CN106188564A - A kind of lipophilic polymer synthetic method of spontaneous recovery under water - Google Patents
A kind of lipophilic polymer synthetic method of spontaneous recovery under water Download PDFInfo
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- CN106188564A CN106188564A CN201610619731.3A CN201610619731A CN106188564A CN 106188564 A CN106188564 A CN 106188564A CN 201610619731 A CN201610619731 A CN 201610619731A CN 106188564 A CN106188564 A CN 106188564A
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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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
- C08G83/006—After treatment of hyperbranched macromolecules
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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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of can the lipophilic polymer synthetic method of spontaneous recovery under water, including synthesis of super branched polyester in polymeric solution；Hyper-branched polyester is dissolved in organic solvent solution, reacts after mixing；Add in alkaline solution and reaction, add in the organic solvent containing slaine, be simultaneously introduced alkaline solution to control the PH of solution；After reaction terminates, it is lyophilized in freeze dryer, takes out solid product and be called for short polymer first.This polymer has metallic ion coordination bond structure so that it is overcome the phenomenon of water shielding macromolecule interaction in the remodeling process of traditional polymer；Activate coordination structure in the basic conditions so that movably dissaving polymer network can be recombinated through crack interface；In the remodeling process of this new polymers, sea water becomes the necessary environment ensureing raw material effective interaction.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of can the lipophilic polymer synthesis side of spontaneous recovery under water
Method.
Background technology
Along with reliability in marine industry application process of expanding economy, polymer and polymer composites and resistance to
Requirement by property is more and more higher.But, so far, self-regeneration underwater for solid polymer lacks always rationally may be used
The scheme of row.Traditional method adding consolidant can be suppressed in water.And self-regeneration process is due to polymer often
It is lipophilic, has the participation of water can form certain interface in course of reaction and prevent diffusion and the collision of macromolecular chain.By
The Ha Meike constant (Van der Waals attraction energy) of Yu Shuizhong reduces, and the stop of water makes electrostatic interaction reduce, polymerization
Thing reparation in water is the most difficult, even if hydrogen bond is used for repairing impaired interface under conditions of acidity, research shows water
It is more prone to the surface with macromole hydrogen bond rupture and forms interaction.Therefore, lipophilic polymer solid under water is carried out
Self-healing property explorative research so that after polymer is destroyed in the seawater, active dissaving polymer network is at fracture location
Resetting, the research of lipophilic solid polymer self-regeneration in the seawater is that the technology that this area is thirsted for solving always is difficult
Topic.
Summary of the invention
The present invention is directed to above-mentioned problems of the prior art, it is provided that a kind of under there is no human intervention, it is possible to
The synthetic method of the lipophilic polymer of self-regeneration under water, solves polymer reparation in water in prior art the most tired
Difficult problem.
For achieving the above object, the method comprises the steps:
Step 1,5～30g mono-aggressiveness A are dissolved in 10～30g organic solvents solution A；1～5g mono-aggressiveness B is dissolved in 10～30g
Organic solvent obtains solution B；Under the conditions of 30～60 DEG C, in dropping 0.2～2 mL catalyst to the mixed liquor of solution A and B, dry
Above-mentioned solution A and solution B are stirred prepolymerization 5 down～10 hours, synthesis of super branched polyester in polymeric solution by dry nitrogen；
Step 2, under the conditions of 10～80 DEG C, the hyper-branched polyester 0.1～1.0g in step 1 polymeric solution is dissolved in 1～5g organic
In solvent solution, stir 1～5 hour, obtain solution C；0.1～1.0g mono-aggressiveness C is dissolved in 1～5g organic solvent, obtains solution
D, after reacting 1～5 hour after solution C and solution D being mixed, temperature is down to 10～20 DEG C, obtains solution E；
Step 3,0.1～2.0g mono-aggressiveness D is dissolved in 10～60g organic solvents, after mixing with step 2 gained solution E, dropwise adds
Enter in alkaline solution and the hydrochloric acid of excess is neutrality to solution, continue reaction 10～20 hours, obtain solution F；
Step 4, above-mentioned solution F add in the organic solvent 5～50mL containing 0.1～1.0g slaine, is simultaneously introduced alkalescence
Solution controls the PH ≈ 8～9 of solution；After reaction terminates, it is lyophilized in freeze dryer, takes out solid product and be called for short polymer
First.
In described step 1, single aggressiveness A be the one in polyethylene, PolyTHF, polystyrene, polrvinyl chloride or
Two kinds.
In described step 1, single aggressiveness B is polyurethanes, isophorone diisocyanate, polyurethane, Carbimide.
One in ester.
In described step 1, catalyst is N, N dimethylaniline, dimethyl open-chain crown ether, di lauric dibutyl
One in stannum.
In described step 2, single aggressiveness C is trihydroxy methyl propanoic acid, dihydromethyl propionic acid, p-methyl benzenesulfonic acid, acrylic acid
One or both in hydroxyl ethyl ester.
In described step 3, single aggressiveness D is catechol ethamine, biatrate, dopamine hydrochloride, hydrochloric acid Proca
One in Yin.
In described step 3, alkaline solution is the one in dimethylformamide, triethylamine, diethylamine, acetonitrile.
In described step 4, slaine is the one in copper chloride, calcium chloride, iron chloride, Chlorizate chromium, calcium sulfate or two
Kind.
In described step 4, alkaline solution is the one in dimethylformamide, triethylamine, diethylamine, acetonitrile.
In described step 1-4, organic solvent is styrene, trichloro ethylene, dimethylformamide, toluene, ethyl acetate
In one or more.
The inventive method is in the building-up process of polymer, introduces metal complex (Cr6+、Cu2+、Fe3+、Ca2+In
One or both) form coordinate bond so that it is have the advantage that 1, overcome the remodeling process of traditional polymer in water
The phenomenon of shielding macromolecule interaction.2, activator metal coordination compound in the basic conditions so that moveable hyperbranched polymerization
Thing network can be recombinated through crack interface.In the remodeling process of this new polymers, sea water (synthetic) becomes
Ensure the necessary environment of raw material effective interaction.
When this polymer in sea water (synthetic) damaged, owing to active metal complex is at alkaline solution bar
It is activated under part, can again be bonded the position of damage so that movably dissaving polymer network can connect through crack
Mouth is recombinated.Utilize this mechanism, polymer can be reinvented with the help of sea water, complete oneself's healing in sea water.
Detailed description of the invention
Embodiment one: film sample is tested.
1. the mixture of 5g polyethylene, PolyTHF is dissolved in 12.5g dimethylformamide.Isocyanates 2 .5g
It is dissolved in 10g dimethylformamide.Under the conditions of 60 DEG C, with 3 dibutyl tin laurates for catalyst in dry nitrogen
By prepolymerization 6 hours, synthesis of super branched polyester under above two solution stirring.
2. under the conditions of 60 DEG C, being dissolved in 5g dimethylformamide by hyper-branched polyester 0.5g in polymeric solution, stirring 3 is little
Time.The mixture of 0.5g dihydromethyl propionic acid, 2-(Acryloyloxy)ethanol is dissolved in 3g dimethylformamide, after two kinds of solution mixing
After reacting 2 hours, temperature is down to 20 DEG C.
3. during 1.0g dopamine hydrochloride is dissolved in 25.5g dimethylformamide, with step 2. in after solution mixes, be added dropwise over
Have in triethylamine and the hydrochloric acid of excess, continue reaction 10 hours.
The most above-mentioned solution adds in the dimethylformamide containing 0.5g Chlorizate chromium, is simultaneously introduced triethylamine molten to control
The PH ≈ 8～9 of liquid.Reaction terminate after, after be lyophilized in freeze dryer, take out solid produce polymer first.
5. prepare polymer first film sample, shred inner at artificial seawater (PH=7.5～9.0), control temperature 25 DEG C, 24
After hour, result shows that wound can be healed, and reference polymer second wound cannot heal.
Embodiment two: dumb-bell shape sample is tested.
1. the mixture of 5g polyethylene, PolyTHF is dissolved in 12.5g dimethylformamide.Isocyanates 2 .5g
It is dissolved in 10g dimethylformamide.Under the conditions of 60 DEG C, with 3 dibutyl tin laurates for catalyst in dry nitrogen
By prepolymerization 6 hours, synthesis of super branched polyester under above two solution stirring.
2. under the conditions of 60 DEG C, being dissolved in 5g dimethylformamide by hyper-branched polyester 0.5g in polymeric solution, stirring 3 is little
Time.The mixture of 0.5g dihydromethyl propionic acid, 2-(Acryloyloxy)ethanol is dissolved in 3g dimethylformamide, after two kinds of solution mixing
After reacting 2 hours, temperature is down to 20 DEG C.
3. during 1.0g dopamine hydrochloride is dissolved in 25.5g dimethylformamide, with step 2. in after solution mixes, be added dropwise over
Have in triethylamine and the hydrochloric acid of excess, continue reaction 10 hours.
The most above-mentioned solution adds in the dimethylformamide containing 0.5g Chlorizate chromium, is simultaneously introduced triethylamine molten to control
The PH ≈ 8～9 of liquid.After reaction terminates, it is lyophilized in freeze dryer, takes out solid and produce polymer first, be prepared as dumbbell shape and gather
Compound.
Dumbbell shape polymer first sample being cut into two panels be clipped between two microscope slides, binder clip clips puts into 25 DEG C of servants
In the sea water (PH=7.5～9.0) of work synthesis 24 hours, tensile strength is then used to carry out the test of test effect.Result
Show that solid polymer first can degree of depth oneself heal in the seawater, and reference polymer second cannot complete self-regeneration.Proof is joined
Position key plays a major role.
Embodiment three: block sample is tested.
1. the mixture of 5g polyethylene, PolyTHF is dissolved in 12.5g dimethylformamide.Isocyanates 2 .5g
It is dissolved in 10g dimethylformamide.Under the conditions of 60 DEG C, with 3 dibutyl tin laurates for catalyst in dry nitrogen
By prepolymerization 6 hours, synthesis of super branched polyester under above two solution stirring.
2. under the conditions of 60 DEG C, in polymeric solution, hyper-branched polyester 0.5g is dissolved in 5g dimethylformamide, stirs 3
Hour.The mixture of 0.5g dihydromethyl propionic acid, 2-(Acryloyloxy)ethanol is dissolved in 3g dimethylformamide, two kinds of solution mixing
After rear reaction 2 hours, temperature is down to 20 DEG C.
3. during 1.0g dopamine hydrochloride is dissolved in 25.5g dimethylformamide, with step 2. in after solution mixes, be added dropwise over
Have in triethylamine and the hydrochloric acid of excess, continue reaction 10 hours.
The most above-mentioned solution adds in the dimethylformamide containing 0.5g Chlorizate chromium, is simultaneously introduced triethylamine and controls
The PH ≈ 8～9 of solution.Reaction terminate after, after be lyophilized in freeze dryer, take out solid produce polymer first, be prepared as bulk.
Bulk sample polymer first surface cutter is marked synthetic sea water (PH under the conditions of cross vestige is placed on 25 DEG C
=7.5～9.0) in, checking that sample, vestige substantially shoal, and check after 24 hours after 24 hours, vestige disappears substantially.Reference
Polymer second vestige is the most substantially, it is impossible to complete self-regeneration.
The preparation of reference polymer, uses and method similar to the above, is simply replaced with by list aggressiveness C in course of reaction
Similar to its type but do not comprise aromatic acid (p-methyl benzenesulfonic acid, amino acid phenylalanine, phthalic acid, the cheese of certain functional group
One in propylhomoserin).
Embodiment four
The inventive method comprises the steps:
Step 1, mono-for 5g aggressiveness A is dissolved in 10g organic solvent solution A；1g mono-aggressiveness B is dissolved in 10g organic solvent molten
Liquid B；Under the conditions of 30 DEG C, drip 0.2 mL catalyst in the mixed liquor of solution A and B, by above-mentioned solution A in dry nitrogen
Prepolymerization lower with solution B stirring 10 hours, synthesis of super branched polyester in polymeric solution；
Step 2, under the conditions of 10 DEG C, the hyper-branched polyester 0.1g in step 1 polymeric solution is dissolved in 1g organic solvent solution, stirs
Mix 1 hour, obtain solution C；Mono-for 0.1g aggressiveness C is dissolved in 1g organic solvent, obtains solution D, anti-after solution C and solution D are mixed
After answering 1 hour, temperature is down to 10 DEG C, obtains solution E；
Step 3,0.1g mono-aggressiveness D is dissolved in 10g organic solvent, after mixing with step 2 gained solution E, is added dropwise over alkalescence molten
In liquid, hydrochloric acid to the solution with excess is neutral, continues reaction 10 hours, obtains solution F；
Step 4, above-mentioned solution F add in the organic solvent 5mL containing 0.1g slaine, is simultaneously introduced alkaline solution and controls
The PH ≈ 8 of solution processed；After reaction terminates, it is lyophilized in freeze dryer, takes out solid product and be called for short polymer first.
In described step 1, single aggressiveness A is polyethylene；Single aggressiveness B is polyurethanes；Catalyst is N, N diformazan
Base aniline；In described step 2, single aggressiveness C is trihydroxy methyl propanoic acid；In described step 3, single aggressiveness D is catechol
Ethamine；Alkaline solution is dimethylformamide；In described step 4, slaine is copper chloride；Alkaline solution is dimethyl formyl
Amine；In described step 1-4, organic solvent is styrene.
Embodiment five
The inventive method comprises the steps:
Step 1, mono-for 30g aggressiveness A is dissolved in 30g organic solvent solution A；5g mono-aggressiveness B is dissolved in 30g organic solvent molten
Liquid B；Under the conditions of 60 DEG C, drip 2 mL catalyst in the mixed liquor of solution A and B, in dry nitrogen by above-mentioned solution A and
The lower prepolymerization of solution B stirring 5 hours, synthesis of super branched polyester in polymeric solution；
Step 2, under the conditions of 80 DEG C, the hyper-branched polyester 1.0g in step 1 polymeric solution is dissolved in 5g organic solvent solution, stirs
Mix 5 hours, obtain solution C；Mono-for 1.0g aggressiveness C is dissolved in 5g organic solvent, obtains solution D, anti-after solution C and solution D are mixed
After answering 5 hours, temperature is down to 20 DEG C, obtains solution E；
Step 3,2.0g mono-aggressiveness D is dissolved in 60g organic solvent, after mixing with step 2 gained solution E, is added dropwise over alkalescence molten
In liquid, hydrochloric acid to the solution with excess is neutral, continues reaction 20 hours, obtains solution F；
Step 4, above-mentioned solution F add in the organic solvent 50mL containing 1.0g slaine, is simultaneously introduced alkaline solution and controls
The PH ≈ 9 of solution processed；After reaction terminates, it is lyophilized in freeze dryer, takes out solid product and be called for short polymer first.
In described step 1, single aggressiveness A is PolyTHF；Single aggressiveness B is isophorone diisocyanate；Catalyst
For dimethyl open-chain crown ether；In described step 2, single aggressiveness C is dihydromethyl propionic acid；In described step 3, single aggressiveness D
For biatrate；Alkaline solution is triethylamine；In described step 4, slaine is calcium chloride；Alkaline solution is triethylamine；
In described step 1-4, organic solvent is dimethylformamide.
Claims (10)
1. the lipophilic polymer synthetic method of a spontaneous recovery under water, it is characterised in that comprise the steps:
Step 1,5～30g mono-aggressiveness A are dissolved in 10～30g organic solvents solution A；1～5g mono-aggressiveness B is dissolved in 10～30g
Organic solvent obtains solution B；Under the conditions of 30～60 DEG C, in dropping 0.2～2 mL catalyst to the mixed liquor of solution A and B, dry
Above-mentioned solution A and solution B are stirred prepolymerization 5 down～10 hours, synthesis of super branched polyester in polymeric solution by dry nitrogen；
Step 2, under the conditions of 10～80 DEG C, the hyper-branched polyester 0.1～1.0g in step 1 polymeric solution is dissolved in 1～5g organic
In solvent solution, stir 1～5 hour, obtain solution C；0.1～1.0g mono-aggressiveness C is dissolved in 1～5g organic solvent, obtains solution
D, after reacting 1～5 hour after solution C and solution D being mixed, temperature is down to 10～20 DEG C, obtains solution E；
Step 3,0.1～2.0g mono-aggressiveness D is dissolved in 10～60g organic solvents, after mixing with step 2 gained solution E, dropwise adds
Enter in alkaline solution and the hydrochloric acid of excess is neutrality to solution, continue reaction 10～20 hours, obtain solution F；
Step 4, above-mentioned solution F add in the organic solvent 5～50mL containing 0.1～1.0g slaine, is simultaneously introduced alkalescence
Solution controls the PH ≈ 8～9 of solution；After reaction terminates, it is lyophilized in freeze dryer, takes out solid product and be called for short polymer
First.
The lipophilic polymer synthetic method of a kind of spontaneous recovery under water the most according to claim 1, it is characterised in that described
In step 1, single aggressiveness A is one or both in polyethylene, PolyTHF, polystyrene, polrvinyl chloride.
The lipophilic polymer synthetic method of a kind of spontaneous recovery under water the most according to claim 1 and 2, it is characterised in that described
Step 1 in, single aggressiveness B is the one in polyurethanes, isophorone diisocyanate, polyurethane, isocyanates.
The lipophilic polymer synthetic method of a kind of spontaneous recovery under water the most according to claim 1, it is characterised in that described
In step 1, catalyst is the one in N, N dimethylaniline, dimethyl open-chain crown ether, dibutyl tin laurate.
The lipophilic polymer synthetic method of a kind of spontaneous recovery under water the most according to claim 1, it is characterised in that described
In step 2, single aggressiveness C is the one in trihydroxy methyl propanoic acid, dihydromethyl propionic acid, p-methyl benzenesulfonic acid, 2-(Acryloyloxy)ethanol
Or two kinds.
The lipophilic polymer synthetic method of a kind of spontaneous recovery under water the most according to claim 1, it is characterised in that described
In step 3, single aggressiveness D is the one in catechol ethamine, biatrate, dopamine hydrochloride, procaine hydrochloride.
7. according to the lipophilic polymer synthetic method of a kind of spontaneous recovery under water described in claim 1 or 6, it is characterised in that described
Step 3 in, alkaline solution is the one in dimethylformamide, triethylamine, diethylamine, acetonitrile.
The lipophilic polymer synthetic method of a kind of spontaneous recovery under water the most according to claim 1, it is characterised in that described
In step 4, slaine is one or both in copper chloride, calcium chloride, iron chloride, Chlorizate chromium, calcium sulfate.
9. according to the lipophilic polymer synthetic method of a kind of spontaneous recovery under water described in claim 1 or 8, it is characterised in that described
Step 4 in, alkaline solution is the one in dimethylformamide, triethylamine, diethylamine, acetonitrile.
The lipophilic polymer synthetic method of a kind of spontaneous recovery under water the most according to claim 1, it is characterised in that described
In step 1-4, organic solvent is one or more in styrene, trichloro ethylene, dimethylformamide, toluene, ethyl acetate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110105562A (en) * | 2019-04-23 | 2019-08-09 | 华东师范大学 | The bi-block copolymer and its synthetic method of the amine ligand containing DOPA and application |
| CN112778905A (en) * | 2019-11-07 | 2021-05-11 | 香港城市大学深圳研究院 | Self-repairing super-hydrophobic coating and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104387563A (en) * | 2014-11-19 | 2015-03-04 | 中山大学 | Hyperbranched polyurethane having self-repairing function in seawater as well as preparation method and application thereof |
-
2016
- 2016-07-29 CN CN201610619731.3A patent/CN106188564A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104387563A (en) * | 2014-11-19 | 2015-03-04 | 中山大学 | Hyperbranched polyurethane having self-repairing function in seawater as well as preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110105562A (en) * | 2019-04-23 | 2019-08-09 | 华东师范大学 | The bi-block copolymer and its synthetic method of the amine ligand containing DOPA and application |
| CN112778905A (en) * | 2019-11-07 | 2021-05-11 | 香港城市大学深圳研究院 | Self-repairing super-hydrophobic coating and preparation method thereof |
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Application publication date: 20161207 |