Preparation method of tensile organic resin

Abstract

The invention belongs to the technical field of resin materials, and particularly relates to a preparation method of tensile organic resin. The preparation method of the organic resin comprises the following steps: mixing epoxy resin, composite polyol, a metal-organic framework material with a three-dimensional network structure and a curing agent, and heating and curing to obtain the organic resin, the composite polyol comprises pentaerythritol, trimethylolpropane, and at least one of p-hydroxybenzyl alcohol or p-hydroxyphenethyl alcohol. According to the organic resin, epoxy resin is used as a main component, composite polyol is used as an auxiliary component, under modification of a metal-organic framework material with a three-dimensional network structure, through addition of a curing agent, the epoxy resin and the composite polyol are subjected to a cross-linking curing reaction, and the organic resin is obtained. A stable three-dimensional space net-shaped structure is formed together with a metal-organic framework material with a three-dimensional net-shaped structure, so that the tensile strength of the organic resin is remarkably improved, and the organic resin has relatively good wear resistance.

Description

Technical Field

[0001] The invention belongs to the technical field of resin materials, and particularly relates to a method for preparing a tensile-resistant organic resin. Background Art

[0002] Epoxy resin is a thermosetting resin with good corrosion resistance and insulation properties. Therefore, epoxy resin is widely used. However, the tensile strength and wear resistance of epoxy resin are not ideal, which greatly reduces the service life of epoxy resin products.

[0003] Therefore, there is an urgent need to provide a method for preparing a tensile-resistant organic resin. Furthermore, the organic resin also has good wear resistance, which is conducive to the application of the organic resin. Summary of the invention

[0004] The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. The present invention provides a method for preparing a tensile-resistant organic resin. The organic resin prepared by the preparation method of the present invention has good tensile strength, for example, the tensile strength is not less than 94MPa, and further, the organic resin also has good wear resistance.

[0005] In order to solve the above problems, the present invention provides the following technical solutions:

[0006] A method for preparing a tensile-resistant organic resin comprises the following steps:

[0007] The epoxy resin, the composite polyol, the metal-organic framework material with a three-dimensional network structure, and the curing agent are mixed and heated to cure to obtain the organic resin;

[0008] The complex polyol includes pentaerythritol, trimethylolpropane, and at least one of p-hydroxybenzyl alcohol or p-hydroxyphenylethanol.

[0009] Preferably, the complex polyol comprises, by weight, 5-20 parts of pentaerythritol, 3-10 parts of trimethylolpropane, and 1-8 parts of p-hydroxybenzyl alcohol and / or p-hydroxyphenylethanol; further preferably, the complex polyol comprises, by weight, 5-15 parts of pentaerythritol, 3-8 parts of trimethylolpropane, and 1-7 parts of p-hydroxybenzyl alcohol and / or p-hydroxyphenylethanol.

[0010] Preferably, the epoxy resin is selected from at least one of bisphenol A epoxy resin and bisphenol F epoxy resin.

[0011] Preferably, the metal-organic framework material having a three-dimensional network structure is a three-dimensional network structure comprising a combination of cobalt ions, 4,4'-di(4-pyridyl)biphenyl ligands, oxalic acid ligands and phosphotungstate anions. The molecular formula of the metal-organic framework material having a three-dimensional network structure is C 210 H 156 N 18 O 92 P2W 18 Co9.

[0012] Preferably, the curing agent comprises isocyanate and imidazole.

[0013] Preferably, the isocyanate is selected from at least one of hexamethylene diisocyanate, toluene diisocyanate and diisohexylmethane diisocyanate.

[0014] Preferably, the imidazole is selected from at least one of 2-methylimidazole and 1-benzyl-2-methylimidazole.

[0015] Preferably, in the curing agent, the weight ratio of isocyanate to imidazole is 1:(1-10), more preferably 1:(2-8).

[0016] Preferably, the weight ratio of the epoxy resin, the complex polyol, the metal-organic framework material with a three-dimensional network structure, and the curing agent is 70:(5-20):(0.5-3.5):(15-30); further preferably, the weight ratio of the epoxy resin, the complex polyol, the metal-organic framework material with a three-dimensional network structure, and the curing agent is 70:(8-15):(1.5-2.5):(20-25).

[0017] Preferably, polydimethylsiloxane is added before the mixing to play a defoaming role, which is beneficial to reducing bubbles in the prepared organic resin and improving the tensile strength and wear resistance of the organic resin.

[0018] Preferably, the curing temperature is 70-100° C. for 1-3 hours, and then 140-150° C. for 1-3 hours.

[0019] Preferably, nano tungsten disulfide is added before mixing.

[0020] Preferably, the weight ratio of the metal-organic framework material with a three-dimensional network structure to nano-tungsten disulfide is 1:(0.1-0.5). Adding a small amount of nano-tungsten disulfide to the epoxy resin and composite polyol system is beneficial to improving the wear resistance of the organic resin by uniformly dispersing the nano-tungsten disulfide in the metal-organic framework material with a three-dimensional network structure.

[0021] Preferably, after the mixing is completed, the obtained mixed material is poured into a mold and then cured to obtain an organic resin of a specific shape, which can be directly used as a component in the equipment.

[0022] A tensile-resistant organic resin is prepared by the above preparation method.

[0023] A device comprises the above organic resin.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] The organic resin of the present invention uses epoxy resin as a main component and composite polyol (the present invention selects a specific polyol, and the composite polyol is formed by dendritic pentaerythritol, trimethylolpropane and p-hydroxybenzyl alcohol or p-hydroxyphenylethanol containing aromatic benzene rings, and the composite polyol is cross-linked and cured with isocyanate to form a rich cross-linked network structure) as an auxiliary component. Under the modification of a metal-organic framework material with a three-dimensional network structure, a curing agent is added to make the epoxy resin and the composite polyol undergo a cross-linking and curing reaction, and form a stable three-dimensional space network structure together with the metal-organic framework material with a three-dimensional network structure, thereby significantly improving the tensile strength of the organic resin and also making the organic resin have better wear resistance. DETAILED DESCRIPTION

[0026] In order to make the technical scheme of the present invention more clearly understood by those skilled in the art, the following embodiments are listed for illustration. It should be pointed out that the following embodiments do not limit the protection scope of the present invention.

[0027] Unless otherwise specified, the raw materials, reagents or devices used in the following examples can be obtained from conventional commercial sources or by existing known methods.

[0028] The metal-organic framework material with a three-dimensional network structure used in the following examples is prepared from Example 1 of CN117964909A.

[0029] Example 1

[0030] A method for preparing a tensile-resistant organic resin comprises the following steps:

[0031] An epoxy resin (bisphenol A epoxy resin), a composite polyol, a metal-organic framework material with a three-dimensional network structure, a curing agent, and polydimethylsiloxane are mixed at a stirring rate of 800 rpm for 40 minutes. After the mixing is completed, the obtained mixture is poured into a mold and heated for curing. The curing temperature is kept at 80° C. for 2 hours, and then kept at 150° C. for 2 hours, and cooled to room temperature to obtain an organic resin;

[0032] The complex polyol is composed of the following components by weight: 10 parts of pentaerythritol, 5 parts of trimethylolpropane, and 4 parts of p-hydroxybenzyl alcohol;

[0033] The weight ratio of epoxy resin, composite polyol, metal-organic framework material with three-dimensional network structure and curing agent is 70:15:1:20;

[0034] The weight ratio of epoxy resin to polydimethylsiloxane is 70:1;

[0035] The curing agent is composed of toluene diisocyanate and 1-benzyl-2-methylimidazole in a weight ratio of 1:5.

[0036] Example 2

[0037] A method for preparing a tensile-resistant organic resin comprises the following steps:

[0038] An epoxy resin (bisphenol A epoxy resin), a composite polyol, a metal-organic framework material with a three-dimensional network structure, a curing agent, and polydimethylsiloxane are mixed at a stirring rate of 800 rpm for 40 minutes. After the mixing is completed, the obtained mixture is poured into a mold and heated for curing. The curing temperature is kept at 80° C. for 2 hours, and then kept at 145° C. for 3 hours, and cooled to room temperature to obtain an organic resin;

[0039] The complex polyol is composed of the following components by weight: 12 parts of pentaerythritol, 6 parts of trimethylolpropane, and 5 parts of p-hydroxyphenylethanol;

[0040] The weight ratio of epoxy resin, composite polyol, metal-organic framework material with three-dimensional network structure, and curing agent is 70:10:1.5:23;

[0041] The weight ratio of epoxy resin to polydimethylsiloxane is 70:1;

[0042] The curing agent is composed of hexamethylene diisocyanate and 1-benzyl-2-methylimidazole in a weight ratio of 1:3.

[0043] Example 3

[0044] A method for preparing a tensile-resistant organic resin comprises the following steps:

[0045] An epoxy resin (bisphenol A epoxy resin), a composite polyol, a metal-organic framework material with a three-dimensional network structure, a curing agent, nano-tungsten disulfide, and polydimethylsiloxane are mixed at a stirring rate of 800 rpm for 40 minutes. After the mixing is completed, the obtained mixture is poured into a mold and heated for curing at a temperature of 80° C. for 2 hours, then at 150° C. for 2 hours, and then cooled to room temperature to obtain an organic resin;

[0046] The complex polyol is composed of the following components by weight: 10 parts of pentaerythritol, 5 parts of trimethylolpropane, and 4 parts of p-hydroxybenzyl alcohol;

[0047] The weight ratio of epoxy resin, composite polyol, metal-organic framework material with three-dimensional network structure and curing agent is 70:15:1:20;

[0048] The weight ratio of epoxy resin to polydimethylsiloxane is 70:1;

[0049] The weight ratio of the metal-organic framework material with a three-dimensional network structure to nano-tungsten disulfide is 1:0.1;

[0050] The curing agent is composed of toluene diisocyanate and 1-benzyl-2-methylimidazole in a weight ratio of 1:5.

[0051] Comparative Example 1

[0052] Compared with Example 1, the only difference of Comparative Example 1 is that an equal amount of trimethylolpropane is used to replace the pentaerythritol in Example 1, and other raw material compositions and preparation processes are the same as those of Example 1.

[0053] Comparative Example 2

[0054] Compared with Example 1, the difference of Comparative Example 2 is that an equal amount of trimethylolpropane is used to replace the p-hydroxybenzyl alcohol in Example 1, and other raw material compositions and preparation processes are the same as those of Example 1.

[0055] Comparative Example 3

[0056] Compared with Example 1, the difference of Comparative Example 3 is that the metal-organic framework-derived nickel silicate prepared in Example 2 of CN113929105A is used to replace the metal-organic framework material with a three-dimensional network structure in Example 1, and the other raw material compositions and preparation process are the same as those in Example 1.

[0057] Product effect testing

[0058] The organic resins prepared in the above examples and comparative examples were taken as samples, and the tensile strength and wear resistance were tested according to the following methods. The results are shown in Table 1. The data in Table 1 are the average values ​​of 3 tests.

[0059] The uniaxial tensile performance test was carried out according to GB / T1040-2006. The specimen was 1BA dumbbell type and the test rate was 2 mm / min until the specimen broke.

[0060] The sliding dry friction performance test was carried out according to GB / T3960-2016. The sample size was 30 mm long, 6 mm wide and 70 mm high. Before the test, it was conditioned at the specified room temperature (23±5)℃ and relative humidity (50±5)% for 20 hours, and then tested at the same temperature and humidity. During the test, the sample remained stationary and the test ring (material: 45 # Steel) rotates at 200 rpm, the test time is 2 hours, and the load is 196 N. The mass wear amount m = m1-m2, where m1 is the mass of the sample before wear, and m2 is the mass of the sample after wear. The smaller m is, the better the wear resistance is.

[0061] Table 1

[0062]

[0063] It can be seen from Table 1 that the organic resin prepared in the embodiment of the present invention has significantly improved tensile strength and wear resistance compared with the comparative example.

[0064] As can be seen from Example 1 and Comparative Examples 1-3, the composite polyol of the present invention is selective in the composition of the polyol, which is mainly formed by dendritic pentaerythritol, trimethylolpropane and p-hydroxybenzyl alcohol or p-hydroxyphenylethanol containing aromatic benzene rings, and the composite polyol is cross-linked and cured with isocyanate to form a rich cross-linked network structure, which is matched with other components to improve the tensile strength and wear resistance of the organic resin finally obtained. The present invention is also selective in the type of organic framework material. The metal-organic framework material with a three-dimensional network structure used in the present invention provides a solid and stable structural basis for the cross-linking and curing reaction between the epoxy resin, the composite polyol and the curing agent due to its specific three-dimensional network structure, so that the prepared organic resin has good tensile strength and good wear resistance.

[0065] The above content describes the basic principle and main features of the present invention and the advantages of the present invention. It should be understood by those skilled in the art that protection scope of the present invention is not limited by the above-described embodiments. Without departing from the spirit and scope of the present invention, the present invention also has various changes and improvements, and these changes and improvements all fall within the scope of the present invention claimed for protection.

Claims

1. A method for preparing an organic resin, characterized in that: The following steps are involved: The epoxy resin, the composite polyol, the metal-organic framework material with a three-dimensional network structure, and the curing agent are mixed and heated to cure to obtain the organic resin; The complex polyol includes pentaerythritol, trimethylolpropane, and at least one of p-hydroxybenzyl alcohol or p-hydroxyphenylethanol.

2. The preparation method according to claim 1, characterized in that: The composite polyol comprises, by weight, 5-20 parts of pentaerythritol, 3-10 parts of trimethylolpropane, and 1-8 parts of p-hydroxybenzyl alcohol and / or p-hydroxyphenylethanol.

3. The preparation method according to claim 1, characterized in that: The epoxy resin is selected from at least one of bisphenol A epoxy resin and bisphenol F epoxy resin.

4. The preparation method according to claim 1, characterized in that: The metal-organic framework material with a three-dimensional network structure is a three-dimensional network structure composed of cobalt ions, 4,4'-di(4-pyridyl)biphenyl ligands, oxalic acid ligands and phosphotungstate anions.

5. The preparation method according to claim 1, characterized in that: The curing agent includes isocyanate and imidazole.

6. The preparation method according to claim 5, characterized in that: The isocyanate is selected from at least one of hexamethylene diisocyanate, toluene diisocyanate, and diisohexylmethane diisocyanate; the imidazole is selected from at least one of 2-methylimidazole and 1-benzyl-2-methylimidazole; in the curing agent, the weight ratio of isocyanate to imidazole is 1:(1-10).

7. The preparation method according to any one of claims 1 to 6, characterized in that: The weight ratio of the epoxy resin, the composite polyol, the metal-organic framework material with a three-dimensional network structure, and the curing agent is 70:(5-20):(0.5-3.5):(15-30).

8. The preparation method according to any one of claims 1 to 6, characterized in that: Polydimethylsiloxane is added before the mixing; and / or the curing temperature is kept at 70-100° C. for 1-3 hours, and then kept at 140-150° C. for 1-3 hours.

9. An organic resin, characterized in that The invention is prepared by the preparation method according to any one of claims 1 to 8.

10. A device, characterized in that: The organic resin comprises an organic resin prepared by the preparation method according to any one of claims 1 to 8 or an organic resin according to claim 9.

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