CN105367752A - Method for preparing polyurethane material with amino in side chain - Google Patents

Abstract

The invention discloses a method for preparing a polyurethane material with amino in a side chain. The method comprises the following steps that 1, polyurethane with alkynyl in the side chain is synthesized, wherein diisocyanate, chain-extender micromolecular diol and soft-segment macromolecular diol are synthesized into polyurethane with alkynyl in the side chain under the action of a catalyst, chain-extender micromolecular diol comprises micromolecular diol containing alkynyl, the mole ratio of the total quantity of soft-segment macromolecular diol and chain-extender micromolecular diol to diisocyanate is 0.5-2, and the mole ratio of micromolecular diol containing alkynyl to diisocyanate is 0.05-2; 2, the obtained polyurethane with alkynyl in the side chain in the step 1 is dissolved in solvent, azido-amine is weighed, a cuprous catalyst is added under protection of nitrogen, and reacting is performed for 15-36 h at the temperature of 10 DEG C-60 DEG C. The method for preparing the polyurethane material with amino in the side chain is efficient, controllable and wide in application range.

Description

A kind of method for preparing the polyurethane material that side chain contains amino group

technical field

The invention relates to the field of polyurethane materials, in particular to a method for preparing polyurethane materials with side chains containing amino groups.

Background technique

The full name of polyurethane is polyurethane, which is a general term for macromolecular compounds containing repeated carbamate groups (NHCOO) on the main chain. It is formed by addition polymerization of organic diisocyanate or polyisocyanate and dihydroxy or polyhydroxy compound. The mechanical properties of polyurethane are highly adjustable. By controlling the ratio between crystalline hard segments and non-crystalline soft segments, polyurethanes can obtain different mechanical properties. Therefore, its products have excellent properties such as wear resistance, temperature resistance, sealing, sound insulation, good processing performance, and degradability. In addition, PU has good biocompatibility and is widely used in the medical field. However, the mechanical properties and biocompatibility of PU materials are still far from meeting the requirements of clinical long-term implantation in the body. In order to broaden the application of PU, PU can be modified by grafting hydrophilic polymers, grafting bioactive molecules, and plasma treatment to meet different needs. Among them, the amino modification of polyurethane has attracted widespread attention. After amino modification of polyurethane, it has the following advantages: (1) non-toxic to cells and tissues; (2) reducing the surface hydrophobicity of materials; (3) and the acidic substances released by the degradation of the implanted material, reducing inflammation; (4) providing active sites for binding with other biomolecules, such as collagen, gelatin, RGD short peptide, etc., fixed on the surface of the material to promote the proliferation and differentiation of cells on the surface of the material (5) Provide a layer-by-layer self-assembled surface. Since the surface contains a large number of positively charged amino groups in the solution, it can be used as a base material for layer-by-layer self-assembly, and bioactive molecules can be self-assembled on it, such as chondroitin sulfate and collagen Layer-by-layer self-assembly on the surface of polyurethane materials containing amino groups on the surface; (6) can be used as a pH-sensitive material; (7) because its surface is positively charged, it is conducive to cell adhesion on the surface of the material;

In the past few years, the amino modification of polyurethane materials has mainly focused on the modification of the surface of the material and the grafted amino groups of the polyurethane molecular chain.

Gorna and his collaborators used the method of ammonia plasma treatment to carry out surface amination treatment for polyurethane materials, which changed the hydrophilicity and hydrophobicity and thermal stability of polyurethane materials (Gorna, K. etal. Polymer Degradation and Stability, 2003.79 (3), 475) , He et al. grafted a large number of amino groups on the surface of the polyurethane material by ammonolysis of propylenediamine, and the surface hydrophilicity of the modified polyurethane material was greatly improved. At the same time, they self-assembled chondroitin sulfate and collagen layer by layer. The surface of the polyurethane material modified by amination can promote the adhesion and proliferation of cells (He, X. et al., Applied Surface Science, 2012.258 (24), 9918; He, X., etal. Journal of Applied Polymer Science, 2012.126 (S1), E354), Zhang et al. obtained polyurethane fibers containing amino groups on the surface by adding ammonium sulfate, and then formed gold nanoparticles on the surface of polyurethane fibers by water reduction method, and obtained polyurethane fiber materials with good conductivity (Zhang, X.-C., et al., Polymer, 2012.53(22), 5190)

Xie et al. use HDI, polycaprolactone (PCL), and modified polyethylene glycol (PEG) as raw materials to obtain polyurethane materials with side chains that are amino groups by protecting and deprotecting the amino group. This approach is introduced in the reaction process. PEG containing amino-protected aspartic acid (PEG-Asp-PEG) was used as a prepolymer. Then react in HDI, PCL and amino-protected PEG-Asp-PEG, and after amino deprotection, a polyurethane with a lower content of side chains is obtained (Xie, Z., et al., European Polymer Journal, 2007.43 (5), 2080). People such as Hung introduce ester group on its side chain when synthesizing polyurethane, then by the method for aminolysis, the molecule that contains amino is inserted into polyurethane side chain, has made the polyurethane material (Yang, T.-f. , etal., Biomacromolecules, 2004.5(5), 1926), in addition, they also adopted glycidyl ether on the ester group by aminolysis grafting, and then diamine reacted with glycidyl ether to graft the amino group to the polyurethane side chain , due to the addition of glycidyl ether, this method has a certain improvement in the hydrophilicity of the material compared to the material obtained by direct aminolysis (Hung, W.C., et al., Journal of Controlled Release, 2009.133(1), 68)

The existing amination modification of polyurethane materials mainly focuses on surface modification. Due to the limited depth of effect of surface modification, its long-term effectiveness is difficult to guarantee. However, the existing method of amination of polyurethane molecular chains uses protection/deprotection. The reaction efficiency is low, and the preparation process involves more chemical reaction steps, which increases the complexity of the process. Another method for amination of polyurethane molecular chains by aminolysis also has low amination efficiency. In addition, due to the effect of aminolysis The point is the ester group on the polyurethane molecular chain, and the polyester will be aminolyzed, so that the polyester polyurethane cannot be modified by aminolysis of the polyurethane molecular chain (only the polyester polyurethane can be modified by aminolysis). Surface amination modification (He, X.etal., Applied Surface Science, 2012.258(24), 9918)), the application range of amination modification of polyurethane molecular chains by aminolysis is greatly limited.

CN102432804A discloses a preparation method of amino-terminated polyurethane. The amino-terminated polyurethane material is prepared by a steric protection method, which is used in a two-component polyurea/polyurethane elastomer system, and the obtained polyurea elastomer has excellent physical and chemical properties.

In previous studies, people have carried out amination modification on polyurethane materials through various modification methods. Among them, ammonia plasma surface modification, ammonium sulfate fiber surface modification, and aminolysis method are all carried out on the surface of polyurethane materials for amination modification of polyurethane materials. Only surface modification, compared with the modification of polyurethane molecular chains, the amino modification is not thorough. It is difficult to guarantee long-term effectiveness, and it is also difficult to control the amount of amino modification of polyurethane materials. People have also carried out amination modification on the polyurethane molecular chain. The existing protection/deprotection reaction efficiency for the amination of the polyurethane molecular chain is low, and the preparation process involves more chemical reaction steps, which increases the complexity of the process. Another method of aminolysis and amination of polyurethane molecular chains also has low amination efficiency. In addition, since the action point of aminolysis is the ester group on the polyurethane molecular chain, the polyester will be aminolyzed, so the polyester type Polyurethane will not be able to modify polyurethane molecular chains by aminolysis, and the scope of use of polyurethane molecular chains by aminolysis is greatly limited.

Contents of the invention

In order to overcome the above-mentioned shortcomings and deficiencies of the prior art, the object of the present invention is to provide a method for preparing polyurethane materials containing amino groups in side chains, which is highly efficient and controllable, and has a wide range of applications.

The object of the present invention is achieved through the following technical solutions:

A method for preparing a polyurethane material whose side chain contains amino groups, comprising the following steps:

(1) Synthesis of side chain containing alkyne group polyurethane: diisocyanate, chain extender small molecule, soft segment macromolecule diol are synthesized side chain containing alkyne group polyurethane under the effect of catalyst; Described chain extender small molecule includes containing Alkyne-based small molecule diols;

Among them, the molar ratio of the total amount of macromolecular diol and small molecular diol to diisocyanate is 0.5-2; the molar ratio of small molecular diol containing alkynyl group to diisocyanate is 0.05-2;

(2) dissolving the side chain alkyne group-containing polyurethane obtained in step (1) in a solvent, weighing azide amine, then adding a cuprous catalyst under nitrogen protection, and reacting at 10-60° C. for 15-36 hours; The mol ratio of described azide amine and alkynyl is 0.1～1.5; The reaction process is shown in the following formula:

The diisocyanates include aliphatic and diisocyanates containing aromatic structures.

The diisocyanate described in step (1) is hexamethylene diisocyanate, p-xylylene diisocyanate, toluene diisocyanate, lysine diisocyanate.

The chain extender small molecule diol in step (1) is composed of a small molecule diol containing an alkynyl group and a small molecule diol (diamine, diacid) not containing an alkynyl group; the small molecule diol containing an alkynyl group It is a mono-, di- or multi-substituted diol, such as 2,2-propynyl-propylene glycol or 3,5-dimethylol-1-propargyl ether benzene, etc.; the small molecule diol without alkynyl (Diamines, diacids) are small molecules containing difunctional groups with a molecular weight below 300, such as ethylene glycol, propylene glycol, butanediol or bisphenol A, butanediamine, succinic acid, etc.

The catalyst in step (1) is triethylenediamine, stannous octoate or dibutyltin dilaurate; the dosage of the catalyst is 0.05mol% to 5mol% of diisocyanate.

The soft segment macromolecule diol is at least one of polyether polymer, polyester polymer, polysiloxane diol and polyolefin diol.

The azide amine described in step (2) is nitrogen ethylamine, azidopropylamine, azidoaniline or 11-azido-3,6,9-trioxaundecane-1-amine and its hydrochloride A sort of.

The cuprous catalyst in step (2) is copper wire, copper powder, copper sulfate pentahydrate/ascorbic acid (sodium)/boric acid or CuBr/PMDETA.

Compared with the prior art, the present invention has the following advantages and beneficial effects:

(1) Compared with the surface modification method of polyurethane, the method of the present invention is more thorough in modification and has wider applicability.

(2) Compared with the method for protecting/deprotecting the amino group on the chain extender, the present invention has higher efficiency, fewer preparation steps and fewer side reactions, which has obvious advantages.

(3) Compared with the polyurethane with amino group in the side chain obtained by the aminolysis method, the present invention can be applied to macromolecular diols whose polyurethane soft segment is a polyester type, and the aminolysis will destroy the polyester structure due to the reaction with the ester group. The application is greatly limited. In addition, because the aminolysis method uses diamine, side reactions such as crosslinking may also occur, and the method of the invention can effectively avoid these problems. At the same time, the CuAAC reaction adopted in the present invention has high reaction efficiency. , the reaction conditions are mild, and the side chain amino group content and polyurethane structure are highly controllable, which is an ideal method for preparing side chain amino group-containing polyurethane materials.

(4) The present invention can prepare different structures and polyurethane materials with different amounts of amino groups in the side chains by designing different polyurethane formulas and types and amounts of azide amines, which enriches the method for side chain amino-containing polyurethane materials. The reaction steps involved in this scheme are simple and easy to operate, and have good application prospects.

Description of drawings

Fig. 1 is the 1HNMR spectrum of the polyester polyurethane material containing alkyne group in the side chain and the polyester polyurethane material containing amino group in the side chain prepared in Example 1.

Fig. 2 is the surface zeta potential diagram of the polyester polyurethane material containing alkyne group in the side chain and the polyester polyurethane material containing amino group in the side chain prepared in Example 1.

Fig. 3 is the Raman spectrum of the polyester polyurethane material containing alkyne group in the side chain and the polyester polyurethane material containing amino group in the side chain of Example 2.

detailed description

The present invention will be described in further detail below in conjunction with the embodiments and the accompanying drawings, but the embodiments of the present invention are not limited thereto.

Example 1

(I) Polycaprolactone diol 2000 (PCL2000) was vacuum dehydrated at 110° C. for 1 h. DPPD was vacuum dehydrated at room temperature for 1 h. Weigh 10g of polycaprolactone 2000 (PCL2000, 1eq) and 1.18g of hexamethylene diisocyanate (HDI, 1.4eq) and then add 0.5mol% stannous octoate of hexamethylene diisocyanate as a catalyst, add 20ml of ultra-dry DMF was stirred at 80°C under nitrogen protection for 4h, then added 0.30g of 2,2-propynyl-propanediol (DPPD, 0.4eq) to continue the reaction under nitrogen for 2h, then heated to 90°C, matured for 2h, purified by methanol co-precipitation, and dried in vacuo to obtain Side chain alkyne-containing polyester polyurethane (4D).

(II) Weigh 3g of the polyurethane (PU-C-4, 1eq) obtained in I and dissolve it in 15mlDMF, weigh 0.084g of azidopropylamine (1.2eq) into the reaction bottle, blow nitrogen to remove oxygen for 0.5h, and weigh 0.03 g copper powder was added to the reaction system, reacted at 50° C. for 15 h under the protection of nitrogen, and the reaction product was coprecipitated and washed with water, and vacuum-dried to obtain a polyester polyurethane material (4N) containing amino groups in the side chain.

Fig. 1 is the 1HNMR spectrum of the two-step product of this example, the solvent is DMSO-d6, 4D is a polyurethane material containing alkynyl groups in the side chain, and 4N is the side chain obtained by grafting amino groups to polyurethane side chains using click chemistry CuAAC reaction. Amino polyurethane material. 4D: HDI: 2.93-2.92(h1, N-CH2), 1.35(h2, N-C-CH2), 1.21(h3, N-C-C-CH2); PCL: 1.5(p2+p4, C-CH2-C) 3.97(p1 ,O-CH2-C)1.30(p5,C-CH2-CO)2.27(p3,C-CH2-C); DPPD: 2.83(1,-C≡CH)2.18(2,CH2-C≡C), 4.0 (HDI-O-CH2-). 4N: 2.93-2.92 (N-CH2), 1.35 (N-C-CH2), 1.21 (N-C-C-CH2); 1.5 (p2+p4, C-CH2-C) 3.97 (O-CH2-C) 1.30 (C-CH2 -CO) 2.27 (C-CH2-C); 7.9 (H-triazolering) The appearance of the peak at 7.9ppm indicates that the triazole ring has been formed, which is due to the azide-alkyne cycloaddition reaction between azidopropylamine and polyurethane (CuAAC ), indicating that we have successfully synthesized a polyurethane material containing amino groups in the side chain, and the analysis of NMR results showed that the reaction efficiency was >99%.

Fig. 2 is the surface zeta potential diagram of the polyester polyurethane material (4N) containing amino groups in the side chain obtained by the polyester polyurethane (4D) containing alkyne group obtained in step (I) of the present embodiment and the polyester polyurethane material (4N) obtained by step (II), Measured by a solid surface zeta potential measuring instrument, at pH 3.0-10, the zeta potential of 4N is higher than that of 4D, which is caused by the relative positive charge of the amino group on the surface of 4N.

Example 2

(I) Polytetrahydrofuran glycol 2000 (PTMG2000) was vacuum dehydrated at 110° C. for 1 h. DPPD was vacuum dehydrated at room temperature for 1 h. Weigh 7.15g polytetrahydrofuran diol 2000 (PTMG2000, 1eq) and 0.992g hexamethylene diisocyanate (HDI, 1.6eq) and then add 0.5mol% stannous octoate of hexamethylene diisocyanate as a catalyst, add 15ml Ultra-dry DMF was stirred and reacted at 80°C under nitrogen protection for 3h, then added 0.326g 2,2-propynyl-propylene glycol (DPPD, 0.6eq) to continue the reaction under nitrogen protection for 3h, then heated to 90°C, matured for 2h, purified by methanol co-precipitation, vacuum Dry to obtain side chain alkyne-containing polyester polyurethane (PD-T-6).

(II) Weigh 1g of the polyurethane (PN-T-6, 1eq) obtained in I and dissolve it in 10ml of DMF, and weigh 0.145g of 11-azido-3,6,9-trioxaundecane-1-amine (1.2eq) was added to the reaction flask, deoxygenated by nitrogen for 0.5h, weighed 0.001gCuBr/0.002gPMDETA and added to the reaction system, reacted at 40°C for 18h under the protection of nitrogen, washed the reaction product with water coprecipitation, and vacuum dried to obtain the side chain Polyether polyurethane material containing amino groups.

Figure 3 is the Raman (Raman) spectrum of the two-step product of this example, wherein PD-T-6 is the product of the first step, and the peak at 2100cm-1 corresponds to the alkynyl group, indicating that we synthesized the first step There are alkyne groups in the polymer. PN-T-6 is the product of PD-T-6 modified by the amino group through the click reaction. The alkynyl peak in PN-T-6 disappears. This is because the alkynyl group participates in the click reaction, and the alkynyl group is consumed. The disappearance of the alkynyl peak indicates that The click reaction is efficient. We can see from the Raman spectrum that we successfully performed the two-step process, as we expected.

Other test data of this embodiment are similar to Implementation 1.

Example 3

(I) Polypropylene oxide diol 1000 (PPG1000) was vacuum dehydrated at 110° C. for 2 hours. DPPD, BDO vacuum dehydration at room temperature for 1h. Weigh 10g of polypropylene oxide diol 1000 (PPG1000, 1eq) and 3.40g of toluene diisocyanate (TDI, 2eq), then add 1mol% stannous octoate of toluene diisocyanate as a catalyst, add 30ml of ultra-dry DMF and nitrogen protection at 80°C Stir the reaction for 3h, then add 0.5938g 2,2-propynyl-propanediol (DPPD, 0.4eq) to continue the reaction under nitrogen protection for 3h, then add 0.5274gBDO (0.6eq) and heat up to 90°C, react for 2h, methanol co-precipitation purification, vacuum Dry to obtain side chain alkyne-containing polyester polyurethane (PU-P-46).

(II) Weigh 3g of the polyurethane (PU-P-46, 1eq) obtained in I and dissolve it in 10mlDMF, weigh 0.135g azidoethylamine (1.2eq) and add it to the reaction flask, pass nitrogen to remove oxygen for 0.5h, and weigh Dissolve 0.005g of anhydrous copper sulfate/0.05g of sodium ascorbate (0.01/0.1eq) in 0.3ml of anaerobic water, then add 0.05g of boric acid into the water, add its aqueous solution to the reaction system, and react at 30°C for 24h under the protection of nitrogen. The reaction product is co-precipitated and washed with water, and vacuum-dried to obtain a polyether polyurethane material with amino groups in the side chain.

The test data of this embodiment is similar to that of Examples 1 and 2.

Example 4

(I) Polycaprolactone diol 2000 (PCL2000) was vacuum dehydrated at 110° C. for 1 h. DPPD was vacuum dehydrated at room temperature for 1 h. Weigh 10g polycaprolactone 2000 (PCL2000, 1eq) and 1.18g hexamethylene diisocyanate (HDI, 1.4eq) then add 0.5mol% stannous octoate of hexamethylene diisocyanate as a catalyst, add 20ml super Stir and react at 80°C under dry DMF under nitrogen for 4h, then add 0.30g of 2,2-propynyl-propanediol (DPPD, 0.4eq) to continue the reaction under nitrogen for 2h, then raise the temperature to 90°C, mature for 2h, purify by methanol co-precipitation, and dry in vacuo An alkyne-containing polyester polyurethane is obtained.

(II) Weigh 3g of the polyurethane (PU-C-4, 1eq) obtained in I and dissolve it in 15ml of DMF, weigh 0.118g of azidopropylamine hydrochloride (1.2eq) and add it to the reaction flask, and ventilate nitrogen to remove oxygen for 0.5h, Weigh 0.002gCuBr/0.002gPMDETA (0.01/0.1eq) and dissolve it in 0.3ml anaerobic water, add its aqueous solution to the reaction system, react at 30°C for 24h under nitrogen protection, wash the reaction product with water co-precipitation, and vacuum dry to obtain side A polyester polyurethane material whose chain contains amino groups.

The test data of this embodiment is similar to that of Examples 1 and 2.

Above-mentioned embodiment is preferred embodiment of the present invention, but embodiment of the present invention is not limited by described embodiment, as diisocyanate also can be that p-xylylene diisocyanate or lysine diisocyanate etc. comprise fat family and diisocyanates containing aromatic structures; chain extender small molecules can also be composed of small molecule diols containing alkynyl groups and small molecule diols (diamines, diacids) that do not contain alkynyl groups; the alkynyl group-containing Small molecule diols are mono-, di- or multi-substituted diols, such as 2,2-propynyl-propylene glycol or 3,5-dimethylol-1-propargyl ether benzene, etc.; the alkynyl-free Small molecule diol (diamine, diacid) is the small molecule that contains difunctional group below molecular weight 300, as ethylene glycol, propylene glycol, butanediol or bisphenol A, butanediamine, succinic acid etc.; Step ( 1) The catalyst can also be triethylenediamine or dibutyltin dilaurate; the soft segment macromolecule glycol can also be polyether type macromolecule, polyester type macromolecule, polysiloxane glycol, polyolefin More than one of dihydric alcohols; any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods, and are all included in the protection of the present invention. within range.

Claims (10)

1. prepare the method that side chain contains amino polyurethane material, it is characterized in that, comprise the following steps:

(1) side chain is containing the synthesis of alkynyl urethane: by vulcabond, chainextender small molecules, and soft section of macromolecular diol synthesizes side chain containing alkynyl urethane under the effect of catalyzer; Described chainextender small molecules comprises the small molecules glycol containing alkynyl;

Wherein, soft section of macromolecular diol and chainextender small molecules total amount and vulcabond mol ratio are 0.5 ~ 2; Small molecules glycol containing alkynyl and vulcabond mol ratio are 0.05 ~ 2;

(2) side chain step (1) obtained dissolves in a solvent containing the urethane of alkynyl, takes nitrine amine, then adds cuprous catalysis agent under nitrogen protection, at 10 ~ 60 DEG C, react 15 ~ 36h; The mol ratio of described nitrine amine and alkynyl is 0.1 ~ 1.5.

2. the method prepared side chain and contain amino polyurethane material according to claim 1, is characterized in that, described vulcabond comprises aliphatics and the vulcabond containing aromatic structure.

3. the method prepared side chain and contain amino polyurethane material according to claim 2, it is characterized in that, the vulcabond described in step (1) is hexamethylene diisocyanate, terephthaldehyde's group diisocyanate, tolylene diisocyanate, lysinediisocyanate.

4. the method prepared side chain and contain amino polyurethane material according to claim 1, it is characterized in that, the described chainextender small molecules of step (1) also comprises not containing the glycol of alkynyl, not containing the diamines of alkynyl, not containing more than one in the diacid of alkynyl.

5. the method prepared side chain and contain amino polyurethane material according to claim 4, is characterized in that, the described small molecules glycol containing alkynyl is 2,2-propynyl-propylene glycol or 3,5-dihydroxymethyl-1-propargyl ether benzene.

6. the method prepared side chain and contain amino polyurethane material according to claim 4, is characterized in that, the described small molecules glycol not containing alkynyl is ethylene glycol, propylene glycol, butyleneglycol or dihydroxyphenyl propane; The described diamines not containing alkynyl is butanediamine; The described diacid not containing alkynyl is succinic acid.

7. the method prepared side chain and contain amino polyurethane material according to claim 1, it is characterized in that, step (1) described catalyzer is triethylene diamine, stannous octoate or dibutyl tin laurate; The consumption of described catalyzer is vulcabond 0.05mol% ~ 5mol%.

8. the method prepared side chain and contain amino polyurethane material according to claim 1, is characterized in that, described soft section of macromolecular diol is more than one in polyether type high polymer, polyester type polymer, polysiloxane binary alcohol, polyolefine dibasic alcohol.

9. the method prepared side chain and contain amino polyurethane material according to claim 1, it is characterized in that, the described nitrine amine of step (2) is the one in nitrogen ethamine, nitrine propylamine, nitrine aniline or 11-nitrine-3,6,9-trioxaundecane-1-amine and hydrochloride thereof.

10. the method prepared side chain and contain amino polyurethane material according to claim 1, it is characterized in that, the described cuprous catalysis agent of step (2) is copper cash, copper powder, cupric sulfate pentahydrate/xitix (sodium)/boric acid or CuBr/PMDETA.