Cable fireproof organic silicon modified novel phenolic fiber reinforced plate as well as preparation method and application thereof

Abstract

The invention discloses a preparation method and application of an organic silicon modified novel phenolic resin fiber reinforced flame-retardant plate, and relates to the technical field of cable fireproof flame-retardant partition plates. Organic silicon oligomer and low-free-phenol hydroxymethylated phenolic resin are blended to prepare organic silicon modified novel phenolic resin, the resin is dissolved in a solvent to prepare steeping liquor, fiber cloth is steeped, and the fiber reinforced flame-retardant partition plate is prepared through a hot pressing process. The novel phenolic resin provided by the invention is low-free-phenol phenolic resin, and the prepared fiber-reinforced partition plate is a halogen-free flame-retardant plate and has excellent flame retardance and mechanical properties, so that the novel phenolic resin has a wide application prospect.

Description

Technical Field

[0001] This invention relates to the field of fire-resistant and flame-retardant cable separator technology, specifically to a novel organosilicon-modified phenolic resin fiber-reinforced flame-retardant board, its preparation method, and its application. Background Technology

[0002] Converter stations and substations lay a large number of cables in their cable trenches. The outer sheaths and insulation layers of these cables are made of polymer materials. Furthermore, the enclosed and narrow environment of these trenches makes them highly susceptible to fires caused by flammable materials. These fires are characterized by rapid temperature rise, high temperatures, and difficulty in fire protection. Currently, the flame-retardant properties and protection standards of fire-resistant partition materials used in converter stations (substations) do not meet the actual service conditions of the power grid, and therefore cannot effectively provide fire protection in the event of a fire, thus failing to protect economic facilities and personnel safety.

[0003] While currently available fire-resistant barrier panels possess strong fire resistance, such as gypsum board, mineral wool fireproof board, expanded perlite fireproof board, fiberglass fireproof board, calcium silicate fireproof board, and steel plate fireproof barrier panels, they suffer from drawbacks including fragility, moisture absorption, and poor durability. Some, like mineral wool fireproof board, contain hazardous substances or produce toxic substances at high temperatures. Furthermore, polyurethane flame-retardant fireproof boards have relatively low flame retardant ratings, making them unsuitable for fire-resistant barrier panel requirements. Even for ordinary phenolic flame-retardant boards, their flame retardant performance still needs improvement.

[0004] Chinese patent application CN115594938A discloses a high-efficiency flame-retardant board and its preparation method. By weight, it comprises the following components: reinforcing fiber cloth: 80-250 parts; boron phenolic resin: 60-95 parts; alcohol: 40-70 parts; magnesium hydroxide: 5-45 parts; ceramic filler: 5-15 parts; and silicate ester and catalyst. This patent, while ensuring an optimal degree of silicate hydrolysis of 20%-40%, precisely calculates the amount of silicate ester used based on the water content of the phenolic resin, the number-average molecular weight of the silicate ester, and the average degree of polymerization of the silicate ester, thereby rationally setting the ratio of silicate ester to phenolic resin. An acidic catalyst is then used to further catalyze the hydrolysis of the silicate ester. The reaction process is gradual and easy to control, and the resulting resin material combines strength and heat resistance. After uniform mixing with inorganic flame-retardant components, the mixture is impregnated with reinforcing fiber cloth and cured under pressure to obtain the high-efficiency flame-retardant board. The overall preparation process is simple, the raw material dosage is precisely controlled, and it is particularly suitable for large-scale industrial application. However, the flame retardant properties of this material are poor, and therefore, further improvement is needed. Summary of the Invention

[0005] The technical problem to be solved by this invention is to provide a method for preparing a novel organosilicon-modified phenolic fiber reinforced flame-retardant board, so as to solve the problem of insufficient flame-retardant performance of current fireproof partition materials for converter stations.

[0006] The present invention solves the above-mentioned technical problems through the following technical means:

[0007] The first aspect of this invention provides a method for preparing a novel fire-retardant cable fireproof silicone-modified phenolic fiber reinforced flame-retardant board, comprising the following steps:

[0008] (1) Mix organosilicon oligomer, novel phenolic resin and glacial acetic acid, and heat and reflux.

[0009] (2) Heat and distill the product obtained in (1) under reduced pressure, add ethanol and mix to obtain the impregnation solution;

[0010] (3) Impregnate the fiber cloth with the impregnation solution obtained in (2), then take out the fiber cloth, dry it, and obtain a semi-cured fiber cloth sheet;

[0011] (4) Press the semi-cured fiber cloth sheets together using a hot press to obtain the final product;

[0012] The structural formula of the organosilicon oligomer is as follows:

[0013] In the formula Connect the connector to CH3;

[0014] The structural formula of the novel phenolic resin is as follows:

[0015] n can be 10 to 20.

[0016] Preferably, in (1), the mass ratio of the organosilicon oligomer to the novel phenolic resin is (10-20):(80-90).

[0017] Preferably, in (1), glacial acetic acid is used as a catalyst, and its amount is 1 to 5% of the total mass of the organosilicon oligomer and the novel phenolic resin, and its concentration is 18 to 22% (v / v), more preferably 20% (v / v).

[0018] Preferably, in (1), the heating temperature is 80-95°C and the reflux time is 2-5 hours.

[0019] Preferably, in (2), the heating temperature is 80-95℃.

[0020] Preferably, in (2), 80-95% (v / v) ethanol is added to dilute the solution to obtain 55-65% (v / v) impregnation solution.

[0021] Preferably, in (3), the fiber cloth is selected from one or more of glass fiber cloth, carbon fiber cloth, acrylic cotton fiber fireproof cloth, basalt fiber cloth, and high silica fiber cloth.

[0022] Preferably, in (3), the drying process specifically involves air drying at room temperature for 10 to 14 hours, followed by drying in an oven at 150 to 200°C for 3 to 15 minutes.

[0023] Preferably, in (4), the hot pressing is specifically as follows: the fiber cloth semi-cured sheet is placed in a hot press preheated to 75-85°C, and the hot press is set to heat up to 160-185°C at a heating rate of 3-5°C / min, and cured at 160-185°C for 1-3 hours to obtain a novel organosilicon modified phenolic fiber reinforced flame retardant board.

[0024] Preferably, in (1), the organosilicon oligomer is prepared by the following process:

[0025] Step 1: Thoroughly mix methyltriethoxysilane and dimethyldiethoxysilane to obtain a mixture;

[0026] Step 2: Heat deionized water to 65-75℃ and then add it dropwise to the mixture;

[0027] Step 3: After the deionized water has been added, add a reflux condenser to raise the temperature to 80-85°C and keep the temperature constant for 4-10 hours.

[0028] Step 4: After the reaction is complete, distill under reduced pressure to obtain the product.

[0029] Preferably, in (1), the novel phenolic resin is prepared by the following process:

[0030] Step 1: Mix methoxydiphenyl ether resin (DETM), phenol, and p-toluenesulfonic acid solution, heat and stir, raise the temperature to 120-180℃, and reflux for 3-5 hours;

[0031] Step 2: Then distill under reduced pressure and cool to room temperature to obtain yellowish-brown blocky resin;

[0032] Step 3: Crush the yellowish-brown blocky resin into powder, dissolve it in ethanol to form a 50% resin dilute solution;

[0033] Step 4: Add ammonia water dropwise, heat and stir, adjust the pH of the reaction solution to 8-9, and stir at a constant temperature for 30-120 minutes;

[0034] Step 5: Add paraformaldehyde, heat to 80-85℃, and reflux for 1-4 hours to obtain a yellowish-brown transparent solution.

[0035] A second aspect of the present invention provides a novel fire-retardant cable fireproof silicone-modified phenolic fiber reinforced flame-retardant board prepared by the above-described method.

[0036] A third aspect of the present invention proposes the application of the above-mentioned flame-retardant board in fire prevention and flame retardancy of cables.

[0037] The beneficial effects of this invention are as follows:

[0038] 1. This invention is based on a novel phenolic resin. By adding a self-made organosilicon oligomer, the flame retardant properties of the material are improved. Subsequently, by adding fiber cloth, the strength of the material is enhanced. Then, by hot pressing, a fireproof partition board with excellent flame retardant properties and good strength is obtained. It can be applied to fireproofing and flame retardant of cables and has broad application prospects.

[0039] 2. The organosilicon compound prepared in this invention has excellent thermal stability and toughness. During thermal decomposition, it can not only release water and carbon dioxide, but also form a silicon dioxide protective layer on the matrix surface. Therefore, its introduction into the novel phenolic resin effectively improves the flame retardant properties of the material. Attached Figure Description

[0040] Figure 1 The infrared spectrum of the organosilicon oligomer in Example 1 of this invention;

[0041] Figure 2 The infrared spectrum of the novel phenolic resin in Example 1 of this invention;

[0042] Figure 3 This is the hydrogen spectrum of the novel phenolic resin in Example 1 of the present invention. Detailed Implementation

[0043] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Unless otherwise defined, the technical terms used below have the same meaning as understood by those skilled in the art.

[0044] Unless otherwise specified, the test materials and reagents used in the following examples are commercially available or prepared by known methods.

[0045] Unless otherwise specified, all techniques or conditions described in the embodiments can be performed in accordance with the techniques or conditions described in the literature in this field or in the product manual. Unless otherwise specified, the quantitative experiments in the following embodiments are all repeated three times or more, and the results are averaged.

[0046] Example 1:

[0047] Organosilicon oligomers are prepared by the following methods:

[0048] Step 1: Take 40 mL of methyltriethoxysilane and 50 mL of dimethyldiethoxysilane solution, and add them sequentially to a 250 mL three-necked flask equipped with a stirrer, and mix thoroughly.

[0049] Step 2: When the temperature rises to 70℃, measure 20mL of deionized water, pour it into a constant pressure funnel, and slowly drip it into the mixture.

[0050] Step 3: After the deionized water has been added, add a reflux condenser. Raise the temperature to 80°C and maintain the reaction temperature for 10 hours. During the reaction, start collecting the distillation product at around 78°C, which is mainly ethanol.

[0051] Step 4: After the reaction is complete, perform vacuum distillation to remove small molecules and byproducts, yielding a transparent organosilicon oligomer with a certain viscosity. The infrared spectrum is shown below. Figure 1 As shown.

[0052] The structure of this organosilicon oligomer is as follows:

[0053] In the formula Connect the connector to CH3.

[0054] The novel phenolic resin is prepared by the following method:

[0055] Step 1: Add 100g of methoxydiphenyl ether resin (DETM), 70g of phenol, and 0.71g of p-toluenesulfonic acid solution (concentration 10%) to a three-necked flask in sequence, heat and stir, raise the temperature to 120℃, and reflux for 4 hours.

[0056] Step 2: After the reaction is complete, distill under reduced pressure and cool to room temperature to obtain a yellowish-brown blocky resin.

[0057] Step 3: Grind the above resin into powder using a pulverizer, dissolve it in 100g of ethanol to form a 50% resin solution. Then pour the resin solution into a three-necked flask equipped with a stirrer.

[0058] Step 4: Set the temperature to 50℃, add an appropriate amount of ammonia water, adjust the pH of the reactant solution to 8, and stir at a constant temperature for 30 minutes.

[0059] Step 5: Add 7.2g of paraformaldehyde, heat to 80℃, and reflux for 1.5h to obtain a yellowish-brown transparent solution, named a novel phenolic resin. Infrared and hydrogen spectra are shown below. Figure 2 , 3 As shown.

[0060] The structure of this novel phenolic resin is shown below:

[0061] n = 15.

[0062] The organosilicon oligomers and novel phenolic resins used in Examples 2-7 and Comparative Example 1 were all prepared in Example 1.

[0063] Example 2:

[0064] A method for preparing a novel fire-retardant cable fireproof silicone-modified phenolic fiber reinforced flame-retardant board includes the following steps:

[0065] (1) Mix 2.5g of organosilicon oligomer with 47.5g of novel phenolic resin, and then add 0.5g of 20% (v / v) glacial acetic acid as a catalyst, and reflux at 80°C for 2h.

[0066] (2) After the reaction is complete, distill under reduced pressure at 80°C for 5 min, and then dilute with 95% ethanol to a 60% concentration impregnation solution;

[0067] (3) The impregnated fiberglass cloth is air-dried at room temperature for 12 hours, and then dried in an oven at 175℃ for 10 minutes to form a fiberglass cloth semi-cured sheet.

[0068] (4) Place the fiber cloth semi-cured sheet into a press preheated to 80°C, and set the press to heat up to 175°C at a heating rate of 4°C / min. Cure at 175°C for 1.5 hours to obtain a novel organosilicon modified phenolic fiber reinforced flame retardant board.

[0069] Example 3:

[0070] The difference between this embodiment and embodiment 2 is that in step (1), there are 5g of organosilicon oligomer, 45g of novel phenolic resin, and 1.5g of 22% (v / v) glacial acetic acid, and the rest is the same as in embodiment 1.

[0071] Example 4:

[0072] The difference between this embodiment and embodiment 2 is that in step (1), there are 7.5g of organosilicon oligomer, 42.5g of novel phenolic resin, and 2.5g of 18% (v / v) glacial acetic acid, and the rest is the same as in embodiment 1.

[0073] Example 5:

[0074] The difference between this embodiment and embodiment 2 is that in step (1), there are 10g of organosilicon oligomer, 40g of novel phenolic resin, and 1g of glacial acetic acid with a concentration of 20% (v / v), and the rest is the same as in embodiment 1.

[0075] Example 6:

[0076] The difference between this embodiment and embodiment 4 is that in step (3), the product is dried in an oven at 150°C for 15 minutes, while the rest is the same as in embodiment 4.

[0077] Example 7:

[0078] The difference between this embodiment and embodiment 4 is that in step (3), the product is dried in an oven at 200°C for 3 minutes.

[0079] In step (4), the fiber cloth semi-cured sheet is placed in a press preheated to 75°C, and the press is set to heat up to 180°C at a heating rate of 3°C / min. It is then cured at 185°C for 1 hour. The rest is the same as in Example 4.

[0080] Example 8:

[0081] The difference between this embodiment and Embodiment 1 is that:

[0082] In the preparation of organosilicon oligomers, in step two: heating at 65℃, and in step three: raising the temperature to 82℃ and reacting for 6 hours;

[0083] In the preparation of the novel phenolic resin, in step one: the temperature is raised to 160℃ and refluxed for 5h; in step (2), the pH value is 8.5 and the temperature is kept constant for 40min; in step five, the temperature is raised to 82℃ and the temperature is kept constant for reflux reaction for 2h.

[0084] The rest is the same as in Example 1.

[0085] Example 9:

[0086] The difference between this embodiment and Embodiment 1 is that:

[0087] In the preparation of organosilicon oligomers, in step two: heating at 75℃, and in step three: raising the temperature to 82℃ and reacting for 4 hours;

[0088] In the preparation of the novel phenolic resin, in step one: the temperature is raised to 180℃ and refluxed for 3 hours; in step (2), the pH value is 9 and the temperature is kept constant for 120 minutes; in step five, the temperature is raised to 85℃ and the temperature is kept constant for reflux for 4 hours.

[0089] The rest is the same as in Example 1.

[0090] Example 10:

[0091] The difference between this embodiment and Embodiment 2 is as follows:

[0092] In (1), the heating temperature is 95℃ and the reflux time is 3h.

[0093] (2) The heating temperature is 95℃; 80% (v / v) ethanol is added to dilute and obtain 65% (v / v) impregnation solution.

[0094] In (3), the drying process is as follows: air-drying at room temperature for 14 hours, followed by drying in an oven at 150℃ for 15 minutes.

[0095] The rest is the same as in Example 1.

[0096] Example 11:

[0097] The difference between this embodiment and Embodiment 2 is as follows:

[0098] In (1), the heating temperature is 82℃ and the reflux time is 5h.

[0099] (2) The heating temperature is 82℃; 85% (v / v) ethanol is added to dilute and obtain 55% (v / v) impregnation solution.

[0100] In (3), the drying process is as follows: air-dry at room temperature for 10 hours, and then dry in an oven at 180℃ for 8 minutes.

[0101] The rest is the same as in Example 1.

[0102] Comparative Example 1:

[0103] The difference between this comparative example and Example 1 is that it lacks organosilicon oligomers; otherwise, it is the same as Example 1.

[0104] The limiting oxygen index test was conducted according to GB / T2406.2-2009; the UL-94 rating test was conducted according to the national standard GB / T 2408-2008. The test results are recorded in the following table:

[0105]

[0106] As can be seen from the table above, the flame-retardant board itself is non-combustible and will not ignite itself in the event of a fire. It can prevent the spread of flames and prevent molten droplets from expanding the fire area.

[0107] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a novel fire-retardant cable fireproof silicone-modified phenolic fiber reinforced flame-retardant board, characterized in that, Includes the following steps: (1) Mix organosilicon oligomer, novel phenolic resin and glacial acetic acid, and heat and reflux. (2) Heat and distill the product obtained in (1) under reduced pressure, add ethanol and mix to obtain the impregnation solution; (3) Impregnate the fiber cloth with the impregnation solution obtained in (2), then take out the fiber cloth, dry it, and obtain a semi-cured fiber cloth sheet; (4) Press the semi-cured fiber cloth sheets together with heat to obtain the final product; The structural formula of the organosilicon oligomer is as follows: In the formula Connect the connector to CH3; The structural formula of the novel phenolic resin is as follows: n can be 10 to 20.

2. The preparation method according to claim 1, characterized in that, The mass ratio of the organosilicon oligomer to the novel phenolic resin is (10-20):(80-90); the amount of glacial acetic acid used is 1-5% of the total mass of the organosilicon oligomer and the novel phenolic resin; the concentration of glacial acetic acid is 18-22%.

3. The preparation method according to claim 1, characterized in that, (1) The heating temperature is 80-95℃ and the reflux time is 2-5h; (2) The heating temperature is 80-95℃; 80-95% (v / v) ethanol is added to dilute and obtain 55-65% (v / v) impregnation solution.

4. The preparation method according to claim 1, characterized in that, The fiber cloth is selected from one or more of the following: glass fiber cloth, carbon fiber cloth, acrylic cotton fiber fireproof cloth, basalt fiber cloth, and high silica fiber cloth.

5. The preparation method according to claim 1, characterized in that, The drying process involves air drying at room temperature for 10–14 hours, followed by drying in an oven at 150–200°C for 3–15 minutes.

6. The preparation method according to claim 1, characterized in that, The hot pressing process involves placing the semi-cured fiber cloth sheet into a hot press preheated to 75-85°C, setting the hot press to heat to 160-185°C at a rate of 3-5°C / min, and curing at 160-185°C for 1-3 hours to obtain a novel organosilicon-modified phenolic fiber-reinforced flame-retardant board.

7. The preparation method according to claim 1, characterized in that, Organosilicon oligomers are prepared through the following process: Methyltriethoxysilane and dimethyldiethoxysilane were thoroughly mixed to obtain a mixture; Deionized water is heated to 65–75°C and then added dropwise to the mixture. After the deionized water has been added, a reflux condenser is added to raise the temperature to 80-85°C and the reaction is kept at a constant temperature for 4-10 hours. After the reaction is complete, distill under reduced pressure to obtain the product.

8. The preparation method according to claim 1, characterized in that, The novel phenolic resin is prepared through the following process: Mix methoxydiphenyl ether resin (DETM), phenol, and p-toluenesulfonic acid solution, heat and stir, raise the temperature to 120-180℃, and reflux for 3-5 hours; Then, the resin was distilled under reduced pressure and cooled to room temperature to obtain a yellowish-brown blocky resin. The yellowish-brown lumpy resin was crushed into powder and dissolved in ethanol to form a 50% dilute resin solution. Add ammonia water dropwise, heat and stir, adjust the pH of the reaction solution to 8-9, and stir at a constant temperature for 30-120 minutes; Then add paraformaldehyde, heat to 80-85℃, and reflux at a constant temperature for 1-4 hours to obtain a yellowish-brown transparent solution.

9. The fire-retardant silicone-modified novel phenolic fiber reinforced flame-retardant board for cables prepared by the preparation method according to any one of claims 1-8.

10. The application of the flame-retardant board according to claim 9 in fire prevention and flame retardancy of cables.

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