A substrate for waterproof wall and floor and its preparation method

Abstract

The present invention discloses a substrate for waterproof wall floors and a preparation method thereof, belonging to the technical field of plates, including a substrate and a melamine decorative paper. The substrate and the melamine decorative paper are bonded through an adhesive. The preparation method comprises the following steps: First step, prepare the substrate; Second step, coat the adhesive on the surface of the substrate, then laminate the melamine decorative paper, and place it at a temperature of 20°C for 3 days to obtain a substrate for waterproof wall floors. The waste printed circuit boards are processed to prepare the substrate with the extracted fiberglass cloth and the dried circuit board powder as raw materials and a self-made adhesive. The substrate in the present invention has good waterproofness, small natural deformation, good nail-holding power and service strength compared with wooden plates. At the same time, the adhesive used is a solvent-free two-component polyurethane adhesive with good environmental protection. The adhesive and the substrate cooperate with each other to better meet the use requirements, and after testing, the water absorption rate of the substrate is less than 0.2%.

Description

Technical Field

[0001] The present invention belongs to the technical field of sheet materials, and particularly relates to a base material for waterproof wall and floor and a preparation method thereof. Background Art

[0002] Wooden sheet materials have a relatively comfortable touch, but are prone to water absorption and swelling or drying deformation, and often have problems such as shrinkage, expansion deformation, warping, and cracking during use. Moreover, they require a large amount of wood, have a long production cycle, and high costs. Waste printed circuit boards are a mixture of fiberglass-reinforced resin and various metals, belonging to typical electronic waste, and can be used as raw materials for sheet materials. If not properly treated and disposed of, it will not only cause a large loss of useful resources, but also cause serious harm to the environment; materials such as resin and fiberglass in waste printed circuit boards are difficult to degrade, and will also pollute underground water sources and soil. At the same time, traditional stacking or landfill methods not only occupy a large amount of space, but also the heavy metals such as mercury, chromium, cadmium and other high-molecular organic substances contained are difficult to degrade under natural conditions, and harmful components will enter the environment through water, air and soil, which will cause potential, long-term and irreparable harm to human health and the ecological environment. The waste printed circuit boards contain raw materials that can be used as sheet materials, becoming materials that can be recycled, which is beneficial to environmental protection and the development and utilization of potential resources, and can create certain economic benefits. Summary of the Invention

[0003] The purpose of the present invention is to provide a base material for waterproof wall and floor and a preparation method thereof to solve the problems in the background art.

[0004] The purpose of the present invention can be achieved through the following technical solutions:

[0005] A base material for waterproof wall and floor, comprising a base plate and a melamine decorative paper, and the base plate and the melamine decorative paper are bonded through an adhesive;

[0006] The base plate is prepared through the following steps:

[0007] Step 1. Pretreatment of waste printed circuit boards: Extract the fiberglass cloth from the waste printed circuit boards, then crush the circuit boards and extract metals, and dry the remaining circuit board powder. The drying conditions are 100 °C, vacuum drying until the water content is less than 3%, using the extracted fiberglass cloth and the dried circuit board powder as raw materials;

[0008] Step 2. Melt and draw the fiberglass cloth to form a fiber mesh; mix the circuit board powder and the adhesive, and then lay them in layers with the fiber mesh. After pre-pressing, hot press them into shape to obtain the base plate.

[0009] The adhesive is prepared through the following steps:

[0010] After mixing modified cashew phenol, polyether polyol, hydroxyl-terminated branched polysiloxane and molecular sieve, dehydrate under vacuum at a temperature of 110 - 120 °C until the water content is less than 1000 ppm to obtain Component A; mix isocyanate, polyether polyol, polyester polyol and chain extender, stir and react at a temperature of 85 - 90 °C, control the content of NCO% to be 15 - 20% to obtain Component B; mix Component A and Component B to obtain the adhesive.

[0011] Further, the mass ratio of the circuit board powder to the adhesive in step two is 8 - 9:100.

[0012] Further, the mass ratio of Component A to Component B is 3:1.

[0013] Further, the isocyanate is one of toluene diisocyanate and isophorone diisocyanate; the polyether polyol is one of polytetrahydrofuran ether diol and polypropylene glycol; the polyester polyol is polycarbonate diol; the chain extender is 1,2-ethylene glycol.

[0014] Further, the hydroxyl-terminated branched polysiloxane is prepared by the following steps:

[0015] Under nitrogen protection and at a temperature of 20 °C, mix tetraethoxysilane, 1,4-butanediol and p-toluenesulfonic acid, heat up and react, and ensure that the distillation temperature is controlled below 78 °C during this period. When the reaction temperature reaches 160 °C, start heat preservation until the distillation temperature drops to 55 °C and then stop heating to obtain hydroxyl-terminated branched polysiloxane. Among them, the dosage ratio of tetraethoxysilane, 1,4-butanediol and p-toluenesulfonic acid is 23 g:36 g:100 mg. The hydroxyl-terminated branched polysiloxane, a polymer mainly composed of Si-O-Si bonds, has excellent heat resistance, toughness, acid and alkali resistance, weather resistance, hydrophobicity and insulation. As a raw material in Component A, the hydroxyl-terminated branched polysiloxane reacts with the components in Component B to introduce Si-O-Si segments into the structure of the adhesive, improving the stability of the adhesive and better enhancing the dimensional stability of the product.

[0016] Further, the modified cashew phenol is prepared by the following steps:

[0017] Under nitrogen protection, 6,6,6-trifluoro-1-iodohexane, sodium bicarbonate, cardanol and sodium dithionite were added to acetonitrile, and the mixture was heated under reflux for 3 h. After the reaction, water and diethyl ether were added for extraction, and the organic phase was retained, dried with anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain an intermediate product. Among them, the dosage ratio of 6,6,6-trifluoro-1-iodohexane, sodium bicarbonate, cardanol, sodium dithionite and acetonitrile was 0.1 mol: 0.02 mol: 0.1 mol: 0.1 mol: 0.1 mol: 200 mL. Using 6,6,6-trifluoro-1-iodohexane and cardanol as raw materials, a trifluoromethyl group was introduced into the structure of cardanol. The surface energy of fluorine element is low, and it is a hydrophobic atom. The fluorine-containing segment can migrate to the surface, resulting in the aggregation of fluorine element on the material surface, thus enhancing the water resistance.

[0018] The intermediate product, mercaptoethanol and photoinitiator α-hydroxyisobutyrophenone were added to ethyl acetate, and the mixture was stirred and reacted under ultraviolet light irradiation for 10 h. After the reaction, saturated sodium chloride aqueous solution was added to the reaction system for washing. After washing, the obtained organic phase was concentrated under reduced pressure to remove the solvent, and modified cardanol was obtained. Among them, the dosage ratio of the intermediate product, mercaptoethanol, α-hydroxyisobutyrophenone and ethyl acetate was 3.5 g: 3 g: 100 mg: 30 mL. After introducing fluorine element by 6,6,6-trifluoro-1-iodohexane, a hydroxyl group was introduced into the structure of cardanol by the "thiol-ene" photoclick reaction, and then an adhesive was prepared using the modified cardanol as a raw material.

[0019] Further, the mesh holes of the fiber mesh in the substrate are 2 - 6 cm.

[0020] Further, the hot pressing temperature is 70 - 80 °C, the pressing time is 2.5 - 4 min / mm of plate thickness, and the surface pressure is 35 - 40 Kg / cm 2 。

[0021] Further, by weight, in component A, there are 20 - 22 parts of modified cardanol, 15 - 18 parts of polyether polyol, 8 - 10 parts of hydroxyl-terminated branched polysiloxane and 8 - 10 parts of molecular sieve; in component B, there are 70 - 80 parts of isocyanate, 8 - 10 parts of polyether polyol, 10 - 30 parts of polyester polyol and 2 - 3 parts of chain extender.

[0022] A preparation method of a substrate for waterproof wall and floor, comprising the following steps:

[0023] The first step is to prepare a substrate;

[0024] The second step is to coat an adhesive on the surface of the substrate, then laminate a melamine decorative paper, and place it at 20 °C for 3 days to obtain a substrate for waterproof wall and floor.

[0025] The beneficial effects of the present invention:

[0026] In the prior art, materials such as wood chips and adhesives are used to form plates through mixing and extrusion. However, due to problems such as the easy water absorption and deformation of wood itself and the release of formaldehyde from the formed composite plates, it will cause harm to the human body and the environmental friendliness is relatively poor. To alleviate this problem, in the present invention, waste circuit boards are processed, and a substrate is prepared with the extracted fiberglass cloth and dried circuit board powder as raw materials and a self-made adhesive. The substrate in the present invention has good waterproofness, small natural deformation, good nail-holding power and use strength compared with wood-based plates. At the same time, the adhesive used is a solvent-free two-component polyurethane adhesive with good environmental friendliness. The adhesive and the substrate cooperate with each other to better meet the use requirements, and after testing, the water absorption rate of the substrate is less than 0.2%. Specific embodiments

[0027] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only a 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 those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present invention.

[0028] A substrate for waterproof wall and floor, comprising a substrate and a melamine decorative paper, and the substrate and the melamine decorative paper are bonded by an adhesive; a preparation method of a substrate for waterproof wall and floor, comprising the following steps:

[0029] The first step is to prepare a substrate;

[0030] The second step is to coat the adhesive on the surface of the substrate, then laminate the melamine decorative paper, and place it at a temperature of 20°C for 3 days to obtain a substrate for waterproof wall and floor.

[0031] Example 1

[0032] Prepare modified cardanol:

[0033] Under the protection of nitrogen, 6,6,6-trifluoro-1-iodohexane, sodium bicarbonate, cardanol and sodium dithionite are added to acetonitrile, and the mixture is heated under reflux for 3 h. After the reaction is completed, water and ether are added for extraction, and the organic phase is retained and dried with anhydrous magnesium sulfate. After concentration under reduced pressure, an intermediate product is obtained; among them, the dosage ratio of 6,6,6-trifluoro-1-iodohexane, sodium bicarbonate, cardanol, sodium dithionite and acetonitrile is 0.1 mol: 0.02 mol: 0.1 mol: 0.1 mol: 0.1 mol: 200 mL.

[0034] The intermediate product, mercaptoethanol, and photoinitiator α-hydroxyisobutyrophenone were added to ethyl acetate, and the mixture was stirred and reacted under ultraviolet light irradiation for 10 h. After the reaction, saturated sodium chloride aqueous solution was added to the reaction system for washing. After washing, the obtained organic phase was concentrated under reduced pressure to remove the solvent, and modified cashew phenol was obtained. Among them, the dosage ratio of the intermediate product, mercaptoethanol, α-hydroxyisobutyrophenone, and ethyl acetate was 3.5 g: 3 g: 100 mg: 30 mL.

[0035] Example 2

[0036] Preparation of hydroxyl-terminated branched polysiloxane:

[0037] Under the protection of nitrogen and at a temperature of 20 °C, tetraethoxysilane, 1,4-butanediol, and p-toluenesulfonic acid were mixed and heated for reaction, during which the distillation temperature was ensured to be controlled below 78 °C. When the reaction temperature reached 160 °C, heat preservation was started until the heating was stopped when the distillation temperature dropped to 55 °C, and hydroxyl-terminated branched polysiloxane was obtained. Among them, the dosage ratio of tetraethoxysilane, 1,4-butanediol, and p-toluenesulfonic acid was 23 g: 36 g: 100 mg.

[0038] Example 3

[0039] Preparation of the substrate:

[0040] Step 1. Pretreatment of waste printed circuit boards: Extract the fiberglass cloth from the waste printed circuit boards, then crush the circuit boards and extract the metal, and dry the remaining circuit board powder. The drying conditions were 100 °C and vacuum drying until the water content was less than 3%. The obtained fiberglass cloth and dried circuit board powder were used as raw materials;

[0041] Step 2. After mixing 20 parts of the modified cashew phenol prepared in Example 1, 15 parts of polyoxypropylene glycol, 8 parts of the hydroxyl-terminated branched polysiloxane prepared in Example 2, and 8 parts of molecular sieve, dehydration was carried out under vacuum at a temperature of 110 °C until the water content was less than 1000 ppm to obtain Component A; 70 parts of isophorone diisocyanate, 8 parts of polytetrahydrofuran ether glycol, 10 parts of polycarbonate diol, and 2 parts of 1,2-ethylene glycol were mixed and stirred and reacted at a temperature of 85 °C, and the content of NCO% was controlled to be 15% to obtain Component B; Component A and Component B were mixed according to a mass ratio of 3:1 to obtain an adhesive; the fiberglass cloth was subjected to hot melt drawing to form a fiber mesh, and the mesh holes of the fiber mesh were 2 - 6 cm; the circuit board powder and the adhesive were mixed and then laid in layers with the fiber mesh. After pre-pressing, hot pressing was carried out to form the substrate. The mass ratio of the circuit board powder to the adhesive was 8:100. The hot pressing temperature was 70 °C, the pressing time was 2.5 min / mm of plate thickness, and the surface pressure was 35 Kg / cm 2 .

[0042] Example 4

[0043] Preparation of substrate:

[0044] Step 1. Pretreatment of waste printed circuit boards: Extract the fiberglass cloth from the waste printed circuit boards, then crush the printed circuit boards to extract metals and dry the remaining printed circuit board powder. The drying conditions are 100°C and vacuum drying until the water content is less than 3%. Use the extracted fiberglass cloth and the dried printed circuit board powder as raw materials;

[0045] Step 2. Mix 22 parts of the modified cashew phenol prepared in Example 1, 18 parts of polypropylene glycol, 10 parts of the hydroxyl-terminated branched polysiloxane prepared in Example 2, and 10 parts of molecular sieve, and dehydrate under vacuum conditions at a temperature of 120°C until the water content is less than 1000 ppm to obtain Component A; Mix 80 parts of isophorone diisocyanate, 10 parts of polytetrahydrofuran ether glycol, 30 parts of polycarbonate diol, and 3 parts of 1,2-ethylene glycol, and stir and react at a temperature of 85°C, controlling the content of NCO% to be 18% to obtain Component B; Mix Component A and Component B according to a mass ratio of 3:1 to obtain an adhesive; Melt and draw the fiberglass cloth to make a fiber mesh, and the mesh holes of the fiber mesh are 2-6 cm; Mix the printed circuit board powder and the adhesive and lay them in layers with the fiber mesh. After pre-pressing, then hot-press to form a substrate. The mass ratio of the printed circuit board powder to the adhesive is 9:100. The hot-pressing temperature is 80°C, the pressing time is 3 min / mm of board thickness, and the surface pressure is 40 Kg / cm 2 .

[0046] Example 5

[0047] Preparation of substrate:

[0048] Step 1. Pretreatment of waste printed circuit boards: Extract the fiberglass cloth from the waste printed circuit boards, then crush the printed circuit boards to extract metals and dry the remaining printed circuit board powder. The drying conditions are 100°C and vacuum drying until the water content is less than 3%. Use the extracted fiberglass cloth and the dried printed circuit board powder as raw materials;

[0049] Step 2: Mix 22 parts of the modified cashew phenol prepared in Example 1, 18 parts of polyoxypropylene glycol, 10 parts of the hydroxyl-terminated branched polysiloxane prepared in Example 2, and 10 parts of molecular sieve, and dehydrate under vacuum at 120°C until the moisture content is less than 1000 ppm to obtain Component A; mix 80 parts of isophorone diisocyanate, 10 parts of polytetrahydrofuran ether glycol, 30 parts of polycarbonate diol, and 3 parts of 1,2-ethylene glycol, and stir and react at 90°C, controlling the NCO% content to be 20% to obtain Component B; mix Component A and Component B according to a mass ratio of 3:1 to obtain an adhesive; perform hot melt drawing on the fiberglass cloth to make a fiber mesh, and the mesh holes of the fiber mesh are 2 - 6 cm; mix the circuit board powder and the adhesive and then lay them in layers with the fiber mesh. After pre-pressing, perform hot pressing to form a substrate. The mass ratio of the circuit board powder to the adhesive is 9:100. The hot pressing temperature is 80°C, the pressing time is 4 min / mm of board thickness, and the surface pressure is 40 Kg / cm 2 。

[0050] Comparative Example 1:

[0051] Compared with Example 5, the hydroxyl-terminated branched polysiloxane is replaced with polyether polyol as polytetrahydrofuran ether glycol, and the other raw materials and preparation processes are the same as those in Example 5.

[0052] Perform performance tests on Examples 3 - 5 and Comparative Examples 1 - 2. Water absorption expansion rate: ① The specimen length is 150 ± 1 mm, the width is 50 ± 1 mm, 2 pieces, one along the length direction and the other along the width direction. ② At 6 points along the edge of the specimen and measure the thickness: ③ Immerse the specimen in water treatment for 24 ± 15 = min (pH value 7 ± 1, temperature 20 ± 1°C);

[0053] High temperature and high humidity means boiling in water at 95°C for 2 h;

[0054] Surface abrasion resistance: ① The specimen length is 100 ± 0.5 mm, the width is 100 ± 0.5 mm, 3 pieces. Divide along the diagonal into four quadrants: ② The sandpaper grain width is P180, the load is 4.9 ± 0.1 N, and the sandpaper is changed every 500 rotations until obvious breakage points appear in three quadrants of the specimen, and record the total number of rotations:

[0055] The results are shown in Table 1:

[0056]

[0057] As can be seen from Table 1, the substrate in the waterproof wall and floor base material prepared by the present invention has good high temperature and high humidity resistance, waterproof and moisture-proof properties, and good wear resistance, and can meet more requirements.

[0058] It should be noted that in this document, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "comprising", "including" or any other variant thereof are intended to cover non-exclusive inclusion, such that a process, method, article or device comprising a series of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article or device.

[0059] Although the embodiments of the present invention have been shown and described, those of ordinary skill in the art can understand that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A substrate for a waterproof wall and floor, comprising a base plate and a melamine decorative paper, and the base plate and the melamine decorative paper are bonded by an adhesive; characterized in that, The substrate is prepared through the following steps: Step 1. Pretreatment of waste printed circuit boards: Using the extracted fiberglass cloth and dried printed circuit board powder as raw materials; Step 2. Under nitrogen protection and at a temperature of 20 °C, mix tetraethoxysilane, 1,4-butanediol, and p-toluenesulfonic acid, heat up for reaction, start heat preservation when the reaction temperature reaches 160 °C, and stop heating until the distillation temperature drops to 55 °C to obtain hydroxyl-terminated branched polysiloxane; After mixing modified cashew phenol, polyether polyol, hydroxyl-terminated branched polysiloxane, and molecular sieve, dehydrate under vacuum at a temperature of 110 - 120 °C until the water content is less than 1000 ppm to obtain Component A; Mix isocyanate, polyether polyol, polyester polyol, and chain extender, stir and react at a temperature of 85 - 90 °C, and control the content of NCO% to be 15 - 20% to obtain Component B; Mix Component A and Component B to obtain an adhesive; Carry out hot melt drawing on the fiberglass cloth to make a fiber mesh; Mix the printed circuit board powder and the adhesive and then lay them in layers with the fiber mesh, after pre-pressing, and then hot press into shape to obtain the substrate; The modified cashew phenol is prepared through the following steps: Under nitrogen protection, add 6,6,6-trifluoro-1-iodohexane, sodium bicarbonate, cashew phenol, and sodium dithionite to acetonitrile, heat under reflux for 3 h to obtain an intermediate product; Add the intermediate product, mercaptoethanol, and photoinitiator α-hydroxyisobutyrophenone to ethyl acetate, and stir and react under ultraviolet light irradiation for 10 h to obtain modified cashew phenol.

2. The base material for a waterproof wall and floor according to claim 1, characterized in that, In Step 2, the mass ratio of Component A to Component B is 3:1; the mass ratio of the printed circuit board powder to the adhesive is 8 - 9:

100.

3. The base material for a waterproof wall and floor according to claim 1, characterized in that The isocyanate is one of toluene diisocyanate and isophorone diisocyanate; the polyether polyol is one of polytetrahydrofuran ether diol and polypropylene glycol; the polyester polyol is polycarbonate diol; the chain extender is 1,2-ethylene glycol.

4. The base material for a waterproof wall and floor according to claim 1, characterized in that, The mesh holes of the fiber mesh in the substrate are 2 - 6 cm.

5. The base material for a waterproof wall and floor according to claim 1, characterized in that, The hot pressing temperature is 70 - 80 °C, the pressing time is 2.5 - 4 min / mm of board thickness, and the surface pressure is 35 - 40 Kg / cm 2 .

6. The base material for a waterproof wall and floor according to claim 1, characterized in that, By weight, Component A contains 20 - 22 parts of modified cashew phenol, 15 - 18 parts of polyether polyol, 8 - 10 parts of hydroxyl-terminated branched polysiloxane, and 8 - 10 parts of molecular sieve; Component B contains 70 - 80 parts of isocyanate, 8 - 10 parts of polyether polyol, 10 - 30 parts of polyester polyol, and 2 - 3 parts of chain extender.

7. The preparation method of a base material for a waterproof wall and floor according to claim 1, characterized in that, It includes the following steps: The first step is to prepare the substrate; The second step is to coat an adhesive on the surface of the substrate, then laminate melamine decorative paper, and place it at a temperature of 20 °C for 3 days to obtain a base material for waterproof wall and floor.

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