CN109929066A - A kind of UV-cured resin, preparation method, coating - Google Patents
A kind of UV-cured resin, preparation method, coating Download PDFInfo
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- CN109929066A CN109929066A CN201711347123.2A CN201711347123A CN109929066A CN 109929066 A CN109929066 A CN 109929066A CN 201711347123 A CN201711347123 A CN 201711347123A CN 109929066 A CN109929066 A CN 109929066A
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Abstract
The invention discloses a kind of UV-cured resin, preparation method, coating, belong to polymeric material field.The chemical structural formula of the UV-cured resin is as follows:Wherein, m is integer, range 20-400；N is integer, range 2-50；P is integer, range 2-30；R1For H or CH3；R2For the alkylidene with 1-11 carbon；R3For ethylidene or isopropyl；Rf is perfluoroalkyl or perfluor alkyl ethide with 1-12 carbon；RI is initiator residue.UV-cured resin provided by the invention not only has high rigidity and rub resistance, and has good hydrophobic oleophobic effect, that is, after the coating formed it into is rubbed, hydrophobic oleophobic effect still maintains good.
Description
Technical field
The present invention relates to polymeric material fields, in particular to UV-cured resin, preparation method, coating.
Background technique
There is low-surface-energy based on fluoropolymer, currently, mostly preparing ultraviolet light solidification using fluoropolymer (referred to as
UV photocuring) coating, to form the light solidifying coating of hydrophobic oleophobic.
The prior art provides a kind of ultraviolet-curing paint being prepared using fluoropolymer, by weight,
The coating include: 10-95 parts of the first prepolymer, 5-60 parts of the second prepolymer, 0.05-8 parts of polysilazane based polyalcohol,
0.05-8 parts of fluorine-containing auxiliary agent, 1-15 parts of photoinitiator and 100-300 parts of solvent.Wherein, the first prepolymer is degree of functionality
The polyurethane acrylate prepolymer of 4-8；Second prepolymer is the acrylic ester prepolymer that degree of functionality is 9-18.
Inventors have found that at least there is following technical problem in the prior art:
In the prior art, fluorochemical monomer is added in the form of auxiliary agent, due to fluorine atom electronegativity with higher, so,
It is very poor with the compatibility of prepolymer, so that its additive amount is lower, and is easy to lose in coating friction process, it is above tight
The hydrophobic oleophobic effect of coating is affected again.
Summary of the invention
To overcome the problems in correlation technique, the present invention provides a kind of UV-cured resin, preparation method, painting
Material, the technical solution is as follows:
In a first aspect, providing a kind of UV-cured resin, the chemical structural formula of the UV-cured resin is as follows
It is shown:
Wherein, m is integer, range 20-400；N is integer, range 2-50；P is integer, range 2-30；
R1For H or CH3；
R2For the alkylidene with 1-11 carbon；
R3For ethylidene or isopropyl；
Rf is perfluoroalkyl or perfluor alkyl ethide with 1-12 carbon；
RI is initiator residue.
Second aspect, provides a kind of preparation method of UV-cured resin, and the preparation method includes:
Under the first preset temperature, make (methyl) alkyl acrylate, (methyl) acrylic acid hydroxy alkyl ester, perfluoroalkyl
(methyl) acrylate carries out polymerization reaction in solvent under the initiation of radical initiator, generates fluorine-containing hydroxyl third
Olefin(e) acid resin；
Under the second preset temperature, make the fluorine-containing Hydroxylated acrylic resin and isocyanates in the catalytic action of catalyst
Under reacted, generate UV-cured resin；
Wherein, the chemical structural formula of the isocyanates is as follows:
R1For H or CH3。
In one possible implementation, first preset temperature is 60-140 DEG C；Second preset temperature is
30-80℃。
In one possible implementation, the catalyst is organotin catalysts.
In one possible implementation, the solvent is selected from seven fluorine pentamethylene, butyl acetate, propylene glycol monomethyl ether, third
At least one of glycol methyl ether acetate, isopropanol, ethyl acetate.
In one possible implementation, described (methyl) alkyl acrylate is methyl acrylate, methacrylic acid
Methyl esters, ethyl acrylate, ethyl methacrylate, n-propyl, n propyl methacrylate, n-butyl acrylate, first
The positive ester of base acrylic acid, tert-butyl acrylate, Tert-butyl Methacrylate, the just own ester of acrylic acid, the just own ester of methacrylic acid, propylene
Sour 2- ethylhexyl, 2-ethyl hexyl acrylate, Isooctyl acrylate monomer, isooctyl methacrylate, lauryl acrylate or methyl-prop
Olefin(e) acid lauryl.
In one possible implementation, described (methyl) acrylic acid hydroxy alkyl ester is hydroxy-ethyl acrylate, methyl-prop
Olefin(e) acid hydroxyl ethyl ester, hydroxypropyl acrylate or hydroxy propyl methacrylate.
In one possible implementation, perfluoroalkyl (methyl) acrylate is acrylic acid trifluoro ethyl ester, first
Base acrylic acid trifluoro ethyl ester, hexafluorobutyl acrylate, Hexafluorobutyl mathacrylate, perluorooctyl acrylate, acrylic acid ten
Difluoro heptyl ester, 2- perfluorooctylethyl group acrylate, 2- perfluorododecyl ethyl propylene acid esters or 2- perfluorododecyl
Ethylmethyl acrylate.
In one possible implementation, the radical initiator is peroxide type initiators and/or azo
Initiator.
The third aspect, provides a kind of coating, and the coating includes UV-cured resin mentioned by first aspect.
Technical solution provided in an embodiment of the present invention has the benefit that
UV-cured resin provided in an embodiment of the present invention, by the way that fluorine-containing groups are introduced into acrylic resin main chain knot
In structure, the compatibility of the two is improved, and then additive amount of the fluorine-containing groups in UV-cured resin can be improved, also, contain
Fluorine chain section is not easy to lose because of friction process；Ultraviolet light curing groups are introduced into backbone structure by polyurethanyl group, are made
It obtains the UV-cured resin and is able to carry out ultraviolet light solidification, be conducive to improve its hardness and abrasion resistant effect.As it can be seen that the present invention is implemented
The UV-cured resin that example provides not only has high rigidity and rub resistance, and has good hydrophobic oleophobic effect, even if
After its coating formed is rubbed, hydrophobic oleophobic effect still maintains good.
Specific embodiment
Unless otherwise defined, all technical terms used in the embodiment of the present invention all have usual with those skilled in the art
The identical meaning understood.It to make the object, technical solutions and advantages of the present invention clearer, below will be to embodiment party of the present invention
Formula is described in further detail.
In a first aspect, the embodiment of the invention provides a kind of UV-cured resin, the chemistry of the UV-cured resin
Structural formula is as follows:
Wherein, m is integer, range 20-400；N is integer, range 2-50；P is integer, range 2-30；
R1For H or CH3；
R2For the alkylidene with 1-11 carbon；
R3For ethylidene or isopropyl；
Rf is perfluoroalkyl or perfluor alkyl ethide with 1-12 carbon；
RI is initiator residue, that is, radical initiator carries out remaining residue after polymerization reaction.
UV-cured resin provided in an embodiment of the present invention, by the way that fluorine-containing groups are introduced into acrylic resin main chain knot
In structure, the compatibility of the two is improved, and then additive amount of the fluorine-containing groups in UV-cured resin can be improved, also, contain
Fluorine chain section is not easy to lose because of friction process；Ultraviolet light curing groups are introduced into backbone structure by polyurethanyl group, are made
It obtains the UV-cured resin and is able to carry out ultraviolet light solidification, be conducive to improve its hardness and abrasion resistant effect.As it can be seen that the present invention is implemented
The UV-cured resin that example provides not only has high rigidity and rub resistance, and has good hydrophobic oleophobic effect, even if
After its coating formed is rubbed, hydrophobic oleophobic effect still maintains good.
It should be noted that in above-mentioned chemical structural formula, m 20,21,22 ... 399,400.N be 2,3,4 ...
49,50；P be 2,3,4 ... 29,30.
Second aspect, the embodiment of the invention provides a kind of preparation method of UV-cured resin, the preparation method packets
Include following steps:
Step 1, under the first preset temperature, make (methyl) alkyl acrylate, (methyl) acrylic acid hydroxy alkyl ester, perfluor
Alkyl (methyl) acrylate in solvent, carries out polymerization reaction under the initiation of radical initiator, generates fluorine-containing hydroxyl
Base acrylic resin.
Step 2, under the second preset temperature, make fluorine-containing Hydroxylated acrylic resin and isocyanates catalyst catalysis make
It is reacted under, generates UV-cured resin.
Wherein, the chemical structural formula of isocyanates is as follows:
R1For H or CH3。
Method provided in an embodiment of the present invention, by drawing the poor fluorine-containing groups of compatibility by free radical polymerization mode
Enter into acrylic resin backbone structure, the compatibility of the two can be effectively improved, is conducive to improve fluorine-containing groups in UV light
Change the additive amount in resin.Molecular weight itself due to acrylic resin backbone structure is larger, intermolecular force and its sheet
Body effectively enhances the binding force of fluorine-containing groups, so that fluorine-containing groups are not easy to lose because of friction process, keeps its hydrophobic thin
The persistence of oily effect is obviously improved.Due to the structure that above-mentioned acrylic resin backbone structure is more official's branched chain types, institute's shape
At UV-cured resin be formed by reticular structure after ultraviolet light solidification crosslinking and assign its higher hardness and wearability.
As it can be seen that the above method provided through the embodiment of the present invention, can be prepared desired UV-cured resin.With
Under above steps given respectively illustrate:
For step 1, by making (methyl) alkyl acrylate, (methyl) acrylic acid hydroxy alkyl ester, perfluor alkane
For base (methyl) acrylate in solvent, it is anti-that three kinds of monomers carry out free radical polymerization under the initiation of radical initiator
It answers, generates fluorine-containing Hydroxylated acrylic resin.
Wherein, in order to obtain desired reaction product, which preferably carries out under an inert atmosphere, such as nitrogen atmosphere.
In order to accurately judge reaction end, which can use 1635cm in infrared detection reaction product-1Neighbouring C=C double bond
Whether absorption peak completely disappears, if completely disappearing, then it is assumed that reaction terminates.
Wherein, the chemical structural formula of (methyl) alkyl acrylate is as follows:
R1For H or CH3；R2For the alkylidene with 1-11 carbon.
Based on this, illustratively, being somebody's turn to do (methyl) alkyl acrylate can be methyl acrylate, methyl methacrylate, third
Olefin(e) acid ethyl ester, ethyl methacrylate, n-propyl, n propyl methacrylate, n-butyl acrylate, methacrylic acid
Positive ester, tert-butyl acrylate, Tert-butyl Methacrylate, the just own ester of acrylic acid, the just own ester of methacrylic acid, acrylic acid 2- ethyl
Own ester, 2-ethyl hexyl acrylate, Isooctyl acrylate monomer, isooctyl methacrylate, lauryl acrylate or lauryl
Ester.
Wherein, the chemical structural formula of (methyl) acrylic acid hydroxy alkyl ester is as follows:
Based on this, illustratively, being somebody's turn to do (methyl) acrylic acid hydroxy alkyl ester can be hydroxy-ethyl acrylate, hydroxyethyl methacrylate second
Ester, hydroxypropyl acrylate or hydroxy propyl methacrylate.
Wherein, the chemical structural formula of perfluoroalkyl (methyl) acrylate is as follows:
Based on this, illustratively, which can be acrylic acid trifluoro ethyl ester, methacrylic acid
Trifluoro ethyl ester, hexafluorobutyl acrylate, Hexafluorobutyl mathacrylate, perluorooctyl acrylate, dodecafluorhe-ptylacrylate,
2- perfluorooctylethyl group acrylate, 2- perfluorododecyl ethyl propylene acid esters or 2- perfluorododecyl ethyl-methyl
Acrylate.
The chemical structural formula for being formed by fluorine-containing Hydroxylated acrylic resin is as follows:
It is understood that R involved in fluorine-containing Hydroxylated acrylic resin1、R2、R3, Rf, RI with above-mentioned each react former
R in material1、R2、R3, Rf, RI it is corresponding, details are not described herein.
In addition, (methyl) alkyl acrylate, (methyl) acrylic acid hydroxy alkyl ester, perfluoroalkyl (methyl) acrylate
Monomeric unit can random alignment in fluorine-containing Hydroxylated acrylic resin.
Illustratively, quality of the corresponding monomeric unit of (methyl) alkyl acrylate in the fluorine-containing Hydroxylated acrylic resin
Score can be 60-80%.The corresponding monomeric unit of (methyl) acrylic acid hydroxy alkyl ester is in the fluorine-containing Hydroxylated acrylic resin
Mass fraction can be 5-30%.Quality of perfluoroalkyl (methyl) acrylate in the fluorine-containing Hydroxylated acrylic resin point
Number can be 2-15%.(methyl) alkyl acrylate, (methyl) can be determined according to the mass fraction of above-mentioned each monomer
The usage amount of acrylic acid hydroxy alkyl ester, perfluoroalkyl (methyl) acrylate.
When carrying out above-mentioned reaction, in order to go on smoothly reaction process, the first preset temperature is 60-140 DEG C, such as 60
DEG C, 70 DEG C, 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C etc.；Second preset temperature be 30-80 DEG C, such as 30 DEG C,
40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C etc..
In step 1, used solvent is selected from seven fluorine pentamethylene, butyl acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether vinegar
At least one of acid esters, isopropanol, ethyl acetate.
Used radical initiator can be peroxide type initiators and/or azo-initiator, for example,
The peroxide type initiators include but is not limited to: cumyl hydroperoxide, di-t-butyl peroxide, di t-amyl peroxide,
Dibenzoyl peroxide, peroxidized t-butyl perbenzoate, peroxidating -2 ethyl hexanoic acid tert-pentyl ester etc..Azo-initiator packet
It includes but is not limited to: azodiisobutyronitrile, azobisisoheptonitrile.
In step 2, for isocyanates, work as R1It can be the AOI- of Showa Denko K. K's production when for H
The unsaturated isocyanate of VM model；
Work as R1For CH3When, it can be the unsaturated isocyanate of the MOI-VM model of Showa Denko K. K's production.
Used catalyst is organotin catalysts, such as dibutyl tin dilaurate and/or stannous octoate.Also,
The quality of catalyst can be the 0.02-0.1% of place reaction system heavy amount.
In addition, the polymerization inhibitor that mass fraction is 0.03-0.1% can also be added into reaction system when carrying out step 2
Agent, this is because isocyanates has acrylic double bond, in order to guarantee that the double bond will not be because during reaction process and storage
For the crosslinking curing that double bond occurs under heat or illumination condition, polymerization inhibitor is added in the process, product storage process can be improved
In stability.Illustratively, which can be p-hydroxyanisole.
In order to accurately judge reaction end, which can use infrared detection reaction product 2265cm-1Neighbouring
Whether NCO absorption peak completely disappears, if completely disappearing, then it is assumed that reaction terminates.
The third aspect, the embodiment of the invention provides a kind of coating, which includes ultraviolet light mentioned by first aspect
Solidified resin.
The UV-cured resin can be used as the resin matrix of coating, which is coated in film thickness, be formed by painting
Film not only has good and lasting hydrophobic oleophobic effect, and has good hardness and abrasion resistant effect.
It is understood that the coating not only includes above-mentioned UV-cured resin, further include photoinitiator and its
He is relevant to be added to, and details are not described herein for the embodiment of the present invention.
Hereinafter the present invention will be further described through by specific embodiment.
In following specific embodiments, condition person is not specified in related operation, according to normal conditions or manufacturer
It is recommended that condition carry out.It is raw materials used production firm is not specified and specification person be can be with conventional products that are commercially available.
It should be noted that can be Showa electrician strain formula for the isocyanates that following embodiment uses
Unsaturated isocyanate (the R of the AOI-VM model of commercial firm's production1For H), alternatively, the unsaturated isocyanate (R of MOI-VM model1
For CH3)。
Embodiment 1
A kind of UV-cured resin is present embodiments provided, is prepared by following methods:
Step 101 weighs 200g butyl acetate solvent as a material；
Step 102, by 160g methyl methacrylate, 40g hexafluorobutyl acrylate, 20g hydroxy-ethyl acrylate, 2.5g mistake
Oxidation dibenzoyl is added in the butyl acetate of 22.5g, is stirred after dissolution and is expected as b.
A material is added in the four-hole boiling flask equipped with condenser pipe, thermometer and nitrogen ingress pipe step 103, is placed in oil
100 DEG C are warming up in bath.The b mixed material is added dropwise by constant pressure funnel and is entered in four-hole boiling flask, when control is added dropwise
Between be 2h, be added dropwise to complete subsequent continuous insulation reaction 6h.Utilize 1635cm in infrared detection reaction product-1Neighbouring C=C double bond is inhaled
It receives peak to completely disappear, it is believed that reaction terminates, and obtains fluorine-containing Hydroxylated acrylic resin.
Step 104 weighs the fluorine-containing Hydroxylated acrylic resin of 100g in reaction flask, and 5.56g AOI-VM type is added thereto
Number isocyanates and mass concentration be 0.05% dibutyl tin dilaurate as catalyst, mass concentration 0.1%
P-hydroxyanisole as polymerization inhibitor.60 DEG C of reactions are warming up to, infrared detection reaction product 2265cm is utilized-1Neighbouring NCO
Absorption peak completely disappears, it is believed that reaction terminates, and obtains the desired UV-cured resin of the present embodiment.
Embodiment 2
A kind of UV-cured resin is present embodiments provided, is prepared by following methods:
Step 201 weighs 200g isopropanol as a material.
Step 202, by 145g butyl methacrylate, 50g Hexafluorobutyl mathacrylate, 25g hydroxyethyl methacrylate second
Ester, 1g cumyl peroxide are added in 21g isopropanol, are stirred after dissolution and are expected as b.
A material is added to condenser pipe is equipped with step 203, in the four-hole boiling flask of thermometer and nitrogen ingress pipe, is placed in
It is warming up to 90 DEG C in oil bath pan, the b mixed material is added dropwise by constant pressure funnel and is entered in four-hole boiling flask, when control is added dropwise
Between be 2h, be added dropwise to complete subsequent continuous insulation reaction 7h, utilize 1635cm in infrared detection reaction product-1Neighbouring C=C double bond is inhaled
It receives peak to completely disappear, it is believed that reaction terminates.Obtain fluorine-containing Hydroxylated acrylic resin.
Step 204 weighs the fluorine-containing Hydroxylated acrylic resin of 100g in reaction flask, and 6.21g AOI-MOI is added thereto
For the dibutyl tin dilaurate that type isocyanates and mass concentration are 0.05% as catalyst, mass concentration is 0.1%
P-hydroxyanisole is as polymerization inhibitor；80 DEG C of reactions are warming up to, infrared detection 2265cm is utilized-1Neighbouring NCO absorption peak is complete
It disappears, it is believed that reaction terminates.Obtain the desired UV-cured resin of the present embodiment.
Embodiment 3
A kind of UV-cured resin is present embodiments provided, is prepared by following methods:
Step 301 weighs 200g propylene glycol methyl ether acetate solvent as a material.
Step 302, by 175g methyl acrylate, 35g perluorooctyl acrylate, 10g hydroxy-ethyl acrylate, 4g peroxidating
Di-t-butyl is added in the propylene glycol methyl ether acetate of 22g, is stirred after dissolution and is expected as b.
A material is added to condenser pipe is equipped with step 303, in the four-hole boiling flask of thermometer and nitrogen ingress pipe, is placed in
It is warming up to 140 DEG C in oil bath pan, the b mixed material is added dropwise by constant pressure funnel and is entered in flask, time for adding is controlled
For 2h, it is added dropwise to complete subsequent continuous insulation reaction 5h, utilizes 1635cm in infrared detection reaction product-1Neighbouring C=C double bond absorbs
Peak completely disappears, it is believed that reaction terminates, and obtains fluorine-containing Hydroxylated acrylic resin.
Step 304 weighs the fluorine-containing Hydroxylated acrylic resin of 100g in reaction flask, and 3.06g MOI-VM type is added thereto
The dibutyl tin dilaurate that isocyanates and mass concentration are 0.05% is as catalyst, pair that mass concentration is 0.1%
Hydroxyanisol is as polymerization inhibitor；30 DEG C of reactions are warming up to, infrared detection reaction product 2265cm is utilized-1Neighbouring NCO absorbs
Peak completely disappears, it is believed that reaction terminates, and obtains the desired UV-cured resin of the present embodiment.
Embodiment 4
A kind of UV-cured resin is present embodiments provided, is prepared by following methods:
Step 401 weighs 200g propylene glycol methyl ether acetate solvent as a material.
Step 402, by 135g the just own ester of methacrylic acid, 66g 2- perfluorooctylethyl group acrylate, 19g metering system
Sour hydroxypropyl acrylate, 10g dibenzoyl peroxide are added in 30g propylene glycol methyl ether acetate, stir after dissolution as b
Material.
A material is added to condenser pipe is equipped with step 403, in the four-hole boiling flask of thermometer and nitrogen ingress pipe, is placed in
It is warming up to 140 DEG C in oil bath pan, the b mixed material is added dropwise by constant pressure funnel and is entered in four-hole boiling flask, control is added dropwise
Time is 2h, is added dropwise to complete subsequent continuous insulation reaction 6h, utilizes 1635cm in infrared detection reaction product-1Neighbouring C=C double bond
Absorption peak completely disappears, it is believed that reaction terminates, and obtains fluorine-containing Hydroxylated acrylic resin.
Step 404 weighs the fluorine-containing Hydroxylated acrylic resin of 100g, and the isocyanic acid of 4.07g MOI-VM type is added thereto
The dibutyl tin dilaurate that ester and mass concentration are 0.05% is as catalyst, the para hydroxybenzene that mass concentration is 0.1%
Methyl ether is as polymerization inhibitor.50 DEG C of reactions are warming up to, infrared detection 2265cm is utilized-1Neighbouring NCO absorption peak completely disappears, it is believed that
Reaction terminates, and obtains the desired UV-cured resin of the present embodiment.
Embodiment 5
Step 501 weighs seven fluorine pentamethylene solvent of 200g as a material.
Step 502, by 166g ethyl acrylate, 36g dodecafluorhe-ptylacrylate, 18g hydroxy propyl methacrylate, 1.5g
Azodiisobutyronitrile is added in seven fluorine pentamethylene of 21.5g, is stirred after dissolution and is expected as b.
A material is added to condenser pipe is equipped with step 503, in the four-hole boiling flask of thermometer and nitrogen ingress pipe, is placed in
It is warming up to 110 DEG C in oil bath pan, the b mixed material is added dropwise by constant pressure funnel and is entered in four-hole boiling flask, control is added dropwise
Time 2h is added dropwise to complete subsequent continuous insulation reaction 6h.Utilize 1635cm in infrared detection reaction product-1Neighbouring C=C double bond is inhaled
It receives peak to completely disappear, it is believed that reaction terminates.Obtain fluorine-containing Hydroxylated acrylic resin.
Step 504, the fluorine-containing Hydroxylated acrylic resin of 100g is weighed in reaction flask, and 4.03g AOI-VM type is added thereto
For the stannous octoate that isocyanates and mass concentration are 0.07% as catalyst, mass concentration is 0.1% p-hydroxyanisole
As polymerization inhibitor.70 DEG C of reactions are warming up to, infrared detection 2265cm is utilized-1Neighbouring NCO absorption peak completely disappears, it is believed that reaction
Terminate, obtains the desired UV-cured resin of the present embodiment.
Embodiment 6
Step 601 weighs 200g ethyl acetate solvent as a material.
Step 602, by 176g methyl acrylate, 35g hexafluorobutyl acrylate, 9g hydroxy-ethyl acrylate, 1g azo two is different
Butyronitrile is added in the ethyl acetate of 21g, is stirred after dissolution and is expected as b.
A material is added to condenser pipe is equipped with step 603, in the four-hole boiling flask of thermometer and nitrogen ingress pipe, is placed in
It is warming up to 60 DEG C in oil bath pan, the b mixed material is added dropwise by constant pressure funnel and is entered in flask, control time for adding is
2h is added dropwise to complete subsequent continuous insulation reaction 6h, utilizes 1635cm in infrared detection reaction product-1Neighbouring C=C double bond absorption peak
It completely disappears, it is believed that reaction terminates, and obtains fluorine-containing Hydroxylated acrylic resin.
Step 604 weighs the fluorine-containing Hydroxylated acrylic resin of 100g in reaction flask, and 2.75g MOI-VM type is added thereto
The dibutyl tin dilaurate that isocyanates and mass concentration are 0.1% is as catalyst, pair that mass concentration is 0.05%
Hydroxyanisol is as polymerization inhibitor.60 DEG C of reactions are warming up to, infrared detection reaction product 2265cm is utilized-1Neighbouring NCO absorbs
Peak completely disappears, it is believed that reaction terminates, and obtains the desired UV-cured resin of the present embodiment.
Embodiment 7
Step 701 weighs 200g butyl acetate solvent as a material.
Step 702, by 132g lauryl methacrylate, 66g Hexafluorobutyl mathacrylate, 21g hydroxypropyl acrylate,
1g azodiisobutyronitrile is added in the butyl acetate of 21g, is stirred after dissolution and is expected as b.
A material is added to condenser pipe is equipped with step 703, in the four-hole boiling flask of thermometer and nitrogen ingress pipe, is placed in
It is warming up to 120 DEG C in oil bath pan, the b mixed material is added dropwise by constant pressure funnel and is entered in flask, time for adding is controlled
For 2h, it is added dropwise to complete subsequent continuous insulation reaction 6h.Utilize 1635cm in infrared detection reaction product-1Neighbouring C=C double bond absorbs
Peak completely disappears, it is believed that reaction terminates, and obtains fluorine-containing Hydroxylated acrylic resin.
Step 704, the fluorine-containing Hydroxylated acrylic resin of 100g is weighed in reaction flask, and 5.73g MOI-VM type is added thereto
The dibutyl tin dilaurate that isocyanates and mass concentration are 0.06% is as catalyst, pair that mass concentration is 0.1%
Hydroxyanisol is as polymerization inhibitor.65 DEG C of reactions are warming up to, infrared detection reaction product 2265cm is utilized-1Neighbouring NCO absorbs
Peak completely disappears, it is believed that reaction terminates, and obtains the desired UV-cured resin of the present embodiment.
Embodiment 8
Step 801 weighs 200g ethyl acetate solvent as a material.
Step 802, by 150g lauryl acrylate, 40g 2- perfluorododecyl ethyl propylene acid esters, 30g metering system
Sour hydroxypropyl acrylate, 5g dibenzoyl peroxide are added in the ethyl acetate of 25g, are stirred after dissolution and are expected as b.
A material is added to condenser pipe is equipped with step 803, in the four-hole boiling flask of thermometer and nitrogen ingress pipe, is placed in
It is warming up to 130 DEG C in oil bath pan, the b mixed material is added dropwise by constant pressure funnel and is entered in four-hole boiling flask, control is added dropwise
Time is 2h, is added dropwise to complete subsequent continuous insulation reaction 6h, utilizes 1635cm in infrared detection reaction product-1Neighbouring C=C double bond
Absorption peak completely disappears, it is believed that reaction terminates.
Step 804 weighs the fluorine-containing Hydroxylated acrylic resin of 100g in reaction flask, and 7.39g MOI-VM type is added thereto
The stannous octoate that isocyanates and mass concentration are 0.08% is as catalyst, the para hydroxybenzene first that mass concentration is 0.1%
Ether is as polymerization inhibitor.55 DEG C of reactions are warming up to, infrared detection reaction product 2265cm is utilized-1Neighbouring NCO absorption peak disappears completely
It loses, it is believed that reaction terminates, and obtains the desired UV-cured resin of the present embodiment.
Comparative example 1
Step 901 weighs 200g propylene glycol monomethyl ether solvent as a material.
Step 902, by 150g methyl acrylate, 60g butyl acrylate, 10g hydroxy-ethyl acrylate, 3g diphenyl peroxide first
Acyl is added in 25g propylene glycol monomethyl ether, is stirred after dissolution and is expected as b.
A material is added to condenser pipe is equipped with step 903, in the four-hole boiling flask of thermometer and nitrogen ingress pipe, is placed in
It is warming up to 140 DEG C in oil bath pan, the b mixed material is added dropwise by constant pressure funnel and is entered in flask, time for adding is controlled
For 2h, it is added dropwise to complete subsequent continuous insulation reaction 6h.Utilize infrared detection reaction product 1635cm-1Neighbouring C=C double bond absorption peak
It completely disappears, it is believed that reaction terminates, and obtains hydroxy acrylate.
Step 904,100g hydroxy acrylate is weighed, 2.76g AOI-VM type isocyanates is added thereto, matter is added
Measuring concentration is 0.05% dibutyl tin dilaurate as catalyst, the p-hydroxyanisole conduct that mass concentration is 0.1%
Polymerization inhibitor.60 DEG C of reactions are warming up to, infrared detection reaction product 2265cm is utilized-1Neighbouring NCO absorption peak completely disappears, it is believed that
Reaction terminates, and obtains comparison UV-cured resin.
Comparative example 2
Step 1001 weighs 200g ethyl acetate solvent as a material.
Step 1002, by 60g butyl acrylate, 130g lauryl methacrylate, 30g hydroxy propyl methacrylate, 6g
Dibenzoyl peroxide is added in 26g propylene glycol monomethyl ether, is stirred after dissolution and is expected as b.
A material is added to being equipped with condenser pipe step 1003, in the four-hole boiling flask of thermometer and nitrogen ingress pipe, juxtaposition
It is warming up to 90 DEG C in oil bath pan, the b mixed material is added dropwise by constant pressure funnel and is entered in flask, time for adding is controlled
For 2h, it is added dropwise to complete subsequent continuous insulation reaction 6h, utilizes 1635cm in infrared detection reaction product-1Neighbouring C=C double bond absorbs
Peak completely disappears, it is believed that reaction terminates, and obtains hydroxy acrylate.
Step 1004,100g hydroxy acrylate is weighed, 7.39g MOI-VM type isocyanates, Yi Jizhi are added thereto
Measuring concentration is 0.05% dibutyl tin dilaurate as catalyst, the p-hydroxyanisole conduct that mass concentration is 0.1%
Polymerization inhibitor.60 DEG C of reactions are warming up to, infrared detection reaction product 2265cm is utilized-1Neighbouring NCO absorption peak, which completely disappears, to be thought
Reaction terminates, and obtains comparison UV-cured resin.
Application Example:
The resin that above-described embodiment 1-8 and comparative example 1-2 are prepared is as coating matrix resin, using in table 1
Shown formula is to prepare coating.
Table 1
| Formula | Additive amount |
| The resin that embodiment/comparative example provides | 50.5% |
| 1- hydroxy-cyclohexyl phenyl ketone | 0.5% |
| 2- hydroxy-2-methyl -1- phenyl -1- acetone | 1% |
| Isopropanol | 16% |
| Butyl acetate | 16% |
| Propylene glycol methyl ether acetate | 16% |
After the completion of inciting somebody to action above each coating proportioning using formula shown in table 1, respectively to polymetylmethacrylate base
Above-mentioned coating is sprayed on material, 5~10 μm of coating thickness, after spraying, 5min is toasted in 55~60 DEG C of baking ovens, then in 800mJ/
Solidified under the UV energy of cm, initial water contact and the test of steel wool wear-resisting property are carried out after solidification.
Wherein, steel wool wear-resisting property test is carried out using friction-resistant tester, and test parameter is 0000# steel wool, 1*
1cm, bear a heavy burden 1kg.Also, when carrying out the test of steel wool wear-resisting property, when recording the water contact angle of coating and being reduced to 100 °, passed through
The abrasion resistance gone through.Test result is as shown in table 2:
Table 2
| Formula number | Initial water contact/° | Wear-resisting test/time |
| Embodiment 1 | 115.84 | 1850 |
| Embodiment 2 | 117.57 | 2350 |
| Embodiment 3 | 114.63 | 1350 |
| Embodiment 4 | 118.26 | 2050 |
| Embodiment 5 | 115.42 | 2200 |
| Embodiment 6 | 113.87 | 1750 |
| Embodiment 7 | 117.93 | 2500 |
| Embodiment 8 | 116.79 | 1600 |
| Comparative example 1 | 81.83 | 50 |
| Comparative example 2 | 83.18 | 50 |
As known from Table 2, UV-cured resin provided in an embodiment of the present invention is formed by coating, initial water contact
110 ° or more can be reached, hydrophobic oleophobic performance with higher, i.e. waterproof antifouling property.Also, at film hardness height, have excellent
Different resistance to steel wool performance.Even if resistance to steel wool performance still is able to reach 1000 times or more still under extremely exacting terms
It is maintained at preferable waterproof antifouling property.It can be seen that UV-cured resin provided in an embodiment of the present invention is anti-in hardening type
It has broad application prospects in terms of water anti-pollution paint resin.
The foregoing is merely presently preferred embodiments of the present invention, the protection scope being not intended to limit the invention, all in this hair
Within bright spirit and principle, any modification, equivalent replacement, improvement and so on should be included in protection scope of the present invention
Within.
Claims (10)
1. a kind of UV-cured resin, which is characterized in that the chemical structural formula of the UV-cured resin is as follows:
Wherein, m is integer, range 20-400；N is integer, range 2-50；P is integer, range 2-30；
R1For H or CH3；
R2For the alkylidene with 1-11 carbon；
R3For ethylidene or isopropyl；
Rf is perfluoroalkyl or perfluor alkyl ethide with 1-12 carbon；
RI is initiator residue.
2. a kind of preparation method of UV-cured resin, which is characterized in that the preparation method includes:
Under the first preset temperature, make (methyl) alkyl acrylate, (methyl) acrylic acid hydroxy alkyl ester, perfluoroalkyl (methyl)
Acrylate carries out polymerization reaction in solvent under the initiation of radical initiator, generates fluorine-containing hydroxy acrylic acid tree
Rouge；
Under the second preset temperature, make the fluorine-containing Hydroxylated acrylic resin and isocyanates under the catalytic action of catalyst into
Row reaction, generates UV-cured resin；
Wherein, the chemical structural formula of the isocyanates is as follows:
R1For H or CH3。
3. preparation method according to claim 2, which is characterized in that first preset temperature is 60-140 DEG C；
Second preset temperature is 30-80 DEG C.
4. preparation method according to claim 2, which is characterized in that the catalyst is organotin catalysts.
5. preparation method according to claim 2, which is characterized in that the solvent be selected from seven fluorine pentamethylene, butyl acetate,
At least one of propylene glycol monomethyl ether, propylene glycol methyl ether acetate, isopropanol, ethyl acetate.
6. preparation method according to claim 2, which is characterized in that (methyl) alkyl acrylate is acrylic acid first
Ester, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl, n propyl methacrylate, third
The positive ester of olefin(e) acid N-butyl, methacrylic acid, tert-butyl acrylate, Tert-butyl Methacrylate, the just own ester of acrylic acid, metering system
The just own ester of acid, 2-EHA, 2-ethyl hexyl acrylate, Isooctyl acrylate monomer, isooctyl methacrylate, lauryl
Ester or lauryl methacrylate.
7. preparation method according to claim 2, which is characterized in that (methyl) acrylic acid hydroxy alkyl ester is acrylic acid
Hydroxyl ethyl ester, hydroxyethyl methacrylate, hydroxypropyl acrylate or hydroxy propyl methacrylate.
8. preparation method according to claim 2, which is characterized in that perfluoroalkyl (methyl) acrylate is propylene
Sour trifluoro ethyl ester, trifluoroethyl methacrylate, hexafluorobutyl acrylate, Hexafluorobutyl mathacrylate, ten trifluoro of acrylic acid
Monooctyl ester, dodecafluorhe-ptylacrylate, 2- perfluorooctylethyl group acrylate, 2- perfluorododecyl ethyl propylene acid esters or
2- perfluorododecyl ethylmethyl acrylate.
9. preparation method according to claim 2, which is characterized in that the radical initiator is peroxide initiation
Agent and/or azo-initiator.
10. a kind of coating, which is characterized in that the coating includes UV-cured resin described in claim 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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