O.L. Figovsky (О.Л. Фиговский)

Abstract: Curent patents in the field on nonisocyanate polyurethanes, applyed by Asian countries. Main raw materials based on vegetable oils.

Polyurethanes (PUs) is a product of the addition polymerization reaction between diisocyanates and diols. The main environmental issue of PU materials concerns the use of isocyanate raw materials. In fact, these compounds are harmful for human and environment. MDI and TDI, the most widely used isocyanates in PU industry, are classified as CMR (Carcinogen, Mutagen and Reprotoxic): Merenyi S. REACH: regulation (EC) No 1907/2006: consolidated version (June 2012) with an introduction and future prospects regarding the area of Chemicals legislation. GRIN Verlag; 2012. Among all methods of non-isocyanate synthesis of polyurethane, reaction of cyclic carbonate with amine is the most attractive (1).

The practical application of NIPU based on primary amine s and five-membered cyclocarbonates (CCs) (1,3,3-dioxolan-2-ones) in coatings, sealants, adhesives, etc. was largely developed back in the USSR by O. Figovsky, V. Mikheev, V. Stroganov and others in the 1970s–1990s. Now main developments of of NIPU are carrying out prof. Vijay Mannary by US Army contract(2). For the period 2017–2022 more than 900 patents have been obtained in this direction. Major Patent Holders: Covestro Deutschland AG, Dow Global Technologies Llc, Sika Technology Ag, 3M Innovative Properties Company, Basf Se, Henkel Ag & Co. Kgaa. At last time a lot of new patents were applied Chinese & other Asian inventors. Below such patents are presented.

CN109796485 (A) - Organosilicon-modified bifunctional urethane acrylate monomer and preparation method and application thereof. The invention discloses an organosilicon-modified bifunctional urethane acrylate monomer and a preparation method and application thereof. The monomer has a large organosilicon hydrophobic chain segment, the flexibility, the smoothness, the hydrophobicity and the fingerprint resistance and the drying speed of a paint film can be improved, internal stress generated during cross-linking and solidification of the paint film is reduced, and therefore, the flexibility and adhesion of the paint film are improved. The nonisocyanate polyurethane structure and amido bonds contained in the monomer can improve the flexibility, the wear resistance and the handfeeling fullness of the paint film can be improved. The monomer contains two polymerizable acrylic ester structures, therefore, the monomer canbe used for polyurethane-crylic acid emulsion polymerization, modification of acrylic resin for stoving varnish and UV light curing, the cross-linking density of the resin can be improved, and the hardness and the salt fog resistance of the paint film can be improved. The synthesis method is simple, the reaction conditions are mild, neither organic solvents nor toxic and high-corrosion substancesare adopted, and the organosilicon-modified bifunctional urethane acrylate monomer is safer and more environmentally friendly.

CN109762008 (A) - Organosilicon modified single functionality urethane acrylate monomer and preparation method and application thereof. The invention discloses an organosilicon modified single functionality urethane acrylate monomer and a preparation method and application thereof. The organosilicon modified single functionality urethane acrylate monomer has two large organosilicon hydrophobic chain segments, flexibility, smoothness, water resistance and cold and hot resistance of a paint film can be improved, meanwhile internal stress generated during cross-linking curing of the paint film can be lowered, thus the flexibility of the paint film is improved, and adhesive force of the paint film is increased; the double organosilicon hydrophobic chain segments can increase the drying speed of the pain film; the organosilicon modified single functionality urethane acrylate monomer contains a nonisocyanate polyurethane structure and amido bonds, the flexibility, abrasion resistance and hand feeling fullness of the paint film can be improved; the organosilicon modified single functionality urethane acrylate monomer containsa polymerizable acrylate structure and can serve as a functional monomer to be applied to polyurethane-acrylic acid composite emulsion polymerization, modification of acrylic resin for stoving varnish and UV light curing; and a synthesizing method is simple and mild in reaction condition, organic solvents and poisonous and highly-corrosive substances are not used, and thus the more environmentally friendly and safer effects are achieved.

CN109593451 (A) - Bisphenol AF-based lyophobic and oleophobic nonisocyanate polyurethane coating, as well as preparation method and application thereof. The invention discloses bisphenol AF-based lyophobic and oleophobic nonisocyanate polyurethane coating, as well as a preparation method and application thereof. The preparation method comprises the following steps: synthesizing bisphenol and perfluorocyclocarbonic ester in the presence of CO2 by using bisphenol AF and perfluoro-epoxy compound as raw materials, and further preparing high-performance nonisocyanate polyurethane coating with different amine curing agents, wherein the bisphenol AF-based cyclocarbonic ester is prepared by the steps of adding a bisphenol AF-based epoxy compound intoa high pressure reactor, adding two organic solvents, adding a catalyst, introducing carbon dioxide, reacting at the pressure intensity of 0.5-4.0Mpa, controlling the reaction temperature to be 60-180DEG C, and reacting for 2-40 hours. The nonisocyanate polyurethane coating has excellent lyophobic and oleophobic performance and corrosion resistance, has high hardness, excellent impact resistanceand chemical resistance, and is expected to become a multifunctional coating replacing traditional polyurethane.

CN109232882 (A) - Organic silicon modified gallic acid-based nonisocyanate.polyurethane and preparation method thereof. The invention discloses organic silicon modified gallic acid-based nonisocyanate polyurethane and a preparation method thereof. The method comprises the steps of reacting polysiloxane having a side chain containing hydrogen with vinyl cyclic carbonate under the presence of a catalyst to prepare organic silicon cyclic carbonate, and copolymerizing with gallic acid-based cyclic carbonate and amino compounds to prepare the organic silicon modified gallic acid-based nonisocyanate.polyurethane. The method for preparing the organic silicon cyclic carbonate is simple and convenient, and has mild reacting conditions; and the nonisocyanate.polyurethane has excellent thermomechanical performance, and the preparation process is safe and environment-friendly.

CN108659689 (A) - Sorbitol-based nonisocyanate polyurethane coating and preparation method thereof. The invention discloses sorbitol-based nonisocyanate polyurethane coating and a preparation method thereof. The preparation method includes: adding sorbitol-based epoxy resin into a high-pressure reactor, adding catalysts, feeding carbon dioxide to keep pressure intensity in a range of 1.0-4.0MPa, performing reaction at a reaction temperature of 60-150 DEG C for 4-30h to obtain sorbitol-based cyclic carbonate solution; well stirring sorbitol-based cyclic carbonate, a diamine curing agent or a polyamine curing agent, a solvent and an antifoaming agent under room-temperature conditions to form the sorbitol-based nonisocyanate polyurethane coating, and performing spray coating and baking-curing to form a film. The prepared sorbitol-based cyclic carbonate is yellow transparent liquid, nontoxicand great in biodegradability. The prepared nonisocyanate polyurethane coating is high in hardness and excellent in impact resistance and chemical resistance and is expected to be excellent-performance environment-friendly coating for substituting traditional polyurethane.

CN108285733 (A) - Preparation method of polyurethane for coating film formation. The invention relates to the field of high polymer material application, and provides a preparation method of polyurethane for coating film formation. The method comprises the following steps of 1, manufacturing epoxidized soybean oil into cyclic-carbonated soybean oil; 2, preparing an amino siloxane hydrolysate; 3, synthesizing nonisocyanate polyurethane. The polyurethane can replace isocyanate polyurethane as film forming materials of surface coatings of synthetic leather, spinning, furniture and the like, and the problem that the toxicity of adopted isocyanate is large in the existing polyurethane preparation process is solved.

CN107857879 (A) - Preparation method and application of diphenolic acid based nonisocyanate polyurethane. The invention discloses a preparation method of diphenolic acid based nonisocyanate polyurethane. The method includes: adopting diphenolic acid as the raw material to synthesize diphenolic acid isopropyl alcohol ester diglycidyl ether, then carrying out reaction with carbon dioxide to obtain diphenolic acid based bicyclic carbonate, and finally carrying out reaction with polyamine to obtain the diphenolic acid based nonisocyanate polyurethane. The invention provides the novel diphenolic acid based nonisocyanate polyurethane and the preparation method thereof, enriches the variety of nonisocyanate polyurethane, and further gives application of the product in preparation of coatings.

CN106750274 (A) - Nonisocyanate polyurethane. The invention discloses nonisocyanate polyurethane which consists of the following raw materials: a component A, including 60-70% of crylic acid carbamic acid ester resin, 0.3-0.5% of a defoaming agent, 0.1-0.2% of a leveling agent A, 0.2-0.5% of a leveling agent B, 0.2-0.5% of a rheology aid, 0.5-1% of a base material wetting agent, 15-20% of n-butyl acetate, 15-20% of propylene glycol monomethyl ether acetate, with the total percentage being 100%; a component B, including 70-80% of ethanol, 10-20% of a cross-linking agent, 5-10% of a drier, 0.5-1% of an ultraviolet absorbent, with the total percentage being 100%; and a component C, including 60-70% of n-butyl acetate and 30-40% of propylene glycol monomethyl ether acetate, with the total percentage being 100%; the nonisocyanate polyurethane is prepared in a weight ratio of component A to component B and component C of 100:(40-50):(20-30). The nonisocyanate polyurethane disclosed by the invention has the characteristics of being high in hardness, good in fullness, high in gloss, good in leveling property, good in collapse resistance and excellent in chemical and weather resistance.

CN106317406 (A) - Method for preparing biodegradable thermoplastic polyurethane with benzene ring structure through nonisocyanate method. The invention discloses a method for preparing biodegradable thermoplastic polyurethane with a benzene ring structure through a nonisocyanate method, and belongs to the technical field of polyurethane. Firstly, dimethyl terephthalate and excess aliphatic diol are subjected to ester exchange, hydroxyl-terminated terephthalic acid diester is obtained and then is subjected to ammonia ester exchange with diammonia ester diol in the presence of a catalyst, self condensation polymerization of a part of diammonia ester diol is accompanied, and the biodegradable thermoplastic polyurethane with the benzene ring structure is obtained. The method has the advantages of simple operation, high efficiency, and green environmental protection; and the obtained polyurethane with an ester group and the benzene ring structure has excellent mechanical properties and good biodegradability.

CN106118172 (A) - Heavy-duty anticorrosive container. The invention discloses a heavy-duty anticorrosive container. The heavy-duty anticorrosive container comprises an aluminum alloy container body and heavy-duty anticorrosive coating layers, wherein the inner wall and outer wall of the aluminum alloy container body are coated with the heavy-duty anticorrosive coating layers. The heavy-duty anticorrosive coating layer is prepared from the following component in parts by weight: 25-35 parts of epoxy-cyclic carbonate, 23-33 parts of nonisocyanate polyurethane, 12-24 parts of cardanol aldehyde amine, 5-10 parts of nanometer titanium dioxide concentrate, 10-20 parts of fusion bonded epoxy powder, 30-40 parts of solvent and 15-25 parts of fluoroalkyl-polysiloxane. By this way, the heavy-duty anticorrosive container has strong wind resistance and snow resistance, good corrosion resistance, excellent ageing resistance, and long service life.

CN105952984 (A) - Steel pipe resistant to acid-base corrosion. The invention discloses a steel pipe resistant to acid-base corrosion. The steel pipe resistant to acid-base corrosion comprises a steel pipe body, an FEVE fluorocarbon coating layer, an epoxy nonisocyanate polyurethane heavy anti-corrosion coating layer, a TiO2 nanometer composite fluorocarbon coating layer and a hydroxyl terminated polybutadiene polyurethane modified epoxy resin anti-corrosion coating layer, wherein the FEVE fluorocarbon coating layer and the epoxy nonisocyanate polyurethane heavy anti-corrosion coating layer are sequentially arranged on the outer surface of the steel pipe body from inside to outside; and the TiO2 nanometer composite fluorocarbon coating layer and the hydroxyl terminated polybutadiene polyurethane modified epoxy resin anti-corrosion coating layer are sequentially arranged on the inner surface of the steel pipe body from outside to inside. In this way, the steel pipe is good in acid-base corrosion resistance and applicable to a highly corrosive environment.

CN105273185 (A) - Method for preparing aliphatic-aromatic mixed block thermoplastic polyurethane through nonisocyanate method. he invention discloses a method for preparing aliphatic-aromatic mixed block thermoplastic polyurethane through a nonisocyanate method, and belongs to the technical field of polyurethane. The method comprises the steps: firstly, carrying out ester exchange of dimethyl terephthalate and excessive aliphatic diol, to obtain a hydroxyl-terminated polydimethyl terephthalate oligomer, then carrying out a reaction with aliphatic dibasic acid and diol to obtain an aliphatic-aromatic mixed block polyester pre-polymer, and then further carrying out condensation polymerization with diurethane diol, to obtain the aliphatic-aromatic mixed block thermoplastic polyurethane. The method is simple to operate, has no pollution and is green and environmentally friendly; and the prepared polyurethane is easy to crystallize, is beneficial for adjustment and control of a structure, and has the advantages of higher melting point and good thermal properties and mechanical properties.

CN105504272 (A) - POSS modified rosin nonisocyanate polyurethane and preparation method of nonisocyanate polyurethane. The invention discloses POSS modified rosin nonisocyanate polyurethane and a preparation method of the nonisocyanate polyurethane. According to the method, epoxy group POSS and CO2 react under the action of a catalyst to synthesize cyclic carbonate-based POSS, then the cyclic carbonate-based POSS is copolymerized with rosin-based cyclic carbonate and an amino compound, and the POSS modified nonisocyanate polyurethane is prepared. The method for preparing the cyclic carbonate-based POSS is simple and convenient, and reaction conditions are mild; the prepared polyurethane material has a good thermodynamic property, no isocyanate with hypertoxicity is adopted in the preparation process, and the preparation process is safe and environmentally friendly.

CN105176349 (A) - Water-borne woodenware coating with formaldehyde decomposing function. The invention discloses a water-borne woodenware coating with a formaldehyde decomposing function. The water-borne woodenware coating comprises components in parts by weight as follows: 40-48 parts of nonisocyanate polyurethane, 0-28 parts of pigment filler, 0-0.2 parts of a defoaming agent, 0-0.4 parts of a wetting agent, 0-0.4 parts of a leveling agent, 0-4 parts of an adhesion promoter, 0-5 parts of a water-borne hand feeling agent, 1-5 parts of a film coalescing aid, 1-3 parts of a dispersing agent, 1-6 parts of a pH regulator, 0-2 parts of a thickening agent, 8-12 parts of an air catalyst, 0-0.3 parts of a sterilizing agent and 7-15 parts of deionized water. The water-borne woodenware coating is prepared from nonisocyanate polyurethane as a raw material, contains no formaldehyde, has the function of decomposing formaldehyde released from other materials indoors and reduces the environment pressure.

TW201525113 (A) - Flame retardant composite material, plate and coating. A flame retardant composite material includes an organic component and an inorganic powder, and the functional group (OH group) of the organic component may generate metal oxygen bond with the inorganic powder. The organic component includes nonisocyanate polyurethane or epoxy-based polymer, copolymer or oligomer. The inorganic powder includes hydroxide, nitride, oxide, carbide, metal salts, or inorganic layered material.

CN104910348 (A) - Polycarbonate polyurethane and green preparation method thereof. The invention relates to polycarbonate polyurethane and a green preparation method thereof. The polycarbonate polyurethane comprises polyurethane structural units and aliphatic polycarbonate structural units which are irregularly distributed. The polycarbonate polyurethane is successfully prepared by a nonisocyanate method, so that isocyanate and solvents are not used, and the development requirements of green chemical industry are met. In addition, the green preparation method of the polycarbonate polyurethane is relatively mild in reaction condition and low in requirement on devices; by selecting raw materials with different structures, the polycarbonate polyurethane having different linear structures and comprising two irregularly distributed structural units can be prepared, so that the structures are diverse and controllable; the prepared polycarbonate polyurethane is free of residue of isocyanate monomers, so that the application of polycarbonate polyurethane to the fields of foods and medicines is broadened.

CN104861866 (A) - Heat-resistant paint and preparation method thereof. The invention relates to the technical field of paints, in particular to heat-resistant paint and a preparation method thereof. The heat-resistant paint is prepared from the following components in parts by mass: 8-12 parts of tung oil, 3-5 parts of quartz powder, 1-3 parts of aluminum phosphate, 4-9 parts of polyarylsulfone resin, 4-9 parts of polyimide resin, 5-7 parts of butanol, 3-7 parts of nonisocyanate polyurethane, 2-4 parts of china clay, 2-4 parts of talcum powder, 5-8 parts of cobalt iso-octoate, 0.2-1.2 parts of an anti-settling agent, 8-18 parts of a curing agent and 2-6 parts of an anti-cracking agent. The heat-resistant paint has the benefits that 1 the heat-resistant paint prepared by mixing the tung oil, the polyarylsulfone resin, the polyimide resin, the butanol, the nonisocyanate polyurethane, the talcum powder and the cobalt iso-octoate is good in heat-resistant effect, and has excellent physical and chemical properties such as the decorative property, the heat resistance, the salt fog resistance, the salt water resistance, the water resistance, the cold tolerance, the oil resistivity, the hydrocarbon solvent resistance, the adhesive force, the impact strength and the flexibility.

CN103951960 (A) - Modified polypropylene carbonate and preparation method thereof. The invention provides modified polypropylene carbonate comprising the following components: 1-15wt% of nonisocyanate polyurethane and 85-99wt% of polypropylene carbonate, wherein nonisocyanate polyurethane has a structure as shown in the formula I. Nonisocyanate polyurethane provided by the invention contains a great number of hydroxyl radicals and urethane bonds and is used as a proton donor, and polypropylene carbonate contains carbonyl and is used as a proton receptor, so that a relatively strong intermolecular hydrogen bonding effect is taken between molecules of nonisocyanate polyurethane and polypropylene carbonate, the compatibility of nonisocyanate polyurethane and polypropylene carbonate is improved, the relatively high tensile strength and young modulus of modified polypropylene carbonate are kept, and meanwhile, the elongation at break of modified polypropylene carbonate is increased. An experimental result shows that the elongation at break of modified polypropylene carbonate is 11.16-36.81%.

CN102336891 (A) - Nonisocyanate polyurethane-epoxy resin material, preparation method thereof, and application thereof. The invention belongs to the field of painting, and provides a nonisocyanate polyurethane-epoxy resin material and a preparation method thereof. The material is prepared through a cross-linking hybridization reaction between nonisocyanate polyurethane and epoxy resin. The invention also provides an application of the nonisocyanate polyurethane-epoxy resin material in painting. A film formed by the material has good mechanical properties, good water resistance, good gasoline resistance, good salt fog resistance, and excellent adhesive force on a substrate.

KR20010071470 (A) - HYBRID NONISOCYANATE POLYURETHANE NETWORK POLYMERS AND COMPOSITES FORMED THEREFROM. This invention relates to a hybrid nonisocyanate polyurethane network polymer formed by cross-linking at least one cyclocarbonate oligomer and at least one amine oligomer. The cyclocarbonate oligomer contains a plurality of terminal cyclocarbonate groups. At least one cyclocarbonate oligomer further comprises from about 4 % to about 12 % by weight of terminal epoxy groups. Because at least one cyclocarbonate oligomer contains both cyclocarbonate and epoxy reactive groups, the network formed therefrom is referred to as a hybrid nonisocyanate polyurethane network. The cyclocarbonate oligomer or oligomers have an average functionality towards primary amines of from about 2.0 to about 5.44. The amine oligomer comprises at least one primary amine-terminated oligomer terminated with primary amine groups and has an average functionality towards cyclocarbonate groups of from about 3.0 to about 3.8. The amine oligomer is present in an amount from about 0.93 to about 0.99 of the amount of the amine oligomer that would be required to achieve a stoichiometric ratio between the primary amine groups of the amine oligomer and the cyclocarbonate groups of the cyclocarbonate oligomer. The hybrid nonisocyanate polyurethane network polymer formed has a gel fraction of not less than about 0.96 by weight. This invention also relates to methods of making hybrid nonisocyanate polyurethane networks and their use as a composite matrix material.

CN101260232 (A) - Mixing type nonisocyanate polyurethane and preparation method thereof. The invention provides a catalyst for the synthesis of nonisocyanate polyurethane. The catalyst consists of metal salt, imidazole-type ionic liquid, pyridine-type ionic liquid and quaternary ammonium salt. The invention also provides a method for preparing the nonisocyanate polyurethane. In the method, multi-ring shaped carbonic ester is catalytically synthesized by using the catalyst, and then the multi-ring shaped carbonic ester is reacted with organic amines to form the nonisocyanate polyurethane. The catalyst has the advantages of simple catalyst system, low cost, high reaction activity and good selectivity; and the preparation method has the advantages of mild reaction conditions, simple process flow and easy operation.

CN1880360 (A) - Method for generating nonisocyanate polyurethane using natural reproducible resource. This invention relates to a method for producing non-isocyanate polyurethane using renewable natural resources, comprising: add epoxy soybean oil and catalyst into the reactor, wherein the amount of catalyst added is 3-5mol% of epoxy soybean oil, and then aerate in carbon dioxide gas, with reaction temperature 100-140Deg C, and reaction pressure 6-14 atmospheric pressure, start the reaction with magnetic stirring . for 25-40h. The produced cyclic carbonates are mixed with amine at 70-80Deg C, perform flaking at 100-110Deg C for 7-8h, perform sulfidization at 90-110Deg C for 24-72h, and are placed at room temperature for 7-9d. This invention synthesizes non-isocyanate polyurethane by replacing petrochemical products with epoxy soybean oil and CO2 via two-step reactions, forming a green, clean, high efficient and simple line for producing non-isocyanate polyurethane.

Inventions of NIPU and others of academician Oleg Figovsky (there are more than 500) are not published In USSR), but created later in USA, were described in the review (3).

References.

1. O.L. Figovsky, O.I. Bol'shakov, I.N. Vikhareva. NONISOCYANATE POLYURETHANES: GREEN SOLUTIONS (Monograph). Chelyabinsk, SUSU Publishing Center, 2023, pp 47.

2. Vijay Mannary. Nonisocyanate Platform for Rain-Erosion Resistant Coating. Report OMB 0704-0188. 2028, pages. 28.

3. N.B. Blank. Selected patents of academician O. Figovsky. In the book "New technologies and science the modern word, VOIR, Rostov, 2023. pp 4-10.