CN108976368B - Film forming method for rapid forming - Google Patents
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- CN108976368B CN108976368B CN201810581792.4A CN201810581792A CN108976368B CN 108976368 B CN108976368 B CN 108976368B CN 201810581792 A CN201810581792 A CN 201810581792A CN 108976368 B CN108976368 B CN 108976368B
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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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
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- 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
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
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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
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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Abstract
The invention belongs to the technical field of polymer synthesis, and particularly relates to a film forming method for rapid molding. In the invention, in the nitrogen atmosphere, a monomer, a reversible addition-chain transfer agent, triethylboron and a doping material are subjected to an 'active'/controllable free radical polymerization reaction under the induction of air in a solvent or in the absence of a solvent to form a polymer film layer with controllable molecular weight and narrow polydispersity. The material provided by the method can be used as a raw material of the ink-jet type 3D printer, the problem of layer-by-layer stacking of 3D printing materials can be solved, and the connection strength between layers is greatly improved. The invention does not use any organic solvent, and accords with the environmental protection concept of green and no pollution. In addition, the invention introduces alkyl boron into the 'active'/controllable free radical polymerization reaction, and provides an effective way for quickly and efficiently synthesizing the target polymer under the conditions of air and room temperature.
Description
Technical Field
The invention belongs to the technical field of polymer synthesis, and particularly relates to a film forming method for rapid molding.
Background
The 3D printing technology is 'rapid prototyping', which appears in the middle of the 90 s of the 20 th century, has basically the same working principle as the common printing, and the printer is filled with 'printing materials' such as liquid or powder, and the 'printing materials' are overlapped layer by layer under the control of a computer after being connected with the computer, so that a blueprint on the computer is finally changed into a real object. The fields that it relates to are also wide: naval vessels, aerospace science and technology, medical field, house building, automobile industry, electronic industry, clothing, shadowless high-heeled shoes and the like. There are many different techniques for 3D printing that differ in that components are created in layers built up in different ways, with available materials; commonly used "printing materials" include nylon glass fiber, durable nylon material, gypsum material, aluminum material, titanium alloy, stainless steel, gold plating, silver plating, rubber material, and the like, and the types adopted are also various such as: extrusion, wire, granular, lamination, photopolymerization, and the like; the accumulation techniques employed are numerous, such as: fused deposition, electron beam melt molding, layered solid fabrication, stereolithography, and the like.
Triethylboron, boron atom has special empty orbit to lead to the development of potential metal property, especially it can take place autoxidation process to produce free radical under the air condition, it is fast and high efficient as initiator to initiate free radical polymerization under the induction of air, monomer conversion rate can reach 100% within 15 min, even when a very thin film is coated on the substrate, the polymerization can be completed instantly. More importantly, the reaction temperature range of the triethylborane in the system is wider than that of the common azodiisobutyronitrile thermal initiator, even can be changed from 80 ℃ to-78 ℃, and the free radical synthesis reaction in water can be realized, thereby providing a basis for developing a new rapid forming film-forming technology.
Disclosure of Invention
The invention aims to provide a film forming method which does not use any organic solvent, is green and environment-friendly and has no pollution and can be used for rapid forming.
The film forming method for rapid forming provided by the invention utilizes an organic small molecular reagent 'triethylborane' to initiate 'active'/controllable free radical polymerization reaction under air induction, thereby realizing air-induced rapid forming. The material obtained by the method can be used as a raw material of an ink-jet type 3D printer, the problem of layer-by-layer stacking of the existing 3D printing material can be solved, and the connection strength between layers is greatly improved. In addition, the invention does not use any organic solvent, and better accords with the environmental protection concept of green and no pollution.
The invention provides a film forming method for rapid forming, which is characterized in that a functional monomer, a chain transfer reagent, triethylboron and a dopant are subjected to an 'active'/controllable free radical polymerization reaction under the induction of air in a solvent or in the absence of a solvent under the atmosphere of nitrogen to form a polymer film layer with controllable molecular weight and narrow polydispersity, and the specific steps are as follows:
(1) mixing functional monomers (such as acrylic acid, acrylate, acrylamide and the like), reversible-addition chain transfer agents (such as dithioester, trithioester and the like), dopants (such as fluorescent dye, conductive material and the like) (water can be added as a solvent, or water is not added);
(2) adding an initiator of triethylboron in a nitrogen atmosphere to form a reaction liquid of a polymerization reaction;
(3) dipping the reaction solution by a brush pen, rapidly drawing a pre-designed pattern on the substrate at room temperature and in an air state, and finishing the polymerization reaction when the pattern is drawn to form a polymer film layer with controllable molecular weight and narrow polydispersity.
In step (1) of the present invention, the functional monomer used is various and may be selected from acrylic acid, methyl acrylate, ethyl acrylate, tert-butyl acrylate, N-isopropylacrylamide, glycidyl methacrylate, methyl methacrylate, etc.
In step (1) of the present invention, the reversible addition-fragmentation chain transfer agent may be selected from dithioesters and trithioesters, and can be obtained by one-pot synthesis. The structure is as follows:
in step (1) of the present invention, a variety of dopants are used, such as fluorescent dyes, e.g., rhodamine, eosin, etc.; and conductive materials such as graphene, nanogold, nanosilver and the like.
In step (3), the substrate may be selected from glass, polyvinylidene fluoride, indium tin oxide, steel, alloy, etc.
In the step (3) of the present invention, the polymerization temperature is 80 ℃ to 78 ℃.
In the invention, the molar mass ratio of the functional monomer, the reversible addition-fragmentation chain transfer agent and the initiator is x:1 (1.0-4.0). Where x is a number of 1 or more, for example, 1 to 107Preferably 10 to 103。
In the present invention, the amount ratio of the dopant may be appropriately added as needed.
The initiator used in the invention is triethylboron which is cheap and easy to obtain. The initiated polymerization reaction is rapid and efficient, the monomer conversion rate is high and can reach 100% within 1 min.
The synthesis method of the present invention can be represented by the following reaction formula:
the invention has the beneficial effects that:
(1) the triethylboron is low in price, and can generate free radicals under the air;
(2) the reaction condition is mild (room temperature), the operation is simple and convenient, and no additional heating is needed;
(3) the polymerization reaction is rapid and efficient, and the conversion rate of the monomer can reach 100 percent within 1 min;
(4) the target molecular weight is controllable, and the polydispersity is narrow;
(5) the chain ends are active and can enhance the tightness between layers.
The rapid film forming method of the present invention can be used in an ink jet printing technique.
The rapid film forming method of the invention can also be used for preparing anticorrosive coatings.
The rapid film-forming process of the present invention can also be used in the preparation of adhesives.
Drawings
FIG. 1 is a symbolic representation of the present invention written by rapid prototyping, showing that the molecular weight distribution of any three points is relatively uniform and narrow.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but it should not be construed that the scope of the subject matter of the present invention is limited to the examples. All the technologies implemented based on the above-mentioned contents of the present invention belong to the scope of the present invention.
Example 1
Air-induced rapid forming film-forming polymerization reaction of methyl acrylate on glass culture dish
Placing methyl acrylate, a reversible addition-fragmentation chain transfer agent and eosin in a 10 mL Schlenk bottle, introducing nitrogen below the liquid surface for 25min, adding triethylboron under the nitrogen atmosphere, continuously introducing nitrogen for 5min, taking out a small amount of sample from a reaction bottle by using an injector with a long needle, dropwise adding the sample on a writing brush, preparing a clean glass culture dish, and quickly writing're-denier' on the culture dish by using the writing brush dipped with a reaction solution. At the moment of writing, randomly taking out three points on the typeface, and adopting1H NMR and GPC characterize the monomer conversion, molecular weight of the polymer and molecular weight distribution. The method shows that the molecular weight of any part of the character is uniform and the molecular weight distribution is narrow. In addition, the method is rapid and efficient, and the molecular weight of the obtained polymer is close to the target molecular weight and the molecular weight distribution is narrow.
Example 2
Air-induced rapid forming film-forming polymerization reaction of tert-butyl acrylate on glass culture dish
Placing tert-butyl acrylate, reversible addition-fragmentation chain transfer agent and eosin in a 10 mL Schlenk bottle, introducing nitrogen for 25min below the liquid surface, adding triethylboron under the nitrogen atmosphere, continuously introducing nitrogen for 5min, taking out a small amount of sample from the reaction bottle by using an injector with a long needle, dropwise adding the sample on a writing brush, preparing a clean glass culture dish, and rapidly drawing various patterns such as a 'faucet' on the culture dish by using the writing brush dipped with reaction liquid. At the moment of drawing, randomly taking out three points on the pattern, and adopting1H NMR and GPC characterize monomer conversion, polymer molecular weight and molecular weight distribution. The method shows that the molecular weight is uniform at any position of the pattern, and the molecular weight distribution is narrow. In addition, the film forming method is rapid and efficient, and the molecular weight of the obtained polymer is close to the target molecular weight and the molecular weight distribution is narrow.
Example 3
Application of air-induced methyl acrylate rapid forming film-forming polymerization reaction in preparation of anticorrosive paint
Putting methyl acrylate and a reversible addition-fragmentation chain transfer reagent into a 10 mL Schlenk bottle, introducing nitrogen for 25min under the liquid surface, adding triethylboron under the nitrogen atmosphere, continuously introducing nitrogen for 5min, taking a small amount of sample out of the reaction bottle by using an injector with a long needle, dropwise adding the sample onto a writing brush, simultaneously preparing a small piece of waste steel, uniformly coating the surface of the steel by using the writing brush dipped with a reaction liquid, standing for 1 min to observe that a layer of uniform film appears on the surface of the steel, soaking the steel with a film on the surface into water to well protect the steel, and randomly taking three points out of the film by adopting a method of adding triethylboron into the reaction liquid and uniformly stirring the steel, and then adding a stirring liquid into the reaction bottle to obtain a solution1H NMR and GPC characterize monomer conversion, polymer molecular weight and molecular weight distribution. The method shows that the molecular weight of any part of the membrane presents uniformity and the molecular weight distribution is narrow. In addition, the method is used for preparing the anticorrosive paint quickly and efficiently, and the molecular weight of the obtained polymer is close to the target molecular weight and the molecular weight distribution is narrow.
Example 4
Application of air-induced rapid forming film-forming polymerization reaction of acrylic acid in preparation of oxygen-loving binder
Placing acrylic acid and a reversible addition-fragmentation chain transfer agent in a 10 mL Schlenk bottle, introducing nitrogen below the liquid level for 25min, adding triethylboron in the nitrogen atmosphere, continuously introducing nitrogen for 5min, taking out a small amount of sample from the reaction bottle by using an injector with a long needle, dropwise adding the sample on a writing brush, preparing two white papers at the same time, coating a 2 cm strip on one of the white papers by using the writing brush dipped with a reaction liquid, then quickly covering the other white paper on the strip, and tightly adhering the two papers after 1 min. Randomly shearing three samples from the strip by1H NMR and GPC characterize monomer conversion, polymer molecular weight and molecular weight distribution. The method shows that the molecular weight of any part of the strip is uniform, and the molecular weight distribution is narrow. In addition, the method is used for preparing the adhesive rapidly and efficiently, and the molecular weight of the obtained polymer is close to the target molecular weight and the molecular weight distribution is narrow.
Example 5
Application of air-induced methyl acrylate rapid forming film-forming polymerization reaction in preparation of flexible electronic device
Putting methyl acrylate, RAFT reagent and carbon nano tube into a 10 mL Schlenk bottle, introducing nitrogen for 25min under the liquid surface, adding triethylboron under the nitrogen atmosphere, continuously introducing nitrogen for 5min, taking out a small amount of sample from the reaction bottle by using an injector with a long needle, dropwise adding the sample on a writing brush, preparing a flexible substrate (indium tin oxide or electronic paper), coating a strip of 2 cm on the flexible substrate by using the writing brush dipped with reaction liquid, waiting for 1 min, randomly cutting off three samples from the strip, and adopting1H NMR and GPC characterize monomer conversion, polymer molecular weight and molecular weight distribution. The method shows that the molecular weight of any part of the strip is uniform, and the molecular weight distribution is narrow. Meanwhile, the conductivity, flexibility, light transmittance and chemical stability of the film are represented. In addition, the method is fast, efficient and low in cost when used for preparing flexible electronic devices, and the molecular weight of the obtained polymer is close to the target molecular weight and the molecular weight distribution is narrow.
Claims (6)
1. A film forming method for rapid forming is characterized in that a functional monomer, a chain transfer reagent, triethylboron and a dopant are subjected to 'activity'/controllable free radical polymerization reaction under the induction of air in a solvent or no solvent in a nitrogen atmosphere to form a polymer film layer with controllable molecular weight and narrow polydispersity, and the specific steps are as follows:
(1) mixing a functional monomer, a reversible-addition chain transfer reagent and a dopant, and adding water as a solvent or not;
(2) adding an initiator of triethylboron in a nitrogen atmosphere to form a reaction liquid of a polymerization reaction;
(3) dipping the reaction solution by a brush pen, rapidly drawing a pre-designed pattern on the substrate at room temperature and in an air state, and finishing the polymerization reaction when the pattern is drawn to form a polymer film layer with controllable molecular weight and narrow polydispersity;
the functional monomer used in the step (1) is selected from acrylic acid, methyl acrylate, ethyl acrylate, tert-butyl acrylate, N-butyl acrylate, N-isopropylacrylamide, glycidyl methacrylate and methyl methacrylate;
the reversible-addition chain transfer reagent used in step (1) may be selected from dithioesters, trithioesters.
2. The film forming method according to claim 1, wherein the dopant used in step (1) is a fluorescent dye or a conductive material.
3. The film forming method according to claim 2, wherein the fluorescent dye is selected from rhodamine, eosin; the conductive material is selected from graphene, nanogold and nanosilver.
4. The film forming method according to claim 3, wherein the substrate in the step (3) is selected from glass, polyvinylidene fluoride, indium tin oxide, and steel.
5. The film-forming method according to any one of claims 1 to 4, wherein the molar mass ratio of the functional monomer, the reversible-addition chain transfer agent and the initiator is x:1 (1.0 to 4.0), 1 < x.ltoreq.107。
6. Use of a film forming process according to any one of claims 1 to 4 in 3D inkjet printing technology, for the preparation of anticorrosive coatings or for the preparation of adhesives.
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| CN107501464A (en) * | 2017-07-24 | 2017-12-22 | 四川大学 | A kind of preparation method of olefin-acrylate copolymer |
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