阅读说明：本技术 含有交联共价网络的新型类玻璃高分子材料的制备方法 (Preparation method of novel glass-like polymer material containing cross-linked covalent network ) 是由 孙政 任晓林 张保刚 陈晓东 祁乔宇 于 2020-12-23 设计创作，主要内容包括：本发明属于新型类玻璃高分子材料制备技术领域,特别是涉及一种含有交联共价网络的新型类玻璃高分子材料的制备方法。由以下步骤组成,(1)将双酚A二给水甘油醚100份、癸二酸75-100份和TBD 5-10份混合,在45-70℃水浴锅中搅拌20-30小时；(2)将步骤(1)中得到的混合物,置于50-60℃的真空干燥器中65-80分钟,装入模具放置到90-95℃下125-135分钟；(3)待混合物变澄清后,在145-150℃下,加热480-520分钟,再在160-170℃下加热固化480-520分钟,取出得到成品。制备方法工艺更加简单,实现批量化生产,从而使得制备得到的材料各方面性能也更加优越。(The invention belongs to the technical field of preparation of novel glass-like high polymer materials, and particularly relates to a preparation method of a novel glass-like high polymer material containing a cross-linked covalent network. The method comprises the following steps of (1) mixing 100 parts of bisphenol A diglycidyl ether, 75-100 parts of sebacic acid and 5-10 parts of TBD, and stirring in a water bath kettle at 45-70 ℃ for 20-30 hours; (2) placing the mixture obtained in the step (1) in a vacuum drier at 50-60 ℃ for 65-80 minutes, placing the mixture in a mould, and placing the mould at 90-95 ℃ for 125-135 minutes; (3) after the mixture becomes clear, the mixture is heated for 480-. The preparation method has simpler process and realizes batch production, thereby ensuring that the prepared material has more excellent performances in all aspects.)

1. A preparation method of a novel glass-like polymer material containing a cross-linked covalent network is characterized by comprising the following steps: the method comprises the following steps of (1) mixing 100 parts of bisphenol A diglycidyl ether, 75-100 parts of sebacic acid and 5-10 parts of TBD, and stirring in a water bath kettle at 45-70 ℃ for 20-30 hours; (2) placing the mixture obtained in the step (1) in a vacuum drier at 50-60 ℃ for 65-80 minutes, placing the mixture in a mould, and placing the mould at 90-95 ℃ for 125-135 minutes; (3) after the mixture becomes clear, the mixture is heated for 480-.

2. The method of claim 1 for preparing a novel glass-like polymeric material containing a cross-linked covalent network, characterized in that: the method comprises the following steps of (1) mixing 100 parts of bisphenol A diglycidyl ether, 75 parts of sebacic acid and 5 parts of TBD, and stirring for 20 hours in a 45 ℃ water bath; (2) placing the mixture obtained in the step (1) in a vacuum drier at 50 ℃ for 65 minutes, filling the mixture into a mold, and placing the mold at 90 ℃ for 130 minutes; (3) after the mixture becomes clear, heating for 480 minutes at 145 ℃, then heating and curing for 480 minutes at 160 ℃, and taking out to obtain a finished product.

3. The method of claim 1 for preparing a novel glass-like polymeric material containing a cross-linked covalent network, characterized in that: the method comprises the following steps of (1) mixing 100 parts of bisphenol A diglycidyl ether, 80 parts of sebacic acid and 5 parts of TBD, and stirring for 24 hours in a 55 ℃ water bath kettle; (2) putting the mixture obtained in the step (1) into a vacuum drier at 55 ℃ for 70 minutes, putting the mixture into a mould, and placing the mould at 95 ℃ for 130 minutes; (3) after the mixture becomes clear, heating for 500 minutes at 150 ℃, then heating and curing for 500 minutes at 165 ℃, and taking out to obtain a finished product.

4. The method of claim 1 for preparing a novel glass-like polymeric material containing a cross-linked covalent network, characterized in that: the method comprises the following steps of (1) mixing 100 parts of bisphenol A diglycidyl ether, 75 parts of sebacic acid and 10 parts of TBD, and stirring for 24 hours in a 55 ℃ water bath kettle; (2) putting the mixture obtained in the step (1) into a vacuum drier at 55 ℃ for 70 minutes, putting the mixture into a mould, and placing the mould at 95 ℃ for 130 minutes; (3) after the mixture becomes clear, heating for 500 minutes at 150 ℃, then heating and curing for 500 minutes at 165 ℃, and taking out to obtain a finished product.

5. The method of claim 1 for preparing a novel glass-like polymeric material containing a cross-linked covalent network, characterized in that: the method comprises the following steps of (1) mixing 100 parts of bisphenol A diglycidyl ether, 100 parts of sebacic acid and 10 parts of TBD, and stirring for 30 hours in a 70 ℃ water bath; (2) placing the mixture obtained in the step (1) in a vacuum drier at 60 ℃ for 80 minutes, filling the mixture into a mold, and placing the mold at 95 ℃ for 135 minutes; (3) after the mixture becomes clear, heating for 520 minutes at 150 ℃, then heating and curing for 520 minutes at 170 ℃, and taking out to obtain a finished product.

Technical Field

The invention belongs to the technical field of preparation of novel glass-like high polymer materials, and particularly relates to a preparation method of a novel glass-like high polymer material containing a cross-linked covalent network.

Background

A glass-like polymeric material is a covalently cross-linked polymeric material that can be reprocessed at high temperatures without melting and also without being soluble in solvents. However, the preparation method of the glass-like polymer material in the prior art has complex steps, can be formed by mixing and processing a plurality of raw materials for many times, contains toxic and volatile substances in each preparation step, is harmful to human bodies in the preparation process, and is very easy to cause danger due to complex process and multiple mixing of materials and excessive mixing. As the Chinese invention patent application number: 201810237415.9, step 1: mixing dichloromethane, ethyl acetate and absolute ethyl alcohol according to the volume ratio of 1:1:8 to obtain a reaction solvent; step 2: mixing a reaction solvent with 1-2mol of aromatic dialdehyde, and magnetically stirring for 20-30 min to obtain a colorless transparent liquid; and step 3: adding 3mL of absolute ethyl alcohol into a mixed solution of 0.2-0.4mol of diamine containing benzene rings as a curing agent and 0.4-0.5mol of triamine as a cross-linking agent, and stirring to obtain a uniform colorless solution; and 4, step 4: pouring the colorless transparent liquid obtained in the step (2) into the solution obtained in the step (3), stirring, and placing in a fume hood for reaction at room temperature for 20-24h to obtain a yellow transparent film; and 5: the resulting yellow transparent film was transferred to an oven and dried at 85-100 ℃ for 24h and then post-cured at 105-120 ℃ for 30-60 min. The preparation of the novel glass-like polymer material can be realized only by mixing and processing for at least four times. The process is complicated, the efficiency is low, danger is easy to occur, multiple mixing is needed, and toxic substances are easy to generate in the production process. Meanwhile, the ultimate tensile strength of the glass-like polymer material in the prior art is about 0.8 basically, and the improvement of the ultimate tensile strength of the material as much as possible is the direction of research on the glass-like polymer material at present, but when the ultimate tensile strength of the glass-like polymer material is increased, the fracture strain value is often reduced remarkably, so that the material cannot meet the requirement of the basic fracture strain parameter.

Disclosure of Invention

The invention provides a preparation method of a novel glass-like polymer material containing a cross-linked covalent network, and solves the technical problems that the existing preparation method of the novel glass-like polymer material is complex in raw materials, low in production efficiency and easy to release toxic substances due to mixing, and can be completed only by multi-step mixing.

In order to achieve the purpose, the embodiment of the invention provides a preparation method of a novel glass-like high polymer material containing a cross-linked covalent network, which comprises the following steps of (1) mixing 100 parts of bisphenol A diglycidyl ether, 75-100 parts of sebacic acid and 5-10 parts of TBD, and stirring for 20-30 hours in a water bath kettle at the temperature of 45-70 ℃; (2) placing the mixture obtained in the step (1) in a vacuum drier at 50-60 ℃ for 65-80 minutes, placing the mixture in a mould, and placing the mould at 90-95 ℃ for 125-135 minutes; (3) after the mixture becomes clear, the mixture is heated for 480-.

Further, the preparation method of the novel glass-like polymer material containing the cross-linked covalent network comprises the following steps of (1) mixing 100 parts of bisphenol A diglycidyl ether, 75 parts of sebacic acid and 5 parts of TBD, and stirring for 20 hours in a 45 ℃ water bath kettle; (2) placing the mixture obtained in the step (1) in a vacuum drier at 50 ℃ for 65 minutes, filling the mixture into a mold, and placing the mold at 90 ℃ for 130 minutes; (3) after the mixture became clear, heating at 145 ℃ for 480 minutes; then heating and curing for 480 minutes at 160 ℃, and taking out to obtain a finished product.

Further, the preparation method of the novel glass-like polymer material containing the cross-linked covalent network comprises the following steps of (1) mixing 100 parts of bisphenol A diglycidyl ether, 80 parts of sebacic acid and 5 parts of TBD, and stirring for 24 hours in a water bath kettle at 55 ℃; (2) putting the mixture obtained in the step (1) into a vacuum drier at 55 ℃ for 70 minutes, putting the mixture into a mould, and placing the mould at 95 ℃ for 130 minutes; (3) after the mixture becomes clear, heating for 500 minutes at 150 ℃; and heating and curing for 500 minutes at 165 ℃ and taking out to obtain a finished product.

Further, the preparation method of the novel glass-like polymer material containing the cross-linked covalent network comprises the following steps of (1) mixing 100 parts of bisphenol A diglycidyl ether, 75 parts of sebacic acid and 10 parts of TBD, and stirring for 24 hours in a water bath kettle at 55 ℃; (2) putting the mixture obtained in the step (1) into a vacuum drier at 55 ℃ for 70 minutes, putting the mixture into a mould, and placing the mould at 95 ℃ for 130 minutes; (3) after the mixture becomes clear, heating for 500 minutes at 150 ℃, then heating and curing for 500 minutes at 165 ℃, and taking out to obtain a finished product.

Further, the preparation method of the novel glass-like polymer material containing the cross-linked covalent network comprises the following steps of (1) mixing 100 parts of bisphenol A diglycidyl ether, 100 parts of sebacic acid and 10 parts of TBD, and stirring for 30 hours in a 70 ℃ water bath kettle; (2) placing the mixture obtained in the step (1) in a vacuum drier at 60 ℃ for 80 minutes, filling the mixture into a mold, and placing the mold at 95 ℃ for 135 minutes; (3) after the mixture became clear, heating at 150 ℃ for 520 minutes; and heating and curing for 520 minutes at the temperature of 170 ℃, and taking out to obtain a finished product.

Compared with the prior art, the invention has the beneficial effects that: through the combination of bisphenol A secondary water glyceryl ether, sebacic acid and TBD, the preparation method is simpler in process, higher in preparation efficiency, capable of realizing mass production, and capable of effectively eliminating the release of toxic substances in the preparation process of the novel glass polymer material, so that the prepared novel glass polymer material has higher ultimate tensile strength and better fracture strain parameter values.

Detailed Description

The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The terms "first" and "second," and the like, in the description and in the claims of embodiments of the present invention are used for distinguishing between different objects and not for describing a particular order of the objects. For example, the first parameter set and the second parameter set, etc. are used to distinguish different parameter sets, rather than to describe a particular order of parameter sets.

In the description of the embodiments of the present invention, the meaning of "a plurality" means two or more unless otherwise specified. For example, a plurality of elements refers to two elements or more.

The term "and/or" herein is an association relationship describing an associated object, and means that there may be three relationships, for example, a display panel and/or a backlight, which may mean: there are three cases of a display panel alone, a display panel and a backlight at the same time, and a backlight alone. The symbol "/" herein denotes a relationship in which the associated object is or, for example, input/output denotes input or output.

In the embodiments of the present invention, words such as "exemplary" or "for example" are used to mean serving as examples, illustrations or descriptions. Any embodiment or design described as "exemplary" or "e.g.," an embodiment of the present invention is not necessarily to be construed as preferred or advantageous over other embodiments or designs. Rather, use of the word "exemplary" or "such as" is intended to present concepts related in a concrete fashion.

The preparation of novel class glass macromolecular material among the prior art needs multiple raw materials, needs to mix many times simultaneously, because various raw materials can not mix simultaneously in the preparation process, needs step by step progressively to mix, consequently leads to the step loaded down with trivial details, and most in the preparation process, produces toxic gas, and the production safety is poor. Through the combination of bisphenol A dihydrate glycerin ether, sebacic acid and TBD, the preparation method is simpler in process, higher in preparation efficiency, capable of realizing mass production, and capable of effectively eliminating the release of toxic substances in the preparation process of the novel glass-like high polymer material, so that the prepared novel glass-like high polymer material has higher ultimate tensile strength and better fracture strain parameter values.

TBD: 1,5,7-Triazabicyclo [4,4,0] dec-5-ene or 1,5,7-Triazabicyclo [4,4,0] dec-5-ene.

The chemical formula for the reaction of bisphenol a dihydrate glycerol ether with sebacic acid is:

according to the invention, bisphenol A dihydrate glycerin ether, sebacic acid and TBD are directly mixed, then the mixture is uniformly stirred in a water bath, and then the mixture is dried to discharge gas, poured into a mold and heated again to be clarified, and then heated and cured, so that the novel glass-like polymer material containing a cross-linked covalent network is prepared.

In order to achieve the above object, the present application provides a method for preparing a novel glass-like polymer material containing a cross-linked covalent network, which comprises the steps of (1) mixing 100 parts of bisphenol A diglycidyl ether, 60-100 parts of sebacic acid and 5-10 parts of TBD, and stirring in a water bath kettle at 45-70 ℃ for 20-30 hours to fully mix the components to obtain a homogeneous mixture; (2) placing the mixture obtained in the step (1) in a vacuum dryer at 50-60 ℃ for 65-80 minutes to remove air bubbles, then loading the mixture into a mold, and placing the mixture and the mold at 90-95 ℃ for 125-135 minutes; (3) after the mixture in the mold becomes clear, heating the mixture for 480 and 520 minutes at the temperature of 145 and 150 ℃; then heating and curing at the temperature of 160-170 ℃ for 480-520 minutes, and taking out to obtain the finished product.

The various novel glass-like polymer materials prepared by the method are tested by experiments, and the lowest detection result of the fracture strain and the tensile strength of the materials is compared with the typical value of the materials in the prior art, wherein the comparison result of the lowest detection result of the fracture strain and the tensile strength of the materials and the typical value of the materials in the prior art is shown in the following table 1.

Table 1:

according to the detection results, the novel glass-like polymer material containing the cross-linked covalent network is prepared by the preparation method of the novel glass-like polymer material containing the cross-linked covalent network, the preparation process is simpler, the mixing times in the preparation process of the novel glass-like polymer material are effectively reduced, the preparation process is simple, batch production can be realized, only one-step mixing is needed, and no toxic substance is released in the preparation process. Meanwhile, compared with the glass polymer material in the prior art, the prepared novel glass polymer material containing the cross-linked covalent network has the advantages that the ultimate tensile strength and the breaking strain are improved, and the parameter requirement that the breaking strain is not lower than 105% is met while the ultimate tensile strength of the material is improved.

Example 1, the preparation method of the novel glass-like polymer material containing the cross-linked covalent network comprises the following steps of firstly mixing 100kg of bisphenol a diglycidyl ether, 75kg of sebacic acid and 5kg of TBD, and stirring in a water bath kettle at 45 ℃ for 20 hours; then placing the mixture obtained in the step in a vacuum drier at 50 ℃ for drying for 65 minutes, exhausting gas in the mixture, then placing the mixture in a mould and placing the mould at 90 ℃ for 130 minutes; after the mixture became clear, heating at 145 ℃ for 480 minutes; then heating and curing for 480 minutes at 160 ℃, and taking out to obtain a finished product.

Example 2, the preparation method of the novel glass-like polymer material containing the cross-linked covalent network comprises the following steps of firstly mixing 100kg of bisphenol a diglycidyl ether, 80kg of sebacic acid and 5kg of TBD, and stirring for 20 hours in a water bath at 45 ℃; then placing the mixture obtained in the step in a vacuum drier at 50 ℃ for drying for 65 minutes, exhausting gas in the mixture, then placing the mixture in a mould and placing the mould at 90 ℃ for 130 minutes; after the mixture became clear, heating at 145 ℃ for 480 minutes; then heating and curing for 480 minutes at 160 ℃, and taking out to obtain a finished product.

Example 3, a method of making the novel glass-like polymeric material containing a cross-linked covalent network, consisting of the steps of (1) mixing 100kg of bisphenol a diglycidyl ether, 75kg of sebacic acid, and TBD10kg, stirring in a 70 ℃ water bath for 30 hours; (2) placing the mixture obtained in the step (1) in a vacuum drier at 60 ℃ for 80 minutes to remove bubbles, then placing the mixture into a mold, and placing the mixture and the mold at 95 ℃ for 135 minutes; (3) after the mixture became clear, heating at 150 ℃ for 520 minutes; and heating and curing for 520 minutes at the temperature of 170 ℃, and taking out to obtain a finished product.

Example 4, the preparation method of the novel glass-like polymer material containing a cross-linked covalent network comprises the following steps of (1) mixing 100kg of bisphenol a diglycidyl ether, 100kg of sebacic acid, and 5kg of TBD, and stirring in a 55 ℃ water bath for 24 hours; (2) placing the mixture obtained in the step (1) in a vacuum drier at 55 ℃ for 70 minutes to discharge gas, then placing the mixture into a mold, and placing the mold and the mold at 95 ℃ for 130 minutes; (3) after the mixture becomes clear, heating for 500 minutes at 150 ℃; and heating and curing for 500 minutes at 165 ℃ and taking out to obtain a finished product.

Example 5, a method of making the novel glass-like polymeric material containing a cross-linked covalent network, consisting of the steps of, (1) mixing 100kg of bisphenol a diglycidyl ether, 100kg of sebacic acid, and TBD10kg, and stirring in a 70 ℃ water bath for 30 hours; (2) placing the mixture obtained in the step (1) in a vacuum drier at 60 ℃ for 80 minutes to remove bubbles, then placing the mixture into a mold, and placing the mixture and the mold at 95 ℃ for 135 minutes; (3) after the mixture became clear, heating at 150 ℃ for 520 minutes; and heating and curing for 520 minutes at the temperature of 170 ℃, and taking out to obtain a finished product.

According to the preparation method of the novel glass-like polymer material containing the cross-linked covalent network, different raw material compositions are produced under the same production process parameters, and the ultimate tensile strength and the breaking strain of the material are detected under the same conditions.

Experimental group 1: bisphenol a diglycidyl ether: sebacic acid: TBD 1: 0.3: 0.05;

experimental group 2: bisphenol a diglycidyl ether: sebacic acid: TBD 1: 0.4: 0.05;

experimental group 3: bisphenol a diglycidyl ether: sebacic acid: TBD 1: 0.5: 0.05;

experimental group 4: bisphenol a diglycidyl ether: sebacic acid: TBD 1: 0.6: 0.05;

experimental group 5: bisphenol a diglycidyl ether: sebacic acid: TBD 1: 0.7: 0.05;

experimental group 6: bisphenol a diglycidyl ether: sebacic acid: TBD 1: 0.75: 0.05;

experimental group 7: bisphenol a diglycidyl ether: sebacic acid: TBD 1: 0.8: 0.05;

experimental group 8: bisphenol a diglycidyl ether: sebacic acid: TBD 1: 0.9: 0.05;

experimental group 9: bisphenol a diglycidyl ether: sebacic acid: TBD 1:1: 0.05;

experimental group 10: bisphenol a diglycidyl ether: sebacic acid: TBD 1: 0.75: 0.06;

experimental group 11: bisphenol a diglycidyl ether: sebacic acid: TBD 1: 0.75: 0.07;

experimental group 12: bisphenol a diglycidyl ether: sebacic acid: TBD 1: 0.75: 0.08;

experimental group 13: bisphenol a diglycidyl ether: sebacic acid: TBD 1: 0.75: 0.09;

experimental group 14: bisphenol a diglycidyl ether: sebacic acid: TBD 1: 0.75: 0.10;

under the same experimental environment, the glass-like polymer materials in the experimental group 1 to the experimental group 15 were tested for breaking strain and ultimate tensile strength, and the test results are shown in tables 2 and 3 below.

Table 2:

	strain at break%	Tensile strength MPa
			Experimental group 1	3	55.9
Experimental group 2	4	51.6
			Experimental group 3	4	40.4
Experimental group 4	5	22.9
			Experimental group 5	91	16.4
Experimental group 6	107	12.69
			Experimental group 7	147	8.32
Experimental group 8	195	3.66
			Experimental group 9	302	0.86

Table 3:

	strain at break%	Tensile strength MPa
			Experimental group 6	107	12.69
Experimental group 10	107.1	12.70
			Experimental group 11	107.2	12.71
Experimental group 12	107.5	12.71
			Experimental group 13	107.4	12.72
Experimental group 14	107.6	12.72

From the detection results of the above examples, it can be seen that with the increase of the relative proportion of the diglycidyl ether of bisphenol a and sebacic acid, the ultimate tensile strength of the prepared novel glass-like polymer material is continuously increased, but the breaking strain thereof shows a significantly decreasing trend. When the TBD content is 0.05 percent, the reaction efficiency is relatively high and sufficient. However, when the ultimate tensile strength reaches 12.69MPa, namely the proportion of the experimental group 6, the fracture strain value is close to the typical value of the existing material, and when the fracture strain value is lower than the typical value, the application range of the material is narrow, so that the material cannot be applied to many fields. Meanwhile, although the experimental groups 10-14 have better ultimate tensile strength, the ultimate tensile strength is not obvious and is slightly increased compared with the experimental group 6, but the catalyst content is higher and the production cost is greatly increased, so that the catalyst proportion reaches 0.05, and the catalyst proportion is an optimal catalyst proportion of the application. Because the ultimate tensile strength value of the material is a more important influence factor than the fracture strain value of the glass-like polymer material in the application, the above detection results show that the bisphenol a diglycidyl ether in the ratio of the experimental group 6: sebacic acid: TBD 1: 0.75: 0.05 is the optimal proportion of the composition. The ultimate tensile strength reaches 12.69MPa, the breaking strain reaches 107 percent, the standard value of the breaking strain is met, and the ultimate tensile strength is obviously improved. Compared with the prior art and other proportioning embodiments, the material has obvious substantive characteristics and remarkable progress.

Analysis may be caused by that due to different reactant ratios of bisphenol a dihydrate glycerol ether and sebacic acid in the reaction process and different catalyst contents, glass-like high polymer materials with different molecular chains are generated, so that in different bisphenol a dihydrate glycerol ethers: under the matching of sebacic acid, glass-like high polymer materials with great difference in performance are generated. When the ratio is 1: at 0.75, the ultimate tensile strength and the breaking strain both reach the optimum requirements, and if the breaking strain value is too low, the ultimate tensile strength is insufficient. Meanwhile, when the TBD is in a proportion of less than 0.05, the product performance is obviously lower, and the product cannot be used at all, when the TBD exceeds 0.05, the product performance is stable, and when the TBD exceeds 0.05, the material performance is slightly improved, but the difference is not large, and the proportion of 0.05 can enable the bisphenol A dihydrate glycerol ether and the sebacic acid to realize sufficient reaction. In addition, the raw materials with different proportions can cause the glass-like high polymer material to contain certain impurities after reaction, and simultaneously, the overall performance of the product has larger difference due to different impurity components. The test results of the application show that the bisphenol A diglycidyl ether: sebacic acid: TBD 1: 0.75: when the weight is 0.5, the product performance is optimal, and the method is also an optimal embodiment of the application. The glass polymer material produced according to the proportion has the advantages of optimal performance and lowest production cost.

Through the combination of bisphenol A secondary water glyceryl ether, sebacic acid and TBD, the preparation method is simpler in process, higher in preparation efficiency, capable of realizing batch production, and capable of effectively eliminating the toxic substance release in the preparation process of the novel glass polymer material, so that the prepared novel glass polymer material has higher ultimate tensile strength and better fracture strain parameter values.

While the invention has been described in terms of its preferred embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.