A acrylonitrile-maleic anhydride copolymer was pre-pared by precipitation polymerization with(NH<sub>4</sub>)<sub>2</sub>S<sub>2</sub>O<sub>8</sub>-NaHSO<sub>3&l...A acrylonitrile-maleic anhydride copolymer was pre-pared by precipitation polymerization with(NH<sub>4</sub>)<sub>2</sub>S<sub>2</sub>O<sub>8</sub>-NaHSO<sub>3</sub> as oxidation-reduction initiator in water.The effects of polymerization conditions(such as contentof adjustment reagent of molecular weight,concentrationof monomers,reaction time and temperature,ratio ofinitiator to monomer and ratio of reductant to oxidizer inmole)on composition,molecular weight and conversionof the copolymer were investigated.The copolymer wascharacterized with IR and Elementary Analysis.Its ther-mal property and crystallinity were determined with DTAand WAXD,respectively.展开更多
The copolymerization of styrene (St) with maleic anhydride (MAh) under gamma radiation at room temperature in the presence of benzyl dithiobenzoate (BDTB) was found to display 'living' nature evidenced by cons...The copolymerization of styrene (St) with maleic anhydride (MAh) under gamma radiation at room temperature in the presence of benzyl dithiobenzoate (BDTB) was found to display 'living' nature evidenced by constant concentration of chain radicals during the copolymerization, linear evolution of molecular weights with conversion and narrow molecular weight distribution (M-w/M-n = 1.23-1.35). The compositional analysis and the sequence structural information of the copolymers obtained from DEPT (Distortionless Enhancement by Polarization Transfer) experiments demonstrate that the copolymers obtained also possess strictly alternating structure.展开更多
The radical copolymerization of ethylene with vinyl acetate and acrylates is an industrialized method to afford branched functional polyolefins under high temperature and high pressure.Herein,we report the Lewis acid ...The radical copolymerization of ethylene with vinyl acetate and acrylates is an industrialized method to afford branched functional polyolefins under high temperature and high pressure.Herein,we report the Lewis acid B(C6F5)3 promoted radical copolymerization of a broad range of olefins including simple olefins of ethylene and propylene,higher α-olefins,isobutylene,styrene,and others with maleic anhydride(MAH)with high activity under mild conditions to afford alternating copolymers with high molecular weights(M_(w)=32−350 kg mol^(−1))and moderate distributions.The anhydride group can be easily transferred to various functionalities.Mechanism investigation reveals that B(C_(6)F_(5))_(3) activates MAH to reduce the energy barrier for generating the initial radical and stabilizes ethylene and MAH ended radical intermediates throughout the procedure.This is attributed to the moderate Lewis acidity and proper steric bulkiness of B(C_(6)F_(5))_(3),allowing it to reversibly chelate to and disassociate from the carboxyl group of MAH.Thus,a radical polymerization system is constructed,and a practically viable platform to access functional polyolefins is built.展开更多
Spherical polyethylene/polypropylene (PE/PP) in-reactor blend granules with various ethylene/propylene molar ratios and high porosity were synthesized using a high yield TiCVMgCl2 supported catalyst. A solution of ben...Spherical polyethylene/polypropylene (PE/PP) in-reactor blend granules with various ethylene/propylene molar ratios and high porosity were synthesized using a high yield TiCVMgCl2 supported catalyst. A solution of benzoyl peroxide (BPO)/maleic anhydride (MAH)/xylene (interfacial reagent) or BPO/MAH/St (comonomer) was absorbed onto the PE/PP in- reactor blend granules, and solid phase graft polymerization of MAH on PE/PP was conducted. The amount of grafted MAH on PE/PP was measured through chemical titration. The results showed that solid phase graft polymerization of MAH in PE/PP in-reactor blend granules produced graft copolymer with high amount of grafted MAH, and the amount of grafted MAH was raised slightly when St was introduced as comonomer. The graft in-reactor blend was fractionated into five fractions through temperature-gradient extraction fractionation (TGEF), and the fractions were analyzed by FTIR. The results revealed that MAH is mainly grafted on the PE segments, whereas MAH was predominantly grafted on the PP segments when St was present in the graft polymerization system. In addition, the final product is still in the form of regular spherical granules, which is beneficial for industrial processing.展开更多
A novel surface modifying agent and internal compatilizer of inorganic and macromolecule composite materials,P(St/MAH/BA)terpolymer,was synthesized in butanone by solution polymerization method using styrene(St),malei...A novel surface modifying agent and internal compatilizer of inorganic and macromolecule composite materials,P(St/MAH/BA)terpolymer,was synthesized in butanone by solution polymerization method using styrene(St),maleic anhydride(MAH),and butyl acrylate(BA)as monomers and azobisisobutyronitrile(AIBN)as an initiator.Some affecting factors on terpolymers yields such as polymerization time,reaction temperature,solvent volume,initiator content,and reactants ratios were studied.Furthermore,the structure and thermal properties of terpolymers were primarily characterized and determined by Fourier Transform Infrared Spectroscopy(FTIR),nuclear magnetic resonance(NMR),thermogravimetric analysis(TGA),and gel permeation chromatography(GPC).The results indicate that the terpolymers are random polymers and the yields are low,but the thermal decomposed temperature of terpolymers P(St/MAH/BA)is around 220 ℃ and the average molecular weights(Mw)achieve 1.189×105 g·mol-1.展开更多
Slightly crosslinked monodisperse poly(maleic anhydride-cyclohexyl vinyl ether-divinylbenzene) (MA-CHVE-DVB) microspheres were prepared via precipitation polymerization while using 2,2- azobisisobutyronitrile as a...Slightly crosslinked monodisperse poly(maleic anhydride-cyclohexyl vinyl ether-divinylbenzene) (MA-CHVE-DVB) microspheres were prepared via precipitation polymerization while using 2,2- azobisisobutyronitrile as an initiator in a mixture of methyl ethyl ketone and n-heptane without any stabilizer. The number-average diameter of the resultant poly(MA-CHVE-DVB) microspheres ranged from 0.478 to 1.386 μm with a polydispersity index of 1.00 to 1.02 that depended on the feed ratios of the MA/CHVE/DVB monomers. The introduction of one electron donor monomer cyclohexyl vinyl ether strongly affected the yield, size, and morphology of these slightly crosslinked microspheres. Quinoline- type chelating resins were obtained after combining the poly(MA-CHVE-DVB) with 8-hydroxyquinoline; the adsorption properties of these materials were measured through their ability to remove Cu^2+ ions from water. The poly(MA-CHVE-DVB) microspheres with low degrees of crosslinking provided more effective functional groups and therefore better ion removal capabilities. These slightly crosslinked microspheres may have applications in water treatment as well as in sensing and drug delivery.展开更多
The effects of various factors on the synthesis process and the performances of product, including batch feeding way and the dosage of the radical initiator, the system concentration, the reaction temperature and the ...The effects of various factors on the synthesis process and the performances of product, including batch feeding way and the dosage of the radical initiator, the system concentration, the reaction temperature and the reaction time were discussed. A kind of polycarboxylate superplasticizer with allyl alcohol polyethylene glycol, maleic anhydride and methacrylic acid sulfonic sodium as main raw materials has been synthesized. Their relative effectiveness as dispersants was evaluated in cement paste by measuring paste fluidity. The optimum parameters of technology and the appropriate proportion of raw materials were obtained. As a result,the new high performance superplasticizer suitable for high-performance concrete has been synthesized. The structure of copolymer was characterized and analyzed by FT-IR spectra. Results indicated that product copolymer structure was consistent with the ideal molecular structure designed.展开更多
A bipolymer maleic anhydride-methyl acrylate (MAMA) was synthesized from maleic anhydride and methyl acrylate based on molecular design.MAMA further reacted with oleylamine or octadecyl alcohol to generate two comb ...A bipolymer maleic anhydride-methyl acrylate (MAMA) was synthesized from maleic anhydride and methyl acrylate based on molecular design.MAMA further reacted with oleylamine or octadecyl alcohol to generate two comb polymers called Oleamide-MAMA (NMAMA) and OctadecanolMAMA (OMAMA),respectively.The structure of both the polymers was confirmed by their infrared spectral analysis (IR),gel permeation chromatography analysis (GPC) and differential scanning calorimeter (DSC).Moreover,the pour point depressing (PPD) properties of these comb polymers were examined experimentally.Experimental results showed that besides the molecular weight and concentration of the polymers,the length of side chains and the number of functional groups also had great influence on the pour point depressing performance.The π bonds and hydrogen bonds between depressants were the key factors for improving the pour point depressing properties.These results suggest that both OMAMA and NMAMA are potential pour point depressants for industry.展开更多
文摘A acrylonitrile-maleic anhydride copolymer was pre-pared by precipitation polymerization with(NH<sub>4</sub>)<sub>2</sub>S<sub>2</sub>O<sub>8</sub>-NaHSO<sub>3</sub> as oxidation-reduction initiator in water.The effects of polymerization conditions(such as contentof adjustment reagent of molecular weight,concentrationof monomers,reaction time and temperature,ratio ofinitiator to monomer and ratio of reductant to oxidizer inmole)on composition,molecular weight and conversionof the copolymer were investigated.The copolymer wascharacterized with IR and Elementary Analysis.Its ther-mal property and crystallinity were determined with DTAand WAXD,respectively.
文摘The copolymerization of styrene (St) with maleic anhydride (MAh) under gamma radiation at room temperature in the presence of benzyl dithiobenzoate (BDTB) was found to display 'living' nature evidenced by constant concentration of chain radicals during the copolymerization, linear evolution of molecular weights with conversion and narrow molecular weight distribution (M-w/M-n = 1.23-1.35). The compositional analysis and the sequence structural information of the copolymers obtained from DEPT (Distortionless Enhancement by Polarization Transfer) experiments demonstrate that the copolymers obtained also possess strictly alternating structure.
基金supported by the NSFC(Project Nos.22331010,U21A20279).
文摘The radical copolymerization of ethylene with vinyl acetate and acrylates is an industrialized method to afford branched functional polyolefins under high temperature and high pressure.Herein,we report the Lewis acid B(C6F5)3 promoted radical copolymerization of a broad range of olefins including simple olefins of ethylene and propylene,higher α-olefins,isobutylene,styrene,and others with maleic anhydride(MAH)with high activity under mild conditions to afford alternating copolymers with high molecular weights(M_(w)=32−350 kg mol^(−1))and moderate distributions.The anhydride group can be easily transferred to various functionalities.Mechanism investigation reveals that B(C_(6)F_(5))_(3) activates MAH to reduce the energy barrier for generating the initial radical and stabilizes ethylene and MAH ended radical intermediates throughout the procedure.This is attributed to the moderate Lewis acidity and proper steric bulkiness of B(C_(6)F_(5))_(3),allowing it to reversibly chelate to and disassociate from the carboxyl group of MAH.Thus,a radical polymerization system is constructed,and a practically viable platform to access functional polyolefins is built.
基金This work was supported by the Special Fund for Major State Basic Research Projects (Grant no. G1999064803).
文摘Spherical polyethylene/polypropylene (PE/PP) in-reactor blend granules with various ethylene/propylene molar ratios and high porosity were synthesized using a high yield TiCVMgCl2 supported catalyst. A solution of benzoyl peroxide (BPO)/maleic anhydride (MAH)/xylene (interfacial reagent) or BPO/MAH/St (comonomer) was absorbed onto the PE/PP in- reactor blend granules, and solid phase graft polymerization of MAH on PE/PP was conducted. The amount of grafted MAH on PE/PP was measured through chemical titration. The results showed that solid phase graft polymerization of MAH in PE/PP in-reactor blend granules produced graft copolymer with high amount of grafted MAH, and the amount of grafted MAH was raised slightly when St was introduced as comonomer. The graft in-reactor blend was fractionated into five fractions through temperature-gradient extraction fractionation (TGEF), and the fractions were analyzed by FTIR. The results revealed that MAH is mainly grafted on the PE segments, whereas MAH was predominantly grafted on the PP segments when St was present in the graft polymerization system. In addition, the final product is still in the form of regular spherical granules, which is beneficial for industrial processing.
基金Nano Project Foundation of Shanghai Technology Committee,China(No.0652nm039)Shanghai Leading Academic Discipline Project,China(No.B502)Shanghai Key Laboratory Proejct,China(No.08DZ2230500)
文摘A novel surface modifying agent and internal compatilizer of inorganic and macromolecule composite materials,P(St/MAH/BA)terpolymer,was synthesized in butanone by solution polymerization method using styrene(St),maleic anhydride(MAH),and butyl acrylate(BA)as monomers and azobisisobutyronitrile(AIBN)as an initiator.Some affecting factors on terpolymers yields such as polymerization time,reaction temperature,solvent volume,initiator content,and reactants ratios were studied.Furthermore,the structure and thermal properties of terpolymers were primarily characterized and determined by Fourier Transform Infrared Spectroscopy(FTIR),nuclear magnetic resonance(NMR),thermogravimetric analysis(TGA),and gel permeation chromatography(GPC).The results indicate that the terpolymers are random polymers and the yields are low,but the thermal decomposed temperature of terpolymers P(St/MAH/BA)is around 220 ℃ and the average molecular weights(Mw)achieve 1.189×105 g·mol-1.
基金The financial supports from the National Science Foundation of China(Grant No.20774037 and 21304037)Shandong Excellent Young Scientist Research Award Fund(No.BS2013CL039)
文摘Slightly crosslinked monodisperse poly(maleic anhydride-cyclohexyl vinyl ether-divinylbenzene) (MA-CHVE-DVB) microspheres were prepared via precipitation polymerization while using 2,2- azobisisobutyronitrile as an initiator in a mixture of methyl ethyl ketone and n-heptane without any stabilizer. The number-average diameter of the resultant poly(MA-CHVE-DVB) microspheres ranged from 0.478 to 1.386 μm with a polydispersity index of 1.00 to 1.02 that depended on the feed ratios of the MA/CHVE/DVB monomers. The introduction of one electron donor monomer cyclohexyl vinyl ether strongly affected the yield, size, and morphology of these slightly crosslinked microspheres. Quinoline- type chelating resins were obtained after combining the poly(MA-CHVE-DVB) with 8-hydroxyquinoline; the adsorption properties of these materials were measured through their ability to remove Cu^2+ ions from water. The poly(MA-CHVE-DVB) microspheres with low degrees of crosslinking provided more effective functional groups and therefore better ion removal capabilities. These slightly crosslinked microspheres may have applications in water treatment as well as in sensing and drug delivery.
基金Funded by the National Natural Science Foundation of China(No.50972170)
文摘The effects of various factors on the synthesis process and the performances of product, including batch feeding way and the dosage of the radical initiator, the system concentration, the reaction temperature and the reaction time were discussed. A kind of polycarboxylate superplasticizer with allyl alcohol polyethylene glycol, maleic anhydride and methacrylic acid sulfonic sodium as main raw materials has been synthesized. Their relative effectiveness as dispersants was evaluated in cement paste by measuring paste fluidity. The optimum parameters of technology and the appropriate proportion of raw materials were obtained. As a result,the new high performance superplasticizer suitable for high-performance concrete has been synthesized. The structure of copolymer was characterized and analyzed by FT-IR spectra. Results indicated that product copolymer structure was consistent with the ideal molecular structure designed.
文摘A bipolymer maleic anhydride-methyl acrylate (MAMA) was synthesized from maleic anhydride and methyl acrylate based on molecular design.MAMA further reacted with oleylamine or octadecyl alcohol to generate two comb polymers called Oleamide-MAMA (NMAMA) and OctadecanolMAMA (OMAMA),respectively.The structure of both the polymers was confirmed by their infrared spectral analysis (IR),gel permeation chromatography analysis (GPC) and differential scanning calorimeter (DSC).Moreover,the pour point depressing (PPD) properties of these comb polymers were examined experimentally.Experimental results showed that besides the molecular weight and concentration of the polymers,the length of side chains and the number of functional groups also had great influence on the pour point depressing performance.The π bonds and hydrogen bonds between depressants were the key factors for improving the pour point depressing properties.These results suggest that both OMAMA and NMAMA are potential pour point depressants for industry.