Melamine-formaldehyde resin composition and its product
10975237 ยท 2021-04-13
Assignee
Inventors
Cpc classification
C08L2201/08
CHEMISTRY; METALLURGY
International classification
Abstract
Provided is a melamine-formaldehyde resin composition. In a first aspect, the melamine-formaldehyde resin composition has at least one melamine oligomer with a mass-to-charge ratio (m/z) ranging from 393 to 692. Based on the total area of all chromatographic peaks in the melamine-formaldehyde resin composition, the sum of the areas of the chromatographic peaks with m/z of 393 to 692 ranges from 2% to 20%. In a second aspect, the melamine-formaldehyde resin composition comprises 2,4,6-tri[bis(methoxymethyl)amino]-1,3,5-triazine, and the area thereof ranges from 15% to 33% based on the total area of all chromatographic peaks in the melamine-formaldehyde resin composition. The melamine-formaldehyde resin composition of the present invention has superior freeze resistance and extended low-temperature storage life.
Claims
1. A melamine-formaldehyde resin composition, comprising at least one melamine oligomer; wherein the melamine-formaldehyde resin composition is analyzed by Liquid Chromatography-Mass Spectrometry (LC-MS), obtaining that the mass-to-charge ratio (m/z) of the at least one melamine oligomer ranges from 393 to 692; wherein based on the total area of all chromatographic peaks in the melamine-formaldehyde resin composition, the sum of the areas of the chromatographic peaks with m/z of 393 to 692 ranges from 2% to 20%.
2. The melamine-formaldehyde resin composition as claimed in claim 1, wherein the at least one melamine oligomer has structure(s) represented by the following Formula (D: ##STR00010## wherein a is an integer from 2 to 6, b is an integer from 1 to 6, and R.sub.1 and R.sub.2 are each independently a hydroxyl group or a methoxy group.
3. The melamine-formaldehyde resin composition as claimed in claim 2, wherein the m/z of the at least one melamine oligomer ranges from 393 to 452.
4. The melamine-formaldehyde resin composition as claimed in claim 3, wherein based on the total area of all chromatographic peaks in the melamine-formaldehyde resin composition, the sum of the areas of the chromatographic peaks with m/z of 393 to 452 ranges from 5% to 15%.
5. The melamine-formaldehyde resin composition as claimed in claim 3, wherein based on the total area of all chromatographic peaks in the melamine-formaldehyde resin composition, the sum of the areas of the chromatographic peaks with m/z of 393 to 452 ranges from 7% to 12%.
6. The melamine-formaldehyde resin composition as claimed in claim 3, wherein based on the total area of all chromatographic peaks in the melamine-formaldehyde resin composition, the sum of the areas of the chromatographic peaks with m/z of 393 to 452 ranges from 5% to 8%.
7. The melamine-formaldehyde resin composition as claimed in claim 4, wherein the at least one melamine oligomer has structure(s) represented by the following Formula (II) to Formula (V): ##STR00011##
8. The melamine-formaldehyde resin composition as claimed in claim 1, wherein the melamine-formaldehyde resin composition further comprises a component represented by the following Formula (VI): ##STR00012## wherein the m/z of the component represented by Formula (VI) ranges from 300 to 310, and based on the total area of all chromatographic peaks in the melamine-formaldehyde resin composition, the area of the chromatographic peak with m/z of 300 to 310 ranges from 1.15% to 2.50%.
9. The melamine-formaldehyde resin composition as claimed in claim 8, wherein the melamine-formaldehyde resin composition further comprises a component represented by the following Formula (VII): ##STR00013## wherein the m/z of the component represented by Formula (VII) ranges from 330 to 340, and based on the total area of all chromatographic peaks in the melamine-formaldehyde resin composition, the sum of the areas of the chromatographic peaks with m/z of 300 to 310 and 330 to 340 ranges from 1.8% to 5.0%.
10. A melamine-formaldehyde resin product, which is formed by solidifying the melamine-formaldehyde resin composition as claimed in claim 1.
11. A melamine-formaldehyde resin composition, comprising 2,4,6-tri[bis(methoxymethyl)amino]-1,3,5-triazine represented by the following Formula (VIII): ##STR00014## wherein the melamine-formaldehyde resin composition is analyzed by LC-MS, obtaining that based on the total area of all chromatographic peaks in the melamine-formaldehyde resin composition, the area of the chromatographic peak of 2,4,6-tri[bis(methoxymethyl)amino]-1,3,5-triazine ranges from 15% to 33%.
12. The melamine-formaldehyde resin composition as claimed in claim 11, wherein based on the total area of all chromatographic peaks in the melamine-formaldehyde resin composition, the area of the chromatographic peak of 2,4,6-tri[bis(methoxymethyl)amino]-1,3,5-triazine ranges from 20% to 31%.
13. The melamine-formaldehyde resin composition as claimed in claim 11, wherein based on the total area of all chromatographic peaks in the melamine-formaldehyde resin composition, the area of the chromatographic peak of 2,4,6-tri[bis(methoxymethyl)amino]-1,3,5-triazine ranges from 20% to 28%.
14. The melamine-formaldehyde resin composition as claimed in claim 11, wherein the melamine-formaldehyde resin composition further comprises at least one melamine oligomer with m/z ranging from 393 to 692, and based on the total area of all chromatographic peaks in the melamine-formaldehyde resin composition, the sum of the areas of the chromatographic peaks with m/z of 393 to 692 ranges from 2% to 20%.
15. The melamine-formaldehyde resin composition as claimed in claim 14, wherein the at least one melamine oligomer has structure(s) represented by the following Formula (I): ##STR00015## wherein a is an integer from 2 to 6, b is an integer from 1 to 6, and R.sub.1 and R.sub.2 are each independently a hydroxyl group or a methoxy group.
16. The melamine-formaldehyde resin composition as claimed in claim 15, wherein the m/z of the at least one melamine oligomer ranges from 393 to 452, and based on the total area of all chromatographic peaks in the melamine-formaldehyde resin composition, the sum of the areas of the chromatographic peaks with m/z of 393 to 452 ranges from 5% to 15%.
17. The melamine-formaldehyde resin composition as claimed in claim 15, wherein the m/z of the at least one melamine oligomer ranges from 393 to 452, and based on the total area of all chromatographic peaks in the melamine-formaldehyde resin composition, the sum of the areas of the chromatographic peaks with m/z of 393 to 452 ranges from 7% to 12%.
18. The melamine-formaldehyde resin composition as claimed in claim 15, wherein the m/z of the at least one melamine oligomer ranges from 393 to 452, and based on the total area of all chromatographic peaks in the melamine-formaldehyde resin composition, the sum of the areas of the chromatographic peaks with m/z of 393 to 452 ranges from 5% to 8%.
19. The melamine-formaldehyde resin composition as claimed in claim 16, wherein the at least one melamine oligomer has structure(s) represented by the following Formula (II) to Formula (V): ##STR00016##
20. The melamine-formaldehyde resin composition as claimed in claim 11, wherein the melamine-formaldehyde resin composition further comprises a component represented by the following Formula (VI): ##STR00017## wherein the m/z of the component represented by Formula (VI) ranges from 300 to 310, and based on the total area of all chromatographic peaks in the melamine-formaldehyde resin composition, the area of the chromatographic peak with m/z of 300 to 310 ranges from 1.15% to 2.50%.
21. The melamine-formaldehyde resin composition as claimed in claim 20, wherein the melamine-formaldehyde resin composition further comprises a component represented by the following Formula (VII): ##STR00018## wherein the m/z of the component represented by Formula (VII) ranges from 330 to 340, and based on the total area of all chromatographic peaks in the melamine-formaldehyde resin composition, the sum of the areas of the chromatographic peaks with m/z of 300 to 310 and 330 to 340 ranges from 1.8% to 5.0%.
22. A melamine-formaldehyde resin product, which is formed by solidifying the melamine-formaldehyde resin composition as claimed in claim 11.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1)
(2)
(3)
(4)
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
(5) Several examples are exemplified below to illustrate the implementations of the melamine-formaldehyde resin composition, while several comparative examples are provided as comparison. A person skilled in the art can easily realize the advantages and effects of the present invention from the following examples and comparative examples. The descriptions proposed herein are just preferable embodiments for the purpose of illustrations only, not intended to limit the scope of the present invention. Various modifications and variations could be made in order to practice or apply the present invention without departing from the spirit and scope of the invention.
(6) Melamine-Formaldehyde Resin Compositions
Examples 1 to 7 (S1 to S7)
(7) As shown in
(8) First, 238 grams (g) of paraform was weighed, and 171 g of methanol was added to the paraform, both of which were stirred to form a mixed solution. The pH value of the mixed solution was adjusted with sodium hydroxide to 10.50.5. The mixed solution was then heated to 50 C. to completely dissolve the paraform. At this time, the mixed solution was transparent.
(9) Next, 106 g of melamine was added to the mixed solution in which the pH value thereof was readjusted to 10.50.5 by adding sodium hydroxide. 94 g of methanol was added, and then the mixed solution was heated to 70 C. and kept for 90 minutes.
(10) After that, 65 g of methanol was added, and the mixed solution was processed with etherification for a period of time indicated in Table 1 below. Upon completing the etherification, the mixed solution was distilled under 760 torr and 98 C. and then distilled under reduced pressure of 80 torr and 105 C.
(11) Subsequently, 270 g of methanol was added to the mixed solution in which the pH value thereof was adjusted by the addition of hydrochloric acid to 4.00.5 and maintained for 20 minutes. Then, the pH value of the mixed solution was adjusted to 9.50.5 by adding an appropriate amount of sodium hydroxide.
(12) Thereafter, the mixed solution was distilled under 760 torr and 98 C. and then distilled under reduced pressure of 80 torr and 105 C. After 60 minutes, the solid residue was filtered to obtain the melamine-formaldehyde resin compositions of Examples 1 to 7.
Comparative Examples 1 to 3 (C1 to C3)
(13) As shown in
(14) First, 367.2 g of hexamethylol melamine (HMM) was weighed, and 413.3 g of methanol was added. The HMM was stirred to be dissolved, and a mixed solution was obtained.
(15) After that, the mixed solution was processed with etherification for a period of time indicated in Table 1 below. Upon completing the etherification, the mixed solution was distilled under 760 torr and 98 C. and then distilled under reduced pressure of 80 torr and 115 C.
(16) Subsequently, 413.3 g of methanol was added to the mixed solution in which the pH value thereof was adjusted to 3.00.5 by the addition of hydrochloric acid. The mixed solution was heated to 691 C. and maintained for 20 minutes. Then, the pH value of the mixed solution was adjusted to 9.50.5 by adding sodium hydroxide.
(17) Thereafter, the mixed solution was distilled under 760 torr and 98 C. and then distilled under reduced pressure of 80 torr and 140 C. After 60 minutes, the solid residue was filtered to obtain the melamine-formaldehyde resin compositions of Comparative Examples 1 to 3.
Test Example 1: High Performance Liquid Chromatography-Mass Spectroscopy (HPLC-MS) Analysis
(18) In this test example, the melamine-formaldehyde resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 were used as test samples, which were analyzed by High Performance Liquid Chromatography (HPLC) coupled with Mass Spectrometry (MS) under the following conditions to respectively clarify components and area ratios thereof in the melamine-formaldehyde resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3.
(19) The parameters of HPLC:
(20) 1. Brand: SHIMADZU;
(21) 2. System Controller: SCL-20A;
(22) 3. Autoinjector: SCL-20A;
(23) 4. Pump: LC-20AT;
(24) 5. Detector: UV/Vis SPD-20A;
(25) 6. Detective Wavelength: 235 nanometers (nm);
(26) 7. Column: Inertsil ODS-2 (inner diameter: 4.6 millimeters (mm), length: 250 mm; particle size: 5 micrometers (m))
(27) 8. Mobile Phase:
(28) (1) 0 minute to 60 minutes: gradient elution with methanol: water from 30:70 gradually increasing to 70:30 (volume percentage), and
(29) (2) 60 minutes to 90 minutes: isocratic elution with methanol: water of 70:30 (volume percentage);
(30) 9. Mobile Phase Velocity: 1 milliliter per minute (mL/min).
(31) The parameters of MS:
(32) 1. Brand and Model: SHIMADZU LCMS-8045;
(33) 2. Ionization Source: Electrospray Ionization (ESI);
(34) 3. Nebulizing Gas Flow: 3 liters per minute (L/min);
(35) 4. Heating Gas Flow: 10 L/min;
(36) 5. Interface Temperature: 300 C.;
(37) 6. DL Temperature: 250 C.;
(38) 7. Heat Block Temperature: 400 C.;
(39) 8. Drying Gas Flow: 10 L/min;
(40) 9. Mass Analyzer: Triple-Quadrupole (QqQ).
(41)
(42) Herein, the area of each of the chromatographic peaks in each of the HPLC chromatograms was identified by a computer. If the width of the signal along the x-axis in an HPLC chromatogram was less than 5 seconds and the UV intensity of the signal was less than 200 per minute, the signal was determined as a noise.
(43) In addition, the mass-to-charge ratio (m/z) of each of the collected fractions under different retention times was analyzed by a mass spectrometer and indicated in Table 1 below. The specific component corresponding to each of the fractions is indicated in
(44) ##STR00008## ##STR00009##
Test Example 2: Freeze Resistance
(45) In this test example, the melamine-formaldehyde resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 were used as test samples. 10 mL of each of the test samples were sampled and respectively put in a 20-mL sample bottle. All the sample bottles were kept still at room temperature for about an hour to ensure that there was no air bubble present in the sample bottles.
(46) Next, all the sample bottles were stored in a 15 C. refrigerator (low-temperature environment). Each of the test samples was examined whether crystals appeared on the liquid surface or on the wall of the sample bottle at the same time on the next day (the 2.sup.nd day). If crystals were observed on the 2.sup.nd day for a test sample that had been stored in the low-temperature environment, it meant the low-temperature storage life of the test sample was less than one day, which was indicated as <1 day. If crystals were not observed on the 2.sup.nd day, it meant the test sample could resist freezing for at least one day. After recording the duration of freeze resistance, the test sample was put back to the 15 C. refrigerator and reexamined on the next day (the 3.sup.rd day). If crystals were not observed on the 2.sup.nd day but were observed on the 3.sup.rd day, it meant the low-temperature storage life of the test sample was more than 1 day but less than 2 days, which was indicated as 1 day. If crystals were not observed on the 3.sup.rd day, it meant the test sample could resist freezing for at least two days. After recording the duration of freeze resistance, the test sample was put back to the 15 C. refrigerator and reexamined on the next day (the 4.sup.th day). All the test samples were examined day by day in a manner mentioned above. If crystals were not observed on the 15.sup.th day, it meant the test sample could resist freezing for at least 14 days. The low-temperature storage life of the test sample was recorded as 14 days, which meant the test sample could resist freezing for more than two weeks. The low-temperature storage life of each of the test samples was indicated in Table 1 below.
(47) TABLE-US-00001 TABLE 1 The etherification time, the area ratios of chromatographic peaks, and the low-temperature storage life of the melamine-formaldehyde resin composition of each of Examples 1 to 7 (S1 to S7) and Comparative Examples 1 to 3 (C1 to C3). S1 S2 S3 S4 S5 S6 S7 C1 C2 C3 Etherification Time (min) 43 55 42 50 52 45 48 56 50 46 Component m/z Area Ratios of Chromatographic Peaks (%) a 303 1.34 1.32 1.38 1.43 1.39 1.19 2.11 1.20 1.11 1.02 b 333 0.51 0.65 0.56 0.59 0.59 0.92 2.46 0.57 0.36 0.50 c 347 9.70 10.39 10.27 10.84 10.67 10.42 13.17 10.03 10.50 10.30 d 377 2.00 3.12 2.07 2.60 2.33 4.89 8.67 1.86 1.59 2.78 e 393 1.04 1.09 1.19 0.84 0.89 1.73 3.07 0.28 0.26 0.22 f 407 0.23 0.39 0.25 0.24 0.23 0.91 1.98 0.05 0.04 0.06 g 391 26.31 29.66 27.45 30.71 30.29 28.80 20.32 34.82 33.19 39.02 h 421 5.37 6.32 5.76 4.37 4.26 7.17 5.34 1.02 1.20 1.16 i 451 0.49 0.62 0.55 0.37 0.37 0.75 0.68 0.07 0.07 0.05 a + b 1.85 1.97 1.94 2.02 1.98 2.11 4.57 1.77 1.47 1.52 e + f + h + i 7.13 8.42 7.75 5.82 5.75 10.56 11.07 1.42 1.57 1.49 Low-Temperature Storage Life (days) 14 14 14 8 5 14 14 <1 1 <1
(48) Discussion
(49) As shown in Table 1 above, based on the total area of all chromatographic peaks in each of the melamine-formaldehyde resin compositions, the sum of the areas of the chromatographic peaks with m/z of 393 to 692 (e.g. the chromatographic peaks of components e, f, h, and i in each of the melamine-formaldehyde resin compositions of Examples 1 to 7) ranges from 2% to 20%. In contrast, based on the total area of all chromatographic peaks in each of the melamine-formaldehyde resin compositions, the sum of the areas of the chromatographic peaks with m/z of 393 to 692 in each of the melamine-formaldehyde resin compositions of Comparative Examples 1 to 3 is beyond the above-mentioned range, i.e., less than 2%. Comparing the low-temperature storage life of the melamine-formaldehyde resin compositions of Examples 1 to 7 to that of Comparative Examples 1 to 3, the low-temperature storage life of the melamine-formaldehyde resin compositions of Examples 1 to 7 is at least 5 days, and even more than 14 days; however, the low-temperature storage life of the melamine-formaldehyde resin compositions of Comparative Examples 1 to 3 is only 1 day or even less than 1 day. Therefore, the experimental results show that controlling the area ratio of the chromatographic peaks with m/z of 393 to 692 increases the freeze resistance of the melamine-formaldehyde resin composition, resulting in a prolonged low-temperature storage life. In addition, the person skilled in the art could also understand that controlling the area ratio of the chromatographic peaks of other components similar to components e, f, h, and i in the melamine-formaldehyde resin composition could also improve the freeze resistance and prolong the storage life in low-temperature environments of the melamine-formaldehyde resin composition.
(50) The experimental results in Table 1 are analyzed from another perspective. Based on the total area of all chromatographic peaks in each of the melamine-formaldehyde resin compositions, the area of the chromatographic peak of component g (2,4,6-tri[bis(methoxymethyl)amino]-1,3,5-triazine) in each of the melamine-formaldehyde resin compositions of Examples 1 to 7 is less than 33%, while the area of the chromatographic peak of component g in each of the melamine-formaldehyde resin compositions of Comparative Examples 1 to 3 is more than 33%. Comparing the low-temperature storage life of the melamine-formaldehyde resin compositions of Examples 1 to 7 to that of Comparative Examples 1 to 3, the low-temperature storage life of the melamine-formaldehyde resin compositions of Examples 1 to 7 is at least 5 days, wherein each of Examples 1 to 3 and 6 to 7 has a low-temperature storage life of even more than 14 days; however, the low-temperature storage life of the melamine-formaldehyde resin compositions of Comparative Examples 1 to 3 is only 1 day or even less than 1 day. The experimental results show that controlling the area ratio of the chromatographic peak of component g would suppress or reduce crystal formation, thereby improving the freeze resistance and prolonging the storage life in low-temperature environments of the melamine-formaldehyde resin composition.
(51) In addition, the components of each of the melamine-formaldehyde resin compositions of Examples 1 to 7 are further analyzed. It is observed that controlling the sum of the area ratios of the chromatographic peak with m/z of 300 to 310 (e.g. the chromatographic peak of component a) and the chromatographic peak with m/z of 330 to 340 (e.g. the chromatographic peak of component b) to be more than 1.80% could increase the freeze resistance of the melamine-formaldehyde resin composition, so that the low-temperature storage life thereof is at least 5 days.
(52) In summary, by controlling the area ratio of the chromatographic peak of the specific component in the melamine-formaldehyde resin composition, e.g. controlling the area ratios of the chromatographic peaks of the melamine oligomers (components e, f, h, and i) or controlling the area ratio of chromatographic peak of 2,4,6-tri[bis(methoxymethyl)amino]-1,3,5-triazine (component g), crystal formation in the melamine-formaldehyde resin composition could be effectively suppressed and freeze resistance of the melamine-formaldehyde resin composition could be improved, thereby increasing the low-temperature storage life and the range of application of the melamine-formaldehyde resin composition.
(53) Even though numerous characteristics and advantages of the present invention have been set forth in the foregoing description, together with details of the structure and features of the invention, the disclosure is illustrative only. Changes may be made in the details, especially in matters of shape, size, and arrangement of parts within the principles of the invention to the full extent indicated by the broad general meaning of the terms in which the appended claims are expressed.