CN111410755B - Self-repairing hydrogel capable of being repeatedly shaped and preparation method thereof - Google Patents
Self-repairing hydrogel capable of being repeatedly shaped and preparation method thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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- C08J2475/04—Polyurethanes
- C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Abstract
The invention relates to the field of carbon dioxide conversion and utilization and the field of self-repairing materials, in particular to a self-repairing hydrogel capable of being repeatedly shaped and a preparation method thereof. The hydrogel is a polyacrylic acid/non-isocyanate polyurethane hydrogel. The non-isocyanate polyurethane is prepared by taking polyethylene glycol diglycidyl ether or polypropylene glycol diglycidyl ether as a raw material and preparing five-membered cyclic carbonate with carbon dioxide under the action of a catalyst. Reacting five-membered cyclic carbonate with binary primary amine to obtain non-isocyanate polyurethane, dispersing the non-isocyanate polyurethane in a solvent, adding glycidyl methacrylate to react to prepare the non-isocyanate polyurethane with different double bond contents, and polymerizing an acrylic monomer and the non-isocyanate polyurethane in a redox system to prepare hydrogel. According to the invention, the non-isocyanate polyurethane with carbon dioxide as a raw material is introduced into the polyacrylic acid hydrogel, so that the mechanical property of the hydrogel is improved, the hydrogel is endowed with good self-repairing capability, and the excellent performance of repeated shaping is shown.
Description
Technical Field
The invention relates to the field of carbon dioxide conversion and utilization and the field of self-repairing materials, in particular to a self-repairing hydrogel capable of being repeatedly shaped and a preparation method thereof.
Background
The hydrogel has a three-dimensional polymer network formed by physical or chemical crosslinking, and has certain strength and other characteristics such as self-repairing performance, pH responsiveness, temperature responsiveness and the like on the basis of absorbing and retaining a large amount of moisture. The polyacrylic acid hydrogel is a hydrogel taking polyacrylic acid as a main chain, has extremely poor strength, can be dissolved after being soaked in water for a long time, and has no practical value. At present, a small molecular crosslinking agent or an ionic crosslinking agent is mostly used for improving the crosslinking degree of polyacrylic acid hydrogel, and products of the small molecular crosslinking agent or the ionic crosslinking agent are widely applied to the fields of cold dressings, cooling pastes, facial masks and the like. The traditional polyurethane uses isocyanate which is highly sensitive to moisture and highly toxic as a main raw material, cannot be directly used for producing aqueous products, needs a two-step process of blocking isocyanate groups in advance and using a solvent for emulsification and dispersion, and has a complex production flow and huge environmental protection pressure. At present, only a few documents report the traditional polyurethane hydrogel, and Chinese patent CN104497219A reports a method for preparing self-repairing polyurethane hydrogel by a two-step method, wherein a hydrophilic polyurethane macromonomer self-assembly body and an alkyl acrylate micelle which are capped by acrylate monomers are firstly prepared, and then the self-assembly body and the alkyl acrylate micelle are subjected to free radical copolymerization with acrylamide monomers under the photo initiation to prepare the hydrogel, and the method has the advantages of complex process and high operation requirement.
The non-isocyanate polyurethane (NIPU) can be prepared by aminolysis of five-membered cyclic carbonate which does not need to be dehydrated in advance, and the five-membered cyclic carbonate is prepared by the reaction of carbon dioxide and epoxy resin, so that the greenhouse gas carbon dioxide is effectively utilized, and the full reaction process is simple in process and environment-friendly. Chinese patent CN106008966B reports a method for preparing hybrid non-isocyanate polyurethane by reacting epoxy soybean oil and bisphenol a epoxy resin (E-54) with carbon dioxide to prepare corresponding five-membered cyclic carbonate, and aminolyzing the mixture. The non-isocyanate polyurethane has a good potential in the aspect of preparing the functional hydrogel due to the existence of a proper amount of hydroxyl on the molecular structure. However, since the five-membered cyclic carbonate can only react with primary amine, does not react with secondary amine or tertiary amine, and cannot prepare a linear non-isocyanate polyurethane molecular chain with high molecular weight, the non-isocyanate polyurethane with high crosslinking degree can only be prepared by aminolysis of polybasic primary amine, so that the molecular weight between crosslinking points is small, the performance is poor, and the application of the non-isocyanate polyurethane in hydrogel is limited. Gennen reported a method of preparing a non-isocyanate polyurethane by aminolysis of five-membered cyclic carbonates using a polyvalent primary amine, followed by swelling by dipping in water to obtain a hydrogel (Polyhydroxuurethane hydrogels: synthesis and catalysis, European polymerjournal,2016,84, 849). The method takes 4 days for immersion and swelling, is time-consuming and has poor performance, and is not beneficial to industrial application. Bourgiginon reported a process for preparing hydrogels by direct aminolysis of five-membered cyclic carbonates with poly-primary amines in water at a suitable pH, with an elongation at break of only 51% (Fast and simple one-pot one-step preparation of biochemical in water at room temperature, ACS stable chem. eng, 2019,7, 12601). At present, no method for preparing hybrid hydrogel by copolymerizing non-isocyanate polyurethane and other monomers is reported.
The invention has the innovation points that the non-isocyanate polyurethane chain segment prepared from carbon dioxide is copolymerized with acrylic acid, and the hydroxyl on the non-isocyanate polyurethane chain segment is utilized to form intramolecular and intermolecular hydrogen bonds in water by adjusting the length, the functionality and the dosage of the chain segment of the non-isocyanate polyurethane, so that the strength of the polyacrylic acid hydrogel is improved, the hydrogel self-repairing capability is endowed, and the repeated shaping function of the hydrogel is realized.
Disclosure of Invention
The invention aims to provide a method for preparing non-isocyanate polyurethane containing double bonds and a novel method for preparing hydrogel by copolymerizing the non-isocyanate polyurethane with acrylic acid.
According to the invention, acrylic acid and non-isocyanate polyurethane are copolymerized, and the interaction between hydrogel molecular chains is regulated and controlled by using the hydroxyl on the non-isocyanate polyurethane chain segment, so that the strength of the polyacrylic acid hydrogel is improved, and the self-repairing capability and the repeated shaping capability of the polyacrylic acid hydrogel are endowed.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention can be divided into the following three preparation processes: in the first step, carbon dioxide and polyethylene glycol diglycidyl ether or polypropylene glycol diglycidyl ether are reacted under the action of a catalyst to prepare polyethylene glycol penta cyclic carbonate or polypropylene glycol penta cyclic carbonate; aminolysis of five-membered cyclic carbonate by using primary diamine to prepare non-isocyanate polyurethane, and then reacting the non-isocyanate polyurethane with glycidyl methacrylate to prepare non-isocyanate polyurethane containing double bonds; and thirdly, initiating free radical copolymerization of the double-bond non-isocyanate polyurethane and acrylic acid in water through a redox system to prepare the polyacrylic acid/non-isocyanate polyurethane hydrogel.
A self-repairing hydrogel capable of being repeatedly shaped is a polyacrylic acid/non-isocyanate polyurethane hydrogel.
A preparation method of a repeatedly moldable self-repairing hydrogel comprises the following steps:
Step 2, preparation of double bond-containing non-isocyanate polyurethane (G-NIPU): adding measured five-membered cyclic carbonate, binary primary amine and catalyst into a three-mouth bottle provided with a condensation reflux device, and introducing N2Replacing air in a reaction system, timing and reacting after first temperature rise, obtaining faint yellow non-isocyanate polyurethane (NIPU) after the reaction is finished, adding metered solvent into the non-isocyanate polyurethane, adding metered Glycidyl Methacrylate (GMA) and antioxidant after the non-isocyanate polyurethane is uniformly diluted, timing and reacting after second temperature rise, decompressing and removing the solvent after the reaction is finished, and obtaining the non-isocyanate poly-ether containing double bondsA urethane;
step 3, preparing the self-repairing hydrogel capable of being repeatedly shaped: uniformly dispersing metered non-isocyanate polyurethane containing double bonds and acrylic acid in deionized water through magnetic stirring, adding metered initiator and catalyst, rapidly stirring uniformly, removing bubbles in the solution under reduced pressure, transferring the defoamed solution into a mold for sealing, and placing the sealed mold into a constant-temperature water bath to initiate free radical polymerization reaction to obtain the self-repairing hydrogel capable of being repeatedly shaped. The vacuum defoaming can rapidly eliminate the micro-bubbles in the reaction solution caused by mechanical stirring, is an important process flow for avoiding bubbles in the hydrogel product, and is one of the key steps for improving the quality of the hydrogel.
Further, the five-membered cyclic carbonate is polyethylene glycol five-membered cyclic carbonate (PEG5CC) or polypropylene glycol five-membered cyclic carbonate (PPG5CC), and the structural formula is as follows:
the structural formula of the double-bond-containing non-isocyanate polyurethane is as follows:
wherein R is
。
Further, the catalyst in the step 1 is macroporous strong basic resin, and the dosage of the catalyst is 5-20% of the weight of the raw material polyethylene glycol diglycidyl ether or polypropylene glycol diglycidyl ether; catalysis of CO using macroporous strongly basic resins2The method has high reaction activity with epoxide, good selectivity and reusability, is beneficial to the separation and treatment of products, does not leave impurities such as organic phosphine, halogen, alkali metal and the like, and is beneficial to the next step of application of the products in hydrogel products.
Further, the pressure of the vacuum in the step 1Is-0.05 to-0.10 Mpa; CO 22The air pressure of the air source is 0.10-0.15 Mpa; the air in the high-pressure reaction kettle is replaced for 3-5 times; the preset reaction temperature is 100-150 ℃, the set pressure is 0.5-3.0 MPa, and the time required for the reaction to be finished is 5-30 h. The reaction is carried out in the temperature and pressure ranges, so that the ideal conversion rate of the five-membered cyclic carbonate can be obtained in a short time, the reaction pressure or temperature is continuously increased, the overhigh fuel power loss is caused, side reactions such as dehydration, oxidation and the like can be caused at high temperature, and the product selectivity is reduced.
Further, the calculation method of the content of the five-membered cyclic carbonate 5CC in the step 1 comprises the following steps:
wherein E is1As the epoxy value (in eq/100g) of polyethylene glycol diglycidyl ether or polypropylene glycol diglycidyl ether measured by the hydrochloric acid-acetone method, E2The epoxy value (eq/100 g) of the product polyethylene glycol pentacyclic carbonate or polypropylene glycol pentacyclic carbonate was measured by the hydrochloric acid-acetone method.
Further, the temperature of the first temperature rise in the step 2 is 80-120 ℃, and the time of the reaction completion after the first temperature rise is 4-6 hours; the temperature of the second temperature rise is 30-50 ℃, and the time of the reaction after the second temperature rise is 3-5 hours. The reaction is carried out below the lower limit of the temperature range of the two heating reactions, so that incomplete reaction and overlong time consumption are easily caused, and the product quality is easily damaged above the upper limit, so that adverse effects such as yellowing, auto-polymerization of active double bonds and the like are caused.
Further, in the step 2, the primary diamine includes one or a mixture of several of ethylenediamine, 1, 6-hexanediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine in any proportion, and the amount ratio of the primary diamine to the five-membered cyclic carbonate substance is 0.5-2: 1. The multiple primary diamines can be selected and combined according to different factors such as chain length, reaction activity, hydrophilic and hydrophobic properties, price and the like and according to the performance requirements of the hydrogel product, so that the raw material range of the hydrogel is greatly expanded.
Further, when the primary diamine is a primary diamine containing no secondary amine, the mass ratio of the primary diamine containing no secondary amine to the five-membered cyclic carbonate is 1.25-2: 1; when the primary diamine is a secondary amine-containing primary diamine, the mass ratio of the secondary amine-containing primary diamine to the pentabasic cyclic carbonate is 0.5-2: 1. The above-mentioned preferred amount ratio of the primary diamine to the pentabasic cyclic carbonate species ensures that sufficient amino groups are provided to react with glycidyl methacrylate during the second temperature-raising reaction, avoiding an insufficient amount of grafting of the active double bond component.
Further, the catalyst in the step 2 is triethylene diamine, and the using amount of the catalyst is 0.1-1.0% of the weight of the five-membered cyclic carbonate;
the solvent is one of water, acetone, butanone and ethanol, wherein the solvent is not removed after the reaction in a system using water as the solvent; the dosage of the solvent is 10 to 50 percent of the mass of the non-isocyanate polyurethane;
the mass ratio of the glycidyl methacrylate to the non-isocyanate polyurethane material is 1.0-2.0: 1;
the antioxidant is one of hydroquinone, hydroquinone dihydroxyethyl ether and 2, 6-di-tert-butyl-p-cresol, and the using amount of the antioxidant is 200-5000 ppm of the weight of the double-bond-containing non-isocyanate polyurethane. The antioxidant can effectively avoid the self-polymerization inactivation of double bonds of the glycidyl methacrylate in the second heating reaction, protects the activity of an intermediate product, and is one of the key steps for improving the quality of the hydrogel.
Still further, the mass ratio of the glycidyl methacrylate to the non-isocyanate polyurethane is further optimized to be 1.0-1.2: 1.
Further, the mass of the acrylic acid in the step 3 accounts for 20-45% of the weight of the repeatedly moldable self-repairing hydrogel;
the using amount of the non-isocyanate polyurethane containing double bonds is 0.5 to 50 percent of the weight of acrylic acid;
the initiator is an ammonium persulfate aqueous solution, the mass fraction of the ammonium persulfate aqueous solution is 10%, wherein the using amount of the ammonium persulfate is 1-5% of the weight of the acrylic acid;
the catalyst is tetramethylethylenediamine, and the using amount of the catalyst is 0.1-5% of the weight of acrylic acid;
the temperature of the constant-temperature water bath is 10-30 ℃;
the time of the free radical polymerization reaction is 10-48 h.
The reaction is carried out below the lower limit of the range of the initiator, the catalyst and the reaction temperature, which is easy to cause the consequences of low reaction activity, long time consumption, poor hydrogel performance and the like, and the reaction is carried out above the upper limit of the range of the initiator, the catalyst and the reaction temperature, which is easy to cause the consequences of short operation time, implosion and the like, and is not beneficial to improving the performance of the hydrogel.
Furthermore, the using amount of the non-isocyanate polyurethane containing double bonds is further optimized to be 1 to 10 percent of the weight of acrylic acid;
the initiator is the amount of ammonium persulfate in the ammonium persulfate aqueous solution, and is further optimized to be 3-4% of the weight of acrylic acid;
the catalyst is tetramethylethylenediamine, and the using amount of the catalyst is further optimized to be 1-2% of the weight of acrylic acid;
the temperature of the constant-temperature water bath is further optimized to 18-23 ℃;
the time of the free radical polymerization reaction is further optimized to be 15-25 h.
Compared with the prior art, the invention has the following advantages:
the use of high-toxicity high-moisture sensitive isocyanate is avoided, the environment is protected, and the process requirement is low;
efficient conversion and utilization of CO2Reducing the discharge amount of greenhouse gases;
the strength and the elongation at break of the polyacrylic acid/non-isocyanate polyurethane hydrogel prepared by copolymerization are obviously superior to those of pure non-isocyanate polyurethane hydrogel, and the polyacrylic acid/non-isocyanate polyurethane hydrogel has self-repairing capability and repeated shaping capability.
Drawings
FIG. 1 is an infrared spectrum of glycidyl ether and cyclic carbonate;
FIG. 2 is an infrared detection spectrum of a double bond-containing non-isocyanate polyurethane (G-NIPU).
Detailed Description
The present invention is further described below with reference to specific examples. The invention refers to Macromolecules, 2009, 42: 3811-3817 discloses methods for determining the mechanical properties of polyacrylic acid/non-isocyanate polyurethane hydrogels at ambient temperatures.
The following examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
Example 1
A preparation method of a repeatedly moldable self-repairing hydrogel comprises the following steps:
100.00g of polyethylene glycol diglycidyl ether (with an epoxy value of 0.29eq/100g) and 20.00g of macroporous strongly basic resin are added into an autoclave, and vacuum of-0.05 MPa and CO of 0.10MPa are alternately used2After replacing the air in the kettle for 3 times, the stirring device is opened and heated to 120 ℃, and 1.0MPa CO is filled2The pressure was maintained, and the reaction was terminated by stopping the heating after 10 hours. Emptying the unreacted CO after the temperature in the kettle is reduced to room temperature2And the resulting product was filtered to separate the catalyst. The epoxy value of the product is analyzed to be zero by adopting a hydrochloric acid-acetone method, the epoxy groups are determined to be completely converted into five-membered cyclic carbonate, and the content is calculated to be 0.26eq/100 g.
100.00g of PEG5CC, 15.81g of ethylenediamine and 0.50g of triethylene diamine (wherein the mass ratio of PEG5CC to ethylene diamine is N (PEG5 CC): N (ethylene diamine): 1:2) were added to a three-necked flask equipped with a condensation reflux apparatus, and N was introduced thereinto2Displacing air in the reaction system, heating to 80 ℃, timing, finishing the reaction for 4 hours to obtain viscous light yellow non-isocyanate polyurethane (NIPU), and adding 30.00g of acetone to reduce the viscosity of the system. After the temperature is reduced to room temperature, 18.71g of glycidyl methacrylate and 0.67g of antioxidant hydroquinone are added (wherein, the mass ratio of NIPU to glycidyl methacrylate N (NIPU) is 1:1, and the content of hydroquinone is 4980ppm of the weight of the product of the double-bond-containing non-isocyanate polyurethane), the temperature is increased to 40 ℃, the timing is started, and the reaction is ended within 4 hours. Removing acetone under reduced pressure to obtain non-isocyanate polyurethane (G-NIPU) containing double bond, and making into 10 wt% water dispersionAnd (4) liquid.
Adding 0.58G of 10 wt% G-NIPU, 11.52G of acrylic acid and 21.91G of deionized water into a 50mL finger-head bottle with a magnetic stirrer, stirring and dispersing for 30min, adding 5.40G of 10 wt% ammonium persulfate aqueous solution, continuously stirring for 10min, adding 0.59G of tetramethylethylenediamine, quickly stirring uniformly, and carrying out vacuum defoaming on the solution. And pouring the defoamed solution into a reaction mold with the thickness of 2mm and a glass test tube with the diameter of 15mm carefully, sealing, and reacting in a constant-temperature water tank at 20 ℃ for 24 hours to obtain the polyacrylic acid/non-isocyanate hydrogel. The tensile strength of the hydrogel was 31KPa, and the elongation at break was 1380%. Cutting off the cylindrical hydrogel from the middle, keeping the fracture in tight butt joint, covering the hydrogel with a plastic preservative film to prevent water loss, placing the hydrogel in a 40 ℃ oven for 24 hours, and observing that the notch disappears, wherein the tensile strength is 30KPa, and the elongation at break is 1800%. Cutting the hydrogel into pieces, pressing the pieces into a reaction mould with the thickness of 2mm tightly, sealing and storing the reaction mould, placing the reaction mould in an oven at 40 ℃ for 48 hours, observing that the hydrogel pieces have the disappearance of the discontinuous surfaces, and reshaping the hydrogel pieces into a new gel sheet with the tensile strength of 25KPa and the elongation at break of 1120%.
Example 2
A preparation method of a repeatedly moldable self-repairing hydrogel comprises the following steps:
100.00g of polyethylene glycol diglycidyl ether (with an epoxy value of 0.29eq/100g) and 15.00g of macroporous strongly basic resin are added into an autoclave, and the vacuum of-0.10 MPa and the CO of 0.15MPa are alternately used2After replacing the air in the kettle for 5 times, opening the stirring device, heating to 100 ℃, and filling 0.5MPa CO2The pressure was maintained, and the reaction was terminated by stopping the heating after 30 hours. Emptying the unreacted CO after the temperature in the kettle is reduced to room temperature2And the resulting product was filtered to separate the catalyst. The epoxy value of the product is analyzed to be zero by adopting a hydrochloric acid-acetone method, the epoxy groups are determined to be completely converted into five-membered cyclic carbonate, and the content is calculated to be 0.26eq/100 g.
100.00g of PEG5CC, 8.78g of ethylenediamine and 0.1g of triethylene diamine (wherein the mass ratio of PEG5CC to ethylene diamine is N (PEG5 CC): N (ethylene diamine): 1:1.11) were added to a three-necked flask equipped with a condensation reflux apparatus, and N was introduced thereinto2Displacement reaction bodyAnd (3) heating the air in the system to 80 ℃, timing, finishing the reaction for 4 hours to obtain viscous light yellow non-isocyanate polyurethane (NIPU), and adding 30.00g of acetone to reduce the viscosity of the system. After the temperature is reduced to room temperature, 2.08g of methacrylic acid glycidyl ether and 0.55g of antioxidant hydroquinone dihydroxyethyl ether are added (wherein the mass ratio of NIPU to the methacrylic acid glycidyl ether N (NIPU) is 1:1, the dosage of hydroquinone dihydroxyethyl ether is 4960ppm of the weight of the product of the double-bond-containing non-isocyanate polyurethane), and the time is counted after the temperature is increased to 40 ℃, and the reaction is finished for 4 hours. Acetone was removed under reduced pressure to produce a non-isocyanate polyurethane (G-NIPU) containing double bonds and formulated as a 10 wt% aqueous dispersion.
Adding 2.99G of 10 wt% G-NIPU, 9.98G of acrylic acid and 16.49G of deionized water into a 50mL finger-head bottle with a magnetic stirrer, stirring and dispersing for 30min, adding 4.68G of 10 wt% ammonium persulfate aqueous solution, continuously stirring for 10min, adding 0.51G of tetramethylethylenediamine, quickly stirring uniformly, and carrying out vacuum defoamation on the solution. And pouring the defoamed solution into a reaction mold with the thickness of 2mm and a glass test tube with the diameter of 15mm carefully, sealing, and reacting in a constant-temperature water tank at 20 ℃ for 24 hours to obtain the polyacrylic acid/non-isocyanate hydrogel. The tensile strength of the hydrogel was 30KPa and the elongation at break was 1271%. Cutting off the cylindrical hydrogel from the middle, keeping the fracture in tight butt joint, covering the hydrogel with a plastic preservative film to prevent dehydration, and placing the hydrogel in an oven at 40 ℃ for 24 hours to observe that the notch disappears, wherein the tensile strength is 28KPa, and the elongation at break is 1540%.
Example 3
A preparation method of a repeatedly moldable self-repairing hydrogel comprises the following steps:
100.00g of polyethylene glycol diglycidyl ether (epoxy value is 0.29eq/100g) and 5.00g of macroporous strongly basic resin are added into an autoclave, and vacuum of-0.05 Mpa and CO of 0.15Mpa are alternately used2After replacing the air in the kettle for 3 times, opening the stirring device, heating to 150 ℃, and filling 3.0MPa CO2The pressure was maintained, and the reaction was terminated by stopping the heating after 20 hours. Emptying the unreacted CO after the temperature in the kettle is reduced to room temperature2And the resulting product is filtered to separate the catalystAnd (3) preparing. The epoxy value of the product is analyzed to be zero by adopting a hydrochloric acid-acetone method, the epoxy groups are determined to be completely converted into five-membered cyclic carbonate, and the content is calculated to be 0.26eq/100 g.
100.00g of PEG5CC, 6.79g of diethylenetriamine and 1.00g of triethylene diamine (wherein the mass ratio of PEG5CC to diethylenetriamine is N (PEG5 CC): N (diethylenetriamine): 2:1) are added into a three-mouth bottle with a condensation reflux device, and N is introduced into the three-mouth bottle2Replacing air in the reaction system, heating to 120 ℃, timing, finishing the reaction for 6 hours to obtain viscous light yellow non-isocyanate polyurethane (NIPU), and adding 20.00g of deionized water to reduce the viscosity of the system. After the temperature is reduced to room temperature, 9.35G of methacrylic acid glycidyl ether and 0.35G of antioxidant hydroquinone (wherein the mass ratio of NIPU to methacrylic acid glycidyl ether N (NIPU) is that n (methacrylic acid glycidyl ether) is 1:1, and the content of hydroquinone is 3014ppm of the weight of the product of the double-bond-containing non-isocyanate polyurethane) are added, the reaction is started to time after the temperature is raised to 35 ℃, 5 hours are carried out to finish the reaction, and the double-bond-containing non-isocyanate polyurethane (G-NIPU) is prepared and prepared into 10 wt% of water dispersion.
Adding 11.52G of 10 wt% G-NIPU, 11.52G of acrylic acid and 10.96G of deionized water into a 50mL finger-head bottle with a magnetic stirrer, stirring and dispersing for 30min, adding 5.40G of 10 wt% ammonium persulfate aqueous solution, continuously stirring for 10min, adding 0.59G of tetramethylethylenediamine, quickly stirring uniformly, and carrying out vacuum defoaming on the solution. And pouring the defoamed solution into a reaction mold with the thickness of 2mm and a glass test tube with the diameter of 15mm carefully, sealing, and reacting in a constant-temperature water tank at 20 ℃ for 24 hours to obtain the polyacrylic acid/non-isocyanate hydrogel. The hydrogel had a tensile strength of 110KPa and an elongation at break of 420%. Cutting off the cylindrical hydrogel from the middle, keeping the fracture in tight butt joint, covering the hydrogel with a plastic preservative film to prevent water loss, and placing the hydrogel in an oven at 40 ℃ for 24 hours to observe that the notch disappears, wherein the tensile strength is 98KPa, and the elongation at break is 410%.
Example 4
A preparation method of a repeatedly moldable self-repairing hydrogel comprises the following steps:
100.00g of polyethylene glycol diglycidyl ether (cyclo)Oxygen value of 0.29eq/100g) and 10.00g of macroporous strongly basic resin are added into a high-pressure reaction kettle, and vacuum of-0.05 Mpa and CO of 0.10Mpa are alternately used2Replacing air in the kettle for 4 times, opening the stirring device, heating to 120 deg.C, and introducing 2.0MPa CO2The pressure was maintained, and the reaction was terminated by stopping the heating after 20 hours. Emptying the unreacted CO after the temperature in the kettle is reduced to room temperature2And the resulting product was filtered to separate the catalyst. The epoxy value of the product is analyzed to be zero by adopting a hydrochloric acid-acetone method, the epoxy groups are determined to be completely converted into five-membered cyclic carbonate, and the content is calculated to be 0.26eq/100 g.
100.00g of PEG5CC, 15.81g of ethylenediamine and 0.50g of triethylene diamine (wherein the mass ratio of PEG5CC to ethylene diamine is N (PEG5 CC): N (ethylene diamine): 1:2) were added to a three-necked flask equipped with a condensation reflux apparatus, and N was introduced thereinto2Displacing air in the reaction system, heating to 100 ℃, timing, finishing the reaction for 5 hours to obtain viscous light yellow non-isocyanate polyurethane (NIPU), and adding 50.00g of ethanol to reduce the viscosity of the system. After the temperature is reduced to room temperature, 37.42G of glycidyl methacrylate and 0.77G of antioxidant hydroquinone (wherein the mass ratio of NIPU to glycidyl methacrylate N (NIPU) is 1:2, and the content of hydroquinone is 5000ppm of the weight of the product of the double-bond-containing non-isocyanate polyurethane) are added, the reaction is started to time after the temperature is increased to 45 ℃, the reaction is ended for 3.5h, the double-bond-containing non-isocyanate polyurethane (G-NIPU) is prepared, and ethanol is removed under reduced pressure to prepare 10 wt% of water dispersion.
Adding 1.15G of 10 wt% G-NIPU, 11.52G of acrylic acid and 21.33G of deionized water into a 50mL finger-head bottle with a magnetic stirrer, stirring and dispersing for 30min, adding 5.76G of 10 wt% ammonium persulfate aqueous solution, continuously stirring for 10min, adding 0.59G of tetramethylethylenediamine, quickly stirring uniformly, and carrying out vacuum defoaming on the solution. And pouring the defoamed solution into a reaction mold with the thickness of 2mm and a glass test tube with the diameter of 15mm carefully, sealing, and reacting in a constant-temperature water tank at 30 ℃ for 10 hours to obtain the polyacrylic acid/non-isocyanate hydrogel. The hydrogel had a tensile strength of 75KPa and an elongation at break of 1120%. Cutting off the cylindrical hydrogel from the middle, keeping the fracture in tight butt joint, covering the hydrogel with a plastic preservative film to prevent water loss, and placing the hydrogel in a 40 ℃ oven for 120h to observe that the notch basically disappears, the tensile strength is 55KPa, and the elongation at break is 980%.
Example 5
A preparation method of a repeatedly moldable self-repairing hydrogel comprises the following steps:
100.00g of polyethylene glycol diglycidyl ether (epoxy value is 0.29eq/100g) and 18.00g of macroporous strongly basic resin are added into an autoclave, and vacuum of-0.05 Mpa and CO of 0.10Mpa are alternately used2After replacing the air in the kettle for 3 times, the stirring device is opened and heated to 110 ℃, and 1.5MPa CO is filled2The pressure was maintained, and the reaction was terminated by stopping the heating after 25 hours. Emptying the unreacted CO after the temperature in the kettle is reduced to room temperature2. The epoxy value of the product is analyzed to be zero by adopting a hydrochloric acid-acetone method, the epoxy groups are determined to be completely converted into five-membered cyclic carbonate, and the content is calculated to be 0.26eq/100 g.
100.00g of PEG5CC, 19.10g of hexamethylenediamine and 0.50g of triethylenediamine (wherein the mass ratio of PEG5CC to hexamethylenediamine is N (PEG5 CC): N (hexamethylenediamine): 1:1.25) were added to a three-necked flask equipped with a condensation reflux apparatus, and N was introduced thereinto2Displacing air in the reaction system, heating to 90 ℃, timing, finishing the reaction for 6 hours to obtain viscous light yellow non-isocyanate polyurethane (NIPU), and adding 15.00g butanone to reduce the viscosity of the system. After the temperature is reduced to room temperature, 4.68G of glycidyl methacrylate and 0.25G of antioxidant 2, 6-di-tert-butyl-p-cresol (wherein the mass ratio of NIPU to glycidyl methacrylate N (NIPU) is that n (glycidyl methacrylate) is 1:1, 2, 6-di-tert-butyl-p-cresol which is 2001ppm of the weight of the non-isocyanate polyurethane containing double bonds, the reaction is finished after the temperature is increased to 40 ℃ and the timing is started and 5h is finished, the non-isocyanate polyurethane (G-NIPU) containing the double bonds is prepared, and butanone is removed under reduced pressure to prepare 90 wt% of water dispersion.
6.40G of 90 wt% G-NIPU, 11.52G of acrylic acid and 17.79G of deionized water are added into a 50mL finger-head bottle with a magnetic stirrer, stirred and dispersed for 30min, then 4.05G of 10 wt% ammonium persulfate aqueous solution is added, stirred for 10min continuously, then 0.23G of tetramethylethylenediamine is added, and the solution is quickly stirred uniformly and defoamed under reduced pressure. And pouring the defoamed solution into a reaction mold with the thickness of 2mm and a glass test tube with the diameter of 15mm carefully, sealing, and reacting in a constant-temperature water tank at 20 ℃ for 30h to obtain the polyacrylic acid/non-isocyanate hydrogel. The tensile strength of the hydrogel was 51KPa, and the elongation at break was 54%. Cutting off the cylindrical hydrogel from the middle, keeping the fracture in tight butt joint, covering the hydrogel with a plastic preservative film to prevent dehydration, and placing the hydrogel in a 40 ℃ oven for 120h to observe that the notch basically disappears, the tensile strength is 30KPa, and the elongation at break is 20%.
Example 6
A preparation method of a repeatedly moldable self-repairing hydrogel comprises the following steps:
100.00g of polypropylene glycol diglycidyl ether (epoxy value of 0.29eq/100g) and 10g of macroporous strongly basic resin are added into an autoclave, and vacuum of-0.05 MPa and CO of 0.15MPa are alternately used2After replacing the air in the kettle for 5 times, opening the stirring device, heating to 140 ℃, and filling 2.5MPa CO2And the pressure was maintained for 30 hours and then the heating was stopped to complete the reaction. Emptying the unreacted CO after the temperature in the kettle is reduced to room temperature2. The epoxy value of the product is analyzed to be zero by adopting a hydrochloric acid-acetone method, the epoxy groups are determined to be completely converted into five-membered cyclic carbonate, and the content is calculated to be 0.26eq/100 g.
100.00g of PPG5CC, 31.14g of ethylenediamine, and 0.50g of triethylenediamine (where the mass ratio of PPG5CC to ethylenediamine was N (PPG5 CC): N (ethylenediamine): 1:2)) were placed in a three-necked flask equipped with a condensing reflux unit, and N was introduced thereinto2Displacing air in the reaction system, heating to 85 ℃, timing, finishing the reaction for 5 hours to obtain viscous light yellow non-isocyanate polyurethane (NIPU), and adding 30.00g of acetone to reduce the viscosity of the system. Cooling to room temperature, adding 18.42G of glycidyl methacrylate and 0.45G of antioxidant hydroquinone (wherein the mass ratio of NIPU to glycidyl methacrylate N (NIPU) is n (glycidyl methacrylate) is 1:1, the amount of hydroquinone is 3000ppm of the weight of the double-bond-containing non-isocyanate polyurethane), heating to 45 ℃, starting timing, finishing the reaction for 3h to obtain double-bond-containing non-isocyanate polyurethane (G-NIPU), and reducing the temperature to obtain the productAcetone was removed under pressure and formulated as a 10 wt% aqueous dispersion.
Adding 0.69G of 10 wt% G-NIPU, 6.91G of acrylic acid and 29.82G of deionized water into a 50mL finger-head bottle with a magnetic stirrer, stirring and dispersing for 30min, adding 2.43G of 10 wt% ammonium persulfate aqueous solution, continuously stirring for 10min, adding 0.14G of tetramethylethylenediamine, quickly stirring uniformly, and carrying out vacuum defoaming on the solution. And pouring the defoamed solution into a reaction mold with the thickness of 2mm and a glass test tube with the diameter of 15mm carefully, sealing, and reacting in a constant-temperature water tank at 25 ℃ for 35 hours to obtain the polyacrylic acid/non-isocyanate hydrogel. The tensile strength of the hydrogel was 42KPa, and the elongation at break was 748%. Cutting off the cylindrical hydrogel from the middle, keeping the fracture in tight butt joint, covering the hydrogel with a plastic preservative film to prevent water loss, and placing the hydrogel in a 40 ℃ oven for 24 hours to observe that the notch basically disappears, the tensile strength is 33KPa, and the elongation at break is 593%.
Example 7
A preparation method of a repeatedly moldable self-repairing hydrogel comprises the following steps:
100.00g of polypropylene glycol diglycidyl ether (epoxy value of 0.29eq/100g) and 5.00g of macroporous strongly basic resin are added into an autoclave, and vacuum of-0.05 MPa and CO of 0.10MPa are alternately used2After replacing the air in the kettle for 3 times, opening the stirring device, heating to 140 ℃, and filling 2.5MPa CO2The pressure was maintained, and the reaction was terminated by stopping the heating after 30 hours. Emptying the unreacted CO after the temperature in the kettle is reduced to room temperature2. The epoxy value of the product is analyzed to be zero by adopting a hydrochloric acid-acetone method, the epoxy groups are determined to be completely converted into five-membered cyclic carbonate, and the content is calculated to be 0.26eq/100 g.
100.00g of PPG5CC, 28.41g of triethylene tetramine, and 0.50g of triethylene diamine (wherein the mass ratio of PPG5CC to triethylene tetramine is N (PPG5 CC): N (triethylene tetramine): 1:1.5)) were put in a three-necked flask equipped with a condensation reflux unit, and N was introduced thereinto2Displacing air in the reaction system, heating to 80 ℃, timing, finishing the reaction for 4 hours to obtain viscous light yellow non-isocyanate polyurethane (NIPU), and adding 50.00g of acetone to reduce the viscosity of the system. After it had cooled to room temperature, 11.05g of methacrylic acid were addedAcid glycidyl ether and antioxidant hydroquinone dihydroxy ethyl ether 0.03G (wherein, the mass ratio of NIPU to methacrylic acid glycidyl ether N (NIPU): n (methacrylic acid glycidyl ether): 1:1.2, the dosage of hydroquinone dihydroxy ethyl ether is 200ppm of the weight of the non-isocyanate polyurethane containing double bonds), heating to 40 ℃, timing, finishing the reaction for 3.5h to prepare the non-isocyanate polyurethane (G-NIPU) containing double bonds, removing acetone under reduced pressure and preparing the non-isocyanate polyurethane into 90 wt% aqueous dispersion.
Adding 2.56G of 90 wt% G-NIPU, 11.52G of acrylic acid and 29.82G of deionized water into a 50mL finger-head bottle with a magnetic stirrer, stirring and dispersing for 30min, adding 1.15G of 10 wt% ammonium persulfate aqueous solution, continuously stirring for 10min, adding 0.01G of tetramethylethylenediamine, quickly stirring uniformly, and carrying out vacuum defoaming on the solution. And pouring the defoamed solution into a reaction mold with the thickness of 2mm and a glass test tube with the diameter of 15mm carefully, sealing, and reacting in a constant-temperature water tank at 20 ℃ for 24 hours to obtain the polyacrylic acid/non-isocyanate hydrogel. The tensile strength of the hydrogel was 65KPa and the elongation at break was 638%. Cutting off the cylindrical hydrogel from the middle, keeping the fracture in tight butt joint, covering the hydrogel with a plastic preservative film to prevent water loss, and placing the hydrogel in an oven at 40 ℃ for 24 hours to observe that the notch basically disappears, the tensile strength is 57KPa, and the elongation at break is 544%.
Example 8
A preparation method of a repeatedly moldable self-repairing hydrogel comprises the following steps:
100.00g of polypropylene glycol diglycidyl ether (epoxy value of 0.29eq/100g) and 20.00g of macroporous strongly basic resin are added into an autoclave, and vacuum of-0.05 MPa and CO of 0.10MPa are alternately used2After replacing the air in the kettle for 4 times, opening the stirring device, heating to 140 ℃, and filling 2.5MPa CO2The pressure was maintained, and the reaction was terminated by stopping the heating after 15 hours. Emptying the unreacted CO after the temperature in the kettle is reduced to room temperature2. The epoxy value of the product is analyzed to be zero by adopting a hydrochloric acid-acetone method, the epoxy groups are determined to be completely converted into five-membered cyclic carbonate, and the content is calculated to be 0.26eq/100 g.
100.00g PPG was added to a three-necked flask equipped with a reflux condenser5CC, 17.20g of hexamethylenediamine and 0.50g of triethylenediamine (wherein the mass ratio of PPG5CC to hexamethylenediamine is N (PPG5 CC): N (hexamethylenediamine): 1:1.14)), N was passed through2Displacing air in the reaction system, heating to 85 ℃, timing, finishing the reaction for 6 hours to obtain viscous light yellow non-isocyanate polyurethane (NIPU), and adding 30.00g of water to reduce the viscosity of the system. After the temperature is reduced to room temperature, 3.95G of methacrylic acid glycidyl ether and 0.18G of antioxidant hydroquinone (wherein the mass ratio of NIPU to methacrylic acid glycidyl ether N (NIPU) is 1:1.5, the content of hydroquinone is 1500ppm of the weight of the product of the double-bond-containing non-isocyanate polyurethane), the reaction is started to time after the temperature is increased to 40 ℃, 4 hours are carried out to finish the reaction, and the double-bond-containing non-isocyanate polyurethane (G-NIPU) is prepared into 10 wt% of water dispersion.
Adding 0.72G of 10 wt% G-NIPU, 14.40G of acrylic acid and 21.71G of deionized water into a 50mL finger-head bottle with a magnetic stirrer, stirring and dispersing for 30min, adding 2.88G of 10 wt% ammonium persulfate aqueous solution, continuously stirring for 10min, adding 0.29G of tetramethylethylenediamine, quickly stirring uniformly, and carrying out vacuum defoaming on the solution. And pouring the defoamed solution into a reaction mold with the thickness of 2mm and a glass test tube with the diameter of 15mm carefully, sealing, and reacting in a constant-temperature water tank at 10 ℃ for 48 hours to obtain the polyacrylic acid/non-isocyanate hydrogel. The hydrogel had a tensile strength of 75KPa and an elongation at break of 1137%. Cutting off the cylindrical hydrogel from the middle, keeping the fracture in tight butt joint, covering the hydrogel with a plastic preservative film to prevent water loss, and placing the hydrogel in a 40 ℃ oven for 96h to observe that the cut basically disappears, the tensile strength is 64KPa, and the elongation at break is 1031%.
FIG. 1 shows the infrared spectrum of glycidyl ether and cyclic carbonate, and the product PEG5CC is 915cm-1The peak shows that the absorption peak of the epoxy group of the polyethylene glycol diglycidyl ether disappears, and is at 1796cm-1And a characteristic absorption peak of the cyclic carbonate appears, indicating that the corresponding cyclic carbonate is generated.
FIG. 2 is an infrared detection spectrum at 913cm of a double bond-containing non-isocyanate polyurethane (G-NIPU)-1The characteristic absorption peak of GMA epoxy group disappears at 1796cm-1The characteristic absorption peak of the five-membered cyclic carbonate disappears at 1640cm-1The absorption peak of C ═ C double bond appears at 1720cm-1Characteristic absorption peaks of carbamate appear.
Claims (12)
1. The self-repairing hydrogel capable of being repeatedly shaped is characterized in that the hydrogel is polyacrylic acid/double-bond-containing non-isocyanate polyurethane hydrogel, wherein the using amount of the double-bond-containing non-isocyanate polyurethane is 0.5-50% of the weight of acrylic acid;
the preparation method of the double bond-containing non-isocyanate polyurethane comprises the following steps: aminolysis of five-membered cyclic carbonate with a diprimary amine to prepare a non-isocyanate polyurethane, and then reacting the non-isocyanate polyurethane with glycidyl methacrylate to prepare a double bond-containing non-isocyanate polyurethane.
2. A preparation method of a repeatedly moldable self-repairing hydrogel is characterized by comprising the following steps:
step 1, preparation of five-membered cyclic carbonate: adding raw materials of polyethylene glycol diglycidyl ether or polypropylene glycol diglycidyl ether and a catalyst into a high-pressure reaction kettle, and alternately using vacuum and CO2After the air in the high-pressure reaction kettle is replaced, the stirring device is opened and heated, and CO is filled when the temperature in the high-pressure reaction kettle reaches the preset reaction temperature2The pressure is maintained until the reaction is finished, the temperature in the high-pressure reaction kettle is reduced to room temperature, and the unreacted CO is discharged2Filtering and separating the catalyst to prepare five-membered cyclic carbonate;
step 2, preparing non-isocyanate polyurethane containing double bonds: adding measured five-membered cyclic carbonate, binary primary amine and catalyst into a three-mouth bottle provided with a condensation reflux device, and introducing N2Replacing air in a reaction system, timing and reacting after first temperature rise, obtaining light yellow non-isocyanate polyurethane after the reaction is finished, adding metered solvent into the non-isocyanate polyurethane, adding metered glycidyl methacrylate and antioxidant after the non-isocyanate polyurethane is uniformly diluted, and opening after second temperature riseTiming and reacting, and removing the solvent under reduced pressure after the reaction is finished to prepare non-isocyanate polyurethane containing double bonds;
step 3, preparing the self-repairing hydrogel capable of being repeatedly shaped: uniformly dispersing metered non-isocyanate polyurethane containing double bonds and acrylic acid in deionized water through magnetic stirring, adding metered initiator and catalyst, rapidly stirring uniformly, removing bubbles in the solution under reduced pressure, transferring the defoamed solution into a mold for sealing, and placing the sealed mold into a constant-temperature water bath to initiate free radical polymerization reaction to obtain the self-repairing hydrogel capable of being repeatedly shaped.
3. The method for preparing the re-shapeable self-repairing hydrogel according to claim 2, wherein the five-membered cyclic carbonate is polyethylene glycol five-membered cyclic carbonate or polypropylene glycol five-membered cyclic carbonate, and the structural formula is as follows:
the structural formula of the double-bond-containing non-isocyanate polyurethane is as follows:
4. the method for preparing the repeatedly moldable self-repairing hydrogel as claimed in claim 2, wherein the catalyst in the step 1 is macroporous strongly basic resin, and the amount of the catalyst is 5-20% of the weight of the raw material polyethylene glycol diglycidyl ether or polypropylene glycol diglycidyl ether.
5. The method for preparing the repeatedly moldable self-repairing hydrogel as claimed in claim 2, wherein the pressure of the vacuum in the step 1 is-0.05 to-0.10 Mpa; CO 22The air pressure of the air source is 0.10-0.15 Mpa; the air in the high-pressure reaction kettle is replaced for 3-5 times; predetermined reactionThe temperature is 100-150 ℃, the set pressure is 0.5-3.0 MPa, and the time required for the reaction to be finished is 5-30 h.
6. The preparation method of the re-shapeable self-repairing hydrogel according to claim 2, wherein the temperature of the first temperature rise in the step 2 is 80 to 120 ℃, and the time of the reaction completion after the first temperature rise is 4 to 6 hours; the temperature of the second temperature rise is 30-50 ℃, and the time of the reaction after the second temperature rise is 3-5 hours.
7. The method for preparing the repeatedly-moldable self-repairing hydrogel according to claim 2, wherein the primary diamine in the step 2 comprises one or a mixture of several of ethylenediamine, 1, 6-hexanediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine in any proportion, and the amount ratio of the primary diamine to the pentabasic cyclic carbonate is 0.5-2: 1.
8. The method for preparing the re-shapeable self-repairing hydrogel according to claim 7, wherein when the primary diamine is a primary diamine without secondary amine, the amount ratio of the primary diamine without secondary amine to the pentatomic cyclic carbonate is 1.25-2: 1; when the primary diamine is a secondary amine-containing primary diamine, the mass ratio of the secondary amine-containing primary diamine to the pentabasic cyclic carbonate is 0.5-2: 1.
9. The method for preparing the repeatedly moldable self-repairing hydrogel as claimed in claim 2, wherein the catalyst in the step 2 is triethylene diamine, and the amount of the triethylene diamine is 0.1-1.0% of the weight of the five-membered cyclic carbonate;
the solvent is one of water, acetone, butanone and ethanol, wherein the solvent is not removed after the reaction in a system using water as the solvent; the using amount of the solvent is 10-50% of the mass of the non-isocyanate polyurethane;
the mass ratio of the glycidyl methacrylate to the non-isocyanate polyurethane material is 1.0-2.0: 1;
the antioxidant is one of hydroquinone, hydroquinone dihydroxyethyl ether and 2, 6-di-tert-butyl-p-cresol, and the using amount of the antioxidant is 200-5000 ppm of the weight of the double-bond-containing non-isocyanate polyurethane.
10. The method for preparing the re-shapeable self-repairing hydrogel according to claim 9, wherein the amount ratio of the glycidyl methacrylate to the non-isocyanate polyurethane is 1.0-1.2: 1.
11. The method for preparing the re-moldable self-repairing hydrogel of claim 2, wherein the mass of the acrylic acid in the step 3 accounts for 20% -45% of the weight of the re-moldable self-repairing hydrogel;
the using amount of the double-bond-containing non-isocyanate polyurethane is 0.5-50% of the weight of acrylic acid;
the initiator is an ammonium persulfate aqueous solution, the mass fraction of the ammonium persulfate aqueous solution is 10%, wherein the using amount of the ammonium persulfate is 1-5% of the weight of the acrylic acid;
the catalyst is tetramethylethylenediamine, and the using amount of the catalyst is 0.1-5% of the weight of acrylic acid;
the temperature of the constant-temperature water bath is 10-30 ℃;
the time of the free radical polymerization reaction is 10-48 h.
12. The method for preparing the re-moldable self-repairing hydrogel of claim 11, wherein the amount of the non-isocyanate polyurethane containing double bonds is 1-10% by weight of acrylic acid;
the initiator is 3-4% of the weight of the acrylic acid in the ammonium persulfate aqueous solution;
the catalyst is tetramethylethylenediamine, and the using amount of the catalyst is 1-2% of the weight of acrylic acid;
the temperature of the constant-temperature water bath is 18-23 ℃;
the time of the free radical polymerization reaction is 15-25 h.
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