CN109021239A - It is a kind of while there is phosphorous and double bond group Polyhedral oligomeric silsesquioxane and its preparation method and application - Google Patents
It is a kind of while there is phosphorous and double bond group Polyhedral oligomeric silsesquioxane and its preparation method and application Download PDFInfo
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- CN109021239A CN109021239A CN201811002435.4A CN201811002435A CN109021239A CN 109021239 A CN109021239 A CN 109021239A CN 201811002435 A CN201811002435 A CN 201811002435A CN 109021239 A CN109021239 A CN 109021239A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
Abstract
The present invention provides a kind of there is phosphorous and double bond group Polyhedral oligomeric silsesquioxane simultaneously, belongs to Polyhedral oligomeric silsesquioxane field.The present invention can adjust phosphorus-containing groups and group containing double bond ratio in Polyhedral oligomeric silsesquioxane according to different actual demands, and the type of phosphorus-containing groups and the type of group containing double bond is also adjusted, and achieve the purpose that control phosphorus content and reactive group amount；The double bond group that Polyhedral oligomeric silsesquioxane contains can be chemically reacted with a variety of groups, can be regulated and controled double bond group and the reaction of corresponding group according to the performance requirement of different polymer, finally be realized multifunction and high performance in the polymeric material；The silicon phosphorus synergistic effect for utilizing polysiloxanes simultaneously, can be realized higher flame retardant property under low content；And it is provided by the invention while having that phosphorous and double bond group thermal stability is good, carbon left is high, V-0 grades of PC composite material UL 94 may be implemented in the case where additive amount is few.
Description
Technical field
The invention belongs to Polyhedral oligomeric silsesquioxane technical fields, more particularly to one kind to have phosphorous and double bond base simultaneously
The Polyhedral oligomeric silsesquioxane and its preparation method and application of group.
Background technique
Polyhedral oligomeric silsesquioxane is a kind of inorganic kernel and apex angle that the silicon oxygen skeleton alternately connected with Si-O is formed
The hybrid inorganic-organic macromolecule of organic group composition can be classified as complete cage type and imperfect according to envelope angle integrity degree
Polyhedral oligomeric silsesquioxane.The three-dimensional dimension of Polyhedral oligomeric silsesquioxane is typically within the scope of nanoscale, is typical
Nano compound, have nanoparticle small-size effect, surface and interfacial effect, quantum size effect, macroscopic quantum tunnel
Channel effect to have stronger comprehensive performance, therefore is preparing high performance mechanical organ, sensor, energy and material and light
The fields such as electric material are with a wide range of applications.
By controlling the difference of Polyhedral oligomeric silsesquioxane apex angle R base, applications different in the polymer may be implemented
Value.Phosphorus-containing groups are introduced in R base, it is preferably fire-retardant to can use P, Si collaboration performance in polymer nanocomposites
Effect, and reactive group is introduced in R base can lay the foundation for further MOLECULE DESIGN.Current most of phosphorous oligomeric silicon
The research of sesquioxyalkane concentrates on trapezoidal and complete cage type field.
Summary of the invention
In view of this, there is phosphorous and double bond group polyhedral oligomeric silicon times simultaneously the purpose of the present invention is to provide a kind of
Half oxygen alkane and its preparation method and application.With phosphorous and double bond group polyhedral oligomeric silicon times while provided by the invention new
Half oxygen alkane belongs to imperfect Polyhedral oligomeric silsesquioxane, can according to different demands control oligomeric silsesquioxane in phosphorus content and
Double bond radical amount.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides having phosphorous and double bond group Polyhedral oligomeric silsesquioxane simultaneously, including with formula A, B
With two or three in structural compounds shown in C:
Described have shown in formula A, B and C that R independently includes R in structural compounds1、R2、R3、R4And R5One of or it is more
Kind, it is described that there is R in structural compounds shown in formula A, B and C to contain R simultaneously1；
Wherein,
R1InFor alkyl or substituted hydrocarbon radical, the substituent group of the substituted hydrocarbon radical is ester group, hydroxyl or ehter bond.
Preferably, the molecular weight of the Polyhedral oligomeric silsesquioxane is 600~3200.
The present invention also provides have phosphorous and double bond group polyhedral oligomeric silicon sesquialter described in above-mentioned technical proposal simultaneously
The preparation method of oxygen alkane, comprising the following steps:
The silane coupling agent of phosphorous silane coupling agent, group containing double bond is mixed with the first organic solvent, obtains mixing molten
Liquid；
After concentrated hydrochloric acid and water is successively added dropwise into the mixed solution, condensation reaction is hydrolyzed, obtains hydrolytic condensation production
Object；
The hydrolysis condensation product is instilled in water, Polyhedral oligomeric silsesquioxane is obtained and the complete silane of unreacted is even
Join the mixture of agent；
It is instilled in n-hexane after the mixture is mixed with the second organic solvent, white solid is precipitated, is had simultaneously
There is phosphorous and double bond group Polyhedral oligomeric silsesquioxane；Second organic solvent includes methylene chloride, benzene, toluene, two
One of toluene and chloroform are a variety of.
Preferably, the molar ratio of the phosphorous silane coupling agent and the silane coupling agent of group containing double bond be 1:0.06~
3.5。
Preferably, the phosphorous silane coupling agent is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide trimethoxy
Miscellaneous -10- phospho hetero phenanthrene -10- oxide the triethoxysilane of base silane, 9,10- dihydro-9-oxy, diphenyl phosphine oxide trimethoxy silicon
Alkane, diphenyl phosphine oxide triethoxysilane, diphenylphosphine trimethoxy silane, diphenylphosphine triethoxysilane, dimethyl phosphine
Trimethoxy silane or dimethyl phosphine triethoxysilane.
Preferably, the silane coupling agent of the group containing double bond is vinyltrimethoxysilane, vinyl triethoxyl
Silane, acrylic trimethoxy silane, acrylic triethoxysilane, γ-methacryloxypropyl trimethoxy silane
Or γ-methacryloxypropyl.
Preferably, the quality of the concentrated hydrochloric acid and the volume ratio of mixed solution are 1g:50~100mL.
Preferably, the temperature of the hydrolysis-condensation reaction is 40~100 DEG C, and the time is 10~36h.
Preferably, first organic solvent includes one of alcohol, acetone, acetonitrile and chloroform of C1~C2 or more
Kind.
The present invention also provides have phosphorous and double bond group polyhedral oligomeric silicon sesquialter described in above-mentioned technical proposal simultaneously
Application of the oxygen alkane in flame retardant area.
There is phosphorous and double bond group Polyhedral oligomeric silsesquioxane simultaneously the present invention provides a kind of.The present invention can be with
According to different actual demands, phosphorus-containing groups and group containing double bond ratio in Polyhedral oligomeric silsesquioxane are adjusted, is also adjusted
The type of phosphorus-containing groups and the type of group containing double bond achieve the purpose that control phosphorus content and reactive group amount；Polyhedral oligomeric silicon
The double bond group that sesquioxyalkane contains can be chemically reacted with a variety of groups, can be adjusted according to the performance requirement of different polymer
Double bond group and the reaction of corresponding group are controlled, finally realizes multifunction and high performance in the polymeric material；It utilizes simultaneously
The silicon phosphorus synergistic effect of polysiloxanes, can be realized higher flame retardant property under low content；And provided by the invention have simultaneously
The thermal stability of phosphorous and double bond group Polyhedral oligomeric silsesquioxane is good, carbon left is high, in the case where additive amount is few
94V-0 grades of PC composite material UL may be implemented, the compatibility of material and the resistance of material can be improved in PC/ABS composite material
Combustion property.
Also, preparation method provided by the invention while that there is phosphorous and double bond group Polyhedral oligomeric silsesquioxane
Raw material sources are extensive, have reaction condition mild, reproducible, and yield is high, easy to operate, are suitble to expanding production.
Detailed description of the invention
Fig. 1 is 1 medium vinyl triethoxysilane of embodiment, the miscellaneous -10- phospho hetero phenanthrene -10- oxide of 9,10- dihydro-9-oxy
The FT-IR spectrogram of triethoxysilane and Polyhedral oligomeric silsesquioxane (1)；
Fig. 2 is 1 medium vinyl triethoxysilane of embodiment, the miscellaneous -10- phospho hetero phenanthrene -10- oxide of 9,10- dihydro-9-oxy
Triethoxysilane and Polyhedral oligomeric silsesquioxane (1)1H-NMR spectrum；
While Fig. 3 is that each main peaks represent in the MALDI-TOF figure of Polyhedral oligomeric silsesquioxane (1) in embodiment 1
With phosphorous and double bond group Polyhedral oligomeric silsesquioxane structural formula；
Fig. 4 is 2 medium vinyl triethoxysilane of embodiment, the miscellaneous -10- phospho hetero phenanthrene -10- oxide of 9,10- dihydro-9-oxy
The FT-IR spectrogram of triethoxysilane and Polyhedral oligomeric silsesquioxane (2)；
Fig. 5 is 2 medium vinyl triethoxysilane of embodiment, the miscellaneous -10- phospho hetero phenanthrene -10- oxide of 9,10- dihydro-9-oxy
Triethoxysilane and Polyhedral oligomeric silsesquioxane (2)1H-NMR spectrum；
Fig. 6 is Polyhedral oligomeric silsesquioxane (2) in embodiment 229Si-NMR spectrogram；
Fig. 7 is tool while each main peaks represent in Polyhedral oligomeric silsesquioxane (2) MALDI-TOF figure in embodiment 2
There is phosphorous and double bond group Polyhedral oligomeric silsesquioxane structural formula；
Fig. 8 is 3 medium vinyl triethoxysilane of embodiment, the miscellaneous -10- phospho hetero phenanthrene -10- oxide of 9,10- dihydro-9-oxy
The FT-IR spectrogram of triethoxysilane and Polyhedral oligomeric silsesquioxane (3)；
Fig. 9 is 3 medium vinyl triethoxysilane of embodiment, the miscellaneous -10- phospho hetero phenanthrene -10- oxide of 9,10- dihydro-9-oxy
Triethoxysilane and Polyhedral oligomeric silsesquioxane (3)1H-NMR spectrum；
While Figure 10 is that each main peaks represent in the MALDI-TOF figure of Polyhedral oligomeric silsesquioxane (3) in embodiment 3
With phosphorous and double bond group Polyhedral oligomeric silsesquioxane structural formula；
Figure 11 is the heat with phosphorous and double bond group Polyhedral oligomeric silsesquioxane while prepared by Examples 1 to 3
Stability curve.
Specific embodiment
The present invention provides having phosphorous and double bond group Polyhedral oligomeric silsesquioxane simultaneously, including with formula A, B
With two or three in structural compounds shown in C:
Described have shown in formula A, B and C that R independently includes R in structural compounds1、R2、R3、R4And R5One of or it is more
Kind, it is described that there is R in structural compounds shown in formula A, B and C to contain R simultaneously1；
Wherein,
R1InFor alkyl or substituted hydrocarbon radical, the substituent group of the substituted hydrocarbon radical is ester group, hydroxyl or ehter bond.
In the present invention, described while there is phosphorous and double bond group Polyhedral oligomeric silsesquioxane to preferably include to have
Structural compounds shown in formula A and B, with structural compounds shown in formula B and C or have formula A, B and C shown in structural compounds.
In the present invention, in Polyhedral oligomeric silsesquioxane described while that there is phosphorous and double bond group, R1Preferably-
HC=CH2, R2Preferably
In the present invention, the molecular weight of the Polyhedral oligomeric silsesquioxane is preferably 600~3200.
In the present invention, the phosphorus content of the Polyhedral oligomeric silsesquioxane is preferably 0.03~25wt%.
In the present invention, the molar ratio of the phosphor-containing structure and group containing double bond structure is preferably 1~7:1~2, in this hair
In bright embodiment, specifically preferably 7:1,1:1,1.5:1,7:2 or 1:2.
The present invention is to the R1And R2、R3、R4Or R5Position there is no special restriction, the R1And R2、R3、R4Or R5It can
With it is adjacent can also be non-conterminous.
The present invention also provides have phosphorous and double bond group polyhedral oligomeric silicon sesquialter described in above-mentioned technical proposal simultaneously
The preparation method of oxygen alkane, comprising the following steps:
The silane coupling agent of phosphorous silane coupling agent, group containing double bond is mixed with the first organic solvent, obtains mixing molten
Liquid；
After concentrated hydrochloric acid and water is successively added dropwise into the mixed solution, condensation reaction is hydrolyzed, obtains hydrolytic condensation production
Object；
The hydrolysis condensation product is instilled in water, Polyhedral oligomeric silsesquioxane is obtained and the complete silane of unreacted is even
Join the mixture of agent；
It is instilled in n-hexane after the mixture is mixed with the second organic solvent, white solid is precipitated, is had simultaneously
There is phosphorous and double bond group Polyhedral oligomeric silsesquioxane, second organic solvent includes methylene chloride, benzene, toluene, two
One of toluene and chloroform are a variety of.
The present invention mixes the silane coupling agent of phosphorous silane coupling agent, group containing double bond with the first organic solvent, obtains
Mixed solution.
In the present invention, the molar ratio of the phosphorous silane coupling agent and the silane coupling agent of group containing double bond is preferably 1:
0.06~3.5, more preferably 1:0.5~2, most preferably 1:1~1.2.
In the present invention, the phosphorous silane coupling agent is preferably the miscellaneous -10- phospho hetero phenanthrene -10- oxidation of 9,10- dihydro-9-oxy
Miscellaneous -10- phospho hetero phenanthrene -10- oxide (DOPO) triethoxysilane of object (DOPO) trimethoxy silane, 9,10- dihydro-9-oxy,
Diphenyl phosphine oxide (DPOP) trimethoxy silane, diphenyl phosphine oxide (DPOP) triethoxysilane, diphenylphosphine (DPP) trimethoxy
Base silane, three second of diphenylphosphine (DPP) triethoxysilane, dimethyl phosphine (DMP) trimethoxy silane or dimethyl phosphine (DMP)
Oxysilane.
In the present invention, the silane coupling agent of the group containing double bond is preferably vinyltrimethoxysilane, vinyl
Triethoxysilane, acrylic trimethoxy silane, acrylic triethoxysilane, γ-methacryloxypropyl front three
Oxysilane or γ-methacryloxypropyl.
In the present invention, the total volume of the phosphorous silane coupling agent and the silane coupling agent of group containing double bond has with first
The volume ratio of solvent is preferably 1:2.3~15, more preferably 1:2.7~8, most preferably 1:4~6.
In the present invention, first organic solvent preferably includes in alcohol, acetone, acetonitrile and the chloroform of C1~C2
It is one or more.When first organic solvent is preferably mixture, ratio of the present invention to each substance in the mixture
There is no special restriction, using the mixture of any mass ratio.
Addition of the present invention to the silane coupling agent and the first organic solvent of the phosphorous silane coupling agent, group containing double bond
The not special restriction of sequence, preferably first by after phosphorous silane coupling agent and the silane coupling agent of group containing double bond again with first
Organic solvent mixing.The present invention does not have special restriction to the hybrid mode, using mixing well known to those skilled in the art
Mode.
In the present invention, described be blended in air or inert gas carries out, the inert gas be preferably argon gas or
Nitrogen.
After obtaining the mixed solution, after concentrated hydrochloric acid and water is successively added dropwise into the mixed solution in the present invention, water is carried out
Condensation reaction is solved, hydrolysis condensation product is obtained.In the present invention, the concentrated hydrochloric acid is catalyst.In the present invention, the concentrated hydrochloric acid
Mass fraction be preferably 36.5%.
In the present invention, the quality of the concentrated hydrochloric acid and the volume ratio of mixed solution are preferably 1g:50~100mL, more excellent
It is selected as 1g:60~70mL.
In the present invention, the drop rate of the concentrated hydrochloric acid is preferably added dropwise.
In the present invention, after the completion of the dropwise addition concentrated hydrochloric acid, be added dropwise product stir 0.5 preferably at 10~30 DEG C of constant temperature~
3 hours.
In the present invention, the drop rate of the water is preferably added dropwise.
In the present invention, the molar ratio of the water and mixed solution is preferably 1:0.2~0.7, and more preferably 1:0.3~
0.5。
In the present invention, the water is preferably added dropwise under conditions of 40~100 DEG C, and more preferably 65~80 DEG C, most preferably
It is 70 DEG C.The present invention does not have special restriction to the heating rate for being warming up to the water dropping temperature, using those skilled in the art
Heating method known to member.
In the present invention, the temperature of the hydrolysis-condensation reaction is preferably 40~100 DEG C, and more preferably 65~80 DEG C, most
Preferably 70 DEG C, the time is preferably 10~36h, more preferably 16~for 24 hours, most preferably 20h.
After obtaining hydrolysis condensation product, the present invention instills the hydrolysis condensation product in water, obtains polyhedral oligomeric silicon times
The mixture of half oxygen alkane and the complete silane coupling agent of unreacted.The present invention can analyse after instilling the hydrolysis condensation product in water
White precipitate out, the present invention are successively filtered the system after instillation, wash and dry, and obtain Polyhedral oligomeric silsesquioxane
With the mixture of the complete silane coupling agent of unreacted.
In the present invention, the volume ratio of the hydrolysis condensation product and water is preferably 1:8~12, more preferably 1:9~11,
Most preferably 1:10.
The concrete mode that the present invention is filtered, washed and dried does not have special restriction, using known to those skilled in the art
Mode.
After obtaining the mixture of Polyhedral oligomeric silsesquioxane and the complete silane coupling agent of unreacted, the present invention will be described
Mixture instills in n-hexane after mixing with the second organic solvent, and white solid is precipitated, and is had phosphorous and double bond base simultaneously
The Polyhedral oligomeric silsesquioxane of group；Second organic solvent includes methylene chloride, benzene,toluene,xylene and chloroform
One of or it is a variety of.When second organic solvent is preferably mixture, the present invention is to each substance in the mixture
Ratio does not have special restriction, using the mixture of any mass ratio.
In the present invention, the volume ratio of the mixture and the mixed mixed system of the second organic solvent and n-hexane is excellent
It is selected as 1:4~6, more preferably 1:5.
After white solid is precipitated, the present invention is preferably successively filtered, washs and dries to product is added dropwise, and is had simultaneously
There is phosphorous and double bond group Polyhedral oligomeric silsesquioxane.The concrete mode that the present invention is filtered, washed and dried is not special
Restriction, using mode well known to those skilled in the art.
The present invention also provides have phosphorous and double bond group polyhedral oligomeric silicon sesquialter described in above-mentioned technical proposal simultaneously
Application of the oxygen alkane in flame retardant area.
Below with reference to embodiment to provided by the invention while there is phosphorous and double bond group polyhedral oligomeric silicon sesquialter oxygen
Alkane and its preparation method and application is described in detail, but they cannot be interpreted as the limit to the scope of the present invention
It is fixed.
Embodiment 1
In air atmosphere, by 28.42g 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide triethoxysilicane
Alkane, the vinyltriethoxysilane of 2.38g and 250mL methanol are mixed and are sufficiently stirred, and 3mL concentrated hydrochloric acid (mass fraction is added dropwise
36.5%), to be warming up to 70 DEG C after mixing to system, 4mL deionized water is added dropwise, reaction is for 24 hours.After reaction, according to
Product is slowly dropped into deionized water by volume ratio 1:11 to be precipitated, and is filtered, washed and dried drying, obtains white powder, this is white
After color powder is dissolved in enough chloroforms, mixed system is added in n-hexane according to volume ratio 1:5, sufficiently after precipitating
It is filtered, washed, dries, there is phosphorous and double bond group Polyhedral oligomeric silsesquioxane simultaneously, be denoted as polyhedral oligomeric silicon
Sesquioxyalkane (1).Phosphor-containing structure and vinyl groups molar ratio are about 7:1 in Polyhedral oligomeric silsesquioxane at this time.
Fig. 1 is vinyltriethoxysilane provided in this embodiment, the miscellaneous -10- phospho hetero phenanthrene -10- of 9,10- dihydro-9-oxy
The FT-IR spectrogram of oxide triethoxysilane and Polyhedral oligomeric silsesquioxane (1).As shown in Figure 1, polyhedral oligomeric silicon sesquialter
Oxygen alkane (1) is in 1080cm-1Nearby there is the characteristic peak of-Si-O-Si- key, and in 3200cm-1There is the spy of-Si-OH key
Levy peak.
Fig. 2 is vinyltriethoxysilane, the miscellaneous -10- phospho hetero phenanthrene-of 9,10- dihydro-9-oxy provided by the present embodiment
10- oxide triethoxysilane and Polyhedral oligomeric silsesquioxane (1)1H-NMR spectrum.As seen from the figure, polyhedral oligomeric silicon
It include-P-CH in sesquioxyalkane (1)2(near 2.0ppm) and-Si-CH2The characteristic peak of (near 0.75ppm), and include 7
- CH=CH at~8ppm at P-phenyl, 5.5~6.2ppm2With the feature hydrogen absorption peak of the vicinity 3.4ppm-Si-OH.
Fig. 3 is that each main peaks represent in the MALDI-TOF figure of Polyhedral oligomeric silsesquioxane (1) provided by the present embodiment
While with phosphorous and double bond group Polyhedral oligomeric silsesquioxane structural formula.
In summary it analyzes, it can be deduced that conclusion, provided Polyhedral oligomeric silsesquioxane (1) they are to contain 9 simultaneously,
The Polyhedral oligomeric silsesquioxane of 10- dihydro-9-oxy miscellaneous -10- phospho hetero phenanthrene -10- oxide and vinyl groups.
Embodiment 2
In air atmosphere, by 28.42g 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide triethoxysilicane
Alkane, the vinyltriethoxysilane of 13.3g and 300mL methanol are mixed and are sufficiently stirred, and 3mL concentrated hydrochloric acid (mass fraction is added dropwise
36.5%), to be warming up to 65 DEG C after mixing to system, 6mL deionized water is added dropwise, reacts 20h.After reaction, according to
Product is slowly dropped into deionized water by volume ratio 1:10 to be precipitated, and is filtered, washed and dried drying, obtains white powder, this is white
After color powder is dissolved in enough chloroforms, mixed system is added in n-hexane according to volume ratio 1:6, sufficiently after precipitating
It is filtered, washed, dries, there is phosphorous and double bond group Polyhedral oligomeric silsesquioxane simultaneously, be denoted as polyhedral oligomeric silicon
Sesquioxyalkane (2).Phosphor-containing structure and vinyl groups molar ratio are about 1:1 in Polyhedral oligomeric silsesquioxane at this time.
Fig. 4 is vinyltriethoxysilane provided in this embodiment, the miscellaneous -10- phospho hetero phenanthrene -10- of 9,10- dihydro-9-oxy
The FT-IR spectrogram of oxide triethoxysilane and Polyhedral oligomeric silsesquioxane (2).As seen from the figure, polyhedral oligomeric silicon sesquialter
Oxygen alkane is in 1080cm-1Nearby there is the characteristic peak of-Si-O-Si- key, and in 3200cm-1There is the feature of-Si-OH key
Peak.
Fig. 5 is vinyltriethoxysilane, the miscellaneous -10- phospho hetero phenanthrene-of 9,10- dihydro-9-oxy provided by the present embodiment
10- oxide triethoxysilane and Polyhedral oligomeric silsesquioxane (2)1H-NMR spectrum.As seen from the figure, polyhedral oligomeric silicon
It include-P-CH in sesquioxyalkane (2)2(near 2.0ppm) and-Si-CH2The characteristic peak of (near 0.75ppm), and include 7
- CH=CH at~8ppm at P-phenyl, 5.5~6.2ppm2With the feature hydrogen absorption peak of the vicinity 3.4ppm-Si-OH.
Fig. 6 is vinyltriethoxysilane, the miscellaneous -10- phospho hetero phenanthrene-of 9,10- dihydro-9-oxy provided by the present embodiment
10- oxide triethoxysilane and Polyhedral oligomeric silsesquioxane (2)29Si-NMR spectrogram.As seen from the figure, polyhedral oligomeric silicon
Sesquioxyalkane produces the Si of three kinds of chemical environments in (2), they are under the jurisdiction of-Si-OH ,-Si-CH respectively2-CH2- DOPO and-
Si-CH=CH2。
Fig. 7 is that each main peaks represent in the MALDI-TOF figure of Polyhedral oligomeric silsesquioxane (2) provided by the present embodiment
While with phosphorous and double bond group Polyhedral oligomeric silsesquioxane structural formula.
In summary it analyzes, it can be deduced that conclusion, synthesized Polyhedral oligomeric silsesquioxane (2) they are to contain 9 simultaneously,
The Polyhedral oligomeric silsesquioxane of 10- dihydro-9-oxy miscellaneous -10- phospho hetero phenanthrene -10- oxide structure and vinyl groups.
Polycarbonate (PC) composite material is prepared with Polyhedral oligomeric silsesquioxane provided in this embodiment (2): by quality
Percentage polycarbonate (97%), Polyhedral oligomeric silsesquioxane (2%), antioxidant (0.6%), polytetrafluoroethylene (PTFE) (0.4%)
By each material mixing it is uniform after, using double screw extruder melting, mixing, extrusion, cooling, pelletizing, it is dry after obtain pellet, so
Afterwards by pellet injection molding machine injection molding.The resistance of prepared Polyhedral oligomeric silsesquioxane (2) and polycarbonate composite material
Performance is fired referring to table 1.
Comparative example prepares polycarbonate (PC) composite material: polycarbonate (99%), antioxidant by weight percent
(0.6%), polytetrafluoroethylene (PTFE) (0.4%) by each material mixing it is uniform after, using double screw extruder melting, be kneaded, squeeze out, it is cold
But, pellet is obtained after pelletizing, drying, then by pellet injection molding machine injection molding.Prepared polycarbonate composite material
Flame retardant property is referring to table 1.As can be seen from Table 1, produced by the present invention while there is phosphorous and double bond group polyhedral oligomeric silicon
Sesquioxyalkane has excellent flame retardant property.
The flame retardant property of polycarbonate composite material made from 1 embodiment 2 of table and comparative example
| Sample | Limit oxygen index (%) | UL-94 grade (1.6mm) |
| Comparative example polycarbonate composite material | 25.6 | V-2 |
| 2 polycarbonate composite material of embodiment | 28.0 | V-0 |
Embodiment 3
Under an argon atmosphere, by 11.2g 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide triethoxysilicane
Alkane, the vinyltriethoxysilane of 10.2g and 50mL ethyl alcohol are mixed and are sufficiently stirred, and 0.8mL concentrated hydrochloric acid (mass fraction is added dropwise
36.5%), to be warming up to 80 DEG C after mixing to system, 3mL deionized water is added dropwise, reacts 16h.After reaction, according to
Product is slowly dropped into deionized water by volume ratio 1:8 to be precipitated, and is filtered, washed and dried drying, obtains white powder.By the white
After powder is dissolved in enough chloroforms, mixed system is added in n-hexane according to volume ratio 1:4, sufficiently mistake after precipitating
Filter, washing, drying, are had phosphorous and double bond group Polyhedral oligomeric silsesquioxane simultaneously, are denoted as polyhedral oligomeric silicon times
Half oxygen alkane (3).Phosphor-containing structure and vinyl groups molar ratio are about 1:2 in Polyhedral oligomeric silsesquioxane at this time.
Fig. 8 is vinyltriethoxysilane provided in this embodiment, the miscellaneous -10- phospho hetero phenanthrene -10- of 9,10- dihydro-9-oxy
The FT-IR spectrogram of oxide triethoxysilane and Polyhedral oligomeric silsesquioxane (3).As seen from the figure, polyhedral oligomeric silicon sesquialter
Oxygen alkane (3) is in 1080cm-1Nearby there is the characteristic peak of-Si-O-Si- key, and in 3200cm-1There is the spy of-Si-OH key
Levy peak.
Fig. 9 is vinyltriethoxysilane, the miscellaneous -10- phospho hetero phenanthrene-of 9,10- dihydro-9-oxy provided by the present embodiment
10- oxide triethoxysilane and Polyhedral oligomeric silsesquioxane (3)1H-NMR spectrum.As seen from the figure, polyhedral oligomeric silicon
It include-P-CH in sesquioxyalkane (3)2(near 2.0ppm) and-Si-CH2The characteristic peak of (near 0.75ppm), and include 7
- CH=CH at~8ppm at P-phenyl, 5.5~6.2ppm2With the feature hydrogen absorption peak of the vicinity 3.4ppm-Si-OH.
Figure 10 is each main peaks generation in the MALDI-TOF figure of Polyhedral oligomeric silsesquioxane (3) provided by the present embodiment
With phosphorous and double bond group Polyhedral oligomeric silsesquioxane structural formula while table.
In summary it analyzes, it can be deduced that conclusion, synthesized Polyhedral oligomeric silsesquioxane are to contain 9,10- bis- simultaneously
The Polyhedral oligomeric silsesquioxane of hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxide structure and vinyl groups.
With phosphorous and double bond group Polyhedral oligomeric silsesquioxane thermal stability while Examples 1 to 3 is made
It is measured, it is as a result as shown in figure 11, as seen from Figure 11, produced by the present invention while there is phosphorous and double bond group cage
Shape oligomeric silsesquioxane excellent heat stability.
Embodiment 4
In air atmosphere, by 28.42g 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide triethoxysilicane
Alkane, the acrylic triethoxysilane of 14.3g and 300mL methanol are mixed and are sufficiently stirred, and 3mL concentrated hydrochloric acid (mass fraction is added dropwise
36.5%), to be warming up to 65 DEG C after mixing to system, 6mL deionized water is added dropwise, reacts 20h.After reaction, according to
Product is slowly dropped into deionized water by volume ratio 1:10 to be precipitated, and is filtered, washed and dried drying, obtains white powder.This is white
After color powder is dissolved in enough chloroforms, mixed system is added in n-hexane according to volume ratio 1:6, sufficiently after precipitating
It is filtered, washed, dries, there is phosphorous and double bond group Polyhedral oligomeric silsesquioxane simultaneously.Have simultaneously at this time and contains
Phosphor-containing structure and propenyl group molar ratio are about 1:1 in the Polyhedral oligomeric silsesquioxane of phosphorus and double bond group.
Embodiment 5
In a nitrogen atmosphere, by 28.42g 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide triethoxysilicane
Alkane, γ-methacryloxypropyl trimethoxy silane (structural formula is shown below) of 17.4g and the mixing of 250mL methanol
And be sufficiently stirred, it is added dropwise 3mL concentrated hydrochloric acid (mass fraction 36.5%), is warming up to 65 DEG C after mixing to system, 6mL is added dropwise
Deionized water reacts 20h.After reaction, product is slowly dropped into deionized water according to volume ratio 1:10 and is precipitated, passed through
Filter, washing and drying, obtain white powder.It, will according to volume ratio 1:6 after the white powder being dissolved in enough chloroforms
Mixed system is added in n-hexane, is sufficiently filtered, washed, is dried after precipitating, is had simultaneously phosphorous and double bond group
Polyhedral oligomeric silsesquioxane.Have in phosphorous and double bond group Polyhedral oligomeric silsesquioxane simultaneously at this time phosphor-containing structure and
γ-methacryloxypropyl radical molar ratio is about 1.5:1.
Embodiment 6
Under an argon atmosphere, by 26.32g diphenylphosphine triethoxysilane, γ-methacryloxy third of 4.96g
Base trimethoxy silane and 250mL methanol are mixed and are sufficiently stirred, and are added dropwise 3mL concentrated hydrochloric acid (mass fraction 36.5%), to body
System is warming up to 65 DEG C after mixing, and 6mL deionized water is added dropwise, and reacts 20h.After reaction, it will be produced according to volume ratio 1:10
Object is slowly dropped into deionized water and precipitates, and is filtered, washed and dried drying, obtains white powder.The white powder is dissolved in enough
Chloroform in after, mixed system is added in n-hexane according to volume ratio 1:6, is sufficiently filtered, washed, does after precipitating
It is dry, there is phosphorous and double bond group Polyhedral oligomeric silsesquioxane simultaneously.There is phosphorous and double bond group simultaneously at this time
Polyhedral oligomeric silsesquioxane in phosphor-containing structure and γ-methacryloxypropyl radical molar ratio be about 7:2.
Cage type POSS's obtained includes the compound with structure shown in following formula:
Embodiment 7
In air atmosphere, by 27.44g diphenyl phosphine oxide triethoxysilane, γ-methacryloxy of 4.96g
Propyl trimethoxy silicane and 250mL methanol are mixed and are sufficiently stirred, and are added dropwise 3mL concentrated hydrochloric acid (mass fraction 36.5%), to
System is warming up to 85 DEG C after mixing, 6mL deionized water is added dropwise, reaction is for 24 hours.It after reaction, will according to volume ratio 1:12
Product is slowly dropped into deionized water and precipitates, and is filtered, washed and dried drying, obtains white powder.The white powder is dissolved in foot
After in the chloroform of amount, mixed system is added in n-hexane according to volume ratio 1:6, is sufficiently filtered, washed, does after precipitating
It is dry, there is phosphorous and double bond group Polyhedral oligomeric silsesquioxane simultaneously.There is phosphorous and double bond group simultaneously at this time
Polyhedral oligomeric silsesquioxane in phosphor-containing structure and γ-methacryloxypropyl radical molar ratio be about 7:1.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. there is phosphorous and double bond group Polyhedral oligomeric silsesquioxane simultaneously, including with structure chemical combination shown in formula A, B and C
Two or three in object:
Described have shown in formula A, B and C that R independently includes R in structural compounds1、R2、R3、R4And R5One of or a variety of, institute
It states and contains R simultaneously with R in structural compounds shown in formula A, B and C1；
Wherein,
R1InFor alkyl or substituted hydrocarbon radical, the substituent group of the substituted hydrocarbon radical is ester group, hydroxyl or ehter bond.
2. according to claim 1 while having phosphorous and double bond group Polyhedral oligomeric silsesquioxane, feature exists
In the molecular weight of the Polyhedral oligomeric silsesquioxane is 600~3200.
3. having the system of phosphorous and double bond group Polyhedral oligomeric silsesquioxane described in claim 1~2 any one simultaneously
Preparation Method, comprising the following steps:
The silane coupling agent of phosphorous silane coupling agent, group containing double bond is mixed with the first organic solvent, obtains mixed solution；
After concentrated hydrochloric acid and water is successively added dropwise into the mixed solution, condensation reaction is hydrolyzed, obtains hydrolysis condensation product；
The hydrolysis condensation product is instilled in water, Polyhedral oligomeric silsesquioxane and the complete silane coupling agent of unreacted are obtained
Mixture；
It is instilled in n-hexane after the mixture is mixed with the second organic solvent, white solid is precipitated, is had contain simultaneously
The Polyhedral oligomeric silsesquioxane of phosphorus and double bond group；Second organic solvent includes methylene chloride, benzene,toluene,xylene
With one of chloroform or a variety of.
4. preparation method according to claim 3, which is characterized in that the phosphorous silane coupling agent and group containing double bond
The molar ratio of silane coupling agent is 1:0.06~3.5.
5. preparation method according to claim 3 or 4, which is characterized in that the phosphorous silane coupling agent is 9,10- bis-
Miscellaneous -10- phospho hetero phenanthrene -10- the oxidation of hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxide trimethoxy silane, 9,10- dihydro-9-oxy
Object triethoxysilane, diphenyl phosphine oxide trimethoxy silane, diphenyl phosphine oxide triethoxysilane, diphenylphosphine trimethoxy
Silane, diphenylphosphine triethoxysilane, dimethyl phosphine trimethoxy silane or dimethyl phosphine triethoxysilane.
6. preparation method according to claim 3 or 4, which is characterized in that the silane coupling agent of the group containing double bond is
Vinyltrimethoxysilane, vinyltriethoxysilane, acrylic trimethoxy silane, acrylic triethoxysilane,
γ-methacryloxypropyl trimethoxy silane or γ-methacryloxypropyl.
7. preparation method according to claim 3, which is characterized in that the quality of the concentrated hydrochloric acid and the volume of mixed solution
Than for 1g:50~100mL.
8. preparation method according to claim 3, which is characterized in that the temperature of the hydrolysis-condensation reaction is 40~100
DEG C, the time is 10~36h.
9. preparation method according to claim 3, which is characterized in that first organic solvent include C1~C2 alcohol,
One of acetone, acetonitrile and chloroform are a variety of.
10. existing while described in claim 1~2 any one with phosphorous and double bond group Polyhedral oligomeric silsesquioxane
Application in flame retardant area.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114031779A (en) * | 2021-11-01 | 2022-02-11 | 兰州瑞朴科技有限公司 | Phosphorus-containing ladder-shaped polysiloxane, preparation method thereof and application of phosphorus-containing ladder-shaped polysiloxane as flame-retardant synergist |
| CN116333594A (en) * | 2021-12-23 | 2023-06-27 | 成都拓米双都光电有限公司 | Modified polyurethane acrylic ester and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101787055A (en) * | 2010-03-17 | 2010-07-28 | 北京理工大学 | Polyhedral oligomeric silsesquioxane containing DOPO group and preparation method thereof |
| CN101906116A (en) * | 2010-07-01 | 2010-12-08 | 湖北大学 | Synthetic method of cagelike oct-polysilsesquioxane with same or different functional groups or non-functional groups |
| CN107446317A (en) * | 2017-07-18 | 2017-12-08 | 北京理工大学 | A kind of POSS modified flame-retardants low-smoke low-toxicity vinyl ester resin composition and preparation method thereof |
| WO2018075787A1 (en) * | 2016-10-19 | 2018-04-26 | Wells Michael Owen | Flame resistant material and resultant products |
-
2018
- 2018-08-30 CN CN201811002435.4A patent/CN109021239A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101787055A (en) * | 2010-03-17 | 2010-07-28 | 北京理工大学 | Polyhedral oligomeric silsesquioxane containing DOPO group and preparation method thereof |
| CN101906116A (en) * | 2010-07-01 | 2010-12-08 | 湖北大学 | Synthetic method of cagelike oct-polysilsesquioxane with same or different functional groups or non-functional groups |
| WO2018075787A1 (en) * | 2016-10-19 | 2018-04-26 | Wells Michael Owen | Flame resistant material and resultant products |
| CN107446317A (en) * | 2017-07-18 | 2017-12-08 | 北京理工大学 | A kind of POSS modified flame-retardants low-smoke low-toxicity vinyl ester resin composition and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114031779A (en) * | 2021-11-01 | 2022-02-11 | 兰州瑞朴科技有限公司 | Phosphorus-containing ladder-shaped polysiloxane, preparation method thereof and application of phosphorus-containing ladder-shaped polysiloxane as flame-retardant synergist |
| CN114031779B (en) * | 2021-11-01 | 2023-02-28 | 兰州瑞朴科技有限公司 | Phosphorus-containing ladder-shaped polysiloxane, preparation method thereof and application of phosphorus-containing ladder-shaped polysiloxane as flame-retardant synergist |
| CN116333594A (en) * | 2021-12-23 | 2023-06-27 | 成都拓米双都光电有限公司 | Modified polyurethane acrylic ester and preparation method and application thereof |
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