CN104250375B - 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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- CN104250375B CN104250375B CN201410488600.7A CN201410488600A CN104250375B CN 104250375 B CN104250375 B CN 104250375B CN 201410488600 A CN201410488600 A CN 201410488600A CN 104250375 B CN104250375 B CN 104250375B
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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, in disproportionated rosin amine molecule
Poly(propylene oxide) chain group is introduced, it is more nearly natural resin, more environmental protection in segment.
Background technology
In Current surface activating agent, there is lack of raw materials, rise in price, and environmental requirement tends to strict, and conventional surfactant closes
One-tenth method cannot meet environmental protection and the demand of cost；In addition, when rosin amine and oxirane carry out polyreaction, to reaction condition
Requirement harsher, its reaction condition, reaction environment are extremely important.Otherwise, contain unreacted rosin amine in product
With by-product Polyethylene Glycol.It is muddy that this unreacted rosin amine can make the aqueous solution of dilution produce, and can irritate skin, to product
Product application is unfavorable.
Content of the invention
Object of the present invention is to provide a kind of preparation method of disproportionated rosin amine polyoxyethylene poly-oxygen propylene aether, this
The bright needs that there is simple for process, environmental protection, chemical fibre job applications can be met.
For reaching above-mentioned purpose, the technical scheme is that：
A kind of preparation method of disproportionated rosin amine polyoxyethylene poly-oxygen propylene aether, comprises the steps：1）With disproportionated rosin
Amine is initiator, carries out polyreaction with oxirane, obtain dihydroxy ethyl disproportionated rosin amine under self-catalysis；2）Alkali is added to urge
Agent and expoxy propane, and continuously add oxirane, polymerization is obtained disproportionated rosin amine polyoxyethylene poly-oxygen propylene aether.
Further, as preferred：
Step 1）In, described disproportionated rosin amine（Guilin Song Quan woods chemical industry Co., Ltd, 90%Min, i.e. purity
90%）Mol ratio with oxirane is 1:2, reaction temperature is 90～150 DEG C, and the response time is 2～10 hours；
Step 2）In, described base catalyst adopts one or more of KOH, NaOH or Feldalat NM；Base catalyst
Addition be the 0.1～1.5% of disproportionated rosin amine and ethylene oxide propylene oxide gross mass, the oxirane adding again with
Expoxy propane, the interpolation of disproportionated rosin amine are than for 10～50:1；Reaction temperature is 90～150 DEG C, and the response time is little for 2～10
When.
A kind of disproportionated rosin amine polyoxyethylene poly-oxygen propylene aether being obtained using above-mentioned preparation method, its structure is：
.
Reaction equation is：
,
Wherein n+m=10-50.
The present invention carries out the synthesis of surfactant from this natural product of disproportionated rosin amine as initiation material, permissible
Reduce the dependence to oil and synthetic resin, product has preferable ecological performance, meets " the raw material of " green " surfactant
Greenization " requires；And rosin amine abundance, low price, China is rosin amine manufacturing country maximum in the world again, yield
Account for 1/3rd of Gross World Product, be a huge available natural regeneration resource.Make full use of this abundant regeneration
Property resource, increase economic efficiency, the species of abundant surfactant, promote rosin-based surfactant development, these all have
Significant.
Specific embodiment
Embodiment 1
The present embodiment adds 285.0g disproportionated rosin amine in 2.5L pressure reaction still, by oxirane measuring tank and pressure
Kettle connects.With nitrogen displacement air 3 times, treat that kettle temperature rises to 125～130 DEG C, keep system pressure 0.2～0.3MPa, start
It is passed through 88.0g oxirane, has led within 0.5 hour, continue reaction 1.0 hours, put into 4.0g KOH solid catalyst ,-
0.1MPa dehydrated under vacuum 1.0 hours, at 150～160 DEG C, keeps system pressure 0.2～0.3MPa, is passed through 132.0g epoxy second
Alkane, has led to after completion of the reaction for 3.5 hours, is cooled to 110 DEG C of pressure releases degassing, at 120～125 DEG C, keep system pressure 0.2～
0.3MPa, continues to be passed through expoxy propane 290.0g, has led within 5 hours after completion of the reaction, cooling, and release obtains brown color thick liquid.
It is raw material that the present embodiment adopts natural product disproportionated rosin amine, has simple for process, environmental protection, can meet chemical fibre work
The needs of application.
Embodiment 2
The present embodiment adds 310.0g disproportionated rosin amine in 2.5L pressure reaction still, by oxirane measuring tank and pressure
Kettle connects.With nitrogen displacement air 3 times, treat that kettle temperature rises to 125～130 DEG C, keep system pressure 0.2～0.3MPa, start
It is passed through 95.0g oxirane, has led within 0.5 hour, continue reaction 1.0 hours, put into 14.3g Feldalat NM solid catalyst ,-
Separating methanol 1.0 hours under 0.1MPa vacuum, at 150～160 DEG C, keep system pressure 0.2～0.3MPa, are passed through 142.0g epoxy
Ethane, has led to after completion of the reaction for 3.5 hours, is cooled to 110 DEG C of pressure releases degassing, at 120～125 DEG C, keep system pressure 0.2～
0.3MPa, continues to be passed through expoxy propane 1250.0g, has led within 10 hours after completion of the reaction, cooling, and release obtains brown color viscous solution
Body.It is raw material that the present embodiment adopts natural product disproportionated rosin amine, has simple for process, environmental protection, can meet chemical fibre
The needs of job applications.
Embodiment 3
The present embodiment adds 280.0g disproportionated rosin amine in 2.5L pressure reaction still, by oxirane measuring tank and pressure
Kettle connects.With nitrogen displacement air 3 times, treat that kettle temperature rises to 125～130 DEG C, keep system pressure 0.2～0.3MPa, start
It is passed through 87.0g oxirane, has led within 0.5 hour, continue reaction 1.0 hours, put into 24.8g NaOH solid catalyst ,-
0.1MPa dehydrated under vacuum 1.0 hours, at 150～160 DEG C, keeps system pressure 0.2～0.3MPa, is passed through 1233.0g epoxy
Ethane, has led to after completion of the reaction for 8 hours, is cooled to 110 DEG C of pressure releases degassing, at 120～125 DEG C, keep system pressure 0.2～
0.3MPa, continues to be passed through expoxy propane 1160.0g, has led within 10 hours after completion of the reaction, cooling, and release obtains brown color viscous solution
Body.It is raw material that the present embodiment adopts natural product disproportionated rosin amine, has simple for process, environmental protection, can meet chemical fibre
The needs of job applications.
After tested, specific targets are such as disproportionated rosin amine polyoxyethylene poly-oxygen propylene aether prepared by the various embodiments described above 1-3
Shown in table 1.
The test result of each embodiment of table 1
In the present invention, by controlling the ratio of each reactant in preparation process, and it is aided with specific reaction condition, makes Colophonium
When amine and oxirane carry out polyreaction, it is maintained in good reaction atmosphere, thus, water in the final product obtaining
The by-products content that grades controls in relatively low scope, and unreacted rosin amine and by-product polyethyleneglycol content are less, it is to avoid
These residues are to the safety risks brought into using process；Meanwhile, different with mode according to the final purpose using, make pine
Fragrant amine and oxirane are reacted under different conditions, to obtain the disproportionated rosin amine polyoxyethylene of different molecular weight distribution
The molecular weight of polyethenoxy ether, such as embodiment 1 is relatively low, compound with other compositions use for environmental protection paint when, its viscosity is relatively low, adds
Dosage can suitably increase；And the molecular weight of embodiment 3 gained disproportionated rosin amine polyoxyethylene poly-oxygen propylene aether is higher, glue accordingly
Degree is also higher, and in compound process, addition just can control in less scope, with meet different environmental protection paints to viscosity,
The requirement that composition compounds, using more convenient.
Above content be with reference to the preferred embodiment of the present invention provided technical scheme is made further specifically
Bright it is impossible to assert that the present invention is embodied as being confined to these explanations above-mentioned, for the common skill of the technical field of the invention
For art personnel, without departing from the inventive concept of the premise, some simple deduction or replace can also be made, all should be considered as
Belong to protection scope of the present invention.
Claims (6)
1. a kind of preparation method of disproportionated rosin amine polyoxyethylene poly-oxygen propylene aether it is characterised in that：Pressure reaction still adds
Enter 285.0g disproportionated rosin amine, oxirane measuring tank is connected with autoclave pressure；Nitrogen displacement air 3 times, treats that kettle temperature rises to
125～130 DEG C, keep system pressure 0.2～0.3MPa, after being passed through 88.0g oxirane in 0.5 hour, continue reaction 1.0
Hour, put into 4.0g KOH solid catalyst, in -0.1MPa dehydrated under vacuum 1.0 hours, at 150～160 DEG C, keep system
Pressure 0.2～0.3MPa, is passed through 132.0g oxirane, has led to after completion of the reaction within 3.5 hours, is cooled to 110 DEG C of pressure release degassings,
At 120～125 DEG C, keep system pressure 0.2～0.3MPa, continue to be passed through expoxy propane 290.0g, led to reaction within 5 hours and finished
Afterwards, cool down, release, obtain brown color thick liquid and be finished product disproportionated rosin amine polyoxyethylene poly-oxygen propylene aether.
2. adopt the disproportionated rosin amine polyoxyethylene poly-oxygen propylene aether of claim 1 methods described preparation it is characterised in that described discrimination
Change Rosin Amine Polyoxyethylene Ether polyethenoxy ether structural formula be：
Wherein, n+m=10-50.
3. a kind of preparation method of disproportionated rosin polyoxyethylene poly-oxygen propylene aether it is characterised in that：Pressure reaction still adds
310.0g disproportionated rosin amine, oxirane measuring tank is connected with autoclave pressure；With nitrogen displacement air 3 times, treat that kettle temperature rises to
125～130 DEG C, keep system pressure 0.2～0.3MPa, after being passed through 95.0g oxirane in 0.5 hour, continue reaction 1.0 little
When, input 14.3g Feldalat NM solid catalyst, separating methanol 1.0 hours under -0.1MPa vacuum, at 150～160 DEG C, keeping body
It is pressure 0.2～0.3MPa, is passed through 142.0g oxirane, led to after completion of the reaction within 3.5 hours, be cooled to 110 DEG C of pressure releases and take off
Gas, at 120～125 DEG C, keeps system pressure 0.2～0.3MPa, continues to be passed through expoxy propane 1250.0g, has led within 10 hours anti-
After should finishing, cooling, release, obtain brown color thick liquid and be finished product disproportionated rosin amine polyoxyethylene poly-oxygen propylene aether.
4. adopt the disproportionated rosin amine polyoxyethylene poly-oxygen propylene aether of claim 3 methods described preparation it is characterised in that described discrimination
Change Rosin Amine Polyoxyethylene Ether polyethenoxy ether structural formula be：
Wherein, n+m=10-50.
5. a kind of preparation method of disproportionated rosin polyoxyethylene poly-oxygen propylene aether it is characterised in that：Pressure reaction still adds
280.0g disproportionated rosin amine, oxirane measuring tank is connected with autoclave pressure；With nitrogen displacement air 3 times, treat that kettle temperature rises to
125～130 DEG C, keep system pressure 0.2～0.3MPa, after being passed through 87.0g oxirane in 0.5 hour, continue reaction 1.0 little
When, put into 24.8g NaOH solid catalyst, in -0.1MPa dehydrated under vacuum 1.0 hours, at 150～160 DEG C, keep system
Pressure 0.2～0.3MPa, is passed through 1233.0g oxirane, has led to after completion of the reaction within 8 hours, is cooled to 110 DEG C of pressure release degassings,
At 120～125 DEG C, keep system pressure 0.2～0.3MPa, continue to be passed through expoxy propane 1160.0g, led within 10 hours and reacted
Bi Hou, cooling, release, obtain brown color thick liquid and be finished product disproportionated rosin amine polyoxyethylene poly-oxygen propylene aether.
6. adopt the disproportionated rosin amine polyoxyethylene poly-oxygen propylene aether of claim 5 methods described preparation it is characterised in that described discrimination
Change Rosin Amine Polyoxyethylene Ether polyethenoxy ether structural formula be：
Wherein, n+m=10-50.
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| 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 |
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