An analysis of the 1H- and 13C-NMR spectra of poly(6-vinyl-1,4-benzodioxane)

Summary The title monomer was synthesized from the corresponding aldehyde via a Wittig reaction. The monomer was polymerized using free radical initiation and its high field ¹H- and ¹³C-NMR spectra were recorded. When analyzed in terms of stereochemistry the spectra showed poly(6-vinyl-1,4-benzodioxane) is an atactic polymer when synthesized via free radical initiation.     

Activated polymers. II: Synthesis and exchange reactions of biologically active poly(8-acryloxyquinoline)

The monomer 8-acryloxyquinoline (8-AQ) was prepared through the reaction of 8-hydroxyquinoline with either acryloyl chloride or acrylic acid in the presence of triethylamine or N,N-dicyclohexylcarbodiimide, respectively . The resulting monomer was polymerized by free radical polymerization using dimethylformamide (DMF) as a solvent and 2,2^'-azobisisobutyronitrile (AIBN) as an initiator. The reactions of the resulting polymers with hydroxyl and amino compounds have been studied. The polymers were characterized by IR and ¹HNMR spectroscopy. Some of the synthesized polymers were tested for their antimicrobial activity against bacteria and fungi. Generally, all the polymers were effective against the tested microorganisms, but their growth-inhibition effects varied.     

新型杂化单体4-(1-丙烯基)氧丁基缩水甘油醚的合成及光聚合性能研究

通过3步反应合成了一种新型杂化单体4-(1-丙烯基)氧丁基缩水甘油醚(POBGE)。使用傅立叶红外光谱和核磁共振仪对相应产物结构进行了表征。同时使用傅立叶实时红外(FT-RTIR)对该杂化单体的光聚合性能进行了研究。考察了引发剂种类,不同浓度光引发剂,不同光照强度对杂化单体的光聚合性能的影响。结果表明,光引发剂硫鎓盐的引发性能要优于碘鎓盐,随着光引发剂浓度以及光照强度的增大杂化单体双键及环氧基团的转化率都相应提高。     

Synthesis and properties of novel phosphorus‐containing poly(ether ether ketone ketone)s

A novel monomer, bis[4‐(4‐fluorobenzoyl)phenyl]phenylphosphine oxide, was synthesized through the reaction of bis(4‐chloroformylphenyl) phenyl phosphine oxide with fluorobenzene. Three poly(ether ether ketone ketone)s derived from bis[4‐(4‐fluorobenzoyl)phenyl]phenylphosphine oxide and different aromatic bisphenols were prepared by aromatic nucleophilic substitution reactions. The resulting polymers had inherent viscosities in the range of 0.55–0.73 dL/g. The structures of the poly(ether ether ketone ketone)s were characterized with Fourier transform infrared and ¹H‐NMR. Thermal analysis indicated that the glass‐transition temperatures of the poly(ether ether ketone ketone)s were higher than 200°C, and the 5% weight loss temperatures in nitrogen were higher than 463°C. All the polymers showed excellent solubility in polar solvents such as N‐methyl‐2‐pyrrolidone, dimethylformamide, and dimethylacetamide and could also be dissolved in chlorinated methane. The polymers afforded transparent and flexible films by solvent casting. Organic phosphorous moieties also imparted good flame‐retardancy to the polymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

A preliminary analysis of the high field 13C-NMR and 1H-NMR spectra of poly(2-thienyl vinyl ketone)

Summary Poly(2-thienyl vinyl ketone) was synthesized via free radical initiation and its 300 H-NMR and 75.5 MHz ¹³C-NMR spectra were recorded and analyzed. The analysis showed that poly(2-thienyl vinyl ketone) is an atactic polymer.     

Poly(ether ketone azomethane)s and poly(ether ketone imide)s containing naphthylene moieties

A new diamine monomer, 1,5-bis[4-(4-aminophenoxy)]benzoyl-2,6-dimethoxynaphthalene, was synthesized via a Friedel–Crafts acylation reaction followed by an aromatic nucleophilic substitution reaction. Six ether–ketone linked polymers, named as poly(ether ketone azomethane)s and poly(ether ketone imide)s, were successfully prepared through the polycondensations of the diamine monomer with dialdehydes and dianhydrides, respectively. These naphthylated polymers exhibited high T _g values (142–288 °C), due to their bulky and rigid chemical structure. Meanwhile, they showed good thermal stability and improved solubility. Typically, some of them were casted into thin flexible film and showed high moduli.     

吡咯烷基-N-甲酸,丙烯酸乙二醇酯的合成及其光聚合动力学的研究

合成了不含氢键的低粘度的吡咯烷基-N-甲酸-丙烯酸乙二醇酯(PLW),并采用实时红外光谱法检测了光强和光引发剂浓度对光聚合动力学的影响。随着光强的增加光聚合的最终转化率基本不变,但是光聚合速率有明显的增加,并且达到最大聚合速率的时间也缩短。随着光引发剂浓度的增加,最终转化率和最大聚合速率都有了显著的增加。所合成单体的转化率在30 s内能达到90%以上。     

New monomers and polymers derived from α‐hydroxymethyl methyl vinyl ketone

2‐Hydroxymethyl‐but‐1‐ene‐3‐one [α‐hydroxymethyl methyl vinyl ketone (HMVK)] was synthesized from methyl vinyl ketone using paraformaldehyde and a tertiary amine catalyst. Free‐radical polymerization of this monomer created transparent, tough polymers that were insoluble in organic solvents. HMVK was converted to trimethylsilyl, acetate, and chloride derivatives. When the hydroxyl group was thus protected or removed, all these monomers could be free radically polymerized in bulk to make soluble polymers. The chlorination reaction is complicated by the formation of 1,1‐bischloromethylacetone, which dehydrohalogenated unexpectedly to the desired α‐chloromethyl methyl vinyl ketone. HMVK will self‐condense to an ether dimer in the presence of a catalytic acid. This reagent is capable of crosslinking many alkene monomers through hydrolytically stable ether bonds. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 509–516, 2000     

An analysis of the 300 MHz spectrum of poly(3-vinyl pyridine)

Summary 3-Vinyl pyridine was synthesized and the monomer was then polymerized employing free radical initiation. The 300 MHz ¹H-NMR spectrum was recorded and analyzed in terms of polymer stereochemistry. The results of the analysis strongly indicate that poly(3-vinyl pyridine) synthesized using free radical initiation is an atactic polymer.     

2-(4-甲氧基苯基)-4,6-双(三氯甲基)-S-三嗪光引发剂的合成及其光聚合动力学性能研究

以对甲氧基苯甲腈和三氯乙腈为原料合成了光引发剂2-(4-甲氧基苯基)-4,6-双(三氯甲基)-S-三嗪(MBTT),通过傅里叶红外光谱仪、核磁共振仪和紫外吸收光谱对所合成的产物结构进行了表征.并利用实时红外(RT-IR)对该引发剂进行了光聚合反应动力学研究,考察了单体、引发剂浓度和光强对引发速率及单体转化率的影响.结果表明,MBTT是一种高效的紫外光引发剂,在引发剂用量为0.1%时光聚合的单体转化率就能达到90%;随着光强的增大,单体的双键转化率和最大反应速率都增大,诱导期缩短;双丙烯酸酯类单体的双键转化率比三丙烯酸酯类单体的双键转化率要高.     

Polymers with pendant isocyanate groups. III. Synthesis and properties of poly(styrene-co-acrylonitrile-co-styrylisocyanate)

The terpolymer poly(styrene-co-acrylonitrile-co-styrylisocyanate) was synthesized by radical initiation directly from styrene, acrylonitrile, and cinnamoyl azide. The monomer feed–terpolymer composition relationship was determined by Slocombe's triangular graph. The solubility, intrinsic viscosity, and melting range of the various terpolymers and the chemical reactions of the pendant isocyanate groups toward alcohol and amines were investigated.     

Synthesis and photopolymerization of 4‐(1‐propenyl)oxybutyl acrylate

Hybrid monomer, 4‐(1‐propenyl)oxybutyl acrylate, with cationic and free radical polymerizable group was synthesized. Real‐time Fourier transform infrared spectroscopy (FTIR) was used to monitor the photopolymerization kinetics of the monomer. Photopolymerization processing conditions, such as light intensity, photoinitiator concentrations have been evaluated. It was found that hybrid monomer showed higher efficiency of photopolymerization in comparison with the blend system. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of novel poly(aryl ether ketone ketone)s containing the o‐dibenzobene moiety

The synthesis of a novel chloro monomer containing the 1,2‐dibenzoylbenzene moiety was described. The chloro monomer was reacted with 4‐(4‐hydroxyphenyl)‐1(2H)‐phthalazinone compound in the presence of excess anhydrous potassium carbonate in an aprotic solvent (Sulfolane), and high molecular weight amorphous poly(aryl ether ketone ketone) was synthesized. The polymers with high glass transition temperature were soluble in solvents such as chloroform and nitrobenzene at room temperature and easily cast into flexible, colorless, and transparent films. The 5% weight loss of the polymers was >400 °C. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1487–1492, 2001     

Preliminary analysis of the 1H- and 13C-NMR spectra of poly(3-vinyl-1-methylindole)

Summary The title monomer was synthesized and polymerized via free radical initiation. The high field ¹H- and ¹³C-NMR spectra were recorded and analyzed. Many resonances displayed multiplicities indicating a sensitivity to polymer stereochemistry but, in most cases, the resolution was insufficient for any reasonable interpretations to be made. The resonances that were well enough resolved for relatively accurate measurements to be made were analyzed in terms of polymer stereochemistry. The analysis suggests that poly(3-vinyl-1-methyl-indole) is an atactic polymer.     

Preliminary analysis of the 1H-NMR and 13C-NMR spectra of poly(2,5-dimethyl-3-vinylfuran)

Summary The title monomer was synthesized by dehydration of the corresponding alcohol. The monomer was polymerized under free radical conditions and H- and ¹³C-NMR spectra were recorded and analyzed. The spectra displayed several resonances with sensitivity to polymer stereochmistry and analysis of these resonances showed poly(2,5-dimethyl-3-furan) to be an atactic polymer.     

The polymerization of 3-methyl-N-(phenylsulfonyl)-1-aza-1,3-butadiene

Summary A study of the polymerizability of the first crystalline 1-azabutadiene carrying an electron-withdrawing group on nitrogen is described. A convenient one-step synthesis of 3-methyl-N-(phenylsulfonyl)-1-aza-1,3-butadiene (MPAB) from methacrolein and benzenesulfonamide using titanium tetrachloride and triethylamine led to a crystalline azabutadiene monomer in good yield. With anionic initiators the monomer readily oligomerized to materials in which MPAB has reacted in a 4,1-fashion. Under radical conditions the monomer did not homopolymerize, but did copolymerize with styrene monomers to polymers with molecular weights up to 10,000. These radical copolymerizations involved exlusive 4,3-propagation (vinyl) for the azadiene monomer.     

(S)-2-(Ethyl propionate)-(O-ethyl xanthate) and (S)-2-(Ethyl isobutyrate)-(O-ethyl xanthate)-mediated RAFT polymerization of N-vinylpyrrolidone

(S)-2-(Ethyl propionate)-(O-ethyl xanthate) (X1) and the newly synthesized (S)-2-(ethyl isobutyrate)-(O-ethyl xanthate) (X2) were used as the reversible addition-fragmentation chain transfer (RAFT) agents for the radical polymerization of N-vinylpyrrolidone (NVP). The former showed the better chain transfer ability in the polymerization at 60 °C. Kinetics study with X1 shows the psuedo-first order kinetics upto 45% monomer conversion. Molecular weight (M _n) of the resulted polymer increases linearly with increase in the monomer conversion upto around 45%. Polydispersity of the corresponding poly(NVP)s increase gradually from 1.2 to 1.9 with increase in the monomer conversion. Chain-end analysis of the resulted polymer by ¹H NMR shows clearly that polymerization started with radical forming out of xanthate mediator. Living nature of the polymerization was confirmed from the successful homo chain extension experiment and also the hetero-chain extension experiment involving synthesis of poly(NVP)-b-polystyrene amphiphilic diblock copolymer.     

刚柔嵌段共聚物聚苯基喹啉-b-聚苯乙烯的合成

利用原子转移自由基聚合合成了端羧基聚苯乙烯,然后与4-氨基苯乙酮反应,生成末端为乙酰基的聚合物,以P2O5为催化剂,将功能化的聚合物与5-乙酰基-2-氨基二苯甲酮共聚,合成出刚柔嵌段共聚物聚苯基喹啉-b-聚苯乙烯(PPO-b-PS),用红外光谱(IR)、氢核磁共振(1HNMR)和热重分析(TGA)对其结构和性能进行了表征,并在三氟乙酸／二氯甲烷混合溶剂中进行了初步的自组装研究。     

Synthesis of UV‐curable difunctional silane monomer based on 3‐methacryloxy propyl trimethoxysilane (3‐MPTS) and its UV‐curing characteristics and thermal stability

In the present investigation, silicon containing UV‐curable difunctional monomer was synthesized by reacting 3‐methacryloxy propyl trimethoxysilane (3‐MPTS) with acrylic acid using anhydrous ether as a solvent under inert atmosphere. The synthesized acryloxymethacryloxy silane monomer was characterized by FTIR, ¹H‐NMR, and ¹³C‐NMR spectroscopy. The silane monomer along with 4 wt % photoinitiator (Darocure 1173) was cured under UV‐light for different exposure time. The curing characteristic of the monomer was investigated using FTIR spectroscopy. The conversion of the double bond due to curing has been evaluated from the peak intensity of the C?C double bond (at 1636 cm^?1) in the FTIR spectrum considering the peak intensity at 1720 cm^?1 due to C?O as internal standard. The maximum double bond conversion is observed to be 72%. The optimum cure time for the silane monomer has been estimated to be 7.8 sec. The UV‐cured sample decomposes at 440°C. The char residue is 35% at 700°C. The synthesized UV‐curable silane monomer may be useful for UV‐coating formulations, for fabrication of 3D‐objects by lithographic technique and as a precursor for organic–inorganic hybrid materials. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Perfectly alternating poly(arylene ether ketone sulfone)'s

Summary In this study, the synthesis of perfectly alternating poly(arylene ether ketone sulfone)'s (PAEKS) via their soluble poly(arylene ether ketimine sulfone) (PAEKetS) intermediates was described. In the first stage of this procedure a new bishalide monomer, 1,1'-bis(4-fluoro(n-benzohydroxylidene aniline)) sulfone (FBHAS) was synthesized. In the second stage, the polymerization of this monomer with various aromatic bisphenols to form the amorphous PAEKetS's and then the hydrolysis of the ketimine groups on the PAEKetS's backbones to ketones in mild acidic conditions in order to obtain perfectly alternating PAEKS's was conducted. Received: 19 July 1999/Revised version: 14 January 2000/Accepted: 14 January 2000