CN109135197A - A kind of Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resin composition and its preparation method and application - Google Patents
A kind of Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resin composition and its preparation method and application Download PDFInfo
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- CN109135197A CN109135197A CN201811002452.8A CN201811002452A CN109135197A CN 109135197 A CN109135197 A CN 109135197A CN 201811002452 A CN201811002452 A CN 201811002452A CN 109135197 A CN109135197 A CN 109135197A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/10—Epoxy resins modified by unsaturated compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
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Abstract
The present invention provides a kind of Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resin compositions, belong to flame retardant area.Cage type POSS is while having phosphorous and double bond group Polyhedral oligomeric silsesquioxane, it can be according to different actual demands, adjust phosphorus-containing groups and group containing double bond ratio in fire retardant, also the type of phosphorus-containing groups and the type of group containing double bond is adjusted, achievees the purpose that control phosphorus content and reactive group amount；The double bond group that cage type POSS 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 composition；The silicon phosphorus synergistic effect for utilizing polysiloxanes simultaneously, can be realized higher flame retardant property under low content, the raising of vinyl ester resin composition anti-flammability may be implemented in the case where additive amount is few, and the compatibility of cage type POSS and vinyl ester resin is good.
Description
Technical field
The invention belongs to field of fire-proof technology more particularly to a kind of Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl esters
Resin combination and its preparation method and application.
Background technique
Vinyl ester resin is a kind of denaturation reacted by bisphenol type or phenol aldehyde type epoxy resin with methacrylic acid
Epoxy resin, alias epoxy acrylic resin are thermosetting resin.Vinyl ester resin has good curability and molding
Property, high temperature resistant, acid-alkali-corrosive-resisting is often made into corrosion resistant article, such as glass reinforced plastic groove tank, pipeline, tower and corrosion-resistant lattice
Grid etc..But the flame retardant property of pure ethylene base ester resin is poor, oxygen index (OI) is only 19% or so.
In the prior art, the Chinese patent of Publication No. CN103396657A is disclosed is blended by bi-phthalonitrile resin
Modified vinyl resin prepares composite material, and the modes such as reinforcing fiber are added in blending resin solution, is prepared for a kind of resistance
Low-smoke vinyl resin composite material is fired, but reinforcing fiber additive amount is big, accounts for the 55%~75% of total weight percent；Publication number
A kind of vinylite base with good impact resistance and heat-resisting quantity is provided for the Chinese patent of CN105037642A
Composite material, but in order to guarantee each additive and resin-based compatibility, 4~8 parts of solubilizer, while various additions need to be added
Agent is various.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl esters trees
Oil/fat composition and the preparation method and application thereof.Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resin provided by the invention
Composition can control phosphorus content and double bond radical amount in oligomeric silsesquioxane according to different demands, realize under few additive
Higher flame retardant property, while the compatibility of cage type POSS and vinyl ester resin is good.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resin composition, including it is following
The component of mass percentage:
The cage type POSS be have simultaneously it is phosphorous with double bond group Polyhedral oligomeric silsesquioxane, including with formula A,
Two or three in structural compounds shown in B and 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,
Or --- CH=CH2
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 cage type POSS is 600~3200.
Preferably, the vinyl ester resin is bisphenol-A epoxide vinylester resin or phenol formaldehyde epoxy vinyl ester resin.
Preferably, the curing agent includes methyl ethyl ketone peroxide, cyclohexanone peroxide, benzoyl peroxide, benzylhydroperoxide
One of the tert-butyl ester and isopropyl benzene hydroperoxide are a variety of.
Preferably, the promotor includes cobalt iso-octoate, cobalt naphthenate, dimethylaniline, diethylaniline and dimethyl
One of open-chain crown ether is a variety of.
Preferably, the cage type POSS is prepared by 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 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, obtains cage type
POSS；Second organic solvent includes one of methylene chloride, benzene,toluene,xylene and chloroform or a variety of.
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.
The present invention also provides Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resins described in above-mentioned technical proposal
The preparation method of composition, comprising the following steps:
Score mixes the vinyl ester resin, cage type POSS and promotor by weight, obtains vinyl ester resin body
System；
It obtains solidifying after vinyl ester resin systems are mixed with curing agent by described, obtains Polyhedral oligomeric silsesquioxane and change
Property flame-proof ethylene base ester resin combination.
The present invention also provides Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resins described in above-mentioned technical proposal
Application of the composition in flame retardant area.
The present invention provides a kind of Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resin composition, the present invention
In, cage type POSS is while having phosphorous and double bond group Polyhedral oligomeric silsesquioxane, can be according to different practical need
It asks, adjusts phosphorus-containing groups and group containing double bond ratio in fire retardant, the type and group containing double bond of phosphorus-containing groups is also adjusted
Type achievees the purpose that control phosphorus content and reactive group amount；The double bond group that cage type POSS contains can occur with a variety of groups
Chemical reaction can regulate and control double bond group and the reaction of corresponding group, finally in composition according to the performance requirement of different polymer
Middle realization multifunction and high performance；The silicon phosphorus synergistic effect for utilizing polysiloxanes simultaneously, can be realized higher under low content
Flame retardant property, may be implemented in the case where additive amount is few vinyl ester resin composition anti-flammability raising；And cage type
The compatibility of POSS and vinyl ester resin is good；Cage type POSS is halogen-free, and belongs to environmentally friendly fire retardant, carbon residue content
Height has the characteristics that cigarette poison is small in combustion, has very important significance to practical application.The tables of data of embodiment
Bright, the limit oxygen index of Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resin composition provided by the invention is 23.4
~25.0%, material at high temperature pyrogen toxic grade is low toxicity, and bending strength is 48~55MPa, bending modulus 3985
~4290MPa.
Also, preparation method provided by the invention is simple, strong operability, is 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.
Specific embodiment
The present invention provides Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resin compositions, including following quality
The component of percentage composition:
The cage type POSS be have simultaneously it is phosphorous with double bond group Polyhedral oligomeric silsesquioxane, including with formula A,
Two or three in structural compounds shown in B and 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,
Or --- CH=CH2
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, the Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resin composition preferably includes
The cage type POSS of 10.5~19% mass percentages, more preferably 18%.
In the present invention, the molecular weight of the cage type POSS is preferably 600~3200.
In the present invention, the cage type POSS is preferably included with structural compounds shown in formula A and B, is had formula B and C institute
Show structural compounds or there are structural compounds shown in formula A, B and C.
In the present invention, R in the cage type POSS1Preferably-HC=CH2, R2Preferably
In the present invention, the phosphorus content of the cage type POSS is preferably 0.03~25wt%.
In the present invention, the molar ratio of phosphor-containing structure and group containing double bond structure is preferably 1~7:1 in the cage type POSS
~2, it is specifically preferably 7:1 or 1:1 in an embodiment of the present invention.
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.
In the present invention, the Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resin composition preferably includes 77
The vinyl ester resin of~84.5% mass percentage.In the present invention, the vinyl ester resin is preferably bisphenol-A epoxy
Vinyl ester resin or phenol formaldehyde epoxy vinyl ester resin.
In the present invention, the Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resin composition preferably includes 3
The curing agent of~9% mass percentage, more preferably 4~4.5%.In the present invention, the curing agent preferably includes peroxide
Change one of methyl ethyl ketone, cyclohexanone peroxide, benzoyl peroxide, t-butyl perbenzoate and isopropyl benzene hydroperoxide or more
Kind.
In the present invention, the Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resin composition preferably includes
The promotor of 0.5~1% mass percentage.In the present invention, the promotor preferably include cobalt iso-octoate, cobalt naphthenate,
One of dimethylaniline, diethylaniline and dimethyl open-chain crown ether are a variety of.
The present invention does not have special restriction to the source of the vinyl ester resin, curing agent and promotor, using ability
Commercial goods known to field technique personnel.
In the present invention, the cage type POSS is preferably prepared by 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 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, obtains cage type
POSS, second organic solvent include one of methylene chloride, benzene,toluene,xylene and chloroform or 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, obtains cage type POSS；Described second is organic
Solvent includes one of methylene chloride, benzene,toluene,xylene and chloroform or a variety of.When second organic solvent is excellent
When being selected as mixture, the present invention does not have special restriction to the ratio of each substance in the mixture, using any mass ratio
Mixture.
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 obtains cage type
POSS.The concrete mode that the present invention is filtered, washed and dried does not have special restriction, using side well known to those skilled in the art
Formula.
The present invention also provides Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resins described in above-mentioned technical proposal
The preparation method of composition, comprising the following steps:
Score mixes the vinyl ester resin, cage type POSS and promotor by weight, obtains vinyl ester resin body
System；
Solidify after the vinyl ester resin systems are mixed with curing agent, obtains the modified resistance of Polyhedral oligomeric silsesquioxane
Fire vinyl ester resin composition.
Present invention score by weight mixes the vinyl ester resin, cage type POSS and promotor, obtains vinyl esters
Resin system.In the present invention, the mixed temperature is preferably 25~100 DEG C.
After obtaining vinyl ester resin systems, the present invention is solid after mixing the vinyl ester resin systems with curing agent
Change, obtains Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resin composition.
In the present invention, the mixed temperature is preferably 25~80 DEG C.
In the present invention, the cured temperature is preferably 40~100 DEG C, and the cured time is preferably 6~for 24 hours,
More preferably 8~12h.
In the present invention, the solidification preferably carries out in a mold, and the mold uses after preferably preheating.In the present invention,
The temperature of the preheating is preferably 40~80 DEG C, and more preferably 60 DEG C, the time of the preheating is preferably 30~60min.
The present invention also provides Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resins described in above-mentioned technical proposal
Application of the composition in flame retardant area.
Below with reference to embodiment to Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resin group provided by the invention
It closes object and the preparation method and application thereof to be described in detail, but they cannot be interpreted as the limit to the scope of the present invention
It is fixed.
Embodiment 1
The preparation of cage type POSS
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 (cage type POSS) simultaneously, be denoted as
Polyhedral oligomeric silsesquioxane (1).Phosphor-containing structure with vinyl groups molar ratio is about in Polyhedral oligomeric silsesquioxane at this time
7:1。
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.
The mass percent of each component is as follows:
Specific preparation step are as follows:
By the mixing of 154g bisphenol-A epoxide vinylester resin, 39g cage type POSS (phosphorus-containing groups: double bond group=7:1)
Object, 6g curing agent methyl ethyl ketone peroxide are added in mixing kettle, stir at 25 DEG C, until being uniformly mixed, obtain vinyl ester resin
System；
Vinyl ester resin systems temperature is warming up to 40 DEG C, 1g promotor cobalt iso-octoate is added, then stirring to mixing
Uniformly；Resin system is poured in the mold of 40 DEG C of preheatings 30 minutes, solidification obtains Polyhedral oligomeric silsesquioxane in 24 hours
Modified flame-retardant vinyl ester resin composition.
Embodiment 2
Cage type POSS preparation
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 (cage type POSS) simultaneously, be denoted as
Polyhedral oligomeric silsesquioxane (2).Phosphor-containing structure with vinyl groups molar ratio is about in Polyhedral oligomeric silsesquioxane at this time
1:1。
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.
The mass percent of each component is as follows:
Specific preparation step are as follows:
168g phenol formaldehyde epoxy vinyl ester resin, the mixture of 21g cage type POSS, 8g curing agent cycloethanone peroxide are added
Enter in mixing kettle, stirred at 40 DEG C, until system is uniformly mixed, obtains vinyl ester resin systems；
Vinyl ester resin systems temperature is warming up to 60 DEG C, 2g promotor cobalt naphthenate is added, then stirring to promotion
Agent is uniformly mixed in resin system；Resin system is poured in the mold of 60 DEG C of preheatings 30 minutes, is solidified 6 hours, then rise
Temperature to 100 degree solidify 6 hours, obtain Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resin composition.
Embodiment 3
Preparing for cage type POSS is similar to Example 2, distinguishes only phosphorous in Polyhedral oligomeric silsesquioxane in embodiment 3
Structure and vinyl groups molar ratio are about 3:1.
Cage type POSS's obtained includes the compound with structure shown in following formula:
The mass percent of each component is as follows:
Specific preparation step are as follows:
Mixing is added in 120g phenol formaldehyde epoxy vinyl ester resin, 30g cage type POSS, 18g curing agent benzoyl peroxide
It in kettle, is stirred at 60 DEG C, until system is uniformly mixed, obtains vinyl ester resin systems；
Vinyl ester resin systems temperature is controlled at 60 DEG C, 2g promotor dimethylaniline is added, then stirring to rush
It is uniformly mixed in resin system into agent；Resin system is poured in the mold of 60 DEG C of preheatings 60 minutes, is solidified 4 hours, then
It is warming up to 100 degree to solidify 8 hours, obtains Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resin composition.
Embodiment 4
Cage type POSS preparation
Under an argon atmosphere, by 26.32g diphenylphosphine triethoxysilane, γ-methacryloxy third of 17.36g
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 (cage type POSS) simultaneously.Have simultaneously at this time phosphorous
Molar ratio with phosphorus-containing groups in the Polyhedral oligomeric silsesquioxane of double bond group and double bond group be about 1:1 (i.e. (R2+R3):
R1=1:1, R2:R3=1:1).
Cage type POSS's obtained includes the compound with structure shown in following formula:
The mass percent of each component is as follows:
Specific preparation step are as follows:
154g bisphenol-A epoxide vinylester resin, 36g cage type POSS, 9g curing agent t-butyl perbenzoate are added mixed
It closes in kettle, is stirred at 60 DEG C, until system is uniformly mixed, obtain vinyl ester resin systems；
Vinyl ester resin systems temperature is controlled at 80 DEG C, 1g promotor cobalt iso-octoate is added, then stirring to solidification
Promotor is uniformly mixed in resin system；Resin system is poured in the mold of 80 DEG C of preheatings 30 minutes, is solidified 4 hours,
It is warming up to 100 degree again to solidify 8 hours, obtains Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resin composition.
To Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resin composition made from Examples 1 to 4 and pure
Vinyl ester resin pours batten for testing, and oxygen index (OI) is tested according to 8924 standard testing of GB/T, specimen size 130mm
×6.5mm×3mm；Combustion heat value is tested according to ISO 1716-2010 standard testing；Material at high temperature pyrogen toxotest according to
GJB 3881-1999 standard；Casting resin bending property is tested according to GB/T 2570-1995 standard testing, and specimen size is
100mm × 15mm × 4mm, as a result such as table 1.As can be seen from Table 1, the modified resistance of Polyhedral oligomeric silsesquioxane produced by the present invention
Firing vinyl ester resin composition has excellent flame retardant property, vinyl esters may be implemented in the case where additive amount is few
Resin combination anti-flammability improves；And the compatibility of cage type POSS and vinyl ester resin is good.
The performance measurement result of Polyhedral oligomeric silsesquioxane fire-retardant polycarbonate made from 1 Examples 1 to 4 of table
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. a kind of Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resin composition, including following mass percentage
Component:
The cage type POSS be have simultaneously it is phosphorous with double bond group Polyhedral oligomeric silsesquioxane, including with formula A, B and C
Two or three in shown structural compounds:
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,
Or --- CH=CH2
R1InFor alkyl or substituted hydrocarbon radical, the substituent group of the substituted hydrocarbon radical is ester group, hydroxyl or ehter bond.
2. Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resin composition according to claim 1, feature
It is, the molecular weight of the cage type POSS is 600~3200.
3. Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resin composition according to claim 1, feature
It is, the vinyl ester resin is bisphenol-A epoxide vinylester resin or phenol formaldehyde epoxy vinyl ester resin.
4. Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resin composition according to claim 1, feature
It is, the curing agent includes methyl ethyl ketone peroxide, cyclohexanone peroxide, benzoyl peroxide, t-butyl perbenzoate and different
One of cumene hydroperoxide is a variety of.
5. Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resin composition according to claim 1, feature
It is, the promotor includes cobalt iso-octoate, cobalt naphthenate, dimethylaniline, diethylaniline and dimethyl open-chain crown ether
One of or it is a variety of.
6. Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resin group described in any one according to claim 1~2
Close object, which is characterized in that the cage type POSS is prepared by 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, obtains cage type POSS；Institute
Stating the second organic solvent includes one of methylene chloride, benzene,toluene,xylene and chloroform or a variety of.
7. Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resin composition according to claim 6, feature
Be, the phosphorous silane coupling agent be 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide trimethoxy silane, 9,
Miscellaneous -10- phospho hetero phenanthrene -10- oxide the triethoxysilane of 10- dihydro-9-oxy, diphenyl phosphine oxide trimethoxy silane, diphenyl
Phosphine oxide triethoxysilane, diphenylphosphine trimethoxy silane, diphenylphosphine triethoxysilane, dimethyl phosphine trimethoxy silicon
Alkane or dimethyl phosphine triethoxysilane.
8. Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resin composition according to claim 6, feature
It is, the silane coupling agent of the group containing double bond is vinyltrimethoxysilane, vinyltriethoxysilane, acrylic
Trimethoxy silane, acrylic triethoxysilane, γ-methacryloxypropyl trimethoxy silane or γ-methyl-prop
Alkene acryloxypropylethoxysilane triethoxysilane.
9. Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resin composition described in claim 1~8 any one
Preparation method, comprising the following steps:
Score mixes the vinyl ester resin, cage type POSS and promotor by weight, obtains vinyl ester resin systems；
It obtains solidifying after vinyl ester resin systems are mixed with curing agent by described, obtains the modified resistance of Polyhedral oligomeric silsesquioxane
Fire vinyl ester resin composition.
10. Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resin composition described in claim 1~8 any one exists
Application in flame retardant area.
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| CN110499004A (en) * | 2019-08-30 | 2019-11-26 | 北京理工大学 | While a kind of trapezoidal POSS modified ethenyl resin and preparation method thereof containing phenyl and vinyl |
| CN110499003A (en) * | 2019-08-30 | 2019-11-26 | 北京理工大学 | A kind of POSS modified flame-retardant enhancing vinyl ester resin and preparation method thereof |
| CN114835903A (en) * | 2022-04-28 | 2022-08-02 | 北京理工大学 | Boron-containing silsesquioxane, preparation method thereof, modified phenolic resin, preparation method and application thereof |
| CN114854091A (en) * | 2021-02-03 | 2022-08-05 | 中国科学院化学研究所 | Flame-retardant vinyl resin and preparation method and application thereof |
| CN114891227A (en) * | 2022-06-09 | 2022-08-12 | 台州市黄岩区武汉理工高性能复合材料技术研究院 | Preparation method of halogen-free flame-retardant modified epoxy resin |
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| CN114891227A (en) * | 2022-06-09 | 2022-08-12 | 台州市黄岩区武汉理工高性能复合材料技术研究院 | Preparation method of halogen-free flame-retardant modified epoxy resin |
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