Hydrophobic and moisture-permeable flame-retardant fireproof material as well as preparation method and application thereof

Abstract

The invention relates to the technical field of flame-retardant fireproof materials, in particular to a hydrophobic and moisture-permeable flame-retardant fireproof material as well as a preparation method and application thereof. The preparation method comprises the following steps: S1, mixing phenol and formaldehyde, adding a catalyst, carrying out a reaction at 80-85 DEG C for 3-4 h, adjusting the pH value to strong acidity, then adding a modifier, carrying out mixing, carrying out a reaction at 80-100 DEG C for 2-6 h, adjusting the pH value to 5-6, and carrying out washing and drying so as to obtain modified phenolic resin; and S2, drying the modified phenolic resin, and carrying out melt blowing, curing, washing and drying to obtain the flame-retardant fireproof material. The prepared non-woven material has excellent flame-retardant and fireproof performance, the hydrophobic and moisture-permeable performance is further improved, the non-woven material is comfortable and durable, the applicability in an extreme environment is excellent, and the application requirement of firefighter uniform or heat insulation clothes can be met.

Description

Technical Field

[0001] The present invention relates to the technical field of flame-retardant and fire-proof materials, and particularly relates to a hydrophobic and moisture-permeable flame-retardant and fire-proof material, a preparation method thereof, and an application thereof. Background Art

[0002] Flame-retardant and fire-proof materials refer to materials that can effectively prevent or delay the combustion process. Through special chemical or physical mechanisms, such materials slow down the flame propagation speed, reduce the heat release rate, and decrease the generation of smoke during a fire, thereby improving the fire safety and fire resistance performance of the materials. Common flame-retardant and fire-proof materials, namely thermal protection materials, mainly include aluminum foil composite flame-retardant fabrics, aerogel felts, or special polymer foams. Their low thermal conductivity and high heat insulation performance can effectively slow down the speed of heat transfer to the wearer. However, since they cannot balance the wear characteristics such as softness, comfort, and breathability with the flame-retardant, heat insulation, and fire-proof performance, there is still room for improvement in their wide application in personal thermal protection materials.

[0003] Meltblown nonwoven materials are ultra-fine fiber materials produced by the meltblowing process. By directly converting polymer resins into nonwoven materials with sub-micron diameter fibers, they have an ultra-fine fiber structure, a high porosity, effectively limit heat convection and heat radiation, and have excellent heat insulation performance. Among many polymer resins, phenolic resin has great application prospects in the field of personal thermal protection materials because its three-dimensional network molecular structure formed by connecting two benzene rings through methylene chains has a large molecular structure bond energy and a high intermolecular cohesive force, making it have excellent flame-retardant and fire-proof performance.

[0004] The invention patent with the publication number CN118207689A discloses a phenolic-based carbon fiber thermal insulation felt, a preparation method thereof, and an application thereof. The invention uses phenolic resin as a raw material and prepares a phenolic fiber felt by the meltblown spinning nonwoven technology, specifically including the following steps: performing meltblown spinning on thermoplastic phenolic resin to obtain a phenolic fiber original felt; placing the phenolic fiber original felt in a mixed solution of aldehyde and acid for heating and curing to obtain a phenolic fiber felt; sequentially performing carbonization treatment and graphitization treatment on the phenolic fiber felt to obtain a phenolic-based carbon fiber thermal insulation felt. However, this material uses thermoplastic phenolic resin for meltblown spinning. Compared with thermosetting phenolic resin, its thermal protection performance is still insufficient, and it does not involve the performance improvement of wear characteristics. When used in the field of personal thermal protection materials, it may cause water vapor accumulation due to poor hydrophobic and moisture-permeable properties, affecting the body feeling and usability. Summary of the Invention

[0005] In view of the deficiencies of the prior art, the present invention discloses a hydrophobic and moisture-permeable flame-retardant and fireproof material, its preparation method and application. The non-woven material based on phenolic resin prepared by the present invention has excellent flame-retardant and fireproof properties, and its hydrophobic and moisture-permeable properties are further improved. It is comfortable and durable, and has excellent applicability in extreme environments, meeting the application requirements of fire-fighting suits or heat-insulating suits.

[0006] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0007] The first aspect of the present invention provides a preparation method of a hydrophobic and moisture-permeable flame-retardant and fireproof material, and the preparation method includes the following steps:

[0008] S1: Mix phenol and formaldehyde, add a catalyst, react at 80 - 85 °C for 3 - 4 h, adjust the pH to strongly acidic, then add a modifier and mix, react at 80 - 100 °C for 2 - 6 h, adjust the pH to 5 - 6, and after washing and drying, obtain modified phenolic resin;

[0009] S2: After drying the modified phenolic resin, obtain the flame-retardant and fireproof material through meltblowing, curing, washing and drying.

[0010] In some embodiments of the present invention, in step S1, the molar ratio of phenol to formaldehyde is 1:(0.7 - 0.8).

[0011] In some embodiments of the present invention, in step S1, the mass ratio of phenol to the modifier is 1:(0.05 - 0.15).

[0012] In some embodiments of the present invention, in step S1, the preparation steps of the modifier are as follows:

[0013] (1) Sequentially add pentaerythritol phosphate, 4-chloro-1-butene and a catalyst into an organic solvent, react under stirring at 25 - 30 °C for 30 - 35 h, and after post-treatment, obtain an intermediate;

[0014] (2) Under an inert atmosphere, add the intermediate obtained in step (1) and acryloxypropyltriethoxysilane into toluene, add an initiator, react at 60 - 80 °C for 5 - 8 h, and after post-treatment, obtain the modifier.

[0015] In some embodiments of the present invention, in step (1), the mass ratio of pentaerythritol phosphate to 4-chloro-1-butene is (4 - 6.5):1.

[0016] In some embodiments of the present invention, in step (2), the mass ratio of the intermediate to acryloxypropyltriethoxysilane is (2 - 3.6):1.

[0017] The present invention prepares a functional modifier by using pentaerythritol phosphate, 4-chloro-1-butene and acryloxypropyltriethoxysilane and adds it to the synthesis of phenolic resin. At this time, the condensation reaction between hydroxymethylphenols and the reaction between hydroxymethylphenols and the modifier proceed simultaneously, thereby introducing flexible alkyl chain segments and hydrophobic chain segments into the phenolic resin chain segments. The introduction of flexible alkyl chain segments reduces the internal stress of the benzene ring on the phenolic resin, improves the flexibility of the phenolic resin, has good processability, and is beneficial to the spraying and fusing process; moreover, the presence of its phosphate group also promotes carbon formation, increases the flame retardant effect to a certain extent, and synergistically introduces hydrophobic chain segments, reducing the problem that the basic heat insulation and fire prevention performance is weakened due to the retention of water vapor during the use of the material, maintaining the thermal stability performance of the phenolic resin, and ensuring its application in the field of flame retardant and fire prevention materials.

[0018] In some embodiments of the present invention, in step S2, the conditions for meltblowing are a melt temperature of 110 - 160 °C, a hot air drawing temperature of 120 - 170 °C, and a receiving distance of 30 - 50 cm during drawing to obtain meltblown fibers.

[0019] In some embodiments of the present invention, in step S2, the curing operation is to soak the meltblown fibers in a mixed solution containing acid and aldehyde for 1 - 2 h, and then heat them to 100 - 120 °C at a heating rate of 1 - 30 °C / min and keep them at this temperature for 1 - 3 h for curing.

[0020] Preferably, the heating rate is 15 - 25 °C / min.

[0021] Preferably, the mass fraction of acid in the mixed solution is 10 - 20%, and the mass fraction of aldehyde is 10 - 20%.

[0022] Preferably, the acid is hydrochloric acid or dilute sulfuric acid, and the aldehyde is formaldehyde.

[0023] Preferably, the mass ratio of the meltblown fibers to the mixed solution is 1:(20 - 80).

[0024] Preferably, the catalyst is a divalent metal salt catalyst, and further preferably zinc acetate.

[0025] The present invention increases the flexibility and hydrophobicity of phenolic resin by limiting the addition amount of the modifier. The obtained modified phenolic resin has excellent meltblowing processability, and then is cured into a three-dimensional cross-linked network structure through an acid / aldehyde cross-linking bath. The obtained flame retardant and fire prevention material has excellent thermal protection performance and hydrophobic and moisture-permeable performance.

[0026] The second aspect of the present invention also provides a hydrophobic and moisture-permeable flame retardant and fire prevention material obtained by the above technical solution.

[0027] The third aspect of the present invention also provides an application of the above flame retardant and fire prevention material in the field of heat insulation clothing or fire fighting clothing.

[0028] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0029] (1) The non-woven material based on phenolic resin prepared by the present invention has excellent flame retardant and fireproof properties, and its hydrophobic and moisture permeability is further improved, making it comfortable and durable to wear, and having excellent applicability in extreme environments, which can meet the application requirements of fire-fighting suits or heat-insulating suits.

[0030] (2) The present invention prepares a functional modifier by using pentaerythritol phosphate, 4-chloro-1-butene and acryloxypropyltriethoxysilane and adds it to the synthesis of phenolic resin. Then, flexible alkyl chain segments and hydrophobic chain segments are introduced into the phenolic resin chain segments, improving the flexibility of the phenolic resin and solving the problem that the basic heat insulation and fireproof properties are weakened due to the retention of water vapor during the use of the material, ensuring its application in the field of flame retardant and fireproof materials.

[0031] (3) By limiting the addition amount of the modifier, the present invention increases the flexibility and hydrophobicity of the phenolic resin. The obtained modified phenolic resin has excellent meltblown processability, and then is cured into a three-dimensional cross-linked network structure through an acid / aldehyde cross-linking bath. The obtained flame retardant and fireproof material has excellent thermal protection performance and hydrophobic and moisture permeability. Specific Embodiments

[0032] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following examples are examples of the present invention, only for explaining the present invention, and not for limiting the present invention. At the same time, all professional terms mentioned below have the same meaning as commonly understood by those skilled in the art. The professional terms used in this article are only for the purpose of describing specific embodiments, and are not intended to limit the protection scope of the present invention. Without departing from the gist or scope of the present invention, other combinations and various improvements within the concept of the present invention can be made.

[0033] Unless otherwise specified, the reagents used below can be easily obtained from commercial companies.

[0034] Unless otherwise specified, the post-treatment steps such as "washing", "drying", and "vacuum distillation" used below are conventional operations of those skilled in the art and can be selected according to actual operations.

[0035] Preparation Example 1

[0036] The preparation steps of the modifier are as follows:

[0037] (1) Add 26 g of pentaerythritol phosphate, 5 g of 4-chloro-1-butene and 0.35 g of DMAP to 100 mL of dichloromethane in sequence. React at 26 °C for 33 h under stirring. After the reaction is completed, dry, filter and vacuum distill the organic phase to obtain the intermediate.

[0038] (2) Under a nitrogen atmosphere, 14 g of the intermediate in step (2) and 5 g of acryloxypropyltriethoxysilane were added to 50 mL of toluene, 0.2 g of azobisisobutyronitrile was added, and the reaction was carried out at 70 °C for 7 h. After post-treatment, the modifier was obtained.

[0039] Preparation Example 2

[0040] The preparation steps of the modifier were the same as those in Preparation Example 1, except that the amount of pentaerythritol phosphate added in step (1) was 35 g.

[0041] Preparation Example 3

[0042] The preparation steps of the modifier were the same as those in Preparation Example 1, except that the amount of the intermediate added in step (2) was 19 g.

[0043] Example 1

[0044] A preparation method of a hydrophobic and moisture-permeable flame-retardant and fire-proof material comprises the following steps:

[0045] S1: 9.4 g of phenol and 5.9 g of 38 wt% formaldehyde solution were mixed, 0.38 g of zinc acetate was added, and the reaction was carried out at 83 °C for 3.5 h. The pH was adjusted to 3, then 0.94 g of the modifier was added and mixed, and the reaction was carried out at 90 °C for 4 h. The pH was adjusted to 5.5, and after washing and drying, a modified phenolic resin was obtained.

[0046] S2: After the modified phenolic resin was dried, at a melt temperature of 140 °C, a hot air drawing temperature of 150 °C, and a receiving distance of 40 cm during drawing, meltblown fibers were obtained by meltblowing. Then, the meltblown fibers were soaked in a mixed solution containing 15 wt% hydrochloric acid and 15 wt% formaldehyde at a solid-liquid ratio of 1:50 for 1.5 h, and then heated to 110 °C at a heating rate of 20 °C / min for heat preservation treatment for 2 h for curing, and then washed and dried to obtain the flame-retardant and fire-proof material.

[0047] The modifier used in step S1 of this example was obtained from Preparation Example 1.

[0048] Example 2

[0049] A preparation method of a hydrophobic and moisture-permeable flame-retardant and fire-proof material comprises the following steps:

[0050] S1: 9.4 g of phenol and 5.9 g of 38 wt% formaldehyde solution were mixed, 0.38 g of zinc acetate was added, and the reaction was carried out at 80 °C for 4 h. The pH was adjusted to 3, then 0.9 g of the modifier was added and mixed, and the reaction was carried out at 80 °C for 4 h. The pH was adjusted to 6, and after washing and drying, a modified phenolic resin was obtained.

[0051] S2: After drying the modified phenolic resin, at a melt temperature of 110°C, a hot air drawing temperature of 120°C, and a receiving distance of 30 cm during drawing, meltblown fibers are obtained by meltblowing. Then, the meltblown fibers are soaked in a mixed solution containing 15 wt% hydrochloric acid and 15 wt% formaldehyde at a solid-liquid ratio of 1:20 for 1.5 h, and then heated to 110°C at a heating rate of 20°C / min and held for 2 h for curing, and then washed and dried to obtain a flame-retardant and fireproof material.

[0052] The modifier used in step S1 of this example is obtained from Preparation Example 1.

[0053] Example 3

[0054] A method for preparing a hydrophobic and moisture-permeable flame-retardant and fireproof material, comprising the following steps:

[0055] S1: Mix 9.4 g of phenol and 5.9 g of 38 wt% formaldehyde solution, add 0.38 g of zinc acetate, react at 85°C for 3 h, adjust the pH to 3, then add 0.9 g of modifier and mix, add 0.5 g of 15 wt% sodium hydroxide solution, react at 100°C for 2 h, adjust the pH to 5, and after washing and drying, obtain a modified phenolic resin;

[0056] S2: After drying the modified phenolic resin, at a melt temperature of 160°C, a hot air drawing temperature of 170°C, and a receiving distance of 50 cm during drawing, meltblown fibers are obtained by meltblowing. Then, the meltblown fibers are soaked in a mixed solution containing 15 wt% hydrochloric acid and 15 wt% formaldehyde at a solid-liquid ratio of 1:80 for 1.5 h, and then heated to 110°C at a heating rate of 20°C / min and held for 2 h for curing, and then washed and dried to obtain a flame-retardant and fireproof material.

[0057] The modifier used in step S1 of this example is obtained from Preparation Example 1.

[0058] Example 4

[0059] A method for preparing a hydrophobic and moisture-permeable flame-retardant and fireproof material, the specific implementation manner is the same as that of Example 1, the difference is that the modifier used in step S1 is obtained from Preparation Example 2.

[0060] Example 5

[0061] A method for preparing a hydrophobic and moisture-permeable flame-retardant and fireproof material, the specific implementation manner is the same as that of Example 1, the difference is that the modifier used in step S1 is obtained from Preparation Example 3.

[0062] Example 6

[0063] A method for preparing a hydrophobic and moisture-permeable flame-retardant and fireproof material, the specific implementation manner is the same as that of Example 1, the difference is that the addition amount of the modifier in step S1 is 1.9 g.

[0064] Comparative Example 1

[0065] A preparation method of a hydrophobic and moisture-permeable flame-retardant and fireproof material, comprising the following steps:

[0066] S1: Mix 9.4 g of phenol and 5.9 g of 38 wt% formaldehyde solution, add 0.38 g of zinc acetate, react at 83 °C for 3.5 h, adjust the pH to 3 to obtain phenolic resin;

[0067] Step S2 is the same as that in Example 1 to obtain the flame-retardant and fireproof material.

[0068] Performance Test

[0069] 1. Hydrophobic property test: Use a contact angle measuring instrument to measure the contact angles of the flame-retardant and fireproof materials obtained in Examples 1 - 6 and Comparative Example 1 of the present invention to characterize the hydrophobic property. The larger the contact angle, the better the hydrophobic property;

[0070] 2. Moisture permeability test: Refer to the standard GB / T 12704.1 - 2009 "Textiles - Test methods for fabric moisture permeability - Part 1: Moisture absorption method" standard, calculate the moisture permeability to characterize the moisture permeability of the flame-retardant and fireproof materials obtained in Examples 1 - 6 and Comparative Example 1 of the present invention. The higher the moisture permeability, the better the moisture permeability;

[0071] 3. Flame retardancy test: Use a TG 209F3 type thermogravimetric analyzer to measure the char residue rate of the flame-retardant and fireproof materials obtained in Examples 1 - 6 and Comparative Example 1 of the present invention to characterize the flame retardancy. The higher the char residue rate, the better the flame retardancy;

[0072] 4. Thermal protection performance test: Refer to the standard ISO17492, conduct a small-scale test by simulating the fire scene environment, and respectively measure the time required for heat to penetrate through the sample to cause second-degree burns to the human skin, i.e., the second-degree burn time, and calculate the thermal protection coefficient value, i.e., TPP, to characterize the thermal protection performance of the flame-retardant and fireproof materials obtained in Examples 1 - 6 and Comparative Example 1 of the present invention. Among them, TPP = qt, q is the specified exposure heat flux, with the unit of cal / cm 2 ·s, and t is the time required for second-degree burns, with the unit of s.

[0073] The specific performance test results are shown in Table 1.

[0074] Table 1

[0075]

[0076] As can be seen from Table 1, the flame-retardant and fireproof materials provided in Examples 1 - 3 of the present invention have excellent flame-retardant and fireproof performance and excellent hydrophobic and moisture-permeable properties.

[0077] It can be seen from the comparison between Example 4 and Example 5 and Example 1 that when the addition ratios of pentaerythritol phosphate in step (1) and the intermediate in step (2) are changed respectively during the preparation of the modifier, the thermal protection effect and the hydrophobic and moisture-permeable effect of the flame-retardant and fire-proof material will both decrease. Among them, Example 4 affects the flame-retardant and fire-proof performance, and Example 5 affects the toughening effect and the hydrophobic and moisture-permeability. Compared with Example 1, the performance of the obtained flame-retardant and fire-proof material decreases to varying degrees. It can be seen from the comparison between Example 6 and Example 1 that when the addition amount of the modifier is changed during the preparation of the modified phenolic resin, the functional modification effect of the modified phenolic resin is poor and the processability is bad, thus affecting the flame-retardant and fire-proof performance and the hydrophobic and moisture-permeable performance of the obtained flame-retardant and fire-proof material. It can be seen from the comparison between Comparative Example 1 and Example 1 that the toughening effect of the flame-retardant and fire-proof material prepared with unmodified phenolic resin is limited and the comprehensive performance is poor.

[0078] The above are only the preferred embodiments of the present invention, and do not impose any form of limitation on the present invention. Although the present invention has been disclosed above with the preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some changes or modifications to the above-disclosed technical content to be equivalent embodiments with equivalent changes within the scope of the technical solution of the present invention. However, as long as it does not depart from the content of the technical solution of the present invention, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A preparation method of a hydrophobic and moisture-permeable flame-retardant and fireproof material, characterized in that, The preparation method comprises the following steps: S1: Mix phenol and formaldehyde, add a catalyst, react at 80 - 85 °C for 3 - 4 h, adjust the pH to strong acidity, then add a modifier and mix, react at 80 - 100 °C for 2 - 6 h, adjust the pH to 5 - 6, and obtain the modified phenolic resin after washing and drying. S2: After drying the modified phenolic resin, obtain the flame-retardant and fireproof material through meltblowing, curing, washing, and drying.

2. The preparation method of the hydrophobic and moisture-permeable flame-retardant and fireproof material according to claim 1, characterized in that, In step S1, the mass ratio of the phenol to the modifier is 1:(0.05 - 0.15).

3. The preparation method of the hydrophobic and moisture-permeable flame-retardant and fireproof material according to claim 1, wherein, The preparation steps of the modifier are as follows: (1) Sequentially add pentaerythritol phosphate, 4-chloro-1-butene, and a catalyst into an organic solvent, react under stirring at 25 - 30 °C for 30 - 35 h, and obtain an intermediate after post-treatment. (2) Under an inert atmosphere, add the intermediate from step (1) and acryloxypropyltriethoxysilane into toluene, add an initiator, react at 60 - 80 °C for 5 - 8 h, and obtain the modifier after post-treatment.

4. The preparation method of the hydrophobic and moisture-permeable flame-retardant and fireproof material according to claim 3, characterized in that, In step (1), the mass ratio of the pentaerythritol phosphate to the 4-chloro-1-butene is (4 - 6.5):

1.

5. The preparation method of the hydrophobic and moisture-permeable flame retardant and fireproof material according to claim 3, characterized in that, In step (2), the mass ratio of the intermediate to the acryloxypropyltriethoxysilane is (2 - 3.6):

1.

6. The preparation method of the hydrophobic and moisture-permeable flame-retardant and fireproof material according to claim 1, characterized in that, In step S2, the conditions for meltblowing are a melt temperature of 110 - 160 °C, a hot air drawing temperature of 120 - 170 °C, and a receiving distance of 30 - 50 cm during drawing to obtain meltblown fibers.

7. The preparation method of the hydrophobic and moisture-permeable flame-retardant and fireproof material according to claim 1, characterized in that, In step S2, the operation for curing is to soak the meltblown fibers in a mixed solution containing an acid and an aldehyde for 1 - 2 h, and then heat up at a heating rate of 1 - 30 °C / min to 100 - 120 °C for heat preservation treatment for 1 - 3 h for curing.

8. The preparation method of the hydrophobic and moisture-permeable flame-retardant and fireproof material according to claim 7, characterized in that, The mass fraction of the acid in the mixed solution is 10 - 20%, and the mass fraction of the aldehyde is 10 - 20%.

9. A hydrophobic and moisture-permeable flame-retardant and fireproof material obtained by the preparation method according to any one of claims 1 - 8.

10. An application of the flame-retardant and fireproof material obtained by the preparation method according to any one of claims 1 - 8 or the flame-retardant and fireproof material according to claim 9 in the field of heat-insulating clothing or fire-fighting clothing.

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