1. An electrical insulating resin represented by the following formula I,

Acryla/Epb-Rr-Cm-X-Rs-C-Rs-X-Cm-Rr-Epb/Acryla

Ⅰ

wherein:

c is selected from: a cyclic structure having a number of carbon atoms of 3 or more and 7 or less or

Rs is straight-chain saturated alkyl, the number of carbon atoms is more than or equal to 0 and less than or equal to 5;

rr is straight-chain saturated alkyl, the number of carbon atoms is more than or equal to 0 and less than or equal to 10;

x is selected from: an ether bond, an amide bond, or an ester group;

cm is a cyclic saturated hydrocarbon group, the number of carbon atoms is more than or equal to 3 and less than or equal to 7;

the Acryl is selected from: -O-C (═ O) -CH ═ CH₂or-O-C (═ O) -CH ═ CH-CH₃；

Ep is selected from the following structures:

and C, Rs, Rr, X and Cm are all SP³Hybrid forms.

2. The electrical insulating resin according to claim 1, wherein s is 0-5, r is 0-10, m is 0-2, a is 0-10, and b is 0-10, wherein s, r, and m cannot be 0 at the same time, and a and b cannot be 0 at the same time.

3. The electrical insulating resin of claim 2, selected from the group consisting of structure ii or structure iii:

4. a method for preparing a structure according to claim 3, structure ii, comprising the steps of:

forming a photosensitive group: containing-O-C (═ O) -CH ═ CH₂Organic acid with a structure and alcohol with a cyclic structure containing more than or equal to 4 and less than or equal to 6 carbon atoms form a photosensitive group under the action of acid;

forming a structure shown in structure II: and C, under the action of acid, connecting photosensitive groups at two ends to obtain the compound.

5. The method according to claim 4, wherein the acid in the step of forming a photosensitive group is phosphoric acid or p-chlorobenzenesulfonic acid, and the acid in the step of forming a structure represented by the structure II is sulfuric acid or hydrobromic acid.

6. A method of making a structure according to claim 3, structure iii, comprising the steps of:

catalytic ring opening: alcohol containing cyclic structure with carbon atom number not less than 5 and not more than 7 and epichlorohydrin are catalyzed by acid to open ring under the condition of heating;

catalytic ring closure: and (3) carrying out base-catalyzed ring closure on the ring-opened alcohol and the epoxy chloropropane under the condition of heating to obtain the product.

7. The method according to claim 6, wherein the acid is a Lewis acid, the heating temperature is 65 to 75 ℃, and the base is sodium hydroxide or potassium hydroxide.

8. The method of claim 7, wherein the heating temperature is 70 ℃.

9. Use of the electrically insulating resin according to any one of claims 1 to 3 in materials for integrated circuit boards, and in materials for strong and weak electrical protection.

Background

With the development of society and the progress of science and technology, the requirement on the insulating property of materials is continuously improved. Particularly, the strong electricity field and the high frequency field have obvious dependence on the high insulating property of materials, the insulating property of the materials almost limits the application of high-level strong electricity and high frequency circuits, and the material relates to super large scale integrated circuits, high-strength electricity protection and the larger fields at the downstream thereof, and is one of the bottleneck factors of scientific and technological development in the fields. Therefore, the development of high-performance electric insulating materials is of great significance.

The existing organic materials, especially the organic materials using aromatic as the core of molecular structure, such as bisphenol a epoxy resin, bisphenol a light-cured resin, aramid fiber, polysulfone ether, polyether ether ketone, etc., have good performance in modulus, strength, high temperature resistance, even flame resistance, etc., but they all exist in the core of aromatic structure, so that the electrical resistance is greatly weakened.

Disclosure of Invention

In view of the above technical problems, the present invention provides an electrical insulating resin, which has an extremely high electrical insulating property, has no leakage current when withstanding 1500V voltage, has a leakage current of less than 0.1mA when withstanding 15000V/mm voltage, and has good crystallization property, high temperature resistance, environmental protection property and operation property.

In order to achieve the above object, the electrical insulating resin is represented by the following formula i:

Acryla/Epb-Rr-Cm-X-Rs-C-Rs-X-Cm-Rr-Epb/Acryla

Ⅰ

wherein:

c is selected from: a cyclic structure having a number of carbon atoms of 3 or more and 7 or less or

Rs is straight-chain saturated alkyl, the number of carbon atoms is more than or equal to 0 and less than or equal to 5;

rr is straight-chain saturated alkyl, the number of carbon atoms is more than or equal to 0 and less than or equal to 10;

x is selected from: an ether bond, an amide bond, or an ester group;

cm is a cyclic saturated hydrocarbon group, the number of carbon atoms is more than or equal to 3 and less than or equal to 7;

the Acryl is selected from: -O-C (═ O) -CH ═ CH₂or-O-C (═ O) -CH ═ CH-CH₃；

Ep is selected from the following structures:

and C, Rs, Rr, X and Cm are all SP³Hybrid forms.

The electrical insulation resin has extremely high electrical insulation performance, good crystallization performance and good microcosmic compactness, and most of molecular chains are in a low-interface tension structure, so that the electrical insulation resin has good operability and thixotropy; using SP³Hybridization energy enables one electron in the s orbit of the outermost layer of the atom to be excited to the p orbit, the atom to be hybridized enters an excited state, the s orbit of the layer is hybridized with three p orbitals, the s orbit and the p orbit with similar energy are superposed, the energy is redistributed and the direction is adjusted by the atom orbitals of different types, 4 equivalent sp3 orbitals are formed, and the spatial configuration of a regular tetrahedron is obtained.

In one embodiment, s is selected from 0-5, r is selected from 0-10, m is selected from 0-2, a is selected from 0-10, and b is selected from 0-10, wherein s, r and m cannot be 0 at the same time, and a and b cannot be 0 at the same time.

In one embodiment, the electrically insulating resin is selected from the following structures ii or iii:

the electric insulation resin with the structure has extremely high electric insulation performance, has no leakage current when enduring 1500V voltage, has leakage current less than 0.1mA when enduring 15000V/mm voltage, and simultaneously has good crystallization performance, high temperature resistance, environmental protection performance and operation performance.

The invention also provides a preparation method of the structure shown in the general formula II, which comprises the following steps:

forming a photosensitive group: containing-O-C (═ O) -CH ═ CH₂Organic acid with a structure and alcohol with a cyclic structure containing more than or equal to 4 and less than or equal to 6 carbon atoms form a photosensitive group under the action of acid;

forming a structure shown in a general formula II: and C, under the action of acid, connecting photosensitive groups at two ends to obtain the compound.

The C obtained by the above method has a cyclic structure with 6 carbon atoms, and has-CH at each end₂And then linked to the photosensitive group by an ether bond.

In one embodiment, the acid in the step of forming the photosensitive group is phosphoric acid or p-chlorobenzenesulfonic acid, and the acid in the step of forming the structure represented by the general formula ii is sulfuric acid or hydrobromic acid. As the acidity is larger and the side reaction is stronger, the side reaction trend meeting the requirement can be obtained by adopting the acid.

The invention also provides a preparation method of the structure shown in the general formula III, which comprises the following steps:

catalytic ring opening: alcohol containing cyclic structure with carbon atom number not less than 5 and not more than 7 and epichlorohydrin are catalyzed by acid to open ring under the condition of heating;

catalytic ring closure: and (3) carrying out base-catalyzed ring closure on the ring-opened alcohol and the epoxy chloropropane under the condition of heating to obtain the product.

C obtained by the above method has a cyclic structure with 6 carbon atoms, and is connected with-CH at two ends by ether bond₂After, andthe structures are connected.

In one embodiment, the acid is a lewis acid, the temperature of the heating is 65-75 ℃, and the base is sodium hydroxide or potassium hydroxide. By adopting the reaction conditions, the reaction at the stage can be cooperated with other stages to obtain the best yield.

In one embodiment, the temperature of the heating is 70 ℃. With the above temperatures, the highest yields were obtained.

The invention also provides the application of the electrical insulating resin in integrated circuit board materials and strong and weak current protection materials.

Compared with the prior art, the invention has the following beneficial effects:

the electric insulating resin has extremely high electric insulating property, has no leakage current when the electric insulating resin withstands 1500V voltage, has leakage current less than 0.1mA when the electric insulating resin withstands 15000V/mm voltage, simultaneously has good crystallization property, better microcosmic compactness, high temperature resistance and environmental protection property, and has a low interface tension structure on most molecular chains, so that the electric insulating resin has good operability and thixotropy.

Drawings

FIG. 1 is a reaction scheme of example 1;

FIG. 2 is a reaction scheme of example 2.

Detailed Description

To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

Defining:

the four-stage carbon atoms of the invention: refers to the case where the core carbon atom is attached to four carbon atoms or other heteroatoms at the same time in the form of covalent single bonds.

SP³Hybridization: refers to the hybridization mode of 1 ns orbit and 3 np orbitals in the same atom.

Ether bond: i.e., the functional group of an ether, which is a product of replacing the hydrogen in the hydroxyl group of an alcohol or phenol with a hydrocarbon group, and has the general formula of R-O-R ', wherein R and R' may be the same or different.

Amide bond: that is, a chemical bond formed by dehydration condensation of a carboxyl group of one amino acid and an amino group of another amino acid, and has a general formula of-CO-NH-.

Ester group: that is, the functional group of the ester in the carboxylic acid derivative has the general formula-COOR (R is generally an alkyl group or other non-H group).

Lewis acid: refers to a substance (including ions, radicals or molecules) that can accept an electron pair.

Strong and weak current: when the voltage is used for the finger discrimination, strong current is set at 36V (human body safety voltage) or more, and weak current is set at 36V (human body safety voltage) or less.

The source is as follows:

reagents, materials and equipment used in the present example are all commercially available sources unless otherwise specified; unless otherwise specified, all the experimental methods are routine in the art.

Example 1

An electrically insulating photocurable resin was prepared.

1. Forming a photosensitive group.

Unsaturated organic acid is addedAnd an alcohol CH2 ═ CH-C (═ O) -OH which is free of a conjugated unsaturated system, were heated to 90 ℃ under the action of phosphoric acid, and reacted for 8 hours to obtain a photosensitive group.

2. An electrically insulating light-curable resin is formed.

Compound containing core ring structureHeating to 90 deg.C under the action of sulfuric acid, reacting for 8 hr, and grafting the photosensitive groups at both ends.

The preparation process is shown in figure 1.

Example 2

An electrically insulating epoxy resin is prepared.

1. Catalytic ring opening.

Will be provided withMixing with epoxy chloropropane, heating to 70 deg.C, adding Lewis acid, and catalytic ring opening.

2. Catalytic ring closure.

Adding sodium hydroxide, controlling the temperature of the reaction system at 70 ℃, carrying out catalytic ring closure, stirring, and measuring an infrared spectrum until the infrared spectrum is 910cm^-1The peak area of the compound reaches the level of a medium-strong peak and is simultaneously 744cm^-1And (4) stopping the reaction when the spectral peak completely disappears, taking out the obtained reaction mixture, filtering, cleaning and distilling to obtain the bifunctional electrical insulation epoxy resin.

The above preparation process is shown in FIG. 2.

Examples of the experiments

Experiment for verifying electrical insulation performance.

1. The material obtained in the embodiment 1 is manufactured into a sample block to be tested with the thickness of 0.73mm, and the leakage current coefficient of the resin block with the thickness is 1000V/0.02mA, namely, when the leakage current is increased by 0.02mA, the corresponding withstand voltage value is increased by 1000V;

2. respectively sticking tinfoil tape paper with the thickness of about 0.5mm on the central position of the sample block to be tested from the two sides according to the aligned positions, so that the tinfoil tape paper on the two sides becomes electrodes stuck on the two sides of the sample block to be tested, and then respectively connecting the electrodes to the two electrodes of the withstand voltage tester;

3. setting the range of the withstand voltage tester at 5.0KV, and respectively measuring the leakage current value of the sample block to be tested when the voltage is 3.0kVAC, 4.0kVAC and 5.0 kVAC;

4. the voltage value when the leakage current reaches the threshold value can be calculated by dividing the difference between the leakage current value and the set leakage current threshold value by 0.02.

Setting the current leakage current value as i0 (mA); the voltage currently applied to both sides of the resin sheet was u0 (V); the leakage current threshold is imax (ma); when the thickness of the resin sheet is t (mm), the ultimate dielectric strength value is calculated by the following formula:

5. the leakage current threshold Imax is set to be the voltage withstanding values which can be reached by 0.1mA, 0.2mA, 0.3mA, 0.5mA, 0.8mA, 1.0mA and 2.0mA, respectively, and the calculation process of the voltage value borne by the 1mm resin sheet is as follows:

6. the pressure resistance value of example 1 was estimated and shown in the following table:

TABLE 1 withstand voltage of example 1

The results show that: taking the representative photocurable resin of example 1 as an example, the withstand voltage values are shown in the table above, and the photocurable resin of example 1 and the epoxy resin of example 2 have key structures, namely, the specific structural core C in the structural unit, and have no relation with functional groups, so that the photocurable resin of example 1 and the epoxy resin of example 2 have excellent insulating properties after continuous curing.

Comparative example 1

An insulating resin was prepared using the raw materials and reaction conditions in example 2, except that the purity of p-dihydroxycyclohexane used in example 2 was 99% and the purity of p-dihydroxycyclohexane used in comparative example 1 was 90%. In the preparation process, as the impurity content is 10%, the partial substances cannot be converted into effective oligomers in a reaction system, and after connection and solidification, the substances cannot be converted into final macromolecules, so that the integral chemical bonds of the macromolecules are destroyed, the mechanical properties of the macromolecular material are finally greatly weakened, and the prepared final product is very fragile and can be broken by impact.

Comparative example 2

The raw materials and reaction conditions used in example 2 were used to prepare an insulating resin, except that the reaction temperature used in comparative example 2 was 100 ℃, and that the hydration was severe due to the excessive temperature during the preparation process, and the chlorine atom in the chlorohydrin was directly hydroxylated to 744cm in the infrared spectrum^-1The absorption peak at (B) also disappears completely, but the resulting product is not an epoxy group, but two hydroxyl groupsFinally, a gelled product is obtained, which cannot be used.

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.