阅读说明：本技术 一种中密度芳纶纤维纸层压板及其制备方法 (Medium-density aramid fiber paper laminated board and preparation method thereof ) 是由 杜旻 王炳生 黄洪驰 刘锋 师强 于 2019-09-26 设计创作，主要内容包括：本发明公开了一种中密度芳纶纤维纸层压板及其制备方法其特征是：中密度芳纶纤维纸层压板是一层或一层以上重叠的浸润有特种树脂胶黏剂的芳纶纤维纸预浸料,在温度170℃～190℃、压力1MPa～23MPa的条件下经热压成型后制得的绝缘板材。本发明中密度芳纶纤维纸层压板的密度为0.67g/cm<Sup>3</Sup>～0.91g/cm<Sup>3</Sup>、板厚度为1mm～6mm、纵向抗张强度为45KN/m～59 KN/m、横向抗张强度为33 KN/m～61KN/m、在90℃变压器油中击穿电压为30KV～38KV,抗张强度及电学性能好。本发明中密度芳纶纤维纸层压板适用于航空航天、轨道交通、大型发电设备等各类工程设备、电器设备等的制造。(The invention discloses a medium-density aramid fiber paper laminated board and a preparation method thereof, which are characterized in that: the medium-density aramid fiber paper laminated board is an insulating board prepared by one or more layers of overlapped aramid fiber paper prepregs soaked with special resin adhesives through hot press molding at the temperature of 170-190 ℃ and the pressure of 1-23 MPa. The density of the aramid fiber paper laminated board is 0.67g/cm 3 ～0.91g/cm 3 The thickness of the plate is 1 mm-6 mm, the longitudinal tensile strength is 45 KN/m-59 KN/m, the transverse tensile strength is 33 KN/m-61 KN/m, the breakdown voltage in 90 ℃ transformer oil is 30 KV-38 KV, and the tensile strength and the electrical property are good. The density aramid fiber paper laminated board is suitable for manufacturing various engineering equipment, electrical equipment and the like such as aerospace, rail transit, large-scale power generation equipment and the like.)

1. The utility model provides a medium density aramid fiber paper laminate which characterized by: the medium-density aramid fiber paper laminated board is prepared by one or more layers of overlapped aramid fiber paper prepregs soaked with special resin adhesives through hot press molding under the conditions of the temperature of 170-190 ℃ and the pressure of 1-23 MPa;

the aramid fiber paper prepreg is prepared by coating aramid fiber paper with the special resin adhesive through a horizontal gluing machine, then passing through a gluing machine drying channel which is 24m long and is divided into 4 sections and 6m sections, and pre-drying at the temperature of 70-180 ℃ and the vehicle speed of 1.0-6.0 m/min;

the aramid fiber paper comprises the following components in percentage by weight: short-cut aramid fiber 1:1 to 2 and an areal density of 30g/m²～60g/m²The water content is 0.5-5%, and the aramid fiber has a polymer structure repeating unit of

the special resin adhesive is prepared by mixing 20-45 parts by weight of high-temperature-resistant epoxy resin, 15-60 parts by weight of modified phenolic resin, 12-35 parts by weight of curing agent, 3-32 parts by weight of inorganic powder, 0.01-2 parts by weight of accelerator and 350-450 parts by weight of solvent;

the high-temperature-resistant epoxy resin is one or a mixture of two of hydantoin epoxy resin, dicyclopentadiene or dicyclopentadiene and phenolic aldehyde polycondensation resin, bisphenol A epoxy resin, biphenyl epoxy resin and o-cresol phenolic aldehyde epoxy resin;

the modified phenolic resin is one or a mixture of two of organic silicon modified phenolic resin, boron modified phenolic resin and benzoxazine modified phenolic resin;

the curing agent is one or a mixture of two of 4, 4-diaminodiphenylmethane, 4-diaminodiphenyl sulfone, m-phenylenediamine and dicyandiamide;

the inorganic powder is one or a mixture of two of nano silicon dioxide, nano montmorillonite, nano vermiculite and nano talcum powder;

the accelerant is one or a mixture of two of 2-methylimidazole, 2-ethyl-4-methylimidazole, boron trifluoride ethylamine, hexamethyltetramine and aluminum acetylacetonate;

the solvent is one or a mixture of more than two of butanone, acetone, glycol or alcohol.

2. The medium density aramid fiber paper laminate of claim 1, wherein: the density of the prepared medium-density aramid fiber paper laminated board is 0.67g/cm³～0.91g/cm³The thickness of the plate is 1 mm-6 mm, the longitudinal tensile strength is 45 KN/m-59 KN/m, the transverse tensile strength is 33 KN/m-61 KN/m, and the breakdown voltage in the 90 ℃ transformer oil is 30 KV-38 KV.

3. The medium density aramid fiber paper laminate of claim 1 or 2, characterized in that: the one or more layers of overlapped aramid fiber paper prepreg soaked with the special resin adhesive is characterized in that: 1-340 layers of overlapped aramid fiber paper prepreg soaked with special resin adhesive.

4. The medium density aramid fiber paper laminate of claim 1 or 2, characterized in that: the medium-density aramid fiber paper laminated board prepared by hot press molding under the conditions of the temperature of 170-190 ℃ and the pressure of 1-23 MPa is characterized in that: under the conditions that the temperature is 170-190 ℃ and the pressure is 1-23 MPa, the medium-density aramid fiber paper laminated board is prepared after hot press molding within 0.5-3 h according to the thickness of the medium-density aramid fiber paper laminated board prepared after molding, and the medium-density aramid fiber paper laminated board is prepared.

5. A preparation method of a medium-density aramid fiber paper laminated board is characterized by comprising the following steps:

a. preparing a special resin adhesive:

at room temperature, sequentially adding 20-45 parts by weight of high-temperature-resistant epoxy resin, 15-60 parts by weight of modified phenolic resin and 3-32 parts by weight of inorganic powder into a glue preparation tank, stirring for 1.5-2.5 hours, adding 12-35 parts by weight of curing agent and 350-450 parts by weight of solvent, stirring for 0.15-1.5 hours, adding 0.01-2 parts by weight of accelerator to adjust the forming time of glue solution, sampling, testing the forming time of the glue solution by using a knife method, and completing preparation of the special resin adhesive when the forming time is 250-440 seconds under the condition of a hot plate at 180 ℃;

the high-temperature-resistant epoxy resin is one or a mixture of two of hydantoin epoxy resin, dicyclopentadiene or dicyclopentadiene and phenolic aldehyde polycondensation resin, bisphenol A epoxy resin, biphenyl epoxy resin and o-cresol phenolic aldehyde epoxy resin;

the modified phenolic resin is one or a mixture of two of organic silicon modified phenolic resin, boron modified phenolic resin and benzoxazine modified phenolic resin;

the curing agent is one or a mixture of two of 4, 4-diaminodiphenylmethane, 4-diaminodiphenyl sulfone, m-phenylenediamine and dicyandiamide;

the inorganic powder is one or a mixture of two of nano silicon dioxide, nano montmorillonite, nano vermiculite and nano talcum powder;

the accelerant is one or a mixture of two of 2-methylimidazole, 2-ethyl-4-methylimidazole, boron trifluoride ethylamine, hexamethyltetramine and aluminum acetylacetonate;

the solvent is one or a mixture of more than two of butanone, acetone, glycol or alcohol;

b. preparing aramid fiber paper prepreg:

taking aramid fiber paper, coating the aramid fiber paper with the special resin adhesive in the step a through a horizontal gluing machine, then passing through a gluing machine drying channel which is 24m long and is divided into 4 sections and 6m in each section, and pre-drying under the conditions that the temperature is 70-180 ℃ and the vehicle speed is 1.0-6.0 m/min to obtain an aramid fiber paper prepreg;

the aramid fiber paper comprises the following components in percentage by weight: short-cut aramid fiber 1:1 to 2 and an areal density of 30g/m²～60g/m²The water content is 0.5-5%, and the aramid fiber has a polymer structure repeating unit of

c. pressing a medium-density aramid fiber paper laminated board:

taking aramid fiber paper prepreg, overlapping one or more layers of aramid fiber paper prepreg on a smooth stainless steel plate with demolding films and embossing materials laid on two surfaces, feeding the aramid fiber paper prepreg into a hot press, and performing hot press molding under the conditions that the temperature is controlled to be 170-190 ℃ and the pressure is 1-23 MPa to obtain the medium-density aramid fiber paper laminated board.

6. The method for preparing the medium-density aramid fiber paper laminate as claimed in claim 5, wherein the method comprises the following steps: and c, performing hot press molding under the conditions that the temperature is controlled to be 170-190 ℃ and the pressure is 1-23 MPa to obtain the medium-density aramid fiber paper laminated board, wherein the process comprises the following steps: controlling the temperature to be 170-190 ℃ and the pressure to be 1-23 MPa, performing hot press molding, and determining the hot press molding time to be within 0.5-3 h according to the thickness of the medium-density aramid fiber paper laminated board after molding to be 1-6 mm, thus obtaining the medium-density aramid fiber paper laminated board.

7. The method for preparing the medium-density aramid fiber paper laminate as claimed in claim 5 or 6, wherein the method comprises the following steps: in the step c, one or more layers of aramid fiber paper prepreg are overlapped and placed, and the steps are as follows: and (3) overlapping 1-340 layers of aramid fiber paper prepreg.

8. The method for preparing the medium-density aramid fiber paper laminate as claimed in claim 5 or 6, wherein the method comprises the following steps: the density of the prepared medium-density aramid fiber paper laminated board in the step c is 0.67g/cm³～0.91g/cm³The thickness of the plate is 1 mm-6 mm, the longitudinal tensile strength is 45 KN/m-59 KN/m, the transverse tensile strength is 33 KN/m-61 KN/m, and the breakdown voltage in the 90 ℃ transformer oil is 30 KV-38 KV.

Technical Field

The invention belongs to a laminated board and preparation thereof, and particularly relates to a medium-density aramid fiber paper laminated board and a preparation method thereof. The medium-density aramid fiber paper laminated board prepared by the invention is suitable for being used as an electric insulation laminated board, and is particularly suitable for various engineering equipment, electrical equipment and the like with special purposes (the fields of aviation, aerospace, rail transit, wind power generation and the like).

Background

With the continuous improvement of living standard and the continuous increase of national electricity consumption, stricter requirements are provided for the oil immersed transformer which is used for power transmission/transformation equipment, particularly outdoor power transmission/transformation equipment, the effective maximum working load, the real-time working efficiency, the maintenance and the maintenance in the use process, the safety, the environmental protection performance and the like. And because the internal overvoltage protection is still mainly supported by the insulating material, the requirements on the performance of the related matched insulating material are continuously improved, even in a crossing mode.

Medium density (density 0.67 g/cm)³～0.91g/cm³) The aramid fiber paper laminated board is widely applied to special fields (aerospace, rail transit, large-scale power generation and the like) due to light weight, excellent transformer oil resistance, good heat resistance, outstanding flame retardance, excellent electrical performance and strong structure designabilityVarious engineering equipment, large-scale electrical equipment and other facilities. However, in the prior art, the aramid fiber paper board is mostly formed by wet paper pulp or wet paper (with a water content of 5-85%) at a high temperature (higher than 300 ℃) and a low pressure (5-10 MPa), the forming process is complex, special assembly line type production equipment is required, and the requirement on the equipment is extremely high. If the board is produced at a low temperature (100-200 ℃) and a medium pressure (10-25 MPa), the prepared board has poor interlayer adhesion, is easy to delaminate after being bent, has large water content in the base paper in the production process, so that the residual water content in the prepared board cannot meet the use requirement in a long-term high-temperature transformer oil field, and is easy to absorb moisture to generate mildew, and the problems always bother various manufacturers in the industry and obstruct the step of large-scale production.

Disclosure of Invention

The invention aims to overcome the defects in the prior art and provides a medium-density aramid fiber paper laminated board and a preparation method thereof. The invention adopts aramid fiber paper as a raw material, and the aramid fiber paper is pressed and formed at a medium temperature (170-190 ℃) and a medium-low pressure (1-23 MPa) at one step, so that the medium-density aramid fiber paper laminated board with good tensile strength and electrical property and the preparation method thereof are provided, and the requirements of the fields of aerospace, rail transit, large-scale power generation equipment and the like on high-performance laminated boards are met.

The content of the invention is as follows: the utility model provides a medium density aramid fiber paper laminate which characterized by: the medium-density aramid fiber paper laminated board is a medium-density aramid fiber paper laminated board (insulating board) prepared by one-step hot press molding of one or more layers of overlapped aramid fiber paper prepregs soaked with special resin adhesives under the conditions of the temperature of 170-190 ℃ (medium temperature) and the pressure of 1-23 MPa (low and medium pressure);

the aramid fiber paper prepreg is prepared by coating aramid fiber paper with the special resin adhesive through a horizontal gluing machine, then passing through a gluing machine drying channel which is 24m long and is divided into 4 sections and 6m sections, and pre-drying the aramid fiber paper at the (baking) temperature of 70-180 ℃ and the vehicle speed of 1.0-6.0 m/min;

the aramid fiberThe fiber paper comprises the following components in percentage by weight: short-cut aramid fiber 1:1 to 2 and an areal density of 30g/m²～60g/m²The water content (namely the weight percentage content of water) is 0.5 to 5 percent, and the high molecular structure repeating unit of the aramid fiber is

The aramid fiber paper of (1);

the special resin adhesive is prepared by mixing 20-45 parts by weight of high-temperature-resistant epoxy resin, 15-60 parts by weight of modified phenolic resin, 12-35 parts by weight of curing agent, 3-32 parts by weight of inorganic powder, 0.01-2 parts by weight of accelerator and 350-450 parts by weight of solvent;

the high-temperature-resistant epoxy resin is hydantoin epoxy resin (the product providing enterprise and product brand can be CY350, Izoda; 28906, Jialong biotechnology; HY-070, Taijixin new wood), dicyclopentadiene or dicyclopentadiene and phenolic polycondensation resin (the product providing enterprise and product brand can be DNE260A75, Tiangao New technology; HP-72000, Jiashend; Picco2100, Islam), bisphenol A epoxy resin (the product providing enterprise and product brand can be E-44/E-51, Balingite; DER-331, Dow; YDH3000, Aditya Birla), biphenyl epoxy resin (the product providing enterprise and product brand can be NC-3000, Jia, Yuded; YX-4000, Mitsubishi; TMBP, Laiwu new wood), o-cresol type phenolic epoxy resin (the product providing enterprise and product brand can be EPON-678, a shell; NPCN-704, southern taiwan; SQCN700, holy spring chemical) or a mixture of two;

the modified phenolic resin is one or a mixture of two of organic silicon modified phenolic resin (product providing enterprises and product brands can be self-made by an applicant), boron modified phenolic resin (product providing enterprises and product brands can be self-made by the applicant), and benzoxazine modified phenolic resin (product providing enterprises and product brands can be self-made by the applicant);

the curing agent is one or a mixture of two of 4, 4-diaminodiphenylmethane, 4-diaminodiphenyl sulfone, m-phenylenediamine and dicyandiamide;

the inorganic powder is one or a mixture of two of nano silicon dioxide, nano montmorillonite, nano vermiculite and nano talcum powder;

the accelerant is one or a mixture of two of 2-methylimidazole, 2-ethyl-4-methylimidazole, boron trifluoride ethylamine, hexamethyltetramine and aluminum acetylacetonate;

the solvent is one or a mixture of more than two of butanone, acetone, glycol or alcohol.

The invention comprises the following steps: the density of the prepared medium-density aramid fiber paper laminated board is 0.67g/cm³～0.91g/cm³The thickness of the plate is 1 mm-6 mm, the longitudinal tensile strength is 45 KN/m-59 KN/m, the transverse tensile strength is 33 KN/m-61 KN/m, and the breakdown voltage in the 90 ℃ transformer oil is 30 KV-38 KV.

The invention comprises the following steps: the one or more layers of overlapped aramid fiber paper prepreg soaked with the special resin adhesive is characterized in that: 1-340 layers of overlapped aramid fiber paper prepreg soaked with special resin adhesive.

The invention comprises the following steps: the medium-density aramid fiber paper laminated board prepared by hot press molding under the conditions of the temperature of 170-190 ℃ and the pressure of 1-23 MPa is characterized in that: under the conditions that the temperature is 170-190 ℃ and the pressure is 1-23 MPa, the medium-density aramid fiber paper laminated board is prepared after hot press molding within 0.5-3 h according to the thickness of the medium-density aramid fiber paper laminated board prepared after molding, and the medium-density aramid fiber paper laminated board is prepared.

Another aspect of the invention is: a preparation method of a medium-density aramid fiber paper laminated board is characterized by comprising the following steps:

a. preparing a special resin adhesive:

at room temperature, sequentially adding 20-45 parts by weight of high-temperature-resistant epoxy resin, 15-60 parts by weight of modified phenolic resin and 3-32 parts by weight of inorganic powder into a glue preparation tank, stirring for 1.5-2.5 hours, adding 12-35 parts by weight of curing agent and 350-450 parts by weight of solvent, stirring for 0.15-1.5 hours, adding 0.01-2 parts by weight of accelerator to adjust the forming time of glue solution, sampling, testing the forming time of the glue solution by using a knife method, and completing preparation of the special resin adhesive when the forming time is 250-440 seconds under the condition of a hot plate at 180 ℃;

the high-temperature-resistant epoxy resin is hydantoin epoxy resin (the product providing enterprise and product brand can be CY350, Izoda; 28906, Jialong biotechnology; HY-070, Taijixin new wood), dicyclopentadiene or dicyclopentadiene and phenolic polycondensation resin (the product providing enterprise and product brand can be DNE260A75, Tiangao New technology; HP-72000, Jiashend; Picco2100, Islam), bisphenol A epoxy resin (the product providing enterprise and product brand can be E-44/E-51, Balingite; DER-331, Dow; YDH3000, Aditya Birla), biphenyl epoxy resin (the product providing enterprise and product brand can be NC-3000, Jia, Yuded; YX-4000, Mitsubishi; TMBP, Laiwu new wood), o-cresol type phenolic epoxy resin (the product providing enterprise and product brand can be EPON-678, a shell; NPCN-704, southern taiwan; SQCN700, holy spring chemical) or a mixture of two;

the modified phenolic resin is one or a mixture of two of organic silicon modified phenolic resin (product providing enterprises and product brands can be self-made by an applicant), boron modified phenolic resin (product providing enterprises and product brands can be self-made by the applicant), and benzoxazine modified phenolic resin (product providing enterprises and product brands can be self-made by the applicant);

the curing agent is one or a mixture of two of 4, 4-diaminodiphenylmethane, 4-diaminodiphenyl sulfone, m-phenylenediamine and dicyandiamide;

the inorganic powder is one or a mixture of two of nano silicon dioxide, nano montmorillonite, nano vermiculite and nano talcum powder;

the accelerant is one or a mixture of two of 2-methylimidazole, 2-ethyl-4-methylimidazole, boron trifluoride ethylamine, hexamethyltetramine and aluminum acetylacetonate;

the solvent is one or a mixture of more than two of butanone, acetone, glycol or alcohol;

b. preparing aramid fiber paper prepreg:

taking aramid fiber paper, coating the aramid fiber paper with the special resin adhesive in the step a through a horizontal gluing machine, then passing through a gluing machine drying channel which is 24m long and is divided into 4 sections and 6m in each section, and pre-drying under the conditions that the (baking) temperature is 70-180 ℃ and the vehicle speed is 1.0-6.0 m/min to obtain an aramid fiber paper prepreg;

the aramid fiber paper comprises the following components in percentage by weight: short-cut aramid fiber 1:1 to 2 and an areal density of 30g/m²～60g/m²The water content (namely the weight percentage content of water) is 0.5 to 5 percent, and the high molecular structure repeating unit of the aramid fiber is

The aramid fiber paper can be commercially available aramid fiber paper at home and abroad;

c. pressing a medium-density aramid fiber paper laminated board:

cutting aramid fiber paper prepreg (cut into required size according to medium density aramid fiber paper laminate process requirement), placing one or more layers of aramid fiber paper prepreg on two sides, spreading demolding film and embossing material (for example, 0.18 g/m)²The alkali-free glass cloth) is sent into a hot press (which can be a common hot press or a vacuum hot press), and the temperature is controlled to be 170-190 ℃ and the pressure is controlled to be 1-23 MPa, and the medium-density aramid fiber paper laminated board is prepared by hot press molding.

In another aspect of the invention: and c, performing hot press molding under the conditions that the temperature is controlled to be 170-190 ℃ and the pressure is 1-23 MPa to obtain the medium-density aramid fiber paper laminated board, wherein the process comprises the following steps: controlling the temperature to be 170-190 ℃ and the pressure to be 1-23 MPa, performing hot press molding, and determining the hot press molding time to be within 0.5-3 h according to the thickness of the medium-density aramid fiber paper laminated board after molding to be 1-6 mm, thus obtaining the medium-density aramid fiber paper laminated board.

In another aspect of the invention: in the step c, one or more layers of aramid fiber paper prepreg are overlapped and placed, and the steps are as follows: and (3) overlapping 1-340 layers of aramid fiber paper prepreg.

In another aspect of the invention: the density of the prepared medium-density aramid fiber paper laminated board in the step c is 0.67g/cm³～0.91g/cm³The thickness of the plate is 1 mm-6 mm, the longitudinal tensile strength is 45 KN/m-59 KN/m, the transverse tensile strength is 33 KN/m-61 KN/m, and the breakdown voltage in the 90 ℃ transformer oil is 30 KV-38 KV.

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

(1) by adopting the invention, the aramid paper prepreg is subjected to one-step compression molding by a medium-temperature/medium-pressure common lamination process. The method breaks through a 2-step forming mode that the traditional aramid fiber paper board is made of paper pulp as a raw material and the pressing process is from low temperature to high temperature and from low pressure to high pressure. In the preparation process, paper pulp needs to be carded and humidified by a special device, and a special customized pressing device is required in a high-temperature (not less than 300 ℃) and high-pressure (not less than 35MPa) pressing mode, so that the whole preparation process has multiple and complex processes;

(2) by adopting the invention, the medium density (0.67 g/cm) can be prepared³～0.91g/cm³) The aramid fiber paper laminated board has high tensile strength, electrical strength in the transformer oil at high temperature and extremely low board water content, and can more strictly meet the use requirements in the transformer oil field with long-term high temperature; for a 1mm thick plate, the test data for the examples show: the longitudinal tensile strength is 46MPa, the transverse tensile strength is 33MPa, the breakdown voltage in oil temperature of 90 ℃ is 38KV, and the water content is 0.36% (the data is a test universal value); the technical problem that the aramid fiber paper laminated board which can meet the requirements of tensile strength (longitudinal strength is more than or equal to 35MPa, and transverse strength is more than or equal to 25MPa), electrical strength (breakdown voltage in 90 ℃ transformer oil is more than or equal to 20KV) and the like and can be used in a high-temperature transformer oil field for a long time can not be prepared by adopting common flat pressing equipment is solved;

(3) the process for preparing the medium-density aramid fiber paper laminated board has the advantages of simplicity, easiness in operation, excellent product quality, reduction in production cost, capability of meeting the requirements of various engineering equipment and electrical equipment with special purposes (aerospace, rail transit, large power generation) and the like on insulating materials, obvious practical use value and application prospect and strong practicability.

Detailed Description

The following examples are intended to further illustrate the present invention and should not be construed as limiting the scope of the invention, which is intended to be covered by the claims appended hereto.

The amounts of each ingredient component material in the following examples are in parts by weight (e.g., grams or kilograms).

Preparation of first part of special resin adhesive