KR101725441B1 - Polyurethane reinforcement elastic nanocomposite crosslinked with single cellulose nanofibrils - Google Patents
Polyurethane reinforcement elastic nanocomposite crosslinked with single cellulose nanofibrils Download PDFInfo
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- KR101725441B1 KR101725441B1 KR1020150041483A KR20150041483A KR101725441B1 KR 101725441 B1 KR101725441 B1 KR 101725441B1 KR 1020150041483 A KR1020150041483 A KR 1020150041483A KR 20150041483 A KR20150041483 A KR 20150041483A KR 101725441 B1 KR101725441 B1 KR 101725441B1
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Abstract
The present invention relates to a polyurethane-based high-strength nanocomposite in which a single-cellulosic nanofiber is crosslinked, and a polyurethane-based elastic nanocomposite according to the present invention is characterized in that a single-cellulosic nanofiber is chemically crosslinked in a three-dimensional network structure to be compared with a conventional polyurethane And the mechanical strength and the dimensional stability against heat are remarkably excellent.
Description
The present invention relates to a polyurethane based high strength nanocomposite in which single cellulosic nanofibers are crosslinked.
Polyurethane elastomers are generally obtained by reacting a polyol component with a diisocyanate component to prepare a prepolymer and adding a chain extender to the polyurethane elastomer.
Generally, polyurethane is a polymer compound having a urea bond in its molecular structure. It is a product obtained by mixing polyol and isocyanate as main materials and mixing a foaming agent, a catalyst and a functional additive. As a substitute for plastic and rubber, . These polyurethanes are used as intermediate materials in various forms ranging from automotive, furniture, bedding, electronics, and clothing to household goods. They are superior to other materials in terms of cushioning, sound absorption, In addition, it is widely used in many advanced countries. In the late 1990s, demand for clothes, shoes, and furniture was sharply reduced due to the transfer of domestic producers overseas. In the latter half of 2007, about 75% of total demand was for automobile materials, membrane materials, I was in charge. Since such automobile materials, membrane materials, and insulating materials commonly require high strength, stability to heat, and light weight of products, studies for improving these properties have been actively and continuously carried out.
In order to improve such characteristics, glass fibers and carbon fibers are used as reinforcing materials for polyurethane based elastic composites composed of various high molecular compounds including polyurethane. Such reinforcing fibers are not only highly dense but also difficult to evenly disperse in a matrix. In addition, a large amount of reinforcing material is used in order to improve the properties. In this case, it is difficult to apply to various parts because it can cause skin and respiratory diseases to the workers during manufacturing of the composite and has an offensive color. have.
Cellulose is one of the abundant natural polymers present in the natural world, and has excellent mechanical strength and low thermal expansion. Therefore, it is widely used in various industries such as paper, electronics, household appliances, medicine, and food. In particular, nanocellulose produced by mechanical or chemical methods of such a cellulose has high specific surface area, low strength and low density, and thus exhibits excellent physical properties when used as a reinforcing material of a polymer composite. In addition, And mechanical properties, and can be very usefully applied to automobile interior and exterior materials and electric / electronic parts materials because of its environmental friendliness and light weight characteristics. In particular, non-patent reference 1 (Yao, X .; Qi, X .; He, Y .; Tan, D .; Chen, F .; Fu, Q. ACS Appl . Mater. Interfaces 2014 , 6 , 2497-2507. ), Oxidation of cellulose with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) yields single cellulosic nanofibers (i.e., 2,2,6,6-tetramethylpiperidin- (E.g., TEMPO-oxidized cellulose nanofibers (TOCNs)).
There is a lot of efforts to improve the properties of the existing composite and to promote its practical use by using nanocellulose reinforced composite having high strength and multi-functional characteristics by taking advantage of the advantages of nanocellulose. However, It is very difficult to simultaneously satisfy the interfacial bonding between the nanocells, and in particular, there is no practical example of a polyurethane based elastic nanocomposite reinforced with a single cellulosic nanofiber chemically bonded with a polyurethane matrix.
Accordingly, the inventors of the present invention have been studying a polyurethane based elastic nanocomposite reinforced with the single cellulosic nanofiber, while the polyurethane based elastic nanocomposite according to the present invention has a problem that the cellulose nanofiber is chemically crosslinked and compared with the conventional polyurethane And it is confirmed that the mechanical strength and the dimensional stability against heat are excellent, and the present invention has been completed.
An object of the present invention is to provide a composition for a polyurethane based elastic nanocomposite in which a single cellulose nanofiber is chemically crosslinked to have excellent mechanical strength and dimensional stability against heat.
Another object of the present invention is to provide a polyurethane based elastic nanocomposite comprising the above composition.
It is still another object of the present invention to provide a process for producing the polyurethane based elastic nanocomposite.
Another object of the present invention is to provide a soft tissue engineering support comprising the polyurethane based elastic nanocomposite.
It is still another object of the present invention to provide a protective film for a display panel comprising the polyurethane based elastic nanocomposite.
In order to achieve the above object, the present invention provides a process for producing a polyalkylene ether or ester polyol, an aromatic or aliphatic di- or tri- isocyanate and a single cellulosic nanofiber, The present invention also provides a composition for a polyurethane based elastic nanocomposite.
The present invention also provides a polyurethane based elastic nanocomposite comprising the composition for a polyurethane based elastic nanocomposite.
Further, the present invention relates to a method for producing a polyurethane foam, which comprises mixing a polyalkylene ether or ester polyol, an aromatic or aliphatic di- or tri- isocyanate and a single cellulosic nanofiber, 1) < / RTI >; and a method for producing the polyurethane based elastic nanocomposite.
The present invention also provides a soft tissue engineering support comprising the polyurethane based elastic nanocomposite.
Further, the present invention provides a protective film for a display panel comprising the polyurethane based elastic nanocomposite.
The polyurethane based elastic nanocomposite according to the present invention is chemically crosslinked with a three-dimensional network structure of single cellulosic nanofibers, and has remarkably excellent mechanical strength and dimensional stability against heat as compared with conventional polyurethane.
FIG. 1 is an image of single cellulosic nanofibers (TOCN) prepared in Preparation Example 1 uniformly dispersed in distilled water at a concentration of 0.1 wt% using transmission electron microscopy.
2 is an image of single cellulosic nanofibers (TOCN) prepared in Preparation Example 1 and uniformly dispersed in dimethylformamide (DMF) using transmission electron microscopy.
Fig. 3 is an image obtained by quenching the polyurethane based elastic nanocomposite prepared in Example 1 and Example 2 in liquid nitrogen, crushing it, and observing the inside of the surface using transmission electron microscopy ((a ) Surface of the polyurethane based elastic nanocomposite of Example 1; (b) the surface of the polyurethane based elastic nanocomposite of Example 2; (c) the interior of the polyurethane based elastic nanocomposite of Example 1; (d) Inside of the polyurethane based elastic nanocomposite of Example 2].
Fig. 4 is a photograph of the polyurethane based elastic nanocomposite prepared in Example 2 and Comparative Example 3 by soxhlet extraction and drying. (A): Example 2; (b): Comparative Example 3].
5 is an image showing a stress-strain curve measured by using a universal testing machine (UTM) for the tensile strength of the composite prepared in Examples 1-2 and 1-3 .
6 is an image showing a differential scanning calorimetry curve measured by differential scanning calorimetry (DSC) on the thermal properties of the composite prepared in Examples 1-2 and 1-3.
7 is a graph showing a thermal mechanical analysis (TMA) curve obtained by differential scanning calorimetry (DSC) of the thermal characteristics of the composite prepared in Examples 1-2 and 1-3. Image.
Hereinafter, the present invention will be described in detail.
The present invention relates to a polyurethane based elastic nanocomposite comprising a polyalkylene ether or ester polyol, an aromatic or aliphatic di- or tri- isocyanate and a single cellulosic nanofiber, ≪ / RTI >
Here, the polyalkylene ether or polyester polyols (Polyalkylene ether or ester polyol) has a number-average molecular weight (M n) of 300 to 5000 g / mol, preferably 1000 to 4000 g / mol, more preferably 1500 to 3000 g / mol, and most preferably 2000 g / mol, of an ether-based or ester-based polyol.
The number average molecular weight (M n) is 300 g / mol is less than the polyalkylene ether or the case of using a polyester polyol, is a problem in that the degree of curing of the polyurethane-based elastomer is made higher and, 5000 g / mol excess of the polyalkylene ether or ester When a polyol is used, there is a problem that the viscosity of the polyurethane-based elastic material to be produced is increased.
Specifically, the polyalkylene ether or the ester polyol may be a compound represented by the following formula (1).
[Chemical Formula 1]
In Formula 1,
R 1 , R 2 , R 3 and R 4 are independently -H or C 1-5 linear or branched alkyl;
n is an integer from 0 to 8;
m is an integer from 3 to 70;
More specifically, the polyalkylene ether or ester polyol may be selected from the group consisting of poly (tetramethylene ether) glycol, poly (tetrahydrofuran) And most preferably poly (tetramethylene ether) glycol (poly (tetramethylene ether) glycol) may be used.
The aromatic or aliphatic di- or tri- isocyanate is preferably a compound represented by the following formula (2), and 4,4-methylenediphenyl diisocyanate (4,4 -Methylene diphenyl diisocyanate) is most preferably used.
(2)
In Formula 2,
R 5 , R 6 and R 7 are independently -H or -NCO;
R 8 is -H, -OH, -NCO or an unsubstituted or substituted C 6-10 aryl,
The aryl of the substituted C 6-10 alkyl is a straight or branched, straight-chain or branched alkoxy and -NCO with a one or more substituents selected from the group consisting of substituted C 6-10 of C 1-5 C 1-5 Aryl;
y is an integer of 1 to 5; However, the compound represented by the general formula (2) includes at least two or more -NCO groups.
The ratio of the -NCO groups included in the aromatic or aliphatic di- or tri- isocyanate to the -OH group contained in the polyalkylene ether or ester polyol (-NCO / -OH) is preferably 0.8 to 1.2, more preferably 0.9 to 1.1, and most preferably 1.0. When the ratio (-NCO / -OH) is less than 0.8 or exceeds 1.2, the polyurethane-based precursor is not synthesized and the synthesis of the polyurethane-based elastomer is not easily induced.
Further, the single-cellulosic nanofibers can be obtained by oxidizing commercial wood pulp (hardwood or conifer) with TEMPO ((2,2,6,6-tetramethylpiperidin-1-yl) oxy) (Yield: 90% or more), a carboxyl group content of 1.0 to 1.6 mmol / g of cellulose, a fiber width of 3 to 20 nm, a fiber length of 1 to 10 μm and an aspect ratio of 100 or more Do. The single-cellulosic nanofibers prepared as described above exhibit excellent dispersibility in a water-based solvent, and are excellent in dimethylformamide, dimethylsulfoxide, dimethylacetamide and the like which are generally used in the production of polyurethane-based elastic nanocomposite by solvent substitution Dispersibility.
In addition, the composition may further include a chain extender. The chain extender may be selected from the group consisting of ethylene diamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane (3,3'-diaminodiphenylmethane ), 4,4'-Diaminodiphnylmethane, 1,4-Diaminobenzene, 3,3'-dimethoxy-4,4'-dia Dimethoxy-4,4'-diamino biphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl (3,3'-Dimethyl-4,4'-diamino biphenyl, 4,4'-diamino biphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl (3,3'-Dichloro-4,4 ' -diamino biphenyl) and the like can be used; As diol chain extender, 1,4-butanediol, 1,4-cyclohexane dimethanol, 1,4-cyclohexanediol, 1,4- cyclohexane diol, p, p'-biphenol, benzene-1,4-diol, quinol, 1,5-naphthalenediol naphthalene diol, 2,3-naphthalene diol, di (4-hydroxyphenyl) sulfone, 2,2- (di (hydroxyphenyl) 2,2-Di (hydroxyphenyl) propane, etc. Preferably, it may include ethylene diamine or 1,4-butanediol, and most preferably, And may include ethylene diamine.
Further, the present invention provides a polyurethane based elastic nanocomposite comprising the above composition.
The present invention also relates to a process for producing a polyalkylene ether or ester polyol, an aromatic or aliphatic di- or tri- isocyanate and a single cellulosic nanofiber, 1) < / RTI >; and a method for producing the polyurethane based elastic nanocomposite.
Hereinafter, the method for producing the polyurethane based elastic nanocomposite according to the present invention will be described in detail.
In the method for producing a polyurethane based elastic nanocomposite according to the present invention, the step 1 may be carried out using a polyalkylene ether or ester polyol, an aromatic or aliphatic di- or tri- isocyanate (Isocyanate) and single cellulosic nanofibers, and the mixing is preferably carried out in a solvent.
At this time, it is important to uniformly disperse the single cellulose nanofibers in the solvent in the step 1 in securing the physical properties of the polyurethane based elastic nanocomposite. The solvent of step 1 may be dimethylformamide, dimethylsulfoxide, dimethylacetamide or the like, preferably dimethylformamide.
The reaction temperature is preferably 50-150 ° C, more preferably 70-120 ° C, and most preferably 90 ° C, but is not limited thereto.
Further, the reaction time is preferably 1-6 hours, more preferably 2-5 hours, and most preferably 3 hours, but is not limited thereto.
By carrying out the step 1, the single-cellulosic nanofiber can be combined with a polyalkylene ether or ester polyol and an aromatic or aliphatic di- or tri- isocyanate to form a three- It forms a network and chemical cross-linking proceeds.
After the above step 1, the above-mentioned preparation method was repeated except that ethylene diamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane (3,3'-Dichloro-4,4'-diaminodiphenylmethane ), 4,4'-Diaminodiphnylmethane, 1,4-Diaminobenzene, 3,3'-dimethoxy-4,4'-dia Dimethoxy-4,4'-diamino biphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl (3,3'-Dimethyl-4,4'-diamino biphenyl, 4,4'-diamino biphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl (3,3'-Dichloro-4,4 ' diamino biphenyl, 1,4-butanediol, 1,4-cyclohexane dimethanol, 1,4-cyclohexane diol, , P'-biphenol, benzene-1,4-diol (Quinol), 1,5-naphthalene diol ), 2,3-naphthalene diol, di (4-hydroxyphenyl) sulfone, (Step 2) of adding at least one chain extender selected from the group consisting of 2,2-di (hydroxyphenyl) propane and 2,2-di (hydroxyphenyl) propane .
At this time, the reaction temperature is preferably 5-50 ° C, more preferably 10-40 ° C, most preferably 20-30 ° C, but is not limited thereto.
The reaction time is preferably 1-6 hours, more preferably 2-5 hours, most preferably 3 hours, but is not limited thereto.
After completion of the
According to the polyurethane-based elastic nanocomposite thus produced, it is possible to obtain a polyurethane-based elastic nanocomposite having cross-linked single-cellulosic nanofibers having both excellent tensile strength and elongation at room temperature and excellent thermal dimensional stability.
Further, the present invention provides a soft tissue engineering support comprising a polyurethane based elastic nanocomposite.
The present invention also provides a display panel protective film comprising a polyurethane based elastic nanocomposite.
The polyurethane based elastic nanocomposite according to the present invention is chemically crosslinked with a three-dimensional network structure of single cellulosic nanofibers, and has remarkably excellent mechanical strength and dimensional stability against heat as compared with conventional polyurethane.
As a result, the polyurethane based elastic nanocomposite prepared in Examples 1 and 2 was significantly superior to Comparative Example 1-3 in evaluating the thermal and mechanical properties of the polyurethane based elastic nanocomposite according to the present invention. Elastic modulus, tensile strength or stress, elongation or strain (see Table 1 in Experimental Example 1).
Further, experiments were conducted to evaluate whether the single cellulosic nanocomposite (TOCN) was uniformly dispersed in the polyurethane based elastic nanocomposite according to the present invention. As a result, the polyurethane based elastic nanocomposite prepared in Examples 1 and 2 It was confirmed that the single cellulosic nanofibers (TOCN) were uniformly dispersed (see FIG. 3 of Experimental Example 2).
Furthermore, the polyurethane based elastic nanocomposite according to the present invention was tested to evaluate whether the single cellulose nanofiber (TOCN) was chemically stably bonded to the polyurethane based elastic nanocomposite according to the present invention. As a result, , Whereas the polyurethane based elastic nanocomposite prepared in Comparative Example 3 showed that a considerable part of the composite was disappeared. Thus, it can be seen that the single cellulosic nanofibers (TOCN) are not physically mixed in the polyurethane based elastic nanocomposite prepared in Example 2, but are stably linked chemically or covalently (Experimental Example 3 4 of FIG.
As a result of conducting an experiment to evaluate the tensile strength of the polyurethane based elastic nanocomposite according to the present invention, it was found that the polyurethane based elastic nanocomposite prepared in Example 1 and Example 2 had a tensile strength higher than that of the composite prepared in Comparative Example 1-3 (See Fig. 5 of Experimental Example 4).
Further, in order to evaluate the thermal properties of the polyurethane based elastic nanocomposite according to the present invention, the thermal properties were evaluated by differential scanning calorimetry (DSC). As a result, it was found that the properties of Examples 1, 2, The glass transition temperatures of the composites prepared in Comparative Example 2 and Comparative Example 3 were found to be about 56 to 58 ° C. That is, it was confirmed that the chemical or physical mixing of single cellulosic nanofibers (TOCN) did not significantly affect the glass transition temperature (see FIG. 6 of Experimental Example 5).
Further, in order to evaluate the thermal properties of the polyurethane based elastic nanocomposite according to the present invention, the thermal properties were evaluated by thermomechanical analysis, and it was found that the composite sample prepared in Comparative Example 1 had a pore size of 3.3 mm at 100 ° C appear. In addition, the composite prepared in Comparative Example 2 and Comparative Example 3 showed a swelling of 3.0 and 2.9 mm reduced at 100 占 폚 per 1 m sample, respectively. Furthermore, the composites prepared in Examples 1 and 2 exhibited further dilatations of 2.5 and 2.3 mm at 100 占 폚 per 1 m sample, respectively.
The results show that the composite thermal expansion of Comparative Example 2 and Comparative Example 3 in which single cellulosic nanofibers (TOCN) were physically mixed was reduced by 7-10% and that the single cellulosic nanofibers (TOCN) were chemically crosslinked, The composite thermal expansion of Example 2 is shown to be reduced by 23-29%. It was confirmed that the thermal expansion coefficient also showed a similar tendency as shown in Table 1 (see FIG. 7 of Experimental Example 6).
Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples.
However, the following examples and experimental examples are illustrative of the present invention, and the contents of the present invention are not limited thereto.
< Manufacturing example 1 > single cellulosic nanofibers ( TOCN )
A method for producing a single cellulosic nanofiber (TOCN) is as follows.
10 g of commercial softwood (or hardwood) bleached kraft pulp (hardwood or conifer) was thoroughly dissociated in 1 L of distilled water, and then 0.16 g of TEMPO ((2,2,6,6-tetramethylpiperidin- (NaClO) 90.23 ml (12 mmol) having an effective chlorine content of 8% was slowly added to the mixture and stirred at room temperature for 3 hours to oxidize The reaction was induced. At this time, the pH of the mixed solution was maintained at 10 to 10.5 with 0.1 M aqueous sodium hydroxide solution. After completion of the reaction, the solution was washed several times with distilled water three times, filtered, and then stirred for 48 hours at room temperature using a 0.5 M aqueous sodium acetate buffer solution to replace the remaining aldehyde groups with carboxyl groups, .
After completion of the reaction, the pH neutrality was washed several times with the third distilled water to the end point and filtration was performed. The carboxyl group content of the pulp oxidized as described above was measured using a conductivity meter (Conductometric Titration), and it was confirmed that the carboxyl group content was 1.5 to 1.6 mmol / g of cellulose when the above method was used.
The pulp treated by the above oxidizing method was added to distilled water to adjust it to a concentration of 0.1 wt%, followed by dissociation at 7500 rpm for 1 minute using a double cylinder type homogenizer. The probe diameter was 7 mm Using an ultrasonic disperser (Sonicator) at 35% amplitude for 2 minutes. After the mechanical treatment, unfibrillated cellulose fraction was separated by treatment with a high performance centrifuge at a gravitational acceleration of 12,000 for 20 minutes. The yield of the single cellulosic nanofibers Was 95% or more.
A single nanofiber (TOCN) having a fiber width of 3 to 20 nm, a fiber length of 1 to 10 μm and an aspect ratio of 100 or more was obtained by the above method (oxidation reaction and mechanical treatment) (FIG.
FIG. 1 is an image of single cellulosic nanofibers (TOCN) prepared in Preparation Example 1 uniformly dispersed in distilled water at a concentration of 0.1 wt% using transmission electron microscopy.
It was found that the width of the single cellulosic nanofibers (TOCN) was about 10 nm or less and the length was 1-5 μm (aspect ratio:> 100). In addition, the carboxyl group content of the single cellulosic nanofibers (TOCN) was confirmed to be 1.0-1.6 mmol / g by conductometic titration.
The single cellulosic nanofibers (TOCN) dispersed in the distilled water were uniformly dispersed in dimethylformamide (DMF) through a solvent substitution method (FIG. 2).
2 is an image of single cellulosic nanofibers (TOCN) prepared in Preparation Example 1 and uniformly dispersed in dimethylformamide (DMF) using transmission electron microscopy.
The width of the single cellulosic nanofibers (TOCN) was found to be about 10 nm or less and the length was 1-10 μm (aspect ratio:> 100).
< Example 1> Polyurethane based elastic nanocomposite [ TPU / TOCN (C0.5)] 1
78.6 wt% of poly (tetramethylene ether) glycol (PTMEG) (number average molecular weight ( M n ): about 2000), 4,4-methylenediphenyl (TOCN / DMF solution at a concentration of 0.15 w / v%) in an amount of 19.7% by weight of diisocyanate (4,4-Methylene diphenyl diisocyanate) and 0.5% by weight of a single cellulosic nanofiber (TOCN) uniformly dispersed in dimethylformamide (DMF) v%. Therefore, 13.0 ml of TOCN / DMF solution and 17.0 ml of pure dimethylformamide (DMF) were added to make the total amount of dimethylformamide to 30.0 ml), and the mixture was reacted at 90 ° C for 3 hours, A prepolymer was prepared.
After the preparation of the precursor polymer was completed, 1.2 wt% of ethylene diamine was added as a chain extender to 100 wt% of the whole, and further reacted at room temperature for 3 hours.
When all the reaction is completed, the reaction product is cast and then cured for 24 hours in a drier (90 ° C) in which the internal air is discharged. Further, in order to completely remove the remaining solvent, Lt; / RTI >
The polyurethane based elastic nanocomposite in which the single cellulosic nanofiber was 0.5% by weight based on the total weight (100%) and was chemically bonded was prepared as described above. Hereinafter, the polyurethane based elastic nanocomposite prepared in Example 1 was named TPU / TOCN (C0.5).
< Example 2> Polyurethane based elastic nanocomposite [ TPU / TOCN (C1.0)] 2
78.2 wt% of poly (tetramethylene ether) glycol (PTMEG) (number average molecular weight ( M n ): about 2000), 4,4-methylenediphenyl (TOCN / DMF solution having a concentration of 0.15 w / w%) of 19.6% by weight of 4,4-Methylene diphenyl diisocyanate and 1.0% by weight of single cellulosic nanofibers (TOCN) uniformly dispersed in dimethylformamide (DMF) v%. Therefore, 26.7 ml of TOCN / DMF solution was added and 3.3 ml of pure dimethylformamide (DMF) was added to make the total amount of dimethylformamide 30.0 ml), followed by reaction at 90 ° C for 3 hours, A prepolymer was prepared.
After the preparation of the precursor polymer was completed, 1.2 wt% of ethylene diamine was added as a chain extender to 100 wt% of the whole, and further reacted at room temperature for 3 hours.
When all the reaction is completed, the reaction product is cast and then cured for 24 hours in a drier (90 ° C) in which the internal air is discharged. Further, in order to completely remove the remaining solvent, Lt; / RTI >
The polyurethane based elastic nanocomposite in which the single cellulose nanofiber was 1.0 wt% based on the total weight (100%) and was chemically bonded was prepared as described above. Hereinafter, the polyurethane based elastic nanocomposite prepared in Example 2 was named TPU / TOCN (C1.0).
< Comparative Example 1> Nanofiller Polyurethane-based elastomer not containing [ TPU ]
79.0 wt% of poly (tetramethylene ether) glycol (PTMEG) (number average molecular weight ( M n ): about 2000), 4,4-methylenediphenyl 19.8 wt% of diisocyanate (4,4-Methylene diphenyl diisocyanate) and 30 mL of dimethylformamide (DMF) were added and reacted at 90 ° C for 3 hours to prepare a prepolymer.
After the preparation of the precursor polymer was completed, 1.2 wt% of ethylene diamine was added as a chain extender to 100 wt% of the whole, and further reacted at room temperature for 3 hours.
When all the reaction is completed, the reaction product is cast and then cured for 24 hours in a drier (90 ° C) in which the internal air is discharged. Further, in order to completely remove the remaining solvent, Lt; / RTI >
A polyurethane elastomer not containing the nanofiller was prepared in the same manner as described above. Hereinafter, the polyurethane based elastomer produced in Comparative Example 1 was designated as TPU.
< Comparative Example 2> Polyurethane based elastic nanocomposite [ TPU / TOCN (P0.5)] 3
79.0 wt% of poly (tetramethylene ether) glycol (PTMEG) (number average molecular weight ( M n ): about 2000), 4,4-methylenediphenyl 19.8 wt% of diisocyanate (4,4-Methylene diphenyl diisocyanate) and 30 mL of dimethylformamide (DMF) were added and reacted at 90 ° C for 3 hours to prepare a prepolymer.
After the preparation of the precursor polymer was completed, 1.2 wt% of ethylene diamine was added as a chain extender to 100 wt% of the whole, and further reacted at room temperature for 3 hours.
When all the reaction is completed, the reaction product is cast and then cured for 24 hours in a drier (90 ° C) in which the internal air is discharged. Further, in order to completely remove the remaining solvent, Lt; / RTI >
30.0 ml of dimethylformamide (DMF) in which 0.5% by weight of single cellulosic nanofibers (TOCN) were uniformly dispersed in 100% by weight of the whole polyurethane elastomer (Comparative Example 1, TPU) The solution was cast and cured for 24 hours in a drier (90 ° C.) in which the internal air was discharged, and further dried using a vacuum dryer to completely remove the remaining solvent And dried at 90 DEG C for 24 hours.
A polyurethane based elastic nanocomposite having a physically simple mixture of the nanofiller was prepared in the same manner as described above. Hereinafter, the polyurethane based elastic nanocomposite prepared in Comparative Example 2 was named TPU / TOCN (P0.5).
< Comparative Example 3> Polyurethane based elastic nanocomposite [ TPU / TOCN (P1.0)] 4
79.0 wt% of poly (tetramethylene ether) glycol (PTMEG) (number average molecular weight ( M n ): about 2000), 4,4-methylenediphenyl 19.8 wt% of diisocyanate (4,4-Methylene diphenyl diisocyanate) and 30 mL of dimethylformamide (DMF) were added and reacted at 90 ° C for 3 hours to prepare a prepolymer.
After the preparation of the precursor polymer was completed, 1.2 wt% of ethylene diamine was added as a chain extender to 100 wt% of the whole, and further reacted at room temperature for 3 hours.
When all the reaction is completed, the reaction product is cast and then cured for 24 hours in a drier (90 ° C) in which the internal air is discharged. Further, in order to completely remove the remaining solvent, Lt; / RTI >
30.0 ml of dimethylformamide (DMF) in which 1.0% by weight of single cellulosic nanofibers (TOCN) were uniformly dispersed in 100% by weight of the whole polyurethane elastomer (Comparative Example 1, TPU) The solution was cast and cured for 24 hours in a drier (90 ° C.) in which the internal air was discharged, and further dried using a vacuum dryer to completely remove the remaining solvent And dried at 90 DEG C for 24 hours.
A polyurethane based elastic nanocomposite having a physically simple mixture of the nanofiller was prepared in the same manner as described above. Hereinafter, the polyurethane-based elasticity produced in Comparative Example 3 The nanocomposite was named TPU / TOCN (P1.0).
< Experimental Example 1> Evaluation of thermal and mechanical properties
In order to evaluate the thermal and mechanical properties of the polyurethane based elastic nanocomposite according to the present invention, the following experiment was conducted. The results are shown in Table 1 below.
1. Glass transition temperature (T g , ° C): The temperature at which the sample was transformed from glass to rubber phase was measured by differential scanning calorimetry (DSC) according to the temperature change (80 to 200 ° C).
2. Melting temperature (T m , ° C): The temperature at which the sample was converted into liquid phase in the rubber according to the temperature change (80 to 200 ° C) was measured by differential scanning calorimetry (DSC).
3. Enthalpy during melting (ΔH f , J / g): Determine the enthalpy required to convert the sample to liquid phase in the rubber (80-200 ° C) by differential scanning calorimetry (DSC) Respectively.
4. The coefficient of thermal expansion (coefficient of expansion, × 10 - 6 m / (m · ℃)).
5. Young's modulus (E): The specimen was prepared using ASTM D1708 and measured using a universal testing machine (UTM) at room temperature (20 to 30 ° C) (ASTM D412).
6. Tensile stress at break (σ b ): A specimen was prepared using ASTM D1708 and measured at room temperature (20 to 30 ° C) using a universal testing machine (UTM) (ASTM D412).
7. Strain at break (ε b ): Specimens were prepared using ASTM D1708 and measured at room temperature (20 to 30 ° C) using a universal testing machine (UTM) (ASTM D412) .
(占 10 -6 m / (m 占 폚))
(MPa)
(MPa)
(%)
As shown in Table 1, the polyurethane based elastic nanocomposite prepared in Examples 1 and 2 exhibited remarkably excellent elastic modulus, tensile strength, stress, elongation or strain than Comparative Example 1-3.
< Experimental Example 2 > single cellulosic nanofibers ( TOCN ) Distribution evaluation
In order to evaluate whether the single cellulosic nanocomposite (TOCN) was uniformly dispersed in the polyurethane based elastic nanocomposite according to the present invention, the polyurethane based elastic nanocomposite prepared in Example 2 was quenched in liquid nitrogen and crushed, It is an image observed by transmission electron microscopy. The results are shown in Fig.
3 is an image obtained by quenching the polyurethane based elastic nanocomposite prepared in Example 2 into liquid nitrogen and crushing it and observing the inside of the surface using transmission electron microscopy (a) and (b) ): Surface of the polyurethane based elastic nanocomposite of Example 2; (c) and (d): the interior of the polyurethane based elastic nanocomposite of Example 2].
As shown in FIG. 3, it was confirmed that the single cellulosic nanofibers (TOCN) were uniformly dispersed in the polyurethane based elastic nanocomposite prepared in Examples 1 and 2.
< Experimental Example 3> Single cellulosic nanofibers ( TOCN ) Evaluation of Bond Stability
To evaluate whether the single cellulosic nanofibers (TOCN) were chemically stably bonded to the polyurethane based elastic nanocomposite according to the present invention, the polyurethane based elastic nanocomposite prepared in Example 2 and Comparative Example 3 was subjected to soxhlet extraction The results are shown in FIG.
The soxhlet extraction was carried out as follows.
The polyurethane based elastic nanocomposite prepared in Example 2 and Comparative Example 3 was cut into a size of about 5 mm x 5 mm and weighed and placed in a cylindrical filter paper of known weight and then mounted on a Soxhlet Soxhlet extraction apparatus, Pyrex, CLS3740S). Extraction was started by adding 150 ml of dimethylformamide (DMF) to a 300 ml round flask, and the temperature was adjusted to be circulated at least 10 times per hour, and the mixture was extracted for 3 hours from the time of the first circulation. The extracted cylindrical filter paper was collected, cooled in a hood for a certain period of time, dried in a dryer at 105 ° C for 24 hours or more, stored in a desiccator, and then measured until there was no change in weight.
Fig. 4 is a photograph of the polyurethane based elastic nanocomposite prepared in Example 2 and Comparative Example 3 by soxhlet extraction and drying. (A): Example 2; (b): Comparative Example 3].
As shown in FIG. 4, it was found that most of the polyurethane based elastic nanocomposite prepared in Example 2 retained its shape, whereas the polyurethane based elastic nanocomposite prepared in Comparative Example 3 showed that a considerable part of the composite was disappeared . Specifically, the content of the complex remaining in the cylindrical filter paper before and after the extraction was compared. In Example 2, 45.2% of the initial amount was left and 13.4% of Comparative Example 3 remained. Thus, it can be seen that the single-cellulosic nanofibers (TOCN) are not physically mixed with the polyurethane based elastic nanocomposite prepared in Example 2, but are chemically or covalently stably linked to each other.
< Experimental Example 4> Evaluation of tensile strength
In order to evaluate the tensile strength of the polyurethane based elastic nanocomposite according to the present invention, a specimen was prepared using ASTM D1708 and measured using a universal testing machine (UTM) at room temperature (20 to 30 DEG C) ASTM D412). The results are shown in Fig.
5 is an image showing a stress-strain curve measured by using a universal testing machine (UTM) for the tensile strength of the composite prepared in Examples 1-2 and 1-3 .
As shown in Fig. 5, the polyurethane based elastic nanocomposite prepared in Examples 1 and 2 exhibited remarkably superior tensile strength than the composite prepared in Comparative Example 1-3.
Specifically, the composite produced in Comparative Example 1 exhibited an elastic modulus (E) of 1.9 MPa, a stress (? B ) of 2.4 MPa, and a strain (? B ) of 457%; The polyurethane based elastic nanocomposite prepared in Comparative Example 2 exhibited an elastic modulus (E) of 2.9 MPa, a stress (? B ) of 3.5 MPa, and a strain (? B ) of 507%; The polyurethane based elastic nanocomposite prepared in Comparative Example 3 exhibited an elastic modulus (E) of 3.2 MPa, a stress (? B ) of 5.2 MPa, and a strain (? B ) of 813%; The polyurethane based elastic nanocomposite prepared in Example 1 exhibited an elastic modulus (E) of 5.2 MPa, a stress (? B ) of 41.4 MPa and a strain (? B ) of 2587%; The polyurethane based elastic nanocomposite prepared in Example 2 had an elastic modulus (E) of 5.5 MPa, a stress (? B ) of 48.1 MPa, and a strain (? B ) of 2663%.
The nanocomposite (Comparative Example 2) physically mixed with the single cellulosic nanofibers (TOCN) increased the elastic modulus (E) by 33%, the stress increased by about 46-120%, and the strain Was increased by about 10-80%. However, the nanocomposite (Example 1) mixed chemically or covalently with single cellulosic nanofibers (TOCN) had an increase in elastic modulus (E) of 180% and a stress of about 1780% (About 18 times) and the strain increased about 500% (about 5 times).
The elastic modulus (E) and strain were slightly increased when the amount of single cellulosic nanofiber was increased from 0.5 wt% to 1.0 wt%.
< Experimental Example 5> Evaluation of Thermal Characteristics 1
In order to evaluate the thermal properties of the polyurethane based elastic nanocomposite according to the present invention, thermal characteristics were evaluated by differential scanning calorimetry (DSC). Concretely, the sample weight was set to 10 mg or more, 50 mL of nitrogen gas was circulated per minute, and the temperature was raised to 150 DEG C at room temperature. Then, peaks due to impurities were removed and the temperature was changed from -80 DEG C to 150 DEG C Were measured. The results are shown in Fig.
6 is an image showing a differential scanning calorimetry curve measured by differential scanning calorimetry (DSC) on the thermal properties of the composite prepared in Examples 1-2 and 1-3.
As shown in FIG. 6, the glass transition temperatures of the composites prepared in Example 1, Example 2, Comparative Example 1, Comparative Example 2, and Comparative Example 3 were found to be about 56 to 58 ° C. In other words, it was confirmed that the chemical or physical mixing of single cellulosic nanofibers (TOCN) did not affect the glass transition temperature.
In addition, the melting point of the composite prepared in Comparative Example 1-3 was about 20 ° C. On the other hand, the composite of Example 1 (including 0.5 wt% TOCN) and Example 2 (including 1.0 wt% TOCN), which chemically form a three-dimensional structure with single cellulosic nanofibers (TOCN), has a melting point of about 10 ° C appear. Furthermore, the enthalpy (ΔH m ) decreased by about 15 J / g. This means that the pure crystallinity of the composite prepared in Comparative Example 1 decreased due to chemical cross-linking with the single cellulose nanofiber. However, the composite crystals of Comparative Example 2 and Comparative Example 3 which were physically mixed with single cellulosic nanofibers (TOCN) showed no significant change compared to the composite of Comparative Example 1. [
Therefore, the polyurethane based elastic nanocomposite prepared in Examples 1 and 2 has a reduced melting point, and the single cellulosic nanofiber (TOCN) has a pure polyurethane elastomer (Comparative Example 1) and a chemical or covalent three-dimensional structure As shown in Fig.
<
Experimental Example
6> Evaluation of
To evaluate the thermal properties of the polyurethane based elastic nanocomposite according to the present invention, thermal properties were evaluated by thermomechanical analysis. Specifically, specimens of 5 mm × 5 mm in size were prepared from the composites prepared in Example 1, Example 2, Comparative Example 1, Comparative Example 2 and Comparative Example 3, and were measured using a thermomechanical analyzer at a rate of 50 (Thermomechanical Analyzer, TMA Q-400, TA Instrument) was used to measure the expansion curve and the thermal expansion coefficient per 1 m of the composite sample when the temperature was raised from 30 ° C to 100 ° C at a heating rate of 5 ° C / . The results are shown in Fig.
7 is a graph showing a thermal mechanical analysis (TMA) curve obtained by differential scanning calorimetry (DSC) of the thermal characteristics of the composite prepared in Examples 1-2 and 1-3. Image.
As shown in Fig. 7, it was found that 3.3 mm expanded at 100 占 폚 per 1 m of the composite sample prepared in Comparative Example 1. In addition, the composite prepared in Comparative Example 2 and Comparative Example 3 showed a swelling of 3.0 and 2.9 mm reduced at 100 占 폚 per 1 m sample, respectively. Furthermore, the composites prepared in Examples 1 and 2 exhibited further dilatations of 2.5 and 2.3 mm at 100 占 폚 per 1 m sample, respectively.
The results show that the composite thermal expansion of Comparative Example 2 and Comparative Example 3 in which single cellulosic nanofibers (TOCN) were physically mixed was reduced by 7-10% and that the single cellulosic nanofibers (TOCN) were chemically crosslinked, The composite thermal expansion of Example 2 is shown to be reduced by 23-29%. It was confirmed that the thermal expansion coefficient also showed a similar tendency as shown in Table 1 above.
Claims (10)
Wherein the single cellulosic nanofibers have a carboxyl group content of 1.0 to 1.6 mmol / g of cellulose g.
Wherein the polyalkylene ether or ester polyol has a number average molecular weight ( M n ) of 300 to 5000 g / mol.
The ratio of the -NCO groups included in the aromatic or aliphatic di- or tri- isocyanate to the -OH group contained in the polyalkylene ether or ester polyol (-NCO / -OH) is from 0.8 to 1.2.
Wherein the single-cellulosic nanofibers are single-cellulose nanofibers derived from wood pulp having an aspect ratio of 100 or more.
The composition may be selected from the group consisting of ethylene diamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 4,4'-diamino (4,4'-diaminodiphenylmethane), 1,4-diaminobenzene, 3,3'-dimethoxy-4,4'-diaminobiphenyl (3,3'- Dimethoxy-4,4'-diamino biphenyl, 3,3'-dimethyl-4,4'-diamino biphenyl, Diamino biphenyl, 3,3'-dichloro-4,4'-diamino biphenyl, 1,4-diamino biphenyl, Butanediol, 1,4-cyclohexane dimethanol, 1,4-cyclohexane diol, p-p-biphenol (1,4-cyclohexane diol) p, p'-biphenol, benzene-1,4-diol, quinol, 1,5-naphthalene diol, 2,3- 2,3-naphthalene diol, di (4-hydroxyphenyl) sulfone and 2,2- (di (hydroxyphenyl) Wherein the composition further comprises at least one chain extender selected from the group consisting of 2,2-di (hydroxyphenyl) propane.
Wherein the single cellulosic nanofibers have a carboxyl group content of 1.0 to 1.6 mmol / g of cellulose g.
After the above step 1, the above-mentioned preparation method was repeated except that ethylene diamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane (3,3'-Dichloro-4,4'-diaminodiphenylmethane ), 4,4'-Diaminodiphnylmethane, 1,4-Diaminobenzene, 3,3'-dimethoxy-4,4'-dia Dimethoxy-4,4'-diamino biphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl (3,3'-Dimethyl-4,4'-diamino biphenyl, 4,4'-diamino biphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl (3,3'-Dichloro-4,4 ' diamino biphenyl, 1,4-butanediol, 1,4-cyclohexane dimethanol, 1,4-cyclohexane diol, , P'-biphenol, benzene-1,4-diol (Quinol), 1,5-naphthalene diol ), 2,3-naphthalene diol, di (4-hydroxyphenyl) sulfone, (Step 2) of adding at least one chain extender selected from the group consisting of 2,2-di (hydroxyphenyl) propane and 2,2-di (hydroxyphenyl) propane Wherein the method comprises the steps of:
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| KR101050266B1 (en) * | 2010-08-02 | 2011-07-19 | 김재호 | Luminous composite materials with thermoplastic polyurethane elastomer and a method thereof |
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