US20120101203A1 - Compound and method for producing the same - Google Patents
Compound and method for producing the same Download PDFInfo
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- US20120101203A1 US20120101203A1 US13/342,034 US201213342034A US2012101203A1 US 20120101203 A1 US20120101203 A1 US 20120101203A1 US 201213342034 A US201213342034 A US 201213342034A US 2012101203 A1 US2012101203 A1 US 2012101203A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
Definitions
- the present invention relates to a compound and method for producing the same, and more particularly, the compound is the waterborne polyurethane-silica composite material. Additionally, the method of the present invention produces the waterborne polyurethane-silica composite material without any extra catalyst.
- organic-inorganic mixing nanocomposite material is a major topic both in the industry and in the academia. It is because the organic-inorganic nanocomposite material has flexibility, ductility, rigidity, and high thermal stability, so as to broaden the applied scope.
- the nanoinorganic of the organic-inorganic nanocomposite material is produced by a sol-gel process of inorganic alkoxide (M(OR) n ), for example, SiO 2 , TiO 2 , and ZnO. Since 1970, the inorganic alkoxide is proceeded a sol-gel process by an in-situ approach to form nanopraticles in an organic polymer, so as to form organic-inorganic nanocomposite material.
- a sol-gel process is to add acid or alkaline catalysts into an inorganic alkoxide which is proceeding a hydrolytic reaction to form an inorganic hydroxide (M(OH) n ). The chemical equation is as followed:
- M Na, Ba, Cu, Al, Si, Ti, Ge, V, W, etc.
- R CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9 ⁇ M(OH) n , in particular, comprises a functional group and thus it can proceed a polymerization reaction to form O-M-O-M three-dimensional network.
- polyurethane has both flexibility and rigidity. It is low in cost, easy to manufacture, and various in design. Thus it is widely applied to coating, building, and electronic sealing. However, polyurethane is low in thermal stability and high in hygroscopicity. On the primes of keeping the features of the polyurethane, introducing inorganic to raise the heat resistance and the water repellency of polyurethane composite material becomes a popular study topic in related scopes.
- polyurethane is classified into non-waterborne polyurethane and waterborne polyurethane.
- the methods apply (A) for producing non-waterborne polyurethane composite material classified as (1) directly introducing silicon dioxide particles (e.g. Min-U-Sil, colloidal silica, or fumed silica); and (2) silicon dioxide formed by a sol-gel process with acid catalysts (e.g. hydrochloric acid, acetic acid) or alkaline catalysts (e.g. ammonia).
- acid catalysts e.g. hydrochloric acid, acetic acid
- alkaline catalysts e.g. ammonia
- the methods apply (B) for producing waterborne polyurethane composite material classified as (1) directly introducing silicon dioxide particles (e.g.
- an aspect of the present invention is to provide a method for producing a compound.
- the compound is a polyurethane composite material and the method of the present invention produces the compound without any extra catalysts.
- the method comprises the following steps:
- PCL polycaprolactone
- DMPA dimethylol propionic acid
- H12MDI 4, 4′-methylenebis (cyclohexyl isocyanate)
- DBT dibutyltin dilaurate
- the first solution is mixed with a triethylamine (TEA) solution to form a second solution and the second solution is mixed with deionized water to form a second aqueous solution.
- the second aqueous solution is mixed with triethylene tetramine (TETA) solution to form a third solution and the third solution is filtered in a pressure-reducing environment to obtain a waterborne polyurethane (WPU) solution.
- the terminal of the waterborne polyurethane comprises an amino group.
- the waterborne polyurethane solution is mixed with tetraethylorthosilicate (TEOS) to form a fourth solution.
- TEOS tetraethylorthosilicate
- Another aspect of the present invention is to provide a compound which is polyurethane composite material produced without any extra catalyst.
- the compound comprises waterborne polyurethane and silicon dioxide.
- the terminal of the waterborne polyurethane comprises an amino group which is primary amine or other proper amino group.
- Silicon dioxide is mixed with the waterborne polyurethane.
- FIG. 1 illustrates a producing flow chart according to one embodiment of the present invention.
- FIG. 2 illustrates FTIR spectrums of PCL, DMPA, H12MDI, TETA and WPU according to the present invention.
- FIG. 3 illustrates 29 Si NMR spectrum of waterborne polyurethane-silica nanocomposite material according to the present invention.
- FIG. 4 illustrates TEM image of waterborne polyurethane-silica nanocomposite material of 20000 times according to the present invention.
- FIG. 5 illustrates contact angle testing result of waterborne polyurethane-silica nanocomposite material according to the present invention.
- FIG. 6 illustrates the tension intensity of waterborne polyurethane-silica nanocomposite material according to the present invention.
- FIG. 7 illustrates thermogravimetric analysis of waterborne polyurethane-silica nanocomposite material according to the present invention.
- the present invention is to provide a compound and method for producing the same.
- the compound is a polyurethane composite material and the method for producing the compound without any extra catalyst. Embodiments of the present invention are disclosed as followed.
- FIG. 1 illustrates a flow chart according to one embodiment of the present invention.
- the method comprises the following steps:
- step S 110 PCL, DMPA, H12MDI, and DBT are mixed in a solvent to form the first solution.
- step S 112 the first solution is mixed with a TEA solution to form a second solution.
- step S 114 the second solution is mixed with deionized water to form a second aqueous solution.
- step S 116 the second aqueous solution is mixed with TETA solution to form a third solution.
- step S 118 the third solution is filtered in a pressure-reducing environment to obtain a waterborne polyurethane solution.
- the terminal of the waterborne polyurethane comprises an amino group.
- step S 120 the waterborne polyurethane solution is stirred rapidly and TEOS is added into the waterborne polyurethane solution simultaneously by an simultaneously by an in-situ approach to form the fourth solution. What is remarkable is the addition of TEOS brings a sol-gel process, so as to produce the compound of the present invention in the fourth solution.
- step S 122 part of the fourth solution is coated on a carrier and the solution on the carrier is heated, so as to form the compound with thin film type.
- a 500 ml PCL is set in a five-necked flask equipped with a proper temperature control apparatus and a pressure-reducing apparatus.
- PCL with magnetic stirring is degassed in a pressure-reducing environment at 110° C. for 30 minutes and cools down to room temperature (30° C.) under pressure-reducing station.
- H12MDI, DMPA, DBT, and some solvent are mixed to form a first solution which is proceeded a polymerization reaction at 60° C. for four hours.
- the composition of the solvent can be acetone.
- the first solution and TEA solution are mixed to form a second solution wherein the TEA solution is formed by TEA mixed with the first solvent and the composition of the first solvent is substantially the same as the solvent.
- the second solution is stirred at 30° C. for one hour and the second solution is mixed with deionized water to form a second aqueous water.
- the second aqueous water is mixed with TETA solution to form a third solution wherein the TETA is mixed with the second solvent to form the TETA solution and the composition of the second solvent is substantially the same as the solvent.
- the third solution is stirred at 60° C. for one hour.
- the third solution After the third solution cools down to room temperature, the third solution is filtered in a pressure-reducing environment to get a waterborne polyurethane solution.
- the waterborne polyurethane is determined by a moisture titrator and the waterborne polyurethane occupies 26.5 wt %.
- the terminal of the waterborne polyurethane comprises an amino group.
- the amino group can be prime amine or other proper amino group.
- the weight ratio of PCL:DMPA:H12MDI:TEA:TETA is 94.3:31.3:5.9:4.5:4.2, but not limited to this.
- the characteristic peak of PCL, DMPA, H12MDI, TETA and waterborne polyurethane (WPU) are determined by FTIR.
- the determining result is as follows.
- the C ⁇ O characteristic peak of PCL exists at 1722 cm ⁇ 1 ;
- the C—O and O—H characteristic peak of DMPA exists at 1683 cm ⁇ 1 and 3359 cm ⁇ 1 respectively;
- the N ⁇ C characteristic peak of H12MDI exists at 2262 cm ⁇ 1 .
- the N ⁇ C (2262 cm ⁇ 1 ) and O-H characteristic peaks (3359 cm ⁇ 1 ) disappear.
- the primary amine —NH 2 exists at 3223 cm ⁇ 1 and 3319 cm ⁇ 1 that can prove the production is amino-terminated anionic waterborne polyurethane.
- the WPU solution with TEOS is proceeded as a sol-gel process.
- TEOS is added into the WPU solution simultaneously by an in-situ approach to form the fourth solution.
- the fourth solution is stirred at room temperature for one hour to proceed as a sol-gel process to obtain a composite solution.
- Part of composite solution is coated on a carrier and the carrier is set in a temperature-controllable non-convection baking oven.
- the temperature raising process is shown in table 1.
- a compound with thin film type on the carrier is obtained.
- the compound with thin film type is formed at 55° C., 75° C., 100° C., and 120° C.
- the compound produced by the method mentioned comprising waterborne polyurethane and silicon dioxide mixed with the waterborne polyurethane wherein the terminal of the waterborne polyurethane comprises an amino group which can be primary amine or other proper amino group.
- Waterborne polyurethane-silica nanocomposite material formed by an in-situ approach raises the heat resistance and the water repellency of polyurethane.
- the rigidity, heat resistance, and the water repellency are rising with the using weight of TEOS.
- Sample a is waterborne polyurethane without silicon dioxide
- Sample b is a waterborne polyurethane-silica nanocomposite material with 5 wt % silicon dioxide (formed by adding 2.42 g TEOS)
- Sample c is a waterborne polyurethane-silica nanocomposite material with 10 wt % silicon dioxide (formed by adding 5.10 g TEOS)
- Sample d is a waterborne polyurethane-silica nanocomposite material with 15 wt % silicon dioxide (formed by adding 8.15 g TEOS).
- sample d (SWPU15) is determined by 29 Si NMR to obtain a silicon spectrum as shown in FIG. 3 .
- FIG. 3 illustrates the character peaks of silicon chemical shift at ⁇ 108.72 ppm, ⁇ 98.14 ppm, and ⁇ 93 ppm.
- the three character peaks correspond to Q 4 , Q 3 , and Q 2 constructions respectively.
- Q 4 , Q 3 , and Q 2 constructions are shown in the top right-hand corner of FIG. 3 .
- the character peak of Q 4 is clear that can prove the TEOS is proceeded as a sol-gel process to produce silicon dioxide.
- FIG. 4 illustrates the TEM image of sample d (SWPU15) of 20000 times.
- the dark particles are silicon dioxide and the white parts are waterborne polyurethane base materials.
- the length of dark particles are approximately 30 ⁇ 40 nm and disturb in the waterborne polyurethane materials uniformly. It shows that TEOS is proceeded as a sol-gel process to produce silicon dioxide. The conclusion is the same as above.
- FIG. 5 illustrates the data of contact angles on the sample surface determined by a contact angle meter.
- the contact angle of sample a (SWPU), without TEOS, is 67.2°.
- Samples with TEOS, for example, sample b (SWPU5, 5 wt % of silicon dioxide), the contact angle)(70.6°) raises 5%, compared with sample a, WPU with silicon dioxide can raise the degree of contact angle.
- Raising the using weight of TEOS of waterborne polyurethane for example, sample c (SWPU10, 10 wt % of silicon dioxide), the determined contact angle compared with sample a raises 13% and sample d (SWPU15, 15 wt % of silicon dioxide), the determined contact angle (78.4)° compared with sample a raises 17%.
- sample c SWPU10, 10 wt % of silicon dioxide
- sample d SWPU15, 15 wt % of silicon dioxide
- the determined contact angle 78.4° compared with sample a raises 17%.
- the contact angle of waterborne polyurethane composite material raises with the using weight of the TEOS (it can produce silicon dioxide).
- FIG. 6 illustrates the testing result of mechanical property of samples with different content of silicon dioxide.
- Sample a (SWPU, waterborne polyurethane without silicon dioxide), sample b (SWPU5, waterborne polyurethane-silica composite material with 5 wt % silicon dioxide), sample c (SWPU10, waterborne polyurethane-silica composite material with 10 wt % silicon dioxide), and sample d (SWPU15, waterborne polyurethane-silica composite material with 15 wt % silicon dioxide) are represented as (a), (b), (c), and (d) respectively in FIG. 6 .
- the magnitude of strain is 100% and the magnitude of stress is 1.5 MPa.
- a waterborne polyurethane base material with little TEOS, for example, sample b (SWPU5) the magnitude of strain is 100% and the magnitude of stress is 1.75 MPa compared with sample a, the magnitude of stress raised by 19%.
- the magnitude of strain is 2.05 MPa for sample c (SWPU10); and the magnitude of strain is 2.10 MP for sample d (SWPU15) compared with the sample a, the magnitude of stress raising 35%.
- the mechanical intensity rises with the weight of TEOS used.
- sample a, b, c and d are tested by TGA at temperature 40 ⁇ 800° C.
- the speed of raising temperature is 10° C./min and N 2 gas is flown during testing.
- the result is shown in FIG. 7 .
- (a), (b), (c), and (d) represent sample a (SWPU), sample b (SWPU5), sample c (SWPU10), and sample d (SWPU15), respectively.
- the upper half of FIG. 7 illustrates the relationship between thermal weight losing and temperature, and the lower half of FIG. 7 illustrates the relationship between first order differentiation of thermal weight losing and temperature.
- Table 3 lists the date of thermal dissolution temperature. From the curve of first order differentiation, every sample has three dissolution stages. The first dissolution temperature is approximately 40 ⁇ 300° C.
- thermal weight decreases lightly and the dissolution temperature rises with the content of silicon dioxide.
- thermal weight changes 6 ⁇ 9 wt % and it may be due to the remainder water or molecules decomposing and the polymer which is aqueous dispersion polymer.
- the aqueous dispersion polymer waterborne polyurethane comprises 26.5 wt % waterborne polyurethane.
- the thermal remainder weight is bigger than waterborne polyurethane without silicon dioxide.
- the temperature of the second dissolution stage is approximately 400 ⁇ 500° C.
- the soft chain of waterborne polyurethane-silica decomposes mainly.
- thermal remainder weight and temperature shows the compound with TEOS with higher thermal resistance than waterborne polyurethane without silicon dioxide.
- the present invention is to provide a method for producing a compound.
- the compound is a polyurethane composite material and the method of the present invention produces the compound without any extra catalyst.
- Polyurethane has the advantages of both being organic and inorganic. It is flexible, ductile, rigid, and high in thermal stability, so as to widen the applied scopes.
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Abstract
The invention provides a compound and method of producing the same. The method of the invention includes the following steps. First of all, Polycaprolactone (PCL), dimethylol propionic acid (DMPA), 4,4′-methylenebis (cyclohexyl isocyanate) (H12MDI), and dibutyltin dilaurate (DBT) are mixed in a solvent in the first place and a solution is formed. This solution is then mixed with triethylamine (TEA) and triethylene tetramine (TETA). After that, amino-terminated anionic waterborne polyurethane (WPU) is produced. A sol-gel process is proceeded with a mixture of amino-terminated anionic waterborne polyurethane, tetraethylorthosilicate (TEOS) without any extra catalyst, and a compound, waterborne polyurethane-silica nanocomposite materials, is eventually produced.
Description
- 1. Field of the Invention
- The present invention relates to a compound and method for producing the same, and more particularly, the compound is the waterborne polyurethane-silica composite material. Additionally, the method of the present invention produces the waterborne polyurethane-silica composite material without any extra catalyst.
- 2. Description of the Prior Art
- Recently, organic-inorganic mixing nanocomposite material is a major topic both in the industry and in the academia. It is because the organic-inorganic nanocomposite material has flexibility, ductility, rigidity, and high thermal stability, so as to broaden the applied scope.
- The nanoinorganic of the organic-inorganic nanocomposite material is produced by a sol-gel process of inorganic alkoxide (M(OR)n), for example, SiO2, TiO2, and ZnO. Since 1970, the inorganic alkoxide is proceeded a sol-gel process by an in-situ approach to form nanopraticles in an organic polymer, so as to form organic-inorganic nanocomposite material. A sol-gel process is to add acid or alkaline catalysts into an inorganic alkoxide which is proceeding a hydrolytic reaction to form an inorganic hydroxide (M(OH)n). The chemical equation is as followed:
-
M(OR)n +nH2O→M(OH)n +nROH - Wherein M=Na, Ba, Cu, Al, Si, Ti, Ge, V, W, etc., and R=CH3, C2H5, C3H7, C4H9− M(OH)n, in particular, comprises a functional group and thus it can proceed a polymerization reaction to form O-M-O-M three-dimensional network.
- Additionally, polyurethane has both flexibility and rigidity. It is low in cost, easy to manufacture, and various in design. Thus it is widely applied to coating, building, and electronic sealing. However, polyurethane is low in thermal stability and high in hygroscopicity. On the primes of keeping the features of the polyurethane, introducing inorganic to raise the heat resistance and the water repellency of polyurethane composite material becomes a popular study topic in related scopes.
- According to the reference of producing polyurethane composite material, polyurethane is classified into non-waterborne polyurethane and waterborne polyurethane. The methods apply (A) for producing non-waterborne polyurethane composite material classified as (1) directly introducing silicon dioxide particles (e.g. Min-U-Sil, colloidal silica, or fumed silica); and (2) silicon dioxide formed by a sol-gel process with acid catalysts (e.g. hydrochloric acid, acetic acid) or alkaline catalysts (e.g. ammonia). Additionally, the methods apply (B) for producing waterborne polyurethane composite material classified as (1) directly introducing silicon dioxide particles (e.g. fumed silica); and (2) silicon dioxide formed by a sol-gel process with acid catalysts (e.g. hydrochloric acid). Moreover, we cannot find any disclosure about sol-gel process with basic catalysts. As mentioned above, if the method of directly introducing silicon dioxide particles is not adopted, the polyurethane composite material is produced with catalysts only.
- Accordingly, an aspect of the present invention is to provide a method for producing a compound. The compound is a polyurethane composite material and the method of the present invention produces the compound without any extra catalysts.
- According to an embodiment of the invention, the method comprises the following steps:
- First of all, polycaprolactone (PCL), dimethylol propionic acid (DMPA), 4, 4′-methylenebis (cyclohexyl isocyanate) (H12MDI), and dibutyltin dilaurate (DBT) are mixed in a solvent to form the first solution. Subsequently, the first solution is mixed with a triethylamine (TEA) solution to form a second solution and the second solution is mixed with deionized water to form a second aqueous solution. The second aqueous solution is mixed with triethylene tetramine (TETA) solution to form a third solution and the third solution is filtered in a pressure-reducing environment to obtain a waterborne polyurethane (WPU) solution. Particularly, the terminal of the waterborne polyurethane comprises an amino group.
- Furthermore, the waterborne polyurethane solution is mixed with tetraethylorthosilicate (TEOS) to form a fourth solution. Finally, part of the fourth solution is coated on a carrier and the solution on the carrier is heated, so as to produce the compound with thin film type.
- Another aspect of the present invention is to provide a compound which is polyurethane composite material produced without any extra catalyst.
- According to one embodiment of the invention, the compound comprises waterborne polyurethane and silicon dioxide. The terminal of the waterborne polyurethane comprises an amino group which is primary amine or other proper amino group. Silicon dioxide is mixed with the waterborne polyurethane.
- The objective of the present invention will no doubt become obvious to those of ordinary skills in the art after reading the following detailed description of the preferred embodiment, which is illustrated in the various figures and drawings.
-
FIG. 1 illustrates a producing flow chart according to one embodiment of the present invention. -
FIG. 2 illustrates FTIR spectrums of PCL, DMPA, H12MDI, TETA and WPU according to the present invention. -
FIG. 3 illustrates 29Si NMR spectrum of waterborne polyurethane-silica nanocomposite material according to the present invention. -
FIG. 4 illustrates TEM image of waterborne polyurethane-silica nanocomposite material of 20000 times according to the present invention. -
FIG. 5 illustrates contact angle testing result of waterborne polyurethane-silica nanocomposite material according to the present invention. -
FIG. 6 illustrates the tension intensity of waterborne polyurethane-silica nanocomposite material according to the present invention. -
FIG. 7 illustrates thermogravimetric analysis of waterborne polyurethane-silica nanocomposite material according to the present invention. - The present invention is to provide a compound and method for producing the same. The compound is a polyurethane composite material and the method for producing the compound without any extra catalyst. Embodiments of the present invention are disclosed as followed.
- Please refer to
FIG. 1 .FIG. 1 illustrates a flow chart according to one embodiment of the present invention. - As shown in
FIG. 1 , in one embodiment, the method comprises the following steps: - In step S110, PCL, DMPA, H12MDI, and DBT are mixed in a solvent to form the first solution. Subsequently, in step S112, the first solution is mixed with a TEA solution to form a second solution. In step S114, the second solution is mixed with deionized water to form a second aqueous solution. In step S116, the second aqueous solution is mixed with TETA solution to form a third solution. In step S118, the third solution is filtered in a pressure-reducing environment to obtain a waterborne polyurethane solution. The terminal of the waterborne polyurethane comprises an amino group. In step S120, the waterborne polyurethane solution is stirred rapidly and TEOS is added into the waterborne polyurethane solution simultaneously by an simultaneously by an in-situ approach to form the fourth solution. What is remarkable is the addition of TEOS brings a sol-gel process, so as to produce the compound of the present invention in the fourth solution. Finally, in step S122, part of the fourth solution is coated on a carrier and the solution on the carrier is heated, so as to form the compound with thin film type.
- The following detailed description describes the environment of the present method. What should be marked is the following procedures, materials, parameters and data are examples of the present invention, but not limited to it.
- First of all, a 500 ml PCL is set in a five-necked flask equipped with a proper temperature control apparatus and a pressure-reducing apparatus. PCL with magnetic stirring is degassed in a pressure-reducing environment at 110° C. for 30 minutes and cools down to room temperature (30° C.) under pressure-reducing station. H12MDI, DMPA, DBT, and some solvent are mixed to form a first solution which is proceeded a polymerization reaction at 60° C. for four hours. In practical application, the composition of the solvent can be acetone.
- After the first solution cools down to room temperature, the first solution and TEA solution are mixed to form a second solution wherein the TEA solution is formed by TEA mixed with the first solvent and the composition of the first solvent is substantially the same as the solvent. The second solution is stirred at 30° C. for one hour and the second solution is mixed with deionized water to form a second aqueous water. The second aqueous water is mixed with TETA solution to form a third solution wherein the TETA is mixed with the second solvent to form the TETA solution and the composition of the second solvent is substantially the same as the solvent. The third solution is stirred at 60° C. for one hour. After the third solution cools down to room temperature, the third solution is filtered in a pressure-reducing environment to get a waterborne polyurethane solution. The waterborne polyurethane is determined by a moisture titrator and the waterborne polyurethane occupies 26.5 wt %.
- In one embodiment, the terminal of the waterborne polyurethane comprises an amino group. In practical application, the amino group can be prime amine or other proper amino group. Additionally, the weight ratio of PCL:DMPA:H12MDI:TEA:TETA is 94.3:31.3:5.9:4.5:4.2, but not limited to this.
- Additionally, the characteristic peak of PCL, DMPA, H12MDI, TETA and waterborne polyurethane (WPU) are determined by FTIR. The determining result is as follows. The C═O characteristic peak of PCL exists at 1722 cm−1; the C—O and O—H characteristic peak of DMPA exists at 1683 cm−1 and 3359 cm−1 respectively; and the N═C characteristic peak of H12MDI exists at 2262 cm−1. After polymerization reaction to form WPU, the N═C (2262 cm−1) and O-H characteristic peaks (3359 cm−1) disappear. The primary amine —NH2 exists at 3223 cm−1 and 3319 cm−1 that can prove the production is amino-terminated anionic waterborne polyurethane.
- Furthermore, the WPU solution with TEOS is proceeded as a sol-gel process. First, pour some WPU solution into a beaker and stir the WPU solution rapidly. TEOS is added into the WPU solution simultaneously by an in-situ approach to form the fourth solution. The fourth solution is stirred at room temperature for one hour to proceed as a sol-gel process to obtain a composite solution. Part of composite solution is coated on a carrier and the carrier is set in a temperature-controllable non-convection baking oven. The temperature raising process is shown in table 1. A compound with thin film type on the carrier is obtained. As shown in table 1, the compound with thin film type is formed at 55° C., 75° C., 100° C., and 120° C.
-
TABLE 1 Process Temperature Time Temperature raised Room temp.~55° C. 16 hrs Holding temperature 55° C. 5 hrs Temperature raised 55° C.~75° C. 10 hrs Holding temperature 75° C. 3 hrs Temperature raised 75° C.~100° C. 5 hrs Holding temperature 100° C. 3 hrs Temperature raised 100° C.~120° C. 5 hrs Holding temperature 120° C. 3 hrs - In one embodiment, the compound produced by the method mentioned comprising waterborne polyurethane and silicon dioxide mixed with the waterborne polyurethane wherein the terminal of the waterborne polyurethane comprises an amino group which can be primary amine or other proper amino group.
- Waterborne polyurethane-silica nanocomposite material formed by an in-situ approach raises the heat resistance and the water repellency of polyurethane. The rigidity, heat resistance, and the water repellency are rising with the using weight of TEOS.
- In practical application, the content of silicon dioxide may change the characters of the compound of the present invention. Table 2 lists four compounds of the invention and weight of TEOS used. Sample a (SWPU) is waterborne polyurethane without silicon dioxide; Sample b (SWPU5) is a waterborne polyurethane-silica nanocomposite material with 5 wt % silicon dioxide (formed by adding 2.42 g TEOS); Sample c (SWPU10) is a waterborne polyurethane-silica nanocomposite material with 10 wt % silicon dioxide (formed by adding 5.10 g TEOS); and Sample d (SWPU15) is a waterborne polyurethane-silica nanocomposite material with 15 wt % silicon dioxide (formed by adding 8.15 g TEOS).
-
TABLE 2 Sample Weight of WPU Used Weight of TEOS Used a (SWPU) 50 g 0 g b (SWPU5) 50 g 2.42 g c (SWPU10) 50 g 5.10 g d (SWPU15) 50 g 8.15 g - In the following, different samples by (1) contact angle, (2) mechanical property, and (3) thermal property will be analyzed.
- First, sample d (SWPU15) is determined by 29Si NMR to obtain a silicon spectrum as shown in
FIG. 3 .FIG. 3 illustrates the character peaks of silicon chemical shift at −108.72 ppm, −98.14 ppm, and −93 ppm. The three character peaks correspond to Q4, Q3, and Q2 constructions respectively. Q4, Q3, and Q2 constructions are shown in the top right-hand corner ofFIG. 3 . The character peak of Q4 is clear that can prove the TEOS is proceeded as a sol-gel process to produce silicon dioxide. - Additionally,
FIG. 4 illustrates the TEM image of sample d (SWPU15) of 20000 times. The dark particles are silicon dioxide and the white parts are waterborne polyurethane base materials. The length of dark particles are approximately 30˜40 nm and disturb in the waterborne polyurethane materials uniformly. It shows that TEOS is proceeded as a sol-gel process to produce silicon dioxide. The conclusion is the same as above. - (1) Contact Angle Testing
-
FIG. 5 illustrates the data of contact angles on the sample surface determined by a contact angle meter. As shown inFIG. 5 , the contact angle of sample a (SWPU), without TEOS, is 67.2°. Samples with TEOS, for example, sample b (SWPU5, 5 wt % of silicon dioxide), the contact angle)(70.6°) raises 5%, compared with sample a, WPU with silicon dioxide can raise the degree of contact angle. Raising the using weight of TEOS of waterborne polyurethane, for example, sample c (SWPU10, 10 wt % of silicon dioxide), the determined contact angle compared with sample a raises 13% and sample d (SWPU15, 15 wt % of silicon dioxide), the determined contact angle (78.4)° compared with sample a raises 17%. As shown inFIG. 5 , the contact angle of waterborne polyurethane composite material raises with the using weight of the TEOS (it can produce silicon dioxide). - (2) Mechanical Property
- Determining the mechanical property by DMA, the strain speed is set 1 N/min and the thickness of the sample is 150 μm. Determine the stress and strain of the samples at room temperature.
FIG. 6 illustrates the testing result of mechanical property of samples with different content of silicon dioxide. Sample a (SWPU, waterborne polyurethane without silicon dioxide), sample b (SWPU5, waterborne polyurethane-silica composite material with 5 wt % silicon dioxide), sample c (SWPU10, waterborne polyurethane-silica composite material with 10 wt % silicon dioxide), and sample d (SWPU15, waterborne polyurethane-silica composite material with 15 wt % silicon dioxide) are represented as (a), (b), (c), and (d) respectively inFIG. 6 . As shown inFIG. 6 , take a sample, the magnitude of strain is 100% and the magnitude of stress is 1.5 MPa. A waterborne polyurethane base material with little TEOS, for example, sample b (SWPU5), the magnitude of strain is 100% and the magnitude of stress is 1.75 MPa compared with sample a, the magnitude of stress raised by 19%. With the same magnitude of stress, the magnitude of strain is 2.05 MPa for sample c (SWPU10); and the magnitude of strain is 2.10 MP for sample d (SWPU15) compared with the sample a, the magnitude of stress raising 35%. The mechanical intensity rises with the weight of TEOS used. - (3) Thermal Property
- The thermal stability of sample a, b, c and d are tested by TGA at
temperature 40˜800° C. The speed of raising temperature is 10° C./min and N2 gas is flown during testing. The result is shown inFIG. 7 . (a), (b), (c), and (d) represent sample a (SWPU), sample b (SWPU5), sample c (SWPU10), and sample d (SWPU15), respectively. The upper half ofFIG. 7 illustrates the relationship between thermal weight losing and temperature, and the lower half ofFIG. 7 illustrates the relationship between first order differentiation of thermal weight losing and temperature. Table 3 lists the date of thermal dissolution temperature. From the curve of first order differentiation, every sample has three dissolution stages. The first dissolution temperature is approximately 40˜300° C. wherein thermal weight decreases lightly and the dissolution temperature rises with the content of silicon dioxide. In the stage, thermal weight changes 6˜9 wt % and it may be due to the remainder water or molecules decomposing and the polymer which is aqueous dispersion polymer. The aqueous dispersion polymer waterborne polyurethane comprises 26.5 wt % waterborne polyurethane. After the TEOS is added to the solution, the content of compound is increased and the content of solvent is decreased. As shown in table 3, the thermal remainder weight is bigger than waterborne polyurethane without silicon dioxide. The temperature of the second dissolution stage is approximately 400˜500° C. The soft chain of waterborne polyurethane-silica decomposes mainly. - The relationship between thermal remainder weight and temperature shows the compound with TEOS with higher thermal resistance than waterborne polyurethane without silicon dioxide.
-
TABLE 3 Thermal remainder weight and temperature First dissolution stage, Second dissolution Third dissolution 40~300° C. stage, 300~400° C. stage, 400~500° C. Thermal Thermal Thermal remainder remainder remainder weighta weighta weighta Sample wt % ° C. Tmax b, ° C. wt % ° C. Tmax b, ° C. wt % ° C. Sample a (SWPU) 91.5 282 321 26.3 380 409 0.2 465 Sample b (SWPU5) 92.8 286 359 32.5 393 418 2.0 492 Sample c (SWPU10) 93.9 288 374 32.0 404 423 4.2 494 Sample d (SWPU15) 93.2 290 383 47.8 396 424 6.1 494 athermal remainder weight at the temperature btemperature of the maximum dissolution speed (Tmax) - To sum up, the present invention is to provide a method for producing a compound. The compound is a polyurethane composite material and the method of the present invention produces the compound without any extra catalyst. Polyurethane has the advantages of both being organic and inorganic. It is flexible, ductile, rigid, and high in thermal stability, so as to widen the applied scopes.
- Although the present invention has been illustrated and described with reference to the preferred embodiment thereof, it should be understood that it is in no way limited to the details of such an embodiment, but is capable of numerous modifications within the scope of the appended claims.
Claims (4)
1. A compound comprising: waterborne polyurethane, wherein the terminal of the waterborne polyurethane comprises an amino group; and silicon dioxide mixed with the waterborne polyurethane.
2. The compound of claim 1 , wherein the amino group is primary amine.
3. The compound of claim 1 , wherein the waterborne polyurethane is formed by the following steps: mixing polycaprolactone, dimethylol propionic acid, 4,4′-methylenebis (cyclohexyl isocyanate), dibutyltin dilaurate, triethylamine, and triethylene tetramine to form a solution; and filtering the solution in a pressure-reducing environment to form another solution comprising waterborne polyurethane.
4. The compound of claim 3 , wherein the solution is mixed with tetraethylorthorsilicate to form a mixing solution and a sol-gel process is proceeded in the mixing solution, so as to produce the compound in the mixing solution.
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CN115558080B (en) * | 2022-11-09 | 2024-05-10 | 贵州民族大学 | Modification method of waterborne polyurethane by hydroxyl silicone oil and boron phenolic aldehyde |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5095069A (en) * | 1990-08-30 | 1992-03-10 | Ppg Industries, Inc. | Internally-curable water-based polyurethanes |
US5908895A (en) * | 1996-06-22 | 1999-06-01 | Herberts Gesellschaft Beschrankter Haftung | Aqueous dispersion of silane-functional polyurethane resins, coating compositions and use thereof |
US6472465B1 (en) * | 1996-12-27 | 2002-10-29 | Bollig & Kemper | Coating composition |
US20040028826A1 (en) * | 2002-07-01 | 2004-02-12 | Stefanie Goecke | Process for coating to obtain special surface effects |
US6811825B1 (en) * | 1999-05-27 | 2004-11-02 | E. I. Du Pont De Nemours And Company | Aqueous dispersion comprising polyurethane-based resins and water-insoluble cellulose ester, methods for preparing and using same, and articles coated with same |
US20050085584A1 (en) * | 2003-09-18 | 2005-04-21 | Rudiger Musch | Aqueous adhesive dispersions |
US20060058453A1 (en) * | 2002-10-31 | 2006-03-16 | Argyropoulos John N | Polyurethane dispersion and articles prepared therefrom |
US20060258800A1 (en) * | 2005-05-11 | 2006-11-16 | Armin Goebel | Aqueous binder dispersions, process for the production thereof and coating compositions formulated therewith |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4554308A (en) * | 1978-10-02 | 1985-11-19 | Wilmington Chemical Corporation | Crosslinked polyurethane dispersions |
NL8401785A (en) * | 1984-06-04 | 1986-01-02 | Polyvinyl Chemie Holland | PROCESS FOR PREPARING AN AQUEOUS DISPERSION OF URETHAN ACRYLATE ENTCOPOLYMERS AND STABLE AQUEOUS DISPERSION THUS OBTAINED. |
US6423425B1 (en) * | 1998-05-26 | 2002-07-23 | Ppg Industries Ohio, Inc. | Article having a chip-resistant electrodeposited coating and a process for forming an electrodeposited coating |
US7261843B2 (en) * | 2004-03-04 | 2007-08-28 | Transitions Optical, Inc. | Photochromic optical article |
US8563212B2 (en) * | 2004-07-16 | 2013-10-22 | Transitions Optical, Inc. | Methods for producing photosensitive microparticles, non-aqueous dispersions thereof and articles prepared therewith |
US20060280949A1 (en) * | 2005-06-13 | 2006-12-14 | Shinsuke Shirakawa | Method for making amine-modified epoxy resin and cationic electrodeposition coating composition |
US7842762B2 (en) * | 2007-08-08 | 2010-11-30 | Ppg Industries Ohio, Inc. | Electrodepositable coating composition containing a cyclic guanidine |
-
2008
- 2008-12-08 US US12/330,382 patent/US8142857B2/en active Active
-
2012
- 2012-01-01 US US13/342,034 patent/US20120101203A1/en not_active Abandoned
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5095069A (en) * | 1990-08-30 | 1992-03-10 | Ppg Industries, Inc. | Internally-curable water-based polyurethanes |
US5908895A (en) * | 1996-06-22 | 1999-06-01 | Herberts Gesellschaft Beschrankter Haftung | Aqueous dispersion of silane-functional polyurethane resins, coating compositions and use thereof |
US6472465B1 (en) * | 1996-12-27 | 2002-10-29 | Bollig & Kemper | Coating composition |
US6811825B1 (en) * | 1999-05-27 | 2004-11-02 | E. I. Du Pont De Nemours And Company | Aqueous dispersion comprising polyurethane-based resins and water-insoluble cellulose ester, methods for preparing and using same, and articles coated with same |
US20040028826A1 (en) * | 2002-07-01 | 2004-02-12 | Stefanie Goecke | Process for coating to obtain special surface effects |
US20060058453A1 (en) * | 2002-10-31 | 2006-03-16 | Argyropoulos John N | Polyurethane dispersion and articles prepared therefrom |
US20050085584A1 (en) * | 2003-09-18 | 2005-04-21 | Rudiger Musch | Aqueous adhesive dispersions |
US20060258800A1 (en) * | 2005-05-11 | 2006-11-16 | Armin Goebel | Aqueous binder dispersions, process for the production thereof and coating compositions formulated therewith |
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US20100143597A1 (en) | 2010-06-10 |
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