CN104774295B - A kind of polymer binder of the amido of DOPA containing class phosphate ester structure and preparation method and application - Google Patents

A kind of polymer binder of the amido of DOPA containing class phosphate ester structure and preparation method and application Download PDF

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CN104774295B
CN104774295B CN201510165924.1A CN201510165924A CN104774295B CN 104774295 B CN104774295 B CN 104774295B CN 201510165924 A CN201510165924 A CN 201510165924A CN 104774295 B CN104774295 B CN 104774295B
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陶磊
危岩
张亚玲
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Tsinghua University
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Abstract

The invention discloses polymer and preparation method and application shown in Formulas I, shown in formula I, molecular weight is 50000~120000;x:Y=1:(0.25‑0.75);N=10 50;n1=2 or 3;R1It is any in alkyl and phenyl selected from C1 C4;R2It is any in group shown in Formula II and formula III.Method is as follows:In the presence of triethylamine, initiator and chain-transferring agent, the aromatic aldehyde, phosphite ester and Methylacrylic acid polyethylene glycol single armor ether ester at ortho position is replaced to be reacted in organic solvent N (3 aminoalkyl) methacrylamide hydrochloride containing amino, dihydroxy, you can.It is that a kind of mussel is bionical and water-based adhesive of environment-friendly and green, it is adaptable to the bonding between a variety of substrates, and bonding can be realized under numerous conditions, possess good adhesive power, and preparation method is simple, raw material sources enrich, it is cheap, it is a kind of potential splendid jointing material.

Description

A kind of polymer binder of the amido of DOPA containing class phosphate ester structure and preparation method thereof With application
Technical field
The invention belongs to adhesive field, and in particular to a kind of polymer binder of the amido of DOPA containing class phosphate ester structure And preparation method and application.
Background technology
Polymer binder is the macromolecular material with bonding force, by the chemical reaction or thing of material in itself with interface Manage interaction and realize solidification, the connection of identical or different material interface or laminating can be reached to the effect of bonding.At present on the market Polymer binder mainly have epoxy resin, cyanoacrylate, phenolic resin class and Lauxite class etc..These are high Molecular adhesion agent is industrial production, need to generally use organic solvent to help to dissolve in use, it is difficult to meet increasingly tight The environmental sanitation of lattice and the requirement of environmental protection, and have larger limitation when the fields such as biological and medical treatment are used.
The content of the invention
It is an object of the invention to provide a kind of polymer binder of the amido of DOPA containing class phosphate ester structure and its preparation Method.
The general structure of the polymer binder of the amido of DOPA containing class phosphate ester structure provided by the present invention such as Formulas I institute Show:
In the Formulas I, x:Y=1:(0.25-0.75), concretely 1:(0.3-0.6);N=10-50, concretely n= 20-30;n1=2 or 3;R1Any of alkyl and phenyl selected from C1-C4;R2In group shown in Formula II and formula III It is any:
In the Formulas I, R3And R4The end group of chain-transferring agent is represented respectively.
The molecular weight of polymer shown in the Formulas I is 50000~120000, concretely 70000~90000.
The preparation method of the polymer binder of the amido of DOPA containing class phosphate ester structure provided by the present invention, including it is as follows Step:Under conditions of the presence of triethylamine, initiator and chain-transferring agent, by N- (3- aminoalkyls) methacryl containing amino Amine hydrochlorate, aromatic aldehyde, phosphite ester and the Methylacrylic acid polyethylene glycol single armor ether ester of o-dihydroxy substitution are in organic solvent It is middle to be reacted, you can to obtain the polymer binder of the amido phosphate ester structure of DOPA containing class.
In above-mentioned preparation method, described N- (3- aminoalkyls) methacrylamide hydrochloride containing amino, o-dihydroxy The mol ratio of substituted aromatic aldehyde, phosphite ester and Methylacrylic acid polyethylene glycol single armor ether ester is 1:(1.1-1.6):(1.2- 1.8):(0.25-0.75).
Described N- (3- aminoalkyls) methacrylamide hydrochloride containing amino concretely N- (3- aminopropyls) first Base acrylamide hydrochloride.
The phosphite ester is specially dimethylphosphite, diethyl phosphite, phosphorous acid dipropyl, dibutyl phosphite Any of with diphenyl phosphite.
The aromatic aldehyde of the o-dihydroxy substitution is concretely in 3,4- 4-dihydroxy benzaldehydes and 2,3- 4-dihydroxy benzaldehydes It is any.
The n values of the Methylacrylic acid polyethylene glycol single armor ether ester are 10-50, concretely n=20-30.
Before the reaction is carried out, also including into question response solution the step of inflated with nitrogen deoxygenation.
The reaction is that reversible addition chain tra nsfer (RAFT) polymerisation and Kabachnik-Fields react.
The reaction temperature of the reaction is 50-75 DEG C, and specially 60 DEG C, the reaction time is 8-16h, specially 10h.
The organic solvent is specially the mixed solvent of ethanol and acetonitrile, wherein, the volume ratio of ethanol and acetonitrile is 1: (0.6-1.2)。
The triethylamine is (1.1-1.3) with the mol ratio of the N- (3- aminoalkyls) methacrylamide hydrochloride: 1, specially 1.2:1.
The initiator concretely ABVN and/or azodiisobutyronitrile, the addition of the initiator is The 0.3%-0.5% of monomer N- (3- aminoalkyls) the methacrylamide hydrochloride quality, specially 0.4%.
The chain-transferring agent is concretelyThe addition of the chain-transferring agent is the monomer N- (3- Aminoalkyl) methacrylamide hydrochloride quality 0.6%-1.0%, specially 0.8%.
When described N- (3- aminoalkyls) methacrylamide hydrochloride containing amino is N- (3- aminopropyls) methyl-prop Acrylamide hydrochloride;When the phosphite ester is diethyl phosphite, the aromatic aldehyde of the o-dihydroxy substitution is 3,4- dihydroxies During benzaldehyde, the chain-transferring agent isThe amidophosphate of DOPA containing class obtained by the preparation method The general structure of the polymer binder of structure is as shown in formula IV:
The molecular weight of polymer shown in the formula IV is 50000~120000, concretely 70000~90000.
In the formula IV, x:Y=1:(0.25-0.75), concretely 1:(0.3-0.6);N=10-50, concretely n =20-30.
Chain-transferring agent is usually three thio ester compounds, there is many chain-transferring agents that can be selected, and consumption is seldom, example Such as:Using heretofore describedWhen, the end group of chain-transferring agent is respectively group shown in formula IV (in formula IV Shown group R in the Formulas I3And R4At position), and the adhesive function of material is not influenceed by end group in the present invention, so Various chain-transferring agents can be selected.
The polymer binder of the amido phosphate ester structure of DOPA containing class obtained by the present invention is in terms of adhesive is prepared Using falling within protection scope of the present invention.
It is yet a further object of the present invention to provide a kind of macromolecule using the amido phosphate ester structure of DOPA containing class The method of adhesive bonding material substrate.
Method of the present invention, comprises the following steps:DOPA containing class is coated in two sheet material substrate surfaces to be bonded The aqueous solution of the polymer binder of amido phosphoric acid ester structure, presses, dries, you can two sheet material substrates of bonding.
In the above method, the concentration of the aqueous solution of the polymer binder of the amido of DOPA containing the class phosphate ester structure is 0.1~2.0g/mL, preferably 1.0g/mL.
The temperature of the drying is 40~80 DEG C, and preferably 60 DEG C, the time is 3~48h, preferably 20h.
The material substrate is any of metallic substrates, high molecule plastic substrate and biological tissue's substrate.
The metallic substrates concretely any of aluminium flake, latten(-tin), stainless steel substrates and titanium alloy piece.
The high molecule plastic substrate concretely any of epoxy sheet, plastics PP and plastics ABS.
Biological tissue's substrate concretely ox bone piece.
The present invention prepares the polymer binder of the amido phosphate ester structure of DOPA containing class using one kettle way, passes through reversible addition Chain tra nsfer (RAFT) polymerization combines Kabachnik-Fields and reacts the polymerization system that comes from different backgrounds and possess different abilities:Pass through 3,4- 4-dihydroxy benzaldehydes Occur the reversible addition chain transfer polymerization of main chain and the Kabachnik- of side chain simultaneously in a heated condition with amino monomers Fields reacts, and polymerize the macromolecule to be formed with reference to water-soluble monomer Methylacrylic acid polyethylene glycol single armor ether ester, with mussel The DOPA amidophosphate of biomimetic features plays adhesive effect, is that a kind of mussel is bionical and water-based adhesive of environment-friendly and green.
The monomer and other raw materials that this method is applied are easy to purchase, and preparation method is simple, prepared high molecular bonding Agent good water solubility, simple to operate, during bonding metal substrate, its shear strength can also bond high molecule plastic base in more than 2MPa Bottom and biological tissue, such as ox bone, it is adaptable to a variety of substrates.
In addition, in the present invention, the polymer binder of the amido of DOPA containing the class phosphate ester structure, in oxidation, alkalescence, many Under conditions of valence metal ion and small molecule crosslinking agent are present, crosslink density and speed can increase, and can accelerate binding speed, section Save the bonding time.Such as:Into the polymer binder of class amido containing the DOPA phosphate ester structure, addition accounts for its quality 10% After small molecule crosslinking agent 1,1,1- trihydroxy methyl ethyl triacrylates, its adhesion strength for bonding aluminium alloy rises to from 2Mpa 3Mpa。
Compared with prior art, adhesive provided by the present invention has following outstanding feature:
1st, the raw material sources needed for preparing polymer binder of the present invention enrich, cheap.
2nd, the preparation method of polymer binder of the present invention is simple, and technological parameter is easily controllable.
3rd, the good water solubility of polymer binder of the present invention, is a kind of water-base macromolecule abhesive agent of environmental protection.
4th, polymer binder bonding effect of the present invention is good, and can to a variety of substrates, including metallic substrates, plastic-substrates and Biological tissue's such as ox bone substrate etc., is bonded.
5th, bonding required time and temperature range are adjustable, it is easy to realize bonding under numerous conditions.
Brief description of the drawings
Fig. 1 is the synthetic route chart of the polymer binder containing class DOPA amido phosphate ester structure in embodiment 1.
Fig. 2 is the nucleus magnetic hydrogen spectrum of the polymer binder (formula IV) containing class DOPA amido phosphate ester structure in embodiment 1 Phenogram.
Embodiment
The method of the present invention is illustrated below by specific embodiment, but the invention is not limited in this, it is all at this Any modification, equivalent and improvement made within the spirit and principle of invention etc., should be included in the protection model of the present invention Within enclosing.
Experimental method described in following embodiments, unless otherwise specified, is conventional method;The reagent and material, such as Without specified otherwise, commercially obtain.
Embodiment 1, the polymer binder for preparing the amido phosphate ester structure of DOPA containing class:
Using one kettle way by monomer N- (3- aminopropyls) methacrylamide hydrochloride, 3,4- 4-dihydroxy benzaldehydes, Asia Diethyl phosphate and Methylacrylic acid polyethylene glycol single armor ether ester (copolymerization monomer) press molar ratio 1:1.2:1.4:0.5 adds Enter to ethanol and acetonitrile mixed solvent (wherein, the volume ratio of ethanol and acetonitrile be 1:1) in, and three second are added thereto again Amine, the mol ratio for making triethylamine and monomer N- (3- aminopropyls) methacrylamide hydrochloride is 1.2:1, add triethylamine Purpose is the hydrochloride of neutralization monomer institute band, (quality accounts for monomer N- (3- aminopropyls) methyl-prop to initiator ABVN Acrylamide hydrochloride quality 0.4%) and chain-transferring agent(quality accounts for monomer N- (3- aminopropyls) methyl Acrylamide hydrochloride quality 0.8%), after inflated with nitrogen deoxygenation, heating response 10 hours to reaction is finished at 60 DEG C, will be anti- Gained reaction solution is answered to dialyse (use universal regenerated fiber bag filter, molecular cut off 7000) in methyl alcohol, after drying The polymer binder of the amido phosphate ester structure of DOPA containing class is obtained, shown in its corresponding structural formula such as Fig. 1 (formula IV), wherein, In Formulas I, x:Y=1:0.5, n=21, molecular weight is 75000.Confirm via nucleus magnetic hydrogen spectrum sign (as shown in Figure 2) prepared The structure of polymer.
Embodiment 2, utilize the polymer binder of the amido phosphate ester structure of DOPA containing class bond between material substrate it is real Test:
1) the polymer binder powder obtained in 1.0g embodiments 1 is taken to be dissolved in water, constant volume obtains 1mL concentration and is The 1g/mL polymer binder aqueous solution;
2) 10 μ L steps 1 are respectively taken) in the polymer binder aqueous solution drip respectively in two sheet material substrate surface 1cm × In 1cm regions, and stand volatilization a moment;
3) by step 2) in two drip have the polymer binder aqueous solution material substrate compress, clamp, be placed in 60 DEG C of bakings Heated 20 hours in case, taking-up is cooled to room temperature, you can two sheet material substrates are bonded together;
Stretching experiment is carried out to two sheet material substrates being bonded together:
Microcomputer manipulation multifunctional digital test machine is tested the shear strength of jointing material substrate, learns that macromolecule glues Mixture is 3MPa to aluminium flake bonding strength, is 2MPa to latten(-tin) bonding strength, is 1.5MPa to stainless steel substrates bonding strength, right Titanium alloy piece bonding strength 1MPa, to epoxy sheet bonding strength 1Mpa, to ox bone piece bonding strength 0.5Mpa, to plastics ABS bonding strength 0.5Mpa, to plastics PP bonding strengths 0.5Mpa.

Claims (10)

1. polymer shown in Formulas I:
In the Formulas I, x:Y=1:(0.25-0.75);N=10-50;n1=2 or 3;R1In alkyl and phenyl selected from C1-C4 It is any;R2Selected from any of group shown in Formula II and formula III,
In the Formulas I, R3And R4The end group of chain-transferring agent is represented respectively;
The molecular weight of polymer shown in the Formulas I is 50000~120000.
2. polymer shown in Formulas I according to claim 1, it is characterised in that:The general structure of polymer shown in Formulas I such as formula Shown in IV:
In the formula IV, x:Y=1:(0.25-0.75), n=10-50;
The molecular weight of polymer shown in the formula IV is 50000~120000.
3. the preparation method of polymer, comprises the following steps shown in the Formulas I described in claim 1:In triethylamine, initiator and chain Under conditions of transfer agent is present, N- (3- aminoalkyls) methacrylamide hydrochloride containing amino, o-dihydroxy are replaced Aromatic aldehyde, phosphite ester and Methylacrylic acid polyethylene glycol single armor ether ester are reacted in organic solvent, that is, are obtained shown in Formulas I Polymer.
4. preparation method according to claim 3, it is characterised in that:The reaction is the reaction of reversible addition chain transfer polymerization With Kabachnik-Fields reactions;
The reaction temperature of the reaction is 50-75 DEG C, and the reaction time is 8-16h;
Described N- (3- aminoalkyls) methacrylamide hydrochloride containing amino, the aromatic aldehyde of o-dihydroxy substitution, phosphorous acid The mol ratio of ester and Methylacrylic acid polyethylene glycol single armor ether ester is 1:(1.1-1.6):(1.2-1.8):(0.25-0.75);
Described N- (3- aminoalkyls) methacrylamide hydrochloride containing amino is N- (3- aminopropyls) Methacrylamide Hydrochloride;
The phosphite ester is dimethylphosphite, diethyl phosphite, phosphorous acid dipropyl, dibutyl phosphite and phosphorous acid Any of diphenyl ester;
The aromatic aldehyde of the o-dihydroxy substitution is any of 3,4- 4-dihydroxy benzaldehydes and 2,3- 4-dihydroxy benzaldehydes;
The n values of the Methylacrylic acid polyethylene glycol single armor ether ester are 10-50;
The triethylamine is (1.1-1.3) with the mol ratio of the N- (3- aminoalkyls) methacrylamide hydrochloride:1;
The initiator is ABVN and/or azodiisobutyronitrile, and the addition of the initiator is the monomer N- The 0.3%-0.5% of (3- aminoalkyls) methacrylamide hydrochloride quality;
The chain-transferring agent isThe addition of the chain-transferring agent is the monomer N- (3- aminoalkyls) first The 0.6%-1.0% of base acrylamide hydrochloride quality.
5. the preparation method according to claim 3 or 4, it is characterised in that:Before the reaction is carried out, also including anti-to treating The step of answering inflated with nitrogen deoxygenation in solution;
The organic solvent is the mixed solvent of ethanol and acetonitrile, wherein, the volume ratio of ethanol and acetonitrile is 1:(0.6-1.2).
6. application of the polymer described in claim 1 or 2 in terms of adhesive is prepared.
7. a kind of method of the polymeric binder material substrate described in utilization claim 1 or 2, comprises the following steps:Waiting to glue The two sheet material substrate surfaces closed coat the aqueous solution of polymer shown in the Formulas I, press, dry, you can two sheet materials of bonding Substrate.
8. method according to claim 7, it is characterised in that:The concentration of the aqueous solution of polymer shown in the Formulas I is 0.1 ~2.0g/mL;
The temperature of the drying is 40~80 DEG C, and the time is 3~48h.
9. the method according to claim 7 or 8, it is characterised in that:The material substrate is metallic substrates, high molecule plastic Any of substrate and biological tissue's substrate.
10. method according to claim 9, it is characterised in that:The metallic substrates are aluminium flake, latten(-tin), stainless steel substrates Any of with titanium alloy piece;
The high molecule plastic substrate is any of epoxy sheet, plastics PP and plastics ABS;
Biological tissue's substrate is any of ox bone piece and pig bone piece.
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