Effect of Polyisobutylene Succinimide on the Physical Stability of an Environmentally Friendly Pesticide Oil Dispersion Suspension

Oil dispersible suspension concentrates are safe,green,and environmentally friendly formulations.Problems such as layering,pasting,and bottoming are frequently encountered during the production,storage,and transportation process.Polyisobutylene succinimide functions as a dispersant and exhibits great potential to improve the physical stability of the oil dispersible suspension concentrate.From a microscopic perspective,the sorption characteristics of the polyisobutylene succinimide dispersant T151 on penoxsulam particle surfaces were comprehensively evaluated with XPS,FTIR,and SEM.The T151 adsorption procedure complied with a pseudo-second-order kinetic adsorption model,and it was a kind of physical sorption with an Ea of 22.57 kJ⋅mol^(−1).The T151 sorption model was consistent with the Langmuir isotherm.The adsorption process was spontaneous and followed by an entropy increase.TheΔH^(θ)of dispersant T151 on the surface of penoxsulam particles was 31.59 kJ⋅mol^(−1).The adsorption procedure was endothermic,and the primary force was hydrogen bonding.The XPS results showed that the F and S electronic peaks at the penoxsulam interface decreased,and that the C electronic peak increased significantly after the adsorption of dispersant T151,indicating the adsorption on the surface of penoxsulam particles.The results of this study provide a vital theoretical basis for the application of polyisobutylene succinimide dispersants in oil dispersible suspension systems.

SYNTHESIS OF POLYISOBUTYLENE WITH SEC-ARYLAMINO TERMINAL GROUP BY COMBINATION OF CATIONIC POLYMERIZATION WITH ALKYLATION

The highly reactive polyisobutylenes(PIBs) withα-double bonds(87.5 mol%) or tert-chloro(tert-Cl) groups(95 mol%) could be prepared via the cationic polymerization of isobutylene(IB) coinitiated by BF_3 or TiCl_4 respectively.The Friedel-Crafts alkylation of diphenylamine(DPA) with the highly reactive PIB withα-double bonds was further conducted under different conditions,such as at different alkylation temperature,in the mixed solvents of CH_2Cl_2/n-hexane with different solvent polarity and at DPA concentr...

Synthesis and Properties of Hydroxytelechelic Polyisobutylenes by End Capping with tert-Butyl-dimethyl-(4-methyl-pent-4-enyloxy)-silane

The low-activity cationic monomer tert-butyl-dimethyl-(4-methyl-pent-4-enyloxy)-silane was synthesized by Grignard reaction and hydroxyl-protection reaction. Living polyisobutylene chains were initially synthesized by controlled cationic polymerization and then capped with tert-butyl-dimethyl-(4-methyl-pent-4-enyloxy)-silane. The hydrolysis of these polyisobutylenes end capped with tert-butyl-dimethyl-(4-methyl-pent-4-enyloxy)-silane gave rise to hydroxytelechelic polyisobutylene. NMR analysis confirmed that the hydrolysis was complete. Results also showed that a low polymerization temperature favored the participation of tert-butyl-dimethyl-(4- methyl-pent-4?enyloxy)-silane in the end-capping reaction. Moreover, polyisobutylene-based polyurethane exhibited greater acid resistance than commercial polyurethane.

SYNTHESIS OF HIGH MOLECULAR WEIGHT POLYISOBUTYLENE VIA CATIONIC POLYMERIZATION AT ELEVATED TEMPERATURES

A novel simple but effective initiating system of H2O/AlCl3/veratrole （VE） has been developed to synthesize high molecular weight polyisobutylene （PIB） at elevated temperatures via cationic polymerization of isobutylene （IB） in solvent mixture of hexane/methylene dichloride （n-Hex/CH2Cl2 = 2/1, V/V）. VE played very important roles in decreasing cationicity of the growing chain ends, suppressing side reactions of chain transfer and termination during polymerization, leading to production of high molecular weight PIBs. PIBs with high yields, having very high weight-average molecular weight （Mw） of 1117000 and 370000 g/tool could be synthesized with H2O/AICl3/VE initiating system at VE concentration of 5.4 mmol/L at -80 and -60 ℃ respectively. Molecular weight of PIB increased remarkably with increasing VE concentration. The reaction order with respect to VE concentration was determined to be -3.52 via FTIR spectroscopy in combination with a diamond tipped attenuated total reflectance （ATR） immersion probe. The negative reaction order of VE was consistent with its retarding effect on IB polymerization by interacting with the propagating species. Molecular weight of PIB decreased with increasing polymerization temperature. The activation energy for polymerization degree （Eop） could be determined to be around -23 kJ/mol when VE concentration was 5.4 mmol/L or 6.4 mmol/L.

Controlling Heat Transfer for the Manufacturing of High Molecular Weight Polyisobutylene via Formation of Micelles

An alternative cationic polymerization method is developed to produce high molecular weight polyisobutylene (HM-PIB) with molecular weights above 5×10^5g/mol. The method involves micelle formation via functionalized low molecular weight polyisobutylene (LM-PIB) in non-polar solvent. One end of LM-PIB is modified with an imidazolium-containing ionic group, which together with the anion (eg. Al2Cl7) works as Lewis acid. While the monomer isobutylene dissolves readily in non-polar solvent, polymerization can occur only within the micelle, which affords stable HM-PIB particles. HM-PIB with a molecular weight (MW) close to 1 × 10^6 g/mol was produced successfully with the described method.

SYNTHESIS OF pH-RESPONSIVE AMPHIPHILIC DIBLOCK COPOLYMERS CONTAINING POLYISOBUTYLENE via OXYANION-INITIATED POLYMERIZATION AND THEIR MULTIPLE SELF-ASSEMBLY MORPHOLOGIES

Two pH-responsive amphiphilic diblock copolymers, namely polyisobutylene-block-poly[2-（N,N- dimethylamino）ethyl methaerylate] （PIB-b-PDMAEMA） and polyisobutylene-block-poly（metharylic acid） （PIB-b-PMAA）, were synthesized via oxyanion-initiated polymerization, and their multiple self-assembly behaviors have been studied. An exo-01efin-terminated highly reactive polyisobutylene （HRPIB） was first changed to hydroxyl-terminated PIB （PIB-OH） via hydroboration-oxidation of C =C double bond in the chain end, and then reacted with KH to yield a potassium alcoholate of PIB （PIB-O-K＋）. PIB-O-K＋ was immediately used as a macroinitiator to polymerize DMAEMA monomer, resulting in a cationic diblock copolymer PIB-b-PDMAEMA. With the similar synthesis procedure, the anionic diblock copolymer PIB-b- PMAA could be prepared via a combination of oxyanion-initiated polymerization of tert-butyl methacrylate （tBMA） and subsequent hydrolysis of tert-butyl ester groups in PtBMA block. The functional PIB and block copolymers have been fully characterized by 1H-NMR, FT-IR spectroscopy, and gel permeation chromatography （GPC）. These samples allowed us to systematically investigate the effects of block composition on the pH responsivity and various self-assembled morphologies of the copolymers in THF/water mixed solvent. Transmission electron microscopy （TEM） images revealed that these diblock copolymers containing small amount of original PIB without exo-olefin-terminated group are able to self-assemble into micelles, vesicles with different particle sizes and cylindrical aggregates, depending on various factors including block copolymer composition, solvent polarity and pH value.

SYNTHESIS OF HIGHLY REACTIVE POLYISOBUTYLENES WITH BF_3·CYCLOHEXANOL INITIATING SYSTEM

The selective cationic polymerization of isobutylene （IB） initiated by a BF3-cyclohexanol （CL） complex was carried out from the mixed Ca fraction feed containing the 4C saturated and unsaturated hydrocarbons at -20℃. The effects of CL concentration, BF3 concentration, solvent for preparing BF3·CL complex and polymerization time on the chemical structure of end groups, number-average molecular weight （Mn） and molecular weight distribution （MWD, Mw/Mn） of the resulting polymers were investigated. The experimental results indicate that the BF3·CL complex initiating system exhibited an extremely high selectivity toward the cationic polymerization of IB in the mixed C4 fraction feed and low molecular weight （Mn = 900-3600） polyisobutylenes （PIBs） with large proportion of exo-double bond end groups were obtained. The exo-double bond content in PIB chain ends increased by increasing CL concentration or by decreasing solvent polarity in initiating system, BF3 concentration and polymerization time. The M, and MWD of the resulting PIBs were dependent on the concentrations of CL and BF3. Highly reactive PIBs with around 90 mol% of exo-double bonds were successfully synthesized by the selective polymerization of IB from the mixed Ca fraction feed, providing a potentially practical process for its simplicity and low costs.

The use of polyisobutylene-based polymers in ophthalmology

A novel polyolefin called poly(styrene-block-isobutylene-block-styrene)(“SIBS”)originated from Joseph P.Kennedy’s laboratory at the University of Akron(Akron,Ohio,United States)and was developed as a biomaterial for long-term implant applications by the author.SIBS has no cleavable groups on its backbone or sidechains,is comprised predominantly of alternating secondary and quaternary carbons on its backbone,which prevents embrittlement and cracking under flexion,and undergoes multiple purification steps which renders it extremely biocompatible and well-suited for long-term applications in the eye.This article explores two ophthalmic devices;1)the PRESERFLO®MicroShunt(Santen Pharmaceutical Co.Ltd.,Osaka,Japan)made from SIBS that lowers intraocular pressure to thwart progression of vision loss from glaucoma,and 2)a novel intraocular lens(IOL)made from crosslinked polyisobutylene,which is under-development by Xi’an Eyedeal Medical Technology Co.,Ltd.(Xi’an,China)that does not glisten nor cloud over time,as do most conventional IOLs.

The Effect of Reaction Conditions on the Synthesis of Thermoplastic Elastomers Containing Polyalloocimene, Polyisobutylene and Tapered Blocks

This work investigates the effect of reaction conditions on the copolymerization of isobutylene (IB) with alloocimene (Allo) in methyl chloride (MeCl) using AlCh and ethylaluminum dichloride (EtAlCh) as coinitiators and adventitious moisture as the initiator. Both AlCh and EtAlCb produced high molecular weight (Mn > 1.0 x 10^5 g/mol) thermoplastic elastomers (TPEs) with good mechanical properties in short reaction time (< 10 min). These unique TPEs have unsaturations in the end blocks, leading to easy functionalization and/or crosslinking.

Biocompatible,Hemocompatible and Antibacterial Acylated Dextran-g-polyisobutylene Graft Copolymers with Silver Nanoparticles

The novel amphiphilic acylated dextran-g-polyisobutylene(AcyDex-g-PIB)graft copolymers with different branch lengths(A4nPtB,2600-5800 g/mol)and grafti ng numbers(GN,5-28 per 1000 Dex mono saccharide)were successfully synthesized via the nu cleophilic substitution of the hydroxyl(-OH)side groups along AcyDex backb one by the living PIB-THF4+chai ns prepared through cati onic polymerizatio n.The crystallizati on of AcyDex backb one in AcyDex-g-PIB graft copolymers was con fined due to the prese nee of PIB branches and the morphology changed from short rod-like crystals to fragment-like crystals with increasing Mn P|B and GN.The obvious microphase separation occurred due to the incompatibility between hard AcyDex backbone and soft PIB branches.AcyDex-g-PIB graft copolymers exhibit excellent biocompatibility towards HeLa cells and good hemocompatibility with red blood cells(RBCs),both of which increase with increasing GN.The in creases of water con tact angle and roughness on the surface of the graft copolymers with in creasi ng A4nP|B and GN manifest the anti-protein adsorption performance.The amphiphilic AcyDex-g-PIB graft copolymers could self-assemble in aqueous solution into nanospheres,which can be used as pH-sensitive drug carriers and can release 100%of the loaded drug within 72 h at pH=7.4.AcyDex-g-PIB graft copolymers bearing silver nanoparticles(Ag-NPs,0.8 wt%-3.9 wt%,4.5-9.5 nm)show good antibacterial properties.This kind of amphiphilic graft copolymer would have a promising prospect in biological and medical fields.

Amphiphilic Graft Copolymers of Hydroxypropyl Cellulose Backbone with Nonpolar Polyisobutylene Branches

The novel amphiphilic graft copolymers with hydrophilic hard polar hydroxypropyl cellulose(HPC)backbone and hydrophobic soft nonpolar polyisobutylene(PIB)branches have been successfully synthesized through nucleophilic substitution reaction of living PIB chains carrying oxonium ions with the-OH groups along HPC backbone.The PIB branch length in the graft copolymers could be designed by living cationic polymerization and the grafting density could be adjusted by PIB+/-OH molar ratio.The living PIB chains carrying oxonium ion were prepared by transformation of allyl bromide end groups in the presence of AgCI0_(4) and silver nanoparticles(3.2±0.3 nm,0.7 wt%-1.8 wt%)generated in situ from AgBr.The phase-separation morphology was formed in the graft copolymers due to their incompatibility between backbone and branches.The hydrophilicity on the surface of graft copolymer films could be turned to hydrophobicity by increasing grafting density or/and length of PIB branches.The soft PIB segments in graft copolymers provided an unique surface wa self-assembly for ant卜protein adsorption against bovine serum albumin.A small amount of Ag nanoparticles in the copolymers contributed to good antibacterial activities against Staphylococcus aureus or Escherichia coli.

CATIONIC POLYMERIZATION OF ISOBUTYLENE COINITIATED BY AICI_3 IN THE PRESENCE OF ETHYL BENZOATE

The cationic polymerizations of isobutylene （IB） coinitiated by AlCl3 were carried out in solvent mixture of nhexane/methylene dichloride （n-hex/CH2Cl2） of 60/40 V/V in the presence of ethyl benzoate （EB） at various temperatures range from -80℃ to -30℃. The effects of EB concentration （[EB]） and polymerization temperature on monomer conversion, weight-average molecular weight （Mw） and molecular weight distribution （MWD, Mw/Mn） of polyisobutylene （PIB） products were investigated. The rate of polymerization decreased while Mw of PIB products increased with increasing [EB]. The polymers with high molecular weight could be prepared in the presence of a suitable amount of EB. Significantly, the polymers with high Mw of 80.2 × 10^4 and 65.4 × 10^4 could be produced at -80℃ and -70℃ at [EB] = 0.24 × 10^3 mol/L respectively, which were much higher than that （Mw = 57.9 × 10^4） of PIB prepared at -100℃ in the absence ofEB. A simple but effective method for preparing the high molecular weight polyisobutylenes was developed in this work. It has been also found that the activation energy for propagation （Ep） depended on the polymerization temperature range in the presence of EB. An obvious inflection of the linear plots of lnXn versus 1/Tp occurred at the temperature range from -60℃ to -50℃ at four different concentrations of EB from 0.19 × 10^3 mol/L to 0.33× 10^3 tool/L, and thus the inflection temperature （Tinf） was in the range of -60℃ to -50℃. When [EB] was in the range of 0.24 × 10^3 mol/L to 0.33× 10^3 mol/L, Ep was determined to be around -12 kJ/mol when the polymerization was carried out at temperatures from -80℃ to Tinf and to be around -28 kJ/mol at temperatures from Tinf to -15℃ respectively.

Phenols/Al(C_(6)F_(5))_(3) Initiation Systems for Cationic Polymerizations of Isobutylene

We report herein the cationic polymerization of isobutylene(IB)under mild conditions is realized with a new binary initiation system generated by simply mixing a Lewis super acid Al(C_(6)F_(5))_(3) and a substituted phenol(RPhOH).Polymers with medium and/or high molecular weights(M_(W)=4.9×10^(4)-27.7×10^(4) g·mol^(-1))can be obtained in toluene and temperatures from-20℃to 0℃.NMR spectrum analysis and DFT sim ulation reveals the in situ generated acidic coordinating complex Ak(C_(6)F_(5))_(3)·RPhOH is the initiating active species,which fu rther tran sformed into the ion-pair[Al(C_(6)F_(5))_(3)ORPh]^(-)[PIB]^(+)of the active intermediates upon growing IB monomers where the counter anion[Al(C_(6)F_(5))_(3)R^(O)Ph]-coordinates to the macrocation via the phenoxy oxygen.The catalyst performances are the concert effects of the steric bulkiness and electronics of the counter anion on the coordinating strength to the macrocation,which is significant to the stability of the active species.

Functionalized Copolymers of Isobutylene with Vinyl Phenol: Synthesis,Characterization, and Property

The random copolymers of isobutylene (IB) with polar comonomers of 4-acetoxystyrene (ACS) or 4-tert-butoxystyrene (TBO), P(IB-co-ACS) and P(IB-co-TBO), could be successfully synthesized via cationic copolymerization with FeCh-based initiating system. The kinetics of the cationic copolymerization process was in situ investigated by inserting a diamond probe into the reaction system by ATR-FTIR spectroscopy. The chemical structure and incorporation content of polar comonomers in the copolymers were characterized by GPC with RI/UV dual detectors and 1H-NMR spectroscopy. The corresponding functionalized random copolymers of IB with vinyl phenol P(IB-co-POH) carrying phenolic hydroxyl side groups could be further prepared via the complete hydrolysis of acetoxyl side groups in P(IB-co-ACS) or tert-butoxyl side groups in P(IB-co-TBO) copolymers. The functionalized P(IB-co-POH) copolymers became hydrophilic with water contact angle (WCA) of ca. 80° for the self-assembly in hot water, compared to the hydrophobic polyisobutylene with WCA of ca. 110°. The functionalized P(IB-co-POH) copolymers also displayed an excellent self-healing property due to the interaction of intermolecular hydrogen bonding and formation of three dimentional supramolecular networks from phenolic hydroxyl side groups. Furthermore, P(IB-co-POH) copolymers also provided a good matrix for the homogeneous dispersion for silica nanoparticles due to the formation of hydrogen bonding between copolymer chains and silica nanoparticles.

Cationic Polymerization of Isobutylene and C4 Mixed Feed Using Complexes of Lewis Acids with Ethers: A Comparative Study

The cationic polymerization of C4 mixed feed and isobutylene co-initiated by AlCl3xOiPr2,iBuAlC12xnOiPr2, and [emim]Cl- FeCl3xnOiPr2 ([emim]Cl: 1 -ethyl-3-methylimidazolium chloride) has been investigated. AlCl3xOiPr2 co-initiated cationic polymerization of C4 mixed feed proceeds at a lower rate than polymerization of isobutylene affording polymers with higher molecular weight. Complexes of iBuAlCh with di isopropyl ether of different compositions are more suitable co-initiators than AlCl3xOiPr2 for the synthesis of highly reactive polyisobutylene (HR PIB) from C4 mixed feed due to their higher activity in the polymerization as well as possibility to prepare polyisobutylenes with lower molecular weight and higher content of exo-olefin end groups. However, iBuA1C12 needs activating via addition of external water (initiator) and/or interaction with salts hydrates in order to increase the reaction rate and the saturated monomer conversion.[Emim]Cl-FeC13/iPr2O is a quite promising catalyst for the preparation of HR PIB with high exo-olefin end group content (> 80%) and relatively low polydispersity (Mw/Mn < 2.8) via cationic polymerization of C4 mixed feed. The sonication of reaction mixture in case of using [emim]Cl-FeCh allowed increasing the reaction rate and decreasing the molecular weight.