Maleation of polylactide (PLA) by reactive extrusion

Free‐radical‐initiated grafting of maleic anhydride (MA) onto a polylactide (PLA) backbone was performed by reactive extrusion. A concentration of 2 wt % MA in the presence of 2,5‐dimethyl‐2,5‐di‐(tert‐butylperoxy)hexane (Lupersol 101) as the free‐radical initiator was used for all experiments. Two reaction temperatures were studied (180 and 200°C) with a peroxide initiator concentration between 0.0 and 0.5 wt %. Under these conditions, between 0.066 and 0.672 wt % MA was grafted onto the PLA chains. Triple‐detector size‐exclusion chromatography (TriSEC), melt flow index (MFI), and thermal gravimetric analysis (TGA) were used to characterize the maleated PLA polymers. Increasing the initiator concentration resulted in an increase in the grafting of MA, as well as a decrease in the molecular weight of the polymer. The maleation of PLA proved to be very efficient in promoting strong interfacial adhesion with corn native starch in composites as obtained by melt blending. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 477–485, 1999     

Graft copolymerization of maleic anhydride onto low‐molecular‐weight polyisobutylene through solvothermal method

The free‐radical graft copolymerization of maleic anhydride (MAH) onto highly reactive low molecular weight polyisobutylene was conducted by the use of benzoyl peroxide as an initiator through the solvothermal method. Fourier transform infrared spectra and ¹H‐NMR spectra confirmed that maleic anhydride was successfully grafted onto highly reactive low molecular weight polyisobutylene backbone, and the grafting mechanism also was proposed. The effect of benzoyl peroxide content, MAH concentration, total reactant amount in the reaction vessels, reaction temperature and time, and different kinds and volumes of solvents on MAH's degree of grafting was investigated in detail. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Co‐agent mediated functionalization of LDPE/iPP mixtures for compatibilization of WEEE‐recovered polyvinylchloride

Mixtures of low density polyethylene/isotactic polypropylene (LDPE/iPP) 80/20 w/w were functionalized in the melt by using maleic anhydride (MAH) as the functionalizing agent, 2,5‐bis(tert‐butylperoxy)‐2,5‐dimethylhexane (L101) as the peroxide initiator and butyl 3‐(2‐furyl)propenoate (BFA) as a co‐agent suitable to prevent the degradation of iPP and to promote inter‐macromolecular reactions. The use of BFA was aimed at favouring the control of radical‐induced side reactions and the formation of interfacial graft copolymers. The functionalization degree and the modification of macromolecular architecture, which were evaluated by selective solvent extractions combined with IR, DSC and SEM analyses, were modulated by varying the L101/MAH/BFA ratio in the feed. The optimized product in terms of functionalization degree value and processability was successfully tested as compatibilizer in a polyolefin/polyvinylchloride mixture, where the polyvinylchloride component resulted from the management of waste of electrical and electronic equipment (WEEE). © 2016 Society of Chemical Industry     

Peroxide‐initiated comonomer grafting of styrene and maleic anhydride onto polyethylene: Effect of polyethylene microstructure

Maleic anhydride has been grafted onto various polyethylenes (PEs) using 2,5‐dimethyl‐2,5‐(di‐t‐butylperoxy)hexane as a free radical initiator in the presence of styrene as a comonomer. Three polyethylenes, differing systematically in their levels of terminal unsaturation and branching, were selected to investigate the effect of these microstructural characteristics on the course of both grafting and crosslinking. It was observed that when polyethylenes containing high levels of terminal unsaturation were reacted in the presence of peroxide or peroxide–maleic anhydride, crosslinking events were enhanced. When styrene was added as comonomer to the reaction medium to eliminate these undesirable side reactions, crosslinking was still observed with those polyethylenes that contained a high concentration of terminal unsaturation. This is attributed to a low reactivity between styrene and the allylic radical generated on the polyethylene backbone, which is believed to be responsible for the increased crosslinking. However, in the presence of high concentrations of styrene, crosslinking was eliminated for PEs containing high degrees of branching. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 96–107, 2001     

Improving the toughening in poly(lactic acid)‐thermoplastic cassava starch reactive blends

Poly(lactic acid) (PLA), a physical blend of PLA and thermoplastic cassava starch (TPCS) (PLA‐TPCS), and reactive blends of PLA with TPCS using maleic anhydride as compatibilizer with two different peroxide initiators [i.e., 2,5‐bis(tert‐butylperoxy)‐2,5‐dimethylhexane (L101) and dicumyl peroxide (DCP)] PLA‐g‐TPCS‐L101 and PLA‐g‐TPCS‐DCP were produced and characterized. Blends were produced using either a mixer unit or twin‐screw extruder. Films for testing were produced by compression molding and cast film extrusion. Morphological, mechanical, thermomechanical, thermal, and optical properties of the samples were assessed. Blends produced with the twin‐screw extruder resulted in a better grade of mixing than blends produced with the mixer. Reactive compatibilization improved the interfacial adhesion of PLA and TPCS. Scanning electron microscopy images of the physical blend showed larger TPCS domains in the PLA matrix due to poor compatibilization. However, reactive blends revealed smaller TPCS domains and better interfacial adhesion of TPCS to the PLA matrix when DCP was used as initiator. Reactive blends exhibited high values for elongation at break without an improvement in tensile strength. PLA‐g‐TPCS‐DCP provides promising properties as a tougher biodegradable film. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46140.     

Grafting of Maleic Anhydride onto Acrylonitrile-Butadiene-Styrene Terpolymer: Synthesis and Characterization

The graft copolymerization of maleic anhydride (MAH) onto a acryloni-trile-butadiene-styrene (ABS) terpolymer was carried out using benzoyl peroxide (BPO) as an initiator and toluene as a solvent. The effects of various parameters such as monomer concentration, initiator concentration, reaction time, and temperature on graft yield were studied. Addition occurs in the butadiene region of the polymer, either by the loss of vinylic hydrogen and subsequent radical formation and addition of monomer or by addition to the double bond. The graft copolymers were characterized by infrared, thermogravirnetric analysis, and differential scanning calorimetry. Thermal stability was improved and T _g was increased.     

线性低密度聚乙烯反应挤出接枝马来酸酐的研究

以过氧化二异丙苯(DCP)为引发剂,在双螺杆挤出机中进行了马来酸酐(MAH)熔融接枝线性低密度聚乙烯(LLDPE)的研究,用红外光谱表征了接枝反应的存在。考察了引发剂用量、单体用量、螺杆转速以及温度对接枝反应的影响,并探讨了苯乙烯(St)作共单体对接枝反应的影响。研究表明:在引发剂含量较低时,用苯乙烯作共单体能够显著提高接枝率。     

Production of alkenyl succinic anhydrides from low‐erucic and low‐linolenic rapeseed oil methyl esters

Fatty acid methyl esters from low‐erucic and low‐linolenic rapeseed oil were used to produce alkenyl succinic anhydrides. A second‐order Doehlert uniform network design was used to investigate the influence of the reaction temperature and the molar ratio between the maleic anhydride and the main unsaturated rapeseed oil methyl esters on the yield of alkenyl succinic anhydride from methyl oleate. Further subjects of investigation were the conversion of methyl oleate, the formation of side reaction products, the Gardner color of the product and its viscosity, and finally the content of maleic anhydride remaining in the medium after the reaction. Alkenyl succinic anhydride from methyl oleate was isolated by column chromatography and analyzed by IR, ¹H‐ and ¹³C‐NMR and MS. The optimal reaction conditions for obtaining the maximum yield of alkenyl succinic anhydride from methyl oleate in the experimental domain (80%) were 210‐220 °C and a maleic anhydride/rapeseed oil methyl ester molar ratio of 1.5. However, the products synthesized in these conditions showed a high degree of viscosity (0.45 kg m^?1 s^?1), a very dark color (18 Gardner color) and a high content of undesirable side products (6%), which could hinder their industrial use. A molar ratio of less than 1.5 led to a clearer and less viscous product, although with a lower alkenyl succinic anhydride content.     

Synthesis and properties of high oil‐absorbent 4‐tert‐butylstyrene‐EPDM‐divinylbenzene graft terpolymer

The graft crosslinking polymerization of 4‐tert‐butylstyrene (tBS) and divinylbenzene (DVB) onto ethylene–propylene–diene (EPDM) was carried out in toluene by using benzoyl peroxide (BPO) as an initiator. The synthesized graft terpolymer, tBS‐EPDM‐DVB (PBED), was extracted with tetrahydrofuran (THF) into gel (called as PBED I) and sol, and then they were identified by infrared (IR) spectroscopy. The effects of solvent amount, molar ratio of DVB to tBS, EPDM content, initiator concentration, reaction temperature, and reaction time on the graft crosslinking polymerization were examined. Among them, solvent amount and molar ratio of DVB to tBS were the important factors for this reaction system. Maximum oil absorbency of PBED I was 84.0 g/g but its oil‐absorption kinetic rate was very low. Sol PBED can be reused as oil absorbent (named as PBED II) through photocrosslinking by ultraviolet light irradiation. Although the oil absorbencies of PBED II were lower than those of PBED I in most cases, their oil absorption kinetic rates were higher than oil absorbencies of PBED I. The highest value of oil absorbency of PBED II was 56.0 g/g. The thermal stability of PBED I was studied by TGA. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2119–2129, 2002     

Synthesis and characterization of solid‐phase graft copolymer of polypropylene with styrene and maleic anhydride

Polypropylene (PP) was modified by solid‐phase graft copolymerization with maleic anhydride (MAH) and styrene (St), using benzoyl peroxide as the initiator and xylene as the interfacial agent. Effects of various factors such as monomer concentration, monomer ratio, initiator concentration on grafting percentage, and acid value were investigated. The graft copolymer was characterized by Fourier transform infrared, pyrolysis gas chromatography—mass spectroscopy, and dynamic mechanical analysis, and the intrinsic viscosity of the extractive from the reaction product was investigated. The results showed that the grafting percentage and acid value of the graft copolymer of PP with two monomers (MAH and St) were considerably higher than those of the graft copolymer of PP with MAH alone. The graft segments were shown to be the copolymer of St and MAH with a substantial molecular weight. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2482–2487, 2000     

Supercritical fluid process for the synthesis of maleated poly(vinylidene fluoride)

Poly(vinylidene fluoride) was grafted with maleic anhydride monomer via a free‐radical mechanism in supercritical carbon dioxide medium. The free‐radical initiator chosen for this study was benzoyl peroxide. The structure of the resultant copolymer pendant groups was determined by ¹H NMR spectroscopy to consist of individual succinyl anhydride functional groups. The degree of functionalization (graft level) was obtained by FTIR spectroscopy through the correlation of absorbance bands using standard samples. The FTIR analysis indicated increased graft level with monomer loading, reaction temperature, and treatment time; however, initiator loading and reaction temperature showed more‐complex behavior. Graft levels increased at moderate benzoyl peroxide initiator loadings (5.0 wt%) and decreased at the highest initiator loadings (10.0 wt%). POLYM. ENG. SCI., 45:631–639, 2005. © 2005 Society of Plastics Engineers     

Effects of some PVC‐grafted maleic anhydrides (PVC‐g‐MAs) on the morphology,and the mechanical and thermal properties of (alfa fiber)‐reinforced PVC composites

This work studied the poly(vinyl chloride) (PVC) chemically modified with maleic anhydride (MA) through reactions in solution, using benzoyl peroxide as an initiator. Quantities of the grafted MA were determined by the titration of carboxylic acid groups derived from the anhydride functions. Estimation of the grafted MA level was also performed by using IR absorbance ratio. Increases in reaction time led to higher levels of grafted MA. The effects of three different PVCs grafted with maleic anhydride (PVC‐g‐MAs) types on the morphological, mechanical, and thermal properties of PVC/alfa (fiber) composites were examined. The interfacial properties between fiber and PVC were improved after the addition of PVC‐g‐MA, as was evident from SEM morphology study. Enhancements of the mechanical properties and thermal stability of the PVC‐g‐MA‐treated composites were strongly dependent on the amount of MA grafts. J. VINYL ADDIT. TECHNOL., 19:225–232, 2013. © 2013 Society of Plastics Engineers     

颜料分散用马来酸酐-乙醇胺-苯乙烯水性高分子助剂的合成

以乙酸乙酯为溶剂,马来酸酐、乙醇胺、苯乙烯为单体,过氧化苯甲酰为引发剂,采用溶液聚合法合成了聚羧酸型马来酸酐–乙醇胺–苯乙烯(MA–EA–St)高分子分散剂,研究了聚合反应温度和时间、引发剂用量及酰化马来酸酐与苯乙烯的摩尔比对TiO2颗粒悬浮率的影响,获得了较佳的聚合反应条件为:n(酰化马来酸酐)∶n(苯乙烯)=1.25,聚合反应温度75°C、时间5 h,引发剂用量占单体总质量的2%。当此条件下合成的MA–EA–St分散剂用量为2.5 g/L时,TiO2颗粒的悬浮率为97.42%,达到较佳的分散效果。     

溶液聚合法合成苯乙烯-马来酸酐交替共聚物

在过氧化苯甲酰(BPO)引发下,以丁酮为溶剂,采用溶液聚合法合成了苯乙烯-马来酸酐共聚物,并详细研究了温度、引发剂用量、苯乙烯与马来酸酐配比、单体(苯乙烯与马来酸酐)质量分数及聚合时间对聚合反应的影响。研究表明,在温度80℃,x(BPO)=0.6%(相对于苯乙烯与马来酸酐),n(苯乙烯)∶n(马来酸酐)=1∶1,w(单体)=15%(相对于混合溶液),反应时间4 h的条件下,聚合物收率可达99%。采用13CNMR、IR、GPC、元素分析对共聚物结构进行了表征。利用TG测定了其热稳定性。结合共聚物的元素分析与13CNMR的分析结果,表明合成的苯乙烯-马来酸酐共聚物是一种交替共聚物。     

Reactive extrusion of polycaprolactone compounds containing wood flour and lignin

Biodegradable polycaprolactone (PCL) was melt‐compounded in a Werner & Pfleiderer twin‐screw extruder (ZSK25) together with wood flour (WF) and lignin with maleic anhydride‐grafted polycaprolactone (PCL‐g‐MA) used as a compatibilizer. The grafting of maleic anhydride onto PCL was achieved with reactive extrusion in the presence of 2,5‐dimethyl‐2,5‐di‐(t‐butylperoxy)hexane as an initiator. The graft copolymers were analyzed with size exclusion chromatography and titration. As a function of the initiator and maleic anhydride addition, the grafted maleic anhydride content varied from 1.4 to 3.1 wt %. Compounds compatibilized with PCL‐g‐MA exhibited improved mechanical properties: a compatibilized PCL compound containing 40 wt % WF gave a Young's modulus of 2300 MPa with respect to 400 MPa for neat PCL and a 100% increase in yield stress. The content of WF, lignin, and PCL‐g‐MA was varied systematically to examine stress–strain and impact behavior. Low contents of grafted maleic anhydride and PCL‐g‐MA were required to improve both mechanical properties and interfacial adhesion. Biodegradation was investigated. Lignin addition was found to retard biodegradation. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1972–1984, 2001     

Bulk modification of styrene–butadiene–styrene triblock copolymer with maleic anhydride

The bulk modification of SBS rubber with maleic anhydride in a mixing chamber of a Haake rheomixer was studied. The effect of temperature, maleic anhydride, and benzoyl peroxide concentrations on the grafting efficiency was evaluated. High grafting efficiency was achieved when the ratio of peroxide and maleic anhydride concentration was high. On the other hand, on this condition high insoluble fraction was generated. The addition of a diamine, 4,4′‐diaminediphenylmethane to the reaction mixture minimizes the amount of insoluble polymer. However, the grafted MAH content also decreases. The graft copolymer was characterized by infrared spectroscopy and the grafting extension was determined by titration. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2953–2960, 2002; DOI 10.1002/app.10355     

The reaction of polypropylene with maleic anhydride

An addition reaction of maleic anhydride with polypropylene takes place in the presence of radical reagents or sunlight. The initial rate of the reaction was proportional to the concentration of polypropylene and maleic anhydride, and one-half power of the concentration of the radical reagents. The increase in the temperature from 80 to 120°C increased the rate of the reaction and di-cumyl peroxide was effective as a radical reagent for this reaction. Ionic crosslinked rubber-like polymers were obtained from the reaction of maleic polypropylene with some alkali metal compounds. They showed the characteristic absorption band due to ? COO^? in their infrared spectra.     

Modification of acrylonitrile‐butadiene‐styrene terpolymer by graft copolymerization with maleic anhydride in the melt. II. Properties and phase behavior

The graft copolymerization of maleic anhydride (MAH) onto acrylonitrile‐butadiene‐styrene terpolymer (ABS) using dicumyl peroxide and benzoyl peroxide as the binary initiator and styrene as the comonomer in the molten state was described. The properties and phase morphologies of the modified products (ABS‐g‐MAH) were studied. The results indicate that the melt flow index (MFI) of ABS‐g‐MAH increases with the increase of MAH content, the initiator concentration, and the screw speed, whereas the MFI decreases with the increase of temperature. The impact strength and the percentage elongation of ABS‐g‐MAH both decreased and the tensile strength of ABS‐g‐MAH increased slightly as the grafting degree increased. The phase inversion behavior of the modified product was observed by transmission electron microscopy. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2834–2839, 2004     

Optimization of the chemoenzymatic epoxidation of soybean oil

The lipase Candida antarctica (Novozyme 435) immobilized on acrylic resin was used as an unconventional catalyst for in situ epoxidation of soybean oil. The reactions were carried out in toluene. The peracid used for converting TG double bonds to oxirane groups was formed by reaction of FFA and hydrogen peroxide. The reaction conditions were optimized by varying the lipase concentration, solvent concentration, molar ratio of hydrogen peroxide to double bond, oleic acid concentration, and reaction temperature. The kinetic study showed that 100% conversion of double bonds to epoxides can be obtained after 4 h. The addition of free acids was not required for the reaction to proceed to conversions exceeding 80%, presumably owing to generation of FFA by hydrolysis of soybean oil. The enzyme catalyst was found to deteriorate after repeated runs.     

Melt grafting of 10‐undecenoic acid onto linear low density polyethylene

The melt grafting of 10‐undecenoic acid (UA) onto a linear low‐density polyethylene (LLDPE) was studied. The grafting reaction was performed in a thermoplastic mixer and 2,5‐dimethyl‐2,5‐di(tert‐butylperoxy) hexane was used as initiator. The concentration of UA and peroxide ranged from 1 to 4% (w/w) and 0.025 to 0.1% (w/w), respectively. Evidence of the grafting of UA as well as its extent was determined by FTIR. Experimental results showed that the amount of UA grafted increases with both the UA and initiator concentrations. However, the greatest efficiency of grafting was found at the lowest concentration of UA investigated. The grafting efficiency ranged from 8 to 40%. The dynamic linear viscoelastic properties of the original polymer and the grafted materials were evaluated at different frequencies at 160°C using a dynamic rotational rheometer. The modification process affected the melt elasticity and viscosity of the LLDPE. When the original polymer was modified only with peroxide both properties increased with respect to those of the original material. However, when UA was grafted onto LLDPE, the resulting polymers displayed values of elastic moduli and viscosity lower than those of the polymer modified with peroxide. Moreover, when a concentration of 4% of UA was used, the values of those properties were even lower than those corresponding to the original LLDPE. These observations combined with the data obtained from the GPC results suggest that scission reactions may be favored by the presence on UA. In contrast with previous observations, the thermal properties measured by DSC were only slightly altered. The fusion temperature of the modified polymers was slightly lower than that corresponding to the original polymer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2303–2311, 2004