Boron phenolic carboxyl nitrile rubber polymer and preparation method thereof

Abstract

The invention relates to a boron phenolic carboxy nitrile rubber polymer and a preparation method thereof. The polymer is composed of boron phenolic resin and carboxy nitrile rubber. The preparation method comprises the following steps: crushing the boron phenolic resin into millet size; adding carboxy nitrile rubber into a stainless steel plate, then adding the crushed boron phenolic resin powder, uniformly mixing with a stainless steel rod, averagely loading into four plates, putting into two layers of an air dry oven, and heating the air dry oven to 130-140 DEG C; after half an hour, roughly and uniformly stirring the materials in the tray by using a stainless steel rod; after half an hour, uniformly stirring with a stainless steel rod once, and changing positions of two trays of materials on each layer up and down once to keep the heated state of each tray of materials consistent, so that the performance of the produced materials is uniform and consistent; and heating to 1 hour, 20 minutes to 1 hour, 30 minutes, taking out all the materials, cooling, lightly cracking, and putting into a plastic bag for storage. According to the invention, the toughening performance of the thermosetting resin is thoroughly realized, and the thermosetting resin can be infinitely toughened in a large range from hard solid to soft rubber.

Description

Technical Field

[0001] The invention relates to a boron phenolic carboxyl nitrile rubber polymer and a preparation method thereof. Background Art

[0002] Epoxy resin and phenolic resin are polymer materials widely used in various countries in the world, from various fields of civil use to military high-tech fields.

[0003] However, with the development of science and technology, the requirements for the performance of polymer materials are becoming higher and more comprehensive. Common knowledge and the performance of the materials themselves often cannot meet the actual needs. For example, there are about dozens of epoxy resins, and there are about a hundred curing agents. If you do a test from beginning to end, it may not be completed in a year. In addition, there are many additives: toughening agents, flame retardants, catalysts, activators, fillers... Even if you ignore the complexity, it is difficult to meet the new performance requirements from beginning to end. For example, smokeless, non-toxic (or low-toxic), long-term 300℃ resistant products, etc.

[0004] Boron phenolic resin has four major functions: high temperature resistance, ablation resistance, clean flame retardancy, and excellent electrical properties. All high temperature resistant resins, such as phenolic resins and epoxy resins, are hard and brittle. In order to improve this hard and brittle disadvantage, they all need to be toughened. However, the existing toughening method has a serious disadvantage: if too much toughening agent is added, the heat resistance decreases, and if too little toughening agent is added, the toughness is not significantly improved. There is no good solution at home and abroad.

[0005] Existing epoxy resins cannot withstand high temperatures above 300°C, are not flame retardant, have poor toughness, and are relatively brittle. Summary of the invention

[0006] In view of this, the present invention provides a boron phenolic carboxyl nitrile rubber polymer and a preparation method thereof to solve the problem of toughening high temperature resistant resins, thereby thoroughly solving the toughening performance of thermosetting resins and being able to infinitely toughen in a wide range, from hard solids to soft rubbers.

[0007] To achieve the above object, the technical solution adopted by the present invention is: boron phenolic carboxyl nitrile rubber polymer, characterized in that the polymer is composed of the following raw materials: boron phenolic resin and carboxyl nitrile rubber.

[0008] The mass ratio of boron phenolic resin to carboxyl nitrile rubber is 10:3-10.

[0009] The preparation method of boron phenolic carboxyl nitrile rubber polymer comprises the following steps:

[0010] 1) Firstly, the thermosetting boron phenolic resin is crushed into the size of millet grains;

[0011] 2) Add carboxylated nitrile rubber to a stainless steel plate, then add the crushed thermosetting boron phenolic resin powder from step 1), mix well with a stainless steel rod, evenly load four plates, and place in two layers of a forced air drying oven.

[0012] 3) Heat the blast drying oven to between 130°C and 140°C;

[0013] 4) After half an hour, use a stainless steel rod to roughly stir the material in the dish;

[0014] 5) After another half an hour, stir once with a stainless steel rod and switch the two plates of material in each layer up and down once to keep the heating state of each plate of material consistent, so that the performance of the produced material is uniform;

[0015] 6) Heat for 1 hour and 20 minutes to 1 hour and 30 minutes, take out all the materials, cool them down, gently break them up, and store them in a plastic bag.

[0016] Compared with the prior art, the present invention has the following beneficial effects:

[0017] 1) The present invention adopts boron phenolic resin and carboxyl nitrile rubber to prepare, retains the characteristics and multifunctionality of boron phenolic resin, and has the functions of toughening, high temperature resistance, ablation resistance, cleanliness and flame retardancy.

[0018] 2) The polymer prepared by the present invention can be used to manufacture gradient functional composite materials and low-density composite materials.

[0019] 3) The polymer prepared by the present invention can be bonded to metals, ceramics, and composite materials, and can achieve self-adhesion or mutual adhesion.

[0020] 4) The present invention can be used to add different epoxy resins to cure multifunctional composite materials and gradient functional composite materials at room temperature, and has excellent electrical and insulating properties, and is used for the packaging of electronic components. The product obtained by adding epoxy resin without using solvent dilution can also be used for filling electronic components, and can be used at 200-300°C, and can work at 400°C-500°C for several hours in a short time. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is a shear strength diagram (20.3° C.) of the polymer obtained in Example 1 of the present invention.

[0022] Figure 2 This is a shear strength diagram (200° C.) of the polymer obtained in Example 1 of the present invention.

[0023] Figure 3 This is a shear strength diagram (300°C) of the polymer obtained in Example 1 of the present invention.

[0024] Figure 4This is a graph showing the shear strength of the polymer obtained in Example 2 of the present invention.

[0025] Figure 5 It is the infrared spectrum of the polymer of the present invention.

[0026] Figure 6 It is a graph of the X, Y, and Z ternary system.

[0027] Figure 7 Interaction graphs can be generated for the three components X, Y, and Z. DETAILED DESCRIPTION

[0028] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with embodiments, and the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0029] Embodiment 1:

[0030] Boron phenolic carboxyl nitrile rubber polymer, the polymer is composed of the following raw materials: boron phenolic resin, carboxyl nitrile rubber;

[0031] The mass ratio of the boron phenolic resin to the carboxylated nitrile rubber is 100g:200g.

[0032] The steps of the preparation method of boron phenolic carboxyl nitrile rubber polymer are:

[0033] 1) First, 100 g of thermosetting boron phenolic resin was crushed into the size of millet grains;

[0034] 2) Add 30 g of carboxylated nitrile rubber to a stainless steel plate, then add the crushed thermosetting boron phenolic resin powder from step 1), mix evenly with a stainless steel rod, evenly load four plates, and place them in two layers of a forced air drying oven;

[0035] 3) Heat the air drying oven to between 130°C and 140°C;

[0036] 4) After half an hour, use a stainless steel rod to roughly stir the materials in the dish (the boron phenolic resin has melted at this time);

[0037] 5) After another half an hour, stir once with a stainless steel rod and switch the two plates of material in each layer up and down once to keep the heating state of each plate of material consistent, so that the performance of the produced material is uniform;

[0038] 6) After heating for 1 hour and 20 minutes to 1 hour and 30 minutes, all the materials can be taken out, cooled, and gently broken to obtain R30 polymer.

[0039] The use method of the R30 polymer prepared above:

[0040] The prepared R30 polymer is broken into pieces, weighed, and placed in a sealable container. An equal amount of ethyl acetate is added and stirred or shaken. It will dissolve into an opaque solution in about 6 hours (it can also be shaken for 20 minutes every 2 hours, and it will be soluble in about 2 to 3 days).

[0041] The solution prepared by the method can be directly used for bonding, coating or making composite materials, and has excellent heat resistance, excellent ablation performance and electrical properties, flame retardancy and good toughness.

[0042] Take 100 parts of this solution, add about 30 parts of filler, mix well, and the bonded steel specimen still has a strength of 3 to 4 MPa at 350°C.

[0043] The R30 polymer is used for bonding performance (20.3°C), as shown in Table 1 and Figure 1 As shown:

[0044] Test plan: Adhesive Tensile Shear Test Protocol Calculation standard: GB / T 7124-1986 Specimen shape: Plate Test Date: 2019-10-14 10:07:27 Test speed: 5mm / min Test unit: Shaanxi Taihang Fire Retardant Polymer Co., Ltd.

[0045] Table 1

[0046]

[0047] The bonding properties of R30 polymer and cured epoxy resin (200°C) are shown in Table 2 and Figure 2 As shown:

[0048] Test plan: Adhesive Tensile Shear Test Protocol Calculation standard: GB / T 7124-1986 Specimen shape: Plate Test Date: 2020-07-15 09:32:59 Test speed: 5mm / min Test unit: Shaanxi Taihang Fire Retardant Polymer Co., Ltd.

[0049] Table 2

[0050]

[0051] The bonding properties of R30 polymer and cured epoxy resin (300°C) are shown in Table 3 and Figure 3 As shown:

[0052] Test plan: Adhesive Tensile Shear Test Protocol Calculation standard: GB / T 7124-1986 Specimen shape: Plate Test Date:2020-07-15 10:13:52 Test speed: 5mm / min Test unit: Shaanxi Taihang Fire Retardant Polymer Co., Ltd.

[0053] Table 3

[0054]

[0055] Embodiment 2:

[0056] Boron phenolic carboxyl nitrile rubber polymer, the polymer is composed of the following raw materials: boron phenolic resin, carboxyl nitrile rubber;

[0057] The mass ratio of the boron phenolic resin to the carboxyl nitrile rubber is 100g:100g.

[0058] The steps of the preparation method of boron phenolic carboxyl nitrile rubber polymer are:

[0059] 1) First, 100 g of thermosetting boron phenolic resin was crushed into the size of millet grains;

[0060] 2) Add 100 g of carboxylated nitrile rubber to a stainless steel plate, then add the crushed thermosetting boron phenolic resin powder obtained in step 1), mix them roughly with a stainless steel rod, evenly load four plates, and place them in two layers of a forced air drying oven;

[0061] 3) Heat the blast drying oven to between 130°C and 140°C;

[0062] 4) After half an hour, use a stainless steel rod to roughly stir the materials in the dish (the boron phenolic resin has melted at this time);

[0063] 5) After another half an hour, stir once with a stainless steel rod and switch the two plates of material in each layer up and down once to keep the heating state of each plate of material consistent, so that the performance of the produced material is uniform;

[0064] 6) After heating for 1 hour and 20 minutes to 1 hour and 30 minutes, all the materials can be taken out, cooled, and gently broken to obtain R100 polymer.

[0065] 7) Tear the prepared R100 polymer into small pieces or cut into small pieces, weigh 100 g, put it into a sealable container, add 100 g of ethyl acetate solution, stir appropriately to dissolve it, and obtain a 50% concentration R100 solution.

[0066] Example 1:

[0067] Application of R100 solution

[0068] Carbon fiber cloth or glass fiber cloth is soaked with R100 solution and dried at room temperature to obtain a flexible composite material. It is placed on the floor and hit with a hammer. It is not easy to be damaged or cracked. After being tested by the application unit, it can withstand an overload of 200,000g (g is the acceleration of gravity).

[0069] Example 2:

[0070] Take 100g of R100 solution, add 50g of epoxy resin E-51#, mix well, and the room temperature shear strength of the bonded steel parts can reach 37-45Mpa.

[0071] The properties of the R100 polymer used in bonding ( 21.2 ), as shown in Table 4 and Figure 4 As shown:

[0072] Test plan: Adhesive Tensile Shear Test Protocol Calculation standard: GB / T 7124-1986 Specimen shape: Plate Test Date: 2019-05-14 10:36:38 Test speed: 5mm / min Shaanxi Taihang Fire Retardant Polymer Co., Ltd.

[0073] Table 4

[0074]

[0075] Example three:

[0076] 1. Burning resistance of boron phenolic carboxyl nitrile rubber polymer:

[0077] Mix 50g R30 solution + 10g inorganic hollow microspheres.

[0078] Foaming and curing at 30℃ for one day, or curing at 80℃ for 2 hours

[0079] Measured according to the national military standard: temperature 3400K.

[0080] The various properties of curing are as follows:

[0081] Density: 0.56g / cm 3

[0082] Thermal conductivity 0.1136w / mk

[0083] Linear ablation / erosion rate: -0.1327mm / s Mass ablation / erosion rate: 0.0481g / s

[0084] 2. 45 # Adhesion of steel: 10 MPa at room temperature, 5 MPa at 300℃

[0085] Flame retardant, difficult to burn, smokeless (alcohol lamp flame burns for 18 seconds).

[0086] 3. The silver powder conductive adhesive for copper clad plate developed by Xijing Electronics Company adopts the formula of 100g R30 ethyl acetate solution + 25g E-51 epoxy resin. After curing at 120℃-h+15℃ / h+180℃-h, the test piece is put into a 300℃ oven for continuous power-on test for 1000 hours. The performance test shows no change. It can also be used at 400-500℃ for 4-5 hours.

[0087] The calculation of preparing R60 (100 g of boron phenolic resin and 60 g of carboxylated nitrile rubber) using Example 1: R30 and Example 2: R100 of the present invention is as follows:

[0088] Use 10g of R30 solution with a concentration of 50% and the same amount of R100 solution with a concentration of 50% to make an R60 solution.

[0089] 10g R30 solution, 5g solid matter, boron phenolic acid = 5*100 / 130 = 3.85g; rubber = 5*30 / 130 = 1.15g.

[0090] From the definition of R60, we know that there are 60 parts of rubber and 100 parts of boron phenolic formaldehyde. If we take Xg of R60 solution, the total solids are 1 / 2Xg. The solids of R100 are equal amounts of phenolic formaldehyde and rubber, that is, 1:1. Therefore, in the total solids of R100 of 1 / 2Xg, phenolic formaldehyde is 1 / 4Xg and rubber is also 1 / 4Xg.

[0091] According to the definition of R60, the total boron phenolic solids are 1 / 4+5*100 / 130, and the total rubber solids are 1 / 4X+5*30 / 130, then

[0092] Solving this equation, we get X = 11.6 g of solution, that is, 11.6 g of R100 solution is enough, the solid content is 5.8 g, and the phenolic acid and rubber are 2.9 g each.

[0093] verify:

[0094] 4. The significance of the X, Y, Z ternary system:

[0095] This patented boron phenolic X-carboxyl nitrile rubber, Y-epoxy resin, Z ternary double internal toughening system has created an integrated change rule of high performance and multifunctionality.

[0096] The three components in this system can produce interactive reactions, such as Figure 7 As shown:

[0097] In the X, Y, Z ternary system graphics (such as Figure 6 ) is expressed as follows:

[0098] X→from infinitesimal to infinite, but not equal to 0

[0099] Y→0→infinity

[0100] Z→0→infinity.

[0101] In this patent, after the design molecular concept of the X, Y, Z ternary system, the boron phenolic resin has an oxygen atom bond, which has a certain toughening effect. After reacting with carboxyl nitrile, it has a new toughening function, and finally forms a double internal toughening structure. This molecular design concept has not been reported at home and abroad.

[0102] The above detailed description of the preferred embodiments of the present invention is only used to help understand the present invention, and is not intended to limit the present invention. Any local modification or replacement within the technical scope disclosed by the present invention by anyone familiar with the technology should be included in the scope of the present invention.

Claims

1. Boron phenolic carboxyl nitrile rubber polymer, characterized in that, The polymer is composed of the following raw materials: boron phenolic resin and carboxyl nitrile rubber.

2. The boron phenolic carboxyl nitrile rubber polymer according to claim 1, characterized in that The mass ratio of the boron phenolic resin to the carboxyl nitrile rubber is 10:3-10.

3. The method for preparing a boron phenolic carboxyl nitrile rubber polymer according to claim 2, wherein: The steps are: 1) First, crush the thermosetting boron phenolic resin into the size of millet grains; 2) Add carboxylated nitrile rubber to a stainless steel plate, then add the crushed thermosetting boron phenolic resin powder from step 1), mix well with a stainless steel rod, evenly load four plates, and place them in two layers of a forced air drying oven. 3) Heat the blast drying oven to between 130℃ and 140℃; 4) After half an hour, use a stainless steel rod to roughly mix the materials in the dish; 5) After another half an hour, stir once with a stainless steel rod and switch the two plates of material on each layer up and down to keep the heating state of each plate of material consistent, so that the performance of the produced material is uniform; 6) Heat for 1 hour and 20 minutes to 1 hour and 30 minutes, remove all the materials, cool them down, gently break them up, and store them in a plastic bag.

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