TWI490246B - Polyurethane gel composition and method for making the same - Google Patents

Description

Polyurethane gel composition and method of producing the same

The present invention relates to a polyurethane gel composition and a method for producing the same, and more particularly to a polyurethane gel composition capable of forming a coating having excellent adhesion, fracture toughness and thermal conductivity, and a process for producing the same method.

Polyurethane (PU) includes hard segments and soft segments. The chemical and physical properties can be changed by adjusting the hard segment and soft segment of the polyurethane, the size of the molecule, and the like. It can be used in various forms such as powders, foams, gels, elastomers, etc. It can be widely used in various applications such as viscose, coating, suspension for anti-vibration or anti-friction, natural rubber substitute, foam, etc. use.

In particular, when it is used as a protective coating layer, the polyurethane needs to have good ductility, permeability to the object to be coated, and good coatability, and it is required to have transparency, adhesion, and non-stickiness of the surface layer (tack). -free) and other features. Specifically, for example, when the glass article is subjected to detection, handling, packaging, transportation, and use, the glass surface has an anti-shattering protective film (layer), which can improve the strength and safety of the glass. For example, U.S. Patent No. 4,086,373 discloses the use of an ultraviolet curable polyurethane composition as a protective layer for glass, although a method of ultraviolet curing does not require the use of a solvent, but a film formed by ultraviolet curing is used. Compared with the film layer formed by coating after polymerization, since the small molecule or oligomer reacts with the photopolymerization initiator, local polymerization, the mechanical strength of the film layer is poor, for example, the fracture toughness is poor, and the fracture toughness means when there is The material resists the property of cracking in cracks. Further, since the photopolymerization initiator is used as a method of ultraviolet curing, there is a disadvantage of residual radicals, and the stability is low.

On the other hand, the thermal conductivity of a typical polyurethane is about 0.02 W/m. K, the thermal conductivity can be improved by mixing a heat conductive material. When the thermal conductivity is increased by 10 to 100 times, the amount of the heat conductive material such as silver, alumina, or cerium oxide may be 50 to 70% by weight. In this case, there is a possibility that the original characteristics of the polyurethane cannot be maintained. . Therefore, the literature has used a nano surface material with a high specific surface area to increase the thermal conductivity while reducing the blending ratio and maintaining the original characteristics of the polyurethane. The thermal conductivity of graphene can reach 10 ³ W/m. K, although the characteristics are very suitable as a heat conductive material, graphene is difficult to uniformly disperse in the polymer, so the use of graphene as a heat conductive material added to the polyurethane requires specific selection depending on the nature of the polyurethane. A suitable method can achieve the effect of increasing the thermal conductivity of the polyurethane.

In view of the above-described background of the invention, in order to meet the industrial requirements, one of the objects of the present invention is to provide a polyurethane gel composition and a method for producing the same, which have good ductility and permeability to an object to be coated. Good coating properties, a coating formed from the polyurethane gel composition of the present invention, having transparency, adhesion and tack-free. Further, by adding graphene, it is uniformly dispersed in the polyurethane gel composition to improve the thermal conductivity, and it can be used as a heat conductive coating. The polyurethane coating composition of the present invention can be applied to applications such as printed circuit boards (PCBs), protective films for glass products, and explosion-proof films.

In order to achieve the above object, according to an embodiment of the present invention, there is provided a polyurethane gel composition comprising: a polyurethane polymer, wherein the polyurethane polymer is composed of at least one glycol And reacting the diisocyanate monomer with a diisocyanate monomer after removing the unreacted monomer; and a second organic solvent; wherein the diol monomer and the diisocyanate monomer are soluble in the first organic The solvent, the polyurethane polymer is insoluble in the first organic solvent but soluble in the second organic solvent.

Furthermore, according to another embodiment of the present invention, a method for producing a polyurethane gel composition comprising: providing at least one diol monomer and a diisocyanate monomer; and the diol monomer and the The diisocyanate monomer is dissolved in a first organic solvent to form a homogeneous mixed solution; the mixed solution is heated, and the polymerization is carried out under physical vibration to produce a solid; the second organic solvent is removed, and the first organic solvent is used. The resulting solid is washed to remove unreacted monomers; a second organic solvent is added and dispersed under physical vibration to form a polyurethane gel composition.

Furthermore, according to another embodiment of the present invention, there is provided a polymer coating which is obtained by coating a polyurethane urethane gel composition on a substrate to form a coating film and drying it. The polyurethane gel composition comprises a polyurethane polymer and a first organic solvent, wherein the polyurethane polymer is composed of at least one diol monomer and a diisocyanate monomer. After the reaction in the second organic solvent, the unreacted monomer is removed, wherein the diol monomer and the diisocyanate monomer are soluble in the second organic solvent, and the polyurethane polymer is insoluble in the first A diorganic solvent but soluble in the first organic solvent.

As described above, the polyurethane coating composition of the present invention and the method for producing the same, the permeability of the polyurethane gel composition to the object to be coated, and good coatability are The coating formed by the polyurethane gel composition has transparency, adhesion and tack-free. Further, by adding graphene, it is uniformly dispersed in the polyurethane gel composition to improve the thermal conductivity, and it can be used as a heat conductive coating. The polyurethane foam composition of the present invention can be applied to various uses such as a printed circuit board (PCB), a protective film for glass products, or an explosion-proof film.

The above and other technical contents, features and advantages of the present invention will be apparent from the following detailed description of the preferred embodiments. In order to thoroughly understand the present invention, detailed steps and compositions thereof will be set forth in the following description. Obviously, the practice of the invention is not limited to the specific details that are apparent to those skilled in the art. On the other hand, well-known components or steps are not described in detail to avoid unnecessarily limiting the invention. The preferred embodiments of the present invention are described in detail below, but the present invention may be widely practiced in other embodiments, and the scope of the present invention is not limited by the scope of the following patents. .

According to a first embodiment of the present invention, a polyurethane (PU) gel composition is disclosed, comprising: a polyurethane polymer, the polyurethane polymer being composed of at least one diol a monomer and a diisocyanate monomer are reacted in a first organic solvent to remove unreacted monomers; and a second organic solvent; wherein the diol monomer and the diisocyanate monomer are soluble in the first The organic solvent, the polyurethane polymer is insoluble in the first organic solvent but soluble in the second organic solvent. The polyurethane polymer of the present invention can be naturally separated from unreacted monomers by the difference in solubility during the synthesis. Due to this The polyurethane urethane gel composition of the invention has good coatability and ductility, and can be formed on any surface by any conventional method, for example, a surface having irregularities, and dip coating can be used. Forming a coating.

The above diol monomer may have the general formula (1): HO-R ¹ -OH, and R ¹ represents a linear or branched divalent alkylene group or a carbon atom having 2 to 16 carbon atoms. 3 to 12 dicyclocycloalkyl (cycloalkylene), the diisocyanate monomer has the general formula (2): OCN-R ² -CH ₂ -R ³ -NCO, and R ² and R ³ each independently represent a carbon number of 2 a linear or branched divalent alkylene of ~16 or a dialkylcycloalkylene having 3 to 12 carbon atoms. In another aspect, the above diol monomer can be a polyester polyol or a polyether polyol. For example, the above diol monomers are ethylene glycol, diethylene glycol, butylene glycol, pentanediol, neopentyl glycol, and hexanediol. The above polyester polyol may have a weight average molecular weight of 1000 to 3000, and may be obtained by reacting adipic acid with a diol selected from the group consisting of ethylene glycol, diethylene glycol, butylene glycol, and pentane. Glycol, neopentyl glycol, hexanediol. The above polyether polyol may have a weight average molecular weight of from 1,000 to 3,000, such as polytetramethylene ether glycol, polypropylene glycol, and polyethylene glycol or a combination thereof.

Furthermore, the polyurethane foam composition of the present invention may further comprise a graphene dispersion as a thermally conductive polyurethane gel composition which may be formed into a thermally conductive coating, a coating film or any shape. . The graphene dispersion may be composed of graphene dispersed in a third organic solvent, and the third organic solvent is, for example, ethyl acetate or ethanol. Further, the graphene dispersion is uniformly dispersed in the polyurethane gel composition of the present invention. The weight average molecular weight of the above polyurethane polymer is from 10,000 to 90,000, preferably from 11,000 to 25,000. Particularly, it is preferably applied to a film (thin coating) or a porous surface, and the weight average molecular weight is preferably low. The second organic solvent is, for example, tetrahydrofuran or ethanol. The first organic solvent is, for example, ethyl acetate or ethanol.

Furthermore, according to a second embodiment of the present invention, a method for producing a polyurethane gel composition is disclosed, comprising the steps of: step S10: providing at least one diol monomer and a diisocyanate monomer; and step S20: Dissolving the diol monomer and the diisocyanate monomer in a first organic solvent to form a uniform mixed solution; Step S30: heating the mixed solution, performing physical polymerization to carry out a polymerization reaction to produce a solid; removing the second organic solvent, washing the generated solid using the first organic solvent to remove unreacted monomers; and step S40 : A second organic solvent is added and dispersed under physical vibration to form a polyurethane gel composition.

After the step S20, the method of the present invention further comprises: adding Dibutyltin Dilaurate as a catalyst in the homogeneous mixed solution, and then uniformly stirring to form a mixed solution.

After the step S40, the method of the present invention further comprises: adding a graphene dispersion, wherein the graphene dispersion is composed of graphene dispersed in a third organic solvent, and uniformly dispersed in the polyurethane condensation In the gel composition. The graphene dispersion may be formed by dispersing graphene in a third organic solvent by ultrasonic vibration or microwave, and the third organic solvent is, for example, ethyl acetate or ethanol.

The above diol monomer may have the general formula (1): HO-R ¹ -OH, and R ¹ represents a linear or branched divalent alkylene group or a carbon atom having 2 to 16 carbon atoms. 3 to 12 dicyclocycloalkyl (cycloalkylene), the diisocyanate monomer has the general formula (2): OCN-R ² -CH ₂ -R ³ -NCO, and R ² and R ³ each independently represent a carbon number of 2 a linear or branched divalent alkylene of ~16 or a dialkylcycloalkylene having 3 to 12 carbon atoms. On the other hand, the above diol monomer may be a polyester polyol or a polyether polyol. The above diol monomers are, for example, ethylene glycol, diethylene glycol, butylene glycol, pentanediol, neopentyl glycol, and hexanediol. The polyester polyol may have a weight average molecular weight of 1000 to 3000, and may be obtained by reacting adipic acid with a diol selected from the group consisting of ethylene glycol, diethylene glycol, butylene glycol, and pentane. Glycol, neopentyl glycol, hexanediol. The polyether polyol may have a weight average molecular weight of from 1,000 to 3,000, such as polytetramethylene ether glycol, polypropylene glycol, and polyethylene glycol. The above physical oscillations are, for example, ultrasonic oscillations.

Furthermore, in accordance with a third embodiment of the present invention, a polymer coating is disclosed which is obtained by applying a polyurethane gel composition to a substrate, forming a coating film, and drying. The polyurethane gel composition comprises a polyurethane polymer and a first organic solvent, wherein the polyurethane polymer is composed of at least one diol monomer and a diisocyanate monomer in a second After the reaction in the organic solvent, the unreacted monomer is removed, wherein the diol monomer and the diisocyanate monomer are soluble in the second organic solvent, and the polyurethane polymer is insoluble in the second organic The solvent is soluble in the first organic solvent.

When the polyurethane gel composition comprises a graphene dispersion, the polymer coating formed from the polyurethane gel composition has a heat transfer coefficient of 0.5 W/m. K or more. The above graphene dispersion is uniformly dispersed in the polyurethane gel composition as described above.

The above diol monomers are also the same as described above, and are, for example, ethylene glycol, diethylene glycol, butylene glycol, pentanediol, neopentyl glycol, hexanediol, polyester polyol, and polyether polyol. The diol monomer may have the general formula (1): HO-R ¹ -OH, and R ¹ represents a linear or branched divalent alkylene group having 2 to 16 carbon atoms or a carbon atom number of 3 ~12 bivalent cycloalkylene, the diisocyanate monomer has the general formula (2): OCN-R ² -CH ₂ -R ³ -NCO, and R ² and R ³ each independently represent a carbon number of 2~ a linear or branched divalent alkylene group of 16 or a cycloalkylene having 3 to 12 carbon atoms.

Example

Example 1

(1) Synthesis of polyurethane polymer

Add pentanediol 4.00 g (0.0385 mol) and isophorone diisocyanate 8.42 g (0.0385 mol) to 20 ml of ethyl acetate, stir well, then add 3 drops of Dibutyltin Dilaurate. Stirring was evenly carried out, and ultrasonic vibration was carried out at about 50 ° C for 10 hours to form a white solid. After removing ethyl acetate, the unreacted monomer was washed away with ethyl acetate, the solvent was removed, and the white color was dried under vacuum. Solid, 9.45 g of polyurethane polymer 1 was obtained. The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the obtained polyurethane polymer 1 were measured by a GPC method to obtain Mn = 14196, Mw = 21079, and PDI = 1.34 (polydispersity index).

(2) Polyurethane gel composition

The polyurethane polymer 1 was added to tetrahydrofuran (THF) or absolute ethanol to have a solid concentration of 50% by weight, which was gelled in an ultrasonic wave for 30 minutes to obtain a polyurethane gel composition. Matter 1.

Example 2

(1) Synthesis of polyurethane polymer

The polyurethane polymer 2 was obtained in the same manner as in Example 1 except that the time of the ultrasonic vibration reaction was changed from 10 hours to 8 hours. The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the obtained polyurethane polymer 2 were measured to obtain Mn=12871, Mw=17981, and PDI=1.32 (polydispersity index).

(2) Polyurethane gel composition

The polyurethane polymer 2 was added to tetrahydrofuran (THF) or absolute ethanol to have a solid concentration of 60% by weight, which was gelled in an ultrasonic wave for 30 minutes to obtain a polyurethane gel composition. Object 2.

Example 3

(1) Synthesis of polyurethane polymer

The polyurethane polymer 3 was obtained in the same manner as in Example 1 except that the time of the ultrasonic vibration reaction was changed from 10 hours to 6 hours. The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the obtained polyurethane polymer 3 were measured to obtain Mn=11965, Mw=16971, and PDI=1.31 (polydispersity index).

(2) Polyurethane gel composition

The polyurethane polymer 3 was added to tetrahydrofuran (THF) or absolute ethanol to have a solid concentration of 60% by weight, which was gelled in an ultrasonic wave for 30 minutes to obtain a polyurethane gel composition. Item 3.

Example 4

(1) Preparation of graphene dispersion

0.5 g of graphene and 30 ml of ethyl acetate were placed in a sample bottle, and shaken for 30 minutes using ultrasonic waves to obtain a graphene dispersion 1.

(2) Thermally conductive polyurethane gel composition

Using the polyurethane coating composition of the polyurethane obtained in Example 1, the polyurethane dispersion composition 1, respectively, the graphene dispersion 1 was added, and the ratio of the graphene was 0.5% by weight to obtain a thermally conductive polyamine. Acid gel composition 1. According to Thermal Balance and Fourier's Law (see "Transport Processes and Seaparation Process Principles", Christie John Geankoplis, Chap. 4, Heat balance and Fourier's law), measuring the heat conduction of the film formed by the thermal conductive polyurethane gel composition, the thermal conductivity of the film at 40 ° C is 0.5 W / m. K. Generally, the thermal conductivity of the polyurethane polymer is about 0.02 W/m. K, significantly increases the thermal conductivity of the polymer.

Example 5

(1) Preparation of graphene dispersion

0.5 g of graphene and 30 ml of ethanol were placed in a sample vial and shaken for 30 minutes using ultrasonic waves to obtain a graphene dispersion 2 .

(2) Thermally conductive polyurethane gel composition

Using the polyurethane coating composition of the polyurethane obtained in Example 1, the polyurethane dispersion composition 1, respectively, the graphene dispersion 2 was added, and the ratio of the graphene was 0.5% by weight to obtain a thermally conductive polyamine. Acid gel composition 2.

Example 6

(1) Synthesis of polyurethane polymer

Pentylene glycol 3.80 g (Mw = 104.15, Tm = -16 ° C), polypropylene glycol (PPG; Mw = 2000) 0.3846 g and isophorone diisocyanate 8.55 g (Mw = 222.29, Tm = -60 ° C, 0.0385 Mo Add 8 ml of ethyl acetate, stir well, add 3 drops of Dibutyltin Dilaurate and stir evenly. Use ultrasonic wave shock reaction at about 50 °C for 10 hours to form a white solid. After ethyl acetate, the unreacted monomer was washed away with ethyl acetate, the solvent was removed, and the white solid was dried under vacuum to obtain 9.45 g (Tm = 117.4 - 141.40 ° C) of the polyurethane polymer 4 .

Example 7

Production of polymer coating

8 g of the polyurethane polymer 1 of Example 1 was dissolved in 8 g of ethanol to prepare a composition solution having a solid concentration of 50% by weight, and the mixture was stirred at room temperature for 30 minutes, and left to stand overnight. Taking 1 ml of the composition solution, forming a film by a solution casting method at room temperature for about 20 seconds, to obtain a polymer coating according to the present invention, in order to dry the coating, heating or standing at room temperature .

As described above, according to the polyurethane composition of the present invention and the method for producing the same, the permeability of the polyurethane gel composition to the object to be coated and the good coatability are The coating formed by the clear polyurethane gel composition has transparency, adhesion and tack-free. Further, by adding graphene, it is uniformly dispersed in the polyurethane gel composition to improve the thermal conductivity, and it can be used as a heat conductive coating. The polyurethane foam composition of the present invention can be applied to various uses such as a printed circuit board (PCB), a protective film for glass products, or an explosion-proof film.

The present invention has been described in detail with reference to the preferred embodiments of the present invention, and the scope of the invention is not limited thereto, and it is understood that various modifications and changes can be made without departing from the spirit and scope of the invention. In addition, any of the objects or advantages or features of the present invention are not required to be achieved by any embodiment or application of the invention. In addition, the abstract sections and headings are only used to assist in the search of patent documents and are not intended to limit the scope of the invention.

Claims (9)

A polyurethane gel composition comprising: a polyurethane polymer, the polyurethane polymer being a glycol monomer of pentanediol and/or polypropylene glycol and a diisocyanate monomer After the reaction under ethyl acetate, the unreacted monomer is removed; and tetrahydrofuran or ethanol; wherein the diol monomer and the diisocyanate monomer are soluble in ethyl acetate, and the polyurethane polymer is insoluble Ethyl acetate but soluble in tetrahydrofuran or ethanol; wherein the diisocyanate monomer has the general formula (2): OCN-R ² -CH ₂ -R ³ -NCO, and R ² and R ³ each independently represent a carbon number of 2~ a linear or branched divalent alkylene or a cycloalkylene having 3 to 12 carbon atoms; and a polypropylene glycol having a weight average molecular weight of 1,000 to 3,000. The polyurethane gel composition according to the first aspect of the patent application, further comprising: a graphene dispersion, which is composed of graphene dispersed in a third organic solvent, and the graphene dispersion is uniformly dispersed In the polyurethane gel composition. The polyurethane coating composition according to the first aspect of the invention, wherein the third organic solvent is ethyl acetate or ethanol. A method for producing a polyurethane gel composition comprising: providing a diol monomer of pentanediol and/or polypropylene glycol and a diisocyanate monomer, wherein the diisocyanate monomer has the general formula (2): OCN -R ² -CH ₂ -R ³ -NCO, R ² and R ³ each independently represent a linear or branched divalent alkylene group having 2 to 16 carbon atoms or a carbon atom number of 3 to 12 Dicycloalkylene (cycloalkylene) having a weight average molecular weight of 1000 to 3000; dissolving the diol monomer and the diisocyanate monomer in ethyl acetate to form a homogeneous mixed solution, adding dilauric acid Butyltin (Dibutyltin Dilaurate), as a catalyst in the homogeneous mixed solution, and then stirred uniformly to become a mixed solution; heating the mixed solution, under physical shock, polymerization is carried out to produce a solid; ethyl acetate is removed, and ethyl acetate is used. The resulting solid is washed to remove unreacted monomers; tetrahydrofuran or ethanol is added and dispersed under physical vibration to form a polyurethane gel composition. According to the method of claim 4, the method further comprises: adding a graphene dispersion, wherein the graphene dispersion is composed of graphene dispersed in a third organic solvent, and uniformly dispersed in the polyamic acid. In the ester gel composition. The method of claim 4, wherein the graphene dispersion is formed by dispersing graphene in a third organic solvent by ultrasonic vibration or microwave, and the third organic solvent is ethyl acetate or ethanol. According to the method of claim 4, wherein the physical oscillation is ultrasonic oscillation. A polymer coating obtained by coating a polyurethane composition on a substrate, forming a coating film, and drying the composition, wherein the polyurethane gel composition comprises a polyamine a formate polymer and tetrahydrofuran or ethanol. The polyurethane polymer is obtained by reacting a diol monomer of pentanediol and/or polypropylene glycol with a diisocyanate monomer under ethyl acetate to remove unreacted Monomer, wherein the diol monomer and the diisocyanate monomer are soluble in ethyl acetate, the polyurethane polymer is insoluble in ethyl acetate but soluble in tetrahydrofuran or ethanol; wherein the diisocyanate is The compound has the general formula (2): OCN-R ² -CH ₂ -R ³ -NCO, and R ² and R ³ each independently represent a linear or branched divalent alkylene group having 2 to 16 carbon atoms (alkylene) Or a cycloalkylene having 3 to 12 carbon atoms, and the polypropylene glycol has a weight average molecular weight of 1,000 to 3,000. The polymer coating according to claim 8 , wherein the polyurethane gel composition further comprises a graphene dispersion, wherein the graphene dispersion is composed of graphene dispersed in a third organic solvent. And uniformly dispersed in the polyurethane gel composition, the polymer coating has a heat transfer coefficient of 0.5 W / m. K or more.