Emulsion polymerization of butadiene and subsequent grafting of methylmethacrylate. High impact properties of blends from this grafted polymer and polyvinylchloride

The paper illustrates the graft emulsion polymerization of methylmethacrylate onto polybutadiene in two steps. In the first butadiene is polymerized using two radical initiators (AIBN and (NH₄)₂S₂O₈), whose ratio does not influence the relative amount of 1,2-, 1,4-trans and 1,4-cis structures. The second step uses AIBN only: the grafting yield is very high. Grafting mechanism is discussed. The grafted polymer has good mechanical properties and its blends with PVC present very high impact strength. The mechanical properties are discussed. A statistical copolymer of butadiene and methylmethacrylate was prepared and compared with the grafted polymer. The copolymer is also a very good additive for PVC to elevate its impact strength.     

Ultrafine full-vulcanized powdered rubbers/PVC compounds with higher toughness and higher heat resistance

A new type of rigid PVC compound with higher toughness and higher heat resistance was prepared by using a new type of PVC modifier, ultrafine full-vulcanized powdered rubber (UFPR). The UFPRs used in this paper were butadiene nitrile UFPR-1 (NBR-UFPR-1) with particle size of about 150 nm and butadiene nitrile UFPR-2 (NBR-UFPR-2) with particle size of about 90 nm. Dynamic mechanical thermal analysis (DMTA) showed that glass transition temperature (T_g) of PVC in compounds increased from 77.52 °C of neat PVC to 82.37 and 85.67 °C, while the notched impact strengths increased from 3.1 kJ/m² of neat PVC to 5.2, 5.5 kJ/m², respectively. It can be found that both T_g and toughness of PVC have been improved simultaneously, and the smaller the particle size of NBR-UFPRs, the higher the T_g and the impact strength. The property could be attributed to larger interface and more interfacial interaction between NBR-UFPRs and PVC matrix. Transmission electron microscopy (TEM) showed that NBR-UFPRs could be well dispersed in PVC matrix.     

粉末改性NR对PVC的增韧作用

用粒径小于０９ｍｍ的粉末改性ＮＲ（ＰＭＮＲ）与ＰＶＣ共混,研究共混体的力学性能及ＰＭＮＲ的性质对共混体冲击强度的影响。试验结果表明,ＰＭＮＲ对ＰＶＣ有显著的增韧效果,ＰＭＮＲ用量由２５份增大到５份,共混体的Ｃｈａｒｐｙ式缺口冲击强度由５１ｋＪ·ｍ－２提高到６４３ｋＪ·ｍ－２。用扫描电镜进行的冲击断面形貌分析表明,共混体的增韧机理为剪切屈服机理。     

Core–shell particles designed for toughening poly(vinyl chloride)

A novel core–shell modifier (MOD) made up of polystyrene and poly(butyl acrylate) (PBA) grafted on a crosslinked styrene‐co‐butadiene core was synthesized by emulsion polymerization. This modifier was used for enhancing effectively the impact ductility of poly(vinyl chloride) (PVC) without losing its transparency. The effects of the MOD on the properties of PVC/MOD blends were explored. It was found that the butyl acrylate (BA) content of the MOD was an important factor affecting the properties of PVC/MOD blends. The Izod impact strength of these blends reached 1200 J m^?1 when the MOD contained 40 wt% BA. The dispersion morphology of the MOD in the PVC matrix was investigated using transmission electron microscopy, with a uniform dispersion of the MOD with higher BA content being obtained. The toughening mechanism of PVC/MOD blends was also investigated. The presence of BA in the MOD enhanced the ductility of the PVC blends due to the increased amount of soft phase (PBA). The dispersion morphology indicated that the interfacial interaction between MOD particles and PVC matrix was improved due to the presence of PBA graft chain in the MOD. TEM of impact fracture samples showed that shear yielding of the PVC matrix and debonding of MOD particles were the major toughening mechanisms for the PVC/MOD blends. Copyright © 2010 Society of Chemical Industry     

PVC/MBS共混物的形态及力学性能

采用种子乳液聚合方法,在聚丁二烯乳胶粒子上接枝甲基丙烯酸甲酯（MMA）和苯乙烯（St）,制得MBS核壳接枝共聚物,并将其作为增韧剂与聚氯乙烯（PVC）共混制备PVC/MBS共混物。考察了接枝不同MMA和St含量的MBS在PVC中的分散状态及其对PVC/MBS共混物力学性能。结果表明,当MBS壳层中MMA含量增加时,MBS粒子在PVC基体中的分散状态被改善;PVC/MBS共混物的冲击强度随之增加,冲击强度最高时为1117.74 J/m;当MBS中接枝少量St时,PVC/MBS共混物呈现韧性断裂,冲击值最高时为1039.33 J/m;当MBS接枝大量St时,会产生内包容现象,不利于提高PVC共混物的冲击强度。     

Waste‐reducing preparation of PE‐g‐MAH and PE‐g‐DBM via solid phase grafting reaction and their application as compatibilizers

Kinetics for grafting two reactive monomers (dibutyl maleate (DBM) and maleic anhydride (MAH)) on polyethylene (PE) was investigated for the modified PE (PE‐g‐MAH and PE‐g‐DBM) using solid phase grafting process. This process avoided solvent waste produced in solution process and high operation temperature in melt process. In the presence of the radical initiator, coupling reactions, between the PE and product, and macromolecular radicals, routinely form gels and/or increase molecular weight, resulting in a worse rheological behavior for the grafting products. By adding small amount of interface agents, using combined initiators and optimizing reactor design, graft copolymers with controlled grafting degrees and good rheological properties were prepared. The grafting degrees of copolymers were determined by chemical analysis. FTIR, DSC, and pure water contact angle characterized the chemical structure, the thermal property, and the hydrophilic property of the grafting copolymers, respectively. The peel strength of the graft copolymer as powder coating on the stainless steel surface was measured as high as 12–24 kgf/cm. Mechanical strength and toughness of PE/kaolin clay, PVC/CPE, and PVC/CPE/CaCO₃ alloys with small amount of the graft copolymer (～5 wt %) added were improved significantly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3781–3790, 2006     

Impact strength in ABS–PPO blends compatibilized with styrene–acrylonitrile–glycidil methacrylate terpolymers

The impact strength of the acrylonitrile-co-butadiene-co-styrene terpolymer–poly(2,6-dimethyl-1,4-phenylene oxide (ABS–PPO) blends compatibilized with styrene–acrylonitrile modified with glycidil methacrylate (SAN–GMA) terpolymer can be significantly enhanced by the various processing conditions in reaction extrusion. Four different ABS terpolymers are used depending on the composition of acrylonitrile, styrene, and butadiene. The morphology of polybutadiene latex in ABS-1, ABS-3, and ABS-4 is an agglomerated type, while that of ABS-2 is a bimodal one. The three different methods in in situ compatibilizing extrusion are employed; the simple mixing of ABS and PPO, the simultaneous mixing of ABS and PPO, the reactive compatibilizer SAN–GMA, maleic anhydride (MA; designated A-series), and then the stepwise mixing of the mixtures of ABS–SAN–GMA in the MA-modified PPO (designated B-series). Although the ABS-4–PPO blend depicted the highest impact strength in the simple mixing, the ABS-3B–PPO blend showed the best impact strength in the stepwise mixing. The former behavior may be arisen from the high content of BR, whereas the latter may be due to the agglomerated rubber phase with SAN–GMA. The highest impact strength (47 kg·cm·cm⁻¹) was observed in ABS-3B–PPO at 50/50 with an inclusion of 10 wt % GMA (2) and 1 wt % MA. Thus, the proposed reaction mechanism is an existence of the compatibility between ABS and SAN–GMA and the reactivity between the MA-modified PPO and SAN–GMA. Phase morphology of the ABS-2–PPO and ABS-3–PPO blends were compared, and more efficient dispersion of ABS was observed in the B-series than in the A-series. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 841–852, 1999     

Effect of the compatibilizers on flame-retardant polycarbonate (PC)/acrylonitrile–butadiene–styrene (ABS) alloy

Polycarbonate (PC) blended with acrylonitrile–butadiene–styrene (ABS) has the maximum notched Izod impact strength, which is 58 kg cm cm^-1 for PC/ABS1 and 66 kg cm cm^-1 for PC/ABS2, at a ratio of 80/20 in this study. We selected the ratio of 80/20 to prepare flame-retardant PC/ABS alloys. The compatibility of flame-retardant PC/ABS alloy was examined by differential scanning calorimetry (DSC). The flame-retardant PC/ABS alloy had two values of the glass transition temperature (T_g), indicating that the alloy was not compatible. Three kinds of compatibilizers, methacrylate–butadiene–styrene (MBS), ethylene–vinyl acetate (EVA), and styrene–maleic anhydride (SMA) were used to improve the phenomenon. DSC measurement revealed that after compatibilization the alloy had only one value of T_g, meaning that the alloy became more compatible. Samples were frozen in liquid nitrogen to look at their morphology. We found that the domain sizes were reduced and the surface boundaries were closed and blurred, a feature that could promote the mechanical properties of the alloy. In this study, we also compared the effects of mechanical properties on differential compatibilizers for the flame-retardant PC/ABS alloy. Cycoloy 2800 is a commercial-grade flame-retardant product and was chosen to compare it with our prepared alloys in this study. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 795-805, 1997     

Novel multimonomer‐grafted polypropylene preparation and application in polypropylene/poly(vinyl chloride) blends

A novel grafted polymer was prepared in one step through free‐radical melt grafting in a single‐screw extruder. It was shown that the addition of styrene (St) to the melt‐grafting system as a comonomer could significantly enhance the grafting degree of methyl methacrylate (MMA) onto polypropylene (PP) and reduce the degradation of the PP matrix by means of Fourier transform infrared and melt flow rate testing, respectively. Then, the potential of using multimonomer‐grafted PP, which was designated PP‐g‐(St‐co‐MMA), as the compatibilizer in PP/poly(vinyl chloride) (PVC) blends was also examined. In comparison with PP/PVC blends, the average size of the dispersed phase was greatly reduced in grafted polypropylene (gPP)/PVC blends because of the addition of the PP‐g‐(St‐co‐MMA) graft copolymer. The tensile strength of the gPP/PVC blends increased significantly, and the impact strength was unchanged from that of the pure PP/PVC blends. The results of differential scanning calorimetry and scanning electron microscopy suggested that the compatibility of the PP/PVC blends was improved. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Permeability of poly-L-methionine membrane and its oxidized membrane to water vapor

The permeability of poly-L -methionine (PLM) membrane and its oxidized form to water vapor was studied. Permeability coefficients of the PLM membrane were large, of the order of 10^?7 cm³ (S.T.P.)·cm/cm²·sec·cm Hg. The sorption and permeation behavior of the PLM membrane was hydrophobic. The oxidized membrane was prepared by treating one or both sides of the PLM membrane with an aqueous solution of hydrogen peroxide. The membrane oxidized from one side is probably not layered but has a gradient of composition from one surface to the other. The amounts of water sorbed by the modified membrane increased with increase in oxidation time. The permeability coefficients of water vapor through the modified membrane were of the order of 10^?6 cm³ (S.T.P.)·cm/cm²·sec·cm Hg.     

Investigation on multiphase polymeric systems of poly(vinyl chloride). I. PVC–chlororubber-20-gp-styrene–acrylonitrile (2 : 1) blends

A graft copolymer [chlororubber-20-gp-styrene–acrylonitrile (2 : 1)] has been synthesized by a solution precipitation polymerization technique grafting styrene and acrylonitrile onto chlororubber-20 main chain. The graft copolymer has been characterised by elemental analysis, IR spectroscopy, and viscometry. It has been blended with PVC by melt mixing using a Brabender plasticorder and extrusiograph. The mechanical properties such as flexural and tensile strengths and impact strength of the blends have been studied to evaluate its performance as an impact modifier. The behavior of PVC–chlororubber-20-gp–styrene-acrylonitrile (2 : 1) blends has also been compared with PVC–chlororubber-20 and PVC–KM-365B (a commercial acrylate modifier) blends. The thermal behavior of these blends has also been studied. It has been found that PVC–chlororubber-20-gp-styrene–acrylonitrile (2 : 1) blends have higher impact strength than PVC–chlororubber-20-gp blends though the PVC–KM-365B blends have the highest impact strength. Based on the authors' previous compatibility studies along with present X-ray diffraction studies and the morphological investigation of the fractured surface by scanning electron microscopy, the mechanical behavior of these blends have been explained in the framework of existing theories. A model has been proposed to account for the optimum dispersion and adhesion of graft polyblends of chlororubber-20 in PVC matrix.     

Scanning electron micrograph study of the impact-improved MBS/PVC blends

The improvement of the impact strength of the telecommunication equipment using injection moldable PVC/MBS and other modifiers were studied. The addition of MBS to the PVC was found with rapid increases in the impact stregths in Kg-cm/cm: 5.5 of pure PVC; 80 of 12 phr and the maximum of 131 of 20 phr of MBS. This increasing impact strength phenomena were subjected to close examinations of SEM, DMTA, and strain-stress diagrams. The DMTA analysis of the retaining of the individual T_g's of MBS and PVC in the MBS/PVC blends, indicates that no miscibility of MBS and PVC has occurred. The DMTA diagrams of 5, 12, 20, and 30 phrs of MBS in PVC were analyzed and the same samples were also subjected to the impact strength measurements and the SEM examinations. SEM photos showed a gradual transition of the linear to the three-dimensional arrangements had occurred in the PVC/MBS blends. The formation of three-dimensional arrangement occurred between 10–20 phr of added MBS. The spacial change from linear to the three-dimensional arrangements observed in SEM photos correlates the rapid increases of the impact strengths of the specimens tested. Injection specimens of the telephone sets made of PVC/MBS blends with 20 phr of MBS in PVC indicate that the impact strength is averaged at 115 Kg-cm/cm with tensile strength of 330 Kg/sq cm and elongation of 150%. The similar change of the spacial arrangement is also observed in their SEM photos.     

甲基丙烯酸甲酯-丁二烯-苯乙烯树脂的合成及其对聚氯乙烯的改性

采用种子乳液接枝聚合技术合成了甲基丙烯酸甲酯(MMA)-丁二烯-苯乙烯树脂(MBS),考察了复合乳化剂浓度、CO2用量对丁苯胶乳粒径及其分布、胶乳稳定性的影响;研究了接枝单体滴加方式和接枝聚合反应温度对MBS体系稳定性和接枝效率的影响;讨论了MBS改性聚氯乙烯(PVC)的影响因素;提出了丁苯胶乳的碳酸化扩径附聚法和MBS胶乳的SO2凝聚新工艺。结果表明:在丁二烯/苯乙烯(质量比)为90/10、阴离子/非离子复合乳化剂浓度为35~40g/L、丁苯胶乳采用CO2附聚扩径、部分MMA预溶胀和其余MMA连续滴加的方式以及MBS胶乳SO2凝聚新工艺的条件下,所得MBS树脂粉料颗粒均匀,40~180目的颗粒质量分数达96%,堆积密度在0.4g/cm3以上;PVC/MBS(质量比为100/8)共混物的冲击强度达22.6kJ/m2。     

One simple and stable coating of mixed‐charge copolymers on poly(vinyl chloride) films to improve antifouling efficiency

An antifouling surface is highly desirable for many biomedical applications. In this study, poly(vinyl chloride) (PVC) films were endowed with the improved properties of resisting nonspecific protein adsorption and platelet adhesion simply through being coated with a kind of mixed‐charge zwitterionic polymer, poly(3‐sulfopropyl methacrylate–methacrylatoethyl trimethyl ammonium chloride–glycidyl methacrylate) (PSTG), with random moieties of negatively charged 3‐sulfopropyl methacrylate potassium, positively charged [2‐(methacryloyloxy)‐ethyl] trimethylammonium chloride, and glycidyl methacrylate. The PSTG‐grafted PVC films were formed by the simple immersion of an amino‐functionalized PVC film into a PSTG solution. A grafting density of 220.84 µg/cm² of PSTG4‐grafted PVC film was successfully obtained. The PSTG4‐grafted PVC film showed a lower contact angle (37.5 °) than the ungrafted PVC film (98.3 °). The in vitro protein adsorption results show that the bovine serum albumin adsorption amount decreased 6.72 µg/cm² in the case of the PSTG4‐grafted PVC film, whereas that on the ungrafted PVC film was 28.54 µg/cm². So, PSTG‐grafted PVC films could be promising materials for medical devices. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44632.     

Polyion Complex Fiber and Capsule Formed by Self‐Assembly of Chitosan and Poly(α,L‐glutamic acid) at Solution Interfaces

Different characteristic surface structures such as spherical capsules, regularly spaced droplets and fibers are formed by electrostatic polysaccharide interaction between chitosan and poly(α,L ‐glutamic acid) via polyion complex (PIC) formation. Spherical droplet‐like PIC capsules of varying diameters form in solutions. Some dyes adsorb on the surface of the capsules, while other dyes and benzoic acid derivatives penetrate into the capsules. The PIC fiber can be prepared by reactive‐spinning at the solution interface, followed by gravity and by removing water in ethanol. The tensile strength of the fiber is 11.2 kg·mm^–2 (1.48 g·denier^–1) and the knotting strength is 2.15 kg·mm^–2 (0.30 g·d^–1). By reaction with an organic cross‐linking agent, ethylene glycol diglycidyl ether (EGDE), the tensile strength of the fiber can be increased to 18.1 kg·mm^–2 (3.14 g·d^–1), and by reacting with hexamethylene diisocyanate (HMDI), the knotting strength of the fiber can be increased to 7.58 kg·mm^–2 (0.89 g·d^–1). The interaction energies (work of adsorption, W_ads) of PLG and chitosan in aqueous solution were estimated by a surface chemical approach, and a relationship between the W_ads values and the tensile strengths of the PIC fibers and the W_ads indicated that the higher W_ads system gives the higher tensile strength. The PIC fiber can be dyed by four different dyeing procedures such as direct and vat dyeings. When the cross‐linked PIC fiber was incubated in an aqueous solution in the presence of endocrine disruptor related compounds such as dibenzofuran and biphenyl, these compounds were accumulated onto and/or into the fibers.     

Peel strength improvement of silicone rubber film by plasma pretreatment followed by graft copolymerization

Here we discuss the improvement in the peel strength of silicone rubber film by O₂ plasma pretreatment followed by grafting with hydrophilic monomers: acrylamide (AAm) and acrylic acid (AA). The peroxides concentration after O₂ plasma treatment was determined by the 1,1-diphenyl-2-picrylhydrazyl (DPPH) method. ESCA analysis was carried out to confirm the existence of AAm. The peroxides concentration and hence the peel strength increased with increasing plasma treatment power and time, reached a maximum value, and then decreased with further increasing plasma treatment power and time. Peel strength of the silicone film with 3M-600 tape was observed to increase with grafting time; however, it was found to decrease with overgrafting. The maximum peel strength of 384.4 g/cm was found for the 20 W, 10 min plasma treated, AAm grafted film with maximum peroxides concentration of 4.86 x 10^-9 mol/cm² and also with maximum nitrogen-to-carbon ratio (N/C) of 0.247. Hydrolysis experiments show that -NH₂ provides higher contribution to adhesion than -COOH does and the grafting degree of AA is lower than that of AAm. The relationship between the degree of grafting and peel strength can be well explained by the mechanical interlocking theory of adhesion.     

接枝率对PVC/PA6-g-SMA共混物结构与性能的影响

采用熔融共混方法制备了聚氯乙烯（PVC）与不同接枝率苯乙烯-马来酸酐共聚物(SMA）接枝改性聚酰胺6（PA6-g-SMA）的共混物,研究了PA6-g-SMA接枝率对PVC/PA6-g-SMA共混物力学性能及凝聚态结构的影响。结果表明,接枝率越高,PA6-g-SMA与PVC的相容性越好,在PVC基体中能以更小的相畴均匀分散,对PVC的增韧增强作用越明显;当PA6-g-SMA的接枝率为5.12 %,添加量为15 ％（质量分数,下同）时,共混物的冲击强度为64.7 kJ/m2,拉伸强度为55 MPa。     

Synthesis of montmorillonite-modified acrylic impact modifiers and toughening of poly(vinyl chloride)

A series of Na-montmorillonite (Na⁺-MMT) modified acrylic impact modifiers (mAIM) were prepared by seeded emulsion polymerization. These mAIM modifiers were characterized by XRD. A 0.24?nm of increased interlayer distance of Na⁺-MMT was an indication of polymer chains intercalation within interlayer spacing. The notched Izod impact tests proved that the impact strength of the PVC/AIM composites prepared by melt blending was 43?J/m, markedly higher than the impact strength of pure PVC. Furthermore, with increasing content of AIM, the composites exhibited changes from brittle fracture to ductile fracture, with the impact strength increasing from 200 to about 1,000?J/m. The impact strength of PVC/mAIM also showed the same trend, although there were drops in some values. The impact strength of PVC/mAIM composites decreased with the increases in Na⁺-MMT content, but the yield strength and modulus of the composites increased with higher Na⁺-MMT content. The result also showed that the tensile strength of mAIM with 2 wt?% Na⁺-MMT is lower than that of mAIM with 0.8 and 1 wt?% contents, but still sufficiently large in comparison to the tensile strength of mAIM with 0 wt?% Na⁺-MMT. The dynamic mechanical analysis (DMA) result showed that the glass transition temperature (T _g) of mAIM did not show obvious changes and the elasticity of mAIM was reduced with the additional Na⁺-MMT content.     

Homogeneous Photoinouced Graft Copolymerization of Acrylamide onto Abs Copolymers in the Presence of 4-Acetyldiphenyl as Photosensitizer.: 1. Influence of Butadiene Content in Abs Copolymers

Photoinduced graft copolymerization of acrylamide (AM) onto two types of acrylonitrile-butadiene-styrene (ABS) copolymers was extensively investigated in homogeneous media. The grafting process was conducted in chloroform in presence of 4-acetyldi-phenyl (4-AD). Ultraviolet (UV) irradiation was used in the range of 310 to 460 nm. The UV spectrum of 4-AD has sλ_max at 285 nm and shows n-π^? transitions. The grafting parameters, such as weight conversion, grafting percentage, and grafting efficiency, were determined as a function of the irradiation time and the concentrations of monomer, initiator, and substrate. A reverse effect was observed between the grafting percentage and the butadiene content in ABS copolymers. The rates of graft copolymerization of AM onto the two types of ABS copolymers were determined. A Trommsdorf effect was observed in certain systems. The IR spectrum of ABS-g-AM graft copolymer shows the appearance of a new peak at 1685 cm^-1 that declares the presence of poly-acrylamide-grafted chains onto the ABS copolymer backbone. A probable copolymerization mechanism was proposed.     

MMA/TPX homograft membrane for oxygen enrichment

Utilizing the factors of degradation and crosslinking of TPX polymer and high O₂/N₂ selectivity of MMA, the performances of MMA homografted TPX membrane are efficiently improved compared to those of pure TPX membrane. The degradation and crosslinking of TPX polymer solution with or without dissolved oxygen during irradiation were observed and proved in existence by the gas permeability, mechanical, and viscosity change study. High O₂/N₂ permeability ratio of 7.6 and fairly high oxygen permeability of 28 × 10^?10 cm³ cm/cm² s cm Hg of the membrane which was cast from the degassing polymer solution, with 20% degree of MMA grafting, can be obtained. Also the membrane for high oxygen permeability of 63 × 10^?10 cm³ cm/cm² s cm Hg with an O₂/N₂ permeability ratio of 4.5, which was cast from the polymer solution with dissolved oxygen, can be obtained under the condition of 60 h irradiation time and about 7% degree of grafting. O₂/N₂ selectivity of TPX membrane can be improved by homografting method with lower MMA grafting degree than that of heterografting method.