CN114907543A - Waterborne polyurethane resin for medicine packaging and preparation method and application thereof - Google Patents
Waterborne polyurethane resin for medicine packaging and preparation method and application thereof Download PDFInfo
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- CN114907543A CN114907543A CN202210703751.4A CN202210703751A CN114907543A CN 114907543 A CN114907543 A CN 114907543A CN 202210703751 A CN202210703751 A CN 202210703751A CN 114907543 A CN114907543 A CN 114907543A
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
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- C08G18/40—High-molecular-weight compounds
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- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
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- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C08G18/67—Unsaturated compounds having active hydrogen
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- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
- C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
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- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention discloses a waterborne polyurethane resin for medicine encapsulation and a preparation method thereof, wherein the method comprises the following steps: dehydrating polyester polyol and hydrophilic monomer at 100-110 ℃, cooling to room temperature, adding aliphatic diisocyanate, stirring for a prepolymerization reaction, adding an organic tin catalyst, uniformly mixing, heating to 70-80 ℃, keeping the temperature, cooling to 50-60 ℃, adding small molecular diol for a chain extension reaction, heating to 60-70 ℃, adding a hydroxyl acrylate monomer and/or epoxy resin, keeping the temperature, performing an addition reaction, cooling to 30-40 ℃, adding organic base for a neutralization reaction to maintain the pH value between 7 and 8, and obtaining polyurethane resin containing an ammonium carboxylate structure; and heating to 60-70 ℃, then dropwise adding purified water, cooling to room temperature, adding an initiator, and uniformly mixing to obtain the waterborne polyurethane resin for medicine packaging. Has lower viscosity and higher heat-seal strength and is environment-friendly.
Description
Technical Field
The invention relates to the technical field of biological medicines, and particularly relates to a waterborne polyurethane resin for medicine encapsulation, and a preparation method and application thereof.
Background
With the development of modern industry, environmental pollution and climate change become serious problems of global concern. Countries around the world set strict limits on the amount of Volatile Organic Compounds (VOCs) contained in chemical materials. China has begun to promote industry transformation or upgrading in related industries. In the field of polymer materials, environment-friendly polymer materials using water as a medium have become a current research hotspot.
The waterborne polyurethane material has been studied and developed for nearly 40 years as an environment-friendly polymer material with a very wide application prospect in China, but the application of the waterborne polyurethane material as a food and drug packaging material has the problems of low bonding strength, poor barrier property, poor sealing property and the like.
Therefore, there is a need to develop an environmentally friendly aqueous polyurethane material having high sealability and barrier properties, having a lower viscosity and a higher heat-seal strength, and meeting the application requirements.
Disclosure of Invention
The invention aims to provide a waterborne polyurethane resin for drug encapsulation and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect of the present invention, there is provided a pharmaceutical encapsulating aqueous polyurethane resin, which is prepared from raw materials including, in mass fraction:
aliphatic diisocyanate: 5.8-8.2 wt.%;
polyester polyol: 14-18.5 wt.%;
hydrophilic monomer: 1-1.5 wt.%;
small-molecule chain extender: 0.2-0.5 wt.%;
hydroxy acrylate ester: 1-2.5 wt.%;
epoxy resin: 0-3.5 wt.%;
organotin catalyst: 0.1-0.3 wt.%;
organic base neutralizer: 0-0.9 wt.%;
purified water: 65-70 wt.%;
initiator: 0.15-0.3 wt.%.
Further, the polyester polyol includes a mixture of one or more of polyethylene glycol-adipate-butanediol-adipate polyol (EGBG), polycaprolactone Polyol (PCL), and polycarbonate Polyol (PCD) having a number average molecular weight in the range of 500-2000.
Further, the hydrophilic monomer is a compound with a molecular structure containing hydrophilic groups such as carboxyl, hydroxyl, sulfonate and the like; comprises one or more of dimethylol propionic acid (DMPA), dimethylol butyric acid (DMBA), 1, 3-propanediol sodium sulfonate and 1, 4-butanediol sodium sulfonate.
Further, the aliphatic diisocyanate comprises a mixture of one or more of isophorone diisocyanate (IPDI), 1, 6-Hexamethylene Diisocyanate (HDI) and 1, 4-dicyclohexylmethane diisocyanate (HMDI).
Further, the organic tin catalyst comprises one or a mixture of two of dibutyltin dilaurate and stannous octoate.
Further, the small molecule dihydric alcohol comprises one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol and 1, 4-butanediol.
Further, the organic base is an amine compound, and comprises one of Triethylamine (TEA), diethanolamine or triethanolamine.
In a second aspect of the present invention, there is provided a method for preparing an aqueous polyurethane resin for drug encapsulation, the method comprising:
dehydrating polyester polyol and hydrophilic monomer at 100-120 ℃, cooling to room temperature, adding aliphatic diisocyanate, stirring, and carrying out prepolymerization reaction to obtain a prepolymer;
adding an organic tin catalyst into the prepolymer, uniformly mixing, heating to 70-80 ℃, keeping the temperature, cooling to 50-60 ℃, adding a small molecular diol to carry out chain extension reaction, and obtaining a high polymer;
heating the high polymer to 60-70 ℃, adding a hydroxyl acrylate monomer and/or epoxy resin, and carrying out heat preservation for addition reaction to obtain an acrylate structure-terminated polymer;
cooling the polymer with the end capped by the acrylate structure to 30-40 ℃, adding organic base for neutralization reaction to maintain the pH value between 7 and 8, and obtaining polyurethane resin with an ammonium carboxylate structure;
heating the polyurethane resin containing the ammonium carboxylate structure to 60-70 ℃, then dropwise adding purified water, cooling to room temperature, adding an initiator, and uniformly mixing to obtain the waterborne polyurethane resin for medicine packaging.
Further, the time of the dehydration treatment is 1-3 h, and the vacuum degree of the dehydration treatment is maintained at 0.098-0.1 MPa; the prepolymerization time is 1-2 h.
Further, the temperature is raised to 70-80 ℃ and the heat preservation time is 3-5 h; and the time of the chain extension reaction is 1-3 h.
In a third aspect of the invention, the application of the aqueous polyurethane resin for drug encapsulation as a high-end coating material or an encapsulation material is provided.
One or more technical solutions in the embodiments of the present invention at least have the following technical effects or advantages:
1. according to the preparation method of the waterborne polyurethane resin for medicine encapsulation, provided by the invention, a carbon-carbon double bond and an epoxy structure are introduced in the aspect of polyurethane molecular structure design, and a crosslinking reaction can be carried out under the heating condition to obtain a high-density crosslinked network structure, so that the sealing property and the barrier property of the material are greatly improved; the polyurethane resin terminated by acrylate monomer or epoxy structure has controllable relative molecular mass and viscosity; the preparation method can obtain the polyurethane aqueous dispersion with high solid content and low viscosity, and is beneficial to processing, forming, application and construction.
2. The polymer system synthesized by the waterborne polyurethane resin for medicine encapsulation provided by the invention takes purified water as a dispersion medium, and compared with the traditional solvent-based polyurethane material, the polymer system does not contain an organic solvent and toxic and harmful organic volatile matters, thereby scientifically solving the problem of VOCs emission and being environment-friendly.
3. The waterborne polyurethane resin can be used as a high-end coating material or a packaging material, and is applied to the fields of packaging, printing and packaging of medical instruments, foods and medicines and the like.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a reaction route diagram of a preparation method of the waterborne polyurethane resin for drug encapsulation provided by the invention.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be obtained by an existing method.
In order to solve the technical problems, the general idea of the embodiment of the application is as follows:
according to an exemplary embodiment of the present invention, there is provided a method for preparing an aqueous polyurethane resin for drug encapsulation, as shown in fig. 1, the method including:
step S1, dehydrating the polyester polyol and the hydrophilic monomer at 100-120 ℃, cooling to room temperature, adding aliphatic diisocyanate, stirring, and carrying out prepolymerization reaction to obtain a prepolymer;
in the step S1, in the above step,
the time of the dehydration treatment is 1-3 h, and the vacuum degree of the dehydration treatment is kept at 0.098-0.1 MPa;
the prepolymerization reaction time is 1-2 h.
The polyester polyol includes a mixture of one or more of polyethylene glycol-adipate-butanediol-adipate polyol (EGBG), polycaprolactone Polyol (PCL), and polycarbonate Polyol (PCD) having a number average molecular weight in the range of 500-.
The hydrophilic monomer is a compound with a molecular structure containing hydrophilic groups such as carboxyl, hydroxyl, sulfonate and the like; comprises one or more of dimethylol propionic acid (DMPA), dimethylol butyric acid (DMBA), 1, 3-propanediol sodium sulfonate and 1, 4-butanediol sodium sulfonate.
The aliphatic diisocyanate comprises a mixture of one or more of isophorone diisocyanate (IPDI), 1, 6-Hexamethylene Diisocyanate (HDI) and 1, 4-dicyclohexylmethane diisocyanate (HMDI).
Step S2, adding an organic tin catalyst into the prepolymer, mixing uniformly, heating to 70-80 ℃, keeping the temperature, cooling to 50-60 ℃, adding small molecular dihydric alcohol, and carrying out chain extension reaction to obtain a high polymer;
in the step S2, in the above step,
the temperature is raised to 70-80 ℃ and the heat preservation time is 3-5 h; and the time of the chain extension reaction is 1-3 h.
The organic tin catalyst comprises one or a mixture of two of dibutyltin dilaurate and stannous octoate.
The small molecule dihydric alcohol comprises one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol and 1, 4-butanediol.
Step S3, heating the high polymer to 60-70 ℃, adding a hydroxyl acrylate monomer and/or epoxy resin, and carrying out an addition reaction to obtain an acrylate structure-terminated polymer;
specifically, heating to 60-70 ℃, adding a hydroxyl acrylate monomer or epoxy resin, and reacting for 2-3 hours in a heat preservation manner;
the hydroxyl acrylate monomer contains hydroxyl in the molecular structure, and can perform addition reaction with the terminal-NCO of the polyurethane prepolymer to obtain a polymer terminated by an acrylate structure.
The molecular structure of the hydroxyl acrylate monomer contains carbon-carbon double bonds (-CH ═ CH-), and under the condition of heating, the initiator initiates free radical polymerization to form an intermolecular crosslinking structure.
The epoxy resin is bisphenol A epoxy resin and comprises epoxy E44 and E51.
The epoxy resin contains hydroxyl in a molecular structure, and can perform addition reaction with terminal-NCO of a polyurethane prepolymer to obtain a polymer terminated with an epoxy structure. The conversion of the isocyanate group (-NCO) was determined by titration according to the method of "determination of the content of isocyanate group in polyurethane prepolymer" HG-T2409-1992, and the end of the blocking reaction was indicated when the-NCO content reached the theoretical value, to obtain a polyurethane resin blocked with a reactive functional group.
The molecular structure of the epoxy resin contains epoxy groups
Under the heating condition, the epoxy group can be mixed with intermolecular hydroxyl (-OH) and amino (-NH) 2 ) And the carboxyl (-COOH) to form an intermolecular crosslinking structure.
Step S4, cooling the polymer with the end capped by the acrylate structure to 30-40 ℃, adding organic base for neutralization reaction to maintain the pH value between 7 and 8, and obtaining polyurethane resin with an ammonium carboxylate structure;
the organic base is an amine compound, and comprises one of Triethylamine (TEA), diethanolamine or triethanolamine.
Adding organic alkali for neutralization reaction for 0.5-1 hour, and maintaining the pH value between 7 and 8;
and the neutralization reaction is an acid-base neutralization reaction between organic base and polyurethane molecular side group carboxyl to obtain the polyurethane resin containing the ammonium carboxylate structure.
Step S5, heating the polyurethane resin containing the ammonium carboxylate structure to 60-70 ℃, then dropwise adding purified water and cooling to room temperature, adding an initiator and mixing uniformly to obtain the waterborne polyurethane resin for medicine packaging.
The temperature of the system is increased to 60-70 ℃, so that the solubility of the polyurethane resin can be increased.
The dropping of purified water is accompanied with strong stirring and dispersion because the polymer is subjected to phase inversion in the process, namely, the hydrophilic ammonium carboxylate groups are outwards inverted and fully contacted with water; the lipophilic/hydrophobic polyurethane backbone or side chain turns inward and curls into clusters away from the aqueous phase. Thereby forming a spherical micelle structure of oil-in-water (O/W).
The strong dispersion is because the viscosity of the resin increases during the phase inversion, and the resistance to dispersion increases accordingly. The strong dispersion aims to obtain a dispersion with micelle particle size distribution of 10-50 nm and blue light and has a Tyndall effect.
The initiator can be decomposed into free radicals under the heating condition, so that the prepolymer containing carbon-carbon double bonds is initiated to carry out a crosslinking reaction, and a crosslinked network structure is generated.
The waterborne polyurethane resin for medicine encapsulation prepared by the method is an aqueous dispersion with blue light, the particle size is 10-50 nm, and the distribution is narrow.
The waterborne polyurethane resin for medicine encapsulation can be used as a coating material or an encapsulating material and widely applied to the fields of medical appliances, food and medicine encapsulation, printing and packaging and the like.
The following will explain in detail a method for preparing an aqueous polyurethane resin for drug encapsulation according to the present application with reference to examples and experimental data.
Example 1
1. The embodiment of the invention provides a preparation raw material of waterborne polyurethane resin for medicine encapsulation, which comprises the following components in parts by weight (wt%):
isophorone diisocyanate (IPDI): 8.1
Polyester polyol (EGBG, 1000): 18.2
Dimethylolpropionic acid (DMPA): 1.2
1, 4-Butanediol (BOD): 0.4
Hydroxyethyl acrylate (HEA) 1.1
Dibutyl tin dilaurate: 0.15
Triethylamine (TEA): 1
Purified water (H) 2 O)： 69.7
Dibenzoyl peroxide (BPO) 0.15.
The embodiment of the invention provides a structural formula of waterborne polyurethane resin for medicine packaging, which is as follows:
2. the invention relates to a preparation method of waterborne polyurethane resin for medicine encapsulation, which comprises the following steps:
adding 1000g of polyester polyol (EGBG-1000) and 67g of hydrophilic monomer (DMPA) into a reaction vessel, and dehydrating at 110-120 ℃ for 1-2 hours; cooling the system to room temperature, adding 444g of isophorone diisocyanate (IPDI), stirring at room temperature, and carrying out prepolymerization reaction for 1-2 hours; then adding 5g of dibutyltin dilaurate, stirring and mixing uniformly, and then heating to 60-80 ℃ for reaction for 3-5 hours in a heat preservation way; reducing the temperature of the system to 40-50 ℃, adding 22.5g of 1, 4-butanediol, and carrying out chain extension reaction for 1-2 hours; heating to 60-70 ℃, adding 116g of hydroxyethyl acrylate (HEA), and reacting for 2-4 hours under the condition of heat preservation; cooling to 30-50 ℃, adding 50.5g Triethylamine (TEA) for neutralization reaction for 1-2 hours; heating to 50-70 ℃, dropwise adding 3848g of purified water, and strongly dispersing to obtain a polyurethane aqueous dispersion; and cooling to room temperature, and adding 8.2g of dibenzoyl peroxide to obtain the waterborne polyurethane resin for medicine packaging.
3. Example 1 material performance test results:
TABLE 1
Example 2
1. The embodiment of the invention provides a preparation raw material of waterborne polyurethane resin for medicine encapsulation, which comprises the following components in parts by weight (wt%):
1, 6-Hexamethylene Diisocyanate (HDI): 5.8
Polycaprolactone polyol (PCL, 1000): 17.2
Dimethylol butyric acid (DMBA): 1.3
epoxy-E513.4
Ethylene glycol: 0.3
Hydroxypropyl acrylate (HPA) 1.1
Dibutyltin dilaurate: 0.15
Triethylamine (TEA): 0.09
Purified water (H) 2 O)： 69.7
Azobisisobutyronitrile (AIBN) 0.15
The embodiment of the invention provides a structural formula of waterborne polyurethane resin for medicine packaging, which is as follows:
2. the invention relates to a preparation method of waterborne polyurethane resin for medicine encapsulation, which comprises the following steps:
adding 1000g of polycaprolactone polyol (PCL-1000) and 74g of hydrophilic monomer (DMBA) into a reaction vessel, and dehydrating at 110-120 ℃ for 1-2 hours; cooling the system to room temperature, adding 336g of 1, 6-Hexamethylene Diisocyanate (HDI), stirring at room temperature, and carrying out prepolymerization reaction for 1-2 hours; then adding 5g of dibutyltin dilaurate, stirring and mixing uniformly, and then heating to 60-80 ℃ for reaction for 3-5 hours in a heat preservation way; reducing the temperature of the system to 40-50 ℃, adding 15.5g of glycol, and carrying out chain extension reaction for 1-2 hours; heating to 60-70 ℃, adding 65g of hydroxypropyl acrylate (HPA), and reacting for 2-4 hours under the condition of heat preservation; cooling to 30-50 ℃, adding 50.5g Triethylamine (TEA) for neutralization reaction for 1-2 hours; heating to 50-70 ℃, dripping 4064.7g of purified water, and strongly dispersing to obtain polyurethane aqueous dispersion; and cooling to room temperature, and adding 8.7g of azobisisobutyronitrile to obtain the waterborne polyurethane resin for medicine packaging.
3. Example 2 material performance test results:
TABLE 2
| Test items | Test method | Test results |
| Appearance of the product | Observation method | Translucent blue dispersion |
| Solid content (%) | GB1725-79 2004 | 30 |
| pH value | GB/T23769-2009 | 7.5 |
| Adhesion force | GB/T 1720-1979(89) | ≤1 |
| Hardness of | GB/T 1720-1979(89) | ≥H |
| Viscosity of the oil | (coating 4 cup at 25 ℃ C.) | 13 +/-1 second |
| Particle size | Dynamic light scattering method | 10-100nm |
| Topography | Scanning Electron Microscopy (SEM) | Spherical shape |
Example 3
1. The embodiment of the invention provides a preparation raw material of waterborne polyurethane resin for medicine encapsulation, which comprises the following components in parts by weight (wt%):
4, 4' -diphenylmethane diisocyanate (HMDI): 7.6
Polycarbonate polyol (PCD, 1000): 14
Dimethylolbutyric acid: 1.08
epoxy-E443.31
1, 3-propanediol: 0.28
Pentaerythritol triacrylate 2.17
Stannous octoate: 0.89
Diethanolamine: 0.77
Purified water (H) 2 O)： 69.7
Azobisisobutyronitrile (AIBN) 0.2
The embodiment of the invention provides a structural formula of waterborne polyurethane resin for medicine packaging, which is as follows:
2. the invention relates to a preparation method of waterborne polyurethane resin for medicine encapsulation, which comprises the following steps:
adding 1000g of polycarbonate polyol (PCD-1000) and 74g of hydrophilic monomer (DMBA) into a reaction vessel, and dehydrating at 110-120 ℃ for 1-2 hours; cooling the system to room temperature, adding 524g of 4, 4-dicyclohexyl methane diisocyanate (HMDI), stirring at room temperature, and carrying out prepolymerization reaction for 1-2 hours; then adding 6.1g of stannous octoate, stirring and mixing uniformly, and then heating to 60-80 ℃ for reaction for 3-5 hours with heat preservation; reducing the temperature of the system to 40-50 ℃, adding 19g of 1, 3-propylene glycol, and carrying out chain extension reaction for 1-2 hours; heating to 60-70 ℃, adding 149g of pentaerythritol triacrylate (TPE3A), and reacting for 2-4 hours under the condition of heat preservation; cooling to 30-50 ℃, adding 52.5g of diethanolamine for neutralization reaction for 1-2 hours; heating to 50-70 ℃, dropwise adding 4772g of purified water, and strongly dispersing to obtain a polyurethane aqueous dispersion; and cooling to room temperature, and adding 13.6g of azobisisobutyronitrile to obtain the waterborne polyurethane resin for medicine packaging.
3. Example 3 material performance test results:
TABLE 3
| Test items | Test method | Test results |
| Appearance of the product | Observation method | Translucent blue dispersion |
| Solid content (%) | GB1725-79 2004 | 30 |
| pH value | GB/T23769-2009 | 7.5 |
| Adhesion force | GB/T 1720-1979(89) | ≤1 |
| Hardness of | GB/T 1720-1979(89) | ≥H |
| Viscosity of the oil | (coating 4 cup at 25 ℃ C.) | 17 +/-1 second |
| Particle size | Dynamic light scattering method | 50-100nm |
| Morphology of | Scanning Electron Microscopy (SEM) | Spherical shape |
Example 4
1. The embodiment of the invention provides a preparation raw material of aqueous polyurethane resin for medicine encapsulation, which comprises the following components in parts by weight (wt.%):
4, 4' -diphenylmethane diisocyanate (HMDI): 8.2
Polycarbonate polyol (PCD, 1000): 15.7
Sodium 1, 4-butanediol-2-sulfonate: 1.5
epoxy-E513.07
1, 4-butanediol: 0.36
Hydroxyethyl methacrylate 1
Stannous octoate: 0.09
Purified water (H) 2 O)： 70
Azobisisobutyronitrile (AIBN) 0.09
The embodiment of the invention provides a structural formula of waterborne polyurethane resin for medicine packaging, which is as follows:
2. the invention relates to a preparation method of waterborne polyurethane resin for medicine encapsulation, which comprises the following steps:
adding 1000g of polycarbonate polyol (PCD-1000) and 96g of hydrophilic monomer 1, 4-butanediol-2-sodium sulfonate into a reaction vessel, and dehydrating at 110-120 ℃ for 1-2 hours; cooling the system to room temperature, adding 524g of 4, 4-dicyclohexyl methane diisocyanate (HMDI), stirring at room temperature, and carrying out prepolymerization reaction for 1-2 hours; then adding 5.7g of stannous octoate, stirring and mixing uniformly, and then heating to 60-80 ℃ for reaction for 3-5 hours with heat preservation; reducing the temperature of the system to 40-50 ℃, adding 22.5g of 1, 4-butanediol, and carrying out chain extension reaction for 1-2 hours; heating to 60-70 ℃, adding 65g of hydroxyethyl methacrylate, and reacting for 2-4 hours under the condition of heat preservation; cooling to 50 ℃, and dripping 4468.1g of purified water for strong dispersion to obtain polyurethane aqueous dispersion; and cooling to room temperature, and adding 5.7g of azobisisobutyronitrile to obtain the waterborne polyurethane resin for medicine packaging.
3. Example 4 material performance test results:
TABLE 4
Example 5
1. The embodiment of the invention provides a preparation raw material of waterborne polyurethane resin for medicine encapsulation, which comprises the following components in parts by weight (wt%):
isophorone diisocyanate (IPDI): 7.18
Polycaprolactone polyol (PCL, 1000): 8.08
Polycarbonate polyol (PCD,1000) 8.08
Dimethylolpropionic acid (DMPA): 1.08
1, 4-Butanediol (BOD): 0.36
Hydroxypropyl Methacrylate (HMEA) 1.05
Epoxy resin-E513.17
Dibutyltin dilaurate: 0.1
Triethylamine (TEA): 0.8
Purified water (H) 2 O)： 70
Dibenzoyl peroxide (BPO) 0.1
The embodiment of the invention provides a structural formula of waterborne polyurethane resin for medicine encapsulation, which is as follows:
2. the invention relates to a preparation method of waterborne polyurethane resin for medicine encapsulation, which comprises the following steps:
adding 500g of polycaprolactone polyol (PCL-1000), 500g of polycarbonate polyol (PCD-1000) and 67g of hydrophilic monomer (DMPA) into a reaction vessel, and dehydrating at 110-120 ℃ for 1-2 hours; cooling the system to room temperature, adding 444g of isophorone diisocyanate (IPDI), stirring at room temperature, and carrying out prepolymerization reaction for 1-2 hours; then adding 5.5g of dibutyltin dilaurate, stirring and mixing uniformly, heating to 60-80 ℃, and carrying out heat preservation reaction for 3-5 hours; reducing the temperature of the system to 40-50 ℃, adding 22.5g of 1, 4-butanediol, and carrying out chain extension reaction for 1-2 hours; heating to 60-70 ℃, adding 65g of Hydroxyethyl Methacrylate (HMEA), and reacting for 2-4 hours under the condition of heat preservation; cooling to 30-50 ℃, adding 50.5g Triethylamine (TEA) for neutralization reaction for 1-2 hours; heating to 50-70 ℃, dripping 4330.7g of purified water, and strongly dispersing to obtain polyurethane aqueous dispersion; and cooling to room temperature, and adding 5.5g of dibenzoyl peroxide to obtain the waterborne polyurethane resin for medicine packaging.
3. Example 5 material performance test results:
TABLE 5
| Test items | Test method | Test results |
| Appearance of the product | Observation method | Translucent blue dispersion |
| Solid content (%) | GB1725-79 2004 | 30 |
| pH value | GB/T23769-2009 | 8 |
| Adhesion force | GB/T 1720-1979(89) | ≤1 |
| Hardness of | GB/T 1720-1979(89) | ≥H |
| Viscosity of the oil | (coating 4 cup at 25 ℃ C.) | 17 +/-1 second |
| Particle size | Dynamic light scattering method | 10-50nm |
| Morphology of | Scanning Electron Microscopy (SEM) | Spherical shape |
In conclusion, the invention introduces hydrophilic functional groups into polyurethane molecules, so that the polymer is dissolved in water or forms polymer micelles in the water; simultaneously, carbon-carbon double bonds or epoxy structures are introduced, and a thermal crosslinking reaction can be generated to form a crosslinking network structure. The polymer has excellent bonding, blocking and sealing performances, and can be used for heat sealing of medicinal aluminum foil and PVC/PVDC plates.
Finally, it should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. The aqueous polyurethane resin for medicine encapsulation is characterized in that the raw materials for preparing the aqueous polyurethane resin for medicine encapsulation comprise the following components in parts by mass:
2. the waterborne polyurethane resin for drug encapsulation as claimed in claim 1, wherein the polyester polyol comprises one or more of polyethylene glycol-adipate-butanediol-adipate polyol (EGBG), polycaprolactone Polyol (PCL) and polycarbonate Polyol (PCD) with number average molecular weight in the range of 500-2000.
3. The waterborne polyurethane resin for drug encapsulation according to claim 1, wherein the hydrophilic monomer is a compound having a molecular structure containing a hydrophilic group such as carboxyl, hydroxyl, sulfonate, etc.; comprises one or more of dimethylol propionic acid (DMPA), dimethylol butyric acid (DMBA), 1, 3-propanediol sodium sulfonate and 1, 4-butanediol sodium sulfonate.
4. The waterborne polyurethane resin for drug encapsulation of claim 1, wherein the aliphatic diisocyanate comprises a mixture of one or more of isophorone diisocyanate (IPDI), 1, 6-Hexamethylene Diisocyanate (HDI) and 1, 4-dicyclohexylmethane diisocyanate (HMDI).
5. The waterborne polyurethane resin for drug encapsulation according to claim 1, wherein the organotin catalyst comprises one or a mixture of two of dibutyltin dilaurate and stannous octoate.
6. The waterborne polyurethane resin for drug encapsulation according to claim 1, wherein the small molecule diol comprises a mixture of one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol and 1, 4-butylene glycol; the organic base is an amine compound, and comprises one of Triethylamine (TEA), diethanolamine or triethanolamine.
7. A method for preparing the aqueous polyurethane resin for drug encapsulation according to any one of claims 1 to 6, which comprises:
dehydrating polyester polyol and hydrophilic monomer at 100-120 ℃, cooling to room temperature, adding aliphatic diisocyanate, stirring, and carrying out prepolymerization reaction to obtain a prepolymer;
adding an organic tin catalyst into the prepolymer, uniformly mixing, heating to 70-80 ℃, keeping the temperature, cooling to 50-60 ℃, adding a small molecular diol to carry out chain extension reaction, and obtaining a high polymer;
heating the high polymer to 60-70 ℃, adding a hydroxyl acrylate monomer and epoxy resin or only adding hydroxyl acrylate, and carrying out an addition reaction to obtain an acrylate structure-terminated polymer;
cooling the polymer with the end capped by the acrylate structure to 30-40 ℃, adding 0-0.9 wt.% of organic alkali to perform a neutralization reaction so as to maintain the pH value between 7 and 8, and obtaining polyurethane resin with an ammonium carboxylate structure;
heating the polyurethane resin containing the ammonium carboxylate structure to 60-70 ℃, then dropwise adding purified water, cooling to room temperature, adding an initiator, and uniformly mixing to obtain the waterborne polyurethane resin for medicine packaging.
8. The preparation method of the waterborne polyurethane resin for drug encapsulation as claimed in claim 7, wherein the time of the dehydration treatment is 1-3 h, and the aggregate vacuum degree of the dehydration treatment is 0.098-0.1 MPa; the prepolymerization time is 1-2 h.
9. The preparation method of the waterborne polyurethane resin for drug encapsulation as claimed in claim 7, wherein the temperature is raised to 70-80 ℃ for 3-5 h; and the time of the chain extension reaction is 1-3 h.
10. Use of the aqueous polyurethane resin for drug encapsulation according to any one of claims 1 to 6 as a high-end coating material or an encapsulation material.
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| CN115558368A (en) * | 2022-09-30 | 2023-01-03 | 武汉弘毅共聚新材料科技有限公司 | Water-based OP agent for medicine packaging and preparation method thereof |
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