CN113336916A - Solvent-free synthesis method of flame-retardant repairable polyurethane material - Google Patents
Solvent-free synthesis method of flame-retardant repairable polyurethane material Download PDFInfo
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Abstract
The invention discloses a solvent-free synthesis method of a flame-retardant repairable polyurethane material, belonging to the field of polyurethane materials and comprising the following preparation steps: step S1: synthesizing a polyurethane prepolymer with a polyhydroxy compound as a terminal group; step S2: and (S1) carrying out chemical reaction on the polyurethane prepolymer with the end group of the polyhydroxy compound, furfuryl amine and the polyhydroxy compound to generate furan-terminated polyurethane prepolymer. According to the invention, the micro-crosslinking flame-retardant repairable polyurethane material is prepared by controlling the proportion of furfuryl amine and polyhydroxy compound, so that the problems of low repair speed and the like of the current crosslinking system flame-retardant repairable polyurethane material are solved, most of polyhydroxy compound is converted into furan ring by virtue of monofunctional furfuryl amine under ice bath, the content of polyurethane prepolymer terminated by two polyhydroxy compounds is greatly reduced, and the gel phenomenon in the reaction process of the polyhydroxy compound and the polyhydroxy compound is further avoided, so that the success rate of experiments can be improved to a certain extent.
Description
Technical Field
The invention belongs to the field of polyurethane materials, and particularly relates to a solvent-free synthesis method of a flame-retardant repairable polyurethane material.
Background
The introduction of the furan/maleimide system can bring repairability to the polyurethane material, namely, when the material receives damage such as micro scratches, the repair of the damage such as scratches can be completed by heating and then carrying out reversible DA reaction, when the temperature is reduced, the DA reaction is carried out again to construct a basic framework of the polyurethane material, and finally the repair of the polyurethane material is realized, thereby having important significance for prolonging the service life of the polyurethane material and ensuring the safety factor of the polyurethane material in the use process.
In order to improve the flame retardant property of polyurethane materials, introducing a flame retardant element or a flame retardant structure is the most commonly used means, and particularly, introducing a reactive flame retardant element or a flame retardant element into a polyurethane material can greatly reduce the reduction of mechanical properties caused by the introduction of a flame retardant.
However, most of the existing flame-retardant repairable polyurethane materials are of a cross-linking type, and although the cross-linking density is increased, the increase of the cross-linking density brings adverse factors to the polyurethane material, on one hand, the polyurethane material becomes hard, the elasticity of the material is reduced, the elongation at break is reduced, on the other hand, the repair speed of the polyurethane material is reduced, the repair time is increased, and the repair temperature is increased, so that a solvent-free synthesis method of the flame-retardant repairable polyurethane material is needed in the market at present to solve the problems.
Disclosure of Invention
The invention aims to: the preparation method of the micro-crosslinking flame-retardant repairable polyurethane aims to solve the problems that the existing flame-retardant repairable polyurethane material is mostly of a crosslinking type, the crosslinking density is improved, but the improvement of the crosslinking density brings adverse factors to the polyurethane material, on one hand, the polyurethane material is hard, the elasticity of the material is reduced, the elongation at break is reduced, on the other hand, the repair speed of the polyurethane material is reduced, the repair time is increased, and the repair temperature is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a solvent-free synthesis method of a flame-retardant repairable polyurethane material comprises the following preparation steps:
step S1: synthesizing a polyurethane prepolymer with a polyhydroxy compound as a terminal group;
step S2: the polyurethane prepolymer with the end group of the polyhydroxy compound in the step S1 is chemically reacted with furfuryl amine and the polyhydroxy compound to generate furan end-capped polyurethane prepolymer;
step S3: and (4) carrying out chemical reaction on the furan-terminated polyurethane prepolymer and the bismaleimide compound to generate the flame-retardant repairable polyurethane material in the step S2.
As a further description of the above technical solution:
the synthesis of the polyurethane prepolymer with the end group of the polyhydroxy compound in the step S1 comprises the following preparation steps:
step a 1: respectively carrying out vacuum dehydration on polyester polyol and flame-retardant polyol at the temperature of 100-110 ℃ for 2-3 hours;
step a 2: taking 100 parts of polyester polyol and 50-100 parts of flame-retardant polyol after the step a1 are finished, sequentially adding the polyester polyol and the flame-retardant polyol into a three-neck flask, sealing the three-neck flask, then placing the three-neck flask to room temperature, and adding 300-400 parts of dihydroxy compound and 100-300 parts of DMF;
step a 3: reacting for 3 hours at 60 ℃ under the atmosphere of nitrogen to obtain the polyurethane prepolymer with the end group of polyhydroxy compound.
As a further description of the above technical solution:
the polyester polyol has a functionality of 2 to 3 and a hydroxyl number of 80 to 120.
As a further description of the above technical solution:
the functionality of the flame-retardant polyol is 2-3, the hydroxyl value is 110-220, and the phosphorus content is 6-8%.
As a further description of the above technical solution:
the dihydroxy compound is diphenylmethane dihydroxy compound, toluene-2, 4-dihydroxy compound.
As a further description of the above technical solution:
the preparation of the furan-terminated polyurethane prepolymer in the step S2 includes the following preparation steps:
step b 1: dissolving 180-320 parts of furfuryl amine in 30-70 parts of DMF, and dropwise adding the polyurethane prepolymer which is prepared in an ice water bath and has the end group of the polyhydroxy compound in the step S1 after half an hour;
step b 2: after the dropwise addition, keeping the ice bath for 1h, then heating to 60 ℃, reacting for 1h, then adding 20-50 parts of polyhydroxy compound dissolved in 10-20 parts of DMF, and continuing to react for 3 h to obtain the furan-terminated polyurethane prepolymer.
As a further description of the above technical solution:
the polyhydroxy compound is glycerol, trimethylolpropane or pentaerythritol.
As a further description of the above technical solution:
the reaction of DMF with the polyhydroxy compound can be determined by infrared analysis to determine whether it is complete.
As a further description of the above technical solution:
the preparation of the flame-retardant and repairable polyurethane material in the step S3 includes the following preparation steps:
step c 1: adding 90-160 parts of bismaleimide compound dissolved in 50-100 parts of the furan-terminated polyurethane prepolymer in step S2;
step c 2: continuously reacting for 5 hours at 60 ℃, vacuumizing for 3-10 minutes, removing bubbles, and transferring to a tetrafluoro disc;
step c 3: putting the film into a 60 ℃ oven to volatilize the DMF solvent to obtain a light yellow flat polyurethane film after volatilization.
As a further description of the above technical solution:
the bismaleimide compound is 4, 4 '-bismaleimide diphenylmethane or N, N' -m-phenylene bismaleimide.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. according to the invention, the micro-crosslinking flame-retardant repairable polyurethane material is prepared by controlling the proportion of furfuryl amine and polyhydroxy compound, so that the problems of low repair speed, high repair temperature, long repair time and the like of the conventional crosslinking system flame-retardant repairable polyurethane material are solved, most of polyhydroxy compound is converted into furan ring by virtue of the monofunctional furfuryl amine under an ice bath, the content of polyurethane prepolymer terminated by two polyhydroxy compounds is greatly reduced, and the gel phenomenon in the reaction process of the polyhydroxy compound and the polyhydroxy compound is avoided, so that the success rate of experiments can be improved to a certain extent.
2. In the invention, the repairing speed of the cross-linked flame-retardant repairable polyurethane is reduced from 2 minutes at 130 ℃ to 30 seconds at 120 ℃, so that the possibility of side reaction in the repairing process is reduced, and on the basis of reducing the cross-linking degree, the mechanical strength of the flame-retardant repairable polyurethane material is about 10 percent higher than that of the cross-linked repairable polyurethane material, and the elongation at break is improved from 220 percent to 320 percent.
3. In the invention, the oxygen index of 31.2 is improved to a certain extent compared with the body type crosslinking flame-retardant repairable polyurethane 26.
Drawings
FIG. 1 is a process flow diagram of a solvent-free synthesis method of a flame-retardant repairable polyurethane material according to the present invention;
FIG. 2 is a process flow chart of the synthesis of a polyurethane prepolymer with a polyol end group in the solvent-free synthesis method of a flame-retardant repairable polyurethane material according to the present invention;
FIG. 3 is a process flow diagram of the preparation of furan terminated polyurethane prepolymer in the solvent-free synthesis method of flame retardant repairable polyurethane material according to the present invention;
fig. 4 is a process flow diagram of a solvent-free synthesis method of a flame-retardant repairable polyurethane material according to the present invention.
Illustration of the drawings:
1. a polyurethane prepolymer terminated with a polyol; 2. furfuryl amine and a polyol; 3. a furan-terminated polyurethane prepolymer; 4. a bismaleimide compound; 5. flame-retardant repairable polyurethane material; 6. a polyester polyol; 7. a flame retardant polyol; 8. a di-polyol compound; 9. DMF; 10. furfuryl amine; 11. a polyol.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1-4, the present invention provides a technical solution: a solvent-free synthesis method of a flame-retardant repairable polyurethane material comprises the following preparation steps:
step S1: synthesizing a polyurethane prepolymer 1 with a terminal group of a polyhydroxy compound 11;
step S2: in the step S1, the polyurethane prepolymer 1 with the end group of the polyhydroxy compound 11 and furfuryl amine and the polyhydroxy compound 2 are subjected to chemical reaction to generate furan end-capped polyurethane prepolymer 3;
step S3: in step S2, the furan-terminated polyurethane prepolymer 3 and the bismaleimide compound 4 react chemically to form the flame-retardant repairable polyurethane material 5.
Specifically, as shown in fig. 2, the synthesis of the polyurethane prepolymer 1 terminated with the polyol 11 in step S1 includes the following preparation steps:
step a 1: respectively carrying out vacuum dehydration on the polyester polyol 6 and the flame-retardant polyol 7 at the temperature of 100 ℃ and 110 ℃ for 2-3 hours;
step a 2: taking 100 parts of polyester polyol 6 and 50-100 parts of flame-retardant polyol 7 after the step a1 are finished, sequentially adding the polyester polyol 6 and the flame-retardant polyol 7 into a three-neck flask, sealing the three-neck flask, then placing the three-neck flask to room temperature, and adding 300-400 parts of the dihydroxy compound 11 compound 8 and 100-300 parts of DMF 9;
step a 3: and reacting for 3 hours at 60 ℃ under the nitrogen atmosphere to obtain the polyurethane prepolymer 1 with the end group of the polyhydroxy compound 11.
Specifically, as shown in FIG. 2, the polyester polyol 6 has a functionality of 2 to 3 and a hydroxyl number of 80 to 120.
Specifically, as shown in FIG. 2, the functionality of the flame retardant polyol 7 is 2-3, the hydroxyl value is 110-220, and the phosphorus content is 6% -8%.
Specifically, as shown in FIG. 2, the compound 8 of the dihydorxy compound 11 is diphenylmethane dihydorxy compound 11, toluene-2, 4-dihydorxy compound 11.
Specifically, as shown in fig. 3, the preparation of furan-terminated polyurethane prepolymer 3 in step S2 includes the following preparation steps:
step b 1: dissolving 180-320 parts of furfuryl amine 10 in 30-70 parts of DMF 9, and dropwise adding the polyurethane prepolymer 1 with the end group of the polyhydroxy compound 11 prepared in the step S1 in an ice-water bath after half an hour;
step b 2: after the dropwise addition, keeping the ice bath for 1h, then heating to 60 ℃, reacting for 1h, adding 20-50 parts of polyhydroxy compound 11 dissolved in 10-20 parts of DMF 9, and continuing to react for 3 h to obtain furan-terminated polyurethane prepolymer 3.
Specifically, as shown in fig. 3, the polyol 11 is glycerol, trimethylolpropane, or pentaerythritol.
Specifically, as shown in FIG. 3, the reaction of DMF 9 with polyhydroxy compound 11 can be determined by infrared analysis to determine whether it is complete.
Specifically, as shown in fig. 4, the preparation of the flame-retardant repairable polyurethane material 5 in step S3 includes the following preparation steps:
step c 1: adding 90 to 160 parts of bismaleimide compound 4 dissolved in 50 to 100 parts of the solution to furan-terminated polyurethane prepolymer 3 in step S2;
step c 2: continuously reacting for 5 hours at 60 ℃, vacuumizing for 3-10 minutes, removing bubbles, and transferring to a tetrafluoro disc;
step c 3: putting the film into a 60 ℃ oven to volatilize the solvent DMF 9 to obtain a light yellow flat polyurethane film after volatilization.
Specifically, as shown in FIG. 4, the bismaleimide compound 4 is 4, 4 '-bismaleimide diphenylmethane or N, N' -m-phenylenebismaleimide.
The working principle is as follows: when in use, the polyester polyol 6 and the flame-retardant polyol 7 are respectively subjected to vacuum dehydration for 2-3 hours at the temperature of 100-110 ℃, 100 parts of the polyester polyol 6 and 50-100 parts of the flame-retardant polyol 7 after the steps are taken and sequentially added into a three-neck flask, the three-neck flask is sealed and then placed to room temperature, 300-400 parts of the dihydroxy compound 11 compound 8 and 100-300 parts of DMF 9 are added, the polyurethane prepolymer 1 with the end group of the polyhydroxy compound 11 is obtained after the reaction for 3 hours at the temperature of 60 ℃ under the nitrogen atmosphere, 320 parts of furfuryl amine 10 of 180-80 are dissolved in 30-70 parts of DMF 9, the polyurethane prepolymer 1 with the end group of the polyhydroxy compound 11 prepared by the step S1 and entering an ice water bath is dripped after half an hour, the ice bath is kept for 1 hour and then the temperature is raised to 60 ℃, 20-50 parts of the polyhydroxy compound 11 dissolved in 10-20 parts of DMF 9 is added after the reaction for 1 hour, and continuously reacting for 3 hours to obtain a furan-terminated polyurethane prepolymer 3, adding 90-160 parts of bismaleimide compound 4 dissolved in 50-100 parts of the furan-terminated polyurethane prepolymer 3 in the step S2, continuously reacting for 5 hours at 60 ℃, vacuumizing for 3-10 minutes to remove bubbles, transferring to a tetrafluoro disc, and putting into an oven at 60 ℃ to volatilize a solvent DMF 9 to obtain a light yellow flat polyurethane film after volatilization.
Example one
Step 1: synthesizing a polyurethane prepolymer 1 with a terminal group of a polyhydroxy compound 11;
the preparation method comprises the following steps of (1) respectively carrying out vacuum dehydration on polyester polyol 6-polybutylene adipate, flame-retardant polyol 7 with the functionality of 2 and the molecular weight of 1000 and the flame-retardant polyol 7 with the brand number of BY3009T of Beijing Baisui chemical Co., Ltd, wherein the functionality of 2, the molecular weight of 1700 and the phosphorus content of 7.0% at the temperature of 100 ℃ for 2-3 hours, adding 100 parts of polyester polyol 6 and 60 parts of flame-retardant polyol 7 into a three-neck flask, sealing, cooling to room temperature, adding 320 parts of diphenylmethane dihydroxy compound 11 and 150 parts of DMF 9, and reacting at the temperature of 60 ℃ for 3 hours under the nitrogen atmosphere to obtain polyurethane prepolymer 1 with the end group of the polyhydroxy compound 11;
step 2: preparing a furan-terminated polyurethane prepolymer 3;
dissolving 240 parts of furfurylamine 10 in 50 parts of DMF 9, dropwise adding the polyurethane prepolymer 1 with the end group of the polyhydroxy compound 11, which is prepared in the step 1 in an ice-water bath, for half an hour, keeping the ice bath for 1 hour after dropwise adding, heating to 60 ℃, reacting for 1 hour, adding 27 parts of trimethylolpropane dissolved in 15 parts of DMF 9, and continuously reacting for 3 hours to obtain a furan-terminated polyurethane prepolymer 3;
and step 3: preparing a flame-retardant repairable polyurethane material 5;
adding 120 parts of 4, 4' -bismaleimide diphenylmethane dissolved in 60 parts into the furan-terminated polyurethane prepolymer 3 obtained in the step 2, continuously reacting for 5 hours at 60 ℃, vacuumizing for 5 minutes to remove bubbles, transferring to a tetrafluoro disc, and putting into an oven at 60 ℃ to volatilize a solvent DMF 9 to obtain a light yellow flat polyurethane film after volatilization;
through tests, the ultimate oxygen index of the final micro-crosslinking flame-retardant repairable polyurethane can reach 31.2, the repair efficiency can reach 91.2%, the breaking tensile strength can reach 50.4MPa, the breaking elongation is improved by 10% compared with that of the body type crosslinking flame-retardant repairable polyurethane, the breaking elongation is improved from 220% to 330%, the repair efficiency is controlled to be 91.2% under the condition of 120 ℃ for 30 seconds, and the repair condition of the crosslinking system flame-retardant repairable polyurethane material 5 is controlled to be 130 ℃ for two minutes.
Example two
Step 1: synthesizing a polyurethane prepolymer 1 with a terminal group of a polyhydroxy compound 11;
the preparation method comprises the following steps of (1) respectively carrying out vacuum dehydration on polyester polyol 6-polybutylene adipate with the functionality of 2 and the molecular weight of 1400 and flame-retardant polyol 7 DOPO-based flame-retardant polyester polyol 6 with the functionality of 205, the molecular weight of 800 and the phosphorus content of 6.2% at the temperature of 100 ℃ and 110 ℃ for 2-3 hours, adding 100 parts of polyester polyol 6 and 80 parts of flame-retardant polyol 7 into a three-neck flask, sealing, then placing to room temperature, adding 400 parts of diphenylmethane dihydroxy compound 11 and 150 parts of DMF 9, and reacting at the temperature of 60 ℃ for 3 hours under the nitrogen atmosphere to obtain polyurethane prepolymer 1 with the end group of polyhydroxy compound 11;
step 2: preparing a furan-terminated polyurethane prepolymer 3;
300 parts of furfurylamine 10 is dissolved in 60 parts of DMF 9, the polyurethane prepolymer 1 which is prepared in step 1 and has the end group of a polyhydroxy compound 11 and is dripped into an ice water bath for half an hour, the ice bath is kept for 1 hour after the dripping is finished, then the temperature is raised to 60 ℃, the reaction is carried out for 1 hour, 34 parts of trimethylolpropane dissolved in 20 parts of DMF 9 is added, and the reaction is continued for 3 hours to obtain a furan end-capped polyurethane prepolymer 3;
and step 3: preparing a flame-retardant repairable polyurethane material 5;
adding 150 parts of 4, 4' -bismaleimide diphenylmethane dissolved in 70 parts into the furan-terminated polyurethane prepolymer 3 obtained in the step 2, continuously reacting for 5 hours at 60 ℃, vacuumizing for 5 minutes to remove bubbles, transferring to a tetrafluoro disc, and putting into an oven at 60 ℃ to volatilize a solvent DMF 9 to obtain a light yellow flat polyurethane film after volatilization;
through tests, the ultimate oxygen index of the final micro-crosslinking flame-retardant repairable polyurethane can reach 29.8, the breaking tensile strength of the final micro-crosslinking flame-retardant repairable polyurethane can reach 49.7MPa, the breaking elongation of the final micro-crosslinking flame-retardant repairable polyurethane is improved by 8.6 percent compared with that of the body type crosslinking flame-retardant repairable polyurethane, the breaking elongation of the final micro-crosslinking flame-retardant repairable polyurethane is improved from 230 percent to 260 percent, the repairing efficiency of the final micro-crosslinking flame-retardant repairable polyurethane under the condition that the repairing condition is controlled at 120 ℃ for 30 seconds is 90.4 percent, and the repairing condition of the crosslinking system flame-retardant repairable polyurethane material 5 is 130 ℃ for two minutes.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical scope of the present invention and the equivalent alternatives or modifications according to the technical solution and the inventive concept of the present invention within the technical scope of the present invention.
Claims (10)
1. A solvent-free synthesis method of a flame-retardant repairable polyurethane material is characterized by comprising the following preparation steps:
step S1: synthesizing a polyurethane prepolymer (1) with a terminal group of a polyhydroxy compound (11);
step S2: the polyurethane prepolymer (1) with the end group of the polyhydroxy compound (11) in the step S1 and furfuryl amine and the polyhydroxy compound (2) are subjected to chemical reaction to generate furan-terminated polyurethane prepolymer (3);
step S3: the furan-terminated polyurethane prepolymer (3) and the bismaleimide compound (4) in the step S2 are chemically reacted to generate the flame-retardant repairable polyurethane material (5).
2. The solvent-free synthesis method of flame-retardant repairable polyurethane material as claimed in claim 1, wherein the synthesis of the polyurethane prepolymer (1) with the end group of polyol (11) in step S1 comprises the following preparation steps:
step a 1: respectively carrying out vacuum dehydration on the polyester polyol (6) and the flame-retardant polyol (7) at the temperature of 100 ℃ and 110 ℃ for 2-3 hours;
step a 2: taking 100 parts of polyester polyol (6) and 50-100 parts of flame-retardant polyol (7) after the step a1 are finished, sequentially adding the polyester polyol and the flame-retardant polyol into a three-neck flask, sealing the three-neck flask, then placing the three-neck flask to room temperature, and adding 300-400 parts of the dihydric compound (11) compound (8) and 100-300 parts of DMF (9);
step a 3: and reacting for 3 hours at 60 ℃ under the nitrogen atmosphere to obtain the polyurethane prepolymer (1) with the end group of the polyhydroxy compound (11).
3. The solvent-free synthesis method of flame-retardant repairable polyurethane material as claimed in claim 2, wherein the functionality of the polyester polyol (6) is 2-3, and the hydroxyl value is 80-120.
4. The solvent-free synthesis method of flame-retardant repairable polyurethane material as claimed in claim 2, wherein the functionality of the flame-retardant polyol (7) is 2-3, the hydroxyl value is 110-220, and the phosphorus content is 6% -8%.
5. The solvent-free synthesis method of a flame-retardant repairable polyurethane material according to claim 2, wherein the compound (8) of the dihydridoch compound (11) is diphenylmethane dihydridoch compound (11), toluene-2, 4-dihydridoch compound (11).
6. The solvent-free synthesis method of flame-retardant repairable polyurethane material according to claim 1, wherein the preparation of the furan-terminated polyurethane prepolymer (3) in step S2 comprises the following steps:
step b 1: dissolving 180-320 parts of furfuryl amine (10) in 30-70 parts of DMF (9), and dropwise adding the polyurethane prepolymer (1) which is provided with the end group of the polyhydroxy compound (11) and is prepared by the step S1 in an ice-water bath after half an hour;
step b 2: after the dropwise addition, the ice bath is kept for 1h, then the temperature is raised to 60 ℃, 20-50 parts of polyhydroxy compound (11) dissolved in 10-20 parts of DMF (9) is added after the reaction is carried out for 1h, and the reaction is continued for 3 h to obtain the furan-terminated polyurethane prepolymer (3).
7. The solvent-free synthesis method of a flame-retardant repairable polyurethane material according to claim 4, wherein the polyol compound (11) is glycerol, trimethylolpropane or pentaerythritol.
8. The solvent-free synthesis method of flame-retardant repairable polyurethane material as claimed in claim 4, wherein the reaction between DMF (9) and polyol (11) can be determined by infrared analysis to determine whether the reaction is completed.
9. The solvent-free synthesis method of flame-retardant repairable polyurethane material according to claim 1, wherein the preparation of the flame-retardant repairable polyurethane material (5) in step S3 comprises the following steps:
step c 1: adding 90 to 160 parts of bismaleimide compound (4) dissolved in 50 to 100 parts of the solution to furan-terminated polyurethane prepolymer (3) in step S2;
step c 2: continuously reacting for 5 hours at 60 ℃, vacuumizing for 3-10 minutes, removing bubbles, and transferring to a tetrafluoro disc;
step c 3: putting the film into a 60 ℃ oven to volatilize the solvent DMF (9) to obtain a light yellow flat polyurethane film after volatilization.
10. The solvent-free synthesis method of a flame-retardant repairable polyurethane material according to claim 1, wherein the bismaleimide compound (4) is 4, 4 '-bismaleimide diphenylmethane, N' -m-phenylenebismaleimide.
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| CN116218202A (en) * | 2023-02-03 | 2023-06-06 | 广东安拓普聚合物科技有限公司 | Sealing ring material and preparation method thereof |
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