CN109265671A - A kind of green synthesis process of novel polyamines polyene polyethers and its application - Google Patents
A kind of green synthesis process of novel polyamines polyene polyethers and its application Download PDFInfo
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- CN109265671A CN109265671A CN201810962155.1A CN201810962155A CN109265671A CN 109265671 A CN109265671 A CN 109265671A CN 201810962155 A CN201810962155 A CN 201810962155A CN 109265671 A CN109265671 A CN 109265671A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
- C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
- C08G65/2624—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aliphatic amine groups
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
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Abstract
The invention discloses a kind of green synthesis process of novel polyamines polyene polyethers and its applications, polyamines polyene and ethylene oxide/propylene oxide synthetic method are made using acidic catalyst, specifically: polyamines polyene and acidic catalyst are added in a high pressure reaction kettle, vacuumize and carry out nitrogen displacement, row pressure to 0~30KPa；It is subsequently passed ethylene oxide and/or propylene oxide, control reaction temperature is 20~120 DEG C and reaction pressure is 0.3MPa~0.5MPa；Post-processing aging is carried out to product polyamines polyene polyethers after the reaction was completed, until reactor pressure no longer declines, shows to complete slaking reaction to maintain temperature of reaction kettle to be 120 DEG C ± 3 DEG C, finally cools down, neutralized with glacial acetic acid and take off low boiling.Have the effect that solution dispersibility is good as nickel ion compounding agent using such novel polyamines polyene polyethers, coating alloy ingredient is uniform in wider current density range, and thickness of coating is uniform, small to equipment and workpiece corrosion, process stabilizing, easy to operate, lower-cost electroplating technology.
Description
Technical field
The present invention relates to the greens of admiro complexing agent technical field more particularly to a kind of novel polyamines polyene polyethers to close
At technique and its application.
Background technique
Zn-ni alloy deposits refer to the alloy layer containing a small amount of nickel (run-of-the-mill score is 5~20%).Admiro
Coating has corrosion resistance more better than pure zinc coating, binding force and solderability, and corrosion resistance and wearability are the 3 of common zinc coat
~6 times, especially there are excellent etch resistant properties in severe industrial atmosphere and harsh marine environment.Therefore, zinc-nickel closes
Gold process has become a hot topic of research already, is one of plating with the fastest developing speed nearly ten years, and oneself is in automobile parts, coal mine
The industries such as machinery, ship hydraulic engineering are used widely.Zn-ni Alloy Plating has acid and alkaline two kinds of systems.Alkalinity
System is due to having many advantages, such as that dispersibility is good, covering power is strong, can continue to use alkaline zinc plating equipment, oneself causes both at home and abroad in recent years
Concern.
And the cyanide being widely used as complexing agent mode there are problems such as: toxicity is big, tight to water pollution
Weight, waste water are difficult to handle etc., as environmental protection concept deepens continuously the popular feeling, using cyanide as the side of coordination galvanization additive
Formula large area is eliminated, but non-cyanide alkali zinc-nickel additive dispersibility in alkaline process is poor, in wider current density model
Interior coating alloy uneven components are enclosed, thickness of coating missing is big to equipment and workpiece corrosion, and process for stabilizing needs are matched according to various
The disadvantages of side constantly adjustment etc..
Non-cyanide alkali zinc-nickel additive-polyamines polyene polyethers of the present invention is not (identical herein to apply in alkaline item
Part, catalyst are that synthetic additive is used, and dosage is few without influencing) in an aqueous medium reaction synthesis nickel ion mixture can promote nickel
Complex, which is dissolved into alkaline bath, to be guaranteed to implement to be electroplated according to electroplating technology requirement in certain temperature range.
Chinese invention patent (application number: 200810120050.8, the applying date: 2008-07-16) discloses a kind of low nickel and contains
The electroplating technology of the non-cyanide alkali admiro of amount, using molar ratio is the diethylenetriamine of 1:1 and epoxychloropropane in 60
Under the conditions of~70 DEG C, nickel complexing agent is synthesized with reacting in hydrolyte.Its epoxychloropropane method used exists containing halogen, miscellaneous
The disadvantages such as matter content is higher, and product purity is low, structure also with we disclosed in polyamines polyene polyethers have differences.
Chinese invention patent (application number: 200610081018.4, the applying date: 2006-05-19) disclose a kind of nickel cobalt phosphorus
Electroplating composition, electroplate liquid and using the electroplate liquid electro-plating method, wherein the misfit agent used be selected from triethylene tetramine,
Diethylenetriamine, ethylenediamine, hydrogen azobenzene or these combination.Illustrate that polyamines polyene substance can be very good to apply in nickel
In cobalt-phosphor electroplating, but it is not directed to polyamines polyene class polyethers.
Chinese invention patent (application number: 201210194776.2, the applying date: 2012-06-13) disclose a kind of no cyanogen leaching
Zinc solution and the filter aluminum alloy cyanide-free electro-plating method for using the solution.Wherein also mention auxiliary complex-former be monoethanolamine,
Diethanol amine, triethanolamine, ethylenediamine tetra-acetic acid, disodium edta, ethylene diamine tetraacetic acid sylvite, tetraethylenepentamine,
One of nitrilotriacetic acid or boric acid or at least two.Illustrate that tetraethylenepentamine also has application in zinc-plated field, but does not refer to zinc
Plating application in terms of nickel alloy.
Compared to patent mentioned above, the problem of high-purity and green syt, many offices are faced with using traditional handicraft
It is sex-limited.Complexing agent generally carries out plating application just for a kind of in nickel or zinc simultaneously.
Summary of the invention
Based on the above the deficiencies in the prior art, technical problem solved by the invention is to provide a kind of novel polyamines polyene
The green synthesis process of polyethers and its application, the technique are small to equipment and workpiece corrosion, process stabilizing, easy to operate, cost compared with
It is low；Prepared novel polyamines polyene polyethers has the effect that solution dispersibility is good as nickel ion compounding agent, wider
Current density range in coating alloy ingredient it is uniform, thickness of coating is uniform；Zine plate can be used or nickel plate makees anode, there is technique
Stablize, the advantages that dispersibility is good, high temperature resistant, coating nickel content are stablized, Zinc-nickel alloy electroplating system can be widely used in.
In order to solve the above technical problem, the present invention provides a kind of green synthesis process of novel polyamines polyene polyethers:
Polyamines polyene and acidic catalyst are added in autoclave, vacuumizes and carry out nitrogen displacement, row pressure to 0~30KPa；Then
It is passed through ethylene oxide and/or propylene oxide, controls reaction temperature and pressure；Product polyamines polyene polyethers is carried out after the reaction was completed
Aging is post-processed, until reactor pressure no longer declines, shows to complete slaking reaction；Finally cool down, neutralized with glacial acetic acid and takes off
Low boiling.
As a preferred embodiment of the above technical solution, the green synthesis process of novel polyamines polyene polyethers provided by the invention is into one
Step includes some or all of following technical characteristic:
As an improvement of the above technical solution, the acidic catalyst includes one of acetic acid, propionic acid, phosphoric acid, sulfuric acid
Or it is a variety of.
As an improvement of the above technical solution, the polyamines polyene includes diethylenetriamine, triethylene tetramine, four ethylene five
One or more of amine, pentaethylene hexamine.
As an improvement of the above technical solution, the additive amount of the acidic catalyst is the 0.05~2% of theoretical load
Between.
As an improvement of the above technical solution, be added control reaction temperature after ethylene oxide and/or propylene oxide be 20~
120 DEG C, reaction pressure is 0.3~0.5MPa.
As an improvement of the above technical solution, it is 117~123 DEG C that temperature of reaction kettle is maintained when product aging.
As an improvement of the above technical solution, the polyamines polyene polyethers ethylene oxide and/or propylene oxide react
Polymerization scope is 1~30.
As an improvement of the above technical solution, the reaction process carries out under high pure nitrogen protection, nitrogen in reaction kettle
Purity >=99.99%, it is ensured that amidine functional group is not influenced by oxygen and the phenomenon that oxidation deepens occurs.
As an improvement of the above technical solution, the novel polyamines polyene polyethers is in non-cyanide alkali Zn-ni Alloy Plating
In be used as admiro complexing agent.
Compared with prior art, technical solution of the present invention has the following beneficial effects:
First technical problem to be solved by this invention is to probe into different types of polyamines polyene polyethers to Alkaline Zinc
The influence of Nickel alloy electroplating performance.
Second technical problem to be solved by this invention is the provision of a kind of synthesis work of new polyamines polyene polyethers
Skill, the narrow ditribution characteristic for improving product keep properties of product more excellent.
Third technical problem to be solved by this invention is to provide a kind of polyamines polyene polyethers in alkaline zinc-nickel alloy
Application method in formula.
First technical problem of the invention is realized by the following technical solutions:
There is also apparent difference, the present invention also puts up with not of the same race for influence due to different types of polyamines polyene to plating
The polyamines polyenes substance such as polyamines polyene of class such as diethylenetriamine, triethylene tetramine, tetraethylenepentamine, pentaethylene hexamine, into
Row analysis, searches out suitable polyamines polyene.
Second technical problem of the invention is realized by the following technical solutions:
Since there are a large amount of wastes (salt) to make color burn for conventional epoxy chloropropane technique, and use traditional tertiary amines
The lower catalyst of catalyst space steric hindrance, catalytic activity is relatively low, and generally requires 100 DEG C or more of hot conditions ability
It catalyzes and synthesizes well, is unfavorable for the narrow ditribution of ethylene oxide under these conditions.And green synthesis process of the present invention
The mode of original epoxychloropropane process requirement distilation can be substituted, thus it is more environmentally-friendly.
Third technical problem of the invention is realized by the following technical solutions:
Application method of the polyamines polyene polyethers in alkaline zinc-nickel alloy formula is constantly subjected to the limit of raw material (polyamines polyene)
System.Because can not meet the needs of admiro well without improved polyamines polyene, be easy to burn there is high area,
The disadvantages of dispersibility is poor, the area covering power Cha Di is without coating, can not meet plating demand well, using polyamines polyene with
The synthesis of epoxy second (third) alkane can be very good to solve electroplating effect by changing epoxy second/propane adduct number.In addition, plating
Formula can also generate certain influence to electroplating effect, and the present invention will also optimize electroplating formula, and it is suitable to search out
Electroplating schemes.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And it can be implemented in accordance with the contents of the specification, and in order to allow above and other objects, features and advantages of the invention can
It is clearer and more comprehensible, below in conjunction with preferred embodiment, detailed description are as follows.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, the attached drawing to embodiment is simply situated between below
It continues.
Fig. 1 be it is bright, half bright, dark-coloured, without coating schematic diagram；
Fig. 2 is the coating schematic diagram using polyamines polyene polyethers prepared by embodiment 1；
Fig. 3 is the coating schematic diagram using polyamines polyene polyethers prepared by embodiment 2；
Fig. 4 is the coating schematic diagram using polyamines polyene polyethers prepared by embodiment 3；
Fig. 5 is the coating schematic diagram using polyamines polyene polyethers prepared by embodiment 4；
Fig. 6 is the coating schematic diagram using polyamines polyene polyethers prepared by embodiment 5；
Fig. 7 is the coating schematic diagram using polyamines polyene polyethers prepared by embodiment 6；
Fig. 8 is the coating schematic diagram using polyamines polyene polyethers prepared by embodiment 7；
Fig. 9 is the coating schematic diagram using polyamines polyene polyethers prepared by embodiment 8；
Figure 10 is the true plating piece figure of coating schematic diagram shown in Fig. 7.
Specific embodiment
The following detailed description of a specific embodiment of the invention, as part of this specification, by embodiment come
Illustrate that the principle of the present invention, other aspects of the present invention, feature and its advantage will become apparent by the detailed description.
Embodiment 1
The diethylenetriamine of 1mol, 3 ‰ acidic catalyst are added in autoclave of the lL with stirring, to reaction kettle into
Row airtight test carries out nitrogen displacement to it under the conditions of 50 DEG C after there is not pressure phenomenon in reaction kettle 1h and takes out true
Do-nothing operation, it is ensured that the pumpdown time be greater than 30min, high pure nitrogen replacement operator 5 times, nitrogen gas purity >=99.99%, row pressure to 0
Then~30KPa is passed through ethylene oxide into reaction kettle, control reaction temperature is 20~120 DEG C and reaction pressure is 0.3MPa
~0.5MPa carries out post-processing aging to product until the total amount for being passed through ethylene oxide stops being passed through ethylene oxide when being 1mol
Maintaining temperature of reaction kettle is 120 DEG C ± 3 DEG C, until reactor pressure no longer declines, shows to complete slaking reaction.60 DEG C are down to,
It is neutralized with glacial acetic acid and takes off low boiling.
Embodiment 2
The triethylene tetramine of 1mol, 3 ‰ acidic catalyst are added in autoclave of the lL with stirring, to reaction kettle into
Row airtight test carries out nitrogen displacement to it under the conditions of 50 DEG C after there is not pressure phenomenon in reaction kettle 1h and takes out true
Do-nothing operation, it is ensured that the pumpdown time be greater than 30min, high pure nitrogen replacement operator 5 times, nitrogen gas purity >=99.99%, row pressure to 0
Then~30KPa is passed through ethylene oxide into reaction kettle, control reaction temperature is 20~120 DEG C and reaction pressure is 0.3MPa
~0.5MPa carries out post-processing aging to product until the total amount for being passed through ethylene oxide stops being passed through ethylene oxide when being 1mol
Maintaining temperature of reaction kettle is 120 DEG C ± 3 DEG C, until reactor pressure no longer declines, shows to complete slaking reaction.60 DEG C are down to,
It is neutralized with glacial acetic acid and takes off low boiling.
Embodiment 3
The tetraethylenepentamine of 1mol, 3 ‰ acidic catalyst are added in autoclave of the lL with stirring, to reaction kettle into
Row airtight test carries out nitrogen displacement to it under the conditions of 50 DEG C after there is not pressure phenomenon in reaction kettle 1h and takes out true
Do-nothing operation, it is ensured that the pumpdown time be greater than 30min, high pure nitrogen replacement operator 5 times, nitrogen gas purity >=99.99%, row pressure to 0
Then~30KPa is passed through ethylene oxide into reaction kettle, control reaction temperature is 20~120 DEG C and reaction pressure is 0.3MPa
~0.5MPa carries out post-processing aging to product until the total amount for being passed through ethylene oxide stops being passed through ethylene oxide when being 1mol
Maintaining temperature of reaction kettle is 120 DEG C ± 3 DEG C, until reactor pressure no longer declines, shows to complete slaking reaction.60 DEG C are down to,
It is neutralized with glacial acetic acid and takes off low boiling.
Embodiment 4
The tetraethylenepentamine of 1mol, 3 ‰ acidic catalyst are added in autoclave of the lL with stirring, to reaction kettle into
Row airtight test carries out nitrogen displacement to it under the conditions of 50 DEG C after there is not pressure phenomenon in reaction kettle 1h and takes out true
Do-nothing operation, it is ensured that the pumpdown time be greater than 30min, high pure nitrogen replacement operator 5 times, nitrogen gas purity >=99.99%, row pressure to 0
~30KPa, is then passed through ethylene oxide into reaction kettle, control reaction temperature be 20~50 DEG C and reaction pressure be 0.3MPa~
0.5MPa carries out post-processing aging dimension to product until the total amount for being passed through ethylene oxide stops being passed through ethylene oxide when being 2mol
Holding temperature of reaction kettle is 120 DEG C ± 3 DEG C, until reactor pressure no longer declines, shows to complete slaking reaction.60 DEG C are down to, is used
Glacial acetic acid neutralizes and takes off low boiling.
Embodiment 5
The diethylenetriamine of 1mol, 3 ‰ acidic catalyst are added in autoclave of the lL with stirring, to reaction kettle into
Row airtight test carries out nitrogen displacement to it under the conditions of 50 DEG C after there is not pressure phenomenon in reaction kettle 1h and takes out true
Do-nothing operation, it is ensured that the pumpdown time be greater than 30min, high pure nitrogen replacement operator 5 times, nitrogen gas purity >=99.99%, row pressure to 0
~30KPa, is then passed through ethylene oxide into reaction kettle, control reaction temperature be 50~70 DEG C and reaction pressure be 0.3MPa~
0.5MPa carries out post-processing aging dimension to product until the total amount for being passed through ethylene oxide stops being passed through ethylene oxide when being 3mol
Holding temperature of reaction kettle is 120 DEG C ± 3 DEG C, until reactor pressure no longer declines, shows to complete slaking reaction.60 DEG C are down to, is used
Glacial acetic acid neutralizes and takes off low boiling.
Embodiment 6
The diethylenetriamine of 1mol, 3 ‰ acidic catalyst are added in autoclave of the lL with stirring, to reaction kettle into
Row airtight test carries out nitrogen displacement to it under the conditions of 50 DEG C after there is not pressure phenomenon in reaction kettle 1h and takes out true
Do-nothing operation, it is ensured that the pumpdown time be greater than 30min, high pure nitrogen replacement operator 5 times, nitrogen gas purity >=99.99%, row pressure to 0
~30KPa, is then passed through ethylene oxide into reaction kettle, control reaction temperature be 70~90 DEG C and reaction pressure be 0.3MPa~
0.5MPa carries out post-processing aging dimension to product until the total amount for being passed through ethylene oxide stops being passed through ethylene oxide when being 4mol
Holding temperature of reaction kettle is 120 DEG C ± 3 DEG C, until reactor pressure no longer declines, shows to complete slaking reaction.60 DEG C are down to, is used
Glacial acetic acid neutralizes and takes off low boiling.
Embodiment 7
The diethylenetriamine of 1mol, 3 ‰ acidic catalyst are added in autoclave of the lL with stirring, to reaction kettle into
Row airtight test carries out nitrogen displacement to it under the conditions of 50 DEG C after there is not pressure phenomenon in reaction kettle 1h and takes out true
Do-nothing operation, it is ensured that the pumpdown time be greater than 30min, high pure nitrogen replacement operator 5 times, nitrogen gas purity >=99.99%, row pressure to 0
Then~30KPa is passed through ethylene oxide into reaction kettle, control reaction temperature is 90~120 DEG C and reaction pressure is 0.3MPa
~0.5MPa carries out post-processing aging to product until the total amount for being passed through ethylene oxide stops being passed through ethylene oxide when being 5mol
Maintaining temperature of reaction kettle is 120 DEG C ± 3 DEG C, until reactor pressure no longer declines, shows to complete slaking reaction.60 DEG C are down to,
It is neutralized with glacial acetic acid and takes off low boiling.
Embodiment 8
The diethylenetriamine of 1mol, 3 ‰ acidic catalyst are added in autoclave of the lL with stirring, to reaction kettle into
Row airtight test carries out nitrogen displacement to it under the conditions of 50 DEG C after there is not pressure phenomenon in reaction kettle 1h and takes out true
Do-nothing operation, it is ensured that the pumpdown time be greater than 30min, high pure nitrogen replacement operator 5 times, nitrogen gas purity >=99.99%, row pressure to 0
~30KPa, is then passed through ethylene oxide and propylene oxide into reaction kettle, and control reaction temperature is 90~120 DEG C and reaction pressure
Power is 0.3MPa~0.5MPa, until stopping when being passed through 1mol ethylene oxide, 4mol propylene oxide, post-process to product old
Changing maintenance temperature of reaction kettle is 120 DEG C ± 3 DEG C, until reactor pressure no longer declines, shows to complete slaking reaction.It is down to 60
DEG C, it is neutralized with glacial acetic acid and takes off low boiling.
Polyamines polyene polyethers prepared by above-described embodiment 1-8 is respectively applied to non-cyanide alkali Zn-ni Alloy Plating
In complexing agent, specific as follows: in zinc oxide 10g/L, sodium hydroxide 120g/L, the basal liquid of five water nickel sulfate 10g/L is added
Independently developed adjuvant 8ml/L, brightener 5ml/L, polyamines polyene polyethers 50g/L, at 22~28 DEG C of temperature, cathode current is close
Spend 3~5A/dm2Under the conditions of be electroplated, gained coating is as shown in figs. 2-9.
It is taken pictures due to the particularity of plating piece and can not show bright, half light, dead color well, without the area between coating
, will not stated diagrammatically behind, as shown in Figure 1, in Fig. 1 A, B, C, D respectively indicate it is bright, half bright, dark-coloured,
Without coating.In order to avoid error plating piece result takes the average value of four plating pieces, the meeting with larger difference plates piece again and makes even again
Mean value keeps the accuracy of result.
Fig. 2 is the coating schematic diagram using polyamines polyene polyethers prepared by embodiment 1；
Fig. 3 is the coating schematic diagram using polyamines polyene polyethers prepared by embodiment 2, plates leaf length: 20cm, wherein
Dark-coloured 13cm, without coating 7cm；Fig. 4 is the coating schematic diagram using polyamines polyene polyethers prepared by embodiment 3, plates length of a film
Degree: 20cm, wherein light 5cm, partly light 9cm, without coating 6cm；Fig. 5 is poly- using polyamines polyene prepared by embodiment 4
The coating schematic diagram of ether, plate leaf length: 20cm, wherein light 10cm, dead color 7cm, without coating 3cm；Fig. 6 is using embodiment
The coating schematic diagram of polyamines polyene polyethers prepared by 5 plates leaf length: 20cm, wherein light 10cm, dead color 10cm；Fig. 7 is to adopt
The coating schematic diagram of the polyamines polyene polyethers prepared by embodiment 6 plates leaf length: 20cm, wherein light 15cm, dead color
3cm, half light 2cm；Fig. 8 is the coating schematic diagram using polyamines polyene polyethers prepared by embodiment 7, plates leaf length:
20cm, wherein dead color 8cm, light 6cm, dead color 6cm；Fig. 9 is the coating using polyamines polyene polyethers prepared by embodiment 8
Schematic diagram plates leaf length: 20cm, wherein dead color 7cm, light 8cm, dead color 5cm.To sum up, electroplating effect is excellent, gained coating face
Color is shallow.It can be seen that the effect of coating shown in Fig. 7 is that effect is best in the above several groups of embodiments, it is true to plate piece situation such as Figure 10
It is shown.
The bound of each raw material cited by the present invention and each raw material of the present invention, section value and technological parameter
Bound, the section value of (such as temperature, time) can realize the present invention, embodiment numerous to list herein.
The above is a preferred embodiment of the present invention, cannot limit the right model of the present invention with this certainly
It encloses, it is noted that for those skilled in the art, without departing from the principle of the present invention, may be used also
To make several improvement and variation, these, which improve and change, is also considered as protection scope of the present invention.
Claims (9)
1. a kind of green synthesis process of novel polyamines polyene polyethers, it is characterised in that: it is more that polyenoid is added in a high pressure reaction kettle
Amine and acidic catalyst vacuumize and carry out nitrogen displacement, row pressure to 0~30KPa；It is subsequently passed ethylene oxide and/or epoxy
Propane controls reaction temperature and pressure；Post-processing aging is carried out to product polyamines polyene polyethers after the reaction was completed, until reaction kettle
Pressure no longer declines, and shows to complete slaking reaction；Finally cool down, neutralized with glacial acetic acid and takes off low boiling.
2. the green synthesis process of novel polyamines polyene polyethers as described in claim 1, it is characterised in that: the acidic catalyst
Agent includes one of acetic acid, propionic acid, phosphoric acid, sulfuric acid or a variety of.
3. the green synthesis process of novel polyamines polyene polyethers as described in claim 1, it is characterised in that: the polyamines polyene
Including one or more of diethylenetriamine, triethylene tetramine, tetraethylenepentamine, pentaethylene hexamine.
4. the green synthesis process of novel polyamines polyene polyethers as described in claim 1, it is characterised in that: the acidic catalyst
The additive amount of agent is the 0.05~2% of theoretical load.
5. the green synthesis process of novel polyamines polyene polyethers as described in claim 1, it is characterised in that: ethylene oxide is added
And/or it is 20~120 DEG C that reaction temperature is controlled after propylene oxide, reaction pressure is 0.3~0.5MPa.
6. the green synthesis process of novel polyamines polyene polyethers as described in claim 1, it is characterised in that: tieed up when product aging
Holding temperature of reaction kettle is 117~123 DEG C.
7. the green synthesis process of novel polyamines polyene polyethers as described in claim 1, it is characterised in that: the polyamines polyene
Polyethers ethylene oxide and/or the polymerization scope of propylene oxide reaction are 1~30.
8. the green synthesis process of novel polyamines polyene polyethers as described in claim 1, it is characterised in that: the reaction process
It is carried out under high pure nitrogen protection, nitrogen gas purity >=99.99% in reaction kettle, it is ensured that amidine functional group is not influenced by oxygen
The phenomenon that now oxidation deepens.
9. the green synthesis process of novel polyamines polyene polyethers as described in claim 1, it is characterised in that: the novel polyenoid
Polyamines polyethers is used as admiro complexing agent in non-cyanide alkali Zn-ni Alloy Plating.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115433352A (en) * | 2022-09-20 | 2022-12-06 | 胜利油田胜利化工有限责任公司 | Modified polyamine demulsifier and preparation method and application thereof |
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| CN101074483A (en) * | 2006-05-19 | 2007-11-21 | 何靖 | Nickel-cobalt-phosphor electroplating composition, electroplating liquid and electroplating method therewith |
| CN101298689A (en) * | 2008-06-11 | 2008-11-05 | 江门市瑞期精细化学工程有限公司 | Non-cyanogen plate silver plating solution |
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| CN101314861A (en) * | 2008-07-16 | 2008-12-03 | 杭州东方表面技术有限公司 | Plating process for low-nickel non-cyanogen alkalescent zinc-nickel alloy |
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| CN115433352A (en) * | 2022-09-20 | 2022-12-06 | 胜利油田胜利化工有限责任公司 | Modified polyamine demulsifier and preparation method and application thereof |
| CN115433352B (en) * | 2022-09-20 | 2023-06-23 | 胜利油田胜利化工有限责任公司 | Modified polyamine demulsifier and preparation method and application thereof |
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