Trimethylsilyl Methacrylate Research Articles

Revolutionizing marine Protection: Innovative designs for In-Situ applicable underwater antifouling superoleophobic coatings

There is a high demand for underwater antifouling coatings for marine engineering and underwater activities. However, In-situ painting coating in a water environment for various large substrate surfaces is ideal but extremely challenging. In this work, we present a novel approach to achieving a fouling-repellent superoleophobic coating that can be directly applied underwater. The coating was prepared facilely via one-pot synthesis using epoxy resin E51 and 2-hydroxyethyl methacrylate as main components. This method involves the hydrolytic migration of side chains (Trimethylsilyl Methacrylate) interlocked with covalent cross-linking, enabling direct adhesion to a variety of wet substrates underwater without the need for surface pre-treatment. The resulting coating exhibits both underwater superoleophobicity (underwater oil contact angle＞150°) and versatile, sustainable substrate adhesion with a shear strength of up to 50 kPa, making it suitable for various underwater applications, such as oil/water separation. This work represents a facile and novel paradigm for designing future underwater antifouling coatings with superoleophobic properties and direct underwater adhesion.

Polyhedral Oligomeric Silsesquioxane Based Silicone Ophthalmic Contact Lens Material Containing Neodymium Nanoparticles.

This research was conducted to analyze the compatibility of used monomers and produce the high functional POSS-based ophthalmic polymer containing silicone monomers and neodymium nanoparticle. Synthesized silicone polymer (SiD), trimethylsilylmethacrylate (TSMA), N-vinyl-2-pyrrolidone (NVP) and neodymium nanoparticles were used as additives for the basic combination of polyhedral oligomeric silsesquioxane (POSS), and methyl methacrylate (DMA). And also, the materials were copolymerized with ethylene glycol dimethacrylate (EGDMA) as the cross-linking agent, azobisisobutyronitrile (AIBN) as the initiator. It is judged that the POSS-co-NVP polymer is optically good and thus have good compatibility. Especially copolymerization with TSMA showed high oxygen permeability, but with SID considered to be more stable judging by lens shape. Physical properties shows that the neodymium nanoparticle increases the wettability while maintaining water content. These materials are considered to make synergy effect each other, so it can be used in functional hydrogel ophthalmic lenses.

Polymerization and Preparation of High Functional Ophthalmic Lens Material Containing 2-Fluoro Styrene with Si and Ag Nanoparticles

This research was conducted to produce the high functional silicone hydrogel ophthalmic lens containing styrene group and nanoparticles. 2F (2-fluorostyrene) was added to enhance polymerization stability during lens formation, Si and Ag nanoparticles were used as additives for the basic combination including Sil-H (Silicone monomer), TSMA (Trimethylsilyl methacrylate), DMA (N,N-Dimethylacetamide) and MMA (methyl methacrylate). And also, the materials were copolymerized with EGDMA (ethylene glycol dimethacrylate) as the crosslinking agent and AIBN (azobisisobutyronitrile) as the initiator. Measurement of the physical, optical, surface and antimicrobial characteristics of the produced material showed the possibility of utilization as an opthalmic contact lens. As a result of the polymerization stability measurement, no significant difference was observed in all the samples, so it can be judged that the stabilization of nanoparticles in the polymer was maintained. Therefore, these materials are expected to satisfy the basic requirements of ophthalmic lenses and used usefully as an antimicrobial material for silicone hydrogel ophthalmic lens.

Analysis of Physical Properties of Hydrogel Lenses Polymer Containing Styrene and PVP

This research is carried out to analyze the effects of Styrene and PVP on the properties of silicone hydrogel lenses. Styrene group and PVP(Polyvinylpyrrolidone) are used as additives for a basic combination containing silicone monomer, TSMA(trimethylsilyl methacrylate) and DMA(n,n-dimethylacrylamide) added to the mix at ratios of 1~10 %. Silicone hydrogel lens is produced by cast-mold method. The polymerized lens sample is hydrated in a 0.9 % saline solution for 24 hours before its optical and physical characteristics are measured. Measurement of the physical characteristics of the produced material shows that the refractive index is 1.3682~1.4321, water content 77.11~45.73 %, visible light transmittance 95.14~88.20 %, and tensile strength 0.0652~0.3113 kgf. The results show a decrease of refractive index as the ratio of additives and water content decreases. The result of the stabilization test of polymerization show an increase of extractables along with increase of the ratio of additives, but the difference is not significant for all samples, so it can be judged that the stabilization of the polymer is maintained. Therefore, the additions of styrene and PVP should be taken into consideration for their effects on the physical properties of silicone hydrogel lens.

Synthesis of triblock and multiblock methacrylate polymers and self‐assembly of stimuli responsive triblock polymers

ABSTRACTMultisegmented poly(methacrylate)s were synthesized using one pot reversible addition fragmentation chain transfer polymerization. Initially, a series of triblock copolymers were synthesized with different ratios of trimethylsilyl methacrylate, di(ethylene oxide) methacrylate, and oligo(ethylene oxide) methacrylate, and different total polymer molecular weights. Additionally, a polymer containing seven distinct blocks of methacrylic monomers was synthesized in one pot. For the triblock copolymers, the trimethylsilyl group was subsequently hydrolyzed, and the self‐assembly of the triblock copolymer was studied in water, under different pH and thermal conditions. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 2548–2555

Poly(methacrylic acid)-l-Polyisobutylene: A Novel Polyelectrolyte Amphiphilic Conetwork

For the first time, a reliable procedure for synthesizing new acidic polyelectrolyte-containing amphiphilic conetworks (APCNs), poly(methacrylic acid)-l-polyisobutylene (PMAA-l-PIB), is described. The thorough characterization of the synthesis products is also presented through elemental analysis, differential scanning calorimetry (DSC), and basic swelling studies. Three series of APCNs were successfully synthesized in wide composition ranges by the macromonomer method using exact bifunctional methacrylate-telechelic PIB cross-linkers (MA−PIB−MA) of three different molecular weights (Mn): 2000, 5000, and 13000. The MA−PIB−MA macromolecular cross-linkers were prepared via quasiliving carbocationic polymerization. To prevent phase separation and thus insufficient network formation during synthesis, the conetworks were synthesized by thermally initiated free radical copolymerization of MA−PIB−MA and trimethylsilyl methacrylate, a hydrophobized precursor of methacrylic acid. After the next critical synthetic...

Statistical copolymers of styrene and 2-vinylpyridine with trimethylsilyl methacrylate and trimethylsilyloxyethyl methacrylate

Statistical copolymers of styrene with trimethylsilyl methacrylate, STMS, and trimethylsilyloxyethyl methacrylate, STME, and of 2-vinylpyridine with trimethylsilyloxyethyl methacrylate, VTME were prepared by free radical copolymerization in benzene with 2,2′-azobisisobutyronitrile, AIBN. The reactivity ratios of the different monomers were estimated using the Finemann–Ross, the inverted Finemann–Ross, and the Kelen–Tüdos or the extended Kelen–Tüdos graphical methods. Structural parameters of the copolymers were obtained by calculating the diad sequence fractions, which were derived using the monomer reactivity ratios. The results were compared with those obtained from the copolymerization of styrene and 2-vinylpyridine with methacrylic acid and 2-hydroxyethyl methacrylate.

Copolymers from tert‐Butyl Methacrylate with Trimethylsilyl Methacrylate or Methacrylic Acid: Models for Resist Polymers

AbstractFree radical copolymerisation of tert‐butyl methacrylate (1) with trimethylsilyl methacrylate (2) and methacrylic acid (3) has been investigated. Reactivity ratios for methacrylic acid and tert‐butyl methacrylate indicate an azeotropic copolymerisation (r1 = 0.476 ± 0.103; r3 = 0.300 ± 0.032), whereas the two esters show preferential incorporation of 2 (r1 = 0.170 ± 0.050; r2 = 1.170 ± 0.124). Thermal cis‐elimination of isobutylene from the tert‐butyl ester and subsequent formation of six‐membered cyclic anhydride moieties has been studied. For poly(methacrylic acid‐co‐tert‐butyl methacrylate) thermogravimetry could be used to determine copolymer composition. Solvolytic desilylation of the trimethylsilyl ester groups has been investigated as an alternative route to poly(methacrylic acid‐co‐tert‐butyl methacrylate). The tert‐butyl ester is not affected under the conditions of desilylation. Sequence distribution of both copolymers has been calculated using the method introduced by Bruns and Motoc. Copolymer composition diagram for tert‐butyl methacrylate/methacrylic acid.imageCopolymer composition diagram for tert‐butyl methacrylate/methacrylic acid.

Effect of Silicon Monomers on the Swelling and Mechanical Properties of (PEGMA-co-HEMA) Hydrogels

A series of novel copolymeric hydrogels were prepared from 2-hydroxyethylmethacrylate (HEMA) and poly(ethyleneglycol) methacrylate (PEGMA), and silicon monomers such as trimethylsilylmethacrylate (TMSM) and 2-(trimethylsilyloxy) ethyl methacrylate (TMSOE). The effect of silicon monomer on the swelling and mechanical properties of the hydrogels was examined. The results showed that the addition of silicon monomers lowered the equilibrium water content of (PEGMA-co-HEMA) hydrogels due to their lower hydrophilicities than PEGMA and HEMA. From the swelling kinetics data, it was found that the hydrophobicity of TMSM is larger than TMSOE. The addition of TMSM effectively lowered Young's modulus and increased elongation of the synthesized hydrogels. The hydrogels containing TMSM showed pH-sensitivities, but those containing TMSOE showed a good stability in acid and base solutions.

Copolymers from Methacrylic Acid and Trimethylsilyl Methacrylate ‐ Synthesis, Reactivity Ratios and Thermal Properties

AbstractCopolymers from methacrylic acid (1) and trimethylsilyl methacrylate (2) have been synthesized by free radical copolymerisation and by controlled desilylation of poly(trimethylsilyl methacrylate) (3). The reactivity ratios were r1 = 2.75, r2 = 0.004. Differential scanning calorimetry showed a linear correlation between the peak temperature of the endotherm for the formation of cyclic anhydrides and the content of methacrylic acid in the copolymer. Obviously, the acid catalyses this reaction. The copolymers as well as poly(trimethylsilyl methacrylate) have a ceiling temperature. Sequence distributions were calculated and used to predict glass transition temperatures for comparison to the experimental results. The microstructure of the copolymers obtained by the different synthetic routes is different as shown from Tg and from their solubility. Those from desilylation are random with “reactivity ratios” of 1, those from copolymerisation seem to have longer sequences of methacrylic acid leading to formation of intermolecular aggregates. Dependence of DSC peak temperature of anhydride formation on methacrylic acid content.magnified imageDependence of DSC peak temperature of anhydride formation on methacrylic acid content.

Online monitoring of Silicone Network Formation by Means of In-Situ Mid-Infrared Spectroscopy

The ReactIR™ reaction analysis system was used to monitor the crosslinking copolymerization of trimethylsilyl methacrylate with α,ω-methacryloyl-terminated oligo(dimethylsiloxane). Characteristic infrared bands proved useful to determine the total methacrylate concentration. After less than 12 h at 60 °C using 0.14% 2,2′-azoisobutyronitrile (AIBN), the methacrylate conversion during the crosslinking reaction exceeded 98%. The comparison of the crosslinking reaction with a methacrylate homopolymerization showed that significant autoacceleration occurred during network formation. Time-dependent monomer conversion [M]/[M]0 for TMSMA homopolymerization (run H in Table 1) and the corresponding crosslinking polymerization (run N) as revealed by the peak at 1 326 cm−1.

Copolymerisation of maleic anhydride with electron-acceptor monomers

Copolymerisation of maleic anhydride with tert.-butyl methacrylate and trimethylsilyl methacrylate was studied. Both monomers form random copolymers with maleic anhydride and in both cases the acceptor monomer is incorporated preferentially into the copolymer. Maleic anhydride which does not homopolymerise has reactivity ratios of approximately zero. The esters have reactivity ratios of 12.8 for trimethylsilyl methacrylate and 2.95 for tert.-butyl methacrylate. Thermal behavior and molar masses were investigated as a function of composition. Conditions for hydrolysis of the trimethylsilyl ester groups to give free acid groups have been established.

Studies on laser action from polymeric matrices based on trimethylsilyl methacrylate doped with pyrromethene 567 dye

The lasing properties of pyrromethene 567 (PM567) dissolved in solid poly-trimethylsilyl-methacrylate (TMSMA) cross-linked with ethylene glycol dimethacrylate (EGDMA) and copolymerized with methyl methacrylate (MMA) have been investigated. The vol/vol proportion of the different comonomers in each copolymer formulation was systematically varied, and the effect of each composition on the laser action of PM567 was evaluated. The laser samples were transversely pumped at 534 nm with 5.5 mJ/pulse from a frequency doubled Q-switched Nd:KGW laser. Lasing efficiencies of up to 14% and good stability with no sign of degradation after 10,000 pump pulses at 1 Hz in the copolymer P(TMSMA:MMA 50:50) were demonstrated. Pumping this sample at 10 Hz, the laser emission of PM567 remained at 45% of its initial value after 40,000 pulses.

Syntheses and adhesion properties of novel syndiotactic block copolymers of alkyl (meth)acrylate with methacrylic acid and its analogues

Block copolymerizations of (1) methyl methacrylate (MMA) with butyl acrylate (BuA), (2) trimethylsilyl methacrylate (TMSMA) with MMA, and (3) TMSMA with BuA were carried out using an organosamarium complex, SmMe(C 5Me 5) 2(THF), as an initiator. All copolymerizations proceeded quantitatively in a short period and the resulting polymers exhibit a high molecular weight ( M n>200 000) with narrow molecular weight distributions ( M w/ M n<1.5). The resulting poly(TMSMA) block in the copolymers was hydrolyzed with aq. HCl solution to afford the corresponding poly(methacrylic acid) block. The viscoelastic and adhesive properties of these block copolymers proved to be very useful, especially in the high temperature range, compared with those obtained using conventional radical initiators.

Structurally controlled polymers with ultimate precision ‐ synthesis, characterization and properties

AbstractThe fusion of polymer synthesis and characterization and their interactive stimulation is inevitable not only for the formation of polymers with highly controlled structures but also for the development of polymer characterization, thereby bringing about the spiral progress of both fields. As a typical example of precise polymer synthesis, the preparation of uniform PMMA with 100% isotacticity is described. Stereospecific living polymerization of 1‐phenyldibenzosuberyl methacrylate with methyl α‐lithioisobutyrate in tetrahydrofuran at −78°C gave an isotactic polymer with narrow molecular weight distribution. The PMMA derived therefrom was found by 750 MHz 1H NMR spectroscopy to consist of 89% of the PMMA which is 100% isotactic in the whole chain, and 11% of the PMMA which is 100% isotactic in the chain with only one racemo diad at the initiating chain end. The PMMA was fractionated into uniform PMMAs by supercritical fluid chromatography. The isotactic uniform PMMAs, crystallized from methanol solutions, showed the degree of crystallinity close to 100%. Highly syndiotactic PMMA was derived from poly(trimethylsilyl methacrylate) prepared with t‐C4H9Li/bis(2,6‐di‐t‐butylphenoxy)methyl‐aluminum in toluene at −95°C. Stereocomplex formation of isotactic and syndiotactic uniform PMMAs were studied by on‐line GPC/NMR measurements at 750 MHz and −15°C in acetone/acetone‐d6. Stereocontrol of ditactic polymers of crotonates (structural isomers of methacrylates) has been achieved for several polymerization systems, i.e., threodiisotactic, disyndiotactic, and diheterotactic polymerizations, which demonstrates another state‐of‐the‐art structural control at ultimately high level.

Synthesis and Characterization of Poly(dimethyl siloxane)−Poly[alkyl (meth)acrylic acid] Block Copolymers

Block copolymers containing dimethyl siloxane and carboxylic acid sequences were synthesized by group transfer polymerization (GTP) of various methacrylates and acrylates using silyl ketene acetal terminated poly(dimethylsiloxane) (PDMS) as initiator, followed by hydrolysis of the ester sequences to the free acid. The block copolymers were obtained with controlled molecular weight and narrow molecular weight distribution. The tert-butyl methacrylate (tBMA) and trimethyl silyl methacrylate (TMSMA) polymerized more slowly than corresponding acrylates. tert-Butyl and trimethyl silyl ester groups in the poly(meth)acrylate block could be quantitatively hydrolyzed. Most copolymers were contaminated by unincorporated homo-PDMS, which was efficiently removed by hexane or supercritical CO2 extraction. The solubility and thermal properties (DSC, TGA) were investigated for the hydrolyzed amphiphilic polymers.

Poly(2-hydroxyethyl methacrylate)-based hydrogels for slow release of pralidoxime chloride

Pralidoxime chloride (PAM-Cl)-loaded poly (2-hydroxyethyl methacrylate) (PHEMA)-based hydrogels were prepared by bulk copolymerization of 2-hydroxyethyl methacrylate (HEMA) with different mol fractions (0.02–0.10) of trimethylsilyl methacrylate. Characterization of the gels was done by dynamic swelling measurements. It was found that copolymerization does not alter the swelling mechanism of PHEMA and it essentially remains Fickian in nature. In vitro drug-release studies show the increase in release time from 6 to 12 h on incorporation of a 0.1 mol fraction of trimethylsilyl methacrylate on the PHEMA backbone. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 267–270, 1997

Synthesis of a water-soluble block copolymer of 2-isopropenylnaphthalene and methacrylic acid bearing a pyrene group

An anionic method for preparation of water-soluble block copolymer of 2-isopropenylnaphthalene and methacrylic acid poly(2-IPN-b-MAA), containing pyrene group as a terminal probe, is described. The polymerization process was carried out by an indirect method employing trimethylsilyl methacrylate monomer. The polymer was characterized by 1H-NMR, UV and fluorescence spectroscopy.

Polymers from multifunctional isocyanates 14. Alternating copolymers from isocyanato alkenes: Copolymerization of 2-propenyl isocyanate with trimethylsilyl methacrylate as electron acceptor monomer

The copolymerization of 2-propenyl isocyanate (1) with trimethylsilyl methacrylate (2) has been investigated. 1 is an electron donor monomer with little tendency to undergo homopolymerization, while 2 is an electron acceptor monomer, capable of free radical homopolymerization. Polymerization to low conversion in benzene gave copolymers with preferential incorporation of 2 and a tendency towards alternating copolymers with increasing amounts of 1 in the feed (1 : 1.13 with a 9 : 1 feed ratio of monomers 1 : 2). The glass transition temperatures of the amorphous polymers are in the range from 100–70°C, with a Tg of poly(trimethylsilyl methacrylate) being 135°C. Desilylation occurs in the presence of water, causing an exothermal reaction above the glass transition temperature probably with formation of amides, a reaction that can be used for crosslinking. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 611–616, 1998

Poly (2-hydroxyethyl methacrylate)-based hydrogels for slow release of pralidoxime chloride

Pralidoxime chloride (PAM-Cl)-loaded poly (2-hydroxyethyl methacrylate) (PHEMA)-based hydrogels were prepared by bulk copolymerization of 2-hydroxyethyl methacrylate (HEMA) with different mol fractions (0.02–0.10) of trimethylsilyl methacrylate. Characterization of the gels was done by dynamic swelling measurements. It was found that copolymerization does not alter the swelling mechanism of PHEMA and it essentially remains Fickian in nature. In vitro drug-release studies show the increase in release time from 6 to 12 h on incorporation of a 0.1 mol fraction of trimethylsilyl methacrylate on the PHEMA backbone. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 267–270, 1997