CN113174087A - Modified graphene flame retardant containing flame-retardant elements and double bonds and preparation method thereof - Google Patents
Modified graphene flame retardant containing flame-retardant elements and double bonds and preparation method thereof Download PDFInfo
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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Abstract
The invention relates to the technical field of flame retardants in polyurethane synthesis systems, and discloses a modified graphene flame retardant containing flame retardant elements and double bonds and a preparation method thereof.
Description
Technical Field
The invention belongs to the technical field of flame retardants in polyurethane synthesis systems, and particularly relates to a modified graphene flame retardant containing flame-retardant elements and double bonds and a preparation method thereof.
Background
The flame retardant is a functional aid for endowing flammable polymers with flame retardancy, and most of high polymer materials used in transportation, buildings, electrical equipment and the like at present are flammable, such as plastics, rubber, fibers and the like, and the flame-retardant safety coefficient is low, so the flame retardant can be added to increase the flame retardancy of the high polymer materials and improve the safety coefficient.
There are two flame retardants currently used in polyurethane synthesis systems:
the first is an additive flame retardant containing flame retardant elements such as dimethyl methyl phosphate and the like, such as phosphorus, chlorine, bromine and the like, and the additive flame retardant has the advantages of high content of flame retardant elements and low price, but has the problems of easy migration, rapid reduction of mechanical properties of materials when the additive amount is large and the like.
The second is that a compound containing a flame retardant element and an active group is used as a reactive flame retardant, but although there are many compounds containing a flame retardant element, not all compounds containing a flame retardant element have an active group and participate in a polyurethane synthesis system, and if the compound containing a flame retardant element itself does not have an active group participating in a polyurethane synthesis system, the compound is liable to migrate and cannot be added in a large amount after being added to a polyurethane synthesis system, resulting in a decrease in the flame retardant effect of the compound in a polyurethane product. Of course, it is also easy to think of introducing active groups into compounds that do not contain active groups participating in polyurethane synthesis systems by chemical synthesis, but most of the existing chemical synthesis methods have complicated synthesis processes and high requirements on reaction conditions, and whether the introduced active groups can adversely affect the flame retardant properties of the original compounds or not is also considered.
Disclosure of Invention
The invention aims to provide a modified graphene flame retardant containing a flame retardant element and a double bond, which has the characteristic that the flame retardant element on 6-pteridine amine is not easy to migrate in a polyurethane product, and the graphene and the 6-pteridine amine have a synergistic flame retardant effect, so that the polyurethane product prepared by using the modified graphene flame retardant containing the flame retardant element and the double bond has a good flame retardant effect.
The above object of the present invention is achieved by the following technical solutions: a modified graphene flame retardant containing a flame-retardant element and a double bond comprises graphene, wherein 6-pteridine amine and p-amino styrene are connected to the graphene through chemical bonds; the modified graphene flame retardant containing the flame-retardant element and the double bonds takes part in the synthesis and addition polymerization reaction of polymer polyol by utilizing the carbon-carbon double bonds on the p-amino styrene.
By adopting the technical scheme, the 6-pteridine amine is bonded with the graphene, the graphene is bonded with the p-amino styrene, the flame retardant elements on the 6-pteridine amine are stably introduced into the polymer polyol by using the double bonds on the graphene and the p-amino styrene, and the polyurethane product is prepared by using the polymer polyol, so that the flame retardant elements in the prepared polyurethane product are not easy to migrate, meanwhile, the 6-pteridine amine and the graphene have a synergistic flame retardant effect, and the polyurethane product prepared by using the modified graphene flame retardant containing the flame retardant elements and the double bonds has a better flame retardant effect.
Further, the modified graphene flame retardant containing the flame retardant element and the double bond is introduced into the polyurethane material in an addition amount of 4.7%.
By adopting the technical scheme, when the modified graphene flame retardant containing the flame-retardant element and the double bonds is introduced into the polyurethane material in an addition amount of 4.7%, the polyurethane material has the best flame-retardant effect, and the oxygen index can reach more than 27%.
The invention also aims to provide a preparation method of the modified graphene flame retardant containing the flame retardant element and the double bonds, and the method is simple in process and easy to operate.
A preparation method of a modified graphene flame retardant containing flame-retardant elements and double bonds comprises the following steps:
s1, ball-milling the graphite flakes and sodium chloride for 0.5-2 hours;
s2, adding p-amino styrene and 6-pteridine amine, mixing and ball-milling for 0.5-2 hours;
s3, finally adding nitrite, mixing and grinding for 4-48 hours, washing, and vacuum drying to obtain the product, namely the modified graphene flame retardant containing the flame retardant element and double bonds.
Further, the graphite flake: sodium chloride: p-aminostyrene: 6-pteridine amine: the mass ratio of the nitrous acid ester is 1: 1-15: 2-50: 2-50: 4-100.
According to the technical scheme, firstly, nitrite reacts with amino in 6-pteridine amine to generate diazonium salt, the diazonium salt removes nitrogen to generate benzene free radical, the benzene free radical and a carbon layer on the surface layer of graphite flake are subjected to addition reaction to enable the 6-pteridine amine and the graphite flake to be chemically bonded together, then the graphite flake and p-amino styrene are chemically bonded together by the same method, modified graphene bonded with the 6-pteridine amine and the p-amino styrene is formed through ball milling, the modified graphene utilizes double bonds in the p-amino styrene and other components of polymeric polyol to carry out polymerization reaction, so that flame retardant elements in the 6-pteridine amine are stably introduced into the polymeric polyol, and then the polymeric polyol is utilized to prepare a polyurethane product. Compared with the method of directly introducing an active group on the 6-pteridine amine through chemical synthesis to ensure that the flame retardant element of the 6-pteridine amine is not easy to migrate in the polyurethane product, the method for modifying the 6-pteridine amine by utilizing the graphene and the p-amino styrene is simpler and easier to operate.
Further, the graphite flake: p-aminostyrene: the mass ratio of the 6-pteridine amine is 1: 5: 10.
by adopting the technical scheme, when the graphite flakes: p-aminostyrene: the mass ratio of the 6-pteridine amine is 1: 5: when the modified graphene flame retardant containing the flame-retardant element and the double bonds is used for polyurethane materials, the flame-retardant effect is optimal.
In conclusion, the invention has the following beneficial effects:
1. the flame retardant element of the 6-pteridine amine can be stably introduced into the polymeric polyol and is not easy to migrate, and meanwhile, the 6-pteridine amine and the graphene have a synergistic flame retardant effect, so that the overall flame retardant effect of the polyurethane flame retardant foam material containing the modified graphene is better;
2. the method for transforming 6-pteridine amine by utilizing substances such as p-amino styrene, graphene and the like so as to stably introduce flame retardant elements of the 6-pteridine amine into polymer polyol has the advantages of simple process and convenient operation.
Detailed Description
The present invention will be described in further detail with reference to examples.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The first embodiment is as follows: a modified graphene flame retardant containing flame-retardant elements and double bonds is prepared by firstly weighing 1 part of graphite flakes and 10 parts of sodium chloride in parts by weight, and carrying out ball milling for 1.5 hours; then adding 5 parts of p-amino styrene and 10 parts of 6-pteridine amine, mixing and ball-milling for 1.5 hours; and finally, adding 18.75 parts of nitrite, mixing and grinding for 24 hours, washing, and drying in vacuum to obtain a product, namely the modified graphene flame retardant containing the flame-retardant elements and double bonds. The modified graphene flame retardant containing the flame-retardant element and the double bond contains graphene, the graphene is connected with 6-pteridine amine and p-amino styrene through a chemical bond, and the modified graphene flame retardant containing the flame-retardant element and the double bond can participate in the synthesis addition polymerization reaction of polymer polyol by utilizing the carbon-carbon double bond on the p-amino styrene, so that the flame-retardant element on the 6-pteridine amine is stably introduced into the polymer polyol, and the flame-retardant effect of a polyurethane product prepared by utilizing the polymer polyol is better.
Example two: a modified graphene flame retardant containing flame-retardant elements and double bonds is prepared by firstly weighing 1 part of graphite flakes and 10 parts of sodium chloride in parts by weight, and performing ball milling for 0.5 hour; then adding 5 parts of p-amino styrene and 5 parts of 6-pteridine amine, mixing and ball-milling for 0.5 hour; and finally, adding 12.5 parts of nitrite, mixing and grinding for 24 hours, washing, and drying in vacuum to obtain a product, namely the modified graphene flame retardant containing the flame-retardant element and the double bond, wherein the modified graphene flame retardant containing the flame-retardant element and the double bond contains graphene, the graphene is connected with 6-pteridine amine and p-amino styrene through a chemical bond, and the modified graphene flame retardant containing the flame-retardant element and the double bond can participate in the synthesis and addition polymerization reaction of polymer polyol by utilizing the carbon-carbon double bond on the p-amino styrene, so that the flame-retardant element on the 6-pteridine amine is stably introduced into the polymer polyol, and the flame-retardant effect of a polyurethane product prepared by utilizing the polymer polyol is better.
Example three: a modified graphene flame retardant containing flame-retardant elements and double bonds is prepared by firstly weighing 1 part of graphite flakes and 15 parts of sodium chloride in parts by weight, and performing ball milling for 2 hours; then adding 10 parts of p-amino styrene and 10 parts of 6-pteridine amine, mixing and ball-milling for 2 hours; and finally, adding 25 parts of nitrite, mixing and grinding for 24 hours, washing, and drying in vacuum to obtain a product, namely the modified graphene flame retardant containing the flame-retardant element and double bonds, wherein the modified graphene flame retardant containing the flame-retardant element and double bonds contains graphene, the graphene is connected with 6-pteridine amine and p-amino styrene through chemical bonds, and the modified graphene flame retardant containing the flame-retardant element and double bonds can participate in the synthesis addition polymerization reaction of polymer polyol by utilizing the carbon-carbon double bonds on the p-amino styrene, so that the flame-retardant element on the 6-pteridine amine is stably introduced into the polymer polyol, and the flame-retardant effect of a polyurethane product prepared by utilizing the polymer polyol is better.
In order to detect the flame retardant effect of the modified graphene flame retardant containing the flame retardant element and the double bond, the following experiment is set:
test article 1: taking 8 parts of the modified graphene flame retardant containing the flame retardant element and the double bond in the first example, 42 parts of high-activity polyether polyol (molecular weight 3000), 35 parts of styrene, 8 parts of acrylonitrile, 2 parts of an initiator, 4 parts of a dispersing agent and 1 part of a chain transfer agent to polymerize to form polymer polyol, then weighing 10 parts of the polymer polyol, weighing 9 parts of high-activity polyether polyol (molecular weight 3000), 6 parts of toluene diisocyanate, 0.3 part of water, 0.1 part of silicone oil, 0.03 part of stannous octoate and 0.02 part of triethanolamine, and preparing a test product 1 by foaming, wherein when the modified graphene flame retardant containing the flame retardant element and the double bond in the test product 1 is prepared, the graphite flakes of the modified graphene flame retardant containing the flame retardant element and the double bond are: p-aminostyrene: the mass ratio of the 6-pteridine amine is 1: 5: 10. the addition amount of the modified graphene flame retardant containing a flame retardant element and a double bond in the test article 1 was 3.14%.
Test article 2: taking 8 parts of the modified graphene flame retardant containing the flame retardant element and the double bond in the second example, 42 parts of high-activity polyether polyol (with a molecular weight of 3000), 35 parts of styrene, 8 parts of acrylonitrile, 2 parts of an initiator, 4 parts of a dispersing agent and 1 part of a chain transfer agent to polymerize to form polymer polyol, then weighing 10 parts of the polymer polyol, weighing 9 parts of high-activity polyether polyol (with a molecular weight of 3000), 6 parts of toluene diisocyanate, 0.3 part of water, 0.1 part of silicone oil, 0.03 part of stannous octoate and 0.02 part of triethanolamine, and preparing a test article 2 by foaming, wherein when the modified graphene flame retardant containing the flame retardant element and the double bond in the test article 2 is prepared, the graphite phosphorus sheet is as follows: p-aminostyrene: the mass ratio of the 6-pteridine amine is 1: 5: 5.
test article 3: taking 8 parts of the modified graphene flame retardant containing the flame retardant element and the double bond in the third example, 42 parts of high-activity polyether polyol (with a molecular weight of 3000), 35 parts of styrene, 8 parts of acrylonitrile, 2 parts of an initiator, 4 parts of a dispersing agent and 1 part of a chain transfer agent to polymerize to form polymer polyol, then weighing 10 parts of the polymer polyol, further weighing 9 parts of high-activity polyether polyol (with a molecular weight of 3000), 6 parts of toluene diisocyanate, 0.3 part of water, 0.1 part of silicone oil, 0.03 part of stannous octoate and 0.02 part of triethanolamine, preparing a test product 3 by foaming, and preparing the modified graphene flame retardant containing the flame retardant element and the double bond in the test product 3 by using a graphite phosphorus sheet: p-aminostyrene: the mass ratio of the 6-pteridine amine is 1: 10: 10.
test article 4: taking 10 parts of the modified graphene flame retardant containing the flame retardant element and the double bond in the first example, 40 parts of high-activity polyether polyol (with a molecular weight of 3000), 35 parts of styrene, 7 parts of acrylonitrile, 3 parts of an initiator, 4 parts of a dispersing agent and 1 part of a chain transfer agent to polymerize to form polymer polyol, then weighing 10 parts of the polymer polyol, further weighing 5 parts of high-activity polyether polyol (with a molecular weight of 3000), 6 parts of toluene diisocyanate, 0.3 part of water, 0.1 part of silicone oil, 0.03 part of stannous octoate and 0.02 part of triethanolamine, and preparing a test article 4 by foaming, wherein the addition amount of the modified graphene flame retardant containing the flame retardant element and the double bond in the test article 4 is 4.7%.
Test article 5: taking 10 parts of the modified graphene flame retardant containing the flame retardant element and the double bond in the first example, 40 parts of high-activity polyether polyol (with a molecular weight of 3000), 25 parts of styrene, 7 parts of acrylonitrile, 3 parts of an initiator, 4 parts of a dispersing agent and 1 part of a chain transfer agent to polymerize to form polymer polyol, then weighing 12 parts of the polymer polyol, weighing 3 parts of high-activity polyether polyol (with a molecular weight of 3000), 6 parts of toluene diisocyanate, 0.3 part of water, 0.1 part of silicone oil, 0.03 part of stannous octoate and 0.02 part of triethanolamine, and preparing a test article 5 by foaming, wherein the addition amount of the modified graphene flame retardant containing the flame retardant element and the double bond in the test article 5 is 6.2%.
Test article 6: taking 5 parts of a substance A (the substance A is obtained by weighing 1 part of graphite flakes and 10 parts of sodium chloride, carrying out ball milling for 24 hours, washing and carrying out vacuum drying), 45 parts of high-activity polyether polyol (with the molecular weight of 3000), 35 parts of styrene, 15 parts of acrylonitrile, 1 part of an initiator, 4 parts of a dispersing agent and 8 parts of a chain transfer agent, polymerizing to form polymer polyol, then weighing 5 parts of the polymer polyol, and further weighing 10 parts of the high-activity polyether polyol (with the molecular weight of 3000), 6 parts of toluene diisocyanate, 0.3 part of water, 0.1 part of silicone oil, 0.03 part of stannous octoate and 0.02 part of triethanolamine, and foaming to obtain a test article 6.
Test article 7: taking 5 parts of a substance B (the substance B is obtained by mixing 1 part of graphite flake with 10 parts of sodium chloride, mixing 10 parts of 6-pteridine amine with 12.5 parts of nitrite, carrying out ball milling for 24 hours, washing and carrying out vacuum drying), polymerizing 45 parts of high-activity polyether polyol (with the molecular weight of 3000), 35 parts of styrene, 15 parts of acrylonitrile, 1 part of an initiator, 4 parts of a dispersing agent and 8 parts of a chain transfer agent to form polymer polyol, then weighing 5 parts of the polymer polyol, weighing 10 parts of high-activity polyether polyol (with the molecular weight of 3000), 6 parts of toluene diisocyanate, 0.3 part of water, 0.1 part of silicone oil, 0.03 part of stannous octoate and 0.02 part of triethanolamine, and foaming to obtain a test product 7.
Test article 8: 5 parts of substance C (6-pteridine amine), 45 parts of high-activity polyether polyol (molecular weight of 3000), 35 parts of styrene, 15 parts of acrylonitrile, 1 part of initiator, 4 parts of dispersant and 8 parts of chain transfer agent are polymerized to form polymer polyol, then 5 parts of the polymer polyol are weighed, 10 parts of the high-activity polyether polyol (molecular weight of 3000), 6 parts of toluene diisocyanate, 0.3 part of water, 0.1 part of silicone oil, 0.03 part of stannous octoate and 0.02 part of triethanolamine are weighed, and a test article 8 is prepared by foaming.
Test article 9: taking 5 parts of a substance D (the substance D is formed by fully mixing 1 part of graphene, 10 parts of sodium chloride, 5 parts of p-amino styrene and 10 parts of 6-pteridine amine), 45 parts of high-activity polyether polyol (molecular weight 3000), 35 parts of styrene, 15 parts of acrylonitrile, 1 part of an initiator, 4 parts of a dispersing agent and 8 parts of a chain transfer agent, polymerizing to form polymer polyol, then weighing 5 parts of the polymer polyol, weighing 10 parts of the high-activity polyether polyol (molecular weight 3000), 6 parts of toluene diisocyanate, 0.3 part of water, 0.1 part of silicone oil, 0.03 part of stannous octoate and 0.02 part of triethanolamine, and preparing a test product 9 by foaming.
Test article 10: 5 parts of dimethyl methylphosphonate, 45 parts of high-activity polyether polyol (with the molecular weight of 3000), 35 parts of styrene, 15 parts of acrylonitrile, 1 part of initiator, 4 parts of dispersant and 8 parts of chain transfer agent are polymerized to form polymer polyol, then 5 parts of the polymer polyol are weighed, 10 parts of the high-activity polyether polyol (with the molecular weight of 3000), 6 parts of toluene diisocyanate, 0.3 part of water, 0.1 part of silicone oil, 0.03 part of stannous octoate and 0.02 part of triethanolamine are weighed, and the test article 10 is prepared by foaming.
The test 1 to the test 10 were subjected to performance tests such as oxygen index, and table 1 was obtained.
Table 1 results of performance testing
As is well known, generally, the higher the oxygen index of the material is, the better the flame retardant effect is, and as can be seen from the data in table 1, the oxygen indexes of the test article 1 to the test article 3 are 26.41%, 25.16% and 24.46%, respectively, and the oxygen index of the test article 1 is greater than the oxygen indexes of the test article 2 and the test article 3, which shows that when the modified graphene flame retardant containing the flame retardant element and the double bond is prepared, the graphite phosphorus flake: p-aminostyrene: the mass ratio of the 6-pteridine amine is 1: 5: the best time is 10 hours, so that the flame retardant effect of the finally obtained product is better.
The oxygen indexes of the test article 1, the test article 4 and the test article 5 are 26.41%, 27.48% and 26.80% respectively, and the oxygen index of the test article 4 is greater than the oxygen indexes of the test article 1 and the test article 5, which shows that when the modified graphene flame retardant containing the flame retardant element and the double bond is introduced at an addition amount of 4.7%, the modified graphene flame retardant is optimal, so that the flame retardant effect of the finally obtained product is better.
The oxygen indexes of the test article 6, the test article 7 and the test article 8 are respectively 21.89%, 23.24% and 20.17%, and the oxygen index of the test article 7 is larger than the oxygen indexes of the test article 6 and the test article 8, which shows that the flame retardant effect of the product obtained by connecting the graphene and the 6-pteridine amine is better than that of the product obtained by independently adding the graphene and the 6-pteridine amine, and the 6-pteridine amine and the graphene have a synergistic flame retardant effect.
The oxygen indexes of the test product 1, the test product 2, the test product 3, the test product 9 and the test product 10 are 26.41%, 25.16%, 24.56%, 23.37% and 22.12% respectively, the oxygen indexes of the test product 1, the test product 2 and the test product 3 are greater than the oxygen indexes of the test product 9 and the test product 10, and the flame retardant effect is better because the modified graphene flame retardant prepared by the preparation method of the invention by utilizing graphite flakes, sodium chloride, p-amino styrene, 6-pteridine amine and nitrite has the advantages that the 6-pteridine amine is bonded with the graphene, the graphene is bonded with the p-amino styrene, the graphene is used as a bridge of the 6-pteridine amine and the p-amino styrene, and the double bond on the p-amino styrene is utilized to stably introduce the flame retardant elements on the 6-pteridine amine into the polymeric polyol, so that the modified graphene flame retardant is not easy to migrate in a polyurethane product, thereby improving the overall flame retardant effect.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (5)
1. The modified graphene flame retardant containing the flame-retardant element and the double bond is characterized by comprising graphene, wherein 6-pteridine amine and p-amino styrene are connected to the graphene through chemical bonds; the modified graphene flame retardant containing the flame-retardant element and the double bonds takes part in the synthesis and addition polymerization reaction of polymer polyol by utilizing the carbon-carbon double bonds on the p-amino styrene.
2. The modified graphene flame retardant containing the flame retardant element and the double bond as claimed in claim 1, wherein the modified graphene flame retardant containing the flame retardant element and the double bond is introduced into the polyurethane material in an addition amount of 4.7%.
3. The preparation method of the modified graphene flame retardant containing the flame retardant element and the double bond according to claim 1, is characterized by comprising the following steps:
s1, ball-milling the graphite flakes and sodium chloride for 0.5-2 hours;
s2, adding p-amino styrene and 6-pteridine amine, mixing and ball-milling for 0.5-2 hours;
s3, finally adding nitrite, mixing and grinding for 4-48 hours, washing, and vacuum drying to obtain the product, namely the modified graphene flame retardant containing the flame retardant element and double bonds.
4. The preparation method of the modified graphene flame retardant containing the flame retardant element and the double bond according to claim 3, wherein the graphite flake: sodium chloride: p-aminostyrene: 6-pteridine amine: the mass ratio of the nitrous acid ester is 1: 1-15: 2-50: 2-50: 4-100.
5. The preparation method of the modified graphene flame retardant containing the flame retardant element and the double bond according to claim 4, wherein the graphite flake: p-aminostyrene: the mass ratio of the 6-pteridine amine is 1: 5: 10.
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| WO2022233108A1 (en) * | 2021-05-06 | 2022-11-10 | 福建师范大学泉港石化研究院 | Modified graphene flame retardant containing flame-retardant elements and double bonds and preparation method therefor |
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| WO2022233108A1 (en) * | 2021-05-06 | 2022-11-10 | 福建师范大学泉港石化研究院 | Modified graphene flame retardant containing flame-retardant elements and double bonds and preparation method therefor |
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