CN102634007A - Polyethylene glycol polymer containing dopamine, preparation method for same and application thereof - Google Patents
Polyethylene glycol polymer containing dopamine, preparation method for same and application thereof Download PDFInfo
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- CN102634007A CN102634007A CN2012100852905A CN201210085290A CN102634007A CN 102634007 A CN102634007 A CN 102634007A CN 2012100852905 A CN2012100852905 A CN 2012100852905A CN 201210085290 A CN201210085290 A CN 201210085290A CN 102634007 A CN102634007 A CN 102634007A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 title abstract description 7
- 229920001223 polyethylene glycol Polymers 0.000 title abstract description 4
- 239000002202 Polyethylene glycol Substances 0.000 title abstract description 3
- 229960003638 dopamine Drugs 0.000 title abstract 3
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 21
- 229920000151 polyglycol Polymers 0.000 claims description 18
- 239000010695 polyglycol Substances 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 13
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 9
- HOGDNTQCSIKEEV-UHFFFAOYSA-N n'-hydroxybutanediamide Chemical compound NC(=O)CCC(=O)NO HOGDNTQCSIKEEV-UHFFFAOYSA-N 0.000 claims description 9
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical compound C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 8
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 7
- 238000004513 sizing Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 8
- 230000001133 acceleration Effects 0.000 abstract description 2
- 239000011230 binding agent Substances 0.000 abstract description 2
- 238000007711 solidification Methods 0.000 abstract description 2
- 230000008023 solidification Effects 0.000 abstract description 2
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 abstract 2
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical compound OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 abstract 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 125000006239 protecting group Chemical group 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- ADXGNEYLLLSOAR-UHFFFAOYSA-N tasosartan Chemical compound C12=NC(C)=NC(C)=C2CCC(=O)N1CC(C=C1)=CC=C1C1=CC=CC=C1C=1N=NNN=1 ADXGNEYLLLSOAR-UHFFFAOYSA-N 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 32
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 239000000047 product Substances 0.000 description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 238000004821 distillation Methods 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 2
- -1 isobutyl alpha-cyanoacrylates Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 0 C*CC(COC(CCC(NCCc(cc1O)ccc1O)=O)=O)O Chemical compound C*CC(COC(CCC(NCCc(cc1O)ccc1O)=O)=O)O 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N Oc1ccccc1O Chemical compound Oc1ccccc1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 241001385887 Tachys Species 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- JJJFUHOGVZWXNQ-UHFFFAOYSA-N enbucrilate Chemical class CCCCOC(=O)C(=C)C#N JJJFUHOGVZWXNQ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- PSACHCMMPFMFAJ-UHFFFAOYSA-N nmm n-methylmorpholine Chemical group CN1CCOCC1.CN1CCOCC1 PSACHCMMPFMFAJ-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a polyethylene glycol polymer containing dopamine, a preparation method for the same and application thereof. The method includes: with AGE (allyl glycidyl ether) and EEGE (ethyoxyl ethyl glycidyl ether) serving as raw materials, preparing linear polymer Poly (EEGE-co-AGE) by means of anionic polymerization under the action of catalyst, then removing a protecting group, introducing a carboxyl group on a side group, and finally introducing the dopamine into a side chain of the polymer. The preparation method is simple in process, easy in purification and suitable for industrial production, and the synthesized polymer can play an obvious solidification acceleration role in an alpha-cyanoacrylate binder system.
Description
Technical field
The present invention relates to material science, particularly a kind of PEG verivate that contains Dopamine HCL and preparation method thereof, this material can quicken the curing of α-Qing Jibingxisuanzhi system.
Background technology
This type of α-Qing Jibingxisuanzhi system sizing agent is the single-component of the one type of unique properties type sizing agent of tachy steroling soon; Comprise well-known 501,502 glue etc.; The part model can also be medical, such as 504 (alpha-cyanoacrylate butyl esters), 661 (isobutyl alpha-cyanoacrylates) etc.
With the ECA sizing agent is example, and the function analysis of its representative formula and each component is as shown in table 1.
Table 1: the representative formula of ECA sizing agent
One thinks that the cohesiveness of this type of α-Qing Jibingxisuanzhi system mainly is because anionoid polymerization has fast taken place for it, connects through the interface material through chemical bond.In the α-Qing Jibingxisuanzhi in its molecular structure strong electrophilic cyanic acid and ester group be positioned at a side of two keys simultaneously, two bonding electron clouds are polarized strongly, anionoid polymerization very easily takes place in this base polymer under weakly alkaline effect.Though it is the polyoxyethylene glycol compounds has certain curing facilitation effect to this type system, also little for the integrally curing speed influence of system.For aldehydes matter, this type curing system is had effective inhibition usually, therefore can be used as the stablizer of this type α-Qing Jibingxisuanzhi system, to prolong storage period.
Summary of the invention
The purpose of this invention is to provide a kind of polyglycol polymer that contains Dopamine HCL, it has tangible acceleration solidification for this type of α-Qing Jibingxisuanzhi binder system.
Another object of the present invention provides the above-mentioned preparation method who contains the polyglycol polymer of Dopamine HCL, and its synthetic method craft is simple, and purifying is suitable for suitability for industrialized production easily.
The objective of the invention is to realize like this: a kind of polyglycol polymer that contains Dopamine HCL, its general structure are suc as formula (1):
Wherein: m and n are 2～30000.
The preparation method who contains the polyglycol polymer of Dopamine HCL is characterized in that comprising following sequential steps:
(1) is raw material with glycidyl allyl ether and ethoxyethyl group glycidyl ether, under the effect of catalyzer triisobutyl aluminium and four octyl group brometo de amonios, made linear polymer Poly (EEGE-co-AGE) through anionoid polymerization;
(2) slough the protection base and obtain polymkeric substance DP (EEGE-co-AGE), introduced carboxyl on the side group through being reflected at of hydroxyl and Succinic anhydried again;
(3) utilize under the katalysis of 1-ethyl-(3-dimethylaminopropyl) carbodiimide, N-hydroxy-succinamide and N-methylmorpholine the side chain that Dopamine HCL is incorporated into step (2) resulting polymers.
The polyglycol polymer that contains Dopamine HCL of the present invention can be used as curing catalyst, plays the curing that promotes the α-Qing Jibingxisuanzhi system, and curing speed can improve more than 1 times at least.
Description of drawings
Fig. 1 is the infrared figure of the polymkeric substance that relates among the embodiment 1-3;
Fig. 2 is the nucleus magnetic hydrogen spectrum of general structure (1) polymkeric substance;
Fig. 3 is the nucleus magnetic hydrogen spectrum of residuum after the commercially available 502 cured product ethanol extractings;
Fig. 4 is commercially available 502 and the nucleus magnetic hydrogen spectrum of general structure (1) polymer blending solidified after-product residuum after the ethanol extracting.
Embodiment
The present invention is a kind of polyglycol polymer that contains Dopamine HCL, and its general structure is suc as formula (1):
Wherein: m and n are 2～30000, and m and n can equate or not wait.Preferably, m and n are 100～20000, and be preferred, and m and n are 5000～15000.
The preparation method that this contains the polyglycol polymer of Dopamine HCL comprises following sequential steps:
(1) is raw material with glycidyl allyl ether and ethoxyethyl group glycidyl ether, under the effect of catalyzer triisobutyl aluminium and four octyl group brometo de amonios (interpolation catalytic amount), made linear polymer Poly (EEGE-co-AGE) through anionoid polymerization.Preferably; In nitrogen atmosphere; With glycidyl allyl ether and ethoxyethyl group glycidyl ether in molar ratio 1: (0.01～300) is dissolved in the aprotic organic solvent ,-50 ℃～40 ℃ stirring reactions 1～72 hour, obtains linear polymer Poly (EEGE-co-AGE).The total mass of glycidyl allyl ether and ethoxyethyl group glycidyl ether accounts for 1～40% of reactant total mass.The productive rate of linear polymer Poly (EEGE-co-AGE) is 46%～100%.
(2) step (1) products therefrom is sloughed the protection base and obtain polymkeric substance DP (EEGE-co-AGE), introduced carboxyl on the side group through being reflected at of hydroxyl and Succinic anhydried again.Preferably, in acid solution, slough the protection base and obtain polymkeric substance DP (EEGE-co-AGE), again with Succinic anhydried 0 ℃～100 ℃ stirring reactions 1～24 hour.Polymkeric substance DP (EEGE-co-AGE) wherein is 1: 1.1～1.3 with the mol ratio of Succinic anhydried.
(3) utilize under the katalysis of 1-ethyl-(3-dimethylaminopropyl) carbodiimide, N-hydroxy-succinamide and N-methylmorpholine (N-methylmorpholine) side chain that Dopamine HCL is incorporated into step (2) resulting polymers.Preferably, under nitrogen protection,, reacted 6-24 hour to 1-ethyl-(3-dimethylaminopropyl) carbodiimide, the N-hydroxy-succinamide of step (2) products therefrom adding catalytic amount; Get the step product, nitrogen protection adds dopamine hydrochloride down, and the N-methylmorpholine of catalytic amount reacted 1～10 hour, and wherein the EEGE in step (2) resulting polymers and the mol ratio of dopamine hydrochloride are 1: 1.1～1.3.
The above-mentioned polyglycol polymer that contains Dopamine HCL that makes can be used as curing catalyst, is used to prepare α-Qing Jibingxisuanzhi class sizing agent.
Instance given below is to do more detailed explanation to the present invention; It is important to point out that following examples can not be interpreted as the restriction to the invention protection domain; The person skilled in the art in this field to some nonessential improvement and adjustment that the present invention makes, must belong to protection scope of the present invention according to the foregoing invention content.
Embodiment 1
1) raw material ethoxyethyl group glycidyl ether (EEGE) is synthetic
In the 100mL round-bottomed flask, the 10g R-GLYCIDOL is dissolved in the 40mL EVE.Add tosic acid 0.25g altogether, the control solution temperature is no more than room temperature, stirs 3 hours in batches.In reaction mixture, add the 100mL saturated sodium bicarbonate aqueous solution, separatory obtains organic layer, adds anhydrous magnesium sulfate drying 1 hour, filters.Add the hydrolith underpressure distillation and collect the cut of 51 ℃/80Pa, the nitrogen protection lower seal is preserved, productive rate 90%.
2) side chain contains the synthetic of Dopamine HCL functional group polyethyleneglycol derivative
Polymerization reactor vacuumizes pyroprocessing; The cooling back adds toluene 10mL, EEGE 1mL (6.6mmol), glycidyl allyl ether (AGE) 0.78mL (6.6mol); Four octyl group brometo de amonio 0.035g (0.06mmol); 0.26mL the toluene solution of triisobutyl aluminium (1.1mol/L), under the nitrogen protection ,-50 ℃ were reacted 12 hours.Add the ethanol termination reaction, 50 ℃ are evacuated to solvent and thoroughly volatilize, wax, productive rate 48.9%.
[P (EEGE-co-AGE)] is dissolved in the ethanolic soln of 3% hydrochloric acid with a certain amount of aforementioned wax, stirs 4 hours, adds yellow soda ash and is neutralized to neutrality, filters, and ethanol is removed in underpressure distillation, and vacuum-drying gets DP (EEGE-co-AGE).Get DP (EEGE-co-AGE) 2.6g (hydroxy radical content 18.9mmol), Succinic anhydried 5.95g (59.5mmol) is dissolved in the 125mL toluene; Be heated to 60 ℃ and refluxed 6 hours, the dried solvent of vacuum rotary steam, the gained mixture dissolves with an amount of methylene dichloride; In cold diethyl ether, precipitate; Filter, repeat this process more than 5 times, products therefrom vacuum-drying 24 hours.
Get the step product and be dissolved in the 60mL methylene dichloride, nitrogen protection adds 1-ethyl-(3-dimethylaminopropyl) carbodiimide (EDC) 3.8g (20mmol), N-hydroxy-succinamide (NHS) 2.3g (20mmol) down; Reacted 12 hours, the dried solvent of vacuum rotary steam, the gained mixture is used dissolve with ethanol; In cold diethyl ether, precipitate; Filter, repeat this process more than 5 times, products therefrom vacuum-drying 24 hours.Get the step product and be dissolved in the 300mL ethanol, nitrogen protection adds dopamine hydrochloride 7.6g (40mmol), N-methylmorpholine (7.6mL) down; Reacted 2.5 hours; Reaction mixture is concentrated into 20mL, and repeated precipitation in cold diethyl ether, gained white product were dialysed 2 days under the condition of pH=3～4; Lyophilize charges into nitrogen-sealed and preserves.The infared spectrum of per step compound is as shown in Figure 1.
Embodiment 2
Polymerization reactor vacuumizes pyroprocessing, and the cooling back adds toluene 10mL, EEGE 1mL (6.6mmol); AGE 0.78mL (6.6mol), four octyl group brometo de amonio 0.035g (0.06mmol), the toluene solution of 0.26mL triisobutyl aluminium (1.1M); Under the nitrogen protection, reacted 24 hours down at 0 ℃.Add the ethanol termination reaction, under 50 ℃, be evacuated to solvent and thoroughly volatilize, get wax, productive rate 100%.A certain amount of P (EEGE-co-AGE) is dissolved in the ethanolic soln of 3% hydrochloric acid, stirred 4 hours, add yellow soda ash and be neutralized to neutrality, filter, ethanol is removed in underpressure distillation, and vacuum-drying gets DP (EEGE-co-AGE).Get DP (EEGE-co-AGE) 3.9g (hydroxy radical content 29.7mmol), Succinic anhydried 7.425g (74.25mmol) is dissolved in the 150mL toluene; Be heated to 60 ℃ and refluxed 6 hours, the evaporated under reduced pressure solvent, the gained mixture dissolves with an amount of methylene dichloride; In cold diethyl ether, precipitate; Filter, repeat this process more than 5 times, products therefrom vacuum-drying 24 hours.Get the step product and be dissolved in the 80mL methylene dichloride, nitrogen protection adds EDC 7.6g (40mmol), NHS 4.6g (40mmol) down; Reacted 24 hours, the dried solvent of vacuum rotary steam, the gained mixture is used dissolve with ethanol; In cold diethyl ether, precipitate; Filter, repeat this process more than 5 times, products therefrom vacuum-drying 24 hours.Get the step product and be dissolved in the 300mL ethanol, nitrogen protection adds dopamine hydrochloride 7.6g (40mmol), N-methylmorpholine (7.6mL) down; Reacted 2.5 hours; Reaction mixture is concentrated into 20mL, and repeated precipitation in cold diethyl ether, gained white product were dialysed 2 days under the condition of pH=3～4; Lyophilize charges into nitrogen-sealed and preserves.The infared spectrum of per step compound is as shown in Figure 1.
Embodiment 3
Polymerization reactor vacuumizes pyroprocessing, and the cooling back adds toluene 10mL, EEGE 1mL (6.6mmol); AGE 0.78mL (6.6mol), four octyl group brometo de amonio 0.035g (0.06mmol), the toluene solution of 0.26mL triisobutyl aluminium (1.1M); Under the nitrogen protection, reacted 72 hours down at 40 ℃.Add the ethanol termination reaction, being evacuated to solvent under 50 ℃ thoroughly volatilizees, wax, productive rate 52.1%.A certain amount of aforementioned wax (containing PEEGE or P (EEGE-co-AGE)) is dissolved in the ethanolic soln of 3% hydrochloric acid, stirs 4h, add yellow soda ash and be neutralized to neutrality, filter, ethanol is removed in underpressure distillation, and vacuum-drying gets DP (EEGE-co-AGE).Get DP (EEGE-co-AGE) 2.6g (hydroxy radical content 18.9mmol), Succinic anhydried 5.95g (59.5mmol) is dissolved in the 125mL toluene; Be heated to 60 ℃ and refluxed 6 hours, the dried solvent of vacuum rotary steam, the gained mixture dissolves with an amount of methylene dichloride; In cold diethyl ether, precipitate; Filter, repeat this process more than 5 times, products therefrom vacuum-drying 24 hours.Get the step product and be dissolved in the 60mL methylene dichloride, nitrogen protection adds EDC 3.8g (20mmol), NHS 2.3g (20mmol) down; Reacted 12 hours, the dried solvent of vacuum rotary steam, the gained mixture is used dissolve with ethanol; In cold diethyl ether, precipitate; Filter, repeat this process more than 5 times, products therefrom vacuum-drying 24 hours.Get the step product and be dissolved in the 300mL ethanol, nitrogen protection adds dopamine hydrochloride 7.6g (40mmol), N-methylmorpholine (7.6mL) down; Reacted 2.5 hours; Reaction mixture is concentrated into 20mL, and repeated precipitation in cold diethyl ether, gained white product were dialysed 2 days under the condition of pH=3～4; Lyophilize charges into nitrogen-sealed and preserves.The infared spectrum of per step compound is as shown in Figure 1.
Simultaneous test:
Get commercially available 502 glue (major ingredient is a α-Qing Jibingxisuanzhi), mensuration is about about 10 seconds set time.The nucleus magnetic hydrogen spectrum of residuum is as shown in Figure 3 after the commercially available 502 cured product ethanol extractings.
Add embodiment 1 prepared compound like structural formula (1) to commercially available 502 glue, mensuration is about 3～4 seconds set time.The nucleus magnetic hydrogen spectrum of general structure (1) polymkeric substance is as shown in Figure 2.Commercially available 502 and the nucleus magnetic hydrogen spectrum of general structure (1) polymer blending solidified after-product residuum after the ethanol extracting as shown in Figure 4.
Add the compound of following structural formula (2)～(4) to commercially available 502 glue, mensuration is about about 10 seconds set time.
Wherein m and n are 2～30000
Conclusion:
After contacting with the α-Qing Jibingxisuanzhi system and solidify like the polymkeric substance of structural formula (1); Two keys on the polymkeric substance and the two keys in the α-Qing Jibingxisuanzhi system have the generation crosslinking reaction, but curing speed is enhanced about more than once than traditional ECA sizing agent.Compound like structural formula (2), (3), (4) does not then quicken the solidified phenomenon to the α-Qing Jibingxisuanzhi system.
Claims (9)
1. polyglycol polymer that contains Dopamine HCL, its general structure are suc as formula (1):
wherein: m and n are 2～30000.
2. the said preparation method who contains the polyglycol polymer of Dopamine HCL of claim 1 is characterized in that comprising following sequential steps:
(1) is raw material with glycidyl allyl ether and ethoxyethyl group glycidyl ether, under the effect of catalyzer triisobutyl aluminium and four octyl group brometo de amonios, made linear polymer Poly (EEGE-co-AGE) through anionoid polymerization;
(2) step (1) products therefrom is sloughed the protection base and obtain polymkeric substance DP (EEGE-co-AGE), introduced carboxyl on the side group through being reflected at of hydroxyl and Succinic anhydried again;
(3) utilize under the katalysis of 1-ethyl-(3-dimethylaminopropyl) carbodiimide, N-hydroxy-succinamide and N-methylmorpholine the side chain that Dopamine HCL is incorporated into step (2) resulting polymers.
3. the preparation method who contains the polyglycol polymer of Dopamine HCL according to claim 2; It is characterized in that: said step (1); In nitrogen atmosphere; With glycidyl allyl ether and ethoxyethyl group glycidyl ether in molar ratio 1: (0.01～300) is dissolved in the aprotic organic solvent ,-50 ℃～40 ℃ stirring reactions 1～72 hour, obtains linear polymer Poly (EEGE-co-AGE).
4. the preparation method who contains the polyglycol polymer of Dopamine HCL according to claim 2 is characterized in that: said step (1), the total mass of glycidyl allyl ether and ethoxyethyl group glycidyl ether accounts for 1～40% of reactant total mass.
5. the preparation method who contains the polyglycol polymer of Dopamine HCL according to claim 2 is characterized in that: said step (1), the productive rate of linear polymer Poly (EEGE-co-AGE) is 46%～100%.
6. the preparation method who contains the polyglycol polymer of Dopamine HCL according to claim 2; It is characterized in that: said step (2); In acid solution, slough the protection base and obtain polymkeric substance DP (EEGE-co-AGE); Again with Succinic anhydried 0 ℃～100 ℃ stirring reactions 1～24 hour, polymkeric substance DP (EEGE-co-AGE) wherein is 1: 1.1～1.3 with the mol ratio of Succinic anhydried.
7. the preparation method who contains the polyglycol polymer of Dopamine HCL according to claim 2; It is characterized in that: in the said step (3); Under nitrogen protection, add 1-ethyl-(3-dimethylaminopropyl) carbodiimide, N-hydroxy-succinamide, reacted 6-24 hour to step (2) products therefrom; Get the step product, nitrogen protection adds dopamine hydrochloride down, and N-methylmorpholine reacted 1～10 hour, and wherein the mol ratio of EEGE and dopamine hydrochloride is 1: 1.1～1.3 in step (2) resulting polymers.
8. the described application that contains the polyglycol polymer of Dopamine HCL as curing catalyst of claim 1.
9. the described polyglycol polymer that contains Dopamine HCL of claim 1 is used to prepare α-Qing Jibingxisuanzhi class sizing agent as curing catalyst.
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| 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 |
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| CN113896865A (en) * | 2021-10-21 | 2022-01-07 | 福州大学 | Naphthalimide polymer semiconductor containing dopamine-derived side chain and preparation method thereof |
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| CN101955595A (en) * | 2010-08-11 | 2011-01-26 | 东南大学 | Method for guiding fixed-point cell growth by preparing chemical micro-patterns on surfaces of various materials |
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| CN101955595A (en) * | 2010-08-11 | 2011-01-26 | 东南大学 | Method for guiding fixed-point cell growth by preparing chemical micro-patterns on surfaces of various materials |
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| 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 |
| CN104387563B (en) * | 2014-11-19 | 2017-01-11 | 中山大学 | Hyperbranched polyurethane having self-repairing function in seawater as well as preparation method and application thereof |
| CN106220841A (en) * | 2016-08-18 | 2016-12-14 | 三明学院 | Based on Fe3+polyalcohol hydrogel that dopamine is modified and preparation method thereof |
| CN106220841B (en) * | 2016-08-18 | 2018-06-08 | 三明学院 | Based on Fe3+Amine-modified polyalcohol hydrogel of DOPA and preparation method thereof |
| CN111253543A (en) * | 2020-01-21 | 2020-06-09 | 西安医学院 | Novel MAP medical adhesive material based on biomimetic synthesis and preparation method thereof |
| CN113896865A (en) * | 2021-10-21 | 2022-01-07 | 福州大学 | Naphthalimide polymer semiconductor containing dopamine-derived side chain and preparation method thereof |
| CN114085331A (en) * | 2021-12-01 | 2022-02-25 | 长兴化学工业(中国)有限公司 | Mussel biomimetic modified acrylic hybrid alkyd resin and preparation method thereof |
| CN114085331B (en) * | 2021-12-01 | 2024-05-28 | 长兴化学工业(中国)有限公司 | Mussel bionic modified acrylic hybrid alkyd resin and preparation method thereof |
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