* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
With 4-N,N-diethaneylamino-4'-phenylbenzophenone Inert atmosphere; UV-irradiation;
2.6. Photo-differential scanning photocalorimetry (Photo-DSC)experiment
Photo-DSC experiments were recorded by Perkin Elmer DSC 6000 at30 C under nitrogen atmosphere (flow rate: 20 mL/min). A UV lamp(intensity: 225 mW cm 2; λ: 250-450 nm) or LED405 nm (intensity:225 mW cm 2) was selected as an light source. The formulation containingBPs/TMPTMA (2/98 wt%) without any additional solvent. Aftercomplete dissolved, the mixture (ca. 15 mg) was loaded in an Al pan andirradiated under similar exposure condition. By integrating the areaunder the exothermic peak, the double bond conversion efficiency (DC)(%) of the acrylate monomer was determined according to the followingequation [38]:Double bond conversion efficiency (DC,%) =ΔHt/ΔHtheoro)*100% Where ΔHt is the totally reaction heat enthalpy evolved at time t andΔHotheor is the theoretical reaction heat enthalpy of acrylate monomerfor complete conversion. The ΔHotheor for double bond in one methacrylateis 54 kJ/mol [39,40]. Further, the rate of polymerization (Rp) isrelated to the heat flow (dH/dt) by the equation:Rp = dC/dt [41].
2
[ 106-91-2 ]
[ 3290-92-4 ]
polymer; monomers: trimethylolpropane trimethacrylate; glycidyl methacrylate[ No CAS ]
formic acid N,N'-diethyl-4-vinylbenzamidine complex[ No CAS ]
[ 3290-92-4 ]
[ 80-62-6 ]
polymer, Mn 7500 Da and PDI 6.3 by GPC, Mn 112000 Da by membrane osmometry; monomer(s): formic acid N,N\-diethyl-4-vinylbenzamidine complex; trimethylolpropane trimethacrylate; methyl methacrylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
34.8%
With 2,2'-azobis(isobutyronitrile) In various solvent(s) at 60 - 80℃; for 336h;
formic acid N,N'-diethyl-4-vinylbenzamidine complex[ No CAS ]
[ 3290-92-4 ]
[ 80-62-6 ]
polymer, Mn 8100 Da and PDI 8.4 by GPC, Mn 162000 Da by membrane osmometry; monomer(s): formic acid N,N\-diethyl-4-vinylbenzamidine complex; trimethylolpropane trimethacrylate; methyl methacrylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
89.8%
With 2,2'-azobis(isobutyronitrile) In various solvent(s) at 60 - 80℃; for 338h;
N,N'-diethyl(4-vinylphenyl)amidine diphenyl phosphate complex[ No CAS ]
polymer, Mn 42200 Da and PDI 18.6 by GPC, Mn 924000 Da by membrane osmometry; monomer(s): trimethylolpropane trimethacrylate; diphenyl phosphate N.N\-diethyl-4-vinylbenzamidine; methyl methacrylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
99.5%
With 2,2'-azobis(isobutyronitrile) In various solvent(s) at 60 - 80℃; for 336h;
N,N'-diethyl(4-vinylphenyl)amidine diphenyl phosphate complex[ No CAS ]
polymer, Mn 31300 Da and PDI 12.7 by GPC, Mn 472000 Da by membrane osmometry; monomer(s): diphenyl phosphate N,N\-diethyl-4-vinylbenzamidine complex; trimethylolpropane trimethacrylate; methyl methacrylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
67.9%
With 2,2'-azobis(isobutyronitrile) In various solvent(s) at 60 - 80℃; for 336h;
With theophylline; 2,2'-azobis(isobutyronitrile) In acetonitrile at 60℃; for 24h;
1
EXAMPLE 1; Preparation of anti-theophylline microspheres; Acetonitrile (50 mL) is mixed with methacrylic acid (MAA, 372.5 mg) and trimethylolpropane trimethacrylate (TRIM, 627.5 mg) in a borosilicate glass tube. Theophylline (115 mg) is suspended in the solution and dissolved after sonication at 60°C. The initiator, azobisisobutyronitrile (AIBN, 17.5 mg) is dissolved, the solution purged with nitrogen for five minutes and the tube sealed under nitrogen. Polymerisation is induced by placing the tube in a water bath preset at 60°C and continued for 24 hours. The microspheres formed are collected by centrifugation at 8000 rpm for 10 minutes using a RC5C superspeed refrigerated centrifuge from BECKMAN (Palo Alto, CA, USA). The print molecule is thoroughly extracted by washing repeatedly with methanol containing 10% acetic acid (v/v), followed by a final wash in acetone. These successive centrifugation and decanting steps extract the print molecule from the polymer. The anti-theophylline microspheres obtained are monodisperse and have an average diameter of 0.2 µm. The microspheres are finally dried in vacuo. The reference (control) microspheres are prepared and treated in exactly the same way, except that no print molecule is used in the polymerisation stage.
With theophylline; 2,2'-azobis(isobutyronitrile) In acetonitrile at 20℃; for 24h; UV-irradiation;
2
EXAMPLE 2; Preparation of anti-theophylline microspheres; Acetonitrile (50 mL) is mixed with MAA (372.5 mg) and TRIM (627.5 mg) in a borosilicate glass tube. Theophylline (11.5 mg) and AIBN (17.5 mg) are dissolved in the solution. The solution is purged with nitrogen for five minutes and the tube sealed under nitrogen. Polymerisation is induced by UV irradiation (350 nm) at 20°C using a RMA-400 Rayonet photochemical reactor from Southern New England Ultraviolet Co. (Bradford, CT, USA) and continued for 24 hours. The microspheres obtained are treated in the same way as in example 1 to remove the print molecule. The reference (control) microspheres are prepared and treated in exactly the same way, except that no print molecule is used in the polymerisation stage.
With 2,2'-azobis(isobutyronitrile); estradiol In acetonitrile at 60℃; for 24h;
3
EXAMPLE 3; Preparation of anti-17β-estradiol microspheres; Acetonitrile (50 mL) is mixed with MAA (372.5 mg) and TRIM (627.5 mg) in a borosilicate glass tube. 17β-Estradiol (250 mg) and AIBN (17.5 mg) are dissolved in the above solution. The solution is purged with nitrogen for five minutes and the tube sealed under nitrogen. Polymerisation is induced by UV irradiation (350 nm) at 20°C using a RMA-400 Rayonet photochemical reactor from Southern New England Ultraviolet Co. (Bradford, CT, USA) and continued for 24 hours. The microspheres obtained are treated in the same way as per example 1 to remove the print molecule. The anti-17β-estradiol microspheres obtained are monodisperse and have an average diameter of 0.3 µm (Figure 3). The reference (control) microspheres are prepared and treated in exactly the same way, except that no print molecule is used in the polymerization stage.
With Sea-Nine 211; tert-butyl peroxypivalate In polyvinyl alcohol (Elvanol 50-42); water at 50 - 90℃;
3A
EXAMPLE 3A; Microencapsulation of DCOIT Biocide with a Dual shell of Acrylic and PVA-urea-resorcinol-gluteraldehyde; [0025] An internal phase is prepared by mixing together molten Kathon 287T (150 g) at a temperature of around 500C, with methyl methacrylate (10 g) 1 , 4, butanediol diacrylate (10 g) and trimethylolpropane trimethacrylate (10 g). Just prior to emulsification, tertbutyl perpivalate (1 g) is mixed in to the internal phase. The internal phase is homogenized into water (254 g) containing polyvinyl alcohol (Elvanol 50-42) (6 g) using a Waring 1 liter blender for 10 minutes until a stable emulsion is formed. The emulsion is then transferred into a 1 -liter beaker with overhead stirring, thermometer and nitrogen supply and deoxygenated with nitrogen for 1 hour while heating to 900C. The batch is then held at 900C for 1.5 hours after nitrogen removal before being cooled down to 45°C. The resulting emulsion contains polymeric particles each comprising a polymeric shell encapsulating the Kathon 287T having a mean particle size of 19 microns.[0026] The particles of encapsulated Kathon 287T are then subjected to a secondary treatment at 45°C involving drop wise additions of aluminum sulfate TG 8.3% (6Og) over 12 minutes, 10 v/v% sulfuric acid (34 g) over 12 minutes, and a mixture of urea (2 g), resorcinol (1.5 g), and water (20 g) over 12 minutes. Then a mixture of 25% gluteraldehyde (5 g) and water (5 g) are added drop wise very slowly over 20 minutes to prevent aggregation. Then a second addition of urea (2 g), resorcinol (1.5 g), and water (20 g) is added over 12 minutes followed by a mixture of 25% gluteraldehyde (5 g) and water (5 g) added drop wise over 12 minutes. Followed by a third addition of urea (2 g), resorcinol (1.5 g), and water (20 g) is added over 12 minutes followed by a mixture of 25% gluteraldehyde (5 g) and water (5 g) added drop wise over 12 minutes. After all additions are made the temperature is increased from 450C to 500C and held overnight to cure for approximately 16 hours. After cooling and pH neutralization the microcapsules are filtered and dried to produce a fine free flowing powder that can be readily incorporated into a marine paint formulation to provide a marine coating in accordance with one embodiment of the invention.
With Sea-Nine 211; tert-butyl peroxypivalate In polyvinyl alcohol (Elvanol 50-42); polyvinyl alcohol (Elvanol 71-30); water at 50 - 90℃; for 2.63333h;
4
EXAMPLE 4; Dual encapsulation process with a first interfacial capsule wall of acrylic polymer and PVA-urea-resorcinol-formaldehyde polymer; [0028] An internal phase is prepared by mixing together molten Kathon 287T (150 g) at a temperature of around 500C, with methyl methacrylate (10 g) 1, 4, butanediol diacrylate (10 g) and trimethylolpropane trimethacrylate (10 g). Just prior to emulsification, tertbutyl perpivalate (1 g) is mixed in to the internal phase. The internal phase is homogenized into water (453 g) containing polyvinyl alcohol (Elvanol 50-42') (6 g) and (Elvanol 71-30) (6 g) using a Waring 1 liter blender for 8 minutes until a stable emulsion is formed. The emulsion is then transferred into a 1.5-liter beaker with overhead stirring, thermometer and nitrogen supply and deoxygenated with nitrogen for 1 hour while heating to 900C. The batch is then held at 900C for 1.5 hours after nitrogen removal before being cooled down to 400C. The resulting emulsion contains polymeric particles each comprising a polymeric shell encapsulating the Kathon 287T having a mean particle size of 19 microns. The particles of encapsulated Kathon 287T are then subjected to a secondary treatment at 4O0C involving drop wise addition of a mixture of urea (3 g), resorcinol (7.5 g), and water (45 g) over 12 minutes. Then a solution of sodium sulfate powder (1.5 g) and water (22.5 g) is added drop wise over 10 minutes. Then a 37% solution of formaldehyde (22.5 ml) is added drop wise over 10 minutes. After a 10-minute hold at 4O0C, 10 v/v% sulfuric acid is added drop wise over 6 minutes. The batch is then stirred and slowly heated to 45°C over 1 hour. Then a second addition of a solution of urea (3 g), resorcinol (4.5 g), water (37.5 g) and 37% formaldehyde (15 ml) is divided in half and added over 12 minutes followed by the second half after a 15 minute hold at 45°C. The batch is then stirred and slowly heated to 48°C over 1 hour. A third addition of urea (3 g), resorcinol (4.5 g), water (37.5 g) and 37% formaldehyde (15 ml) is added over 12 minutes. After all additions are made the temperature is increased from 48°C to 500C and held overnight to cure for approximately 16 hours. After cooling and pH neutralization the microcapsules are filtered and dried to produce a dry product that can be readily incorporated into a marine paint formulation to provide a marine coating in accordance with one embodiment of the invention.
With azobutyronitrile In toluene at 45 - 70℃; for 48.0833h;
2
Example 2; Synthesis of MIP using pyridine carbinol as template; To pyridine methanol (97μl) 3.74 ml of purified TRIM (purified over basic alumina), functional monomer MAA (1020 μl), porogenic solvent toluene (7.1 ml) and finally initiator ABDV (63 mg) were added and stirred until a clear solution was obtained. The solution was transferred to a glass vial, purged with nitrogen for 5 minutes and flame sealed. Heat induced polymerization was carried out at 45°C for 24 hours. The polymer mixture was then cured at 700C for a further 24 hours.Processing of the crude MIP material was as follows: the MIP was coarsely crushed and transferred to a Soxhlet thimble. It was extensively washed first with methanol for 12 hours and then with acetic acid for 12 hours in order to remove any remaining template and other non-reacted monomers. After these first extraction steps, the polymer was vacuum dried and then ground and sieved to a fine powder within a size range of 20 to 90 μm. As a final extraction step, the finely ground MIP was subjected to a 40 minutes microwave assisted solvent extraction using formic acid as the extraction solution. After drying, the MIP was ready for use.
Preferred examples of compounds having two or more reactive double bonds include divinylbenzene, divinylsulfone, allyl methacrylate, ethylene glycol dimethacrylate, ... 2,2-bis[4-(acryloxyethoxy-polyethoxy)phenyl]propane, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane triacrylate, ...
40
[ 100-43-6 ]
[ 3290-92-4 ]
polymer, cross-linked; monomer(s): 4-vinylpyridine; trimethylolpropane trimethacrylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With diethylene glycol dimethyl ether; 2,2-dimethoxy-2-phenylacetophenone UV-irradiation;
14
Example 14. Photoinitiated copolymerization of (meth)acrylate and vinyl ether monomers; [00194] Photocurable compositions were prepared by blending together the components described in Table 2.Table 2. Photocurable (meth)acrylate/vinylether compositions at 4.4/1 and 3.9/1 for TMPTA (Blend A) and TMPTMA (Blend B) equivalent weight ratios, respectively[00195] The UV light initiated curing of the Formulations A and B were examined using photo DSC as described in Example 13 and an exposure time of 60 seconds. The acrylate product (Formulation A) had a peak exotherm of 34 seconds and an enthalpy of 296 J/g. In contrast, when the acrylate monomer alone was irradiated under the same conditions, it had an exotherm peak after 67 seconds and enthalpy of 15 J/g, corresponding to a conversion of 5% normalized to Blend A.[00196] The methacrylate product gave a peak exotherm of 40 seconds and an enthalpy of1 10 J/g. In contrast, when the methacrylate monomer alone was irradiated under the same conditions, it gave an exotherm peak after 34 seconds, but the enthalpy of 10 J/g. The results are summarized in Table 3 and show the degrees of cure for each of the compositions normalized to that of Blend A for formulations containing TMPTA and to the composition of Example 13 for formulations containing TMPTMA. Table 3. PhotoDSC results or vin lether/(meth)acrylate hybrid s stems[00197] The significantly higher enthalpy and conversions observed for acrylate/vinyl ether blend A compared to methacrylate/vinyl ether blend B can be attributed to the copolymerization of the vinyl ether and acrylate components in A which does not occur to any significant extent in B. The normalized conversion in B, 65%, scales closely with the amount of methacrylate in the formulation.[00198] This result demonstrates that the vinyl ether functionalized with (α,α-disubstituted β- diketone can be used as a self-initiating photopolymer system for acrylate resins by means of a copolymerization reaction. Although it also functions as a photoinitiator for methacrylates, there does not appear to be any significant copolymerization in that system. Figure 5 shows the photo DSC traces for Blend A and corresponding control sample, TMPTA (shutter opened after 60 seconds).
14
Example 14. Photoinitiated copolymerization of (meth)acrylate and vinyl ether monomers; [00194] Photocurable compositions were prepared by blending together the components described in Table 2.Table 2. Photocurable (meth)acrylate/vinylether compositions at 4.4/1 and 3.9/1 for TMPTA (Blend A) and TMPTMA (Blend B) equivalent weight ratios, respectively[00195] The UV light initiated curing of the Formulations A and B were examined using photo DSC as described in Example 13 and an exposure time of 60 seconds. The acrylate product (Formulation A) had a peak exotherm of 34 seconds and an enthalpy of 296 J/g. In contrast, when the acrylate monomer alone was irradiated under the same conditions, it had an exotherm peak after 67 seconds and enthalpy of 15 J/g, corresponding to a conversion of 5% normalized to Blend A.[00196] The methacrylate product gave a peak exotherm of 40 seconds and an enthalpy of1 10 J/g. In contrast, when the methacrylate monomer alone was irradiated under the same conditions, it gave an exotherm peak after 34 seconds, but the enthalpy of 10 J/g. The results are summarized in Table 3 and show the degrees of cure for each of the compositions normalized to that of Blend A for formulations containing TMPTA and to the composition of Example 13 for formulations containing TMPTMA. Table 3. PhotoDSC results or vin lether/(meth)acrylate hybrid s stems[00197] The significantly higher enthalpy and conversions observed for acrylate/vinyl ether blend A compared to methacrylate/vinyl ether blend B can be attributed to the copolymerization of the vinyl ether and acrylate components in A which does not occur to any significant extent in B. The normalized conversion in B, 65%, scales closely with the amount of methacrylate in the formulation.[00198] This result demonstrates that the vinyl ether functionalized with (α,α-disubstituted β- diketone can be used as a self-initiating photopolymer system for acrylate resins by means of a copolymerization reaction. Although it also functions as a photoinitiator for methacrylates, there does not appear to be any significant copolymerization in that system. Figure 5 shows the photo DSC traces for Blend A and corresponding control sample, TMPTA (shutter opened after 60 seconds).
With tetramethylammonium methyl carbonate at 70℃; for 12h; Molecular sieve; Green chemistry;
With p-methylanizole; TEMPOL at 70 - 115℃; Industry scale;
1
EXAMPLE 1775 kg of trimethylolpropane, 1018 kg of methyl methacrylate (MMA) and also 1433 kg of recycled MMA from Comparative Example 1, 0.123 kg of hydroquinone monomethyl ether as inhibitor and a mixture of 10 kg of calcium oxide and 2.5 kg of lithium chloride as catalyst are combined in a 6 m3 stirred tank reactor provided with agitator, steam heating, distillation column and condenser and the mixture is stirred while passing in air. To stabilize the column, a total of 151 kg of MMA containing 0.12 kg of hydroquinone monomethyl ether and 0.016 kg of 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl in dissolved form are introduced into the column runback during the course of the reaction. The apparatus is heated to a temperature at the bottom of 100° C., with the column initially being operated under total reflux. As soon as the temperature at the top of the column drops below 70° C., the methanol/MMA mixture is taken off at a reflux ratio of 4:1. The MMA stock in the reactor is supplemented by introduction of equal parts of fresh MMA per part of methanol/MMA mixture taken off. A total of 1414 kg of MMA are in this way introduced over a period of 5 hours. Over a period of 8 hours, the reflux ratio is adapted to the decreasing formation of methanol to 27:1. A total of 1410 kg of methanol/MMA mixture are discharged. Above a temperature at the top of the column of 85° C., the methanol/MMA mixture is low in methanol and is collected in a separate vessel for reuse as raw material in the next batch. At a temperature at the bottom of 115° C., the reaction is complete and excess MMA is taken off under reduced pressure, with the pressure gradually being reduced to 100 mbar. When no more MMA distills off, the vacuum is broken. The contents of the tank, which comprise the catalyst-containing trimethyipropane trimethacrylate, are admixed with 18 kg of bleaching earth and 12 kg of aluminium silicate (Perlite) as filter aid and freed of the catalyst by washcoat filtration. The filtrate is fed into a continuous evaporator (area: 3.5 m2) having a rotating wiper system at a pressure of 18 torr and an evaporator temperature of 134° C. A total of 1830 kg of trimethylolpropane trimethacrylate are obtained from the bottom product.
2-methylacrylic acid 8-phosphonooxyoctyl ester[ No CAS ]
[ 629-41-4 ]
[ 79-41-4 ]
[ 109-16-0 ]
[ 1189-08-8 ]
6-methacryloxyhexyl phosphate[ No CAS ]
10-methacryloxydecyl phosphate[ No CAS ]
[ 3290-92-4 ]
[ 120358-73-8 ]
Yield
Reaction Conditions
Operation in experiment
EXAMPLES
'TMPTMA' refers to trimethylolpropane trimethacrylate; 'MHP' refers to 6-methacryloxyhexyl phosphate, prepared as described in ; 'MDP' refers to 10-methacryloxydecyl phosphate, prepared as described in ; 'MOP' refers to 8-methacryloxyoctyl phosphate, prepared from 1,8-octanediol using the method essentially as described for the preparation of MHP and MDP in ; 'HEMA' refers to 2-hydroxyethyl methacrylate; '1,3-BDDM' refers to 1,3-butanediol dimethacrylate; 'MA' refers to methacrylic acid; 'TEGDMA' refers to triethyleneglycol dimethacrylate; '2-TMSEM' refers to 2-(trimethoxysiloxy)ethyl methacrylate (obtained from Polysciences Inc., Warrington, PA;
1.1 First, the synthesis of sulfur-containing cross-linking agent
Use a constant pressure dropping funnel to slowly add 0.1 to the intermediate product 3JS2Molar TMPTA, the control reaction temperature is about 10 ,Reaction time is 6-8 hours, sampling infrared analysis of the presence of thiol peak,Peak 2568cm disappear stop reaction,The final product was named 3JS22-1.
1.4 4,4JS24 series (containing 2 epoxy groups 4 vinyl groups)
With a constant pressure dropping funnel to the intermediate product 4JS2 continue to slowly drop0.2 moles of TMPTA, the reaction temperature was controlled at about 15 ° C,Reaction time is 6-8 hours, sampling infrared analysis of the presence of mercapto peak, Peak 2568cm disappeared to stop the reaction,The final product was named 4JS24-1.
A constant pressure dropping funnel was added dropwise to the intermediate product 4JS2 by 0.1 molDVE-3, 0.1 moles of TMPTA, the reaction temperature was controlled at about 10 C,Reaction time is 6-8 hours, sampling infrared analysis of the presence of mercapto peak, Peak 2568cm disappeared to stop the reaction, the final product named 4JS23-1.