CN106905656A - A kind of wab board modified phenolic foam composite and preparation method thereof - Google Patents

Abstract

A modified phenolic foam composite material for an abdominal muscle board and a preparation method thereof. The composite material is formed by impregnating a paper honeycomb in a phenolic resin matrix, mixed with a toughened modified material, and then molded and cured; the toughened modified material The raw material composition is: 30-45 parts of phenolic resin matrix, 12-18 parts of modified polyurethane prepolymer, 7-10 parts of polymethylsiloxane, 8-13 parts of reinforcing agent, 4-6 parts of composite fiber, hair 3-6 parts of a foaming agent, 6-8 parts of a surfactant, 6-10 parts of a curing agent and 1-3 parts of an antioxidant, and an admixture whose weight accounts for 6-8% of the total weight of the raw materials of the toughened modified material. The modified phenolic foam composite material for the abdominal muscle board prepared by the invention can prevent the brittle fracture and pulverization of the material, and can eliminate the static electricity on the surface of the material, so that the worthy abdominal muscle board is more humanized.

Description

Modified phenolic foam composite material for abdominal muscle board and preparation method thereof

technical field

The invention relates to the technical field of sports equipment, in particular to a modified phenolic foam composite material for an abdominal muscle board and a preparation method thereof.

Background technique

The abdominal muscle board is a supine board, which is a sports equipment for fitness, abdominal thinning, sit-ups, back retraction, supine leg raising and other training functions. The material of the existing abdominal muscle board is generally steel, because of its cross comfort, it is necessary to wrap plastic on the outside. Phenolic foam has the characteristics of low density, light weight, low thermal conductivity, large temperature range, and good dimensional stability. Compared with polyvinyl chloride foam, polyethylene foam, and polyurethane foam, phenolic foam has excellent toughness. Combustible, self-extinguishing, low smoke, and resistant to flame penetration. Therefore, in recent years, phenolic foam has been widely used in fields such as ships, aviation equipment, and sports equipment.

However, due to the tight stacking of rigid aromatic rings linked by methylene groups in the molecular structure, phenolic hydroxyl groups and methylene groups are easily oxidized, which makes phenolic foam plastics have poor oxidation resistance and poor mechanical properties, especially brittleness and easy pulverization. , this defect greatly limits its application, especially the application on outdoor sports equipment. In the field of sports equipment, in order to make phenolic foam plastics wear-resistant, cushioning, shockproof, etc., and meet the strength requirements, it must be reinforced and toughened, and at the same time, it must also meet the advantages of light weight, flame retardancy, and low cost.

Contents of the invention

The purpose of the present invention is to provide a modified phenolic foam composite material for an abdominal muscle board and a preparation method thereof, so that the modified phenolic foam can be applied to outdoor sports equipment.

The technical solution adopted by the present invention to achieve the above object is: a modified phenolic foam composite material for abdominal muscle board, which is formed by impregnating paper honeycomb in phenolic resin matrix, mixing with toughening modified material, molding and curing. In parts by weight, the raw materials of the toughened modified material consist of: 30-45 parts of phenolic resin matrix, 12-18 parts of modified polyurethane prepolymer, 7-10 parts of polymethylsiloxane, reinforcing agent 8-13 parts, 4-6 parts of composite fiber, 3-6 parts of foaming agent, 6-8 parts of surfactant, 6-10 parts of curing agent and 1-3 parts of antioxidant, and also add a weight accounted for toughening modification The admixture of 6-8% of the total weight of the raw material raw materials; wherein, the reinforcing agent consists of alumina micropowder, muscovite powder, sodium carboxymethylcellulose and modified sepiolite wool, in order according to the weight ratio of 4-5: The ratio of 8-9:2-3:1-1.2 is mixed; the composite fiber is composed of carbon nanofiber, polyacrylonitrile fiber and diethylene glycol dibenzoate, and the weight ratio is 1-2:2- 3: Mixed in a ratio of 8-10.

Among them, the surfactant is composed of Tween-80 and water-soluble silicone oil with a weight ratio of 1:2.

Among them, the blowing agent is composed of n-pentane and n-hexane with a weight ratio of 2:1.

Among them, the curing agent is composed of p-toluenesulfonic acid, phosphoric acid, boric acid and water in a weight ratio of 2:1:1:2.

The method for preparing a modified phenolic foam composite material for an abdominal muscle plate as described above comprises the following steps:

Step 1. Select the uncured paper honeycomb of the target size according to the needs, soak it in the phenolic resin matrix for 3 hours, then take out the paper honeycomb, spread it on the flat foam mold, fix it and put it in an oven at 140°C Heating in medium temperature for 1.5h, finally take out the paper honeycomb, cool to room temperature, and set aside;

Step 2. According to the above weight parts, first preheat the phenolic resin matrix to 40°C in a water bath, then add the modified polyurethane prepolymer, and stir at a speed of 450-500r/min for 20-30min; then sequentially Add reinforcing agent, composite fiber and polymethyl siloxane, stir at 550-600r/min for 20-30min; then add surfactant, foaming agent, antioxidant and admixture in turn, at 550-600r/min Stir at a speed of 15-20min; then add a curing agent, stir at a speed of 650-700r/min for 5-10min to prepare a mixed solution, pour the mixed solution into a mold coated with a release agent and preheated to 40°C Press the paper honeycomb prepared in step 1 into the mold, close the mold, and move the mold to an oven at 75°C to solidify for 2 hours, and finally cool to room temperature and demould to obtain the modified phenolic foam composite material.

Further, the preparation method of modified polyurethane prepolymer is:

(1) In the silica sol, add silicon micropowder accounting for 2-3% of the weight of the silica sol, potassium hexatitanate whiskers of 1-2% of the weight of the silica sol, and sodium acetate of 0.8-1% of the weight of the silica sol, and then add Stir at 70-80°C for 1-2h to prepare the modified silica sol for later use;

(2) Add surface modifier I accounting for 3-5% by weight of nano-titanium dioxide to nano-titanium dioxide, stir to obtain modified nano-titanium dioxide, and set aside; wherein, surface modifier I consists of barium hydroxide, sodium carbonate and KH570 , followed by mixing according to the weight ratio of 3-4:1-2:30;

(3) Take the MDI type polyurethane prepolymer, add modified filler and mix and stir to obtain the modified polyurethane prepolymer; wherein, the weight ratio of the modified filler to the MDI type polyurethane prepolymer is 7:6; the modified filler Di-n-octyl phthalate, acetone, the modified silica sol prepared in step (1) and the modified nano-titanium dioxide prepared in step (2), in sequence according to the weight ratio of 2:3:1:1 mixed.

Further, the preparation method of the reinforcing agent is:

(1) After mixing sepiolite wool with surface modifier II accounting for 3-5% of its weight, let it stand for 1-2 hours, filter and dry to obtain modified sepiolite wool; among them, the surface modifier II is made by mixing KH550, ethanol, acetone and barium hydroxide in sequence according to the weight ratio of 3-4:80:2-3:1-2;

(2), according to the weight ratio of 4-5:8-9:2-3:1-1.2, take alumina micropowder, muscovite powder, carboxymethyl cellulose sodium and the modified Mix the non-toxic sepiolite wool evenly to prepare the reinforcing agent.

Further, the preparation method of the admixture is as follows: according to the weight ratio, mix ethyl orthosilicate and deionized water according to the ratio of 1:8-10, and then add 1-2 parts of sepiolite wool, and Glacial acetic acid with 10% by weight of ethyl silicate and conductive carbon black accounting for 5% by weight of ethyl orthosilicate were mixed evenly for reaction. During the reaction, ultrasonic waves with a frequency of 250-270kHz were applied to the reaction system for 1min every 20min. After the reaction is finished, the reaction system is subjected to ultrafiltration to obtain a solid powder, and finally the solid powder is fully burned under aerobic conditions to remove the carbon powder, and the admixture is obtained.

In the present invention, the paper honeycomb adopts nomex paper honeycomb with a thickness of 0.5-0.1 mm, a cell side length of 1.8-4.5 mm, and a nominal bulk density of 30-48 kg/m ³ .

In the present invention, preferably, the conductive carbon black has a specific surface area of 700-850m ² /g, an average particle diameter of 20nm, and a resistance of less than 0.6 Ω·m; carbon nanofibers have an average diameter of 15-100 nm and a length of 20-50 nm. μm, the specific surface area is 15-20 m ² /g; the antioxidant is phosphite antioxidant.

In the present invention, the MDI type polyurethane prepolymer is modified, and the modified polyurethane prepolymer reacts with the methylol group in the phenolic resin matrix, which shows that the introduction of a small amount of polyurethane prepolymer can play a good role in toughening ; During the reaction process, the isocyanate group in the modified polyurethane prepolymer cross-links with the methylol group in the phenolic resin to form an interpenetrating network structure, which improves the strength and toughness of the foamed plastic, thereby reducing brittleness and is not easy At the same time, the surface of nano-titanium dioxide particles contains a certain amount of oxygen-containing functional groups, which is convenient for chemical bonding or physical bonding between titanium dioxide and other substances at high temperatures. Under the impact of external forces, nano-titanium dioxide particles can absorb more deformation energy. , and produce a "pinning-climbing" effect, which increases the resistance of the crack when it expands, thereby increasing its toughness.

In the present invention, the reinforcing agent contains modified sepiolite wool and nano-alumina micropowder, and these two materials can be uniformly dispersed in the plastic when kneading with the assistance of sodium carboxymethyl cellulose. On the one hand, the modified sepiolite The pumice wool has a large internal surface area, and its microporous structure can effectively reduce and absorb the external force; The group connects the modified sepiolite wool and the matrix through a chemical reaction to ensure that the two have good interfacial bonding.

In the present invention, polymethylsiloxane can improve the toughness of foamed plastics to a certain extent, and at the same time improve the compatibility of reinforcing agent, composite fiber and phenolic resin matrix; , so as to prevent the brittle fracture and pulverization of the material, and the diethylene glycol dibenzoate contained in the composite fiber can further enhance the plasticity and toughness of the material, and can make the fiber and the matrix material tightly combined.

The invention adopts the combination of inorganic acid and organic acid, which not only ensures the efficiency, but also can better control the whole foaming process. In addition, conductive carbon black and carbon nanofibers also contribute to the mechanical properties of phenolic foam materials. More importantly, the two form a three-dimensional conductive network structure in phenolic foam materials, making phenolic foam plastics have certain conductivity. Eliminate static electricity on the surface of the material, making the worthy abs board more humane.

detailed description

The present invention will be further described below in conjunction with specific examples, so that those skilled in the art can better understand the present invention and implement it, but the given examples are not intended to limit the present invention.

A modified phenolic foam composite material for an abdominal muscle board, which is formed by impregnating a paper honeycomb in a phenolic resin matrix, mixing with a toughening modified material, and then compression molding and curing. In parts by weight, the toughened modified material The raw material composition is: 30-45 parts of phenolic resin matrix, 12-18 parts of modified polyurethane prepolymer, 7-10 parts of polymethylsiloxane, 8-13 parts of reinforcing agent, 4-6 parts of composite fiber, hair 3-6 parts of foaming agent, 6-8 parts of surfactant, 6-10 parts of curing agent and 1-3 parts of antioxidant, and an admixture whose weight accounts for 6-8% of the total weight of the toughened modified material raw materials is added; Wherein, the reinforcing agent is composed of alumina micropowder, muscovite powder, sodium carboxymethyl cellulose and modified sepiolite wool, in sequence according to the weight ratio of 4-5:8-9:2-3:1-1.2 It is formed by mixing; the composite fiber is formed by mixing carbon nanofibers, polyacrylonitrile fibers and diethylene glycol dibenzoate in a weight ratio of 1-2:2-3:8-10 in sequence.

Example 1

A kind of preparation method of modified phenolic foam composite material for abdominal muscle plate, comprises the following steps:

Step 1. Into the silica sol, add silicon micropowder accounting for 3% of the weight of the silica sol, potassium hexatitanate whiskers of 1% of the weight of the silica sol, and sodium acetate of 0.9% of the weight of the silica sol, and then stir at 80°C for 1 hour. Modified silica sol is prepared for subsequent use;

Step 2, adding surface modifier I accounting for 5% by weight of nano-titanium dioxide to nano-titanium dioxide, stirring to obtain modified nano-titanium dioxide, for subsequent use; wherein, surface-modifying agent I consists of barium hydroxide, sodium carbonate and KH570, followed by It is mixed with a weight ratio of 4:1:30;

Step 3: Take the MDI type polyurethane prepolymer, add modified filler and mix and stir to obtain the modified polyurethane prepolymer; wherein, the weight ratio of the modified filler to the MDI type polyurethane prepolymer is 7:6; the modified filler is made of Di-n-octyl phthalate, acetone, the modified silica sol prepared in step 1 and the modified nano-titanium dioxide prepared in step 2 are mixed successively according to the ratio of 2:3:1:1 by weight;

Step 4, mix the sepiolite wool with surface modifier II accounting for 3-5% of its weight, let it stand for 1-2h, filter and dry to obtain modified sepiolite wool; wherein, surface modifier II It is made by mixing KH550, ethanol, acetone and barium hydroxide in sequence according to the weight ratio of 4:80:2:1;

Step 5. According to the weight ratio of 5:8:3:1, take alumina micropowder, muscovite powder, sodium carboxymethyl cellulose and the modified sepiolite wool prepared in step 4 and mix them evenly to obtain reinforced agent;

Step 6: According to the weight ratio, mix ethyl orthosilicate with deionized water in a ratio of 1:8, and then add 2 parts of sepiolite wool, glacial acetic acid accounting for 10% by weight of ethyl orthosilicate and Conductive carbon black accounting for 5% of the weight of tetraethyl orthosilicate was mixed evenly for reaction. During the reaction, an ultrasonic wave with a frequency of 260 kHz was applied to the reaction system for 1 minute every 20 minutes. After the reaction was completed, the reaction system was ultra-filtered to obtain a solid powder. Finally, the solid powder is fully burned to remove the carbon powder under aerobic conditions, and the admixture is obtained, which is set aside;

Step 7. Select the uncured paper honeycomb of the target size according to the needs, soak it in the phenolic resin matrix for 3 hours, then take out the paper honeycomb, spread it on the flat foam mold, fix it and put it in an oven at 140°C Heating in medium temperature for 1.5h, finally take out the paper honeycomb, cool to room temperature, and set aside;

Step 8, in parts by weight, get 45 parts of phenolic resin substrates, 15 parts of modified polyurethane prepolymers made in step 3, 7 parts of polymethylsiloxane, 8 parts of reinforcing agents made in step 5, compound 4 parts of fiber, 5 parts of foaming agent, 6 parts of surfactant, 8 parts of curing agent, 2 parts of antioxidant and 7 parts of admixture that step 6 makes, standby; Wherein, composite fiber is made of carbon nanofiber, polyacrylonitrile Fiber and diethylene glycol dibenzoate are mixed sequentially in a weight ratio of 1:1:4; the surfactant is composed of Tween-80 and water-soluble silicone oil in a weight ratio of 1:2; foaming agent It is composed of n-pentane and n-hexane with a weight ratio of 2:1; the curing agent is composed of p-toluenesulfonic acid, phosphoric acid, boric acid and water with a weight ratio of 2:1:1:2;

First, preheat the phenolic resin matrix to 40°C in a water bath, then add the modified polyurethane prepolymer, and stir at a speed of 450r/min for 20min; then add the reinforcing agent, composite fiber and polymethylsiloxane in sequence, Stir at a speed of 550r/min for 20min; then add surfactant, foaming agent, antioxidant and admixture in turn, and stir for 15min at a speed of 550r/min; then add a curing agent and stir at a speed of 650r/min Prepare the mixed solution after 5 minutes, pour the mixed solution into a mold coated with a release agent and preheated to 40°C, press into the paper honeycomb prepared in step 7, close the mold, and move the mold to an oven at 75°C After curing for 2 hours, it was finally cooled to room temperature and demolded to obtain a modified phenolic foam composite material.

Example 2

A kind of preparation method of modified phenolic foam composite material for abdominal muscle plate, comprises the following steps:

Step 1. Adding silicon micropowder accounting for 2% of the weight of the silica sol, potassium hexatitanate whiskers of 2% of the weight of the silica sol, and sodium acetate of 1% of the weight of the silica sol to the silica sol, and then stirring at 70°C for 1 hour. Modified silica sol is prepared for subsequent use;

Step 2, adding surface modifier I accounting for 3% of the weight of nano titanium dioxide to nano titanium dioxide, stirring to obtain modified nano titanium dioxide, for subsequent use; wherein, surface modifier I consists of barium hydroxide, sodium carbonate and KH570, followed by It is mixed with a weight ratio of 3:1:30;

Step 3: Take the MDI type polyurethane prepolymer, add modified filler and mix and stir to obtain the modified polyurethane prepolymer; wherein, the weight ratio of the modified filler to the MDI type polyurethane prepolymer is 7:6; the modified filler is made of Di-n-octyl phthalate, acetone, the modified silica sol prepared in step 1 and the modified nano-titanium dioxide prepared in step 2 are mixed successively according to the ratio of 2:3:1:1 by weight;

Step 4, mix the sepiolite wool with surface modifier II accounting for 3-5% of its weight, let it stand for 1-2h, filter and dry to obtain modified sepiolite wool; wherein, surface modifier II It is made by mixing KH550, ethanol, acetone and barium hydroxide in sequence according to the weight ratio of 3:80:3:2;

Step 5. According to the weight ratio of 4:9:2:1.2, take alumina micropowder, muscovite powder, sodium carboxymethyl cellulose and the modified sepiolite wool prepared in step 4 and mix them evenly to obtain reinforced agent;

Step 6: According to the weight ratio, mix ethyl orthosilicate with deionized water at a ratio of 1:10, and then add 1 part of sepiolite wool, glacial acetic acid accounting for 10% by weight of ethyl orthosilicate and Conductive carbon black accounting for 5% of the weight of tetraethyl orthosilicate was mixed evenly for reaction. During the reaction, an ultrasonic wave with a frequency of 270 kHz was applied to the reaction system for 1 minute every 20 minutes. After the reaction was completed, the reaction system was ultra-filtered to obtain a solid powder. Finally, the solid powder is fully burned to remove the carbon powder under aerobic conditions, and the admixture is obtained, which is set aside;

Step 7. Select the uncured paper honeycomb of the target size according to the needs, soak it in the phenolic resin matrix for 3 hours, then take out the paper honeycomb, spread it on the flat foam mold, fix it and put it in an oven at 140°C Heating in medium temperature for 1.5h, finally take out the paper honeycomb, cool to room temperature, and set aside;

Step 8, in parts by weight, get 30 parts of phenolic resin substrates, 18 parts of modified polyurethane prepolymers made in step 3, 8 parts of polymethylsiloxane, 13 parts of reinforcing agents made in step 5, compound 5 parts of fiber, 3 parts of foaming agent, 8 parts of surfactant, 6 parts of curing agent, 1 part of antioxidant and 5.52 parts of admixture that step 6 makes, standby; Wherein, composite fiber is made of carbon nanofiber, polyacrylonitrile Fiber and diethylene glycol dibenzoate are mixed sequentially at a weight ratio of 1:3:10; the surfactant is composed of Tween-80 and water-soluble silicone oil at a weight ratio of 1:2; foaming agent It is composed of n-pentane and n-hexane with a weight ratio of 2:1; the curing agent is composed of p-toluenesulfonic acid, phosphoric acid, boric acid and water with a weight ratio of 2:1:1:2;

First, preheat the phenolic resin matrix to 40°C in a water bath, then add the modified polyurethane prepolymer, and stir at a speed of 500r/min for 25min; then add the reinforcing agent, composite fiber and polymethylsiloxane in sequence, Stir at a speed of 600r/min for 25min; then add surfactant, foaming agent, antioxidant and admixture in turn, and stir for 18min at a speed of 600r/min; then add a curing agent and stir at a speed of 700r/min Prepare the mixed solution after 6 minutes, pour the mixed solution into a mold coated with a release agent and preheated to 40°C, press into the paper honeycomb prepared in step 7, close the mold, and move the mold to an oven at 75°C After curing for 2 hours, it was finally cooled to room temperature and demolded to obtain a modified phenolic foam composite material.

Example 3

A kind of preparation method of modified phenolic foam composite material for abdominal muscle plate, comprises the following steps:

Step 1. Add 2.5% of silica sol weight silica micropowder, 1.5% silica sol weight potassium hexatitanate whiskers and 0.8% silica sol weight sodium acetate in succession, then stir at 75°C for 2 hours, Modified silica sol is prepared for subsequent use;

Step 2, adding surface modifier I accounting for 3-5% of the weight of nano titanium dioxide to the nano titanium dioxide, stirring to obtain modified nano titanium dioxide, for subsequent use; wherein, the surface modifier I consists of barium hydroxide, sodium carbonate and KH570, Mixed in turn according to the weight ratio of 3:2:30;

Step 3: Take the MDI type polyurethane prepolymer, add modified filler and mix and stir to obtain the modified polyurethane prepolymer; wherein, the weight ratio of the modified filler to the MDI type polyurethane prepolymer is 7:6; the modified filler is made of Di-n-octyl phthalate, acetone, the modified silica sol prepared in step 1 and the modified nano-titanium dioxide prepared in step 2 are mixed successively according to the ratio of 2:3:1:1 by weight;

Step 4, mix the sepiolite wool with surface modifier II accounting for 3-5% of its weight, let it stand for 1-2h, filter and dry to obtain modified sepiolite wool; wherein, surface modifier II It is made by mixing KH550, ethanol, acetone and barium hydroxide in sequence according to the weight ratio of 3:80:2:1;

Step 5. According to the weight ratio of 4.5:8.5:2:1, take alumina micropowder, muscovite powder, sodium carboxymethyl cellulose and the modified sepiolite wool prepared in step 4 and mix evenly to obtain reinforced agent;

Step 6: According to the weight ratio, mix ethyl orthosilicate with deionized water in a ratio of 1:9, and then add 1.5 parts of sepiolite wool, glacial acetic acid accounting for 10% by weight of ethyl orthosilicate and Conductive carbon black accounting for 5% of the weight of tetraethyl orthosilicate was mixed evenly for reaction. During the reaction, an ultrasonic wave with a frequency of 250 kHz was applied to the reaction system for 1 minute every 20 minutes. After the reaction was completed, the reaction system was ultra-filtered to obtain a solid powder. Finally, the solid powder is fully burned to remove the carbon powder under aerobic conditions, and the admixture is obtained, which is set aside;

Step 7. Select the uncured paper honeycomb of the target size according to the needs, soak it in the phenolic resin matrix for 3 hours, then take out the paper honeycomb, spread it on the flat foam mold, fix it and put it in an oven at 140°C Heating in medium temperature for 1.5h, finally take out the paper honeycomb, cool to room temperature, and set aside;

Step 8, in parts by weight, take 40 parts of phenolic resin matrix, 12 parts of modified polyurethane prepolymers made in step 3, 10 parts of polymethylsiloxane, 10 parts of reinforcing agent made in step 5, compound 6 parts of fiber, 6 parts of foaming agent, 7 parts of surfactant, 10 parts of curing agent, 3 parts of antioxidant and 8.32 parts of admixture that step 6 makes, standby; Wherein, composite fiber is made of carbon nanofiber, polyacrylonitrile Fiber and diethylene glycol dibenzoate are mixed sequentially at a weight ratio of 1:3:9; the surfactant is composed of Tween-80 and water-soluble silicone oil at a weight ratio of 1:2; foaming agent It is composed of n-pentane and n-hexane with a weight ratio of 2:1; the curing agent is composed of p-toluenesulfonic acid, phosphoric acid, boric acid and water with a weight ratio of 2:1:1:2;

First, preheat the phenolic resin matrix to 40°C in a water bath, then add the modified polyurethane prepolymer, and stir at a speed of 480r/min for 30min; then add the reinforcing agent, composite fiber and polymethylsiloxane in sequence, Stir at a speed of 580r/min for 30min; then add surfactant, foaming agent, antioxidant and admixture in turn, and stir for 20min at a speed of 580r/min; then add a curing agent and stir at a speed of 680r/min Prepare the mixed solution after 10 minutes, pour the mixed solution into a mold coated with a release agent and preheated to 40°C, press into the paper honeycomb prepared in step 7, close the mold, and move the mold to an oven at 75°C After curing for 2 hours, it was finally cooled to room temperature and demolded to obtain a modified phenolic foam composite material.

Example 4: In parts by weight, take 42 parts of phenolic resin matrix, 14 parts of modified polyurethane prepolymer, 9 parts of polymethylsiloxane, 12 parts of reinforcing agent, 5.5 parts of composite fiber, and 4 parts of foaming agent , 6.5 parts of surfactant, 7 parts of curing agent, 2.5 parts of antioxidant and 7.7 parts of admixture, these raw materials are mixed according to the operation step of step 8 in the embodiment, and carry out compression molding with paper honeycomb, obtain modified phenolic foam composite.

The phenolic foam composite material that above-mentioned four embodiments make is carried out performance test, and test result is as shown in the table below:

The curing agent plays an important role in the control of cell size, structure and porosity in foamed plastics. When the phenolic resin uses an inorganic acid as a catalyst, it promotes the polycondensation reaction between the resin molecules, thereby expanding the emulsified resin and accelerating foaming and curing, but the viscosity of the resin increases rapidly, and the foaming process is difficult to control, and the resulting phenolic foam The residual acid in the body is highly corrosive; organic acid is used as a curing agent, although it is easier to control and non-corrosive, but its foaming speed is slow, which affects production efficiency. The present invention adopts the method of combining inorganic acid and organic acid for curing, which not only ensures the efficiency, but also can better control the whole foaming process.

The present invention adopts acetone to treat the MDI type polyurethane prepolymer, the reacted prepolymer reacts with the methylol group in the phenolic resin, and then the excess MDI reacts with the methylol group in the phenolic resin, showing the introduction of a small amount of polyurethane prepolymerization The body can play a good role in toughening. During the reaction process, the isocyanate groups in the modified polyurethane prepolymer cross-link with the methylol groups in the phenolic resin to form an interpenetrating network structure, and a large amount of flexible carbamic acid is introduced into the phenolic resin. The ester segment changes the rigid structure of the phenolic resin, increases the compressive strength and toughness of the phenolic foam, thereby reducing the brittleness and making it difficult to pulverize.

The Nomex paper honeycomb used in the present invention is first impregnated with a phenolic resin matrix to set the shape. In the subsequent molding process, the impregnated paper honeycomb can be effectively compounded with the resin matrix, so that the phenolic foam and the Nomex paper honeycomb can be used as an integral material to jointly resist The destruction of external force improves the overall mechanical properties of the material; moreover, the Nomex paper honeycomb acts as a skeleton for the overall foam material, further reducing the pulverization rate of the material; in addition, the modified phenolic foam has a honeycomb-like structure, which is similar to Similar to Nomex paper honeycomb, the material is characterized by small-pore honeycomb-like phenolic foam nested in large-pore Nomex paper honeycomb, which can improve the mechanical properties of the material to a certain extent.

The above is only a preferred embodiment of the present invention, it should be pointed out that for those of ordinary skill in the art, without departing from the method of the present invention, some improvements and supplements can also be made, and these improvements and supplements should also be considered Be the protection scope of the present invention.

Claims (9)

1. A modified phenolic foam composite material for the abdominal muscle board, which is formed by impregnating the paper honeycomb in the phenolic resin matrix, then mixing with the toughening modified material, and then molding and solidifying, characterized in that: by weight parts Calculated, the raw material composition of the toughened modified material is: 30-45 parts of phenolic resin matrix, 12-18 parts of modified polyurethane prepolymer, 7-10 parts of polymethylsiloxane, 8-13 parts of reinforcing agent, compound 4-6 parts of fiber, 3-6 parts of foaming agent, 6-8 parts of surfactant, 6-10 parts of curing agent and 1-3 parts of antioxidant. -8% admixture; Wherein, the reinforcing agent is composed of alumina micropowder, muscovite powder, sodium carboxymethyl cellulose and modified sepiolite wool, in sequence according to the weight ratio of 4-5:8-9:2-3:1-1.2 mixed; The composite fiber is formed by mixing carbon nanofibers, polyacrylonitrile fibers and diethylene glycol dibenzoate in a weight ratio of 1-2:2-3:8-10 in sequence. 2. A modified phenolic foam composite material for an abdominal muscle board as claimed in claim 1, wherein the surfactant is composed of Tween-80 and water-soluble silicone oil in a weight ratio of 1:2. 3. A modified phenolic foam composite material for an abdominal muscle board as claimed in claim 1, wherein the foaming agent is composed of n-pentane and n-hexane with a weight ratio of 2:1. 4. A kind of modified phenolic foam composite material for abdominal muscle board as claimed in claim 1, it is characterized in that: described curing agent is by weight ratio 2:1:1:2 p-toluenesulfonic acid, phosphoric acid, Composed of boric acid and water. 5. prepare the method for a kind of abdominal muscle plate with modified phenolic foam composite material as claimed in claim 1, it is characterized in that, comprise the following steps: Step 1. Select the uncured paper honeycomb of the target size according to the needs, soak it in the phenolic resin matrix for 3 hours, then take out the paper honeycomb, spread it on the flat foam mold, fix it and put it in an oven at 140°C Heating in medium temperature for 1.5h, finally take out the paper honeycomb, cool to room temperature, and set aside; Step 2. According to the parts by weight according to claim 1, first preheat the phenolic resin matrix to 40°C in a water bath, then add the modified polyurethane prepolymer, and stir at a speed of 450-500r/min for 20- 30min; then add reinforcing agent, composite fiber and polymethylsiloxane in turn, and stir at a speed of 550-600r/min for 20-30min; then add surfactant, foaming agent, antioxidant and admixture in turn, Stir at a speed of 550-600r/min for 15-20min; then add a curing agent, stir at a speed of 650-700r/min for 5-10min to prepare a mixed solution, pour the mixed solution into a mold release agent and preheat Press the paper honeycomb prepared in step 1 into a mold at 40°C, close the mold, move the mold to an oven at 75°C for 2 hours, and finally cool to room temperature to demould to obtain a modified phenolic foam composite material. 6. prepare a kind of method for abdominal muscle board with modified phenolic foam composite material as claimed in claim 5, it is characterized in that, the preparation method of modified polyurethane prepolymer is: (1) In the silica sol, add silicon micropowder accounting for 2-3% of the weight of the silica sol, potassium hexatitanate whiskers of 1-2% of the weight of the silica sol, and sodium acetate of 0.8-1% of the weight of the silica sol, and then add Stir at 70-80°C for 1-2h to prepare the modified silica sol for later use; (2) Add surface modifier I accounting for 3-5% by weight of nano-titanium dioxide to nano-titanium dioxide, stir to obtain modified nano-titanium dioxide, and set aside; wherein, surface modifier I consists of barium hydroxide, sodium carbonate and KH570 , followed by mixing according to the weight ratio of 3-4:1-2:30; (3) Take the MDI type polyurethane prepolymer, add modified filler and mix and stir to obtain the modified polyurethane prepolymer; wherein, the weight ratio of the modified filler to the MDI type polyurethane prepolymer is 7:6; the modified filler Di-n-octyl phthalate, acetone, the modified silica sol prepared in step (1) and the modified nano-titanium dioxide prepared in step (2), in sequence according to the weight ratio of 2:3:1:1 mixed. 7. prepare a kind of method for abdominal muscle board with modified phenolic foam composite material as claimed in claim 5, it is characterized in that, the preparation method of reinforcing agent is: (1) After mixing sepiolite wool with surface modifier II accounting for 3-5% of its weight, let it stand for 1-2 hours, filter and dry to obtain modified sepiolite wool; among them, the surface modifier II is made by mixing KH550, ethanol, acetone and barium hydroxide in sequence according to the weight ratio of 3-4:80:2-3:1-2; (2), according to the weight ratio of 4-5:8-9:2-3:1-1.2, take alumina micropowder, muscovite powder, carboxymethyl cellulose sodium and the modified Mix the non-toxic sepiolite wool evenly to prepare the reinforcing agent. 8. the method for preparing a kind of modified phenolic foam composite material for abdominal muscle board as claimed in claim 5, is characterized in that, the preparation method of admixture is: according to weight ratio, get tetraethyl orthosilicate and deionized water Mix according to the ratio of 1:8-10, then add 1-2 parts of sepiolite wool, glacial acetic acid accounting for 10% by weight of ethyl orthosilicate and conductive carbon black accounting for 5% by weight of ethyl orthosilicate Mix evenly for reaction. During the reaction, apply ultrasonic waves with a frequency of 250-270kHz to the reaction system for 1 minute every 20 minutes. After the reaction is completed, perform ultrafiltration on the reaction system to obtain solid powder. Burn off the carbon powder to obtain the admixture. 9. the method for preparing a kind of modified phenolic foam composite material for abdominal muscle board as claimed in claim 8, is characterized in that: paper honeycomb adopts the nomex paper honeycomb that thickness is 0.5-0.1mm, and cell side length is 1.8- 4.5mm, the nominal bulk density is 30-48kg/m ³ .