CN113494025A - Polymer-skeleton interface nano reinforcing agent and preparation method thereof - Google Patents
Polymer-skeleton interface nano reinforcing agent and preparation method thereof Download PDFInfo
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- CN113494025A CN113494025A CN202110780427.8A CN202110780427A CN113494025A CN 113494025 A CN113494025 A CN 113494025A CN 202110780427 A CN202110780427 A CN 202110780427A CN 113494025 A CN113494025 A CN 113494025A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/693—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural or synthetic rubber, or derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
- B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
- B29B15/10—Coating or impregnating independently of the moulding or shaping step
- B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
- B29B15/14—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length of filaments or wires
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
- D06M11/28—Halides of elements of Groups 8, 9, 10 or 18 of the Periodic System
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/11—Compounds containing epoxy groups or precursors thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
Abstract
The invention discloses a polymer-skeleton interface nano reinforcing agent and a preparation method thereof, wherein the polymer-skeleton interface reinforcing agent comprises the following components: 100 parts by mass of polar polymer, 0.05-50 parts by mass of nano filler, 0.01-10 parts by mass of polyphenol compound and 0.01-10 parts by mass of polyvalent metal salt. The preparation method of the polymer-framework interface reinforcing agent comprises the following steps: firstly, under the assistance of a polyphenol compound, dispersing a nano filler in a solvent A under a certain condition to obtain a dispersion liquid A; then, dispersing the polar polymer in a solvent B under a certain condition to obtain a dispersion liquid B, wherein the solvent A and the solvent B are the same or can be mutually soluble; and finally, mixing the dispersion liquid A and the dispersion liquid B under certain conditions to obtain the interface enhancer dispersion liquid.
Description
Technical Field
The invention belongs to the technical field of polymer-framework adhesion, and particularly relates to a polymer-framework interface nano reinforcing agent and a preparation method thereof.
Background
The skeleton structure can remarkably improve the mechanical and structural stability of polymer products, and can reduce the mechanical relaxation phenomenon (creep and stress relaxation) of the polymer products, so that the skeleton structure can be used as a structural member to replace a metal structural member, is favorable for the light weight of the products, and has wide application requirements in the fields of aerospace, automobiles, rail transit and the like.
The common polymer product framework materials comprise cord threads, cord fabrics, glass fibers, glass fiber cloth, carbon fibers, carbon fiber cloth, steel wires and the like, the framework materials not only have smooth microscopic surfaces, but also present physical/chemical inertness and have no strong physical/chemical action with a polymer matrix, the interface action between the polymer matrix and the framework is weaker due to the combined action of the two aspects, the polymer matrix and the framework are easy to delaminate under the action of external force, and external loads cannot be effectively transferred to the framework, so that the framework cannot play a role in reinforcement. Therefore, the backbone must be modified to increase the interfacial adhesion between the backbone and the polymer matrix.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a polymer-skeleton interface nano reinforcing agent and a preparation method thereof, wherein the strength of the interface reinforcing agent is improved on one hand, and the roughness of the skeleton is improved on the other hand through the introduction of nano fillers, so that the adhesion between a polymer matrix and the skeleton is further improved.
The invention is realized by the following technical scheme: a polymer-framework interface nano reinforcing agent comprises the following components in parts by mass: 100 parts by mass of polar polymer, 0.05-50 parts by mass of nano filler, 0.01-10 parts by mass of polyphenol compound and 0.01-10 parts by mass of polyvalent metal salt.
Preferably, the polar polymer is: one or more of phenolic resin, urea resin, melamine resin, epoxy resin, novolac epoxy resin, polyurethane, polyurea, polyvinyl chloride, chlorinated polyethylene, chlorosulfonated polyethylene, chloroprene rubber, brominated butyl rubber, nitrile rubber, polyacrylic acid, polymethacrylic acid, polyvinyl acetate, acrylate rubber, fluororubber and derivatives thereof.
Preferably, the nano-filler is: graphene, carbon black, fullerene, carbon nano tube, graphene, metal particles, metal compounds, calcium carbonate, boric acid, borate, halloysite nano tube, hydroxyapatite, clay with the number of layers less than or equal to 20, graphite with the number of layers less than or equal to 20, boron nitride with the number of layers less than or equal to 20, black phosphorus with the number of layers less than or equal to 20 and one or more mixtures of derivatives of the black phosphorus and the black phosphorus.
Preferably, the polyphenolic compound is: one or more compounds with the structure that the number of phenolic hydroxyl groups is more than or equal to 2.
Preferably, the polyvalent metal salt is: one or more mixtures of metal salts containing metal ions with the valence more than or equal to 2.
A method for preparing a polymer-skeleton interface nano reinforcing agent,
1) dispersing the nano filler: dispersing the nano filler in a solvent A under a certain condition with the assistance of a polyphenol compound to obtain a dispersion liquid A;
2) dissolution of polar polymer: dispersing a polar polymer in a solvent B under a certain condition to obtain a dispersion liquid B, wherein the solvent A and the solvent B are the same or can be mutually soluble;
3) preparing an interface reinforcing agent: mixing the dispersion liquid A and B under a certain condition, and then adding a polyvalent metal salt to obtain an interfacial enhancer dispersion liquid.
The invention has the beneficial effects that: according to the invention, a tackifying system with a physical action structure is successfully constructed by using a low-cost commercial polyphenol compound, and the bonding strength between a polymer and a skeleton is remarkably improved by virtue of a synergistic effect of the low-cost commercial polyphenol compound and the commercial polyphenol compound; compared with the commercial interface reinforcing agent, the nano adhesion system provided by the invention has more excellent effect on improving the adhesion of the polymer-framework.
Drawings
FIG. 1 is a scanning electron micrograph of an unmodified cord of example 1.
FIG. 2 is a scanning electron micrograph of a modified cord of the self-made interface enhancer of example 1.
Detailed Description
The invention is explained in further detail below by means of specific embodiments with reference to the drawings. It is to be understood that the following examples are intended to illustrate the invention and are not intended to limit its scope.
Comparative example 1:
a polymer-skeleton interface nano reinforcing agent, which comprises the following components: 100 parts of chloroprene rubber, 10 parts of polyethyleneimine and 5 parts of cobalt chloride. The interface reinforcing agent is prepared by the following steps:
1) at the temperature of 60 ℃ and at the speed of 4500 r/min, adding chloroprene rubber into 200 parts by mass of acetone, and stirring for 3 hours to prepare a chloroprene rubber solution;
2) firstly, stirring and mixing the prepared chloroprene rubber solution for 1 h at the temperature of 25 ℃ and the speed of 1000 r/min; then, cobalt chloride is added in sequence and stirred for 1 hour, and the polymer-framework interface enhancer dispersion liquid is prepared.
According to the national standard GB/T2942-2009, an average withdrawal force of the cord was measured to be 43.3N, which is a small improvement over an average withdrawal force of 37.2N for the untreated cord.
Example 1:
a polymer-skeleton interface nano reinforcing agent, which comprises the following components: 100 parts of chloroprene rubber, 2 parts of graphene, 5 parts of tea tannin and 5 parts of cobalt chloride. The interface reinforcing agent is prepared by the following steps:
1) adding graphene into 100 parts by mass of water under the condition of 45 ℃ and 1000 r/min and with the aid of tea tannin, and stirring for 1 h to prepare a graphene dispersion liquid;
2) at the temperature of 60 ℃ and at the speed of 4500 r/min, adding chloroprene rubber into 200 parts by mass of acetone, and stirring for 3 hours to prepare a chloroprene rubber solution;
3) firstly, stirring and mixing the prepared graphene dispersion liquid and a chloroprene rubber solution for 1 h at the temperature of 25 ℃ and the speed of 1000 r/min; then, cobalt chloride is added in sequence to prepare the polymer-skeleton interface enhancer dispersion liquid.
According to the national standard GB/T2942-2009, the average withdrawal force of the cord is measured to be 56.7N, which is greatly improved compared with the untreated cord average withdrawal force of 37.2N.
The prepared polymer-framework interface reinforcing agent dispersion liquid is coated on the surface of a polyester cord by dipping, and after the cord is dried, the cord and the tire tread rubber are vulcanized together. From a comparison of fig. 1 and 2, it was found that the surface of the unmodified cord was smooth, while the cord surface roughness after modification with the interface enhancer was significantly increased.
Claims (6)
1. A polymer-backbone interface nanoenhancer, characterized by: the composition comprises the following components in parts by mass: 100 parts by mass of polar polymer, 0.05-50 parts by mass of nano filler, 0.01-10 parts by mass of polyphenol compound and 0.01-10 parts by mass of polyvalent metal salt.
2. The polymer-backbone interface nanoenhancer of claim 1, wherein: the polar polymer is: one or more of phenolic resin, urea resin, melamine resin, epoxy resin, novolac epoxy resin, polyurethane, polyurea, polyvinyl chloride, chlorinated polyethylene, chlorosulfonated polyethylene, chloroprene rubber, brominated butyl rubber, nitrile rubber, polyacrylic acid, polymethacrylic acid, polyvinyl acetate, acrylate rubber, fluororubber and derivatives thereof.
3. The polymer-backbone interface nanoenhancer of claim 1, wherein: the nano filler is as follows: graphene, carbon black, fullerene, carbon nano tube, graphene, metal particles, metal compounds, calcium carbonate, boric acid, borate, halloysite nano tube, hydroxyapatite, clay with the number of layers less than or equal to 20, graphite with the number of layers less than or equal to 20, boron nitride with the number of layers less than or equal to 20, black phosphorus with the number of layers less than or equal to 20 and one or more mixtures of derivatives of the black phosphorus and the black phosphorus.
4. The polymer-backbone interface nanoenhancer of claim 1, wherein: the polyphenol compound is: one or more compounds with the structure that the number of phenolic hydroxyl groups is more than or equal to 2.
5. The polymer-backbone interface nanoenhancer of claim 1, wherein: the polyvalent metal salt is: one or more mixtures of metal salts containing metal ions with the valence more than or equal to 2.
6. A method for preparing a polymer-skeleton interface nano reinforcing agent according to any one of claims 1 to 5, characterized in that:
dispersing the nano filler: dispersing the nano filler in a solvent A under a certain condition with the assistance of a polyphenol compound to obtain a dispersion liquid A;
dissolution of polar polymer: dispersing a polar polymer in a solvent B under a certain condition to obtain a dispersion liquid B, wherein the solvent A and the solvent B are the same or can be mutually soluble;
preparing an interface reinforcing agent: mixing the dispersion liquid A and B under a certain condition, and then adding a polyvalent metal salt to obtain an interfacial enhancer dispersion liquid.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110780427.8A CN113494025A (en) | 2021-07-09 | 2021-07-09 | Polymer-skeleton interface nano reinforcing agent and preparation method thereof |
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| CN202110780427.8A CN113494025A (en) | 2021-07-09 | 2021-07-09 | Polymer-skeleton interface nano reinforcing agent and preparation method thereof |
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| CN113494025A true CN113494025A (en) | 2021-10-12 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115353729A (en) * | 2022-09-05 | 2022-11-18 | 江南大学 | Non-covalent bond cross-linked high-strength high-toughness plastic recyclable composite material and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110106712A (en) * | 2019-05-29 | 2019-08-09 | 青岛科技大学 | A kind of polymer that imitative mussel is sticked enough-skeleton Interface enhancer and preparation method thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110106712A (en) * | 2019-05-29 | 2019-08-09 | 青岛科技大学 | A kind of polymer that imitative mussel is sticked enough-skeleton Interface enhancer and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115353729A (en) * | 2022-09-05 | 2022-11-18 | 江南大学 | Non-covalent bond cross-linked high-strength high-toughness plastic recyclable composite material and preparation method and application thereof |
| CN115353729B (en) * | 2022-09-05 | 2024-02-13 | 江南大学 | Non-covalent bond crosslinked high-strength high-toughness plastic recyclable composite material and preparation method and application thereof |
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