CN110294846B - Cage-net structure hybrid silsesquioxane flame retardant containing DOPO group and preparation method and application thereof - Google Patents
Cage-net structure hybrid silsesquioxane flame retardant containing DOPO group and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a cage-net structure hybrid silsesquioxane flame retardant containing DOPO groups, and a preparation method and application thereof, and belongs to the technical field of flame retardant preparation and application. The general formula of the cage-network structure hybrid silsesquioxane flame retardant containing DOPO groups is as follows: wherein the R group is an R1 group, or a combination of R1 and one or any two of R2, R3 and R4 groups, and R2 or R3 and R4 are not simultaneously present. The cage-net structure hybrid silsesquioxane flame retardant containing the DOPO group is halogen-free, non-toxic, good in flame retardant effect, good in compatibility with a polymer matrix, simple in preparation method and suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of preparation and application of flame retardants, and particularly relates to a cage-network structure hybrid silsesquioxane flame retardant containing DOPO groups, and a preparation method and application thereof.
Background
With the development of high technology, high polymer materials are widely applied in the fields of electronic appliances, transportation, aerospace, home building materials and the like. However, most of high polymer materials belong to flammable and combustible materials, and have the advantages of high heat release rate during combustion, high flame propagation speed, generation of dense smoke and toxic gas and great threat to life safety. Therefore, the flame retardant research of the polymer material becomes a problem which needs to be solved in safe production and life.
The flame retardant may be classified into inorganic flame retardants, halogen flame retardants, phosphorus flame retardants, silicon flame retardants, and the like according to the type of the flame retardant element. The inorganic flame retardant mainly comprises aluminum hydroxide and magnesium hydroxide, the flame retardant has low flame retardant efficiency and high addition amount, and the mechanical property of the material is reduced by excessively high addition amount. When the halogen flame retardant is burnt, a large amount of dense smoke is released, and corrosive gases such as hydrogen halide and toxic substances are generated, so that secondary harm is easily caused. The phosphorus flame retardant can simultaneously play a flame retardant role in a condensed phase and a gas phase during combustion. However, the addition of a single phosphorus-based flame retardant lowers the glass transition temperature of the polymer and the flame retardant effect is not significant. The flame retardant mechanism of the silicon flame retardant is mainly condensed phase flame retardant, which not only can improve the flame retardance of the polymer, but also can improve the heat stability and weather resistance of the polymer. At present, the development of environment-friendly efficient halogen-free flame retardant has become a common pursuit target in scientific research and industrial circles.
In recent years, the synthesis and application of flame retardants using 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) as an intermediate have received great attention. The DOPO and the derivative thereof are halogen-free, low in toxicity, non-migratory and durable in flame retardant property, can be used as an additive type or reactive flame retardant to be introduced into a high polymer material, and have good flame retardant effect.
Silsesquioxanes (POSS) are a class of compounds having the general structure (RSi O)1.5)xIn the molecular structure of the silane compound, R is H or various alkyl, aryl and derivatives thereof. The molecular structure mainly comprises a random structure, a trapezoidal structure, a partial cage structure and a cage structure. The unique organic-inorganic hybrid molecular structure of POSS endows the POSS with excellent thermal performance, thermal oxidation stability, mechanical property, flame retardant property and the like. Yangrojie et al, Beijing university of technology, reported (CN10178755A) a method for preparing a DOPO group-containing cage-type oligomeric silsesquioxane. However, POSS with a regular cage structure has higher in-cage action strength, and the structure causes the POSS to have poorer processing performance when being mixed with resin and is difficult to be applied to the resinIs uniformly dispersed (European Polymer journal,2010,46, 14-23). Zhang et al (Polymer degradation and stability,2010,95, 2541-. US2008/0020213a1 reports silsesquioxane oligomers containing ethylenic bonds in a cage or partial cage structure, which are added to polymers to effectively improve the heat resistance and mechanical properties of the polymers. CN106008981A reports a preparation method of a hybrid silsesquioxane resin, in which siloxane or chlorosilane is used to terminate the hybrid silsesquioxane, thereby eliminating silanol bonds, and facilitating the extension of the storage life of the resin.
Disclosure of Invention
The invention aims to provide a cage-net structure hybrid silsesquioxane flame retardant containing DOPO groups and a preparation method thereof.
The structural formula of the DOPO group-containing cage-net structure hybrid silsesquioxane flame retardant provided by the invention is shown as the formula I:
m and n represent polymerization degrees, m is 1-10,0000, such as 10-8,0000,50-5,0000, 100-1, 0000,100-5000 and the like, and n is 1-10,0000, such as 10-8,0000,50-5,0000, 100-1, 0000,100-5000 and the like.
In formula I, the R group can be an R1 group, or a combination of R1 and one or any two of R2, R3, and R4 groups, and R2 or R3 and R4 are not present at the same time (i.e., the R group can be a combination of R1 and R2, a combination of R1 and R3, a combination of R1 and R4, a combination of R1 and R2 and R3).
The DOPO group-containing cage-network structure hybrid silsesquioxane flame retardant shown in the formula I is prepared by the method comprising the following steps of:
under the action of alkali, the mixture of DOPO-VTMS or DOPO-VTMS and functionalized trimethoxy silane is subjected to hydrolytic condensation reaction to obtain the DOPO group-containing cage-network structure hybrid silsesquioxane flame retardant shown as I.
In the above method, the structural formula of DOPO-VTMS is as follows:
DOPO-VTMS can be synthesized according to literature reports (Journal of Materials Science,2017,52: 8603-.
The functionalized trimethoxy silane can be one or two of 3-aminopropyl trimethoxy silane, 2- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane and 3-glycidyloxypropyl trimethoxy silane, and the 3-aminopropyl trimethoxy silane or the 2- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane and the 3-glycidyloxypropyl trimethoxy silane do not occur simultaneously.
The molar ratio of the DOPO-VTMS to the functionalized trimethoxy silane can be 1 (0-0.5).
The alkali can be one or more of tetramethylammonium hydroxide, sodium hydroxide, potassium bicarbonate, sodium bicarbonate and triethylamine.
The molar ratio of the DOPO-VTMS or the mixture of the DOPO-VTMS and the functionalized trimethoxy silane to the alkali can be 1: 0.001-0.01.
The reaction is carried out in an organic solvent, wherein the organic solvent can be one of toluene, benzene, chloroform, dichloromethane, tetrahydrofuran, acetone, butanone, n-hexane, cyclohexane and methanol or a mixture thereof.
The proportion of the mixture of the DOPO-VTMS or the DOPO-VTMS and the functionalized trimethoxy silane to the organic solvent can be 1 g: 1 to 50 ml.
The preparation method comprises the following specific operations:
1) adding DOPO-VTMS or a mixture of DOPO-VTMS and functionalized trimethoxy silane into a reactor provided with a mechanical stirring and refluxing condenser pipe, adding an organic solvent, and stirring for 1-2 h; maintaining the temperature of the reaction system at-10-30 ℃, and then adding alkali; after the addition is finished, heating to 50-110 ℃, dropwise adding deionized water, and after the dropwise adding is finished, continuing the reaction for 30-70 h; after the reaction is finished, cooling to room temperature;
2) standing and layering, collecting a lower organic phase, washing for 3-5 times, adding a drying agent, drying, filtering, and removing an organic solvent to obtain white solid powder, namely the cage-net structure hybrid silsesquioxane flame retardant containing the DOPO group.
In the step 1), the proportion of the mixture of DOPO-VTMS or DOPO-VTMS and the functionalized trimethoxy silane to the deionized water is 1 mol: 50-150 ml.
In the step 2), the drying agent is one or a mixture of anhydrous sodium sulfate and anhydrous magnesium sulfate.
The drying time can be 6-24 h.
The application of the DOPO group-containing cage-net structure hybrid silsesquioxane flame retardant shown in the formula I also belongs to the protection scope of the invention.
The DOPO group-containing cage-network structure hybrid silsesquioxane flame retardant shown in the formula I can be independently added into a polymer matrix or added into the polymer matrix after being compounded with other general flame retardants to prepare the flame-retardant high polymer material.
The polymer matrix can be epoxy resin, polycarbonate and organic silicon resin, and can be epoxy resin specifically.
The invention also provides a flame-retardant high polymer material system containing the DOPO group-containing cage-net structure hybrid silsesquioxane flame retardant shown in the formula I.
The invention provides a cage-net structure hybrid silsesquioxane flame retardant containing DOPO groups, and a preparation method and application thereof. Compared with the prior art, the method has the following beneficial effects:
1. the flame retardant provided by the invention combines a DOPO group and a cage-network structure hybrid silsesquioxane unit into the same molecular structure, achieves the purpose of phosphorus-silicon synergistic flame retardance, has higher phosphorus content, silicon content, heat resistance and flame retardance, and simultaneously has good technological properties due to the intramolecular cage-network structure hybrid silsesquioxane unit, so that the flame retardant can be used as an additive flame retardant with good compatibility and an ideal reactive flame retardant to prepare a flame retardant polymer, thereby greatly improving the flame retardance of the flame retardant. The preparation method of the flame retardant is simple and is suitable for large-scale production.
2. The cage-net structure hybrid silsesquioxane flame retardant containing the DOPO group synthesized by the invention can be widely applied to the preparation of various flame-retardant high polymer materials, and the phosphorus-silicon flame retardant prepared by the invention can generate good flame-retardant effect when added into the high polymer materials.
Drawings
FIG. 1 is a synthesis route diagram of a cage-network structure hybrid silsesquioxane flame retardant Poly (DOPO-POSS) containing DOPO groups prepared by the embodiment of the invention.
FIG. 2 is a Fourier infrared spectrum of a cage-network hybrid silsesquioxane flame retardant Poly (DOPO-POSS) containing DOPO groups prepared in example 1 of the present invention.
FIG. 3 is an X-ray diffraction pattern of a cage-network structure hybrid silsesquioxane flame retardant Poly (DOPO-POSS) containing DOPO groups prepared in example 1 of the present invention.
FIG. 4 is a Fourier infrared spectrum of a cage-network structure hybrid silsesquioxane flame retardant Poly (DOPO/EP-POSS) -1 containing DOPO and epoxy groups prepared in example 2 of the present invention.
FIG. 5 is an X-ray diffraction pattern of a cage-network structure hybrid silsesquioxane flame retardant Poly (DOPO/EP-POSS) -1 containing DOPO and epoxy groups prepared in example 2 of the present invention.
Detailed Description
The present invention will be described below with reference to specific examples, but the present invention is not limited thereto.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Examples 1,
The cage-network hybrid silsesquioxane flame retardant Poly (DOPO-POSS) containing DOPO groups was prepared according to the synthesis scheme shown in FIG. 1.
72.846g DOPO-VTMS, 150ml butanone and 20ml methanol were added to a three-necked flask equipped with a mechanically stirred, reflux condenser, and stirred slowly for 1h to dissolve completely. Controlling the temperature of the reaction system at 0-5 ℃, adding 0.06g of sodium hydroxide, continuously stirring and heating to 60 ℃. 15ml of deionized water were slowly added dropwise. After the dropwise addition, the reaction is continued at 60 ℃ for 32h, and the temperature is reduced to room temperature after the reaction is finished.
Standing and layering, washing the organic phase for 3-5 times, adding anhydrous sodium sulfate to remove water in the organic phase, filtering the drying agent after 6 hours, and removing the organic solvent by rotary evaporation to obtain white solid powder, namely the DOPO-group-containing cage-net-structure hybrid silsesquioxane flame retardant Poly (DOPO-POSS) with the yield of 92%.
The structural representation of the prepared cage-network structure hybrid silsesquioxane flame retardant containing DOPO groups is as follows: the infrared spectrum is shown in FIG. 2. FT-IR (KBr, cm)-1):1477cm-1Is P-Ph stretching vibration peak, 1408cm-1Is P-CH on an aliphatic chain2Peak vibration 1207cm-1Is the oscillation peak of P ═ O, 1080cm-1Stretching vibration peak of Si-O-Si with irregular structure, 1114cm-1Is a stretching vibration peak of a regular cage structure Si-O-Si. As shown in FIG. 3, it can be seen that Poly (DOPO-POSS) has an amorphous structure. According to the Bragg equation, 2 theta is 5.5 degrees corresponding to the intermolecular spacing
2 θ corresponds to 13.54 °
And 2 θ corresponds to 20.74 ° f
The above characteristic data show that the structure of Poly (DOPO-POSS) conforms to the characteristics of cage structure.
Examples 2,
To a three-necked flask equipped with a mechanically stirred, reflux condenser, 18.22g DOPO-VTMS, 1.2319g2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, and 100ml tetrahydrofuran and 5ml methanol were added and stirred slowly for 1.5h to dissolve completely. Controlling the temperature of the reaction system at 15-20 ℃, adding 0.05g of tetramethylammonium hydroxide, continuously stirring and heating to 55 ℃. 8ml of deionized water were slowly added dropwise. After the dropwise addition, the reaction is continued for 60 hours at 55 ℃, and the temperature is reduced to room temperature after the reaction is finished.
Standing and layering, washing the organic phase for 3-5 times, adding anhydrous magnesium sulfate to remove water in the organic phase, filtering the drying agent after 22 hours, and removing the organic solvent by rotary evaporation to obtain white solid powder, namely the DOPO group-containing cage-net structure hybrid silsesquioxane flame retardant Poly (DOPO/EP-POSS) -1 with the yield of 95%.
The infrared spectrum is shown in FIG. 4. The X-ray diffraction pattern is shown in fig. 5.
Examples 3,
To a three-necked flask equipped with a mechanically stirred, reflux condenser, 18.22g DOPO-VTMS, 4.034g 3-aminopropyltrimethoxysilane and 500ml dichloromethane and 20ml methanol were added and stirred slowly for 2h to dissolve completely. Controlling the temperature of the reaction system at-5-0 ℃, adding 0.04g of sodium bicarbonate, continuously stirring and heating to 50 ℃. 9ml of deionized water were slowly added dropwise. After the dropwise addition, the reaction is continued at 50 ℃ for 70h, and the temperature is reduced to room temperature after the reaction is finished.
Standing and layering, washing the organic phase for 3-5 times, adding anhydrous magnesium sulfate to remove water in the organic phase, filtering the drying agent after 24 hours, and removing the organic solvent by rotary evaporation to obtain white solid powder, namely the DOPO group-containing cage-net structure hybrid silsesquioxane flame retardant Poly (DOPO/NH2-POSS) with the yield of 87%.
Examples 4,
To a three-necked flask equipped with a mechanically stirred, reflux condenser, 18.22g DOPO-VTMS, 1.23g 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 1.18g 3-glycidyloxypropyltrimethoxysilane and 180ml toluene and 10ml methanol were added and stirred slowly for 0.5h to complete dissolution. The temperature of the reaction system is controlled at 25-30 ℃, 0.05g of triethylamine is added, stirring is continued, and the temperature is raised to 100 ℃. 12ml of deionized water were slowly added dropwise. After the dropwise addition, the reaction is continued at 100 ℃ for 55 hours, and the temperature is reduced to room temperature after the reaction is finished.
Standing and layering, washing the organic phase for 3-5 times, adding anhydrous sodium sulfate to remove water in the organic phase, filtering the drying agent after 6 hours, and removing the organic solvent by rotary evaporation to obtain white solid powder, namely the DOPO group-containing cage-mesh structure hybrid silsesquioxane flame retardant Poly (DOPO/EP-POSS) -2 with the yield of 96%.
The flame retardant effect of the DOPO group-containing cage-network structure hybrid silsesquioxane flame retardant prepared in the embodiment of the invention is illustrated by specific application examples. The flame retardant effect of the flame retardant is inspected through oxygen index and vertical combustion performance tests.
Application examples 1,
The cage-network hybrid silsesquioxane flame retardant containing the DOPO group prepared in the example 1 was added to epoxy resin (E-51 epoxy resin, DDM curing agent) according to the ratio in Table 1 to prepare a flame-retardant epoxy resin sample strip, 130mm × 6.5mm × 3mm was used for a Limit Oxygen Index (LOI) test, 130 × 13mm × 3mm was used for a UL94 vertical burning performance test, the Limit Oxygen Index (LOI) test was performed by a JF-3 type oxygen index meter, and the UL94 vertical burning performance test was performed by a CZF-2 vertical burning meter, respectively. The flame retardant of the embodiment 1 of the invention is added into the epoxy resin, so that the flame retardant effect is obviously improved, the flame retardant performance is also improved along with the increase of the addition amount of the flame retardant, and the dripping phenomenon is avoided. The test results are shown in table 1 below.
TABLE 1 Effect of flame retardant epoxy resin of the invention example
Application examples 2,
The cage-network hybrid silsesquioxane flame retardant containing the DOPO group prepared in the example 2 was added to epoxy resin (E-51 epoxy resin, DDM curing agent) according to the ratio in Table 2 to prepare a flame-retardant epoxy resin sample strip, 130mm × 6.5mm × 3mm was used for a Limit Oxygen Index (LOI) test, 130 × 13mm × 3mm was used for a UL94 vertical burning performance test, the Limit Oxygen Index (LOI) test was performed by a JF-3 type oxygen index meter, and the UL94 vertical burning performance test was performed by a CZF-2 vertical burning meter, respectively. The flame retardant of the embodiment 2 of the invention is added into the epoxy resin, so that the flame retardant effect is obviously improved, the flame retardant performance is also improved along with the increase of the addition amount of the flame retardant, and the dripping phenomenon is avoided. The test results are shown in table 2 below.
TABLE 2 Effect of flame retardant epoxy resin in the examples of the present invention
Application examples 3,
The cage-network hybrid silsesquioxane flame retardant containing the DOPO group prepared in the above example 3 was added to epoxy resin (E-51 epoxy resin, DDM curing agent) according to the ratio in Table 3 to prepare a flame-retardant epoxy resin sample strip, 130mm × 6.5mm × 3mm was used for a Limit Oxygen Index (LOI) test, 130 × 13mm × 3mm was used for a UL94 vertical burning performance test, the Limit Oxygen Index (LOI) test was performed by a JF-3 type oxygen index meter, and the UL94 vertical burning performance test was performed by a CZF-2 vertical burning meter, respectively. The flame retardant of embodiment 3 of the invention is added into the epoxy resin, so that the flame retardant effect is obviously improved, the flame retardant performance is also improved along with the increase of the addition amount of the flame retardant, and the dripping phenomenon is avoided. The test results are shown in table 3 below.
TABLE 3 Effect of flame retardant epoxy resin of the invention example
Application examples 4,
The cage-network hybrid silsesquioxane flame retardant containing the DOPO group prepared in the above example 4 was added to an epoxy resin (E-51 epoxy resin, DDM curing agent) in the ratio shown in Table 4 to prepare a flame-retardant epoxy resin sample strip, 130mm × 6.5mm × 3mm was used for a Limit Oxygen Index (LOI) test, 130 × 13mm × 3mm was used for a UL94 vertical burning performance test, a JF-3 type oxygen index (LOI) test was performed respectively, and a CZF-2 vertical burning instrument was used for a UL94 vertical burning performance test. The flame retardant of the embodiment 4 of the invention is added into the epoxy resin, so that the flame retardant effect is obviously improved, the flame retardant performance is also improved along with the increase of the addition amount of the flame retardant, and the dripping phenomenon is avoided. The test results are shown in table 4 below.
TABLE 4 Effect of flame retardant epoxy resin of the invention example
Claims (10)
1. A cage-net structure hybrid silsesquioxane flame retardant containing DOPO groups has a structural formula shown as formula I:
in the formula I, R is R1A group, or is R1And R2,R3And R4One or a combination of any two of the groups, and R2Or R3And R4Not appearing at the same time;
m and n represent polymerization degrees, m is 1-10,0000, and n is 1-10, 0000.
2. A method for preparing the DOPO group-containing cage-network structure hybrid silsesquioxane flame retardant of formula I in claim 1, comprising:
under the action of alkali, the mixture of DOPO-VTMS or DOPO-VTMS and functionalized trimethoxy silane is subjected to hydrolytic condensation reaction to obtain the DOPO group-containing cage-network structure hybrid silsesquioxane flame retardant shown as I.
3. The method of claim 2, wherein: the functionalized trimethoxy silane is selected from one or two of 3-aminopropyl trimethoxy silane, 2- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane and 3-glycidyloxypropyl trimethoxy silane, and the 3-aminopropyl trimethoxy silane or the 2- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane and the 3-glycidyloxypropyl trimethoxy silane do not occur simultaneously.
4. A method according to claim 2 or 3, characterized in that: the molar ratio of the DOPO-VTMS to the functionalized trimethoxy silane is 1 (0-0.5).
5. The method of claim 2, wherein: the alkali is selected from one or a mixture of more of tetramethylammonium hydroxide, sodium hydroxide, potassium bicarbonate, sodium bicarbonate and triethylamine;
the molar ratio of the DOPO-VTMS or the mixture of the DOPO-VTMS and the functionalized trimethoxy silane to the alkali is 1: 0.001-0.01.
6. The method of claim 2, wherein: the reaction is carried out in an organic solvent,
the organic solvent is one or a mixture of toluene, benzene, chloroform, dichloromethane, tetrahydrofuran, acetone, butanone, n-hexane, cyclohexane and methanol;
the proportion of the mixture of the DOPO-VTMS or the DOPO-VTMS and the functionalized trimethoxy silane to the organic solvent is 1 g: 1 to 50 ml.
7. The method of claim 2, wherein: the method is realized by the following operations:
1) adding DOPO-VTMS or a mixture of DOPO-VTMS and functionalized trimethoxy silane into a reactor provided with a mechanical stirring and refluxing condenser pipe, adding an organic solvent, and stirring for 1-2 h; maintaining the temperature of the reaction system at-10-30 ℃, and then adding alkali; after the addition is finished, heating to 50-110 ℃, dropwise adding deionized water, and after the dropwise adding is finished, continuing the reaction for 30-70 h; after the reaction is finished, cooling to room temperature;
2) standing and layering, collecting a lower organic phase, washing for 3-5 times, adding a drying agent, drying, filtering, and removing an organic solvent to obtain white solid powder, namely the cage-net structure hybrid silsesquioxane flame retardant containing the DOPO group.
8. The method of claim 7, wherein: in the step 1), the proportion of the mixture of DOPO-VTMS or DOPO-VTMS and functionalized trimethoxy silane to deionized water is 1 mol: 50-150 ml;
in the step 2), the drying agent is one or a mixture of anhydrous sodium sulfate and anhydrous magnesium sulfate;
the drying time is 6-24 h.
9. A flame-retardant polymer material system containing the cage-network structure hybrid silsesquioxane flame retardant containing DOPO groups shown in formula I in claim 1.
10. A method of making the flame retardant polymeric material system of claim 9, comprising: adding the DOPO group-containing cage-network hybrid silsesquioxane flame retardant shown in formula I in claim 1 into a polymer matrix to obtain a flame-retardant high polymer material system.
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| US5939576A (en) * | 1998-01-05 | 1999-08-17 | The United States Of America As Represented By The Secretary Of The Air Force | Method of functionalizing polycyclic silicones and the compounds so formed |
| CN101787055A (en) * | 2010-03-17 | 2010-07-28 | 北京理工大学 | Polyhedral oligomeric silsesquioxane containing DOPO group and preparation method thereof |
| CN101792537A (en) * | 2010-03-17 | 2010-08-04 | 北京理工大学 | Silane coupling agent containing DOPO group and preparation method thereof |
| CN106008981A (en) * | 2016-06-08 | 2016-10-12 | 中国船舶重工集团公司第七二五研究所 | Preparation method for hybrid silsesquioxane resin |
| CN106750317A (en) * | 2017-01-13 | 2017-05-31 | 山东船舶技术研究院 | One kind is based on caged polysilsesquioxane phosphonium flame retardant and preparation method thereof |
| CN107090083A (en) * | 2017-04-12 | 2017-08-25 | 湖北大学 | It is nitrogen phosphorus siliceous copolymer of main chain and preparation method and application containing double-deck silsesquioxane |
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