CN102634007B - 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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- 229920000642 polymer Polymers 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920001223 polyethylene glycol Polymers 0.000 title abstract description 4
- 239000002202 Polyethylene glycol Substances 0.000 title abstract description 3
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 title abstract 6
- 229960003638 dopamine Drugs 0.000 title abstract 3
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical compound OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000006239 protecting group Chemical group 0.000 claims abstract description 6
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 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
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 9
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 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
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 238000003756 stirring 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
- 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
- 238000010539 anionic addition polymerization reaction Methods 0.000 abstract 1
- 238000009776 industrial production Methods 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
- FGBJXOREULPLGL-UHFFFAOYSA-N ethyl cyanoacrylate Chemical compound CCOC(=O)C(=C)C#N FGBJXOREULPLGL-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000010992 reflux Methods 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
- -1 isobutyl alpha-cyanoacrylates Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 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
- 125000004093 cyano group Chemical group *C#N 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 compound CN1CCOCC1.CN1CCOCC1 PSACHCMMPFMFAJ-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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 derivative containing Dopamine HCL and preparation method thereof, this material can accelerate solidifying of α-cyanoacrylate system.
Background technology
The single-component that this class sizing agent of α-cyanoacrylate system is the class unique properties type sizing agent of tachy steroling soon, comprise well-known 501,502 glue etc., part model can also be medical, such as 504 (alpha-cyanoacrylate butyl esters), 661 (isobutyl alpha-cyanoacrylates) etc.
Take ethyl α-cyanoacrylate sizing agent as example, the function analysis of its representative formula and each component is as shown in table 1.
Table 1: the representative formula of ethyl α-cyanoacrylate sizing agent
One thinks, the cohesiveness of this class system of α-cyanoacrylate is mainly because anionoid polymerization has fast occurred for it, and material is connected by chemical bond by interface.In α-cyanoacrylate, in its molecular structure, strong electrophilic cyano group and ester group are positioned at a side of two keys simultaneously, and two bonding electron clouds are polarized strongly, and anionoid polymerization very easily occurs this base polymer under the effect of weak base.Although polyoxyethylene glycol compounds has certain curing facilitation effect to this class system, also little for the integrally curing rate of system.For aldehydes matter, this class curing system is had to effective inhibition conventionally, therefore can be used as the stablizer of this class α-cyanoacrylate system, to extend storage period.
Summary of the invention
The object of this invention is to provide a kind of polyglycol polymer containing Dopamine HCL, it has obvious acceleration solidification for this class binder system of α-cyanoacrylate.
Another object of the present invention is to provide the preparation method of the above-mentioned polyglycol polymer containing Dopamine HCL, and its synthetic method craft is simple, and easily purifying, is suitable for suitability for industrialized production.
The object of the present invention is achieved like this: a kind of polyglycol polymer containing Dopamine HCL, and its general structure is 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) take glycidyl allyl ether and ethoxyethyl group glycidyl ether as raw material, under the effect of catalyzer triisobutyl aluminium and four octyl group brometo de amonios, by anionoid polymerization, made linear polymer Poly (EEGE-co-AGE);
(2) slough protecting group and obtain polymkeric substance DP (EEGE-co-AGE), then on side group, introduced carboxyl by the reaction of hydroxyl and Succinic anhydried;
(3) utilize the side chain that under the katalysis of 1-ethyl-(3-dimethylaminopropyl) carbodiimide, N-hydroxy-succinamide and N-methylmorpholine, Dopamine HCL is incorporated into step (2) resulting polymers.
Polyglycol polymer containing Dopamine HCL of the present invention can be used as curing catalyst, plays and promotes solidifying of α-cyanoacrylate system, and curing speed can improve more than at least 1 times.
Accompanying drawing explanation
Fig. 1 is the infrared figure of the polymkeric substance that relates in 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 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 ethanol extracting.
Embodiment
The present invention is a kind of polyglycol polymer containing Dopamine HCL, and its general structure is suc as formula (1):
Wherein: m and n are that 2～30000, m and n can not equate or not etc.Preferably, m and n are 100～20000, preferred, and m and n are 5000～15000.
Should, containing the preparation method of the polyglycol polymer of Dopamine HCL, comprise following sequential steps:
(1) take glycidyl allyl ether and ethoxyethyl group glycidyl ether as raw material, under the effect of catalyzer triisobutyl aluminium and four octyl group brometo de amonios (interpolation catalytic amount), by anionoid polymerization, made linear polymer Poly (EEGE-co-AGE).Preferably, in nitrogen atmosphere, by glycidyl allyl ether and ethoxyethyl group glycidyl ether in molar ratio 1: (0.01～300) is dissolved in aprotic organic solvent,-50 ℃～40 ℃ stirring reactions 1～72 hour, obtain 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 to protecting group and obtain polymkeric substance DP (EEGE-co-AGE), then on side group, introduced carboxyl by the reaction of hydroxyl and Succinic anhydried.Preferably, in acid solution, slough protecting group and obtain polymkeric substance DP (EEGE-co-AGE), then with Succinic anhydried 0 ℃～100 ℃ stirring reactions 1～24 hour.Polymkeric substance DP (EEGE-co-AGE) is wherein 1: 1.1～1.3 with the mol ratio of Succinic anhydried.
(3) utilize the side chain that under the katalysis of 1-ethyl-(3-dimethylaminopropyl) carbodiimide, N-hydroxy-succinamide and N-methylmorpholine (N-methylmorpholine), Dopamine HCL is incorporated into step (2) resulting polymers.Preferably, under nitrogen protection, to step (2) products therefrom, add 1-ethyl-(3-dimethylaminopropyl) carbodiimide, the N-hydroxy-succinamide of catalytic amount, reaction 6-24 hour; Get step product, under nitrogen protection, add dopamine hydrochloride, the N-methylmorpholine of catalytic amount, reacts 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 containing Dopamine HCL making can be used as curing catalyst, and application is for the preparation of α-cyanoacrylate class sizing agent.
Example given below is so that the present invention will be described in more detail; it is important to point out that following examples can not be interpreted as the restriction to invention protection domain; some nonessential improvement and adjustment that the person skilled in the art in this field makes the present invention according to foregoing invention content, must belong to protection scope of the present invention.
Embodiment 1
1) raw material ethoxyethyl group glycidyl ether (EEGE) is synthetic
In 100mL round-bottomed flask, 10g R-GLYCIDOL is dissolved in to 40mL EVE.Add tosic acid 0.25g altogether in batches, control solution temperature and be no more than room temperature, stir 3 hours.In reaction mixture, add 100mL saturated sodium bicarbonate aqueous solution, separatory obtains organic layer, adds anhydrous magnesium sulfate drying 1 hour, filters.Add hydrolith underpressure distillation to collect the cut of 51 ℃/80Pa, nitrogen protection lower seal is preserved, productive rate 90%.
2) side chain synthesizing containing Dopamine HCL functional group polyethyleneglycol derivative
Polymerization reactor vacuumizes pyroprocessing; after cooling, add toluene 10mL; EEGE 1mL (6.6mmol); glycidyl allyl ether (AGE) 0.78mL (6.6mol); four octyl group brometo de amonio 0.035g (0.06mmol); the toluene solution (1.1mol/L) of 0.26mL triisobutyl aluminium, under nitrogen protection ,-50 ℃ are reacted 12 hours.Add ethanol termination reaction, 50 ℃ are evacuated to solvent and thoroughly volatilize, and obtain wax, productive rate 48.9%.
A certain amount of aforementioned wax [P (EEGE-co-AGE)] is dissolved in the ethanolic soln of 3% hydrochloric acid, stirs 4 hours, add sodium carbonate to be neutralized to neutrality, filter, ethanol is removed in underpressure distillation, and vacuum-drying obtains DP (EEGE-co-AGE).Get DP (EEGE-co-AGE) 2.6g (hydroxy radical content 18.9mmol), Succinic anhydried 5.95g (59.5mmol), be dissolved in 125mL toluene, be heated to 60 ℃ and reflux 6 hours, the dry solvent of vacuum rotary steam, gained mixture dissolves with appropriate methylene dichloride, in cold diethyl ether, precipitate, filter, repeat this process more than 5 times, products therefrom vacuum-drying 24 hours.
Getting step product is dissolved in 60mL methylene dichloride; under nitrogen protection, add 1-ethyl-(3-dimethylaminopropyl) carbodiimide (EDC) 3.8g (20mmol); N-hydroxy-succinamide (NHS) 2.3g (20mmol); react the dry solvent of vacuum rotary steam, gained mixture dissolve with ethanol 12 hours; in cold diethyl ether, precipitate; filter, repeat this process more than 5 times, products therefrom vacuum-drying 24 hours.Getting step product is dissolved in 300mL ethanol; under nitrogen protection, add dopamine hydrochloride 7.6g (40mmol); N-methylmorpholine (7.6mL); react 2.5 hours; reaction mixture is concentrated into 20mL, repeated precipitation in cold diethyl ether, gained white product is dialysed 2 days under the condition of pH=3～4; lyophilize, is filled with nitrogen-sealed and preserves.The infared spectrum of every step compound as shown in Figure 1.
Embodiment 2
Polymerization reactor vacuumizes pyroprocessing; after cooling, add toluene 10mL; EEGE 1mL (6.6mmol); AGE 0.78mL (6.6mol); four octyl group brometo de amonio 0.035g (0.06mmol); the toluene solution (1.1M) of 0.26mL triisobutyl aluminium under nitrogen protection, reacts 24 hours at 0 ℃.Add ethanol termination reaction, at 50 ℃, be evacuated to solvent and thoroughly volatilize, obtain wax, productive rate 100%.A certain amount of P (EEGE-co-AGE) is dissolved in the ethanolic soln of 3% hydrochloric acid, stirs 4 hours, add sodium carbonate to be neutralized to neutrality, filter, ethanol is removed in underpressure distillation, and vacuum-drying obtains DP (EEGE-co-AGE).Get DP (EEGE-co-AGE) 3.9g (hydroxy radical content 29.7mmol), Succinic anhydried 7.425g (74.25mmol), be dissolved in 150mL toluene, be heated to 60 ℃ and reflux 6 hours, evaporated under reduced pressure solvent, gained mixture dissolves with appropriate methylene dichloride, in cold diethyl ether, precipitate, filter, repeat this process more than 5 times, products therefrom vacuum-drying 24 hours.Getting step product is dissolved in 80mL methylene dichloride; under nitrogen protection, add EDC 7.6g (40mmol); NHS 4.6g (40mmol); react the dry solvent of vacuum rotary steam, gained mixture dissolve with ethanol 24 hours; in cold diethyl ether, precipitate; filter, repeat this process more than 5 times, products therefrom vacuum-drying 24 hours.Getting step product is dissolved in 300mL ethanol; under nitrogen protection, add dopamine hydrochloride 7.6g (40mmol); N-methylmorpholine (7.6mL); react 2.5 hours; reaction mixture is concentrated into 20mL, repeated precipitation in cold diethyl ether, gained white product is dialysed 2 days under the condition of pH=3～4; lyophilize, is filled with nitrogen-sealed and preserves.The infared spectrum of every step compound as shown in Figure 1.
Embodiment 3
Polymerization reactor vacuumizes pyroprocessing; after cooling, add toluene 10mL; EEGE 1mL (6.6mmol); AGE 0.78mL (6.6mol); four octyl group brometo de amonio 0.035g (0.06mmol); the toluene solution (1.1M) of 0.26mL triisobutyl aluminium under nitrogen protection, reacts 72 hours at 40 ℃.Add ethanol termination reaction, being evacuated to solvent at 50 ℃ thoroughly volatilizees, and obtains 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 sodium carbonate to be neutralized to neutrality, filter, ethanol is removed in underpressure distillation, and vacuum-drying obtains DP (EEGE-co-AGE).Get DP (EEGE-co-AGE) 2.6g (hydroxy radical content 18.9mmol), Succinic anhydried 5.95g (59.5mmol), be dissolved in 125mL toluene, be heated to 60 ℃ and reflux 6 hours, the dry solvent of vacuum rotary steam, gained mixture dissolves with appropriate methylene dichloride, in cold diethyl ether, precipitate, filter, repeat this process more than 5 times, products therefrom vacuum-drying 24 hours.Getting step product is dissolved in 60mL methylene dichloride; under nitrogen protection, add EDC 3.8g (20mmol); NHS 2.3g (20mmol); react the dry solvent of vacuum rotary steam, gained mixture dissolve with ethanol 12 hours; in cold diethyl ether, precipitate; filter, repeat this process more than 5 times, products therefrom vacuum-drying 24 hours.Getting step product is dissolved in 300mL ethanol; under nitrogen protection, add dopamine hydrochloride 7.6g (40mmol); N-methylmorpholine (7.6mL); react 2.5 hours; reaction mixture is concentrated into 20mL, repeated precipitation in cold diethyl ether, gained white product is dialysed 2 days under the condition of pH=3～4; lyophilize, is filled with nitrogen-sealed and preserves.The infared spectrum of every step compound as shown in Figure 1.
Simultaneous test:
Get commercially available 502 glue (major ingredient is α-cyanoacrylate), measure and be about about 10 seconds set time.After commercially available 502 cured product ethanol extractings, the nucleus magnetic hydrogen spectrum of residuum as shown in Figure 3.
To commercially available 502 glue, add embodiment 1 prepared as the compound of structural formula (1), measure and be about 3～4 seconds set time.The nucleus magnetic hydrogen spectrum of general structure (1) polymkeric substance 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 ethanol extracting as shown in Figure 4.
To commercially available 502 glue, add the compound of following structural formula (2)～(4), measure and be about about 10 seconds set time.
Wherein m and n are 2～30000
Conclusion:
As after the polymkeric substance of structural formula (1) contacts with α-cyanoacrylate system and solidifies, two keys in two keys and α-cyanoacrylate system on polymkeric substance have generation crosslinking reaction, but curing speed is enhanced about more than once than traditional ethyl α-cyanoacrylate sizing agent.As the compound of structural formula (2), (3), (4) does not accelerate curing phenomenon to α-cyanoacrylate system.
Claims (9)
1. containing the polyglycol polymer of Dopamine HCL, its general structure is suc as formula (1):
2. the preparation method who contains the polyglycol polymer of Dopamine HCL described in claim 1, is characterized in that comprising following sequential steps:
(1) take glycidyl allyl ether and ethoxyethyl group glycidyl ether as raw material, under the effect of catalyzer triisobutyl aluminium and four octyl group brometo de amonios, by anionoid polymerization, made linear polymer Poly (EEGE-co-AGE);
(2) step (1) products therefrom is sloughed to protecting group and obtain polymkeric substance DP (EEGE-co-AGE), then on side group, introduced carboxyl by the reaction of hydroxyl and Succinic anhydried;
(3) utilize the side chain that under the katalysis of 1-ethyl-(3-dimethylaminopropyl) carbodiimide, N-hydroxy-succinamide and N-methylmorpholine, Dopamine HCL is incorporated into step (2) resulting polymers.
3. the preparation method of the polyglycol polymer containing Dopamine HCL according to claim 2, it is characterized in that: described step (1), in nitrogen atmosphere, by glycidyl allyl ether and ethoxyethyl group glycidyl ether 1:(0.01～300 in molar ratio) be dissolved in aprotic organic solvent,-50 ℃～40 ℃ stirring reactions 1～72 hour, obtain linear polymer Poly (EEGE-co-AGE).
4. the preparation method of the polyglycol polymer containing Dopamine HCL according to claim 2, is characterized in that: described 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 of the polyglycol polymer containing Dopamine HCL according to claim 2, is characterized in that: described step (1), linear polymer Poly(EEGE-co-AGE) productive rate be 46%～100%.
6. the preparation method of the polyglycol polymer containing Dopamine HCL according to claim 2; it is characterized in that: described step (2); in acid solution, slough protecting group 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) is wherein 1: 1.1～1.3 with the mol ratio of Succinic anhydried.
7. the preparation method of the polyglycol polymer containing Dopamine HCL according to claim 2, it is characterized in that: in described step (3), under nitrogen protection, to step (2) products therefrom, add 1-ethyl-(3-dimethylaminopropyl) carbodiimide, N-hydroxy-succinamide, reaction 6-24 hour; Get step product, under nitrogen protection, add dopamine hydrochloride, N-methylmorpholine, reacts 1～10 hour, and wherein in step (2) resulting polymers, the mol ratio of ethoxyethyl group glycidyl ether section and dopamine hydrochloride is 1: 1.1～1.3.
8. the polyglycol polymer containing Dopamine HCL claimed in claim 1 is as the application of curing catalyst.
Polyglycol polymer containing Dopamine HCL claimed in claim 1 as curing catalyst for the preparation of α-cyanoacrylate class sizing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210085290.5A CN102634007B (en) | 2012-03-27 | 2012-03-27 | Polyethylene glycol polymer containing dopamine, preparation method for same and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201210085290.5A CN102634007B (en) | 2012-03-27 | 2012-03-27 | Polyethylene glycol polymer containing dopamine, preparation method for same 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 |
| 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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