2 ~ 0.3MPa, after passing into 87.0g oxyethane in 0.5 hour, continue reaction 1.0 hours, drop into 24.8g NaOH solid catalyst,-0.1MPa dehydrated under vacuum 1.0 hours, at 150 ~ 160 DEG C, keep system pressure 0.2 ~ 0.3MPa, pass into 1233.0g oxyethane, within 8 hours, lead to after completion of the reaction, be cooled to 110 DEG C of pressure releases degassed, at 120 ~ 125 DEG C, keep system pressure 0.2 ~ 0.3MPa, continue to pass into propylene oxide 1160.0g, within 10 hours, lead to after completion of the reaction, cooling, release, obtain brown color thick liquid and be finished product disproportionated rosin amine polyoxyethylene poly-oxygen propylene aether.
5. adopt the disproportionated rosin amine polyoxyethylene poly-oxygen propylene aether that described in any one of claim 1-4 prepared by method, it is characterized in that, the structural formula of described disproportionated rosin amine polyoxyethylene poly-oxygen propylene aether is:
。
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Cited By (5)
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| CN106317401A (en) * | 2016-08-19 | 2017-01-11 | 浙江皇马科技股份有限公司 | Synthetic method of low color value polyether |
| CN111171306A (en) * | 2020-02-29 | 2020-05-19 | 江苏斯德瑞克化工有限公司 | Preparation method of gemini block polyether |
| CN114106277A (en) * | 2021-11-30 | 2022-03-01 | 北京东方华盛科技有限公司 | Preparation method of C polyoxyethylene rosin amine |
| CN114656627A (en) * | 2022-03-11 | 2022-06-24 | 华东理工大学 | Rosin amine polyoxyethylene ether and preparation method and application thereof |
| CN119145229A (en) * | 2024-11-20 | 2024-12-17 | 淄博云川化工有限公司 | Refining agent for improving permeability and emulsifying property and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106317401A (en) * | 2016-08-19 | 2017-01-11 | 浙江皇马科技股份有限公司 | Synthetic method of low color value polyether |
| CN111171306A (en) * | 2020-02-29 | 2020-05-19 | 江苏斯德瑞克化工有限公司 | Preparation method of gemini block polyether |
| CN114106277A (en) * | 2021-11-30 | 2022-03-01 | 北京东方华盛科技有限公司 | Preparation method of C polyoxyethylene rosin amine |
| CN114656627A (en) * | 2022-03-11 | 2022-06-24 | 华东理工大学 | Rosin amine polyoxyethylene ether and preparation method and application thereof |
| CN119145229A (en) * | 2024-11-20 | 2024-12-17 | 淄博云川化工有限公司 | Refining agent for improving permeability and emulsifying property and preparation method thereof |
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