The delayed crosslinking amphiphilic polymer gel system based on multiple emulsion for in-depth profile control

Delayed crosslinking polymer gel systems are widely used in-depth profile control technology for water production control. In this paper, an amphiphilic polymer P(AM-NaA-DDAM) was synthesized by a free radical micellar polymerization method and a delayed crosslinking amphiphilic polymer gel system was prepared based on multiple emulsion of W₁/O/W₂ emulsion which was prepared by a two-step emulsification method. The optimized formulation of amphiphilic polymer gel systems is: 0.15% P(AM-NaA-DDAM), 0.3% methenamine, 0.02% resorcinol, and 0.3% citric acid. The delayed gelation time of the delayed crosslinking amphiphilic polymer gel system is closely related to the stability of the W₁/O emulsion. By using multiple emulsion delayed crosslinking method, the delayed crosslinking amphiphilic polymer gel system with diesel as the oil phase can delay the gelation time up to 168 hours.     

Characterization of resulting network polymer precursors in stepwise crosslinking diepoxide/diamine polymerization

Our previous mechanistic discussion of network formation in chainwise crosslinking multiallyl polymerization was extended to stepwise crosslinking diepoxide/diamine polymerization, typically including bisphenol‐A diglycidyl ether (BADGE) and 4,4′‐diaminodiphenylmethane (DDM). In allyl polymerization a monomer chain transfer is an essential termination reaction, providing only oligomeric primary polymer chains. Therefore, crosslinking multiallyl polymerization could be in the category of a classical gelation theory. Thus, the gelation behavior was discussed by comparing the actual gel point with the theoretical one. Then the resulting network polymer precursors (NPPs) were characterized by size‐exclusion chromatography‐multiangle laser light scattering‐viscometry to clarify the stepwise crosslinking BADGE/DDM polymerization mechanism. Notably, the intrinsic viscosity ratio [η]_NPP/[η]_Linear tended to decrease with the progress of crosslinking and finally, it reached less than 0.2. This suggests that the structure of resulting NPP becomes dendritic at a conversion close to the gel point. These dendritic NPPs can collide with each other to form crosslinks between NPPs, eventually leading to gelation as a reflection of the high concentration of NPP. The dilution effect on gelation was marked in polar solvent; no gelation was observed at a dilution of 1/5. However, in nonpolar solvent the gelation was promoted by dilution; this is ascribed to enhanced crosslink formation between NPPs through hydrogen bonding due to abundant hydroxyl groups in the NPP generated by the polyaddition reaction. Finally, the subject of “Is cured epoxy resin inhomogeneous?” is briefly discussed. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Effect of Composition of HPAM/Chromium(III) Acetate Gels on Delayed Gelation Time

A delayed crosslinking system employed with hydrolyzed polyacrylamide (HPAM) and chromium acetate was developed for high profile control in low-temperature reservoirs. The crosslinking system formed strong gel at polymer concentration range of 3000–5000 mg/L, and the gelation time was delayed to 8–30 days, which offered the crosslinking system enough time to flow into deep water-producing zones and plug large pore paths, forcing follow-up fluids to enter low-permeability layer and reduce disproportionate permeability. The effect of polymer hydrolysis degree, polymer concentration, pH, and crosslinker concentration on delaying gelation time was evaluated using bottle testing. Meanwhile, sand-packed tube displacement experiments revealed the plugging performance of delayed crosslinking system. According to Fourier transform infrared spectroscopy (FTIR) analysis, as well as crosslinking mechanism between polymer and chromium acetate, the delayed mechanism of crosslinked system demonstrated that due to stronger affinity of acetate complexes as a ligand, its substitution in situ by carboxylate group of polyacrylamide slowed down the initial rate-determining step of crosslinking reaction.     

Radiation-induced polymerization at high dose rate. V. Butadiene in bulk

Bulk butadiene was polymerized by a cationic mechanism in a wide dose rate range. The M?_n of the product was about 2300, independent of dose rate. The polymer had 83% residual unsaturation and the remaining double bond was 77% trans and 23% vinyl and had no cis unit. When the polymer yield exceeded 10% gel was formed, but the value of the residual unsaturation in the polymer remained unchanged. This indicated a mechanism that correlated propagation, cyclization, and crosslinking reactions with a cationic intermediate.     

Gel growth in free radical crosslinking copolymerization: Effect of inactive gel radicals

A kinetic model is presented for the post‐gelation period of free‐radical crosslinking copolymerization. The model takes into account the trapped radical centers in the gel forming system. It was shown that the weight fraction of sol, W_s, relates to the number of crosslinked units per weight‐average primary molecule, ε, through the equation where n = 2 for Flory's most probable molecular weight distribution, and n = 3 for primary molecules formed by radical combination. Calculation results demonstrate that the existence of trapped radicals significantly affects the growth rate of the gel molecule. It increases the total radical concentration and accelerates the gel growth. The difference in the predictions with and without considering the trapped radicals becomes significant as the crosslinker concentration decreases or, as the vinyl group reactivity on the crosslinker or on the polymer decreases.     

Photocrosslinking reaction of vinyl‐functional polyphenylsilsesquioxane sensitized with aromatic bisazide compounds

Photochemical reactions of aromatic azide groups were applied for a novel photosensitive silicone ladder polymer, that is, partially vinyl‐substituted polyphenylsilsesquioxane sensitized with aromatic bisazide compounds as a photocrosslinker. The photocrosslinking reaction in this system was investigated from the viewpoint of the efficiency of the photocrosslinker, that is, the ratio of the photocrosslinker consumed for crosslinking. The numbers of photodecomposed azide groups and crosslinks in the polymer were determined by Fourier transform infrared measurements. At a higher bisazide concentration, the predominant reaction of nitrenes formed as the intermediary radical by the photolysis of azide was a coupling reaction that could not contribute to the gelation of the polymer. The ratio of the bisazide compound consumed for crosslinking showed the highest value at its concentration of 3 wt % and decreased with the addition of a larger amount. The semiempirical molecular orbital calculations were applied to the theoretical analysis of the photoreaction of nitrenes using phenylnitrene as a model structure. The calculation results indicated that the coupling reaction of nitrenes should proceed more easily than the photocrosslinking reaction in N₂ atmosphere, and the fact that the oxidation of nitrenes should proceed exclusively in the atmosphere including O₂ agreed with the experimental results. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 4196–4205, 2001     

流变学法研究部分水解聚丙烯酰胺/Cr(III)交联反应I.浓度的影响

采用流变学法系统地考察了部分水解聚丙烯酰胺（HPAM）/Cr(III)交联体系的 反应动力学。HPAM溶液的粘性模量G”大于弹性模量G’,且其数值随时间不发生变 化,体系为粘性溶液。而HPAM/Cr(III)体系的G’和G”的数值都随时间变化,G” 在反应开始阶段大于G’,当反应进行一段时间后,G’超过G”占据主要地位,体 系成为弹性体系。交联过程可分为三个阶段：第一上升阶段,平缓上升阶段和第二 上升阶段。利用G’～ t曲线可以推测反应机理。实验发现成胶速率随反应物HPAM 和Cr(III)的浓度的增加而增加,而成胶时间缩短。在羧基浓度过量的情况下,交 联反应对Cr(III)浓度的反应级数是1。凝胶的有效弹性交联密度随聚合物浓度的增 加而增,且随凝胶反应的进行而增加。凝胶的交联点间的平均分子量随Cr(III)浓 度的增加和交联反应的进行而下降。     

The Nature of Crosslinking in N‐Vinylformamide Free‐Radical Polymerization

N‐Vinylformamide (NVF) free‐radical polymerization was found to form polymer gels at high conversions both in bulk and in solution. The polymerization was conducted at different temperatures, monomer and initiator concentrations to show the gelation conditions. Gel fractions and gel swelling ratios were also measured after separating the gel from the polymer samples. In order to confirm the crosslinking unit, a series of hydrolysis experiments were conducted on the gel samples. The hydrolysis results showed that the crosslinks in PNVF gels could be destroyed by alkaline hydrolysis. The most appropriate explanation to this fact is that crosslinking takes place via the amide group.     

Study on formation of gels formed by polymer and zirconium acetate

The gel system used in the preparation of dispersed particle gel for water shutoff treatments, which is composed of polyacrylamides and zirconium acetate, was investigated. The gelation process, the effects of various parameters on the gelation properties, the thermal stability, and the microstructure were addressed. The cross-linking reaction process is divided into three successive steps: induction, rapid cross-linking, and stabilization. High polymer and crosslinker concentrations reduce gelation time and increase gel strength. In addition, adding salts to the brine or increasing the temperature also decrease gelation time and increase gel strength. The optimum pH for the gel system is 7.49. In field applications, this gel system is recommended to be used within 130 °C using differential scanning calorimetry. The gel formed in a three-dimensional network structure was confirmed through environmental scanning electron microscopy.     

Aggregation behaviour below the gelation threshold for metal-olefin coordination in diene polymers

This study focuses on aggregation below the gelation threshold in ternary solutions containing diene polymers, atactic 1,2-polybutadiene (PBu) or 3,4-polyisoprene (PI), and an inorganic salt, bis(acetonitrile) dichloropalladium(II). Upon mixing, effective coordination crosslinks are formed because the acetonitrile ligands of the palladium salt are displaced by olefinic pendant groups of the polymers. In all cases, the aggregation kinetics correlate with PdCl₂ concentration because the polymer concentration is 100 times greater than the salt concentration. Aggregation is the process that occurs prior to gelation as the transition-metal salt forms a coordination bridge between two different polymer chains. Differential analysis of the initial aggregation rate on the basis of light scattering data at 45° relative to the incident throughput beam reveals that the ‘true’ order of the coordination reaction is close to unity. This suggests that coordination crosslinking is diffusion-controlled in the early stages of aggregation. Half-life analysis of viscous solutions yields an overall reaction order of 1.6 for aggregation of polybutadiene and palladium chloride in tetrahydorfuran (THF). Scaling analysis of the weight-average molecular weight dependence of the root-mean-square size of isolated scattering particles yields an effective exponent of 0.7 for polymer/metal-salt complexes at infinite dilution. This experimental scaling law agrees with literature values for cross-linked polymer networks. In all cases, the size of the aggregates increases at higher PdCl₂ concentration. For polybutadiene/PdCl₂ mixtures in THF or toluene below the gelation threshold, the light-scattering-detected average aggregation number (AN = M_{w, complex}/M_{w, pure polymer} via Zimm-plot intercepts) for low-viscosity solutions is 2, while AN ∼ 9 for viscous THF solutions. In contrast, low aggregation numbers (AN ∼ 2) were calculated for viscous ternary mixtures of 3,4-polyisoprene and PdCl₂ in THF.     

Topological bonding formation between an ultra‐high molecular weight linear polymer and a prepolymer at an early stage of free‐radical crosslinking polymerization

The free‐radical crosslinking polymerization of diallyl adipate (DAA) was carried out in the presence of poly(benzyl methacrylate) (poly(BzMA)) as a chemically inactive polymer in order to clarify the topological bonding formation between linear polymer and prepolymer before gelation; we found by chance that even at an early stage of the polymerization, the topological bonding was formed between ultra‐high molecular weight poly(BzMA) and poly(DAA) prepolymer.     

Effect of SDS on the gelation of hydroxypropylmethylcellulose hydrogels

Thermal behavior of aqueous hydroxypropylmethylcellulose (HPMC)/surfactant mixtures was studied in the dilute concentration regime using micro-differential scanning calorimetry (DSC). The surfactant used was sodium n-dodecyl sulfate (SDS). The heat capacity of HPMC gel with various concentrations of SDS was much higher than that of the pure HPMC gel. The addition of SDS at different concentrations showed dissimilar influences on the gelation of HPMC; SDS at lower concentrations (≤6 mM) did not affect gelation temperature significantly except for enhancing the heat capacity whilst SDS at higher concentrations (≥6 mM) not only resulted in the gelation of HPMC at higher temperatures but also changed the pattern of the gelation thermograph from a single mode to a bimodal. On the basis of the observed thermal behavior of HPMC/SDS systems, the mechanism behind the sol-gel transition was discussed in terms of the properties of the surfactant and their influences on the extent of polymer/surfactant binding and polymer/polymer hydrophobic association. Gelation kinetics was analysed using the results from the DSC measurements. The kinetic parameters were determined.     

间规聚丙烯过氧化物在多官能团单体存在下的交联

过氧化物交联;交联动力学;间规聚丙烯过氧化物在多官能团单体存在下的交联     

Effect of hydrogen bonds on gelation by introduction of carboxyl groups in the free‐radical crosslinking copolymerization of butyl methacrylate with 1,6‐hexanediol dimethacrylate

The preliminary study of the effect of physical crosslinking on the gelation in monovinyl/divinyl copolymerizations is described. Thus, mono(2‐methacryloyloxyethyl) succinate was added to the crosslinking copolymerization of butyl methacrylate with 1,6‐hexanediol dimethacrylate and the gelation was explored in terms of the effect of hydrogen bonds formed between carboxyl groups introduced into the primary polymer chain.     

Effect of Acetylene on the γ-Ray Crosslinking Polymerization of Various Kinds of Acrylic Monomers

The γ-radiation-induced crosslinking polymerization of methyl methacrylate (MMA), methacrylic acid (MAA), 2-hydroxyethyl methacrylate (HEMA), methyl acrylate (MA), and acrylic acid (AA) was carried out in bulk. The polymerization rates of AA and HEMA were much larger than those of other monomers. Acetylene had no influence on the polymerization rate in the initial stage, and the rate was dependent only on the kinds of monomers. In the absence of acetylene, gelation took place in PMA, PAA, and PHEMA obtained at complete conversion, but not in PMMA and PMAA. By the addition of acetylene, complete gelation of PMMA was observed, but no gel formation was observed for PMAA. Volume and weight swelling ratios were measured for PMA, PAA, PHEMA, and PMMA with complete gelation. It was found that by the addition of acetylene the molar concentration of crosslinks increased as much as about twice for PMA and PHEMA, and over about one hundred times for PMMA AND PAA. The relation between volume S_v and weight swelling ratio S_w was studied theoretically. S_v was expressed by the the equation, S_v = (p_p /p+)S_w+ (1 -p_p/p_s), as a function of S_w and the densities of pure polymer (p_p) and solvent (p_s) in swollen polymer.     

Temperature-induced association and gelation of aqueous solutions of pectin. A dynamic light scattering study

Dynamic light scattering (DLS) measurements were carried out on aqueous solutions of low-methoxyl pectin at different temperatures and polymer concentration. Low temperature and increased polymer concentration promote the formation of multichain aggregates. The time correlation data obtained from the DLS experiments revealed, for all polymer solutions, the existence of two relaxation modes, one single exponential at short times followed by a stretched exponential at longer times. In the semidilute regime, a temperature reduction induced enhanced chain associations in the solutions with high values of the slow relaxation time and a strong wave vector dependence of the slow mode. These features could be rationalized in the framework of the coupling model of Ngai. At low temperatures (10 °C), gelation occurs in the semidilute regime and a transparent gel is formed. In this state, the profile of the correlation function changes and nonergodic signs are observed. The conjecture is that the association complexes and the gel network are stabilized through intermolecular hydrogen bonds, which are broken-up at higher temperatures. The hydrogen-bonded structures are formed in a process where the polymer chains have been “zipped” together in a cooperative manner.     

Radiation-induced crosslinking of polyvinyltrimethylsilane in the presence of ethylene glycol dimethacrylate and allyl methacrylate

Radiation-induced crosslinking of homogeneous glassy polyvinyltrimethylsilane was carried out either by the γ-irradiation of the polymeric films containing 3–20 wt% of ethylene glycol dimethacrylate or by the radiation-induced grafting of allyl methacrylate from vapour phase onto films made of pure polymer. The dependence of grafting value on the absorbed γ-irradiation dose and film thickness was investigated. The modified films were analyzed for the sol/gel content and the dependence of gel fraction yield of crosslinked polymer on absorbed dose, concentration of the crosslinking agents and film thickness.The radiation-chemical yields of crosslinking and degradation as well as gelation doses were calculated. The permeability of oxygen and nitrogen through the crosslinked films was determined.     

Induced changes of polymer organization in a gel of poly(vinyl alcohol) crosslinked by Congo red

Different gel microstructures are induced at variable poly(vinyl alcohol) (PVA) and Congo red concentrations, as revealed by ultrarapid freezing and a replica technique for transmission electron microscopy. The polymer microstructures observed include random coils, rigid polymer rods, and long fibers. The development of the different polymer conformations is proposed to be dependent on the degree of intramolecular and intermolecular crosslinking and on the electrostatic interactions of the Congo red ions. The rigid‐rod conformation appears to be the most energetically stable form; it is disrupted by electrostatic effects around the polymer overlap concentration (C*_PVA). We propose that the gel microstructure influences the physical properties of the gel. Gels possessing the rigid‐rod microstructure have increased Young's storage modulus values. Two possible mechanisms of gelation are suggested. The first describes a one‐stage reaction when the polymer concentration approximates C*_PVA, where polymers in an extended random‐coil conformation undergo intermolecular crosslinking without any microstructural changes. The second describes a two‐stage reaction when the polymer concentration is less than or greater than C*, where a disorder–order transition results in the formation of rigid polymer rods and fibers followed by the formation of a macromolecular network. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1471–1483, 2001     

Effect of mixed solvent on solution properties and gelation behavior of poly(vinyl alcohol)

In this work, the static and dynamic light scattering measurements were used to investigate the solution properties and the aging effects on PVA/DMSO/water ternary system in dilute region at 25 °C. It was found that the phase separation and aggregate behavior occurs rapidly and obviously when DMSO mole fraction (X₁) in the solvent mixture is between 0.2 and 0.33, especially at 0.25. In this solvent composition range, a broad peak which indicates phase separation and chain aggregation can be observed from static light scattering measurement. However, when DMSO mole fraction is increased to 0.37, no such peak is present. For this ternary system, the gelation mechanism and the relationship between the phase separation behavior and the gelation of the formed physical gels were also investigated through the gelation kinetic analyses in the dilute and semi-dilute region. It is concluded that the cononsolvency effect in the dilute solution is not the sole origin that affects the phase separation, aggregation, and gelation behavior for the ternary system in a higher polymer concentration range. The hydrodynamic factors such as the higher viscosity and slower polymer chain diffusion that are resulted from higher polymer concentration should be also considered.     

多官能团乙烯基单体原子转移自由基交联聚合机理

乙烯基单体;原子转移自由基交联聚合;聚合机理;交联网络