A kind of waterproof density board made of waste epoxy resin powder and its preparation method

Abstract

The present invention provides a waterproof density board made of waste epoxy resin powder and a preparation method thereof. The waterproof density board made of waste epoxy resin powder comprises the following components in parts by weight: 80-90 parts of epoxy resin mixture, 10-15 parts of adhesive, 20-40 parts of plant fiber, 2-8 parts of waterproof agent, 0.5-5 parts of dispersant, 5-10 parts of flame retardant, and 1-4 parts of polyetheramine. The waterproof density board made of waste epoxy resin powder prepared in the present application has good flame retardancy, water absorption, bending and wear resistance after being placed in a cold environment for a long time. The waterproof density board made of waste epoxy resin powder has good stability when placed for a long time at low temperature.

Description

Technical Field

[0001] The invention belongs to a board material, and in particular relates to a waterproof density board made from waste epoxy resin powder and a preparation method thereof. Background Art

[0002] Epoxy resin powder is a multifunctional chemical material, which occupies a pivotal position in the industrial field with its unique chemical properties and physical form. Due to its excellent bonding, sealing, insulation and anti-corrosion properties, it is widely used as a material in the electronics, coatings and adhesives industries. Among them, due to the increasingly rapid replacement of electronic equipment, the abandonment of a large number of electronic products, especially circuit boards, is the most common. Because discarded electronic circuit boards inevitably contain a large amount of waste such as epoxy resin. If these discarded epoxy resin powders are not properly handled, they will pose a serious threat to the environment, such as soil and water pollution. In the prior art, electronic circuit board powder is obtained by mechanically treating discarded electronic circuit boards and then used to make boards, which not only reduces the environmental load, but also effectively utilizes the waste electronic circuit board powder containing waste epoxy resin powder, thereby reducing the production cost of boards, and has been widely studied.

[0003] Waterproof sheet materials can not only withstand water splashes and humid environments in daily life, but also have waterproof properties in some places with high humidity or direct contact with water, such as bathrooms and kitchens, and have become an indispensable material in the research and development of sheet materials. For example, waterproof sheet materials have been studied in patents with announcement numbers "CN102686667B" and "CN101555356B". In the patent with announcement number "CN102686667B", the sheet materials made by using waste electronic circuit board powder, phenolic resin glue and chemical fiber are good in waterproofness, and the tensile strength and end face strength are relatively good, but the wear resistance and bending strength still need to be further improved, and the flame retardancy is relatively poor; in the patent with announcement number "CN101555356B", plastic, waste circuit board recycling powder and activated calcium carbonate are used together to have waterproof and non-deformation properties, but there is also a situation where the flame retardancy is not significantly improved and the waterproofness still needs to be further improved.

[0004] In view of the problems existing in the prior art, how to provide a waste epoxy resin powder with good water absorption, bending elasticity, flame retardancy and wear resistance for making waterproof density board is a problem to be solved urgently by the present invention. Summary of the invention

[0005] The purpose of the present invention is to provide a waterproof density board made of waste epoxy resin powder and a preparation method thereof, so as to solve the problems raised in the above background technology.

[0006] To achieve the above-mentioned purpose, the present invention provides the following technical solutions: On the one hand, the present invention provides a waterproof density board made of waste epoxy resin powder, which comprises the following components in parts by weight: 80-90 parts of epoxy resin mixture, 10-15 parts of adhesive, 20-40 parts of plant fiber, 2-8 parts of waterproofing agent, 0.5-5 parts of dispersant, 5-10 parts of flame retardant and 1-4 parts of polyether amine.

[0007] As a further improvement, the flame retardant is a boron-containing flame retardant and a phosphorus-containing flame retardant.

[0008] As a further improvement, boron-containing flame retardants include but are not limited to sodium octaborate tetrahydrate, sodium metaborate, ammonium metaborate, ammonium pentaborate, zinc borate, and the like.

[0009] As a further improvement, the dispersant is prepared by reacting 2-acrylamide-2-methylpropane sulfonic acid, allyl polyoxyethylene ether, and methacryloyloxyethyl trimethylammonium chloride.

[0010] As a further improvement, a method for preparing a dispersant comprises the following steps: after mixing 2-acrylamide-2-methylpropane sulfonic acid and water, placing the mixture in a reactor in an inert environment, removing air, heating the reactor to a suitable temperature, adding allyl polyoxyethylene ether and methacryloyloxyethyl trimethylammonium chloride while stirring, adding an initiator solution dropwise, reacting sufficiently, cooling the mixture to room temperature after the reaction is completed, adjusting the system to be neutral, and performing post-treatment to obtain a dispersant.

[0011] As a further improvement, the amount of methacryloyloxyethyl trimethyl ammonium chloride used is 2-4% of the total mass of allyl polyoxyethylene ether and 2-acrylamide-2-methylpropane sulfonic acid.

[0012] As a further improvement, the mass ratio of the boron-containing flame retardant to the phosphorus-containing flame retardant is 1:2-5, for example, it can be 1:2, 1:3, 1:4, 1:5 or any ratio range therebetween.

[0013] As a further improvement, the epoxy resin-containing mixture is epoxy resin and waste electronic circuit board powder.

[0014] As a further improvement, a method for preparing a phosphorus-containing flame retardant includes the following steps: placing 10-(2,5-dihydroxyphenyl)-10-hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide and a catalyst in an inert environment in a reactor, removing air, adding phenyl dichlorophosphate, and then raising the temperature to a suitable temperature to allow a sufficient reaction. After the reaction is completed, washing, filtering, and vacuum drying are performed to obtain a phosphorus-containing flame retardant.

[0015] As a further improvement, the waterproofing agent is silicone waterproofing agent and white oil.

[0016] On the other hand, the present invention also provides a method for preparing a waterproof density board using waste epoxy resin powder, comprising the following steps:

[0017] (1) Mix the dried epoxy resin mixture, adhesive, plant fiber, waterproofing agent, dispersant, flame retardant and polyetheramine, evenly feed them into the paving system at a constant speed, flatten them with a sweeping roller, pre-press them into slabs, trim them vertically and horizontally, and press them into shape;

[0018] (2) Pull out the sheet formed by pressing in step (1), then turn over, cool, sand and determine thickness, perform quality inspection, and put into storage.

[0019] Compared with the prior art, the beneficial effects of the present invention are: the waterproof density board made of waste epoxy resin powder prepared in the present application has good flame retardancy, water absorption, bending and wear resistance after being placed in a cold environment for a long time, and the waterproof density board made of waste epoxy resin powder has good stability when placed for a long time at low temperature. DETAILED DESCRIPTION

[0020] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following embodiments are examples of the present invention and are only used to illustrate the present invention, but not to limit the present invention. Other combinations and various modifications within the concept of the present invention may be performed without departing from the spirit or scope of the present invention.

[0021] In the following embodiments, except for dispersant A and phosphorus-containing flame retardant A, the other compound monomers and related reagents used can be purchased from the market, among which allyl polyoxyethylene ether (Mw is 1000) was purchased from Hai'an Petrochemical Plant in Jiangsu Province; adhesive was purchased from Condis Chemical (Hubei) Co., Ltd., CAS No. 101-68-8; waste electronic circuit board powder is obtained by crushing and screening discarded circuit boards or scraps of circuit board production and other waste materials, removing the metal parts therein, and the remaining non-metallic powder was purchased from Suzhou Haizhou Material Recycling Co., Ltd. provided by Environmental Protection Co., Ltd.; polyetheramine was purchased from Shandong Yousuo Chemical Technology Co., Ltd., model D230; silicone waterproofing agent was purchased from Tuoda (Shandong) New Materials Technology Industry Group Co., Ltd., item number 99887; plant fiber was purchased from Hebei Siruite Mineral Products Co., Ltd., item number 00003; epoxy resin was purchased from Guangzhou Tanhua New Materials Co., Ltd., model DER354; sodium octaborate tetrahydrate CAS number is 12280-03-4; polycarboxylate dispersant was purchased from Guangdong Zhongtai Lianhua New Materials Co., Ltd., model AG-196.

[0022] The preparation method of dispersant A comprises the following steps:

[0023] 67.4 g of 2-acrylamide-2-methylpropanesulfonic acid and 250 mL of water were mixed and placed in a reactor in a nitrogen environment. After the air was excluded, the reactor was heated to 70° C., 32.6 g of allyl polyoxyethylene ether and 3 g of methacryloyloxyethyl trimethylammonium chloride were added while stirring, and 30 mL of 20 mg / mL potassium persulfate solution was added dropwise. The potassium persulfate solution was added for 1.5 h. After the addition was completed, the mixture was reacted for 3 h, cooled to room temperature, and the system was adjusted to be neutral. Then, the mixture was placed in a 2000-4000 Da dialysis bag for dialysis. During dialysis, the water was changed every 12 h. After dialysis for 72 h, the mixture was dried in a vacuum drying oven (temperature of 60° C.) to obtain dispersant A.

[0024] The preparation method of phosphorus-containing flame retardant A comprises the following steps:

[0025] 100 g of 10-(2,5-dihydroxyphenyl)-10-hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide and 0.42 g of aluminum chloride were placed in a reactor in a nitrogen environment. After the air was excluded, 65.9 g of phenyl dichlorophosphate was added, and then the temperature was raised to 140°C and reacted for 2 hours. The temperature was then continued to be raised to 200°C and the reaction was continued for 0.5 hours. The reaction was terminated, washed with distilled water, filtered, and vacuum dried (temperature was 45°C) to obtain phosphorus-containing flame retardant A.

[0026] The method for preparing a waterproof density board using waste epoxy resin powder of Example 1-7 is characterized by comprising the following steps:

[0027] (1) After the dried epoxy resin mixture, adhesive, plant fiber, waterproofing agent, dispersant, flame retardant, and polyetheramine are mixed, they are uniformly and uniformly fed into the paving system and flattened with a sweeping roller, and then fed into a pre-pressing machine to be pressed into a slab with a thickness of 15 mm, and then sent to the conveyor belt for longitudinal and transverse trimming. The width after longitudinal and transverse trimming is 1000 mm and the length is 2000 mm. Then, the slab is conveyed to a multi-layer hot press to be pressed and formed. When the slab is pressed and formed by the multi-layer hot press, it is first pressurized for 1 minute to make the surface pressure of the slab reach 10 Mps, and then it is allowed to stand for 2 minutes before being pressurized again. The pressurization pressure reaches 15 Mps. After the pressurization time lasts for 5 minutes, the exhaust is exhausted and the pressure is released. The pressure release process decreases smoothly and evenly. After the epoxy resin mixture, adhesive, plant fiber, waterproofing agent, dispersant, flame retardant, and polyetheramine are dried, the water content is 3%;

[0028] (2) Pull out the sheet formed by pressing in step (1), then turn over, cool, sand and determine thickness, perform quality inspection, and put into storage.

[0029] The components required in Examples 1-7 and the contents of each component are shown in Table 1-2:

[0030] Table 1

[0031]

[0032] Table 2

[0033]

[0034] The waterproof density boards made from the waste epoxy resin powder obtained in Examples 1-7 were subjected to water absorption tests, bending strength tests, flame retardancy tests, and wear resistance tests. During the tests, the waterproof density boards made from the waste epoxy resin powder obtained in Examples 1-7 had been placed in a -1°C environment for 6 months.

[0035] The specific test method is as follows:

[0036] Water absorption test: Tested in accordance with GB / T 1934.1-2009 standard;

[0037] Flame retardancy test: Tested in accordance with GB 8624-2012 standard;

[0038] Bending strength test: Tested in accordance with GB / T 35160.2-2027 standard;

[0039] Abrasion resistance test: Tested in accordance with GB / T 35160.4-2017 standard.

[0040] The test results are shown in Table 3, as follows:

[0041] Table 3

[0042]

[0043] From the comparison between Example 1 and Examples 4-5, it can be seen that when the water absorption rate, bending strength and wear resistance are kept within the appropriate performance range, the boron-containing flame retardant and the phosphorus-containing flame retardant provided by the present application are used, and the mass ratio of the boron-containing flame retardant to the phosphorus-containing flame retardant is within the appropriate range, the flame retardancy of the waterproof density board made of the waste epoxy resin powder obtained is better even if it is placed at low temperature for a long time. When it is stored in a cold environment, it has good stability and still maintains good flame retardancy;

[0044] From the comparison between Example 1 and Example 6, it can be seen that when conventional phosphorus-containing flame retardants are used instead of the phosphorus-containing flame retardants provided in the present application and used in combination with boron-containing flame retardants, the flame retardancy of the waterproof density board made of the waste epoxy resin powder obtained in a cold environment is relatively poor;

[0045] From the comparison between Example 1 and Example 7, it can be seen that the waterproof density board made of waste epoxy resin powder prepared by using the dispersant provided by the present application has better flame retardancy, water absorption, bending and wear resistance after being placed in a cold environment for a long time;

[0046] From the comparison of Examples 1-3, it can be seen that the waterproof density board made from the waste epoxy resin powder prepared using the components and contents provided in this application has good flame retardancy, water absorption, bending and wear resistance after being placed in a cold environment for a long time, and has good stability at low temperatures.

[0047] The above implementation modes are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with this technology to understand the content of the present invention and implement it, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. A waterproof density board made from waste epoxy resin powder, characterized in that: The waste epoxy resin powder used to make the waterproof density board comprises the following components in parts by weight: 80-90 parts of epoxy resin mixture, 10-15 parts of adhesive, 20-40 parts of plant fiber, 2-8 parts of waterproofing agent, 0.5-5 parts of dispersant, 5-10 parts of flame retardant, and 1-4 parts of polyetheramine; The flame retardant is a boron-containing flame retardant and a phosphorus-containing flame retardant; The dispersant is prepared by reacting 2-acrylamide-2-methylpropane sulfonic acid, allyl polyoxyethylene ether, and methacryloyloxyethyl trimethylammonium chloride; The mass ratio of the boron-containing flame retardant to the phosphorus-containing flame retardant is 1:2-5; The epoxy resin-containing mixture is epoxy resin and waste electronic circuit board powder; The preparation method of the phosphorus-containing flame retardant comprises the following steps: placing 10-(2,5-dihydroxyphenyl)-10-hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide and a catalyst in a reaction kettle in an inert environment, removing air, adding phenyl dichlorophosphate, raising the temperature to a suitable temperature, carrying out a sufficient reaction, and washing, filtering, and vacuum drying after the reaction is completed to obtain the phosphorus-containing flame retardant.

2. The method for making waterproof density board using waste epoxy resin powder according to claim 1, characterized in that: The preparation method of the dispersant comprises the following steps: After 2-acrylamide-2-methylpropanesulfonic acid and water are mixed, they are placed in a reactor in an inert environment. After the air is removed, the reactor is heated to a suitable temperature, allyl polyoxyethylene ether and methacryloyloxyethyl trimethylammonium chloride are added while stirring, and then an initiator solution is added dropwise to react fully. After the reaction is completed, the mixture is cooled to room temperature, and the system is adjusted to be neutral, and then post-processed to obtain a dispersant.

3. The method for making waterproof density board using waste epoxy resin powder according to claim 2, characterized in that: The amount of methacryloyloxyethyl trimethylammonium chloride used is 2-4% of the total mass of allyl polyoxyethylene ether and 2-acrylamide-2-methylpropane sulfonic acid.

4. The method for making waterproof density board using waste epoxy resin powder according to claim 1, characterized in that: The waterproofing agent is organic silicon waterproofing agent and white oil.

5. The method for preparing waterproof density board from waste epoxy resin powder according to any one of claims 1 to 4, characterized in that: The following steps are involved: (1) Mix the dried epoxy resin mixture, adhesive, plant fiber, waterproofing agent, dispersant, flame retardant and polyetheramine, evenly feed them into the paving system at a constant speed, flatten them with a sweeping roller, pre-press them into slabs, trim them vertically and horizontally, and press them into shape; (2) The sheet formed by pressing in step (1) is pulled out, and then turned over, cooled, sanded to determine thickness, quality inspected, and put into storage.

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