Aminated starch composition as well as preparation method and application thereof
Through room temperature solid phase reaction method and sodium dodecyl sulfonate assisted catalysis, a high-substitution amination starch composition was prepared, solving the difficulty of existing modified starch in industrial applications, and achieving the effect of improving PU leather performance and biodegradability of materials.
Patent Information
- Application Number
- CN202411827308.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-12
- Publication Date
- 2025-04-11
AI Technical Summary
The substitution degree of modified starch in the prior art is not high, and there is a certain difficulty in industrial application, which limits the widespread application of starch in industry.
A room temperature solid phase reaction method and the auxiliary catalysis of the surfactant sodium dodecyl sulfonate was prepared, including 8 to 12 parts by mass of soluble starch, 1.5 to 1.7 parts by mass of sodium dodecyl sulfonate and 8.3 to 8.5 parts by mass of alkanolamine.
Through this process, the amination starch prepared has a high degree of substitution and is suitable for PU leather additive powder materials, which improves the performance of PU leather, is relatively cheap, and promotes the biodegradability of the material.
Smart Images
Figure CN119798796A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of polymer materials, and in particular to an aminated starch composition and a preparation method and application thereof. Background Art
[0002] Starch is a widely available, biodegradable natural polymer material, but its inherent properties have limited its application in industry. In the prior art, the methods for modifying starch mainly include chemical modification, physical modification, bioenzyme modification and genetic modification. In general, the degree of substitution of modified starch is not high, and it is also difficult to apply starch modification in industry using general methods. Summary of the invention
[0003] Based on the above shortcomings, the present invention uses a room temperature solid phase reaction method and uses a surfactant sodium dodecyl sulfate to assist in catalysis (composite modification) to prepare an aminated starch. The present invention provides an aminated starch composition and a preparation method and application thereof. The content of the present invention is as follows: The first object of the present invention is to provide an aminated starch composition, which comprises 8 to 12 parts by mass of soluble starch, 1.5 to 1.7 parts by mass of sodium dodecyl sulfate and 8.3 to 8.5 parts by mass of alkanolamine.
[0004] In order to better implement the above technical solution, the particle size of the soluble starch in the aminated starch composition of the present invention is 300-500 mesh.
[0005] In order to better realize the above technical scheme, the alkanolamine in the aminated starch composition of the present invention is at least one of ethanolamine, diethanolamine and triethanolamine.
[0006] The second object of the present invention is to provide a method for preparing aminated starch, which comprises the following steps: Step 1, accurately weighing soluble starch, sodium dodecyl sulfate and alkanolamine and placing them in a reaction dish to obtain a mixture; Step 2, putting the mixture obtained in step 1 into a ball mill, adding steel balls, tightly covering the ball mill and labeling it, and using a planetary ball mill for ball milling; Step 3: After the ball milling in step 2 is completed, wait for 8 to 12 minutes to allow the ball mill to cool, then take out the powder material obtained by ball milling and place it in an ethanol aqueous solution with a volume fraction of 40 to 60 wt%; Step 4: After the standing is completed, the powder material is repeatedly filtered and washed using a circulating water vacuum pump until no obvious bubbles appear on the surface of the filtrate in the filtration bottle; Step 5: Pour the dried powder material into a clean 1000 mL beaker and place it in an oven for drying. The oven temperature is set to 80-100°C and the drying time is 46-50 hours. Step six, using a pulverizer to pulverize the dried sample and pass it through a 300-500 mesh sieve, then store it in a sample bag and seal it to obtain the aminated starch.
[0007] In order to better implement the above technical solution, in step 2 of the method for preparing aminated starch of the present invention, the operating conditions of the star ball mill are set as follows: the ball milling speed is 140-160 r / min, and the ball milling time is 80-100 min.
[0008] In order to better implement the above technical solution, the standing time in step 3 of the method for preparing aminated starch of the present invention is 100 to 140 minutes.
[0009] In order to better implement the above technical solution, the number of washing times in step 4 of the method for preparing aminated starch of the present invention is 6 to 10 times.
[0010] The second object of the present invention is to provide an application of aminated starch, and the technical point is that the aminated starch is used as a PU leather auxiliary powder material in PU leather.
[0011] The aminated starch composition of the present invention comprises 8-12 parts by weight of soluble starch, 1.5-1.7 parts by weight of sodium dodecyl sulfate and 8.3-8.5 parts by weight of alkanolamine, is non-toxic and pollution-free, is environmentally friendly, and embodies the advantages of green and clean production.
[0012] The aminated starch of the present invention is prepared by a room temperature solid phase reaction method and using a surfactant sodium dodecyl sulfate as an auxiliary catalysis (composite modification), and the process is simple to operate.
[0013] Compared with the existing PU leather auxiliary powder materials (poplar wood powder and pine wood powder) on the market, the application of the aminated starch of the present invention as a PU leather auxiliary powder material in PU leather improves the performance of PU leather, has relatively low cost, and can promote the biodegradability of the material. BRIEF DESCRIPTION OF THE DRAWINGS
[0014] Figure 1 It is a combination diagram of Fourier transform infrared spectra of soluble starch and prepared aminated starch; Figure 2 X-ray diffraction spectra of soluble starch and prepared aminated starch; Figure 3 is the SEM image of soluble starch (ST); Figure 4This is a SEM image of the aminated starch (ST-MEA) prepared in Example 1; Figure 5 This is a SEM image of the aminated starch (ST-DEA) prepared in Example 2; Figure 6 This is the SEM image of the aminated starch (ST-TEA) prepared in Example 3. DETAILED DESCRIPTION
[0015] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be clearly and completely described below in combination with the specific embodiments of the present invention and the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. Example 1
[0016] An aminated starch composition includes 10 g of soluble starch (ST), 1.6 g of sodium dodecyl sulfate and 8.4 g of alkanolamine.
[0017] Furthermore, the particle size of the soluble starch in this embodiment is 400 mesh.
[0018] Furthermore, the alkanolamine in this embodiment is ethanolamine.
[0019] The preparation method of an aminated starch of the present embodiment comprises the following steps: Step 1, accurately weighing soluble starch, sodium dodecyl sulfate and ethanolamine and placing them in a reaction dish to obtain a mixture; Step 2, putting the mixture obtained in step 1 into a ball mill, adding steel balls, tightly covering the ball mill and labeling it, and using a planetary ball mill for ball milling; Step 3: After the ball milling in step 2 is completed, wait for 10 minutes to allow the ball mill to cool down, then take out the powder material obtained by ball milling and place it in a 50wt% ethanol aqueous solution; Step 4: After the standing is completed, the powder material is repeatedly filtered and washed using a circulating water vacuum pump until no obvious bubbles appear on the surface of the filtrate in the filtration bottle; Step 5: Pour the dried powder material into a clean 1000 mL beaker and place it in an oven for drying. The oven temperature is set to 90°C and the drying time is 48 hours. Step 6: Use a grinder to grind the dried sample and pass it through a 400-mesh sieve, then store it in a sealed sample bag to obtain aminated starch (referred to as ST-MEA, such as Figure 4 SEM images shown).
[0020] Furthermore, in step 2 of this embodiment, the operating conditions of the star ball mill are set as follows: the ball milling speed is 150 r / min, and the ball milling time is 90 min.
[0021] Furthermore, in step three of this embodiment, the standing time is 120 minutes.
[0022] Furthermore, the number of washing times in step 4 of this embodiment is 8 times.
[0023] The aminated starch prepared in this example was used as a PU leather auxiliary powder material (wood powder) in PU leather to prepare a PU leather product (denoted as JX-2). Example 2
[0024] An aminated starch composition includes 8 g of soluble starch (ST), 1.5 g of sodium dodecyl sulfate and 8.3 g of alkanolamine.
[0025] Furthermore, the particle size of the soluble starch in this embodiment is 300 mesh.
[0026] Furthermore, the alkanolamine in this embodiment is diethanolamine.
[0027] The preparation method of an aminated starch of the present embodiment comprises the following steps: Step 1, accurately weighing soluble starch, sodium dodecyl sulfate and diethanolamine and placing them in a reaction dish to obtain a mixture; Step 2, putting the mixture obtained in step 1 into a ball mill, adding steel balls, tightly covering the ball mill and labeling it, and using a planetary ball mill for ball milling; Step 3: After the ball milling in step 2 is completed, wait for 8 minutes to allow the ball mill to cool down, then take out the powder material obtained by ball milling and place it in an ethanol aqueous solution with a volume fraction of 40wt%; Step 4: After the standing is completed, the powder material is repeatedly filtered and washed using a circulating water vacuum pump until no obvious bubbles appear on the surface of the filtrate in the filtration bottle; Step 5: Pour the dried powder material into a clean 1000 mL beaker and place it in an oven for drying. The oven temperature is set to 80°C and the drying time is 50 hours. Step 6: Use a grinder to grind the dried sample and pass it through a 300-mesh sieve, then store it in a sealed sample bag to obtain aminated starch (referred to as ST-DEA, such as Figure 5 SEM images shown).
[0028] Furthermore, in step 2 of this embodiment, the operating conditions of the star ball mill are set as follows: the ball milling speed is 140 r / min, and the ball milling time is 100 min.
[0029] Furthermore, in step 3 of this embodiment, the standing time is 100 minutes.
[0030] Furthermore, the number of washing times in step 4 of this embodiment is 6 times.
[0031] The aminated starch prepared in this example was used as a PU leather auxiliary powder material (wood powder) in PU leather to prepare a PU leather product (denoted as JX-3). Example 3
[0032] An aminated starch composition includes 12 g of soluble starch (ST), 1.7 g of sodium dodecyl sulfate and 8.5 g of alkanolamine.
[0033] Furthermore, the particle size of the soluble starch in this embodiment is 500 mesh.
[0034] Furthermore, the alkanolamine in this embodiment is triethanolamine.
[0035] The preparation method of an aminated starch of the present embodiment comprises the following steps: Step 1, accurately weighing soluble starch, sodium dodecyl sulfate and triethanolamine and placing them in a reaction dish to obtain a mixture; Step 2, putting the mixture obtained in step 1 into a ball mill, adding steel balls, tightly covering the ball mill and labeling it, and using a planetary ball mill for ball milling; Step 3: After the ball milling in step 2 is completed, wait for 12 minutes to allow the ball mill to cool down, then take out the powder material obtained by ball milling and place it in an ethanol aqueous solution with a volume fraction of 60wt%; Step 4: After the standing is completed, the powder material is repeatedly filtered and washed using a circulating water vacuum pump until no obvious bubbles appear on the surface of the filtrate in the filtration bottle; Step 5: Pour the dried powder material into a clean 1000 mL beaker and place it in an oven for drying. The oven temperature is set to 100°C and the drying time is 46 hours. Step 6: Use a grinder to grind the dried sample and pass it through a 500-mesh sieve, then store it in a sealed sample bag to obtain aminated starch (referred to as ST-TEA, such as Figure 6 SEM images shown).
[0036] Furthermore, in step 2 of this embodiment, the operating conditions of the star ball mill are set as follows: the ball milling speed is 160 r / min, and the ball milling time is 80 min.
[0037] Furthermore, in step 3 of this embodiment, the standing time is 140 minutes.
[0038] Furthermore, the number of washing times in step 4 of this embodiment is 10 times.
[0039] The aminated starch prepared in this example was used as a PU leather auxiliary powder material (wood powder) in PU leather to prepare a PU leather product (denoted as JX-4).
[0040] Test example The nitrogen content of the aminated starch and soluble starch (ST) prepared in Examples 1-3 was analyzed. The analysis results are shown in Table 1: The PU leather products prepared in Examples 1-3, the PU leather product (JX-1) prepared by the original formula of the enterprise, and the PU leather product (JX-1) prepared by replacing the wood powder in the original formula of the enterprise with soluble starch were tested for performance. The test results are shown in Table 2: Table 1 sample ST ST-MEA ST-DEA ST-TEA Nitrogen content 4.46% 20.01% 14.23% 11.17% Table 2 product JX-0 JX-1 JX-2 JX-3 JX-4 Tensile Strength 3.3 3.0 4.6 3.61 4.5 Elongation at break 5.3% 5.4% 8.5% 6.6% 7.5% Peel strength 3.1 2.9 3.4 3.7 4.2 from Figure 1 It can be seen that compared with soluble starch, the prepared aminated starch has a higher -1 A new stretching vibration peak of amino group (-NH2) appeared, which means that the amino group in the alcoholamine has been grafted onto the starch molecule, that is, the aminated starch was successfully prepared.
[0041] from Figure 2 It can be seen that the strongest diffraction peak of soluble starch is at 2θ of 17 o , so it can be determined that it is type A crystal. After reacting with ethanolamine, diethanolamine, and triethanolamine respectively, the diffraction angle 2θ of the aminated starch shifts to a wide angle, and the diffraction intensity decreases, which means that when the alcohol amino group replaces the hydrogen atom in the hydroxyl group of starch, the different spatial volumes of the amine group itself cause different steric hindrances. This leads to the difference in the XRD spectra of the aminated starch and the similarity of the crystal form, indicating that when the starch is aminated, the reaction only occurs in the amorphous region of the starch.
[0042] Figure 3 The results show that the microscopic surface morphology of soluble starch is mainly elliptical and spherical, with smooth surface and edge, and particle size of 10~50μm.
[0043] Figure 4 It shows that after starch reacts with ethanolamine, the surface morphology of the obtained aminated starch changes greatly, the surface of the original starch is destroyed, and pits, splits and agglomerations appear; this shows that starch does react with ethanolamine.
[0044] Figure 5It shows that after starch reacts with diethanolamine, the surface morphology of the obtained aminated starch changes greatly. The surface morphology of the original starch almost disappears, and it appears in large blocks, with wrinkles on the edges of the particles and severe agglomeration; this indicates that starch reacts with ethanolamine.
[0045] Figure 6 It shows that after the starch reacts with triethanolamine, the surface morphology of the aminated starch changes greatly, making the surface morphology of the original starch particles spherical, pitted, irregular, and rough. This indicates that the starch reacts with triethanolamine.
[0046] Due to the differences in the molecular size and polarity of the alcoholamines, the microscopic morphologies of the aminated starches are different, as well as the nitrogen content in the aminated starches.
[0047] Compared with the existing PU leather auxiliary powder materials (poplar wood powder and pine wood powder) on the market, the PU leather products prepared by this method have improved the performance of PU leather, are relatively low in cost, and can promote the biodegradability of materials. This technology and method has a wide range of applications and can have a certain effect on the chemical modification of biomass powder.
[0048] The above description is only an embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent substitution, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.
Claims
1. An aminated starch composition, characterized in that The invention comprises 8 to 12 parts by weight of soluble starch, 1.5 to 1.7 parts by weight of sodium dodecyl sulfate and 8.3 to 8.5 parts by weight of alkanolamine.
2. An aminated starch composition according to claim 1, characterized in that: The particle size of the soluble starch is 300-500 meshes.
3. An aminated starch composition according to claim 1, characterized in that: The alkanolamine is at least one of ethanolamine, diethanolamine and triethanolamine.
4. A method for preparing aminated starch, characterized in that: The following steps are involved: Step 1, accurately weighing soluble starch, sodium dodecyl sulfate and alkanolamine and placing them in a reaction dish to obtain a mixture; Step 2, putting the mixture obtained in step 1 into a ball mill, adding steel balls, tightly covering the ball mill and labeling it, and using a planetary ball mill for ball milling; Step 3: After the ball milling in step 2 is completed, wait for 8 to 12 minutes to allow the ball mill to cool, then take out the powder material obtained by ball milling and place it in an ethanol aqueous solution with a volume fraction of 40 to 60 wt%; Step 4: After the standing is completed, the powder material is repeatedly filtered and washed using a circulating water vacuum pump until no obvious bubbles appear on the surface of the filtrate in the filtration bottle; Step 5: Pour the dried powder material into a clean 1000 mL beaker and place it in an oven for drying. The oven temperature is set to 80-100°C and the drying time is 46-50 hours. Step six, using a pulverizer to pulverize the dried sample and pass it through a 300-500 mesh sieve, then store it in a sample bag and seal it to obtain the aminated starch.
5. The method for preparing an aminated starch according to claim 4, characterized in that: The operating conditions of the star ball mill in step 2 are set as follows: the ball milling speed is 140-160 r / min, and the ball milling time is 80-100 min.
6. The method for preparing an aminated starch according to claim 4, characterized in that: The standing time in step 3 is 100 to 140 minutes.
7. The method for preparing an aminated starch according to claim 4, characterized in that: The washing times in step 4 are 6 to 10 times.
8. An application of aminated starch, characterized in that: The aminated starch is used as a PU leather auxiliary powder material in PU leather.