The effects of thermal processing on PVC—X. The interaction between bound antioxidants and tin stabilizers

It is shown that a thiol u.v. stabilizer and a thiol heat stabilizer can be effectively bound to PVC during processing in the presence of an alkyltin stabilizer. Thiol u.v. stabilizer interferes with the processing stability of PVC to a lesser extent than does a conventional u.v. stabilizer (2-hydroxy-4-octoxybenzophenone).     

The effects of thermal processing on PVC—IX. A polymer reactive u.v. stabilizer as a thermal stabilizer for PVC

It is shown that a thiol u.v. stabilizer (4-ethoxymercaptoaceto-2-hydroxybenzophenone, EBHPT) becomes efficiently bound to PVC during normal processing at 170° in the presence of dibutyltin maleate (DBTM). This combination is an effective melt stabilizer and shows synergism as a heat stabilizer at 140°. This is shown to be due to the protection of DBTM by the PD antioxidant function in EBHPT and a synergistic optimum is observed. In the absence of DBTM or in the presence of a thiotin stabilizer binding of the u.v. stabilizer is incomplete.     

Post irradiation degradation of polypropylene radiation durability of polypropylene stabilized with phenolic stabilizer (II)

Post irradiation degradation of ⁶⁰Co gamma irradiated polypropylene stabilized with a phenolic type stabilizer has been followed up to two years after being irradiated. The effectiveness of the stabilizer at various concentrations on the polypropylene samples irradiated up to 150 kGy has been studied and the buildup of carbonyl group in the irradiated samples measured. The obtained results indicated that the oxidative reactions are retarded by addition of stabilizer. The variation of bend strength of the irradiated samples with and without stabilizer was also followed. This property was found to be greatly improved for the stabilized samples irradiated at low doses. However at high doses the effectiveness of the stabilizer declined. In order to correlate these results with the change in the molecular weight of polymer, trends of the change in rheological behaviour such as melt viscosity (μ_a) and flow behavior parameters (K, n) of both stabilized and unstabilized samples have been investigated. Results showed that at low doses, addition of the stabilizer greatly reduces the extent of chain scission, and therefore, the mechanical properties of the irradiated polymer are retained.     

稀土复合稳定剂在PVC塑料门窗型材中的应用

根据人们对环保产品的需求，对新型环保产品RE－4稀土复合稳定剂的热稳定性，流变性，抗硫化污染等方面铅盐体系进行了分析对比，其结果表明RE－4稀土复合稳定剂不但具有良好的热稳定性而且对配方中的无机成分具有良好的包覆与分散作用；从而能提高物料的流动性能和产品质量。     

On the origin of colloidal particles in the dispersion polymerization of aniline

When aniline is oxidized in an aqueous medium in the presence of a steric stabilizer, colloidal polyaniline (PANI) dispersions are obtained. The generally accepted model of the stabilization assumes that the macromolecules of the water-soluble steric stabilizer are adsorbed at the polymer, precipitating during the dispersion polymerization, and provide steric protection against further aggregation. An alternative mechanism of conducting-polymer particle formation is proposed in the present study. We suggest that the steric stabilizer provides a site for adsorption of oligoaniline initiation centers; subsequent polymerization from anchored centers yields particle nuclei that grow to produce colloidal PANI particles. This hypothesis is based on the observation that the colloidal particles are obtained only in the case where the steric stabilizer is introduced in the early stages of polymerization when aniline oligomers are present in the reaction mixture. If the stabilizer had been added during the growth of PANI chains, colloidal dispersions would not have been produced. The process of particle growth is completely analogous to the formation of conducting PANI films on the surface of microparticles and various materials. There, the polymerization of aniline at the surfaces is preferred to the same process proceeding in the bulk of the reaction mixture. While the films grow at the interfaces with the reaction mixture, the dispersion particles similarly emanate from the stabilizer chains. The particle size, the formation of nonspherical morphologies, the importance of the chemical nature of the stabilizer chains, and the general relation between the conducting-polymer film and particle growth are discussed in the light of the proposed model.     

Photostabilization of recycled pigmented polypropylene crate material

The photostabilizing efficiencies of various light stabilizer systems in recycled pigmented polypropylene crate materials, previously in use for 6–7 years, have been examined using the standard carbonyl index and time to embrittlement methods. Thirty-two polymer film samples with and without additional stabilizer have been prepared and exposed in both a Xenotest-150 and Microscal apparatus. The performance of the various light stabilizer systems in both exposure units are compared and discussed.     

Formation of polymer-bonded nitroxyl radicals in the UV stabilization of polypropylene by a bifunctional hindered amine light stabilizer

The formation of polymer-bonded stabilizer derivatives during photooxidation of isotactic polypropylene, which contains the hindered amine light stabilizer bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate and the corresponding bisnitroxyl radical, was investigated. The photooxidized polypropylene films that contain these additives were studied by ESR, IR, and nitrogen analysis before and after exhaustive solvent extraction of the photooxidized films. ESR showed that under the conditions in use a maximum of 20% of the nitroxyl radicals formed from the hindered amine was bonded to the polymer chain. Regeneration of nitroxyl radicals from the polymer-bonded stabilizer derivatives under photooxidative conditions indicated that the stabilizer was bonded to the polymer chain by O-alkyl-substituted hydroxylamine linkages >N? O? PP.     

A study of the photolysis of a commercial hindered amine light stabilizer

The photolysis of a commercial hindered amine light stabilizer (HALS) has been studied with a range of experimental methods. The results show that the stabilizer is easily photolyzed and photolysis mechanisms are proposed.     

Dispersion polymerization of methyl methacrylate: Mechanism of particle formation

The mechanism for the formation of micron-size polymer particles in the dispersion polymerization of methyl methacrylate was investigated by applying dynamic light scattering to monitor the evolution of the average particle size in the early stages of the polymerization. In addition, the contributions of physically adsorbed stabilizer and graft copolymer were evaluated by measuring the bound, unbound (adsorbed), and free stabilizer, and by determining the amount of added stabilizer required in seeded dispersion polymerizations. Twenty nanometer particles (termed nuclei) were the smallest particles detected and are considered to be formed by aggregation of growing polymer chains precipitating from solution as they exceed their critical chain length. Aggregation of these nuclei with themselves and their aggregates continues until mature and stable particles are formed. This occurs when sufficient stabilizer occupies the particle surface which includes both the polymeric stabilizer [poly(vinylpyrrolidone)] and its graft copolymer which is created in situ. The effects of process variables are discussed based on this mechanistic picture of the dispersion polymerization process. © 1994 John Wiley & Sons, Inc.     

The effect of thermal processing on PVC—IV. Photo-oxidation of stabilized PVC

The effects of a tin maleate stabilizer and of typical processing lubricants (Wax E and calcium stearate) on the photo-oxidation of PVC have been examined. The latter are found to have a relatively minor effect but the tin maleate stabilizer introduces an induction period to photo-oxidation, related to the amount remaining from the thermal processing operation. The function of the stabilizer is to eliminate the formation of polyconjugated unsaturation and of peroxides during thermal processing; this function persists to the photo-oxidation stage.     

Synthesis of a water-soluble macromolecular light stabilizer containing hindered amine structures

A novel water-soluble macromolecular light stabilizer was synthesized by grafting 2-chloro-4,6-bis- [(2,2,6,6-tetramethylpiperidin-4-yl)amino]-l,3,5-triazine onto polyvinylamine.The intermediate 2- chloro-4,6-bis-[(2,2,6,6-tetramethylpiperidin-4-yl)arnino]-1,3,5-triazine and the obtained macromolecular light stabilizer were characterized by ~1H NMR,HRMS,IR and UV spectroscopy.Cotton fabrics dyed with C.l.Reactive Yellow 145,C.I.Reactive Red 195 and C.I.Reactive Blue 19 were finished with the macromolecular light stabilizer,and the lightfastness of the dyes was tested.The results showed that the lightfastness of the reactive dyes was improved by 0.5-1.0 grade after being finished and the macromolecular light stabilizer exhibited good wash fastness and thermal stability.     

Effect of stabilizer and pigment on photodegradation of polypropylene as revealed by macromolecule scission and crosslinking measurements

Photodegradation depth-profiles have been generated using computer-aided molecular weight distribution analysis for 3 mm thick polypropylene injection moldings containing (i) a stabilizing package that included hindered amine light stabilizers and a phenolic stabilizer, (ii) titanium dioxide pigment and (iii) both the pigment and the stabilizing package. The inhibiting effect of the additives has been determined quantitatively by comparing macromolecule scission and crosslinking rates with those in samples containing no stabilizer or pigment. TiO₂ pigment gave more effective protection against molecular degradation than the stabilizer package; there was very little advantage to be gained by adding stabilizer when the pigment was present. The inhibition caused by having pigment or stabilizer present was measured to be very large: degradation was reduced by at least a factor of 10 and often by a factor of several hundred times. The relative amount of scission and crosslinking differed according to the additives present and the depth from the exposed surface: high reaction rates favoured scission and lower reaction rates resulted in a higher relative crosslinking concentration.     

Role of the UV absorber as a matrix in matrix‐assisted laser desorption/ionization mass spectrometric analysis of a mixture of a UV absorber and a stabilizer

A mixture of a UV absorber (Tinuvin 234 or Tinuvin 329) and a UV stabilizer (Tinuvin 770) was analyzed using matrix‐assisted laser desorption/ionization mass spectrometry (MALDI‐MS) without any matrix. Fragmentation patterns of the UV absorbers and stabilizer were also investigated. The mass spectra showed the [M+H]⁺ ions and some fragment ions. Tinuvin 234, Tinuvin 329, and Tinuvin 770 generated three (m/z 119, 370, 432), one (m/z 252), and two (m/z 124 and 140) fragment ions, repectively. These fragment ions can be used to identify the chemical structures of the UV absorbers and stabilizer. Since the UV absorber performed a role as the matrix, the ion abundance of the UV stabilizer was enhanced by mixing with the UV absorber. When organic materials extracted from polypropylene (PP) containing the UV absorber and stabilizer were directly analyzed using MALDI‐MS without any matrix, the protonated molecule of the UV stabilizer was detected in abundance but the product ions of the UV absorber were not observed. When 2,5‐dihydroxybenzoic acid was used as a matrix, the protonated molecule of the UV absorber was observed. Copyright © 2010 John Wiley & Sons, Ltd.     

CRYSTALLIZATION BEHAVIOR OF PURE AND ADDITIVE-CONTAINING POLY (ETHYLENE TEREPHTHALATE)

The isothermal crystallization of poly (ethylene terephthalate ) (PET),which is free of catalyst, stabilizer, oligomer and diethylene glycol (DEG), was studied by DSC. The crystallization behaviour of pure PET is different from commercial PET and a reasonable explanation is presented. The influences of catalyst, stabilizer, oligomer and DEG on the crystallization of pure PET were examined. It is shown that catalyst (Manganese acetate)and stabilizer (Triphenyl phosphite) result in an increase of the crystallization rate of PET; on the contrary, DEG and oligomer (cyclotetramer) result in a reduction of the crystallization rate. When catalyst and stabilizer coexist together, both of them promote the crystallization at lower temperature ,only a smaller effect was found at higher temperature, it is evident that metal phosphite is formed between the catalyst and stabilizer at higher temperature.     

Thiol-ended polyethylene oxide as reactive stabilizer for dispersion polymerization of styrene

 Radical dispersion polymerization of styrene in aqueous ethanol solutions was performed in the presence of a new reactive polyethylene oxide stabilizer with thiol end groups. This reactive stabilizer was compared to the more conventional poly (N-vinyl pyrrolidone). Particles size distribution, molecular weights and kinetics were investigated. Monodispersed polymer particles with diameter in the range 200–2000 nm were obtained depending on the amount of stabilizer used. In all cases, the polyethylene oxide (PEO) sequence of the dispersant was partly incorporated at the surface of the latex particles, but the grafting yield of polyethylene oxide chains was always limited and did not exceed 15%. Part of the stabilizer being unreacted or reacted with low molecular weight polystyrene remained in the continuous phase. Received: 26 September 1996 Accepted: 4 March 1997     

硫酸铵水溶液中丙烯酰胺与正离子单体的分散共聚研究

以硫酸铵(AS)水溶液为介质,进行丙烯酰胺(AM)与正离子单体甲基丙烯酰氧乙基三甲基氯化铵(DMC)分散共聚合,制备出水溶性聚合物分散体.研究了盐浓度、分散稳定剂浓度及其分子量、单体浓度等对反应体系及分散体粒径的影响.结果表明,随着分散稳定剂的用量从6%增加到14%,分散体的平均粒径先下降,后又随之上升.分散稳定剂分子量越大,所得分散体的平均粒径越小.硫酸铵和单体的浓度对平均粒径和粒子形态等影响显著,只有在较小的范围内才能制备出粒径较均一的正离子型水溶性聚合物分散体;硫酸铵浓度越大,生成聚合物分子量越低.     

高分子光稳定剂的研究——溶解度参数与光稳定效率的关系

<正> 添加光稳定剂是阻止聚合物因光照氧化降解,延长聚合物制品的使用寿命的有效方法。显然只有当光稳定剂能最大程度地均匀分散在聚合物中才能充分地发挥它的光稳定效率,这对高分子光稳定剂来说尤为重要。 光稳定剂与被稳定的聚合物的相容性对光稳定效率的影响已有过研究。如Ambrovic等曾经报道:随着2-羟基4-烷氧基二苯甲酮中烷基的碳原子数增加,它对聚丙烯的光稳定效率提高。高分子光稳定剂本身是一个有一定分子量的聚合物,使用时它与被稳定聚合物形成了共混体系。我们研究了高分子光稳定剂的溶解度参数和它对聚丙烯的光稳定效率的关系。     

Synthesis and characterization of fluorescently labelled poly(vinyl acetate) particles

Nonaqueous dispersions of poly(vinyl acetate) particles stabilized with poly(2-ethylhexyl methacrylate) and labelled with fluorescent dyes in the core and stabilizer polymer phases were prepared. The materials were characterized using a broad range of techniques (NMR, UV, and fluorescence spectroscopy. GPC, particle sizing, and DSC). The data show that dispersion polymerization of vinyl acetate in the presence of stabilizers containing certain fluorescent dye derivatives, instead of unlabelled stabilizer, results in changes in the mean particle size, size distribution, composition, and molecular weights of the colloidal polymer particles. It was found that increasing the amounts of fluorescent groups in the stabilizer resulted in smaller mean particle sizes and larger amounts of irreversibly attached stabilizer. When the average number of labels in stabilizer exceeded one per chain, a new ultra-high molecular weight polymer fraction appeared. The fluorescence spectra for several of these materials are reported. We describe how fluorescence decay curves can be used to assess block formation and local phase separation in particles labelled with phenanthrene groups. These materials are intended to be used for more detailed studies by fluorescence spectroscopy. Those results will be published in due course.     

反应原料组成对单分散苯乙烯微球粒径及其分布的影响

采用分散聚合工艺制备微米级单分散聚苯乙烯微球，并对分散聚合反应的内部影响因素(分散稳定剂、助稳定剂、单体、引发剂)进行了研究．结果表明，随着分散稳定剂和助稳定剂用量的增加，聚苯乙烯微球的粒径减小；随着单体和引发剂用量的增加，聚苯乙烯微球的粒径增大．分散稳定剂和单体用量是影响聚苯乙烯微球粒径分布的两个主要内部因素．     

Photoinitiated dispersion polymerization of methyl methacrylate: A quick approach to prepare polymer microspheres with narrow size distribution

Photoinitiated dispersion polymerization of methyl methacrylate was carried out in a mixture of ethanol and water as dispersion medium in the presence of poly(N‐vinylpyrrolidone) (PVP) as the steric stabilizer and Darocur 1173 as photoinitiator. 93.7% of conversion was achieved within 30 min of UV irradiation at room temperature, and microspheres with 0.94 μm number–average diameter and 1.04 polydispersity index (PDI) were obtained. X‐ray photoelectron spectroscope (XPS) analysis revealed that only parts of surface of the microspheres were covered by PVP. The particle size decreased from 2.34 to 0.98 μm as the concentration of PVP stabilizer increased from 2 to 15%. Extra stabilizer (higher than 15%) has no effect on the particle size and distribution. Increasing medium polarity or decreasing monomer and photoinitiator concentration resulted in a decrease in the particle size. Solvency of reaction medium toward stabilizer, which affects the adsorption of stabilizer on the particle surface, was shown to be crucial for controlling particle size and uniformity because of the high reaction rate in photoinitiated dispersion polymerization. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1329–1338, 2008