The present disclosure discloses a thiocarbonyl-based poly(O-thiocarbamate) compound and a preparation method and use thereof, belonging to the technical field of polymer chemistry and material science. The present disclosure provides a new thiocarbonyl-based poly(O-thiocarbamate)compound with a structure represented by Formula I, which has sulfur element introduced, and has good solubility and high molecular weight. The thiocarbonyl-based poly(O-thiocarbamate) compound provided has good thermal stability and a very high refractive index, and is expected to have desirable applications in the optical field.

##STR00001##

The present disclosure provides a crystalline polythiocarbonate and a preparation method thereof. The crystalline polythiocarbonate is a random copolymer and includes five structural units L1 to L5 as shown in the following formula. The method includes carrying out a polymerization reaction natively or in solution using carbon disulfide, ethylene oxide, selectively added third monomer, initiator, Lewis acid, selectively added chain transfer agent, and selectively added solvent as raw materials. This method provides a new way for high value-added application of carbon disulfide and ethylene oxide by using inexpensive carbon disulfide and ethylene oxide as monomers; the product is a random copolymerized crystalline polythiocarbonate with novel structure, which has various chain link structures and excellent mechanical properties, processing properties and degradability.

The present disclosure provides a crystalline polythiocarbonate and a preparation method thereof. The crystalline polythiocarbonate is a random copolymer and includes five structural units L1 to L5 as shown in the following formula. The method includes carrying out a polymerization reaction natively or in solution using carbon disulfide, ethylene oxide, selectively added third monomer, initiator, Lewis acid, selectively added chain transfer agent, and selectively added solvent as raw materials. This method provides a new way for high value-added application of carbon disulfide and ethylene oxide by using inexpensive carbon disulfide and ethylene oxide as monomers; the product is a random copolymerized crystalline polythiocarbonate with novel structure, which has various chain link structures and excellent mechanical properties, processing properties and degradability.

Radical cascade reactions enabling sequence-controlled ring-closing polymerization and ring-opening polymerization for the controlled synthesis of polymers with complex main-chain structures are provided. Facile syntheses leading to low-strain macrocyclic monomers consisting of the ring-opening triggers and extended main-chain structures are also provided. The present disclosure further provides methods for excellent control over polymer molecular weights and molecular weight distributions and high chain-end fidelity allows for the preparation of polymeric systems with well-defined architectures. Further provided are the general nature of the radical cascade-triggered transformations in polymer chemistry, and its application to the synthesis of polymers with diverse main-chain structural motifs with tailored functions. This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present disclosure.

The invention provides a new class of synthetic sequence-defined polymer (SDP) and a method of synthesizing the same. The synthetic sequence-defined polymers have dithiocarbamate incorporated to the backbone. The method introduces a functional group dithiocarbamate in the backbone by using a new support-free, protection-deprotection free three-component reaction strategy. Dithiocarbamate-SDP is prepared from a unique bifunctional monomer, CS.sub.2 and chloroacetyl chloride. Chloracetyl chloride is used as a co-monomer. Different functional groups may be introduced in the dithiocarbamate-SDP via custom synthesis of monomers with the desired functional group, using the method disclosed. The SDPs may undergo modular post-synthetic modification through multiple paths. SDP is produced in multi-gram scale at low cost and in an eco-friendly manner through the method. No hazardous waste is produced in the process as HCl gas released from the reaction may be neutralized by bicarbonate in the medium.

The present invention relates to a kind of organic metal-free catalysts containing both electrophilic and nucleophilic dual-functions, preparation methods of making the same, and uses thereof. The organic metal-free catalysts in the present invention have the chemical structure shown in formula (I):

##STR00001##

Compared with the metal-free organic polymerization catalytic systems that have been reported before, the organic metal-free catalysts in this invention have the combined advantages of simple preparation, high reactivity, easy operation, low cost, wide applicability, easy for industrial production.

The present invention relates to a kind of organic metal-free catalysts containing both electrophilic and nucleophilic dual-functions, preparation methods of making the same, and uses thereof. The organic metal-free catalysts in the present invention have the chemical structure shown in formula (I):

##STR00001##

Compared with the metal-free organic polymerization catalytic systems that have been reported before, the organic metal-free catalysts in this invention have the combined advantages of simple preparation, high reactivity, easy operation, low cost, wide applicability, easy for industrial production.

The present invention relates to a kind of organic metal-free catalysts containing both electrophilic and nucleophilic dual-functions, preparation methods of making the same, and uses thereof. The organic metal-free catalysts in the present invention have the chemical structure shown in formula (I): ##STR00001##
Compared with the metal-free organic polymerization catalytic systems that have been reported before, the organic metal-free catalysts in this invention have the combined advantages of simple preparation, high reactivity, easy operation, low cost, wide applicability, easy for industrial production.

The present invention relates to a kind of organic metal-free catalysts containing both electrophilic and nucleophilic dual-functions, preparation methods of making the same, and uses thereof. The organic metal-free catalysts in the present invention have the chemical structure shown in formula (I): ##STR00001##
Compared with the metal-free organic polymerization catalytic systems that have been reported before, the organic metal-free catalysts in this invention have the combined advantages of simple preparation, high reactivity, easy operation, low cost, wide applicability, easy for industrial production.

A process for preparing preferably degradable copolymers by free radical ring-opening polymerization using thionolactone monomers or thionocarbonate monomers, in the presence of a radical polymerization initiator. Also, the copolymers, which include thioester or thiocarbonate bonds, that are obtained by carrying out the process including the free radical ring-opening polymerization using thionolactone monomers or thionocarbonate monomers.