KR20190129520A - 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, chain-extended polyurethane using the same, and a producing method of the chain-extended polyurethane and, more specifically, to a solid dispersion for chain extension, chain-extended polyurethane using the same, and a producing method of the chain-extended polyurethane which are easy to store and use, reduce transportation costs, prevent or improve coagulation and sinking occurring during product storage, improve work efficiency, reduce process costs, and improve strength when applied to polyurethane by using an isotropic material and/or an anisotropic material derived from an inorganic substance or an organic substance as a dispersoid and dispersing the material in a dispersion medium such as polyol and sugar which are solid at a room temperature.

Description

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

The present invention relates to a solid dispersion for extending the chain, a method for producing a chain-extended polyurethane and a chain-extended polyurethane using the same, more particularly, dispersoids of isotropic and / or anisotropic materials derived from inorganic or organic By using it as a dispersion in a dispersion medium such as polyols and sugars that are solid at room temperature, it is easy to store and use, transportation costs are reduced, and it is possible to prevent or improve the aggregation and sinking phenomenon occurring during product storage, A solid dispersion for chain extension, which can improve the working efficiency, reduce the process cost, and improve the strength when applied to polyurethane, and a method for producing the chain-extended polyurethane and chain-extended polyurethane using the same will be.

Isotropic and / or anisotropic materials derived from inorganic or organic materials are light weight materials, hybrid materials, surface protective agents, conductive pastes, conductive inks, sensors, precision analysis devices, optical memories, liquid crystal display devices, nano magnets, thermoelectric media, and high performance fuel cells. It is used as a main material in applications such as catalysts, organic solar cells, nanoglass devices, abrasives, drug carriers, environmental catalysts, paints, printing inks, inkjet inks, color filter resists, and writing instrument inks. At this time, the isotropic material and / or anisotropic material derived from the inorganic material or organic material are used to prepare a dispersion as fine particles in an aqueous dispersion medium or a non-aqueous dispersion medium, thereby efficiently improving processing characteristics, product characteristics and material properties, It is used industrially as a substance which contributes to quality stabilization and the yield improvement at the time of manufacture.

However, it is difficult to stably disperse the dispersant due to the material change of the dispersoid, the micronization of the particle size, or the control of the particle shape, so that the dispersant causes aggregation or sinking in the dispersion medium in a short time. The problem of aggregation and sinking of dispersoids not only leads to lower productivity, lower processing characteristics, lower handling properties and lower product yield, but also lowers the properties, material properties, and quality of the final product. In addition, it is known to cause undesirable phenomena such as deterioration of transparency, gloss and coloring power, color spots and cracks in appearance. Dispersants have been used to suppress aggregation and sinking of such dispersoids and to achieve dispersion stabilization.

Conventionally, as disclosed in Korean Patent Laid-Open Publication No. 10-2013-0023254 or 10-2013-0096307, a study has been made to obtain a stable dispersion composition by suppressing agglomeration of the dispersion using a dispersant. In terms of diversification of the dispersoid, miniaturization of the particle size of the dispersoid, diversification of the particle shape, high quality of the final product, improved productivity, and high demand for processing characteristics, the previously proposed dispersant can satisfy the required characteristics. none.

The biggest problem of the existing dispersion composition is that when the dispersion composition using water as a dispersion medium is applied to a polyurethane resin and an epoxy resin, etc., a process in which a master batch of water and polyol or a master batch of water and epoxy is additionally required There is a need for a surfactant to prevent aggregation of dispersoids.

Therefore, without the use of a separate dispersant or surfactant, there is a need for the development of a dispersion composition that can prevent or improve the aggregation and sinking of the dispersoid, and the development of a chain extender for applying it to a polyurethane or the like.

In order to solve the above problems, the present invention, by using an isotropic and / or anisotropic material derived from inorganic or organic material as a dispersoid, it is an anhydrosugar alcohol, a hydrogenated sugar, an alkane diol or mixtures thereof, which are solid at room temperature. By dispersing in the dispersion medium, it is easy to store and use, reduce transportation cost, and prevent or improve the aggregation and sinking occurring during product storage, improve the work efficiency and reduce the process cost It is an object of the present invention to provide a chain dispersion solid dispersion which can improve the strength when applied to polyurethane, a method of producing chain-extended polyurethane and chain-extended polyurethane using the same.

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

According to another aspect of the invention, the method comprising the steps of mixing the dispersoid and the dispersion medium; And melting the dispersion medium in the mixture, wherein the dispersion is an organic particle, an inorganic particle or a mixture thereof, and the dispersion medium is an anhydrosugar alcohol, a hydrogenated sugar, an alkane diol or A method for producing a solid dispersion for chain extension, which is a mixture thereof, is provided.

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

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

The solid dispersion for chain extension in which the isotropic materials and / or anisotropic materials derived from inorganic or organic materials according to the present invention are dispersed can reduce or eliminate agglomeration phenomenon during product storage, and through this, process input when using a product (solid dispersion). Time can be reduced, and additional steps or time to redistribute the aggregated product can be reduced or eliminated, and the work can be improved with little or no concern for worker labor and safety. In addition, the chain dispersion solid dispersion of the present invention is evenly dispersed in a large amount of dispersoid, when used as a chain extender of the polyurethane, it can provide the polyurethane with improved strength compared to the conventional chain extender.

Hereinafter, the present invention will be described in detail.

The present invention relates to a room temperature solid dispersion for chain extension comprising a dispersion and a dispersion medium in which the dispersion is dispersed, wherein the dispersion is an organic particle, an inorganic particle or a mixture thereof, and the dispersion medium is an anhydrosugar alcohol or a hydrogenated sugar. , Alkane diols or mixtures thereof.

The chain dispersion solid dispersion 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 includes a dispersoid dispersed in a dispersion medium. When applying the dispersion included in the solid dispersion for chain extension to the polyurethane production, it may play a role of improving the electrical, thermal and / or mechanical properties of the polyurethane, depending on 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, the inorganic particles include iron, aluminum, chromium, nickel, cobalt, zinc, tungsten, indium, tin, palladium, zirconium, titanium, copper, silver (for example, silver particles, silver nanowires, silver nanorods, etc.). ), Gold (eg, gold particles, gold nanowires, gold nanorods, etc.), platinum, alloys of two or more metals thereof, or a mixture of two or more thereof. In this case, in order to stably extract the inorganic particles described above from the medium, alkanes, fatty acids, hydroxycarboxylic acids, alicyclic carboxylic acids, aromatic carboxylic acids, alkenyl succinic anhydrides, thiols, and phenol derivatives are derived. It may be coated with protective agents such as retention, amines, amphiphilic polymers, high molecular 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 fiber, carbon nanofibers or carbon nanotubes (single wall carbon nanotubes, double wall carbon nanotubes, multiwall carbon nanotubes) may be used as the inorganic particles, but is not limited thereto.

Examples of the organic particles include azo compounds, diazo compounds, condensed azo compounds, thioindigo compounds, indanthrone compounds, quinacridone compounds, anthraquinone compounds, benzimidazolone compounds, perylene 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 (e.g. nano cellulose Fibrils, nano cellulose crystals, etc.), hemicellulose, lignin, chitin, chitosan, starch, polyacetal, aramid resin, polycarbonate, polyphenylene ether, polyether ether ketone, polyether ketone, polybutylene terephthalate, polyethylene Polymer resins such as phthalate, polybutylene naphthalate, polysulfone, polyphenylene sulfide or polyimide; Or mixtures thereof, but is not limited thereto.

The dispersoid particles dispersed in the dispersion medium of the present invention may be a crystalline phase or an amorphous phase. 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 is preferably nano cellulose fibrils, nano cellulose crystals, graphene, graphite, carbon nanotubes, carbon nanofibers, silver particles, silver nanowires, silver nanorods, gold At least one selected from the group consisting of particles, gold nanowires, gold nanorods, or a combination thereof, but is not limited thereto.

As the dispersoid particles in the present invention, those obtained by a known method can be used. As a method for preparing dispersoid fine particles, a top-down method of mechanically crushing coarse particles and miniaturizing them, and generating a plurality of unit particles, and bottoming up the particles to form through aggregated cluster states. There are two types of (bottom-up) methods, but those prepared by either method can be preferably used. In addition, the preparation method of microparticles | fine-particles may be based on either of the wet method and the dry method. In addition, although the bottom-up system has a physical method and a chemical method, it may be based on either method.

In order to demonstrate the bottom up method more specifically, the preparation method of a metal nanoparticle among the said dispersoid particles is illustrated. Among the bottom-up methods, a representative example of the physical method is an evaporation method in a gas in which bulk metals are evaporated in an inert gas and cooled and condensed by collision with the gas to produce nanoparticles. Examples of the chemical method include a liquid phase reduction method for reducing metal ions in the presence of a protective agent in a liquid phase and stabilizing the generated zero-valent metal to a nano size, or thermal decomposition of a metal complex. As the liquid phase reduction method, a chemical reduction method, an electrochemical reduction method, a photoreduction method, or a method combining a chemical reduction method and a light irradiation method can be used.

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

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

 As a dispersion medium that can be used in the present invention, a non-aqueous dispersion medium that can be changed into a liquid phase when heated to a temperature above room temperature but solid at room temperature can be used. By using such a non-aqueous dispersion medium, when the solid dispersion is stored at room temperature, dispersion stabilization can be achieved by preventing or improving the dispersion from agglomerating or disappearing.

The non-aqueous dispersion medium may preferably play a role of extending the chain of the polyurethane, for example, anhydrosugar alcohols such as monounsaturated alcohol and dianhydrosugar alcohol; Hydrogenated sugars; One or more selected from alkane diols or mixtures thereof can be used.

The type of monounsaturated alcohol is not particularly limited, and may be used without limitation as long as it is converted into a liquid phase at elevated temperatures from room temperature to solid and higher than room temperature, for example, tetratritan, pentitan, hexane, heptitan Or mixtures thereof and the like may be used, and preferably hextans such as sorbitan, mannitane, iditan, galactitane or mixtures thereof may be used.

The type of the dianhydrosugar alcohol is not particularly limited, and may be used without limitation as long as it is converted into a liquid phase at a temperature higher than room temperature while being solid at room temperature. For example, dianhydrosugar hexitol may be used, and the like. 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 converted into a liquid phase at a temperature higher than room temperature and solid at room temperature. For example, tetratriol, pentitol, hexitol, heptitol or the like Mixtures and the like can be used, preferably hexitols such as sorbitol, mannitol, iditol, galactitol or mixtures thereof can be used.

The kind of the alkane diol is not particularly limited and may be used without limitation as long as it is converted into a liquid phase at a temperature higher than room temperature and solid at room temperature. For example, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol or mixtures thereof can be used.

In the solid dispersion of the present invention, the content of the dispersoid may vary depending on the type of dispersant used, based on 100 parts by weight of the dispersion medium, 0.0001 parts by weight, 0.01 parts by weight, 0.05 parts by weight, 0.1 parts by weight or more , 0.5 part 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. To 95 parts by weight, preferably 0.05 to 80 parts by weight, but is not limited thereto. When the content of the dispersion is too small, the strength improvement of the polyurethane to which the solid dispersion is applied may be insignificant. When the content of the dispersion is too large, the dispersion is not evenly dispersed in the solid dispersion, and the dispersion They can be intertwined with each other.

According to another aspect of the present invention, there is provided a method for mixing a dispersoid and a dispersion medium; And melting the dispersion medium in the mixture, wherein the dispersion is an organic particle, an inorganic particle or a mixture thereof, and the dispersion medium is an anhydrosugar alcohol, a hydrogenated sugar, an alkane diol or A method for producing a solid dispersion for chain extension, which is a mixture thereof, 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 equal to or higher than 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 invention, (1) adding to the polyurethane prepolymer, the solid dispersion for chain extension of the present invention; And (2) reacting the resultant mixture of step (1).

In the process for producing the chain extended polyurethanes of the present invention, the polyurethane prepolymers can be obtained by reacting polyols with polyisocyanates, for example 12 to 36 at 50 to 100 ° C, preferably 70 to 90 ° C. After the polyol and the polyisocyanate, which have been sufficiently vacuum dried for a period of time, preferably 20 to 28 hours, were charged in a four-necked 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 a time, preferably 0.5 to 2 hours.

Although it does not specifically limit as a polyol which can be used by this invention, A polyether polyol can be used, For example, a polyethylene or a block copolymer of polyethyleneglycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide, and propylene oxide. And random copolymers of ethylene oxide and butylene oxide, block copolymers and the like can be used.

Although it does not restrict | limit especially as a polyisocyanate compound which can be used by this invention, Specifically, 1, 3- phenylene diisocyanate, 1, 4- phenylene diisocyanate, 2, 4- tolylene diisocyanate (TDI), 2, 6- tolyl Rendiisocyanate, 4,4'-diphenylene methane diisocyanate (MDI), 2,4-diphenylmethane diisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4 ' -Diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 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-undecane triisocyanate, 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'-dicyclohexyl methane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyane Alicyclic polyisocyanate compounds, such as Itoethyl) -4-cyclohexene-1, 2-dicarboxylate, 2, 5- norbornane diisocyanate, and 2, 6- norbornane diisocyanate, etc. are mentioned. These polyisocyanate compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

In the process for producing the chain-extended polyurethane of the present invention, after adding the solid dispersion for chain extension to the polyurethane prepolymer, they are put in a coated mold and then 80 to 200 ° C, preferably 100 to 150 The chain elongated polyurethane can be prepared by curing at 10 ° C. for 10 to 30 hours, preferably 15 to 25 hours.

According to another aspect, the present invention provides a chain elongated polyurethane, which is prepared by the reaction of a polyurethane prepolymer with the chain dispersion solid dispersion of the present invention.

In the present specification, each of the components described in the method for preparing the chain-extending solid dispersion, the chain-extended polyurethane and the method for producing the chain-extended polyurethane are the same as those of the above-mentioned solid dispersion for chain extension.

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

EXAMPLE

<Preparation of solid dispersion for chain extension>

Example A1: Solid Dispersion Containing Nanocellulose Fibrils and Anhydrosugar Alcohols

Into a rotary concentrator, 100 g of isosorbide (Samyang) and 100 g of an aqueous solution in which nanocellulose fibrils were dispersed at 1% by weight (KB101, Asia Nanocellulose Co., Ltd.) were added and mixed uniformly. Thereafter, the mixture was melted under vacuum at a temperature of 80 ° C. above the melting point of isosorbide while removing moisture. The molten mixture was then cooled to room temperature to produce isosorbide (solid dispersion) in which nanocellulose fibrils were dispersed.

Example A2: Solid Dispersion Including Nanocellulose Fibrils and Hydrogenated Sugars

Into a rotary concentrator, 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 and mixed uniformly. Thereafter, the mixture was melted while applying vacuum under a temperature condition of 100 ° C. which is equal to or higher than the melting point of sorbitol. The molten mixture was then cooled to room temperature to prepare sorbitol (solid dispersion) in which nanocellulose fibrils were dispersed.

Example A3: Solid Dispersion Including Nanocellulose Fibrils and Alkanediols

Into a rotary concentrator, 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 and mixed uniformly. Thereafter, the mixture was melted while applying vacuum under a temperature condition of 40 ° C. which is equal to or higher than the melting point of 1,4-butanediol. The molten mixture was then cooled to room temperature to prepare 1,4-butanediol (solid dispersion) in which nanocellulose fibrils were dispersed.

Example A4: Solid Dispersion Including Graphene and Anhydrosugar Alcohol

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

Example A5: Solid Dispersion Including Graphene and Hydrogenated Sugars

Into a rotary concentrator, 100 g of sorbitol (Samyang Corporation) and 100 g of an aqueous solution in which graphene was dispersed at 1.5 mg / mL (WDG, MexFlorer, Inc.) were added and mixed uniformly. Thereafter, the mixture was melted while applying vacuum under a temperature condition of 100 ° C. which is equal to or higher than the melting point of sorbitol. Subsequently, the molten mixture was cooled to room temperature to prepare sorbitol (solid dispersion) in which graphene was dispersed.

Example A6: Solid Dispersion Including Graphene and Alkanediols

Into the rotary concentrator, 100 g of 1,4-butanediol (Sigma Aldrich) and 100 g of aqueous solution in which graphene was dispersed at 1.5 mg / mL (WDG, Mexplore Inc.) were added and mixed uniformly. Thereafter, the mixture was melted while applying vacuum under a temperature condition of 40 ° C. which is equal to or higher than the melting point of 1,4-butanediol. Subsequently, the molten mixture was cooled to room temperature to prepare 1,4-butanediol (solid dispersion) in which graphene was dispersed.

Comparative example  A1: Nano cellulose With fibrils  Liquid Dispersion Containing Polypropylene Glycol

Into a rotary concentrator, 100 g of liquid polypropylene glycol (PPG-3000, Kumho Petrochemical) and 100 g of aqueous solution in which nano cellulose fibrils were dispersed at 1 wt% (KB101, Asia Nanocellulose Co., Ltd.) were added and mixed uniformly at room temperature. . Thereafter, water was removed under vacuum to prepare polypropylene glycol (liquid dispersion) in which nanocellulose fibrils were dispersed.

Comparative Example A2: Liquid Dispersion Containing Graphene and Polypropylene Glycol

100 g of liquid polypropylene glycol (PPG-3000, Kumho Petrochemical) and 100 g of aqueous solution in which graphene was dispersed at 1.5 mg / mL were added to a rotary concentrator (WDG, MexFloror) and mixed uniformly. Thereafter, a vacuum was applied to remove moisture to prepare polypropylene glycol (liquid dispersion) in which graphene was dispersed.

Production of Chain Extended Polyurethane

Example  B1: Nano cellulose With fibrils Anhydrosugar  Solids containing alcohol Dispersion  Preparation of Polyurethanes Used

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) sufficiently vacuum-dried at 80 ° C for 24 hours. After the reactor was charged in a four-necked reactor, a 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 isosorbide in which the nanocellulose fibrils dispersed in Example A1 were dispersed was added as a chain extender, and these were treated with a coating. After the addition into the mold was cured for 16 hours at 110 ℃ to prepare a chain-extended polyurethane.

Example  B2: Graphene and Anhydrosugar  Solids containing alcohol Dispersion  Preparation of Polyurethanes Used

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

Example  B3: Nano cellulose With fibrils Alkanes Dior  Containing solid Dispersion  Preparation of Polyurethanes Used

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

Example  B4: Graphene and Alkanes Dior  Containing solid Dispersion  Preparation of Polyurethanes Used

As the chain extender, the dispersion prepared in Example A6 (1,4-butanediol in which graphene is dispersed) was used instead of the dispersion prepared in Example A1 (isosorbide in which nanocellulose fibrils were dispersed). Except that, a chain-extended polyurethane was prepared in the same manner as in Example B1.

Example  B5: Nano cellulose With fibrils  Solids containing hydrogenated sugars Dispersion  Preparation of Polyurethanes Used

Except for using the dispersion prepared in Example A2 (sorbitol in which nanocellulose fibrils are dispersed) instead of the dispersion prepared in Example A1 (isosorbide in which nanocellulose fibrils were dispersed) as a chain extender. Then, a chain-extended polyurethane was prepared in the same manner as in Example B1.

Example  B6: Graphene and  Solids containing hydrogenated sugars Dispersion  Preparation of Polyurethanes Used

Except for using the dispersion prepared in Example A5 (sorbitol with graphene dispersed) in place of the dispersion prepared in Example A1 (isosorbide in which nanocellulose fibrils were dispersed) as a chain extender. In the same manner as in Example B1, a chain-extended polyurethane was prepared.

Comparative Example B1: Preparation of Polyurethane Using Anhydrous Sugar Alcohol as Chain Extender

Polyurethane extended in the same manner as in Example B1 was used, except that isosorbide was used instead of the dispersion prepared in Example A1 (isosorbide in which nanocellulose fibrils were dispersed) as a chain extender. Prepared.

Comparative example  B2: Anhydrosugar  Use alcohol as chain extender, separate Nano cellulose  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 fibril, which were sufficiently vacuum dried at 80 ° C. for 24 hours, were charged to a four-necked reactor, followed by stirring under a nitrogen atmosphere. It was. Subsequently, 50.5 g (0.2 mol) of 4,4'-methylene diphenyl diisocyanate (MDI) was added to a four-necked reactor under a nitrogen atmosphere, and then reacted for 1 hour while maintaining a temperature of 60 ° C to prepare a polyurethane prepolymer. It was. Subsequently, when the NCO% of the polyurethane prepolymer was measured to reach the theoretical NCO%, 14.6 g of isosorbide was added as a chain extender, and these were added to a coated mold and cured at 110 ° C. for 16 hours. To prepare a chain elongated polyurethane.

Comparative example  B3: Anhydrosugar  Use alcohol as chain extender, separate Graphene  Preparation of Added Polyurethane

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

Comparative example  B4: Nano cellulose With fibrils  Preparation of Polyurethane Using Liquid Dispersion Containing Polypropylene Glycol

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

Comparative example  B5: Graphene and  Liquid phase containing polypropylene glycol Dispersion  Preparation of Polyurethanes Used

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

<Measurement method of physical property>

Redispersibility Evaluation Method

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. Thus, a sample was prepared. Subsequently, the degree of dispersion of the dispersoid in the prepared sample was visually observed, and the results are shown in Table 1 below.

○ ○: The dispersed state of the dispersoid is the same as compared with immediately after the preparation of the dispersion composition.

(Circle): The dispersion state of a dispersoid is a state in which a small lump floats compared with just after manufacture of a dispersion composition.

X: The dispersion state of a dispersoid is a state in which a big lump is leaving compared with just after manufacture of a dispersion composition.

××: dispersoid is insoluble in water

[Storage Stability Evaluation Method]

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

○ ○: dispersoids do not aggregate and do not sink

○: small amount of dispersoid aggregates and sinks

X: Most of the dispersoids aggregate and sink

[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 Examples A1 to A6 according to the present invention, the dispersion was in a solid state at room temperature, so that the storage stability was excellent, and thus, long-term storage was easy and redispersibility was confirmed. It was.

However, in the case of a dispersion in which the dispersion medium is in a liquid state at room temperature (Comparative Examples A1 and A2), the dispersoids are entangled with each other to form a small agglomerate, which results in poor redispersibility, and when stored at room temperature for a long time Agglomeration and sinking occurred, confirming poor storage stability.

In addition, as shown in Table 2, in Examples B1 to B6 according to the present invention, by using a dispersion in which the dispersoid (nanocellulose fibril or graphene) is evenly dispersed, a chain-extended polyurethane It can be seen that the tensile stress of significantly improved to 30 Mpa or more.

However, in the case of Comparative Example B1 in which anhydrosugar alcohol alone was used as the chain extender, the tensile stress was significantly worse than that of the example, and the additive (nanocellulose fibril or graphene was used while the anhydrosugar alcohol alone was used as the chain extender. In the case of Comparative Examples B2 and B3 in which) is mixed with the polyol of the prepolymer, the additive is not evenly dispersed, and in the case of the polyurethane to which the additive is applied, agglomeration occurs and the tensile stress itself cannot be measured.

In addition, in the case of Comparative Examples B4 and B5 using the dispersion in which the dispersoid was dispersed but existed in the liquid phase at room temperature, the dispersoids were entangled with each other to aggregate and sink in small lumps. The additional process of stirring before it has to be carried out, the long-term storage had a problem that the dispersion is agglomerated and does not disperse well even by stirring.

Claims (11)

A room temperature solid dispersion for chain extension comprising a dispersion and a dispersion medium in which the dispersion is dispersed,
The dispersion is an organic particle, an inorganic particle or a mixture thereof, and the dispersion medium is an anhydrosugar alcohol, hydrogenated sugar, alkane diol or a mixture thereof. The method of claim 1, wherein 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, 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 fiber, carbon nano A solid dispersion for chain extension, selected from the group consisting of fibers, carbon nanotubes, alloys of two or more metals thereof, or mixtures of two or more thereof. The method of claim 1, wherein the organic particles are azo compounds, diazo compounds, condensed azo compounds, thioindigo compounds, indanthrone compounds, quinacridone compounds, anthraquinone compounds, benzimidazolone compounds, peryl Lenne compound, phthalocyanine compound, anthrapyridine compound, dioxazine 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, aramid resin, polycarbonate, polyphenylene ether, polyether ether ketone, polyether ketone, polybutylene terephthalate, polyethylene Naphthalate, Polybutylenenaphthalate, Polysulfone , Polyphenylene sulfide, polyimide or a mixture thereof. The method of claim 1, wherein the dispersion medium is isosorbide, isomannide, isoidide, tetritol, pentitol, heptitol, sorbitol, mannitol, iditol, galactitol, 1,4-butanediol, 1,6-hexanediol , 1,9-nonanediol or a combination thereof. The solid dispersion for chain extension according to claim 1, wherein the content of the dispersoid is 0.0001 parts by weight to 95 parts by weight based on 100 parts by weight of the dispersion medium. Mixing the dispersoid and the dispersion medium; And
A method for producing a solid dispersion for chain extension comprising melting the dispersion medium in a mixture,
The dispersion is an organic particle, an inorganic particle or a mixture thereof, and the dispersion medium is an anhydrosugar alcohol, hydrogenated sugar, alkane diol or a mixture thereof. The method of claim 6, wherein the melting of the dispersion medium in the mixture comprises melting the mixture while removing moisture by applying a vacuum at a temperature equal to or higher than the melting point of the dispersion medium. Polyurethane prepolymer,
Prepared by the reaction of the chain dispersion solid dispersion of any one of claims 1 to 5,
Chain-extended polyurethane. (1) adding to the polyurethane prepolymer a solid dispersion for chain extension according to any one of claims 1 to 5; And
And (2) reacting the resultant mixture of step (1). The method of claim 9, wherein the polyurethane prepolymer,
It is obtained by reacting the polyol and polyisocyanate vacuum dried at 50 to 100 ℃ for 12 to 36 hours at a temperature of 50 to 100 ℃ in a nitrogen atmosphere for 0.1 to 5 hours,
Process for the preparation of chain extended polyurethanes. The method of claim 9, wherein the step of reacting the resultant mixture of step (1),
It is carried out by curing for 10 to 30 at 80 to 200 ℃,
Process for the preparation of chain extended polyurethanes.