CN111138671A - Metal-organic high molecular compound and preparation method thereof - Google Patents
Metal-organic high molecular compound and preparation method thereof Download PDFInfo
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- CN111138671A CN111138671A CN201811305685.5A CN201811305685A CN111138671A CN 111138671 A CN111138671 A CN 111138671A CN 201811305685 A CN201811305685 A CN 201811305685A CN 111138671 A CN111138671 A CN 111138671A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G83/008—Supramolecular polymers
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Abstract
The invention discloses a metal-organic polymer compound and a preparation method thereof. The main components of the metal-organic high molecular compound comprise: polyvinyl chloride resin, micromolecular metal organic compounds, initiators, auxiliaries and the like. The metal-organic high molecular compound can be prepared by a solid phase chemical reaction method such as high-energy vibromilling or microwave irradiation. The metal-organic polymer compound provided by the invention has very high dielectric constant and good mechanical property. The material can be used as a precursor material of an electrorheological material and a magnetorheological material, can also be used for manufacturing high-performance polyvinyl chloride pipes, profiles, thin-film materials and the like, and has very wide application prospects in the fields of magnetism, light, electricity, special gas storage and the like, and the aspects of high-quality high-low temperature welding and the like.
Description
Technical Field
The invention relates to the technical field of polymer and metal compound crossing, in particular to a metal-organic high molecular compound and a preparation method thereof.
Technical Field
The metal-organic compound belongs to the interdiscipline of organic and inorganic fields, and the emergence of the metal-organic compound opens up a new research field for interdiscipline application and provides wider 'soil' for the emergence of more new high-performance materials. The metal-organic compound combines the performance advantages of the metal compound and the organic compound, so that the metal-organic compound has performance characteristics which can not be achieved by a single compound, such as outstanding thermal performance, excellent electromagnetic performance, photoelectric performance, high-efficiency hydrogen storage capacity and the like.
The organic polymer compound is a compound prepared by addition polymerization, condensation polymerization and the like on the basis of a small molecular organic compound, and has the performance characteristics of a common small molecular organic compound and performance advantages brought by high molecular weight, such as: high specific strength, high specific modulus, stable chemical properties and the like. If the compound can be combined with metal compounds to form complementary advantages, exciting effects are generated, and new hopes are brought to the field of materials. However, the difficulty of selecting suitable reactants and the limitation of the conventional reaction method are hindered, and the work of preparing the metal-organic polymer compound by combining the organic polymer compound and the metal compound is still a difficult problem in the field.
Disclosure of Invention
The invention aims to provide a metal-organic polymer compound and a preparation method thereof, so as to promote the development of the technical field.
The technical difficulty of the invention is to find an organic polymer compound and a metal compound which are suitable for matching, so that the provided metal-organic polymer compound has high dielectric constant and good mechanical property.
The specific technical scheme for realizing the above purpose of the invention is as follows:
the invention provides a metal-organic polymer compound, which comprises the following components in parts by weight: 100phr of polyvinyl chloride resin, 12-40phr of micromolecule metal organic compound, 1-5phr of initiator and 0-30phr of auxiliary agent are obtained by solid phase chemical reaction.
In the above technical solution of the present invention, the small molecule metal-organic compound is preferably selected from ferrocene and a metal-organic compound having the following structure:
wherein X is H, CmH2m+1、CmH2m-1、C2H2An aromatic compound and a derivative thereof or an alicyclic compound and a derivative thereof, wherein m is 1-20; n is 1-4; me is Zn, Cu, Sn, Pb, Mg, Ca, Ba, Al or Na. I.e. may be one or more of these small molecule organometallic compounds.
In the above technical solution of the present invention, the initiator is preferably selected from dicumyl peroxide, ammonium persulfate, potassium persulfate, hydrogen peroxide, azobisisobutyronitrile and benzoyl peroxide, i.e. may be one or more of them.
In the above technical solution of the present invention, the auxiliary agent is preferably selected from deionized water, benzene, toluene, xylene, petroleum ether, methanol, ethanol, ethyl acetate, glycerol and tetrahydrofuran, i.e., may be one or more of them.
The metal-organic polymer compound provided by the invention can be prepared by a method mainly comprising the following steps:
(1) placing the polyvinyl chloride resin, the micromolecular metal organic compound, the initiator and the auxiliary agent in a formula ratio in a mixer, and mixing for not less than 24 hours at 10-30 ℃ to ensure that all reactants are fully contacted;
(2) and (3) placing the fully and uniformly mixed mixture in a solid phase chemical reaction device such as a microwave reactor or a high-energy vibration mill for solid phase reaction, and preparing the metal-organic high molecular compound after full reaction.
In the preparation method of the metal-organic polymer compound, the solid phase chemical reaction device is a high-energy vibration mill, and the reaction condition is that the reaction is carried out for 20 to 40 hours at the temperature of between 30 and 50 ℃.
In the preparation method of the metal-organic polymer compound, the solid phase chemical reaction device is a microwave reactor, and the reaction condition is that the reaction is carried out for 10min to 30min at the temperature of 30 ℃ to 50 ℃.
Compared with all C chain high molecular compounds such as polyethylene, polypropylene and the like, the dissociation activation energy of C-Cl bonds in the polyvinyl chloride is lower, so that the chemical reaction activity of the polyvinyl chloride is higher. In addition, a certain amount of head-head structures, allyl chloride structures, tertiary chloride structures and other defect structures exist on the PVC molecular chain, and compared with the normal head-tail structures, the defect structure points have high energy and higher activity, are easily activated in a specific environment, and can be used as starting points to initiate an expected chemical reaction with the organic end of the small-molecular metal organic compound. Based on the above knowledge, the inventors have selected polyvinyl chloride and a specific pair of small-molecule organometallic compounds to produce a metal-organic polymer compound.
The metal-organic polymer compound provided by the invention has high dielectric constant and good mechanical properties (see the embodiment), can be used as a precursor material of an electrorheological material and a magnetorheological material, can also be used for manufacturing high-performance polyvinyl chloride plates, pipes, sections, thin film materials and the like, and has very wide application prospects in the fields of magnetic, optical, electric, special gas storage and the like, and the aspects of high-quality high-low temperature welding and the like.
Detailed description of the preferred embodiment
The present invention is described in detail below by way of examples to facilitate understanding of the present invention by those skilled in the art. It should be particularly noted that the examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as those skilled in the art will be able to make insubstantial modifications and variations of this invention in light of the above teachings, and will nevertheless fall within the scope of this invention.
In the following examples, parts of the components are parts by weight (phr).
Example 1:
accurately weighing 100phr of polyvinyl chloride resin, 37phr of ferrocene, 4phr of azodiisobutyronitrile and 23phr of tetrahydrofuran, and then placing the weighed materials in a mixer to mix for 28 hours at 20 ℃ to ensure that all reactants are fully contacted; the mixture after being fully and uniformly mixed is placed in a high-energy vibration mill and reacts for 22 hours at the temperature of 40 ℃. Thus obtaining the metal-organic high molecular compound No. 1.
Example 2:
accurately weighing 100phr of polyvinyl chloride resin, 20phr of copper oleate, 2.5phr of hydrogen peroxide and 8phr of ethanol, and then placing the weighed materials into a mixer to mix for 40 hours at 15 ℃ to ensure that all reactants are fully contacted; the mixture after being fully and uniformly mixed is placed in a high-energy vibration mill and reacts for 30 hours at the temperature of 50 ℃. Thus obtaining the metal-organic high molecular compound 2 #.
Example 3:
accurately weighing 100phr of polyvinyl chloride resin, 5phr of sodium methacrylate, 9phr of stannous acetate and 1.6phr of dicumyl peroxide, and then placing the materials in a mixer to mix for 26 hours at 30 ℃ to ensure that all reactants are fully contacted; the mixture after being fully and uniformly mixed is placed in a high-energy vibration mill and reacts for 38 hours at the temperature of 30 ℃. Thus obtaining the metal-organic high molecular compound No. 3.
Example 4:
100phr of polyvinyl chloride resin, 5phr of calcium maleate, 10phr of barium propionate, 3phr of zinc itaconate, 2phr of ammonium persulfate and 10phr of glycerol are accurately weighed and then placed in a mixer to be mixed for 32 hours at 25 ℃, so that all reactants are fully contacted; the mixture after being fully and uniformly mixed is placed in a microwave reactor and reacts for 26min at the temperature of 35 ℃. Thus obtaining the metal-organic high molecular compound No. 4.
Example 5:
accurately weighing 100phr of polyvinyl chloride resin, 27phr of aluminum benzoate and 3phr of benzoyl peroxide, and then placing the weighed materials in a mixer for mixing for 48 hours at 18 ℃ to ensure that all reactants are fully contacted; the mixture after being fully and uniformly mixed is placed in a microwave reactor and reacts for 13min at the temperature of 50 ℃. Thus obtaining the metal-organic high molecular compound No. 5.
The test results of the samples are as follows:
Claims (7)
1. a metal-organic polymer compound is characterized by comprising the following components in parts by weight:
2. the metal-organic polymeric compound of claim 1, wherein the small molecule metal-organic compound is selected from the group consisting of ferrocene and metal-organic compounds having the following structure:
wherein X is H, CmH2m+1、CmH2m-1、C2H2An aromatic compound and a derivative thereof or an alicyclic compound and a derivative thereof, wherein m is 1-20; n is 1-4; me is Zn, Cu, Sn, Pb, Mg, Ca, Ba, Al or Na.
3. The metal-organic high molecular compound according to claim 1, wherein the initiator is selected from the group consisting of dicumyl peroxide, ammonium persulfate, potassium persulfate, hydrogen peroxide, azobisisobutyronitrile and benzoyl peroxide.
4. The metal-organic polymer compound according to claim 1, wherein the auxiliary agent is selected from the group consisting of deionized water, benzene, toluene, xylene, petroleum ether, methanol, ethanol, ethyl acetate, glycerol, and tetrahydrofuran.
5. A method for producing a metal-organic high molecular compound according to any one of claims 1 to 4, characterized by mainly comprising the steps of:
(1) placing the polyvinyl chloride resin, the micromolecular metal organic compound, the initiator and the auxiliary agent in a formula ratio in a mixer, and mixing for not less than 24 hours at 10-30 ℃ to ensure that all reactants are fully contacted;
(2) and (3) placing the fully and uniformly mixed mixture in a microwave reactor or a high-energy vibration mill solid-phase chemical reaction device for solid-phase reaction, and preparing the metal-organic high molecular compound after full reaction.
6. The method for producing a metal-organic polymer compound according to claim 5, wherein the PVC resin, the small-molecular metal organic compound, the initiator and the auxiliary agent are mixed uniformly and subjected to solid-phase reaction in a high-energy vibration mill at 30 to 50 ℃ for 20 to 40 hours.
7. The method for producing a metal-organic polymer compound according to claim 5, wherein the PVC resin, the small-molecular metal organic compound, the initiator and the auxiliary agent are mixed uniformly and subjected to solid-phase reaction in a microwave reactor at 30 to 50 ℃ for 10 to 30 minutes.
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|---|---|---|---|---|
| JPS4916554B1 (en) * | 1969-12-05 | 1974-04-23 | ||
| US5110392A (en) * | 1983-05-20 | 1992-05-05 | Toagosei Chemical Industry Co., Ltd. | Primer composition containing an organometallic compound for binding substrates with a cyanocrylate adhesive |
| CN1062912A (en) * | 1990-12-27 | 1992-07-22 | 北美爱托化学股份有限公司 | Stable halogen-containing polymer compositions |
| US20060194704A1 (en) * | 2003-07-11 | 2006-08-31 | Akzo Nobel N.V. | Highly over-based light colored liquid alkaline earth metal carboxylate |
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| US20160357108A1 (en) * | 2015-06-06 | 2016-12-08 | Yu-Hsiang Hsu | Photoconductive layer with adjustable electrical property |
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2018
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|---|---|---|---|---|
| JPS4916554B1 (en) * | 1969-12-05 | 1974-04-23 | ||
| US5110392A (en) * | 1983-05-20 | 1992-05-05 | Toagosei Chemical Industry Co., Ltd. | Primer composition containing an organometallic compound for binding substrates with a cyanocrylate adhesive |
| CN1062912A (en) * | 1990-12-27 | 1992-07-22 | 北美爱托化学股份有限公司 | Stable halogen-containing polymer compositions |
| US20060194704A1 (en) * | 2003-07-11 | 2006-08-31 | Akzo Nobel N.V. | Highly over-based light colored liquid alkaline earth metal carboxylate |
| CN104177726A (en) * | 2014-07-31 | 2014-12-03 | 青岛吉顺隆商贸有限公司 | High-toughness PVC (polyvinyl chloride) pipe |
| US20160357108A1 (en) * | 2015-06-06 | 2016-12-08 | Yu-Hsiang Hsu | Photoconductive layer with adjustable electrical property |
| CN107501461A (en) * | 2017-08-18 | 2017-12-22 | 天津科技大学 | A kind of copoly type PVC special assistant difunctional with heat stabilizer and plasticising |
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| 冯珊等: "聚氯乙烯无毒金属皂热稳定剂的研究", 《塑料加工》 * |
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| 潘祖仁等: "《塑料工业手册聚氯乙烯》", 31 August 1999, 化学工业出版社 * |
| 祁美丽等: "二茂铁功能化PVC及其应用研究", 《2016年全国高分子材料科学与工程研讨会》 * |
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