CN104479106B - Vinyl ester resin and preparation method thereof - Google Patents
Vinyl ester resin and preparation method thereof Download PDFInfo
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- CN104479106B CN104479106B CN201410740001.XA CN201410740001A CN104479106B CN 104479106 B CN104479106 B CN 104479106B CN 201410740001 A CN201410740001 A CN 201410740001A CN 104479106 B CN104479106 B CN 104479106B
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Abstract
The invention discloses vinyl ester resin and a preparation method thereof, belongs to the technical field of high molecular materials, and provides a technical scheme, that is, vinyl ester resin which can be cured under a certain damp condition, for solving the problem that the conventional vinyl ester resin is greatly affected by moisture in the curing process. A compound with an epoxy resin structure generates ring opening polymerization reaction with unsaturated monocarboxylic acid and the generated product is diluted in a reaction type diluent to generate vinyl ester resin. The curing degree of the resin under the damp environment condition is increased, a novel solution to application of the vinyl ester resin to anti-corrosion construction in a damp environment is provided, the influence of the environment factor on construction is reduced, the construction period is shortened, and the construction efficiency is improved.
Description
Technical field
The invention belongs to technical field of polymer materials and in particular to a kind of under certain wet condition solidification vinyl
Ester resin and preparation method thereof.
Background technology
Vinyl ester resin is that vinyl group is contained in molecule end, and middle skeleton is that one kind of epoxy resin structural is special not
Saturated polyester resin, is typically reacted by esterification by ring opening with unsaturated monoacid by epoxy resin and is obtained, have concurrently epoxy with
The feature of two kinds of thermosetting resins of unsaturated polyester (UP)；Vinyl ester resin remains the basic segment of epoxy resin, has insatiable hunger again
With the good process performance of polyester resin, after can solidifying under optimum conditions, show some special premium properties, such as excellent
Mechanical performance, thermostability and chemical resistance.
The solidification of vinyl ester resin is a kind of free radicals copolymerization reaction, typically adopts peroxide under room temperature, such as peroxide
Change butanone (Methyl Ethyl Ketone Peroxide), carry out solid under the catalysis of the accelerator such as cobalt (Cobalt) slaine
Change.This solidification process affected by moisture larger, when in resin contain a certain amount of moisture when, resin solidification can be led to be difficult to,
It is mainly shown as resin solidification degree not, resin feels like jelly no hardness.And resin actually used when, be frequently encountered moist bar
Moisture etc. is contained containing in moisture, reinforcing fiber in big, the moist construction interface of part, such as air humidity, filler or adjuvant.
If being constructed with Natural ethylene base ester resin, often produce state of cure inadequate situations such as and lead to do over again, largely effect on and apply
Work efficiency rate, increases construction cost.
In order to avoid there is the inadequate situation of state of cure, at present, when being constructed under running into wet condition, Ren Menzhu
Will be to add substantial amounts of room temperature peroxide initiator (such as：Methyl ethyl ketone peroxide) and reach necessary solidification effect, but excessively
The interpolation of peroxide initiator content in resin for the initiator end group can be led to increase, the chemistry of impact resin is fine and close
Degree, reduces the decay resistance after resin solidification.On the other hand, the excessive initiator adding also results in and decomposes little point producing
Son increases, and these small molecules form bubble in resin, can weaken the corrosion resistance after resin solidification further.
For the solidification of vinyl ester resin under wet environment, patent US 4611015 discloses by adding crosslinked water suction
The method of resin is it is ensured that cross-linking reaction under peroxide initiation for the unsaturated-resin (inclusion vinylite).Its application
It is the solidification of concrete, crosslinked water-absorbing resin mixes solid again with unsaturated-resin after being pre-mixed with concrete in granular form
Change.If apply the vinyl ester resin being dispersed with the strong water-absorbing resin of hydrophilic in corrosion-resistant field, matrix can not meet for
The requirement of highly corrosion resistant.
Patent US4431782 discloses another kind of method solidifying vinyl ester resin at high humidity.I.e. part ring
It is converted into sulfosalt to improve the compatibility of vinylite and water after oxygen groups and thiol reactant, and pass through such as ultraviolet or electricity
The technique of beamlet radiation is solidified.Due to not doing initiator using peroxide, the method can be used for various base materials in height
Coated solidified in the case of humidity or even high-moisture.But because its curing reaction needs radiation condition, therefore seriously limit
The method is in the application at anticorrosive construction scene.
Patent JPS5513763 discloses a kind of sky dry type unsaturated polyester resin coating composition, this resin combination owner
Polyhydric alcohol to be passed through, allyl ether compound and acrylic acid condensation substance, mixed with one of arsenous hydricde, antimonous hydride or two kinds
Close, add acids additive, reduce the inhibition to resin solidification for the oxygen, improve surface drying after resin solidification.
Same patent CN200810036708 is also to disclose a kind of preparation method of air-drying property vinyl ester resin, and the method is using double
Cyclopentadiene is modified to vinyl ester resin, to reach good air-drying property.The method that above-mentioned two patents are related to is all
It is surface drying after raising resin solidifies in atmosphere, can not solve and improve resin in wet condition, containing moisture
In the case of problem of solidification.
Therefore, study a kind of New Types of Vinyl Ester Resins so as in wet environment, during containing moisture, remain to do not changing
Carry out normal cure on the premise of curing process, and reach resin solidification degree requirement, extremely important.
Content of the invention
Affected larger problem in current vinyl ester resin solidification process by moisture, the invention provides one kind exists
The vinyl ester resin technical solution of certain wet condition curable, and realized by following purpose.
It is an object of the invention to provide a kind of vinyl ester resin in certain wet condition curable.
Another object of the present invention is to provide a kind of preparation of the vinyl ester resin in certain wet condition curable
Method.
It is a further object of the present invention to provide a kind of vinyl ester resin in certain wet condition curable is in base
Material is external coating, frp lining and the fiberglass products formed of concrete, and has factory's terrace of heavy antisepsis requirement, dirt
The application of the aspects such as water treating pond, groove, pipeline, pressure vessels for the chemical industry or chemical industry equipment.
The present invention provide a kind of curable vinyl ester resin technical solution under certain wet condition be, institute
State vinyl ester resin and there is the vinyl ester-functional shown in structure formula I：
Wherein, group R1Selected from C2～C10Alkene, C5～C20Cycloalkane, C5～C20Cycloolefins, C6～C20Aromatic hydrocarbon；
Group R2Selected from H, OH, C1～C5Alkane；
Group R3Selected from H, CH3, halogen atom；
Group R4Selected from H, CH3, halogen atom.
In vinyl ester resin of the present invention, the epoxy resin as framing structure can be selected from bisphenol A-type ring
Oxygen tree fat (Bisphenol A Epoxy Resin), bisphenol f type epoxy resin (Bisphenol F Epoxy Resin), phenolic aldehyde
Type epoxy resin (Novolac Type Epoxy Resin), tetrabromobisphenol A type epoxy resin (Tetrabromo-Bisphenol
A Epoxy Resin) one or more of combination.
The present invention provides a kind of preparation method of above-mentioned vinyl ester resin, and step includes：Change containing epoxy resin structural
Compound and unsaturated monocarboxylic acid carry out ring-opening polymerization, and it generates product dilution in response type diluent.
Wherein, the unsaturated monocarboxylic acid being adopted is the mixture of special unsaturated monocarboxylic acid and methacrylic acid,
Wherein special unsaturated monocarboxylic acid is 1 with the equivalent proportion of methacrylic acid:0.05～9；
Wherein, the structure of special unsaturated monocarboxylic acid is as shown in structure formula II：
Wherein, group R1Selected from C2‐C10Alkene, C5‐C20Cycloalkane, C5‐C20Cycloolefins, C6‐C20Aromatic hydrocarbon；
Group R2Selected from H, OH, C1‐C5Alkane；
Group R3Selected from H, CH3, halogen atom；
Group R4Selected from H, CH3, halogen atom.
In preparation method of the present invention, the equivalent proportion of compound containing epoxy resin structural and unsaturated monocarboxylic acid
It is preferably 1:0.8～1.2, more preferably 1:0.9～1.1.
The described compound containing epoxy resin structural, is well-known to those skilled in the art, can be used for the present invention
Arbitrarily epoxy resin, can be such as selected from bisphenol A type epoxy resin (Bisphenol A Epoxy Resin), bisphenol F type epoxy
Resin (Bisphenol F Epoxy Resin), phenol aldehyde type epoxy resin (Novolac Type Epoxy Resin), tetrabromo are double
One of which in phenol A type epoxy resin (Tetrabromo-Bisphenol A Epoxy Resin) or several combinations.
Described ring-opening polymerization condition is reacted 2～6 hours at being preferably 90～130 DEG C.
The response type diluent of vinyl ester resin of the present invention is selected from single unsaturated functional group monomer or how unsaturated
One of which in monomer or several mixture；The weight of wherein response type diluent accounts for vinyl ester resin gross weight
25%～75%, preferably 30%～70%.
Wherein, single unsaturated functional group monomer, including vinyltoluene (Methylstyrene), styrene
(Styrene), 2- phenyl -1- propylene (2-Phenyl-1-propene), acrylic acid (Acrylic acid), acrylic acid methyl ester.
(Methyl acrylate), glycidyl acrylate (GMA, Glycidyl methacrylate), acrylic acid 2 hydroxy methacrylate
(2-Hydroxyethyl acrylate), Hydroxypropyl acrylate (Hydroxypropyl acrylate), 2- methacrylic acid
(Methacrylic acid), methacrylate (Methyl propiolate), glycidyl methacrylate
(Glycidyl methacrylate), methacrylic acid 2 hydroxy methacrylate (Hydroxyethyl methacrylate), methyl-prop
The mixture of one or more of olefin(e) acid hydroxypropyl acrylate (Hydroxy propyl methacrylate).
Wherein, how unsaturated monomer, including divinylbenzene (Divinylbenzene), dicyclopentadiene propylene
Acid esters (dicyclopentadienyl acrylate), tripropylene glycol diacrylate (Tripropylene glycol
Diacrylate), trimethylolpropane trimethacrylate (Trimethylolpropane triacrylate), trihydroxy methyl third
One of alkane diallyl ether (Trimethylolpropane diallylether) monomer or several mixture.
Vinyl ester resin of the present invention can be solidified by peroxide compound.
Vinyl ester resin of the present invention, under certain wet condition, can be solidified, and wherein certain wet condition can
Represented by moisture in resin, its moisture is：0～15%.
The purposes of the vinyl ester resin that the present invention provides, it is applied to base material is the external coating of concrete, fiberglass
Liner and fiberglass products formed, and there is factory's terrace of heavy antisepsis requirement, treatment tank, groove, pipeline, pressure vessels for the chemical industry
Or chemical industry equipment etc..
The vinyl ester resin that the present invention provides is it is characterised in that the solidification relative humidity of described vinyl ester resin exists
5% to 100%, 25% to 100%, more preferably solidification relative humidity is 30% to 100% for preferred consolidation relative humidity.Solidification
When, the moisture in resin accounts for the 0～15% of resin total amount.
It is an advantage of the invention that：
The concrete surface coating decoration of Natural ethylene base ester resin is it is desirable to concrete moisture content must be square within 2%
Can construct, the moisture content more than 2% is it is not recommended that construct；And adopt the present invention provide vinyl ester resin, can in moisture content
Up to the concrete surface to 10% is constructed, thus overcoming the problem of solidification that substrate moisture brings.
For when constructing or running into plum rain season in coastal area, can meet when being constructed using Natural ethylene base ester resin
To resin solidification speed is slow, state of cure not, after easily resin solidification, case hardness is not high, and that meets that water turns white shows
As leading to doing over again or construction of delaying of engineering；And be not likely to produce surface using the vinyl ester resin that the present invention provides and turn white
Phenomenon, thus avoiding the problems such as engineering accident because environmental factorss lead to, claim for eot, reduces construction cost.
The application of vinyl ester resin of the present invention, improves state of cure under moist environmental conditions for the resin, is ethylene
Base ester resin carries out anticorrosive construction in wet condition provides new solution route, you can carry out anti-corrosion under moist environmental conditions
Construction, reduces the impact to construction for the environmental factorss, shortens the construction period, improve efficiency of construction.
Specific embodiment
In order to further appreciate that the present invention, it is described in detail to various aspects of the present invention below, as no specific instructions, this
Bright various raw materials all can be obtained by market purchasing；Or prepared according to the conventional method of this area.Unless otherwise fixed
Justice or explanation, all specialties used herein and scientific words and meaning phase familiar to those skilled in the art institute
With.It is understood that these descriptions following are simply to further illustrate the features and advantages of the present invention, rather than to the present invention
The restriction of claim.
The invention provides a kind of vinyl ester resin in certain wet condition curable, described vinyl ester resin
There is the vinyl ester-functional shown in structure formula I；Wherein, group R1Selected from C2～C10Alkene, C5～C20Cycloalkane, C5~
C20Cycloolefins, C6～C20Aromatic hydrocarbon；Group R2Selected from H, OH, C1～C5Alkane；Group R3Selected from H, CH3, halogen atom；Group R4
Selected from H, CH3, halogen atom.
In vinyl ester resin of the present invention, the epoxy resin as framing structure can be selected from bisphenol A-type ring
Oxygen tree fat (Bisphenol A Epoxy Resin), bisphenol f type epoxy resin (Bisphenol F Epoxy Resin), phenolic aldehyde
Type epoxy resin (Novolac Type Epoxy Resin), tetrabromobisphenol A type epoxy resin (Tetrabromo-Bisphenol
A Epoxy Resin) in one of which or several combination.
For example, can use and ring-opening reaction, obtained bisphenol-A are carried out by bisphenol type epoxy and unsaturated monocarboxylic acid
Type vinyl ester resin；Can use and ring-opening reaction, obtained phenol aldehyde type second are carried out by phenolic epoxy and unsaturated monocarboxylic acid
Alkenyl esters resin；Or ring-opening reaction, obtained brominated flame retardant are carried out by tetrabromobisphenol A type epoxy and unsaturated monocarboxylic acid
Type vinyl ester resin.
Unsaturated monocarboxylic acid in vinyl ester resin of the present invention, is special unsaturated monocarboxylic acid and methyl-prop
The mixture of olefin(e) acid, wherein special unsaturated monocarboxylic acid is 1 with the equivalent proportion of methacrylic acid:0.05～9, preferably 1:
0.1～5；The structure of wherein special unsaturated monocarboxylic acid as shown in structure formula II, wherein, group R1Selected from C2～C10Alkene
Hydrocarbon, C5～C20Cycloalkane, C5～C20Cycloolefins, C6～C20Aromatic hydrocarbon；Group R2Selected from H, OH, C1～C5Alkane；Group R3It is selected from
H、CH3, halogen atom；Group R4Selected from H, CH3, halogen atom.
The response type diluent of vinyl ester resin of the present invention, selected from single unsaturated functional group monomer or how unsaturated
One of which in monomer or several mixture；The weight of wherein response type diluent accounts for vinyl ester resin gross weight
25%～75%, preferably 30%～70%.
Single unsaturated functional group monomer mentioned above, including vinyltoluene (Methylstyrene), styrene
(Styrene), 2- phenyl -1- propylene (2-Phenyl-1-propene), acrylic acid (Acrylic acid), acrylic acid methyl ester.
(Methyl acrylate), glycidyl acrylate (GMA, Glycidyl methacrylate), acrylic acid 2 hydroxy methacrylate
(2-Hydroxyethyl acrylate), Hydroxypropyl acrylate (Hydroxypropyl acrylate), 2- methacrylic acid
(Methacrylic acid), methacrylate (Methyl propiolate), glycidyl methacrylate
(Glycidyl methacrylate), methacrylic acid 2 hydroxy methacrylate (Hydroxyethyl methacrylate), methyl-prop
One of which in olefin(e) acid hydroxypropyl acrylate (Hydroxy propyl methacrylate) or several mixture.
How unsaturated monomer mentioned above, including divinylbenzene (Divinylbenzene), bicyclic penta 2
Alkene acrylate (dicyclopentadienyl acrylate), tripropylene glycol diacrylate (Tripropylene
Glycol diacrylate), trimethylolpropane trimethacrylate (Trimethylolpropane triacrylate), three
One of which monomer in hydroxymethyl-propane diallyl ether (Trimethylolpropane diallylether) or several list
The mixture of body.
As needed, vinyl ester resin of the present invention can further include available additive, such as reaction suppression
Preparation, to suppress the autohemagglutination of reaction monomers, reaction suppressor does not have specific restriction, arbitrarily can realize the reaction suppression of above-mentioned purpose
Preparation all can use, for example benzoquinone (benzoquinone), but is not chosen as limiting with above-mentioned；With vinyl ester resin for 100
On the basis of weight portion, reaction suppressor highest consumption is up to 0.2 weight portion.
In the preparation method of vinyl ester resin of the present invention, compound containing epoxy resin structural and unsaturated unitary
The equivalent proportion of carboxylic acid is preferably 1：0.8～1.2, more preferably 1：0.9～1.1.
The described compound containing epoxy resin structural, can be bisphenol A type epoxy resin (Bisphenol A Epoxy
Resin), bisphenol f type epoxy resin (Bisphenol F Epoxy Resin), phenol aldehyde type epoxy resin (Novolac Type
Epoxy Resin), one of tetrabromobisphenol A type epoxy resin (Tetrabromo-Bisphenol A Epoxy Resin)
Or several combination, but it is not chosen as limiting with above-mentioned.
In above-mentioned ring-opening polymerization step, as long as compound and the insatiable hunger comprising epoxy resin structural can be made
The condition carrying out ring-opening polymerization with monocarboxylic acid all can use, the no specific restriction of its polymeric reaction condition, but preferably 90
Polyreaction 2～6 hours at～130 DEG C.
Vinyl ester resin of the present invention can be solidified by peroxide compound, and wherein, peroxide compound can
Be methyl ethyl ketone peroxide (Methyl Ethy Ketone Peroxide), benzoyl peroxide (Benzoyl peroxide),
Cumyl hydroperoxide (Cumene hydroperoxide), but be not chosen as limiting with above-mentioned.
5% to 100%, preferred consolidation relative humidity exists the solidification relative humidity of the vinyl ester resin that the present invention provides
25% to 100%, more preferably solidification relative humidity is 30% to 100%.Condition of cure is that the moisture in resin accounts for resin
The 0～15% of total amount.
Below by specific embodiment and comparative example, to vinyl ester resin of the present invention and preparation method thereof, carry out in detail
Introduction and description to be better understood from present invention it should be appreciated that following embodiment is not intended to limit this
The scope of bright technical scheme.
Comparative example 1
Carry out ring-opening polymerization using bisphenol A type epoxy resin and methacrylic acid, its reactant is dilute with styrene again
Release, obtained bisphenol A-type vinyl ester resin (model RIPOXY R-802, Shanghai Zhaohe High Molecule Co., Ltd. is for selling),
Its solids content is 55%.
Comparative example 2
Carry out ring-opening polymerization using phenol aldehyde type epoxy resin and methacrylic acid, its reactant is dilute with styrene again
Release, obtained phenol aldehyde type vinyl ester resin (model RIPOXY H-630, Shanghai Zhaohe High Molecule Co., Ltd. is for selling), its
Solids content is 65%.
Embodiment 1
Carry out ring-opening polymerization using bisphenol A type epoxy resin and unsaturated monocarboxylic acid, its equivalent proportion is bisphenol-A ring
Oxygen tree fat：Special unsaturated monocarboxylic acid：Methacrylic acid=1.0:0.9:0.1；Its reactant is diluted with styrene again, benzene second
Alkene content is 45%, obtained bisphenol A-type vinyl ester resin.
Embodiment 2
Carry out ring-opening polymerization using bisphenol A type epoxy resin and unsaturated monocarboxylic acid, its equivalent proportion is bisphenol-A ring
Oxygen tree fat：Special unsaturated monocarboxylic acid：Methacrylic acid=1.0:0.6:0.4；Its reactant is diluted with styrene again, benzene second
Alkene content is 45%, obtained bisphenol A-type vinyl ester resin.
Embodiment 3
Carry out ring-opening polymerization using bisphenol A type epoxy resin and unsaturated monocarboxylic acid, its equivalent proportion is bisphenol-A ring
Oxygen tree fat：Special unsaturated monocarboxylic acid：Methacrylic acid=1.0:0.4:0.6；Its reactant is diluted with styrene again, benzene second
Alkene content is 45%, obtained bisphenol A-type vinyl ester resin.
Embodiment 4
Carry out ring-opening polymerization using bisphenol A type epoxy resin and unsaturated monocarboxylic acid, its equivalent proportion is bisphenol-A ring
Oxygen tree fat：Special unsaturated monocarboxylic acid：Methacrylic acid=1.0:0.1:0.9；Its reactant is diluted with styrene again, benzene second
Alkene content is 45%, obtained bisphenol A-type vinyl ester resin.
Embodiment 5
Carry out ring-opening polymerization using phenol aldehyde type epoxy resin and unsaturated monocarboxylic acid, its equivalent proportion is phenol aldehyde type ring
Oxygen tree fat：Special unsaturated monocarboxylic acid：Methacrylic acid=1.0:0.9:0.1；Its reactant is diluted with styrene again, benzene second
Alkene content is 35%, obtained phenol aldehyde type vinyl ester resin.
Embodiment 6
Carry out ring-opening polymerization using phenol aldehyde type epoxy resin and unsaturated monocarboxylic acid, its equivalent proportion is phenol aldehyde type ring
Oxygen tree fat：Special unsaturated monocarboxylic acid：Methacrylic acid=1.0:0.6:0.4；Its reactant is diluted with styrene again, benzene second
Alkene content is 35%, obtained phenol aldehyde type vinyl ester resin.
Embodiment 7
Carry out ring-opening polymerization using phenol aldehyde type epoxy resin and unsaturated monocarboxylic acid, its equivalent proportion is phenol aldehyde type ring
Oxygen tree fat：Special unsaturated monocarboxylic acid：Methacrylic acid=1.0:0.4:0.6；Its reactant is diluted with styrene again, benzene second
Alkene content is 35%, obtained phenol aldehyde type vinyl ester resin.
Embodiment 8
Carry out ring-opening polymerization using phenol aldehyde type epoxy resin and unsaturated monocarboxylic acid, its equivalent proportion is phenol aldehyde type ring
Oxygen tree fat：Special unsaturated monocarboxylic acid：Methacrylic acid=1.0:0.1:0.9；Its reactant is diluted with styrene again, benzene second
Alkene content is 35%, obtained phenol aldehyde type vinyl ester resin.
At normal temperatures, in comparative example and embodiment preparation vinyl ester resin, when the moisture of resin is respectively
0%th, 5%, 10%, 15% when, add 0.4phr 6% cobalt naphthenate, after mixing and stirring, add 1.8phr peroxidating
Butanone (MEKPO, Akzo Noble company) simultaneously is again stirring for uniformly, then resin-cast being become the virgin resin that thickness is 3mm
Casting plate, the case hardness (bus hardness) after test resin normal temperature cure 24 hours, evaluate resin under moisture existence condition
Solidification effect, test result is shown in Table 1.
Table 1
From table 1 it follows that in anhydrous conditions, each vinyl ester resin all can normal cure, and have one
Determine case hardness；But under conditions of containing certain moisture, Natural ethylene base ester resin is affected significantly by moisture, and the present invention it
Vinyl ester resin is also affected by moisture, but still can be solidified, and has certain case hardness.
At normal temperatures, using the vinyl ester resin of preparation in comparative example and embodiment, respectively humidity be 30%,
60%th, in the environment of 80%, 100%, resin passes through to add 6% cobalt naphthenate of 0.4phr, after mixing and stirring, adds
The methyl ethyl ketone peroxide (MEKPO, Akzo Noble company) of 1.8phr simultaneously is again stirring for uniformly, then being pasted into using handss with resin
Type method, makes the glass steel sheet that thickness is 2mm, case hardness after normal temperature cure 24 hours for the test glass steel sheet
(bus hardness), evaluates solidification effect under damp condition for the resin, and test result is shown in Table 2.
Table 2
From Table 2, it can be seen that for relative humidity be less than 60%, each vinyl ester resin all can normal cure,
And there is certain surface hardness；But when relative humidity exceedes to a certain degree, Natural ethylene base ester resin is affected significantly by humidity,
And the vinyl ester resin of the present invention is also affected by humidity, but still can be solidified, and be there is certain case hardness.
The vinyl ester resin in certain wet condition curable of the present invention, can be widely applied to base material is concrete
External coating, frp lining and fiberglass products formed, and have factory's terrace of heavy antisepsis requirement, treatment tank,
The aspects such as groove, pipeline, pressure vessels for the chemical industry or chemical industry equipment.
The present invention can be applied under conditions of environment, condition and humidity are unfavorable for the construction of Natural ethylene base ester resin
Work.For example, the concrete surface coating decoration of Natural ethylene base ester resin is it is desirable to concrete moisture content must be square within 2%
Can construct, the moisture content more than 2% is it is not recommended that construct；And adopt the present invention provide vinyl ester resin, can in moisture content
Up to the concrete surface to 10% is constructed, thus overcoming the problem of solidification that substrate moisture brings, improves efficiency of construction, matter
Amount.
For when constructing or running into plum rain season in coastal area, its ambient humidity larger (70～90%), using common
Can run into when vinyl ester resin is constructed that resin solidification speed is slow, state of cure not, after easily resin solidification occurring
Case hardness is not high, meets the phenomenon that water turns white, and leads to doing over again or construction of delaying of engineering, waits suitable construction environment condition to enter
Row construction；And the vinyl ester resin using the present invention to provide, affected by wet environment little during its resin solidification, be not likely to produce
The phenomenon such as turning white in surface, thus avoiding the problems such as engineering accident because environmental factorss lead to, claim for eot, reduces construction cost.
Above the specific embodiment of the present invention is described in detail, but it has been intended only as example, the present invention has not limited
It is formed on particular embodiments described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and
Replace also all among scope of the invention.Therefore, the impartial conversion done under without departing from the principle and scope of the present invention and
Modification, all should cover in the range of technical solution of the present invention.
Claims (13)
1. a kind of vinyl ester resin, described vinyl ester resin has structural formula（Ⅰ）Shown vinyl ester-functional：
（Formula I）
In formula, group R1Selected from C2-C10Alkene, C5-C20Cycloalkane, C5-C20Cycloolefins, C6-C20Aromatic hydrocarbon,
Group R2Selected from H, OH, C1-C5Alkane,
Group R3Selected from H, CH3, halogen atom,
Group R4Selected from H, CH3, halogen atom,
Its preparation method is as follows：Epoxy resin and unsaturated monocarboxylic acid as framing structure carry out ring-opening polymerization, its
Generate product dilution in response type diluent；Described ring-opening polymerization condition is reacted 2～6 hours at being 90～130 DEG C；
Wherein, the unsaturated monocarboxylic acid being adopted is the mixture of special unsaturated monocarboxylic acid and methacrylic acid, described
The structure of special unsaturated monocarboxylic acid such as structural formula（Ⅱ）Shown：
（Formula II）
In formula, group R1Selected from C2-C10Alkene, C5-C20Cycloalkane, C5-C20Cycloolefins, C6-C20Aromatic hydrocarbon,
Group R2Selected from H, OH, C1-C5Alkane,
Group R3Selected from H, CH3, halogen atom,
Group R4Selected from H, CH3, halogen atom.
2. vinyl ester resin as claimed in claim 1, is characterized in that, described vinyl ester resin passes through
Peroxide compound is solidified, and condition of cure is that the moisture in resin accounts for the 0～15% of resin total amount.
3. vinyl ester resin as claimed in claim 1 is it is characterised in that the solidification relative humidity of described vinyl ester resin
5% to 100%.
4. vinyl ester resin as claimed in claim 3 is it is characterised in that the solidification relative humidity of described vinyl ester resin
For 25% to 100%.
5. vinyl ester resin as claimed in claim 4 is it is characterised in that the solidification relative humidity of described vinyl ester resin
For 30% to 100%.
6. vinyl ester resin as claimed in claim 1 is it is characterised in that the epoxy resin as framing structure is selected from bis-phenol
One of which in A type epoxy resin, bisphenol f type epoxy resin, phenol aldehyde type epoxy resin, tetrabromobisphenol A type epoxy resin or
Several compositions.
7. vinyl ester resin as claimed in claim 1, is characterized in that, as the epoxy resin and unsaturated one of framing structure
The equivalent proportion of first carboxylic acid is 1:0.8～1.2.
8. vinyl ester resin as claimed in claim 7, is characterized in that, as the epoxy resin and unsaturated one of framing structure
The equivalent proportion of first carboxylic acid is 1:0.9～1.1.
9. vinyl ester resin as claimed in claim 1, is characterized in that, wherein special unsaturated monocarboxylic acid and metering system
The equivalent proportion of acid is 1:0.05～9.
10. vinyl ester resin as claimed in claim 9, is characterized in that, wherein special unsaturated monocarboxylic acid and methyl-prop
The equivalent proportion of olefin(e) acid is 1:0.1～5.
11. vinyl ester resins as claimed in claim 1 are it is characterised in that the response type of described vinyl ester resin dilutes
Agent is selected from one of which or several mixture in single unsaturated functional group monomer or how unsaturated monomer；Wherein anti-
The weight answering type diluent accounts for the 25%～75% of vinyl ester resin gross weight.
12. vinyl ester resins as claimed in claim 11 are it is characterised in that the response type of described vinyl ester resin dilutes
Agent is selected from one of which or several mixture in single unsaturated functional group monomer or how unsaturated monomer；Wherein anti-
The weight answering type diluent accounts for vinyl ester resin gross weight for 30%～70%.
A kind of 13. applications of vinyl ester resin as claimed in claim 1, vinyl ester resin base material for concrete table
Face application, frp lining and fiberglass products formed, and have factory's terrace of heavy antisepsis requirement, treatment tank, groove,
Application in pipeline, pressure vessels for the chemical industry or chemical industry equipment.
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| CN101747491B (en) * | 2009-12-11 | 2014-11-05 | 上海新天和树脂有限公司 | Fast thickening vinyl ester resin as well as preparation method and application thereof |
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