TWI384005B - Compound and method for producing the same - Google Patents

Description

Composite and preparation method thereof

The present invention relates to a composite and a process for the preparation thereof, and in particular, the composite is an aqueous polyurethane-ceria composite, and the process of the present invention can obtain the aqueous polyurethane-ceria composite without the need for an external catalyst.

In recent years, organic-inorganic hybrid nanocomposites have been regarded as the main research and application topics in academia or industry because organic-inorganic nanocomposites have both organic properties (flexibility, ductility). Ductility)) and inorganic properties (rigidity, high thermal stability), and then the application of amplifying materials.

An organic-inorganic hybrid nanocomposite, which contains a nano-inorganic material, generally obtained by a sol-gel process of an inorganic alkoxide (M(OR) _n ), such as SiO ₂ , TiO ₂ , ZnO, etc. From 1970, the inorganic alkoxide was subjected to a hydrolysis/condensation procedure in an in-situ manner to form nanoparticles in an organic polymer to form an organic-inorganic nanocomposite. The hydrolysis/condensation procedure is carried out by introducing an acidic or basic catalyst into an inorganic alkoxide to hydrolyze the inorganic alkoxide to form an inorganic hydroxide (M(OH) _n ). The reaction formula can be expressed as follows: M ( OR) _n +nH ₂ O → M(OH) _n +n ROH

Wherein M = Na, Ba, Cu, Al, Si, Ti, Ge, V, W, ..., R = CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ , and the like. In particular, since M(OH) _n has a reactive functional group, polycondensation can be continued to form a three-dimensional network of -O-M-O-M.

In addition, polyurethane is a kind of polymer with both elastic and hard properties. It has low cost, convenient processing and diversified design. Therefore, it is widely used in coatings, building materials, people's livelihood, electronic packaging and other applications. However, polyurethane has the disadvantages of low thermal stability and high hygroscopicity. Therefore, under the premise of taking into account the properties of the polymer, the introduction of inorganic substances enhances heat resistance and water repellency, and the formation of polyurethane polymer composites has become a hot topic in related fields. research direction.

Regarding the preparation of polyurethane polymer composite materials, the basic properties of polyurethanes can be classified into (A) non-latex polyurethane (non-aqueous), and (B) latex polyurethane (aqueous). The method of using (A) non-latex polyurethane to make a polyurethane polymer composite can be further divided into (1) direct introduction of cerium oxide particles (such as natural crystalline cerium (Min-U-Sil), cerium oxide sol (colloidal) Silica) or fumed silica, and (2) hydrolysis/condensation procedures via acidic catalysts such as hydrochloric acid or acetic acid or basic catalysts such as ammonia Formation of cerium oxide. In addition, the method of using (B) latex polyurethane to form a polyurethane polymer composite material may also be classified into (1) direct introduction of cerium oxide particles (such as fumed silica), and (2) acidity. The catalyst (such as hydrochloric acid, etc.) undergoes a hydrolysis/condensation procedure to form cerium oxide; whereas the hydrolysis/condensation procedure with a basic catalyst is not observed. As apparent from the above description, if it is not desired to directly introduce the cerium oxide particles, the preparation of the polyurethane composite material can be carried out only by the catalyst.

Accordingly, one aspect of the present invention is to provide a method for preparing a composite which can be a polyurethane polymer composite and which can be prepared without the need for an external catalyst.

According to a specific embodiment, the method according to the invention comprises the steps of: firstly mixing a polycaprolactone polyol, dicyclohexylmethane diisocyanate, dimethylolpropionic acid and dibutyltin dilaurate in a solvent, To form a first Solution. Subsequently, the first solution and the triethylamine solution are mixed to form a second solution. Next, the second solution and a deionized water are mixed to form a second aqueous solution. The second aqueous solution and a triethylenetetramine solution are further mixed to form a third solution, and the third solution is filtered under a reduced pressure to obtain an aqueous polyurethane solution. In particular, the terminal of the aqueous polyurethane in the aqueous polyurethane solution contains an amino group.

Further, the aqueous polyurethane solution and tetraethoxysilane are mixed to form a fourth solution. Finally, a portion of the fourth solution is coated on a carrier, and the carrier and a portion of the fourth solution coated on the carrier are heated to form a film type on the carrier. Complex.

Another aspect of the present invention is to provide a composite which can be a polyurethane polymer complex and which can be prepared without the need for an external catalyst.

According to a particular embodiment of the invention, the composite comprises an aqueous polyurethane and a cerium oxide. The terminal of the aqueous polyurethane contains an amino group which may be primary ammonia or other suitable amino group, and the cerium oxide is mixed in the aqueous polyurethane.

The advantages and spirit of the present invention will be further understood from the following detailed description of the invention.

The present invention provides a compound and a method for preparing the complex. The composite may be a polyurethane polymer complex, and the method can prepare the composite without the need for an external catalyst. Specific embodiments in accordance with the present invention are disclosed below.

Referring to FIG. 1, FIG. 1 is a flow chart of a method according to an embodiment of the present invention.

As shown in FIG. 1, in the specific embodiment, the method comprises the following steps: First, in step S110, mixing polycaprolactone polyol, dicyclohexylmethane diisocyanate, dimethylolpropionic acid, and dilaurin Dibutyltin acid forms a first solution in a solvent. Subsequently, in step S112, the first solution and the triethylamine solution are mixed to form a second solution. Next, in step S114, the second solution and the deionized water are mixed to form a second aqueous solution. Next, in step S116, the second aqueous solution and the triethylenetetramine solution are mixed to form a third solution.

Subsequently, in step S118, the third solution is filtered under a reduced pressure environment to obtain an aqueous polyurethane solution, and the terminal of the aqueous polyurethane in the aqueous polyurethane solution contains an amino group. Also, in step S120, the aqueous polyurethane solution is rapidly stirred while tetraethoxy decane is added to form a fourth solution in situ. Please note that since the addition of the aqueous polyurethane solution to the tetraethoxy decane produces hydrolysis/condensation, resulting in the formation of the complex of the invention in the fourth solution. Finally, in step S122, a portion of the fourth solution is applied to the carrier and the carrier and a portion of the fourth solution applied to the carrier are heated to form a composite in a film form on the carrier.

The implementation environment of the method of the present invention will be specifically described below. It is to be noted that the following processes, materials, experimental parameters, and various data are merely illustrative of the invention and are not intended to limit the scope of the invention.

First, the polycaprolactone polyol (PCL) is placed in a 500 ml five-port separation reaction bottle, and appropriate temperature control equipment and a pressure reducing device are used to magnetically agitate the polycaprolactone polyol at 110 ° C. After removing the water for 30 min under reduced pressure, the mixture was cooled to room temperature (about 30 ° C) under reduced pressure. After removing the pressure reducing device, dicyclohexylmethane diisocyanate (H ₁₂ MDI), dimethylolpropionic acid (DMPA), dibutyltin dilaurate (DBT), and an appropriate amount of solvent are successively added to form a first The solution was subjected to polymerization at a temperature of 60 ° C for 4 hours. In practice, the component of the solvent may be acetone.

After the first solution is cooled to room temperature (about 30 ° C), the first solution and a triethylamine (TEA) solution are mixed to form a second solution, wherein the triethylamine solution is mixed with triethylamine. Formed by a solvent, and the composition of the first solvent is substantially the same as the solvent. After the second solution was stirred at a temperature of 30 ° C for 1 hour, the second solution and a deionized water were mixed to form a second aqueous solution. Mixing the second aqueous solution and a triethylenetetramine (TETA) solution to form a third solution, wherein the triethylenetetramine solution is formed by mixing a second solvent with triethylenetetramine, and the composition of the second solvent It is substantially the same as the solvent. The third solution was stirred at a temperature of 60 ° C for 1 hour. After the third solution is cooled to room temperature, the third solution is filtered under a reduced pressure to remove the solvent to obtain an aqueous polyurethane solution. Finally, the aqueous polyurethane is used to measure the aqueous polyurethane in the aqueous polyurethane solution to be 26.5. Wt%.

In this embodiment, the terminal of the aqueous polyurethane in the aqueous polyurethane solution contains an amino group. In practice, the amino group can be a primary ammonia or other suitable amino group. In addition, in practical applications, the weight ratio of the aforementioned polycaprolactone polyol: dicyclohexylmethane diisocyanate: dimethylolpropionic acid: triethylamine: triethylenetetramine may be, but is not limited to, 94.3: 31.3: 5.9:4.5:4.2.

In addition, for polycaprolactone polyol (PCL), dimethylolpropionic acid (DMPA), dicyclohexylmethane diisocyanate (H ₁₂ MDI), triethylenetetramine (TETA) and the aqueous polyurethane (WPU) The characteristic peaks of each material were measured by Fourier transform infrared spectroscopy (FTIR), and the measured data is shown in Fig. 2. The C=O characteristic peak of the polycaprolactone polyol (PCL) of the raw material appeared at 1722 cm ^-1 , and the characteristic peaks of C=O and O-H of dimethylol propionic acid (DMPA) appeared at 1683 cm ^- The N=C characteristic peak of ¹ and 3359 cm ^-1 , dicyclohexylmethane diisocyanate (H ₁₂ MDI) appeared at 2262 cm ^-1 , and was polymerized to form the aqueous polyurethane (WPU) at 2262 cm ^-1 (N =C stretching), the characteristic peak of 3359 cm ^-1 (O-H stretching) disappeared, and the characteristic peak of primary ammonia-NH ₂ appeared at 3223 cm ^-1 and 3319 cm ^-1 , which proved that the product was terminal ammonia. Aqueous polyurethane polymer.

Further, the aqueous polyurethane solution is subjected to a hydrolysis/condensation procedure using tetraethoxydecane. First, an appropriate amount of the aqueous polyurethane solution is placed in a beaker, the aqueous polyurethane solution is rapidly stirred, and tetraethoxy decane is added during the rapid stirring of the aqueous polyurethane solution to form a fourth solution in situ. After the fourth solution was stirred at room temperature for 1 hour to carry out a hydrolysis/condensation procedure, a complex solution was obtained. Applying a portion of the composite solution to a carrier and placing the carrier in a temperature-programmable non-convection oven, setting a temperature increasing procedure as shown in Table 1, a film type can be obtained on the carrier. Complex. As shown in Table 1, the film type composites were formed at temperatures of 55 ° C, 75 ° C, 100 ° C, and 120 ° C.

In this embodiment, the composite prepared by the foregoing method comprises an aqueous polyurethane, and cerium oxide, mixed in the aqueous polyurethane. Also, the terminal of the aqueous polyurethane contains an amino group which may be a primary ammonia or other suitable form of an amino group.

The polyurethane-ceria nanocomposite formed in this way can improve the thermal stability and water repellency of the polyurethane polymer. Moreover, the amount of tetraethoxy decane (which can form cerium oxide) is increased, and the mechanical strength, water repellency and thermal stability are also good.

In practical applications, different levels of cerium oxide may alter the properties of the composite of the present invention. Table 2 lists four samples of the composite of the present invention, and the amount of tetraethoxynonane used in each sample. Where sample a (SWPU) is an aqueous polyurethane sample containing no cerium oxide; sample b (SWPU5) is an aqueous polyurethane containing about 5 wt% cerium oxide prepared using 2.42 g of tetraethoxy decane- a sample of cerium oxide composite; sample c (SWPU10) is an aqueous polyurethane-cerium oxide composite sample containing about 10 wt% of cerium oxide produced using 5.10 g of tetraethoxy decane; sample d ( SWPU 15) is an aqueous polyurethane-ceria composite sample containing about 15% by weight of ceria produced using 8.15 g of tetraethoxynonane.

The following is an analysis of the (i) contact angle test, (b) mechanical properties, and (iii) thermal properties of various samples of different cerium oxide contents.

First, the sample d (SWPU15) was measured by solid-state ²⁹ Si NMR as shown in Fig. 3. Figure 3 shows the characteristic shifts of the chemical shifts in the samples at -108.72 ppm, -98.14 ppm and -93 ppm. The three characteristic peaks should be the structures of Q ⁴ , Q ³ and Q ² , respectively, where Q ⁴ and Q ^The structures of ³ and Q ² are shown in the supplementary diagram at the top right of Figure ² , respectively, and the characteristic peaks of Q ⁴ are extremely obvious, confirming that tetraethoxy decane is hydrolyzed/condensed to form cerium oxide.

In addition, Figure 4 shows an image of a sample d (SWPU15) at a magnification of 20,000 using a transmission electron microscope (TEM), in which the black particles are cerium oxide and the white bottom is an aqueous polyurethane substrate. The black fine-grained cerium oxide has a size of about 30 to 40 nm and is uniformly distributed in the aqueous polyurethane substrate, showing that the tetraethoxy decane is hydrolyzed/condensed to form cerium oxide, and the Q-type is obtained by solid-state ²⁹ Si NMR. The results are mutually reinforcing.

(1) Contact angle test

The contact angle data of the sample surface measured by the contact angle meter is shown in Fig. 5. Figure 5 shows a sample a (SWPU) contact angle of 67.2° without addition of tetraethoxy decane, when a small amount of tetraethoxy decane, such as sample b (SWPU5) (about 5 wt% cerium oxide), is added. The contact angle is increased by about 5% (70.6°), indicating that the WPU has an increased contact angle due to the presence of cerium oxide. Increasing the amount of tetraethoxynonane in an aqueous polyurethane substrate, such as sample c (SWPU10) (about 10 wt% ceria), the contact angle measured by 13% larger than sample a (SWPU), and the sample The contact angle of d(SWPU15) (about 15 wt% ceria) was about 17% (78.4°) higher than that of sample a (SWPU). Therefore, it is apparent from Fig. 5 that the contact angle of the aqueous polyurethane polymer composite increases with the increase in the amount of tetraethoxysilane (which can form cerium oxide).

(2) Mechanical properties

The mechanical properties of the mechanical thermal analyzer were measured using a dynamic mechanical thermal analyzer (DMA). The tensile speed of the mechanical thermal analyzer was set to 1 N/min, and the thickness of the test sample was 150 μm. The stress of the test sample was measured at room temperature. The change in strain, Figure 6 shows the mechanical properties of the composite sample with various cerium oxide contents. Sample a (SWPU, aqueous polyurethane sample without ceria), sample b (SWPU5, aqueous polyurethane-ceria composite sample containing about 5 wt% ceria), sample c (SWPU10, approx. 10 wt% of cerium oxide aqueous polyurethane-cerium oxide composite sample) and sample d (SWPU15, about 15 wt% of cerium oxide aqueous polyurethane-cerium oxide composite sample) are respectively shown in Figure 6. (a), (b), (c) and (d) show that Figure 6 shows the sample a (SWPU) with a stress value of 1.5 MPa at a tensile force of 100%; when a trace amount of tetraethoxynonane is added In the aqueous polyurethane substrate, for example, the sample b (SWPU5), the stress under the same tensile force is 1.75 MPa, which is a significant increase of about 19% compared to the sample a (SWPU); the sample c (SWPU10) is under the same tensile force. The stress value is 2.05 MPa; the stress value of the sample d (SWPU15) under the same tensile force is 2.10 MPa, which is about 35% higher than the sample a (SWPU). The overall mechanical strength is shown with tetraethoxy decane. Increased in the amount of (which can form cerium oxide).

(3) Thermal properties

The sample a to the sample d were tested for thermal stability by a thermogravimetric analyzer (TGA) at a temperature ranging from 40 to 800 ° C, and the heating rate during the test was 10 ° C / min. The result was shown in a N ₂ atmosphere. In Fig. 7, the labels (a), (b), (c), and (d) indicate sample a (SWPU), sample b (SWPU5), sample c (SWPU10), and sample d (SWPU15), respectively. The upper part of Fig. 7 is the relationship between the thermogravimetric loss and the temperature, and the lower part is the relationship between the first-order differential of the thermogravimetric loss and the temperature, and the thermal decomposition temperature data is summarized in Table 3. From the curve of the first-order differential line, it is seen that each sample has a three-stage decomposition phenomenon. The decomposition temperature of the first stage is about 40~300 °C. At this stage, the decomposition shows a slight thermal weight drop phenomenon and the decomposition temperature. As the content of cerium oxide increases, the slight change in the thermal weight (6~9 wt%) in this stage may be due to the decomposition of water and small molecules in the residual part of the sample, and the polymer is In the water-dispersed aqueous polyurethane solution, since the aqueous polyurethane is 26.5 wt%, after the tetraethoxy decane is added to the solution, the solid content of the composite relative to the same liquid amount is The amount of tetraethoxy decane added was increased, so that the amount of liquid was relatively decreased. It is apparent from Table 3 that the thermogravimetric residual value of the composite is larger than that of the aqueous polyurethane containing no cerium oxide. The second stage decomposition temperature range is about 300~400 °C, which is mainly the decomposition of the hard segment of polyurethane. The third stage decomposition temperature range is about 400~500 °C, which is mainly the decomposition of the soft segment of polyesteramine. Looking at the relationship between the residual value of the thermogravimetry and the temperature, it is apparent that the composite after adding tetraethoxysilane (which can form cerium oxide) has higher heat resistance than the aqueous polyurethane containing no cerium oxide.

^a temperature (T _max ) at the maximum decomposition rate of the thermogravimetric residual value ^b at this temperature

In summary, the present invention provides a method of preparing a composite, which may be a polyurethane polymer complex, and the method can prepare the composite without the need for an external catalyst. The polyurethane polymer composite combines the advantages of high molecular organic substances and inorganic substances, and has organic property (flexibility, ductility) and inorganic properties (rigidity, high thermal stability). ), and then the field of application of the amplified material.

The features and spirit of the present invention will be more apparent from the detailed description of the preferred embodiments. On the contrary, the intention is to cover various modifications and equivalents within the scope of the invention as claimed. Therefore, the scope of the patented scope of the invention should be construed as broadly construed in the

S110~S122‧‧‧ Process steps

1 is a flow chart showing a method of fabricating a composite according to an embodiment of the present invention.

2 is a graph showing polycaprolactone polyol (PCL), dimethylolpropionic acid (DMPA), dicyclohexylmethane diisocyanate (H ₁₂ MDI), triethylenetetramine (TETA) and the like according to the present invention. Fourier transform infrared spectroscopy (FTIR) image of aqueous polyurethane (WPU).

Figure 3 is a graph showing the solid state ²⁹ Si NMR spectrum of the aqueous polyurethane-ceria nanocomposite according to the present invention.

Figure 4 is a diagram showing a transmission electron microscope (TEM) image of the aqueous polyurethane-ceria nanocomposite according to the present invention at 20,000 times.

Figure 5 is a schematic view showing the results of contact angle test of the aqueous polyurethane-niobium oxide nanocomposite according to the present invention.

Figure 6 is a schematic view showing the tensile strength of the aqueous polyurethane-niobium oxide nanocomposite according to the present invention.

Figure 7 is a thermogravimetric analysis diagram of an aqueous polyurethane-niobium oxide nanocomposite according to the present invention.

S110~S122‧‧‧ Process steps

Claims (8)

A method for preparing a composite comprising the steps of: mixing a polycaprolactone polyol, dicyclohexylmethane diisocyanate, dimethylolpropionic acid, and dibutyltin dilaurate to form a first solution in a solvent; Mixing the first solution and the triethylamine solution to form a second solution; mixing the second solution and a deionized water to form a second aqueous solution; mixing the second aqueous solution and a triethylenetetramine solution to form a first a third solution; filtering the third solution under a reduced pressure to obtain an aqueous polyurethane solution, wherein the aqueous polyurethane ester has an amino group at the end of the aqueous polyurethane solution; mixing the aqueous polyurethane solution and tetraethoxy decane to form a fourth a solution; and coating a portion of the fourth solution on a carrier and heating the fourth solution to the carrier and the portion coated on the carrier to form a film pattern on the carrier The complex. The method of claim 1, wherein the polycaprolactone polyol: dicyclohexylmethane diisocyanate: dimethylolpropionic acid: triethylamine: triethylenetetramine is present in a weight ratio of 94.3:31.3: 5.9:4.5:4.2. The method of claim 1, wherein the component of the solvent is acetone. The method of claim 3, wherein the triethylamine solution is formed by mixing a first solvent with triethylamine, and the component of the first solvent is the same as the solvent. The method of claim 3, wherein the triethylenetetramine solution It is formed by mixing a second solvent with triethylenetetramine, and the composition of the second solvent is the same as the solvent. The method of claim 1, wherein the composite is formed at a temperature of 55 ° C, 75 ° C, 100 ° C, and 120 ° C. The method of claim 1, wherein the amino group at the end of the aqueous polyurethane solution is a primary ammonia. The method of claim 1, further comprising the steps of: rapidly stirring the aqueous polyurethane solution; and adding the tetraethoxy decane to form the fourth solution in situ during rapid stirring of the aqueous polyurethane solution; The aqueous polyurethane solution is added to the tetraethoxy decane to produce a hydrolysis/condensation process to produce the complex in the fourth solution.