Synthesis and copolymerization of new phosphorus‐containing acrylates

Two phosphorus‐containing acrylate monomers were synthesized from the reaction of ethyl α‐chloromethyl acrylate and t‐butyl α‐bromomethyl acrylate with triethyl phosphite. The selective hydrolysis of the ethyl ester monomer with trimethylsilyl bromide (TMSBr) gave a phosphonic acid monomer. The attempted bulk polymerizations of the monomers at 57–60 °C with 2,2′‐azobisisobutyronitrile (AIBN) were unsuccessful; however, the monomers were copolymerized with methyl methacrylate (MMA) in bulk at 60 °C with AIBN. The resulting copolymers produced chars on burning, showing potential as flame‐retardant materials. Additionally, α‐(chloromethyl)acryloyl chloride (CMAC) was reacted with diethyl (hydroxymethyl)phosphonate to obtain a new monomer with identical ester and ether moieties. This monomer was hydrolyzed with TMSBr, homopolymerized, and copolymerized with MMA. The thermal stabilities of the copolymers increased with increasing amounts of the phosphonate monomer in the copolymers. A new route to highly reactive phosphorus‐containing acrylate monomers was developed. A new derivative of CMAC with mixed ester and ether groups was synthesized by substitution, first with diethyl (hydroxymethyl)phosphonate and then with sodium acetate. This monomer showed the highest reactivity and gave a crosslinked polymer. The incorporation of an ester group increased the rate of polymerization. The relative reactivities of the synthesized monomers in photopolymerizations were determined and compared with those of the other phosphorous‐containing acrylate monomers. Changing the monomer structure allowed control of the polymerization reactivity so that new phosphorus‐containing polymers with desirable properties could be obtained. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2207–2217, 2003     

Ternary structure design based on hydrogen bonding for transparent and flame retardant PMMA with good mechanical properties

The synthesis of intrinsic flame retardant copolymer by copolymerization with reactive flame retardants is the most potential method to prepare transparent and flame retardant poly (methyl methacrylate) (PMMA) at present,but the main challenge of this method is that the copolymer usually has poor mechanical properties and heat resistance. In this work, the hydrogen bond enhancement strategy is adopted, and the flame retardant PMMA with excellent comprehensive properties is obtained by ternary copolymerization with methyl methacrylate (MMA) as matrix unit, diethyl (methacryloyloxymethyl) phosphonate (DEP) as flame retardant unit and methacrylamide (MAA) as hydrogen bond unit. Due to the formation of intermolecular hydrogen bond via MAA unit, the storage modulus, flexural strength and impact strength of the terpolymer containing 15 mol% MAA are 48%, 19%, and 24% higher than those of the copolymer of MMA and DEP, and its hardness, glass transition temperature and load thermal deformation temperature (increased by 7°C) are also superior. Moreover, owing to the gas-phase dilution and charring flame retardancy of MAA unit, the terpolymer shows increased limiting oxygen index (24.3%) and UL94 rating (V-1). This work not only provides a promising flame retardant PMMA for practical application, but also offers a new strategy to design flame retardant polymers with good mechanical properties.     

Preparation and degradation of copolymers of methyl methacrylate with alkali metal methacrylates—IV. The relationship of product yields to sequence distribution

Experimental yields of methanol and methyl methacrylate (MMA), produced in degradation to 500° of copolymers of MMA with lithium, sodium and potassium methacrylates (KMA) respectively, have been compared with the amounts expected on the basis of composition and sequence distribution. Rates of formation of these products under isothermal conditions have also been measured and activation energies for MMA formation at various compositions in the KMA-MMA copolymer series have been evaluated. The activation energy changes from 35 ± 5 kcal mole^?1 in PMMA to 52 ± 5 kcal mole^?1 in a 75 mole% KMA copolymer, indicating increasing difficulty in depolymerization to MMA as the MMA sequences become shorter. The primary route to methanol is by a cyclization involving adjacent ester and salt units in the chain, giving anhydride rings and metal methoxide as the initial products. Methanol yields and the positions of the maxima in the yield vs copolymer composition curves, however, are found to be inconsistent with those predicted from sequence distribution calculations. It is argued that water retained by the copolymers plays a key part in the reaction scheme by converting the metal methoxide to methanol and hydroxide; the latter then causes conversion of ester groups to salt units, so permitting further cyclization in copolymers initially rich in MMA. Mechanisms are discussed in detail.     

Contribution of the comonomers to the bulk and surface properties of methacrylate copolymers

Relationships between formulation, bulk properties, and surface properties are investigated on series of copolymers prepared with hydroxyethylmethacrylate (HEMA), methylmethacrylate (MMA), and ethylmethacrylate (EMA) monomers, and on the homopolymers PMMA and PHEMA. The bulk water content, swelling ratio, and static (sessile drop and captive bubble) and dynamic (Wilhelmy plate technique) contact angles and the electrokinetic potential (streaming potential) are measured. The bulk water content and swelling ratio of HEMA copolymers are proportional to the amount of HEMA and are linearly correlated to the contact angle hysteresis. Periodic instabilities in the wetting cycles, similar to Haines jumps, are observed with HEMA copolymers and support a bidirectional relaxation of the hydrophilic groups respectively towards external water and capillary water. The origin of the electrokinetic potential of these nonionizable polymers is attributed to specific adsorption of [Formula: see text] ions. Its dependence on surface hydrophobicity and statistical length of the side-chains is interpreted in terms of the properties of water molecules near the interface.     

Synthesis and radiation degradation of vinyl polymers with fluorine: Search for improved lithographic resists

Homopolymers of methyl α-fluoroacrylate (MFA), trifluoroethyl methacrylate (TFEM), and hexafluoroisopropyl methacrylate (HFIM) were prepared, as were their methyl methacrylate (MMA) copolymers. Copolymers of vinylidene fluoride (VDF) and chlorotrifluoroethylene (CTFE) with MMA were also prepared. The radiation susceptibilities of these polymers were measured by the ⁶⁰Co γ-irradiation method, in which molecular weights were measured by membrane osmometry and gel permeation chromatography (GPC). All the copolymers degraded by predominant chain scission except poly(methyl α-fluoroacrylate), (PMFA), which crosslinks even at low doses (ca. 1 Mrad). The G_s - G_x and G_s values of the chain scissioning polymers and copolymers are higher than those of poly(methyl methacrylate) PMMA reference. The high susceptibility of PMFA homopolymer to crosslinking is in contrast to that of poly(methyl α-chloroacrylate), as we reported earlier. This effect is interpreted as resulting from extensive hydrogen fluoride and polyenlyl radical formation, which leads to facile crosslinking. However, incorporation of the MFA monomer unit causes the (22/78) MFA/MMA copolymer to degrade with a larger value of G_s that PMMA. Apparently a second-order process leads to crosslinking in PMFA and this is retarded in the copolymer. In the hehomopolymers of HFIM and TFEM and in the HFIM-MMA and TFEM-MMA copolymers the HFIM and TFEM components facilitate degradation with negligible crosslinking. The increased degradation susceptibility of VDF and CTFE copolymers with MMA over that of PMMA is attributed to processes at the VDF or CTFE components present in smaller concentrations (3-5 mole %) than the threshold levels (25-50% necessary for significant crosslinking).     

Hydrocarbon formation in the pyrolytic decomposition of methacrylate copolymers

A series of methyl methacrylate (MMA)–methacrylic acid (MAA) copolymers containing up to 50% methacrylic acid and the respective homopolymers were reproducibly pyrolyzed at 900°C and the fragments identified by gas chromatography (GC) or GC–mass spectroscopy. It was shown that PMMA and the MMA portions of blocky or random copolymers yielded 99% MMA, while a large portion (50–60%) of the MAA broke down to give a wide variety of hydrocarbons via decarboxylation and/or anhydride formation. Both unsaturated aliphatic and aromatic hydrocarbons, as well as the minor products of the MMA decomposition, support free-radical processes for these decompositions. It was also shown that the copolymers readily complex oxygenated solvents (which did not affect decomposition) and metal ions (which markedly affected the products).     

Contribution to the study of the mechanism of curing of unsaturated polyester resins

The mechanism of copolymerization of monomethyl and dimethyl maleates and fumarates with styrene was studied by analysis of the conformation of the acid units of the resulting copolymers. The absorption bands for C?O stretching and OH stretching in the spectra of the copolymers are fully identical. They are quite different from the spectra of the copolymers obtained from maleic anhydride and styrene that are subsequently treated with absolute methanol to give the monoester which is then esterified with diazomethane to give the diester. The acid units of the copolymers derived from maleic anhydride exist in a gauche configuration; copolymers derived from fumaric units exist in a trans conformation. The identity of copolymers derived from maleic units with those derived from fumaric units but not with those derived from maleic anhydride indicates that the first step in the copolymerization of the maleic units is an isomerization to fumaric units, which are actually the genuine comonomers.     

Synthesis and thermal characterization of poly(dimethyl bicyclobutane‐1,3‐dicarboxylate) and its copolymers

Dimethyl bicyclobutane‐1,3‐dicarboxylate was synthesized. Its homopolymer (PDBD) containing exclusively cyclobutane rings in its backbone was prepared by free radical polymerization. The copolymers of this bicyclobutane monomer with methyl methacrylate were also prepared. The glass transition temperature of the homopolymer is 159°C, while those of its copolymers are 143 and 121°C with 75/25 and 50/50 of the P(DBD/MMA) composition ratio, respectively. The T_g of PDBD homopolymer is substantially higher than that of commercial PMMA homopolymer despite a lower molecular weight, and is also much higher than that of its monomethyl cyclobutanecarboxylate analogue. These DBD homopolymer and copolymers also show better thermostability than the PMMA homopolymer. The weight‐average molecular weight of homopolymer is 37,000. The polydispersities of these polymers are relatively narrow, with the range of 1.6–1.9. These polymers form clear colorless films resembling PMMA film. The DBD homopolymer film shows a very similar optical cutoff compared to PMMA. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1569–1575, 1999     

Property modification of poly(methyl methacrylate) through copolymerization with fluorinated aryl methacrylate monomers

Copolymers of methyl methacrylate (MMA) with 2,3,5,6‐tetrafluorophenyl methacrylate (TFPMA), pentafluorophenyl methacrylate (PFPMA), and 4‐trifluoromethyl‐2,3,5,6‐tetrafluorophenyl methacrylate (TFMPMA) were investigated. All the three systems showed a random copolymerization character. The composition, glass transition temperature (T_g), and refractive index of the copolymers obtained were studied. T_gs of TFPMA/MMA and PFPMA/MMA copolymers were found to deviate positively from the Gordon–Taylor equation. However, T_gs of TFMPMA/MMA copolymers were well fit with the Gordon–Taylor equation. These results indicated the existence of interaction between MMA and either TFPMA or PFPMA units in copolymers. This interaction resulted in the enhancement of the T_g of MMA polymers through the copolymerization with TFPMA and PFPMA. The refractive index and the light transmittance of copolymers were close to those of PMMA. Copyright © 2007 John Wiley & Sons, Ltd.     

Head-to-head vinyl polymers. XI. Preparation and characterization of poly(methyl acrylate) and poly(methyl methacrylate) consisting of head-to-head and head-to-tail units through cyclopolymerization of acrylic and methacrylic anhydrides

Acrylic anhydride (AAn) and methacrylic anhydride (MAAn) were polymerized with radical initiator in polar solvents at high temperatures. The polymers obtained were found to consist of five-and six-membered ring structures by comparing IR spectra of the polymers with those of model compounds, succinic anhydride, and glutaric anhydride. Hydrolysis and methylation of the polymers gave new polymers composed of head-to-head (HH) and head-to-tail (HT) methyl acrylate (MA) or methyl methacrylate (MMA) units. The content of HH unit of these HH/HT polymers was determined by ¹H-NMR and ¹³C-NMR spectra. The softening, glass transition, and thermal degradation temperatures of the poly(MA) with HH and HT units were found to somewhat increase with increasing of the content of the HH units. On the other hand, the glass transition and thermal degradation temperatures of the poly(MMA) with HH and HT units increased similarly, but the softening temperature decreased as the content of the HH units increased.     

The effect of zinc bromide on the thermal degradation of poly(methyl methacrylate): Part 2—Reaction products,structural changes and degradation mechanism

Blends of poly(methyl methacrylate) (PMMA) and zinc bromide containing 11·25, 2 and 1 MMA chain units per ZnBr₂ molecule, respectively, have been studied under temperature-programmed and isothermal conditions. The products of degradation have been identified and quantitative measurements have been made of the production of MMA, methyl bromide and methanol. Structural changes in the partially degraded polymer have also been followed, and the residue at 500°C has been shown to consist of zinc oxide, zinc and carbon.A mechanism has been suggested which is consistent with all the experimental observations. At room temperature, ZnBr₂ forms a complex with PMMA. On heating, the most important process to occur at low temperatures (130–300°C) is the release of CH₃Br and the formation of zinc methacrylate chain units. An alternative reaction of the original complex—also yielding CH₃Br, and, in this case, producing, in addition, ZnO—leads to some anhydride rings in the polymer chain. Both of these new chain structures block the unzipping of PMMA to produce monomer. Methanol and CO are thought to result from the decomposition of single MMA units. At higher temperatures, the products are those expected from the decomposition of zinc polymethacrylate and the anhydride rings.     

Preparation and physical properties of flame retardant acrylic resin containing nano-sized aluminum hydroxide

Poly(methylmethacrylate) (PMMA) shows high strength and transparency but is a flammable material. In this study, the surface of aluminum hydroxide was modified with methacrylate containing phosphoric acid moieties before dispersion in MMA, and organic-inorganic nano-hybrid materials were obtained by bulk polymerization in the presence of the surface-modified aluminum hydroxide. The resulting hybrid materials retained the high transparency of PMMA, with transparency values similar to that of pure PMMA. Moreover, the flame resistance of the hybrid materials was improved in comparison with that of pure PMMA, with depression of the horizontal burning rate becoming a maximum at an inorganic content of 3 wt%. These results suggest that the use of aluminum hydroxide surface-modified with phosphoric acid groups is an efficient method for obtaining good performance fire-resistant polymer materials.     

N,N-二乙基硫代氨基甲酰硫基团(S_2CNEt_2)为假卤原子转移的原子转移自由基聚合新体系

综述了原子转移自由基聚合 (ATRP)中 ,以N ,N 二乙基硫代氨基甲酰硫基团 (S2 CNEt2 )转移实现活性聚合、控制聚合物结构的 4种新方法 :非卤化物 ,N ,N 二乙基二硫代氨基甲酸亚铜 [Cu(S2 CNEt2 ) ]催化甲基丙烯酸甲酯 (MMA)的正向ATRP ;2 ,2′ 联吡啶存在的条件下 ,过氧化苯甲酰 (BPO)与Cu(S2 CNEt2 )的氧化还原反应控制MMA的本体反向ATRP;同时含可转移卤原子、基团的氯化二乙基二硫代氨基甲酸铜 [Cu(S2 CNEt2 ) Cl]成功地用于偶氮二异丁腈或BPO引发的乙烯类单体反向ATRP.假卤原子S2 CNEt2 转移的ATRP得到窄分布的精确结构聚合物分子链ω 端含有光敏基团S2 CNEt2 ,可引发乙烯类单体的常温光聚合 ,实现ATRP与光聚合相结合制备嵌段共聚物     

Syntheses of 4-methacryloxy-2,3,5,6-tetrabromobenzyl phosphonates and effects of flame retardancy on their Co-PMMA

4-Methacryloxy-2,3,5,6-tetrabromobenzyl phosphonates (MTBBP) are prepared by the reaction of corresponding 4-hydroxy-2,3,5,6-tetrabromobenzyl phosphonates (HTBBP) with methacryloyl chloride. Comparisons of flame retardancy among the copolymers of methylmethacrylate (MMA) with MTBBP or with 4-methacryloxy-2,3,5,6-tetrabromotoluene(MTBT) and the mixture of poly(methyl methacrylate) (PMMA) with triphenyl phosphite reveal that the combination of phosphorus and bromine elements produces a synergistic effect on flame retardancy, and the chemical grafting of the fire-resistant elements into the polymer backbone gives a better effect than the physical mixing of their compounds with polymer. The unsatisfactory results of homopolymers of the synthesized methacrylate monomers prepared by free radical polymerization in solution may be due to their less reactivities; however, they can readily copolymerize with a liquid vinyl monomer such as MMA by means of bulk polymerization.     

Copolymers of methyl methacrylate with N‐trifluorophenyl maleimides: High glass transition temperature and low birefringence polymers

Copolymers of methyl methacrylate (MMA) with 2,3,4‐ and 2,4,6‐trifluorophenyl maleimides (TFPMIs) were synthesized by a free radical initiator, azobisisobutyronitrile, in 1,4‐dioxane and also in bulk. The refractive indexes of the copolymers were in the range of 1.49–1.52 at 532 nm. The T_gs were 133–195 °C depending on copolymer compositions. In addition, the copolymers were thermally stable, T_d > 350 °C. The orientational and photoelastic birefringence of the copolymers were also investigated. As both of the orientational and photoelastic birefringences of PMMA are negative, whereas those of poly(TFPMI)s are positive, we could obtain nearly zero orientational and photoelastic birefringence polymers when the ratios of 2,3,4‐TFPMI/MMA were 15/85 and 5/95 mol %, respectively. For 2,4,6‐TFPMI, zero orientational and photoelastic birefringences could be obtained when the ratios of 2,4,6‐TFPMI/MMA were 12/88 and 3/97 mol %, respectively. The T_gs of those copolymers with zero birefringences were in the range of 135–140 °C. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

用双硫酯链转移法合成嵌段聚合物

研究了以双硫酯为链转移剂进行的均聚和嵌段共聚物的合成 .首先合成大分子链转移剂 ,得到分子量可控、多分散性系数较小的均聚物PMMA、PBMA、PEMA、PEA、PBA、PMA、PSt,多分散性系数一般小于 1 30 .在相同的条件下 ,甲基丙烯酸酯类的聚合速度最快 ,苯乙烯其次 ,丙烯酸酯类最慢 .用末端带有双硫酯基团的PSt、PBMA、PBA为链转移剂 ,加入多种第二单体聚合得到实测分子量与理论分子量接近 ,且多分散性系数较小的两嵌段聚合物 .在链转移剂和引发剂的比例为 3∶1～ 6∶1的范围内 ,聚苯乙烯同样可以作为第一嵌段得到和其它酯类单体的两嵌段聚合物 .1 H NMR方法证明了聚合物的末端带有双硫酯基团 .嵌段聚合时必须加入微量的自由基引发剂以形成大分子自由基 ,达到较好的控制聚合效果     

Organosilicon hydrides in macromolecular design: Reactions of chain-transfer and hydrosilylation

The chain-transfer constants through silicon hydrides in bulk polymerization of styrene and methyl methacrylate (MMA) were measured with using 15 organosilicon compounds belonging to four classes: oligoorganohydrosilanes, oligoorganohydrosiloxanes, disilalkanes and alkylhydrosilanes. The linear dependences of the logarithm of chain-transfer constant on the sum of the Taft inductive constants of substituents at silicon atoms of a Si-H group were found. The negative values of reaction constants ρ indicate that an electrophilic attack of macroradical onto a hydrogen atom occurs at the limiting stage of the process. Oligoorganohydrosilanes proved to be the most effective chain-transfer agents that can be explained by high electron-donating properties of R₃Si substituents. The increase of the chain-transfer constant values takes place on the accumulation of both trimethylsilyl and silicon hydride groups in a molecule of hydrosilane. The high electrophilicity of PMMA macroradical as compared with a macroradical of polystyrene (PS) is responsible for a greater sensitivity of the polymerization reaction of MMA to the change of the electron density on a hydrogen atom of the organosilicon chain-transfer agent. In the radical polymerization of MMA and styrene in the presence of the chain-transfer agents till high conversion the polymers with a narrower molecular weight distribution (MWD) in comparison with those synthesized by usual polymerization in bulk are formed. The polymers prepared in the presence of multifunctional silanes can be functionalized by the reaction of hydrosilylation and further used in the synthesis of block copolymers.     

N-对溴苯基甲基丙烯酰胺的合成及其与甲基丙烯酸甲酯共聚合的研究

<正> 我们曾报道过甲基丙烯酸甲酯(MMA)与N-PhMA共聚合研究,指出共聚体与PMMA相比具有较高的耐热性和更好的耐水性。本文探讨了在N-苯基取代甲基丙烯酰胺中当本基上引入取代基时对单体反应活性的影响。实验结果表明,苯基上引入溴对单体的反应活性与共聚体性能有明显影响。 仅器与药品 甲基丙烯酸、苯甲酰氯、氯化亚砜、苯胺、三氯甲烷等均是化学纯,对溴     

The effects of some transition-metal compounds on the flame retardance of poly(styrene-co-4-vinyl pyridine) and poly(methyl methacrylate-co-4-vinyl pyridine)

Several copolymers of both styrene and methyl methacrylate with 4-vinyl pyridine have been prepared and modified by coordination with the transition-metal compounds vanadium acetylacetonate (VO[acac]₂), vanadyl dichloride (VOCl₂) and ferric chloride. The flame-retardant effects of these modifications have been assessed by measurements of limiting oxygen indices, by thermogravimetric analysis, and by examination of chars by scanning electron microscopy. Effects on mechanical properties have been assessed by dynamic mechanical thermal analysis. The limiting oxygen indices of the modified polymers are significantly higher than those of the parent polymers, and the production of considerable amounts of rigid, intumescent chars suggests predominantly condensed-phase mechanisms of flame retardance.     

Improvement of the physical properties of poly(methyl methacrylate) by copolymerization with N-pentafluorophenyl maleimide; zero-orientational and photoelastic birefringence polymers with high glass transition temperatures

Copolymers of N-pentafluorophenyl maleimide (PFPMI) with methyl methacrylate (MMA) were synthesized by a free radical initiator, such as AIBN. The refractive indexes of the copolymers remained nearly constant (1.4970 at 532 nm) regardless of the polymer composition. These copolymers also showed high thermal stability. The orientational and photoelastic birefringence of the copolymers obtained were measured. Since both of the orientational and photoelastic birefringences of PMMA are negative whereas poly(PFPMI) exhibits positive, thus we have obtained nearly zero orientational and photoelastic birefringence polymers when the ratios of MMA/PFPMI were 91.8/8.2 and 97.0/3.0 mol%, respectively. Based on the experimental data, the ratios of MMA/PFPMI for zero birefringence were determined to be 88.9/11.1 and 93.8/6.2 mol% for orientational and photoelastic birefringence, respectively. The Tgs of corresponding copolymers were estimated to be 128 and 122 ℃.