CN114479120B - Acrylic ester modified polyurethane adhesive hydrogel material and preparation method thereof - Google Patents
Acrylic ester modified polyurethane adhesive hydrogel material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 36
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000853 adhesive Substances 0.000 title claims abstract description 24
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- SYGAXBISYRORDR-UHFFFAOYSA-N ethyl 2-(hydroxymethyl)prop-2-enoate Chemical compound CCOC(=O)C(=C)CO SYGAXBISYRORDR-UHFFFAOYSA-N 0.000 claims description 4
- RFUCOAQWQVDBEU-UHFFFAOYSA-N methyl 2-(hydroxymethyl)prop-2-enoate Chemical compound COC(=O)C(=C)CO RFUCOAQWQVDBEU-UHFFFAOYSA-N 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 3
- 230000001804 emulsifying effect Effects 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention belongs to the field of hydrogel materials and preparation methods thereof, and specifically adopts the technical scheme that: the acrylic ester modified polyurethane adhesive hydrogel material and the preparation method thereof comprise the following raw materials in parts by weight: according to the invention, by means of the acrylate end-capped modified polyurethane, polyurethane emulsion particles can directly participate in free radical polymerization reaction, and due to the difference of hydrophilia, the polyurethane emulsion is used as a stable one-phase and cross-linked polyacrylamide chain, so that the gel has outstanding adhesion performance under the premise of high cross-linking degree, an adhesion object covers various organic and inorganic materials including polytetrafluoroethylene, the water resistance is improved, and the adhesion hydrogel material can be used as a matrix of a wearable flexible sensor and has wide application characteristics.
Description
Technical Field
The invention belongs to the field of hydrogel materials and preparation methods thereof, and particularly relates to an acrylic ester modified polyurethane adhesive hydrogel material and a preparation method thereof.
Background
Hydrogels are a three-dimensional network of polymer structures containing a large amount of water, and are a stretchable elastomeric material. The hydrogel is widely applied to the fields of biological medicines and flexible materials, such as wound dressing, tissue engineering bracket, drug slow release carrier, flexible conductive material, super capacitor, sensor, intelligent soft robot and the like.
The hydrogel prepared from the polyacrylamide is one of medical hydrogels which are studied more at present, the strength of the polyacrylamide hydrogel is reduced, polyurethane is generally added to improve the strength of the polyacrylamide hydrogel, and the improvement of the adhesive property is important for expanding the application of the hydrogel in application scenes such as wound dressing, wearable devices and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides an acrylic ester modified polyurethane adhesive hydrogel material with good mechanical properties and wide adhesion and a preparation method thereof. Meanwhile, hydrogels have a broad adhesion to organic and inorganic materials including polytetrafluoroethylene.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: an acrylic ester modified polyurethane adhesive hydrogel material comprises the following raw materials in parts by weight: 5-90 parts of acrylic ester modified polyurethane emulsion, 0.4 part of water-soluble initiator, 8-15 parts of gel monomer and 0-80 parts of water.
The preparation method of the acrylic ester modified polyurethane adhesive hydrogel material comprises the following steps:
step A1, dissolving acrylic ester modified polyurethane emulsion, a water-soluble initiator and a gel monomer in water according to a proportion, and stirring for 2-3 minutes at 200-500 rpm to obtain a mixed emulsion system;
and A2, placing the mixed emulsion system prepared in the step A1 into a mould, fully reacting for 6-8 hours at the temperature of 40-80 ℃, taking out and cooling to obtain the acrylic ester modified polyurethane adhesive hydrogel material.
The gel monomer is one of acrylamide or acrylic acid, and the water-soluble initiator is one of ammonium persulfate or potassium persulfate.
The specific preparation process of the acrylic ester modified polyurethane emulsion is as follows:
and S1, dehydrating polyether polyol, a catalyst, diisocyanate, a chain extender, a blocking agent and triethylamine. Adding polyether polyol, diisocyanate and a catalyst into a three-necked flask, heating to 90 ℃ for reaction for 2 hours, cooling to 80 ℃, adding a chain extender for reaction for 1 hour, cooling to 70 ℃, and adding a blocking agent for reaction for 3 hours to obtain a prepolymer. The prepolymer was cooled, and triethylamine was added thereto to conduct neutralization reaction for 30 minutes.
And S2, adding 100 parts of water into 30 parts of the prepolymer obtained in the step S1, and stirring and emulsifying at 1100rpm for 30 minutes to obtain the acrylic ester modified polyurethane emulsion.
The molecular weight of the polyether polyol is 2000-4000, the diisocyanate is isophorone diisocyanate, and the blocking agent is one of hydroxyethyl methacrylate, hydroxypropyl methacrylate, methyl 2- (hydroxymethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate and alpha-methacrylic acid. The catalyst is one of dibutyl tin dilaurate and bismuth carboxylate. The chain extender is 1, 4-butanediol and 2, 2-dimethylolpropionic acid, and the mass ratio of the two is 1:4-1:5.
The addition amount of the catalyst is 1% of the mass of isophorone diisocyanate, and the total addition amount of the chain extender is 7% -10% of the total mass.
The isocyanate index in the formula is 1.30-1.50.
The blocking agent is added in an amount of 130% -200% of the theoretical value of the molar number of the excessive isocyanate groups, namely the molar number of the polyisocyanate groups minus the molar number of the polyol hydroxyl groups.
Wherein, as a preferable raw material ratio: polyether polyol (PPG 2000) 21.3g-14.2g, diisocyanate (IPDI) 10.5g, capping agent (HEA): 2.9g-3.9g, chain extender (DMPA) 2.6g, butanediol (BDO): 0.6g, triethylamine (TEA) 2g.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the double bond is blocked on the aqueous polyurethane emulsion, so that the aqueous polyurethane emulsion directly participates in free radical polymerization reaction to form the micron-level microphase-separated hydrogel material, and the mechanical properties of the material are improved on the premise of keeping the flexibility of the material.
2. The hydrogel has wide adhesion to organic and inorganic materials including polytetrafluoroethylene, can be applied to the aspects of wound dressing and the like, can be used as a matrix of a wearable flexible sensor, and has wide application characteristics.
Drawings
FIG. 1 is a diagram showing the practical application of the hydrogel material of the present invention on a glass substrate, a polypropylene plastic substrate, a polytetrafluoroethylene plastic substrate, and a stainless steel substrate, respectively.
FIG. 2 is a graph comparing compression properties of hydrogels prepared without polyurethane and hydrogels prepared with polyurethane.
FIG. 3 is a graph comparing the adhesion properties (smooth glass substrates) of the hydrogels prepared without the addition of polyurethane and the hydrogels prepared with the addition of polyurethane examples 1,2 and 4.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
The specific preparation method of the acrylic ester modified polyurethane adhesive hydrogel material comprises the following steps:
1. preparation of acrylate modified polyurethane emulsion:
step S1, adding polyether polyol PPG2000 into a three-necked flask, placing the flask into a vacuum oven, heating to 120 ℃, vacuum-maintaining for 3h for dehydration, and cooling to 80 ℃. Dibutyl tin dilaurate, diisocyanate, 1, 4-butanediol, 2-dimethylolpropionic acid, hydroxyethyl methacrylate, triethylamine, etc. were dehydrated using a 4A molecular sieve for pretreatment for 48 hours. Adding diisocyanate and dibutyltin dilaurate into a three-necked flask, heating to 90 ℃ for reaction for 2 hours, cooling to 80 ℃, adding a chain extender for reaction for 1 hour, cooling to 70 ℃, and adding a blocking agent for reaction for 3 hours to obtain a prepolymer. The prepolymer was cooled, and triethylamine was added thereto to conduct neutralization reaction for 30 minutes. Wherein the addition amounts of PPG2000, isophorone diisocyanate, dibutyl tin dilaurate, hydroxyethyl methacrylate, 1, 4-butanediol, 2-dimethylolpropionic acid and triethylamine are respectively as follows: 21.3:10.5:0.1:0.6:2.6:3:2.
and S2, adding 100g of water into 30g of the prepolymer obtained in the step S1, and stirring and emulsifying at 1100rpm for 30 minutes to obtain the acrylic ester modified polyurethane emulsion.
2. Preparation of acrylate modified polyurethane adhesive hydrogel materials:
step A1, dissolving an acrylic ester modified polyurethane emulsion, ammonium persulfate and acrylamide in water according to a proportion, and fully stirring to obtain a mixed emulsion system, wherein the acrylic ester modified polyurethane emulsion, ammonium persulfate, acrylamide and water have a proportion of 1:0.03:1:5.
and A2, placing the mixed emulsion system prepared in the step A1 in a mould, fully reacting for 6 hours at 60 ℃, taking out and cooling to obtain the acrylic ester modified polyurethane adhesive hydrogel material.
As shown in FIG. 3, the adhesion performance of the prepared hydrogel material is tested, and the adhesion performance of the hydrogel prepared by adding polyurethane on a smooth glass substrate is greatly improved.
Example two
The specific preparation method of the acrylic ester modified polyurethane adhesive hydrogel material comprises the following steps:
1. preparation of acrylate modified polyurethane emulsion:
step S1, the preparation process is the same as in example one except that the polyether polyol used is PPG3000, the catalyst used is bismuth carboxylate, and the end capping agent used is hydroxypropyl methacrylate. Wherein, the addition amounts of PPG3000, isophorone diisocyanate, bismuth carboxylate, hydroxypropyl methacrylate, 1, 4-butanediol, 2-dimethylolpropionic acid and triethylamine are respectively as follows: 17.75:10.5:0.1:0.6:2.6:3:2.
step S2 corresponds to the step in the first embodiment.
2. Preparation of acrylate modified polyurethane adhesive hydrogel materials:
step A1, dissolving an acrylic ester modified polyurethane emulsion, potassium persulfate, acrylamide and water in water according to a proportion, and fully stirring to obtain a mixed emulsion system, wherein the proportion of the acrylic ester modified polyurethane emulsion, the potassium persulfate, the acrylamide and the water is 2:0.03:1:4.3;
and A2, placing the mixed emulsion system prepared in the step A1 into a mold, fully reacting for 8 hours at the temperature of 40 ℃, taking out, and cooling to obtain the acrylic ester modified polyurethane adhesive hydrogel material.
As shown in FIG. 3, the adhesion performance of the prepared hydrogel material is tested, and the adhesion performance of the hydrogel prepared by adding polyurethane on a smooth glass substrate is greatly improved.
Example III
The specific preparation method of the acrylic ester modified polyurethane adhesive hydrogel material comprises the following steps:
1. preparation of acrylate modified polyurethane emulsion:
step S1, the procedure is as in example I, except that the polyether polyol used is PPG4000 and the capping agent used is methyl 2- (hydroxymethyl) acrylate. Wherein the addition amounts of PPG4000, isophorone diisocyanate, dibutyl tin dilaurate, methyl 2- (hydroxymethyl) acrylate, 1, 4-butanediol, 2-dimethylolpropionic acid and triethylamine are respectively as follows: 14.2:10.5:0.1:0.6:2.6:3:2.
step S2 corresponds to the step in the first embodiment.
2. Preparation of acrylate modified polyurethane adhesive hydrogel materials:
step A1, dissolving acrylic ester modified polyurethane emulsion, ammonium persulfate and acrylic acid in water according to a proportion, and fully stirring to obtain a mixed emulsion system, wherein the proportion of the acrylic ester modified polyurethane emulsion, the ammonium persulfate, the acrylic acid and the water is 2:0.03:1:4.3;
and A2, placing the mixed emulsion system prepared in the step A1 into a mold, fully reacting for 6 hours at 80 ℃, taking out, and cooling to obtain the acrylic ester modified polyurethane adhesive hydrogel material.
As shown in FIG. 2, the compression performance of the hydrogel prepared by adding polyurethane is greatly improved.
Example IV
The specific preparation method of the acrylic ester modified polyurethane adhesive hydrogel material comprises the following steps:
1. preparation of acrylate modified polyurethane emulsion:
step S1, the procedure is as in example I, except that the polyether polyol used is PPG3000 and the capping agent used is ethyl 2- (hydroxymethyl) acrylate. Wherein the PPG3000, isophorone diisocyanate, dibutyl tin dilaurate, ethyl 2- (hydroxymethyl) acrylate, 1, 4-butanediol, 2-dimethylolpropionic acid and triethylamine are respectively added in the following amounts: 21.3:10.5:0.1:0.6:2.6:3:2.
step S2 corresponds to the step in the first embodiment.
2. Preparation of acrylate modified polyurethane adhesive hydrogel materials:
step A1, dissolving an acrylic ester modified polyurethane emulsion, ammonium persulfate and acrylamide in water according to a proportion, and fully stirring to obtain a mixed emulsion system, wherein the acrylic ester modified polyurethane emulsion, ammonium persulfate, acrylamide and water have a proportion of 4:0.03:1:2.8;
and A2, placing the mixed emulsion system prepared in the step A1 in a mould, fully reacting for 6 hours at 60 ℃, taking out and cooling to obtain the acrylic ester modified polyurethane adhesive hydrogel material.
As shown in FIG. 1, the hydrogel material prepared by the method of the present invention is applied to glass substrates, polypropylene plastic substrates, polytetrafluoroethylene plastic substrates and stainless steel substrates, respectively.
As shown in FIG. 3, the adhesion performance of the prepared hydrogel material is tested, and the adhesion performance of the hydrogel prepared by adding polyurethane on a smooth glass substrate is greatly improved.
The acrylic ester modified polyurethane emulsion was changed to N, N' -methylenebisacrylamide, and polyacrylamide hydrogel was prepared as a comparative example. The two prepared hydrogel materials were subjected to mechanical and adhesive property tests, and the results are shown in Table one. The results show that compared with the polyacrylamide hydrogel, the acrylate modified polyurethane hydrogel has good mechanical properties and adhesive strength.
Table-performance index for examples 1-4 and comparative examples:
the foregoing description of the preferred embodiment of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (2)
1. The preparation method of the acrylate modified polyurethane adhesive hydrogel material is characterized by comprising the following components in parts by weight: 5-90 parts of acrylate modified polyurethane emulsion, 0.4 part of water-soluble initiator, 8-15 parts of gel monomer and 0-80 parts of water;
the preparation method comprises the following steps:
step A1, dissolving an acrylic ester modified polyurethane emulsion, a water-soluble initiator and a gel monomer in water according to a proportion, and stirring for 2-3 minutes at 200-500 rpm to obtain a mixed emulsion system;
step A2, placing the mixed emulsion system prepared in the step A1 in a mold, fully reacting for 6-8 hours at the temperature of 40-80 ℃, taking out and cooling to obtain an acrylic ester modified polyurethane adhesive hydrogel material;
the gel monomer is any one of acrylamide or acrylic acid, and the water-soluble initiator is any one of ammonium persulfate or potassium persulfate;
the specific preparation process of the acrylic ester modified polyurethane emulsion comprises the following steps:
step S1, dehydrating polyether polyol, a catalyst, diisocyanate, a chain extender, a blocking agent and triethylamine; polyether polyol, diisocyanate and a catalyst are added into a three-neck flask, and the mixed solvent is heated to 90 ℃ to react 2 h; then cooling to 80 ℃, adding a chain extender and reacting 1 h; cooling to 70 ℃, and adding a blocking agent to react 3h to obtain a prepolymer; cooling the prepolymer to room temperature, and adding triethylamine to perform neutralization reaction for 30 minutes;
step S2, adding 100 parts of water into 30 parts of the prepolymer prepared in the step S1, and stirring and emulsifying for 30 minutes at 1100rpm to obtain an acrylic ester modified polyurethane emulsion;
the molecular weight of the polyether polyol is 2000-4000;
the diisocyanate is isophorone diisocyanate;
the end capping agent is any one of hydroxyethyl methacrylate, hydroxypropyl methacrylate, methyl 2- (hydroxymethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate and alpha-methacrylic acid;
the catalyst is any one of dibutyl tin dilaurate and bismuth carboxylate;
the chain extender is a mixture of 1, 4-butanediol and 2, 2-dimethylolpropionic acid, and the mass ratio of the 1, 4-butanediol to the 2, 2-dimethylolpropionic acid is 1:4-1:5.
2. The method for preparing the acrylate modified polyurethane adhesive hydrogel material according to claim 1, wherein the method comprises the following steps:
the catalyst addition amount is 1% of the mass of isophorone diisocyanate;
the total addition amount of the chain extender is 7% -10% of the total mass of the acrylic ester modified polyurethane emulsion;
the addition content of the blocking agent is 130% -200% of the calculated mole number of the residual isocyanate groups.
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Application publication date: 20220513 Assignee: Shanxi Lingde Technology Co.,Ltd. Assignor: Taiyuan University of Technology Contract record no.: X2024980008158 Denomination of invention: Acrylate modified polyurethane adhesive hydrogel material and its preparation method Granted publication date: 20230627 License type: Common License Record date: 20240626 |