CN113121778A - Polyurethane flame-retardant foam material containing modified graphene and preparation method thereof - Google Patents
Polyurethane flame-retardant foam material containing modified graphene and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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Abstract
The invention relates to the technical field of polyurethane flame-retardant foaming materials, and discloses a polyurethane flame-retardant foaming material containing modified graphene and a preparation method thereof. The polyurethane flame-retardant foaming material containing the modified graphene has a good flame-retardant effect.
Description
Technical Field
The invention belongs to the technical field of polyurethane flame-retardant foaming materials, and particularly relates to a polyurethane flame-retardant foaming material containing modified graphene and a preparation method thereof.
Background
The polyurethane foam material is a high molecular polymer which is prepared by mixing isocyanate, polyether polyol, polymer polyol and the like serving as main raw materials under the action of various auxiliary agents such as a foaming agent, a catalyst, a flame retardant and the like through special equipment and performing high-pressure spraying and on-site foaming, and is widely applied to the fields of clothes, shoes and hats, building outer walls, furniture, automobiles, medical treatment and the like due to the excellent characteristics of light weight, small heat conductivity and the like. However, the common polyurethane foaming material has poor flame retardant property, and has a 'pushing and rolling' effect when buildings and equipment are on fire, so that the flame retardant property of the polyurethane foam is always the focus of research.
To improve the flame retardant property of polyurethane materials, there are two ways:
the first is to add flame retardant containing phosphorus, chlorine, bromine or other flame retardant elements in the formula, and the additive flame retardant has the advantages of high content of flame retardant elements and low price, but the additive flame retardant has the problems of easy migration and serious influence on the mechanical properties of the material when the additive amount is large. For example, the mechanical property of the material is reduced sharply when the mass fraction of the dimethyl methylphosphonate (DMMP) is more than 8%.
Secondly, a reactive flame retardant such as a polyhydroxy compound containing a flame retardant element is added into the formula, however, although a plurality of compounds containing the flame retardant element exist, all the compounds containing the flame retardant element do not have active groups to be bonded with other components of the foaming material in a reaction way, and some compounds containing the flame retardant element can introduce the active groups by a chemical reaction and other methods, but the reaction process is complicated, and the requirement on the reaction condition is high, so that the stable introduction of the flame retardant element into the foaming material is limited.
Disclosure of Invention
The invention aims to provide a polyurethane flame-retardant foam material containing modified graphene, which has the advantages that 2-amino-1, 3, 5-triazine containing flame-retardant elements is not easy to migrate, and graphene and 2-amino-1, 3, 5-triazine are flame-retardant in a synergistic manner, so that the obtained polyurethane flame-retardant foam material containing modified graphene has a good flame-retardant effect.
The above object of the present invention is achieved by the following technical solutions: the polyurethane flame-retardant foam material containing the modified graphene comprises the following raw materials in parts by weight: 5-15 parts of polymer polyol, 5-15 parts of high-activity polyether polyol, 2-8 parts of isocyanate, 0.2-0.5 part of water, 0.05-0.12 part of silicone oil and 0.01-0.05 part of first catalyst; the polymeric polyol is prepared by polymerizing 1-10 parts of modified graphene, 30-55 parts of high-activity polyether polyol, 15-30 parts of styrene, 10-19 parts of acrylonitrile, 0.2-6 parts of initiator, 1-8 parts of dispersant and 5-10 parts of chain transfer agent; the modified graphene is prepared by ball-milling graphite flakes and sodium chloride, adding p-amino styrene and 2-amino-1, 3, 5-triazine, finally adding tert-butyl nitrite, fully reacting, ball-milling, washing and drying.
By adopting the technical scheme, firstly, tert-butyl nitrite reacts with amino in 2-amino-1, 3, 5-triazine to generate diazonium salt, the diazonium salt removes nitrogen to generate benzene free radical, the benzene free radical reacts with a carbon layer on the surface layer of graphite flake to chemically bond the 2-amino-1, 3, 5-triazine and the graphite flake together, then the graphite flake and p-amino styrene are chemically bonded together by the same method, finally, modified graphene bonded with the 2-amino-1, 3, 5-triazine and the p-amino styrene is formed by ball milling, the modified graphene carries out polymerization reaction by utilizing double bonds in the p-amino styrene and other components of polymerized polyol to stably introduce flame-retardant elements in the 2-amino-1, 3, 5-triazine into the polymer polyol, and then foaming the polymer polyol and other components of the polyurethane foam material to obtain the polyurethane flame-retardant foam material containing the modified graphene, wherein the 2-amino-1, 3, 5-triazine containing flame-retardant elements in the polyurethane flame-retardant foam material is not easy to migrate, and the 2-amino-1, 3, 5-triazine and the graphene have a synergistic flame-retardant effect, so that the polyurethane flame-retardant foam material containing the modified graphene has a better overall flame-retardant effect.
Further, the graphite flake: sodium chloride: p-aminostyrene: 2-amino-1, 3, 5-triazine: the mass ratio of tert-butyl nitrite is 1: 1-15: 2-50: 2-50: 4-100.
Further, the molecular weight of the high activity polyether polyol is 2000-5000.
Further, the first catalyst is a mixture of an organotin catalyst and triethanolamine, and the organotin catalyst is one or more of stannous octoate and dibutyltin diacetate.
Further, the isocyanate is one or more of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI), and Lysine Diisocyanate (LDI).
Another object of the present invention is to provide a method for preparing a polyurethane flame-retardant foam material containing modified graphene, which can stably introduce substances, such as 2-amino-1, 3, 5-triazine, which do not contain active groups reactive with other components of polyurethane into a polyurethane foam material and are not prone to migration, and at the same time, the method for stably introducing 2-amino-1, 3, 5-triazine into a polyurethane foam material is simple and easy to operate.
The above object of the present invention is achieved by the following technical solutions: a polyurethane flame-retardant foam material containing modified graphene is prepared according to the following steps:
s1, ball-milling graphite flakes and sodium chloride, adding p-amino styrene and 2-amino-1, 3, 5-triazine, fully mixing and ball-milling, adding tert-butyl nitrite for full ball-milling, and finally washing and drying to obtain modified graphene;
s2, mixing the modified graphene obtained in the S1 with high-activity polyether polyol, styrene, acrylonitrile, an initiator, a dispersing agent and a chain transfer agent to obtain a first mixture, completely dripping the first mixture into another high-activity polyether polyol, completely reacting the first mixture with the another high-activity polyether polyol, standing and cooling to obtain polymer polyol;
and S3, foaming the polymer polyol obtained in the step S2 with another high-activity polyether polyol, isocyanate, water, silicone oil and a first catalyst to obtain the polyurethane flame-retardant foaming material containing the modified graphene.
By adopting the technical scheme, 2-amino-1, 3, 5-triazine, p-amino styrene and graphite flake are used as raw materials, tert-butyl nitrite is utilized to react with diazo of the 2-amino-1, 3, 5-triazine and p-amino styrene to generate active groups, so that the 2-amino-1, 3, 5-triazine and p-amino styrene are bonded with graphene to form graphene containing flame retardant elements and double bonds, and the double bonds of the graphene are utilized to polymerize with other components of polymer polyol, so that the flame retardant elements are stably introduced into the polymer polyol.
Further, in the step S1, the ball milling time of the graphite flakes and sodium chloride is 0.5 to 2 hours, the ball milling time after adding p-amino styrene and 2-amino-1, 3, 5-triazine is 0.5 to 2 hours, and the ball milling time after adding tert-butyl nitrite is 2 to 48 hours.
Further, the reaction temperature of the first mixture and the other high-activity polyether polyol in the step S2 is 80-130 ℃, and the reaction time is 0.5-1.5 hours.
In conclusion, the invention has the following beneficial effects:
1. the flame retardant elements on the 2-amino-1, 3, 5-triazine can be stably introduced into the polymeric polyol and are not easy to migrate, and meanwhile, the 2-amino-1, 3, 5-triazine 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 introducing the flame-retardant elements in the 2-amino-1, 3, 5-triazine into the polymer polyol by utilizing the p-amino styrene, the graphite flakes, the tert-butyl nitrite and ball milling is simple and easy to operate.
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 polyurethane flame-retardant foam material containing modified graphene is prepared by weighing 10 parts of graphite flakes and 100 parts of sodium chloride by weight, performing ball milling for 2 hours, adding 50 parts of p-amino styrene and 100 parts of 2-amino-1, 3, 5-triazine, fully mixing and performing ball milling for 2 hours, adding 180 parts of tert-butyl nitrite, performing full ball milling for 48 hours, and finally washing and drying to obtain modified graphene; weighing 10 parts of modified graphene, 15 parts of high-activity polyether polyol (with the molecular weight of 5000), 25 parts of styrene, 15 parts of acrylonitrile, 4 parts of initiator, 5 parts of dispersant and 6 parts of chain transfer agent, mixing to obtain a first mixture, completely dropwise adding the first mixture into another 30 parts of high-activity polyether polyol (with the molecular weight of 5000), wherein the reaction temperature is 130 ℃, the reaction time is 1.5 hours, and after complete reaction, standing and cooling to obtain polymer polyol; weighing 20 parts of the polymeric polyol, and in addition, weighing 10 parts of high-activity polyether polyol (with the molecular weight of 5000), 10 parts of isocyanate (toluene diisocyanate), 0.5 part of water, 0.12 part of silicone oil and 0.05 part of first catalyst (0.03 part of stannous octoate and 0.02 part of triethanolamine) for foaming to obtain a final product, namely the polyurethane flame-retardant foaming material containing the modified graphene.
Example two: a polyurethane flame-retardant foam material containing modified graphene is prepared by weighing 10 parts by weight of graphite flakes and 100 parts by weight of sodium chloride, performing ball milling for 1.5 hours, adding 50 parts by weight of p-aminostyrene and 50 parts by weight of 2-amino-1, 3, 5-triazine, fully mixing and ball milling for 1.5 hours, adding 120 parts by weight of tert-butyl nitrite, fully performing ball milling for 48 hours, and finally washing and drying to obtain modified graphene; weighing 10 parts of modified graphene, 20 parts of high-activity polyether polyol (with the molecular weight of 3000), 45 parts of styrene, 15 parts of acrylonitrile, 1 part of initiator, 5 parts of dispersant and 8 parts of chain transfer agent, mixing to obtain a first mixture, completely dropwise adding the first mixture into another 25 parts of high-activity polyether polyol (with the molecular weight of 3000), reacting at the temperature of 118 ℃ for 1 hour, standing and cooling after complete reaction to obtain polymer polyol; weighing 10 parts of the polymeric polyol, and in addition, weighing 10 parts of high-activity polyether polyol (with the molecular weight of 3000), 8 parts of isocyanate (diphenylmethane diisocyanate), 0.4 part of water and 0.03 part of first catalyst (0.02 part of stannous octoate and 0.01 part of triethanolamine) for foaming to obtain a final product, namely the polyurethane flame-retardant foaming material containing the modified graphene.
Example three: a polyurethane flame-retardant foam material containing modified graphene is prepared by weighing 10 parts of graphite flakes and 100 parts of sodium chloride by weight, performing ball milling for 2 hours, adding 20 parts of p-amino styrene and 50 parts of 2-amino-1, 3, 5-triazine, fully mixing and performing ball milling for 2 hours, adding 84 parts of tert-butyl nitrite, performing full ball milling for 48 hours, and finally washing and drying to obtain modified graphene; weighing 1 part of the modified graphene, 15 parts of high-activity polyether polyol (molecular weight 2000), 30 parts of styrene, 10 parts of acrylonitrile, 2 parts of initiator, 1 part of dispersant and 5 parts of chain transfer agent, mixing to obtain a first mixture, completely dropwise adding the first mixture into another 15 parts of high-activity polyether polyol (molecular weight 2000), reacting at the temperature of 80 ℃ for 0.5 hour, and standing and cooling after complete reaction to obtain polymer polyol; weighing 5 parts of the polymeric polyol, and in addition, weighing 5 parts of high-activity polyether polyol (molecular weight 2000), 4 parts of isocyanate (dicyclohexylmethane diisocyanate), 0.2 part of water and 0.01 part of first catalyst (0.008 part of stannous octoate and 0.002 part of triethanolamine) for foaming to obtain a final product, namely the polyurethane flame-retardant foaming material containing the modified graphene.
Comparative example:
comparative example one: the modified graphene is replaced by a substance A and then is mixed with other components of polymer polyol, wherein the substance A is obtained by weighing 10 parts of graphite flakes and 100 parts of sodium chloride, performing ball milling for 2 hours, adding 50 parts of p-amino styrene, fully mixing and performing ball milling for 2 hours, then adding 60 parts of tert-butyl nitrite, fully performing ball milling for 48 hours, and finally washing and drying.
Comparative example two: the modified graphene is replaced by a substance B and then is mixed with other components of polymer polyol, wherein the substance B is obtained by weighing 10 parts of graphite flakes and 100 parts of sodium chloride, performing ball milling for 2 hours, adding 100 parts of 2-amino-1, 3, 5-triazine, fully mixing and ball milling for 2 hours, adding 120 parts of tert-butyl nitrite, performing full ball milling for 48 hours, and finally washing and drying.
Comparative example three: the difference from example one is that the modified graphene of the present invention is mixed with other components of polymer polyol after being replaced with a substance C, which is a mixture of 10 parts of graphite flake 50 parts of p-amino styrene and 100 parts of 2-amino-1, 3, 5-triazine.
Comparative example four: the difference from example one is that the modified graphene of the present invention is mixed with other components of the polymer polyol after being replaced with dimethyl methylphosphonate.
Comparative example five: it differs from example one in that the modified graphene of the present invention is replaced with a mixture of graphene and 2-amino-1, 3, 5-triazine and then mixed with the other components of the polymer polyol.
Comparative example six: the difference from example one is that the modified graphene of the present invention is mixed with other components of the polymer polyol after being replaced with graphene.
Comparative example seven: the difference from example one is that the modified graphene of the present invention is mixed with other components of the polymer polyol after being replaced with 2-amino-1, 3, 5-triazine.
The performance tests were performed on examples one to three, and comparative examples one to seven, to obtain table 1.
Table 1 results of performance testing
It can be seen from the data in table 1 that the oxygen indexes of the first to third examples are 27.52%, 26.31% and 24.87%, respectively, while the oxygen indexes of the first to third comparative examples are 23.23%, 24.98% and 22.87%, respectively, and the oxygen indexes of the first to third examples are greater than those of the first to third comparative examples, which are more excellent in flame retardant effect, mainly because the modified graphene obtained by the present invention has 2-amino-1, 3, 5-triazine bonded to graphene, the graphene is bonded to p-amino styrene, the graphene is used as a bridge between 2-amino-1, 3, 5-triazine and p-amino styrene, and the double bond on the p-amino styrene is used to stably introduce the flame retardant element on the 2-amino-1, 3, 5-triazine into the polymeric polyol so that 2-amino-1, 3, the flame-retardant element in the 5-triazine is stably introduced into the polymer polyol, so that the modified graphene-containing polyurethane flame-retardant foam material prepared from the polymer polyol is not easy to migrate, and the polyurethane flame-retardant foam material containing the modified graphene has a good overall flame-retardant effect.
The oxygen index of the first embodiment is 27.52%, the oxygen index of the fourth embodiment is 22.94%, the oxygen index of the first embodiment is larger than that of the fourth embodiment, the flame retardant effect is better, and compared with a flame retardant (dimethyl methylphosphonate) frequently used in the prior art, the modified graphene has good stability in the polyurethane flame retardant foaming material, and the graphene and 2-amino-1, 3, 5-triazine have a synergistic flame retardant effect, so that the flame retardant effect of the polyurethane flame retardant foaming material obtained in the first embodiment is better than that of the polyurethane flame retardant foaming material obtained in the fourth embodiment.
The oxygen index of the fifth comparative example is 23.98%, while the oxygen indexes of the sixth comparative example and the seventh comparative example are 21.89% and 23.11%, and the oxygen index of the fifth comparative example is larger than that of the sixth comparative example and the seventh comparative example, so that the flame retardant effect is better, which shows that when the graphene and the 2-amino-1, 3, 5-triazine exist simultaneously, the flame retardant effect is better than that when the graphene and the 2-amino-1, 3, 5-triazine exist separately, and the 2-amino-1, 3, 5-triazine and the graphene have the synergistic 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 (8)
1. The modified graphene-containing polyurethane flame-retardant foam material is characterized by comprising the following raw materials in parts by weight: 5-15 parts of polymer polyol, 5-15 parts of high-activity polyether polyol, 2-8 parts of isocyanate, 0.2-0.5 part of water, 0.05-0.12 part of silicone oil and 0.01-0.05 part of first catalyst; the polymeric polyol is prepared by polymerizing 1-10 parts of modified graphene, 30-55 parts of high-activity polyether polyol, 30-55 parts of styrene, 10-19 parts of acrylonitrile, 0.2-6 parts of initiator, 1-8 parts of dispersant and 5-10 parts of chain transfer agent; the modified graphene is prepared by ball-milling graphite flakes and sodium chloride, adding p-amino styrene and 2-amino-1, 3, 5-triazine, finally adding tert-butyl nitrite, fully reacting, ball-milling, washing and drying.
2. The polyurethane flame-retardant foam material containing modified graphene according to claim 1, wherein the ratio of graphite flakes: sodium chloride: p-aminostyrene: 2-amino-1, 3, 5-triazine: the mass ratio of tert-butyl nitrite is 1: 1-15: 2-50: 2-50: 4-100.
3. The polyurethane flame-retardant foam material containing modified graphene as claimed in claim 1, wherein the molecular weight of the high-activity polyether polyol is 2000-5000-.
4. The polyurethane flame-retardant foaming material containing the modified graphene as claimed in claim 1, wherein the first catalyst is a mixture of an organotin catalyst and triethanolamine, and the organotin catalyst is one or more of stannous octoate and dibutyltin diacetate.
5. The polyurethane flame-retardant foaming material containing modified graphene according to claim 1, wherein the isocyanate is one or more of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI) and Lysine Diisocyanate (LDI).
6. The preparation method of the polyurethane flame-retardant foam material containing the modified graphene according to claim 1, which is characterized by comprising the following steps:
s1, ball-milling graphite flakes and sodium chloride, adding p-amino styrene and 2-amino-1, 3, 5-triazine, fully mixing and ball-milling, adding tert-butyl nitrite for full ball-milling, and finally washing and drying to obtain modified graphene;
s2, mixing the modified graphene obtained in the S1 with high-activity polyether polyol, styrene, acrylonitrile, an initiator, a dispersing agent and a chain transfer agent to obtain a first mixture, completely dripping the first mixture into another high-activity polyether polyol, completely reacting the first mixture with the another high-activity polyether polyol, standing and cooling to obtain polymer polyol;
and S3, foaming the polymer polyol obtained in the step S2 with another high-activity polyether polyol, isocyanate, water, silicone oil and a first catalyst to obtain the polyurethane flame-retardant foaming material containing the modified graphene.
7. The method for preparing the polyurethane flame retardant foaming material containing the modified graphene as claimed in claim 6, wherein in the step S1, the ball milling time of the graphite flakes and the sodium chloride is 0.5-2 hours, the ball milling time after the p-amino styrene and the 2-amino-1, 3, 5-triazine are added is 0.5-2 hours, and the ball milling time after the tert-butyl nitrite is added is 2-48 hours.
8. The method for preparing the polyurethane flame-retardant foaming material containing the modified graphene according to claim 6, wherein the reaction temperature of the first mixture and the another high-activity polyether polyol in the step S2 is 80-130 ℃, and the reaction time is 0.5-1.5 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114957962A (en) * | 2022-05-27 | 2022-08-30 | 浙江奥康鞋业股份有限公司 | Preparation method and application of graphene foam material |
| CN116478528A (en) * | 2023-03-13 | 2023-07-25 | 安徽誉林新材料科技有限公司 | Graphene modified polyurethane resin material and preparation process thereof |
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