CN110499003A - A kind of POSS modified flame-retardant enhancing vinyl ester resin and preparation method thereof - Google Patents
A kind of POSS modified flame-retardant enhancing vinyl ester resin and preparation method thereof Download PDFInfo
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- CN110499003A CN110499003A CN201910813285.3A CN201910813285A CN110499003A CN 110499003 A CN110499003 A CN 110499003A CN 201910813285 A CN201910813285 A CN 201910813285A CN 110499003 A CN110499003 A CN 110499003A
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The present invention provides a kind of POSS modified flame-retardant enhancing vinyl ester resins and preparation method thereof, are related to field of fire-proof technology.POSS modified flame-retardant enhancing vinyl ester resin provided by the invention is by including that the component of following mass fraction is prepared: 50~98 parts of vinyl ester resin, 0.5~10 part of curing agent, 0.1~2 part of promotor, 2~50 parts of POSS；The POSS includes trapezoidal POSS and/or trihydroxy cage type POSS；Wherein, the trapezoidal POSS is the mixture of one or more of structure shown in formula I, and the structure of the trihydroxy cage type POSS is as shown in formula II.POSS modified flame-retardant provided by the invention enhances vinyl ester resin good mechanical properties, has the characteristics that low cigarette and low-heat release in combustion.The present invention provides the preparation methods of POSS modified flame-retardant enhancing vinyl ester resin, and process is simple, and the period is short, are suitble to mass production.
Description
Technical field
The present invention relates to field of fire-proof technology, in particular to a kind of POSS (polyhedral oligomeric silsesquioxane) modified flame-retardant
Enhance vinyl ester resin and preparation method thereof.
Background technique
Vinyl ester resin refers to that unsaturated double-bond is contained in molecule end, and intermediate skeleton is the denaturation tree of epoxy resin structural
The product of rouge, usually epoxy resin and a kind of unsaturated monocarboxylic acid addition condensation containing carboxyl, and through a kind of reactivity
Monomer dilution.The processing performance of vinyl ester resin is similar to unsaturated polyester resin, and chemical structure is again close with epoxy resin,
Thus vinyl ester resin has the good characteristic of epoxy resin and unsaturated polyester resin, i.e., good moulding process and fibre concurrently
Preferable caking property, high temperature resistance, fatigue durability, resistance to chemical corrosion etc. are tieed up, composite material is in chemical anticorrosion, cigarette
Desulfurization, communications and transportation, electronic apparatus etc. are widely used.But the performance of some aspects, such as mechanical performance and
Flame retardant property is not met by the particular/special requirement of certain engineering products, and not only smoke amount, heat are released when pure ethylene base ester resin burns
Amplification, and bending strength is only 48MPa or so after solidification, and mechanical property is poor.
The Chinese patent of Publication No. CN107057290A discloses " epoxy vingl ester resin composite material and its preparation side
Method ", the invention spray to cotton stalk bark fibre felt after mixing vinyl ester resin and curing agent, then heat admittedly after spraying promotor
Change prepares composite material, efficiently uses cotton planting waste, promotes the tensile property and bending property of composite material, but cotton stalk
Hide fiber need to be by the processes such as degumming, bleaching, softening, for the first time combing, drying, oil supply and second of combing, manufacturing process
Complexity consumes more manpower and material resources.
The Chinese patent of Publication No. CN106519586A discloses a kind of " glass fibre/vinyl ester resin composite wood
Material and preparation method thereof ", which uses the glass fibre of surface modification of carbon nanotube for reinforcing material, is formulated medium vinyl ester
Resin, methyl ethyl ketone peroxide, N,N-dimethylformamide, cobalt naphthenate and carbon nano-tube modification glass fiber quality ratio are 100:
2:1.5:0.5~5:100~130, composite material have preferable intensity and shock resistance.But carbon nanotube was handled
Journey uses more hazardous agents, and modified glass-fiber additive amount is higher, and composite material manufacture craft is cumbersome.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of increasings of POSS (polyhedral oligomeric silsesquioxane) modified flame-retardant
Strong vinyl ester resin and preparation method thereof.Modified ethenyl resin mechanical property provided by the invention is good, in combustion process
Low cigarette and low-heat release, and preparation method is simple, the period is short, is suitble to mass production.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical schemes:
The present invention provides a kind of POSS modified flame-retardants to enhance vinyl ester resin, by the component including following mass fraction
It is prepared:
The POSS includes trapezoidal POSS and/or trihydroxy cage type POSS；Wherein, the trapezoidal POSS is knot shown in formula I
The mixture of one or more of structure:
In formula I, n is the integer more than or equal to 0；
The structure of the trihydroxy cage type POSS is as shown in formula II:
Preferably, the vinyl ester resin includes bisphenol A-type vinyl ester resin and/or phenol aldehyde type vinyl esters tree
Rouge.
Preferably, the curing agent includes methyl ethyl ketone peroxide, cyclohexanone peroxide, diacetone peroxide, peroxidating
One or more of benzoyl, dilauroyl peroxide, t-butyl perbenzoate and isopropyl benzene hydroperoxide.
Preferably, the promotor includes cobalt iso-octoate, cobalt naphthenate, dodecyl sodium sulfate, triethylenediamine, two
One or more of methylaniline, diethylaniline and dimethyl open-chain crown ether.
The present invention provides the preparation methods of the enhancing vinyl ester resin of POSS modified flame-retardant described in above scheme, including with
Lower step:
(1) vinyl ester resin and the POSS are mixed, obtains the first mixed system；
(2) first mixed system and promotor are mixed, obtains the second mixed system；
(3) curing reaction is carried out after mixing second mixed system and curing agent, obtains the POSS modified flame-retardant
Enhance vinyl ester resin.
Preferably, the temperature mixed in the step (1) is 25~120 DEG C.
Preferably, the temperature mixed in the step (2) is 15~40 DEG C.
Preferably, the temperature mixed in the step (3) is 15~40 DEG C.
It preferably, further include to second mixed system and curing agent in the step (3) before carrying out curing reaction
It mixes resulting curing system and carries out vacuum defoamation processing；The vacuum degree of the vacuum defoamation processing is -0.01~-0.09MPa.
Preferably, in the step (3) curing reaction temperature be 25~100 DEG C, the time be 4~for 24 hours.
The present invention provides a kind of POSS modified flame-retardants to enhance vinyl ester resin, by the component including following mass fraction
It is prepared: 50~98 parts of vinyl ester resin, 0.5~10 part of curing agent, 0.1~2 part of promotor, 2~50 parts of POSS；Institute
Stating POSS includes trapezoidal POSS and/or trihydroxy cage type POSS.For the present invention using POSS as modifying agent, the POSS is trapezoidal
POSS and/or trihydroxy cage type POSS, anti-flammability is strong, thermal stability is good, good with vinyl ester resin compatibility, has low-heat
The effect of release and suppression cigarette；And stable trapezoidal or cage type Si-O structure can be obviously improved composite material in the POSS
Mechanical property.Therefore, POSS modified flame-retardant provided by the invention enhances vinyl ester resin good mechanical properties, in combustion process
In have the characteristics that low cigarette and low-heat release.
The present invention provides the preparation methods of POSS modified flame-retardant enhancing vinyl ester resin.System provided by the invention
Preparation Method is simple, and the period is short, is suitble to mass production.
Specific embodiment
The present invention provides a kind of POSS modified flame-retardants to enhance vinyl ester resin, by the component including following mass fraction
It is prepared:
The POSS includes trapezoidal POSS and/or trihydroxy cage type POSS；Wherein, the trapezoidal POSS is knot shown in formula I
The mixture of one or more of structure:
In formula I, n is integer more than or equal to 0, preferably 2~10；
The structure of the trihydroxy cage type POSS is as shown in formula II:
In terms of mass fraction, the component for preparing POSS modified flame-retardant enhancing vinyl ester resin provided by the invention includes second
50~98 parts of alkenyl esters resin, preferably 60~85 parts, more preferably 65~75 parts.In the present invention, the vinyl esters tree
Rouge preferably includes bisphenol A-type vinyl ester resin and/or phenol aldehyde type vinyl ester resin.The present invention is to the bisphenol A-type ethylene
The source and model of base ester resin and phenol aldehyde type vinyl ester resin do not require particularly, using corresponding tree well known in the art
Fat prod.
On the basis of the mass fraction of vinyl ester resin, POSS modified flame-retardant enhancing vinyl provided by the invention is prepared
The component of ester resin includes 0.5~10 part of curing agent, preferably 1.5~8.5 parts, more preferably 2~7 parts.In the present invention, institute
It states curing agent and preferably includes methyl ethyl ketone peroxide, cyclohexanone peroxide, diacetone peroxide, benzoyl peroxide, peroxidating
One or more of two lauroyl, t-butyl perbenzoate and isopropyl benzene hydroperoxide.The present invention carrys out the curing agent
Source does not require particularly, using commercial product well known in the art.
On the basis of the mass fraction of vinyl ester resin, POSS modified flame-retardant enhancing vinyl provided by the invention is prepared
The component of ester resin includes 0.1~2 part of promotor, preferably 0.5~1.5 part, more preferably 0.7~1.2 part.In the present invention
In, the promotor preferably includes cobalt iso-octoate, cobalt naphthenate, dodecyl sodium sulfate, triethylenediamine, dimethyl benzene
One or more of amine, diethylaniline and dimethyl open-chain crown ether.The present invention is to the source of the promotor without spy
Other requirement, using commercial product well known in the art.
On the basis of the mass fraction of vinyl ester resin, POSS modified flame-retardant enhancing vinyl provided by the invention is prepared
The component of ester resin includes 2~50 parts of POSS, preferably 5~45 parts, more preferably 15~35 parts.POSS (polyhedral oligomeric silicon
Sesquioxyalkane) it is a kind of organic-nothing that the silicon oxygen skeleton alternately connected with Si-O forms for inorganic kernel and apex angle organic group
Machine hybrid material, the structure by designing apex angle group can realize POSS functional diversities, can be divided into disordered structure, trapezoidal knot
Structure, cagelike structure and imperfect cagelike structure etc..In the present invention, the POSS includes trapezoidal POSS and/or trihydroxy cage type
POSS.In the present invention, the trapezoidal POSS is one of structure shown in formula I (i.e. n be a certain numerical value) or several (i.e. n is
Different numerical value) mixture；When the trapezoidal POSS is mixture several in structure shown in formula I, the present invention is to described mixed
The mixed proportion for closing different structure in object does not require particularly, can be mixed with arbitrary proportion.In the present invention, described trapezoidal
Hydroxyl group possessed by phenyl group and ladder type POSS compound outside POSS molecule can be such that it is easy to and ethylene
Base ester resin reaches molecular level combination, and carbon residue is high, can reduce smoke release and heat release.Meanwhile stable Si-O ladder type knot
Structure can promote the mechanical property of composite material.In the present invention, the structure of the trihydroxy cage type POSS is as shown in formula II；Institute
Stating trihydroxy cage type POSS is a kind of three-dimensional hybrid inorganic-organic materials with nano-scale, and surrounding molecules have structure
Metastable phenyl group and hydroxyl compared with high reaction activity, can be easy to reach molecular water reef knot with vinyl ester resin
It closes, carbon residue is high, can reduce cigarette release and heat release, and Si-O cagelike structure can promote the mechanical property of composite material.In this hair
In bright, when the POSS is the mixture of trapezoidal POSS and trihydroxy cage type POSS, the present invention is to the trapezoidal POSS and three
The mixed proportion of hydroxyl cage type POSS does not require particularly, can be mixed with arbitrary proportion.The present invention to the trapezoidal POSS and
The source of trihydroxy cage type POSS does not have particular/special requirement, prepare using commercial product or using method well known in the art
It can.
POSS modified flame-retardant provided by the invention enhances vinyl ester resin good mechanical properties, has in combustion
The characteristics of low cigarette and low-heat discharge.
The present invention provides the preparation methods of the enhancing vinyl ester resin of POSS modified flame-retardant described in above scheme, including with
Lower step:
(1) vinyl ester resin and the POSS are mixed, obtains the first mixed system；
(2) first mixed system and promotor are mixed, obtains the second mixed system；
(3) curing reaction is carried out after mixing second mixed system and curing agent, obtains the POSS modified flame-retardant
Enhance vinyl ester resin.
The present invention mixes vinyl ester resin and the POSS, obtains the first mixed system.It is embodied in the present invention
In example, the mixing carries out preferably in mixing kettle.The present invention does not require the mixed method particularly, using ability
The POSS is homogeneously dispersed in vinyl ester resin by method known to domain, is specifically such as stirred.In this hair
In bright, the mixed temperature is preferably 25~120 DEG C, and more preferably 50~80 DEG C, i.e., by vinyl ester resin and described
POSS is added in mixing kettle, is mixed at said temperatures.
After obtaining the first mixed system, the present invention mixes first mixed system and promotor, obtains the second mixing
System.The present invention does not require the mixed method particularly, using method well known in the art by promotor equably
It is scattered in first mixed system, to be ready for subsequent cure reacting balance, specifically as stirred
Mixing.In the present invention, the mixed temperature is preferably 15~40 DEG C, and more preferably 20~30 DEG C；When first mixing
When the temperature of system is higher than this mixing temperature, the temperature of first mixed system is down to this blend temperature range by the present invention
It is interior, it adds promotor and is mixed.
After obtaining the second mixed system, the present invention solidify anti-after mixing second mixed system and curing agent
It answers, obtains the POSS modified flame-retardant enhancing vinyl ester resin.The present invention does not require the mixed method particularly,
Guarantee for second mixed system and curing agent to be uniformly mixed using method well known in the art, it is specifically as mixed in stirred
It closes.In the present invention, the mixed temperature is preferably 15~40 DEG C, and more preferably 20~30 DEG C.In the present invention, it is carrying out
It further preferably include mixing resulting curing system to second mixed system and curing agent to carry out vacuum defoamation before curing reaction
Resulting curative systems, i.e., be placed in vacuum tank, then vacuumize to vacuum tank by processing；The vacuum defoamation is handled true
Reciprocal of duty cycle is preferably -0.01~-0.09MPa, more preferably -0.04~-0.06MPa；After vacuum degree reaches requirement, the present invention is preferred
5min is kept under above-mentioned vacuum degree condition.The present invention can be removed by vacuum defoamation processing by the second mixed system and solidification
The bubble generated in the curing system of agent composition, it is uniform to obtain pattern, do not have defective cured article.Vacuum defoamation processing
Afterwards, the curing system is transferred out of vacuum environment by the present invention, starts to carry out curing reaction.In the present invention, the solidification is anti-
The temperature answered is preferably 25~100 DEG C, and the time is preferably 4~for 24 hours.In the present invention, the curing reaction preferably includes successively
The first cure stage, the second cure stage and the third cure stage carried out.In the present invention, the temperature of first cure stage
Preferably 25~35 DEG C of degree, the time is preferably 6~12h, after the completion of first cure stage, system heating is carried out second and is consolidated
The change stage；The temperature of second cure stage is preferably 50~70 DEG C, and the time is preferably 2~10h, second cure stage
After the completion, system is heated up and carries out third cure stage；The temperature of the third cure stage is preferably 90~100 DEG C, the time
Preferably 2~8h.In the present invention, to issue raw free radical polymerization anti-in curing agent and promotor effect for vinyl ester matrix
It answers, wherein curing agent provides initial radical, causes double-bond polymerization reaction in vinyl ester resin；And trapezoidal POSS and trihydroxy
Cage type POSS is not involved in radical reaction, but can be evenly dispersed in resin by intermolecular force, e.g., hydroxyl in POSS
Base is combined in the form of hydrogen bond with hydroxyl abundant in resin.After the completion of solidification, the POSS modified flame-retardant enhancing ethylene is obtained
Base ester resin.
The present invention provides the preparation methods of POSS modified flame-retardant described above enhancing vinyl ester resin.The present invention provides
Preparation method it is simple, the period is short, be suitble to mass production.
Below with reference to embodiment to POSS modified flame-retardant provided by the invention enhancing vinyl ester resin and preparation method thereof
It is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
In embodiments of the present invention, used trapezoidal POSS is the structure of n=2~10 in formula I.
Embodiment 1
A kind of POSS modified flame-retardant enhancing vinyl ester resin, by bisphenol A-type vinyl ester resin, promotor isooctyl acid
Cobalt, curing agent methyl ethyl ketone peroxide and the trapezoidal POSS of modifying agent, trihydroxy cage type POSS are prepared, the quality percentage of each component
Than as follows:
Specific preparation step are as follows:
1) by the mixing of 156g bisphenol A-type vinyl ester resin, the trapezoidal POSS and 19.5g trihydroxy cage type POSS of 19.5g
Object is added in mixing kettle, stirs at 60 DEG C, until being uniformly mixed, obtains the first mixed system；
2) 1) the first mixed system temperature in is controlled at 25 DEG C, 1g promotor cobalt iso-octoate is added, then stir to
Promotor is uniformly mixed with resin system, obtains the second mixed system；
3) 2) the second mixed system temperature in is controlled at 25 DEG C, 4g curing agent methyl ethyl ketone peroxide is added, then stirs
It mixes to curing agent and is uniformly mixed with resin system, obtain curing system；
4) by the curing system vacuumize process in 3), when vacuum degree reaches -0.06MPa or so, 5min is kept；
5) 4) mixed liquor in is poured out, solidifies 3h under the conditions of solidifying 12 hours, 60 DEG C under the conditions of room temperature (25 DEG C),
Solidify 2h under the conditions of 100 DEG C, obtains POSS modified flame-retardant enhancing vinyl ester resin.
Embodiment 2
A kind of POSS modified flame-retardant enhances vinyl ester resin, by phenol aldehyde type vinyl ester resin, promotor cobalt naphthenate,
The mixture of curing agent cyclohexanone peroxide and the trapezoidal POSS of modifying agent, trihydroxy cage type POSS, the mass percent of each component
It is as follows:
Specific preparation step are as follows:
1) by the mixing of 140.0g phenol aldehyde type vinyl ester resin, the trapezoidal POSS and 20.0g trihydroxy cage type POSS of 32.0g
Object is added in mixing kettle, stirs at 100 DEG C, until being uniformly mixed, obtains the first mixed system；
2) 1) the first mixed system temperature in is controlled at 30 DEG C, 2g promotor cobalt naphthenate is added, then stir to
Promotor is uniformly mixed with resin system, obtains the second mixed system；
3) 2) the second mixed system temperature in is controlled at 30 DEG C, 6g curing agent cyclohexanone peroxide is added, then stirs
It mixes to curing agent and is uniformly mixed with resin system, obtain curing system；
4) by the curing system vacuumize process in 3), when vacuum degree reaches -0.07MPa or so, 5min is kept；
5) 4) mixed liquor in is poured out, solidifies 8h at 35 DEG C, solidifies 8h under the conditions of 60 DEG C, solidify under the conditions of 100 DEG C
4h obtains POSS modified flame-retardant enhancing vinyl ester resin.
Embodiment 3
A kind of POSS modified flame-retardant enhancing vinyl ester resin, by bisphenol A-type vinyl ester resin, promotor diethylbenzene
Amine, curing agent dilauroyl peroxide and the trapezoidal POSS of modifying agent are prepared, and the mass percent of each component is as follows:
Specific preparation step are as follows:
1) 160.0g bisphenol A-type vinyl ester resin, the trapezoidal POSS of 34.0g are added in mixing kettle, are stirred at 60 DEG C, directly
To being uniformly mixed, the first mixed system is obtained；
2) 1) the first mixed system temperature in is controlled at 30 DEG C, 2g promotor diethylaniline is added, then stirs
It is uniformly mixed to promotor with resin system, obtains the second mixed system；
3) 2) the second mixed system temperature in is controlled at 30 DEG C, 4g curing agent dilauroyl peroxide is added, then
Stirring is uniformly mixed to curing agent with resin system, obtains curing system；
4) by the curing system vacuumize process in 3), when vacuum degree reaches -0.06MPa or so, 5min is kept；
5) 4) mixed liquor in is poured out, solidifies 3h under the conditions of solidifying 10 hours, 70 DEG C under the conditions of room temperature (25 DEG C),
Solidify 2h under the conditions of 100 DEG C, obtains POSS modified flame-retardant enhancing vinyl ester resin.
Embodiment 4
A kind of POSS modified flame-retardant enhancing vinyl ester resin, by bisphenol A-type vinyl ester resin and phenol aldehyde type vinyl
Mixture, promotor cobalt naphthenate, curing agent methyl ethyl ketone peroxide and the modifying agent trihydroxy cage type POSS of ester resin are prepared into
It arrives, the mass percent of each component is as follows:
Specific preparation step are as follows:
1) by 60.0g bisphenol A-type vinyl ester resin, 80.0g phenol aldehyde type type vinyl ester resin, 53.0g trihydroxy cage
The mixture of shape POSS is added in mixing kettle, stirs at 50 DEG C, until being uniformly mixed, obtains the first mixed system；
2) 1) the first mixed system temperature in is controlled at 25 DEG C, 1g promotor cobalt naphthenate is added, then stir to
Promotor is uniformly mixed with resin system, obtains the second mixed system；
3) 2) the second mixed system temperature in is controlled at 25 DEG C, 6g curing agent methyl ethyl ketone peroxide is added, then stirs
It mixes to curing agent and is uniformly mixed with resin system, obtain curing system；
4) by the curing system vacuumize process in 3), when vacuum degree reaches -0.08MPa or so, 5min is kept；
5) 4) mixed liquor in is poured out, solidifies 8h under the conditions of 30 DEG C, solidify 8h under the conditions of 70 DEG C, it is solid under the conditions of 90 DEG C
Change 4h, obtains POSS modified flame-retardant enhancing vinyl ester resin.
Embodiment 5
A kind of POSS modified flame-retardant enhancing vinyl ester resin, by bisphenol A-type vinyl ester resin and phenol aldehyde type vinyl
Mixture, promotor cobalt naphthenate, curing agent cyclohexanone peroxide, the trapezoidal POSS of modifying agent and the trihydroxy cage type of ester resin
The mixture of POSS is prepared, and the mass percent of each component is as follows:
Specific preparation step are as follows:
1) by 70.0g bisphenol A-type vinyl ester resin, 70.0g phenol aldehyde type vinyl ester resin, the trapezoidal POSS of 20.0g and
The mixture of 32.0g trihydroxy cage type POSS is added in mixing kettle, stirs at 80 DEG C, until being uniformly mixed, obtains the first mixing
System；
2) 1) the first mixed system temperature in is controlled at 20 DEG C, 2g promotor cobalt naphthenate is added, then stir to
Promotor is uniformly mixed with resin system, obtains the second mixed system；
3) 2) the second mixed system temperature in is controlled at 20 DEG C, 6g curing agent cyclohexanone peroxide is added, then stirs
It mixes to curing agent and is uniformly mixed with resin system, obtain curing system；
4) by the curing system vacuumize process in 3), when vacuum degree reaches -0.05MPa or so, 5min is kept；
5) 4) mixed liquor in is poured out, solidifies 8h under the conditions of 30 DEG C, solidify 10h under the conditions of 60 DEG C, under the conditions of 100 DEG C
Solidify 6h, obtains POSS modified flame-retardant enhancing vinyl ester resin.
Performance test:
The enhancing vinyl ester resin of POSS modified flame-retardant prepared by Examples 1 to 5 is poured into mould according to standard size
Batten needed for being prepared into test in tool.
Smoke density selects 50kW/m according to ISO 5659-2 standard testing, radiant cone2, nonflame；Heat release test is using cone
Shape calorimeter, according to 5660 standard of ISO, radiant power 50kW/m2；Casting resin bending property is tested according to GB/T
2570-1995 standard testing, specimen size are 100mm × 15mm × 4mm.
The performance test results such as 1 institute of table of pure ethylene base ester resin and the modified ethenyl resin of each embodiment preparation
Show:
The modified ethenyl resin the performance test results of 1 pure ethylene base ester resin of table and the preparation of each embodiment
As can be seen from Table 1, the present invention utilizes high thermal stability, the Halogen of trapezoidal POSS and/or trihydroxy cage type POSS
And good compatibility, it is function modified to vinyl ester resin progress, obtain the cigarette release drop of Vinyl Ester Resin Composites
Low 30% or so, heat release reduces nearly 20%；Meanwhile the bending strength of composite material is lifted beyond 100%.As it can be seen that this hair
The POSS modified ethenyl resin of bright offer has good low-heat, suppression cigarette and reinforcing effect, and preparation method is simple, is suitble to
Mass production.
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 POSS modified flame-retardant enhances vinyl ester resin, which is characterized in that by the component system including following mass fraction
It is standby to obtain:
The POSS includes trapezoidal POSS and/or trihydroxy cage type POSS；Wherein, the trapezoidal POSS is in structure shown in formula I
One or more of mixtures:
In formula I, n is the integer more than or equal to 0；
The structure of the trihydroxy cage type POSS is as shown in formula II:
2. POSS modified flame-retardant according to claim 1 enhances vinyl ester resin, which is characterized in that the vinyl esters
Resin includes bisphenol A-type vinyl ester resin and/or phenol aldehyde type vinyl ester resin.
3. POSS modified flame-retardant according to claim 1 enhances vinyl ester resin, which is characterized in that the curing agent packet
It includes methyl ethyl ketone peroxide, cyclohexanone peroxide, diacetone peroxide, benzoyl peroxide, dilauroyl peroxide, cross benzene first
One or more of tert-butyl acrylate and isopropyl benzene hydroperoxide.
4. POSS modified flame-retardant according to claim 1 enhances vinyl ester resin, which is characterized in that the promotor packet
Include cobalt iso-octoate, cobalt naphthenate, dodecyl sodium sulfate, triethylenediamine, dimethylaniline, diethylaniline and dimethyl
One or more of open-chain crown ether.
5. POSS modified flame-retardant described in Claims 1 to 4 any one enhances the preparation method of vinyl ester resin, feature exists
In, comprising the following steps:
(1) vinyl ester resin and the POSS are mixed, obtains the first mixed system；
(2) first mixed system and promotor are mixed, obtains the second mixed system；
(3) curing reaction is carried out after mixing second mixed system and curing agent, obtains the POSS modified flame-retardant enhancing
Vinyl ester resin.
6. preparation method according to claim 5, which is characterized in that the temperature mixed in the step (1) is 25~120
℃。
7. preparation method according to claim 5, which is characterized in that the temperature mixed in the step (2) is 15~40
℃。
8. preparation method according to claim 5, which is characterized in that the temperature mixed in the step (3) is 15~40
℃。
9. preparation method according to claim 5, which is characterized in that the step (3) is also wrapped before carrying out curing reaction
It includes and resulting curing system progress vacuum defoamation processing is mixed to second mixed system and curing agent；At the vacuum defoamation
The vacuum degree of reason is -0.01~-0.09MPa.
10. preparation method according to claim 5, which is characterized in that the temperature of curing reaction is 25 in the step (3)
~100 DEG C, the time be 4~for 24 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109135197A (en) * | 2018-08-30 | 2019-01-04 | 北京理工大学 | A kind of Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resin composition and its preparation method and application |
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2019
- 2019-08-30 CN CN201910813285.3A patent/CN110499003A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109135197A (en) * | 2018-08-30 | 2019-01-04 | 北京理工大学 | A kind of Polyhedral oligomeric silsesquioxane modified flame-retardant vinyl ester resin composition and its preparation method and application |
Non-Patent Citations (1)
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| 吴昆 等: "环氧树脂/笼型倍半硅氧烷纳米复合材料的阻燃性能与热解机理", 《高分子材料科学与工程》 * |
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Application publication date: 20191126 |