Provided herein are poly-1-hydroxymethylethylene hydroxymethyl formal (PHF)-based drug delivery systems. Also disclosed are methods of making antibody-drug conjugates and methods of treatment using these conjugates.

Embodiments of the invention are directed to a macromolecular chemotherapeutic. A non-limiting example of the macromolecular chemotherapeutic includes a block copolymer. The block copolymer can include a water-soluble block, a cationic block, and a linker, wherein the linker is connected to the water-soluble bock and the charged block.

A method of producing a polyether polyol includes reacting a low molecular weight initiator with ethylene oxide in the presence of a polymerization catalyst, and the low molecular weight initiator has a nominal hydroxyl functionality at least 2. The polymerization catalyst is a Lewis acid catalyst having the general formula M(R.sup.1).sub.1(R.sup.2).sub.1(R.sup.3).sub.1(R.sup.4)0 or 1, whereas M is boron, aluminum, indium, bismuth or erbium, R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are each independent, R.sup.1 includes a fluoroalkyl-substituted phenyl group, R.sup.2 incudes a fluoroalkyl-substituted phenyl group or a fluoro/chloro-substituted phenyl group, R.sup.3 includes a fluoroalkyl-substituted phenyl group or a fluoro/chloro-substituted phenyl group, and optional R.sup.4 includes a functional group or functional polymer group, R.sup.1 being different from at least one of R.sup.2 and R.sup.3.

A method of producing an alcohol ethoxylate surfactant or lubricant, the method including reacting a low molecular weight initiator with ethylene oxide in the presence of a polymerization catalyst, the low molecular weight initiator having a nominal hydroxyl functionality at least 1, and the polymerization catalyst being a Lewis acid catalyst having the general formula M(R.sup.1).sub.I(R.sup.2).sub.I(R.sup.3).sub.I(R.sup.4).sub.0 or 1, whereas M is boron, aluminum, indium, bismuth or erbium, R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are each independent, R.sup.1 includes a first fluoroalkyl-substituted phenyl group, R.sup.2 includes a second fluoroalkyl-substituted phenyl group or a first fluoro/chloro-substituted phenyl group, R.sup.3 includes a third fluoroalkyl-substituted phenyl group or a second fluoro/chloro-substituted phenyl group, and optional R.sup.4 includes a functional group or functional polymer group, R.sup.1 being different from at least one of R.sup.2 and R.sup.3. The method further including forming an alcohol ethoxylate surfactant or lubricant having a number average molecular weight of greater than the number average molecular weight of the low molecular weight initiator in the presence of the Lewis acid catalyst.

A method of producing a polyether polyol includes reacting a low molecular weight initiator with one or more monomers in the presence of a polymerization catalyst, and the low molecular weight initiator has a nominal hydroxyl functionality of at least 2. The one or more monomers includes at least one selected from propylene oxide and butylene oxide. The polymerization catalyst is a Lewis acid catalyst having the general formula M(R.sup.1)1(R.sup.2)1(R.sup.3)1(R.sup.4)0 or 1, whereas M is boron, aluminum, indium, bismuth or erbium, R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are each independent, R.sup.1 includes a fluoroalkyl-substituted phenyl group, R.sup.2 incudes a fluoroalkyl-substituted phenyl group or a fluoro/chloro-substituted phenyl group, R.sup.3 includes a fluoroalkyl-substituted phenyl group or a fluoro/chloro-substituted phenyl group, and optional R.sup.4 includes a functional group or functional polymer group, R.sup.1 being different from at least one of R.sup.2 and R.sup.3.

An example of a bottlebrush polymer has a polymer backbone and a plurality of individual brush moieties bonded to the polymer backbone. The individual brush moieties include a ketone, a hydrophilic segment, and a surface adhesive terminal group. The brush moieties can be functionalized and/or cross-linked.

Poly(cyclic acetal)s, methods of making same, and uses of same. The poly(cyclic acetal)s may have a number average molecular weight (Mn) of 10 to 3000 kiloDaltons (kDa) and over 50% of the chain ends may exclude hydroxyl groups. The poly(cyclic acetal) may be a homopolymer or copolymer(s) of poly(1,3-dioxolane) (PDXL). The poly(cyclic acetal)s may have one or more or all of: a thermal stability (Td,5%) of 337? C. to 392? C.; a thermal stability of (Td.50%) of 377? C. to 462? C.; or an Arrhenius activation energy (Ea) of 85.0 kJ/mol with 2 mol % of strong acid (e.g., pKa less than or equal to 4). Methods of polymerizing poly(cyclic acetal)s may comprise reacting cyclic acetal monomers with either Lewis acid catalysts and haloalkyl ether initiators or organic cation salt catalyst(s) and proton traps. Methods of chemically recycling poly(cyclic acetal)s into cyclic acetals may react poly(cyclic acetal)s with strong acids.

Embodiments of the invention are directed to a macromolecular chemotherapeutic. A non-limiting example of the macromolecular chemotherapeutic includes a block copolymer. The block copolymer can include a water-soluble block, a cationic block, and a linker, wherein the linker is connected to the water-soluble bock and the charged block.

Provided herein are poly-1-hydroxymethylethylene hydroxymethyl formal (PHF)-based drug delivery systems. Also disclosed are methods of making antibodydrug conjugates and methods of treatment using these conjugates.

The invention provides semi-solid systems for delivering biologically active materials that include a polymer comprising 1) one or more polycaprolactone (PCL) units and 2) at least one or more polyethylene glycol (PEG) units; wherein at least one of said polycaprolactone units is conjugated to a PEG forming an acetal group.