CN114103281B - Moisturizing three-layer material and preparation method thereof - Google Patents

Moisturizing three-layer material and preparation method thereof Download PDF

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CN114103281B
CN114103281B CN202111404818.6A CN202111404818A CN114103281B CN 114103281 B CN114103281 B CN 114103281B CN 202111404818 A CN202111404818 A CN 202111404818A CN 114103281 B CN114103281 B CN 114103281B
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coupling agent
elastomer
hydrogel
brush
layer material
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CN114103281A (en
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吉笑盈
李东亮
罗诚
赵丽娟
吴锦荣
王�义
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China Tobacco Sichuan Industrial Co Ltd
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China Tobacco Sichuan Industrial Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/10—Interconnection of layers at least one layer having inter-reactive properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/18—Layered products comprising a layer of natural or synthetic rubber comprising butyl or halobutyl rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—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
    • C08J2333/24—Homopolymers or copolymers of amides or imides
    • C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide

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  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

The invention provides a moisturizing three-layer material and a preparation method thereof, wherein the moisturizing three-layer material is formed by chemically connecting an upper layer elastomer, a middle layer hydrogel and a lower layer brush-shaped elastomer through a coupling agent; the hydrogel is polyacrylamide hydrogel containing a moisturizing factor and a coupling agent, and the elastomer is brominated butyl rubber containing the coupling agent; the brush-shaped elastomer is an elastomer taking brush-shaped polysiloxane as a matrix; the material has good bonding effect and good water retention effect, can intelligently regulate and control the release and absorption of the material to water according to the humidity change of the external environment, has excellent mechanical property and buffer liner effect, and is very suitable for the moisture retention protection of cigars and the like.

Description

Moisturizing three-layer material and preparation method thereof
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a moisturizing three-layer material and a preparation method thereof.
Background
Cigars are produced, stored and sold for 1-2 years from the end to the end of the time of the consumer, during which the temperature is 18-20 ℃ and the relative humidity is 65-70% which are the most suitable conditions for the preservation and maintenance of cigars. However, the environment outside the cigar is subject to different humidity and temperature variations, and the moisture content of the cigar will vary drastically if no effective moisture preservation measures are taken. Cigars with higher water content are difficult to ignite and keep burning, and the smoking quality is also affected; even bad phenomena such as eggplant coat cracking can occur when the water content is low. Therefore, regulating the humidity of the cigar preservation microenvironment is significant in the transportation, storage and sales of cigars. Therefore, how to regulate the humidity of the cigar package microenvironment, maintain the sensory quality of the cigar product, and improve the market competitiveness of cigar storage is an important problem to be solved.
The polymer hydrogel is a functional polymer material formed by a three-dimensional crosslinked network and capable of swelling by water, and has excellent water absorption and water retention characteristics. The hydrogel has wide application prospect in the fields of biomedicine, wet cultural relic protection, wearable and implantation equipment and the like. Brominated butyl rubber (BIIR) is an isobutylene-isoprene elastomer copolymer containing active bromine, and a carbon-carbon main chain structure endows the copolymer with good flexibility, chemical inertness, acid and alkali corrosion resistance, barrier property and good weather resistance, and plays roles of buffering, damping and isolating oxygen. Brush polymers are also called polymer molecular brushes, which refer to a type of polymer system with a specific structure formed by grafting polymer chains onto a polymer backbone. Due to the steric hindrance, these polymer side chains repel each other and stretch outwards, so that a structure similar to a laboratory flask brush is achieved at the molecular level; the brush-shaped polymer has adjustable free volume, plays a role in regulating and controlling the diffusion and absorption of water, and can be applied to cigar protection to prevent the cigar from losing water in a low-humidity environment and inhibit the cigar from absorbing water in a high-humidity environment, so that the cigar can keep constant moisture content for a long time.
Disclosure of Invention
The brominated butyl rubber elastomer material, the moisturizing hydrogel material and the brush-shaped polymer material for preventing reverse osmosis of moisture in the hydrogel are organically combined together to form a three-layer material, wherein the inner layer is a brush-shaped elastomer, the middle layer is the moisturizing hydrogel, and the outer layer is an elastomer layer. However, the application of the material with the special three-layer structure in the cigar micro-humidity environment regulation field is rarely reported.
The invention aims to provide a composite material with excellent humidity regulating performance, and in particular, the invention adopts the following technical scheme:
a three-layer material for moisture preservation is formed by chemically connecting an upper layer elastomer, a middle layer hydrogel and a lower layer brush-shaped elastomer through a coupling agent;
the hydrogel is polyacrylamide hydrogel at least containing a moisturizing factor and a coupling agent, and the elastomer is brominated butyl rubber containing the coupling agent; the brush-shaped elastomer is an elastomer taking brush-shaped polysiloxane as a matrix.
The polyacrylamide hydrogel is formed by polymerizing monomers under the action of an initiator, a catalyst and a crosslinking agent, wherein the monomers comprise acrylamide.
The thickness ratio of the elastomer, the hydrogel and the brush-shaped elastomer is (0.2-10): 0.5-30): 0.2-10. Preferably, the thickness ratio of the elastomer, the hydrogel to the brush-like elastomer is (0.1-0.6): 1 (0.1-0.7).
In the three-layer material for moisture preservation, the thickness of the brush-shaped elastomer accounts for 10% -30% of the total thickness of the three-layer material for moisture preservation, for example, the thickness ratio of the brush-shaped elastomer accounts for 11%, 15%, 17%, 20%, 22%, 25%, 26.5%, 27%, 29% and the like; the thickness of the elastomer (brominated butyl rubber) accounts for 15% -20% of the total thickness of the three-layer material with moisture retention, such as the thickness ratio of the elastomer is 16%, 17%, 17.5%, 18%, 19%, 20% and the like; the thickness of the hydrogel is 50% -75% of the total thickness of the three-layer material for moisture retention, such as the thickness ratio of the hydrogel is 55%, 60%, 65%, 68%, 70%, 72%, 75%, etc. The total thickness of the three layers of the material for moisture retention is selected according to actual needs.
The brush-like polysiloxane is: any one of a trimethylsiloxane-terminated vinylmethylsiloxane-dimethylsiloxane copolymer, a trimethylsiloxane-terminated tetramethyldivinyl disiloxane-dimethylsiloxane copolymer, a trimethylsiloxane-terminated tris (trimethylsilyl) oxyvinylsilane-dimethylsiloxane copolymer and the like is used as a main chain, and the number average molecular weight thereof is about 50000-80000g/mol; the end group is a hydrogen atom end-capped polydimethylsiloxane as a side chain, and the number average molecular weight of the polydimethylsiloxane is about 3000-6000g/mol; brush polysiloxane prepared by using polydimethylsiloxane with two hydrogen atom end groups as cross-linking agent, and the number average molecular weight of the cross-linking agent is about 6000-10000g/mol. The mass ratio of the main chain to the side chain to the cross-linking agent is 1 (1.4-1.6) (0.04-0.06); preferably, the mass ratio of the main chain, the side chain and the crosslinking agent is 1:1.5:0.05.
The coupling agent is a silane coupling agent, preferably a vinyl-containing silane coupling agent such as vinyltrimethoxysilane and vinyltriethoxysilane.
The mass fraction of the coupling agent contained in the hydrogel is 0.1-0.5%, preferably 0.33% relative to the acrylamide monomer.
The mass fraction of the coupling agent contained in the elastomer is 0.1 to 0.8%, preferably 0.5% relative to the brominated butyl rubber.
The hydrogel contains the moisturizing factor which is 20-60% and preferably 40% relative to the mass fraction of the acrylamide monomer; the moisturizing factor is at least one of glycerol, L-serine, sodium alginate and sodium pyrrolidone carboxylate.
The initiator is potassium persulfate, and the dosage of the initiator is 0.01 to 0.04g relative to each 15g of acrylamide monomer; the catalyst is tetramethyl ethylenediamine, and the dosage of the catalyst is 20-40 mu L relative to each 15g of acrylamide monomer; the cross-linking agent is N, N-methylene bisacrylamide, and the dosage of the cross-linking agent is 3-5 mg relative to each 15g of acrylamide monomer.
The preparation method of the three-layer material comprises the following steps:
(1) Dissolving acrylamide, a cross-linking agent, a moisturizing factor and a coupling agent in water, adding an initiator and a catalyst under an anaerobic condition, uniformly mixing to obtain a mixed solution, and curing the mixed solution at 30-60 ℃ for 1-3 hours to obtain hydrogel;
(2) And (3) uniformly mixing a coupling agent and brominated butyl rubber, curing to obtain an elastomer, uniformly mixing the coupling agent and siloxane, wherein the siloxane comprises polydimethylsiloxane with a main chain, a side chain and two end groups blocked by hydrogen atoms, curing to obtain a brush-shaped elastomer, placing the hydrogel obtained in the step (1) between the elastomer and the brush-shaped elastomer, and standing for 20-30 h at room temperature to obtain the three-layer material.
The step (2) is characterized in that the coupling agent and the brominated butyl rubber are uniformly mixed and cured: uniformly mixing a coupling agent and brominated butyl rubber, and curing for 2-10 min at 100-150 ℃ under the action of a cross-linking agent tert-butylpyridine;
the coupling agent and the siloxane are uniformly mixed and cured: mixing one of main chains such as trimethylsiloxane end-capped vinyl methyl siloxane and dimethyl siloxane, mono-hydride end-capped polydimethylsiloxane (side chain), dihydro end-capped polydimethylsiloxane (cross-linking agent) and coupling agent uniformly, and curing at 70-90 ℃ for 25-40 h under the action of platinum catalyst.
In the preparation of the brominated butyl rubber elastomer, a cross-linking agent tert-butylpyridine is also used, and the mass ratio of the brominated butyl rubber to the tert-butylpyridine is (95-155): 1. the coupling agent used for the brush elastomer is a vinyl-containing silane coupling agent such as vinyltrimethoxysilane or vinyltriethoxysilane.
The invention has the beneficial effects that: the sandwich type bionic skin transparent moisturizing material is obtained by compounding the functional hydrogel and the two high polymer elastomers, the brominated butyl rubber is used for buffering, damping and isolating oxygen, the hydrogel is used for humidifying, and the brush-shaped elastomer is used for regulating and controlling the diffusion and absorption of water, so that the cigar is prevented from losing water in a low-humidity environment, the cigar is prevented from absorbing water in a high-humidity environment, and the cigar can keep constant moisture content for a long time. The hydrogel and the elastomer react with each other through the bonding molecules to form covalent bonding, so that the separation in the use process is prevented. The material has the characteristics of high transparency, good water retention effect, excellent mechanical property and the like, and is suitable for regulating and controlling the humidity of cigars.
It should be apparent that, in light of the foregoing, various modifications, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Drawings
FIG. 1 is a block diagram of a bionic skin transparent moisturizing material of the present disclosure. In the figure, the number 1 is an upper layer elastomer, the number 2 is an intermediate layer hydrogel, and the number 3 is a lower layer brush-like elastomer.
FIG. 2 is a graph depicting the adhesive properties of the materials of the present invention.
FIG. 3 is a graph showing the mechanical properties of the materials of comparative examples 1 and 2 and example 1 according to the present invention.
FIG. 4 is a graph showing the moisture retention properties of the materials of comparative examples 1 and 2 and example 1 according to the present invention.
FIG. 5 is a graph showing the humidity control performance of the cigar microenvironment by the material in example 1 of the present invention.
Detailed Description
The above-described aspects of the present invention will be described in further detail below with reference to specific embodiments in the form of examples. It should not be understood that the scope of the above subject matter of the present invention is limited to the following examples only. All techniques implemented based on the above description of the invention are within the scope of the invention.
The raw materials and equipment used in the invention are all known products and are obtained by purchasing commercial products.
EXAMPLE 1 preparation of the three-layer Material of the invention
Adding 15g of Acrylamide (AM) into 50g of water to form a mixed solution, adding 0.005g of cross-linking agent N, N-Methylene Bisacrylamide (MBA) after the AM is uniformly dissolved, stirring on a magnetic stirrer for 2min, adding 6g of glycerin, deoxidizing for 15min, adding 0.05g of coupling agent vinyltrimethoxysilane, adding 0.04g of initiator potassium persulfate (KPS) and catalyst tetramethyl ethylenediamine (TMEDA) for 25 mu L, stirring for 3min, pouring into a mould, and carrying out water bath at 60 ℃ for 3h to obtain the moisturizing hydrogel material.
According to the mass ratio of 1:4 mixing brominated butyl rubber (10 g) with toluene, adding 0.1g of tert-butylpyridine, and mixing at normal temperature to obtain BIIR precursor solution. To the precursor solution was added 0.05g of the coupling agent vinyltrimethoxysilane. Standing for 20h at room temperature, and crosslinking and curing for 5 minutes at 130 ℃ after the solvent volatilizes to obtain the brominated butyl rubber (BIIR) containing the coupling agent.
According to the mass ratio of 1:1.5:0.05 mixing a trimethylsiloxane-terminated vinylmethylsiloxane-dimethylsiloxane copolymer (number average molecular weight: 65000 g/mol), a polydimethylsiloxane terminated with one hydrogen atom (number average molecular weight: 4500 g/mol) and a polydimethylsiloxane terminated with two hydrogen atoms (number average molecular weight: 8000 g/mol), mixing at room temperature to obtain a precursor solution, and adding 2. Mu.L of a coupling agent vinyltrimethoxysilane to the precursor solution. And (3) reacting for 40 hours at 80 ℃ under the action of a platinum catalyst to obtain the brush-shaped elastomer containing the bonding molecules.
The brominated butyl rubber elastomer containing the coupling agent is solidified in a surface dish to form a film with the film thickness of about 3mm, the brush-shaped elastomer containing the coupling agent is in the surface dish to form a film with the film thickness of 2mm, the hydrogel containing the coupling agent is formed into a film with the film thickness of 15mm, the brominated butyl rubber elastomer containing the coupling agent and the brush-shaped elastomer are respectively attached to two sides of a hydrogel film containing the coupling agent, and the interface is formed to be bonded after 30 hours at room temperature to obtain the bionic skin transparent moisturizing material C with the thickness of 20mm. The schematic structure is shown in fig. 1.
EXAMPLE 2 preparation of the three-layer Material of the invention
Adding 15. 15gAM to 50g of water to form a mixed solution, adding 0.005g of MBA after AM is uniformly dissolved, stirring on a magnetic stirrer for 2min, adding 6g L-serine, deoxidizing for 15min, adding 0.015g of coupling agent vinyltrimethoxysilane, adding 0.04g of initiator KPS and 25 mu L of tetramethyl ethylenediamine, stirring for 3min, pouring into a mould, and carrying out water bath at 60 ℃ for 3h to obtain the moisturizing gel material.
Brominated butyl rubber (10 g) and toluene are mixed according to a mass ratio of 1:3, and then 0.1g of tertiary butyl pyridine is added, and the mixture is mixed at normal temperature to obtain BIIR precursor solution. To the precursor solution was added 0.01g of the coupling agent vinyltrimethoxysilane. Standing for 20h at room temperature, and crosslinking and curing for 5min at 130 ℃ after the solvent volatilizes to obtain the brominated butyl rubber (BIIR) containing the coupling agent.
According to the mass ratio of 1:1.5:0.05 mixing a trimethylsiloxane-terminated vinylmethylsiloxane-dimethylsiloxane copolymer (number average molecular weight: 50000 g/mol), a polydimethylsiloxane terminated with one hydrogen atom (number average molecular weight: 3000 g/mol) and a polydimethylsiloxane terminated with two hydrogen atoms (number average molecular weight: 6000 g/mol) were mixed at room temperature to obtain a precursor solution, and 2. Mu.L of vinyltriethoxysilane was added to the precursor solution. And (3) reacting for 40 hours at 80 ℃ under the action of a platinum catalyst to obtain the brush-shaped elastomer containing the bonding molecules.
The brominated butyl rubber elastomer containing the coupling agent is solidified in a surface dish to form a film with the film thickness of about 3mm, the brush-shaped elastomer containing the coupling agent is in the surface dish to form a film with the film thickness of 2mm, the hydrogel containing the coupling agent is formed into a film with the film thickness of 15mm, the brominated butyl rubber elastomer containing the coupling agent and the brush-shaped elastomer are respectively attached to two sides of a hydrogel film containing the coupling agent, and the interface is formed to be bonded after 20 hours at room temperature to obtain the bionic skin transparent moisturizing material D with the thickness of 20mm.
EXAMPLE 3 preparation of the three-layer Material of the invention
Adding 15. 15gAM into 50g of water to form a mixed solution, adding 0.005g of MBA after AM is uniformly dissolved, stirring on a magnetic stirrer for 2min, adding 6g of sodium alginate, deoxidizing for 15min, adding 0.075g of coupling agent vinyl trimethoxysilane, adding 0.04g of initiator KPS and 25 mu L of tetramethyl ethylenediamine, stirring for 3min, pouring into a mould, and carrying out water bath at 60 ℃ for 3h to obtain the moisturizing hydrogel material.
According to the mass ratio of 1:4 mixing brominated butyl rubber (10 g) with toluene, adding 0.1g of tert-butylpyridine, and mixing at normal temperature to obtain BIIR precursor solution. To the precursor solution was added 0.08g of the coupling agent vinyltrimethoxysilane. Standing for 20h at room temperature, and crosslinking and curing for 5min at 130 ℃ after the solvent volatilizes to obtain the brominated butyl rubber (BIIR) containing the coupling agent.
According to the mass ratio of 1:1.5:0.05 mixing a trimethylsiloxanecond tetramethyldivinyl disiloxane-dimethylsiloxane copolymer (number average molecular weight: 80000 g/mol), a polydimethylsiloxane having one hydrogen atom end group (number average molecular weight: 6000 g/mol), and a polydimethylsiloxane having two hydrogen atom end groups end group end groups (number average molecular weight: 10000 g/mol), mixing at room temperature to obtain a precursor solution, and adding 2. Mu.L of vinyltriethoxysilane to the precursor solution. And (3) reacting for 40 hours at 70 ℃ under the action of a platinum catalyst to obtain the brush-shaped elastomer containing the bonding molecules.
The brominated butyl rubber elastomer containing the coupling agent is solidified in a surface dish to form a film with the film thickness of about 0.3mm, the brush-shaped elastomer containing the coupling agent is in the surface dish to form a film with the film thickness of 0.2mm, the hydrogel containing the coupling agent is formed into a film with the film thickness of 0.5mm, the brominated butyl rubber elastomer containing the coupling agent and the brush-shaped elastomer are respectively attached to two sides of a hydrogel film containing the coupling agent, and after 30 hours at room temperature, an interface is formed to be bonded to obtain the bionic skin transparent moisturizing material E with the thickness of 1mm.
EXAMPLE 4 preparation of the three-layer Material of the invention
Adding 15. 15gAM to 50g of water to form a mixed solution, adding 0.005g of MBA after AM is uniformly dissolved, stirring on a magnetic stirrer for 1min, adding 3g of glycerol, deoxidizing for 10min, adding 0.05g of coupling agent vinyl trimethoxysilane, adding 0.04g of initiator KPS and 25 mu L of tetramethyl ethylenediamine, stirring for 2min, pouring into a mould, and carrying out water bath at 60 ℃ for 1h to obtain the moisturizing hydrogel material.
According to the mass ratio of 1:4 mixing brominated butyl rubber (10 g) with toluene, adding 0.1g of tert-butylpyridine, and mixing at normal temperature to obtain BIIR precursor solution. To the precursor solution was added 0.05g of the coupling agent vinyltrimethoxysilane. Standing for 20h at room temperature, and crosslinking and curing for 2min at 130 ℃ after the solvent volatilizes to obtain the brominated butyl rubber (BIIR) containing the coupling agent.
According to the mass ratio of 1:1.4:0.04 mixing a trimethylsiloxane-terminated tris (trimethylsilyl) oxyvinylsilane-dimethylsiloxane copolymer (number average molecular weight: 65000 g/mol), a polydimethylsiloxane terminated with one hydrogen atom (number average molecular weight: 4500 g/mol), and a polydimethylsiloxane terminated with two hydrogen atoms (number average molecular weight: 8000 g/mol), mixing at room temperature to obtain a precursor solution, and adding 2. Mu.L of vinyltriethoxysilane to the precursor solution. And (3) reacting for 25 hours at 90 ℃ under the action of a platinum catalyst to obtain the brush-shaped elastomer containing the bonding molecules.
The brominated butyl rubber elastomer containing the coupling agent is solidified in a surface dish to form a film with the thickness of about 10mm, the brush-shaped elastomer containing the coupling agent is in the surface dish to form a film with the thickness of 10mm, the hydrogel containing the coupling agent is formed into a film with the thickness of 30mm, the brominated butyl rubber elastomer containing the coupling agent and the brush-shaped elastomer are respectively attached to two sides of a hydrogel film containing the coupling agent, and the interface is formed to be bonded after 30 hours at room temperature to obtain the bionic skin transparent moisturizing material F with the thickness of 50mm.
EXAMPLE 5 preparation of the three-layer Material of the invention
Adding 15. 15gAM to 50g of water to form a mixed solution, adding 0.005g of MBA after AM is uniformly dissolved, stirring on a magnetic stirrer for 3min, adding 6g of sodium pyrrolidone carboxylate, deoxidizing for 30min, adding 0.05g of coupling agent vinyl triethoxysilane, adding 0.04g of initiator KPS and 25 mu L of tetramethyl ethylenediamine, stirring for 5min, pouring into a mould, and carrying out water bath at 50 ℃ for 3h to obtain the moisturizing hydrogel material.
According to the mass ratio of 1:4 mixing brominated butyl rubber (10 g) with toluene, adding 0.1g of tert-butylpyridine, and mixing at normal temperature to obtain BIIR precursor solution. To the precursor solution was added 0.05g of the coupling agent vinyltriethoxysilane. Standing for 20h at room temperature, and crosslinking and curing for 10min at 100 ℃ after the solvent volatilizes to obtain the brominated butyl rubber (BIIR) containing the coupling agent.
According to the mass ratio of 1:1.6:0.06 mixing a trimethylsiloxane-terminated vinylmethylsiloxane-dimethylsiloxane copolymer (number average molecular weight: 65000 g/mol), a polydimethylsiloxane terminated with one hydrogen atom (number average molecular weight: 4500 g/mol) and a polydimethylsiloxane terminated with two hydrogen atoms (number average molecular weight: 8000 g/mol) were mixed to obtain a precursor solution, and 2. Mu.L of vinyltriethoxysilane was added to the precursor solution at room temperature. And (3) reacting for 40 hours at 80 ℃ under the action of a platinum catalyst to obtain the brush-shaped elastomer containing the bonding molecules.
The brominated butyl rubber elastomer containing the coupling agent is solidified in a surface dish to form a film with the film thickness of about 3mm, the brush-shaped elastomer containing the coupling agent is in the surface dish to form a film with the film thickness of 2mm, the hydrogel containing the coupling agent is formed into a film with the film thickness of 15mm, the brominated butyl rubber elastomer containing the coupling agent and the brush-shaped elastomer are respectively attached to two sides of a hydrogel film containing the coupling agent, and the interface is formed to be bonded after 30 hours at room temperature to obtain the bionic skin transparent moisturizing material G with the thickness of 20mm.
Comparative example 1 preparation of hydrogel and elastomer bilayer Material
Adding 15. 15gAM into 50g of water to form a mixed solution, adding 0.005g of MBA after AM is uniformly dissolved, stirring on a magnetic stirrer for 2min, adding 6g of glycerol, deoxidizing for 15min, adding 0.05g of coupling agent vinyl trimethoxysilane, adding 0.04g of initiator KPS and 25 mu L of tetramethyl ethylenediamine, stirring for 3min, pouring into a mould, and carrying out water bath at 60 ℃ for 3h to obtain the moisturizing hydrogel material.
According to the mass ratio of 1:4 mixing brominated butyl rubber (10 g) with toluene, adding 0.1g of tert-butylpyridine, and mixing at normal temperature to obtain BIIR precursor solution. To the precursor solution was added 0.05g of the coupling agent vinyltrimethoxysilane. Standing for 20h at room temperature, and crosslinking and curing for 5 minutes at 130 ℃ after the solvent volatilizes to obtain the brominated butyl rubber (BIIR) containing the coupling agent.
The brominated butyl rubber elastomer containing the coupling agent and the hydrogel were formed into a film in a petri dish, the thickness of the brominated butyl rubber elastomer film was 3mm, and the thickness of the hydrogel film was 17mm. The brominated butyl rubber elastomer containing the coupling agent is attached to the hydrogel film containing the coupling agent, and the interface forms adhesion after 30 hours at room temperature to obtain a comparative example A, and the thickness is 20mm.
Comparative example 2 preparation of hydrogel and Brush elastomer bilayer Material
Adding 15. 15gAM into 50g of water to form a mixed solution, adding 0.005g of MBA after AM is uniformly dissolved, stirring on a magnetic stirrer for 2min, adding 6g of glycerol and 0.05g of vinyltrimethoxysilane, deoxidizing for 15min, adding 0.04g of initiator KPS and 25 mu L of tetramethyl ethylenediamine, stirring for 3min, pouring into a mould, and carrying out water bath at 60 ℃ for 3h to obtain the moisturizing hydrogel material containing bonding molecules.
According to the mass ratio of 1:1.5:0.05 mixing a trimethylsiloxane-terminated vinylmethylsiloxane-dimethylsiloxane copolymer (number average molecular weight: 65000 g/mol), a polydimethylsiloxane terminated with one hydrogen atom (number average molecular weight: 4500 g/mol), and a polydimethylsiloxane terminated with two hydrogen atoms (number average molecular weight: 8000 g/mol), mixing at room temperature to obtain a precursor solution, and adding 0.05g of vinyltrimethoxysilane to the precursor solution. And (3) reacting for 40 hours at 80 ℃ under the action of a platinum catalyst to obtain the brush-shaped elastomer containing the bonding molecules.
The hydrogel containing the coupling agent was formed into a film with a brush elastomer film thickness of 18mm and a brush elastomer film thickness of 2mm in a petri dish. The brush-like elastic body containing the coupling agent was bonded to the hydrogel film containing the coupling agent, and after 30 hours at room temperature, the interface was bonded to give comparative example B having a thickness of 20mm.
The following experiments prove the beneficial effects of the invention.
Experimental example 1 characterization of the three-layer Material of the invention
1. Experimental method
(1) Mechanical property test
The tensile stress-strain behavior of example 1 and comparative examples 1-2 (comparative examples a, B) was tested using a universal tensile tester Instron 5567 at a tensile rate of 100mm/min, the samples were stretched until fracture, and the stress-strain curves were recorded.
(2) Characterization of adhesive Properties
And stripping the upper layer elastomer from the other two layers of materials, and observing the residual hydrogel on the surface of the stripped upper layer elastomer. In addition, in order to distinguish that the three-layer material is not broken due to poor mechanical properties of the hydrogel in the peeling process, a uniaxial tensile test is performed on the bulk hydrogel with the same thickness as the hydrogel in the three-layer material, and the mechanical properties of the bulk hydrogel are evaluated.
(3) Moisture retention performance test
The materials of example 1, comparative example 1 and comparative example 2 were weighed at various time points within 12 hours at 25 ℃ after saturation with water, and the moisture retention was calculated according to the following formula, and the moisture retention ability of the materials was evaluated:
W＝m 2 /m 1 ×100％
wherein: w is moisture retention, m 1 Sample mass, m, saturated with water absorption of the sample 2 Is the mass of the sample that was weighed the time.
(4) Regulating and controlling performance test of material on cigar micro-environment humidity
The moisturizing material obtained in example 1 was placed in a cigar case, with a blank cigar case without moisturizing material as a control. The two groups of cigar boxes are respectively placed in environments of 40% RH and 90% RH, and the change of the humidity inside the cigar boxes along with time is monitored, so that the regulating and controlling effects of the material on the humidity of the cigar microenvironment are examined.
2. Experimental results
As can be seen from fig. 1, the humidity controlling material C of example 1 of the present invention shows a three-layer structure, wherein the upper and lower layers are respectively a silicone elastomer layer and a brush-like elastomer layer, which respectively play roles of buffering, blocking and controlling water diffusion; the middle is a hydrogel layer which has the functions of releasing and absorbing water.
It can be seen from fig. 2a that after the upper elastomer layer and the other two layers of the three-layer material obtained in example 1 of the present invention are peeled, a large amount of middle layer hydrogel flakes remain on the surface of the upper elastomer layer, which indicates that a good adhesion between the elastomer and the hydrogel is formed. In addition, the intermediate layer hydrogel alone was found to have good mechanical properties by tensile testing (fig. 2 b), demonstrating that the formation of hydrogel fragments during peeling is not due to poor mechanical properties of the hydrogel itself, but rather due to good adhesion between the elastomer and the hydrogel.
As can be seen from fig. 3, the breaking strength and breaking strain of comparative example a of the two-layer structure formed of the brominated butyl rubber and the hydrogel were 0.84MPa and 430%, respectively, and the breaking strength and breaking strain of comparative example B of the two-layer structure formed of the hydrogel and the brush-like elastomer were 0.43MPa and 240%, respectively. The breaking strength and breaking strain of the moisturizing three-layer material C of the embodiment 1 of the invention are respectively 1.53MPa and 825%, which are higher than the mechanical properties of the comparative examples A and B, and even are obviously higher than the sum of the mechanical properties of the comparative examples A and B, which proves that the composite synergy of the brominated butyl rubber, the hydrogel and the brush-shaped elastomer three-layer material of the invention improves the mechanical properties of the bionic skin moisturizing material.
As can be seen from fig. 4, the moisturizing trilayer material C of example 1 of the present invention has a higher moisturizing rate than the corresponding moisturizing rates of comparative example 1 (a) and comparative example 2 (B) within 12 hours, indicating that the trilayer structure of the biomimetic skin conditioning material has more excellent moisturizing properties than the two-layer structure of the brominated butyl rubber and the hydrogel or the hydrogel and the brush-like elastomer.
As can be seen from fig. 5, after the cigar box is placed for 48 hours under the environment of 40 ℃ and 40% rh, the humidity in the blank cigar box without the moisturizing material is reduced to below 60% rh, and the humidity-controlling material C of the present invention can increase the humidity in the cigar box to about 70% rh; after the cigar box is placed for 48 hours at 40 ℃ and 90% RH, the humidity in the blank cigar box is increased to about 90% RH, and the humidity regulating material C can control the humidity in the cigar box to about 80% RH. The results show that the humidity-regulating material can control the release and absorption of the moisture in the material according to the change of the external humidity, not only can prevent cigars from losing water in a low-humidity environment, but also can inhibit the cigars from absorbing water in a high-humidity environment, thereby reducing the influence of the external environment and keeping the cigars at constant moisture content.
In summary, the invention provides a three-layer material with intelligent humidity regulating effect, which plays a role in regulating and controlling the diffusion and absorption of water, is applied to cigar protection, not only can prevent the cigar from losing water in a low humidity environment, but also can inhibit the cigar from absorbing water in a high humidity environment, so that the cigar can keep constant moisture content for a long time, has excellent mechanical property and buffer gasket effect, and is very suitable for regulating and controlling the micro humidity environment of the cigar.

Claims (9)

1. The moisturizing three-layer material is characterized by being formed by chemically connecting an upper layer elastomer, a middle layer hydrogel and a lower layer brush-shaped elastomer through a coupling agent;
the hydrogel is polyacrylamide hydrogel at least containing a moisturizing factor and a coupling agent, and the elastomer is brominated butyl rubber containing the coupling agent; the brush-shaped elastomer is an elastomer taking brush-shaped polysiloxane as a matrix; the brush-like polysiloxane is: any one of a trimethylsiloxane-terminated vinylmethylsiloxane-dimethylsiloxane copolymer, a trimethylsiloxane-terminated tetramethyldivinyl disiloxane-dimethylsiloxane copolymer and a trimethylsiloxane-terminated tris (trimethylsilyl) oxyvinylsilane-dimethylsiloxane copolymer is used as a main chain, and the number average molecular weight thereof is 50000-80000g/mol; the end group is a hydrogen atom end-capped polydimethylsiloxane as a side chain, and the number average molecular weight of the polydimethylsiloxane is 3000-6000g/mol; brush-shaped polysiloxane prepared by taking polydimethylsiloxane with two hydrogen atom end groups as a cross-linking agent, wherein the number average molecular weight of the cross-linking agent is 6000-10000 g/mol;
the polyacrylamide hydrogel is formed by polymerizing monomers under the action of an initiator, a catalyst and a crosslinking agent, wherein the monomers comprise acrylamide.
2. The three-layer material of claim 1, wherein the thickness ratio of the elastomer, hydrogel to brush elastomer is (0.2-10): (0.5-30): (0.2-10).
3. The three-layer material according to claim 1 or 2, wherein the coupling agent used in the preparation of the moisture-retaining three-layer material, the coupling agent in the elastomer, and the coupling agent in the hydrogel are all vinyl-containing silane coupling agents.
4. A three-layer material according to claim 3, wherein the coupling agent contained in the hydrogel is 0.1% -0.5% by mass relative to the acrylamide monomer.
5. A three-layer material according to claim 3, wherein the elastomer contains a coupling agent in an amount of 0.1% to 0.8% by mass relative to the brominated butyl rubber.
6. The three-layer material according to claim 1 or 2, wherein the hydrogel contains a moisture retention factor of 20% -60% relative to the mass fraction of the acrylamide monomer; the moisturizing factor is at least one of glycerol, L-serine, sodium alginate and sodium pyrrolidone carboxylate.
7. The three-layer material according to claim 1 or 2, wherein in the preparation process of the polyacrylamide hydrogel, the initiator is potassium persulfate, and the dosage of the initiator is 0.01-0.04 g for every 15g of acrylamide monomer; the catalyst is tetramethyl ethylenediamine, and the dosage of the catalyst is 20-40 mu L relative to each 15g of acrylamide monomer; the cross-linking agent is N, N-methylene bisacrylamide, and the dosage of the cross-linking agent is 3-5 mg relative to each 15g of acrylamide monomer.
8. The method for preparing the three-layer material according to any one of claims 1 to 7, comprising the steps of:
(1) Dissolving acrylamide, a cross-linking agent, a moisturizing factor and a coupling agent in water, adding an initiator and a catalyst under an anaerobic condition, uniformly mixing to obtain a mixed solution, and curing the mixed solution at 30-60 ℃ for 1-3 hours to obtain hydrogel;
(2) And (3) uniformly mixing a coupling agent and brominated butyl rubber, curing to obtain an elastomer, uniformly mixing the coupling agent and siloxane, wherein the siloxane comprises polydimethylsiloxane with a main chain, a side chain and two hydrogen atom end groups, curing to obtain a brush-shaped elastomer, and placing the hydrogel obtained in the step (1) between the elastomer and the brush-shaped elastomer, and standing for 20-30 hours at room temperature to obtain the three-layer material.
9. The method of claim 8, wherein the step (2) of mixing and curing the coupling agent and the brominated butyl rubber is: uniformly mixing a coupling agent and brominated butyl rubber, and curing for 2-10 min at 100-150 ℃ under the action of a cross-linking agent tert-butylpyridine;
the coupling agent and the siloxane are uniformly mixed and cured: and uniformly mixing the main chain, the side chain, the polydimethylsiloxane with the end groups blocked by two hydrogen atoms and the coupling agent, and curing at 70-90 ℃ for 25-40 h under the action of a platinum catalyst.
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