Provided is a hydrogenated product of a cyclic polymer including a cyclic chain that includes a repeating unit of a ring-opened cycloolefin.

Recent progress in photoinitiated ring-opening metathesis polymerization (photo-ROMP) has enabled the lithographic production of patterned films from olefinic resins. The use of a latent ruthenium catalyst (e.g., HeatMet) in combination with a photosensitizer (e.g., 2-isopropylthioxanthone) to rapidly photopolymerize metathesis-monomers (e.g., dicyclopentadiene (DCPD)) upon irradiation with UV light has previously been demonstrated. See U.S. application Ser. No. 17/677,558. In addition to the exemplary catalysts and photosensitizers described in that work, a variety of alternative catalysts and photosensitizers are commercially available that allows for tuning of thermomechanical properties, potlifes, activation rates, and irradiation wavelengths. As an example, fourteen catalysts and eight photosensitizers were surveyed for the photo-ROMP of DCPD and the structure-activity relationships of the catalysts examined. Properties relevant to photopolymerization-based additive manufacturing—potlifes, printing irradiation dose, conversion—were characterized to develop catalyst and photosensitizer libraries. Two optimized catalyst/photosensitizer systems were demonstrated in the rapid stereolithographic printing of complex, multidimensional pDCPD structures with microscale features under ambient conditions.

A cycloolefin ring-opened copolymer includes a structural unit derived from a norbornene compound that includes a heteroelement-containing hydrocarbon group and a structural unit derived from a norbornene compound that includes a heteroelement-free hydrocarbon group. In this copolymer, the structural unit derived from the norbornene compound that includes the heteroelement-containing hydrocarbon group has a proportional content of not less than 0.01 mol % and not more than 15.00 mol % when all structural units included in the copolymer are taken to be 100 mol %.

The invention is directed to the selective dual wavelength olefin metathesis polymerization for additive manufacturing. Dual-wavelength stereolithographic printing uses ring-opening metathesis polymerization of the metathesis-active polymers. As an example, a resin formulation based on dicyclopentadiene was produced using a photolatent olefin metathesis catalyst, various photosensitizers and photobase generators to achieve efficient initiation by light at one wavelength (e.g., blue) and fast catalyst decomposition and polymerization deactivation by light at a second wavelength (e.g., ultraviolet). This process enables 2-dimensional stereolithographic printing, either using photomasks or with patterned, collimated light. Importantly, the same process was readily adapted for 3-dimensional continuous additive manufacturing, with printing rates of up to 36 mm h.sup.−1 for patterned light and up to 180 mm h.sup.−1 using un-patterned, high intensity light.

Provided herein is method of making a three-dimensional object (31) by stereolithography, comprising: (a) providing a polymerizable liquid comprising: (i) a light polymerizable component; (ii) a cyclic olefin monomer and/or prepolymer, (iii) an inhibited ring-opening metathesis polymerization (ROMP) catalyst, and (iv) a photoinitiator; (b) producing a three-dimensional intermediate from said polymerizable liquid by stereolithography (11); (c) optionally cleaning (12) said intermediate; and (d) heating (13) a surface of said three-dimensional intermediate to activate the inhibited ROMP catalyst, polymerize the cyclic olefin monomer and/or prepolymer by frontal ring-opening metathesis polymerization and form said three-dimensional object. Resins, build platforms (20) and apparatus useful for performing the method are also provided.

A method of producing a substrate with a fine uneven pattern is a method of producing a substrate having a fine uneven pattern on a surface thereof, the method including a step (a) of preparing a laminate provided with a substrate and a first resin layer provided on the substrate and having a first fine uneven pattern formed on a surface thereof; and a step (b) of forming a second fine uneven pattern corresponding to the first fine uneven pattern on the surface of the substrate by etching the surface of the first fine uneven pattern using the first resin layer as a mask, in which the first resin layer is formed of a resin composition (P) including a fluorine-containing cyclic olefin polymer (A) or a cured product of the resin composition (P).

Porous compositions such as flexible polymers with side chain porosity are generally provided. In some embodiments, the composition comprises a flexible polymer backbone and a plurality of rigid side chains. In some embodiments, the rigid side chains form pores. In some embodiments, the rigid side chains may comprise two or more [2.2.2] bicyclic cores (e.g., formed by a ring opening metathesis polymerization. The compounds and methods described herein may be useful in various applications including, for example, gas separation.

Provided is a resin material for forming an underlayer film which is used to form a resist underlayer film used in a multi-layer resist process, the resin material including a cyclic olefin polymer (I), in which a temperature at an intersection between a storage modulus (G′) curve and a loss modulus (G″) curve in a solid viscoelasticity of the resin material for forming an underlayer film which is as measured under conditions of a measurement temperature range of 30° C. to 300° C., a heating rate of 3° C./min, and a frequency of 1 Hz in a nitrogen atmosphere in a shear mode using a rheometer is higher than or equal to 40° C. and lower than or equal to 200°.

The present invention provides: a reaction injection molding liquid mixture comprising a norbornene-based monomer, a metathesis polymerization catalyst that includes tungsten as a center metal, an activator, and an ether compound represented by a formula (1), wherein R.sup.1 to R.sup.4 are independently an alkyl group having 1 to 6 carbon atoms, the reaction injection molding liquid mixture comprising the activator and the ether compound in a molar ratio (ether compound/activator) of 0.7/1 to 30/1; a method for producing a reaction injection molded product comprising a reaction injection molding step that includes subjecting the reaction injection molding liquid mixture according to any one of claims 1 to 4 to bulk polymerization inside a mold; a reaction injection molded product obtained using the method for producing a reaction injection molded product. Consequently, the present invention provides: a reaction injection molding liquid mixture that makes it possible to obtain a reaction injection molded product that has an excellent surface (surface state) and exhibits excellent strength while preventing a situation in which the resin remains on the surface of the mold when the resin is removed from the mold, a method for producing a reaction injection molded product using the same, and a reaction injection molded product obtained using the method. ##STR00001##

Gas separation membranes are provided and more particularly, a series of addition-type and ROMP type polynorbornenes with substituents derived from Mizoroki-Heck reactions are provided and have particular utility as gas separation membranes for natural gas upgrading.