Phosphorus-based flame retardant, product and manufacturing method thereof
By introducing styrene functional group and phosphorus-based main structure into the flame retardant, a phosphorus-based flame retardant resin sheet with low dielectric constant and high fire resistance performance was prepared, which solved the dielectric characteristics of the existing flame retardant that cannot meet the high requirements in the field of fire retardant. The problem has achieved effective application in electronic products and power equipment.
Patent Information
- Application Number
- CN202310917998.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Priority Date
- 2023-06-14
- Filing Date
- 2023-07-25
- Publication Date
- 2024-12-17
AI Technical Summary
Existing flame resistant agents cannot meet the strict dielectric characteristics requirements in the future, especially in the areas of high-demand fire protection such as electronic products and power equipment, and cannot achieve low dielectric constant and high fire resistance at the same time.
A new phosphorus-based flame-resistant agent composed of styrene functional groups and phosphorus-based backbone was used to react the phenolic functional groups with chloromethyl styrene in a butanone solvent, and potassium iodide was added, and the treatment was made after stirring and oven. The phosphorus-forming flame resistant agent is then stirred with the cross-linking accelerator, the solvent is removed in a vacuum oven, the powder is ground and heat-pressed into a resin sheet.
The made phosphorus-based flame-resistant resin sheet has low dielectric constant and high fire resistance, with a dielectric constant less than 3.0 and a dielectric loss less than 0.0080, which is better than traditional flame-resistant agents and is suitable for high-demand fire protection fields.
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Figure CN119143801A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to a flame retardant, a product and a method for manufacturing the same, and to a phosphorus-based flame retardant, a product and a method for manufacturing the same. Background Art
[0002] Flame retardants are chemicals that prevent objects from burning and can be added to products such as building materials, textiles or vehicle interiors to improve their fire resistance. Many countries have relevant fire protection standards and regulations that require the use of flame retardants to improve the fire resistance of buildings and products. Therefore, the development of new flame retardant technology has become an important area of today's chemical industry. The current flame retardants can no longer meet the stringent dielectric property requirements of the future.
[0003] Based on the above, how to develop a low dielectric reactive flame retardant as a new type of fireproof material, which has the characteristics of low dielectric constant and high fireproof performance and can be applied to high-demand fireproof fields such as electronic products and power equipment, is a goal that technicians in this field are eager to develop. Summary of the invention
[0004] The present invention provides a phosphorus flame retardant, a product and a method for manufacturing the same. The phosphorus flame retardant has a novel phosphorus flame retardant modified structure, which is a structure containing a styrene functional group and a phosphorus backbone, and has a low dielectric constant and high fire resistance.
[0005] The method for preparing the phosphorus flame retardant of the present invention comprises the following steps. A flame retardant containing a phenol functional group and chloromethylstyrene are added to a reaction tank, and butanone is added as a solvent and potassium iodide, and stirred. After stirring, the solvent is drained and placed in an oven to prepare a phosphorus flame retardant. The flame retardant containing a phenol functional group has a chemical structure shown in the following formula (1), chloromethylstyrene has a chemical structure shown in the following formula (2), and the phosphorus flame retardant has a chemical structure shown in the following formula (3) or formula (4):
[0006]
[0007]
[0008] In formula (1), X is H, OH, F, Cl or Br.
[0009] When X in formula (1) is H, F, Cl or Br, the prepared phosphorus flame retardant has a chemical structure shown in formula (3), wherein Y is H, F, Cl or Br.
[0010] When X in formula (1) is OH, the prepared phosphorus-based flame retardant has a chemical structure shown in formula (4).
[0011] In one embodiment of the present invention, the molar ratio of the flame retardant containing phenol functional groups to chloromethylstyrene is 0.1 to 5.
[0012] In one embodiment of the present invention, the amount of the solvent added is 100 to 200 phr, based on the total weight of the flame retardant containing phenol functional groups and chloromethylstyrene.
[0013] In one embodiment of the present invention, the amount of potassium iodide added is 1 phr to 10 phr, based on the total weight of the flame retardant containing phenol functional groups and chloromethylstyrene.
[0014] In one embodiment of the present invention, the stirring speed is 60 rpm to 600 rpm, the stirring time is 12 hours to 48 hours, and the stirring temperature is 50° C. to 90° C.
[0015] In one embodiment of the present invention, the temperature of the oven is 80° C. to 120° C., and the placement time in the oven is 1 hour to 6 hours.
[0016] The phosphorus flame retardant of the present invention is prepared by the above-mentioned method for preparing the phosphorus flame retardant, and the phosphorus flame retardant has a chemical structure represented by the following formula (3) or formula (4):
[0017]
[0018] In formula (3), Y is H, F, Cl or Br,
[0019]
[0020] The product of the present invention is made of the above phosphorus flame retardant, and the product includes a resin sheet.
[0021] The method for manufacturing the product of the present invention comprises the following steps. Using butanone as a solvent, the phosphorus flame retardant and the crosslinking accelerator are stirred, and then placed in a vacuum oven to remove the solvent to obtain a mixture. Thereafter, the mixture is ground into powder and filled into a mold, and then pressed using a hot press to produce a product. The crosslinking accelerator includes a peroxide, the peroxide includes Luf, and the product includes a resin sheet.
[0022] In one embodiment of the present invention, the weight ratio of the phosphorus-based flame retardant to the cross-linking accelerator is 50 to 500.
[0023] In one embodiment of the present invention, the amount of the solvent added is 100 phr to 200 phr, based on the total weight of the phosphorus-based flame retardant and the crosslinking accelerator.
[0024] In one embodiment of the present invention, the stirring speed is 40 rpm to 400 rpm, the stirring time is 0.5 hour to 2 hours, and the stirring temperature is 25° C. to 75° C.
[0025] In one embodiment of the present invention, the temperature of the oven is 80° C. to 120° C., and the placement time in the oven is 1 hour to 6 hours.
[0026] In one embodiment of the present invention, the pressing time of the hot press is 1 hour to 6 hours, and the temperature is 150° C. to 300° C.
[0027] After lamination, the resin sheet must conform to a square shape with a thickness of 0.3μm to 1.3μm and a side length of 3cm to 13cm to facilitate subsequent dielectric constant measurement.
[0028] Based on the above, the present invention provides a phosphorus-based flame retardant, a product and a method for manufacturing the same. The phosphorus-based flame retardant has a novel phosphorus-based flame retardant modified structure, which is a structure containing styrene functional groups and a phosphorus-based backbone. It is different from the concept of conventional addition and can be regarded as a reactive flame retardant resin. It also has a low dielectric constant and high fire retardant properties, and can be used in high-demand fire protection fields such as electronic products and power equipment. BRIEF DESCRIPTION OF THE DRAWINGS
[0029] none DETAILED DESCRIPTION
[0030] Hereinafter, embodiments of the present invention will be described in detail. However, these embodiments are illustrative only, and the present invention is not limited thereto.
[0031] In this article, the range expressed by "a value to another value" is a summary expression method to avoid listing all the values in the range one by one in the specification. Therefore, the description of a specific numerical range covers any value in the numerical range and a smaller numerical range defined by any value in the numerical range, just as the arbitrary value and the smaller numerical range are written in the description text of the specification.
[0032] The method for preparing the phosphorus flame retardant of the present invention comprises the following steps. A flame retardant containing a phenol functional group and chloromethylstyrene are added to a reaction tank, and butanone is added as a solvent and potassium iodide, and stirred. After stirring, the solvent is drained and placed in an oven to prepare a phosphorus flame retardant. The flame retardant containing a phenol functional group has a chemical structure shown in the following formula (1), chloromethylstyrene has a chemical structure shown in the following formula (2), and the phosphorus flame retardant has a chemical structure shown in the following formula (3) or formula (4):
[0033]
[0034]
[0035] In formula (1), X is H, OH, F, Cl or Br.
[0036] When X in formula (1) is H, F, Cl or Br, the prepared phosphorus flame retardant has a chemical structure shown in formula (3), wherein Y is H, F, Cl or Br.
[0037] When X in formula (1) is OH, the prepared phosphorus-based flame retardant has a chemical structure shown in formula (4).
[0038] In this embodiment, the molar ratio of the flame retardant containing phenol functional groups to chloromethylstyrene is, for example, 0.1 to 5. Based on the total weight of the flame retardant containing phenol functional groups and chloromethylstyrene, the amount of solvent added is, for example, 100 to 200 phr, and the amount of potassium iodide added is, for example, 1 to 10 phr. The stirring speed is, for example, 60 rpm to 600 rpm, the stirring time is, for example, 12 hours to 48 hours, and the stirring temperature is, for example, 50° C. to 90° C. The temperature of the oven is, for example, 80° C. to 120° C., and the oven placement time is, for example, 1 hour to 6 hours.
[0039] The present invention also provides a phosphorus flame retardant, which is prepared by the above-mentioned method for preparing a phosphorus flame retardant, wherein the phosphorus flame retardant has a chemical structure represented by the following formula (3) or formula (4):
[0040]
[0041] In formula (3), Y is H, F, Cl or Br,
[0042]
[0043] The present invention also provides a product made of the above-mentioned phosphorus-based flame retardant. The product may include a resin sheet, such as a 5G high-frequency substrate, but the present invention is not limited thereto.
[0044] The method for manufacturing the product of the present invention comprises the following steps. Using butanone as a solvent, the phosphorus flame retardant and the crosslinking accelerator are stirred, and then placed in a vacuum oven to remove the solvent to obtain a mixture. Thereafter, the mixture is ground into powder and filled into a mold, and then pressed using a hot press to form a product. The crosslinking accelerator may include a peroxide, the peroxide may include Luf, and the product may include a resin sheet, such as a 5G high-frequency substrate.
[0045] In the present embodiment, the weight ratio of the phosphorus flame retardant to the crosslinking accelerator is, for example, 50 to 500. Based on the total weight of the phosphorus flame retardant and the crosslinking accelerator, the amount of solvent added is, for example, 100 phr to 200 phr. The stirring speed is, for example, 40 rpm to 400 rpm, the stirring time is, for example, 0.5 hour to 2 hours, and the stirring temperature is, for example, 25°C to 75°C. The temperature of the oven is, for example, 80°C to 120°C, and the placement time in the oven is, for example, 1 hour to 6 hours. The pressing time of the hot press is, for example, 1 hour to 6 hours, and the temperature is, for example, 150°C to 300°C.
[0046] The phosphorus-based flame retardant and its products of the present invention are described in detail below by means of experimental examples. However, the following experimental examples are not intended to limit the present invention.
[0047] Experimental example
[0048] In order to illustrate that the phosphorus-based flame retardant of the present invention can make the produced resin sheet have both low dielectric constant and high fire retardancy, the following experimental example is specifically made.
[0049] Test Method
[0050] Dielectric constant Dk: The dielectric constant Dk was measured at a frequency of 10 GHz using a dielectric analyzer (HP Agilent E4991A).
[0051] Dielectric loss Df: The dielectric loss Df at a frequency of 10 GHz was measured using a dielectric analyzer (HP Agilent E4991A).
[0052] Preparation, testing and evaluation of phosphorus flame retardants and their products
[0053] Example 1
[0054] 1 mol of a phenolic functional flame retardant having a chemical structure shown in formula (1) and 2.5 mol of chloromethylstyrene are added to a reaction tank, and butanone is added as a solvent and potassium iodide, and stirred at 80°C for 24 hours. After stirring, the solvent is drained and placed in an oven at a temperature of 100°C. After confirming that the solvent is removed, a phosphorus-based flame retardant having a chemical structure shown in formula (3) can be prepared. After that, 25 grams of the obtained phosphorus-based flame retardant and 0.25 grams of the cross-linking promoter Luf are stirred for 30 minutes using butanone as a solvent, and then placed in a vacuum oven at 100°C for 3 hours to remove the solvent to obtain a mixture. Next, the mixture is ground into powder and filled into a mold, and then pressed at 200°C for 2 hours using a hot press to prepare a finished resin sheet.
[0055] Example 2
[0056] Basically, the preparation conditions and methods of the phosphorus-based flame retardant and its products are the same as those of Example 1, except that in Example 2, the flame retardant containing a phenolic functional group having a chemical structure shown in formula (1), X in formula (1) is OH, and therefore, the prepared phosphorus-based flame retardant has a chemical structure shown in formula (4).
[0057] Comparative Example 1
[0058] Basically, the preparation of the phosphorus-based flame retardant and its products is the same as the preparation conditions and methods of Example 1, except that the flame retardant having a chemical structure represented by formula (5) and the commercially available product NORYL SA9000SABIC having a chemical structure represented by formula (6) are used to replace the flame retardant containing a phenolic functional group having a chemical structure represented by formula (1) and chloromethylstyrene, respectively.
[0059]
[0060]
[0061] Comparative Example 2
[0062] Basically, the preparation conditions and methods of the phosphorus-based flame retardant and its products are the same as those of Comparative Example 1, except that the flame retardant having the chemical structure shown in formula (5) is replaced by the flame retardant having the chemical structure shown in formula (7).
[0063]
[0064] Comparative Example 3
[0065] Basically, the preparation conditions and methods of the phosphorus-based flame retardant and its products are the same as those of Comparative Example 1, except that the flame retardant having the chemical structure shown in formula (5) is replaced by the flame retardant having the chemical structure shown in formula (8).
[0066]
[0067] The test results of Example 1, Example 2, and Comparative Examples 1 to 3 are shown in Table 1 below. It can be seen that under the same reaction preparation conditions, in Example 1 and Example 2, the phosphorus-based flame retardant prepared by using the flame retardant containing phenol functional groups of the present invention and chloromethylstyrene contains a structure composed of styrene functional groups and phosphorus-based backbones, and therefore, can have both low dielectric constant and high fire resistance. In contrast, Comparative Examples 1 to 3 use conventional DOPO flame retardants, which have the disadvantage of being unable to react with existing resins, resulting in poor dielectric constant and dielectric loss.
[0068] Table 1
[0069] Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Dk@10GHz 2.77 2.77 3.23 3.57 5.11 Df@10GHz 0.0062 0.0064 0.0111 0.0173 0.0255
[0070] In summary, the present invention provides a phosphorus-based flame retardant, a product and a method for manufacturing the same. The phosphorus-based flame retardant has a novel phosphorus-based flame retardant modified structure, which is a structure containing a styrene functional group and a phosphorus-based backbone. It is different from the concept of conventional addition and can be regarded as a reactive flame retardant resin. It also has a low dielectric constant and high fire resistance. The resulting product resin sheet has a dielectric constant (@10GHz) less than 3.0 / dielectric loss (10GHz) less than 0.0080, which are both superior to conventional flame retardants (dielectric constant (@10GHz) greater than 3.0 / dielectric loss (@10GHz) greater than 0.0100). Therefore, it can be used in high-requirement fire protection fields such as electronic products and power equipment.
Claims
1. A method for producing a phosphorus flame retardant, characterized in that: include: Add a flame retardant containing a phenol functional group and chloromethylstyrene into a reaction tank, add butanone as a solvent and potassium iodide, and stir; as well as After stirring, the solvent is drained and placed in an oven to prepare a phosphorus flame retardant. The flame retardant containing a phenol functional group has a chemical structure represented by the following formula (1), chloromethylstyrene has a chemical structure represented by the following formula (2), and the phosphorus-based flame retardant has a chemical structure represented by the following formula (3) or (4): In formula (1), X is H, OH, F, Cl or Br, When X in formula (1) is H, F, Cl or Br, the prepared phosphorus flame retardant has a chemical structure as shown in formula (3), wherein Y is H, F, Cl or Br, When X in formula (1) is OH, the prepared phosphorus-based flame retardant has a chemical structure shown in formula (4).
2. The method for producing a phosphorus flame retardant according to claim 1, characterized in that: The molar ratio of the flame retardant containing phenol functional groups to chloromethylstyrene is 0.1 to 5.
3. The method for producing a phosphorus flame retardant according to claim 1, characterized in that: The added amount of the solvent is 100 to 200 phr based on the total weight of the flame retardant containing phenol functional groups and chloromethylstyrene.
4. The method for producing a phosphorus flame retardant according to claim 1, characterized in that: The amount of potassium iodide added is 1 to 10 phr based on the total weight of the flame retardant containing phenol functional groups and chloromethylstyrene.
5. The method for producing a phosphorus flame retardant according to claim 1, characterized in that: The stirring speed is 60 rpm to 600 rpm, the stirring time is 12 hours to 48 hours, and the stirring temperature is 50°C to 90°C.
6. The method for producing a phosphorus flame retardant according to claim 1, characterized in that: The temperature of the oven is 80° C. to 120° C., and the placement time in the oven is 1 hour to 6 hours.
7. A phosphorus flame retardant, characterized in that: The phosphorus flame retardant is prepared by the method for preparing the phosphorus flame retardant according to any one of claims 1 to 6, wherein the phosphorus flame retardant has a chemical structure represented by the following formula (3) or formula (4): In formula (3), Y is H, F, Cl or Br, 8. A product, characterized in that The product is made of the phosphorus-based flame retardant according to claim 7, and comprises a resin sheet.
9. A method for manufacturing a product, characterized in that: include: Using butanone as a solvent, stirring the phosphorus flame retardant and the crosslinking accelerator described in claim 7, and then placing in a vacuum oven to remove the solvent to obtain a mixture; The mixture is ground into powder and filled into a mold, and then pressed using a hot press to form a product. The cross-linking accelerator comprises a peroxide, the peroxide comprises Luf, and the product comprises a resin sheet.
10. The method for manufacturing a product according to claim 9, characterized in that: The weight ratio of the phosphorus flame retardant to the crosslinking accelerator is 50 to 500.
11. The method for manufacturing a product according to claim 9, characterized in that: Based on the total weight of the phosphorus-based flame retardant and the crosslinking accelerator, the added amount of the solvent is 100 phr to 200 phr.
12. The method for manufacturing a product according to claim 9, characterized in that: The stirring speed is 40 rpm to 400 rpm, the stirring time is 0.5 hour to 2 hours, and the stirring temperature is 25°C to 75°C.
13. The method for manufacturing a product according to claim 9, characterized in that: The temperature of the oven is 80° C. to 120° C., and the placement time in the oven is 1 hour to 6 hours.
14. The method for manufacturing a product according to claim 9, characterized in that: The pressing time of the hot press is 1 hour to 6 hours, and the temperature is 150° C. to 300° C.