CN111269361B - Preparation method of fluorine-containing acrylic ester modified polyurethane emulsion with fluorescence performance - Google Patents
Preparation method of fluorine-containing acrylic ester modified polyurethane emulsion with fluorescence performance Download PDFInfo
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Abstract
The invention discloses a preparation method of fluorine-containing acrylic ester modified polyurethane emulsion with fluorescence performance, which takes a mixture of fluorine-containing acrylic ester and butyl acrylate as a monomer, adopts self-made dihydric alcohol with a fluorescent group as a chain extender for preparing polyurethane materials, and leads the fluorescent group to be connected into a polyurethane chain through a chemical bond, and prepares polyacrylate for modifying polyurethane through free radical reaction. The invention solves the problem of poor weather resistance of fluorescent polyester materials; the prepared modified polyurethane emulsion has stable luminous performance under the stimulation of external light, introduces a large amount of fluorine elements, adopts a core-shell structure with fluorine-containing polyacrylate as a shell, is beneficial to migration of fluorine to the surface, and can protect fluorescent groups and polyurethane in the structure, so that the waterproof performance of the coating is effectively improved.
Description
Technical Field
The invention relates to the technical field of fluorescent polymers, in particular to a preparation method of fluorine-containing acrylic ester modified polyurethane emulsion with fluorescent performance.
Background
Fluorescent materials are widely used in various fields such as sensors, probes, imaging, display, etc. because of their excellent luminescence properties. Meanwhile, in some fields, in order to improve safety or creative and fashion sense, some products are required to have fluorescence emission performance. The aqueous polyurethane material is novel polyurethane which takes water as a dispersion medium and contains a small amount of solvent or no solvent in a formed dispersion liquid, has good wear resistance and bonding performance, and simultaneously has the advantages of environmental protection, no toxicity, good safety, good applicability, energy conservation, low cost and the like. Therefore, aqueous polyurethane is also one of the trends of development of fluorescent materials as a matrix for fluorescent materials.
At present, the literature on fluorescent substance modified aqueous polyurethane materials has been reported in the literature, and the following two methods are mainly available.
1. The fluorescent substance is present in the polyurethane material in doped (blended) form:
jie Zhiqian dissolving fluorescent small molecule 4-amino-4' - (N, N-diphenylamino) -1, 2-stilbene (ADAS) in DMF
Then adding water-based polyurethane, adding water, and mixing uniformly to obtain the invented water-based polyurethane fluorescent material (functional polymer report, 2014,27 (04): 426-431)]。
Sun Guanghui and the like by employing an in situ polymerization method 2 (H 2 O) 2 ](Hdmpy)(H 2 O) 2 Rare-earth composite material [ functional material, 2012 (12): 1569-1573 ]]。
Li Xue the CdTe quantum dot is modified with thioglycollic acid and then subjected to electrostatic interaction with cationic polyurethaneFe is prepared 3 O 4 CdTe/polyurethane nanocomposites [ Polymer journal 2012 (6): 606-612]。
The fluorescent substances in the scheme are in the doped form in the polyurethane, and the fluorescent substances and the polyurethane material have poor compatibility, so that the fluorescent small molecules are easy to migrate, fall off and decompose, and the fluorescent performance is poor. And simultaneously, the comprehensive properties (such as elongation at break, wear resistance, cohesiveness and the like) of the polyurethane material are deteriorated.
2. The fluorescent substance is combined in polyurethane molecular chain by chemical bond linkage:
han Xixi first, N-dihydroxyethyl-aniline-Terpyridine (TPYOH) at the alpha position is complexed with metal ions, and the complex is used as a catalyst and an initiator for caprolactone polymerization to obtain fluorescent polycaprolactone, wherein the fluorescent polycaprolactone has the following structural formula:
The structural formula of the rhodamine fluorescent dye modified by Zhou et al is as follows:
Li Meng and the like synthesize 7-amino-4-trifluoromethyl coumarin (AFC) by a one-step method, and the structural formula of the AFC is shown as follows:
the fluorescent polyurethane [ chemical progress 2015,34 (11): 4001-4005+4013 ] is prepared by introducing the fluorescent polyurethane as a blocking agent into polyurethane]。
Huang Xiao A fluorescent polyacrylate is synthesized, and is used as a chain extender, and the structural formula is as follows:
The fluorescent substances in the scheme are combined in the polyurethane molecular chain in a chemical bonding mode, and the fluorescent groups can be firmly combined in the polyurethane molecules through the linking action of the chemical bonds, so that incompatibility of the fluorescent substances and polyurethane materials is avoided, migration, falling and decomposition of the fluorescent molecules are avoided, and the service life of the fluorescent polyurethane materials is greatly prolonged.
However, the structure of the aqueous polyurethane contains more hydrophilic groups, so that the aqueous polyurethane has poor waterproof and water-resistant properties. In addition, the fluorescent chromophore is generally composed of a large number of conjugated double-bond benzene rings or heterocyclic rings, so that the fluorescent polyurethane material containing the structure has poor weather resistance and is easy to cause yellowing, gloss reduction and the like under the ultraviolet irradiation condition. Currently, few solutions exist in the prior literature to improve both the waterproof and weather resistance of fluorescent polyurethane materials.
Therefore, the waterproof performance and the weather resistance of the fluorescent polyurethane material can be effectively improved while the excellent fluorescent performance of the fluorescent polyurethane material is ensured, and the fluorescent polyurethane material has important significance.
Disclosure of Invention
The invention provides a preparation method of fluorine-containing acrylic ester modified polyurethane emulsion with fluorescence performance, and the fluorescence polyurethane material has excellent fluorescence performance, and can effectively improve the waterproof performance and weather resistance.
In order to achieve the above purpose, the preparation method of the fluorine-containing acrylic ester modified polyurethane emulsion with fluorescence performance provided by the invention sequentially comprises the following steps:
step one, synthesizing a fluorescent chain extender:
slowly dropwise adding an acetone solution of methacryloyl chloride into an acetone solution containing triethylamine and 7-hydroxycoumarin under the ice water bath condition, controlling the dropwise adding time to be 0.5h, and reacting for 12h at 25 ℃; after the reaction is completed, slowly adding water to quench the reaction, then heating to 60 ℃, slowly dropwise adding ethanol solution of diethanolamine, and stirring the mixture under the condition of condensation and reflux for reaction for 8 hours; after the reaction is finished, removing the solvent by rotary evaporation under the conditions of 50 ℃ and minus 0.1MPa to obtain the fluorescent chain extender;
step two, -synthesis of NCO-terminated fluorescent polyurethane prepolymer:
taking isophorone diisocyanate and polycaprolactone diol as raw materials, taking dibutyl dilaurate as a catalyst, reacting for 1h at 80 ℃, then dissolving the fluorescent chain extender obtained in the step one and 2, 2-dimethylolpropionic acid in acetone according to a certain molar ratio, adding the mixture, and reacting for 2.5h to obtain an-NCO-terminated polyurethane prepolymer;
step three, synthesizing fluorine-containing acrylic ester modified polyurethane emulsion with fluorescence performance:
dissolving trimethylolpropane in acetone, dripping the solution into the system in the second step, and reacting for 2 hours at 80 ℃; adding a grafting agent, and reacting for 1h until the-NCO group disappears; then cooling to 40 ℃, adding acetone to dilute and reduce the viscosity for 0.5h. And adding triethylamine, neutralizing for 0.5h, removing condensation and nitrogen, adding deionized water, and stirring at a high speed for 1.5h to obtain the fluorescent polyurethane emulsion. Adding sodium dodecyl sulfate accounting for 3 percent of the total mass of the acrylic monomer after the emulsification is completed, slowly heating to 80 ℃ at the same time, protecting with nitrogen, adding potassium persulfate accounting for 1 percent of the total mass of the acrylic monomer, and adding a mixture (m R12SH :m IPA =1:10), then a mixture of fluoroacrylate and butyl acrylate was slowly added dropwise. After 2.5h of incubation, naHCO was used 3 And neutralizing to obtain the fluorine-containing acrylic ester modified polyurethane emulsion with fluorescence performance.
The molar ratio of the fluorescent chain extender to the 2, 2-dimethylolpropionic acid in the second step is as follows: 1:1, 2:1, 3:1, 4:1, or 5:1.
The grafting agent in the third step is one of hydroxyethyl methacrylate and hydroxyethyl acrylate.
The mass ratio of the fluorine-containing acrylic ester to the butyl acrylate in the third step is 1:1, 2:1 or 3:1
The fluorine-containing acrylic ester in the third step is one of trifluoroethyl methacrylate, hexafluorobutyl methacrylate and dodecafluoroheptyl methacrylate.
Compared with the prior art, the invention has the beneficial effects that:
1. the polyurethane coating has photoluminescence performance: according to the invention, the self-made dihydric alcohol with the fluorescent group is used as the chain extender for preparing the polyurethane material, the fluorescent group is connected into the polyurethane chain through a chemical bond, and the fluorescent group is not easy to fall off and decompose, and has stable luminous performance under the stimulation of external light.
2. Improving the water resistance of the aqueous polyurethane: the polyacrylate for modifying polyurethane is prepared by taking the mixture of fluorine-containing acrylic ester and butyl acrylate as monomers through free radical reaction, and a large amount of fluorine elements are introduced into the side chain of the composite material, so that after the fluorine-containing chain segments migrate to the surface of the coating, the outer surface of the coating is more fully covered and protected, and fluorine has lower surface energy, so that the waterproof performance of the coating is effectively improved.
3. The weather resistance of the polyurethane material is improved: the acrylic ester modified waterborne polyurethane coating solves the problem of poor weather resistance of fluorescent polyester materials; the core-shell structure which takes the polyurethane containing the fluorescent groups as the core and the polyacrylate containing fluorine as the shell is formed, so that the migration of fluorine to the surface is facilitated, and the fluorescent groups and the polyurethane in the structure can be protected.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but embodiments of the present invention include, but are not limited to, the scope of the following examples.
A preparation method of a fluorine-containing acrylic ester modified polyurethane emulsion with fluorescent property (total mass is 1000 parts), which comprises the following steps:
(1) Synthesis of fluorescent chain extender: a1:1 molar solution of triethylamine and 7-hydroxycoumarin in acetone (25% strength) was slowly added dropwise with an equimolar solution of chlorine methacrylate in acetone (20% strength) under ice bath conditions. The dropwise addition was completed within 0.5h, and the reaction was carried out at 25℃for 12h. After the reaction was completed, water was slowly added to quench the reaction, and after heating to 60 ℃, dropwise addition of an ethanol solution (25% concentration) of diethanolamine in an equimolar amount was started, and the reaction was stirred under reflux condensation condition for 8 hours. After the completion, spin-evaporating the solvent at 50 ℃ and-0.1 MPa to obtain a fluorescent chain extender;
(2) -synthesis of NCO-terminated fluorescent polyurethane prepolymer: putting 42-90 parts of isophorone diisocyanate, 63-135 parts of polycaprolactone diol and dibutyltin dilaurate into a flask, reacting for 1h at 80 ℃, then dissolving 2-9 parts of 2, 2-dimethylolpropionic acid (DMPA) and 15-25 parts of the fluorescent chain extender obtained in the step (1) into acetone with the mass being 5 times according to a given molar ratio, adding into the system, and reacting for 2.5h to obtain an-NCO-terminated fluorescent polyurethane prepolymer;
(3) Synthesis of fluorine-containing acrylic ester modified polyurethane emulsion with fluorescent performance: 2-6 parts of trimethylolpropane is dissolved in acetone with the mass being 8 times and is added into the polyurethane prepolymer prepared in the step (2) in a dropwise manner, and the polyurethane prepolymer reacts for 2 hours at the temperature of 80 ℃; then 7-16 parts of grafting agent is added for reaction for 1h, and the reaction is carried out until the-NCO group disappears by a di-n-butylamine titration method. Then cooling to 40 ℃, adding acetone to dilute and reduce the viscosity for 0.5h. Then adding 1-7 parts of triethylamine, neutralizing for 0.5h, slowly dripping 317-661 parts of deionized water, and stirring at a high speed for 1.5h to obtain the fluorescent polyurethane emulsion. After the emulsification is completed, adding 2-21 parts of sodium dodecyl sulfate, simultaneously slowly heating to 80 ℃, protecting by nitrogen, adding 0.6-6 parts of potassium persulfate, 0.06-0.5 part of mercaptoethanol and 0.6-5 parts of isopropanol, and slowly dropwise adding a mixture of 25-381 parts of fluorine-containing acrylic ester and 25-135 parts of butyl acrylate. After 2.5 hours of thermal insulation reaction, 0.2 to 1.6 parts of NaHCO is used 3 And neutralizing to obtain the fluorine-containing acrylic ester modified polyurethane emulsion with fluorescence performance.
The principle of the preparation method of the invention is as follows:
the reaction equation for synthesizing the fluorescent chain extender in the step (1) is as follows:
the reaction equation for synthesizing the-NCO-terminated fluorescent polyurethane prepolymer in the step (2) is as follows:
the reaction equation for synthesizing the fluorine-containing acrylic ester modified polyurethane emulsion with fluorescent property in the step (3) is as follows.
The invention will be further illustrated with reference to specific examples.
The reagents in the examples all need to be dried before being used, the relative molecular weight of the polycaprolactone diol used is 1000, and the WPU-PA composite emulsion is the fluorine-containing acrylic ester modified polyurethane emulsion with fluorescence performance.
Embodiment one:
1.012g (0.0100 mol) of triethylamine and 1.621g (0.0100 mol) of 7-hydroxycoumarin are accurately weighed and dissolved in 10g of acetone, the mixture is added into a three-necked flask, 1.045g (0.0100 mol) of methacryloyl chloride is dissolved in 5g of acetone under ice bath condition and slowly added dropwise into the flask, the addition is completed within 0.5h, and then the reaction is carried out for 12h at 25 ℃. After the reaction was completed, water was slowly added to quench the reaction, and after heating to 60 ℃, dropwise addition of 1.051g (0.0100 mol) of diethanolamine dissolved in 5g of ethanol was started, and the reaction was stirred under reflux for 8 hours. After the completion, the solvent is removed by spin evaporation under the conditions of 50 ℃ and minus 0.1MPa, and the fluorescent chain extender is obtained for standby.
13.337g (0.0600 mol) of isophorone diisocyanate and 20.000g (0.0200 mol) of polycaprolactone diol are accurately weighed and added into a three-necked flask, and the mixture is added into a three-necked flask under N 2 Heating and stirring under the conditions of protection and condensation reflux, adding 3 drops of dibutyltin dilaurate to react for 1 hour when the system temperature reaches 80 ℃, dissolving 3.353g (0.0100 mol) of the fluorescent chain extender obtained in the step (1) and 1.341g (0.0100 mol) of 2, 2-dimethylolpropionic acid in 20g of acetone, adding into a flask, and continuously reacting for 2.5 hours to obtain the fluorescent polyurethane prepolymer terminated by-NCO;
dissolving 0.894g (0.0067 mol) of trimethylolpropane in 5g of acetone, dropwise adding the mixture into the system in the step (2), and reacting for 2 hours at 80 ℃; 2.322g (0.0200 mol) of hydroxyethyl acrylate are added and reacted for 1h by di-n-butylamine titration until the-NCO group has disappeared. Then cooling to 40 ℃, adding a certain amount of acetone to dilute and reduce the viscosity for 0.5h. Then, 1.012g (0.0100 mol) of TEA was added to neutralize for 0.5 hours, and then 98.609g of deionized water was slowly added dropwise and stirred at a high speed for 1.5 hours to prepare a double bond-terminated fluorescent polyurethane emulsion.
After the emulsification is completed, 0.399g of sodium dodecyl sulfate is added, and simultaneously, the temperature is slowly raised to 80 ℃ and the nitrogen is used for protecting, 0.100g of potassium persulfate, 0.009g of mercaptoethanol and 0.090g of isopropanol are added, then 3.831g of mixture of trifluoroethyl methacrylate and 3.831g of butyl acrylate is slowly added dropwise, the reaction is carried out for 2.5 hours after the heat preservation, and then 0.031g of NaHCO is used 3 And neutralizing to obtain the fluorine-containing acrylic ester modified polyurethane emulsion with fluorescence performance.
Embodiment two:
1.349g (0.0133 mol) of triethylamine and 2.162g (0.0133 mol) of 7-hydroxycoumarin are accurately weighed and dissolved in 14g of acetone, the mixture is added into a three-neck flask, 1.394g (0.0133 mol) of methacryloyl chloride dissolved in 7g of acetone is slowly added dropwise into the flask under the ice bath condition, the addition is completed within 0.5h, and then the reaction is carried out for 12h at 25 ℃. After completion of the reaction, the reaction was quenched by slowly adding water, and after heating to 60 ℃, 1.402g (0.0133 mol) of diethanolamine dissolved in 7g of ethanol was started to be added dropwise, and the reaction was stirred under reflux for 8 hours. After the completion, the solvent is removed by spin evaporation under the conditions of 50 ℃ and minus 0.1MPa, and the fluorescent chain extender is obtained for standby.
13.337g (0.0600 mol) of isophorone diisocyanate and 20.000g (0.0200 mol) of polycaprolactone diol are accurately weighed and added into a three-necked flask, and the mixture is added into a three-necked flask under N 2 Protection ofHeating and stirring under the condition of condensing and refluxing, adding 3 drops of dibutyltin dilaurate to react for 1 hour when the temperature of the system reaches 80 ℃, dissolving 4.471g (0.0133 mol) of the fluorescent chain extender obtained in the step (1) and 0.894g (0.0067 mol) of 2, 2-dimethylolpropionic acid in 20g of acetone, adding into a flask, and continuously reacting for 2.5 hours to obtain the-NCO-terminated fluorescent polyurethane prepolymer;
dissolving 0.894g (0.0067 mol) of trimethylolpropane in 5g of acetone, dropwise adding the mixture into the system in the step (2), and reacting for 2 hours at 80 ℃; 2.322g (0.0200 mol) of hydroxyethyl acrylate are added and reacted for 1h by di-n-butylamine titration until the-NCO group has disappeared. Then cooling to 40 ℃, adding a certain amount of acetone to dilute and reduce the viscosity for 0.5h. Then, 0.675g (0.0067 mol) of TEA was added to neutralize for 0.5 hours, and 99.286g of deionized water was slowly added dropwise and stirred at high speed for 1.5 hours to prepare a double bond-terminated fluorescent polyurethane emulsion.
After the emulsification is completed, 1.611g of sodium dodecyl sulfate is added, the temperature is slowly raised to 80 ℃ at the same time, the nitrogen is used for protecting, 0.403g of potassium persulfate, 0.037g of mercaptoethanol and 0.366g of isopropanol are added, then 25.300g of mixture of hexafluorobutyl methacrylate and 12.650g of butyl acrylate is slowly added dropwise, the temperature is kept for 2.5 hours, and then 0.125g of NaHCO is added 3 And neutralizing to obtain the fluorine-containing acrylic ester modified polyurethane emulsion with fluorescence performance.
Embodiment III:
1.518g (0.0150 mol) of triethylamine and 2.432g (0.0150 mol) of 7-hydroxycoumarin are accurately weighed and dissolved in 16g of acetone, the mixture is added into a three-neck flask, 1.568g (0.0150 mol) of methacryloyl chloride dissolved in 8g of acetone is slowly added dropwise into the flask under ice bath condition, the addition is completed within 0.5h, and then the reaction is carried out for 12h at 25 ℃. After the reaction was completed, water was slowly added to quench the reaction, and after heating to 60 ℃, 1.577g (0.0150 mol) of diethanolamine dissolved in 8g of ethanol was started to be added dropwise, and the reaction was stirred under reflux for 8 hours. After the completion, the solvent is removed by spin evaporation under the conditions of 50 ℃ and minus 0.1MPa, and the fluorescent chain extender is obtained for standby.
13.337g (0.0600 mol) of isophorone diisocyanate and 20.000g (0.0200 mol) of polycaprolactone diol are accurately weighed and added into a three-necked flask, and the mixture is added into a three-necked flask under N 2 Protection and coolingHeating and stirring under the condition of reflux condensation, adding 3 drops of dibutyltin dilaurate to react for 1h when the temperature of the system reaches 80 ℃, dissolving 5.030g (0.0150 mol) of the fluorescent chain extender obtained in the step (1) and 0.671g (0.0050 mol) of 2, 2-dimethylolpropionic acid in 20g of acetone, adding into a flask, and continuously reacting for 2.5h to obtain the-NCO-terminated fluorescent polyurethane prepolymer; dissolving 0.894g (0.0067 mol) of trimethylolpropane in 5g of acetone, dropwise adding the mixture into the system in the step (2), and reacting for 2 hours at 80 ℃; 2.322g (0.0200 mol) of hydroxyethyl acrylate are added and reacted for 1h by di-n-butylamine titration until the-NCO group has disappeared. Then cooling to 40 ℃, adding a certain amount of acetone to dilute and reduce the viscosity for 0.5h. Then, 0.506g (0.0050 mol) of TEA was added to neutralize for 0.5 hours, and 99.776g of deionized water was slowly added dropwise and stirred at a high speed for 1.5 hours to prepare a double bond-terminated fluorescent polyurethane emulsion.
After emulsification is completed, 6.470g of sodium dodecyl sulfate is added, and simultaneously, the temperature is slowly raised to 80 ℃ and nitrogen protection is carried out, 1.618g of potassium persulfate, 0.147g of mercaptoethanol and 1.470g of isopropanol are added, then 119.574g of mixture of dodecafluoroheptyl methacrylate and 42.180g of butyl acrylate is slowly added dropwise, and after heat preservation reaction is carried out for 2.5 hours, 0.503g of NaHCO is further added 3 And neutralizing to obtain the fluorine-containing acrylic ester modified polyurethane emulsion with fluorescence performance.
Claims (2)
1. A preparation method of fluorine-containing acrylic ester modified polyurethane emulsion with fluorescent performance is characterized by comprising the following steps:
the method sequentially comprises the following steps of:
step one, synthesizing a fluorescent chain extender:
slowly dropwise adding an acetone solution of methacryloyl chloride into an acetone solution containing triethylamine and 7-hydroxycoumarin under the ice water bath condition, controlling the completion of dropwise adding of 0.5-h, and reacting at 25 ℃ for 12h; after the reaction is completed, slowly adding water to quench the reaction, then heating to 60 ℃, slowly dropwise adding ethanol solution of diethanolamine, and stirring to react under the condition of condensation and reflux for 8h; after the reaction is finished, removing the solvent by rotary evaporation under the conditions of 50 ℃ and minus 0.1MPa to obtain the fluorescent chain extender;
step two, -synthesis of NCO-terminated fluorescent polyurethane prepolymer:
reacting isophorone diisocyanate and polycaprolactone diol serving as raw materials with dibutyl dilaurate serving as a catalyst at 80 ℃ for 1h, dissolving the fluorescent chain extender obtained in the step one and 2, 2-dimethylolpropionic acid in acetone according to a certain molar ratio, adding the mixture, and reacting for 2.5h to obtain an NCO-terminated polyurethane prepolymer;
step three, synthesizing fluorine-containing acrylic ester modified polyurethane emulsion with fluorescence performance:
dissolving trimethylolpropane in acetone, dripping into the system in the second step, and reacting at 80 ℃ for 2h; adding a grafting agent, reacting 1-h, and allowing the reaction to proceed until the-NCO group disappears; cooling to 40deg.C, and diluting with acetone to reduce viscosity by 0.5 and h; then adding triethylamine, neutralizing 0.5h, removing condensation and nitrogen, adding deionized water and stirring at a high speed for 1.5h to obtain fluorescent polyurethane emulsion; adding sodium dodecyl sulfate accounting for 3% of the total mass of the acrylic monomers after the emulsification is completed, slowly heating to 80 ℃ at the same time, protecting by nitrogen, adding potassium persulfate accounting for 1% of the total mass of the acrylic monomers and a mixture of mercaptoethanol and isopropanol accounting for 1% of the total mass of the acrylic monomers, wherein the mass ratio of mercaptoethanol to isopropanol is 1:10, and slowly dropwise adding the mixture of fluorine-containing acrylic ester and butyl acrylate; after incubation for 2.5 and h, naHCO was used 3 Neutralizing to obtain the fluorine-containing acrylic ester modified polyurethane emulsion with fluorescence performance;
in the second step, the molar ratio of the fluorescent chain extender to the 2, 2-dimethylolpropionic acid is as follows: 1:1, 2:1, 3:1, 4:1, or 5:1;
in the third step, the grafting agent is hydroxyethyl acrylate;
in the third step, the mass ratio of the fluorine-containing acrylic ester to the butyl acrylate is 1:1, 2:1 or 3:1.
2. The method for preparing the fluorine-containing acrylic ester modified polyurethane emulsion with fluorescent property according to claim 1, which is characterized in that:
in the third step, the fluorine-containing acrylic ester is one of trifluoroethyl methacrylate, hexafluorobutyl methacrylate and dodecafluoroheptyl methacrylate.
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