N-Vinyl Caprolactam/Maleic-Based Copolymers as Kinetic Hydrate Inhibitors: The Effect of Internal Hydrogen Bonding

Abstract

Kinetic hydrate inhibitors (KHIs) have been used for over 25 years to prevent gas hydrate formation in oil and gas production flow lines, but they are some of the most expensive oilfield production chemicals. The main component in KHI formulations is a water-soluble polymer with many amphiphilic groups. Usually, in commercial KHI polymers, the hydrophilic part of these groups is the amide group. In addition, KHI polymers are often incompatible with film-forming corrosion inhibitors. Therefore, we sought to find cheaper but effective KHIs that could also act as a flow line corrosion inhibitor. Continuing earlier work from our group with maleic-based polymers, we have now explored maleic acid/N-vinyl caprolactam (MAcid/VCap) copolymers to introduce VCap, a well-known KHI monomer, together with the cheaper MA monomer. KHI performance screening tests were conducted under high pressure with a structure II-forming natural gas mixture in steel rocking cells using the slow (1 °C/h) constant-cooling test method. Surprisingly, the MAcid/VCap copolymer showed very poor KHI efficacy. GFN2-xTB molecular dynamics simulations revealed that MAcid/VCap exhibits intra-hydrogen bond networks that trap the polymer morphology in the globular form. In this scenario, the caprolactam ring is encapsulated inside the polymer structure due to the intra-hydrogen bonds and the hydrophobic interactions that minimize its ability to interact with the hydrate surfaces, which significantly reduces the MAcid/VCap kinetic inhibition performance. However, the polymer in such globular forms still displays an important amount of its carboxylic groups exposed to water, which explains the water solubility. In contrast to MAcid/VCap copolymers, maleimide derivatives with dibutylamino end groups were effective KHIs and even better with dibutylamine oxide end groups. A terpolymer of MA/VCap reacted with N,N-dibutylaminopropylamine followed by subsequent oxidation of the end groups to dibutylamine oxide and gave the best performance of any maleic-based polymer reported to date. The combination of caprolactam and dibutylamine oxide groups can be thought of as synergism within the same polymer, akin to the excellent synergy of the separate molecules, tributylamine oxide and PVCap.

Maleic and Methacrylic Homopolymers with Pendant Dibutylamine or Dibutylamine Oxide Groups as Kinetic Hydrate Inhibitors

“…Polymaleic anhydride (PMA) was made in o -xylene as previously described to give a low-molecular-weight polymer . As the o -xylene forms an end cap, this means the average number of MA monomer units in the polymer is about seven.…”

“…Maleic anhydride (≥99%, Merck), methacryloyl chloride (97%, Sigma-Aldrich), 3-(dibutylamino)-1-propylamine (DBAPA, 98% Sigma-Aldrich), 2-(dibutylamino)-ethanol (DBAE, 99% Sigma-Aldrich), o -xylene (99%, VWR), 2,2′-azobis­(isobutyronitrile) (AIBN, 98%, Sigma-Aldrich), 2-butoxyethanol ( n -BGE, 99%, Acros Organics), 1,2-dimethoxyethane (DME, 99%, VWR), and 2-propanol (iPrOH, 99%, VWR) were used as received. CDCl 3 was purchased from Cambridge Isotope Laboratories, Inc. Synthesis of polymaleic anhydride (PMA, M w = 800, dispersity 3.8) was carried out according to the literature, except that toluene was replaced by o -xylene . Poly­( N -vinyl caprolactam) (PVCap) (MW approximately 2–4 kg/mol) was supplied from BASF as Luvicap EG, a 41.1 wt % solution of the polymer in monoethyleneglycol (MEG).…”

“…Two examples of polymers with good KHI performance are given in Figure 3 that contain the amine oxide from the reaction of maleic anhydride monomer units with 3-(dibutylamino)-1-propylamine (DBAPA). 19,20 DBAPA proved to be a very useful amine to react with maleic anhydride polymers, giving pendant groups that are easily transformed into dibutylamine oxide groups via treatment with hydrogen peroxide. However, we did not explore the amine oxide homopolymers using polymaleic anhydride (PMA).…”

“…We also explored ways to improve the performance of maleic-based copolymers by introducing amine oxide groups. Two examples of polymers with good KHI performance are given in Figure that contain the amine oxide from the reaction of maleic anhydride monomer units with 3-(dibutylamino)-1-propylamine (DBAPA). , …”

Inhibition of Asphaltene Precipitation by Ionic Liquid Polymers Containing Imidazole Pendants and Alkyl Branches

“…Asphaltene deposition often causes pipe blockage in pipelines and coke in oil processing. Asphaltene contains aromatic fused rings and heteroatoms such as S, N, O, and V. − Because of π–π delocalization of aromatic rings, hydrogen bonding, and acid–base interaction between heteroatoms and metal elements, asphaltenes are apt to form disordered nanoaggregates, resulting in precipitation. − …”