CN112898498B - Recyclable foam material and preparation method thereof - Google Patents
Recyclable foam material and preparation method thereof Download PDFInfo
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- CN112898498B CN112898498B CN202110185667.3A CN202110185667A CN112898498B CN 112898498 B CN112898498 B CN 112898498B CN 202110185667 A CN202110185667 A CN 202110185667A CN 112898498 B CN112898498 B CN 112898498B
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- 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
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/46—Applications of disintegrable, dissolvable or edible materials
- B65D65/466—Bio- or photodegradable packaging materials
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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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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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
- 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
- C08J2333/04—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 esters
- C08J2333/06—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 esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/08—Homopolymers or copolymers of acrylic acid esters
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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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/06—Unsaturated polyesters
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Abstract
The invention discloses a recyclable foam packaging material and a preparation method thereof, wherein the recyclable foam packaging material is prepared from unsaturated monomers and an initiator, the unsaturated monomers at least comprise modified tetravinyl polycaprolactone, and the preparation method comprises the following steps: the foam material has a loose structure, strong shock resistance and no harmful substances, can absorb water and moisture, can be repeatedly used for shock-proof packaging of fragile articles and high-grade precise instruments, and has good application prospect in the field of recyclable packaging materials.
Description
Technical Field
The invention relates to the field of preparation of high polymer materials, in particular to a recyclable foam material and a preparation method thereof.
Background
Currently, in the transportation and storage of precision instruments, foam is required to be padded around the instrument to protect the instrument.
Patent CN202011206882.9 discloses a degradable foam material based on polylactic acid, which uses polylactic acid of plant extract to mix with paraffin, calcium stearate, butane, bio-based polyol to prepare raw material for producing biodegradable plastic, so as to increase the permeability of air and oxygen.
Patent CN112281013A discloses a surface chemical plating alumina hollow microsphere/magnesium-based composite foam material, which is prepared by utilizing the pressure effect generated by the gravity of liquid magnesium alloy to permeate into the gaps of alumina hollow microspheres which are compactly stacked in a corundum tube and coated with magnesium oxide on the surface. The foam material has certain porosity, and the specific gravity of the material is reduced.
Patent CN201910619514.8 discloses a biomass-based cushioning packaging foam material, the raw materials of which comprise a combined material A and isocyanate, and the packaging material prepared by the invention has low foam density and certain cushioning property.
The existing foam material has unsatisfactory impact protection effect on instruments with complicated shapes due to unadjustable hardness. In addition, most of the foam packaging materials are disposable and non-recyclable, which not only causes resource waste, but also causes environmental pollution, so that the development of the reusable and recyclable foam packaging materials with the hardness adjustable according to the needs of instruments is necessary.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a recyclable foam packaging material and a preparation method thereof.
The invention is realized by the following technical means:
the recyclable foam packaging material is prepared from unsaturated monomers and an initiator, wherein the unsaturated monomers at least comprise modified tetravinyl polycaprolactone, and the structure of the modified tetravinyl polycaprolactone is as follows:
wherein R is a group having a vinyl group at the terminal.
As a further improvement of the present invention, the modified tetravinyl polycaprolactone is 2-40wt% of the unsaturated monomer.
As a further improvement of the invention, the recyclable foam packaging material comprises the following raw materials in parts by weight:
as a further improvement of the invention, the preparation of the tetravinyl polycaprolactone comprises the following raw materials in parts by weight:
the preparation method of the recyclable foam material comprises the following steps:
s1, synthesis of modified tetravinyl polycaprolactone:
1-5 parts of polyol, 30-40 parts of epsilon-caprolactone, 0.02-0.05 part of catalyst and 10-15 parts of methacrylic acid-2-isocyanate are polymerized to obtain a polymerization product, and the polymerization product is dissolved in dichloromethane, precipitated by absolute ethyl alcohol and dried;
s2, monomer phase:
mixing 10-20 parts of styrene, 30-60 parts of butyl acrylate and 10-20 parts of butyl methacrylate to form a monomer, and dissolving the modified tetravinyl polycaprolactone in the monomer;
s3, preparing emulsion and polymerizing:
and stirring and mixing the initiator aqueous solution and the monomer of S2 to obtain emulsion, and solidifying, washing and drying the emulsion to obtain the recyclable foam packaging material.
The invention has the beneficial technical effects that:
the recyclable foam material adopts modified tetravinyl polycaprolactone as a cross-linking agent, the modified tetravinyl polycaprolactone is of a four-arm polycaprolactone structure, and the four-arm structure can better form a bridge bond between an oil phase and water. In addition, the modified tetravinyl polycaprolactone is an easily degradable crosslinking agent, and when the foam material disclosed by the invention is used, the thermosetting foam can be converted into the thermoplastic foam by degrading a crosslinking component, so that the foam material can be recovered.
The foam material has a loose structure and strong shock resistance, does not contain harmful substances, can be repeatedly used for shock-proof packaging of fragile objects and high-grade precise instruments, and has good application prospect in the field of recyclable packaging materials.
Drawings
FIG. 1 is a structural formula of modified tetravinyl polycaprolactone obtained in example 1;
FIG. 2 is a NMR spectrum of modified tetraenylpolycaprolactone obtained in example 1;
FIG. 3 is a view showing the internal structure of a recyclable foam obtained in example 1;
FIG. 4 is an IR spectrum of a recoverable foam obtained from example 1.
Detailed Description
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. In case of conflict, the present specification, including definitions, will control.
The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or range defined by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise numerical value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
In order to achieve the above object, the present invention provides a recyclable foam packaging material, which is prepared from an unsaturated monomer and an initiator, wherein the unsaturated monomer at least comprises modified tetravinyl polycaprolactone, and the structure of the modified tetravinyl polycaprolactone is as follows:
wherein R is a group having a vinyl group at the terminal.
Further, n is an integer of 1 to 50.
The components of the recyclable foam packaging material according to the present invention are described below:
unsaturated monomer:
examples of the unsaturated monomer include ethylenically unsaturated monomers, aromatic ethylenically unsaturated monomers, and ethylenically unsaturated acid monomers, and examples thereof include styrene, vinyltoluene, α -methylstyrene, p-methylstyrene, α -butylstyrene, 4-n-butylstyrene, divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, divinylbenzene, diallyl phthalate, trimethylolpropane tri (meth) acrylate, ethylene glycol di (meth) acrylate, styrene, Tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, and the like.
The unsaturated monomer is preferably an unsaturated monomer having a (meth) acrylic group, and more preferably an unsaturated monomer having 2 or more (meth) acrylic groups.
The unsaturated monomer is preferably an unsaturated monomer having a styrene group and an unsaturated monomer having a (meth) acrylic group, and more preferably an unsaturated monomer having a styrene group and an unsaturated monomer having 2 or more (meth) acrylic groups.
Among the above unsaturated monomers, the (meth) acrylic acid based unsaturated monomer accounts for 60 wt% or more, preferably at least 80 wt% of the unsaturated monomer.
Among the above unsaturated monomers, the styrene-based unsaturated monomer accounts for at most 40% by weight of the unsaturated monomer, and preferably the styrene-based unsaturated monomer accounts for 20% by weight of the unsaturated monomer. The unsaturated monomer with the composition has the characteristics of easy molding, low surface viscosity and strong flexibility. When the proportion of the styrene-based unsaturated monomer is less than 5 wt%, the hardness of the unsaturated monomer is reduced, the viscosity of the unsaturated monomer is increased, and the molding is affected, and when the proportion of the styrene-based unsaturated monomer is more than 40wt%, the hardness of the unsaturated monomer is increased, the viscosity of the unsaturated monomer is reduced, so that the packaging material is easy to damage, and the use of the packaging material is affected.
Polycaprolactone:
the cyclic ester with a functional group-COO-is lactone, which comprises beta-propiolactone, delta-valerolactone, epsilon-caprolactone, beta-dimethyl valerolactone and the like. The chemical structural formula of the epsilon-caprolactone is as follows:
the polycaprolactone is a product of ring-opening polymerization of epsilon-caprolactone.
Modified tetraenylpolycaprolactone:
in order to improve the degradation rate of polycaprolactone, the invention adopts the copolymerization reaction of polycaprolactone and a substance containing hydroxyl and caprolactone to form a polymer with the characteristic of a multi-component microphase separation structure.
The hydroxyl group-containing substance includes alcohol compounds and phenol compounds, and specifically includes glycerol, propylene glycol, ethylene glycol, pentaerythritol, polyethylene glycol, polypropylene glycol, trimethylolethane, xylitol, sorbitol, phenol, o-cresol, m-cresol, p-cresol, 2, 3-xylenol, 2, 4-xylenol, 2, 5-xylenol, 2, 6-xylenol, 3, 4-xylenol, 3, 5-xylenol, p-ethylphenol, p-isopropylphenol, p-tert-butylphenol, p-chlorophenol, p-bromophenol, and the like.
The hydroxyl group-containing substance is preferably an alcohol compound, and more preferably pentaerythritol. Because the alcohol compound is easy to remove water molecules to form a double-bond structure in the polymerization reaction process, the alcohol compound can better form a bridge bond to crosslink other components.
As a further improvement of the invention, the modified tetravinyl polycaprolactone accounts for 2-40wt% of the unsaturated monomer.
As a further improvement of the invention, the recyclable foam packaging material comprises the following raw materials in parts by weight:
initiator:
in the present invention, the initiator is not particularly limited, and a known water-soluble initiator, oil-soluble redox initiator, hydroperoxide initiator, and the like can be used. Specific examples of the initiator include potassium persulfate, sodium persulfate, ammonium persulfate, benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyvalerate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, and the like.
In the present invention, a preferred initiator is a water-soluble initiator, specifically ammonium persulfate and/or potassium persulfate.
As a further improvement of the invention, the initiator is an aqueous solution of ammonium persulfate and/or potassium persulfate dissolved in sodium chloride or calcium chloride.
As a further improvement of the invention, the concentration of the ammonium persulfate and/or the potassium persulfate in the aqueous solution is 0.05-2%.
Preferably, the concentration of the ammonium persulfate and/or the potassium persulfate in the aqueous solution is 0.5%.
As a further improvement of the invention, the preparation of the tetravinyl polycaprolactone comprises the following raw materials in parts by weight:
polyol:
in the present invention, specific examples of the initiator include pentaerythritol, ethylene glycol, 2-propylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, trimethylolpropane, glycerol, and the like.
In the present invention, the preferred polyhydric alcohol is pentaerythritol or ethylene glycol.
Catalyst:
in the present invention, the catalyst may be an organic metal catalyst, a tin salt catalyst, a rare earth compound catalyst, or the like. Specific examples of the catalyst include methyl fluorosulfonic acid, ethyl fluorosulfonic acid, methyl nitrobenzenesulfonic acid, methyl methanesulfonate, tert-butyl lithium, tert-butyl oxylithium, potassium permanganate, and stannous chloride.
The invention preferably selects tin salt catalysts which comprise stannous chloride, stannic oxide, stannic tetrachloride, stannous acetate, stannous octoate and the like, and the catalysts can be used as active centers of chain growth reaction, thereby influencing the molecular weight, molecular weight distribution and end group functionality of modified tetravinyl polycaprolactone. The modified tetravinyl caprolactone with high molecular weight and high end group functionality can better form a bridge bond to connect the monomer and the initiator, so that the crosslinking effect of the crosslinking agent is achieved, and meanwhile, the chemical bond of the polycaprolactone with high molecular weight is easy to break in the degradation process, so that the foam material is easier to be converted from thermosetting into thermoplastic, and the degradation efficiency of the foam material is accelerated.
As a further development of the invention, the recyclable foam packaging material comprises an emulsifier, the emulsifier being 5 to 15 parts by weight.
The emulsifier is not particularly limited, and a known nonionic emulsifier can be used. Specific examples of the catalyst include sorbitol fatty acid esters, sorbitol fatty acid ester ethylene oxide adducts, diglycerol fatty acid esters, diglycerol polypropylene glycol ethers, oleic acid polyoxyethylene esters, stearic acid polyoxyethylene esters, rosin acid polyoxyethylene esters, lauryl alcohol polyoxyethylene ethers, isooctyl polyoxyethylene ethers, stearyl alcohol polyoxyethylene ethers, isotridecyl alcohol polyoxyethylene ethers, and phenethyl phenol polyoxyethylene ethers.
As a further improvement of the invention, the emulsifier is a mixture of span 60 and polyether polyol, and preferably, the mass ratio of span 60 to polyether polyol is 1: 1.
A method of making a recyclable foam packaging material, comprising the steps of:
s1, synthesis of modified tetravinyl polycaprolactone:
1-5 parts of polyol, 30-40 parts of epsilon-caprolactone, 0.02-0.05 part of catalyst and 10-15 parts of methacrylic acid-2-isocyanate are polymerized to obtain a polymerization product, and the polymerization product is dissolved in dichloromethane, precipitated by absolute ethyl alcohol and dried;
s2, monomer phase:
mixing 10-20 parts of styrene, 30-60 parts of butyl acrylate and 10-20 parts of butyl methacrylate to form a monomer, and dissolving the modified tetravinyl polycaprolactone in the monomer;
s3, preparing emulsion and polymerizing:
and stirring and mixing the initiator aqueous solution and the monomer of S2 to obtain emulsion, and solidifying, washing and drying the emulsion to obtain the recyclable foam packaging material.
As a further improvement of the invention, the step of preparing the emulsion and polymerizing S3 further comprises adding an emulsifier into the monomer phase of S2.
Preferably, the preparation method of the recyclable foam packaging material specifically comprises the following steps:
s1, synthesis of modified tetravinyl polycaprolactone:
1-5 parts of pentaerythritol as an initiator and 0.02-0.05 part of stannous chloride as a catalyst, carrying out polymerization reaction on epsilon-caprolactone for 5-7 hours at the temperature of 110-130 ℃ to obtain tetraene polycaprolactone, adding 10-15 parts of methacrylic acid-2-isocyanate into tetraethylene polycaprolactone, reacting for 4-6 hours at the temperature of 40-60 ℃ to obtain a reactant, dissolving the reactant in dichloromethane, precipitating with absolute ethyl alcohol to obtain a precipitate, and drying the precipitate to obtain modified tetraene polycaprolactone;
s2, monomer phase:
mixing 10-20 parts of styrene, 30-60 parts of butyl acrylate and 10-20 parts of butyl methacrylate to form a monomer, and ultrasonically dissolving the modified tetravinyl polycaprolactone in the monomer;
s3, preparing emulsion and polymerizing:
adding 1-5 parts of emulsifier into the monomer of S2 to obtain a mixture solution, dripping an aqueous solution containing 0.5-20 parts of initiator into the mixture solution, magnetically stirring the mixture solution in the process of dripping the initiator to obtain an emulsion, putting the emulsion into an oven to be cured for 14-18 hours to obtain a cured substance, and washing and drying the cured substance to obtain the recyclable foam packaging material.
In a preferred embodiment of the present invention, the magnetic stirring speed is 600 rpm.
As a preferable embodiment of the present invention, after the initiator is completely dropped into the mixture solution, the magnetic stirring is maintained for 10 minutes.
As a preferred scheme of the invention, in order to adapt to different instrument shapes, the emulsion is firstly injected into a set mould before curing, and then the mould is placed into an oven for curing.
As a preferred scheme of the invention, the temperature of the oven is 50-80 ℃.
In a preferred embodiment of the present invention, the cured product is washed with hot water at 40 to 90 ℃.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
Example 1
The preparation method of the recyclable foam material adopts the following raw materials in parts by mass:
s1, synthesis of modified tetravinyl polycaprolactone:
wherein dichloromethane is used as solvent, and absolute ethyl alcohol is used as precipitant.
Pentaerythritol is used as an initiator, stannous chloride is used as a catalyst, polymerization reaction is carried out on epsilon-caprolactone for 6 hours at 120 ℃ to obtain tetraene polycaprolactone, methacrylic acid-2-isocyanate is added into the tetraene polycaprolactone, reaction is carried out for 5 hours at 50 ℃ to obtain a reactant, the reactant is dissolved in dichloromethane and is precipitated by absolute ethyl alcohol to obtain a precipitate, and the precipitate is dried to obtain the modified tetraene polycaprolactone.
The structural formula of the prepared modified tetravinyl polycaprolactone is shown in figure 1, and the nuclear magnetic resonance spectrum of the modified tetravinyl polycaprolactone shown in figure 2 shows that 4.24(i), 4.08(a), 4.04(e), 2.33-2.29 (b), 1.95(k), 1.69-1.61 (C) and 1.42-1.34 ppm (d) respectively represent the chemical shift of a characteristic peak of-CH 2-, and 6.13(f) and 5.60ppm (g) represent the chemical shift of a characteristic peak of C ═ CH-CO.
S2, monomer phase:
the initiator is an aqueous solution of ammonium persulfate dissolved in sodium chloride, and the concentration of the ammonium persulfate in the aqueous solution is 0.5%.
The aqueous solution of ammonium persulfate is used as a water phase.
The emulsifier is a mixture of span 60 and polyether polyol.
The polyether polyol is polyether L81, and the mass ratio of the polyether polyol to the polyether L81 is 1: 1.
Mixing styrene, butyl acrylate and butyl methacrylate to form a monomer, ultrasonically dissolving modified tetravinyl polycaprolactone in the monomer, wherein the modified tetravinyl polycaprolactone is a cross-linking agent, and the cross-linking agent and the monomer are uniformly mixed to form an oil phase.
S3, preparing emulsion and polymerizing:
adding an emulsifier into a monomer of S2 to obtain a mixture solution, dripping an initiator into the mixture solution, carrying out magnetic stirring on the mixture solution in the initiator dripping process to obtain an emulsion, wherein the magnetic stirring speed is 600rpm, keeping the magnetic stirring for 10 minutes after the initiator is completely dripped into the mixture solution, injecting the emulsion into a fixed mold, then placing the fixed mold into an oven at 60 ℃ for curing for 18 hours to obtain a cured product, washing the cured product with hot water at 70 ℃, and drying to obtain the recyclable foam packaging material.
The internal structure of the prepared recyclable foam material is shown in FIG. 3, and 3025cm is known from the infrared spectrum of the recyclable foam material shown in FIG. 4 -1 The absorption peak is the C-H vibration peak of the benzene ring, 1599cm -1 And 1491cm -1 The peak is the vibration peak of the skeleton on the benzene ring, 697cm -1 And 753cm -1 Is a vibration peak mono-substituted by a benzene ring and corresponds to a group 1731cm on polycaprolactone -1 Is the stretching vibration peak of-C ═ O.
Degradation of a recyclable foam packaging material:
the foam packaging material was immersed in 1 mol/l aqueous sodium hydroxide solution at 50 ℃ for 20 days to remove the crosslinked structure, and a recyclable foam was obtained.
Example 2
The preparation method of the recyclable foam material adopts the following raw materials in parts by mass:
s1, synthesis of modified tetravinyl polycaprolactone:
wherein dichloromethane is used as solvent, and absolute ethyl alcohol is used as precipitant.
The method comprises the steps of carrying out polymerization reaction on epsilon-caprolactone for 7 hours at 115 ℃ by taking pentaerythritol as an initiator and stannous chloride as a catalyst to obtain tetraene polycaprolactone, adding methacrylic acid-2-isocyanate into tetraethylene polycaprolactone, reacting for 6 hours at 40 ℃ to obtain a reactant, dissolving the reactant in dichloromethane, precipitating with absolute ethyl alcohol to obtain a precipitate, and drying the precipitate to obtain the modified tetraene polycaprolactone.
S2, monomer phase:
the initiator is an aqueous solution of ammonium persulfate dissolved in sodium chloride, and the concentration of the ammonium persulfate in the aqueous solution is 0.05%.
The aqueous solution of ammonium persulfate is used as a water phase.
The emulsifier is a mixture of span 60 and polyether polyol.
The polyether polyol is polyether L81, and the mass ratio of the polyether polyol to the polyether L81 is 1: 1.
Mixing styrene, butyl acrylate and butyl methacrylate to form a monomer, ultrasonically dissolving modified tetravinyl polycaprolactone in the monomer, wherein the modified tetravinyl polycaprolactone is a cross-linking agent, and the cross-linking agent and the monomer are uniformly mixed to form an oil phase.
S3, preparing emulsion and polymerizing:
adding an emulsifier into a monomer of S2 to obtain a mixture solution, dripping an initiator into the mixture solution, carrying out magnetic stirring on the mixture solution in the initiator dripping process to obtain an emulsion, wherein the magnetic stirring speed is 600rpm, keeping the magnetic stirring for 10 minutes after the initiator is completely dripped into the mixture solution, injecting the emulsion into a fixed mold, then placing the fixed mold into an oven at 70 ℃ for curing for 17 hours to obtain a cured product, washing the cured product with hot water at 50 ℃, and drying to obtain the recyclable foam packaging material.
Degradation of a recyclable foam packaging material:
the foam packaging material is immersed in 1 mol/L sodium hydroxide aqueous solution, and the cross-linking structure is removed at 55 ℃ for 18 days to obtain recyclable foam.
Example 3
The preparation method of the recyclable foam material adopts the following raw materials in parts by mass:
s1, synthesis of modified tetravinyl polycaprolactone:
wherein dichloromethane is used as solvent, and absolute ethyl alcohol is used as precipitant.
The method comprises the steps of carrying out polymerization reaction on epsilon-caprolactone for 5 hours at 130 ℃ by taking pentaerythritol as an initiator and stannous chloride as a catalyst to obtain tetraene polycaprolactone, adding methacrylic acid-2-isocyanate into tetraethylene polycaprolactone, reacting for 4 hours at 60 ℃ to obtain a reactant, dissolving the reactant in dichloromethane, precipitating with absolute ethyl alcohol to obtain a precipitate, and drying the precipitate to obtain the modified tetraene polycaprolactone.
S2, monomer phase:
the initiator is an aqueous solution of potassium persulfate dissolved in sodium chloride, and the concentration of the potassium persulfate in the aqueous solution is 2%.
The aqueous solution of potassium persulfate was used as the aqueous phase.
The emulsifier is a mixture of span 60 and polyether polyol.
The polyether polyol is polyether L81, and the mass ratio of the polyether polyol to the polyether L81 is 1: 1.
Carrying out polymerization reaction on styrene, butyl acrylate and butyl methacrylate to form a monomer, ultrasonically dissolving modified tetravinyl polycaprolactone in the monomer, wherein the modified tetravinyl polycaprolactone is a cross-linking agent, and the cross-linking agent and the monomer are uniformly mixed to form an oil phase.
S3, preparing emulsion and polymerizing:
adding an emulsifier into a monomer of S2 to obtain a mixture solution, dripping an initiator into the mixture solution, carrying out magnetic stirring on the mixture solution in the initiator dripping process to obtain an emulsion, wherein the magnetic stirring speed is 600rpm, keeping the magnetic stirring for 10 minutes after the initiator is completely dripped into the mixture solution, injecting the emulsion into a fixed mold, then placing the fixed mold into an oven at 80 ℃ for curing for 14 hours to obtain a cured product, washing the cured product with hot water at 90 ℃, and drying to obtain the recyclable foam packaging material.
Degradation of a recyclable foam packaging material:
the foam packaging material was immersed in 1 mol/l aqueous sodium hydroxide solution at 45 ℃ for 21 days to remove the crosslinked structure, and a recyclable foam was obtained.
Example 4
The preparation method of the recyclable foam material adopts the following raw materials in parts by mass:
s1, synthesis of modified tetravinyl polycaprolactone:
wherein dichloromethane is used as solvent, and absolute ethyl alcohol is used as precipitant.
Pentaerythritol is used as an initiator, stannous chloride is used as a catalyst, polymerization reaction is carried out on epsilon-caprolactone for 6 hours at 120 ℃ to obtain tetraene polycaprolactone, methacrylic acid-2-isocyanate is added into the tetraene polycaprolactone, reaction is carried out for 5 hours at 50 ℃ to obtain a reactant, the reactant is dissolved in dichloromethane and is precipitated by absolute ethyl alcohol to obtain a precipitate, and the precipitate is dried to obtain the modified tetraene polycaprolactone.
S2, monomer phase:
the initiator is an aqueous solution of calcium chloride dissolved in mixed ammonium persulfate and potassium persulfate, and the concentration of the ammonium persulfate and the potassium persulfate in the aqueous solution is 0.15%.
The aqueous solution of ammonium persulfate and potassium persulfate serves as an aqueous phase.
The emulsifier is a mixture of span 60 and polyether polyol.
The polyether polyol is polyether L81, and the mass ratio of the polyether polyol to the polyether L81 is 1: 1.
Mixing styrene, butyl acrylate and butyl methacrylate to form a monomer, ultrasonically dissolving modified tetravinyl polycaprolactone in the monomer, wherein the modified tetravinyl polycaprolactone is a cross-linking agent, and the cross-linking agent and the monomer are uniformly mixed to form an oil phase.
S3, preparing emulsion and polymerizing:
adding an emulsifier into a monomer of S2 to obtain a mixture solution, dripping an initiator into the mixture solution, carrying out magnetic stirring on the mixture solution in the initiator dripping process to obtain an emulsion, wherein the magnetic stirring speed is 600rpm, keeping the magnetic stirring for 10 minutes after the initiator is completely dripped into the mixture solution, injecting the emulsion into a fixed mold, then placing the fixed mold into an oven at 60 ℃ for curing for 15 hours to obtain a cured product, washing the cured product with hot water at 40 ℃, and drying to obtain the recyclable foam packaging material.
Degradation of a recyclable foam packaging material:
the foam packaging material was immersed in 1 mol/l aqueous sodium hydroxide solution at 48 ℃ for 22 days to remove the crosslinked structure, and a recyclable foam was obtained.
Example 5:
the preparation method of the recyclable foam material adopts the following raw materials in parts by mass:
s1, synthesis of modified tetravinyl polycaprolactone:
wherein dichloromethane is used as solvent, and absolute ethyl alcohol is used as precipitant.
The preparation method comprises the steps of carrying out polymerization reaction on epsilon-caprolactone for 5.5 hours at 125 ℃ by using pentaerythritol as an initiator and stannous chloride as a catalyst to obtain tetraene polycaprolactone, adding methacrylic acid-2-isocyanate into tetraethylene polycaprolactone, reacting for 5 hours at 55 ℃ to obtain a reactant, dissolving the reactant in dichloromethane, precipitating with absolute ethyl alcohol to obtain a precipitate, and drying the precipitate to obtain the modified tetraene polycaprolactone.
S2, monomer phase:
the initiator is an aqueous solution of ammonium persulfate dissolved in calcium chloride, and the concentration of the ammonium persulfate in the aqueous solution is 0.25%.
The aqueous solution of ammonium persulfate and potassium persulfate serves as an aqueous phase.
Mixing styrene, butyl acrylate and butyl methacrylate to form a monomer, ultrasonically dissolving modified tetravinyl polycaprolactone in the monomer, wherein the modified tetravinyl polycaprolactone is a cross-linking agent, and the cross-linking agent and the monomer are uniformly mixed to form an oil phase.
S3, preparing emulsion and polymerizing:
dropping an initiator into the monomer of S2, carrying out magnetic stirring on the monomer in the initiator dropping process to obtain emulsion, wherein the magnetic stirring speed is 600rpm, keeping the magnetic stirring for 10 minutes after the initiator is completely dropped into the monomer, injecting the emulsion into a fixed mold, then placing the fixed mold into an oven at 70 ℃ for curing for 17 hours to obtain a cured product, washing the cured product with hot water at 80 ℃, and drying to obtain the recyclable foam packaging material.
Degradation of a recyclable foam packaging material:
the foam packaging material was immersed in 1 mol/l aqueous sodium hydroxide solution at 45 ℃ for 26 days to remove the crosslinked structure, and a recyclable foam was obtained.
Example 6:
the preparation method of the recyclable foam material adopts the following raw materials in parts by mass:
s1, synthesis of modified tetravinyl polycaprolactone:
wherein dichloromethane is used as solvent, and absolute ethyl alcohol is used as precipitant.
The preparation method comprises the steps of carrying out polymerization reaction on epsilon-caprolactone for 5.5 hours at 125 ℃ by using pentaerythritol as an initiator and stannous chloride as a catalyst to obtain tetraene polycaprolactone, adding methacrylic acid-2-isocyanate into tetraethylene polycaprolactone, reacting for 5 hours at 55 ℃ to obtain a reactant, dissolving the reactant in dichloromethane, precipitating with absolute ethyl alcohol to obtain a precipitate, and drying the precipitate to obtain the modified tetraene polycaprolactone.
S2, monomer phase:
the initiator is an aqueous solution of ammonium persulfate dissolved in calcium chloride, and the concentration of the ammonium persulfate in the aqueous solution is 0.25%.
The aqueous solution of ammonium persulfate and potassium persulfate serves as an aqueous phase.
The emulsifier is a mixture of span 60 and polyether polyol.
The polyether polyol is polyether L81, and the mass ratio of the polyether polyol to the polyether L81 is 1: 1.
Mixing styrene, butyl acrylate and butyl methacrylate to form a monomer, ultrasonically dissolving modified tetravinyl polycaprolactone in the monomer, wherein the modified tetravinyl polycaprolactone is a cross-linking agent, and the cross-linking agent and the monomer are uniformly mixed to form an oil phase.
S3, preparing emulsion and polymerizing:
adding an emulsifier into a monomer of S2 to obtain a mixture solution, dripping an initiator into the mixture solution, carrying out magnetic stirring on the mixture solution in the initiator dripping process to obtain an emulsion, wherein the magnetic stirring speed is 600rpm, keeping the magnetic stirring for 10 minutes after the initiator is completely dripped into the mixture solution, injecting the emulsion into a fixed mold, then placing the fixed mold into an oven at 70 ℃ for curing for 17 hours to obtain a cured product, washing the cured product with hot water at 80 ℃, and drying to obtain the recyclable foam packaging material.
Degradation of a recyclable foam packaging material:
the foam packaging material is immersed in 1 mol/l sodium hydroxide aqueous solution, and the cross-linking structure is removed at 45 ℃ for 22 days to obtain recyclable foam.
Claims (9)
1. The recyclable foam packaging material is characterized in that the recyclable foam packaging material is prepared from an unsaturated monomer and an initiator, wherein the unsaturated monomer at least comprises modified tetravinyl polycaprolactone, and the structure of the modified tetravinyl polycaprolactone is as follows:
wherein R is a group with a terminal containing vinyl, and the recyclable foam packaging material comprises the following raw materials in parts by weight:
10-20 parts of styrene;
30-60 parts of butyl acrylate;
10-20 parts of butyl methacrylate;
2-30 parts of modified tetravinyl polycaprolactone;
0.5-20 parts of an initiator;
the recyclable foam packaging material is obtained by stirring and mixing an initiator aqueous solution and a monomer to obtain an emulsion, and solidifying, washing and drying the emulsion.
2. The recyclable foam packaging material of claim 1, wherein the modified tetravinyl polycaprolactone is 2-40wt% of the unsaturated monomer.
3. The recyclable foam packaging material of claim 1, wherein the preparation of the tetravinyl polycaprolactone comprises the following raw materials in parts by weight:
1-5 parts of pentaerythritol;
30-40 parts of epsilon-caprolactone;
0.02-0.05 part of catalyst;
10-15 parts of methacrylic acid-2-isocyanate;
dichloromethane;
anhydrous ethanol.
4. The recyclable foam packaging material of claim 1, wherein the initiator is ammonium persulfate and/or potassium persulfate.
5. The recyclable foam packaging material of claim 1, wherein the recyclable foam packaging material comprises an emulsifier.
6. The recyclable foam packaging material of claim 5, wherein the emulsifier is 5 to 15 parts by weight.
7. The recyclable foam packaging material of claim 5, wherein the emulsifier is a mixture of span 60 and polyether polyol in a mass ratio of 1: 1.
8. A method of making a recyclable foam packaging material, comprising the steps of:
s1, synthesis of modified tetravinyl polycaprolactone:
1-5 parts of pentaerythritol, 30-40 parts of epsilon-caprolactone, 0.02-0.05 part of catalyst and 10-15 parts of methacrylic acid-2-isocyanate are polymerized to obtain a polymerization product, the polymerization product is dissolved in dichloromethane and precipitated by absolute ethyl alcohol and dried;
s2, monomer phase:
mixing 10-20 parts of styrene, 30-60 parts of butyl acrylate and 10-20 parts of butyl methacrylate to form a monomer, and dissolving 2-30 parts of modified tetraenylpolycaprolactone in the monomer;
s3, preparing emulsion and polymerizing:
and stirring and mixing the initiator aqueous solution and the monomer of S2 to obtain emulsion, and solidifying, washing and drying the emulsion to obtain the recyclable foam packaging material.
9. The method of claim 8, wherein the step of S3 preparing the emulsion and polymerizing further comprises adding an emulsifier to the monomer phase of S2.
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| US20120108692A1 (en) * | 2010-10-27 | 2012-05-03 | John Collins Dyer | Preparation of foam materials derived from renewable resources |
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