KR102129907B1 - Solid dispersion for chain extension, chain-extended polyurethane using the same and method for preparing the chain-extended polyurethane - Google Patents

Abstract

The present invention relates to a solid dispersion for chain extension, a method for manufacturing a chain-extended polyurethane and a chain-extended polyurethane using the same, and more specifically, to disperse an isotropic and/or anisotropic material derived from an inorganic substance or an organic substance. By dispersing it in a dispersion medium such as polyol and saccharide, which is solid at room temperature, it is easy to store and use, reduces transportation costs, and can prevent or improve agglomeration and sedimentation occurring during product storage, A method for manufacturing a solid dispersion for chain extension, a chain-extended polyurethane and a chain-extended polyurethane using the same, which can improve work efficiency, reduce process costs, and improve strength when applied to polyurethane. will be.

Description

Solid dispersion for chain extension, and method for preparing chain-extended polyurethane and chain-extended polyurethane using the same and method for preparing the chain-extended polyurethane}

The present invention relates to a solid dispersion for chain extension, a method for manufacturing a chain-extended polyurethane and a chain-extended polyurethane using the same, and more specifically, to disperse an isotropic and/or anisotropic material derived from an inorganic substance or an organic substance. By dispersing it in a dispersion medium such as polyol and saccharide, which is solid at room temperature, it is easy to store and use, reduces transportation costs, and can prevent or improve agglomeration and sedimentation occurring during product storage, A method for manufacturing a solid dispersion for chain extension, a chain-extended polyurethane and a chain-extended polyurethane using the same, which can improve work efficiency, reduce process costs, and improve strength when applied to polyurethane. will be.

Isotropic and/or anisotropic materials derived from inorganic or organic materials include lightweight materials, hybrid materials, surface protectors, conductive pastes, conductive inks, sensors, precision analysis elements, optical memories, liquid crystal displays, nano magnets, thermoelectric media, fuel cells It is used as a main material in applications such as catalysts, organic solar cells, nano glass devices, abrasives, drug carriers, environmental catalysts, paints, printing inks, inkjet inks, color filter resists, writing tool inks, and the like. At this time, the isotropic material and/or the anisotropic material derived from the inorganic material or the organic material is prepared by using a dispersion as microparticles in an aqueous dispersion medium or a non-aqueous dispersion medium, thereby effectively improving processing properties, product properties, and material properties, It is used in industry as a material that contributes to stabilization of quality and improvement of yield during manufacturing.

However, it is difficult to stably disperse the dispersoid as the material of the dispersoid is changed, the size of the particle size is reduced, or the particle shape is controlled, so that the dispersoid causes aggregation or settling in a short time in the dispersion medium. The problem of agglomeration and sinking of the dispersoid not only leads to a decrease in productivity, a reduction in processing characteristics, a decrease in handling properties, and a decrease in product yield in the production of the dispersion, but also a decrease in properties, material properties and quality of the final product. In addition, it is known to cause undesirable phenomena such as a decrease in transparency, gloss and coloring power, and color stains and cracks. Dispersing agents are used to suppress aggregation and sinking of such dispersoids and to achieve dispersion stabilization.

Conventionally, as disclosed in Korean Patent Application Publication No. 10-2013-0023254 or 10-2013-0096307, a study has been conducted to obtain a stable dispersion composition by suppressing aggregation of the dispersion using a dispersing agent. From the viewpoint of diversification of dispersoids, micronization of particle size of dispersoids, diversification of particle shape, high quality of final products, improvement of productivity, and high demands on processing characteristics, the previously proposed dispersant can sufficiently meet the required characteristics. none.

The biggest problem of the existing dispersion composition is that when a dispersion composition using water as a dispersion medium is applied to a polyurethane resin and an epoxy resin, a process of preparing a master batch of water and polyol or a master batch of water and epoxy is additionally required. It is necessary, and there is a problem that a surfactant is needed to prevent aggregation of the dispersoid.

Accordingly, there is a need to develop a dispersion composition capable of preventing or improving agglomeration and sinking of the dispersoid, without the use of a separate dispersant or surfactant, and the development of a chain extender to apply it to polyurethane or the like.

In order to solve the above problems, the present invention uses an isotropic and/or anisotropic material derived from an inorganic substance or an organic substance as a dispersing substance, such as anhydrous sugar alcohols, hydrogenated sugars, alkanediols or mixtures thereof solid at room temperature. By dispersing in a dispersion medium, it is easy to store and use, reduces transportation costs, and prevents or improves agglomeration and sinking occurring during product storage, thereby improving work efficiency and reducing process costs. , It is an object of the present invention to provide a solid dispersion for chain extension that can improve strength when applied to polyurethane, a method for manufacturing a chain-extended polyurethane and a chain-extended polyurethane using the same.

In order to solve the above technical problem, the present invention is a room temperature solid dispersion for chain extension comprising a dispersion medium and a dispersion medium in which the dispersion is dispersed, wherein the dispersion is organic particles, inorganic particles or mixtures thereof, and Provided is a solid dispersion for chain extension, wherein the dispersion medium is anhydrosugar alcohol, hydrogenated sugar, alkanediol, or mixtures thereof.

According to another aspect of the invention, mixing the dispersoid and the dispersion medium; And melting the dispersion medium in the mixture, wherein the dispersion is organic particles, inorganic particles or mixtures thereof, and the dispersion medium is anhydrosugar alcohol, hydrogenated sugar, alkanediol or A mixture of these, a method of making a solid dispersion for chain extension is provided.

According to another aspect of the present invention, there is provided a chain extended polyurethane, which is prepared by reaction of a polyurethane prepolymer with a solid dispersion for chain extension according to the present invention.

According to another aspect of the present invention, (1) adding a solid dispersion for chain extension according to the present invention to a polyurethane prepolymer; And (2) reacting the resultant mixture of step (1), a method for producing a chain-extended polyurethane is provided.

The solid dispersion for extending a chain in which an isotropic material and/or anisotropic material derived from an inorganic or organic material according to the present invention is dispersed can reduce or eliminate agglomeration when storing a product, and through this, process input when using a product (solid dispersion) It is possible to shorten the time, and to reduce or eliminate the additional process or time for redistributing the agglomerated product, and to improve the work efficiency because there is little or no concern about worker's labor and safety in such additional work. In addition, the solid dispersion for chain extension of the present invention is evenly dispersed in a large amount of dispersoid, and when it is used as a chain extender of polyurethane, it can provide improved strength to polyurethane compared to a conventional chain extender.

Hereinafter, the present invention will be described in detail.

The present invention is a room temperature solid dispersion for chain extension comprising a dispersoid and a dispersion medium in which the dispersoid is dispersed, wherein the dispersoid is organic particles, inorganic particles or mixtures thereof, and the dispersion medium is anhydrosugar alcohol, hydrogenated sugar , Alkanediols or mixtures thereof, to solid dispersions for chain extension.

The solid dispersion for chain extension of the present invention may be a room temperature solid dispersion that is solid at room temperature.

The solid dispersion for chain extension of the present invention contains a dispersoid dispersed in a dispersion medium. When the dispersion contained in the solid dispersion for chain extension is applied to the production of polyurethane, the electrical properties, thermal properties and/or mechanical properties of polyurethane may be improved according to the type of the dispersion, It is not limited to this.

The dispersoid particles dispersed in the dispersion medium of the present invention may be selected from inorganic particles, organic particles, or mixtures thereof.

For example, as inorganic particles, iron, aluminum, chromium, nickel, cobalt, zinc, tungsten, indium, tin, palladium, zirconium, titanium, copper, silver (for example, silver particles, silver nanowires, silver nanorods, etc.) ), gold (e.g., gold particles, gold nanowires, gold nanorods, etc.), platinum, alloys of two or more of these metals, or mixtures of two or more of these can be used. At that time, in order to stably extract the above-mentioned inorganic particles from the medium, alkanoic acids, fatty acids, hydroxycarboxylic acids, alicyclic carboxylic acids, aromatic carboxylic acids, alkenyl succinic anhydrides, thiols, phenol induction They may be coated with protective agents such as retention, amines, amphiphilic polymers, polymer surfactants, and low molecular surfactants.

In addition, kaolin, clay, talc, mica, bentonite, dolomite, calcium silicate, magnesium silicate, asbestos, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, aluminum sulfate, aluminum hydroxide, iron hydroxide, aluminum silicate, zirconium oxide , Magnesium oxide, aluminum oxide, titanium oxide, iron oxide, zinc oxide, antimony trioxide, indium oxide, indium tin oxide, silicon carbide, silicon nitride, boron nitride, barium titanate, diatomaceous earth, carbon black, graphite, rock wool, glass wool, glass fiber , Graphene, graphite, carbon fibers, carbon nanofibers or carbon nanotubes (single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes) and the like can be used as inorganic particles, but are not limited thereto.

In addition, as the organic particles, azo-based compounds, diazo-based compounds, condensed azo-based compounds, thioindigo-based compounds, indanthrone-based compounds, quinacridone-based compounds, anthraquinone-based compounds, benzimidazolones-based compounds, perylene-based compounds, Organic pigments such as phthalocyanine compounds, anthrapyridine compounds or dioxazine compounds; Polyethylene resin, polypropylene resin, polyester resin, nylon resin, polyamide resin, aramid resin, acrylic resin, vinylon resin, urethane resin, melamine resin, polystyrene resin, polylactic acid, acetate fiber, cellulose (for example, nanocellulose) Fibril, nanocellulose crystal, etc.), hemicellulose, lignin, chitin, chitosan, starch, polyacetal, aramid resin, polycarbonate, polyphenylene ether, polyether ether ketone, polyether ketone, polybutylene terephthalate, polyethylene na Polymer resins such as phthalate, polybutylene naphthalate, polysulfone, polyphenylene sulfide or polyimide; Or a mixture of these may be used, but is not limited thereto.

The dispersoid particles dispersed in the dispersion medium of the present invention may be crystalline or amorphous. In addition, the dispersoid particles dispersed in the dispersion medium of the present invention may be isotropic particles, anisotropic particles, or fibrous.

The dispersoid particles dispersed in the dispersion medium of the present invention are preferably nanocellulose fibrils, nanocellulose crystals, graphene, graphite, carbon nanotubes, carbon nanofibers, silver particles, silver nanowires, silver nanorods, gold It may be one or more selected from the group consisting of particles, gold nanowires, gold nanorods, or a combination thereof, but is not limited thereto.

In the present invention, as the dispersoid particles, those obtained by a known method can be used. As a method for preparing dispersoid fine particles, a top-down method of mechanically crushing and coarsening the coarse particles, and a number of unit particles are generated, and the bottom-up of the particles is formed through the aggregated cluster state. There are two types of (bottom-up) methods, but those prepared by any method can be preferably used. Moreover, as a method for preparing fine particles, any of the wet method and the dry method may be used. Further, there are physical methods and chemical methods in the bottom-up method, but any method may be used.

In order to describe the bottom-up method in more detail, a method for preparing metal nanoparticles among the dispersoid particles is illustrated. Among the bottom-up methods, a representative example of a physical method is an evaporation method in a gas in which bulk metal is evaporated in an inert gas, cooled and condensed by collision with the gas to generate nanoparticles. Further, the chemical method includes a liquid phase reduction method in which metal ions are reduced in the presence of a protective agent in a liquid phase, and the resulting zero-valent metal is stabilized to a nano size, or a thermal decomposition method of a metal complex. As the liquid phase reduction method, a chemical reduction method, an electrochemical reduction method, a photoreduction method, or a combination of a chemical reduction method and a light irradiation method can be used.

In addition, the dispersoid particles that can be preferably used in the present invention may be obtained by any of the top-down method and bottom-up method, as described above, and they are produced in any of an aqueous liquid phase, a non-aqueous liquid phase, and a gas phase. It may be done.

The solid dispersion for chain extension of the present invention includes a dispersion medium for dispersing the dispersoid. When the dispersion medium contained in the solid dispersion for chain extension is applied to the production of polyurethane, it may serve to extend the chain of polyurethane.

The dispersion medium that can be used in the present invention is a solid phase at room temperature, but a non-aqueous dispersion medium that can be transformed into a liquid phase when heated to a temperature exceeding room temperature can be used. By using such a non-aqueous dispersion medium, when the solid dispersion is stored at room temperature, dispersion stabilization may be achieved by preventing or improving the dispersoid from flocculating or decaying.

The non-aqueous dispersion medium is preferably capable of performing a role of extending the chain of polyurethane, for example, anhydrosugar alcohols such as mono- and di-sugar alcohols; Hydrogenated sugars; One or more selected from alkane diols or mixtures thereof can be used.

The type of the mono-sugar alcohol is not particularly limited, and can be used without limitation as long as it is solid at room temperature and is converted to a liquid when heated to a temperature above room temperature. For example, Tetritan, Pentitanium, Hexytan, Heptane Or a mixture of these and the like can be used, and preferably, hexitane, such as sorbitan, mannitane, iditan, galactan, or a mixture selected from the group consisting of these can be used.

The type of the dianhydrosugar alcohol is not particularly limited, and may be used without limitation as long as it is solid at room temperature and is converted to a liquid when heated to a temperature above room temperature. For example, dianhydrosugar hexitol may be used, preferably Any one selected from the group consisting of isosorbide, isomannide, isoidide, or mixtures thereof can be used.

The type of the hydrogenated sugar is not particularly limited, and can be used without limitation as long as it is solid at room temperature and is converted to a liquid phase when heated to a temperature above room temperature. For example, tetritol, pentitol, hexitol, heptitol, or these Mixtures and the like can be used, preferably hexitol, such as sorbitol, mannitol, iditol, galactitol or those selected from the group consisting of mixtures thereof can be used.

The type of the alkane diol is not particularly limited, and can be used without limitation as long as it is solid at room temperature and is converted to a liquid phase when heated to a temperature above room temperature. For example, 1,6-hexanediol, 1,9-nonanediol Alternatively, a mixture selected from the group consisting of these can be used.

In the solid dispersion of the present invention, the content of the dispersoid may vary depending on the type of dispersoid used, but based on 100 parts by weight of the dispersion medium, 0.0001 parts by weight or more, 0.01 parts by weight or more, 0.05 parts by weight or more, 0.1 parts by weight or more , 0.5 parts by weight or more, or 1 part by weight or more, 95 parts by weight or less, 90 parts by weight or less, 85 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less or 50 parts by weight or less, for example, 0.0001 parts by weight It may be from 95 parts by weight, preferably 0.05 parts by weight to 80 parts by weight, but is not limited thereto. If the content of the dispersoid is too small, the strength improvement of the polyurethane to which the solid dispersion is applied may be weak, and when the dispersoid is too large, it does not exist evenly dispersed in the solid dispersion, and the dispersoid They may exist in an intertwined state.

According to another aspect of the invention, mixing the dispersoid and the dispersion medium; And melting the dispersion medium in the mixture, wherein the dispersion is organic particles, inorganic particles or mixtures thereof, and the dispersion medium is anhydrosugar alcohol, hydrogenated sugar, alkanediol or A mixture of these, a method of making a solid dispersion for chain extension is provided.

Although not particularly limited, in the step of melting the dispersion medium in the mixture, the mixture may be melted while removing moisture by applying a vacuum at a temperature above the melting point of the dispersion medium. In addition, the molten mixture may then be cooled to room temperature to obtain a solid dispersion.

According to another aspect of the present invention, (1) adding a solid dispersion for chain extension of the present invention to a polyurethane prepolymer; And (2) reacting the resultant mixture of step (1), a method for producing a chain-extended polyurethane is provided.

In the method for producing the chain-extended polyurethane of the present invention, the polyurethane prepolymer can be obtained by reacting a polyol with a polyisocyanate, for example, 12 to 36 at 50 to 100°C, preferably 70 to 90°C After the polyol and polyisocyanate sufficiently vacuum-dried for a period of time, preferably 20 to 28 hours, in a four-neck reactor, 0.1 to 5 while maintaining a temperature of 50 to 100°C, preferably 50 to 70°C under a nitrogen atmosphere. The polyurethane prepolymer can be prepared by reacting for an hour, preferably 0.5 to 2 hours.

The polyol that can be used in the present invention is not particularly limited, but polyether polyol can be used. For example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, random copolymer or block copolymer of ethylene oxide and propylene oxide , A random copolymer or block copolymer of ethylene oxide and butylene oxide can be used.

The polyisocyanate compound that can be used in the present invention is not particularly limited, but specifically, 1,3-phenylenediisocyanate, 1,4-phenylenediisocyanate, 2,4-tolylenediisocyanate (TDI), 2,6-tolyl Rendiisocyanate, 4,4'-diphenylenemethane diisocyanate (MDI), 2,4-diphenylmethane diisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4' -Diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylenediisocyanate, 4,4',4''-triphenylmethanetriisocyanate, aromatic polyisocyanate compounds such as m-isocyanatophenylsulfonyl isocyanate and p-isocyanatophenylsulfonyl isocyanate; Ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecantriisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis(2-isocyanatoethyl)fumarate, bis(2-isocyanatoethyl)carbonate, 2-isocyanatoethyl-2,6 -Aliphatic polyisocyanate compounds such as diisocyanatohexanoate; Isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylenediisocyanate, methylcyclohexylenediisocyanate (hydrogenated TDI), bis(2-isocyane And alicyclic polyisocyanate compounds such as isoethyl)-4-cyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, and 2,6-norbornane diisocyanate. These polyisocyanate compounds may be used alone or in combination of two or more.

In the method for producing a chain-extended polyurethane of the present invention, after adding a solid dispersion for chain extension to the polyurethane prepolymer, they are put into a coated mold and then 80 to 200°C, preferably 100 to 150 Curing at 10° C. for 10 to 30 hours, preferably 15 to 25 hours, can produce a chain-extended polyurethane.

According to another aspect of the present invention, there is provided a chain-extended polyurethane, which is prepared by reaction of a polyurethane prepolymer with the solid dispersion for chain extension of the present invention.

In the present specification, each component described in the method for preparing the solid dispersion for chain extension, the method for manufacturing the chain extended polyurethane and the chain extended polyurethane is the same as the components of the solid dispersion for chain extension described above.

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples. However, the scope of the present invention is not limited to these.

[Example]

<Preparation of a solid dispersion for chain extension>

Example A1: Solid dispersion comprising nanocellulose fibrils and anhydrosugar alcohol

100 g of isosorbide (Samyang Corporation) and 100 g of an aqueous solution in which nanocellulose fibrils were dispersed at 1 wt% (KB101, Asia Nanocellulose Co., Ltd.) were added to the rotary concentrator and mixed uniformly. Thereafter, under the temperature condition of 80° C. above the melting point of isosorbide, the mixture was melted while vacuum was removed to remove moisture. Subsequently, the molten mixture was cooled to room temperature to prepare isosorbide (solid dispersion) in which nanocellulose fibrils were dispersed.

Example A2: Solid dispersion comprising nanocellulose fibrils and hydrogenated sugars

100 g of sorbitol (Samyang Corporation) and 100 g of aqueous solution in which nanocellulose fibrils were dispersed at 1% by weight (KB101, Asia Nanocellulose Co., Ltd.) were added to the rotary concentrator and mixed uniformly. Thereafter, under the temperature condition of 100° C. above the melting point of sorbitol, the mixture was melted while vacuum was removed to remove moisture. Subsequently, the molten mixture was cooled to room temperature to prepare sorbitol (solid dispersion) in which nanocellulose fibrils were dispersed.

Example A3: Solid dispersion comprising nanocellulose fibrils and alkane diols

100 g of 1,4-butanediol (Sigma Aldrich) and 100 g of an aqueous solution in which nanocellulose fibrils were dispersed at 1% by weight (KB101, Asia Nanocellulose Co., Ltd.) were added to a rotary concentrator and mixed uniformly. Thereafter, under the temperature condition of 40° C. above the melting point of 1,4-butanediol, the mixture was melted while vacuum was removed to remove moisture. Subsequently, the molten mixture was cooled to room temperature to prepare 1,4-butanediol (solid dispersion) in which nanocellulose fibrils were dispersed.

Example A4: Solid dispersion comprising graphene and anhydrosugar alcohol

100 g of isosorbide (Samyang Co.) and 100 g of an aqueous solution in which graphene is dispersed at 1.5 mg/mL (WDG, MexFlorer Co., Ltd.) were added to the rotary concentrator and mixed uniformly. Thereafter, under the temperature condition of 80° C. above the melting point of isosorbide, the mixture was melted while vacuum was removed to remove moisture. Subsequently, the molten mixture was cooled to room temperature to prepare isosorbide (solid dispersion) in which graphene is dispersed.

Example A5: Solid dispersion comprising graphene and hydrogenated sugar

100 g of sorbitol (Samyang Corporation) and 100 g of an aqueous solution of graphene dispersed in 1.5 mg/mL (WDG, MexFlorer Co., Ltd.) were added to the rotary concentrator and mixed uniformly. Thereafter, under the temperature condition of 100° C. above the melting point of sorbitol, the mixture was melted while vacuum was removed to remove moisture. Subsequently, the molten mixture was cooled to room temperature, thereby preparing sorbitol (solid dispersion) in which graphene was dispersed.

Example A6: Solid dispersion comprising graphene and alkane diol

100 g of 1,4-butanediol (Sigma Aldrich) and 100 g of an aqueous solution of graphene dispersed at 1.5 mg/mL (WDG, MexFlorer Co., Ltd.) were added to the rotary concentrator and mixed uniformly. Thereafter, under the temperature condition of 40° C. above the melting point of 1,4-butanediol, the mixture was melted while vacuum was removed to remove moisture. Subsequently, the molten mixture was cooled to room temperature to prepare 1,4-butanediol (solid dispersion) in which graphene was dispersed.

Comparative example A1: Nanocellulose Fibrils Liquid dispersion comprising polypropylene glycol

100 g of liquid polypropylene glycol (PPG-3000, Kumho Petrochemical) and nanocellulose fibrils dispersed at 1% by weight were added to a rotary concentrator at room temperature (KB101, Asia Nanocellulose Co., Ltd.) and uniformly mixed. . Thereafter, vacuum was applied to remove moisture to prepare polypropylene glycol (liquid dispersion) in which nanocellulose fibrils were dispersed.

Comparative Example A2: Liquid dispersion containing graphene and polypropylene glycol

The rotary concentrator was charged with 100 g of liquid polypropylene glycol (PPG-3000, Kumho Petrochemical) at room temperature and 100 g of aqueous solution in which graphene was dispersed at 1.5 mg/mL (WDG, MexFlorer Co., Ltd.) and mixed uniformly. Thereafter, vacuum was applied to remove moisture to prepare polypropylene glycol (liquid dispersion) in which graphene is dispersed.

<Preparation of chain-extended polyurethane>

Example B1: Nanocellulose Fibrils Anhydrous sugar Solids containing alcohol Dispersion Preparation of used polyurethane

100 g (0.1 mol) of poly(tetramethylene ether glycol) (PTMEG, molecular weight: 1,000) and 50.5 g (0.2 mol) of 4,4'-methylene diphenyl diisocyanate (MDI) which were sufficiently vacuum dried at 80° C. for 24 hours. After the 4th reactor, the polyurethane prepolymer was prepared by reacting for 1 hour while maintaining a temperature of 60°C under a nitrogen atmosphere. Subsequently, when the NCO% of the polyurethane prepolymer was measured and the theoretical NCO% was reached, 14.6 g of the isosorbide in which the nanocellulose fibrils prepared in Example A1 was dispersed was added as a chain extender, and these were coated. After pouring into the mold, it was cured at 110° C. for 16 hours to prepare a chain-extended polyurethane.

Example B2: With graphene Anhydrous sugar Solids containing alcohol Dispersion Preparation of used polyurethane

As the chain extender, the dispersion prepared in Example A4 (isosorbide in which graphene is dispersed) was used instead of the dispersion prepared in Example A1 (isosorbide in which nanocellulose fibrils were dispersed). Then, a chain-extended polyurethane was prepared in the same manner as in Example B1.

Example B3: Nanocellulose Fibrils Alkanes Dior Containing solid Dispersion Preparation of used polyurethane

As the chain extender, instead of the dispersion prepared in Example A1 (isosorbide in which nanocellulose fibrils are dispersed), the dispersion prepared in Example A4 (1,4-butanediol in which nanocellulose fibrils are dispersed) A chain-extended polyurethane was prepared in the same manner as in Example B1, except that was used.

Example B4: With graphene Alkanes Dior Containing solid Dispersion Preparation of used polyurethane

As the chain extender, instead of the dispersion prepared in Example A1 (isosorbide dispersed with nanocellulose fibrils), the dispersion prepared in Example A6 (1,4-butanediol dispersed in graphene) was used. A chain-extended polyurethane was prepared in the same manner as in Example B1 except for the above.

Example B5: Nanocellulose Fibrils Solids containing hydrogenated sugars Dispersion Preparation of used polyurethane

As the chain extender, the dispersion prepared in Example A2 (sorbitol dispersed with nanocellulose fibrils) was used instead of the dispersion prepared in Example A1 (isosorbide with nanocellulose fibrils dispersed). Then, a chain-extended polyurethane was prepared in the same manner as in Example B1.

Example B6: With graphene Solids containing hydrogenated sugars Dispersion Preparation of used polyurethane

As the chain extender, except that the dispersion prepared in Example A5 (sorbitol dispersed in graphene) was used instead of the dispersion prepared in Example A1 (isosorbide dispersed with nanocellulose fibrils). , Chain-extended polyurethane was prepared in the same manner as in Example B1.

Comparative Example B1: Preparation of polyurethane using anhydrosugar alcohol as chain extender

The chain-extended polyurethane was prepared in the same manner as in Example B1, except that isosorbide was used instead of the dispersion prepared in Example A1 (isosorbide dispersed with nanocellulose fibrils) as a chain extender. It was prepared.

Comparative example B2: Anhydrous sugar Alcohol is used as a chain extender. Nanocellulose Preparation of polyurethane with fibrils

100 g (0.1 mol) of poly(tetramethylene ether glycol) (PTMEG, molecular weight: 1,000) and 0.146 g of nanocellulose fibrils were sufficiently vacuum dried at 80° C. for 24 hours, and then slowly stirred under a nitrogen atmosphere. Did. Subsequently, 50.5 g (0.2 mol) of 4,4'-methylene diphenyl diisocyanate (MDI) was introduced in a 4-neck reactor under a nitrogen atmosphere, and then reacted for 1 hour while maintaining a temperature of 60°C to prepare a polyurethane prepolymer. Did. Subsequently, when the NCO% of the polyurethane prepolymer was measured and the theoretical NCO% was reached, 14.6 g of isosorbide was added as a chain extender, and these were put into a coated mold, followed by curing at 110° C. for 16 hours. , Chain-extended polyurethane was prepared.

Comparative example B3: Anhydrous sugar Alcohol is used as a chain extender. Graphene Preparation of added polyurethane

A chain-extended polyurethane was prepared in the same manner as in Comparative Example B2, except that 0.146 g of graphene was added instead of 0.146 g of nanocellulose fibrils.

Comparative example B4: Nanocellulose Fibrils Preparation of polyurethane using liquid dispersion containing polypropylene glycol

As the chain extender, instead of the dispersion prepared in Example A1 (isosorbide in which nanocellulose fibrils are dispersed), the dispersion prepared in Comparative Example A1 (polypropylene glycol in which nanocellulose fibrils are dispersed) was used. A chain-extended polyurethane was prepared in the same manner as in Example B1 except for the above.

Comparative example B5: With graphene Liquid containing polypropylene glycol Dispersion Preparation of used polyurethane

As the chain extender, the dispersion prepared in Comparative Example A2 (polypropylene glycol dispersed in graphene) was used instead of the dispersion prepared in Example A1 (isosorbide dispersed in nanocellulose fibrils). Then, a chain-extended polyurethane was prepared in the same manner as in Example B1.

<Method for measuring physical properties>

[Method for evaluating redispersibility]

After the dispersions prepared in Examples A1 to A6 and Comparative Examples A1 to A2 were stored at room temperature for 24 hours, 10 g of each dispersion was placed in a vial containing 15 ml of water, and stirred for 1 hour using a magnetic bar. By doing so, a sample was prepared. Subsequently, the degree of dispersion of the dispersion in the prepared sample was visually observed, and the results are shown in Table 1 below.

○○: the dispersion state of the dispersoid is the same as that of the dispersion composition immediately after preparation

(Circle): The dispersion state of the dispersoid is a state in which a small lump floats compared to immediately after the dispersion composition is prepared.

X: The dispersion state of the dispersoid is a state in which a large lump leaves as compared to immediately after preparation of the dispersion composition.

××: dispersoid is insoluble in water

[How to evaluate storage stability]

Samples were prepared in the same manner as described in the redispersibility evaluation method above. Subsequently, after each of the prepared samples was stored at room temperature for 1 hour, the degree of aggregation and subsidence of the dispersoid was visually observed, and the results are shown in Table 1 below.

○○: dispersoid is not aggregated and does not sink

(Circle): Dispersion|aggregation is a little aggregated and sinks.

×: Most of the dispersoid aggregated and subsided

[Evaluation method of tensile stress]

For the polyurethane specimens prepared in Examples B1 to B6 and Comparative Examples B1 to B5, tensile stress was measured using a universal tensile tester according to ASTM D412, and the results are shown in Table 2 below.

As shown in Table 1, in the case of Examples A1 to A6 according to the present invention, the dispersion was present in a solid state at room temperature, and thus storage stability was excellent, thereby making it easy to store for a long time and also excellent in redispersibility. Did.

However, in the case of a dispersion in which the dispersion medium is present in a liquid state at room temperature (Comparative Examples A1 and A2), the dispersoids are entangled with each other, resulting in agglomeration in the form of small lumps, which results in poor redispersibility, and also when stored at room temperature for a long time. It was confirmed that storage stability was poor due to aggregation and sinking.

In addition, as described in Table 2, in the case of Examples B1 to B6 according to the present invention, as the dispersion (nanocellulose fibril or graphene) is well-dispersed dispersion, chain-extended polyurethane It can be seen that the tensile stress of was significantly improved to 30 Mpa or more.

However, in the case of Comparative Example B1, where the anhydrosugar alcohol was used alone as the chain extender, tensile stress was significantly poor compared to the examples, and while using the anhydrosugar alcohol alone as the chain extender, additives (nanocellulose fibrils or graphene) In the case of Comparative Examples B2 and B3 in which) was mixed with the polyol of the prepolymer, the additives were not evenly dispersed, and in the case of the polyurethane to which it was applied, aggregation occurred, so that the tensile stress itself could not be measured.

In addition, in the case of Comparative Examples B4 and B5 in which the dispersoid is dispersed, and the dispersion exists in a liquid state at room temperature, the dispersoid is entangled with each other and aggregates and sinks into small lumps, so that the sample is used. It is necessary to perform an additional process of stirring before, and when it is stored for a long time, there is a problem that the dispersoid aggregates and is not well dispersed even by stirring.

Claims (11)

As a room temperature solid dispersion for chain extension comprising a dispersion medium and a dispersion medium in which the dispersion material is dispersed,
The dispersoid is an organic particle, an inorganic particle or a mixture thereof, and the dispersion medium is anhydrosugar alcohol, hydrogenated sugar, alkane diol or a mixture thereof,
The inorganic particles are iron, aluminum, chromium, nickel, cobalt, zinc, tungsten, indium, tin, palladium, zirconium, titanium, copper, silver, gold, platinum, kaolin, clay, talc, mica, bentonite, dolomite, calcium silicate , Magnesium silicate, asbestos, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, aluminum sulfate, aluminum hydroxide, iron hydroxide, aluminum silicate, zirconium oxide, magnesium oxide, aluminum oxide, titanium oxide, iron oxide, zinc oxide, trioxide Antimony, indium oxide, indium oxide tin, silicon carbide, silicon nitride, boron nitride, barium titanate, diatomaceous earth, carbon black, graphite, rock wool, glass wool, glass fiber, graphene, carbon fiber, carbon nanotube, two or more of these An alloy of metal, or a mixture of two or more of them,
The organic particles are azo-based compounds, diazo-based compounds, condensed azo-based compounds, thioindigo-based compounds, indanthrone-based compounds, quinacridone-based compounds, anthraquinone-based compounds, benzimidazole-based compounds, perylene-based compounds, phthalocyanine-based Compound, anthrapyridine-based compound, dioxazine-based compound, polyethylene resin, polypropylene resin, polyester resin, nylon resin, polyamide resin, aramid resin, acrylic resin, vinylon resin, urethane resin, melamine resin, polystyrene resin, polylactic acid, Acetate fiber, cellulose, hemicellulose, lignin, chitin, chitosan, starch, polyacetal, polycarbonate, polyphenylene ether, polyether ether ketone, polyether ketone, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, It is selected from the group consisting of polysulfone, polyphenylene sulfide, polyimide or mixtures thereof,
The alkane diol is selected from 1,6-hexanediol, 1,9-nonanediol or a mixture thereof,
Solid dispersion for chain extension. delete delete The method of claim 1, wherein the dispersion medium is isosorbide, isomannide, isoidide, tetritol, pentitol, heptitol, sorbitol, mannitol, iditol, galactitol, 1,6-hexanediol, 1,9-nonane A solid dispersion for chain extension, selected from the group consisting of diols or combinations thereof. According to claim 1, The content of the dispersion is based on 100 parts by weight of the dispersion medium, 0.0001 parts by weight to 95 parts by weight, the solid dispersion for chain extension. Mixing a dispersoid and a dispersion medium; And
A method for producing a solid dispersion for chain extension comprising the step of melting the dispersion medium in the mixture,
The dispersoid is an organic particle, an inorganic particle or a mixture thereof, and the dispersion medium is anhydrosugar alcohol, hydrogenated sugar, alkane diol or a mixture thereof,
The inorganic particles are iron, aluminum, chromium, nickel, cobalt, zinc, tungsten, indium, tin, palladium, zirconium, titanium, copper, silver, gold, platinum, kaolin, clay, talc, mica, bentonite, dolomite, calcium silicate , Magnesium silicate, asbestos, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, aluminum sulfate, aluminum hydroxide, iron hydroxide, aluminum silicate, zirconium oxide, magnesium oxide, aluminum oxide, titanium oxide, iron oxide, zinc oxide, trioxide Antimony, indium oxide, indium oxide tin, silicon carbide, silicon nitride, boron nitride, barium titanate, diatomaceous earth, carbon black, graphite, rock wool, glass wool, glass fiber, graphene, carbon fiber, carbon nanotube, two or more of these An alloy of metal, or a mixture of two or more of them,
The organic particles are azo-based compounds, diazo-based compounds, condensed azo-based compounds, thioindigo-based compounds, indanthrone-based compounds, quinacridone-based compounds, anthraquinone-based compounds, benzimidazole-based compounds, perylene-based compounds, phthalocyanine-based Compound, anthrapyridine-based compound, dioxazine-based compound, polyethylene resin, polypropylene resin, polyester resin, nylon resin, polyamide resin, aramid resin, acrylic resin, vinylon resin, urethane resin, melamine resin, polystyrene resin, polylactic acid, Acetate fiber, cellulose, hemicellulose, lignin, chitin, chitosan, starch, polyacetal, polycarbonate, polyphenylene ether, polyether ether ketone, polyether ketone, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, It is selected from the group consisting of polysulfone, polyphenylene sulfide, polyimide or mixtures thereof,
The alkane diol is selected from 1,6-hexanediol, 1,9-nonanediol or a mixture thereof,
Method for preparing a solid dispersion for chain extension. The method of claim 6, wherein the step of melting the dispersion medium in the mixture is to melt the mixture while removing moisture by applying vacuum at a temperature above the melting point of the dispersion medium. Polyurethane prepolymers,
It is produced by the reaction of the solid dispersion of any one of claims 1, 4, and 5 for chain extension,
Chain-extended polyurethane. (1) adding to the polyurethane prepolymer, the solid dispersion for chain extension according to any one of claims 1, 4, and 5; And
(2) A method for producing a chain-extended polyurethane comprising the step of reacting the resulting mixture of step (1). The polyurethane prepolymer of claim 9,
It is obtained by reacting polyol and polyisocyanate vacuum-dried at 50 to 100°C for 12 to 36 hours at a temperature of 50 to 100°C under nitrogen atmosphere for 0.1 to 5 hours.
Method for manufacturing chain-extended polyurethane. The method of claim 9, wherein the step of reacting the resulting mixture of step (1),
It is carried out by curing for 10 to 30 at 80 to 200 ℃,
Method for manufacturing chain-extended polyurethane.